CN103221490A - 用于生产聚合物官能化的填料颗粒的方法 - Google Patents
用于生产聚合物官能化的填料颗粒的方法 Download PDFInfo
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- CN103221490A CN103221490A CN201180056102XA CN201180056102A CN103221490A CN 103221490 A CN103221490 A CN 103221490A CN 201180056102X A CN201180056102X A CN 201180056102XA CN 201180056102 A CN201180056102 A CN 201180056102A CN 103221490 A CN103221490 A CN 103221490A
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Images
Classifications
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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Abstract
本发明涉及一种用于生产聚合物官能化的填料颗粒的方法,涉及通过该方法生产的聚合物官能化的填料颗粒,并且涉及这些颗粒在橡胶混合物中的用途。
Description
技术领域
本发明涉及一种用于生产聚合物官能化的填料颗粒的方法,涉及通过该方法获得的聚合物官能化的填料颗粒,并且涉及它们在橡胶混合物中的用途。
背景技术
混合的有机-无机材料的物理特性明显地取决于其厚度,并且还取决于其中存在的组分之间的界面的结构和特性。偶联试剂通常用于增强在聚合物相与填料相之间的相互作用。它们通常是在聚合物系统的硫化和/或固化过程中能够建立到填料表面的共价键的官能化的烷基-、烷氧基-或卤代硅烷类。这种常规方法的缺点在于常常只达到低的偶联密度。如果有,对于聚合物基质与填料表面之间的相间的受控操纵,它也只提供有限的范围。
可逆加成断裂链转移(RAFT)是以受控方式进行自由基聚合的一种有前景的方法。所谓的RAFT剂的选择和化学构造可以变化以便控制该聚合物至该表面的结构性键合(structural binding)。该RAFT剂的官能位点在聚合过程中典型地直接留在该表面上(Z-基团法,见图1和图1a)。这些所谓的R-基团因此留在该聚合物上并且可以导致特定的官能化,虽然因该RAFT剂的使用而在结构上受到限制。至该填料表面上的键合典型地经由特定RAFT剂上的可偶联的甲硅烷基取代基进行,这些取代基经常被称为Z-基团(例如像-Si(OAlk)3、-SiAlk(OAlk)2或-SiAlk2(OAlk))。制备这些硅烷取代的RAFT剂以及硅烷封端聚合物链的单独的硅烷基团的偶联可能性描述于DE102007000833德国公开说明书(Offenlegungsschrift)中。然而,所属领域技术人员已经例如从D.H.Nguyen,P.Vana,先进技术聚合物(Polymers for AdvancesTechnologies),2006,17,625中或从L.Barner,T.P.Davis,M.H.Stenzel,C.Barner-Kowollik,大分子快讯(Macromol.RapidCommun.),2007,28,539中了解了硅烷取代的RAFT剂的制备。类似地,RAFT剂经由可偶联的甲硅烷基基团的附接被描述于各种出版物中,例如,在C.H.Liu,C.Y.Pan,聚合物(Polymer),2007,48,3679或Y.L.Zhao,S.Perrier,大分子(Macromolecules),2006,39,8603中。常规方法包括赋予聚合物以下端基:这些端基对于填料表面是反应性的并且因此在混合或硫化操作过程中能够实现与该填料表面的共价键合或其他键合。例如,US6,998,452披露了一种RAFT剂,它具有被赋予一个可偶联的甲硅烷基取代基的一个Z-基团。该Z-基团是使自由基中间体在一种聚合物链的加成之后稳定的官能团。这种聚合方法被称为“接枝到(grafting to)”法。此处的缺点是低接枝密度和一定程度的不稳定性,因为该控制剂的硫代羰基硫基团(thiocarbonylthio group)涉及到与该填料的键合。另外,将该接枝基团定位在该填料表面上意味着对该聚合物的第二、自由端的进一步改性不再是可能的。再者,这些生长链与这些表面附接的链之间的位阻在这种方法中变得越来越有影响力,因为这些反应链首先必须扩散通过聚合物的表面上键合的层以便于它们可以与官能性RAFT基团反应。RAFT聚合碳黑颗粒的可能性从Q.Yang,L.Wang,W.D.Xiang,J.F.Zhou,Q.H.Tan,聚合物(Polymer)2007,48,3444中已经得到了解。然而,这些作者们使用了一种不同的附接机制,就此而言该碳黑需要被进行深入的表面改性,这是成本高昂的并且不方便,因为需要多个步骤并且仅可以制备较少的量。
发明内容
本发明所解决的问题因此就是提供一种用于生产聚合物官能化的填料颗粒的方法以及通过所述方法获得的聚合物官能化的填料颗粒以便于获得多种优点,特别是关于:
-更高的接枝密度;
-改进的化学稳定性;
-后续的可改性能力(modifiability);以及
-在固相与聚合物基质之间的界面上可施加的特定控制;并从而能够防止上述的缺点。将本发明的聚合物官能化的填料颗粒混合进一种橡胶混合物中在交联之后,将会在填料-聚合物相互作用方面产生明显的改进并因此就该混合物而言产生明显优化的特性。
这个问题通过一种用于生产聚合物官能化的填料颗粒的方法并通过由该方法获得的聚合物官能化的填料颗粒得到解决,其中该方法的特征为至少以下步骤:
-将至少含有一个可偶联的甲硅烷基基团S的一种用于受控自由基聚合的控制剂或一种用于受控自由基聚合的狄尔斯–阿尔德(Diels-Alder)控制剂键合至填料颗粒的表面上,其中该RAFT剂的R基团经由一个R1基团键合至填料颗粒的表面上,其中R1是至少一个甲硅烷基基团或至少一个狄尔斯–阿尔德反应性官能团,并且
-然后使用键合至该填料颗粒上的控制剂进行单体的受控自由基聚合。
具体实施方式
带有甲硅烷基的RAFT剂和狄尔斯–阿尔德RAFT剂的键合因此在以上方法中经由该R-基团进行,并且随后的RAFT聚合因此从填料材料的固体表面上进行。术语“RAFT剂”在此与术语“用于受控自由基聚合的控制剂”可互换地使用。该可偶联的甲硅烷基基团优选是-Si(OAlk)3、-SiAlk(OAlk)2或-SiAlk2(OAlk),其中Alk是具有1至18个碳原子的二价碳。出人意料地发现,在该RAFT剂的可离去的(leaving-capable)R-基团上建立该可偶联的甲硅烷基基团或狄尔斯–阿尔德基团(R-基团法,见图2)具有以下优点:用于生长自由大分子基(free macroradical)加成的反应性位点在聚合过程中远离该表面而移动。这关于经由该Z-基团的附接而言,暗示了生长链与表面附接的链之间的减少的位阻以及由此更高的占用度。这对于难以控制的单体例如特别是1,3-二烯类是重要的。在受控自由基聚合已经结束之后,该RAFT剂的官能团是处于链的自由端,即,未附接至填料表面上的一端。这为该官能化的填料的后续改性打开了门路。有别于Z-基团法,与该聚合物的附接不是经由RAFT基团的事实还暗示着就终产物而言增强的稳定性。该RAFT剂至填料表面上、更具体地说至硅石表面上的附接是定量的并且因此可以经由这些材料的所用重量来加以控制。具有非常宽范围的负载密度的改性/官能化的填料颗粒因此可获得而具有所陈述的优点。
该填料优选是硅石或碳黑,但也可以使用在橡胶工业中使用的其他极性或非极性填料类型。
可以使用所属领域技术人员已知的任何RAFT剂。特别是将发现来自以下组中的RAFT剂是有利的:二硫代酯类,二硫代苯甲酸酯类,例如二硫代苯甲酸枯酯类(CDB)、三硫代碳酸酯类、二硫代氨基甲酸酯类,例如1-苯基乙基9H-咔唑-9-二硫代氨基甲酸酯(BCC),以及黄酸酯类(也叫做黄原酸盐类)。
特别优选的RAFT剂是三硫代碳酸酯(=三硫代碳酸的盐)类别的那些,因为它们容易合成并且即使在RAFT基团的破坏情况下,硫醇也被留下作为官能团(也见图3)。其中,必须特别地提及的是丙基苯甲基三硫代碳酸酯(PPT)和丙基(三甲氧基硅烷)乙基苯基甲基三硫代碳酸酯(PPTS)和1,6-己基二((三甲氧基硅烷)乙基苯基甲基)三硫代碳酸酯(HDPS)以及双(1-苯乙基)三硫代碳酸酯(BPETC)。
现将描述对单独的优选的RAFT剂的制备:
作为用于在硅石表面上进行RAFT聚合的RAFT剂的丙基(三甲氧基
硅烷)乙基苯基甲基三硫代碳酸酯(PPTS)的制备
一个典型反应包括向甲醇(30ml)和甲醇钠(19.65g,0.09mol)在甲醇的25%溶液的冰冷却的溶液中逐滴添加丙硫醇(6.85g,0.09mol)。将该反应溶液在室温下搅拌两小时。在这之后是逐滴添加二硫化碳(6.85g,0.09mol)并且随后在室温下搅拌该反应溶液四小时。在这之后是添加氯甲基苯基三甲氧基硅烷(25.00g,0.09mol)并且在室温下搅拌反应溶液12小时。接着,在真空中去除该溶剂并且将剩余物吸收于氯仿(60ml)中。将有机相用水(30ml)洗涤并且随后经硫酸镁干燥。在高真空中去除溶剂从而以75%的产率获得所希望的产物,一种浅黄色油状物(26.32g)。
作为用于在硅石表面上进行RAFT聚合的RAFT剂的1,6-己基二((三
甲氧基硅烷)乙基苯基甲基)三硫代碳酸酯(HDPS)的制备
合成工序类似于用于丙基(三甲氧基硅烷)乙基苯基甲基三硫代碳酸酯(PPTS)的反应方案,除了使用1,6-己二硫醇(6.83g,0.046mol)代替丙硫醇。
另外可以添加未键合的RAFT剂用于在硅石表面上的RAFT聚合的增强控制。
双(1-苯乙基)三硫代碳酸酯(BPETC)的制备
将二硫化碳(1.90g,0.025mol)和碳酸铯(8.14g,0.025mol)在N,N-二甲基乙酰胺(20ml)中的混合物在室温下搅拌20分钟。反应混合物变成深红色。在这之后是逐步添加在N,N-二甲基乙酰胺(5ml)中的1-溴乙基苯(4.62g,0.025mol)。将该反应溶液在室温下搅拌24小时并且随后转移到冰-水(150mol)中。用乙酸乙酯(3次50ml)萃取水相。将合并的有机相经硫酸钠干燥并且在高真空中去除溶剂。以98%的产率获得所希望的产物,一种浅黄色油状物(7.79g)。
丙基苯甲基三硫代碳酸酯(PPT)的制备
将三乙胺(4.78g,0.047mol)逐步添加至丙硫醇(3.00g,0.039mol)在氯仿(200ml)中的溶液中。将该反应混合物在室温下搅拌一小时。在这之后是添加二硫化碳(7.50,0.098mol)并且将该反应混合物在室温下搅拌另外两小时。在这之后是添加苄基溴(8.08g,0.047mol)并且将反应溶液在室温下搅拌24小时。在这之后是添加10%盐酸(200ml)。分离出有机相并且用水洗涤(3次100ml)。将合并的有机相经硫酸钠干燥并且在高真空中去除溶剂。以98%的产率获得呈所希望的产物,为浅黄色油状物(9.36g)。
2-溴丙酸糠酯的制备
将三乙胺(5.26g,0.052mol)添加至2-呋喃甲醇(5.10g,0.052mol)在70ml氯仿中的冰冷却的溶液中。在这之后是逐步添加在10ml氯仿中的2-溴丙酰溴(9.93g,0.046mol)。将该反应混合物在室温(RT)下搅拌24小时。为进行处理(workup),将该反应混合物用水(1次80ml)、10%硫酸(1次80ml)并用饱和NaHCO3溶液(2次50ml)进行洗涤。将有机相经硫酸镁干燥、浓缩并在高真空中干燥。产率为67%。
2-溴丙烷硫代糠酯(furfuryl2-bromopropanethioate)的制备
合成工序类似于用于2-溴丙酸糠酯的反应方案,除了使用2-呋喃甲硫醇(5.94g,0.052mol)代替2-呋喃甲醇。
三硫代碳酸丙钠(sodium propyl trithiocarbonate)的制备
将丙硫醇(4.00g,0.053mol)在50ml四氢呋喃中的冰冷却的溶液与50%氢氧化钠溶液混合。在这之后是逐步添加CS2(4.00g,0.053mol)。这必须小心进行以确保温度不会上升到10°C以上。将该反应混合物在室温下搅拌24小时并且从己烷中再结晶。产率为64%。
丙基糠基丙酸酯三硫代碳酸酯(propyl furfurylpropanioate
trithiocarbonate)的制备
将三硫代碳酸丙钠(1.12g,0.0064mol)在10ml DMSO中的溶液添加至2-溴丙酸糠酯(1.49g,0.0064mol)在DMSO(25mol)的溶液中。将该反应混合物在室温下搅拌48小时并接着用乙醚洗涤(3次20ml)。将合并的这些有机相用水洗涤并且经硫酸钠干燥。在高真空中蒸发该溶剂从而以72%的产率获得产物。
将至少含有一个可偶联的甲硅烷基基团S的RAFT剂经由R基团键合至填料表面上,其中R是-Si(OAlk)3、-SiAlk(OAlk)2或-SiAlk2(OAlk),其中当该填料是硅石时,Alk是具有1至18个碳原子的二价烃。
当填料是碳黑时,该RAFT剂是通过狄尔斯–阿尔德反应被键合至填料颗粒的表面上(见图4、5和6)
经由该狄尔斯–阿尔德反应的附接以及该RAFT剂的结构暗示了以下优点:
1)键合在不形成副产物的情况下发生并且可以在温和的反应条件下进行。
2)没有任何物质需要进一步添加(即使催化量也不添加)。
3)固定(immobilization)可以在一阶段或两阶段式的合成策略中进行。该固定还有可能经由Steglich酯化反应来实现。
4)固定不是定量的。然而,负载密度可以经由反应时间和温度来进行控制并且任选地使用元素分析来检查。
5)由于RAFT剂的结构,在聚合反应结束之后聚合物链可以在酯/硫代酯键处分裂,以便允许就分子量和分子量分布进行分析。固定经由R-基团进行,从而产生以下优点:
1)用于生长自由大分子基的加成的反应性位点在聚合过程中远离该表面而移动。这关于经由Z-基团的连接而言,暗示了生长链与表面附接的链之间的减少的空间位阻。因此,可以实现更高的占用度。
2)在受控自由基聚合已经结束之后,该RAFT剂的官能团是处于链的自由端,即,未附接至填料表面上的一端。这为该链端的后续改性打开了门路。
3)在聚合物链端处建立官能性RAFT基团暗示了例如可以在硫化中使用的一定比例的硫原子。
以一阶段式合成方法制备表面改性的碳黑颗粒
一个例子见图4。
一个典型反应包括将丙基2-糠基-2-丙酸酯三硫代碳酸酯(propyl2-furfuryl-2-propanioate trithiocarbonate)(1.31g,0.0043mol)添加至碳黑(0.557g,0.046mol)在30ml二苄醚中的悬浮液中并且在100°C下搅拌反应混合物24小时。之后,将碳黑用THF在Soxhlet中洗涤数小时并接着在高真空中干燥。
与未处理的碳黑相比较,元素分析发现负载密度为每克碳黑0.118mmol的RAFT剂。
以二阶段式合成方法制备表面改性的碳黑颗粒
一个例子见图5。
一个典型反应包括将2-溴丙酸糠酯(2.09g,0.009mol)逐滴添加至碳黑(5.40g,0.450mol)在200ml二苄醚中的悬浮液中并且在130°C下搅拌反应混合物48小时。之后,将碳黑用THF在Soxhlet中洗涤并且在高真空中干燥。
将干燥的碳黑(5.40g,0.450mol)悬浮在二甲亚砜中,并接着与三硫代碳酸丙钠(1.71g,0.009mol)混合。将该反应混合物在室温下搅拌24小时、用THF在Soxhlet中洗涤并且在高真空中干燥。
与未处理的碳黑相比较,元素分析发现负载密度为每克碳黑0.192mmol的RAFT剂。
当硅石是该填料时,三甲氧基硅烷基团实现该键合。
附接在四个步骤中进行。在第一个步骤中,将这些三甲氧基硅烷基团在水的存在下水解,以便形成对应的硅烷醇。在第二个反应步骤中这些硅烷醇缩合在一起并形成低聚物。这些低聚物与羟基基团在硅石表面上键合以便形成强的氢键。最后,通过消去水而与该基质的表面形成一个共价键。
此处在硅石颗粒上的负载密度可以经由用于该材料的合适起始重量来加以控制。
在一个典型实验中,将丙基(三甲氧基硅烷)乙基苯基甲基三硫代碳酸酯(0.332g,0.851mmol)逐滴添加至硅石(17.75g)在甲苯(350ml)中的剧烈搅拌的悬浮液中。逐滴添加一个催化量的饱和马来酸酐溶液(1ml)并接着将该反应混合物在60°C下强烈搅拌24小时。在反应结束后,将硅石用二氯甲烷在Soxhlet中洗涤数小时。在这种情况下的固定是定量的,所以负载密度可以计算为每克硅石0.048mmol的RAFT剂。在RAFT剂已经键合至填料颗粒的表面上之后,利用键合至填料颗粒上的控制剂实现单体的受控自由基聚合。因此聚合直接远离填料颗粒的表面而进行。RAFT剂的官能团处于聚合物链的自由端上并且远离该表面而移动,见图7和8。这提供了以上提及的优点。
任何可自由基聚合的单体都可以单一地或组合地使用,所以在聚合完成时获得均聚物或共聚物或嵌段聚合物或嵌段共聚物。使用的单体优选是1,2-丁二烯、1,3-丁二烯、异戊二烯、苯乙烯、丙烯腈、2-丙烯腈、乙烯基化合物、甲基丙烯酰基化合物、丙烯酰基化合物、以及所谓的“烯(ene)”化合物,例如像降冰片烯。将会发现二烯单体并且其中优选地丁二烯单体特别有利于形成聚丁二烯或丁二烯共聚物。
通过本发明解决的另外一个问题是提供这样的橡胶混合物,这些混合物具有改进的聚合物-填料键以及填料在橡胶混合物中改进的分散。作为结果,橡胶混合物展现优化的物理特性。
当橡胶混合物含有通过根据本发明的方法获得的聚合物官能化的填料颗粒时,这个问题得到解决。这些聚合物官能化的填料颗粒的上述特性赋予了橡胶混合物优化的物理特性。
该橡胶混合物用于制造轮胎,尤其是汽车轮胎、卡车轮胎、两轮车轮胎或工业轮胎,这些轮胎还可以采用固体橡胶轮胎的形式。本发明的橡胶混合物优选用作胎面,但作为用于胎体综合体的橡胶混合物的使用也是可能的。该橡胶混合物进一步用于制造工业橡胶物品,例如皮带、传动皮带、柔性管、密封件、风箱、以及印花毡。
除了从聚合物改性的填料颗粒方面已经存在的橡胶外,该橡胶混合物可以进一步包含至少一种另外的极性或非极性橡胶。这种极性或非极性橡胶选自下组,该组由以下各项组成:天然聚异戊二烯和/或合成聚异戊二烯和/或丁二烯橡胶和/或苯乙烯-丁二烯橡胶和/或溶液聚合的苯乙烯-丁二烯橡胶和/或乳液聚合的苯乙烯-丁二烯橡胶和/或液体橡胶和/或卤代丁基橡胶和/或聚降冰片烯和/或异戊二烯-异丁烯共聚物和/或乙烯-丙烯-二烯单体橡胶和/或丁腈橡胶和/或氯丁二烯橡胶和/或丙烯酸酯橡胶和/或氟橡胶和/或硅酮橡胶和/或聚硫橡胶和/或表氯醇橡胶和/或苯乙烯-异戊二烯-丁二烯三聚物和/或氢化丙烯腈-丁二烯橡胶和/或异戊二烯-丁二烯共聚物和/或氢化苯乙烯-丁二烯橡胶。
在例如皮带、传动皮带以及柔性管的工业橡胶物品的制造中尤其使用了丁腈橡胶、氢化丙烯腈-丁二烯橡胶、氯丁二烯橡胶、丁基橡胶、卤代丁基橡胶或乙烯-丙烯-二烯单体橡胶。该橡胶混合物进一步包含本发明的聚合物官能化的填料颗粒。如所提及的,该填料优选是硅石或碳黑。
当硅石是该填料时,该橡胶混合物包含从1至300phr、优选地从1至250phr、更优选地从1至200phr、甚至更优选地从1至150phr、并且仍然甚至更优选地从1至100phr的聚合物官能化的硅石颗粒。当碳黑是该填料时,该橡胶混合物包含从1至180phr、更优选地从1至170phr并且甚至更优选地从1至100phr的聚合物官能化的碳黑颗粒。该橡胶混合物还有可能仅包含聚合物官能化的硅石颗粒或聚合物官能化的碳黑颗粒或其组合。在橡胶工业中已知的其他填料,例如矾土、滑石、高岭土、碳酸盐类、金属氧化物类(例如,氧化镁类、氧化铁类、氧化钛类)、云母、碳纤维类、粘土矿物类、改性页硅酸盐类以及其他物质,是可能的。类似有可能的是,例如芳族聚酰胺或尼龙的纤维类、中空的微球类或玻璃鳞片类另外存在于该橡胶混合物之中。
该橡胶混合物进一步包含更进一步添加的物质。进一步添加的物质主要是指增塑剂类、氧化锌、交联体系(交联剂、硫供体和/或元素硫、促进剂以及延迟剂)、臭氧控制剂类、老化控制剂类、塑炼辅助剂类以及另外的活化剂/加工助剂。可归于进一步添加的物质的总量的比例是从3至150phr、优选地从3至100phr并且更优选地从5至80phr。
使用的增塑剂优选是矿物油类,例如DAE(馏出的芳香族提取液)、RAE(残留的芳香族提取液)、TDAE(经处理的馏出的芳香族提取液)、MES(温和提取的溶剂)和/或环烷油类和/或合成增塑剂类和/或脂肪酸类和/或脂肪酸衍生物和/或树脂和/或油膏和/或植物油类或生物质液体(biomass-to-liquid;BTL)油类和/或液体聚合物类。
如在此使用的phr应理解为表示按重量计每一百份橡胶的份数,这是橡胶工业中用于报告混合配方的惯例。因此这些单独物质的按重量计的份数的配量总是基于所有存在于该混合物中的这些橡胶总质量的100重量份。
现将参考对比例和操作实例来更具体地阐述本发明,这些实例总结在表1和2中。标记“E”的混合物是本发明的混合物,而标记“V”的混合物是对比混合物。表1描述了聚合物官能化的填料颗粒的构造,而表2在上部分中展示了混合物组成并且在下部分中展示了该混合物的物理特性。
在常规条件下在实验室规模的切向混炼机中在多个阶段中产生了这些混合物。全部这些混合物通过硫化而用于产生多个试样,这些试样被用于测定橡胶工业典型的材料特性。对试样的上述测试采用了以下方法:
·按照DIN53512在室温和70°C下的回弹性
·按照DIN53505在室温和70°C下的肖氏A硬度
·按照DIN53504在室温在100%和200%应变下的应力值(模量)
·按照DIN53504在室温下的断裂伸长率
·按照DIN53504在室温下的抗拉强度
·按照DIN53513在8%应变下在-25°C下的动态储能模量E’
表1
表2
*Δ:在t100下自硫化仪曲线的损耗角,Δ越小,滚动阻力行为越好。
**根据Eplexor温度扫描,在较低温度下的刚度越低,低温柔性和随之的冬季特性越好。
Claims (10)
1.一种用于生产聚合物官能化的填料颗粒的方法,其特征在于,至少以下步骤:
-将至少含有一个可偶联的甲硅烷基基团S的一种用于受控自由基聚合的控制剂或一种用于受控自由基聚合的狄尔斯–阿尔德控制剂键合至填料颗粒的表面上,其中该RAFT剂的R基团经由一个R1基团键合至填料颗粒的表面上,其中R1是至少一个甲硅烷基基团或至少一个狄尔斯–阿尔德反应性官能团,并且
-然后使用键合至该填料颗粒上的控制剂进行单体的受控自由基聚合。
2.如权利要求1所述的方法,其特征在于,这些填料颗粒是硅石颗粒。
3.如权利要求1所述的方法,其特征在于,这些填料颗粒是碳黑颗粒。
4.如权利要求1至3中任一项所述的方法,其特征在于,用于受控自由基聚合的该控制剂是选自由三硫代碳酸酯类组成的组。
5.如权利要求1至4中任一项所述的方法,其特征在于,这些单体中的至少一个是一种二烯单体。
6.聚合物官能化的填料颗粒,是通过如权利要求1至5中任一项所述的方法获得的。
7.一种橡胶混合物,其特征在于,该橡胶混合物包含如权利要求6所述的聚合物官能化的填料颗粒。
8.如权利要求7所述的橡胶混合物在轮胎制造中的用途。
9.如权利要求8所述的橡胶混合物在轮胎的胎面或胎体混合物的制造中的用途。
10.如权利要求7所述的橡胶混合物在皮带、传动皮带或柔性管的制造中的用途。
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