US4948856A — Homogeneous addition copolymers of ethylene and c…

Claim 1

Independent Claim 184 words

A process for preparing homogeneous addition copolymers by copolymerization of a monomer having a norbornene group with ethylene within a vessel by contacting ethylene gas with a liquid reaction medium comprised of monomer having a norbornene group and an effective amount of a halogen containing addition polymerization catalyst/cocatalyst system which is soluble in said monomer having a norbornene group, wherein the reaction medium is maintained at a temperature in the range of about -50° C. to about 40° C.; the molar ratio of monomer having a norbornene group to ethylene within the vessel is maintained above about 90:10; the ethylene pressure in the reaction medium is maintained above 1 psig to about 10 psig; and the concentration of monomer having a norbornene group within the reaction medium is maintained above about 35% by volume, wherein the addition polymerization catalyst of the halogen-containig catalyst/cocatalyst system is a vanadium compound soluble in the monomer having a norbornene group and the cocatalyst of the halogen-containing catalyst/cocatalyst system is selected from an alkyl aluminum halide or an alkoxy alkyl aluminum soluble in the monomer having a norbornene group.

Claim 2

Dependent Claim 184 words

A process for preparing homogeneous addition copolymers by copolymerization of a monomer having a norbornene group with ethylene within a vessel by contacting ethylene gas with a liquid reaction medium comprised of monomer having a norbornene group and an effective amount of a halogen containing addition polymerization catalyst/cocatalyst system which is soluble in said monomer having a norbornene group, wherein the reaction medium is maintained at a temperature in the range of about -50° C. to about 40° C.; the molar ratio of monomer having a norbornene group to ethylene within the vessel is maintained above about 90:10; the ethylene pressure in the reaction medium is maintained above 1 psig to about 10 psig; and the concentration of monomer having a norbornene group within the reaction medium is maintained above about 35% by volume, wherein the addition polymerization catalyst of the halogen-containig catalyst/cocatalyst system is a vanadium compound soluble in the monomer having a norbornene group and the cocatalyst of the halogen-containing catalyst/cocatalyst system is selected from an alkyl aluminum halide or an alkoxy alkyl aluminum soluble in the monomer having a norbornene group.

Claim 3

Dependent Claim 165 words

A process as in claim 1 wherein the vanadium compound is of the formula V(O).sub.a (OR').sub.b (X).sub.c wherein X is halogen, R' is the hydrocarbon portion of an alkoxy group having from 1 to 20 carbon atoms, a is 0 or 1, b is a whole number of from 0 to 3 and c is a whole number of from 1 to 5, subject to the proviso that where a=1 then b+c=3 and where b=0 then c is from 3 to 5, and the co-catalyst is of the formula (X).sub.a,Al(R").sub.b,(OR).sub.c, wherein R" is an alkyl group of from 1 to 6 carbon atoms, R is the hydrocarbon portion of an alkoxy group having from 1 to 4 carbon atoms, X is halogen, a' is an integer having a value ranging from 1 to 2, b' is an integer having a value ranging from 1 to 2 and c' is an integer having a value ranging from 0 to 1 subject to the proviso that a'+b'+c'=3.

Claim 4

Dependent Claim 26 words

A process as in claim 1 wherein the reaction is terminated before the concentration of addition copolymer within the reaction medium exceeds 25 percent by volume.

Claim 5

Dependent Claim 64 words

A process as in claim 1 wherein the monomer having a norbornene group is selected from monomers of the formulas ##STR3## wherein R 2 and R 3 are independently selected from hydrogen, halogen and alkyl groups of 1 to 20 carbon atoms or together form saturated and unsaturated hydrocarbon cyclic groups containing 4 to 7 carbon atoms with the 2 ring carbons connected thereto.

Claim 6

Dependent Claim 23 words

A process as in claim 1 wherein the monomer having a norbornene group is selected from the group consisting of methylnorbornene and methyltetracyclododecene.

Claim 7

Dependent Claim 19 words

A process as in claim 1 wherein at least two monomers having a norbornene group are copolymerized with ethylene.

Claim 8

Dependent Claim 32 words

A process as in claim 1 wherein the reaction medium contains an additional olefinic monomer selected from the group consisting of non-conjugated acyclic α-olefins which are substantially liquid at the reaction temperature.

Claim 9

Dependent Claim 16 words

A process as in claim 1 wherein the reaction medium is substantially free of diluent solvent.

Claim 10

Dependent Claim 51 words

A process as in claim 1 wherein the reaction medium comprises from about 10 to about 65 percent by volume of a solvent selected from the group consisting of aliphatic and cycloaliphatic hydrocarbon solvents of from 4 to 10 carbon atoms and aromatic hydrocarbon solvents containing 6 to 14 carbon atoms.

Claim 11

Dependent Claim 18 words

A process as in claim 1 wherein the pressure of ethylene gas is maintained substantially constant during reaction.

Claim 12

Dependent Claim 32 words

A process as in claim 1 wherein the copolymerization reaction is terminated before the concentration of addition copolymer within the reaction medium exceeds about 10 percent by volume of the reaction medium.

Claim 13

Dependent Claim 112 words

A process as in claim 1 wherein the vanadium catalyst is selected from the group consisting of VCl 5 , VOCl 3 , VCl 3 , VO(OC 2 H 5 ) 2 Cl, VO(OCH 3 ) 2 Cl, VO(OCH 3 )Cl 2 , VO(OCH 3 ) 3 , VO(OC 3 H 7 )Cl 2 , VCl 4 and VO(OC 3 H 7 ) 3 and the co-catalyst is selected from the group consisting of Al(CH 3 ) 2 Cl, AlCH 3 Cl 2 , Al(OC 4 H 9 )(C 4 H 9 )Cl, Al(C 2 H 5 ) 2 Cl and Al 2 (C 2 H 5 ) 3 Cl 3 .

Claim 14

Dependent Claim 24 words

An alternating addition copolymer of ethylene monomer units and a monomer having a norbornene group prepared in accordance with the process of claim 1.

Claim 15

Dependent Claim 49 words

An alternating addition copolymer as in claim 13 wherein the monomer having a norbornene group is a monomer selected from the group consisting of 5-methyl-2-norbornene, 9-methyl-tetracyclo[6,2,1,1 3 ,6, 0 2 ,7 ]dodecene-4, 2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, tetracyclododecene, 9-ethyl-tetracyclo[6,2,1,1 3 ,6,0 2 .7 ]dodecene-4 and 9-propyl-tetracyclo[6,2,1,1 3 ,6,0 2 ,7 ]dodecene-4.

Claim 16

Dependent Claim 72 words

An alternating amorphous addition copolymer of ethylene monomer units and having a norbornene group, wherein the monomer having a norbornene group is selected from monomers of the formulas ##STR4## wherein R 2 and R 3 are independently selected from hydrogen, halogen and alkyl groups of 1 to 20 carbon atoms or together form saturated and unsaturated hydrocarbon cycle groups containing 4 to 7 carbon atoms with the 2 ring carbons connected thereto.

Claim 17

Dependent Claim 72 words

An alternating amorphous addition copolymer of ethylene monomer units and having a norbornene group, wherein the monomer having a norbornene group is selected from monomers of the formulas ##STR4## wherein R 2 and R 3 are independently selected from hydrogen, halogen and alkyl groups of 1 to 20 carbon atoms or together form saturated and unsaturated hydrocarbon cycle groups containing 4 to 7 carbon atoms with the 2 ring carbons connected thereto.

Claim 18

Dependent Claim 19 words

An amorphous, alternating addition copolymer of claim 13 which comprises at least two different monomers having a norbornene group.

Claim 19

Dependent Claim 21 words

An amorphous addition copolymer of ethylene and methyltetracyclododecene having a glass transition temperature between about 200° C. and about 216° C.

Claim 20

Dependent Claim 21 words

An amorphous addition copolymer of ethylene and methyltetracyclododecene having a glass transition temperature between about 200° C. and about 216° C.

Claim 21

Dependent Claim 22 words

An amorphous alternating addition copolymer of ethylene and methylnorbornene having a glass transition temperature between about 120° C. and about 129° C.

Claim 22

Dependent Claim 22 words

An amorphous alternating addition copolymer of ethylene and methylnorbornene having a glass transition temperature between about 120° C. and about 129° C.

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1993-08-13	1994-02-12	1994-08-14	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1997-08-13	1998-02-12	1998-08-14	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2001-08-13	2002-02-12	2002-08-14	$7700.00	Window Closed / Lapsed

Homogeneous addition copolymers of ethylene and cycloolefin monomers and method for producing same

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