WO2014151543A1 - Controlled radical polymerization initiators - Google Patents

Controlled radical polymerization initiators Download PDF

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Publication number
WO2014151543A1
WO2014151543A1 PCT/US2014/025960 US2014025960W WO2014151543A1 WO 2014151543 A1 WO2014151543 A1 WO 2014151543A1 US 2014025960 W US2014025960 W US 2014025960W WO 2014151543 A1 WO2014151543 A1 WO 2014151543A1
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Prior art keywords
independently
group
formula
represented
substituted
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PCT/US2014/025960
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French (fr)
Inventor
Charles R. Hickenboth
Cynthia Kutchko
Matthew J. Kryger
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Ppg Industries Ohio, Inc.
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Priority claimed from US13/833,828 external-priority patent/US8889807B2/en
Application filed by Ppg Industries Ohio, Inc. filed Critical Ppg Industries Ohio, Inc.
Publication of WO2014151543A1 publication Critical patent/WO2014151543A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C09K9/02—Organic tenebrescent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate

Definitions

  • the present invention relates to controlled radical polymerization
  • Initiators that include a spirooxazine compound or an indenonaphthopyran compound, polymers and polymer compositions prepared therefrom, and mechanochromic articles that include such polymers and/or polymer compositions.
  • Various articles, such as protective articles and support articles are typically fabricated at least In part from polymeric materials.
  • Protective articles, such as helmets, safety lenses, and protective housings, and support articles, such as beams can be subjected to stresses and/or impacts that result in damage to the article, which couid lead to catastrophic failure of the article at a point in time after the damage occurred.
  • the occurrence or presence of such damage is not accompanied by a visually observable indication thereof in the article.
  • the damaged article would not likely be withdrawn from use, and an unexpected catastrophic failure of the article couid occur.
  • Mechanochromic materials change color in response to a change in mechanical stress, such as impacts, ft is known thai mechanochromic materials can be incorporated into certain articles so as to provide a visual indication that the article has undergone a threshold mechanical stress event, which could result in catastrophic failure thereof.
  • Some mechanochromic materials can undergo a reduction in stability over time, which can result in reduced mechanochromic properties, A reduction in mechanochromic properties can be accompanied by an undesirable reduction in a visually observable indication that the article in question has undergone a threshold mechanical stress event.
  • a controlled radical polymerization Initiator comprising at least one radically transferable group
  • the controlled radical polymerization initiator comprises at least one of, (a) a spirooxazine compound and (b) an indenonap thopyran compound, that each independently comprise at least one radically transferable group.
  • n is from 1 to 4
  • p is from 1 to 2
  • q is from 1 to 4
  • R independently for each n, R 2 independently for each p, R 3 independently for each q, R , R s , and R 6 are each independently selected from hydrogen, hydrocarby! and substituted hydrocarby! each optionally interrupted with at least one of repeatedly o ⁇ , ⁇ S ⁇ » ⁇ C(Q ⁇ -, -0(0)0-, -OC(0)0-, -S(O)-, -S0 2 -, -N(R 1 )- S and -Si(R )(R 12 ⁇ - wherein R 1 and R 12 are each independently selected from hydrogen, hydrocarby! and substituted hydrocarby!, and combinations of two or more thereof.
  • the indenonaphthopyran is represented by the following Formula (If),
  • x is from 1 to 4
  • y is from 1 to 4
  • R 7 independently for each x, R 8 independently for each y, R 9 , and R 0 are each independently setected from hydrogen, hydrocarbyi and substituted hydrocar yi each optionally interrupted with at least one of -0-, -S-, -C(Oh -C(0)O, -OC(0)0-, -S(O)-, -S0 2 - » -N ⁇ R 1 1 ⁇ -, and -Si ⁇ R 11 ) ⁇ R 12 )- wherein R" and R 12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof, and
  • B and B' are each independently selected from unsubstituted aryl, substituted ary!, unsubstituted heteroaryl, substituted heteroaryl, and poiya!koxy, or B and B' taken together form a ring structure selected from unsubstituted fiuoren-9-y!idene, substituted fiuoren-9-yiidene, saturated spiro-monocyciic hydrocarbon ring, saturated spiro-bicycitc hydrocarbon ring, and spiro-tricyciic hydrocarbon ring.
  • a polymer composition comprising at least one polymer prepared by controlled radical polymerization initiated in the presence of a controlled radical polymerization initiator having at least one radically transferable group, wherein each polymer prepared by controlled radical polymerization Is independently represented by the following Formula (V),
  • fvl independently for each v is a residue of a monomer
  • ⁇ is a residue of the controlled radical polymerization initiator that Is free of the radically transferable group
  • X independently for each z, is or is derived from the radically transferable group
  • w Independently for each z, is an integer of at least 2
  • z is an integer of at least 1.
  • the controlled radical polymerization initiator from which the polymer represented by Formula (V) Is prepared is selected from (a) the spirooxazine compound represented by Formula (I) and/or (b) the indenonaphthopyran represented by Formula (II) as described above, and in each case as described in further detail herein.
  • linking groups such as divalent linking groups
  • left-to-right representations of linking groups are inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations.
  • the !eft-to ⁇ right representation of the divalent linking group is inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations.
  • molecular weight values of polymers such as weight average molecular weights (Mw) and number average molecular weights (Mn) are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
  • poiydispersit index (PD!) values represent a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/fvln).
  • polymer means homopolymers (e.g.. prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers,
  • (meth)acryiate and similar terms, such as “(meth)acry!ic acid ester” means methacrylates and/or acrylates.
  • (meth)acrylic acid means methacrylic acid and/or acrylic acid,
  • the terms “formed over,” “deposited over,” “provided over,” “applied over,” residing over,” or “positioned over,” mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct ⁇ or abutting) contact with the underlying element, or surface of the underlying element.
  • a layer “positioned over” a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.
  • ring position and related terms, such as “ring positions,” means a particular position in a ring structure, such as the fused ring structure, of a chemical compound, such as the spirooxazine compounds represented by Formula ⁇ 1 ⁇ and the indenonaphthopyran compounds represented by Formula (SI), and which are depicted herein in accordance with some embodiments by numbers within the ring structures of the related representative chemical formulas.
  • a chemical compound such as the spirooxazine compounds represented by Formula ⁇ 1 ⁇ and the indenonaphthopyran compounds represented by Formula (SI), and which are depicted herein in accordance with some embodiments by numbers within the ring structures of the related representative chemical formulas.
  • linear or branched groups such as linear or branched aiky!, are herein understood to include: a methylene group or a methyl group; groups that are linear, such as linear C 2 -C 2 o a!kyl groups; and groups that are appropriately branched, such as branched C 3 ⁇ C 20 alky! groups.
  • hydrocarbyf and similar terms such as “hydrocarbyl subsiiiuent,” means: linear or branched C C 25 alkyi (e.g. , linear or branched d-C 10 alkyi); linear or branched C 2 -C25 alkenyl ⁇ e.g., linear or branched C 2 ⁇ C10 alkenyl); linear or branched C 2 -C 25 alkynyl (e.g., linear or branched C 2 -C 10 alkynyl); C 3 -C1 ⁇ 2 cycloalkyi (e.g., C 3 ⁇ C- i0 cycloaikyl); C3-C 12 heterocycioalky!
  • C 5 -C ⁇ 8 aryi including polycyc!ic aryl groups
  • C 3 -Cio aryi including polycyc!ic aryl groups
  • C 5 "C 8 heteroary! having at least one hetero atom in the aromatic ring
  • Ce-C 24 aralkyl e.g., C 6 -C 10 araikyl
  • Representative alkyi groups include but are not limited to methyl, ethyl, propyl, isopropyi, butyl, isobutyl, sec-butyl, tert-butyi, pen ' tyf, neopentyl, hexyl, heptyi, octyi, nonyl and decyl.
  • Representative alkenyl groups include but are not limited to vinyl, ally! and propenyi.
  • Representative alkynyl groups include but are not limited to ethynyi, 1-propynyf, 2-propynyi, 1 -butynyl, and 2-butynyl.
  • Representative cycloaikyl groups include but are not limited to cyclopropyi, cyciobutyi, cyclopentyl, cyclohexy!, and cyciooctyl substituents.
  • Representative heierocyc!oa!kyi groups include buf are not limited to tetrahydrofuranyl, tetrahydropyranyl and piperidsnyi.
  • Representative aryl groups include but are not limited to phenyl, naphthyl, and triptycene.
  • Representative heteroary! groups include but are not limited to furanyi, pyranyl and pyridinyl.
  • Representative araikyi groups include but are not limited to benzyl, and pheneihy!,
  • cydoa!kyi as used herein also includes: bridged ring polycycloaiky! groups (or bridged ring polycycfic alkyl groups), such as but not limited to, bicyc!o[2.2.1]heptyl (or norbomyl) and bicyclo[2.2.2]octyl; and fused ring polycycioa!kyl groups (or fused ring polycyciic aikyi groups ⁇ , such as. but not limited to, octahydro-1 H-indenyS, and decahydronaphthaienyL
  • substituted hydrocarbyl means a hydrocarbyi group in which at least one hydrogen thereof has been substituted with a group that is other than hydrogen, such as, but not limited to, halo groups, hydroxy! groups, ether groups, thiol groups, thio ether groups, carboxy!ic acid groups, carboxyiic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (e.g...
  • aikyi aikenyi, alkynyl, cycioaikyi, heterocyc!oa!kyi, aryi, heteroaryl, and araikyi groups
  • amine groups such as - iRn'XR ⁇ ') where R ⁇ ' and R 2 ' are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyi,
  • substituted hydrocarbyl is inclusive of halohydrocarbyl (or halo substituted hydrocarbyl) substltuents.
  • halohydrocarbyl as used herein, and similar terms, such as halo substituted hydrocarbyl, means that at least one hydrogen atom of the hydrocarbyl (e.g., of the alkyl, aikenyl, alkynyl, cycioaikyi, heterocycloalkyi, aryi, heteroaryl, and araikyi groups) is replaced with a halogen atom selected from chlorine, bromine, fluorine and iodine.
  • the degree of ha!ogenatton can range from at least one hydrogen atom but less than all hydrogen atoms being replaced by a halogen atom ⁇ e.g., a fluorom ethyl group), to full haiogenation (perhalogenation) in which all replaceable hydrogen atoms on the hydrocarbyi group have each been replaced by a halogen atom (e.g., trifluoromethyi or perfluoromethyi).
  • a halogen atom e.g., trifluoromethyi or perfluoromethyi
  • Perhalohydrocarbyl group as used herein means a hydrocarbyl group in which all replaceable hydrogens have been replaced with a halogen. Examples of perhalohydrocarbyl groups include, but are not limited to, perhaiogenaied phenyl groups and perhaiogenaied alkyl groups.
  • hydrocarbyi and substituted hydrocarbyl groups from which the various groups described herein can each be independently selected such as, but not limited to, R-rRio, R 11 , R 12 , is, and R 14 can in each case be independently and optionally interrupted with at least one of -0-, -S-, -C(O)-, -C ⁇ 0)0- r -0C(0)O, -S(O)-, -S0 2 -, -N(R 11 )- and -Si(R 1 t )(R 12 )-.
  • interrupted with at least one of - ⁇ -, -S-, -C(O)-, -C(0)0-, -OC(0)0-, -S(0 ⁇ , ⁇ S0 2 -, -N(R 11 )-, and -Si(R 11 )(R 12 )- means that at least one carbon of, but less than all of the carbons of, the hydrocarbyi group or substituted hydrocarbyi group, is in each case independently replaced with one of the recited divalent non-carbon linking groups.
  • the hydrocarbyi and substituted hydrocarbyi groups can be interrupted with two or more of the above recited linking groups, which can be adjacent to each other or separated by one or more carbons.
  • a combination of adjacent - C(0) ⁇ and -N(R 11 ⁇ - can provide a divalent amide linking or interrupting group, ⁇ C(Q)- N(R 1 ⁇
  • a combination of adjacent - N(R 11 ⁇ -, -C(Q - and -O- can provide a divalent carbamate (or urethane) linking or interrupting group, ⁇ N(R 11 )-C(0)-0-, where R 11 Is hydrogen.
  • mechanochromic and similar terms, such as “mechanochramic compound” means having an absorption spectrum for at least visible radiation that varies in response to mechanical stress.
  • mechanochramic material means any substance that is adapted to display mechanochromic properties (such as, adapted to have an absorption spectrum for at least visible radiation that varies In response to mechanical stress) and which includes at least one mechanochromic compound, at least one polymer, and/or a polymer composition according to the present invention,
  • the mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present invention are, with some embodiments, capable of converting from a first state, for example a "clear state * ' or a "colorless state” to a second state, for example a "colored state,” in response to mechanical stress.
  • a first state for example a "clear state * ' or a "colorless state”
  • a second state for example a "colored state”
  • the mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present invention undergo minimal, or are substantially free of, reversion back to the previous state (such as a clear or colorless state) after exposure to and optional removal of the mechanical stress.
  • the terms “first” and “second” are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties.
  • the first state and the second state of a mechanochromic compounds, polymers, polymer compositions, and articles of the present invention cars differ with respect to at least one optica! property, such as but not limited to the absorption of visible and/or UV radiation.
  • the mechanochromic compounds, polymers, polymer compositions, and articles of the present invention can have a different absorption spectrum in each of the first and second state.
  • a mechanocnromic compounds, polymers, polymer compositions, and articles of the present invention can be clear in the f rst state and colored in the second state.
  • mechanocnromic compounds, polymers, polymer compositions, and articles of the present invention can have a first color in the first state and a second color in the second state.
  • actinic radiation means electromagnetic radiation that is capable of causing a response In a material, such as, but not limited to, transforming a photochromic material from one form or state to another state, or initiating polymerization.
  • film means a pre- ormed layer having a generally uniform thickness thai is not capable of self-support.
  • sheet means a pre-formed layer having a generally uniform thickness that is capable of self-support.
  • coating means a supported film derived from a flowable composition, which can have a uniform thickness or non-uniform thickness, and specifically excludes polymeric- sheets and unsupported polymer films.
  • a coating that includes one or more mechanochromic polymers or compositions of the present invention can, with some embodiments, be a mechanochromic coating,
  • controlled radical polymerization and related terms such as "controlled radical polymerization method(s)” includes, but is not limited to, atom transfer radical polymerization (ATRP), single electron transfer polymerization (SETP), reversible addition-fragmentation chain transfer (RAFT), and nitroxide-mediated polymerization (N P).
  • ATRP atom transfer radical polymerization
  • SETP single electron transfer polymerization
  • RAFT reversible addition-fragmentation chain transfer
  • N P nitroxide-mediated polymerization
  • Controlled radical polymerization such as ATRP, is described generally as a "living polymerization," i.e., a chain-growth polymerization that propagates with essentially no chain transfer and essentially no chain termination.
  • the molecular weight of a polymer prepared by controlled radical polymerization can be controlled by the stoichiometry of the reactants, such as the initial concentration of monomer(s) and initiators), in addition, controlled radical polymerization also provides polymers having characteristics including, but not limited to: narrow molecular weight distributions, such as pofydispersity Index (PDl) values less than 2.5; and/or well defined polymer chain structure, such as block copolymers and alternating copolymers, with some embodiments.
  • PDl pofydispersity Index
  • the ATRP process is described in further detail as follows.
  • the ATRP process can be described generally as including: polymerizing one or more radically polymerizable monomers in the presence of an initiation system; forming a polymer; and isolating the formed polymer.
  • the initiation system includes, with some embodiments: an initiator having at least one radically transferable atom or group; a transition metal compound, such as a catalyst, which participates In a reversible redox cycle with the Initiator; and a ligand, which coordinates with the transition metal compound.
  • the ATRP process is described in further detail In U.S, Pat. Nos.
  • the polymers and polymer compositions of the present invention prepared by controlled radical polymerization are prepared generally in accordance with the ATRP method disclosed at column 4, line 12, through column 5, line 67 of United States Patent No. 6,265,489 B1 , which disclosure is incorporated herein by reference.
  • controlled radical polymerization Initiators having at least one radically transferable group, in which the controlled radical polymerization initiators include at least one spirooxazine compound represented by Formula (I), and/or at least one indenonapbthopyran compound represented by Formula (li), as described previously herein,
  • the controlled radical polymerization Initiators of the present invention are each independently mechanochromic controlled radical polymerization Initiators.
  • polymers prepared from the controlled radical polymerization Initiators of the present invention are mechanochromic polymers
  • polymer compositions that include the polymers of the present invention are mechanochromic polymer composition.
  • articles that include the polymers of the present invention are mechanochromic articles.
  • the controlled radical polymerization initiators of the present invention can, with some embodiments, each independently have at least one radicall transferable group, such as from 1 to 20, or from 1 to 15, or from 1 to 10, or from 1 to 5, or from 1 to 4, or from 1 to 3, or 1 or 2 radically transferable groups.
  • the controlled radical polymerization initiators of the present Invention each independently have at least 2 radically transferable groups, such as from 2 to 20, or from 2 to 15, or from 2 to 10, or from 2 to 5, or from 2 to 4, or 2 or 3.
  • each controlled radical polymerization initiator of the present invention independently has two (2) radically transferable groups,
  • the spirooxazine represented by Formula (I) at least one of Ri Independently for each n, and RJI independently for each p, Independently include the first radically transferable group; and at least one of R 3 independently for each q, R 4 , R. s and R 6 independently comprise the second radically transferable group.
  • Each first radically transferable group and each second radically transferable grou can be the same or different.
  • each first radically transferable group is positioned so as to be on one side of the spirooxazine relative to bond (a ' ) ⁇ at least one R, and/or at least one R 2 each independentl including a first radically transferable group), and each second radically transferabie group is positioned so as to be on the other side of the spirooxazine relative to bond (a') (at least one R 3 , and/or R 4l and/or R 5 , and/or Re each independently include a second radically transferable group),
  • Each first radically transferable group and each second radically transferable group can be the same or different.
  • each first radically transferable group is positioned so as to be on one side of the indenonaphthopyran relative to bond (a) (B and/or B' each independently including a first radically transferable group), and each second radically transferable group is positioned so as to be on the other side of the indenonaphthopyran relative to bond (a) (at least one R 7 , and/or at least one R 8 , and/or R 9s and/or R-io each Independently include a second radically transferable group).
  • the spirooxazine represented by Formula (!) includes one first radically transferable group, and one second radically transferrabie group.
  • R or R ? Includes the first radically transferable group; and one of R 3 , R 4 , R 5 , and R 6 includes the second radically transferable group,
  • B or B' includes the first radically transferable group; and one of R 7> R s , Rg, and R 0 includes the second radically transferable group.
  • the spirooxazine represented by Formula (I) includes, with some further embodiments, one first radically transferable group, and one second radically transferrabie group,
  • one R 2 includes the first radically transferable group
  • one R 3 includes the second radically transferable group
  • the indenonaphthopyran represented by Formula (ii), with some embodiments, includes one first radically transferable group, and one second radically transferable group.
  • 8 or 8' includes the first radically transferable group; and one R 7 or one R s Includes the second radically transferable group.
  • Each radically transferable group of the controlled radical polymerization initiators of the present Invention can each be independently selected from one or more atoms or groups that are radically transferable under controlled radical polymerization conditions.
  • the Rf group ⁇ of OR f is linear or branched C C 20 alky! group, in which at least one hydrogen group is optionai!y substituted with a halo group, such as F or CI).
  • Each R 9 is Independently selected from ary! or a linear or branched CrC 20 alkyl group. With the N ⁇ R 9 ) 2 group, the R s groups can loin to form a 5-, 6- or 7-membered heterocyclic ring.
  • each radically transferable group of the controlled radical polymerization initiators of the present invention are independently selected from CI, Br, and 1, With some further embodiments, each radically transferable group of the controlled radical polymerization initiators of the present invention is Br.
  • R- t , R 2> R 3 , R, 5 , R 5 , and R 6 independently include, or is, a group represented by the Formula (ill), and described in further detail below.
  • R 7 , Rs, Rg, io. B, and B' each independently include, or is, a group represented by the following Formula (III);
  • R 3 is a divalent linking group selected from a bond, a divalent hydrocarbyi group and a divalent substituted hydrocarbyi group each optionally interrupted with at least one of -0-, ⁇ S ⁇ , -C(O)-, -0(0)0-, ⁇ 0C(0)0 ⁇ , -8(0)-, -SQr, -N(R 15 )- and -Si(R s )(R 16 )- and combinations of two or more thereof.
  • R 15 and R 1e groups are in each case independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi.
  • R is a divalent linking group selected from a bond, divalent hydrocarbyi, and divalent substituted hydrocarbyi and X is the radically transferable group.
  • R 13 is selected from a bond, divalent C C 2 o linear or branched alkyl divalent C-s-C ⁇ cyciic a!kyl, divalent C 3 -C 10 heterocyclic alkyl, divalent aryi, divalent heteroaryi, and combinations thereof optionally interrupted with at least one of -O- and -S- and combinations of two or more thereof.
  • R 14 is selected from divalent CrC 2 ⁇ > linear or branched alkyl, and X is selected from a halo group,
  • R 3 is selected from a bond, divalent C r C 0 linear or branched alkyl, divalent C 3 -Ci 0 heterocyclic aikyi, divalent aryi, and combinations thereof optionally interrupted with at least one of -0-.
  • R 14 is selected from divalent CrC-io linear or branched alkyl, and the halo group from which X is selected is CI, Br, or I.
  • the divalent linking group R 3 is bonded directly to the spirooxazine represented by Formula (I).
  • the divalent linking group i 3 of Formula (III) can, with some embodiments, be bonded to another group that is bonded to the spirooxazine represented by Formula (I), such as R-i, R 2 , R 3 , R 4 , R 5 , and/or R 5 .
  • the divalent linking group R 13 of the group represented by Formula (III), with some embodiments, is bonded directly to the indenonaphthopyran represented by Formula (II).
  • the divalent linking group R 13 of Formula (III) can, with some embodiments, be bonded to another group that Is bonded to the indenonaphihopyran represented by Formula ⁇ !( ⁇ , such as R 7l R 8 , R 8 , R 1C) B, and/or B ! .
  • one 2 independently includes, or is, the group represented by Formula (IH), and one R 3 Independently includes, or is, the group represented by Formula (III),
  • one R 2 independently includes, or is, the group represented by Formula (111), which is bonded to ring position 5' of the spirooxazine represented by- Formula (I);
  • one R 3 independently includes, or is, the group represented by Formula (Hi), which bonded to ring position 5 of the spirooxazine represented by Formula (i); and the remaining groups R,, R 2 , R 3 , R , R 5 , and R 6 are free of the group represented by Formula (ill).
  • one 8 or 8' Independently includes, or is, the group represented by Formula (Hi)
  • one R 7 or R s Independently includes, or is, the group represented by Formula (III).
  • one B or B * at ring position 3 independently includes, or is, the group represented by Formula (Hi); one Re independently includes, or is, the group represented by Formula (ill), which is bonded to ring position 1 1 of the Indenonaphihopyran represenied by Formula (II); and the remaining groups B or 8', R 7 , R 8 , Rg, and R 10 are free of the group represented by Formula (ill).
  • the group represented by Formula (III) is selected from one or more groups represented by the following Formulas (l!i-A) through (ifi-F)
  • X In each case is independently a radically transferable group, such as a halo group, such as CI, Br, or I.
  • 3 ⁇ 4 independently for each n and R 2 independently for each p are each independently selected from hydrogen, ary!, mono ⁇ CrC 6 )a!koxyaryl, di(Ci-C6)a)koxyary!, mono(CrC 6 )aikylaryl, di(CrC 6 )alkyiaryl, bromoaryl, ch!oroaryl, fiuoroaryl, C3-C7 cycloalkylaryi, C 3 ⁇ C 7 cyc!oa!kyl, C3-C7 cyc!oa!ky!oxy, C3-C7 cycioaikytoxy(Ci-C8)alkyi, C3-C7
  • aryioxy(C-i -C 6 )alky! aryioxy(CrC6>a!koxy, mono- or ds(C r Cg)a!kylary1 ⁇ Ci-C 6 ⁇ alkyl, mono- -or diCCi -C 6 )alkoxyafy!(Cr C 6 )a!kyi, mono- or di(Ci-C 6 ⁇ alkyiaryl(C r C 6 )a!koxy, mono- or di(Ci 1 ⁇ 4)a!koxyaryi ⁇ CrC 6 )aikoxy, amino, mono(CrC 6 )aikyfanriino, d!(CrC 6 )aikylarrtino, dsarylamino, N-(Ci-C 6 )alkylp!perazino, N-arylpiperazino, aziridino, indoiino, piperidino, aryfpiperidino, ary
  • R 3 of the spirooxazine represented by Formula (I) is, independently for each q, chosen from hydrogen, C 1 -C5 alkyi, d-C 5 aikoxy, nitro, cyano, Ci-C 8 a!koxycarbonyl, acyloxy(C,- C 6 alkyi), acyioxy(C 3 ⁇ C 7 cycloalkyl), acyioxy(aryl),, halo, C C monohaloaiky! or C r C 4 polyhaloalkyl; said halo substiiuenis being chioro, fiuoro, iodo or bromo.
  • R 4 of the spirooxazine represented by Formula (I) is chosen from hydrogen, Ci ⁇ C 8 alkyl, C3-C7 cycloalkyl, phen ⁇ C C )alkyl, naphth ⁇ Ci-C 4 )alkyl, ally!, acryiylpxy(C 2 -C 6 )alkyl, methacrylyloxy(C 2 -C 6 )alkyi > C 2 -C 4 acyioxy ⁇ C 2 -C 6 )aikyl, carboxy ⁇ C 2 -C 6 )a!kyl, eyano(C 2 - C 6 )alkyi, hydroxy(C 2 -C 8 )alky!, triarylsilyi, triaryisilyioxy, tri(C Ce)aiky!silyi,
  • R 5 and e of the spirooxazine represented by Formula (I) are each independently selected from hydrogen, C r C 5 alkyl, acyloxy ⁇ C C 6 alkyl), acyfoxy(C 3 -C 7 cycloalkyl), acyloxy ⁇ ary1), benzyl, phenyl, mono- or di-substiiuted phenyl, said phenyl substituents being Ci-C 5 alkyl or C C 5 aikoxy; or R s and R 6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom.
  • Ri independently for each n and R 2 independently for each p are each independently selected from hydrogen, aryl, rnono ⁇ CrC 6 )alkoxyaryl, di(Ci-C e )a!ky1amirso, piperklino, morpho!ino, Ci-C 6 aikoxy, or fluoro.
  • R 3 of the spirooxazine represented by Formula (I) is, independently for each q, selected from hydrogen, C r C 5 alky!, Ci-C 5 aikoxy, C C 8 aikoxycarbonyi, acy!oxy ⁇ CrCs aikyl), acyjoxy ⁇ C3-C? cycloafkyi), acy!oxy(aryi),, halo, Ci ⁇ C monohaioa!kyi or C C poiyhaloaikyi; and said ha!o substituents being chloro or fluoro.
  • R 4 of the spirooxazine represented by Formula (!) is selected from hydrogen, C C 8 aikyl, phen(C r -C 4 )alkyi, acryiyfoxy ⁇ C 2 -C8)a!kyl, methacryiy!oxy(CrC 6 )a!ky!,
  • R 5 and R 6 of the spirooxazine represented by Formula (I) are each independently selected from hydrogen, Ci-C 5 aikyl, phenyl; or R s and R 6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom.
  • R 7 independently for each x and R s independently for each y are each independently selected from; hydrogen; a compatibiizing substituent; halogen selected from fluoro and chloro; Ci ⁇ C 2 o atkyi; C 3 - Cio cycloaikyl; acyioxy(C G 6 aikyl), acy!oxy(C 3 -C 7 cycloaikyl), acyioxy(aryi); substituted or unsubstituted phenyl, the phenyl substituents being selected from hydroxy!, halogen, carbonyl, C -C 20 aikoxycarbonyi, cyano, halo(CrC 2 o)aikyl, C C 2 o aikyl or Ci-C 20 aikoxy; -G-R 10 ' or -C ⁇ 0)-R 1c Or wherein
  • substituted phenyl(C C 2 o)a!kyl mono(CrC 20 )aikoxy substituted phenyl ⁇ C r C 2 o)alkyf, (d -C 20 ⁇ aikoxy(C 2 -C 2 o)a!kyl, C 3 - C 10 cycloaikyl, or mono(Ci ⁇ C 20 )alkyi substituted C 3 -C 10 cycloaikyl;
  • R ⁇ ' and R 12 are each independently hydrogen, Ci-C 20 aikyl, phenyl, naphfhyi, furanyl, benzofuran-2 ⁇ yl, benzofuran-3 ⁇ yl ( thienyl, ⁇ benzothien-2-y!, .benzothien-3-yl, dibenzofuranyi, dibenzothienyl, benzopyridyi, fiuorenyl, Ci-C 2Q alky!aryl, C 3 -Ci 0 cycioaikyi, CrC 2G bicycloaikyl, C 5 - C 20 tricyc alkyl or Ci- C w alkoxyafkyf, wherein said aryi group is phenyl or naphthyl, or Rn' and R 2 * come together with the nitrogen atom to form a C 3 -C 20 hetero-bicycloaikyl ring or a C 4 -C 20 hetero-tricyc!o
  • R 7 independently for each x and R 8 independently for each y are each independently selected from a nitrogen containing ring represented by the following graphic Formula (IVA),
  • each -V- is independently chosen for each occurrence from -CH 2 - ( -CHiR-ia )-, ⁇ C(R 13 ! ) 2 - ⁇ -CH(aryi)-, ⁇ C(aryl) 2 ⁇ , and - C ⁇ R 13 ')(aryl)-, and Z is -Y-, -0-, ⁇ S ⁇ , -3(0)-, -S0 2 -, -NH-, -N(R 13 ')-, or -N(aryl)-, wherein each R 3 ' is independently C1-C 20 aikyi, each aryi is independently phenyl or naphthyl, m is an integer 1 , 2 or 3, and p is an integer 0, 1, 2, or 3 and provided that when p is 0, Z is ⁇ .
  • R 7 independently for each x and R@ independently for each y are each independently selected from a group represented by one of the following graphic Formulas (IVB) or (iVC):
  • Ri 5 , R 6 , and R 17 are each independently hydrogen, d-Ce aikyi, phenyl, or naphthyl, or the groups R 15 and R3 ⁇ 4 6 together form a ring of 5 to 8 carbon atoms and each R d is independentiy for each occurrence selected from C r -C 20 aikyi, Ci-C 20 alkoxy, fluoro or chioro, and Q is an integer 0, 1 , 2, or 3.
  • R 7 Independently for each x and R s independently for each y are each independently selected from unsubstiluted, mono-, or di-substiiuted C 4 -C 1g spirobicyciic amine, or unsubstituted, mono-, and di- substituted C4-C18 spirotri cyclic amine, wherein said substituents are independently aryi, C C 2 o aikyi, C r C 2 o aikoxy, or phenyi(C 1 ⁇ C 2 o)aikyi.
  • T and T are each independently oxygen or the group -NRn'-, where R ⁇ ', R 5 , and R 6 are as set forth above.
  • R 9 and R 0 are each independently selected from the following classes of groups (i) through (v).
  • R 9 and R 10 of Formula (II) are each independently selected from, (i) hydrogen, C C 20 aikyi, C -C 20 haioalkyi, C 3 ⁇ C 0 cycloa!ky!, acyloxy(Ci-0 6 aikyi), acyfoxy(C 3 -C7 cycloa!kyl), acyioxy(aryl), ailyi, benzyl, or mono-substituted benzyl, said benzyl substituents being chosen from halogen, C1-C20 aikyi or CrC 20 aikoxy.
  • R 9 and R 10 of Formula (il) are each independently selected from, (il) an unsubstituted, mono- di-or tri-substituted group chosen from phenyl, naphthyl, phenanthryi, pyren l, quinoiyl, isoquinolyl, benzofuranyl, thienyl, benzofbienyl, dtbenzofuranyl, dibenzothienyl, carbazoiyi, or indoly!, said group substituents in each case being independently chosen from halogen, C C 20 aikyi or C C 2 Q aikoxy.
  • R g and R 10 of Formula (il) are each independently selected from, (ill) mono-substituted phenyl, said substiiuent located at the para position being - ⁇ CH 2 ) or ⁇ 0-(CH 2 ) ⁇ , wherein t is the intege 1 , 2, 3, 4, 5 or 6, said subsiituent being connected to an ary! grou which is a member of a photochromic material.
  • F3 ⁇ 4 and 0 of Formula ⁇ !!) are each independently selected from, (iv) the group ⁇ CH(R 10 )G, wherein R 18 is hydrogen, d-Cr, aiky! or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, and G is -Cr ⁇ OR 19 , wherein R 19 is hydrogen, -C(0)R 10 , C C 2 o alkyt, C -C 20 aikoxy(Cr'C2o)aSkyl, pheny1(C C 20 ⁇ a!kyl, mono(C C3 ⁇ 4))aikoxy substituted pheny!(Ci- C 2 o)alkyl, or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, each of said phenyl and naphthyl group substituents being C
  • R 9 and R 0 together form a spiro subsiituent selected from a substituted or unsubstituted spiro-carbocyciic ring containing 3 to 6 carbon atoms, a substituted or unsubstituted spiro-heterocyc!ic ring containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms Including the spirocarbon atom, said spiro- carbocyciic ring and spiro-heterocyc!Ec ring being anrte!iated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C Czc aikyi.
  • B and 8' are each independently: an aryl group that is mono-substituted with a compatiblizing
  • a substituted phenyl a substituted aryl; a substituted 9-juloilndinyl; a substituted heteroaromatic group chosen from pyridyl, furantyl, benzofuran-2-yl, benzofuran-3-yi, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,
  • dibenzoihienyl, carbazoyi, benzopyridyi, indolinyi, and fiuorenyi wherein the phenyl, aryl, 9 ⁇ ju blind inyL or heteroaromatic substituent is a reactive subsiituent R; an unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group; 9-ju!o!idinyf; or an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyf, furanyl, benzofuran-2-yl, benzofuran-3-yi, thienyl, benzothien-2-yi, benzotbien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyi, benzopyridyi, indoiinyl, and fiuorenyi.
  • the phenyl, aryl and heteroaromatic substituents, from which B and B' can each be independently selected, are in each case independently: hydroxy!, a group -C ⁇ 0)R 2 i, wherein R 21 is -OR 22l ⁇ N(R 23 )R 2 4, piperidino, or morpho!ino, wherein R22 is aiiyl, C r -C 20 aikyl, phenyl, mono(Ci-C 2 o)aikyi substituted phenyl, mono(Ci- C 20 )aikoxy substituted phenyl, pbenyl(C r -C 20 )alky!, mono ⁇ CrC 20 )aiky!
  • B23 and R 24 are each independently C1-C20 alkyf, C 3 -C 0 cyc!oaikyl, phenyl or substituted phenyl, the phenyl substituenis being C1-C20 a!ky!
  • B and B ' are each independently an unsubststuted or mono-substituted group chosen from pyrazo!y!, imidazoiyl, pyrazoiinyi, imidazollnyl, pyrrolinyi, phenothiaziny!, pbenoxazinyl,
  • phenaziny! and acridinyl.
  • substituenis are, with some embodiments, Ci-C 20 alkyl, C1-C20 aikoxy, phenyl, or halogen.
  • B and B' are each independently a roup represented by one of:
  • K is -CH 2 - or -0-, and is -O- or substituted nitrogen, provided that when M is substituted nitrogen, K is - CH 2 -, the substituted nitrogen substituents being hydrogen, d-Cao alkyl, or CrC 20 acyi, each R 25 being independently chosen for each occurrence from CrC 20 aikyi, C r C 2 o aikoxy, hydroxy, and halogen, R 26 and R 2 each being independently hydrogen or C C 2 o alkyl, and u Is an intege ranging from 0 to 2.
  • B and B' are each independently, a group represented by:
  • F1 ⁇ 2 is hydrogen or C r C20 aikyl
  • R 2 g is an unsubstituted, mono-, or di-substituted group chosen from nap thyi, phenyl, furanyi, and thienyl, in which the substituents are C1-C2 0 aiky!, C C 2 o alkoxy, or haiogen,
  • R 7 independently for each x and R B independently for each y, of the indenonaphthopyran represented by Formula (II), are each independently selected from, hydrogen, Ci ⁇ C 6 aikyl, C3-C7 cycioalkyi, morphoiino, morphoiino substituted with Ci-C 8 linear or branched aikyl, C Ce haioalky!, fiuoro, chioro, and -O-R 10 '.
  • R 9 and R 10 of the indenonaphthopyran represented by Formula ( ⁇ ), are each independently selected from hydrogen, Cr-Cg aikyl, C Cg haloaikyi, and C3-C7 cycioalkyi, or together form a spiro substiiuent selected from a substituted or unsubstituted spi o-carbocyclie ring containing 3 to 8 carbon atoms.
  • 8 and 8', of the indenonaphthopyran represented by Formula (II), are each Independently selected from aryi, ary! substituted with C- r C 6 alkoxy, and aryi substituted with morphoiino,
  • R 7 and R 8 can each be independently selected from a compatibilizing substiiuent; and B and B : can each be selected from an aryi group that is mono-substituted with a compatibilizing substiiuent. If the indenonaphthopyran includes multiple compatibilizing substituents, each compatibilizing substiiuent can be independently chosen.
  • Each compatibilizing substiiuent can independently be represented by one of the following;
  • Non-limiting examples of groups that ' -D- can represent according to various non-limiting embodiments include a diamine residue or a derivative thereof, wherein a first amino nitrogen of said diamine residue can form a bond with -A'-, or a substituent or an available position on the indeno-fused naphthopyran, and a second amino nitrogen of said diamine residue can form a bond with -E-, -G- or -J; and an amino alcohol residue or a derivative thereof, wherein an amino nitrogen of said amino alcohol residue can form a bond with ⁇ A' ⁇ , or a substituent or an available position on the indeno-fused naphthopyran, and an alcohol oxygen of said amino alcohol residue can form a bond with - ⁇ --, -G- or ⁇ j.
  • the amino nitrogen of the amino alcohol residue can form a bond with -E-, -G- or -J
  • the alcohol oxygen of the amino alcohol residue can form a bond with -A'-, or a substituent or an available position on the indenonap ' hthopyran.
  • Non-limiting examples of suitable diamine residues that -O- can represent include an aliphatic diamine residue, a cycio aliphatic diamine residue, a diazacycloalkane residue, an azacyclo aliphatic amine residue, a diazacrown ether residue, and an aromatic diamine residue, More particular, illustrative and non- limiting examples of diamine residues that can be used in conjunction with various non-llmlting embodiments disclosed herein include the following:
  • Non-limiting examples of suitable amino alcohol residues that -D- can represent include an aliphatic amino alcohol residue, a cycio aliphatic amino alcohol residue, an azacyclo aliphatic alcohol residue, a diazacycio aliphatic alcohol residue and an aromatic amino alcohol residue, More particular, illustrative and non-limiting examples of amino alcohol residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following;
  • -E- can represent a dicarboxyiic acid residue or a derivative thereof, wherein a first carbonyi group of said dicarboxyiic acid residue can form a bond with -G- or -D-, and a second carbonyi group of said dicarboxyiic acid residue can form a bond with -G-.
  • suitable dicarboxyiic acid residues that -E- can represent include an aliphatic dicarboxyiic acid residue, a cyc!oa!iphatic dicarboxyiic acid residue and an aromatic dicarboxyiic acid residue. More particular, illustrative and non-limiting examples of dicarboxyiic acid residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
  • ⁇ G- can represent a group represented by the following general formula
  • oxygen of the polyo! residue forms a bond with a group - ⁇ .(OC 2 H 4 )x(OC 3 H 6 ) y ⁇ OC 4 H 8 )J- (i.e., to form the group 4(00 2 ⁇ 4 ) ⁇ (00 3 ⁇ ⁇ ) ⁇ (OC 4 H B ) 2 K3-) 1 and the second polyo! oxygen forms a bond with -E- or -J.
  • suitable poiyoi residues that -G ⁇ can represent include an aliphatic poiyoi residue, a cycio aliphatic poiyoi residue and an aromatic poiyoi residue,
  • poiyois from which the poiyoi residues that -G- can represent can be formed according to various non-limiting embodiments disclosed herein include (a) low molecular weight poiyois having an average molecular weight less than 500, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col, 4, lines 48-50, and co!. 4, line 55 to col, 8, line 5, which disclosure is hereby specifically incorporated by reference herein: (b) polyester poiyois, such as, but not limited to, those set forth in U.S. Patent No. 8,555,028 at col.
  • -J can represent a group - , wherein - represents a group such as, but not limited to, -CH z COOH, ⁇ CH(CH 3 )COOH, -C(OXCH 2 ⁇ w COOH, -C 6 H 4 S0 3 H, -C 5 H 10 SO 3 H, -C 4 H 8 S0 3 H, -C 3 M 6 S0 3 H, -C 2 H 4 SO 3 H and ⁇ S0 3 H, wherein " " ranges from 1 to 18.
  • ⁇ J can represent hydrogen that forms a bond with an oxygen or a nitrogen of linking group to form a reactive moiety such as -OH or -NH.
  • -J can represent hydrogen, provided that if ⁇ J represents hydrogen, -J is bonded to an oxygen of ⁇ D- or -G-, or a nitrogen of --D-.
  • ⁇ J can represent a group -L or residue thereof, wherein -L can represent a reactive moiety.
  • -L can represent a group such as, but not limited to, acry!, methacryl, croty!, 2- (methacryloxy)ethyicarbarnyi, 2- ⁇ methacryloxy ⁇ ethoxycarbony!, 4-vinylphenyi. vinyl, 1-chlorovinyl or epoxy.
  • the terms aory!, methacryl, crotyl, 2- (rnethacryioxy)ethylcarbaroyl, 2-(methacryloxy)eihoxycarbonyl, 4-vinyiphenyl, vinyl, 1-chlorovm l, and epoxy refer to the following structures:
  • -G- can represent a residue of a polyoi, which Is defined herein to include hydroxy-containlng carbohydrates, such as those set forth in U.S. Patent No. 6,555,028 at col. 7, line 56 to coi. 8, line 17, which disclosure Is hereby specifically incorporated by reference herein.
  • the poiyol residue can be formed, for example and without limitation herein, by the reaction of one or more of the po!yol hydroxyl groups with a precursor of -A'-, such as a carboxylic acid or a methylene halide, a precursor of po!yalkoxylated group, such as polyalkyiene glycol, or a hydroxy!
  • the polyoi can be represented by « ⁇ (OH) a and the residue of the polyoi can be represented by the formula -0-g ⁇ (OHJ a .-, wherein q is the backbone or main chain of the polyhydroxy compound and "a" is at least 2.
  • one or more of the poiyol oxygens of -G- can form a bond with -j (i.e., forming the group -G-J),
  • -j i.e., forming the group -G-J
  • the reactive and/or compatibilizing substituent comprises the
  • ⁇ J represents a group ⁇ K that contains a suifo o sulfono terminating group
  • -G-J can be produced by acidic condensation of one or more of the polyoi hydroxy! groups with HOC 6 H 4 S0 3 H; HOC 5 H 10 SO 3 H; HOC 4 H 8 S0 3 H; HOC 3 H 6 S0 3 H; HOC 2 H 4 S0 3 H; or H 2 SO 4 , respectively.
  • -G- represents a polyoi residue
  • -J represents a group -L chosen from acry!
  • methacryl 2-( efnacryioxy)ethylearbamy1 and epoxy
  • -L can be added by condensation of the poiyof residue with acryi y! chloride, methacryloyl chloride, 2 ⁇ isocyanatoethyl methacryiate o epichlorohydrin, respectively.
  • the spirooxazine compounds of the present invention can be prepared by art-recognized methods. With some embodiments, the spirooxazine compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 6,019,914 at column 9, lines 7-48, which disclosure is incorporated herein by reference.
  • the spirooxazine compounds of the present invention are prepared in accordance with the synthetic descriptions provided in the examples further herein.
  • the indenonaphthopyran compounds of the present invention can be prepared by art-recognized methods.
  • the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No, 6,296,785, at column 10, line 52 through column 29, line 18, which disclosure is incorporated herein by reference.
  • the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 7,527,754 B2 at column 13, line 52 through column 14, line 62, which disclosure is incorporated herein by reference.
  • the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 5,645,767, at column 5, line 6 through column 1 1 , line 31 which disclosure is incorporated herein by reference.
  • the indenonaphthopyran compounds of the present invention are prepared in accordance with the synthetic descriptions provided In the examples further herein.
  • the present invention also relates to a polymer composition that includes at least one polymer prepared by controlled radical polymerization initiated in the presence of a controlled radical polymerization initiator having at least one radically transferable group, in -which each polymer prepared by controlled radical polymerization is independently represented by Formula (V) as described previously herein,
  • the controlled radical polymerization initiator is selected from a spirooxazine represented by Formula (I), and an indenonaphthopyran represented by Formula (l!), which are each as described previously herein.
  • the ATRP process can be described generally as Including: polymerizing one or more radically polymerlzable monomers in the presence of an initiation system; forming a polymer; and Isolating the formed polymer.
  • the initiation system includes, with some embodiments: an initiator having at least one radically transferable atom or group; a transition metal compound, such as a catalyst, which participates in a reversible redox cycle with the initiator; and a iigand, which coordinates with the transition metal compound.
  • the initiator used to prepare the polymers of the polymer compositions of the present invention, includes the spirooxazine compound represented by Formula (i) and/or the indenonaphthopyran compound represented by Formula (!l), with some embodiments.
  • Catalysts that can be used with some embodiments in preparing polymers, by controfled radical polymerization (such as ATRP), include any transition metal compound that can participate In a redox cycle with the initiator and the growing polymer chain. With some embodiments, the transition metal compound is selected such that It does not form direct carbon-metal bonds with the polymer chain. Transition metal catalysts useful in the present invention can be represented by the following Formula (VI),
  • TM represents the transition metal
  • t is the formal charge on the iransition metal having a value of from 0 to 7
  • X Is a countenon or covalently bonded component
  • the transition metal (TM) include, but are not limited to, Cu, Fe, Au, Ag, Hg, Pd, Pi, Co, Mn, Ru, Mo, b and n
  • Examples of X include, but are not limited to, halogen, hydroxy, oxygen, C r C 5 - afoxy, cyano, cyanato, thiocyanato and azido.
  • the transition metal is Cu(l) and X is a halogen, such as chloride.
  • a class of transition metal catalysts are the copper ha!ides, such as Cu(!CI.
  • the transition metal catalyst contains a small amount, such as 1 mole percent, of a redox conjugate, for example, Cu(H)CI 2 when Cu(l)CI is used,
  • 0131J Llgands that can be used in preparing the polymers of the present Invention, by controlled radical polymerization include, but are not limited to compounds having one or more nitrogen, oxygen, phosphorus and/or sulfur atoms, which can coordinate to the transition metal catalyst compound, such as through sigma and/or pi bonds.
  • Classes of useful ligands include but are not limited to: unsubsiituted and substituted pyridines and bipyridines; porphyrins; eryptands; crown ethers, such as 18-crown-6; polyamines, such as ethylenedlamine; glycols, such as aikyiene glycols, such as ethylene glycol; carbon monoxide; and coordinating monomers, such as styrene, acryionitrile and hydroxya!kyi (meth)acrylates.
  • the Hgand is selected from one or more substituted bipyridines, such as 4,4'-dialky!bipyridy!s.
  • the amounts and relative proportions of initiator, transition metal compound and llgand are those for which ATRP is most effectively performed.
  • the amount of initiator used can vary widely and is typically present In the reaction medium in a concentration of from 10 '4 moles/liter (M) to 3 M, such as, from 10 "3 M to 10 "1 M.
  • M molecular weight
  • the molar ratio of initiator to monomer can be an important factor in polymer preparation, with some embodiments.
  • the molar ratio of initiator to monomer is, with some embodiments, within the range of 1G ⁇ 4 :1 to 0.5:1 , or 10 "3 :1 to 5x10 "2 :1.
  • the molar ratio of transition metal compound to initiator is, with some embodiments, In the range of 10 "4 :1 to 10:1, or 0,1 :1 to 5:1.
  • the molar ratio of iigand to transition metal compound Is with some embodiments, within the range of 0.1 :1 to 100:1 , or 0.2:1 to 10:1.
  • subscript z is an integer of at least 1 , such as from 1 to 10, or 1 to 5, or from 1 to 4, or from 1 to 3, or 1 or 2.
  • Subscript z is at least 2, such as fro 2 to 10, or from 2 to 5, or from 2 to 4, or 2 or 3, or 2.
  • subscript z is equal to the number of radically transferable groups present on the controlfed radical polymerization initiator.
  • subscript is an integer of at least 2, such as from 2 to 1000, or from 2 to 500, or from 2 to 300, or from 2 to 200, or from 2 to 100, or from 2 to 50, or from 2 to 40, or from 2 to 30, or from 2 to 25, or from 2 to 20, or from 2 to 10, or from 2 to 5,
  • X independently for each z, is or is derived from the radically transferable group that was originally bonded to the controlled radical polymerization Initiator.
  • the radically transferable group(s) of the controlled radical polymerization initiator such as the spirooxazine compound represented by Formula (1) and the indenonaphthopyran represented by Formula (II) ⁇ is a halo group, such as Br
  • the X can be the radically transferable bromo group (Br), with some embodiments.
  • the radically transferable group can, with some embodiments, optionally be (a) removed, or (b) chemically converted to another moiety.
  • the symbol X is considered herein to be derived from the radically transferable group of the initiator.
  • the radically transferable group can be removed by substitution with a nucfeophi!tc compound, such as an alkali metal aikoxyiate, with some embodiments.
  • the method by which the radically transferable group is either removed or chemically converted is relatively mild with regard to the reactive functionality of the polymer. Many nucleophiJic substitution reactions can result in loss of reactive functionality from the polymer.
  • the polymer has oxirane functionality, which can be lost in the presence of a nucleophile, such as an alkali metal aikoxyiate.
  • the halogen when the radically transferable group i.s a halogen, the halogen can be removed by a mild dehalogenation reaction, which does not reduce sensitive functionality of the polymer, if any (such as oxirane functionality, with some embodiments).
  • the reaction is typically performed as a post-reaction after the polymer has been formed, and in the presence of at least an ATRP catalyst.
  • the dehalogenation post-reaction is performed In the presence of both an ATRP catalyst and its associated ligand.
  • the mild dehalogenation reaction is performed by contacting the halogen terminated polymer of the present invention: with one or more ethylenically unsaturated compounds, which are not readily radically po!ymerizab!e under at least a portion of the spectrum of conditions under which controlled radical polymerizations, such as atom transfer radical polymerizations, are performed, hereinafter referred to as "limited radically polymeri convincede ethySenically unsaturated compounds" (LRPEU compound).
  • LRPEU compound limited radically polymeri convincede ethySenically unsaturated compounds
  • the reaction between the halogen terminated polymer and one or more LRPEU compounds results int. (1 ) removal of the terminal halogen group; and (2 ⁇ the addition of at least one carbon-carbon double bond where the terminal carbon-halogen bond Is broken.
  • the dehalogenation reaction Is typically conducted at a temperature in the range of 0°C to 200 e C, or from 0°C to 160°C, and a pressure in the range of 0.1 to 100 atmospheres, or from 0.1 to 50 atmospheres, with some embodiments.
  • the reaction is also typically performed in less than 24 hours, such as between 1 and 8 hours.
  • the LRPEU compound can be added in less than a stoichiometric amount, it is typically added in at least a stoichiometric amount relative to the moles of terminal halogen present in the polymer. When added in excess of a stoichiometric amount, the LRPEU compound is typically present in an amount of no greater than 5 mole percent, such as 1 to 3 mole percent, in excess of the total moles of terminal halogen, with some embodiments.
  • LRPEU compounds are described in further detail at column 12, line 15 through column 13, line 18 of United States Patent No. 8,268,433 B1 , which disclosure is incorporated herein by reference.
  • the LRPEU is free of halogen groups.
  • LRPEU compounds include, but are not limited to, 1 , 1-dimefhyiethyiene, 1 , 1 -diphenyiethylene, Ssopropenyi acetate, alpha- methyl styrene, 1 , 1-dialkoxy olefin and mixtures thereof.
  • Additional examples of LRPEU compounds include, but are not limited to, dimethyl itaconate and diisobutene (2 ,4,4-irimethyl-l -pentene).
  • ethyienicaily unsaturated radically po!ymerizable monomer and similar terms includes, hut are not limited to, vinyl monomers, aiiyilc monomers, olefins and other ethyienica!iy unsaturated monomers thai are radically polymerizable,
  • Classes of vinyl monomers from which each M of Formula (V) can he independentiy derived include, but are not limited to, (meth)acryiates, vinyl aromatic monomers, vinyl haiides, and vinyl esters of carboxyiic acids, each of which can, with some embodiments, optionally include one or more functional groups selected from hydroxyl groups, thiol groups, primary amine groups, secondary amine groups, and oxirane groups.
  • the (meth)acryEates are selected from at least one of: alkyi (meth)acrylates having from 1 to 20 carbon atoms in the alky!
  • alkyi group includes or Is substituted with one or more functional groups selected from hydroxyl groups, thiol groups, primary amine groups, secondary amine groups, and oxirane groups.
  • alkyi (meih)acrylates having from 1 to 20 carbon atoms in the alkyi group examples include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acryiate, propyl (meth)acrylate, isopropyl (meth)acry!ate, butyl (meth)acry!ate, isobutyl (meth)acrylate, tert-butyi (rneth)acryiate, 2-ethyihexyi (meth)acrylate, iauryf (meth)acryfate, isobomyi (meth)acryiaie, cyclohexyl ⁇ meth)acryiate and 3,3,5-trimethylcyclohexyl ⁇ meth)acrylate, one or more of which can, with some embodiments, optionally include in the alkyi group thereof one or more functional groups selected from hydroxyl groups, thio
  • oxirane functional monomers from which each M of Formula (V) can be derived include, but are not limited to, glycidyl (meih)acrylate, 3, 4-epoxy cyclohex l methyl (meth)acrylate, 2- ⁇ 3,4- epoxycyciohexyl)efhyl (meth)acry!ate and ally! glycidyl ether.
  • oxirane functionality can be incorporated into the polymer by post- reaction, such as by preparing a hydroxyl functional precursor polymer and converting the precursor polymer to an oxirane functional polymer by reacting at least
  • Examples of vinyl aromatic monomers from which each M of Formuia (V) can be independently derived include, but are not limited to, styrene, p- chloromethyistyrene, divinyi benzene, vinyl naphtha iene and divinyi naphthalene.
  • Vinyl ha!ides from which each can be independently derived include, but are not limited to, vinyl chloride and vinylldene fluoride.
  • Vinyl esters of carboxy!tc acids include, but are not limited to, vinyl acetate, vinyl butyraie, vinyl 3,4- dimethoxybenzoate and vinyl benzoate.
  • olefin and like terms is meant unsaturated aliphatic hydrocarbons having one or more double bonds, such as obtained by cracking petroleum fractions.
  • examples of olefins from which each M of Formula (V) can be independently dervied include, but are not limited to, propylene, 1-butene, 1 ,3- butadtene, isobutyiene and diisobutylene.
  • allyllc monomer(s) monomers containing substituted and/or unsubstiiuted alSylic functionality, such as one or more radicals represented by the following Formuia (VII),
  • R 1 is hydrogen, halogen or a Ci to C 4 alkyi group. With some embodiments, R 1 is hydrogen or methyl and consequently Formula (VII) represents an unsubstiiuted (meth)a!!yl radical.
  • allyllc monomers include, but are not limited to; (meth)a!!yl alcohol; (meth)a!!yi ethers, such as methyl (meth)al!y! ether; ally! esters of carfooxy!ic acids, such as (rneth)ai!y! acetate, (meth)al!y! butyrate, (meth)a!lyt 3,4-dimethoxybenzoate and (meth)aiiy! benzoate,
  • ethylenically unsaturated radically poiymerizable monomers from which each M of Formuia (V) can be independently derived include, but are not limited to: cyclic anhydrides, such as ma!eic anhydride, 1-cyc!opentene-1 ,2- dicarboxylic anhydride and itaconic anhydride; esters of acids that are unsaturated but do not have alpha, beta-ethyienic unsaturatson, such as methyl ester of undecy!enic acid; and d iesters of ethylenically unsaturated dibasic acids, such as diethyl ma!eate.
  • cyclic anhydrides such as ma!eic anhydride, 1-cyc!opentene-1 ,2- dicarboxylic anhydride and itaconic anhydride
  • the polymers of the present invention can, with some embodiments, have polymer architecture selected from linear polymers, branched polymers, hyperbrancbed polymers, star polymers, graft polymers and mixtures thereof.
  • the form, or gross architecture, of the polymer can be controlied by the choice of initiator and monomers used in its preparation.
  • Linear polymers can be prepared by using initiators, such as represented by Formulas ⁇ [) and (il), having one or two radically transferable groups.
  • Branched polymers can be prepared by using branching monomers, such as monomers containing radically transferable groups or more than one ethylenicaliy unsaturated radically polyrneriza le group, such as 2 ⁇ (2 ⁇ bromopropionoxy)ethyl acrylate, p-ch!oromethylstyrene and diethyleneglycol bis(methacryiate). Hyperbrancbed polymers can be prepared by increasing the amount of branching monomer used.
  • branching monomers such as monomers containing radically transferable groups or more than one ethylenicaliy unsaturated radically polyrneriza le group, such as 2 ⁇ (2 ⁇ bromopropionoxy)ethyl acrylate, p-ch!oromethylstyrene and diethyleneglycol bis(methacryiate).
  • Hyperbrancbed polymers can be prepared by increasing the amount of branching monomer used.
  • Star polymers can be prepared using initiators having three or more radically transferable groups, such as represented by Formulas ⁇ 1 ⁇ and (II).
  • Star- polymers can be prepared by art-recognized core-arm or arm-core methods. In the core-arm method, the star polymer is ' repared by polymerizing monomers in the presence of the po!yfunctional initiator. Polymer chains, or arms, of similar composition and architecture grow out from the initiator core, in the core-arm method. With the arm-core method, the arms are prepared separately from the core and can optionally have different compositions, architecture, molecular weight and polydispersiiy indices (PDI's).
  • PDI's polydispersiiy indices
  • the arms can have different equivalent weights (such as different active hydrogen equivalent weights), and some can have no functionality. After the preparation of the arms, they are attached to the core by art-recognized methods, so as to result in the formation of a arm-core polymer.
  • the polymers of the present invention prepared by controlled radical polymerization can have, with some embodiments, a functional equivalent weight of at least 100 grams/equivalent, or at least 200 grams/e uivalent.
  • the functional equivalent weight of the polymer is, with some embodiments, iess than 10,000 grams/equivalent, or less than 5,000 grams/equivalent, or iess than 1 ,000 grams/equivalent.
  • the functional equivalent weight of the polymers of the present invention prepared by controlled radical polymerization can range between any combination of these values, inclusive of the recited values, such as from 100 to 10,000 grams/equivalent, or from 200 to 5,000 grams/equivalent, or from 200 to 1 ,000 grams/equivalent, inclusive of the recited values.
  • the functionality (or functional groups) of the polymer can, with some embodiments, be selected from hydroxy! groups, thiol groups, primary amine groups, secondary amine groups, and oxi ane groups.
  • the number average molecular weight (Mn) of the polymers of the present invention prepared by conirolied radical polymerization is with some embodiments at least 250, or at least 500, or at least 1 ,000, or at least 2,000.
  • the polymers of the present invention prepared by controlled radical polymerization also have, with some embodiments, an Mn of less than 16,000, or less than 10,000, or less than 5,000.
  • the Mn of the polymers of the present Invention prepared by controlled radical polymerization can, with some embodiments, range between any combination of these values, inclusive of the recited values, such as from 250 to 16,000, or from 500 to 10,000, or from 1 ,000 to 8,000, or from 2,000 to 7,000, inclusive of the recited values.
  • the controlled radical polymerization (CRP) catalyst such as the ATRP transition metal catalyst, and its associated ligand are, with some embodiments, separated or removed from the polymer.
  • the CRP catalyst such as the ATRP catalyst is removed, with some embodiments, prior to conversion of a precursor polymer to a functional polymer. Removal of the ATRP catalyst is achieved, with some embodiments, using known methods, including, for example, adding a catalyst binding agent to the a mixture of the polymer, solvent and catalyst, followed by filtering. Examples of suitable catalyst binding agents include, but are not limited to, alumina, silica, clay or combinations thereof.
  • a mixture of the polymer, solvent and ATRP catalyst can be passed through a bed of catalyst binding agent, with some embodiments.
  • the ATRP catalyst can be oxidized in situ and retained in the polymer polymer.
  • the polymers of the present invention can be prepared, with some embodiments, in the absence of solvent, such as by a bulk polymerization process. With some embodiments, the polymer is prepared in the presence of a solvent, such as water and/or an organic solvent.
  • a solvent such as water and/or an organic solvent.
  • Classes of useful organic solvents include, but are not limited to, esters of carboxyiic acids, ethers, cyclic ethers, C 5 -Ci 0 alkanes, C5- C e cycloalkanes, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amides, nitrites, sulfoxides, sulfones and mixtures thereof.
  • Supercritical solvents such as CO z , C C 4 alkanes and fluorocarbons
  • aromatic hydrocarbon solvents such as xylene
  • mixed aromatic solvents such as those commercially available from Exxon Chemical America under the trademark SOLVESSO.
  • z is at least 2; and the spirooxazine represented by Formula (I) includes at least one first radically transferable group, and at least one second radically transferrabie group, in which for the spirooxazine represented by formuia (!) at least one of R 1 independently for each n, and R 2 Independently for each p, independently comprise said first radically transferable group, and at least one of R 3 independently for each q, R , R 5 and R 6 independently comprise said second radically transferable group.
  • the indenonapbtbopyran represented by Formula (II) includes at least one first radically transferable group, and at least one second radically transferrabie group, in which for the indenonapbthopyran represented by Formula (li) at least one of B and B' independently comprise said first radically transferable group, and at least one of R 7 Independently for each x, R 8 independently for each y, R s and R 1Q independently comprise said second radically transferable group.
  • z is 2; and the spirooxazine represented by Formula ⁇ 1 ⁇ includes one first radically transferable group, and one second radically transferrabie group, In which for the spirooxazine represented by Formula (I) one R 2 comprises said first radically transferable group, and one R 3 comprises said second radically transferable group.
  • the Indenonapbthopyran represented by Formula (il) includes one first radically transferable group, and one second radically transferrabie group, In which for the indenonapbthopyran represented by Formula (II) one of B and S' comprises said first radically transferable group, and one R 8 comprises said second radically transferable group,
  • one or more groups of the spirooxazine represented b Formula (1), such as Ri, R 2 , R3, R , Rs, and/or R 6 include a group represented by Formula (ill), as described previously herein.
  • one or more groups of the indenonapbthopyran represented by Formuia (II) such as R 7 , R 8 , R 9 , R 10l B, and/or B' in each case independently include the group represented by the Formula (III), as described previously herein.
  • X of the group represented by Formuia (IIS) can, with some embodiments be a halo group, such as CI, Br, and I,
  • Each polymer prepared by controlled radical polymerization of the polymer composition of the present invention can Independentl be a thermoplastic polymer or a curable polymer.
  • the polymer is a curable polymer it has, with some embodiments, one or more functional groups thai are reactive with the (i) functional groups of another material, such as a crossiinking agent, and/or (ii) other functional groups on the same polymer,
  • Each polymer prepared by controlled radical polymerization of the polymer composition of the present invention can independently be a thermoplastic polymer or a curable poiymer.
  • the polymer prepared by controlled radical polymerization Is a curable poiyme it has, with some embodiments, one or more functional groups that are reactive with the (!) functional groups of another material, such as a crossiinking agent, and/or (si) other functional groups on the same polymer prepared by controlled radical polymerization.
  • the poiymer prepared by controlled radical polymerization includes at least one first reactive group; and the poiymer composition further includes at least one crossiinking agent that includes at least two second reactive groups that are reactive with and form covalent bonds with the first reactive group(s) of the poiymer prepared by controlled radical polymerization.
  • the polymer that is prepared by controlled radical polymerization, includes at least one active hydrogen group selected from hydroxy!, thiol, carboxylic acid, primary amine, and secondary amine; and the polymer compositio further includes at least one crossiinking agent that Includes at least two functional groups seiected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, ihioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates, With some further embodiments, the crossiinking agent includes at least two functional groups selected from oxiranes, thiooxiranes, isocyanates, ihioisocyanates. The crossiinking agent, in accordance with some additional embodiments, includes at least two functional groups selected from oxiranes and isocyanates.
  • the crossiinking agent includes a separate polymer according to the present invention that is prepared by controlled radical polymerization, which Includes at least two functional groups selected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, ihioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates.
  • the crossiinking agent polymer can be prepared in accordance with the description provided previously herein, using a spirooxazine represented by Formula (I) or an indenonaphthopyran represented by Formula (II) as a controlled radical polymerization initiator.
  • the crosslinking agent is prepared by controlled radical polymerization, but is not prepared using a spirooxazine represented by Formula (I) or an indenonaphthopyran represented by Formula (ii) as a controlled radical polymerization initiator. With some further embodiments, the crosslinking agent is not prepared by controlled radical polymerization.
  • the polymers prepared by controlled radical polymerization include at least one, such as two or more, radically poiymerlzable ethylenicaliy unsaturated groups, such as, but not limited to, (meth)acry!oyi groups and a!lyiic groups.
  • the polymer compositions of the present invention can be cured by exposure to actinic radiation in the presence of a suitable initiator, such as a photopolymerization initiator, and an optional crosslinking agent that has two or more radically polymerizable ethylenicaily unsaturated groups, in accordance with art- re cognized methods.
  • a suitable initiator such as a photopolymerization initiator
  • an optional crosslinking agent that has two or more radically polymerizable ethylenicaily unsaturated groups
  • isocyanate functional materials from which the crosslinking agent can be selected include but are not limited to, toiuene-2,4-diisocyanate; toluene ⁇ 2.6-ditsocyanate; diphenyl methane ⁇ 4,4' ⁇
  • diisocyanate diphenyl methane ⁇ 2,4' ⁇ diisocyanaie; para-phenylene diisocyanate;
  • biphenyi diisocyanate S.S'-dimethyM ⁇ '-diphersylene diisocyanate; tetramethylene- 1 ,4-diisocyanate; hexamethy!ene-1 ,6-diisocyanate; 2,2,4-trimethyi hexane-1 ,6- diisocyanate; lysine methyl ester diisocyanate; bis(isocyanato ethyf)fumarate;
  • isophorone diisocyanate ethylene diisocyanate; dodecane-1 ,12-diisocyanate;
  • the poiyisocyanate crosslinking agent can, with some embodiments, be selected from polyisocyanates prepared from dimers and trimers of diisocyante monomers. Dimers and trimers of diisocyanate monomers can be prepared by art- recognized methods, such as described in U.S. Pat. No. 5,777,061 at column 3, line 44 through column 4, line 40. Dimers and trimers of the above recited diisocyanate monomers can contain linkages selected from the group consisting of isocyanurate, uretdione, biuret; aiiophanaie and com inatio s thereof.
  • the ssocyanate functional crossiinking agent can also be selected from (i) polyisocyanaie functional polymer having at least two isocyanafe groups, (si) oligomeric polyisocyanaie functional adduci and mixtures thereof.
  • the polyisocyanaie functional polymer and oligomenc polyisocyanaie functional adduci can each contain structural linkages selected from urethane, i.e., -NH-C(0 ⁇ -0-, thiourethane, i.e., -NH-C(0) ⁇ S-, urea, e.g., -NH-C ⁇ 0)-NH ⁇ , and combinations of these structural linkages.
  • the pofyisocyanate polymer can be prepared, by art-recognized methods, from one or more monomers having at least two reactive hydrogen groups, such as thiol, hydroxy, primary amine and secondary amine groups, and one or more monomers having two or more isocyanafe groups.
  • the molar equivalent rat o of reactive hydrogen groups to isocyanafe groups is selected such that the resulting polymer has the desired end groups, i.e., isocyanafe groups,
  • the number average molecular weight ( n) of the polyisocyanaie-funciionai polymer is less than 20,000, such as from 1 ,000 and 10,000, with some embodiments.
  • the polyisocyanaie functional polymer is a polyisocyanaie functional po!yurethane prepared from aliphatic diois and aliphatic dtisocyanates.
  • the polyisocyanaie functional po!yurethane ma be prepared using relatively small amounts of monomers having three or more functional groups, such as triols and/or tiisocyanaies, to increase the functionality and branching of the polyurethane, in accordance with art-recognized methods,
  • oligomeric polyisocyanaie functional adduci a material that is substantially free of polymeric chain extension.
  • Oligomeric polyisocyanaie functional adducts can be prepared by art-recognized methods from, for example, a compound containing three or more active hydrogen groups, such as trimeihylolpropane (T P), and an Isocyanafe monomer, such as 1-isocyanato-3,3,5- irimethyl-5-isocyanatomethyicyciohexane (!PDI), in a molar ratio of 1 :3, respectively.
  • T P trimeihylolpropane
  • Isocyanafe monomer such as 1-isocyanato-3,3,5- irimethyl-5-isocyanatomethyicyciohexane (!PDI
  • TMP-31PDI an oligomeric adduci having an average isocyanafe functionality of 3 can be prepared ("TMP-31PDI" ⁇ .
  • the oligomeric polyisocyanaie functional adduct can contain structural linkages selected from the urethane, ihiourethane, urea and combinations thereof, as described previously herein.
  • the active hydrogen group containing compound is aliphatic with some embodiments, such as T P, trishydroxyisocyanurate, peniaerythrito! and trlmethylolpropane tris(mereaptoacetate).
  • the isocyanate monomer is, with some embodiments, a diisocyanate monomer and can be selected from those described previously herein,
  • the isocyanate groups of the isocyanate functional crossiinki rig agent can, with some embodiments, be capped or blocked with a capping / blocking agent. After exposure to elevated temperature, the capping / blocking agent separates from the isocyanate functional material, allowing the free / unblocked Isocyanate groups thereof to react and form covalent bonds with the active hydrogen groups of the polymer prepared by controlled radical polymerization according to the present invention. After unblocking or decapping from the polyisocyanate, the capping agent can voiatrze out of the composition ⁇ prior to the composition becoming vitrified) and/or remain in the composition, such as a pjasticizer. With some embodiments, it is desirable that the capping agent not form bubbles in the composition and/or overly plasticize the composition after decapping.
  • the capping groups of the capped polyisocyanate crosslinking agent ca be selected from, with some embodiments hydroxy functional compounds, 1 H- azoles, lactams, ketoximes and mixtures thereof.
  • Classes of hydroxy functional compounds include, but are not limited to, aliphatic, cycioa!iphatic, or aromatic aikyi monoaicohois or phenolics.
  • Specific examples of hydroxy functional compounds useful as capping agents include, but are not limited to: lower aliphatic alcohols such as methanol, ethanoi, and rv-butanol; cycloaliphatic alcohols such as cyc!ohexano!
  • the hydroxy functional capping groups include the phenolics, examples of which include, but are not limited to, phenol itself and substituted phenols, such as cresol, nitrophenof and p-hydroxy methyl enzoate.
  • Examples of i H-azoies that are useful as capping groups include, but are not limited to IH-imidazole, I H-pyrazoie, 1 H-3,5 ⁇ dimethyl pyrazole, 1 H ⁇ 2.5 ⁇ dimethyi pyrazole, 1 H-1 ,2,3-triazole, 1 H-1 ,2,3-benzotriazole, 1 H-1 ,2,4-triazole, 1 H-5-methyi- 1 ,2,4-triazole, and 1 H-3-amrno-1 ,2,4-triazole.
  • Kefoximes useful as capping groups include those prepared from aliphatic or cycloaiip atic ketones.
  • ketoxime capping groups include, but are limited to, 2-propanone oxime (acetone oxime), 2-fautanone oxime, 2-pentanone oxime, 3-pentanone oxime, 3-meihyl-2-butanone oxime, 4-methyi-2-penianone oxime, 3,3-dimethyi-2-buianone oxime, 2-heptanone oxime, 3-heptanone oxime, 4- heptanone oxime, 5-methyi-3- heptanone oxime, 2,6-dime ⁇ ftyi-4-heptartone oxime, eyclopentanone oxime, cydohexanone oxime, 3-methylcyclobexanone oxime, 3,3,5- trimethyicyclohexanone oxime and 3,5,5-trimethyl-2-cydohexene-5-one oxime.
  • lactam capping groups include, but are not limited to, e- caproiaciam and 2-pyro!idinone.
  • Other suitable capping groups include, morphoiine, 3-aminopropyi morphoiine and -hydroxy phthaiimide.
  • Oxirane functional crosslinking agents can be prepared by reacting a hydroxy! functional material having at least two hydroxy! groups with a
  • 2-(haiomethyl)oxirane such as 2-(chioromethyl)oxirane, which Is also referred to as epiehiorohydnn.
  • polyois that can be used to prepare oxirane functional crosslinking agents include, but are not limited to, glycerin, trimethylolpropane, trirnethylolethane, irishydroxyethylisocyanurate, pentaerythritol, ethylene glycol, propylene glycol, trimetbyiene glycol, butanedioi, hepianedioi, hexanediol, octanedioi, 4,4' ⁇ propene-2 !
  • 2-diyl)dicyclohexanoi 4,4'-methyienedicyclohexanol, neopentyi glycol, 2,2,3-frimethyipentane-l ,3-diol, 1 ,4-dimethyiolcyclohexane, 2,2,4- thmeihyipentane dioi, 4 ! 4'-(propane-2,2-diyl)diphenol ( and 4 i 4'-methyienediphenoL
  • the oxirane functional crosslinking agent can be a polymeric material.
  • the polymeric oxirane functional crosslinking agent can be prepared from an oxirane functional material having at least two oxirane groups and an active hydrogen functional material having at least two active hydrogen groups, such as at least two hydroxy! groups.
  • Examples of polyois that can be used to prepare polymeric oxirane functional crosslinking agents include, but are not limited to those classes and examples recited previously herein with regard to preparing the oxirane functional crosslinking agent.
  • the polymer prepared by controlled radical polymerization is present in the polymer composition of the present invention in an amount of at least 2 percent by weight, or at least 10 percent by weight, or at least 20 percent by weight, or at least 30 percent by weight, or at least 50 percent by weight, or at least 70 percent by weight, or at least 80 percent by weight, based on total weight of resin solids of the polymer composition.
  • the polymer composition also, with some embodiments, contains the polymer prepared by controlled radical polymerization in an amount of less than or equal to 98 percent by weight, or less than or equal to 95 by weight, or less than or equal to 90 percent by weight, based on total weight of resin solids of the polymer composition.
  • the polymer prepared by controlled radical polymerization can, with some embodiments, be present in the polymer composition of the present invention in an amount ranging between any combination of these values, inclusive of the recited values, such as from 2 to 98 percent by weight, or from 10 to 98 percent by weight, or from 20 to 98 percent by weight, or from 30 to 98 percent by weight, or from 50 to 98 percent by weight, or from 70 to 95 percent by weight, or from 80 to 90 percent by weight, in each case based on total weight of resin solids of the polymer composition.
  • the polymer prepared by controlled radical polymerization is present in the polymer composition of the present invention in an amount of from 20 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 25 percent by weight, in each case based on total weight of resin solids of the polymer composition.
  • the cross!inking agent is present, with some embodiments, In the polymer composition of the present invention in an amount of at least 2 percent by weight, or at least 5 percent by weight, or at least 10 percent by weight, based on total weight of resin solids of the polymer composition.
  • the crosslinking agent can also, with some embodiments be present in the polymer composition in an amount of less than or equal to 70 percent by weight, or an amount of less than or equal to 50 percent by weight, or less than or equal to 30 percent by weight, or less than or equal to 20 percent by weight, based on total weight of resin solids of the polymer composition.
  • the crosslinking agent can be present in the polymer composition of the present invention in an amount ranging between an combination of these values, inclusive of the recited values, such as from 2 to 70 percent by weight, or from 2 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 20 percent by weight, based on total weight of resin soiids of the curable particulate composition, and , inclusive of the recited values.
  • the polymer prepared by controlled radical polymerization is present in the polymer composition, with some embodiments, in an amount of from 30 to 98 percent by weight, based on total resin solids weight of the polymer composition; and the crosslinking agent is present in the polymer composition, with some embodiments, in an amount of from 2 to 70 percent by weight, based on total resin solids weight of the polymer composition.
  • the polymer compositions of the present invention include one or more additional polymers that do not include ⁇ and are free of) a residue of a mechanochramic compound, such as represented by Formulas (i) and (II), which can be referred to as non-mechanochromic polymers.
  • nors-mechanochromic polymers include, but are not limited to, polyester polymers, po!yurethane polymers, polycarbonate polymers, poiyether polymers, pofyamide polymers, polyimide polymers, polyamideimide polymers, poiyurea polymers, poiysulfone polymers, poiyketone polymers, polyvinyl polymers, po!yolefins, poly(meth)acrylates, and combinations of two or more thereof.
  • Each non-mechanochromic polymer can include, with some embodiments: one or more (such as two or more) active hydrogen groups, such as hydroxy!, thiol, carboxyiic acid, primary amine, and secondary amine; and/or one or more (such as two or more) functional groups that are reactive with active hydrogen groups, such as, cyclic carboxyiic acid anhydrides, oxiranes, thiooxiranes, isocyanaies, thioisocyanates, cyclic carboxyiic acid esters, cyclic amides, and cyclic carbonates.
  • active hydrogen groups such as hydroxy!, thiol, carboxyiic acid, primary amine, and secondary amine
  • functional groups that are reactive with active hydrogen groups such as, cyclic carboxyiic acid anhydrides, oxiranes, thiooxiranes, isocyanaies, thioisocyanates, cyclic carboxyiic acid esters, cyclic amides, and cycl
  • the non-mechanochromic polymer is present in an amount of from 2 to 98 percent by weight, or from 10 to 80 percent by weight, or from 20 to 70 percent by weight, or from 30 to 60 percent by weight, or from 30 to 50 percent by weight, where the percent by weights are in each case based on the total weight of the polymer of the present invention (which includes a residue of a mechanochromic compound such as represented b Formulas (! and (I!)) and the non-mechanochromic polymer.
  • the equivalent ratio of active hydrogen equivalents of the polymer prepared by controlled radical polymerization, to isocyanate or oxirane equivalents of the crossiinklng agent is, with some embodiments, from 0.7: 1 to 2:1 , or from 0.8:1 to 1,3:1.
  • the polymer composition o the present Invention can be cured by any suitable methods.
  • the polymer composition is thermosetting, and is curable by exposure to elevated temperature.
  • cured is meant a three dimensional crosslink network formed by covending bond formation, such as between the active hydrogen groups of the polymer prepared by controlled radical polymerization and the isocyanate or oxirane groups of the crossiinklng agent.
  • the temperature at which the thermosetting polymer composition of the present invention is cured is variable and depends in part on the amount of time during which curing Is conducted.
  • thermosetting po ymer composition is cured at a temperature within the range of 90°C to 204°C, or from 149°C to 204°C, or from 154°C to 177°C. for a period of 20 to 80 minutes.
  • the polymer compositions of the present invention can also, with some embodiments, include pigments and fillers.
  • pigments include, but are not limited to: inorganic pigments, such as titanium dioxide and iron oxides; organic pigments, such as phthalocyanines, anthraquinones, quinacridones and thioindigos; and carbon blacks.
  • fillers include, but are not limited to: silica, such as precipitated silicas; clay; and barium sulfate.
  • pigments and fillers can, with some embodiments, be present in amounts of from 0,1 percent to 70 percent by weight, based on the total solids weight of the polymer composition (excluding solvent).
  • the polymer compositions of the present invention can, with some embodiments, optionall contain additives such as, but not limited to: waxes for flow and wetting; flow control agents, such as poiy ⁇ 2 ⁇ ethyihexyl)acryla?e; antioxidants; and ultraviolet (UV) light absorbers.
  • additives such as, but not limited to: waxes for flow and wetting; flow control agents, such as poiy ⁇ 2 ⁇ ethyihexyl)acryla?e; antioxidants; and ultraviolet (UV) light absorbers.
  • useful antioxidants and UV light absorbers include, but are not limited to, those available commercially from BASF under the trademarks !RGANOX and TiNUVSN.
  • These optional additives, when used, can be present In amounts up to 20 percent by weight, based on total solids weight of the polymer composition (excluding solvent).
  • the polymer compositions of the present can, with some embodiments, include solvents, selected from water, organic solvents, and combinations thereof.
  • Classes of organic solvents that can be present in the polymer compositions of the present invention include , but are not limited to: alcohols, e.g., methanol, ethanol, n-propano!, iso-propanol, n-butanoi, sec-butyl alcohol, fert-butyl alcohol, iso-butyi alcohol, furfuryi alcohol and tetrabydrofurfuryi alcohol; ketones or ketoalconois, e.g., acetone, methyl ethyl ketone, and diaceione alcohol; ethers, e.g., dimethyl ether and methyl ethyl ether; cyclic ethers, e.g., tetrahydrofuran and dioxane; esters, e.g., ethyl acetate., ethyl lactate, ethylene carbonate and propylene carbonate; poiyhydric alcohols, e.g.,
  • Selles(s) can be present in the polymer compositions of the present invention, in an amount of at least 5 percent by weight, or at least 15 percent by weight, or at least 30 percent by weight, based on the total weight of the polymer composition.
  • the sives(s) can also be present in the polymer composition In an amount of less than 95 percent by weight, or less than 80 percent by weight, or less than 60 percent by weight, based on the total weight of the pigment dispersion.
  • the amount of solvent present in the polymer composition can range between any combination of these values, inclusive of the recited values, with some embodiments, such as from 5 to 95 percent by weight, or from 15 to 80 percent by weight, or from 30 to 60 percent by weight, in each case based on the total weight of the polymer composition,
  • the polymer composition Includes an additive selected from heat stabilizers, light stabilizers, and combinations thereof.
  • useful heat stabilizers and light absorbers include, but are not limited to, those available commercially from BASF under the trademarks IRGA OX and TJNUVIN.
  • the optional heat stabilizers and light stabilizers, when used, can be present in amounts up to 20 percent by weight, based on total solids weight of the polymer composition (excluding solvent).
  • the present invention also relates to mechanochromic articles that include the polymer composition of the present invention as described previously herein.
  • the mechanochromic article is selected from films, sheets, and 3-dimens!onai articles.
  • the 3-dimensionai articles from which the mechanochromic articles of the present invention can be selected include, but are not limited to, ophthalmic articles, display articles, windows, mirrors, protective articles and support articles.
  • the mechanochromic articles of the present invention are selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, and magnifying lenses.
  • ophthalmic means pertaining to or associated with the eye and vision.
  • Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but no!
  • bifocal lenses bifocal lenses, trifocal lenses and progressive lenses
  • other elements used to correct, protect, or enhance (cosmetically or otherwise) vision including without limitation, contact lenses, intra-ocular lenses, magnifying lenses, and protective lenses or visors.
  • the mechanochromic articles of the present invention are selected from display articles, and the display articles are selected from screens, monitors, and security elements.
  • display means the visible or machine-readable representation of information In words, numbers, symbols, designs or drawings.
  • Non-limiting examples of display articles, elements and devices include screens, monitors, and security elements, such as security marks.
  • the mechanochromic articles of the present invention are selected from protective articles, and the protective articles are selected from protective lenses, protective visors, protective headgear, and protective housings.
  • protective lenses include, but are not limited to, safety glasses and safety goggles, such as used in a laboratory and/or a work shop, such as a metal shop, welding shop, wood-working shop, automotive shop/garage, and the like.
  • protective visors include, but are not limited to, those used with racing helmets (such as automotive, motorcycle, and boat racing helmets), aircraft helmets, hockey helmets, metal working helmets, and helmets used by ground military personnel.
  • protective headgear include, but are not limited to, motorcycle helmets, aircraft helmets, speed boat helmets, automotive race helmets, baseball helmets, hockey helmets, equestrian helmets, helmets used by ground military personnel, construction helmets, oil filed helmets, and helmets used by metal workers.
  • protective housings include, but are not limited to, housings for sensitive equipment, such as, analytical equipment, guidance systems (such as missile guidance systems), and medical equipment (such as insulin pumps),
  • the mechanochromic articles of the present invention are, with some embodiments, selected from support articles, and the support articles are selected from rods, beams, crossarms, and combinations thereof.
  • the rods, beams, and crossarms can be substantially unitary articles, or composed of a plurality of components, in which at least some of the components are the mechanochromic articles of the present invention.
  • the mechanochromic article of the present invention is selected from a 3-dimensionai article, and the 3 ⁇ dimenslonsal article includes a layer residing over at least a portion of at least one surface of the 3-dsmensiona! article, in which the layer includes the polymer composition of the present invention as described previously herein, and is a mechanochromic layer.
  • the mechanochromic layer can be selected from fiims, sheets, and/or coatings.
  • the mechanochromic article of the present, invention is selected from a 3-dimenstona! article, and the 3-dimensionsal article includes a coating residing over at least a portion of at least one surface of the 3-dimensfona! article, in which the coating includes the polymer composition of the present invention as described previously herein, and is a mechanochromic coating.
  • the coating is the polymer composition of the present invention, and the coating is a mechanochromic coating.
  • the coating can be a single layer coating or a multiple layer coating, In which each layer thereof can have the same or a different composition.
  • the coating is a multiple layer coating that includes a primer over at least a portion of a surface of the 3-dimensionai article, a mechanochromic layer formed over the primer layer (in which the mechanochromic layer Includes the polymer composition of the present invention), and an optional clear layer formed over the mechanochromic layer.
  • the mechanochromic layer can be pigmented or unpigmented, with some embodiments.
  • the optional clear layer which resides over the mechanochromic layer, can include an additive selected from heat stabilizers and/or light stabilizers.
  • the heat stabilizers and light stabilizers can be present in amounf(s) and the thickness of the clear layer can be selected such that photochromic activation of the residue of the controlled radical polymerization initiator ⁇ represented by Formula (I) and/or (II), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantially eliminated.
  • the heat stabilizers and light stabilizers can be present in the clear layer in a total amount of up to 40% by weight, based on the total solids weight of the dear layer.
  • a mechanochromic article that includes the polymer composition of the present invention, in which the mechanochromic article further includes a coating residing over at least a portion of at least one surface of the mechanochromic article.
  • the coating is free of the polymer composition of the present invention, and the coating includes an additive selected from heat stabilizers, Sight stabilizers, and combinations thereof.
  • the coating residing over the mechanochromic article can be referred to as an overcoating.
  • the overcoating, which resides over the mechanochromic article can be a clear overcoating, with some embodiments of the present invention.
  • the heat stabilizers and light stabilizers can be present in amount(s) and the thickness of the clear overcoating can be selected such that photoch.ro mi c activation of the residue of the controlled radical polymerization initiator (represented by Formula (i) and/or (!l), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantiall eliminated.
  • the heat stabilizers and light stabilizers can be present In the clear overcoating In a total amount of up to 40% by weight, based on the total solids weight of the clear overcoat,
  • Part 1 describes the synthesis of controlled radical polymerization initiators
  • Part 2 describes the preparation of polymers made by controlled radical polymerization using the initiators of Part 1.
  • frlethylamine (1.1 Sg ) was added dropwise. The resulting dark solution was reffuxed for 1 hour, then cooled to room temperature and a blue product was collected via filtration. This was immediately placed into a Nitrogen-flushed 2oz jar. To the jar was added i !eihyiamine (2.88g), and dichloromethane (8.5 ml). This mixture was cooled in a dry ice/ethanol bath, and a solution of 2-bromoisobutyry! bromide (3.94g) In dichloromethane (1.5 mL) was added. The jar was reseaied and allowed to warm to room temperature. After stirring for 2 hours, the residue was dry packed onto a 6 inch by % inch silica plug and eluted with 500 mL of a 2: 1 solution of
  • indeno[2 : ,3 ! :3,4]naphtho:[1 ,2-b]pyran (0.1g) was placed into a Nitrogen-flushed 25 mL round bottomed flask. To the flask was added dichioromethane (1.5g), then the mixture was cooled In an ice water bath. Triethylamine (0.0647g) was added, followed by 2-bromoisobutyryl bromide (0.08%,). The flask was allowed to warm to room temperature. After stirring overnight, the solvent was removed and the residue was redisso!ved in diethyl ether. The salts were removed via filtration, and the e!uent was concentrated.
  • the mixture was allowed to stir overnight at room temperature, after which a significant increase in viscosity was observed.
  • the material was dissolved in teirahydroiuran (THF, 20.7g) and stirred open to the atmosphere for 5 minutes, at which time the viscous solution was filtered.
  • the polymer was purified by precipitation into methanol. The off-white polymer was collected and dried under vacuum. The resulting polymeric compound was found to be reversibly photochromic under UV irradiation.
  • Example 2 1 ,3,3-trimethy!spiro[indo!ine-2,3'-naphiho[2, 1 -b][1 ,4]oxazine3-5,5'-diyi bis(2-bromo-2- methyipropionate) of Example 2 (0.5g, 1 equiv), Cu metal (0.029g, 2 equivs), tris(2 ⁇ dimethylaminoethyijamsne (0,79 g, 2 equivs), and dry butyl acetate (1.3 mL). The resulting mixture was purged with dry Nitrogen for 20 min.
  • Methyl acryiate (0.73, 37 equiv) and hydroxypropyl acryiate (0,96g, 33 equiv) were then added to the flask. The mixture was allowed to stir overnight at room temperature, after which a significant increase in viscosity was observed. The material was dissolved in THF (20.7g) then filtered through a plug of glass wool. To the filtrate was added
  • Example 3 4]nap tho 1 ,2-bJpyran of Example 3 (0.030Sg) was subjected to the conditions described in Example 8 except that 0.008g Cu, 0.029g tris(2- dimethylaminoethyi)amine, 4.32g of methyl acryjate, and 2.8g of D SO was used.
  • Gel Permeation Chromatography in THF indicated a peak MW of 128,614 (theory 140,000) relative to a linear polystyrene standard,
  • the initiator 1 ,3,3-frimethylspiroj;!ndoilne-2,3 , -naphtho(2,1-b] 1 ,4]oxazlne]-5 5 -diyi bis(2-bromo-2-melhylpropionate ⁇ of Example 2 (24.4 mg) was subjected to the polymerization conditions described in Example 6 except that 0.0094g Cu, 0.034g tris ⁇ 2-dimethyiaminoethyl)amine, 5.19g of methyl acryiate, and 3.4g of DMSO was used.

Abstract

The present invention relates to controlled radical polymerization (CRP) initiators that include at least one radically transferable group. The CRP initiators include at least one of the following, (a) a spirooxazine compound represented by the following Formula (I), and (b) an indenonaphthopyran represented by the following Formula (II), One or more of R1, R2, R3, R4, R5, and R6 of the spirooxazine, and one or more of R7, R8, R9, R10, B, and B' independently include the radically transferable group. The present invention also relates to polymers, such as mechanochromic polymers, that are prepared from such CRP initiators, polymer compositions that include such polymers, and mechanochromic articles that include such polymer compositions.

Description

CONTROLLED RADICAL POLYMERIZATION INITIATORS
CROSS REFERENCE TO RELATED PATENT APPLICATIO
[001] The present patent application is a continuation in part of and claims priority to United States Patent Application No, 13/447,604, filed on April 16, 2012, the disclosure of which is incorporated herein in its entirety.
FIELD OF THE INVENTION
[002] The present invention relates to controlled radical polymerization
Initiators that include a spirooxazine compound or an indenonaphthopyran compound, polymers and polymer compositions prepared therefrom, and mechanochromic articles that include such polymers and/or polymer compositions.
BACKGROUND OF THE INVE TIOM
[003] Various articles, such as protective articles and support articles are typically fabricated at least In part from polymeric materials. Protective articles, such as helmets, safety lenses, and protective housings, and support articles, such as beams can be subjected to stresses and/or impacts that result in damage to the article, which couid lead to catastrophic failure of the article at a point in time after the damage occurred. In some instances, the occurrence or presence of such damage is not accompanied by a visually observable indication thereof in the article. In the absence of a visually observable indication of the damage, the damaged article would not likely be withdrawn from use, and an unexpected catastrophic failure of the article couid occur.
|004] Mechanochromic materials change color in response to a change in mechanical stress, such as impacts, ft is known thai mechanochromic materials can be incorporated into certain articles so as to provide a visual indication that the article has undergone a threshold mechanical stress event, which could result in catastrophic failure thereof. Some mechanochromic materials can undergo a reduction in stability over time, which can result in reduced mechanochromic properties, A reduction in mechanochromic properties can be accompanied by an undesirable reduction in a visually observable indication that the article in question has undergone a threshold mechanical stress event.
[005] It would be desirable to develop new mechanochromic materials that can be used to provide a visually observable indication that an article, which incorporates such mechanochromic materials, has undergone a threshold mechanical stress event. It would be additionally desirable that such newly developed mechanochromic materials posses improved stability.
SUMMARY OF THE INVENTION
[OQSj in accordance with the present invention, there Is provided a controlled radical polymerization Initiator comprising at least one radically transferable group, wherein the controlled radical polymerization initiator comprises at least one of, (a) a spirooxazine compound and (b) an indenonap thopyran compound, that each independently comprise at least one radically transferable group.
[007] The spirooxazine compound is represented by the foiiowing Formula (I),
Figure imgf000004_0001
[008] With reference to Formula (I), n is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and R : independently for each n, R2 independently for each p, R3 independently for each q, R , Rs, and R6 are each independently selected from hydrogen, hydrocarby! and substituted hydrocarby! each optionally interrupted with at least one of„o~, ~S~» ~C(Q}-, -0(0)0-, -OC(0)0-, -S(O)-, -S02-, -N(R1 )-S and -Si(R )(R12}- wherein R 1 and R12 are each independently selected from hydrogen, hydrocarby! and substituted hydrocarby!, and combinations of two or more thereof.
[009] The indenonaphthopyran is represented by the following Formula (If),
Figure imgf000005_0001
[010] With reference to Formula (!i), x is from 1 to 4, y is from 1 to 4, R7 independently for each x, R8 independently for each y, R9, and R 0 are each independently setected from hydrogen, hydrocarbyi and substituted hydrocar yi each optionally interrupted with at least one of -0-, -S-, -C(Oh -C(0)O, -OC(0)0-, -S(O)-, -S02-» -N{R1 1}-, and -Si{R11){R12)- wherein R" and R12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof, and
{011J With further reference to Formula (II), B and B' are each independently selected from unsubstituted aryl, substituted ary!, unsubstituted heteroaryl, substituted heteroaryl, and poiya!koxy, or B and B' taken together form a ring structure selected from unsubstituted fiuoren-9-y!idene, substituted fiuoren-9-yiidene, saturated spiro-monocyciic hydrocarbon ring, saturated spiro-bicycitc hydrocarbon ring, and spiro-tricyciic hydrocarbon ring.
[012] With further reference to the spirooxazine represented by Formula (I), there is the proviso that at least one of R, independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and Re, independently comprise the radically transferable group,
[013j With further reference to the indenonaphthopyran represented by Formula (II), there Is the proviso that at least one of R7 independently for each x, R8 independently for each y, Rs> Rio, 8, and B', independently comprise the radically transferable group.
[0141 In accordance with the present invention, there is further provided a polymer composition comprising at least one polymer prepared by controlled radical polymerization initiated in the presence of a controlled radical polymerization initiator having at least one radically transferable group, wherein each polymer prepared by controlled radical polymerization Is independently represented by the following Formula (V),
Figure imgf000006_0001
[015] With reference to Formula (V); fvl independently for each v is a residue of a monomer; φ is a residue of the controlled radical polymerization initiator that Is free of the radically transferable group; X, independently for each z, is or is derived from the radically transferable group; w, Independently for each z, is an integer of at least 2; and z is an integer of at least 1.
[016] The controlled radical polymerization initiator from which the polymer represented by Formula (V) Is prepared is selected from (a) the spirooxazine compound represented by Formula (I) and/or (b) the indenonaphthopyran represented by Formula (II) as described above, and in each case as described in further detail herein.
[017] The features that characterize the present invention are pointed out with particularity in the claims, which are annexed to and form a part of this disclosure. These and other features of the invention, its operating advantages and the specific objects obtained by Its use will be more fully understood from the following detailed description in which non-iimiting embodiments of the invention are illustrated and described.
DETAILED DESCRIPTION OF THE INVENTION
[018] As used herein, the articles "a," "an," and "the" include plural referents unless otherwise expressly and unequivocally limited to one referent
|019j Unless otherwise indicated, all ranges or ratios disclosed herein are to be understood to encompass any and all subranges or subratios subsumed therein. For example, a stated range or ratio of "1 to 10" should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges or subratios beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, such as but not limited to, 1 to 6.1 , 3.5 to 7,8, and 5.5 to 10. [020] As used herein, unless otherwise indicated, left-to-right representations of linking groups, such as divalent linking groups, are inclusive of other appropriate orientations, such as, but not limited to, right-to-left orientations. For purposes of non-limiting illustration, the !eft-to~right representation of the divalent linking group
Q .Q or eqUjva|enjjy .-C{0)0~, is Inclusive of the rig t-to-feft
o representation thereof, O C ; o equivalent^ -0(0 )C- or -OC(O)-.
[0211 Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the term "about,"
[022] As used herein, molecular weight values of polymers, such as weight average molecular weights (Mw) and number average molecular weights (Mn), are determined by gel permeation chromatography using appropriate standards, such as polystyrene standards.
[023] As used herein, poiydispersit index (PD!) values represent a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polymer (i.e., Mw/fvln).
[024] As used herein, the term "polymer' means homopolymers (e.g.. prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), and graft polymers,
[025] As used herein, the term "(meth)acryiate" and similar terms, such as "(meth)acry!ic acid ester" means methacrylates and/or acrylates. As used herein, the term "(meth)acrylic acid" means methacrylic acid and/or acrylic acid,
[026] As used herein, spatial or directional terms, such as "left", "right", "Inner", "outer", "above", "below", and the like, relate to the invention as it is depicted in the drawing figures. However, it Is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting.
[027] As used herein, the terms "formed over," "deposited over," "provided over," "applied over," residing over," or "positioned over," mean formed, deposited, provided, applied, residing, or positioned on but not necessarily in direct {or abutting) contact with the underlying element, or surface of the underlying element. For example, a layer "positioned over" a substrate does not preclude the presence of one or more other layers, coatings, or films of the same or different composition located between the positioned or formed layer and the substrate.
[028] As used herein, the term "ring position" and related terms, such as "ring positions," means a particular position in a ring structure, such as the fused ring structure, of a chemical compound, such as the spirooxazine compounds represented by Formula {1} and the indenonaphthopyran compounds represented by Formula (SI), and which are depicted herein in accordance with some embodiments by numbers within the ring structures of the related representative chemical formulas.
[029] All documents, such as but not limited to issued patents and patent applications, referred to herein, and unless otherwise indicated, are to be considered to be "incorporated by reference" in their entirety,
:[030j As used herein, recitations of "linear or branched" groups, such as linear or branched aiky!, are herein understood to include: a methylene group or a methyl group; groups that are linear, such as linear C2-C2o a!kyl groups; and groups that are appropriately branched, such as branched C3~C20 alky! groups.
|031J As used herein the term "hydrocarbyf and similar terms, such as "hydrocarbyl subsiiiuent," means: linear or branched C C25 alkyi (e.g. , linear or branched d-C10 alkyi); linear or branched C2-C25 alkenyl {e.g., linear or branched C2~ C10 alkenyl); linear or branched C2-C25 alkynyl (e.g., linear or branched C2-C10 alkynyl); C3-C½ cycloalkyi (e.g., C3~C-i0 cycloaikyl); C3-C12 heterocycioalky! (having at least one hetero atom in the cyclic ring); C5-C<8 aryi (including polycyc!ic aryl groups) (e.g., C3-Cio aryi); C5"C 8 heteroary! (having at least one hetero atom in the aromatic ring); and Ce-C24 aralkyl (e.g., C6-C10 araikyl).
[032| Representative alkyi groups include but are not limited to methyl, ethyl, propyl, isopropyi, butyl, isobutyl, sec-butyl, tert-butyi, pen'tyf, neopentyl, hexyl, heptyi, octyi, nonyl and decyl. Representative alkenyl groups include but are not limited to vinyl, ally! and propenyi. Representative alkynyl groups include but are not limited to ethynyi, 1-propynyf, 2-propynyi, 1 -butynyl, and 2-butynyl. Representative cycloaikyl groups Include but are not limited to cyclopropyi, cyciobutyi, cyclopentyl, cyclohexy!, and cyciooctyl substituents. Representative heierocyc!oa!kyi groups include buf are not limited to tetrahydrofuranyl, tetrahydropyranyl and piperidsnyi. Representative aryl groups include but are not limited to phenyl, naphthyl, and triptycene. Representative heteroary! groups include but are not limited to furanyi, pyranyl and pyridinyl. Representative araikyi groups include but are not limited to benzyl, and pheneihy!,
[033] The term "cydoa!kyi" as used herein also includes: bridged ring polycycloaiky! groups (or bridged ring polycycfic alkyl groups), such as but not limited to, bicyc!o[2.2.1]heptyl (or norbomyl) and bicyclo[2.2.2]octyl; and fused ring polycycioa!kyl groups (or fused ring polycyciic aikyi groups}, such as. but not limited to, octahydro-1 H-indenyS, and decahydronaphthaienyL
[034] The term "substituted hydrocarbyl" as used herein means a hydrocarbyi group in which at least one hydrogen thereof has been substituted with a group that is other than hydrogen, such as, but not limited to, halo groups, hydroxy! groups, ether groups, thiol groups, thio ether groups, carboxy!ic acid groups, carboxyiic acid ester groups, phosphoric acid groups, phosphoric acid ester groups, sulfonic acid groups, sulfonic acid ester groups, nitro groups, cyano groups, hydrocarbyl groups (e.g.. aikyi, aikenyi, alkynyl, cycioaikyi, heterocyc!oa!kyi, aryi, heteroaryl, and araikyi groups), and amine groups, such as - iRn'XR^') where R^' and R 2' are each independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyi,
[035] The term "substituted hydrocarbyl" is inclusive of halohydrocarbyl (or halo substituted hydrocarbyl) substltuents. The term "halohydrocarbyl" as used herein, and similar terms,, such as halo substituted hydrocarbyl, means that at least one hydrogen atom of the hydrocarbyl (e.g., of the alkyl, aikenyl, alkynyl, cycioaikyi, heterocycloalkyi, aryi, heteroaryl, and araikyi groups) is replaced with a halogen atom selected from chlorine, bromine, fluorine and iodine. The degree of ha!ogenatton can range from at least one hydrogen atom but less than all hydrogen atoms being replaced by a halogen atom {e.g., a fluorom ethyl group), to full haiogenation (perhalogenation) in which all replaceable hydrogen atoms on the hydrocarbyi group have each been replaced by a halogen atom (e.g., trifluoromethyi or perfluoromethyi). Correspondingly, the term Perhalohydrocarbyl group" as used herein means a hydrocarbyl group in which all replaceable hydrogens have been replaced with a halogen. Examples of perhalohydrocarbyl groups include, but are not limited to, perhaiogenaied phenyl groups and perhaiogenaied alkyl groups.
[038J The hydrocarbyi and substituted hydrocarbyl groups from which the various groups described herein can each be independently selected, such as, but not limited to, R-rRio, R11, R12, is, and R14 can in each case be independently and optionally interrupted with at least one of -0-, -S-, -C(O)-, -C{0)0-r -0C(0)O, -S(O)-, -S02-, -N(R11)- and -Si(R1 t)(R12)-. As used herein, by interrupted with at least one of -Ο-, -S-, -C(O)-, -C(0)0-, -OC(0)0-, -S(0}~, ~S02-, -N(R11)-, and -Si(R11)(R12)-, means that at least one carbon of, but less than all of the carbons of, the hydrocarbyi group or substituted hydrocarbyi group, is in each case independently replaced with one of the recited divalent non-carbon linking groups. The hydrocarbyi and substituted hydrocarbyi groups can be interrupted with two or more of the above recited linking groups, which can be adjacent to each other or separated by one or more carbons. For purposes of non-limiting illustration, a combination of adjacent - C(0)~ and -N(R11}- can provide a divalent amide linking or interrupting group, ~C(Q)- N(R 1}~, For purposes of further non-limiting illustration, a combination of adjacent - N(R11}-, -C(Q - and -O- can provide a divalent carbamate (or urethane) linking or interrupting group, ~N(R11)-C(0)-0-, where R11 Is hydrogen.
[037] As used herein, the term "mechanochromic" and similar terms, such as "mechanochramic compound" means having an absorption spectrum for at least visible radiation that varies in response to mechanical stress. Further, as used herein the term "mechanochramic material" means any substance that is adapted to display mechanochromic properties (such as, adapted to have an absorption spectrum for at least visible radiation that varies In response to mechanical stress) and which includes at least one mechanochromic compound, at least one polymer, and/or a polymer composition according to the present invention,
[038] The mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present invention are, with some embodiments, capable of converting from a first state, for example a "clear state*' or a "colorless state" to a second state, for example a "colored state," in response to mechanical stress. With some embodiments of the present Invention, the mechanochromic compounds, materials, polymers, polymer compositions, and articles of the present invention undergo minimal, or are substantially free of, reversion back to the previous state (such as a clear or colorless state) after exposure to and optional removal of the mechanical stress.
[039] As used herein to modify the term "state," the terms "first" and "second" are not intended to refer to any particular order or chronology, but instead refer to two different conditions or properties. For purposes of non-limiting Illustration, the first state and the second state of a mechanochromic compounds, polymers, polymer compositions, and articles of the present invention cars differ with respect to at least one optica! property, such as but not limited to the absorption of visible and/or UV radiation. Thus, according to various non-limiting embodiments disclosed herein, the mechanochromic compounds, polymers, polymer compositions, and articles of the present invention can have a different absorption spectrum in each of the first and second state. For example, while not limiting herein, a mechanocnromic compounds, polymers, polymer compositions, and articles of the present invention can be clear in the f rst state and colored in the second state. Alternatively, mechanocnromic compounds, polymers, polymer compositions, and articles of the present invention can have a first color in the first state and a second color in the second state.
[040] As used herein, the term "actinic radiation" means electromagnetic radiation that is capable of causing a response In a material, such as, but not limited to, transforming a photochromic material from one form or state to another state, or initiating polymerization.
[041] As used herein the term "film" means a pre- ormed layer having a generally uniform thickness thai is not capable of self-support.
[042] As used herein the term "sheet" means a pre-formed layer having a generally uniform thickness that is capable of self-support.
[043] As used herein the term "coating" means a supported film derived from a flowable composition, which can have a uniform thickness or non-uniform thickness, and specifically excludes polymeric- sheets and unsupported polymer films. A coating that includes one or more mechanochromic polymers or compositions of the present invention can, with some embodiments, be a mechanochromic coating,
[044] As used herein, the term controlled radical polymerization" and related terms such as "controlled radical polymerization method(s)" includes, but is not limited to, atom transfer radical polymerization (ATRP), single electron transfer polymerization (SETP), reversible addition-fragmentation chain transfer (RAFT), and nitroxide-mediated polymerization (N P).
[04S] Controlled radical polymerization, such as ATRP, is described generally as a "living polymerization," i.e., a chain-growth polymerization that propagates with essentially no chain transfer and essentially no chain termination. The molecular weight of a polymer prepared by controlled radical polymerization can be controlled by the stoichiometry of the reactants, such as the initial concentration of monomer(s) and initiators), in addition, controlled radical polymerization also provides polymers having characteristics including, but not limited to: narrow molecular weight distributions, such as pofydispersity Index (PDl) values less than 2.5; and/or well defined polymer chain structure, such as block copolymers and alternating copolymers, with some embodiments. [046] For purposes of non-limiting illustration of controlled radical polymerization processes, the ATRP process is described in further detail as follows. The ATRP process can be described generally as including: polymerizing one or more radically polymerizable monomers in the presence of an initiation system; forming a polymer; and isolating the formed polymer. The initiation system includes, with some embodiments: an initiator having at least one radically transferable atom or group; a transition metal compound, such as a catalyst, which participates In a reversible redox cycle with the Initiator; and a ligand, which coordinates with the transition metal compound. The ATRP process is described in further detail In U.S, Pat. Nos. 5,763,548, 5,789,487, 5,807,937, 6,538,091 , 6,887,962, and 7,572,874. With some embodiments, the polymers and polymer compositions of the present invention prepared by controlled radical polymerization, are prepared generally in accordance with the ATRP method disclosed at column 4, line 12, through column 5, line 67 of United States Patent No. 6,265,489 B1 , which disclosure is incorporated herein by reference.
[047] With some embodiments, there are provided controlled radical polymerization Initiators having at least one radically transferable group, in which the controlled radical polymerization initiators include at least one spirooxazine compound represented by Formula (I), and/or at least one indenonapbthopyran compound represented by Formula (li), as described previously herein,
[048] The controlled radical polymerization Initiators of the present invention, with some embodiments, are each independently mechanochromic controlled radical polymerization Initiators. With some further embodiments, polymers prepared from the controlled radical polymerization Initiators of the present invention are mechanochromic polymers, in accordance with some additional embodiments of the present invention, polymer compositions that include the polymers of the present invention are mechanochromic polymer composition. With some additional embodiments, articles that include the polymers of the present invention are mechanochromic articles.
[0491 The controlled radical polymerization initiators of the present invention can, with some embodiments, each independently have at least one radicall transferable group, such as from 1 to 20, or from 1 to 15, or from 1 to 10, or from 1 to 5, or from 1 to 4, or from 1 to 3, or 1 or 2 radically transferable groups. With some further embodiments, the controlled radical polymerization initiators of the present Invention each independently have at least 2 radically transferable groups, such as from 2 to 20, or from 2 to 15, or from 2 to 10, or from 2 to 5, or from 2 to 4, or 2 or 3. With some embodiments, each controlled radical polymerization initiator of the present invention independently has two (2) radically transferable groups,
[OSOj With some embodiments of the controlled radical polymerization initiator of the present invention, and with further reference to the spirooxazine represented by Formula (I), at least two of, R independently for each n, R2 independently for each p, R3 independently for each q, R4, R5, and RSf independently comprise the radically transferable group,
[051] With some embodiments of the controlled radical polymerization initiator of the present invention, and with further reference to the indenonaphthopyran represented by Formula (!i), at least two of, R? independently for each x, R8 independently for each y, Rg, R10f B, and 8', independently comprise the radically transferable group.
[§52] The spirooxazine represented b Formula (I), with some embodiments, includes at least one first radically transferable group, and at least one second radically transferrabie group. In further accordance with some embodiments, for the spirooxazine represented by Formula (I): at least one of Ri Independently for each n, and RJI independently for each p, Independently include the first radically transferable group; and at least one of R3 independently for each q, R4, R.s and R6 independently comprise the second radically transferable group. Each first radically transferable group and each second radically transferable grou can be the same or different.
[053] While not intending to be bound by any theory, and with reference to Formula (I), it is believed based on the evidence at hand that the spirooxazine compound of the present invention, with some embodiments, is converted from a first state (which can be visibly non-colored) to a second state (which can be visibly colored) when bond (a") between ring positions 3' and 4' is broken. As such, and with some embodiments, when the spirooxazine represented by Formula (I) Includes at least one first radically transferable group and at least one second radically transferrabie group, each first radically transferable group is positioned so as to be on one side of the spirooxazine relative to bond (a') {at least one R, and/or at least one R2 each independentl including a first radically transferable group), and each second radically transferabie group is positioned so as to be on the other side of the spirooxazine relative to bond (a') (at least one R3, and/or R4l and/or R5, and/or Re each independently include a second radically transferable group),
[054] The indenonaphthopyran represented by Formula (Si), with some embodiments, includes at least one first radically transferabie group, and at least one second radically transferrabie group, in further accordance with some embodiments, for the indenonaphthopyran represented by Formula (II): at least one of B and B' independently include the first radically transferable group; and at least one of R7 independently for each x, R8 independently for each y, R9 and R10 independently include the second radically transferable group. Each first radically transferable group and each second radically transferable group can be the same or different.
[0S5J While not intending to be bound by any theory, and with reference to Formula (II), it is believed based on the evidence at hand that the indenonaphthopyran compound of the present invention, with some embodiments, is converted from a first state {which can be visibly non-colored) to a second state (which can be visibly colored) when bond (a) between ring positions 3 and 4 is broken. As such, and with some embodiments, when the indenonaphthopyran represented by Formula (II) includes at least one first radically transferable group and at least one second radically transferable group, each first radically transferable group is positioned so as to be on one side of the indenonaphthopyran relative to bond (a) (B and/or B' each independently including a first radically transferable group), and each second radically transferable group is positioned so as to be on the other side of the indenonaphthopyran relative to bond (a) (at least one R7, and/or at least one R8, and/or R9s and/or R-io each Independently include a second radically transferable group).
[056] In accordance with some additional embodiments of the present invention, the spirooxazine represented by Formula (!) includes one first radically transferable group, and one second radically transferrabie group. In further accordance with some embodiments, for the spirooxazine represented by Formula (I); R or R? Includes the first radically transferable group; and one of R3, R4, R5, and R6 includes the second radically transferable group,
[0S?J The indenonaphthopyran represented by Formula (Π), with some embodiments, includes one first radically transferable group, and one second radically transferrabie group. For the indenonaphthopyran represented by Formula (If), and in accordance with some embodiments: B or B' includes the first radically transferable group; and one of R7> Rs, Rg, and R 0 includes the second radically transferable group.
[058] The spirooxazine represented by Formula (I) includes, with some further embodiments, one first radically transferable group, and one second radically transferrabie group, For the spirooxazine represented by Formula (I), in accordance with some embodiments: one R2 includes the first radically transferable group; and one R3 includes the second radically transferable group,
[QS9] The indenonaphthopyran represented by Formula (ii), with some embodiments, includes one first radically transferable group, and one second radically transferable group. For the indenonaphthopyran represented by Formula (II), and in accordance with some embodiments; 8 or 8' includes the first radically transferable group; and one R7 or one Rs Includes the second radically transferable group.
[060] Each radically transferable group of the controlled radical polymerization initiators of the present Invention can each be independently selected from one or more atoms or groups that are radically transferable under controlled radical polymerization conditions. With some embodiments, each radically transferable group is independently selected from CI, Br, I, ORf , SR9, SeR8, OC(-0)R8 OP(=0)Rs, OP(=0)(ORs)2, OP(=0)OR9 Q~ (R% S-C(=S)N{R9)2> CM, NC, SCN, CNS, OCN, CNO, and N3. The Rf group {of ORf) is linear or branched C C20 alky! group, in which at least one hydrogen group is optionai!y substituted with a halo group, such as F or CI). Each R9 is Independently selected from ary! or a linear or branched CrC20 alkyl group. With the N{R9)2 group, the Rs groups can loin to form a 5-, 6- or 7-membered heterocyclic ring.
[061] With some further embodiments, each radically transferable group of the controlled radical polymerization initiators of the present invention are independently selected from CI, Br, and 1, With some further embodiments, each radically transferable group of the controlled radical polymerization initiators of the present invention is Br.
[082] For the spirooxazine represented by Formula (!}, and in accordance with some embodiments of the present Invention, at least one of R-t, R2> R3, R,5, R5, and R6 independently include, or is, a group represented by the Formula (ill), and described in further detail below..
[003] For the indenonaphthopyran represented by Formula (H), and in accordance with some further embodiments of the present invention, at least one of R7, Rs, Rg, io. B, and B' each independently include, or is, a group represented by the following Formula (III);
Figure imgf000016_0001
[084] With reference to Formula (Hi), and independently for the spirooxazine represented by Formula {(} and the indenonaphthopyran represented by Formula (II), R 3 is a divalent linking group selected from a bond, a divalent hydrocarbyi group and a divalent substituted hydrocarbyi group each optionally interrupted with at least one of -0-, ~S~, -C(O)-, -0(0)0-, ~0C(0)0~, -8(0)-, -SQr, -N(R15)- and -Si(R s)(R16)- and combinations of two or more thereof. The R15 and R1e groups are in each case independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi. With further reference to Formula (ill), R, is a divalent linking group selected from a bond, divalent hydrocarbyi, and divalent substituted hydrocarbyi and X is the radically transferable group.
[Q65J With some embodiments, and with further reference to Formula (Hi), R13 is selected from a bond, divalent C C2o linear or branched alkyl divalent C-s-C^ cyciic a!kyl, divalent C3-C10 heterocyclic alkyl, divalent aryi, divalent heteroaryi, and combinations thereof optionally interrupted with at least one of -O- and -S- and combinations of two or more thereof. With further reference to Formula (ill), and in accordance with some embodiments, R14 is selected from divalent CrC2<> linear or branched alkyl, and X is selected from a halo group,
[068] With additional reference to Formula (HI) and in accordance with some embodiments, R 3 is selected from a bond, divalent CrC 0 linear or branched alkyl, divalent C3-Ci0 heterocyclic aikyi, divalent aryi, and combinations thereof optionally interrupted with at least one of -0-. With further reference to Formula (ill), and in accordance with some embodiments, R14 is selected from divalent CrC-io linear or branched alkyl, and the halo group from which X is selected is CI, Br, or I.
[087] With some embodiments, and with reference to Formula (ill), the divalent linking group R 3 is bonded directly to the spirooxazine represented by Formula (I). The divalent linking group i3 of Formula (III) can, with some embodiments, be bonded to another group that is bonded to the spirooxazine represented by Formula (I), such as R-i, R2, R3, R4, R5, and/or R5.
[088] The divalent linking group R13 of the group represented by Formula (III), with some embodiments, is bonded directly to the indenonaphthopyran represented by Formula (II). The divalent linking group R13 of Formula (III) can, with some embodiments, be bonded to another group that Is bonded to the indenonaphihopyran represented by Formula {!(}, such as R7l R8, R8, R1C) B, and/or B!.
[069] In accordance with some embodiments of the present invention, for the spirooxazine represented by Formula (I), one 2 independently includes, or is, the group represented by Formula (IH), and one R3 Independently includes, or is, the group represented by Formula (III),
[070] With the spirooxazine represented by Formula (I), and with some embodiments: one R2 independently includes, or is, the group represented by Formula (111), which is bonded to ring position 5' of the spirooxazine represented by- Formula (I); one R3 independently includes, or is, the group represented by Formula (Hi), which bonded to ring position 5 of the spirooxazine represented by Formula (i); and the remaining groups R,, R2, R3, R , R5, and R6 are free of the group represented by Formula (ill).
[071] in accordance with some further embodiments of the present invention, for the indenonaphihopyran represented by Formula (II), one 8 or 8' Independently includes, or is, the group represented by Formula (Hi), and one R7 or Rs Independently includes, or is, the group represented by Formula (III).
[072] With the indenonaphihopyran represented by Formula (II), and with some embodiments: one B or B* at ring position 3 independently includes, or is, the group represented by Formula (Hi); one Re independently includes, or is, the group represented by Formula (ill), which is bonded to ring position 1 1 of the Indenonaphihopyran represenied by Formula (II); and the remaining groups B or 8', R7, R8, Rg, and R10 are free of the group represented by Formula (ill).
[0733 With some embodiments, the group represented by Formula (III) is selected from one or more groups represented by the following Formulas (l!i-A) through (ifi-F)
Figure imgf000018_0001
[074] With reference to the above Formulas (i!l-A) through (!!i-F), X In each case is independently a radically transferable group, such as a halo group, such as CI, Br, or I.
[075] With the spirooxazine compound of the present invention as represented by Formula (I), and in accordance with some embodiments, ¾ independently for each n and R2 independently for each p are each independently selected from hydrogen, ary!, mono{CrC6)a!koxyaryl, di(Ci-C6)a)koxyary!, mono(CrC6)aikylaryl, di(CrC6)alkyiaryl, bromoaryl, ch!oroaryl, fiuoroaryl, C3-C7 cycloalkylaryi, C3~C7 cyc!oa!kyl, C3-C7 cyc!oa!ky!oxy, C3-C7 cycioaikytoxy(Ci-C8)alkyi, C3-C7
cyc!oa!kyloxy{C C6)afkoxy< aryl(GrC-6)aikyl, ar '1(C -C6}a!koxy, ary!oxy,
aryioxy(C-i -C6)alky! , aryioxy(CrC6>a!koxy, mono- or ds(CrCg)a!kylary1{Ci-C6}alkyl, mono- -or diCCi -C6)alkoxyafy!(Cr C6)a!kyi, mono- or di(Ci-C6}alkyiaryl(CrC6)a!koxy, mono- or di(Ci ¼)a!koxyaryi{CrC6)aikoxy, amino, mono(CrC6)aikyfanriino, d!(CrC6)aikylarrtino, dsarylamino, N-(Ci-C6)alkylp!perazino, N-arylpiperazino, aziridino, indoiino, piperidino, aryfpiperidino, morphoiino, thiomorphoiino,
tetrahydroquinolino, teirahydroisoquinolino, pyrryl, C C6 alkyl, Ci-C6 bromoa!kyl, Ch- C6 ch!oroaikyl, C C6 fluoroalkyi, C C6 aikoxy, mono{C1-C6)afkoxy(Cr-C4)aikyi, acryloxy, methacry!oxy, acyioxy{CrC6 alkyl), acyloxy(C3-C7 cycloalkyl), acy!oxy{aryl), bromo, chioro or fiuoro.
[078] In accordance with some embodiments of the present invention, R3 of the spirooxazine represented by Formula (I) is, independently for each q, chosen from hydrogen, C1-C5 alkyi, d-C5 aikoxy, nitro, cyano, Ci-C8 a!koxycarbonyl, acyloxy(C,- C6 alkyi), acyioxy(C3~C7 cycloalkyl), acyioxy(aryl),, halo, C C monohaloaiky! or Cr C4 polyhaloalkyl; said halo substiiuenis being chioro, fiuoro, iodo or bromo.
[077] Irs accordance with some further embodiments of the present invention, R4 of the spirooxazine represented by Formula (I) is chosen from hydrogen, Ci~C8 alkyl, C3-C7 cycloalkyl, phen{C C )alkyl, naphth{Ci-C4)alkyl, ally!, acryiylpxy(C2-C6)alkyl, methacrylyloxy(C2-C6)alkyi> C2-C4 acyioxy{C2-C6)aikyl, carboxy{C2-C6)a!kyl, eyano(C2- C6)alkyi, hydroxy(C2-C8)alky!, triarylsilyi, triaryisilyioxy, tri(C Ce)aiky!silyi,
tri(CrCg)alkylsiiy!oxy, tri(CrC6)a!koxysHyl, tri(C C6)aikoxysiiyloxy,
dKC CgJalky CrCe afkoxy)silyi, d CrC6)alkyi(Ci-C6 a!koxy)silyloxy,
di(CrC6)aikoxy{Ci-C6 alkyt)silyl, di(Ci-C6)alkoxy(CrC6 a!kyl)siiyloxy, C C6 aikoxy(C2~ C4)aik ! or (C2H40)rCH3, wherein r is an integer from 1 to 6.
|078] in accordance with some additional embodiments of the present invention, R5 and e of the spirooxazine represented by Formula (I) are each independently selected from hydrogen, CrC5 alkyl, acyloxy{C C6 alkyl), acyfoxy(C3-C7 cycloalkyl), acyloxy{ary1), benzyl, phenyl, mono- or di-substiiuted phenyl, said phenyl substituents being Ci-C5 alkyl or C C5 aikoxy; or Rs and R6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom. [0791 With the spirooxazine compound of the present invention as represented by Formula (I), and in accordance with some embodiments, Ri independently for each n and R2 independently for each p are each independently selected from hydrogen, aryl, rnono{CrC6)alkoxyaryl, di(Ci-Ce)a!ky1amirso, piperklino, morpho!ino, Ci-C6 aikoxy, or fluoro.
[080] In accordance with some embodiments of the present invention, R3 of the spirooxazine represented by Formula (I) is, independently for each q, selected from hydrogen, CrC5 alky!, Ci-C5 aikoxy, C C8 aikoxycarbonyi, acy!oxy{CrCs aikyl), acyjoxy{C3-C? cycloafkyi), acy!oxy(aryi),, halo, Ci~C monohaioa!kyi or C C poiyhaloaikyi; and said ha!o substituents being chloro or fluoro.
[081] In accordance with some further embodiments of the present invention, R4 of the spirooxazine represented by Formula (!) is selected from hydrogen, C C8 aikyl, phen(Cr-C4)alkyi, acryiyfoxy{C2-C8)a!kyl, methacryiy!oxy(CrC6)a!ky!,
carboxy(C2-C6)aiky!, tn(Cr-C6)alkylsilyl, tri(CrC6)alkyisifyloxy, tn(C5-C6)alkoxysiiyis tri(C, -C6)alkoxysilyioxy, di(CrCs)aiky!(Ci-G6 alkoxy)silyl, di(Ci-Ce)alkyl(C Ce a!koxy)silyioxy, di(CrC6)aikoxy(CrC6 aikyi)sslyl or dl(Ci-C6)aikoxy(CrC6
a!ky!)sifyioxy.
[082] In accordance with some additional embodiments of the present invention, R5 and R6 of the spirooxazine represented by Formula (I) are each independently selected from hydrogen, Ci-C5 aikyl, phenyl; or Rs and R6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom.
[083] For the indenonaphthopyran represented by Formula (il), and in accordance with some embodiments, R7 independently for each x and Rs independently for each y are each independently selected from; hydrogen; a compatibiizing substituent; halogen selected from fluoro and chloro; Ci~C2o atkyi; C3- Cio cycloaikyl; acyioxy(C G6 aikyl), acy!oxy(C3-C7 cycloaikyl), acyioxy(aryi); substituted or unsubstituted phenyl, the phenyl substituents being selected from hydroxy!, halogen, carbonyl, C -C20 aikoxycarbonyi, cyano, halo(CrC2o)aikyl, C C2o aikyl or Ci-C20 aikoxy; -G-R10' or -C{0)-R1cOr
Figure imgf000020_0001
wherein R10' is hydrogen, C C20 aikyl, phenyl{Ci-C20)a!kyi, rnono(C C20)alky! substituted phenyl(C C2o)a!kyl, mono(CrC20)aikoxy substituted phenyl{CrC2o)alkyf, (d -C20}aikoxy(C2-C2o)a!kyl, C3- C10 cycloaikyl, or mono(Ci~C20)alkyi substituted C3-C10 cycloaikyl;
Figure imgf000020_0002
wherein R^' and R12 are each independently hydrogen, Ci-C20 aikyl, phenyl, naphfhyi, furanyl, benzofuran-2~yl, benzofuran-3~yl( thienyl, · benzothien-2-y!, .benzothien-3-yl, dibenzofuranyi, dibenzothienyl, benzopyridyi, fiuorenyl, Ci-C2Q alky!aryl, C3-Ci0 cycioaikyi, CrC2G bicycloaikyl, C5- C20 tricyc alkyl or Ci- Cw alkoxyafkyf, wherein said aryi group is phenyl or naphthyl, or Rn' and R 2 * come together with the nitrogen atom to form a C3-C20 hetero-bicycloaikyl ring or a C4-C20 hetero-tricyc!oa!kyi ring.
[084] For the indenonaphthopyran represented by Formula (II), and in accordance with some further embodiments, R7 independently for each x and R8 independently for each y are each independently selected from a nitrogen containing ring represented by the following graphic Formula (IVA),
Figure imgf000021_0001
[085] With reference to hormuSa (IVA), each -V- is independently chosen for each occurrence from -CH2-( -CHiR-ia )-, ~C(R13 !)2-< -CH(aryi)-, ~C(aryl)2~, and - C{R13')(aryl)-, and Z is -Y-, -0-, ~S~, -3(0)-, -S02-, -NH-, -N(R13')-, or -N(aryl)-, wherein each R 3' is independently C1-C20 aikyi, each aryi is independently phenyl or naphthyl, m is an integer 1 , 2 or 3, and p is an integer 0, 1, 2, or 3 and provided that when p is 0, Z is ·¥·.
[086] For the indenonaphthopyran represented by Formula (H), and in accordance with some further embodiments, R7 independently for each x and R@ independently for each y are each independently selected from a group represented by one of the following graphic Formulas (IVB) or (iVC):
Figure imgf000021_0002
[087] With reference to Formulas (IVB) and (IVC), Ri5, R 6, and R17 are each independently hydrogen, d-Ce aikyi, phenyl, or naphthyl, or the groups R15 and R¾6 together form a ring of 5 to 8 carbon atoms and each Rd is independentiy for each occurrence selected from Cr-C20 aikyi, Ci-C20 alkoxy, fluoro or chioro, and Q is an integer 0, 1 , 2, or 3. [0881 For the indenonaphthopyran represented by Formula (!!), and in accordance with some additional embodiments, R7 Independently for each x and Rs independently for each y are each independently selected from unsubstiluted, mono-, or di-substiiuted C4-C1g spirobicyciic amine, or unsubstituted, mono-, and di- substituted C4-C18 spirotri cyclic amine, wherein said substituents are independently aryi, C C2o aikyi, CrC2o aikoxy, or phenyi(C1~C2o)aikyi.
[089] In accordance with some embodiments, and with further reference to the indenonaphthopyran represented by Formula (Π), two adjacent R7 groups, or two adjacent Re groups, independently together form a group represented by one of the following Formulas (IVD) and (IVE);
Figure imgf000022_0001
[09OJ With reference to Formulas (IVD) and (IVE), T and T are each independently oxygen or the group -NRn'-, where R^', R 5, and R 6 are as set forth above.
[091] in accordance with some further embodiments, and with further reference to the indenonaphthopyran represented by Formula (if), R9 and R 0 are each independently selected from the following classes of groups (i) through (v).
[092] With some embodiments, R9 and R10 of Formula (II) are each independently selected from, (i) hydrogen, C C20 aikyi, C -C20 haioalkyi, C3~C 0 cycloa!ky!, acyloxy(Ci-06 aikyi), acyfoxy(C3-C7 cycloa!kyl), acyioxy(aryl), ailyi, benzyl, or mono-substituted benzyl, said benzyl substituents being chosen from halogen, C1-C20 aikyi or CrC20 aikoxy.
[O03 With some embodiments, R9 and R10 of Formula (il) are each independently selected from, (il) an unsubstituted, mono- di-or tri-substituted group chosen from phenyl, naphthyl, phenanthryi, pyren l, quinoiyl, isoquinolyl, benzofuranyl, thienyl, benzofbienyl, dtbenzofuranyl, dibenzothienyl, carbazoiyi, or indoly!, said group substituents in each case being independently chosen from halogen, C C20 aikyi or C C2Q aikoxy.
[094] With some embodiments, Rg and R10 of Formula (il) are each independently selected from, (ill) mono-substituted phenyl, said substiiuent located at the para position being -{CH2) or ~0-(CH2) ~, wherein t is the intege 1 , 2, 3, 4, 5 or 6, said subsiituent being connected to an ary! grou which is a member of a photochromic material.
[095] With some embodiments, F¾ and 0 of Formula {!!) are each independently selected from, (iv) the group ~CH(R10)G, wherein R18 is hydrogen, d-Cr, aiky! or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, and G is -Cr^OR19, wherein R19 is hydrogen, -C(0)R10, C C2o alkyt, C -C20 aikoxy(Cr'C2o)aSkyl, pheny1(C C20}a!kyl, mono(C C¾))aikoxy substituted pheny!(Ci- C2o)alkyl, or the unsubstituted, mono- or di-substituted aryl groups phenyl or naphthyl, each of said phenyl and naphthyl group substituents being Cr-C20 alky! or C ·-·€¾! aikoxy.
[098] With some embodiments, (v) R9 and R 0 together form a spiro subsiituent selected from a substituted or unsubstituted spiro-carbocyciic ring containing 3 to 6 carbon atoms, a substituted or unsubstituted spiro-heterocyc!ic ring containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms Including the spirocarbon atom, said spiro- carbocyciic ring and spiro-heterocyc!Ec ring being anrte!iated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C Czc aikyi.
[097] in accordance with some additional embodiments, and with further reference to the indenonaphthopyran represented by Formula (II), B and 8' are each independently: an aryl group that is mono-substituted with a compatiblizing
subsiituent; a substituted phenyl; a substituted aryl; a substituted 9-juloilndinyl; a substituted heteroaromatic group chosen from pyridyl, furantyl, benzofuran-2-yl, benzofuran-3-yi, thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,
dibenzoihienyl, carbazoyi, benzopyridyi, indolinyi, and fiuorenyi, wherein the phenyl, aryl, 9~ju blind inyL or heteroaromatic substituent is a reactive subsiituent R; an unsubstituted, mono-, di-, or tri-substituted phenyl or aryl group; 9-ju!o!idinyf; or an unsubstituted, mono- or di-substituted heteroaromatic group chosen from pyridyf, furanyl, benzofuran-2-yl, benzofuran-3-yi, thienyl, benzothien-2-yi, benzotbien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyi, benzopyridyi, indoiinyl, and fiuorenyi.
[098] The phenyl, aryl and heteroaromatic substituents, from which B and B' can each be independently selected, are in each case independently: hydroxy!, a group -C{~0)R2i, wherein R21 is -OR22l ~N(R23)R24, piperidino, or morpho!ino, wherein R22 is aiiyl, Cr-C20 aikyl, phenyl, mono(Ci-C2o)aikyi substituted phenyl, mono(Ci- C20)aikoxy substituted phenyl, pbenyl(Cr-C20)alky!, mono{CrC20)aiky! substituted pheny!(Ci-C20)aikyl, mono(C C2o)a!koxy substituted phenyi(C C2o}aikyi, C1-C20 aikoxy(C2-C2o)aiky! or CrC20 haloa!kyi, B23 and R24 are each independently C1-C20 alkyf, C3-C 0 cyc!oaikyl, phenyl or substituted phenyl, the phenyl substituenis being C1-C20 a!ky! or CrC2o a!koxy, and said haio substituent is chloro or f!uoro, aryl, mono(CrC2o)alkoxyaryl( di(Ci-C2o)a!koxyaryj, mono{CrC2o)a!ky!aryi, di(Ci~
C2o)aikyiaryi, haioary!, C3-C10 cycloa!kyiaryi, C3-C10 cycloa!ky!, C3-C10 cycloatkyloxy, C3-C10 cyc!oaiky!oxy(Ci-C2o)a!kyl, C3-C10 cycfoalkyloxy{Ci -C2o)aikoxy, aryl(Cr C¾))afkyi, aryi(CrC20)aikoxy> aryioxy, aryloxy(Ci-C2o)alkyl, aryloxy(CrCSG}alkoxy, mono- or d (C C2o)aikylar ](Ci~C2o)alk i, mono- or di-(C C2o)a!kox afyi{C C2o)ai !, mono- or di-(CrC2o}aikyiaryi(C-rC2o}aikoxy, mono- or di-(CrC2o)aikoxyaryl(Cr C20)alkoxy, amino, mono- or di-(C1-C2o)aikylamirio1 diaryiamino, piperazino, N~{C-,~ C2o)a!kylpiperazino, W-aryl iperazino, aziridino, indolino, pipendino, morphoiino, ihiomorpho!ino, tetra ydroquinoiino, teirahydroisoquinoiino, pyrroiidyi, C1-C20 a!kyi, C1-C20 haioalky!, C C20 aikoxy, mono{CrC20)a!koxy(Ci -Chalk ! , acryloxy, methacryioxy, acy!oxy(C C6 a!ky!), acyioxy(C3-C7 cye!oaiky!), acy!oxy{aryl}, or halogen,
[0981 accordance with some alternative embodiments, and with further reference to the indenonaphthopyran represented by Formula (II), B and B' are each independently an unsubststuted or mono-substituted group chosen from pyrazo!y!, imidazoiyl, pyrazoiinyi, imidazollnyl, pyrrolinyi, phenothiaziny!, pbenoxazinyl,
phenaziny!, and acridinyl. Each of these substituenis are, with some embodiments, Ci-C20 alkyl, C1-C20 aikoxy, phenyl, or halogen.
[0100] in accordance with some alternative embodiments, and with further reference to the Indenonaphthopyran represented by Formula (II), B and B' are each independently a roup represented by one of:
Figure imgf000024_0001
[0101] With reference to the formulas immediately above, K is -CH2- or -0-, and is -O- or substituted nitrogen, provided that when M is substituted nitrogen, K is - CH2-, the substituted nitrogen substituents being hydrogen, d-Cao alkyl, or CrC20 acyi, each R25 being independently chosen for each occurrence from CrC20 aikyi, Cr C2o aikoxy, hydroxy, and halogen, R26 and R2 each being independently hydrogen or C C2o alkyl, and u Is an intege ranging from 0 to 2.
[0102] In accordance with some alternative embodiments, and with further reference to the indenonaphthopyran represented by Formula (II), B and B' are each independently, a group represented by:
Figure imgf000025_0001
[0103] With reference to the formula immediately above, F½ is hydrogen or Cr C20 aikyl, and R2g is an unsubstituted, mono-, or di-substituted group chosen from nap thyi, phenyl, furanyi, and thienyl, in which the substituents are C1-C20 aiky!, C C2o alkoxy, or haiogen,
[0104] !n accordance with some embodiments, B and 8', of Formula (II), taken together form one of a fluoren-9-ylidene, mono-, or di-substituted fiuoren-9-ylidene, each of said fluoren-9-yiidene, in which the substituents are each independently chosen from C C20 aikyl, C1-C20 alkoxy, and halogen.
[01 OS] With some embodiments, R7 independently for each x and RB independently for each y, of the indenonaphthopyran represented by Formula (II), are each independently selected from, hydrogen, Ci~C6 aikyl, C3-C7 cycioalkyi, morphoiino, morphoiino substituted with Ci-C8 linear or branched aikyl, C Ce haioalky!, fiuoro, chioro, and -O-R10'.
[0106] With some further embodiments, R9 and R10, of the indenonaphthopyran represented by Formula (Π), are each independently selected from hydrogen, Cr-Cg aikyl, C Cg haloaikyi, and C3-C7 cycioalkyi, or together form a spiro substiiuent selected from a substituted or unsubstituted spi o-carbocyclie ring containing 3 to 8 carbon atoms.
[0107] With some additional embodiments, 8 and 8', of the indenonaphthopyran represented by Formula (II), are each Independently selected from aryi, ary! substituted with C-rC6 alkoxy, and aryi substituted with morphoiino,
[01O8J As previously discussed with regard to the indenonaphthopyran represented by Formula (li); R7 and R8, can each be independently selected from a compatibilizing substiiuent; and B and B: can each be selected from an aryi group that is mono-substituted with a compatibilizing substiiuent. If the indenonaphthopyran includes multiple compatibilizing substituents, each compatibilizing substiiuent can be independently chosen.
[0109] Each compatibilizing substiiuent can independently be represented by one of the following;
-A'-D-E-G-J (Xll !); -G-E-G-j (XVI); -D-E-G-J (XIX);
~A'-D-J (XIV); ■D-G-J (XVII); ~D-J (XX);
-A'-G-J (XV); ■G-J (XVIII); and •A'-J (XXI).
9 "5 [0110] With formulas (XI II) through (XXf), non-limiting examples of groups thai - A'- can represent according to various non-limiting embodiments disclosed herein include -0-, -C(=G}-, -C r, -OC(=0)~ and -NHC(=0)-, provided thai if ~A'~ represents -0-, -A'- forms at least one bond with -J.
[0111] Non-limiting examples of groups that '-D- can represent according to various non-limiting embodiments include a diamine residue or a derivative thereof, wherein a first amino nitrogen of said diamine residue can form a bond with -A'-, or a substituent or an available position on the indeno-fused naphthopyran, and a second amino nitrogen of said diamine residue can form a bond with -E-, -G- or -J; and an amino alcohol residue or a derivative thereof, wherein an amino nitrogen of said amino alcohol residue can form a bond with ~A'~, or a substituent or an available position on the indeno-fused naphthopyran, and an alcohol oxygen of said amino alcohol residue can form a bond with -Ε--, -G- or ~j. Alternatively, according to various non-limiting embodiments disclosed herein the amino nitrogen of the amino alcohol residue can form a bond with -E-, -G- or -J, and the alcohol oxygen of the amino alcohol residue can form a bond with -A'-, or a substituent or an available position on the indenonap'hthopyran.
[0112] Non-limiting examples of suitable diamine residues that -O- can represent include an aliphatic diamine residue, a cycio aliphatic diamine residue, a diazacycloalkane residue, an azacyclo aliphatic amine residue, a diazacrown ether residue, and an aromatic diamine residue, More particular, illustrative and non- limiting examples of diamine residues that can be used in conjunction with various non-llmlting embodiments disclosed herein include the following:
Figure imgf000026_0001
[0113] Non-limiting examples of suitable amino alcohol residues that -D- can represent include an aliphatic amino alcohol residue, a cycio aliphatic amino alcohol residue, an azacyclo aliphatic alcohol residue, a diazacycio aliphatic alcohol residue and an aromatic amino alcohol residue, More particular, illustrative and non-limiting examples of amino alcohol residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following;
Figure imgf000027_0001
[0114] With continued reference to formulas (XIII) through (XXI) above, according to various non-limiting embodiments disclosed herein, -E- can represent a dicarboxyiic acid residue or a derivative thereof, wherein a first carbonyi group of said dicarboxyiic acid residue can form a bond with -G- or -D-, and a second carbonyi group of said dicarboxyiic acid residue can form a bond with -G-. Non-limiting examples of suitable dicarboxyiic acid residues that -E- can represent include an aliphatic dicarboxyiic acid residue, a cyc!oa!iphatic dicarboxyiic acid residue and an aromatic dicarboxyiic acid residue. More particular, illustrative and non-limiting examples of dicarboxyiic acid residues that can be used in conjunction with various non-limiting embodiments disclosed herein include the following:
Figure imgf000027_0002
101151 According to various non-limiting embodiments disclosed herein, ~G- can represent a group represented by the following general formula,
~[(OC2H,.),(OC3H6)y(OC4Ha)j-0- in which x, y and z are each independently chosen and range from 0 to 50, and a sum of x, y, and z ranges from 1 to 50; a polyol residue or a derivative thereof, wherein a first po!yo! oxygen of said polyol residue can form a bond with -A'-, ~P~( ~E~ , or a substituent or an available position on the indeno-fused naphthopyran, and a second polyol oxygen of said polyol can form a bond with -E~ or -J; or a combination thereof, wherein the first polyo! oxygen of the polyo! residue forms a bond with a group -{.(OC2H4)x(OC3H6)y{OC4H8)J- (i.e., to form the group 4(002Η4)Χ(003Ηβ)ν (OC4HB)2K3-)1 and the second polyo! oxygen forms a bond with -E- or -J. Non- iimiting examples of suitable poiyoi residues that -G~ can represent include an aliphatic poiyoi residue, a cycio aliphatic poiyoi residue and an aromatic poiyoi residue,
[9118] More particular, Illustrative and non-limiting examples of poiyois from which the poiyoi residues that -G- can represent can be formed according to various non-limiting embodiments disclosed herein include (a) low molecular weight poiyois having an average molecular weight less than 500, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col, 4, lines 48-50, and co!. 4, line 55 to col, 8, line 5, which disclosure is hereby specifically incorporated by reference herein: (b) polyester poiyois, such as, but not limited to, those set forth in U.S. Patent No. 8,555,028 at col. 5, lines 7-33, which disclosure is hereby specifically incorporated by reference herein; (c) po!yether poiyois, such as but not limited to those set forth in U.S. Patent No, 6,555,028 at col. 5, lines 34-50, which disclosure is hereby specifically incorporated by reference herein; (d) amide-containing poiyois, such as, but not limited to, those set forth In U.S. Patent No. 8,555,028 at col. 5, lines 51-62, which disclosure is hereby specifically mcorporated by reference; (e) epoxy poiyois, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col. 5 line 83 to col, 6, line 3, which disclosure is hereby specifically incorporated by reference herein; (f) pofyhydric polyvinyl alcohols, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col, 6, lines 4-12, which disclosure is hereby specificaliy incorporated by reference herein; (g) urethane poiyois, such as, but not limited to those set forth in U.S. Patent No. 6,555,028 at col, 8, lines 13-43, which disclosure is hereby specifically incorporated by reference herein; (h) poiyacryllc poiyois, such as, but not limited to those set forth in U.S. Patent No, 6,555,028 at col. 6, lines 43 to col. 7, line 40, which disclosure is hereby specifically incorporated by reference herein; (i) polycarbonate poiyois, such as, but not limited to, those set forth in U.S. Patent No. 6,555,028 at col. 7, lines 41 -55, which disclosure is hereby specificaliy incorporated by reference herein; and (j) mixtures of such poiyois.
[0117] With further reference to formulas (Xili) through (XXI), according to various non-limiting embodiments disclosed herein, -J can represent a group - , wherein - represents a group such as, but not limited to, -CHzCOOH, ■■ CH(CH3)COOH, -C(OXCH2}wCOOH, -C6H4S03H, -C5H10SO3H, -C4H8S03H, -C3M6S03H, -C2H4SO3H and ~S03H, wherein " " ranges from 1 to 18. According to other non-limiting embodiments ~J can represent hydrogen that forms a bond with an oxygen or a nitrogen of linking group to form a reactive moiety such as -OH or -NH. For example, according to various non-limiting embodiments disclosed herein, -J can represent hydrogen, provided that if ~J represents hydrogen, -J is bonded to an oxygen of ~D- or -G-, or a nitrogen of --D-.
[0118] According to still further non-!imlting embodiments, ~J can represent a group -L or residue thereof, wherein -L can represent a reactive moiety. For example, according to various non-limiting embodiments disclosed herein -L can represent a group such as, but not limited to, acry!, methacryl, croty!, 2- (methacryloxy)ethyicarbarnyi, 2-{methacryloxy}ethoxycarbony!, 4-vinylphenyi. vinyl, 1-chlorovinyl or epoxy. As used herein, the terms aory!, methacryl, crotyl, 2- (rnethacryioxy)ethylcarbaroyl, 2-(methacryloxy)eihoxycarbonyl, 4-vinyiphenyl, vinyl, 1-chlorovm l, and epoxy refer to the following structures:
Figure imgf000029_0001
-'- : ' Hset sacry vs e oxycaj oii
|0119] As previously discussed, -G- can represent a residue of a polyoi, which Is defined herein to include hydroxy-containlng carbohydrates, such as those set forth in U.S. Patent No. 6,555,028 at col. 7, line 56 to coi. 8, line 17, which disclosure Is hereby specifically incorporated by reference herein. The poiyol residue can be formed, for example and without limitation herein, by the reaction of one or more of the po!yol hydroxyl groups with a precursor of -A'-, such as a carboxylic acid or a methylene halide, a precursor of po!yalkoxylated group, such as polyalkyiene glycol, or a hydroxy! substituent of the indenonaphthopyran. The polyoi can be represented by «~(OH)a and the residue of the polyoi can be represented by the formula -0-g~ (OHJa.-,, wherein q is the backbone or main chain of the polyhydroxy compound and "a" is at least 2.
[0120] Further, as discussed above, one or more of the poiyol oxygens of -G- can form a bond with -j (i.e., forming the group -G-J), For example, although not limiting herein, wherein the reactive and/or compatibilizing substituent comprises the
2? group -G-J, If -G- represents a poiyof residue and -J represents a group -K that contains a carboxyl terminating group, -G-J can he produced by reacting one or more poiyo! hydroxy! groups to form the group -K (for example as discussed with respect to Reactions B and C at coi. 13, line 22 to col. 16, line 15 of U.S. Patent No. 6,555,028, which disclosure is hereby specifically incorporated by reference herein) to produce a carboxy!ated po!yol residue. Alternatively, if ~J represents a group ~K that contains a suifo o sulfono terminating group, although not limiting herein, -G-J can be produced by acidic condensation of one or more of the polyoi hydroxy! groups with HOC6H4S03H; HOC5H10SO3H; HOC4H8S03 H; HOC3H6S03H; HOC2H4S03H; or H2SO4, respectively. Further, although not limiting herein, if -G- represents a polyoi residue and -J represents a group -L chosen from acry!, methacryl, 2-( efnacryioxy)ethylearbamy1 and epoxy, -L can be added by condensation of the poiyof residue with acryi y! chloride, methacryloyl chloride, 2~isocyanatoethyl methacryiate o epichlorohydrin, respectively.
[0121] Further non-limiting examples of reactive and/or compattbiiizing subsiiiuents are set forth in U.S. Patent No. 8,555,028, at col. 3, line 45 to col. 4, line 26, and U.S. Patent No. 6, 1 13,814 at coi. 3, lines 30-64, which disclosures are hereby specifically incorporated by reference herein,
[0122] The spirooxazine compounds of the present invention can be prepared by art-recognized methods. With some embodiments, the spirooxazine compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 6,019,914 at column 9, lines 7-48, which disclosure is incorporated herein by reference.
[0123] With some embodiments, the spirooxazine compounds of the present invention are prepared in accordance with the synthetic descriptions provided in the examples further herein.
[0124] The indenonaphthopyran compounds of the present invention can be prepared by art-recognized methods. With some embodiments, the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No, 6,296,785, at column 10, line 52 through column 29, line 18, which disclosure is incorporated herein by reference. With some further embodiments, the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 7,527,754 B2 at column 13, line 52 through column 14, line 62, which disclosure is incorporated herein by reference. With some additional further embodiments, the indenonaphthopyran compounds of the present invention can be synthesized in general accordance with the description provided in United States Patent No. 5,645,767, at column 5, line 6 through column 1 1 , line 31 which disclosure is incorporated herein by reference.
£0125] With some embodiments, the indenonaphthopyran compounds of the present invention are prepared in accordance with the synthetic descriptions provided In the examples further herein.
{0126] The present invention also relates to a polymer composition that includes at least one polymer prepared by controlled radical polymerization initiated in the presence of a controlled radical polymerization initiator having at least one radically transferable group, in -which each polymer prepared by controlled radical polymerization is independently represented by Formula (V) as described previously herein, As described previously herein, the controlled radical polymerization initiator is selected from a spirooxazine represented by Formula (I), and an indenonaphthopyran represented by Formula (l!), which are each as described previously herein.
[0127] .As discussed previously herein and for purposes of non-limiting illustration of controlled radical polymerization processes, the ATRP process can be described generally as Including: polymerizing one or more radically polymerlzable monomers in the presence of an initiation system; forming a polymer; and Isolating the formed polymer. The initiation system includes, with some embodiments: an initiator having at least one radically transferable atom or group; a transition metal compound, such as a catalyst, which participates in a reversible redox cycle with the initiator; and a iigand, which coordinates with the transition metal compound.
[0128] The initiator, used to prepare the polymers of the polymer compositions of the present invention, includes the spirooxazine compound represented by Formula (i) and/or the indenonaphthopyran compound represented by Formula (!l), with some embodiments.
[01291 Catalysts that can be used with some embodiments in preparing polymers, by controfled radical polymerization (such as ATRP), include any transition metal compound that can participate In a redox cycle with the initiator and the growing polymer chain. With some embodiments, the transition metal compound is selected such that It does not form direct carbon-metal bonds with the polymer chain. Transition metal catalysts useful in the present invention can be represented by the following Formula (VI),
TMn+Xt {VI )
[0130] With reference to Formula (VI), TM represents the transition metal, t is the formal charge on the iransition metal having a value of from 0 to 7, and X Is a countenon or covalently bonded component, Examples of the transition metal (TM) include, but are not limited to, Cu, Fe, Au, Ag, Hg, Pd, Pi, Co, Mn, Ru, Mo, b and n, Examples of X include, but are not limited to, halogen, hydroxy, oxygen, CrC5- afoxy, cyano, cyanato, thiocyanato and azido. With some embodiments, the transition metal is Cu(l) and X is a halogen, such as chloride. Accordingly, with some embodiments, a class of transition metal catalysts are the copper ha!ides, such as Cu(!)CI. With some embodiments the transition metal catalyst contains a small amount, such as 1 mole percent, of a redox conjugate, for example, Cu(H)CI2 when Cu(l)CI is used,
0131J Llgands that can be used in preparing the polymers of the present Invention, by controlled radical polymerization (such as ATRP), include, but are not limited to compounds having one or more nitrogen, oxygen, phosphorus and/or sulfur atoms, which can coordinate to the transition metal catalyst compound, such as through sigma and/or pi bonds. Classes of useful ligands, include but are not limited to: unsubsiituted and substituted pyridines and bipyridines; porphyrins; eryptands; crown ethers, such as 18-crown-6; polyamines, such as ethylenedlamine; glycols, such as aikyiene glycols, such as ethylene glycol; carbon monoxide; and coordinating monomers, such as styrene, acryionitrile and hydroxya!kyi (meth)acrylates. With some embodiments, the Hgand is selected from one or more substituted bipyridines, such as 4,4'-dialky!bipyridy!s.
[0132] In preparing the polymers of the present invention, by controlled radical polymerization (such as AT P), the amounts and relative proportions of initiator, transition metal compound and llgand are those for which ATRP is most effectively performed. The amount of initiator used can vary widely and is typically present In the reaction medium in a concentration of from 10'4 moles/liter (M) to 3 M, such as, from 10"3 M to 10"1 M. As the molecular weight of the polymer can be directly related to the relative concentrations of initiator and monomers), the molar ratio of initiator to monomer can be an important factor in polymer preparation, with some embodiments. The molar ratio of initiator to monomer is, with some embodiments, within the range of 1G~4 :1 to 0.5:1 , or 10"3 :1 to 5x10"2 :1. [0133J in preparing the polymers of the present invention by controlled radical polymerization, such as by ATRP, the molar ratio of transition metal compound to initiator is, with some embodiments, In the range of 10"4 :1 to 10:1, or 0,1 :1 to 5:1. The molar ratio of iigand to transition metal compound Is, with some embodiments, within the range of 0.1 :1 to 100:1 , or 0.2:1 to 10:1.
[01341 With reference to Formula (V), subscript z is an integer of at least 1 , such as from 1 to 10, or 1 to 5, or from 1 to 4, or from 1 to 3, or 1 or 2. Subscript z, with some embodiments, is at least 2, such as fro 2 to 10, or from 2 to 5, or from 2 to 4, or 2 or 3, or 2. With some embodiments, subscript z is equal to the number of radically transferable groups present on the controlfed radical polymerization initiator.
[0135] With further reference to Formula (V), subscript , independently for each z, is an integer of at least 2, such as from 2 to 1000, or from 2 to 500, or from 2 to 300, or from 2 to 200, or from 2 to 100, or from 2 to 50, or from 2 to 40, or from 2 to 30, or from 2 to 25, or from 2 to 20, or from 2 to 10, or from 2 to 5,
[0136] With additional reference to Formula (V), X, independently for each z, is or is derived from the radically transferable group that was originally bonded to the controlled radical polymerization Initiator. With some embodiments, when the radically transferable group(s) of the controlled radical polymerization initiator (such as the spirooxazine compound represented by Formula (1) and the indenonaphthopyran represented by Formula (II)} is a halo group, such as Br, the X can be the radically transferable bromo group (Br), with some embodiments.
[0137| The radically transferable group can, with some embodiments, optionally be (a) removed, or (b) chemically converted to another moiety. With either of (a) or (b), the symbol X is considered herein to be derived from the radically transferable group of the initiator. The radically transferable group can be removed by substitution with a nucfeophi!tc compound, such as an alkali metal aikoxyiate, with some embodiments. With some embodiments, the method by which the radically transferable group is either removed or chemically converted is relatively mild with regard to the reactive functionality of the polymer. Many nucleophiJic substitution reactions can result in loss of reactive functionality from the polymer. For purposes of non-limiting illustration, with some embodiments the polymer has oxirane functionality, which can be lost in the presence of a nucleophile, such as an alkali metal aikoxyiate.
[01381 With some embodiments of the present Invention, when the radically transferable group i.s a halogen, the halogen can be removed by a mild dehalogenation reaction, which does not reduce sensitive functionality of the polymer, if any (such as oxirane functionality, with some embodiments). The reaction is typically performed as a post-reaction after the polymer has been formed, and in the presence of at least an ATRP catalyst. With some embodiments, the dehalogenation post-reaction is performed In the presence of both an ATRP catalyst and its associated ligand.
[0139] The mild dehalogenation reaction is performed by contacting the halogen terminated polymer of the present invention: with one or more ethylenically unsaturated compounds, which are not readily radically po!ymerizab!e under at least a portion of the spectrum of conditions under which controlled radical polymerizations, such as atom transfer radical polymerizations, are performed, hereinafter referred to as "limited radically polymerizahle ethySenically unsaturated compounds" (LRPEU compound). As used herein, by "halogen terminated" and similar terms is meant to be inclusive also of pendent halogens, such as would be present in branched, comb and star polymers.
[01401 Not intending to be bound by any theory, it is believed, based on the evidence at hand, that the reaction between the halogen terminated polymer and one or more LRPEU compounds results int. (1 ) removal of the terminal halogen group; and (2} the addition of at least one carbon-carbon double bond where the terminal carbon-halogen bond Is broken. The dehalogenation reaction Is typically conducted at a temperature in the range of 0°C to 200eC, or from 0°C to 160°C, and a pressure in the range of 0.1 to 100 atmospheres, or from 0.1 to 50 atmospheres, with some embodiments. The reaction is also typically performed in less than 24 hours, such as between 1 and 8 hours. While the LRPEU compound can be added in less than a stoichiometric amount, it is typically added in at least a stoichiometric amount relative to the moles of terminal halogen present in the polymer. When added in excess of a stoichiometric amount, the LRPEU compound is typically present in an amount of no greater than 5 mole percent, such as 1 to 3 mole percent, in excess of the total moles of terminal halogen, with some embodiments.
[0141], LRPEU compounds are described in further detail at column 12, line 15 through column 13, line 18 of United States Patent No. 8,268,433 B1 , which disclosure is incorporated herein by reference. With some embodiments, the LRPEU is free of halogen groups. Examples of LRPEU compounds include, but are not limited to, 1 , 1-dimefhyiethyiene, 1 , 1 -diphenyiethylene, Ssopropenyi acetate, alpha- methyl styrene, 1 , 1-dialkoxy olefin and mixtures thereof. Additional examples of LRPEU compounds include, but are not limited to, dimethyl itaconate and diisobutene (2 ,4,4-irimethyl-l -pentene).
0142] As discussed previously herein with reference to Formula (V), , independentiy for each w, is a residue of a monomer. More particularly, , independently for each w, Is a residue of an ethyienicai!y unsaturated radically ppiymerizab!e monomer. As used herein, the term "ethyienicaily unsaturated radically po!ymerizable monomer" and similar terms includes, hut are not limited to, vinyl monomers, aiiyilc monomers, olefins and other ethyienica!iy unsaturated monomers thai are radically polymerizable,
[0143] Classes of vinyl monomers from which each M of Formula (V) can he independentiy derived include, but are not limited to, (meth)acryiates, vinyl aromatic monomers, vinyl haiides, and vinyl esters of carboxyiic acids, each of which can, with some embodiments, optionally include one or more functional groups selected from hydroxyl groups, thiol groups, primary amine groups, secondary amine groups, and oxirane groups. With some embodiments, the (meth)acryEates are selected from at least one of: alkyi (meth)acrylates having from 1 to 20 carbon atoms in the alky! group; and afkyl (meth)acry!ates having from 1 to 20 carbon atoms in the alkyi group, In which the alkyi group includes or Is substituted with one or more functional groups selected from hydroxyl groups, thiol groups, primary amine groups, secondary amine groups, and oxirane groups. Examples of alkyi (meih)acrylates having from 1 to 20 carbon atoms in the alkyi group that can be used include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acryiate, propyl (meth)acrylate, isopropyl (meth)acry!ate, butyl (meth)acry!ate, isobutyl (meth)acrylate, tert-butyi (rneth)acryiate, 2-ethyihexyi (meth)acrylate, iauryf (meth)acryfate, isobomyi (meth)acryiaie, cyclohexyl {meth)acryiate and 3,3,5-trimethylcyclohexyl {meth)acrylate, one or more of which can, with some embodiments, optionally include in the alkyi group thereof one or more functional groups selected from hydroxyl groups, thiol groups, primary amine groups, secondary amine groups, and oxirane groups.
[0144] Examples of oxirane functional monomers from which each M of Formula (V) can be derived, with some embodiments, include, but are not limited to, glycidyl (meih)acrylate, 3, 4-epoxy cyclohex l methyl (meth)acrylate, 2-{3,4- epoxycyciohexyl)efhyl (meth)acry!ate and ally! glycidyl ether. With some embodiments, oxirane functionality can be incorporated into the polymer by post- reaction, such as by preparing a hydroxyl functional precursor polymer and converting the precursor polymer to an oxirane functional polymer by reacting at least
¾¾ some of the hydroxy! groups with epichlorohydrin, in accordance with art-recognized methods,
[0145] Examples of vinyl aromatic monomers from which each M of Formuia (V) can be independently derived include, but are not limited to, styrene, p- chloromethyistyrene, divinyi benzene, vinyl naphtha iene and divinyi naphthalene. Vinyl ha!ides from which each can be independently derived include, but are not limited to, vinyl chloride and vinylldene fluoride. Vinyl esters of carboxy!tc acids include, but are not limited to, vinyl acetate, vinyl butyraie, vinyl 3,4- dimethoxybenzoate and vinyl benzoate.
[0146] As used herein, by "olefin" and like terms is meant unsaturated aliphatic hydrocarbons having one or more double bonds, such as obtained by cracking petroleum fractions. Examples of olefins from which each M of Formula (V) can be independently dervied include, but are not limited to, propylene, 1-butene, 1 ,3- butadtene, isobutyiene and diisobutylene.
[0 47] As used herein, by "allyllc monomer(s)" is meant monomers containing substituted and/or unsubstiiuted alSylic functionality, such as one or more radicals represented by the following Formuia (VII),
H2c=C(R1)— CH2— (vii)
[0148] With reference to Formula (VI i), R1 is hydrogen, halogen or a Ci to C4 alkyi group. With some embodiments, R1 is hydrogen or methyl and consequently Formula (VII) represents an unsubstiiuted (meth)a!!yl radical. Examples of allyllc monomers include, but are not limited to; (meth)a!!yl alcohol; (meth)a!!yi ethers, such as methyl (meth)al!y! ether; ally! esters of carfooxy!ic acids, such as (rneth)ai!y! acetate, (meth)al!y! butyrate, (meth)a!lyt 3,4-dimethoxybenzoate and (meth)aiiy! benzoate,
[0149] Other ethylenically unsaturated radically poiymerizable monomers from which each M of Formuia (V) can be independently derived include, but are not limited to: cyclic anhydrides, such as ma!eic anhydride, 1-cyc!opentene-1 ,2- dicarboxylic anhydride and itaconic anhydride; esters of acids that are unsaturated but do not have alpha, beta-ethyienic unsaturatson, such as methyl ester of undecy!enic acid; and d iesters of ethylenically unsaturated dibasic acids, such as diethyl ma!eate.
[0150] The polymers of the present invention can, with some embodiments, have polymer architecture selected from linear polymers, branched polymers, hyperbrancbed polymers, star polymers, graft polymers and mixtures thereof. The form, or gross architecture, of the polymer can be controlied by the choice of initiator and monomers used in its preparation. Linear polymers can be prepared by using initiators, such as represented by Formulas {[) and (il), having one or two radically transferable groups. Branched polymers can be prepared by using branching monomers, such as monomers containing radically transferable groups or more than one ethylenicaliy unsaturated radically polyrneriza le group, such as 2~(2~ bromopropionoxy)ethyl acrylate, p-ch!oromethylstyrene and diethyleneglycol bis(methacryiate). Hyperbrancbed polymers can be prepared by increasing the amount of branching monomer used.
[0151] Star polymers can be prepared using initiators having three or more radically transferable groups, such as represented by Formulas {1} and (II). Star- polymers can be prepared by art-recognized core-arm or arm-core methods. In the core-arm method, the star polymer is' repared by polymerizing monomers in the presence of the po!yfunctional initiator. Polymer chains, or arms, of similar composition and architecture grow out from the initiator core, in the core-arm method. With the arm-core method, the arms are prepared separately from the core and can optionally have different compositions, architecture, molecular weight and polydispersiiy indices (PDI's). The arms can have different equivalent weights (such as different active hydrogen equivalent weights), and some can have no functionality. After the preparation of the arms, they are attached to the core by art-recognized methods, so as to result in the formation of a arm-core polymer.
[0152] The polymers of the present invention prepared by controlled radical polymerization can have, with some embodiments, a functional equivalent weight of at least 100 grams/equivalent, or at least 200 grams/e uivalent. The functional equivalent weight of the polymer is, with some embodiments, iess than 10,000 grams/equivalent, or less than 5,000 grams/equivalent, or iess than 1 ,000 grams/equivalent. The functional equivalent weight of the polymers of the present invention prepared by controlled radical polymerization can range between any combination of these values, inclusive of the recited values, such as from 100 to 10,000 grams/equivalent, or from 200 to 5,000 grams/equivalent, or from 200 to 1 ,000 grams/equivalent, inclusive of the recited values. The functionality (or functional groups) of the polymer can, with some embodiments, be selected from hydroxy! groups, thiol groups, primary amine groups, secondary amine groups, and oxi ane groups. [0153] The number average molecular weight (Mn) of the polymers of the present invention prepared by conirolied radical polymerization is with some embodiments at least 250, or at least 500, or at least 1 ,000, or at least 2,000. The polymers of the present invention prepared by controlled radical polymerization also have, with some embodiments, an Mn of less than 16,000, or less than 10,000, or less than 5,000. The Mn of the polymers of the present Invention prepared by controlled radical polymerization can, with some embodiments, range between any combination of these values, inclusive of the recited values, such as from 250 to 16,000, or from 500 to 10,000, or from 1 ,000 to 8,000, or from 2,000 to 7,000, inclusive of the recited values.
{9154) Prior to use in the polymer compositions of the present Invention, the controlled radical polymerization (CRP) catalyst, such as the ATRP transition metal catalyst, and its associated ligand are, with some embodiments, separated or removed from the polymer. The CRP catalyst, such as the ATRP catalyst is removed, with some embodiments, prior to conversion of a precursor polymer to a functional polymer. Removal of the ATRP catalyst is achieved, with some embodiments, using known methods, including, for example, adding a catalyst binding agent to the a mixture of the polymer, solvent and catalyst, followed by filtering. Examples of suitable catalyst binding agents include, but are not limited to, alumina, silica, clay or combinations thereof. A mixture of the polymer, solvent and ATRP catalyst can be passed through a bed of catalyst binding agent, with some embodiments. Alternatively, the ATRP catalyst can be oxidized in situ and retained in the polymer polymer.
[0155] The polymers of the present invention can be prepared, with some embodiments, in the absence of solvent, such as by a bulk polymerization process. With some embodiments, the polymer is prepared in the presence of a solvent, such as water and/or an organic solvent. Classes of useful organic solvents include, but are not limited to, esters of carboxyiic acids, ethers, cyclic ethers, C5-Ci0 alkanes, C5- Ce cycloalkanes, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amides, nitrites, sulfoxides, sulfones and mixtures thereof. Supercritical solvents, such as COz, C C4 alkanes and fluorocarbons, can also be employed. With some embodiments aromatic hydrocarbon solvents are used, such as xylene, and mixed aromatic solvents such as those commercially available from Exxon Chemical America under the trademark SOLVESSO.
[01581 With some embodiments of the polymer composition of the present invention, and with further reference to Formula (V): z is at least 2; and the spirooxazine represented by Formula (I) includes at least one first radically transferable group, and at feast one second radically transferrabie group, in which for the spirooxazine represented by formuia (!) at least one of R1 independently for each n, and R2 Independently for each p, independently comprise said first radically transferable group, and at least one of R3 independently for each q, R , R5 and R6 independently comprise said second radically transferable group. In addition, when z is at least 2, and with some embodiments, the indenonapbtbopyran represented by Formula (II) includes at least one first radically transferable group, and at least one second radically transferrabie group, in which for the indenonapbthopyran represented by Formula (li) at least one of B and B' independently comprise said first radically transferable group, and at feast one of R7 Independently for each x, R8 independently for each y, Rs and R1Q independently comprise said second radically transferable group.
[0157] With some further embodiments of the polymer composition of the present invention, and with further reference to Formula (V): z is 2; and the spirooxazine represented by Formula {1} includes one first radically transferable group, and one second radically transferrabie group, In which for the spirooxazine represented by Formula (I) one R2 comprises said first radically transferable group, and one R3 comprises said second radically transferable group. In addition, when z is 2, and with some embodiments, the Indenonapbthopyran represented by Formula (il) Includes one first radically transferable group, and one second radically transferrabie group, In which for the indenonapbthopyran represented by Formula (II) one of B and S' comprises said first radically transferable group, and one R8 comprises said second radically transferable group,
[0158] With some embodiments of the polymer composition of the present Invention, one or more groups of the spirooxazine represented b Formula (1), such as Ri, R2, R3, R , Rs, and/or R6 include a group represented by Formula (ill), as described previously herein. With some additional embodiments of the polymer composition of the present invention, one or more groups of the indenonapbthopyran represented by Formuia (II), such as R7, R8, R9, R10l B, and/or B' in each case independently include the group represented by the Formula (III), as described previously herein. As discussed previously herein, X of the group represented by Formuia (IIS) can, with some embodiments be a halo group, such as CI, Br, and I,
[0159] Each polymer prepared by controlled radical polymerization of the polymer composition of the present invention can Independentl be a thermoplastic polymer or a curable polymer. When the polymer is a curable polymer it has, with some embodiments, one or more functional groups thai are reactive with the (i) functional groups of another material, such as a crossiinking agent, and/or (ii) other functional groups on the same polymer,
[0160] Each polymer prepared by controlled radical polymerization of the polymer composition of the present invention can independently be a thermoplastic polymer or a curable poiymer. When the polymer prepared by controlled radical polymerization Is a curable poiyme it has, with some embodiments, one or more functional groups that are reactive with the (!) functional groups of another material, such as a crossiinking agent, and/or (si) other functional groups on the same polymer prepared by controlled radical polymerization.
[0161] in accordance with some embodiments of the polymer composition of the present invention: the poiymer prepared by controlled radical polymerization includes at least one first reactive group; and the poiymer composition further includes at least one crossiinking agent that includes at least two second reactive groups that are reactive with and form covalent bonds with the first reactive group(s) of the poiymer prepared by controlled radical polymerization.
[0162] In accordance with some embodiments of the polymer composition of the present invention: the polymer, that is prepared by controlled radical polymerization, includes at least one active hydrogen group selected from hydroxy!, thiol, carboxylic acid, primary amine, and secondary amine; and the polymer compositio further includes at least one crossiinking agent that Includes at least two functional groups seiected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, ihioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates, With some further embodiments, the crossiinking agent includes at least two functional groups selected from oxiranes, thiooxiranes, isocyanates, ihioisocyanates. The crossiinking agent, in accordance with some additional embodiments, includes at least two functional groups selected from oxiranes and isocyanates.
[01631 The crossiinking agent, with some embodiments, includes a separate polymer according to the present invention that is prepared by controlled radical polymerization, which Includes at least two functional groups selected from cyclic carboxylic acid anhydrides, oxiranes, thiooxiranes, isocyanates, ihioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates. The crossiinking agent polymer can be prepared in accordance with the description provided previously herein, using a spirooxazine represented by Formula (I) or an indenonaphthopyran represented by Formula (II) as a controlled radical polymerization initiator.
£0184] With some embodiments, the crosslinking agent is prepared by controlled radical polymerization, but is not prepared using a spirooxazine represented by Formula (I) or an indenonaphthopyran represented by Formula (ii) as a controlled radical polymerization initiator. With some further embodiments, the crosslinking agent is not prepared by controlled radical polymerization.
[0185] The polymers prepared by controlled radical polymerization, with some further embodiments, include at least one, such as two or more, radically poiymerlzable ethylenicaliy unsaturated groups, such as, but not limited to, (meth)acry!oyi groups and a!lyiic groups. When the polymers of the present invention include radically poiymerizable ethylenicaliy unsaturated groups, the polymer compositions of the present invention can be cured by exposure to actinic radiation in the presence of a suitable initiator, such as a photopolymerization initiator, and an optional crosslinking agent that has two or more radically polymerizable ethylenicaily unsaturated groups, in accordance with art- re cognized methods. The a!!ylic groups of the polymers according to the present invention, with some embodiments, can be described with reference to Formula (VII) previously herein.
[0166] Examples of isocyanate functional materials from which the crosslinking agent can be selected,, with some embodiments, include but are not limited to, toiuene-2,4-diisocyanate; toluene~2.6-ditsocyanate; diphenyl methane~4,4'~
diisocyanate; diphenyl methane~2,4'~diisocyanaie; para-phenylene diisocyanate;
biphenyi diisocyanate; S.S'-dimethyM^'-diphersylene diisocyanate; tetramethylene- 1 ,4-diisocyanate; hexamethy!ene-1 ,6-diisocyanate; 2,2,4-trimethyi hexane-1 ,6- diisocyanate; lysine methyl ester diisocyanate; bis(isocyanato ethyf)fumarate;
isophorone diisocyanate; ethylene diisocyanate; dodecane-1 ,12-diisocyanate;
cyclobutane-1 ,3-diisocyanate; cyc!ohexane-1 ,3-diisocyanate; cyclohexane-1 ,4- diisocyanate; methyl cyclohexyl diisocyanate; hexahydrotoluene-2,4-dii$ocyanate; hexahydrotoluene~2,6-diisocyanate; hexahydrophenyiene-1 ,3-diisocyanate;
hexahydrophenylene-1 ,4-diisocyanate; perhydrodiphenylmethane-2,4'-diisocyanate; perhydrodiphenyfmethane-4,4'-diisocyanate and mixtures thereof.
[0187] The poiyisocyanate crosslinking agent can, with some embodiments, be selected from polyisocyanates prepared from dimers and trimers of diisocyante monomers. Dimers and trimers of diisocyanate monomers can be prepared by art- recognized methods, such as described in U.S. Pat. No. 5,777,061 at column 3, line 44 through column 4, line 40. Dimers and trimers of the above recited diisocyanate monomers can contain linkages selected from the group consisting of isocyanurate, uretdione, biuret; aiiophanaie and com inatio s thereof.
[0168] The ssocyanate functional crossiinking agent can also be selected from (i) polyisocyanaie functional polymer having at least two isocyanafe groups, (si) oligomeric polyisocyanaie functional adduci and mixtures thereof. The polyisocyanaie functional polymer and oligomenc polyisocyanaie functional adduci can each contain structural linkages selected from urethane, i.e., -NH-C(0}-0-, thiourethane, i.e., -NH-C(0)~S-, urea, e.g., -NH-C{0)-NH~, and combinations of these structural linkages. The pofyisocyanate polymer can be prepared, by art-recognized methods, from one or more monomers having at least two reactive hydrogen groups, such as thiol, hydroxy, primary amine and secondary amine groups, and one or more monomers having two or more isocyanafe groups. The molar equivalent rat o of reactive hydrogen groups to isocyanafe groups is selected such that the resulting polymer has the desired end groups, i.e., isocyanafe groups, The number average molecular weight ( n) of the polyisocyanaie-funciionai polymer is less than 20,000, such as from 1 ,000 and 10,000, with some embodiments.
[0169] With some embodiments of the present Invention, the polyisocyanaie functional polymer is a polyisocyanaie functional po!yurethane prepared from aliphatic diois and aliphatic dtisocyanates. Optionally, the polyisocyanaie functional po!yurethane ma be prepared using relatively small amounts of monomers having three or more functional groups, such as triols and/or tiisocyanaies, to increase the functionality and branching of the polyurethane, in accordance with art-recognized methods,
[0170] As used herein, by "oligomeric polyisocyanaie functional adduci" is meant a material that is substantially free of polymeric chain extension. Oligomeric polyisocyanaie functional adducts can be prepared by art-recognized methods from, for example, a compound containing three or more active hydrogen groups, such as trimeihylolpropane (T P), and an Isocyanafe monomer, such as 1-isocyanato-3,3,5- irimethyl-5-isocyanatomethyicyciohexane (!PDI), in a molar ratio of 1 :3, respectively. In the case of TMP and !PDI, by employing art-recognized starved feed and/or dilute solution synthesis techniques, an oligomeric adduci having an average isocyanafe functionality of 3 can be prepared ("TMP-31PDI"}.
[0171] Depending on the type of active hydrogen group containing compound(s) used (e.g., polyo!s, po!yamines and polythiols) the oligomeric polyisocyanaie functional adduct can contain structural linkages selected from the urethane, ihiourethane, urea and combinations thereof, as described previously herein. The active hydrogen group containing compound is aliphatic with some embodiments, such as T P, trishydroxyisocyanurate, peniaerythrito! and trlmethylolpropane tris(mereaptoacetate). The isocyanate monomer is, with some embodiments, a diisocyanate monomer and can be selected from those described previously herein,
[0172] The isocyanate groups of the isocyanate functional crossiinki rig agent can, with some embodiments, be capped or blocked with a capping / blocking agent. After exposure to elevated temperature, the capping / blocking agent separates from the isocyanate functional material, allowing the free / unblocked Isocyanate groups thereof to react and form covalent bonds with the active hydrogen groups of the polymer prepared by controlled radical polymerization according to the present invention. After unblocking or decapping from the polyisocyanate, the capping agent can voiatrze out of the composition {prior to the composition becoming vitrified) and/or remain in the composition, such as a pjasticizer. With some embodiments, it is desirable that the capping agent not form bubbles in the composition and/or overly plasticize the composition after decapping.
[0173] The capping groups of the capped polyisocyanate crosslinking agent ca be selected from, with some embodiments hydroxy functional compounds, 1 H- azoles, lactams, ketoximes and mixtures thereof. Classes of hydroxy functional compounds include, but are not limited to, aliphatic, cycioa!iphatic, or aromatic aikyi monoaicohois or phenolics. Specific examples of hydroxy functional compounds useful as capping agents, include, but are not limited to: lower aliphatic alcohols such as methanol, ethanoi, and rv-butanol; cycloaliphatic alcohols such as cyc!ohexano! and tetrahydrofuran; aromatic-alkyi alcohols, such as phenyl carbinoi and methylphenyl carbinoi; and glycol ethers, e.g., ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether. With some embodiments, the hydroxy functional capping groups include the phenolics, examples of which include, but are not limited to, phenol itself and substituted phenols, such as cresol, nitrophenof and p-hydroxy methyl enzoate.
[0174] Examples of i H-azoies that are useful as capping groups include, but are not limited to IH-imidazole, I H-pyrazoie, 1 H-3,5~dimethyl pyrazole, 1 H~2.5~dimethyi pyrazole, 1 H-1 ,2,3-triazole, 1 H-1 ,2,3-benzotriazole, 1 H-1 ,2,4-triazole, 1 H-5-methyi- 1 ,2,4-triazole, and 1 H-3-amrno-1 ,2,4-triazole. [0175] Kefoximes useful as capping groups include those prepared from aliphatic or cycloaiip atic ketones. Examples of ketoxime capping groups include, but are limited to, 2-propanone oxime (acetone oxime), 2-fautanone oxime, 2-pentanone oxime, 3-pentanone oxime, 3-meihyl-2-butanone oxime, 4-methyi-2-penianone oxime, 3,3-dimethyi-2-buianone oxime, 2-heptanone oxime, 3-heptanone oxime, 4- heptanone oxime, 5-methyi-3- heptanone oxime, 2,6-dime†ftyi-4-heptartone oxime, eyclopentanone oxime, cydohexanone oxime, 3-methylcyclobexanone oxime, 3,3,5- trimethyicyclohexanone oxime and 3,5,5-trimethyl-2-cydohexene-5-one oxime.
0178] Examples of lactam capping groups include, but are not limited to, e- caproiaciam and 2-pyro!idinone. Other suitable capping groups include, morphoiine, 3-aminopropyi morphoiine and -hydroxy phthaiimide.
[0177] Oxirane functional crosslinking agents can be prepared by reacting a hydroxy! functional material having at least two hydroxy! groups with a
2-(haiomethyl)oxirane, such as 2-(chioromethyl)oxirane, which Is also referred to as epiehiorohydnn. Examples of polyois that can be used to prepare oxirane functional crosslinking agents include, but are not limited to, glycerin, trimethylolpropane, trirnethylolethane, irishydroxyethylisocyanurate, pentaerythritol, ethylene glycol, propylene glycol, trimetbyiene glycol, butanedioi, hepianedioi, hexanediol, octanedioi, 4,4'~{propene-2!2-diyl)dicyclohexanoi, 4,4'-methyienedicyclohexanol, neopentyi glycol, 2,2,3-frimethyipentane-l ,3-diol, 1 ,4-dimethyiolcyclohexane, 2,2,4- thmeihyipentane dioi, 4!4'-(propane-2,2-diyl)diphenol( and 4i4'-methyienediphenoL
[01 8J The oxirane functional crosslinking agent can be a polymeric material. With some embodiments, the polymeric oxirane functional crosslinking agent can be prepared from an oxirane functional material having at least two oxirane groups and an active hydrogen functional material having at least two active hydrogen groups, such as at least two hydroxy! groups. Examples of polyois that can be used to prepare polymeric oxirane functional crosslinking agents include, but are not limited to those classes and examples recited previously herein with regard to preparing the oxirane functional crosslinking agent.
[0179] The polymer prepared by controlled radical polymerization, with some embodiments, is present in the polymer composition of the present invention in an amount of at least 2 percent by weight, or at least 10 percent by weight, or at least 20 percent by weight, or at least 30 percent by weight, or at least 50 percent by weight, or at least 70 percent by weight, or at least 80 percent by weight, based on total weight of resin solids of the polymer composition. The polymer composition also, with some embodiments, contains the polymer prepared by controlled radical polymerization in an amount of less than or equal to 98 percent by weight, or less than or equal to 95 by weight, or less than or equal to 90 percent by weight, based on total weight of resin solids of the polymer composition. The polymer prepared by controlled radical polymerization can, with some embodiments, be present in the polymer composition of the present invention in an amount ranging between any combination of these values, inclusive of the recited values, such as from 2 to 98 percent by weight, or from 10 to 98 percent by weight, or from 20 to 98 percent by weight, or from 30 to 98 percent by weight, or from 50 to 98 percent by weight, or from 70 to 95 percent by weight, or from 80 to 90 percent by weight, in each case based on total weight of resin solids of the polymer composition. With some further embodiments, the polymer prepared by controlled radical polymerization is present in the polymer composition of the present invention in an amount of from 20 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 25 percent by weight, in each case based on total weight of resin solids of the polymer composition.
[0180] The cross!inking agent is present, with some embodiments, In the polymer composition of the present invention in an amount of at least 2 percent by weight, or at least 5 percent by weight, or at least 10 percent by weight, based on total weight of resin solids of the polymer composition. The crosslinking agent can also, with some embodiments be present in the polymer composition in an amount of less than or equal to 70 percent by weight, or an amount of less than or equal to 50 percent by weight, or less than or equal to 30 percent by weight, or less than or equal to 20 percent by weight, based on total weight of resin solids of the polymer composition. The crosslinking agent can be present in the polymer composition of the present invention in an amount ranging between an combination of these values, inclusive of the recited values, such as from 2 to 70 percent by weight, or from 2 to 50 percent by weight, or from 5 to 30 percent by weight, or from 10 to 20 percent by weight, based on total weight of resin soiids of the curable particulate composition, and , inclusive of the recited values.
[01811 The polymer prepared by controlled radical polymerization is present in the polymer composition, with some embodiments, in an amount of from 30 to 98 percent by weight, based on total resin solids weight of the polymer composition; and the crosslinking agent is present in the polymer composition, with some embodiments, in an amount of from 2 to 70 percent by weight, based on total resin solids weight of the polymer composition. [0182] in accordance with some embodiments, the polymer compositions of the present invention include one or more additional polymers that do not include {and are free of) a residue of a mechanochramic compound, such as represented by Formulas (i) and (II), which can be referred to as non-mechanochromic polymers. Examples of such nors-mechanochromic polymers include, but are not limited to, polyester polymers, po!yurethane polymers, polycarbonate polymers, poiyether polymers, pofyamide polymers, polyimide polymers, polyamideimide polymers, poiyurea polymers, poiysulfone polymers, poiyketone polymers, polyvinyl polymers, po!yolefins, poly(meth)acrylates, and combinations of two or more thereof. Each non-mechanochromic polymer can include, with some embodiments: one or more (such as two or more) active hydrogen groups, such as hydroxy!, thiol, carboxyiic acid, primary amine, and secondary amine; and/or one or more (such as two or more) functional groups that are reactive with active hydrogen groups, such as, cyclic carboxyiic acid anhydrides, oxiranes, thiooxiranes, isocyanaies, thioisocyanates, cyclic carboxyiic acid esters, cyclic amides, and cyclic carbonates. With some embodiments, the non-mechanochromic polymer is present in an amount of from 2 to 98 percent by weight, or from 10 to 80 percent by weight, or from 20 to 70 percent by weight, or from 30 to 60 percent by weight, or from 30 to 50 percent by weight, where the percent by weights are in each case based on the total weight of the polymer of the present invention (which includes a residue of a mechanochromic compound such as represented b Formulas (!) and (I!)) and the non-mechanochromic polymer.
[0183] To achieve a suitable level of cure with the polymer composition of the present invention, the equivalent ratio of active hydrogen equivalents of the polymer prepared by controlled radical polymerization, to isocyanate or oxirane equivalents of the crossiinklng agent is, with some embodiments, from 0.7: 1 to 2:1 , or from 0.8:1 to 1,3:1.
[0184] The polymer composition o the present Invention can be cured by any suitable methods. With some embodiments, the polymer composition is thermosetting, and is curable by exposure to elevated temperature. As used herein, by "cured" is meant a three dimensional crosslink network formed by covaient bond formation, such as between the active hydrogen groups of the polymer prepared by controlled radical polymerization and the isocyanate or oxirane groups of the crossiinklng agent. The temperature at which the thermosetting polymer composition of the present invention is cured is variable and depends in part on the amount of time during which curing Is conducted. With some embodiments, the thermosetting po ymer composition is cured at a temperature within the range of 90°C to 204°C, or from 149°C to 204°C, or from 154°C to 177°C. for a period of 20 to 80 minutes.
[0185] The polymer compositions of the present invention can also, with some embodiments, include pigments and fillers. Examples of pigments include, but are not limited to: inorganic pigments, such as titanium dioxide and iron oxides; organic pigments, such as phthalocyanines, anthraquinones, quinacridones and thioindigos; and carbon blacks. Examples of fillers include, but are not limited to: silica, such as precipitated silicas; clay; and barium sulfate. When used in the polymer compositions of the present invention, pigments and fillers can, with some embodiments, be present in amounts of from 0,1 percent to 70 percent by weight, based on the total solids weight of the polymer composition (excluding solvent).
[0188] The polymer compositions of the present invention can, with some embodiments, optionall contain additives such as, but not limited to: waxes for flow and wetting; flow control agents, such as poiy{2~ethyihexyl)acryla?e; antioxidants; and ultraviolet (UV) light absorbers. Examples of useful antioxidants and UV light absorbers include, but are not limited to, those available commercially from BASF under the trademarks !RGANOX and TiNUVSN. These optional additives, when used, can be present In amounts up to 20 percent by weight, based on total solids weight of the polymer composition (excluding solvent).
[0187] The polymer compositions of the present can, with some embodiments, include solvents, selected from water, organic solvents, and combinations thereof.
[01881 Classes of organic solvents that can be present in the polymer compositions of the present invention include , but are not limited to: alcohols, e.g., methanol, ethanol, n-propano!, iso-propanol, n-butanoi, sec-butyl alcohol, fert-butyl alcohol, iso-butyi alcohol, furfuryi alcohol and tetrabydrofurfuryi alcohol; ketones or ketoalconois, e.g., acetone, methyl ethyl ketone, and diaceione alcohol; ethers, e.g., dimethyl ether and methyl ethyl ether; cyclic ethers, e.g., tetrahydrofuran and dioxane; esters, e.g., ethyl acetate., ethyl lactate, ethylene carbonate and propylene carbonate; poiyhydric alcohols, e.g., ethylene glycol, dsethyiene glycol, triethyiene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, 2-methyi- 2,4-pentanediol and 1 ,2,6-hexantrio!; hydroxy functional ethers of a!kylene glycols, e.g., butyl 2~hydroxyethyl ether, hexyl 2~hydroxyethyl ether, methyl 2-hydroxypropyl ether and phenyl 2-hydroxypropyl ether; nitrogen containing cyclic compounds, e.g., pyrrolidine, N~methy1~2~pyrrolidone and †,3-dimethy!-2-imidazolidinone; and sulfur containing compounds -such as thiogiycol, dimethyl sulfoxide and tetramethylene susfcne.
[0189] Soivent(s) can be present in the polymer compositions of the present invention, in an amount of at least 5 percent by weight, or at least 15 percent by weight, or at least 30 percent by weight, based on the total weight of the polymer composition. The soivent(s) can also be present in the polymer composition In an amount of less than 95 percent by weight, or less than 80 percent by weight, or less than 60 percent by weight, based on the total weight of the pigment dispersion. The amount of solvent present in the polymer composition can range between any combination of these values, inclusive of the recited values, with some embodiments, such as from 5 to 95 percent by weight, or from 15 to 80 percent by weight, or from 30 to 60 percent by weight, in each case based on the total weight of the polymer composition,
[0190] With some embodiments, the polymer composition Includes an additive selected from heat stabilizers, light stabilizers, and combinations thereof. Examples of useful heat stabilizers and light absorbers include, but are not limited to, those available commercially from BASF under the trademarks IRGA OX and TJNUVIN. The optional heat stabilizers and light stabilizers, when used, can be present in amounts up to 20 percent by weight, based on total solids weight of the polymer composition (excluding solvent).
[0191 } The present invention also relates to mechanochromic articles that include the polymer composition of the present invention as described previously herein. With some embodiments, the mechanochromic article is selected from films, sheets, and 3-dimens!onai articles.
101921 The 3-dimensionai articles from which the mechanochromic articles of the present invention can be selected include, but are not limited to, ophthalmic articles, display articles, windows, mirrors, protective articles and support articles.
[0193] The mechanochromic articles of the present invention, with some embodiments, are selected from ophthalmic articles, and the ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, and magnifying lenses. As used herein the term "ophthalmic" means pertaining to or associated with the eye and vision. Non-limiting examples of ophthalmic articles or elements include corrective and non-corrective lenses, including single vision or multi-vision lenses, which can be either segmented or non-segmented multi-vision lenses (such as, but no! limited to, bifocal lenses, trifocal lenses and progressive lenses), as well as other elements used to correct, protect, or enhance (cosmetically or otherwise) vision, including without limitation, contact lenses, intra-ocular lenses, magnifying lenses, and protective lenses or visors.
[0194] The mechanochromic articles of the present invention, with some embodiments, are selected from display articles, and the display articles are selected from screens, monitors, and security elements. As used herein the term "display" means the visible or machine-readable representation of information In words, numbers, symbols, designs or drawings. Non-limiting examples of display articles, elements and devices include screens, monitors, and security elements, such as security marks.
[0195] The mechanochromic articles of the present invention, with some embodiments, are selected from protective articles, and the protective articles are selected from protective lenses, protective visors, protective headgear, and protective housings. Examples of protective lenses include, but are not limited to, safety glasses and safety goggles, such as used in a laboratory and/or a work shop, such as a metal shop, welding shop, wood-working shop, automotive shop/garage, and the like. Examples of protective visors include, but are not limited to, those used with racing helmets (such as automotive, motorcycle, and boat racing helmets), aircraft helmets, hockey helmets, metal working helmets, and helmets used by ground military personnel. Examples of protective headgear Include, but are not limited to, motorcycle helmets, aircraft helmets, speed boat helmets, automotive race helmets, baseball helmets, hockey helmets, equestrian helmets, helmets used by ground military personnel, construction helmets, oil filed helmets, and helmets used by metal workers. Examples of protective housings include, but are not limited to, housings for sensitive equipment, such as, analytical equipment, guidance systems (such as missile guidance systems), and medical equipment (such as insulin pumps),
[0106] The mechanochromic articles of the present invention are, with some embodiments, selected from support articles, and the support articles are selected from rods, beams, crossarms, and combinations thereof. The rods, beams, and crossarms can be substantially unitary articles, or composed of a plurality of components, in which at least some of the components are the mechanochromic articles of the present invention.
|O107] The mechanochromic article of the present invention, with some embodiments, is selected from a 3-dimensionai article, and the 3~dimenslonsal article includes a layer residing over at least a portion of at least one surface of the 3-dsmensiona! article, in which the layer includes the polymer composition of the present invention as described previously herein, and is a mechanochromic layer. The mechanochromic layer can be selected from fiims, sheets, and/or coatings.
[0198] The mechanochromic article of the present, invention, with some embodiments, is selected from a 3-dimenstona! article, and the 3-dimensionsal article includes a coating residing over at least a portion of at least one surface of the 3-dimensfona! article, in which the coating includes the polymer composition of the present invention as described previously herein, and is a mechanochromic coating.
[0199] With some embodiments, the coating is the polymer composition of the present invention, and the coating is a mechanochromic coating. The coating can be a single layer coating or a multiple layer coating, In which each layer thereof can have the same or a different composition. With some embodiments the coating is a multiple layer coating that includes a primer over at least a portion of a surface of the 3-dimensionai article, a mechanochromic layer formed over the primer layer (in which the mechanochromic layer Includes the polymer composition of the present invention), and an optional clear layer formed over the mechanochromic layer. The mechanochromic layer can be pigmented or unpigmented, with some embodiments. With some embodiments, the optional clear layer, which resides over the mechanochromic layer, can include an additive selected from heat stabilizers and/or light stabilizers. The heat stabilizers and light stabilizers can be present in amounf(s) and the thickness of the clear layer can be selected such that photochromic activation of the residue of the controlled radical polymerization initiator {represented by Formula (I) and/or (II), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantially eliminated. With some embodiments, and for purposes of non-limiting illustration, the heat stabilizers and light stabilizers can be present in the clear layer in a total amount of up to 40% by weight, based on the total solids weight of the dear layer.
[0200] There is also provided a mechanochromic article that includes the polymer composition of the present invention, in which the mechanochromic article further includes a coating residing over at least a portion of at least one surface of the mechanochromic article. The coating is free of the polymer composition of the present invention, and the coating includes an additive selected from heat stabilizers, Sight stabilizers, and combinations thereof. The coating residing over the mechanochromic article can be referred to as an overcoating. The overcoating, which resides over the mechanochromic article, can be a clear overcoating, with some embodiments of the present invention. The heat stabilizers and light stabilizers can be present in amount(s) and the thickness of the clear overcoating can be selected such that photoch.ro mi c activation of the residue of the controlled radical polymerization initiator (represented by Formula (i) and/or (!l), which resides within the polymer backbone of the polymer of the present invention) by actinic radiation is at least minimized, or substantiall eliminated. With some embodiments, and for purposes of non-limiting illustration, the heat stabilizers and light stabilizers can be present In the clear overcoating In a total amount of up to 40% by weight, based on the total solids weight of the clear overcoat,
f0201] The present invention is more particularly described in the following examples, which are intended to be illustrative only, since numerous modifications and variations therein will be apparent to those skilled in the art. Unless otherwise specified, all parts and percentages are by weight.
EXAMPLES
The examples of Part 1 describe the synthesis of controlled radical polymerization initiators, Part 2 describes the preparation of polymers made by controlled radical polymerization using the initiators of Part 1.
Part 1. Preparation of controlled radical polymizeraflon initiators
Example 1.
Figure imgf000051_0001
Into a 2oz jar flushed with Nitrogen was added 3-phenyi-3-{4-(2- hydroxyetnoxyphenyi}}-6,7--dimefhoxy- 13-ethy!-13-(2--h droxyethoxy}-3, 13-dihydro- indeno[2',3':3l4]naphtho[1 ,2-b3pyTan (0.56g, 1 equiv), triethylamlne (0.28g, 3.1 equiv), and dichloromethane (10, 2g). This mixture was cooled in a dry ice/eihanol bath, and a solution of 2-bromopropionyi bromide (0.58g, 3 equiv) in dichloromethane (1.5g) was added. The jar was reseated and allowed to warm to room temperature. After stirring for 18 hours, TOmL of water was added. The layers were separated, and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were washed with saturated sodium bicarbonate, dried over MgS04, and concentrated under vacuum, The residue was filtered through a plug of silica, ©luting with dichloromethane. After concentration of the eluent, 0.83g of a brown oil was obtained, which was consistent with 3-phenyi-3-(4-{2-(2- bromopropionaioJeihoxypheny J-ej-dimethoxy-l 3-ethyi-13-(2- bromopropionatoethoxyJ-S.I S-dihydro-indeno^'.S^S^jnap thoil ,2-bjpyran by 1H and 1¾ NMR.
Example 2.
Figure imgf000052_0001
A solution of 1-nitroso-2,3-dihydroxynaphtha1ene, (1.08g) in 13.75 mL of 1,2- dichloroethane was charged to a round bottomed flask and warmed to reflux, A mixture of 5-hydroxy~1 ,2,3,3-tetramethyl-3H~indoi-1-ium iodide (1.74g) and
frlethylamine (1.1 Sg ) was added dropwise. The resulting dark solution was reffuxed for 1 hour, then cooled to room temperature and a blue product was collected via filtration. This was immediately placed into a Nitrogen-flushed 2oz jar. To the jar was added i !eihyiamine (2.88g), and dichloromethane (8.5 ml). This mixture was cooled in a dry ice/ethanol bath,, and a solution of 2-bromoisobutyry! bromide (3.94g) In dichloromethane (1.5 mL) was added. The jar was reseaied and allowed to warm to room temperature. After stirring for 2 hours, the residue was dry packed onto a 6 inch by % inch silica plug and eluted with 500 mL of a 2: 1 solution of
dichloromethane: heptanes, increasing to 5:1 dichioromethane:heptanes. The filtrate was concentrated, then the residue was purified by column chromatography with an eiution gradient of 1 :1 dichloromethanerheptanes, up to 4:1
drchloromethane:hepta.nes on siiica, to provide 1 ,3,3- rimethyispiro[indoiine-2,3'- naphtho{2, 1 -b][1 ,4]oxazine]-5,5'-diyl bis(2-bromo-2-methylpropionate) as a dark brown solid which was photochromic upon exposure to UV irradiation. Example 3.
Figure imgf000053_0001
Into a 20 ml. scintillation vial was charged 3-{4-meihoxyphenyl)-3~(4~(2- hydroxy0thoxypheny!))-6,7-dimethoxy-1 1 -carboxy-13, 13-dimetbyf-3,13-dihydro- ,2-bjpyran (0, 1323g), dicydohexyicarbodiimide (DCC, 0.044g}, ethylene glycol (0.57g), dimethyiarntfiopyridsne (0.0013g), and
dichioromethane (3.2 ml) The resulting solution was stirred at room temperature for 3 hours, at which time TLC analysis (100% ethyl acetate) on silica gei indicated complete consumption of starting material. The reaction was partitioned between dichioromethane and water, and the layers were separated. The organic layer was washed with water, dried over sodium sulfate and concentrated, yielding a green solid. This material was then converted to the initiator according to the general procedure in example 2, using 0.19g of bromoisobutyryl bromide, 0.103g
triethyiamine and 3 mL of dichioromethane (1.5 mL). Purification via column chromatography (methylene chloride, siiica gel} yielded 0.1 1g of a photochromic compound consistent with 3~(4~methoxypheny!}-3-(4~(2-bromo-2- methylpropronato}ethoxypheny[))-8,7-dimethoxy-11 ~(2~bromo-2- methylpropionatoethoxyoxyi) - 13,13-di methyi-3, 3-dihydro~
irsdeno[2',3':3,4]naphtho[1 ,2-bjpyran by \H and 3C MR.
Example 4:
Figure imgf000053_0003
3-{4-2-hydroxyeihoxyphenyl)-3-{4-methoxyphenyi)-6-mefrsoxy-7-(3- hydroxymethyl)piperidin-1 ~yi)-13, 13-dimethyi~3,13~dihydro-
Figure imgf000054_0001
(0.03%) was placed into a Nitrogen-flushed 2 02 jar. To the jar was added triethylamine (0.0289), and dichioromethane (1g). This mixture was cooled in a dry ice/ethanol bath, and 2-bromoisobutyryl bromide (0,05g,) in dichioromethane (1g) was added. The jar was resealed and .allowed to warm to room temperature. After stirring overnight, the reaction was diluted with 4m L of water. The layers were separated, and the aqueous layer was extracted three times with dichioromethane. The combined organics were dried over gS04, and concentrated under vacuum. The residue purified by column chromatography (silica gel) using an elution gradient from 100% cyclohexane to 1 : 1 cyc!ohexanerdiethyi ether. After concentration of the eluent, 13.4mg of 3-(4-(2-brorno-2- methyipropionyiethoxyphenyi)-3-(4-meihoxyphenyi)-6-methoxy-7-(3-{2-bromo-2- metbyipropionyioxymethy!)piperidin~1 ~yi)~13, 13-dimethyi-3,13-d ihydro- sndeno[2!,3':3,4]naphfho[1 ,2-b]pyran was obtained as a phoiochromic soiid.
Example 5;
Figure imgf000054_0002
3-(4-(3-hydroxymethyipiperidin-1-y1))-3-pheriy!-6-rneihoxy-7-(3- hydroxymethyi)piperidin-1 -yi)-1 1 -bromo-13, 13~dimethyi~3, 13-dihydro~
indeno[2:,3!:3,4]naphtho:[1 ,2-b]pyran (0.1g) was placed into a Nitrogen-flushed 25 mL round bottomed flask. To the flask was added dichioromethane (1.5g), then the mixture was cooled In an ice water bath. Triethylamine (0.0647g) was added, followed by 2-bromoisobutyryl bromide (0.08%,). The flask was allowed to warm to room temperature. After stirring overnight, the solvent was removed and the residue was redisso!ved in diethyl ether. The salts were removed via filtration, and the e!uent was concentrated. The residue was filtered through a short silica column to provide 3-(4-(3-(2-bromo-2-methylpropionyioxymethy!)piperidin-1-y!))-3-phenyl-6-meihoxy-7- (3-(2-bromo-2-methyipropionyloxymethyl)piperidin-1-y!)- 1 -bromo-13,13-dimethyi- 3,13-dihydro-indeno 2, !3,;3l4]naphtho[1 ,2-b]pyfan (0.1 16g, 84%) as a b!uish-b!ack photochromic solid.
Part 2. Preparation of poiymer dyes by controlled radical polymerization
Example 6.
Into a flask immersed in a room temperaiure water bath was placed the initiator 3- phenyl'3~(4-(2-(2-bromopropionato)ethoxyph
bromopropionaioethoxy)-3, 13"dihydro-indeno[2\3':3,4jnaphthon ,2-bjpyran of Example 1 (0.1g, 1 equiv), Cu metal {0.03g, 4 equivs), tris(2~ dimethy!aminoethy!)amine (0.1 g, 4 equivs), and dry D SO (10.7 mL). The resulting mixture was purged with dry Nitrogen for 20 min. Methyl aeryiaie (21.3g, 2500 equivs) was filtered through a plug of alumina, purged with Nitrogen for 20 minutes, then added to the flask. The mixture was allowed to stir overnight at room temperature, after which a significant increase in viscosity was observed. The material was dissolved in teirahydroiuran (THF, 20.7g) and stirred open to the atmosphere for 5 minutes, at which time the viscous solution was filtered. The polymer was purified by precipitation into methanol. The off-white polymer was collected and dried under vacuum. The resulting polymeric compound was found to be reversibly photochromic under UV irradiation.
Example 7.
Into a flask Immersed in a room temperature water bath was placed the initiator
1 ,3,3-trimethy!spiro[indo!ine-2,3'-naphiho[2, 1 -b][1 ,4]oxazine3-5,5'-diyi bis(2-bromo-2- methyipropionate) of Example 2 (0.5g, 1 equiv), Cu metal (0.029g, 2 equivs), tris(2~ dimethylaminoethyijamsne (0,79 g, 2 equivs), and dry butyl acetate (1.3 mL). The resulting mixture was purged with dry Nitrogen for 20 min. Methyl acryiate (0.73, 37 equiv) and hydroxypropyl acryiate (0,96g, 33 equiv) were then added to the flask. The mixture was allowed to stir overnight at room temperature, after which a significant increase in viscosity was observed. The material was dissolved in THF (20.7g) then filtered through a plug of glass wool. To the filtrate was added
approximately 2g of AMBERLITE® lRC-748 (an ion exchange resin availabfe from Dow Chemical) and 4 drops of acetic acid. This was stirred for 1 h, then filtered and concentrated to yield a thick oil, 1 H NMR was consistent with the expected polymerization product containing the residue of the initiator of Example 1. The resulting polymeric materia! was found to be reversibiy photochromic under UV Irradiation.
Example 8;
The initiator 3-{4-me{hoxyphenyl)-3-( -(2-bromo~2-methylpropionaio)ethoxyphenyi)}- 6,7-dimethoxy-11 ~{2~bromo~2-met ylpropionatoethoxyoxyl) - 13, 13-dimethyl-3,13- di ydro-indeno[2'!3!:3)4]nap tho 1 ,2-bJpyran of Example 3 (0.030Sg) was subjected to the conditions described in Example 8 except that 0.008g Cu, 0.029g tris(2- dimethylaminoethyi)amine, 4.32g of methyl acryjate, and 2.8g of D SO was used. Gel Permeation Chromatography in THF indicated a peak MW of 128,614 (theory 140,000) relative to a linear polystyrene standard,
Example 9:
The initiator 3-{4-{2-bromo-2-methyfpropionyiethoxyphenyi}-3-(4-methoxyphenyi)-6- methoxy-7-(3-(2-bromo-2-meihyipropionyloxymethyl)p!peridin-1-yi)-13,13~dimethyf- 3, 13-dihydro-indeno(2'>3,:3,4]naphtho[1 ,2-b]pyran of Example 4 (13.4 mg) was subjected to the polymerization conditions described in Example 6 except that 0.0035g Cu, 0.013g tris(2-dimethy!aminoethyi)amine, 1.9g of methyl acrylaie, and 1.2g of DMSO was used. Gel Permeation Chromatography In THF indicated a peak MW of 163569 (theory 140,000) relative to a linear polystyrene standard.
Example 10:
The initiator 1 ,3,3-frimethylspiroj;!ndoilne-2,3,-naphtho(2,1-b] 1 ,4]oxazlne]-5 5 -diyi bis(2-bromo-2-melhylpropionate} of Example 2 (24.4 mg) was subjected to the polymerization conditions described in Example 6 except that 0.0094g Cu, 0.034g tris{2-dimethyiaminoethyl)amine, 5.19g of methyl acryiate, and 3.4g of DMSO was used. Gel Permeation Chromatography in THF indicated a peak MW of 183811 (theory 140,000) relative to a linear polystyrene standard.
Example 1 1 :
The initiator 3~{4~(3-(2~bromo~2-methyipropionyioxymethy!)piperidin-1-yl))-3-phenyi-6- methoxy-7-{3-(2-brorno-2"methyipropionyioxyrnethy!)piperidin-1-yl)-1 1 -bromo-13, 13- dimethyl-3,1 S-dih dro-indeno^'.S'^^jna hthon ,2-b}pyran of Example 5 (0.0815g) was placed into a flask immersed in a room temperature water. To this was added Cu powder (0,0096g), iris{2-dimethylaminoethyl)amine (0.027 g), and dry butyl acetate (1 ,0 mL). The resulting mixture was purged with dry Nitrogen for 10 minutes. Methyl acryiate (0,24) and hydroxypropyl acry!ate (0.242g) were then added to the flask. The mixture was allowed to stir overnight at room temperature, after which no significant increase in viscosity was observed. The mixture was then heated to 70°C and stirred for six hours, then cooled and stirred overnight. The resulting material was dissolved in THF (10ml) then filtered through a plug of glass wool. To the filtrate was added approximately 2g of AMBERLITE IRC-748 resin and 4 drops of acetic acid. This was stirred for 1 h, then filtered and concentrated to yield a thick oil. The resulting materia! was found to be reversibiy photochromic under UV Irradiation.
The present invention has been described with reference to specific details of particular embodiments thereof. It is not intended that such details be regarded as limitations upon the scope of the invention except insofar as and to the extent that they are included in the accompanying claims.

Claims

WHAT IS CLAIMED IS;
1. A controlled radical polymerization initiator comprising at least one radically transferable group, wherein said controlled radical polymerization initiator comprises at least one of,
(a) a spirooxazine compound represented by the following Formula (I),
Figure imgf000058_0001
independently for each n, R2 independentiy for each p, R3 independently for each q, R-4, R5, and Re are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi each optionally interrupted with at least one of -0-, -S-, - C(O)-, -C(0)0-, ~OC{0)i ; -S(O)-, -SO > -N(R11)-, and•Si(R11)(R12}- wherein R1 and R12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof,
provided that for the spirooxazine represented by Formula (!) at least one of R , independently for each n, R2 independently for each p, R3 independently for each q, R4, s, and R6, independentiy comprise said radically transferable group, and
(b) an indenonaphthopyran represented by the following Formula (II),
Figure imgf000058_0002
wherein x is from 1 to 4, y is from 1 to 4, R7 independently for each x, R8 independently for each y, R9( and R 0 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi each optionally interrupted with at least one of -0~, -S-, -C(0}-( ~C(0)0~, -OC(0)0-, -S(O)-, -SO , -N( 11)-, and
-Si(R1 '!)(R"12}" wherein R" and R12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof, and
B and B' are each independently selected from unsubstituted aryi, substituted aryi, unsubstituted heteroaryl, substituted heteroaryl, and poiyalkoxy, or B and B' taken together form a ring structure selected from unsubstituted fiuoren-9- yiidene, substituted f!uoren-9-yiidene, saturated spiro-monocyc!ic hydrocarbon ring, saturated sprro-bicyclic hydrocarbon ring, and spiro-tricycfic hydrocarbon ring,
provided that for the indenona phthopyran represented by Formula (II) at least one of R7 independently for each x, R8 independently for each y, R9, R10l B, and B\ Independently comprise said radically transferable group.
2. The controlled radical polymerization initiator of claim 1 , wherein for the spirooxazine represented by Formula (I) at least two of, Ri independently for each n, R2 Independently for each p, R3 independently for each q, R4, R5, and R6 independently comprise said radically transferable group, and wherein for the indenonaphthopyran represented by Formula (II) at least two of, R7 independently for each x, R8 Independently for each y, R9> R]0, B, and B' Independently comprise said radically transferable group.
3. The controlled radical polymerization Initiator of claim 1, wherein the spirooxazine represented by Formula (I) comprises at least one first radically transferable group, and at least one second radically transferable group,
further wherein for the spirooxazine represented by Formula (i) at least one of R independently for each n, and R2 independently for each p,
Independently comprise said first radically transferable group, and at feast one of R3 Independently for each q, R4, R5 and Rs independently compose said second radically transferable group, and
wherein the indenonaphthopyran represented by Formula (II) comprises at least one first radically transferable group, and at least one second radically transferrab!e group, further wherein for the indenonaphthopyran represented by Formula (if) at 'east one of 6 and B' independently comprise said first radically transferabie group, and at least one of R7 independently for each x, RB independently for each y, R9 and R10 independently comprise said second radically transferable group.
4. The controlled radical polymerization initiator of claim 1 , wherein the spirooxazine represented by Formula (!) comprises one first radically transferable group, and one second radically transferrable group,
further wherein for the spirooxazine represented by Formula (1) one of R, and R2 comprises said first radically transferable group, and one of R3, i¾, R5, and R6 comprises said second radicaiiy transferable group, and
wherein the indenonaphthopyran represented by Formula (II) comprises one first radically transferable group, and one second radicaiiy
transferrable group,
further wherein for the indenonaphthopyran represented by Formula (ii) one of B and B' comprises said first radically transferabie group, and one of Ry, Re, R9, and R 0 comprises said second radically transferable group.
5. The controlled radical polymerization initiator of claim 3, wherein the spirooxazine represented by Formula (I) comprises one first radically transferable group, and one second radically transferrable group,
further wherein for the spirooxazine represented by Formula (I) one R2 comprises said first radically transferabie group, and one R3 comprises said second radically transferable group, and
wherein the indenonaphthopyran represented by Formula (II) comprises one first radically transferable group, and one second radically
iransferrabie group,
further wherein for the indenonaphthopyran represented by Formula (II) one of B and B' comprises said first radically transferable group, and one of R? and R8 comprises said second radically transferabie group.
6. The controlled radical polymerization initiator of claim 1 , wherein said radically transferabie group is a halo group selected from CI, Br and I.
7. The controlled radical polymerization initiator of claim 1 wherein, for the spirooxazine represented by Formula (!) at least one of R1 ( !¾, R3, R4, R5, and R6 independently comprise a group represented by the following Formula (III), and
for the mdenonaphthopyran represented by Formula (il) at least one of R7, Rs, R9, Rio, B, and B' case independently comprise said group represented by the following Formula (III),
Figure imgf000061_0001
wherein is a divalent linking group selected from a bond, a divalent hydrocarbyl group and a divalent substituted hydrocarbyl group each optionally Interrupted with at teas! one of -0-, ~S~, -C(0 , -0(0)0-, -OC{0)O- -S(0)-, -S02-, - N{R55)- and -Si(Ria)(R16)~ and combinations of two or more thereof, wherein R s and R16 are in each case independently selected from hydrogen, hydrocarbyl and substituted hydrocarbyl, and R 4 is a divalent linking group selected from a bond, divalent hydrocarbyl, and divalent substituted hydrocarbyl, and X is said radically fransferrabie group.
8. The controlled radical polymerization initiator of claim 7, wherein R13 is selected from a bond, divalent C1-C20 linear or branched alkyl, divalent C3-C10 cyclic alkyl, divalent C3-C10 heterocyclic alkyl, divalent aryl, divalent heteroaryi, and combinations thereof optionally interrupted with at least one of -O- and -S- and combinations of two or more thereof, R14 is selected from divalent C C20 linear or branched alkyl, and X is selected from a halo group.
9. The controlled radical polymerization initiator of claim 8, wherein R 3 Is selected from a bond, divalent C C,o linear or branched a!kyl, divalent C3-C10 heterocyclic alkyl, divalent aryl, and combinations thereof optionally
interrupted with at [east one of -0-, R1 is selected from divalent Cr-C10 linear or branched alkyl, and said halo group from which X is selected is CI, Br, or I.
10. The controlled radical polymerization initiator of claim 7 wherein, for the spirooxazine represented by Formula (0, one R2 independently comprises said group represented by Formula (III), and one R3 independently comprises said group represented by Formula (ill), and
for the indenonapbihopyran represented by Formula (II), one of B and 8' independently comprises said group represented by Formula (III), and one of R7 and R8 independently comprises said group represented by Formula (III),
1 1. The controlled radical polymerization initiator of claim 1 wherein,
for the spirooxazine compound represented by Formula (I),
Rj independently for each n and R2 independently for each p are each independently selected from hydrogen, aryl, mono(CrC6)aikoxyaryl, dr(CrC6)a!kox aryl, mono(Ci-C6)alkyiary!, di{Cr-C6)alkylaryL bromoaryl, chioroaryi, fluoroary!, C3-C7 cycloalkyiaryi, C3-C7 cycloaikyl, C3-C7 cycloaikyioxy, C3-C7
cyc!oalkyioxy{CrCg)aiky! , C3-C7.cycloalky}oxy(Ci-C8)afkoxy, aryl(CrC6)alkyl, aryl(CrCe)aikoxy, aryfoxy, aryloxy(C C6)a!kyl, aryioxy(C C6)alkoxy, mono- or di(Ci~C6)aikylaryl(C;-C6)a!kyl, mono- or di(C C6)aikoxyaryi(CrCe)aikyf, mono- or di{C Cs)a!kylaryl(CrCs)a!koxy, mono- or di{Cr-C6)alkoxyaryi(CrC6)alkoxy, amino, rnono(Ci-C6)a!kyiamfno, di(C C6)alkyia !no: diarylamino, -(Cr-Ce)alkylpipera2ino, N-aryipiperazino, azi ldlno, indollno, pipertdino, ary!piperidino, morpho!ino, thiomorpho!ino, teirahydroquinoHno, tetrahydroisoquinolino, pyrryi, C C6 a!kyl, Ci-C6 bromoa!kyi, CrC6 ch!oroa!kyl, C Ce fluoroalkyi, Ci-C6 alkoxy, mono(C.rCe)a!koxy(Cr C4)aikyj, acryloxy, methacryloxy, acyloxy(CrCe aiky!), acy!oxy(C3-C7 cycloaikyl}, acyloxy(aryl), bromo, chloro or fiuoro,
R3 is, independently for each q, chosen from hydrogen, C C5 alkyl, Cf- C5 alkoxy, nitro, cyano, C C8 aikoxycarbonyf, acyioxy(Ci-C6 aikyi), acyioxy(C3-C7 cycloaikyl), acy!oxy(ary!),, halo, C C4 mono'haioaikyi or CrC4 polyhaloalkyl; said halo substituents being chloro, fiuoro, iodo or bromo,
R4 is chosen from hydrogen, CrC8 alkyl, C3-C7 cycloaikyl, phen(C1-C4)a!kyi, naphth(CrC4)aikyi, aiiyi, acfyiyloxy(C2-Ce)aikyl , methacryiyloxy{C2- C6)alkyl, C2-C4 acyloxy(C2-C6)aikyl, carboxy(C C6)alkylt cyano(C2-C6)alkyl, hydroxy(G2-C6)alkyl, triarylsi!yi, triarylsiiyioxy, iri(Ci-C6)alkylsiiyl,
tri(CrC5)alkyisilyloxy( tr!(CrCe)aikoxysliyi, thC'C CeJaikoxysilyloxy,
di(CrCe)a!kyl(C C6 alkoxyjsiiyl, di(CrC6)alkyl{C C6 alkoxy)silyloxy.
di(CrC8)aikoxy{Cr C6 alkyl)siSyi, di(C C6)alkoxy(CrC6 alkyi)sily!oxy, CrC6 aikoxy(C2- C4)alkyi or (C2H40)fCH3, wherein r is an integer from 1 to 6, R5 and R6 are each independently selected from hydrogen, Gr C5 aikyl, acyioxy(CrC6 aiky!), acyjoxy(C3-C7 cycioaikyl), acy1oxy(aryl), benzyl, phenyl, mono- or di-substituted phenyl, said phenyl substituents being C Cs aikyl or C C5 alkoxy; or Rs and R6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spire carbon atom,
for the indenonaphihopyran represented by Formula (li),
R7 independently for each x and R8 independently for each y are each independently selected from,
hydrogen;
a compatib!iztng substttuent;
halogen selected from fluoro and chloro;
C1-C20 aikyl;
C3-C10 cycioaikyl;
acyloxy(Ci-C6 aikyl), acyloxy{C3-C7 cycioaikyl), acyioxy(aryi);
substituted or urtsubstiiuted phenyl, the phenyl substituents being selected from hydroxy!, halogen, carbonyi, CrC2o alkoxycarbonyl, cyano, haio(CrC2o)aikyi, C1-C20 aikyl or CrC2.o aikoxy;
-O-R10' or -qOJ-R o -C(Q OR,0 wherein R10' is hydrogen, C1-C20 aikyl, phenyl(CrC2o)alky!, roono(CrC2o)a!kyi substituted phenyf(Cr C;¾)aikyf, mono(Cr'C2o}alkoxy substituted phenyi{Ci-C2o)aikyi, (C,~ C2o)aikox {Q2-C2o)alkyl, C3-C10 cycioaikyl, or mono{CrC2o)aikyi substituted C3~G10 cycioaikyl;
Figure imgf000063_0001
and R12' are each independently hydrogen, C1-C20 aikyi, phenyl, naphfhyi, furanyf, benzofuran-2-yl, benzofuran-3- y!, ihienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,
dibenzothienyl, benzopyridyl, fluorenyl, CrC2o alkylaryi, C3*C10
cycioaikyl, C4-C20 bicycioaikyl, Cg~ C20 trrcycfoa!kyl or C C20
a!koxyalkyl, wherein said aryl group is phenyl or naphthyl, or R ,' and R12' come together with the nitrogen atom to form a C3-C.20 heiero bicycioaikyl ring or a C4-C2o hetero-tricycloalkyi ring;
a nitrogen containing ring represented by the following graphic formula IVA,
Figure imgf000064_0001
wherein each -Y- is independently chosen for each occurrence from - CH2-, -CH{Ri3')-, -C{R13')2-> -CHiarylh -C(aryl)2-, and -CifWXaryl)-, and Z is -Y-, -0-, -S-, -S(O)-, -S02-, -NH-, -N(R13 !)-, or -N(ar l)-, wherein each R13' is independently CrC20 alkyl, each aryl is independently phenyl or naphthyi, m Is an integer 1 , 2 or 3, and p is an integer 0, 1 , 2, or 3 and provided that when p is 0, 2. is -Y-;
a group represented by one of the following graphic formulas IVB or rvc,
Figure imgf000064_0002
wherein R15, R16, and R17 are each independently hydrogen, C C6 alkyl, phenyl, or naphthyi, or the groups R s and R 6 together form a ring of 5 to 8 carbon atoms and each Ra is independently for each occurrence selected from C1-C20 alkyl, CrC20 aikoxy, fluoro or chloro, and Q is an integer 0, 1 , 2, or 3; and
unsubstituted, mono-, or di-substituted C4-C18 spirobicycilc amine, or unsubstituted, mono-, and di-substituted C -C18 spirotricyclic amine, wherein said substiiuents are independently aryl, Ci-C20 alkyl, CrC20 aikoxy, or phenyi(C-i-C2o)alkyl; or
two adjacent R7 groups, or two adjacent Rs groups,
independently together form a group represented by one of IVD and IVE:
IVD IVE
Figure imgf000064_0003
wherein T and T are each independently oxygen or the group -NRn'-, where R^', R 5, and R 6 are as set forth above,
R9 and R10 are each independently selected from,
(i) hydrogen, C C2o aikyl, C Cao haloalkyi, C3-Cj0 cycloa!ky!, acyloxy(CrC6 aikyl), acyioxy{CVC7 cycioalky!), acyloxy(aryi), aiiyi, benzyl, or mono-substituted benzyl, said benzyl substituents being chosen from halogen, -C20 aikyl or G1-C20 a!koxy;
(is) an unsubstituted, mono- di-or tri-substiiuted group chosen from phenyl, naphihyi, phenanthryi, pyrenyl, qutnoiy!, isoqutnoiyi,
benzofuranyl, ihienyi, benzothienyi, dibenzofuranyi, dibenzothienyi, carbazo!yi, or indo!y!, said group substituenis in each case being independently chosen from halogen, Cr jo aiky! or C C2o alkoxy;
(iii) mono-substituted phenyl, said substituent located at the para position being -(CH2) ~ or ~0-(CH2) , wherein t is the integer 1 , 2, 3, 4, 5 or
6, said substituent being connected to an aryl group which is a member of a photochrome materia!;
(Iv) the group -CH(R18)G, wherein R18 is hydrogen, C C6 aikyi or the unsubstituted, mono- or dhsubstituied aryl groups phenyl or naphthyl, and G Is -CH2OR19, wherein R1S is hydrogen, -C(0)R10, C C20 aikyl, Cr-C20
aikoxy{CrC2o)aikyl, phenyl(CrC20)alkyl, mono(Ci -C20)a!koxy substituted phenyi(Cr- C2o)aikyf, or the unsubstituted, mono- or di~subsiituted aryl groups phenyl or naphthyl, each of said phenyl and naphthyl group substituents being C C20 aikyl or C-rC2o alkoxy; or
(v) Rg and R 0 together form a spiro substituent selected from a substituted or unsubstituted spiro-carbocycllc ring containing 3 to 8 carbon atoms, a substituted or unsubstituted spiro-heterocyciic ring containing 1 or 2 oxygen atoms and 3 to 6 carbon atoms including the spirocarbon atom, said spiro- carbocyciic ring and spiro-heterocyciic ring being anne!Sated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C1-C20 aikyi; and
B and 6' are each independently;
an aryl group that is mono-substituted with a compatiblizing substituent; a substituted phenyl; a substituted aryl; a substituted 9- juiolindinyl; a substituted heteroaromatic group chosen from pyridyi, furany!, benzofuran-2-yl, benzofuran-3-yi, ihienyi, benzothien-2-yi, benzothien-3-yi, dibenzofuranyi, dibenzothienyi, carhazoyl, benzopyridyi, indolinyl, and fluorenyl, wherein the phenyl, aryl, 9- juiolindinyl, or heteroaromaiic substituent is a reactive substituent R; an unsubstituted, mono-, di-, or tri-substituted phenyl or ary! group;: 9~ ju!ofidinyi; or an unsubstituted, mono- or di-subststuted heteroaromaBc group chosen from pyridyf, furany!, benzofuran-2-yl, benzofuran-3-yi, thieny!, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,
dibenzothienyi, carbamoyl, benzopyridyl, indo!iny!, and fiuorenyl, wherein each of the phenyl, ary! and heteroaromaiic substituents are each independently;
hydroxy!, a group -C{~0)R21, wherein R21 is -OR22, - (R23)R2 , piperidino, or morpho!ino, wherein R22 is a!fyi, CrC2 a!kyi, phenyl, mono(Ci-C2o)aikyi substituted phenyl, mono(Cr
C2o)aikoxy substituted phenyl, phenyl^ -Caolaikyi, mono(C C20)aikyi substituted phenyl(CrC2o}aikyi, mono(CrC2o)aikoxy substituted phenyl(CrC2o)aikyi, CrC20 alkoxy(C2-C2o)alkyl or CrC2o haloalkyl, R23 and R24 are each independently C C20 aiky!, C5-C10 cycloatkyl, phenyl or substituted phenyl, the phenyl substituents being GrC20 aiky! or Cr-C2C alkoxy, and said halo substituent Is chforo or fluoro, aryi, mono(Cr
C2o}afkoxyaryi, di(Ci-C2o)aikoxyaryl, mono(CrC2o)aikyiaryl, di(C C2o)alkylary{, haloaryl,. C3-C10 cycloaikyiaryl, C3-C10 cycioalkyl, cyc!oaikyioxy, C3-C 0 cycfoaikyioxy{C
C2o)alk i, C3~C10 cycloa!kyloxy(CrC2o)a!koxy, ary!(C C20)alkyi, aryi(C1-C2o)a koxy! aryioxy, aryfoxy{CrC20)aiky!, arytoxy(Cr C2o)aikoxy, mono- or di{CrC20)a!ky{aryi(Ci-C2o}alkyi, mono- or di-{CrC20)alkoxyary1(C C2o)alkyl, mono- or di-(C
C2o)aSky!aryi{CrC2o)alkoxy, mono- or di-{CrC2o)a!koxyary!(Cr Cao)alkoxy, amino, mono- or di-( Ci-C20}alkyiamino(
diaryiamino, piperazino, W-(Ci-C20)aiky!p!perazino, N- arylpiperazino, aziridino, indoiino, piperidino, morphoiino, thiomorphoiino, tetrahydroquino!ino, tetrahydroisoquinolino, pyrro!idy!, C1-C20 alkyl, C C20 haloalkyl, Cr-C20 alkoxy, mono{CrC2o)aikoxy(CrC20)alkyl, acryloxy, methacryloxy, acyioxy(C C6 alkyl), acyloxy(C3-C7 cycioalkyl), acyloxy(aryl), or halogen;
an unsubstituted or mono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl, imidazollnyl, pyrrolinyi, phenothia2tnyi, phenoxazinyi, phenazlnyi, and acridinyl, each of said substituents being C C2o a!kyi, C1-C20 aikoxy, phenyl, or halogen;
Figure imgf000067_0001
wherein K is »CH2- or -0-, and is -O- or substituted nitrogen, provided that when is substituted nitrogen, K is -CHr, the substituted nitrogen substituents being hydrogen, C1-C20 aiky!, or Cr C20 acyi, each R26 being independently chosen for each occurrence from C C2G alkyl, C1-C20 aikoxy, hydroxy, and haiogen, R26 and R27 each being independently hydrogen or C C2o alkyl, and u is an integer ranging from 0 to 2; or a group represented by:
Figure imgf000067_0002
wherein R28 Is hydrogen or CrC20 alkyi, and R29 is an unsubstituted, mono-, or di-substituted group chosen from naphthyi, phenyl, furanyi, and thienyl, wherein the substituenis are d-Cao alkyl, C C20 aikoxy, or haiogen; or
8 and B: taken together form one of a fluoren-9-ylidene, mono- , or di-substituted fluoren-9-yiidene, each of said fluofen 9-y!idene substituents being independently chosen from C -C2o alkyl, C1-C20 aikoxy, and haiogen.
12, The controlled radical polymerization initiator of claim 11 wherein,
for the spirooxazine compound represented by Formula (I),
Ri independently for each n and R2 independently for each p are each independently selected from hydrogen, aryi, mono(C C6)alkoxyary{, di(CrC6)alkylamino, piperidfno, morpholino, C C6 aikoxy, or fiuoro,
R3 is, independently for each q, selected from hydrogen, C-rC5 a!kyl, C1-C5 aikoxy, C Ce alkoxycarbonyl, acyloxy(C.-rC6 alkyl), aoyloxy(C3-C7 cycioaikyl), acyloxy(aryl),, halo, CrC4 monohatoalkyl or C1-C4 polyhaioalkyl; and said halo substituents being ch!oro or fiuoro, R4 Is selected from hydrogen, C C8 afkyl, phen(Cr~C4)alky1, acrylyioxy(C2-C6)aikyi, methaeryiyloxy(C2-C3)a!kyi, carboxy(C2-C6)aikyi,
in(C -Cg)aikylsiiy[, iri{Ci-Ce)a!kylsilyloxy, tri{CrC6)ajkoxysilyi, tri(CrCe)a!koxysi!y!oxy, di(CrC6)alkyl(Ci-C6 alkoxy)silyi, di{Ci-C6)alkyl(C C6 a!koxy)siiyioxy,
di(C-t -C6)alkoxy(C1 -Ce alkyl)silyi or di(Ci-C6)alkoxy(C C6 a!ky!)siiytoxy, and
R5 and Re are each Independently selected from hydrogen, C C§ aiky!, phenyl'; or R5 and R6 taken together form a group chosen from a cyclic ring of from 5 to 8 carbon atoms which includes the spiro carbon atom, and
for the indenonaphthopyran represented by Formula (il),
R7 independently for each x and R8 independently for each y are each independently selected from, hydrogen, Cr-C6 a!kyl, C3- C7 cycioalkyj, morpholino, morpholino substituted with Cy-Ca linear or branched aiky!, Ci-C8 haloaikyi, fluoro, chloro, and -O~R10\
R9 and R10. are each independently selected from hydrogen, Ci~C8 alkyl, Ci-Ca haloaikyi, and C3-C7 cycioaikyl, or together form a spiro substituent selected from a substituted or unsubstituted spiro-carbocyciic ring containing 3 to 6 carbon atoms, and
B and B' are each independently selected from aryi, aryl substituted with CrCe a!koxy, and aryi substituted with morpholino.
13. A polymer composition comprising at least one polymer prepared by controlled radical polymerization initiated in the presence of a controlled radical polymerization initiato having at least one radically transferable group, wherein each polymer prepared by controlled radical polymerization is independently represented by the following Formula (V),
(V)
Figure imgf000068_0001
wherein independently for each w is a residue of a monomer, φ is a residue of said controlled radical polymerization Initiator that is free of said radically transferable group,
X, independently for each z, is or is derived from said radically transferable group,
w, independently for each z, is an integer of at least 2, and z is an integer of at least 1 , further wherein said controlled radical polymerization Initiator is selected from,
(a) a spirooxazine compound represented by the following Formula (I),
(0
Figure imgf000069_0001
wherein n is from 1 to 4, p is from 1 to 2, q is from 1 to 4, and Ri independently for each n, R2 independently for each p, R3 Independently for each q, R4, Rs, and R,¾ are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi each optionally interrupted with at least one of -0-, -S-, - C{0)-, -C(0)0~, -OC(0)0-, -S(O)-, -S02-, -N(R11)-, and -Si(R 1)(R12)- wherein R1 1 and R12 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi, and combinations of two or more thereof, and
(b) an !ndenonaphthopyran represented by the following Formula (if),
Figure imgf000069_0002
wherein x is from 1 to 4, y is from 1 to 4, R7 independently for each x, R8 independently for each y, R9( and R 0 are each independently selected from hydrogen, hydrocarbyi and substituted hydrocarbyi each optionally interrupted with at least one of -Ο-, -S-, -C(0}~, -C(0)0-, -OC(Op-, -S(O)-, -S02-, -N(R11)-> and
-Si(R1 )(R12)- wherein R1 and R 12 are each independently selected from hydrogen, bydrocarbyf and substituted hydrocarbyi, and combinations of two or more thereof, and
B and 8' are each independently selected from unsubstituied ary!, substituted ary!, unsubstituied heteroaryi. substituted heteroaryl, and poiyaikoxy, or B and B' taken together form a ring structure selected from unsubstituied f!uoren-9- yltdene, substituted iiuoren-9-yiidene, saturated spiro-monocycHc hydrocarbon ring, saturated spiro-bicycltc hydrocarbon ring, and spiro-tricyciic hydrocarbon ring,
provided that for the spirooxazine represented by Formula (!) at least one of R-i independently for each n, f¾ independently for each p, R3 independently for each q, R4, R5, and R6 independently comprise said radically transferable group, and
provided for the indenonaphthopyran represented by Formula (II) at least one of R7 independently for each x, R8 independently for each y, R9, R10, , and B' independently comprise said radically transferable group.
14. The polymer composition of claim 13 wherein, z is at least 2,
the spirooxazine represented by Formula (I) comprises at least one first radically transferable group, and at least one second radically transferable group,
further wherein for the spirooxazine represented by Formula (I) at least one of Ri independently for each n, and R2 independently for each p, independently comprise said first radically transferable group, and at least one of R3 independently for each q, R4( Rs and R6 independently comprise said second radically transferable group, and
the indenonaphthopyran represented by Formula (II) comprises at least one first radically transferable group, and at teast one second radically transferable group,
further wherein for the indenonaphthopyran represented by Formula (IS) at least one of B and 8' independently comprise said first radically transferable group, and at teast one of R? independently for each x, R8 independently for each y, Rg and R10 independently comprise said second radically transferable group.
15. The polymer composition of claim 13 wherein, 2 is 2, the spirooxazine represented by Formula (!) comprises one first radically transferable group, and one second radically transferable group,
further wherein for the spirooxazine represented by Formula (I) one F comprises said first radically transferable group, and one i¾ comprises said second radically transferable group, and
the Indenonaphthopyran represented by Formula (II) comprises one first radically transferable group, and one second radically transferable group,
further wherein for the indenonaphthopyran represented by Formula (Si) one of B and 8' comprises said first radically transferable group, and one R3 comprises said second radically transferable group.
16, The polymer composition of claim 13 wherein, for the spirooxazine represented by Formula (I) at teast one of Ri, R2,
R3, R4, Rs, and Re comprise a group represented by the following Formula (Hi), and for the indenonaphthopyran represented by Formula (II) at least one of
Rv, R8, R9l R¾0, B, and 8' in each case independently comprise said group
represented by the following Formula (III),
Figure imgf000071_0001
wherein R13 is a divalent linking group selected from a bond, a divalent hydrocarby! group and a divalent substituted hydrocarbyf group each optionally interrupted with at least one of -0-, -S-, ~C(G)-, -C{0)0-, -OC(0)CK ~S(0)~, ~SO > - N(R10)- and -Si(R1&)(R16)- and combinations of two or more thereof, wherein R 5 and R16 are in each case independently selected from hydrogen, hydrocarby! and substituted hydrocarby!, and R 4 is a divalent linking group selected from a bond, divalent hydrocarby!, and divalent substituted hydrocarby!, and X is said radically transferrab!e group,
17. The polymer composition of claim 16, wherein said radically transferable group Is a halo group selected from Ci, Br and I.
18. The polymer composition of claim 13, wherein said polymer comprises at least one active hydrogen group selected from hydroxy!, thiol,
carboxy!ic acid, primary amine, and secondary amine, and said poiymer composition further comprises at least one cross!inking agent comprising at least two functional groups selected from cyclic earbaxyiic acid anhydrides, oxiranes, thiooxiranes, isocyanates, tbioisocyanates, cyclic carboxylic acid esters, cyclic amides, and cyclic carbonates,
19, The polymer composition of claim 13 further comprising an additive selected from heat stabilizers, light stabilizers, and combinations thereof,
20, A mechanochromic articie comprising the polymer composition of claim 1 , wherein said mechanochromic article is selected from films, sheets, and 3-dimensional articles.
21 , The mechanochromic articie of claim 20 wherein said 3- dimensional articles are selected from ophthalmic articles, display articles, windows, mirrors, protective articles and support articles,
22, The mechanochromic article of claim 21 wherein said mechanochromic article is selected from ophthalmic articles, and said ophthalmic articles are selected from corrective lenses, non-corrective lenses, contact lenses, and magnifying lenses.
23, The mechanochromic articie of claim 21 wherein said mechanochromic article is selected from display articles, and said display articles are selected from screens, monitors, and security elements.
24, The mechanochromic article of claim 21 wherein said mechanochromic article is selected from protective articles, and said protective articles are selected from protective lenses, protective visors, protective headgear, and protective housings.
25, The mechanochromic articie of claim 21 wherein said mechanochromic article is selected from support articles, and said support articles are selected from rods, beams, crossarms, and combinations thereof,
26, The mechanochromic article of claim 20 wherein said mechanochromic article Is selected from 3-dimensional articles, and each 3- dimensionsal article comprises a coating residing over at least a portion of at least one surface of each 3-dimensionai article, further wherein said coating comprises said polymer composition of claim 14.
27, A mechanochromic article comprising the polymer composition of claim 14 wherein said mechanochromic article further comprises a coating residing over at least a portion of at least one surface of said mechanochromic article, said coating being free of said polymer composition of claim 1 , and said coating comprising an additive selected from heat stabilizers, light stabilizers, and combinations thereof.
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