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EP0313838A2 Expired / Lapsed EP ⏱️ 0.0 years remaining

Cycloolefin polymers obtained from resinous monomers

Assignee: Goodrich Corp
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Filing: 1988-09-27
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Granted: —
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Expires: 2008-09-27
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Abstract

Abstract The compositions provided by this invention comprise ring-opened polymerized polymers obtained from cycloolefin monomers wherein a portion of said monomer is comprised of high molecular weight, resinous cycloolefin monomers. These resinous cycloolefin monomers provide high heat distortion temperatures without significantly affecting processability when polymerized in a solvent. When ring-opened polymerized cycloolefin monomers and resinous cycloolefin monomers are polymerized in bulk, in a mold, there is no need for processability and molecular weight control. These resinous cycloolefin monomers are obtained by Diels-Alder reaction of cyclopentadiene with cycloolefin monomers and/or olefins. Significant improvements (increases) in glass transition are seen, which correlates with higher heat distortion temperatures. The polymers obtained exhibit glass transition temperatures suitable for automotive and other engineering plastic applications.

Inventors

  • 👤 Linwood P. Tenney
  • 👤 Parley C. Lane
  • 👤 Paul T. Stricharczuk

Bibliographic Details

Application Number —
Jurisdiction EP
Data Source google_patents
Last Synchronized 2026-11-04 03:44
CPC Classifications
C; C08; C08G; C08G61/00; C08G61/02; C08G61/04; C08G61/06; C08G61/08

Claims Analysis

Total Claims: 22
Claim 1
Independent Claim 288 words
A composition comprised of a ring-opened polymerized polymer derived from cycloolefin monomers of which at least about 5 weight percent, based on the total weight of cycloolefin monomers, are one or more resinous cycloolefin monomers conforming to a formula selected from the group consisting of formulas I and II below: wherein: (a) n of Formula I is a whole number of from 1 to 10 having a average value greater than 1 for all the resinous cycloolefin monomers of Formula I in said ring-opened polymerized polymer; (b) both m and m′ of Formula II are independently whole numbers of from 1 to 9 wherein the sum of m+m′ is less than 10 for each resinous cycloolefin monomer and the average value of m+m′ for all the resinous cycloolefin monomers of Formula II in said ring-opening polymerized polymer is greater than 2; and (c) where n is 2 or more, A and B of Formula I are (i) independently selected from hydrogen, halogen, alkyl groups of from 1 to 12 carbon atoms, alkylene groups of from 2 to 12 carbon atoms, substituted and unsubstituted aryl groups of from 6 to 20 carbon atoms, saturated and unsaturated cycloalkyl and substituted cycloalkyl groups of from 6 to 20 carbon atoms or (ii) combined together to form cyclic groups of 4 to 12 carbon atoms with the two ring carbon atoms connected thereto and are selected from unsaturated cyclic structures, saturated cyclic structures and combinations of both, and (d) where n is equal to 1, A and B are combined together to form cyclic groups of 4 to 12 carbon atoms with the two ring carbon atoms connected thereto and are selected from unsaturated cyclic structures, cyclic structures and combinations of both.
Claim 2
Dependent Claim 288 words
A composition comprised of a ring-opened polymerized polymer derived from cycloolefin monomers of which at least about 5 weight percent, based on the total weight of cycloolefin monomers, are one or more resinous cycloolefin monomers conforming to a formula selected from the group consisting of formulas I and II below: wherein: (a) n of Formula I is a whole number of from 1 to 10 having a average value greater than 1 for all the resinous cycloolefin monomers of Formula I in said ring-opened polymerized polymer; (b) both m and m′ of Formula II are independently whole numbers of from 1 to 9 wherein the sum of m+m′ is less than 10 for each resinous cycloolefin monomer and the average value of m+m′ for all the resinous cycloolefin monomers of Formula II in said ring-opening polymerized polymer is greater than 2; and (c) where n is 2 or more, A and B of Formula I are (i) independently selected from hydrogen, halogen, alkyl groups of from 1 to 12 carbon atoms, alkylene groups of from 2 to 12 carbon atoms, substituted and unsubstituted aryl groups of from 6 to 20 carbon atoms, saturated and unsaturated cycloalkyl and substituted cycloalkyl groups of from 6 to 20 carbon atoms or (ii) combined together to form cyclic groups of 4 to 12 carbon atoms with the two ring carbon atoms connected thereto and are selected from unsaturated cyclic structures, saturated cyclic structures and combinations of both, and (d) where n is equal to 1, A and B are combined together to form cyclic groups of 4 to 12 carbon atoms with the two ring carbon atoms connected thereto and are selected from unsaturated cyclic structures, cyclic structures and combinations of both.
Claim 3
Dependent Claim 37 words
A composition as in claim 1 wherein the average value of n for all the resinous cycloolefin monomers of Formula I within the ring-opened polymerized polymer falls in the range of above about 1 to about 2.
Claim 4
Dependent Claim 88 words
A composition as in claim 1 wherein the one or more resinous cycloolefin monomers are copolymerized with a cycloolefin monomer which conforms to a formula selected from the group consisting of wherein R² and R³ are (a) independently selected from hydrogen, halogen, C₁-C₁₂ alkyl groups, C₂-C₁₂ alkylene groups, C₆-C₂₀ cycloalkyl groups and C₆-C₂₀ aryl groups or (b) together form cyclic groups of from 4 to 12 carbon atoms with the two ring carbon atoms connected thereto selected from saturated cyclic structures, unsaturated cyclic structures and combinations of both.
Claim 5
Dependent Claim 80 words
A composition as in claim 3 wherein the one or more resinous cycloolefin monomers which conform to Formula I also conform to a formula selected from the group consisting of wherein n is a whole number of from 1 to 10 and has an average value greater than 1 and below about 6 for all resinous cycloolefin monomers of Formulas III, IV and V, and R and R¹ are independently selected from hydrogen C₁-C₄ alkyl groups and C₂-C₄ alkylene groups.
Claim 6
Dependent Claim 35 words
A composition as in claim 4 wherein the cycloolefin monomer copolymerized with the one or more resinous cycloolefin monomers is selected from the group consisting of tetracyclododecene, 2-norbornene, dicyclopentadiene, tricyclopentadiene 5-methyl-2-norbornene, 5-ethyl-2-norbornene, methyl-tetracyclododecene and ethyl-tetracyclododecene.
Claim 7
Dependent Claim 23 words
A composition as in claim 4 wherein the one or more resinous cycloolefin monomers are additionally copolymerized with a non-conjugated acyclic olefin monomer.
Claim 8
Dependent Claim 25 words
A composition as in claim 4 which further comprises components selected from the group consisting of impact modifiers, flame retardants, UV stabilizers, pigments and fillers.
Claim 9
Dependent Claim 75 words
A composition as in claim 4 wherein said ring-opened polymerized polymer is a copolymer derived from monomers comprised of cycloolefin monomers of which about 15 to 30 weight percent are one or more resinous cycloolefin monomers of Formulas III, IV and V and from about 50 to 85 weight percent are one or more cycloolefin monomers of Formulas VI and VII, wherein said weight percent is based on the total weight of said cycloolefin monomers.
Claim 10
Dependent Claim 18 words
A composition as in claim 8 which additionally comprises from 1 to 10 percent by weight impact modifier.
Claim 11
Dependent Claim 23 words
A composition as in claim 9 wherein said impact modifier is selected from polybutadiene, polyisoprenes, polyethylene, styrene-butadiene-styrene block copolymers, and ethylene-propylene-diene modified copolymers.
Claim 12
Dependent Claim 14 words
A composition as in claim 8 which additionally comprises 5-20% by weight flame retardant.
Claim 13
Dependent Claim 21 words
A composition as in claim 11 wherein said flame retardant is comprised of antimony oxide and an organic halogen containing compound.
Claim 14
Dependent Claim 20 words
A composition as in claim 12 wherein said organic halogen containing compound is selected from decabromodiphenyl ether and octabromodiphenyl ether.
Claim 15
Dependent Claim 24 words
A composition as in claim 1 wherein said ring-opened polymerized polymer is produced by a bulk polymerization process, in the substantial absence of solvent.
Claim 16
Dependent Claim 16 words
A composition as in claim 14 wherein said ring-opened polymerized polymer is formed within a mold.
Claim 17
Dependent Claim 23 words
A composition as in claim 1 wherein said ring-opened polymerized polymer is produced by a solution polymerization process, in the presence of solvent.
Claim 18
Dependent Claim 64 words
A composition substantially comprised of a ring-opened polymerized polymer derived from monomers comprised of (a) 40 to 95 % by weight of a cycloolefin selected from the group consisting of dicyclopentadiene, ethylidene­norbornene and ethylidene-tetracyclododecene methyl-­norbornene, methyl-tetracyclododecene, norbornene and tetracyclododecene; (b) 5 to 25% by weight cyclopentadiene trimer; (c) 0.5 to 10% by weight and cyclopentadiene tetramer; (d) 0 to 1% by weight cyclopentadiene pentamer.
Claim 19
Dependent Claim 64 words
A composition substantially comprised of a ring-opened polymerized polymer derived from monomers comprised of (a) 40 to 95 % by weight of a cycloolefin selected from the group consisting of dicyclopentadiene, ethylidene­norbornene and ethylidene-tetracyclododecene methyl-­norbornene, methyl-tetracyclododecene, norbornene and tetracyclododecene; (b) 5 to 25% by weight cyclopentadiene trimer; (c) 0.5 to 10% by weight and cyclopentadiene tetramer; (d) 0 to 1% by weight cyclopentadiene pentamer.
Claim 20
Dependent Claim 20 words
A composition substantially comprised of a ring-opened polymerized polymer derived from about 5% to about 100% by weight hexacycloheptadecene monomers.
Claim 21
Dependent Claim 20 words
A composition substantially comprised of a ring-opened polymerized polymer derived from about 5% to about 100% by weight hexacycloheptadecene monomers.
Claim 22
Dependent Claim 23 words
A composition as in claim 17 wherein cyclopentadiene trimer, cyclopentadiene tetramer and cyclopentadiene pentamer are obtained by Diels-Alder reaction of cyclopentadiene with dicyclopentadiene.

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