Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts

Claim 2

The catalyst composition of claim 1 wherein said substituent is selected from the group consisting of methyl, ethyl, isopropyl, tert -butyl, cyclohexyl, octyl, nonyl, phenyl, bromo, chloro, fluoro, ethoxy, methoxy, cyclopropane, trifluoromethyl, methylsulfonyl, and benzyl groups.

Claim 3

The catalyst composition of claim 1 further comprising a stabilizer compound.

Claim 4

The catalyst composition of claim 3 wherein said stabilizer compound is a Lewis base.

Claim 5

The catalyst composition of claim 3 wherein said stabilizer compound is selected from the group consisting of diethylether; ethylene glycol dimethylethers, 2-methoxy ethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, benzonitrile, acetonitrile, tetrahydrofuran, phenols having one aromatic ring, bisphenols having two aromatic rings, polyphenols having more than two aromatic rings and mixtures thereof.

Claim 6

The catalyst composition of claim 5 wherein said phenol is selected from the group consisting of 2,6-di- t -butyl-4-methyl phenol and 2,6-di- tert -butyl-4- sec -butylphenol; said bisphenols are selected from the group consisting of 4,4'-methylenebis(2,6- dimethylphenol); 4,4'-methylenebis(2,6-di- tert -butylphenol; 2,2'-methylenebis(4-ethyl-6-butylphenol); 2,2'-ethylenebis(4,6-di- tert -butylphenol; 2,2'-methylenebis(4-ethyl-6-(1-methylcyclohexyl)phenol; 4,4'-butylidenebis(6- tert -butyl-3-methylphenol) under the tradename Lowinox 44B25; 4,4'-thiobis(6- tert -butyl-3-methylphenol); 1,1'-thiobis(2-naphthol) sold under the tradename SAO-30; 2,2'-thiobis(4-methyl-6- tert -butylphenol); 2,2'-isobutylidene-bis(4,6-dimethylphenol; and 2,2'-methylenebis(4-methyl-6-cyclohexyl)phenol) and said polyphenols are selected from the group consisting of 1,3,5-trimethyl-2,4-6-tris(3,5-di- t -butyl-4-hydroxybenzene)benzene; sterically hindered polynuclear phenols and a butylated reaction product of p -cresol and dicylopentadiene.

Claim 7

The catalyst composition of claim 1 wherein said catalyst is effective in polymerization of dicyclopentadiene at concentrations of monomer to catalyst of 4000:1 and lower.

Claim 8

A polymerization feed composition comprising: (a) a metathesis polymerizable cycloolefin; (b) a metathesis polymerization catalyst represented by the formula WOX 4-x (OAr) x ; wherein X is selected from the group consisting of bromine, chlorine and fluorine; x is 1, 2 or 3 and OAr represents a mono-, di- tri-, tetra-, or penta-substituted phenoxy group; and (c) a catalyst activator.

Claim 9

The polymerization feed composition of claim 8 wherein X is chlorine.

Claim 10

The polymerization feed composition of claim 8 wherein said catalyst activator is selected from the group consisting of trialklyaluminum, dialkylaluminum halides, alkylaluminum dihalides, dialkyl(alkoxy)aluminum, alkyl(alkoxy)aluminum halide; dialkylzincs, alkylzinc halides, diarylzinc, arylzinc halides, alkylsilanes, tetraalkyltins, trialkyltin hydrides, dialkyltin dihydrides, triaryltin hydrides, alkyllead hydrides and aryllead hydrides.

Claim 11

The polymerization feed composition of claim 8 wherein said catalyst activator is selected from the group consisting of ethylaluminum dichloride, diethylaluminum chloride, triethylaluminum, diethylzinc, dibutylzinc, ethyl- n -propoxyaluminum chloride, diphenylzinc, tri- n -butyltin hydride, trioctyltin hydride, diphenyltin dihydride, and triphenyltin hydride.

Claim 12

The polymerization feed composition of claim 8 wherein said cycloolefin is a monomer selected from the group consisting of dicyclopentadiene, higher order cyclopentadiene oligomers, norbornene, norbornadiene, 4-alkylidene norbornenes, dimethanohexahydronaphthalene, dimethanohexahydronaphthalene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methyl-2-norbornene, 5-phenyl-2-norbornene, ethylidenetetracyclododecane, methyltetracyclododecane, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octylnorbornene, 5-dodecyl-2-norbornene, tetracyclododecane, hexacycloheptadecene, methyltetracyclododecene, ethylidenetetracyclododecene and mixtures of two or more of said monomers.

Claim 13

The polymerization feed composition of claim 8 wherein said Ar in said metathesis polymerization catalyst is a phenyl ring, wherein said ring is substituted with substituents selected from the group consisting of hydrogen, bromo, chloro, fluoro, iodo, nitro, cyano, aldehyde, carboxy, hydroxymethyl, alkoxy, alkylthio, arylthio, acyl, aroyl, acyloxy, alkoxycarbonyl, cycloalkanes, dialkylamino, diarylamino, alkylsulfonyl, arylsulfonyl, alkylsulfonate, arylsulfonate, aryl, aralkyl, aryloxy, alkyl groups containing 1-20 carbon atoms, fluoroalkyl groups containing 1 to 10 carbon atoms and allyl groups.

Claim 14

The polymerization feed composition of claim 13 wherein said phenyl ring is substituted with substituents selected from the group consisting of methyl, ethyl, isopropyl, tert -butyl, cyclohexyl, octyl, nonyl, phenyl, bromo, chloro, fluoro, ethoxy, methoxy, cyclopropane, trifluoromethyl, methylsulfonyl, and benzyl groups.

Claim 15

The polymerization feed composition of claim 8 further comprising a rate moderator compound.

Claim 16

The polymerization feed composition of claim 15 wherein said rate moderator compound is selected from the group consisting of phosphines, phosphites, phosphinites, phosphonites, pyridines, and pyrazines.

Claim 17

The polymerization feed composition of claim 8 wherein said metathesis polymerization catalyst further comprises a stabilizer compound.

Claim 18

The polymerization feed composition of claim 17 wherein said stabilizer compound is a Lewis base.

Claim 19

The polymerization feed composition of claim 18 wherein said stabilizer compound is selected from the group consisting of diethylether; ethylene glycol dimethyl ethers, 2-methoxy ethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, benzonitrile, acetonitrile, tetrahydrofuran, phenols having one aromatic ring, bisphenols having two aromatic rings, polyphenols having more than two aromatic rings and mixtures thereof.

Claim 20

The polymerization feed composition of claim 18 wherein said stabilizer compound further comprises a phenol.

Claim 21

A process for preparing molded objects comprising charging to a mold a liquid reaction mass comprising the polymerization feed composition of claims 8, 9, 10, 11, 12, 13 or 14, wherein after said liquid reaction mass is charged to said mold, said reaction mass polymerizes in said mold.