首页> 外国专利> A PROCESS FOR PRODUCING A POLYMER HAVING A BIMODAL MOLECULAR WEIGHT DISTRIBUTION, A PROCESS FOR MODIFYING THE MOLECULAR WEIGHT DISTRIBUTION OF A RANDOM COPOLYMER OF ISOBUTYLENE, A POLYMER PRODUCT AND A POLYMER COMPOSITION BASED THEREON

A PROCESS FOR PRODUCING A POLYMER HAVING A BIMODAL MOLECULAR WEIGHT DISTRIBUTION, A PROCESS FOR MODIFYING THE MOLECULAR WEIGHT DISTRIBUTION OF A RANDOM COPOLYMER OF ISOBUTYLENE, A POLYMER PRODUCT AND A POLYMER COMPOSITION BASED THEREON

机译:具有双峰分子量分布的聚合物的制备方法,异丁烯的无规共聚物,聚合物产物和基于其的聚合物组成的分子量分布的改性方法

摘要

1. A process for producing a polymer having a bimodal molecular weight distribution from a polymer having a monomodal molecular weight distribution, molecular weight of which decreases when it is subjected to high shear mixing optionally in the presence of free radical polymerization initiator, characterised in that starting polymer is selected from the group, consisting of polypropylene, copolymers of propylene with up to 10 wt % ethylene, polyisobutylene, copolymers of a C4-C7 isomonoolefin with up to 10 wt % isoprene and copolymers of a C4-C7 isomonoolefin with up to 20 wt % of para-alkylstyrene; the mixture of such polymer with polyunsaturated crosslinking agent and, optionally, a free radical initiator is heated to form a uniform mixture, further subjecting the mixture to high shear mixing conditions sufficient to obtain the polymer having a bimodal molecular weight distribution, produced polymer has a portion having a molecular weight lower than the starting molecular weight of the polymer and a portion having a higher molecular weight than the starting molecular weight of the polymer with proviso that presence of a free radical initiator is optional only in case when the starting polymer is a polymer, capable to form radicals under high shear mixing. 2. The process of claim 1, wherein said mixing step is conducted in the presence of a free radical initiator. 3. The process of claim 2, wherein said polyunsaturated cross-linking agent is a bifunctional compound, containing diallyl, divinyl or diethylenic unsaturated group. 4. The process of claim 2, wherein said polyunsaturated cross-linking agent is selected from the group consisting of polymaleimides, polyallylphosphates, polyallylcyanurates, polyallyl esters of organic acids, polyallylamines; alkyleneglycolpoly(meth)acrylates and polyvinylbenzenes. 5. The process of claim 4, wherein said polyunsaturated cross-linking agent is an organic bismaleimide. 6. The process of claim 5, wherein said polyunsaturated cross-linking agent is a phenylenebismaleimide. 7. The process of claim 2, wherein said free radical initiator is an organic peroxide. 8. The process of claim 7, wherein said organic peroxide is selected from the group consisting of benzoyl peroxide; tert-butylperoxypivalate; 2,4-dichlorobenzoyl peroxide; decanoyl peroxide; propionyl peroxide; hydroxyheptyl peroxide; cyclohexanone peroxide; tert-butylperbenzoate; dicumyl peroxide; 2,5-dimethyl-2,5-di(tert-butylperoxyl)-3-hexyne; 2,5-dimethyl-2,5-di(tert-butylperoxy) hexane; 2,5-dimethyl-2,5-dibenzoylperoxyhexane; tert-butylperoxide; cumene hydroperoxide; 2,5-dimethyl-2,5-di(hydroperoxy)hexane; tert-butylhydroperoxide; lauroyl peroxide and tert-amylperbenzoate. 9. The process of claim 1, wherein said polyunsaturated cross-linking agent is present at a level of from 0.005 to 1.0 millimoles per gram of said polymer. 10. The process of claim 9, wherein said polyunsaturated cross-linking agent level is from 0.01 to 0.5 millimoles. 11. The process of claim 9, wherein said free radical initiator is an organic peroxide present in said composition at a level of from 0.0005 to 0.1 millimoles per gram of said polymer. 12. The process of claim 11, wherein the level of organic peroxide is from 0.001 to 0.05 millimoles. 13. The process of claim 2, wherein said polymer is a statistical copolymer of isobutylene containing up to 20 wt % of polymerized para-methylstyrene. 14. The process of claim 8, wherein said organic peroxide is selected from the group consisting of 2,5-dimethyl-2,5-di(tert-butylperoxyl)-3-hexyne, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide and mixtures thereof. 15. The process of claim 2, wherein said free radical initiator is added to said mixture after step of heating and prior the step of mixing. 16. The process of claim 2, wherein said high shear mixing is conducted for a period of from 1 to 10 minutes. 17. The process of claim 16, wherein said high shear mixing is conducted at a temperature in the range of from 150 degree C to 210 degree C. 18. A process for modifying the molecular weight distribution of a statistical copolymer of isobutylene containing up to 20 wt % of polymerized para-methylstyrene, which produced copolymer has a portion having a molecular weight lower than the starting molecular weight of the copolymer and a portion having a higher molecular weight than the starting molecular weight of the copolymer, and wherein the higher molecular weight portion comprises at least 1.0 wt % of the polymeric material, which process comprises: a) forming a mixture of said copolymer and from 0.05 to 0.5 millimoles per gram of said polymer of a polyunsaturated cross-linking agent; b) heating said mixture to form a uniform melt mixture; and c) subjecting said melt mixture to high shear mixing conditions in the presence of an organic peroxide sufficient to obtain a polymer having a bimodal molecular weight distribution. 19. The process of claim 18, wherein said organic peroxide is present in said mixture at a level of from 0.001 to 0.05 millimoles per gram of said copolymer. 20. The process of claim 18, wherein said polyunsaturated cross-linking agent is an organic bismaleimide. 21. The process of claim 20, wherein said organic peroxide is selected from the group consisting of 2,5-dimethyl-2,5-di(tert-butylperoxyl)-3-hexyne, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide and mixtures thereof. 22. A product produced by the process of claims 1, 5 or 18. 23. A polymer composition comprising a polymeric material selected from the group consisting of polypropylene, copolymers of propylene with up to 10 wt % ethylene, polyisobutylene, copolymers of a C4-C7 isomonoolefin with up to 10 wt % isoprene, copolymers of a C4-C7 isomonoolefin with up to 20 wt % of para-alkylstyrene and mixtures thereof, said polymeric material having a number average molecular weight in the range of from 5000 to 5000000, and is characterised as having a bimodal molecular weight distribution containing a lower molecular weight species and a higher molecular weight species, said higher molecular weight species comprising at least 1.0 weight percent of said polymeric material. 24. The composition of claim 23, containing from 1 to 25 weight percent of said higher molecular weight species. 25. The composition of claim 23, wherein said polymeric material has a number average molecular weight in the range of from 10000 to 1000000. 26. The composition of claim 25, wherein said polymeric material is a random copolymer of isobutylene containing up to 20 wt % of polymerized para-methylstyrene.
机译:1.一种由具有单峰分子量分布的聚合物制备具有双峰分子量分布的聚合物的方法,其特征在于,当其任选地在自由基聚合引发剂的存在下进行高剪切混合时,其分子量降低。起始聚合物选自聚丙烯,丙烯与至多10 wt%的乙烯的共聚物,聚异丁烯,C4-C7异单烯烃与至多10 wt%的异戊二烯的共聚物以及C4-C7异单烯烃与至多10 wt%的共聚物20重量%的对烷基苯乙烯;将该聚合物与多不饱和交联剂和任选的自由基引发剂的混合物加热以形成均匀的混合物,进一步使该混合物经受足以获得具有双峰分子量分布的聚合物的高剪切混合条件,制得的聚合物具有分子量低于聚合物起始分子量的部分和分子量高于聚合物起始分子量的部分,前提是仅当起始聚合物为聚合物时,自由基引发剂的存在是可选的聚合物,能够在高剪切混合下形成自由基。 2.权利要求1的方法,其中所述混合步骤在自由基引发剂的存在下进行。 3.权利要求2的方法,其中所述多不饱和交联剂是含有二烯丙基,二乙烯基或二烯键式不饱和基团的双官能化合物。 4.权利要求2的方法,其中所述多不饱和交联剂选自聚马来酰亚胺,聚烯丙基磷酸酯,聚烯丙基氰尿酸酯,有机酸的聚烯丙基酯,聚烯丙基胺;和亚烷基二醇聚(甲基)丙烯酸酯和聚乙烯苯。 5.权利要求4的方法,其中所述多不饱和交联剂是有机双马来酰亚胺。 6.权利要求5的方法,其中所述多不饱和交联剂是亚苯基双马来酰亚胺。 7.权利要求2的方法,其中所述自由基引发剂是有机过氧化物。 8.权利要求7的方法,其中所述有机过氧化物选自过氧化苯甲酰;和过氧新戊酸叔丁酯; 2,4-二氯苯甲酰过氧化物;癸酰过氧化物过氧化丙酰过氧化羟庚基;过氧化环己酮过苯甲酸叔丁酯;过氧化二枯基; 2,5-二甲基-2,5-二(叔丁基过氧基)-3-己炔; 2,5-二甲基-2,5-二(叔丁基过氧)己烷; 2,5-二甲基-2,5-二苯甲酰基过氧己烷;叔丁基过氧化物;异丙苯氢过氧化物; 2,5-二甲基-2,5-二(氢过氧)己烷;叔丁基过氧化氢;月桂酰过氧化物和叔戊基过苯甲酸酯。 9.权利要求1的方法,其中所述多不饱和交联剂的存在量为每克所述聚合物0.005-1.0毫摩尔。 10.权利要求9的方法,其中所述多不饱和交联剂含量为0.01至0.5毫摩尔。 11.权利要求9的方法,其中所述自由基引发剂是存在于所述组合物中的有机过氧化物,其含量为每克所述聚合物0.0005-0.1毫摩尔。 12.权利要求11的方法,其中有机过氧化物的含量为0.001至0.05毫摩尔。 13.权利要求2的方法,其中所述聚合物是异丁烯的统计共聚物,其包含至多20重量%的聚合的对甲基苯乙烯。 14.权利要求8的方法,其中所述有机过氧化物选自2,5-二甲基-2,5-二(叔丁基过氧化羟基)-3-己炔,2,5-二甲基-2,5-二(叔丁基过氧)己烷,过氧化二枯基及其混合物。 15.权利要求2的方法,其中在加热步骤之后且在混合步骤之前将所述自由基引发剂添加到所述混合物中。 16.权利要求2的方法,其中所述高剪切混合进行1至10分钟的时间。 17.权利要求16的方法,其中所述高剪切混合是在150℃至210℃的温度范围内进行的。18.一种用于改性异丁烯的统计共聚物的分子量分布的方法,所述共聚物的分子量最高为150℃。所生产的共聚物的20wt%的聚合的对甲基苯乙烯具有分子量低于该共聚物的起始分子量的部分和分子量高于该共聚物的起始分子量的部分,并且其中较高的分子量重量份包含至少1.0重量%的聚合物材料,该方法包括:a)形成所述共聚物和每克所述聚合物0.05-0.5毫摩尔的多不饱和交联剂的混合物; b)加热所述混合物以形成均匀的熔融混合物; c)在足以获得具有双峰分子量分布的聚合物的有机过氧化物的存在下,使所述熔融混合物经受高剪切混合条件。 19.根据权利要求18所述的方法,其中所述有机过氧化物以每克所述共聚物0.001至0.05毫摩尔的水平存在于所述混合物中。 20.权利要求18的方法,其中所述多不饱和交联剂是有机双马来酰亚胺。 21.权利要求20的方法,其中所述有机过氧化物选自2,5-二甲基-2,5-二(叔丁基过氧化羟基)-3-己炔,2,5-二甲基-2,5-二(叔丁基过氧)己烷,过氧化二枯基及其混合物。 22.通过权利要求1、5或18的方法生产的产品。23.一种聚合物组合物,其包含选自聚丙烯,丙烯与至多10wt%的乙烯的共聚物,聚异丁烯,C 4的共聚物的聚合物材料。 -C 7异单烯烃与最多10 wt%的异戊二烯,C4-C7异单烯烃与最多20 wt%的对烷基苯乙烯的共聚物及其混合物,所述聚合物材料的数均分子量为5000-5000000,并且其特征在于具有包含较低分子量种类和较高分子量种类的双峰分子量分布,所述较高分子量种类包含至少1.0重量%的所述聚合物材料。 24.权利要求23的组合物,其包含1至25重量%的所述较高分子量的物质。 25.根据权利要求23所述的组合物,其中所述聚合物材料的数均分子量为10000至1000000。26.根据权利要求25所述的组合物,其中所述聚合物材料为异丁烯的最多20重量%的无规共聚物。聚合的对甲基苯乙烯的百分比。

著录项

  • 公开/公告号EA001222B1

    专利类型

  • 公开/公告日2000-12-25

    原文格式PDF

  • 申请/专利权人 EXXON CHEMICAL PATENTS INC.;

    申请/专利号EA19970000428

  • 发明设计人 WHIT DONALD ANDREW;

    申请日1996-05-23

  • 分类号C08F8/00;

  • 国家 EA

  • 入库时间 2022-08-22 01:25:37

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