Polycyclic aromatic hydrocarbon functionalized isobutylene copolymers for dispersing graphene and graphite

Patent metadata

Field	Value
Publication number	US-9914817-B2
Application number	US-201615242963-A
Country	US
Kind code	B2
Filing date	Aug 22, 2016
Priority date	Sep 30, 2015
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

Polycyclic aromatic hydrocarbon (PAH) functionalized isobutylene copolymers, methods for making a PAH functionalized isobutylene copolymer comprising combining a halogenated copolymer with a PAH in a solvent under basic conditions at a temperature ranging from 30° C. to 150° C., the use of these PAH functionalized copolymers as a dispersant in elastomeric nanocomposite compositions comprising a halobutyl rubber matrix and nanoparticles of graphite or graphene, and a tire innerliner or innertube produced from these elastomeric nanocomposite compositions is disclosed.

First claim

What is claimed is:

1. A nanofiller dispersant composition comprising:
(a) the reaction product of: (i) at least one halogenated copolymer comprising units derived from isoolefins having from 4 to 7 carbons and a para-alkylstyrene; and (ii) at least one polycyclic aromatic hydrocarbon (PAH); and
(b) at least one nanofiller.

2. The composition of claim 1 , wherein the PAH is polynuclear.

3. The composition of claim 2 , wherein the PAH is selected from the group consisting of anthracenes, pyrenes, benzopyrenes, coronenes, ovalenes, and combinations thereof.

4. The composition of claim 1 ,
wherein the halogenated copolymer is brominated poly(isobutylene-co-p-methylstyrene) (BIMSM),
wherein the BIMSM comprises a benzylic bromine functionality, and
wherein from 4% to 80% of the benzylic bromine functionality is covalently bonded to the PAH.

5. The composition of claim 1 , wherein the PAH comprises a functional group.

6. The composition of claim 5 , wherein the functional group is selected from the group consisting of an amine group, an alcohol group, an aldehyde group, an alkoxide group, an alkene group, a carboxylic acid group, a thiol group, an acid halide group, an acid anhydride group, an aziricline group, an epoxide group, an amide group, and combinations thereof.

7. A method for producing a nanofiller dispersant composition, the method comprising:
(a) combining
(i) at least one halogenated copolymer comprising units derived from isoolefins having from 4 to 7 carbons and a para-alkylstyrene; and
(ii) at least one polycyclic aromatic hydrocarbon (PAH)
in a solvent under basic conditions at a temperature ranging from 30° C. to 150° C. to produce a reaction product; and
(b) mixing the reaction product with at least one nanofiller.

8. The method of claim 7 , wherein the PAH is polynuclear.

9. The method of claim 7 , wherein the solvent is selected from the group consisting of C 6 to C 8 aliphatic hydrocarbons, C 6 to C 20 aryls, halogenated C 6 to C 20 aryls, and mixtures thereof.

10. The method of claim 7 , wherein the halogenated copolymer is brominated poly(isobutylene-co-p-methylstyrene) (BIMSM).

11. The composition of claim 7 , wherein the PAH comprises a functional group selected from the group consisting of an amine group, an alcohol group, an aldehyde group, an alkoxide group, an alkene group, a carboxylic acid group, a thiol group, an acid halide group, an acid anhydride group, an aziridine group, an epoxide group, an amide group, and combinations thereof.

12. The method of claim 7 , further comprising mixing the nanofiller dispersant composition with at least one halogenated elastomer component comprising units derived from isoolefins having from 4 to 7 carbons to obtain an elastomeric nanocomposite composition, wherein the nanocomposite composition comprises from 0.01 wt % to 15.0 wt % of the nanofiller and from 0.5 wt % to 45 wt % of the nanofiller dispersant, wherein the weight percentages are based on the total weight of the nanofiller dispersant, the elastomer component, and the nanofiller.

13. The method of claim 7 , wherein the nanofiller is selected from the group consisting of graphite, expanded graphite, nano graphene platelets (NGPs), graphene, and mixtures thereof.

14. The method of claim 12 , wherein the halogenated elastomer component is selected from the group consisting of chlorinated poly(isobutylene-co-isoprene) (CIIR), brominated poly(isobutylene-co-isoprene) (BIIR), and mixtures thereof.

15. The method of claim 14 , wherein the oxygen permeability of the elastomeric nanocomposite at 40° C. is at least 15% lower than the permeability of the halogenated elastomer component.

16. An elastomeric nanocomposite composition comprising:
(a) a nanofiller dispersant comprising the reaction product of
(i) at least one halogenated copolymer comprising units derived from isoolefins having from 4 to 7 carbons and a para-alkylstyrene; and
(ii) at least one polycyclic aromatic hydrocarbon (PAH),
(b) at least one halogenated elastomer component comprising units derived from isoolefins having from 4 to 7 carbons; and
(c) at least one nanofiller,
wherein the nanofiller dispersant is present from 0.5 wt % to 45 wt % based on the total weight of the nanofiller dispersant, the elastomer component, and the nanofiller;
and wherein the nanofiller is present at from 0.01 wt % to 15.0 wt % based on the total weight of the nanofiller dispersant, the elastomer component, and the nanofiller.

17. The composition of claim 16 , wherein the PAH is polynuclear.

18. The composition of claim 16 , wherein the nanofiller is selected from the group consisting of graphite, expanded graphite, NGPs, graphene, and mixtures thereof.

19. The composition of claim 16 , wherein the halogenated elastomer component is selected from the group consisting of chlorinated poly(isobutylene-co-isoprene) (CIIR), brominated poly(isobutylene-co-isoprene) (BIIR), and mixtures thereof.

20. The composition of claim 19 , wherein the oxygen permeability of the elastomeric nanocomposite at 40° C. is at least 15% lower than the permeability of the halogenated elastomer component.

21. The composition of claim 16 , wherein the halogenated copolymer is brominated poly(isobutylene-co-p-methylstyrene) (BIMSM).

22. The composition of claim 16 , wherein the PAH comprises a functional group selected from the group consisting of an amine group, an alcohol group, an aldehyde group, an alkoxide group, an alkene group, a carboxylic acid group, a thiol group, an acid halide group, an acid anhydride group, an aziridine, group, an epoxide group, an amide group, and combinations thereof.

23. The composition of claim 16 , further comprising at least one component selected from the group consisting of additional fillers, processing oils, cure additives, and mixtures thereof, wherein the cure additives are selected from the group consisting of metal oxides, organic acids, alkyl disulfides, and mixtures thereof.

24. An innerliner for a tire comprising the composition of claim 16 .

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Tsou Andy H
• Bradshaw Hillary L
• Yang Yong

Classifications

• C08L15/02 Primary

  Rubber derivatives containing halogen · CPC title

• C08L2205/025

  containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure · CPC title

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08K3/046

  Carbon nanorods, nanowires, nanoplatelets or nanofibres · CPC title

• C08L2666/55

  Carbon · CPC title