Stable star-structured functional polyolefins

Patent metadata

Field	Value
Publication number	US-11053396-B2
Application number	US-201816058516-A
Country	US
Kind code	B2
Filing date	Aug 8, 2018
Priority date	Dec 4, 2014
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

Stable star-structured functional polyolefins and methods of making them, the functional polyolefins comprising a polyolefin bound at any position along its chain length to at least one nucleophile-containing silane of the following formula:

wherein Y is a di- or trivalent linker group selected from heteroatoms, C1 to C10 alkylenes, and other groups disclosed herein; Nu is a nucleophilic atom or unsaturation group; R5 is selected from hydrogen, and C1 to C10 alkyls, and other groups as disclosed herein; X is a divalent group selected from linear and branched alkylenes and heteroatom-alkylenes, and other groups as disclosed herein; and PO is a polyolefin having a weight average molecular weight of at least 400 g/mole; with the proviso that at least one of R1, R2, and R3 is selected from the same or different functional polyolefin moieties. Star-structured functional polyolefins are useful as filler dispersive additives in tire formulations and processing aids.

First claim

The invention claimed is:

1. A functional polyolefin comprising the reaction product of:
(a) at least one polyolefin comprising at least one nucleophile-reactive group or unsaturation at one or both of the chain ends; and
(b) at least one aminosilane compound of the following formula:

wherein R1, R2, and R3 are independently selected from hydrogen, hydroxide, C1 to C10 alkoxys, C6 to C30 aryloxys, C7 to C30 arylalkyloxys, and C1 to C10 alkylamines, wherein any 2 or more groups can form an aliphatic or aromatic cyclic structure that includes the silicon atom;
R5 and R6 are independently selected from, C1 to C10 aminoalkyls, C6 to C20 aryls, C7 to C22 alkylaryls, C7 to C22 aminoaryls, and C7 to C22 arylalkyls;
R+ and R++ are independently selected from hydrogen and C1 to C5 alkyls;
m and n are each integers ≥ , wherein the sum of m and n ranges from 0 to 2; and
wherein any one of R1, R2, or R3 may form a 5 to 10 membered alkylene or aminoalkylene ring with the nitrogen atom.

2. The functional polyolefin of claim 1 , wherein R+ and R++ are each methyl groups.

3. The functional polyolefin of claim 1 , wherein R5 is selected from C1 to C10 aminoalkyls.

4. The functional polyolefin of claim 1 , wherein the at least one polyolefin comprising at least one nucleophile-reactive group or unsaturation is selected from the group consisting of polybutadienes, polyisoprenes, isobutylene-isoprene copolymer, halogenated isobutylene-isoprene copolymer, isobutylene-p-methylstyrene copolymer, halogenated isobutylene-p-methylstyrene copolymer, ethylene-propylene-diene terpolymers, vinyl/vinylidene-terminated polypropylenes, vinyl/vinylidene-terminated polyethylenes, and vinyl/vinylidene-terminated ethylene-propylene copolymers.

5. The functional polyolefin of claim 4 , wherein the at least one polyolefin comprising at least one nucleophile-reactive group or unsaturation is selected from the group consisting of polybutadienes, polyisoprenes, and isobutylene-isoprene copolymer.

6. The functional polyolefin of claim 1 , wherein the functional polyolefin has a branching number of 7 or below.

7. A tire tread formulation comprising the functional polyolefin of claim 1 .

8. A method of forming a functional polyolefin comprising combining:
(a) at least one polyolefin comprising at least one nucleophile-reactive group or unsaturation at one or both of the chain ends; and
(b) at least one aminosilane compound of the following formula:

wherein R1, R2, and R3 are independently selected from hydrogen, hydroxide, C1 to C10 alkoxys, C6 to C30 aryloxys, C7 to C30 arylalkyloxys, and C1 to C10 alkylamines, wherein any 2- or more groups can form an aliphatic or aromatic cyclic structure that includes the silicon atom;
R5 and R6 are independently selected from C1 to C10 aminoalkyls, C6 to C20 aryls, C7 to C22 alkylaryls, C7 to C22 aminoaryls, and C7 to C22 arylalkyls;
R+ and R++ are independently selected from hydrogen and C1 to C5 alkyls;
m and n are each integers ≥0, wherein the sum of m and n ranges from 0 to 2; and
wherein any one of R1, R2, or R3 may form a 5 to 10 membered alkylene or aminoalkylene ring with the nitrogen atom.

9. The method of claim 8 , wherein the sum of m and n is selected from 0 or 1.

10. The method of claim 8 , wherein R+ and R++ are each methyl groups.

11. The method of claim 8 , wherein R5 is selected from C1 to C10 aminoalkyls.

12. The method of claim 8 , wherein the at least one polyolefin comprising at least one nucleophile-reactive group or unsaturation is selected from the group consisting of polybutadienes, polyisoprenes, isobutylene-isoprene copolymer, halogenated isobutylene-isoprene copolymer, isobutylene-p-methylstyrene copolymer, halogenated isobutylene-p -methylstyrene copolymer, ethylene-propylene-diene terpolymers, vinyl/vinylidene -terminated polypropylenes, vinyl/vinylidene-terminated polyethylenes, and vinyl/vinylidene -terminated ethylene-propylene copolymers.

13. The method of claim 12 , wherein the at least one polyolefin comprising at least one nucleophile-reactive group or unsaturation is selected from the group consisting of polybutadienes, polyisoprenes, and isobutylene-isoprene copolymer.

14. The method of claim 8 , wherein the combining occurs under hydroaminoalkylation conditions.

15. The method of claim 8 , wherein the at least one polyolefin comprising at least one nucleophile-reactive group or unsaturation is treated first, prior to combining with the at least one aminosilane compound, by direct epoxidation and/or hydrosilylation.

16. The method of claim 8 , further comprising combining the functional polyolefin with at least one elastomer and silica to form a tire tread composition.

17. A method of tailoring the branching number of a functional polyolefin of claim 8 , comprising choosing the structure of the aminosilane compound and/or the conditions under which the combining is performed.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Yang Yong
• Tsou Andy H
• Slaughter Kimari T M

Classifications

• C08L83/10

  Block- or graft-copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C08L51/08, C08L53/00) · CPC title

• C08L83/00

  Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers · CPC title

• B60C1/0016

  Compositions of the tread · CPC title

• C08F8/42

  Introducing metal atoms or metal-containing groups · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title