Cross-linked plastomers as a replacement for rubber

Patent metadata

Field	Value
Publication number	US-11845836-B2
Application number	US-201917276724-A
Country	US
Kind code	B2
Filing date	Sep 30, 2019
Priority date	Oct 2, 2018
Publication date	Dec 19, 2023
Grant date	Dec 19, 2023

Abstract

Articles comprising a polymer composition, wherein the polymer composition is obtainable by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups, wherein the polymer composition shows high gel content and low compression set at −25° C. These articles have applications in automotive weather-stripping, such as sealing systems for doors, trunks and hoods.

First claim

The invention claimed is:

1. An article comprising:
a polymer composition,
wherein the polymer composition is obtained by grafting an ethylene copolymer with comonomer units comprising hydrolysable silane groups, and
wherein, the polymer composition has an amount of more than 0.5 wt. % of the comonomer units comprising hydrolysable silane groups, based on the total weight amount of monomer units in the polymer composition,
wherein the said ethylene copolymer comprises alpha-olefin comonomer units having from 6-12 carbon atoms, and
wherein the said ethylene copolymer is characterized as having:
a density of from 840 to 890 kg/m 3 ,
wherein the ratio of cis to trans groups in the ethylene copolymer is greater than 1, and
a total unsaturation of from 20 to 100 unsaturated bonds per 100,000 CH n groups.

2. The article according to claim 1 , wherein the ethylene copolymer comprises from 10 wt. % to 50 wt. % of alpha olefin comonomer units having from 6 to 12 carbon atoms based on the total amount of monomer units in the ethylene copolymer (as determined using NMR).

3. The article according to claim 1 , wherein the alpha olefin comonomer units are selected from 1-octene or 1-hexene.

4. The article according to claim 1 , wherein the ratio of vinyl groups to total unsaturated groups in the ethylene copolymer is less than 0.6.

5. The article according to claim 1 , wherein the ethylene copolymer has a crystallinity between 5 and 8% when measured by DSC using 50° C./min cooling and heating rates.

6. The article according to claim 1 , wherein the polymer composition comprises further polymer components.

7. The article according to claim 1 , wherein the polymer composition has been cross-linked after forming the article by hydrolysing the silane groups in the presence of a silanol condensation catalyst (SCC).

8. The article according to claim 7 , wherein after crosslinking the article has a compression set (ISO 815-1:2010-9 at −25° C.) of from 0% to 5% when measured at −25° C.

9. The article according to claim 7 , wherein after crosslinking the article has a compression set (ISO 815-1:2010-9 at 23° C.) of from 0 to 20%, when measured at 23° C.

10. The article according to claim 7 , wherein the composition after crosslinking has a gel content of from 75% to 99%.

11. The article according to claim 7 , wherein the ethylene copolymer has an MFR 2 (ISO 1133; 190° C.; 2.16 kg) in the range of from 0.01 to 5.0 g/10 min.

12. The article according to claim 7 , wherein the silanol condensation catalyst (SCC) used in the cross-linking step is a sulphonic acid.

13. The article according to claim 12 , wherein the silanol condensation catalyst is an aromatic organic sulphonic acid comprising the structural element:
Ar(SO 3 H) x   (IV)

wherein Ar is an aryl group which may be substituted or non-substituted, and if substituted, then substituted with at least one hydrocarbyl group comprising up to 50 carbon atoms, and wherein x is at least 1;
or wherein said structural element is a precursor of the sulphonic acid of formula (IV) including an acid anhydride thereof or a sulphonic acid of formula (IV) that has been provided with a hydrolysable protective group.

14. A process for the production of the article according to claim 1 , the process comprising the steps of:
a) providing an ethylene copolymer,
wherein the ethylene copolymer comprises alpha-olefin comonomer units having from 6-12 carbon atoms,
wherein the ethylene copolymer is characterized as having:
a density of from 840 to 890 kg/m 3 ,
wherein the ratio of cis to trans groups in the ethylene copolymer is greater than 1, and
a total unsaturation of from 20 to 100 unsaturated bonds per 100,000 CH n groups,
b) obtaining a polymer composition by grafting comonomer units comprising hydrolysable silane groups into the ethylene copolymer with a grafting agent to obtain a polymer composition with from 0.5 wt. % to 10 wt. % comonomer units comprising hydrolysable silane groups,
c) blending the silane grafted polymer composition from step b) with a silanol condensation catalyst,
d) forming the composition from step c) into an article.

15. The process according to claim 14 , wherein after step d) the article is cross-linked in the presence of water, to obtain a gel content (measured according to ASTM D 2765-01, Method A) of 75% to 99%.

Assignees

• Borealis Ag

Inventors

• Ruskeeniemi Jari-Jussi
• Oderkerk Jeroen
• Prieto Oscar
• Hellström Stefan
• Piel Tanja
• Mileva Daniela
• Prades Floran

Classifications

• C08G77/442 Primary

  containing vinyl polymer sequences · CPC title

• C08J3/24

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title

• C08J2383/10

  Block- or graft-copolymers containing polysiloxane sequences · CPC title

• C08F255/02 Primary

  on to polymers of olefins having two or three carbon atoms · CPC title

• C08F8/00

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title