WO2001092366A1 - Polymeres reticules de maniere reversible, agents de reticulation benzyle, et procede correspondant - Google Patents

Polymeres reticules de maniere reversible, agents de reticulation benzyle, et procede correspondant Download PDF

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Publication number
WO2001092366A1
WO2001092366A1 PCT/US2000/014722 US0014722W WO0192366A1 WO 2001092366 A1 WO2001092366 A1 WO 2001092366A1 US 0014722 W US0014722 W US 0014722W WO 0192366 A1 WO0192366 A1 WO 0192366A1
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Prior art keywords
benzylic
group
polymer
compound
reaction
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PCT/US2000/014722
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English (en)
Inventor
Herman P. Benecke
Richard A. Markle
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Battelle Memorial Institute
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Priority to PCT/US2000/014722 priority Critical patent/WO2001092366A1/fr
Priority to EP00936379A priority patent/EP1294789A1/fr
Priority to CA002411001A priority patent/CA2411001A1/fr
Priority to CN00819680.XA priority patent/CN1454229A/zh
Priority to AU2000251701A priority patent/AU2000251701A1/en
Priority to US09/722,203 priority patent/US6559263B1/en
Publication of WO2001092366A1 publication Critical patent/WO2001092366A1/fr
Priority to US10/404,979 priority patent/US20040014928A1/en
Priority to US10/404,284 priority patent/US6989466B2/en
Priority to US11/338,334 priority patent/US20060160979A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups

Definitions

  • the invention involves crosslinked polyurethanes and other polymers not conventionally known as polyurethanes, with added urethane crosslinks where the , crosslinkers are based on compounds having one or more benzylic hydroxyl groups, and methods of making the polymers and crosslinkers.
  • the polymers are useful to make fibers, sheets, moldings, coatings and other articles typically produced from polymers.
  • Organic polyisocya nates have been used with compounds having active hydrogen groups, such as hydroxyl groups, to produce a wide variety of useful materials such as coatings, hot-melt adhesives, moldings.
  • the materials have been used in injection molding applications and in composite or laminate fabrications. Typical of the art is the patent to Markle et al, US 5,097,010.
  • Urethane bonds are used ubiquitously in polymer chemistry to produce a wide variety of useful compositions.
  • the urethane bond is conveniently obtained by the addition reaction of an isocyanate group (either an aliphatic or an aromatic isocyanate) and an aliphatic alcohol or an aromatic (also known as aryl) hydroxyl group (a phenolic group). This reaction is reversible at sufficiently high temperatures as indicated by showing the following reaction as an equilibrium process. O ki II
  • R is alkyl or aryl and R' independently is alkyl or aryl.
  • the equilibrium constant K is defined as k ⁇ /k 2 where ki is the rate constant of the forward, or urethane forming reaction, where k 2 is the rate constant of the reverse reaction involving reformation of R ⁇ CO and R'OH.
  • ki is the rate constant of the forward, or urethane forming reaction
  • k 2 is the rate constant of the reverse reaction involving reformation of R ⁇ CO and R'OH.
  • the equilibrium constant will range from quite high values at ambient temperature but can become relatively smaller at sufficiently high temperatures so that significant and useful concentrations of isocyanate groups will be present.
  • the forward, or urethane forming reaction can be affected by simply heating an equimolar mixture of isocyanate and hydroxyl groups to the temperature at which ki is large enough that urethane formation occurs in an acceptable, or practical, period of time (from a few minutes to several hours).
  • Catalysts such as tertiary amines or certain organotin compounds, can speed both the forward and reverse processes but that are not necessary to bring about the urethane forming reaction or the establishment of equilibrium. If both compound types are difunctional, that is, if they are diisocyanates and dialcohols or diphenols, the forward reaction will produce polymeric products (polyurethanes) of very high molecular weights.
  • the achievable molecular weight of fully reacted (i.e., of essentially non-reversed) pairs will be limited by the presence and concentration of monofunctional isocyanates or monofunctional alcohols; by the isocyanate concentration and the dialcohol or the diphenol concentrations not being equal to each other; or, by the intervention of adventitious impurities which deplete the amount of either NCO or OH by side reactions.
  • the temperature of the polyurethane is further increased and k 2 increases faster in comparison to the increase in ki, significant and measurable reverse reaction to isocyanate and either alcohol or phenol will occur.
  • temperatures are or approximate values which represent the onset of reversal or a temperature where the practical effect of reversal, such as the onset of distillation or evaporation of phenol or butanol from a heated mixture, or where infrared spectroscopy of heated samples can record the onset of isocyanate and alcohol or phenol formation from a previously unreversed urethane compound.
  • polymers may be formed at some elevated temperature, by first heating the mixture of reactive components to some temperature above the practical onset of reversibility temperature such that a mixture of molten, or dissolved, partially assembled, urethane bond-containing, polymer fragments is established.
  • the polymer forming isocyanates and hydroxyl functional groups will fully form (or reform) urethane bonds providing a high molecular weight, crosslinked, polymer structure.
  • the polymer product will be insoluble in a known solvent for the uncrosslinked polymer. But will swell in such a solvent to various degrees ranging from nil at high levels of crosslinking to moderate to high swell (e.g. 10 or more times increase in volume) at low levels.
  • Low to high crosslinking levels, or crosslinking density may range from about one crosslink per 100 to 200 or more polymer backbone repeat units, to one crosslink per 3 to 5 backbone repeat units.
  • crosslinking are expected to show great utility in terms of mechanical (such as tensile or flexural) strength, rigidity (i.e. very high modulus valuesO scratch or abrasion resistance, resistance to organic solvents or water or various pH aqueous solutions, and other important properties, when used in such practical applications as molded parts, composite structures (e.g. glass fiber or fabric, carbon fiber or fabric, various particulate, and the like, filled structures),coatings on various substrates such as metals, glass reinforced moldings or composites, ceramics, silicon wafers or electronic components, and so on, very strong, including structural strength, adhesives for use to bond substrates such as described for coatings, and in other useful applications.
  • These useful properties are expected to be obtained from subambient temperatures up to temperatures of 150°C or higher, or in some cases up to about 180°C or higher. The need exists for new materials having both improved processing and end use characteristics. The present invention seeks to address those needs.
  • the invention discloses a polymer having a crosslinked structure wherein the crosslinked structure comprises one or more urethane bonds made by the reaction of a benzylic hydroxyl group and an isocyanate group.
  • a further embodiment provides for one or more urethane bonds made by the reaction of a benzylic hydroxyl group and an isocyanate group that are also present in the polymer backbone of individual polymer chains.
  • the one or more of the urethane bonds begins to dissociate at a temperature above about 150°C
  • a further embodiment of the invention includes a polymer described above, wherein the crosslinked structure is:
  • Ri is H
  • R 2 represents a group selected from -H, hydrocarbon groups containing up to ten carbon atoms, and halogen groups
  • Y represents a group selected from an isocyanate residue.
  • the isocyanate residue is selected from the group consisting of monoisocyanate, diisocyanate, and triisocyanate residues.
  • the isocyanate residue may also be selected from the group consisting of aromatic monoisocyanate, aromatic, diisocyanate, aromatic triisocyanate, benzylic monoisocyanate, benzylic diisocyanate, benzylic triisocyanate, aliphatic monoisocyanate, aliphatic diisocyanate, and aliphatic triisocyanate residues.
  • the polymer is a polyurethane and 0.01 to 99% of the urethane bonds in the polyurethane are obtained by reaction between a benzylic hydroxyl group and an isocyanate group.
  • the polymer is a polyurethane and 0.1 to 50% of the urethane bonds in the polyurethane are obtained by reaction between a benzylic hydroxyl group and an isocyanate group
  • a yet further embodiment of the invention includes a polymer having a crosslinked structure including a polyol with a high molecular weight; a polyicocyanate; a polyol with a low molecular weight; and trifunctional crosslinking compound selected from the group: (1) a compound having one benzylic hydroxyl group and two aliphatic hydroxyl groups; (2) a compound having two benzylic hydroxyl groups and one aliphatic hydroxyl group; (3) a compound having three benzylic hydroxyl groups; and wherein 0.01 to 99 mol % of bonds in the crosslinked structure comprise urethane bonds obtained by the reaction between a benzylic hydroxyl group and an isocyanate group.
  • a yet further embodiment includes a polymer having a crosslinked structure of a polyol; a polyicocyanate; a trifunctional crosslinking compound selected from the group: (1) a compound having one benzylic hydroxyl group and two aliphatic hydroxyl groups; (2) a compound having two benzylic hydroxyl groups and one aliphatic hydroxyl group; (3) a compound having three benzylic hydroxyl groups; and wherein 0.01 to 99 mol % of bonds in the crosslinked structure comprise urethane bonds obtained by the reaction between a benzylic hydroxyl group and an isocyanate group.
  • An additional embodiment includes a compound such as: wherein Ri and R 2 are identical or different and represent a group selected from -H, hydrocarbon groups containing up to ten carbon atoms, and halogen groups; wherein B and R4 are identical or different and represent a group selected from -H, and hydrocarbon groups containing up to ten carbon atoms; R 5 represents hydrogen, methyl, ethyl, or propyl; Re represents hydrogen, methyl, or ethyl; Xi (left arm), X 2 (right arm) and Z may be the same or different and represent none (no additional segment present), methylene, ethylene, or p-phenylene; the benzylic hydroxyl moiety may be positioned the para, meta or ortho position.
  • the compound is 2-([(4-hydroxymethyl)benzyl]ox ⁇ -l f 3-propan diol. Another embodiment includes the use of this compound to crosslink neighboring polymer chains.
  • An additional embodiment includes a compound of a poly-benzylic hydroxyl group capped polymer or oligomer obtained by reacting compounds containing one primary aliphatic hydroxyl group and one or more benzylic hydroxyl groups with low molecular weight polyisocyanates In a molar ratio of one primary aliphatic hydroxyl group per isocyanate group in the polyisocya ⁇ ate.
  • crosslinker compositions consisting of bis- isocyanate capped low molecular weight polyols, which structures result from the reaction of 2-20 moles of diisocyanates as represented by OCN-R-NCOO where R is aliphatic, cycloaliphatic, bisbenzylic, or aromatic, with 1 mole of low molecular weight diols which include aliphatic dlols with from 2 to 18 carbon atoms, cycloaliphatic diols with from 5 to 12 carbon atoms and bis- (beta-hydroxyethyl) or bis-(beta-hydroxyethoxy) substituted aromatic rings, including benzene, napthalene, pyridine or pyrazine rings.
  • This embodiment likewise includes the use of the crosslinker compositions to crosslink polymers containing 1 or more pendant benzylic hydroxyl groups on the backbone of the polymer.
  • Another embodiment includes, a crosslinker composition consisting of isophorone diisocyanate or TMXPI diisocyanate capped 1,4-butane diol such that a short oligomeric product described by the formula or expression
  • OCN-IPDI[-NH-CO-0-BD-0-OC-HN-IPDI-] n -NH-CO-0-BD-0-IPDI-NCO where n 0, 1, 2, 3, 4, 5, etc. but is predominately 0.
  • IPDI may be replaced with TMXDI, and is useful as a crosslinker of polymers containing pendant benzylic-hydroxyl groups.
  • the Figure illustrates a method for producing Compound 1 including chemical structures associated with starting materials, intermediates, byproducts, and final product.
  • This invention meets the needs for new polymers by providing thermally reversible polymer compositions having reversible polyurethane linkages in crosslinks between neighboring chains.
  • the number of crosslinks can be controlled so as to obtain polymers with desired properties.
  • the polyurethane crosslinks are based on bonds from benzylic hydroxyl groups and isocyanate groups. New compounds having such groups are also disclosed herein so as to achieve the desired reversible characteristics.
  • the invention discloses new materials and methods for preparing and crosslinking polymers to form polyurethanes, and other polymers not conventionally known as polyurethanes that consist of polymers with added urethane crosslinks, having enhanced properties.
  • One broad embodiment of the invention discloses new crosslinkers useful for obtaining polymers with enhanced properties. Another broad embodiment of the invention discloses new polymers obtained with the new crosslinkers. Other broad embodiments of the invention include methods and processes for preparing the polymers and crosslinkers. Yet another embodiment discloses selective preparation of new oligomeric chain extenders and crosslinkers derived from a simple compound type containing only one benzylic hydroxyl group and one primary aliphatic hydroxyl group.
  • model compounds In order to identify more specific types of isocyanate groups and alcohol or phenol groups which might be expected to provide reversibility temperatures to meet these criteria and needs, some preliminary work was carried out using model compounds. These were based on the benzylic hydroxyl group (an aralkyl hydroxyl group intermediate, between a normal aliphatic hydroxyl group and the pure aromatic hydroxyl group of a phenol) as represented by p-hydroxymethylbenzoic acid (HMB), the phenol group of p- hydroxylbenzoic acid (PHBA) and the cycloaliphatic isocyanate groups of isophoronediisocyanate (IPDI) and the araalkyl isocyanate groups of TMXDI (l,3-bis(l-isocyanato-l-methyl-ethyl) benzene).
  • HMB p-hydroxymethylbenzoic acid
  • PHBA phenol group of p- hydroxylbenzoic acid
  • IPDI isophorone
  • the isocyanate groups of IPDI and TMXDI are both expected to result in an onset reversibility temperature intermediate between an aromatic diisocyanate (such as MDI) and an aliphatic diisocyanate such as HDI, with any given hydroxyl group.
  • the benzylic hydroxyl group is expected to result in an onset reversibility temperature intermediate between a normal aliphatic alcohol such as n-butanol (or a n-aliphatic diol such as 1,4-butanedrol) and a phenol hydroxyl group.
  • n-butanol or a n-aliphatic diol such as 1,4-butanedrol
  • Example Al The preparation of the PHBA-BD andHMB-C18 alcohol products is described in Example Al and Example A2.
  • IR infrared spectroscopic
  • the samples were scanned in transmission mode using a Digilab FTS-60A, FT-spectrometer at 4 cm "1 resolution.
  • the sample as prepared as described in Example A3, and placed in the sample holder, between two 2 mm thick KBr salt plates.
  • the IR samples were estimated to be about 0.1 mm thick.
  • the sample holder was custom made by Harrick and is equipped with a resistance heater and coolant circulation connections for cooling the cell.
  • the cell was heated and cooled with Therminol 59, a heat transfer fluid.
  • the sample was heated from room temperature to 230°C ( ⁇ 5°C/min) and then cooled to room temperature ( ⁇ 82°C/min).
  • both Pair 2 and Pair 3 have a midpoint reversion temperature in the target range of 190-200°C and both are higher than the reversion temperature of Pair 1. This means the benzylic hydroxyl formed a more stable urethane bond than the phenol groups as expected. In fact, based on the pre-defined process temperature range (190-200°C), both Pair 2 and Pair 3 have acceptable reversible temperatures for fiber spinning at 195°C.
  • Compound 1 having three functional groups, a reversible benzylic hydroxyl group available for crosslinking and two primary aliphatic groups available for incorporation into the polymer backbone, was synthesized for incorporation in a polymer via urethane linkages, in particular a thermoplastic elastic polyurethane. It was expected that Compound 1 would polymerize with a diisocyanate like MDI by forming very stable urethane bonds via the two primary aliphatic hydroxyl groups, but with a pendant unreacted benzylic hydroxyl group.
  • HMB 4-Hydroxymethyl benzoic acid
  • C18 n- octadecanol
  • the HMB-C18 crude product was dissolved in 10 ml acetone and reprecipitated from 100 ml of methanol to remove the unreacted HMB.
  • the H-NMR of this product indicated 20 mole percent of unreacted n-octadecanol.
  • n-octadecanol was removed by dissolving the HMB-C18 in methylene chloride and precipitating from hexane, which is a solvent for 1-octadecanol, before it was used for the reactive blending study.
  • EXAMPLE A3 - IPDI-BD and PHBA-BD The isocyanate containing oligomers and hydroxyl containing oligomers were weighted into dry test tubes. They were combined in weight ratios such that equal molar amounts of NCD and OH groups were present. The mixtures were then heated to 160°C under a blanket of Argon with the test tube immersed in a heated Wood's metal bath. The reaction mixtures were maintained at 160°C for about 20 minutes with intermittent stirring under an argon gas purge. After the reaction, thin films were prepared from the oligomer reactive blended materials by pressing at about 180-190°C between 10 mil sheets of Teflon on a surface temperature controlled hot plate.
  • the invention discloses new polymers that contain urethane based crosslinks that start to reversibly dissociate at temperatures at about 150°C so as to obtain appropriate melt viscosities which allow melt preparation of various materials such as fibers, sheets, etc.
  • Another embodiment of the invention also includes a trifunctional crosslinking compound which contains one to three benzylic hydroxyl functions and none to two primary or secondary aliphatic hydroxyl functions. All hydroxyl functions are either benzylic hydroxyl functions or primary or secondary aliphatic hydroxyl functions.
  • a further embodiment of the invention includes a tetrafunctional crosslinking compound containing from two to four benzylic hydroxyl groups and from none to two aliphatic and primary or secondary hydroxyl groups. All hydroxyl functions are either benzylic hydroxyl functions or primary or secondary aliphatic hydroxyl functions.
  • backbone or "polymer backbone” as used herein indicates the extended linear repeating chain of an oligomer or polymer.
  • a benzylic hydroxyl group is a hydroxymethyl (-CH 2 OH) group substituted on a benzene ring, or a benzene ring containing other substituent groups.
  • a polyol with a high molecular weight useful according to the teachings of the invention typically includes polyester polyols represented by all of the below: Polyethylene butylene sebacate and the like; polybutylene adipate; polycaprolactone diol; aliphatic polycarbonate polyols such as those obtained by transesterification of polyhydroxyl compounds such as 1,4-butanediol, 1,6- hexanediol, 2,2-dimethyl(-l,3-propanediol, 1,8-octanediol and the like, with an aryl carbonate, for example, diphenyl carbonate; polyester polycarbonate polyols, for example reaction products of alkylene carbonates and polyester glycols such as polycaprolactone or products obtained by conducting a reaction of ethylene carbonate with a polyhydric alcohol (such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol and the like; and
  • a polyol with a low molecular weight useful with the invention typically includes difunctional, trifunctional and tetrafunctional benzylic hydroxyl compounds as represented by 1,2-ethanediol; 1,3-propanediol; 1,4- butanediol; 1,5-pentanediol; 1,6-hexanediol; 1,8-octanediol; 2,2-dimethyl-l,3- propanediol and the like, and also 1,4-cyclohexanedimethanol; l,4-bis(beta- hydroxymethoxy) benzene; l,3-bis-(beta-hydroxyethoxy) benzene; 1,4-bis- (hydroxyethyl) ester of terephthalic acid; l,3-bis(beta-hydroxyethyl) ester of isophthalic acid, and the like.
  • 1,2-ethanediol 1,3-propan
  • Additional polyisocyanates useful with the invention include: aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate (MDI); 1,5- naphthalene diisocyanate' (NDI); 1,4-phenylene diisocyanate (PDI); 2,4 and 2,6-Toluene diisocyanate (commonly available as an 80/20 mixture of 2,4/2,6) and the like; benzylic diisocyanates such as TMXDI, p-xylylene diisocyanate, m-xylene diisocyanate; aliphatic diisocyanates such as 1,6- hexamethylene diisocyanate (HDI) and alicyclic diisocyanates such as 1,4- cyclohexane diisocyanate 4,4'dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like.
  • aromatic diisocyanates such as 4,4'-dip
  • Isocyanates with more than two isocyanate groups per molecule are also available and include the trimerized products of the simple diisocyanates listed above in which three isocyanate groups are symmetrically located on an isocyanate nucleus, these are exemplified herein by the HDI Trimer (Tolonate (® HDI) from Rhone Poulenc.
  • HDI Trimer Tolonate (® HDI) from Rhone Poulenc.
  • polyisocyanates with varying functionality greater than 2 from Upjohn such as Isonate 143L and the PAPI series.
  • the difunctional benzylic hydroxyl compounds are used in the polymer backbone to obtain special properties.
  • the trifunctional and tetrafunctional benzylic hydroxyl compounds may be used both in the backbone of the polymer chains and in the crosslinks between neighboring backbone or polymer chains-
  • Useful difunctional benzylic hydroxyl compounds include: those in the benzene series represented by 1,4- ben ⁇ enedimetha ⁇ ol, 1,3-be ⁇ zene-dlmethanol; and 1,2-benzened ⁇ methanol; those in the pyridine series represented by 2,6-bis(hydroxymethyl) ⁇ yrldine; those in the pyrazine series represented by 2,5-bis(hydro ⁇ yrnethyl)pyra2lne; 2,3- b ⁇ s(hydroxymethyl) pyrazine; an 2,6-bls(hydroxymeth ⁇ l)pyrazine.
  • Useful trifunctional benzylic hydroxyl compounds include those having one benzylic hydroxyl group and two primary or secondary aliphatic groups represented by Compound 1 and its analogues; those having three benzylic hydroxyl groups represented by 1,2,4-benzenetrimethanol; 1,3,5- benzenetrimethanol; and 2,4,6-benzenetrimethanol.
  • Useful tetrafunctional benzylic hydroxyl compounds include those having four benzylic hydroxyl groups represented by 1,2,4, 5,-tetra(hydroxymethyl)benzene
  • New compounds having a benzylic hydroxyl group useful for forming urethane and ester linkages are represented by the formula:
  • i and R 2 are identical or different and represent a group selected from -H, hydrocarbon groups containing up to ten carbon atoms, and halogen groups;
  • R3 and 4 are identical or different and represent a group selected from -H, and hydrocarbon groups containing up to ten carbon atoms;
  • R 5 represents hydrogen, methyl, ethyl or propyl;
  • Re represents hydrogen, methyl, or ethyl;
  • X x (left arm), X 2 (right arm) and Z may be the same or different and represent none (no additional segment present), methylene, ethylene, or p-phenylene; the benzylic hydroxyl moiety may be positioned in the para, meta or ortho position
  • R 2 represents a group selected from -H, hydrocarbon groups containing up to ten carbon atoms, and halogen groups
  • R3 and R 4 are identical or different and represent a group selected from -H, and hydrocarbon groups containing up to ten carbon atoms
  • R5 represents hydrogen, methyl, ethyl, or propyl
  • e represents hydrogen, methyl, or ethyl
  • X and Z may be the same or different and represent none (no additional segment present), methylene, ethylene, or p-phenylene
  • the benzylic hydroxyl moiety may be any isomer in the para, meta or ortho position.
  • the hydrocarbon groups of R 2 through R 4 are no more than five hydrocarbon groups and the benzylic hydroxyl moiety may be positioned in the ortho or para position, most preferably the para position.
  • benzylic hydroxyl compounds have three functional groups, a reversible benzylic hydroxyl group available for crosslinking and two primary aliphatic groups available for incorporation into the polymer backbone.
  • the compound owes its unique characteristics to the fact that the benzylic hydroxyl groups are more readily reversible than the aliphatic groups.
  • a polyisocyanate useful with the invention typically includes diisocyantes and other polyisocyanates.
  • Diisocyanates are represented by isophorone diisocyanate (IPDI), TMXDI, phenylenediisocyanate (PDI), toluenediisocyanate (TDI), hexanediisocyanate (HDI); methylenediphenyl- diisocyanate (MDI), naphthalene diisocyanate (NDI), and others disclosed US patent 4,608,418 to Czerwinski et al,, which is hereby incorporated by reference. Additional useful isocyanates are disclosed in US patent 5,097,010 to Markle et al, which is hereby incorporated by reference.
  • Diols useful for making crosslinkers containing benzylic hydroxyl according to the invention include 1,2-ethanediol; propanediols represented by 1,2-propanediol or 1,3-propanediol; butanediols represented by 1,3- butanediol or 1,4,-butanediol; pentanediols represented by 1,5-pentanediol; hexanediols represented by 1,6-hexanediol; and the like.
  • Triols useful for making crosslinkers containing benzylic hydroxyl groups according to the invention include 1,2,3-propanetriol (glycerin), 1,2,3- or 1,2,4-trishydroxybutane, and higher aliphatic triols with at least two of the hydroxyls in the 1,2- position.
  • Preferred crosslinking compounds containing benzylic hydroxyl groups useful with the invention typically include a tetrafunctional crosslinking compound containing from two to four benzylic hydroxyl groups and from none to two aliphatic and primary hydroxyl groups, and a trifunctional crosslinking compound containing from one to three benzylic hydroxyl groups and from none to two aliphatic and primary hydroxyl groups.
  • a typical and preferred benzylic hydroxyl compound is 2- ⁇ [(4-hydroxymethyl)benzyl]oxy ⁇ - 1,3-propanediol (Compound 1).
  • This example illustrates a method for the preparation of a typical benzylic hydroxyl crosslinker useful with the invention.
  • the method produces a trifunctional crosslinking compound containing one benzylic hydroxyl group and two aliphatic and primary hydroxyl groups (2- ⁇ [(4-hydroxymethyl)- benzyl]oxy ⁇ -l,3-propanediol - labeled as Compound 1).
  • Compound 1 was synthesized for incorporation into the backbone of polyurethanes by using its aliphatic hydroxyl groups while leaving its benzylic hydroxyl group available to form reversible urethane-based crosslinks.
  • Intermediate E was prepared to determine if blocking of the benzylic hydroxyl group by a readily removable group (a methoxyacetic acid ester) in Compound 1 was necessary to allow its appropriate incorporation into the urethane backbone.
  • the synthetic route that was developed involves the initial synthesis of Intermediate E which was then deblocked to form Compound l.
  • Intermediate A is composed of two isomers and is named as follows by IUPAC: cis- and trans-2-phenyl-l,3-dioxan-5-ol.
  • a one liter, three neck, round bottom flask was equipped with a Barrett tube attached to a reflux condenser which was attached to an argon inlet via a mineral oil bubbler.
  • This flask which contained a magnetic stir bar and was positioned in a heating mantle, was flushed with argon and then charged with 200 ml of benzene, 160.0 grams (1.51 moles) of benzaldehyde, 150.0 grams (1.63 moles) of glycerin and 1.00 grams of p-toluenesulfonic acid monohydrate.
  • a blanket of argon was kept over the flask during the reaction period.
  • the reaction mixture was refluxed until close to the theoretical amount of water had collected in the Barrett tube and transferred to a one liter separatory funnel.
  • One hundred ml of 0.1M sodium hydroxide was added to achieve pH 9-10 and the mixture was extracted with 350 ml of diethyl ether.
  • the ether extract was first treated with a saturated solution of sodium hydrosulfite (32.75 grams/ 100 ml water) causing the formation of some solid in the ether layer, then washed with water (150 ml), followed by a 5% sodium bicarbonate (100 ml) treatment. After a water wash (2 x 150 ml), the ethereal layer was dried over sodium sulfate overnight.
  • the ether layer was washed with 5 x 120 ml water (pH 2), passed through cotton, dried over sodium sulfate overnight, and then stripped to obtain a yellow-orange liquid (139.1 grams).
  • This material produce a low melting solid when placed in a refrigerator. When brought to ambient temperature, the liquid phase was decanted and the remaining solid was dissolved in a total of 400 ml of dry toluene at room temperature. After addition of 400 ml of hexane, a copious amount of white solid precipitated at room temperature. After this mixture was placed in a refrigerator overnight, a fine white solid was filtered and dried which weighed 74.33 grams (27.4% yield).
  • Intermediate B is composed of tow isomers and is named as follows by IUPAC: cis- and trans-5- ⁇ [4-bromomethyl)benzyl]oxy ⁇ -2-phenyl-l,3-dioxane.
  • a two liter, three neck, round bottom flask equipped with an argon inlet and mechanical stirrer was first flushed with argon and then charged with 1167 ml dimethylsulfoxide (dried over molecular sieves) and 26.10 grams powdered potassium hydroxide (0.466 moles). This mixture was stirred for five minutes and then 21.00 grams 1,3-benzylidene glycerin (0.1165 moles) was added followed by addition (all at once) of 92.26 grams ⁇ , ⁇ '-dibromo-p- xylene (0.3495 moles). The lemon yellow reaction mixture was stirred while maintaining it under an argon blanket (via a mineral oil bubbler) for an additional eighty minutes at ambient temperature.
  • the reaction mixture was then added to a six liter separatory funnel containing 250 grams of ice and 2250 ml of water and considerable yellow solid formed at this point.
  • the aqueous layer was extracted with methylene chloride (a 2000 ml portion followed by 2 x 1300 ml portions).
  • the combined organic layers were split in half, filtered through cotton to remove the yellow solid, and each half was washed with 3 x 1800 ml water.
  • the methylene chloride was passed through a cotton plug and dried over sodium sulfate.
  • the solvent was stripped on a rotating evaporator and the resulting solid was dried in a vacuum oven with phosphorous pentoxide to obtain 88.50 grams yellow solid.
  • Intermediate C is composed of two isomers and is named as follows by IUPAC: cis- and trans-4- ⁇ [(2-phenyl-l,3-dioxan-5-yl)oxy]methyl ⁇ benzyl methoxyacetate.
  • Potassium methoxyacetate was prepared by dissolving 52.47 grams methoxyacetic acid (0.5800 moles) in 150 ml of distilled water in an Erlenmeyer flask and initially adding 32.50 grams potassium hydroxide (nominally 0.580 moles).
  • a 300 ml, three neck, round bottom flask containing a magnetic stir bar and equipped with a reflux condenser and gas inlet tube was positioned in a heating mantle and flushed with argon. This flask was maintained under an argon blanket using a bubbler filled with mineral oil. The flask was charged with 0.9147 grams 18-crown-6 (3.461 mmoles) and 134 ml acetonitrile was transferred from an anhydrous source using syringe techniques. Potassium methoxyacetate (18.85 grams; 0.1471 moles) was added and the milky white suspension was stirred at ambient temperature for 50 minutes to allow coordination of the 18-crown-6 with the potassium ion.
  • Byproduct F was found to be present.
  • Byproduct F is named as follows by IUPAC: bis-l,4- ⁇ [2-hydroxy-l-(hydroxymethyl)ethoxy]methyl ⁇ benzene was found to be present.
  • this material was magnetically stirred with 345 ml methylene chloride for three hours and this mixture was then filtered through a 0.45 micron filter. The filter cake was washed with methylene chloride and dried at ambient temperature under high vacuum to give 0.975 grams Byproduct F.
  • the proton and carbon-13 NMR spectra of Byproduct F were in agreement with its structure.
  • Compound 1 is named as follows by IUPAC: 2- ⁇ [4-(hydroxymethyl) benzyl]oxy ⁇ propane-l,3-diol.
  • Proton and carbon-13 NMR spectra obtained from the second crop were in accord with the structure of Compound 1.
  • Two crops of crystals were obtained from the third recrystallization, the first crop weighing 71 mg and the second crop weighing 35 mg.
  • GC analysis of the first crop indicated that this material was approximately 97 % pure with one slightly later eluting peak representing approximately 2 % of the total peak area.
  • the proton NMR spectrum of the first crop was essentially identical to the spectrum of the second crop obtained by recrystallization described above.
  • IPDI-BD-IPDI isophoronediisocyanate capped 1,4-b.utanediol
  • CHCI 3 Burdick and Jackson B&D
  • a pre-flame-dried, water cooling equipped reflux condenser was placed in the other side joint.
  • the assembled apparatus was all re-flame-dried and cooled while argon flushing.
  • the argon was passed through the top of the dropping funnel, which had a side-arm gas inlet adapter affixed, through the reaction flask, and exited from a gas outlet adapter at the top of the water cooling equipped condenser.
  • the outlet gas was then passed through a mineral oil bubbler to allow adjustment and visual observation of the gas flow rate.
  • the center port of the reaction flask was closed with a 24/40 stopper.
  • reaction flask assembly was removed from its mounted position on the rack, while maintaining a slow argon flush, and 222.5 g (1.00 Mole) of center cut vacuum distilled isophorone diisocyanate (Aldrich 31,62-4, IPDI) was added to the unmounted reaction flask assembly, which was placed on a large torsion balance to accurately weigh the IPDI.
  • the IPDI was poured from the argon flushed 1 liter Pyrex round bottom distillation receiver into which it had been distilled (under argon in a flame dried Pyrex distillation assembly).
  • the theoretical yield of IPDI-BD-IPDI crosslinker was calculated to be 26.9 g (0.0105 Mole BD x 538.74 g/Mole molecular weight of the expected IPDI-BD-IPDI product).
  • 167 grams (11 lcc) of dry B&D CHCI 3 solvent was added to the reaction flask and the assembly was then remounted on the rack in the hood.
  • the separately prepared BD in CHCI3 solution (Erienmeyer flask) was transferred directly to the dropping funnel and rinsed in with three small portions ( ⁇ 10 cc each) of CHCI3 to insure that all BH was transferred, leaving the Fluka 3A molecular sieve in the 2 liter Erienmeyer flask.
  • the reaction flask was then heated to 50°C using a thermostatically temperature controlled mineral oil bath mounted on a lab jack, which was raised until the preheated mineral oil level was well above the level of the magnetically stirred clear, colorless IPDI/CHCI3 solution.
  • the CHCI 3 solvent quickly boiled and refluxed gently.
  • the CHCI 3 /BD solution in the dropping funnel was then added in rapid-dropwise fashion over a 2.5 hour period, while maintaining a steady, slow (1 bubble per 2 or 3 seconds) argon purge.
  • the reaction was maintained at 50°C for 24 hours after BD addition was complete. Then the heat was turned off and the reaction mixture cooled to ambient temperature by removing the 50°C mineral oil bath and letting the mixture stand over the weekend, while maintaining the slow argon purge.
  • the CHCI 3 was then vacuum distilled (stripped) from the reaction flask, while stirring was maintained, by replacing the reflux condenser with a vacuum pump connected through a large capacity, dry ice cooled, trap to collect the distillate.
  • the dropping funnel was also removed and replaced with just the argon inlet adapter. Argon flow was adjusted to nil when vacuum was applied.
  • the mineral oil bath was replaced around the reaction flask and heated only very slightly to maintain a temperature near ambient ( ⁇ 25- 27°C).
  • the CHCI 3 was stripped carefully, to avoid foaming, until 175.9 g of a fairly thin, clear, very light yellow, presumably CHCI 3 free liquid was obtained. Apparently 51.1 g of IPDI had codistilled with CHCI 3 since the total weight of BD + IPDI originally was 227.0 grams.
  • the two product portions were then combined into a 100 cc, flame dried, one neck, Pyrex round bottom flask using several small ( ⁇ 10 cc) amounts of the bone dry CH 2 CI 2 solvent.
  • the CH 2 CI 2 was carefully stripped in a vacuum oven at ambient temperature, then dried overnight in the vacuum oven ( 1 Torr) with mild heating ( ⁇ 35°C). Obtained were 11.87 grams of a clear, very light yellow, extremely viscous oil or liquid. This was a 44.1% yield based on the theoretical yield of 26.94 grams. A significant portion of the product was apparently removed during the hexane precipitation purification process.
  • TMXDI-BD-TMXDI dibutyltindilaurate catalyzed preparation of TMXDI capped 1,4-butanediol crosslinker
  • Example Cl The same two liter reaction flask, magnetic stir bar and handling and flask drying procedures were used as in Example Cl. Thus, 244.3 grams (1.000 mole) of as received l,3-bis(l-isocyanato-l-methyl-ethyl) benzene (TMXDI, CYTEC Industries) were added to the dried and argon flashed reaction flask. Then 4.506 grams (0.050 moles) 1,4-butanediol (BD) were added. The two reactants were immiscible.
  • TXDI l,3-bis(l-isocyanato-l-methyl-ethyl) benzene
  • BD 1,4-butanediol
  • This upper layer consisted of hexane and presumably most of the unreacted TMXDI, which is readily soluble in hexane, as well as some portion of the product codissolved in the hexane/TMXDI mixture. It was decanted and the thin, clear product layer rinsed with about 10 cc of anhydrous hexane twice. The viscous, clear, colorless liquid was redissolved in about 10 cc of dry methylene chloride (CH 2 CI 2 )and reprecipitated in 100 cc anhydrous hexane as before.
  • CH 2 CI 2 dry methylene chloride
  • Compound G 4-Hydroxymethyl-beta-(hydroxyethoxy)benzene, hereafter referred to as Compound G, is reacted with MDI in a mole ratio of two moles of compound G and one mole of MDI. This constitutes an equimolar ratio of aliphatic primary hydroxyl and isocyanate groups.
  • the reaction is carried out by melting together under anhydrous and air-excluded conditions the two component reactants. They are heated while stirring and kept under a very slow purge of inert gas such as dry nitrogen or dry argon. They are heated to a temperature of at least about 180°C and perhaps beneficially to a temperature of about 200°C.
  • the mixture is cooled slowly to the temperature at which the mixture solidifies. This will be done over about a 30-60 minute time period. Obtained will be the bis-hydroxymethyl-capped-diurethane coupled product from the formation of stable urethane bonds between the two primary aliphatic hydroxyethyl groups and the two MDI isocyanate groups.
  • the benzylic hydroxyl groups will be essentially uncombined and will constitute the end of groups of this bis-urethane.
  • EXAMPLE C4 Compound G of the previous example is reacted with the tri-isocyanate compound available commercially.
  • This compound is Compound H from Rhone-Poulenc known as Tolonate® (HDT) Trimer.
  • Compound G is reacted with Compound H in a mole ratio of three moles of Compound G and one mole of Compound H. This constitutes an equimolar ratio of aliphatic primary hydroxyl and isocyanate groups.
  • the reaction is carried out following the procedure of Example C3 obtained will be the tris(hydroxymethyl)-capped-tri- urethane coupled product obtained from the formation of stable urethane bonds between the three primary hydroxyethyl groups of Compound G and the three isocyanate groups of Compound H.
  • the three benzylic hydroxyl groups will be essentially uncombined and will constitute available reactive groups for the formation of reversible urethane crosslinking bonds when combined in a minor amount (less than or equal to 50 mole percent of the hydroxyl groups used) polymer with a major amount (less than or equal to 50 mole percent of the hydroxyl groups used, from di-benzylic hydroxyl compounds or oligomers such as 1,4-benzenedimethanol and/or the di- hydroxymethyl compound product of Example C3.
  • a control polyurethane was prepared without using any Compound 1.
  • Diphenylmethane diisocyanate commonly referred to as methylenediphenyl- diisocyanate (MDI), polybutylene adipate (PBA) with a molecular weight of about 1986 (a high molecular weight polyol with two end group aliphatic- hydroxybutyl-hydroxyl groups), and 1,4-butanediol (BD) were used.
  • MDI and BD were reagent grade chemicals obtained from Aldrich (MDI, Aldrich 25,643-9; BD, Aldrich 24,055-9) but were vacuum distilled before use.
  • the PBA is a commercially available polyurethane polymerization quality aliphatic polyester diol.
  • a post polymerization treatment to insure that polymerization was complete was carried out by heating the polymer mass overnight at 80°C in a vacuum oven set at about 1 Torr.
  • the product, both before and after this vacuum oven treatment was a strong, tough, elastic thermoplastic.
  • a small piece readily dissolved in dry dimethyl formamide (DMF) in several hours at room temperature.
  • a small piece was also submitted for gel permeation chromatography (GPC) molecular weight analysis. This was done using a Waters GPC instrument and columns with tetrahydrofuran (THF) solvent. The GPC was calibrated using four narrow molecular polystyrene standards.
  • the GPC molecular weight of a commercial Spandex-type, melt processible, elastic thermoplastic polyurethane was also measured at the same time.
  • thermoplastic polyurethane elastomer TPE
  • pendant benzylic hydroxyl groups TPE
  • the polymerization was performed in silylated Pyrex reaction tubes ( ⁇ 50 cc volume) equipped with 24/40 joints and using a molten Woods metal bath for heating.
  • a 24/40 adapter with an argon inlet was inserted into the top of the Pyrex reaction tube. Dry argon was slowly, but constantly, flushed through a small opening in the reactor tube during the reaction.
  • the reaction mixture was stirred with a thin stainless steel spatula inserted through a small opening in the top of gas inlet adapter. Constant, slow stirring was performed due to the small scale used and the requirement that ingredients be mixed but not spread upward on the tube surface. This assured that all material was available for reaction.
  • the total hydroxyl content of the reaction mixture was 5.0793 mMole, while the total isocyanate content was 5.0796 mole.
  • the Compound 1 hydroxyl content represented 5 mMolar % replacement of butanediol mMolar hydroxyl content.
  • Table 3 shows the quantities of all components used to prepare the polymer.
  • Example P2 The reactor tube of Example P2 was then removed from the hot Woods metal bath and 2.2250 g of the thermoplastic polyurethane elastomer with pendant benzylic hydroxyl groups was removed (73.85% of the calculated total weight of 3.0129g), thus leaving a calculated quantity of 0.7878 g of the thermoplastic polyurethane (26.15%) (TPE) with (presumably mostly unreacted) pendant benzylic hydroxyl groups in the reaction tube.
  • TPE thermoplastic polyurethane (26.15%)
  • This polymer contained a calculated quantity of 0.0180 mMole of Compound 1.
  • Great care was taken while removing this control polyurethane portion of Example P2, to not leave any polymer deposits on the walls of the reactor tube, above the polymer melt line.
  • the reactor tube was then placed back in the molten metal bath (maintained at about 200°C) and the crosslinker was very carefully and thoroughly mixed into the quite viscous melt over a five minute period.
  • the viscosity of the molten polyurethane was essentially the same as the final melt viscosity of the control TPU in Example PI and the experimental TPU product final melt viscosity in Example P2, both before and after adding the IPDI-BD-IPDI crosslinker. Hence essentially no crosslinking was in evidence at the 200°C reaction temperature.
  • This product a quite viscous but still readily hand-stirrable melt, was then cooled. Very importantly, a small piece of this material when placed in dimethylformamide (DMF) at ambient temperature swelled slightly over 3-4 hours. It did not change (swell) any additional amount after 24 hours more at room temperature. The fact that it did not dissolve showed that it was crosslinked, as desired.
  • DMF dimethylformamide
  • This example illustrates the production of a reversible thermoplastic polyurethane elastomer (TPE) but which contains, at room temperature crosslinked MDI urethane bonds, by using Compound 1 at 5 mole percent replacement of 1,4-BD and an amount of MDI sufficient to provide an isocyanate content that is equivalent to the total hydroxyl content, including the benzylic hydroxyl content.
  • the benzylic urethane crosslinks will be present at room temperature and up to at least about 150°C, but will reverse when heated above this temperature to about 200°C, allowing the TPE to melt
  • the polymerization is performed in silylated Pyrex reaction tubes ( ⁇ 50 cc volume) equipped with 24/40 joints and using a molten Woods metal bath for heating.
  • a 24/40 adapter with an argon inlet is inserted into the top of the Pyrex reaction tube. Dry argon is slowly, but constantly, flushed through a small opening in the reactor tube during the reaction.
  • the reaction mixture is stirred with a thin stainless steel spatula inserted through a small opening in the top of gas inlet adapter. Constant, slow stirring is performed due to the small scale used and the requirement that ingredients be mixed but not spread upward on the tube surface. This assures that all material is available for reaction.
  • 0.1177 g (1.3063 mMole) of 1,4-BD is quantitatively carefully added directly onto the still argon flushed prepolymer mixture from a preweighed 1000 microliter syringe, which is also reweighed after addition of 1,4-BD to insure accurate weight addition by difference.
  • 0.0146 g (0.0688 mMole) of Compound 1 is added, also carefully placing it on top of the reaction mixture.
  • the end capper, diethyleneglycol ethyl ether, 0.0107 g (0.0797 mMole) is then added from a microsyringe, again weighing the syringe before and after the addition. These additions are performed while maintaining the argon flow. As soon as the additions are complete, the reactor tube is lowered back into the Woods metal bath and the mixture is heated at 197-200°C while carefully stirring for 30 minutes.
  • the total reactive hydroxyl content of the reaction mixture is 5.1476 mMole, while the total isocyanate content is 5.1484 mole.
  • the Compound 1 hydroxyl content represents 5 mMolar % replacement of butanediol mMolar hydroxyl content.
  • Table 4 shows the quantities of all components that will be used to prepare the polymer.

Abstract

La présente invention concerne un polymère ayant une structure réticulée, obtenu à partir d'un polyol et d'un isocyanate, les réticulations correspondant à une liaison uréthane obtenue grâce à la réaction d'un groupe hydroxyle benzylique avec un groupe isocyanate.
PCT/US2000/014722 2000-05-25 2000-05-25 Polymeres reticules de maniere reversible, agents de reticulation benzyle, et procede correspondant WO2001092366A1 (fr)

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PCT/US2000/014722 WO2001092366A1 (fr) 2000-05-25 2000-05-25 Polymeres reticules de maniere reversible, agents de reticulation benzyle, et procede correspondant
EP00936379A EP1294789A1 (fr) 2000-05-25 2000-05-25 Polymeres reticules de maniere reversible, agents de reticulation benzyle, et procede correspondant
CA002411001A CA2411001A1 (fr) 2000-05-25 2000-05-25 Polymeres reticules de maniere reversible, agents de reticulation benzyle, et procede correspondant
CN00819680.XA CN1454229A (zh) 2000-05-25 2000-05-25 可逆的交联聚合物、苄基交联剂及方法
AU2000251701A AU2000251701A1 (en) 2000-05-25 2000-05-25 Reversible crosslinked polymers, benzyl crosslinkers and method
US09/722,203 US6559263B1 (en) 2000-05-25 2000-11-24 Reversible crosslinked polymers, benzylic hydroxl crosslinkers and method
US10/404,979 US20040014928A1 (en) 2000-05-25 2003-03-31 Reversible crosslinked polymers, benzylic hydroxyl crosslinkers and method
US10/404,284 US6989466B2 (en) 2000-05-25 2003-03-31 Reversible crosslinked polymers, benzylic hydroxyl crosslinkers and method
US11/338,334 US20060160979A1 (en) 2000-05-25 2006-01-23 Method for forming a crosslinked polymer by temperature control

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WO2004037901A1 (fr) * 2002-10-25 2004-05-06 The Furukawa Electric Co., Ltd. Polymeres reticules recyclables a chaine principale saturee et a points de reticulation urethanne thermiquement reversible
US7910170B2 (en) 2005-10-18 2011-03-22 Valspar Sourcing, Inc. Coating compositions for containers and methods of coating
US8092876B2 (en) 2004-10-20 2012-01-10 Valspar Sourcing, Inc. Coating compositions for cans and methods of coating
US8465846B2 (en) 2003-04-02 2013-06-18 Valspar Sourcing, Inc. Aqueous dispersions and coatings
US8502012B2 (en) 2009-06-16 2013-08-06 The Procter & Gamble Company Absorbent structures including coated absorbent material
US8747979B2 (en) 2009-07-17 2014-06-10 Valspar Sourcing, Inc. Coating compositions and articles coated therewith
US8840966B2 (en) 2009-09-18 2014-09-23 Valspar Sourcing, Inc. Polyurethane coating composition
US10563010B2 (en) 2009-04-09 2020-02-18 The Sherwin-Williams Company Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom

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EP3199575A1 (fr) * 2016-01-29 2017-08-02 Evonik Degussa GmbH Nouvel agent de reticulation d'hetero-diels-alter et son utilisation dans des systemes polymeres a reticulation reversible
KR102579834B1 (ko) * 2018-06-08 2023-09-15 리전츠 오브 더 유니버시티 오브 미네소타 가역적 중합체 네트워크를 멜트 블로잉함으로써 생성되는 가교결합된 부직포

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WO2004037901A1 (fr) * 2002-10-25 2004-05-06 The Furukawa Electric Co., Ltd. Polymeres reticules recyclables a chaine principale saturee et a points de reticulation urethanne thermiquement reversible
US8465846B2 (en) 2003-04-02 2013-06-18 Valspar Sourcing, Inc. Aqueous dispersions and coatings
US8911874B2 (en) 2003-04-02 2014-12-16 Valspar Sourcing, Inc. Aqueous dispersions and coatings
US8142868B2 (en) 2004-10-20 2012-03-27 Valspar Sourcing, Inc. Coating compositions for cans and methods of coating
US9415900B2 (en) 2004-10-20 2016-08-16 Valspar Sourcing, Inc. Coating compositions for aluminum beverage cans and methods of coating same
US8173265B2 (en) 2004-10-20 2012-05-08 Valspar Sourcing, Inc. Coating compositions for cans and methods of coating
US8617663B2 (en) 2004-10-20 2013-12-31 Valspar Sourcing, Inc. Coating compositions for cans and methods of coating
US8092876B2 (en) 2004-10-20 2012-01-10 Valspar Sourcing, Inc. Coating compositions for cans and methods of coating
US10336909B2 (en) 2004-10-20 2019-07-02 The Sherwin-Williams Company Coating compositions for aluminum beverage cans and methods of coating same
US9862854B2 (en) 2004-10-20 2018-01-09 Valspar Sourcing, Inc. Coating compositions for aluminum beverage cans and methods of coating same
US8129495B2 (en) 2005-10-18 2012-03-06 Valspar Sourcing, Inc. Coating compositions for containers and methods of coating
US8519085B2 (en) 2005-10-18 2013-08-27 Valspar Sourcing, Inc. Coating compositions for containers and methods of coating
US7910170B2 (en) 2005-10-18 2011-03-22 Valspar Sourcing, Inc. Coating compositions for containers and methods of coating
US10961344B2 (en) 2009-04-09 2021-03-30 The Sherwin-Williams Company Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom
US10563010B2 (en) 2009-04-09 2020-02-18 The Sherwin-Williams Company Polymer having unsaturated cycloaliphatic functionality and coating compositions therefrom
US8502012B2 (en) 2009-06-16 2013-08-06 The Procter & Gamble Company Absorbent structures including coated absorbent material
US8747979B2 (en) 2009-07-17 2014-06-10 Valspar Sourcing, Inc. Coating compositions and articles coated therewith
US9061798B2 (en) 2009-07-17 2015-06-23 Valspar Sourcing, Inc. Coating composition and articles coated therewith
US9487672B2 (en) 2009-09-18 2016-11-08 Valspar Sourcing, Inc. Polyurethane coating composition
US9206332B2 (en) 2009-09-18 2015-12-08 Valspar Sourcing, Inc. Coating composition including an unsaturated polymer
US9011999B2 (en) 2009-09-18 2015-04-21 Valspar Sourcing, Inc. Coating composition including an unsaturated polymer
US8840966B2 (en) 2009-09-18 2014-09-23 Valspar Sourcing, Inc. Polyurethane coating composition

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