WO1997017380A2 - Compositions polymerisables comprenant des monomeres d'hydrocarbures d'alphaolefines, et procedes d'utilisation - Google Patents

Compositions polymerisables comprenant des monomeres d'hydrocarbures d'alphaolefines, et procedes d'utilisation Download PDF

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WO1997017380A2
WO1997017380A2 PCT/US1996/005227 US9605227W WO9717380A2 WO 1997017380 A2 WO1997017380 A2 WO 1997017380A2 US 9605227 W US9605227 W US 9605227W WO 9717380 A2 WO9717380 A2 WO 9717380A2
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alpha
composition according
polymer
catalyst
group
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PCT/US1996/005227
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English (en)
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WO1997017380A3 (fr
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Katherine A. Brown
William M. Lamanna
Allen R. Siedle
Edward G. Stewart
Penelope J. Swanson
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Minnesota Mining And Manufacturing Company
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Priority to KR1019980703292A priority Critical patent/KR19990067308A/ko
Priority to US08/637,727 priority patent/US5942461A/en
Priority to JP51814297A priority patent/JP2001524134A/ja
Priority to EP96912789A priority patent/EP0859799A2/fr
Publication of WO1997017380A2 publication Critical patent/WO1997017380A2/fr
Publication of WO1997017380A3 publication Critical patent/WO1997017380A3/fr

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    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/14—Monomers containing five or more carbon atoms
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Definitions

  • This invention relates to polymerizable compositions comprising alpha-olefin hydrocarbon monomers and a method for their polymerization, wherein the method is tolerant of both oxygen and water.
  • Catalysts for the polymerization include organometallic complexes of Group VIII metals (CAS version of the Periodic Table), preferably Pd or Ni Methods for polymerizing the polymerizable composition in open air and in the presence of water to provide novel polymers are described.
  • Non-free radical polymerizations of ethylenically-unsaturated monomers are well known .
  • these polymerizations use catalysts instead of initiators to effect polymerizations .
  • Examples of such catalyzed polymerizations include Ziegler-Natta (ZN) polymerizations of alpha-olefins, ring-opening metathesis polymerizations (ROMP) of cyclic olefins, group-transfer polymerizations (GTP), and cationic and anionic polymerizations of activated olefins such as styrene or acryiate esters.
  • ZN and metallocene catalysts for alpha-olefin polymerizations are susceptible to deactivation by adventitious oxygen and water, requiring that such deactivating materials be rigorously excluded from all reagents as well as the reaction vessel.
  • European Patent Application No 454231 describes a polymerization catalyst and a method of polymerizing ethylene, other olefins, and alkynes using a polymerization catalyst whose cationic portion has the formula
  • M is a Group VIII metal
  • L is a ligand or ligands stabilizing the Group VIII metal
  • R is H, a hydrocarbyl radical or a substituted hydrocarbyl radical, and a substituted tetraphenylborate anion as the counterion.
  • a preferred cationic portion has the formula
  • L' is a two-electron donor ligand and L" L" are chelating ligands wherein each L" is a neutral two-electron donor ligand, and M is nickel or palladium.
  • All olefin polymerizations were conducted with ethylene, were carried out under dry, oxygen-free nitrogen atmospheres and all solvents were thoroughly dried under nitrogen by distillation from, e.g., sodium/benzophenone. High polymer (M w > 90,000) was not disclosed.
  • R 1 is H or methyl, or the two R 1 s taken together are 1,8-naphthalene-diyl, i.e. ,
  • COD 1,3-cyclooctadiene
  • U.S. Patent No . 5,296,566 describes certain organometallic catalysts for ROMP of ring-strained cyclic olefins that are stable towards oxygen and water. However, these catalysts are ineffective for polymerization of linear alpha-olefin monomers.
  • Japanese Patent Application No. JP 0725932 describes Group VIII catalysts (such as Ni) which polymerize ethylene.
  • U.S. Patent No 4,724,273 describes the use of nickel catalysts to polymerize alpha-olefins, yielding polymers with methyl branching points.
  • U.S. Patent No 5,030,606 describes nickel-containing catalysts which are useful for producing copolymers of ethylene and polar or non-polar comonomers.
  • the present invention describes a polymerizable composition
  • a polymerizable composition comprising one or more alpha-olefin hydrocarbon monomers, an effective amount of an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Ni or Pd, and a polydentate ligand providing steric bulk sufficient to permit formation of high polymer, and at least one of water and air.
  • an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Ni or Pd
  • a polydentate ligand providing steric bulk sufficient to permit formation of high polymer, and at least one of water and air.
  • the invention describes a method of polymerizing a composition, the composition comprising at least one alpha-olefin monomer, as catalyst an effective amount of the above-mentioned organometallic catalyst comprising a Group VIII metal, preferably Ni or Pd, and at least one of water and air.
  • the present invention provides an alpha-olefin polymer comprising a plurality of C 3 or larger alpha-olefin units wherein the polymer M w is greater than 90,000, preferably greater than 100,000, and the polymer has an average number of branch points less than one per alpha-olefin unit.
  • the present invention provides a mixture comprising an alpha-olefin polymer comprising at least one of 1) a plurality of C 3 or larger alpha-olefin units wherein the polymer has an average number of branch points less than one per monomer unit, and 2) a plurality of C 2 alpha-olefin units wherein the polymer has an average number of branch points greater than 0 01, preferably greater than 0 05, per alpha-olefin unit, the mixture further comprising water in an amount sufficient to form a second phase.
  • the polymer M w is greater than 90,000, and most preferably greater than 100,000.
  • the present invention provides crosslinked alpha-olefin polymers
  • a method employing high-energy irradiation of the polymer preferably by electron beam irradiation, is used
  • a method employing ultraviolet (UV) irradiation is used, preferably further comprising the addition of UV-activated crosslinking agents.
  • the present invention provides improved one-part catalysts which are organometallic salts useful for the polymerization of alpha-olefin monomers in the presence of at least one of water and air.
  • two-part catalysts comprising a neutral
  • organometallic compound and a cocatalyst useful for the polymerization of alpha-olefins, optionally in the presence of one or both of air and water, and methods of preparation thereof, are also provided.
  • the present invention provides an improved method of preparing an organometallic catalyst wherein a neutral organometallic compound is reacted with a salt of a non-coordinating counterion to give an organometallic salt as catalyst and a halide salt as by-product. Variations of the method involve different process conditions, to give one-part and two-part catalysts Different variations may be preferred in specific applications.
  • alpha-olefin and alpha-olefin hydrocarbon are equivalent and mean a hydrocarbon containing a double bond in the 1 -position, more particularly, ethylene or a 1-olefin containing three or more carbon atoms which can be acyclic or cyclic and preferably is an acyclic alpha-olefin;
  • alpha-olefin polymer means a polymer formed from at least one alpha olefin monomer which, not considering end groups, contains an average of two bonds connecting each monomer unit to other monomer units;
  • branch point means a CH unit in the polymer, bonded to three other carbon atoms, e.g.,
  • stereo bulk means a size large enough and a location in the ligand sufficient to physically block access to non-polymerizing sites on the metal;
  • alpha-olefin unit means a group of carbon atoms in a polymer derived by polymerization from a single alpha-olefin molecule
  • high polymer means a polymer having a weight average molecular weight (M w ) greater than 90,000, preferably greater than 100,000;
  • poly means two or more;
  • organometallic catalyst means a catalyst comprising a Group VIII metal, preferably one of Pd and Ni, a bidentate ligand having steric bulk sufficient to permit formation of high polymers, and a metal to R bond, wherein R is H, a hydrocarbyl radical, or a hydrocarbyl radical substituted by at least one alkyl, haloalkyl or aryl group, each group having up to 20 carbon atoms;
  • group means a chemical species that allows for substitution or which may be substituted by conventional substituents that do not interfere with the desired product;
  • Me means methyl (CH 3 -);
  • Et means ethyl (CH,CH 2 -);
  • i-Pr means isopropyl
  • gel fraction means the fraction of polymer that is insoluble in an appropriate solvent, e.g., toluene, particularly after crosslinking
  • polymerization reactions of the invention proceed in the presence of air and/or water at useful rates and produce in high yields high polymers that have useful properties.
  • Water may occur naturally in the monomer, especially in liquid monomer.
  • the polymerization reaction can even be carried out successfully in systems in which water is present or added in amounts sufficient to form a second (aqueous) phase. It is advantageous to be able to eliminate the costs and process steps associated with drying and deoxygenating monomers and solvents.
  • Neither ZN nor metallocene catalysts containing Periodic Groups IIIB, IVB, or VB metals are active in the presence of oxygen or water.
  • Cocatalysts such as alkylaluminum compounds,
  • methylaluminoxane, alkyl zinc compounds and the like are also sensitive to air and moisture and are not useful under the conditions in this invention and
  • organometallic catalysts employing these cocatalysts are outside the scope of this invention.
  • useful polymers are made from the polymerizable compositions described herein. Depending on the process conditions, such as the amount of air or water present, the amount and type of catalyst, and the monomer or monomer(s) selected, polymers having different properties can be produced. Certain of these polymers may be preferred for specific applications.
  • the polymers of the invention find use as functional and decorative coatings, as molded or extruded articles, and as binders.
  • a distinct aqueous phase is present in the polymerizable composition such as in aqueous emulsion or suspension polymerizations and provides processing advantages such as reduction or elimination of organic solvents. Also, it provides a thermal sink to aid in process temperature control.
  • a distinct aqueous phase is present in addition to the polymer and this mixture provides processing advantages such as lower overall viscosity.
  • compositions comprising two or more monomers and copolymers produced from such compositions are also within the scope of the present invention.
  • the present invention describes a polymerizable composition
  • a polymerizable composition comprising an alpha-olefin hydrocarbon monomer, an effective amount of an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Ni or Pd, and a polydentate ligand having steric bulk sufficient to permit formation of high polymer, and at least one of water and air (oxygen).
  • an organometallic catalyst comprising a Group VIII metal (CAS version of the Periodic Table), preferably Ni or Pd
  • a polydentate ligand having steric bulk sufficient to permit formation of high polymer, and at least one of water and air (oxygen).
  • Alpha-olefin hydrocarbon monomers useful in the invention include substituted and unsubstituted, including acyclic, branched, and cyclic alpha-olefins, wherein substituents on the olefin do not interfere with the polymerization process.
  • substituents on the olefin include carboxylic acid and ester groups.
  • Alpha-olefins preferred for polymerizations of the invention can have from 2 to about 30 carbon atoms, and include acyclic alpha-olefins such as ethylene, propene, 1 -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and the like, and cyclic alpha-olefins such as cyclopentene, and combinations thereof.
  • acyclic alpha-olefins such as ethylene, propene, 1 -butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eico
  • alpha-olefins include propene, 1 -butene, 1-hexene, 1 -octene, and other alpha-olefins up to about C 20 .
  • liquid monomers are preferred, and higher boiling alpha-olefins, e.g., 1-octene to about 1-hexadecene, are particularly preferred.
  • More than one monomer may be present in the polymerizable composition, and copolymers of two or more different monomers are within the scope of this invention.
  • Copolymers may be random or blocky (block copolymers), depending on polymerization kinetics and processes.
  • Useful comonomers can include other alpha-olefins, alkyl acrylates and methacrylates, and acrylic and methacrylic acids and salts thereof.
  • Organometallic catalysts useful in the invention comprise metals of Periodic Group VIII, ligands providing steric bulk sufficient to permit formation of high polymers, and a metal to R bond, wherein R is H, a hydrocarbyl radical, or a hydrocarbyl radical substituted by at least one of alkyl, haloalkyl or aryl groups
  • Periodic Group VIII metals include Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt, and preferred metals are Co, Ni and Pd Ni and Pd are especially preferred, and Pd is most preferred
  • Ligands (L) can be selected so that, when they are coordinated to the metal atom, they are of sufficient size so as to block steric access to certain coordination sites on the metal atom
  • Preferred catalysts comprise ligands that are chelating.
  • Chelating means that a ligand molecule contains two or more atoms or groups of atoms that are able to form coordinate links to a central metal atom.
  • Preferred atoms or groups of atoms are two-electron donors, preferably containing nitrogen, more preferably containing an imine group.
  • Most preferably a chelating ligand comprises two imine groups. Imine groups bearing a substituted or unsubstituted group on the nitrogen are preferred, more preferably such groups are polysubstituted aryl, and most preferably they are 2,6-disubstituted aryl.
  • Substitutents on the aryl ring include alkyl, haloalkyl, and aryl, preferably alkyl, more preferably methyl or isopropyl, and most preferably isopropyl.
  • Catalysts also comprise an atom or group R, defined below, which preferably is H or methyl, most preferably methyl.
  • Organometallic catalysts useful in the invention can be one-part or two-part.
  • One-part catalysts are organometallic salts of a Group VIII metal and a polydentate ligand having steric bulk sufficient to permit formation of high polymer, and an anion selected from the group consisting of B(C 6 F 5 ) 4 -, PF 6- , SbF 6 -, AsF 6- , BF 4- , B ⁇ 3,5-C 6 H 3 (CF 3 ) 3 ⁇ 4- , (R f SO 2 ) 2 CH-, (R f SO 2 ) 3 C-, (R f SO 2 ) 2 N-, and R f SO 3- , wherein R f is as defined below, which, when added to monomer, can immediately begin to form polymer, such that no additional reagents or further reactions are necessary to generate an active polymerization catalyst.
  • Such catalysts are advantageous in certain processes, particularly when it is desired that a catalyst is to be added to the reaction mixture immediately before polymerization is to begin.
  • Such catalysts can be useful in batch reactions used to prepare polymer.
  • One-part catalysts can be isolated and are essentially pure compounds.
  • One-part catalysts are preferably cationic complexes, and further comprise non-coordinating counterions.
  • M is a Group VIII metal
  • L is a two-electron donor ligand or ligands, as defined above, stabilizing the Group VIII metal
  • R is H, a hydrocarbyl radical or a substituted hydrocarbyl radical, wherein the substituting groups can be alkyl (1 to 10 carbon atoms), aryl (5 to 20 carbon atoms), or halogen substituted alkyl.
  • M is exemplified as cobalt and a substituted tetraphenylborate anion is described as the counterion.
  • Preferred in the reference is tetraarylborate with (CF 3 ) substituents and B ⁇ 3,5-C 6 H 3 (CF 3 ) 2 ⁇ 4 - . is exemplified
  • a preferred cationic portion has the formula
  • each L 1 is a two-electron donor ligand as defined above, and M and R are as previously defined.
  • Pd(II)- and Ni(II)-based catalysts for olefin polymerizations are cationic metal methyl complexes of the general formula
  • a preferred catalyst is
  • R 2 can be -CH 3 , t-butyl, or -CH 2 (CF 2 ) 6 CF 3 , as reported by Johnson et al. (J. Am. Chem. Soc, 1996, 118, 267-268 and supplementary material) to be useful in inert atmospheres.
  • the present invention provides new compositions of matter useful as one-part catalysts.
  • One preferred counterion is B(C 6 F 5 ) 4- , which is safer to prepare than B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 -, as judged by the number of reported explosions, and is commercially available from Boulder Scientific Company, Mead, CO, and provides better control over polymer molecular weight.
  • Multiple reports have appeared concerning the hazards associated with the preparation of trifluoromethyl-substituted tetraarylborate compounds, including the explosion of intermediate aryl magnesium compounds (see I C. Appleby, Chemistry and
  • polymerizable compositions comprising a second (aqueous) phase.
  • anions useful as the anionic portion of the catalysts of the present invention may be generally classified as fluorinated (including highly fluorinated and perfluorinated) alkyl- or arylsulfonyl-containing compounds, as represented by Formulas XIIa through Xlld:
  • each R f is independently selected from the group consisting of highly fluorinated or perfluorinated alkyl or fluorinated aryl radicals.
  • Compounds of Formulas Xlla, Xllb and XIIc may also be cyclic, when a combination of any two R f groups are linked to form a bridge.
  • the R f alkyl chains may contain from 1-20 carbon atoms, with 1-12 carbon atoms preferred.
  • the R f alkyl chains may be straight, branched, or cyclic and preferably are straight. Heteroatoms or radicals such as divalent non-peroxidic oxygen, trivalent nitrogen or hexavalent sulfur may interrupt the skeletal chain.
  • R f is or contains a cyclic structure, such structure preferably has 5 or 6 ring members, 1 or 2 of which can be heteroatoms.
  • the alkyl radical R f is also free of ethylenic or other carbon-carbon unsaturation: e.g., it is a saturated aliphatic, cycloaliphatic or heterocyclic radical.
  • highly fluorinated is meant that the degree of fluorination on the chain is sufficient to provide the chain with properties similar to those of a perfluorinated chain. More particularly, a highly fluorinated alkyl group will have more than half the total number of hydrogen atoms on the chain replaced with fluorine atoms. Although hydrogen atoms may remain on the chain, it is preferred that all hydrogen atoms be replaced with fluorine to form a perfluoroalkyl group, and that any hydrogen atoms beyond the at least half replaced with fluorine that are not replaced with fluorine be replaced with bromine and/or chlorine.
  • At least two out of three hydrogens on the alkyl group be replaced with fluorine, still more preferred that at least three of four hydrogen atoms be replaced with fluorine and most preferred that all hydrogen atoms be replaced with fluorine to form a perfluorinated alkyl group.
  • the fluorinated aryl radicals of Formulas Xlla through Xlld may contain from 6 to 22 ring carbon atoms, preferably 6 ring carbon atoms, where at least one, and preferably at least two, ring carbon atoms of each aryl radical is substituted with a fluorine atom or a highly fluorinated or perfluorinated alkyl radical as defined above, e.g. , CF 3 .
  • anions useful in the practice of the present invention include:
  • F in the ring means the ring carbon atoms are perfluorinated, and the like. More preferred anions are those described by Formulas Xllb and XIIc wherein R f is a perfluoroalkyl radical having 1-4 carbon atoms.
  • Anions of this type, and representative syntheses, are described in, e.g., U.S. Patent Nos 4,505,997, 5,021,308, 4,387,222, 5,072,040, 5, 162, 177, and
  • diethyl ether can be useful but it is preferable to avoid its use because it can be dangerous to store and handle due to its extreme flammability and tendency to form explosive peroxides.
  • Alternative useful ethers are organic compounds containing one ether-type oxygen atom and include tetrahydrofuran and methyl t-butyl ether. Methyl t-butyl ether is particularly preferred.
  • the present invention provides improved one-part catalysts useful for the polymerization of alpha-olefin monomers. These catalysts are designed with the advantages of improved counterions and ethers, and are new compositions of matter. Preferred compositions can be of the formula
  • Q can be selected from B(C 6 F 5 ) 4 , anions as shown in Formulas XIIa through Xlld, PF 6 , SbF 6 , AsF 6 , and BF 4 .
  • Particularly preferred are compounds wherein ether is methyl t-butyl ether and Q is selected from B(C 6 F 5 ) 4 and anions as shown in Formulas Xlla through Xlld.
  • Examples of preferred novel one-part catalysts include:
  • Two-part catalysts comprise two reagents, a neutral organometallic compound and a cocatalyst salt, that react upon mixing optionally in the presence of monomer to yield an active catalyst.
  • Two-part catalysts are particularly
  • Two-part catalysts may also allow for the in situ generation of active catalytic compounds which cannot be isolated, and may also be preferred for those situations where the added time and expense of isolating a one-part catalyst are not warranted.
  • Two-part catalysts preferably comprise a neutral organometallic Pd or Ni compound which includes a ligand or ligands as previously defined, a moiety R which is H, hydrocarbyl radical, or substituted hydrocarbyl radical, and a halogen atom (preferably chlorine), and a cocatalyst.
  • Preferred neutral compounds can be of the general formula
  • X represents a halogen atom, preferably chlorine or bromine, most preferably chlorine.
  • Examples of preferred neutral compounds include:
  • Especially preferred neutral compounds include
  • Useful cocatalyst salts are of the general formula
  • a + Q- wherein A is selected from silver, thallium, and metals of Periodic Group IA, and Q is selected from B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 , B(C 6 F 5 ) 4 , anions as shown in Formulas Xlla through Xlld, PF 6 , SbF 6 , AsF 6 , and BF 4 , and solvates and hydrates thereof.
  • silver salts are preferred and can have the formulae
  • ne can be an aromatic hydrocarbon group having 6 to 18 carbon atoms that can be substituted by up to 6 alkyl or aryl groups each having up to 12 carbon atoms, preferably arene can be benzene, toluene, ortho-, meta-, or para-xylene, and mesitylene, and p can be an integer 1, 2, or 3.
  • the less expensive alkali metal salts Periodic Group 1A
  • Particular counterions may be preferred under specific reaction conditions. For example, in two-part systems comprising a second aqueous phase, B(C 6 F 5 ) 4 is preferred .
  • Examples of preferred cocatalyst salts include: Ag + ⁇ B(C 6 F 5 ) 4 ⁇ -(toluene) 3 , Ag + ⁇ B(C 6 F 5 ) 4 ⁇ -(xylene) 3 , Ag + ⁇ B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ⁇ - (toluene), Li + ⁇ B(C 6 F 5 ) 4 ⁇ -, Na + ⁇ B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ⁇ -, Li + ⁇ N(SO 2 CF 3 ) 2 ⁇ -, Li + ⁇ B(C 6 F 5 ) 4 ⁇ -(Et 2 O) 2 , Li + ⁇ N(SO 2 CF 3 )(SO 2 C 4 F 9 ) ⁇ -, Li + ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ -, Li
  • One- and two-part catalysts can be present in the invention mixture in the range of 0 0001 to about 3 weight percent, preferably 0 001 to 1 weight percent.
  • the present invention provides an improved method of preparation of organometallic catalyst .
  • a neutral organometallic compound is reacted with a salt of a non-coordinating counterion preferably comprising fluorine (F) to give an organometallic catalyst and a halide salt as by-product.
  • a salt of a non-coordinating counterion preferably comprising fluorine (F)
  • F fluorine
  • excess A + Q- may be preferred since A + Q- may function as a surfactant in the reaction mixture.
  • the first variation of the method provides a one-part catalyst by reacting the silver salt of a non-coordinating counterion Ag + Q-, wherein Q is as defined above, or solvate thereof with a neutral organometallic compound of the formula
  • halogen is Cl, Br, or I, preferably Cl or Br, most preferably Cl.
  • the reaction is conducted in an ether solvent, or mixture of solvents containing an ether at or near room temperature (20° to 25°C)
  • the one-part catalyst is isolated from the reaction mixture by removal of solvent
  • filtration to remove and recover AgCI by-product and further purification by methods such as solvent extraction (for example, dissolution of catalyst in an organic solvent such as CH 2 Cl 2 , optional filtration, washing of this solution with a portion of water, and removal of organic solvent) or recrystallization are apparent to those skilled in the art and are within the scope of this invention.
  • One-part Pd catalysts have been prepared according to this method with various counterions, including ⁇ N(SO 2 C 4 F 9 ) 2 ⁇ - , ⁇ CH(SO 2 CF 3 ) 2 ⁇ -, (SO 3 CF 3 )-, (SbF 6 )-, (BF 4 )-, and (PF 6 )-.
  • This method is particularly preferred for counterions wherein the corresponding silver salt is readily available. It is also a useful method for rapid synthesis when water-sensitive counterions are used.
  • the organic layer is separated from solid AgCI (which may be recovered and recycled) and the aqueous layer, and removal of solvent produces clean one-part Pd catalyst in good yield.
  • This method is preferred because it provides for rapid synthesis of one-part catalyst in good yield, and does not require the preparation and isolation of the silver salt of a non-coordinating counterion.
  • a fourth variation of the method provides two-part catalysts.
  • a neutral organometallic compound as defined in the third variation is used in combination with a cocatalyst comprising a silver salt of a non-coordinating counterion.
  • the advantages of two-part catalysts have been previously described.
  • a fifth variation of this method provides two-part catalysts useful in two-phase systems.
  • This variation of a two-part catalyst comprises a neutral organometallic compound as described above and a cocatalyst of a Group IA metal in a two phase system.
  • Such a catalyst system may be preferred because the second (preferably aqueous) phase provides a heat sink which moderates polymerization exotherms.
  • This variation also avoids the expense of silver-containing reagents. In the presence of an aqueous phase, these two-part catalysts rapidly initiate polymerization.
  • Adjuvants optionally useful in any of the methods of catalyst synthesis of the invention include solvents such as methylene chloride, and the like
  • Additives, adjuvants and fillers as are known in the art can be added to the polymerizable composition of the invention, providing they do not interfere with the intended polymerization process or adversely affect the chemical and physical properties of the resultant polymers.
  • Additives, adjuvants and fillers can include, but are not limited to, glass or ceramic microspheres or microbubbles, pigments, dyes, or other polymers.
  • Adjuvants may be present in the composition in the range of 0 1 to 90 weight percent.
  • stabilizers containing phosphorus are also known as additives in polymers. These secondary antioxidants halt polymerization. They can therefore be useful for stopping polymerization as, for example, when it is desired to prevent formation of very viscous solutions, and they may also provide other benefits, for example, lighter color, but they are not usefully added to monomer prior to polymerization . Sulfur containing compounds such as thiols are also useful in halting polymerization, as are strong oxidants such as bleach (sodium hypochlorite).
  • Monomers or comonomers containing organic functional groups such as carboxylic acids, and carboxylic acid salts and carboxylic esters, can also be useful in the invention. Such monomers may be useful to modify polymer properties.
  • aqueous phase When water is present in major amounts above the solubility limit of the organic phase, it forms a second (aqueous) phase which can provide process advantages such as lower overall viscosity, higher polymer molecular weight or yield, temperature control, reduction or elimination of organic solvents, and is preferred in certain applications.
  • the aqueous phase may be continuous, discontinuous, or cocontinuous with the organic phase.
  • Polymerizable compositions may further comprise surfactants.
  • Surfactants are preferred when a second aqueous phase is present. Ionic surfactants are preferred.
  • Suitable surfactants include sodium and ammonium sulfonates
  • Specific examples of suitable surfactants include sodium heptadecyl sulfate, sodium lauryl sulfate, and ammonium lauryl sulfate.
  • Certain surfactants contain groups which reduce catalyst activity, and these should be avoided in the practice of this invention.
  • polyether groups and halides such as are found in polyether sulfonate or tetraalkylammonium halide surfactants, should be avoided
  • Surfactants can be present in the composition in the range of about 0.01 to 5 weight percent .
  • the present invention also is directed toward a method of polymerizing a composition comprising at least one alpha-olefin monomer, an effective amount of an organometallic complex of a Group VIII metal, preferably Ni or Pd, as a catalyst, and at least one of water and air.
  • a composition comprising at least one alpha-olefin monomer, an effective amount of an organometallic complex of a Group VIII metal, preferably Ni or Pd, as a catalyst, and at least one of water and air.
  • polymerizations of the invention have been demonstrated to take place both in open air and in the presence of water.
  • the above-mentioned one- or two-part palladium catalyst is mixed with the alpha-olefin monomer (for example, 1-octene) in a container and polymerization is allowed to proceed.
  • organic solvents may be used to dissolve or disperse catalysts and may be present in amounts from about 0 5 to 99 percent by weight.
  • Polymerizations can be conducted at various temperatures.
  • the reaction temperature is -78° to +35° C, more preferably -40° to +25° C, and most preferably -10° to +20° C
  • Temperatures above about 40° C may deactivate the catalyst, and good thermal control may be preferred since the polymerization of alpha-olefin monomers is exothermic. It may be particularly advantageous to employ a second aqueous phase as a heat sink to aid in the control of reaction temperature.
  • Polymerizations can be conducted at pressures greater than atmospheric, particularly in cases where one or more of the monomers is a gas. However, to avoid the expense of pressurized reaction vessels, liquid monomers may be preferred.
  • catalyst and monomer can be mixed and coated onto a substrate, and the mixture allowed to polymerize without protection from the ambient atmosphere.
  • Particularly preferred are monomers with boiling points greater than about 100°C. , such as 1-octene and higher alpha-olefin monomers. Variations in "temperature, concentration and the like may be employed. See:
  • Water can be present in the polymerizable composition and during polymerization in the range of 0.001 up to 99 weight percent of the total composition.
  • Water may be present in minor amounts when care is not taken to dry the monomer or optional organic solvents. Preferably it is present in naturally-occurring amounts, in monomers as supplied and handled in air. For example, water is soluble in 1-hexene to the extent of approximately 480 parts per million at room temperature, and such concentration is within the scope of the present invention, since water at that concentration is known to deactivate ZN and metallocene catalysts.
  • Monomers are often supplied with varying amounts of water, from 0.001 weight percent up to the maximum solubility of water in the monomer, depending on temperature, specific monomer, ambient humidity, storage conditions, and the like.
  • Optional solvents similarly contain varying amounts of water.
  • Oxygen can be present in an amount of 0.001 to about 2 weight percent or more of the total composition.
  • Monomers and solvents may contain varying amounts of oxygen from the atmosphere depending on temperature, specific monomer or solvent, storage conditions, and the like.
  • Oxygen can also be present in atmospheric amounts in environments surrounding the polymerizable mixture, such as headspace in a reaction vessel It is advantageous to avoid the expense and process steps of drying and deoxygenating monomer and solvent.
  • polymerization of the present invention monomers can take place when water is present in sufficient amount to form a second aqueous phase.
  • Surfactants can be added to the aqueous phase prior to or after addition of a mixture of monomer and catalyst, or in any other useful sequence.
  • process conditions such as stirring rate, amount of surfactant, and other additives, polymer particles of different properties, including particle size, may be formed. Agglomeration of polymer may occur, again depending on variables such as monomer, reaction temperature, and additives, and is desirable in some processes (for example, where polymer is to be separated from the water) and undesirable in others (for example, where polymer is to be coated from the aqueous mixture).
  • the present invention provides alpha-olefin polymers comprising a plurality of C 3 or larger alpha-olefin units wherein the polymer M w is greater than 90,000, preferably greater than 100,000, and the polymer has an average number of branch points less than one per alpha-olefin unit
  • polymers obtained using catalysts of the invention consist essentially of two types of repeating units: ⁇ -CH 2 -CHR 4 - ⁇ x and ⁇ -(CH 2 ) n - ⁇ y wherein n is the number of carbon atoms in the alpha-olefin monomer used to make the polymer and R 4 is ⁇ CH 3 (CH 2 ) (n-3) - ⁇ .
  • the number of branched units ⁇ -CH 2 -CHR 4 - ⁇ is less than the total number of monomer units in the polymer, that is x has a value from 0.01 to 0.99, preferably 0.20 to 0.95, more preferably 0.40 to 0.90, and (x + y) has a value of 0.90 to 1.00
  • the polymer structure will vary as the monomer or monomers used in the polymerizable composition vary.
  • a polymer made from 1-octene that is, n is 8 has a structure consisting essentially of ⁇ -CH 2 -CH(n-hexyl)- ⁇ x and ⁇ -(CH 2 ) 8 - ⁇ y , wherein x is in the range 0.45 to 0.70, and (x + y) is in the range 0.90 to 0 98.
  • a polymer made from 1-hexene, that is, n is 6, has a structure consisting essentially of ⁇ -CH 2 -CH(n-butyl)- ⁇ x and ⁇ -(CH 2 ) 6 - ⁇ y , wherein x is in the range 0.50 to 0.75, and (x + y) is in the range 0 90 to 0.98.
  • x is in the range 0.50 to 0.75
  • (x + y) is in the range 0 90 to 0.98.
  • a high polymer (M w over 90,000, preferably over 100,000, up to about 10,000,000, preferably up to about 2,000,000) is highly desirable, resulting in improved product performance.
  • High polymers can be obtained by, for instance, an appropriate choice of catalyst-to-monomer ratio.
  • high polymers can be obtained by continuing the polymerization reaction essentially to completion, that is, consumption of substantially all available monomer.
  • a crosslinked polymer provides better product performance.
  • Crosslinking may be accomplished during the polymerization reaction by copolymerization with a polyfunctional monomer, or may be effected by chemical reactions brought about by thermal means or actinic radiation, including high energy sources such as electron beams, gamma radiation, or ultraviolet irradiation, occurring after polymerization .
  • Crosslinked polymers are within the scope of this invention.
  • Polyolefins prepared using organometallic catalysts described above, especially those comprising Ni or Pd, can be crosslinked via irradiation with electron beams at dosages preferably in the range of 20 MRad or less, more preferably 10 MRad or less. It is known that polyethylene can be crosslinked to produce a useful material upon irradiation without significant polymer degradation whereas polypropylene degrades much faster than it crosslinks, and polyolefins prepared via traditional Ziegler-Natta polymerizations are only modestly affected by irradiation. However, treatment of polyolefins of the present invention with electron beams produces crosslinked polymers as indicated by the presence of a polymer gel fraction.
  • the crosslinked polyolefins are free of added chemical crosslinking agents that might otherwise impair the chemical or physical properties of the polymer or be disadvantageous in subsequent use, for example, due to color or leaching.
  • electron-beam crosslinking can be carried out after fabrication or other processing of the polyolefin by, e.g., extrusion, solvent casting, coating, molding, and the like, to give crosslinked shaped articles such as fibers, tubes, blocks, profiles, films, and the like.
  • Other useful high-energy sources are known, and are within the scope of the present invention.
  • Polymers of the present invention can also be crosslinked by ultraviolet irradiation.
  • additives that absorb ultraviolet light and subsequently react to give radicals by homolytic cleavage and/or hydrogen abstraction are mixed with the polymer prior to irradiation
  • Typical additives include trihalomethyl-substituted s-triazines (such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine), aryl alkyl ketones (such as acetophenone, benzoin ethers, and ketals of benzil), and diaryl ketones (such as benzophenone and anthraquinone).
  • Crosslinking by ultraviolet irradiation is preferred in certain processes and product constructions, wherein it is necessary to process an uncrosslinked polymer, as in a solution or an extrusion process, prior to crosslinking.
  • Alpha-olefin polymers of the present invention are useful as molded or extruded articles, as functional or decorative coatings, and as binders.
  • the ligand was prepared according to the procedure described in H. t. Dieck, M. Svoboda, T Greiser Z. Naturforsch. 36b, 823-832.
  • a mixture of 625 mL methanol, 41 .7 g 2,3-butanedione, 171.75 g 2,6-diisopropylaniline and 6.75 g formic acid was prepared in air, then stirred under nitrogen atmosphere at ambient temperature for approximately 18 hr. A yellow precipitate formed, and was collected by filtration.
  • This ligand can be handled and stored in air.
  • the compound was prepared according to the procedure described in R. Rulke, J. M. Ernsting, A. L. Spek, C. . Elsevier, P. W. N. M. van Meeuwen, K. Vrieze Inorg. Chem., 1993, 32, 5769-5778. All procedures were conducted in a dry nitrogen atmosphere.
  • This neutral organometallic compound was prepared according to the procedure described in L. K. Johnson, C. M. Killian, M Brookhart J. Am. Chem. Soc, 1995, 117, 6414-6415 and supplementary material.
  • 31.64 g (1,5-cyclooctadiene)Pd(Me)Cl (synthesis B, above) was placed in 375 mL of dry deoxygenated diethyl ether.
  • Ag(toluene) 3 B(C 6 F 5 ) 4 was prepared as follows, and is referred to as Ag-A throughout these examples. Under a nitrogen atmosphere, using dry, oxygen-free solvents, a solution of 200 mL hexane, 50 mL diethyl ether, and 17.29 g BrC 6 F 5 was cooled to -78°C. Thirty mL of 2.5 M n-BuLi in hexane was added all at once with stirring. The reaction was stirred for 30 minutes, during which time an orange precipitate formed. (CAUTION!
  • This example illustrates the polymerization of 1-octene (C 8 ) in air
  • Catalyst was prepared from 121 mg Pd-A and 190 mg Ag-A in 10.14 g tetrahydrofuran.
  • Sample 2-A comparative
  • a 1 4 g portion of the catalyst solution was mixed with 4.70 g of dry, oxygen-free C 8 in inert atmosphere.
  • Sample 2-B 0.75 g of catalyst solution was mixed with 4.8 g C 8 in air.
  • Sample 2-C 1 .5 g of catalyst solution was placed in a vial, and solvent was removed. The resulting solids were mixed with 5 .0 g C 8 in air Samples 2-A and 2-B became viscous within 15 minutes, forming polymer at similar rates. Sample 2-C became viscous and hot (due to the polymerization exotherm) within ten minutes.
  • Samples 2-A and 2-B showed that polymerization was occurring at comparable rates in air and inert atmosphere, note that 2-B contained less catalyst than 2-A.
  • Sample 2-C showed a 100 percent solids (no solvent) formulation, which polymerized at a faster rate.
  • This example illustrates the polymerization of propylene (C 3 ) in air.
  • the monomer is a gas at ambient temperature and pressure, so the polymerization was conducted in a high pressure reactor.
  • Catalyst was prepared from 260 mg Pd-A and 441 mg Ag-A in 6.49 g diethyl ether. Ether was removed, and the resulting solids were mixed with 26 g CH 2 Cl 2 in air. The catalyst solution was placed in the reactor, which was then cooled to below -24°C, evacuated (so as to maximize the amount of C 3 that could be charged to the reactor) and filled with 150 g C 3 . The reactor was shaken and allowed to warm at room temperature over a period of about four hours, then left for an additional 20 hours. Excess C 3 was vented, and 30 g of polymer was recovered from the reactor.
  • This example illustrates a polymerizable composition
  • a polymerizable composition comprising alpha-olefin monomer, catalysts, and water in an amount sufficient to form a second, aqueous phase.
  • Catalyst was prepared from 84 mg Pd-A and 132 mg Ag-A in 5 mL diethyl ether. Ether was removed, and the resulting solids mixed with 3.66 g CH 2 Cl 2 in air 271 g deionized water, 121 g 1 -octene and 1.32 g sodium heptadecyl sulfate (Tergitol 7TM, Union Carbide, New York, New York) were placed in a flask, and stirred with a magnetic stir bar. A milky mixture resulted.
  • the catalyst solution was added as the mixture was stirred Polymer could be observed within five minutes (by adding a small aliquot of the reaction mixture to methanol, which dissolved water and C 8 , but from which polymer precipitated), and over the next 36 minutes, the temperature of the mixture rose from 23 to 25°C due to the polymerization exotherm. Soon after, polymer (designated Sample 4) began to collect on glass surfaces in the reaction vessel. The reaction was stopped at 41 minutes, and the large agglomerates of polymer which had formed were collected by filtration, washed with methanol, and dried in vacuum Yield: 12.4 g.
  • Samples 5-A, 5-B, and 5-C were generally performed as described in the previous examples.
  • Pd-A and Ag-A were mixed in diethyl ether, ether was removed, solvent (CH 2 Cl 2 unless otherwise indicated) was used to dissolve the resulting solids in air, and this solution was mixed with monomer and other additives, as indicated.
  • Samples 5-D, 5-E, and 5-I employed one part catalyst Pd-B, dissolved in CH 2 Cl 2 and added to monomer.
  • Sample 5-F also employed a one-part catalyst dissolved in CH 2 Cl 2 except that a second, aqueous phase, was present.
  • Samples 5-G and 5-H were prepared in a manner similar to 5-D, using a one-part catalyst and, instead of solvent, vigorous mixing, with phosphite additives added after polymerization had occurred.
  • a temperature "r.t .” indicates room temperature (about 23 °C).
  • Sample 5-B contained Irganox 1010TM (Ciba Geigy Corp , Ardsley, NY), a hindered-phenol-type stabilizer throughout the polymerization . This sample was compared to 5-A, and no significant differences in polymerization rate were observed. Polymer yields at about 2 days were 62% for 5-A and 63% for 5-B.
  • This example illustrates one method of preparing a two-part catalyst.
  • a neutral organometallic compound was used in combination with a cocatalyst comprising a silver salt of a non-coordinating counterion.
  • two-part catalysts were prepared by weighing equimolar amounts of Pd-A and Ag-A into a container and adding a solvent, typically an ether such as diethyl ether or THF. This was performed either under inert atmosphere to prevent adsorption of water by the silver salt (which might result in inaccuracies in weighing), or in air. Within minutes, the color of the mixture changed, and a precipitate (presumably AgCI) formed. The solution could be handled in air and added to monomer at this point, or ether or THF solvent (which affect
  • polymerization rates could be substantially removed to yield a yellow-brown solid which could be suspended in monomer or used in a different solvent
  • Variations in order of addition, stoichiometry, amounts and kinds of solvent, atmosphere (e.g , pure oxygen or air of high or low humidity) and the like are within the scope of this invention.
  • two-part catalysts may be preferred to control the onset of polymerization.
  • a one-part catalyst was prepared by reacting the silver salt of a non-coordinating counterion with a neutral organometallic compound.
  • catalyst Pd-B was prepared from equimolar amounts of Pd-A and
  • Pd catalysts containing the following counterions were prepared: ⁇ C(SO 2 CF 3 ) 3 ⁇ -, ⁇ B(C 6 H 5 ) 4 ⁇ -, ⁇ B ⁇ 3,5-C 6 H 3 (CF 3 ) 2 ⁇ 4 ⁇ -, (SO 3 C 4 F 9 )-, ⁇ N(SO 2 C 2 F 5 ) 2 ⁇ -, and ⁇ NSO 2 (CF 2 ) 2 SO 2 ⁇ -.
  • This example shows that a neutral organometallic catalyst can be prepared without the necessity of isolating an intermediate silver salt of the counterion.
  • a neutral organometallic catalyst can be prepared directly from a lithium salt of a noncoordinating anion without the need to use a silver salt. Although reaction time is longer, the method requires few steps and uses less expensive and less hazardous reagents.
  • Examples 10 and 1 1 show that alpha-olefin polymerization can take place in a simple, rapid, one-pot procedure without the need to isolate the catalyst or to use relatively expensive silver salts.
  • a large volume of water was used as a sink for the heat of polymerization, and the reaction was carried out at a sufficiently low temperature that good polymer yield and molecular weight were achieved.
  • catalyst was mixed with monomer and optional solvent as indicated. Polymerization was conducted at the temperature and for the time indicated. All procedures were conducted in air and with no attempt to remove water from monomer or solvent.
  • A contained one-part catalyst, and varying amounts of liquid monomer and CH 2 Cl 2 solvent
  • the amounts by weight of monomer to CH 2 Cl 2 are: A-1, 1 to 1; A-2, 3 to 1, A-4, 7.7 to 1, A-5, 1 to 2, A-6, 3.8 to 1; A-7, 5 portions of each comonomer to 1 portion of CH 2 Cl 2 ; and A-8, 5 to 1.
  • reaction mixture was homogeneous initially, and polymer precipitated in some cases depending on monomer, temperature and extent of reaction.
  • one-part catalyst was dissolved in CH 2 Cl 2 in a pressure vessel and gaseous monomer was added, but the exact amount of monomer charged was not recorded.
  • reaction times are shown as unknown, reaction progress was not carefully monitored and reaction times were greater than 100 hours, but not known with certainty.
  • reaction B contained one-part catalyst, 4 portions by weight of ethyl acetate, and 1 portion by weight of monomer. Reaction mixture was initially homogeneous, but polymer soon began to precipitate from solution.
  • Example 1 contained two phase (monomer and water) mixture with two-part catalyst, as described in Example 1 1.
  • D contained one-part catalyst and monomer, with no solvent Reaction mixture formed a solution and polymer precipitated from the solution as it formed Reaction progress was not carefully monitored and reaction times were greater than 100 hours, but not known with certainty.
  • D* contained one-part catalyst and 1 portion by weight of each of two comonomers.
  • copolymerizations were conducted by mixing the two or more comonomers listed with one-part catalyst in the amounts indicated .
  • Polyhexene was prepared by adding 100 0 gm of 1-hexene (cooled to 0°C) to
  • the polymers were dissolved in toluene (25% polymer by weight), 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine (the preparation of which is described in German Patent No 1,200,314), was added in the amount of 0.15% by weight of polymer, and the solutions were coated onto 1 mil (0.025 mm) polyester film and dried as described in Example 10 to give a dry film coating weight of 40.13 ⁇ 10 -4 g/cm 2 (9.6 +/- 0.2 grains per 24 square inches).
  • the films were irradiated under nitrogen with two medium pressure mercury lamps (high intensity, 200 watt/2 54 cm) made by Aetek International, Division of GEO, Plainfield, Illinois.
  • Example 15 Preparation of a molded article.
  • This example shows the use of one-part catalysts with varying non- coordinating counterions.
  • the catalyst was mixed in the amount specified with 10 g CH 2 Cl 2 and 10 g 1-octene. Mixing and polymerization occurred at 0°C. No attempt was made to remove or exclude water or air.
  • Reaction progress was monitored by removing an aliquot from each sample at the times indicated, and drying each aliquot to determine the amount of non-volatile polymer present, from which the weight yield of polymer at that time was calculated. The molecular weight of the polymers formed after 24 hr of reaction time was measured.
  • catalysts wherein Q is N(SO 2 CF 3 ) or B(C 6 F 5 ) 4 provided better control of polymerization outcomes such as polymer molecular weight distribution than catalyst wherein Q is B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 in polymerizable compositions of this invention, that is, in the presence of water and air.

Abstract

La présente invention concerne une composition polymérisable comprenant un monomère d'hydrocarbure d'alphaoléfine, une quantité efficace d'un catalyseur organométallique ayant pour base un métal du groupe VIII, de préférence Ni ou Pd, et de l'eau, ou de l'air, ou les deux. Des catalyseurs nouveaux pour la polymérisation de monomères d'hydrocarbures d'alphaoléfines permettent d'améliorer les procédés et les produits obtenus. Les procédés selon l'invention consistent à polymériser la composition en plein air et en présence d'eau, afin d'obtenir des polymères nouveaux.
PCT/US1996/005227 1995-11-06 1996-04-15 Compositions polymerisables comprenant des monomeres d'hydrocarbures d'alphaolefines, et procedes d'utilisation WO1997017380A2 (fr)

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KR1019980703292A KR19990067308A (ko) 1995-11-06 1996-04-15 알파-올레핀 탄화수소 단량체를 포함하는 중합성 조성물 및이를 사용하기 위한 방법
US08/637,727 US5942461A (en) 1995-11-06 1996-04-15 Polymerizable compositions comprising alpha-olefin hydrocarbon monomers and methods of use therefor
JP51814297A JP2001524134A (ja) 1995-11-06 1996-04-15 αオレフィン炭化水素モノマーを含む重合可能な組成物およびそれらの使用方法
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