Halogenated elastomers with Mooney viscosity stability and method for preparing same

Patent metadata

Field	Value
Publication number	US-10889704-B2
Application number	US-201815938012-A
Country	US
Kind code	B2
Filing date	Mar 28, 2018
Priority date	May 22, 2017
Publication date	Jan 12, 2021
Grant date	Jan 12, 2021

Abstract

Methods of improving Mooney stability of a brominated elastomer comprising: neutralizing a brominated elastomer effluent with a neutralizing agent and water to form a neutralized effluent comprising a hydrocarbon solvent; removing the solvent from the neutralized effluent to form a brominated elastomer slurry; and separating a brominated elastomer from the brominated elastomer slurry, wherein a Mooney stabilizer package comprising an amine-functional hindered amine stabilizer (HAS) and an acid scavenger can be added, together or separately, before the removing step are provided herein. The acid scavenger can comprise a protonatable atom with a pKa greater than the pKa of the HAS nitrogen atom. The separated brominated elastomer can have a delta Mooney of not more than about 10 Mooney units after ˜7 days at ˜80° C. Stabilized brominated elastomer compositions can be made using this method, and articles can be made from those compositions.

First claim

What is claimed is:

1. A method of improving Mooney stability of a brominated elastomer, the method comprising:
neutralizing a brominated elastomer effluent with a neutralizing agent and water to form a neutralized effluent comprising a hydrocarbon solvent;
removing the hydrocarbon solvent from the neutralized effluent to form a brominated elastomer slurry; and
separating a brominated elastomer from the brominated elastomer slurry,
wherein an amine-functional hindered amine stabilizer (HAS) and an acid scavenger are added i) to the brominated elastomer effluent prior to neutralizing, ii) when neutralizing the brominated elastomer effluent, or iii) to the neutralized effluent prior to removing the hydrocarbon solvent, together or separately, and
wherein the amine-functional HAS comprises a HAS nitrogen atom having a first pKa and the acid scavenger comprises a protonatable atom with a pKa greater than the pKa of the HAS nitrogen atom.

2. The method of claim 1 , wherein the separated brominated elastomer has an aged Mooney viscosity of not more than about 10 Mooney units higher than an initial Mooney viscosity of the separated brominated elastomer.

3. The method of claim 1 , wherein the acid scavenger is an amine-functional acid scavenger such that the protonatable atom is a nitrogen atom, and wherein at least about 500 wppm of amine-functional HAS and at least about 1000 wppm of amine-functional acid scavenger are added.

4. The method of claim 1 , wherein the amine-functional HAS comprises one or more compounds having a moiety with a piperidinyl nitrogen according to formula (I):

wherein:
R 1 is a hydroxyl or a heteroatom-containing linker connecting to one or more other moieties of formula (I) at a corresponding R 1 or at an R 2 of each other moiety;
R 2 is hydrogen, a C 1 -C 8 optionally heteroatom-containing hydrocarbon moiety having a carbon atom single-bonded to the piperidinyl nitrogen, or is a heteroatom-containing linker connecting to one or more other moieties of formula (I) at a corresponding R 2 or at an R 1 of each other moiety; and
R 3 , R 4 , R 5 , and R 6 are independently a C 1 -C 6 hydrocarbon moiety.

5. The method of claim 4 , wherein the amine-functional HAS comprises 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol or an esterified dimer or polymer thereof with R 1 being connected as a heteroatom-containing linker to another moiety of formula (I) at an R 2 of the other moiety.

6. The method of claim 1 , wherein the amine-functional HAS comprises one or more compounds having a moiety with a piperidinyl nitrogen according to formula (I):

wherein:
R 1 is a hydroxyl, a C 1 -C 18 optionally heteroatom-containing hydrocarbon moiety, or an optionally heteroatom-containing linker connecting to one or more other moieties of formula (I) at a corresponding R 1 or at an R 2 of each other moiety;
R 2 is hydrogen, a C 1 -C 8 optionally heteroatom-containing hydrocarbon moiety having a carbon atom single-bonded to the piperidinyl nitrogen, or is a heteroatom-containing linker connecting to one or more other moieties of formula (I) at a corresponding R 2 or at an R 1 of each other moiety;
R 3 and R 6 are each hydrogen; and
R 4 and R 5 are each independently a C 3 -C 10 optionally heteroatom-containing hydrocarbon moiety.

7. The method of claim 1 , wherein the acid scavenger is an amine-functional acid scavenger such that the protonatable atom is a nitrogen atom, and wherein the amine-functional acid scavenger comprises one or more compounds having a formula:
NR 7 R 8 R 9 , wherein:
R 7 and R 8 are each independently a C 2 -C 18 optionally heteroatom-containing hydrocarbon moiety; and
R 9 is either hydrogen or a C 1 -C 18 optionally heteroatom-containing hydrocarbon moiety.

8. The method of claim 7 , wherein the amine-functional acid scavenger comprises dioctylamine.

9. The method of claim 1 , wherein the solvent comprises pentane, hexane, heptane, cyclohexane, cyclopentane, mono-, di-, or tri-halogenated C 1 -C 6 paraffinic hydrocarbon, or a combination thereof.

10. A brominated elastomer prepared by the method of claim 1 .

11. An article comprising the brominated elastomer of claim 10 , wherein the article is a tire innerliner or a tire bladder or is incorporated as a layer into a tire, a bladder, a hose, a belt, a pneumatic spring, or a vehicle body mount.

12. A brominated elastomer composition comprising:
a copolymer made from a C 4 to C 7 isomonoolefin and at least one monomer or polymerizable unit selected from isoprene and alkylstyrene; and
a Mooney stabilizer comprising an amine-functional hindered amine stabilizer (HAS) and an acid scavenger,
wherein the brominated elastomer composition has an initial Mooney viscosity of no more than about 10 Mooney units lower than an aged Mooney viscosity after being subject to 80° C. for seven days.

13. The brominated elastomer composition of claim 12 , wherein the acid scavenger is an amine-functional acid scavenger such that the protonatable atom is a nitrogen atom.

14. The brominated elastomer composition of claim 12 , wherein the Mooney stabilizer additive consists essentially of the amine-functional hindered amine stabilizer (HAS) and the amine-functional acid scavenger.

15. The brominated elastomer composition of claim 12 , further comprising 0.001 to 0.2 mol % of an allylic alcohol.

16. An oxidatively-stable brominated elastomer composition comprising:
a copolymer made from a C 4 to C 7 isomonoolefin and at least one monomer or polymerizable unit selected from isoprene and alkylstyrene; and
an oxidized Mooney stabilizer additive comprising an oxidized nitroxy-functional hindered amine stabilizer (HAS) and an acidified quaternary ammonium,
wherein the brominated elastomer composition has an initial Mooney viscosity of no more than about 10 Mooney units lower than an aged Mooney viscosity after being subject to 80° C. for 7 days.

17. The brominated elastomer composition of claim 16 , further comprising 0.001 to 0.2 mol % of an allylic alcohol.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Gu Leming
• Barbee Thomas R
• Schmieg Joel E

Classifications

• B60C1/0008 Primary

  Compositions of the inner liner · CPC title

• C08K5/005

  Stabilisers against oxidation, heat, light, ozone · CPC title

• C08L2201/08

  Stabilised against heat, light or radiation or oxydation · CPC title

• C08L15/02 Primary

  Rubber derivatives containing halogen · CPC title

• C08L23/283

  Iso-olefin halogenated homopolymers or copolymers · CPC title