Activated isobutylene-isoprene rubber and thermoset rubber therefrom

Patent metadata

Field	Value
Publication number	US-10676598-B2
Application number	US-201816053048-A
Country	US
Kind code	B2
Filing date	Aug 2, 2018
Priority date	Aug 2, 2017
Publication date	Jun 9, 2020
Grant date	Jun 9, 2020

Abstract

In one or more embodiments, the present invention provides an way to modify the isoprene unit using an alder-ene reaction to form thermoset compounds comprising the resultant electron-deficient, readily crosslinkable polyisobutylene-based rubber that avoids the use of corrosive bromine or chlorine to make the activated butyl rubber, is easier to crosslink than the halobutyls, allows crosslinking with a simple organic base or a peroxide, and has mechanical properties as good as or better than sulfur crosslinked butyl rubbers.

First claim

What is claimed is:

1. A curable rubber compound comprising one or more curative and an isobutylene-isoprene rubber derivative having the structure:

where R is an organic group, alkyl group, alkoxy group, aryl group or hydrogen, x is an average number from 20 to 100, and n is an average number from 20 to 500.

2. The curable rubber compound according to claim 1 , wherein R is selected from the group consisting of methoxy, ethoxy, t-butoxy, phenoxy, pentafluorophenoxy, methyl, ethyl, t-butyl, and phenyl, and combinations thereof.

3. The curable rubber compound according to claim 1 , wherein said one or more curative comprises sulfur.

4. The curable rubber compound according to claim 1 , wherein said one or more curative comprises an organic base.

5. The curable rubber compound according to claim 1 , wherein said one or more curative comprises a peroxide.

6. The curable rubber compound according to claim 1 , wherein said one or more curative comprises a phenolic resin curative.

7. The curable rubber compound according to claim 1 further comprising one or more coagents.

8. A method for making the curable rubber compound according to claim 1 comprising:
A) preparing an isobutylene-isoprene rubber derivative having the structure:

where R is an organic group, alkyl group, alkoxy group, aryl group or hydrogen, x is an average number from 20 to 100, and n is an average number from 20 to 500; and

B) adding a curative; and
C) mixing to distribute the curative throughout said isobutylene-isoprene rubber derivative.

9. The method of claim 8 wherein the step of preparing an isobutylene-isoprene rubber derivative (step A) comprises reacting an isobutylene-isoprene rubber with an acetylenyl organic carbonyl compound having the structure:

where R is an organic group or hydrogen.

10. The method of claim 8 wherein the step of preparing an isobutylene-isoprene rubber derivative comprises:
1) preparing an isobutylene-isoprene rubber having the formula:

where R is an organic group, alkyl group, alkoxy group, aryl group, or hydrogen, x is an average number from 20 to 100, and n is an average number from 20 to 500;

2) preparing a an acetylenyl organic carbonyl compound having the structure:

where R is an organic group or hydrogen;

3) combining said isobutylene-isoprene rubber and said acetylenyl organic carbonyl compound in a saturated hydrocarbon solvent and initiating a alder-ene reaction between the triple bond in said acetylenyl organic carbonyl compound and the unsaturated double bond in an isoprene unit in said isobutylene-isoprene rubber to produce the isobutylene-isoprene rubber derivative of step A.

11. The method of claim 9 wherein R is selected from the group consisting of methoxy, ethoxy, t-butoxy, phenoxy, pentafluorophenoxy, methyl, ethyl, t-butyl, and phenyl, and combinations thereof.

12. The method of claim 10 wherein R is selected from the group consisting of methoxy, ethoxy, t-butoxy, phenoxy, pentafluorophenoxy, methyl, ethyl, t-butyl, and phenyl, and combinations thereof.

13. The method of claim 9 wherein the reaction between the isobutylene-isoprene rubber with the acetylenyl organic carbonyl compound is carried out in a saturated hydrocarbon solvent at a temperature between 20° C. to 150° C.

14. The method of claim 10 wherein the alder-ene reaction is carried out in said saturated hydrocarbon solvent at a temperature between 20° C. to 150° C.

15. The method of claim 10 wherein the alder-ene reaction between the isobutylene-isoprene rubber with the acetylenyl organic carbonyl compound is catalyzed by a Lewis acid.

16. The method of claim 15 wherein said Lewis acid is selected from the group consisting of aluminum trichloride, ethylaluminum dichloride, tris(pentafluorophenyl)boron, titanium tetrachloride, and combinations thereof.

17. The method of claim 8 wherein the step of adding a curative (step B) comprises adding a curative selected group the group consisting of sulfur-based curatives, organic base-based curatives, peroxide-based curatives, and combinations thereof.

18. The method of claim 9 wherein the step of adding a curative (step B) further comprises adding one or more co-agent.

19. An organic base-cured rubber compound comprising the curable rubber compound of claim 4 .

20. The organic base-cured rubber compound of claim 19 , having a tensile strength as measured by a tensometer, toughness as measured by a tensometer, or elongation as measured by tensometer, that is at least as good as a comparable sulfur cured isobutylene-isoprene butyl rubber.

21. A peroxide-cured rubber compound comprising the curable rubber compound of claim 5 .

22. The peroxide-cured rubber compound of claim 21 , having a tensile strength as measured by a tensometer, toughness as measured by tensometer, or elongation as measured by tensometer, that is at least as good as a comparable sulfur cured isobutylene-isoprene butyl rubber.

Assignees

• Jia Li
• Sun Yu
• Kuenen Mara
• Univ Akron

Inventors

• Jia Li
• Sun Yu
• Kuenen Mara

Classifications

• C08C19/28

  Reaction with compounds containing carbon-to-carbon unsaturated bonds (graft polymers C08F279/00) · CPC title

• C08L9/00 Primary

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title

• C08F255/10

  on to butene polymers · CPC title

• C08K5/14

  Peroxides · CPC title

• C08K5/3442

  having two nitrogen atoms in the ring · CPC title