IP Library Granted Patent US 12,173,097
Granted Patent B2
US 12,173,097 · App. 18/691,751 · Granted Dec 24, 2024

Ionomers and/or chain extended/branched copolymers of impact modified vinylidene aromatic monomer and unsaturated compounds

Inventors: Mark Georges Vreys (Oostakker, BE); Claude T. E. Van Nuffel (Oostakker, BE); Abidin Balan (Breda, NL)
Assignee: TRINSEO EUROPE GMBH
C08F212/08C08F2/38C08F220/06C08F220/325C08F279/02F25D23/066
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Quick Facts
Patent No.
US 12,173,097
App. No.
18/691,751
Granted
Dec 24, 2024
Kind
B2
Abstract

A composition includes one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, and the copolymer has on average about 0.01 to about 15.0 percent by weight of nucleophilic groups pendant from the copolymer. The copolymer is chain extended and/or branched by one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups, or a portion of the chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups are crosslinked with other chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups by ionic bonding of anions formed from the pendant nucleophilic groups with a metal cation having a valence of 2 or greater or complexation between pendant acid groups and metal oxides.

Claims (32)

1. A composition comprising one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.01 to about 15.0 percent by weight of nucleophilic groups pendant from the copolymer, wherein;

a) the copolymer is chain extended and or branched by one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups; or,

b) a portion of the chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups are crosslinked with other chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups by i) ionic bonding of anions formed from the pendant nucleophilic groups with a metal cation having a valence of 2 or greater or ii) complexation between pendant nucleophilic groups and metal oxides;

wherein the composition contains a rubber based impact modifier; and,

has a Mz+1 of about 600,000 to about 2,500,00 measured by gel permeation chromatography (GPC) and a gel content of 30 or higher measured as described in the description.

2. A composition according to claim 1 wherein the composition exhibits a Brinkman Crosslink Index of from 0.6 to 0.8.

3. A composition according to claim 1 , wherein the content of the rubber impact modifier is about 6 percent by weight or greater based on the weight of the copolymer and the impact modifier.

4. A composition according to claim 1 , wherein the impact modifier has a volumetric mean particle size of about 2 to about 10 microns greater measured by an extensional viscosity measurement as described in the description.

5. A composition according to claim 1 , wherein the elongational viscosity after 3 seconds at 200° C. is 75,000 Pas or greater measured by an extensional viscosity measurement as described in the description.

6. The composition according to claim 1 , wherein one or more copolymers of one or more vinylidene aromatic monomers and one or more one or more unsaturated compounds containing nucleophilic groups, the copolymer having about 0.01 to about 15.0 percent by weight of the one or more unsaturated compounds containing nucleophilic groups wherein the nucleophilic groups are pendant from the copolymer; wherein a portion of the chains of the copolymer of one or more vinylidene aromatic monomers and one or more unsaturated acids are crosslinked with other chains of the copolymer of one or more vinylidene aromatic monomers and one or more unsaturated acids by i) ionic bonding of anions formed from the pendant nucleophilic groups with the metal cation having a valence of 2 or greater or ii) complexation between the pendant nucleophilic groups and the metal oxides.

7. The composition according to claim 1 , wherein the one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.02 to about 3.0 percent by weight of nucleophilic groups pendant from the copolymer, the copolymer being chain extended and or branched by one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups.

8. The composition according to claim 1 , wherein the one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.01 to about 15.0 percent by weight of nucleophilic groups pendant from the copolymer, wherein

a) the copolymer being chain extended and or branched by one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups in an amount sufficient to react with about 0.02 to about 3.0 percent by weight of nucleophilic groups pendant from the copolymer; and,

b) a portion of the chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups are crosslinked with other chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups by i) ionic bonding of anions formed from the pendant nucleophilic groups with the metal cation having a valence of 2 or greater or ii) complexation between the pendant nucleophilic groups and the metal oxides.

9. The composition according to claim 1 , wherein the nucleophilic groups are carboxylate, carboxylic acid, alcohol, phenol, amine, aniline, imidazole, tetrazole, thiol, boronic acid, glycol, hydrazine and hydroxyl amine groups and the electrophilic groups are one or more of epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate and isothiocyanate groups.

10. The composition according to claim 9 , wherein the nucleophilic groups are carboxylic acid groups and the electrophilic groups are one or more of epoxide groups.

11. The composition according to claim 1 , wherein the crosslinks i) ionic bonding of anions formed from the pendant nucleophilic groups with the metal cation having a valence of 2 or greater or ii) complexation between the pendant nucleophilic groups and the metal oxides are reversible and the weight average molecular weight of the copolymer of one or more vinylidene aromatic monomers and the one or more unsaturated acids is substantially the same after the crosslinking is reversed as it is before crosslinking.

12. The composition according to claim 1 , wherein the metal cation and the metal oxides are one or more of transition metals, post transition metals, metalloids or an alkaline earth metals.

13. The composition according to claim 1 , wherein the equivalents ratio of metal ions to equivalents of anions formed from pendant nucleophilic groups on the copolymer is from about 40:1 to about 1:40.

14. A structure comprising a sheet having a polymeric layer comprising a composition comprising one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.01 to about 15.0 percent by weight of nucleophilic groups pendant from the copolymer, wherein;

a) the copolymer is chain extended and or branched by one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups; or,

b) a portion of the chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups are crosslinked with other chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups by i) ionic bonding of anions formed from the pendant nucleophilic groups with a metal cation having a valence of 2 or greater or ii) complexation between pendant nucleophilic groups and metal oxides;

wherein the composition contains a rubber based impact modifier; and,

has a Mz+1 of about 600,000 to about 2,500,00 measured by gel permeation chromatography (GPC) and a gel content of 30 or higher measured as described in the description.

15. A structure according to claim 14 wherein the sheet has more than one layer and one of the outer most layer comprises a composition according to any one of the preceding claims .

16. The composition according to claim 14 , wherein one or more copolymers of one or more vinylidene aromatic monomers and one or more one or more unsaturated compounds containing nucleophilic groups, the copolymer having about 0.01 to about 15.0 percent by weight of the one or more unsaturated compounds containing nucleophilic groups wherein the nucleophilic groups are pendant from the copolymer; wherein a portion of the chains of the copolymer of one or more vinylidene aromatic monomers and one or more unsaturated acids are crosslinked with other chains of the copolymer of one or more vinylidene aromatic monomers and one or more unsaturated acids by i) ionic bonding of anions formed from the pendant nucleophilic groups with a metal cation having a valence of 2 or greater or ii) complexation between pendant nucleophilic groups and metal oxides.

17. The composition according to claim 14 , wherein the one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.02 to about 3.0 percent by weight of nucleophilic groups pendant from the copolymer, the copolymer being chain extended and or branched by one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups.

18. The composition according to claim 14 , wherein the one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds containing nucleophilic groups, the copolymer having on average about 0.01 to about 15.0 percent by weight of nucleophilic groups pendant from the copolymer, wherein

a) the copolymer being chain extended and or branched by one or more copolymers of one or more vinylidene aromatic monomers and one or more unsaturated compounds having electrophilic groups in an amount sufficient to react with about 0.02 to about 3.0 percent by weight of nucleophilic groups pendant from the copolymer; and,

b) a portion of the chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups are crosslinked with other chains of the copolymer of one or more vinylidene aromatic monomers and one or more nucleophilic groups by i) ionic bonding of anions formed from the pendant nucleophilic groups with a metal cation having a valence of 2 or greater or ii) complexation between pendant acid groups and metal oxides.

19. The composition according to claim 14 , wherein the nucleophilic groups are carboxylate, carboxylic acid, alcohol, phenol, amine, aniline, imidazole, tetrazole, thiol, boronic acid, glycol, hydrazine and hydroxyl amine groups and the electrophilic groups are one or more of epoxide, anhydride, imide, ester, acyl halide, acyl nitrile, aldehyde, ketone, isocyanate and isothiocyanate groups.

20. The composition according to claim 19 , wherein the nucleophilic groups are carboxylic acid groups and the electrophilic groups are one or more of epoxide groups.

Assignments (4)
SECURITY INTEREST Recorded Jan 29, 2025
From: TRINSEO EUROPE GMBH
To: ALTER DOMUS (US) LLC
Reel/Frame 070048/0159 →
SECURITY INTEREST Recorded Jan 29, 2025
From: TRINSEO EUROPE GMBH
To: ALTER DOMUS (US) LLC
Reel/Frame 070048/0204 →
PATENT SECURITY AGREEMENT Recorded Jan 17, 2025
From: TRINSEO EUROPE GMBH
To: DEUTSCHE BANK AG NEW YORK BRANCH, AS COLLATERAL AGENT
Reel/Frame 069940/0035 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 10, 2024
From: VREYS, MARK GEORGES; VAN NUFFEL, CLAUDE T.E.; BALAN, ABIDIN
To: TRINSEO EUROPE GMBH
Reel/Frame 067948/0977 →
Priority Claims (1)
EP 21196543 · Sep 14, 2021 · regional
Continuity (1)
Related Publication 20240327555A1 · Oct 3, 2024