Isobutylene-based polymers with olefinic side chain substituents and curable compositions containing the same

Patent metadata

Field	Value
Publication number	US-12043729-B2
Application number	US-201917040845-A
Country	US
Kind code	B2
Filing date	Mar 29, 2019
Priority date	Apr 3, 2018
Publication date	Jul 23, 2024
Grant date	Jul 23, 2024

Abstract

Provided herein are isobutylene-based polymer compositions comprising functionalized isobutylene-based polymer with olefinic side chain substituents, and a sulfur donor and/or accelerator cure system. The functionalized polymer is produced via nucleophilic substitution reaction in solution. The present functionalized isobutylene-based polymer compositions together with various accelerators and sulfur donors can form thermosets useful for pharmaceutical and tire applications without the use of zinc or a zinc oxide activator.

First claim

The invention claimed is:

1. An isobutylene-based polymer composition comprising:
(a) an isobutylene-based functionalized polymer; and
(b) one of or a combination of any of the following:
(i) a sulfur donor;
(ii) a blend of sulfur and a sulfur donor; and
(iii) an accelerator cure system;

wherein the isobutylene-based polymer composition has less than 0.01 wt % zinc based on a total weight of the isobutylene-based polymer composition.

2. The isobutylene-based polymer composition of claim 1 , wherein the isobutylene-based functionalized polymer is a modified poly(isobutylene-co-para-methylstyrene) amine-ionomer, wherein the poly(isobutylene-co-para-methylstyrene) amine-ionomer is selected from the group consisting of 1°, 2°, and 3° amine nucleophiles with one or more pendant vinyl groups.

3. The isobutylene-based polymer composition of claim 2 , wherein an amount of the poly(isobutylene-co-para-methylstyrene) amine-ionomer present in the isobutylene-based functionalized polymer is about 0.5 wt % to about 50 wt % based on the total weight of the isobutylene-based functionalized polymer.

4. The isobutylene-based polymer composition of claim 1 , wherein the isobutylene-based functionalized polymer is a modified poly(isobutylene-co-para-methylstyrene)-phosphine ionomer, wherein the modified poly(isobutylene-co-para-methylstyrene)-phosphine ionomer is selected from diphenylphosphinostyrene, allyldiphenylphosphine, diallylphenylphosphine, diphenylvinylphosphine, triallylphosphine, and combinations thereof.

5. The isobutylene-based polymer composition of claim 4 , wherein an amount of the phosphine ionomer present in the isobutylene-based functionalized polymer is about 0.5 wt % to about 50 wt % based on the total weight of the isobutylene-based functionalized polymer.

6. The isobutylene-based polymer composition of claim 1 , further comprising at least one filler.

7. The isobutylene-based polymer composition of claim 1 , wherein the sulfur donor is selected from the group consisting of tetramethyl thiuram disulfide (“TMTD”), 4,4′-dithiodimorpholine, dipentamethylene thiuram tetrasulfide (“DPTT”), and thiocarbamyl sulfonamide.

8. The isobutylene-based polymer composition of claim 1 , wherein the accelerator cure system comprises one or more of thiazoles, amines, guanidines, sulfenamides, thiurams, dithiocarbamates, and/or zanthates.

9. The isobutylene-based polymer composition of claim 8 , wherein the accelerator cure system is N-cyclohexyl-2-benzothiazole sulfenamide (“CBS”) or diphenylguanidine (“DPG”).

10. The isobutylene-based polymer composition of claim 6 , wherein the filler is selected from a group of carbon black, white filler, and combinations thereof.

11. The isobutylene-based polymer composition of claim 1 , wherein the composition is useful as a thermoset in pharmaceutical and tire applications.

12. A thermoset composition comprising:
(a) an isobutylene-based functionalized polymer; and
(b) one of or a combination of any of the following:
(i) a sulfur donor;
(ii) a blend of sulfur and a sulfur donor; and
(iii) an accelerator cure system;

wherein the thermoset composition has less than 0.01 wt % zinc based on the total weight of the thermoset composition.

13. The thermoset composition of claim 12 , wherein the isobutylene-based functionalized polymer is a modified poly(isobutylene-co-para-methylstyrene) amine-ionomer, wherein the poly(isobutylene-co-para-methylstyrene) amine-ionomer is selected from the group consisting of 1°, 2°, and 3° amine nucleophiles with one or more pendant vinyl groups.

14. The thermoset composition of claim 13 , wherein an amount of the poly(isobutylene-co-para-methylstyrene) amine-ionomer present in the isobutylene-based functionalized polymer is about 0.5 wt % to about 50 wt % based on the total weight of the isobutylene-based functionalized polymer.

15. The thermoset composition of claim 12 , wherein the isobutylene-based functionalized polymer is a modified poly(isobutylene-co-para-methylstyrene)-phosphine ionomer, wherein the phosphine ionomer is selected from diphenylphosphinostyrene, allyldiphenylphosphine, diallylphenylphosphine, diphenylvinylphosphine, triallylphosphine, and combinations thereof.

16. The thermoset composition of claim 15 , wherein an amount of the phosphine ionomer present in the isobutylene-based functionalized polymer is about 0.5 wt % to about 50 wt % based on the total weight of the isobutylene-based functionalized polymer.

17. The thermoset composition of claim 12 , further comprising at least one filler.

18. The thermoset composition of claim 12 , wherein the sulfur donor is selected from the group consisting of tetramethyl thiuram disulfide (“TMTD”), 4,4′-dithiodimorpholine, dipentamethylene thiuram tetrasulfide (“DPTT”), and thiocarbamyl sulfonamide.

19. The thermoset composition of claim 12 , wherein the accelerator cure system comprises one or more of thiazoles, amines, guanidines, sulfenamides, thiurams, dithiocarbamates, and/or zanthates.

20. The thermoset composition of claim 19 , wherein the accelerator cure system is N-cyclohexyl- 2 -benzothiazole sulfenamide (“CBS”) or diphenylguanidine (“DPG”).

21. The thermoset composition of claim 17 , wherein the filler is selected from a group of carbon black, white filler, and combinations thereof.

22. A rubber composition comprising the thermoset composition of claim 12 .

23. The rubber composition of claim 22 further comprising a hydrocarbon resin.

24. An article comprising the rubber composition of claim 22 .

Assignees

• Exxonmobil Chemical Patents Inc
• Exxonmobil Engineering & Tech Company

Inventors

• Nguyen Paul Tu Quang
• Tripathy Ranjan
• Mann Jason A
• Chen Yuan-Ju
• Blok Edward J
• Dias Anthony J
• Jangda Abdul M

Classifications

• C08L2312/00

  Crosslinking · CPC title

• C08K5/44

  Sulfenamides · CPC title

• C08K5/435

  Sulfonamides · CPC title

• C08K5/40

  Thiurams, {i.e. compounds containing[IMAGE cpc-sch-C08K-1011.gif] groups} · CPC title

• C08K5/31

  Guanidine; Derivatives thereof · CPC title