Process to produce a polyolefin reactive telechelic pre-polymer, polyolefin reactive telechelic pre-polymers and crosslinked elastomers and high molecular weight elastomers

Patent metadata

Field	Value
Publication number	US-10005878-B2
Application number	US-201415024948-A
Country	US
Kind code	B2
Filing date	Sep 18, 2014
Priority date	Sep 30, 2013
Publication date	Jun 26, 2018
Grant date	Jun 26, 2018

Abstract

A process to produce a polyolefin reactive telechelic pre-polymer comprising reacting alkyl-cis-cyclooctene and optionally cis-cyclooctene, in the presence of a difunctional chain transfer agent under ring opening metathesis polymerization conditions to form an unsaturated polyolefin reactive telechelic pre-polymer is provided. Further provided are unsaturated and hydrogenated reactive pre-polymers, crosslinked elastomers and high molecular weight elastomers.

First claim

We claim:

1. A process to produce a crosslinked elastomer comprising:
reacting alkyl-cis-cyclooctene and optionally cis-cyclooctene, in the presence of a difunctional chain transfer agent and/or a polyfunctional chain transfer agent under ring opening metathesis polymerization conditions to form an unsaturated polyolefin reactive telechelic pre-polymer;
hydrogenating the unsaturated polyolefin reactive telechelic pre-polymer to produce a hydrogenated polyolefin reactive telechelic pre-polymer; and
thermally crosslinking the hydrogenated polyolefin reactive telechelic pre-polymer with a polyfunctional compound which is reactive with the hydrogenated polyolefin reactive telechelic pre-polymer, optionally in the absence of a catalyst, to form a crosslinked elastomer.

2. The process according to claim 1 , wherein the polyfunctional compound is selected from the group of polyamines and polyepoxides.

3. The process according to claim 1 , wherein the polyfunctional compound which is reactive with the hydrogenated polyolefin reactive telechelic pre-polymer is polyfunctional aziridine.

4. The process according to claim 3 , wherein the polyfunctional aziridine is trimethylolpropane tri(2-methyl-1-aziridine propionate).

5. The process according to claim 1 , wherein a mole ratio of the functionalities of the polyfunctional compound to the functionalities of the hydrogenated polyolefin reactive telechelic pre-polymer is from 1:0.94 to 1:1.06.

6. The crosslinked elastomer produced by the process of claim 1 , wherein the crosslinked elastomer has one or more properties selected from the group consisting of: (a) gel fraction of equal to or less than 0.99 and equal to or greater than 0.3; (b) a T d of equal to or greater than 310° C.; (c) a glass transition temperature, T g , less than or equal to or less than −25° C.; (d) hysteresis of 20% or less; and (e) a difference in an elastic modulus at 0° C. and the elastic modulus at a temperature 1° C. less than the decomposition temperature is less than 35%.

7. A process to produce a chain extended polyolefin reactive telechelic pre-polymer comprising:
reacting alkyl-cis-cyclooctene and optionally cis-cyclooctene, in the presence of a difunctional chain transfer agent and/or a polyfunctional chain transfer agent under ring opening metathesis polymerization conditions to form an unsaturated polyolefin reactive telechelic pre-polymer;
hydrogenating the unsaturated polyolefin reactive telechelic pre-polymer to produce a hydrogenated polyolefin reactive telechelic pre-polymer; and
chain extending the hydrogenated polyolefin reactive telechelic pre-polymer with a difunctional compound which is reactive with the hydrogenated polyolefin reactive telechelic pre-polymer, optionally in the absence of a catalyst, to form a high molecular weight elastomer.

8. The process according to claim 7 , wherein the difunctional compound is selected from the group of diamines and diepoxides.

9. The process according to claim 7 , wherein the difunctional compound which is reactive with the hydrogenated polyolefin reactive telechelic pre-polymer is difunctional aziridine.

10. The process according to claim 9 , wherein the difunctional aziridine is butane-1,4-diylbis(3-(2-methylaziridin-1-yl)propanoate).

11. A process to produce a crosslinked and chain extended elastomer comprising:
reacting alkyl-cis-cyclooctene and optionally cis-cyclooctene, in the presence of a difunctional chain transfer agent and/or a polyfunctional chain transfer agent under ring opening metathesis polymerization conditions to form an unsaturated polyolefin reactive telechelic pre-polymer;
hydrogenating the unsaturated polyolefin reactive telechelic pre-polymer to produce a hydrogenated polyolefin reactive telechelic pre-polymer; and
simultaneously thermally crosslinking the hydrogenated polyolefin reactive telechelic pre-polymer with a polyfunctional compound which is reactive with the hydrogenated polyolefin reactive telechelic pre-polymer and chain extending the hydrogenated polyolefin reactive telechelic pre-polymer with a difunctional compound which is reactive with the hydrogenated polyolefin reactive telechelic pre-polymer, optionally in the absence of a catalyst, to form a crosslinked and chain extended elastomer.

12. The process according to claim 11 , wherein the polyfunctional compound which is reactive with the polyolefin reactive telechelic pre-polymer is polyfunctional aziridine and the difunctional compound which is reactive with the hydrogenated polyolefin reactive telechelic pre-polymer is difunctional aziridine.

13. The process according to claim 12 , wherein the polyfunctional aziridine is trimethylolpropane tri(2-methyl-1-aziridine propionate).

14. The process according to claim 12 , wherein the difunctional aziridine is butane-1,4-diylbis(3-(2-methylaziridin-1-yl)propanoate).

15. The process according to claim 11 , wherein the polyfunctional compound is selected from the group of polyamines and polyexpodies.

16. The process according to claim 11 , wherein the difunctional compound is selected from the group of diamines and diepoxides.

17. The crosslinked and chain extended elastomer produced by the process of claim 11 , wherein the crosslinked and chain extended elastomer has one or more properties selected from the group consisting of: (a) gel fraction of equal to or less than 0.99 and equal to or greater than 0.3; (b) a T d of equal to or greater than 310° C.; (c) a glass transition temperature, T g , less than or equal to or less than −25° C.; (d) hysteresis of 20% or less; and (e) a difference in an elastic modulus at 0° C. and the elastic modulus at a temperature 1° C. less than the decomposition temperature is less than 35%.

Assignees

• Dow Global Technologies Llc
• Univ Minnesota

Inventors

• Martinez Henry
• Hillmyer Marc A
• Munro Jeffrey C
• Walton Kim L
• Hughes Morgan M

Classifications

• C08G61/08 Primary

  of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring · CPC title

• C08G2261/418

  Ring opening metathesis polymerisation [ROMP] · CPC title

• C08G2261/135

  Cross-linked structures · CPC title

• C08G61/06 Primary

  prepared by ring-opening of carbocyclic compounds · CPC title

• C08G2261/1412

  Saturated aliphatic units · CPC title