Addition polymers derived from norbornene-functional monomers and process therefor

Claim 2

A reaction mixture for forming an addition polymer comprising at least one norbornene-functional monomer, a solvent, a single or multicomponent catalyst system each comprising a Group VIII transition metal ion source and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms having two hydrogen atoms attached thereto.

Claim 3

The reaction mixture of claim 1 wherein said single component catalyst system consists essentially of a cation of a Group VIII metal complex, and a weakly coordinating counteranion; said cation having a hydrocarbyl group directly bound to said Group VIII metal by a single metal-C σ-bond, and by not more than three π-bonds, to a weakly coordinating neutral donating ligand.

Claim 4

The reaction mixture of claim 2 wherein said metal is selected from the group consisting of nickel, palladium, and cobalt.

Claim 5

The reaction mixture of claim 3 wherein said single component catalyst system is represented by the formula: ##STR27## wherein M represents Ni or Pd, L 1 , L 2 and L 3 represent ligands of M; only one ligand having a σ-bond, and all the ligands together having 2 or 3 π-bonds; and, CA - represents a counter anion chosen to solubilize said cation in said solvent.

Claim 6

The reaction mixture of claim 4 wherein M represents Ni, and said weakly coordinating neutral donating ligand is selected from the group consisting of a cyclo(C 6 -C 12 )alkadiene, norbomadiene, cyclo(C 10 -C 20 )triene, benzene, toluene, xylene, and mesitylene.

Claim 7

The reaction mixture of claim 4 wherein said weakly coordinating counteranion is selected from the group consisting of BF 4 - ; PF 6 - ; AlF 3 O 3 SCF 3 - ; SbF 6 - ; SbF 5 SO 3 F - , CF 3 SO 3 - ; B C 6 F 5 ! 4 - ; and B C 6 H 3 (CF 3 ) 2 ! 4 - .

Claim 8

The reaction mixture of claim 1 wherein said solvent is a halohydrocarbon solvent.

Claim 9

The reaction mixture of claim 1 wherein said multicomponent catalyst system comprises a Group VIII transition metal compound, an organoaluminum compound, an optional third component selected from the group consisting of Lewis acids, strong Bronsted acids, halogenated compounds, electron donating compounds.

Claim 10

The reaction mixture of claim 8 wherein said Lewis acids are selected from the group consisting of BF 3 .etherate, TiCl 4 , SbF 5 , BCl 3 , B(OCH 2 CH 3 ) 3 , and tris(perfluorophenyl) boron, said strong Bronsted acids are selected from the group consisting of HSbF 6 , HPF 6 , CF 3 CO 2 H, FSO 3 H.SbF 5 , H 2 C(SO 2 CF 3 ) 2 , CF 3 SO 3 H and paratoluenesulfonic acid; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; wherein said electron donating compounds are selected from aliphatic and cycloaliphatic diolefins, phosphines and phosphites, and mixtures thereof.

Claim 11

The reaction mixture of claim 8 wherein the organoaluminum compound is selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and mixtures thereof.

Claim 12

The reaction mixture of claim 8 wherein the Group VIII transition metal compound comprises a Group VIII transition metal ion bonded to one or more moieties selected from the group consisting of monodentate, bidentate, and multidentate ionic or neutral ligands, and mixtures thereof.

Claim 13

The reaction mixture of claim 11 wherein said Group VIII transition metal is selected from the group consisting of Ni, Co, Pd, Pt, Fe and Ru.

Claim 14

The reaction mixture of claim 11 wherein the Group VIII transition metal compound is selected from the group consisting of: nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, cobalt neodecanoate, iron napthenate, palladium ethylhexanoate, NiCl 2 (PPh 3 ) 2 , NiCl 2 (PPh 2 CH 2 ) 2 , nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, trans-Pd Cl 2 (PPh 3 ) 2 , palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate) 2 (PPh 3 ) 2 , palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate, cobalt (II) tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel, palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride, platinum bis(triethylphosphine) hydrobromide, ruthenium tris(triphenylphosphine) dichloride, ruthenium tris(triphenylphosphine) hydrido chloride, ruthenium trichloride, ruthenium tetrakis(acetonitrile) dichloride, ruthenium tetrakis(dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris(triphenylphosphine) trichloride.

Claim 15

An essentially anhydrous reaction mixture in which a processable addition polymer is formed, said reaction mixture comprising, (a) one or more norbornene-functional monomers, and optionally one or more monocyclomonoolefins; (b) a pre-formed single component complex metal catalyst of a Group VIII metal which initiates and maintains chain growth of a polymer by an insertion reaction in combination with; (c) a predetermined amount of a terminal olefinic chain transfer agent, in the absence of an organometal cocatalyst; said pre-formed single component catalyst consisting essentially of (i) a cation of said organo Group VIII metal complex, and (ii) a weakly coordinating counteranion; said cation having a hydrocarbyl group directly bound to said Group VIII metal by a single metal-C σ-bond, and by not more than three π-bonds, to a weakly coordinating neutral donating ligand, and (d) a hydrocarbon or halohydrocarbon solvent in which said cycloolefin monomer, said catalyst and said chain transfer agent are soluble.

Claim 16

An essentially anhydrous reaction mixture in which a processable addition polymer is formed, said reaction mixture comprising, (a) one or more norbornene-functional monomers, and optionally one or more monocyclomonoolefins; (b) a pre-formed single component complex metal catalyst of a Group VIII metal which initiates and maintains chain growth of a polymer by an insertion reaction in combination with; (c) a predetermined amount of a terminal olefinic chain transfer agent, in the absence of an organometal cocatalyst; said pre-formed single component catalyst consisting essentially of (i) a cation of said organo Group VIII metal complex, and (ii) a weakly coordinating counteranion; said cation having a hydrocarbyl group directly bound to said Group VIII metal by a single metal-C σ-bond, and by not more than three π-bonds, to a weakly coordinating neutral donating ligand, and (d) a hydrocarbon or halohydrocarbon solvent in which said cycloolefin monomer, said catalyst and said chain transfer agent are soluble.

Claim 17

The reaction mixture of claim 14 wherein said pre-formed single component organometal complex catalyst is represented by ##STR28## wherein M represents Ni or Pd, L 1 , L 2 and L 3 represent ligands of M; only one ligand having a σ-bond, and all the ligands together having 2 or 3 π-bonds; and, CA - represents a counter anion chosen to solubilize said cation in said solvent.

Claim 18

The reaction mixture of claim 15 wherein M represents Ni, and said weakly coordinating neutral donating ligand is selected from the group consisting of a cyclo(C 6 -C 12 )alkadiene, norbornadiene and cyclo(C 10 -C 20 )triene, benzene, toluene, xylene, and mesitylene.

Claim 19

The reaction mixture of claim 16 wherein said weakly coordinating counteranion is selected from the group consisting of BF 4 - ; PF 6 - ; AlF 3 O 3 SCF 3 - ; SbF 6 - ; SbF 5 SO 3 F - , CF 3 SO 3 - ; B C 6 F 5 ! 4 - ; and B C 6 H 3 (CF 3 ) 2 ! 4 - .

Claim 20

A reaction mixture for forming an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising, (a) a Group VIII transition metal ion source; (b) an organoaluminum compound; (c) an optional third component selected from the group consisting of Lewis acids, strong Bronsted acids, electron donating compounds selected from aliphatic and cycloaliphatic diolefins, and mixtures thereof, and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto.

Claim 21

A reaction mixture for forming an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising, (a) a Group VIII transition metal ion source; (b) an organoaluminum compound; (c) an optional third component selected from the group consisting of Lewis acids, strong Bronsted acids, electron donating compounds selected from aliphatic and cycloaliphatic diolefins, and mixtures thereof, and a chain transfer agent selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms has two hydrogen atoms attached thereto.

Claim 22

The reaction mixture of claim 18 wherein the Group VIII transition metal ion source is selected from a compound represented by the formula: C.sup.c'.sub.c M.sup.m'.sub.m X.sup.x'.sub.x Y.sup.y'.sub.y L.sub.l ! wherein C represents a cation; M represents a Group VIII transition metal selected from the group of iron, cobalt, nickel, ruthenium, palladium, and platinum; X and Y independently represent anionic ligands; L represents a neutral ligand; x', y' and l are 0 to 15 with the proviso that x', y' and l cannot all be zero at the same time; c is 0, 1, 2 or 3; c' is the charge of C m is 1 to 4; m' is the oxidation state of the Group VIII transition metal M which is determined by the equation ##EQU2## x' is the absolute value of the charge of X; y' is the absolute value of the charge of Y; wherein C, if present, represents a cation selected from the group consisting of organoammonium, organoarsonium, organophosphonium and pyridinium ligands; X and Y independently represent ligands selected from the group consisting of hydride, halides, pseudohalides, (C 1 -C 40 ) branched and unbranched alkylanions, (C 6 -C 24 ) arylanions, cyclopentadienylide anions, π-allyl groupings, enolates of β-dicarbonyl compounds, carboxylates, halogenated carboxylates, nitrates, nitrites, bisulphate, aluminates, silicates, phosphates, sulfates, amides, imides, oxides, phosphides, sulfides, (C 6 -C 24 ) aryloxides, (C 1 -C 20 ) branched and unbranched alkoxides, hydroxide, hydroxy (C 1 -C 20 ) branched and unbranched alkyl, PF 6 - , AlF 3 O 3 SCF - 3 , SbF - 6 , and ligands selected from compounds of the formulae: Al(R.sup.7).sub.4.sup.-, B(X).sub.4.sup.- wherein R 7 and X independently represent halide, or a branched or unbranched hydrocarbyl group, or X represents 3,5-trifluoromethylphenyl; and L represents a neutral ligand selected from the group consisting of acetylenes, (C 2 -C 12 ) mono-, di-, and triolefins, (C 5 -C 12 ) cyclomono, di-, tri-, and tetraolefins, carbon monoxide, nitric oxide, ammonia, pyridine, pyridine derivatives, 1,4-dialkyl-1,3-diazabutadienes, amines, ureas, nitriles, organic ethers, tetrahydrofuran, furan, organic sulfides, arsines, stibines, phosphines, phosphites, phosphinites, phosphonites, phosphorus oxyhalides, phosphonates, ketones, and sulfoxides.

Claim 23

The reaction mixture of claim 18 wherein said organoaluminum compound is represented by the formula: AlR.sup.12.sub.3-x Q.sub.x wherein R 12 independently represents, branched and unbranched (C 1 -C 20 ) alkyl, (C 6 -C 24 ) aryl, Q is a halide or pseudohalide selected from the group consisting of chlorine, fluorine, bromine, iodine, branched and unbranched (C 1 -C 20 ) alkoxy, and (C 6 -C 24 ) aryloxy; and x is a number from 0 to 2.5.

Claim 24

The reaction mixture of claim 20 wherein the organoaluminum compound is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, trioctylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, isobutylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, and isobutylaluminum sesquichloride.

Claim 25

The reaction mixture of claim 18 wherein the said Lewis acids are selected from the group consisting of BF 3 .etherate, TiCl 4 , SbF 5 , BCl 3 , B(OCH 2 CH 3 ) 3 , and tris(perfluorophenyl) boron, said strong Bronsted acids are selected from the group consisting of HSbF 6 and HPF 6 , CF 3 CO 2 H, FSO 3 H.SbF 5 , H 2 C(SO 2 CF 3 ) 2 ; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

Claim 26

The reaction mixture of claim 1, 2, 4, 8, 14, 15, or 18 wherein said norbornene-functional monomer is selected from a compound represented by the formula: ##STR29## wherein R 4 , R 4' R 5 , and R 5' independently represent hydrogen, halogen, branched and unbranched (C 1 -C 20 ) alkyl, (C 1 -C 20 ) haloalkyl, substituted and unsubstituted cycloalkyl, (C 1 -C 6 ) alkylidenyl, (C 6 -C 40 ) aryl, (C 6 -C 40 ) haloaryl, (C 7 -C 15 ) aralkyl, (C 7 -C 15 ) haloaralkyl, (C 2 -C 20 ) alkynyl, vinyl, (C 3 -C 20 ) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula --C n F 2n+1 , wherein n is 1 to 20, R 4 and R 5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or double bond, and "z" is 1 to 5; when R 4 , R 4' R 5 , and R 5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R 4 to R 5 cannot be alkylidenyl.

Claim 27

The reaction mixture of claim 23 wherein said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornene selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkylnorbornenes, branched and unbranched (C 1 -C 20 ) haloalkylnorbornenes, (C 1 -C 6 ) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkyltetracyclododecenes, (C 1 -C 6 ) alkylidenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbomadiene; (f) tetracyclododecadiene; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

Claim 28

The reaction mixture of claim 23 further comprising a repeating unit derived from a monocyclomonoolefin selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, and mixtures thereof.

Claim 29

The reaction mixture of claim 1, 2, 4, 8, 14, 15 or 18 wherein said chain transfer agent is selected from a compound represented by the following formula: ##STR30## wherein R' and R" are independently hydrogen, branched or unbranched (C 1 -C 40 ) alkyl, (C 1 -C 40 ) branched or unbranched alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, halogen, or the group ##STR31## wherein R'" is (C 1 -C 10 ) alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

Claim 30

The reaction mixture of claim 26 wherein said chain transfer agent is selected from the group consisting of an α-olefin having 2 to 30 carbon atoms; isobutylene; 1,7-octadiene, and 1,6-octadiene.

Claim 31

The reaction mixture of claim 27 wherein said chain transfer agent is ethylene or isobutylene.

Claim 32

A reaction mixture for forming an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising: (a) a Group VIII transition metal compound wherein said Group VIII transition metal is selected from the group consisting of nickel, cobalt, and palladium; (b) an organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and (c) optionally, a third component selected from the group consisting of Lewis acids, strong Bronsted acids, halogenated compounds, electron donating compounds selected from (C 4 -C 12 ) conjugated dienes and (C 6 -C 12 ) cycloaliphatic diolefins; and mixtures thereof.

Claim 33

A reaction mixture for forming an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising: (a) a Group VIII transition metal compound wherein said Group VIII transition metal is selected from the group consisting of nickel, cobalt, and palladium; (b) an organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and (c) optionally, a third component selected from the group consisting of Lewis acids, strong Bronsted acids, halogenated compounds, electron donating compounds selected from (C 4 -C 12 ) conjugated dienes and (C 6 -C 12 ) cycloaliphatic diolefins; and mixtures thereof.

Claim 34

The reaction of claim 29 wherein said third component is present and is selected from the group consisting of BF 3 .etherate, TiCl 4 , SbF 5 , BCl 3 , B(OCH 2 CH 3 ) 3 , and tris(perfluorophenyl) boron, HSbF 6 and HPF 6 , CF 3 CO 2 H, FSO 3 H.SbF 5 , H 2 C(SO 2 CF 3 ) 2 , CF 3 SO 3 H, paratoluenesulfonic acid; and mixtures thereof.

Claim 35

The reaction mixture of claim 29 wherein said third component is present and is selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, chloranil, and mixtures thereof.

Claim 36

The reaction mixture of claim 29, 30 or 31 further comprising a chain transfer agent selected from a compound represented by the formula: ##STR32## wherein R' and R" are independently hydrogen, branched or unbranched (C 1 -C 40 ) alkyl, (C 1 -C 40 ) branched or unbranched alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, halogen, or the group ##STR33## wherein R'" is (C 1 -C 10 ) alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

Claim 37

The reaction mixture of claim 32 wherein said chain transfer agent is selected from the group consisting of an α-olefin having 2 to 30 carbon atoms; isobutylene; 1,7-octadiene, and 1,6-octadiene.

Claim 38

The reaction mixture of claim 33 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, and 1-decene, 1-dodecene, and mixtures thereof.

Claim 39

A reaction mixture for an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising: (a) a nickel ion source; (b) an organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum chlorides, and mixtures thereof; and (c) a component selected from the group consisting of BF 3 .etherate, HSbF 6 , butadiene, cyclooctadiene, and mixtures thereof.

Claim 40

A reaction mixture for an addition polymer comprising one or more norbornene-functional monomers and optionally a monocyclomonoolefin, a solvent, and a multicomponent catalyst system comprising: (a) a nickel ion source; (b) an organoaluminum compound selected from the group consisting of trialkylaluminums, dialkylaluminum chlorides, and mixtures thereof; and (c) a component selected from the group consisting of BF 3 .etherate, HSbF 6 , butadiene, cyclooctadiene, and mixtures thereof.

Claim 41

The reaction mixture of claim 35 wherein said nickel ion source is a nickel salt selected from compounds selected from the group consisting of: nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, NiCl 2 (PPh 3 ) 2 , NiCl 2 (PPh 3 CH 2 ) 2 , nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate.

Claim 42

The reaction mixture of claim 36 wherein said organoaluminum compound is selected from the group consisting of triethylaluminums, diethylaluminum chlorides, and mixtures thereof.

Claim 43

The reaction mixture of claim 37 wherein said component (c) comprises BF 3 .etherate and HSbF 6 .

Claim 44

The reaction mixture of claim 38 wherein the molar ratio of aluminum metal: BF 3 .etherate: nickel metal: HSbF 6 is 10:9:1:1 to 2.

Claim 45

The reaction mixture of claim 35, 36, 37, 38 or 39 further comprising a chain transfer agent selected from the group consisting of an α-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

Claim 46

The reaction mixture of claim 40 wherein said chain transfer agent is selected from the group ethylene, propylene, 4-methyl-1-pentene, and 1-decene, 1-dodecene, and mixtures thereof.

Claim 47

The reaction mixture of claim 29, 30, 31, 35, 36, 37, 38 or 39 wherein said solvent is a halohydrocarbon and said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornene selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkylnorbornenes, branched and unbranched (C 1 -C 20 ) haloalkylnorbornenes, (C 1 -C 6 ) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkyltetracyclododecenes, (C 1 -C 6 ) alkylidenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene; (f) tetracyclododecadiene; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

Claim 48

The reaction mixture of claim 32 wherein said solvent is a halohydrocarbon and said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornenes selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkylnorbornenes, branched and unbranched (C 1 -C 20 ) haloalkylnorbornenes, (C 1 -C 6 ) alkyledenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkyltetracyclododecenes, (C 1 -C 6 ) alkyledenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene; (f) tetracyclododecadiene; (g) symmetrical and asynmmetrical trimers of cyclopentadiene; and mixtures thereof.

Claim 49

The reaction mixture of claim 42 wherein said halohydrocarbon solvent is selected from the group consisting of methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, perchloroethylene, chlorobenzene, dichlorobenzene and trichlorobenzene.

Claim 50

In an essentially anhydrous reaction mixture in which a processable addition polymer is formed by coordination polymerization, said reaction mixture including at least one or more norbornene-functional monomers, a solvent for said monomer, a Group VB, VIB, VIM, or VIII transition metal compound, and an alkylaluminoxane in an amount effective to convert said at least 50% by weight of said monomer into said addition polymer, the improvement consisting essentially of, a minor molar amount relative to the moles of said monomer, of an olefinic chain transfer agent selected from the group consisting of ethylene and a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms having two hydrogen atoms attached thereto, said chain transfer agent being present in a predetermined amount correlatable with a desired number average molecular weight M w in the range from about 20,000 to about 500,000, of said addition polymer.

Claim 51

In an essentially anhydrous reaction mixture in which a processable addition polymer is formed by coordination polymerization, said reaction mixture including at least one or more norbornene-functional monomers, a solvent for said monomer, a Group VB, VIB, VIM, or VIII transition metal compound, and an alkylaluminoxane in an amount effective to convert said at least 50% by weight of said monomer into said addition polymer, the improvement consisting essentially of, a minor molar amount relative to the moles of said monomer, of an olefinic chain transfer agent selected from the group consisting of ethylene and a compound having a terminal olefinic double bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one of said adjacent carbon atoms having two hydrogen atoms attached thereto, said chain transfer agent being present in a predetermined amount correlatable with a desired number average molecular weight M w in the range from about 20,000 to about 500,000, of said addition polymer.

Claim 52

The reaction mixture of claim 45 wherein said chain transfer agent is selected from a compound represented by the following formula: ##STR34## wherein R' and R" are independently hydrogen, branched or unbranched (C 1 -C 40 ) alkyl, branched or unbranched (C 7 -C 40 ) aralkyl, branched or unbranched (C 3 -C 40 ) alkenyl, halogen, or the group ##STR35## wherein R'" is branched or unbranched (C 1 -C 10 ) alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, substituted or unsubstituted (C 6 -C 15 ) aryl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

Claim 53

The reaction mixture of claim 46 wherein said monomer is a first monomer selected from the group consisting of norbornene and substituted norbornenes; said polymer is a homopolymer; and, said chain transfer agent is present in an amount less than 50 mole % relative to said multi-ringed monomer.

Claim 54

The reaction mixture of claim 46 wherein said monomer is a first monomer selected from the group consisting of norbornene and substituted norbornenes present in a major amount relative to a second monomer; said polymer is a copolymer of said first and second monomers; and, said chain transfer agent is present in an amount less than 50 mole % relative to said multi-ringed monomer.

Claim 55

The reaction mixture of claim 48 wherein said second monomer is selected from the group consisting of a multi-ringed cyclomonoolefin structure derived from at least one norbornene unit, said structure including up to four fused rings; a cyclodiolefin having one norbornene unit; a mono(C 4 -C 8 )cycloolefin; norbornadiene; and trimer of cyclopentadiene.

Claim 56

The reaction mixture of claim 49 wherein one of said rings has a substituent selected from the group consisting of an acyclic (C 1 -C 20 )alkyl, (C 3 -C 20 )alkenyl, or (C 1 -C 6 )alkylidene substituent.

Claim 57

In an essentially anhydrous reaction mixture in which a processable addition polymer is formed by coordination polymerization, said reaction mixture including at least one norbornene-functional monomer, a solvent for said monomer, and, a Group VB, VIB, VIEB or VIII metal compound in combination with an alkylaluminoxane co-catalyst in an amount effective to convert said at least one monomer into said addition polymer, wherein said metal is selected from the group consisting of chromium, cobalt, molybdenum, tungsten, manganese, nickel, palladium and platinum, the improvement consisting essentially of, said solvent being a halohydrocarbon solvent; whereby the conversion of monomer to polymer is at least 100% higher than when said reactants are polymerized in an essentially non-polar solvent.

Claim 58

In an essentially anhydrous reaction mixture in which a processable addition polymer is formed by coordination polymerization, said reaction mixture including at least one norbornene-functional monomer, a solvent for said monomer, and, a Group VB, VIB, VIEB or VIII metal compound in combination with an alkylaluminoxane co-catalyst in an amount effective to convert said at least one monomer into said addition polymer, wherein said metal is selected from the group consisting of chromium, cobalt, molybdenum, tungsten, manganese, nickel, palladium and platinum, the improvement consisting essentially of, said solvent being a halohydrocarbon solvent; whereby the conversion of monomer to polymer is at least 100% higher than when said reactants are polymerized in an essentially non-polar solvent.

Claim 59

The reaction mixture of claim 51 wherein said halohydrocarbon solvent is halo(C 1 -C 4 )alkyl or haloaryl solvent.

Claim 60

The reaction mixture of claim 52 wherein said halohydrocarbon solvent is selected from the group consisting of methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, perchloroethylene, chlorobenzene, dichlorobenzene and trichlorobenzene.

Claim 61

The reaction mixture of claim 52 wherein said metal is nickel.

Claim 62

The reaction mixture of claim 2 wherein said catalyst is present on an active catalyst support.

Claim 63

The reaction mixture of claim 55 wherein said active catalyst support is selected from the group consisting of aluminum trifluoride and an alkylaluminoxane on silica.

Claim 64

The reaction mixture of claim 1 wherein said solvent is selected from the group consisting of non-polar hydrocarbons, and halohydrocarbons.

Claim 65

The reaction mixture of claim 1 wherein said solvent is a halohydrocarbon solvent selected from the group consisting of halo(C 1 -C 4 )alkanes and haloaromatics.

Claim 66

A reaction mixture for the polymerization of an addition polymer comprising one or more norbornene-functional monomers, a halohydrocarbon solvent, and a multi-component catalyst system comprising: (a) a Group VIII transition metal ion source; (b) an aluminoxane; and (c) a component selected from the group consisting of BF 3 .etherates, TiCl 3 , SbF 5 , BCl 3 , B(OCH 2 CH 3 ) 3 , and tris(perfluorophenyl) boron, said strong Bronsted acids are selected from the group consisting of HSbF 6 and HPF 6 , CF 3 CO 2 H, FSO 3 H.SbF 5 , H 2 C(SO 2 CF 3 ) 2 , CF 3 SO 3 H, paratoluenesulfonic acid; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

Claim 67

A reaction mixture for the polymerization of an addition polymer comprising one or more norbornene-functional monomers, a halohydrocarbon solvent, and a multi-component catalyst system comprising: (a) a Group VIII transition metal ion source; (b) an aluminoxane; and (c) a component selected from the group consisting of BF 3 .etherates, TiCl 3 , SbF 5 , BCl 3 , B(OCH 2 CH 3 ) 3 , and tris(perfluorophenyl) boron, said strong Bronsted acids are selected from the group consisting of HSbF 6 and HPF 6 , CF 3 CO 2 H, FSO 3 H.SbF 5 , H 2 C(SO 2 CF 3 ) 2 , CF 3 SO 3 H, paratoluenesulfonic acid; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

Claim 68

The reaction mixture of claim 59 further comprising a chain transfer agent selected from a compound having a terminal olefinic bond between adjacent carbon atoms, excluding styrenes, vinyl ethers, and conjugated dienes, and at least one said adjacent carbon atoms has two hydrogen atoms attached thereto.

Claim 69

The reaction mixture of claim 60 wherein said chain transfer agent is selected from a compound represented by the following formula: ##STR36## wherein R' and R" are independently hydrogen, branched or unbranched (C 1 -C 40 ) alkyl, (C 1 -C 40 ) branched or unbranched alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, halogen, or the group ##STR37## wherein R'"is (C 1 -C 10 ) alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

Claim 70

The reaction mixture of claim 61 wherein said chain transfer agent is selected from the group consisting of an α-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

Claim 71

The reaction mixture of claims 62 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-decene, and 1-dodecene.

Claim 72

A reaction mixture for forming an addition polymer comprising at least one norbornene-functional monomer, a solvent selected from the group consisting of a non-polar hydrocarbon solvent, a halohydrocarbon solvent, and mixtures thereof, and a multicomponent catalyst system consisting essentially of a Group VIII transition metal compound wherein said Group VIII transition metal is selected from the group consisting of nickel, palladium, and cobalt; and an alkylaluminum compound.

Claim 73

A reaction mixture for forming an addition polymer comprising at least one norbornene-functional monomer, a solvent selected from the group consisting of a non-polar hydrocarbon solvent, a halohydrocarbon solvent, and mixtures thereof, and a multicomponent catalyst system consisting essentially of a Group VIII transition metal compound wherein said Group VIII transition metal is selected from the group consisting of nickel, palladium, and cobalt; and an alkylaluminum compound.

Claim 74

The reaction mixture of claim 64 wherein said Group VIII transition metal compound is selected from the group consisting of nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, cobalt neodecanoate, palladium ethylhexanoate, NiCl 2 (PPh 3 ) 2 , NiCl 2 (PPh 2 CH 2 ) 2 , nickel (II) hexafluoroacetylacetonate tetrahydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahydrate, trans-Pd Cl 2 (PPh 3 ) 2 , palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate) 2 (PPh 3 ) 2 , palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate, cobalt (II) tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel, palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride.

Claim 75

The reaction mixture of claim 65 wherein said Group VIII transition metal compound is selected from the group consisting of nickel ethylhexanoate, palladium ethylhexanoate, and cobalt neodecanoate.

Claim 76

The reaction mixture of claim 64 wherein said non-polar hydrocarbon solvent is selected from the group consisting of hexane, cyclohexane, heptane, isooctane, toluene, xylene, and methylcyclohexane.

Claim 77

The reaction mixture of claim 64 wherein said polar hydrocarbon solvent is selected from the group consisting of 1,2-dichloroethane, dichloromethane, chlorobenzene, and o-dichlorobenzene.

Claim 78

The reaction mixture of claim 64 wherein said alkylaluminum compound is selected from a monoalkylaluminum dihalide, and mixtures thereof.

Claim 79

The reaction mixture of claim 69 wherein said monoalkylaluminum dihalide is selected from the group consisting of ethylaluminum dichloride, isobutylaluminum dichloride, and mixtures thereof.

Claim 80

The reaction mixture of claims 64, 65, 66, 67, 68, 69 or 70 further comprising a chain transfer agent selected from a compound represented by the formula: ##STR38## wherein R' and R" are independently hydrogen, branched or unbranched (C 1 -C 40 ) alkyl, (C 1 -C 40 ) branched or unbranched alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, halogen, or the group ##STR39## wherein R'" is (C 1 -C 10 ) alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

Claim 81

The reaction mixture set forth in claim 64 wherein said norbornene-functional monomer is selected from a compound represented by the formula: ##STR40## wherein R 4 , R 4' R 5 , and R 5' independently represent hydrogen, halogen, branched and unbranched (C 1 -C 20 ) alkyl, (C 1 -C 20 ) haloalkyl, substituted and unsubstituted cycloalkyl, (C 1 -C 6 ) alkylidenyl, (C 6 -C 40 ) aryl, (C 6 -C 40 ) haloaryl, (C 7 -C 15 ) aralkyl, (C 7 -C 15 ) haloaralkyl, (C 2 -C 20 ) alkynyl, vinyl, (C 3 -C 20 ) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula --C n F 2n+1 , wherein n is 1 to 20, R 4 and R 5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or double bond, and "z" is 1 to 5; when R 4 , R 4' R 5 , and R 5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R 4 to R 5 cannot be alkylidenyl.

Claim 82

The reaction mixture of claim 72 wherein said norbornene-functional monomer is selected from the group consisting of (a) norbornene; (b) substituted norbornenes selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkylnorbornenes, branched and unbranched (C 1 -C 20 ) haloalkylnorbornenes, (C 1 -C 6 ) alkylidenylnorbornenes, vinyl norbornene (c) tetracyclododecene and substituted tetracyclododecenes selected from the group consisting of branched and unbranched (C 1 -C 20 ) alkyltetracyclododecenes, (C 1 -C 6 ) alkylidenyltetracyclododecenes; (d) dicyclopentadiene; (e) norbornadiene; (f) tetracyclododecadiene; (g) symmetrical and asymmetrical trimers of cyclopentadiene; and mixtures thereof.

Claim 83

The reaction mixture of claim 73 wherein said reaction mixture further comprises: a monocycloolefin selected selected from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, and mixtures thereof.

Claim 84

A reaction composition comprising a Group VIII metal complex comprising at least one metal-hydride σ-bond; a solvent; at least one norbornene functional monomer; and a chain transfer agent selected from a compound having a terminal olefinic non-styrenic, non-vinyl ether double bond between adjacent carbon atoms (excluding conjugated dienes) and at least one said adjacent carbon atoms has two hydrogen atoms attached thereto.

Claim 85

A reaction composition comprising a Group VIII metal complex comprising at least one metal-hydride σ-bond; a solvent; at least one norbornene functional monomer; and a chain transfer agent selected from a compound having a terminal olefinic non-styrenic, non-vinyl ether double bond between adjacent carbon atoms (excluding conjugated dienes) and at least one said adjacent carbon atoms has two hydrogen atoms attached thereto.

Claim 86

The composition of claim 75 wherein said Group VIII metal of said Group VIII metal-hydride is selected from the group consisting of Ni, Pd, and Co.

Claim 87

The composition of claim 75 wherein said solvent is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and mixtures thereof.

Claim 88

The composition of claim 75 further containing an alkylaluminum compound.

Claim 89

The composition of claim 78 wherein said alkylaluminum compound is an alkylaluminum halide.

Claim 90

The composition of claim 78 or 79 wherein the alkylaluminum compound is selected from the group consisting of trialkylaluminums, dialkylaluminum halides, monoalkylaluminum dihalides, and alkylaluminum sesquihalides; and mixtures thereof.

Claim 91

The composition of claim 78 further containing a component selected from the group consisting of Lewis acids, strong Bronsted acids, halogenated compounds electron donating compounds selected from aliphatic and cycloaliphatic diolefins, phosphines, phosphites, and mixtures thereof.

Claim 92

The composition of claim 81 wherein said Lewis acids are selected from the group consisting of BF 3 .etherate, TiCl 4 , SbF 5 , BCl 3 , B(OCH 2 CH 3 ) 3 , and tris(perfluorophenyl) boron, said strong Bronsted acids are selected from the group consisting of HSbF 6 and HPF 6 , CF 3 CO 2 H, FSO 3 H.SbF 5 , H 2 C(SO 2 CF 3 ) 2 , partoluenesulfonic acid; and said halogenated compounds are selected from the group consisting of hexachloroacetone, hexafluoroacetone, 3-butenic acid-2,2,3,4,4-pentachlorobutyl ester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil; and mixtures thereof.

Claim 93

The composition of claim 75, 76, 77, or 82 wherein said chain transfer agent is selected from a compound represented by the following formula: ##STR41## wherein R' and R" are independently hydrogen, branched or unbranched (C 1 -C 40 ) alkyl, (C 1 -C 40 ) branched or unbranched alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, halogen, or the group ##STR42## wherein R'" is (C 1 -C 10 ) alkyl, branched or unbranched (C 3 -C 40 ) alkenyl, X is chlorine, fluorine, bromine or iodine, and n is 0 to 20.

Claim 94

The composition of claim 83 wherein said chain transfer agent is selected from the group consisting of an α-olefin having 2 to 30 carbon atoms, isobutylene, 1,7-octadiene, and 1,6-octadiene.

Claim 95

The composition of claim 84 wherein said chain transfer agent is selected from the group consisting of ethylene, propylene, 4-methyl-1-pentene, 1-decene, and 1-dodecene.

Claim 96

The composition of claim 85 wherein said norbornene functional monomer is selected from a compound represented by the formulae: ##STR43## wherein R 4 , R 4' R 5 , and R 5' independently represent hydrogen, halogen, branched and unbranched (C 1 -C 20 ) alkyl, (C 1 -C 20 ) haloalkyl, substituted and unsubstituted cycloalkyl, (C 1 -C 6 ) alkylidenyl, (C 6 -C 40 ) aryl, (C 6 -C 40 ) haloaryl, (C 7 -C 15 ) aralkyl, (C 7 -C 15 ) haloaralkyl, (C 2 -C 20 ) alkynyl, vinyl, (C 3 -C 20 ) alkenyl, provided the alkenyl radical does not contain a terminal double bond, halogenated alkyl of the formula --C n F 2n-1 , wherein n is 1 to 20, R 4 and R 5 when taken with the two ring carbon atoms to which they are attached represent saturated and unsaturated cyclic groups containing 4 to 12 carbon atoms or an aromatic ring containing 6 to 17 carbon atoms, "a" represents a single or double bond, and "z" is 1 to 5, when R 4 , R 4' R 5 , and R 5' represent an alkylidene radical, the carbon atom to which the alkylidene radical is attached cannot have another substituent, and when "a" is a double bond R 4 to R 5 cannot be alkylidenyl.