阅读说明：本技术 具有门尼粘度稳定性的卤化弹性体及其制备方法 (Halogenated elastomers having Mooney viscosity stability and process for their preparation ) 是由 顾乐明 T·R·巴比 J·E·施米格 于 2018-03-28 设计创作，主要内容包括：本文提供了改进溴化弹性体的门尼稳定性的方法,其包括：用中和剂和水中和溴化弹性体流出物来形成包含烃溶剂的中和的流出物；从该中和的流出物中除去所述溶剂来形成溴化弹性体浆体；和从该溴化弹性体浆体中分离溴化弹性体,其中在所述除去步骤之前,可以一起或者分别加入包含胺官能化的受阻胺稳定剂(HAS)和除酸剂的门尼稳定剂包。所述除酸剂可以包含可质子化原子,其的pKa大于HAS氮原子的pKa。所分离的溴化弹性体在～80℃～7天之后Δ门尼可以不大于大约10个门尼单位。使用这种方法可以制造稳定的溴化弹性体组合物,和由那些组合物可以制造制品。(Provided herein is a method of improving the mooney stability of a brominated elastomer, comprising: neutralizing the brominated elastomer effluent with a neutralizing agent and water to form a neutralized effluent comprising a hydrocarbon solvent; removing said solvent from the neutralized effluent to form a brominated elastomer slurry; and separating the brominated elastomer from the brominated elastomer slurry, wherein a Mooney stabilizer package comprising an amine functionalized Hindered Amine Stabilizer (HAS) and an acid scavenger can be added together or separately prior to the removing step. The acid scavenger may comprise a protonatable atom having a pKa greater than the pKa of the HAS nitrogen atom. The isolated brominated elastomer may have a delta mooney of no greater than about 10 mooney units after-80 ℃ to 7 days. Stable brominated elastomer compositions can be made using this method, and articles can be made from those compositions.)

1. A method of improving the mooney stability of a brominated elastomer, the method comprising:

neutralizing the brominated elastomer effluent with a neutralizing agent and water to form a neutralized effluent comprising a hydrocarbon solvent;

removing said solvent from the neutralized effluent to form a brominated elastomer slurry; and

separating the brominated elastomer from the brominated elastomer slurry,

wherein the amine functionalized Hindered Amine Stabilizer (HAS) and the acid scavenger are mixed together or separately: i) added to the brominated elastomer effluent prior to neutralization, ii) added while neutralizing the brominated elastomer effluent, or iii) added to the neutralized effluent prior to removal of the hydrocarbon solvent, and

wherein the amine-functionalized HAS comprises a HAS nitrogen atom having a first pKa, and the acid scavenger comprises a protonatable atom having a pKa greater than the pKa of the HAS nitrogen atom.

2. The method of claim 1, wherein said amine functionalized HAS and acid scavenger are added prior to said removing step.

3. The method of claim 2, wherein the amine-functionalized HAS and acid scavenger together or separately: i) added to the brominated elastomer effluent prior to neutralization, ii) added while neutralizing the brominated elastomer effluent, or iii) added to the neutralized effluent prior to removal of the hydrocarbon solvent.

4. The process of any preceding claim, wherein the aged Mooney viscosity of said isolated brominated elastomer is no more than about 10 Mooney units greater than the initial Mooney viscosity of the isolated brominated elastomer.

5. The process of any preceding claim, wherein the acid scavenger is an amine-functionalized acid scavenger such that the protonatable atoms are nitrogen atoms, and wherein at least about 500wppm of amine-functionalized HAS and at least about 1000wppm of amine-functionalized acid scavenger are added during the process of making the brominated elastomer.

6. The method of any of the preceding claims, wherein the amine functionalized HAS comprises one or more compounds having a piperidinyl nitrogen bearing moiety according to formula (I):

wherein:

R₁is a hydroxyl group or a heteroatom-containing linking group at the corresponding R₁R at or in the respective other moiety₂To one or more other moieties of formula (I);

R₂is hydrogen, C₁-C₈Optionally heteroatom-containing hydrocarbon moieties having a carbon atom singly bonded to the piperidinyl nitrogen, or a heteroatom-containing linking group at the corresponding R₂R at or in the respective other moiety₁To one or more other moieties of formula (I); and

R₃、R₄、R₅and R₆Independently is C₁-C₆A hydrocarbon moiety.

7. The method of claim 6, wherein the amine functionalized HAS comprises 4-hydroxy-2, 2, 6, 6-tetramethyl-1-piperidineethanol or an esterified dimer or polymer thereof, wherein R is₁As containing hetero compoundsR with linking group of atoms in other part₂To another moiety of formula (I).

8. The method of any of the preceding claims, wherein the amine functionalized HAS comprises one or more compounds having a piperidinyl nitrogen bearing moiety according to formula (I):

wherein:

R₁is hydroxy, C₁-C₁₈Optionally heteroatom-containing hydrocarbon moiety, or optionally heteroatom-containing linker at the corresponding R₁R at or in the respective other moiety₂To one or more other moieties of formula (I);

R₂is hydrogen, C₁-C₈Optionally heteroatom-containing hydrocarbon moieties having a carbon atom singly bonded to the piperidinyl nitrogen, or a heteroatom-containing linking group at the corresponding R₂R at or in the respective other moiety₁To one or more other moieties of formula (I); and

R₃and R₆Each is hydrogen; and

R₄and R₅Each is independently C₃-C₁₀Optionally a heteroatom-containing hydrocarbon moiety.

9. The process of any preceding claim, wherein the acid scavenger is an amine-functionalized acid scavenger such that the protonatable atom is a nitrogen atom, and wherein the amine-functionalized acid scavenger comprises one or more compounds having the formula:

NR₇R₈R₉，

wherein:

R₇and R₈Each is independently C₂-C₁₈Optionally a heteroatom-containing hydrocarbon moiety; and

R₉is hydrogen or C₁-C₁₈Optionally a heteroatom-containing hydrocarbon moiety.

10. The process of claim 9, wherein the amine-functionalized acid scavenger comprises dioctylamine.

11. The process of any preceding claim, wherein the solvent comprises pentane, hexane, heptane, cyclohexane, cyclopentane, mono-, di-or tri-halogenated C₁-C₆A paraffin, or a combination thereof.

12. A brominated elastomer prepared by the process of any preceding claim.

13. An article comprising the brominated elastomer of claim 12, wherein the article is a tire innerliner or tire bladder, or is incorporated as a layer in a tire, bladder, hose, belt, pneumatic spring, or vehicle body chassis.

14. A brominated elastomer composition comprising:

from C₄-C₇Copolymers made of an isomonoolefin and at least one monomer or polymerizable unit selected from isoprene and alkylstyrene; and

mooney stabilizers comprising an amine functionalized Hindered Amine Stabilizer (HAS) and an acid scavenger,

wherein the initial Mooney viscosity of the brominated elastomer composition is no more than about 10 Mooney units less than the Mooney viscosity of aging after being subjected to 80 ℃ for 7 days.

15. The brominated elastomer composition of claim 14, wherein the acid scavenger is an amine-functionalized acid scavenger such that the protonatable atom is a nitrogen atom.

16. The brominated elastomer composition of claims 14-15, wherein the mooney stabilizer additive consists essentially of an amine functionalized Hindered Amine Stabilizer (HAS) and an amine functionalized acid scavenger.

17. The brominated elastomer composition of claims 14-16, further comprising 0.001 to 0.2 mol% of an allyl alcohol.

18. An oxidation-stable brominated elastomer composition comprising:

from C₄-C₇Copolymers made of an isomonoolefin and at least one monomer or polymerizable unit selected from isoprene and alkylstyrene; and

an oxidized Mooney stabilizer additive comprising an oxidized nitroxyl-functionalized Hindered Amine Stabilizer (HAS) and an acidified quaternary ammonium,

wherein the initial Mooney viscosity of the brominated elastomer composition is no more than about 10 Mooney units less than the Mooney viscosity of aging after being subjected to 80 ℃ for 7 days.

19. The brominated elastomer composition of claim 18, further comprising 0.001 to 0.2 mol% of an allylic alcohol.

Examples