CN101568584A - 包含聚合物纳米颗粒的橡胶组合物 - Google Patents

包含聚合物纳米颗粒的橡胶组合物 Download PDF

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CN101568584A
CN101568584A CNA2007800478952A CN200780047895A CN101568584A CN 101568584 A CN101568584 A CN 101568584A CN A2007800478952 A CNA2007800478952 A CN A2007800478952A CN 200780047895 A CN200780047895 A CN 200780047895A CN 101568584 A CN101568584 A CN 101568584A
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conjugated diolefine
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詹姆斯·P·克莱克纳
威廉姆·J·欧布里斯克
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Abstract

提供一种组合物,其包括至少两种(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶和包含聚(单乙烯基芳香族)核和聚(单乙烯基芳香族化合物-共轭二烯)表面层的聚合物纳米颗粒;其中所述聚合物纳米颗粒的核具有约150℃至约600℃之间的玻璃化转变温度(Tg),以及所述聚合物纳米颗粒的聚(单乙烯基芳香族化合物-共轭二烯)表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基含量的约50%至约150%之间的单乙烯基芳香族含量。

Description

包含聚合物纳米颗粒的橡胶组合物
技术领域
本公开提供引入纳米颗粒的橡胶组合物,所述纳米颗粒包括核和表面层,其中所述表面层包括聚(单乙烯基芳香族化合物-共轭二烯)(poly(mono-vinyl aromatic-conjugated diene)),所述核具有约150℃至约600℃之间的玻璃化转变温度(Tg)。
背景技术
有时,对于提供具有高水平操作性,即驾驶响应性、高水平抓着力和低燃料消耗的轮胎,存在日益增加的兴趣。提高轮胎驾驶响应性的通用方法是使用具有高刚度的胎面橡胶。高刚度配混物典型地具有高的动态贮能模量。用于增大动态贮能模量的常规配混技术包括使用高的填料加入量、使用具有高表面积的填料、使用较少的软化剂和使用具有高苯乙烯含量的苯乙烯-丁二烯聚合物。然而,这些常规方法各自具有性能折衷。
例如,上述常规技术能够增大橡胶配混物的滞后。增大橡胶的滞后导致更多的作为热的能量损失,因而增加燃料消耗。
此外,增大填料加入量、使用具有高表面积的填料和降低软化剂水平能够对加工具有负面影响,这是因为其总是增加将填料分散于橡胶中花费的时间。
因此,需要保持改进橡胶配混物的动态模量而不明显影响配混物的滞后或配混物的加工。
发明内容
提供包括橡胶和聚合物纳米颗粒的组合物,所述聚合物纳米颗粒包括聚(单乙烯基芳香族)核和聚(单乙烯基芳香族化合物-共轭二烯)表面层,其中所述聚合物纳米颗粒的核具有约150℃至约600℃之间的玻璃化转变温度(Tg)。
还提供一种组合物,其包括至少两种(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶和聚合物纳米颗粒,所述聚合物纳米颗粒包括聚(单乙烯基芳香族)核和聚(单乙烯基芳香族化合物-共轭二烯)表面层;其中所述聚合物纳米颗粒的核具有约150℃至约600℃之间的玻璃化转变温度(Tg),以及所述聚合物纳米颗粒的聚(单乙烯基芳香族化合物-共轭二烯)表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基含量的约50%至约150%之间的单乙烯基芳香族含量。
此外,提供包括胎面的轮胎。所述胎面包括橡胶和聚合物纳米颗粒,所述聚合物纳米颗粒包含聚(单乙烯基芳香族)核和聚(单乙烯基芳香族化合物-共轭二烯)表面层,其中所述聚合物纳米颗粒的核具有约150℃至约600℃之间的玻璃化转变温度(Tg)。
附图说明
图1为在实施例1中利用的纳米颗粒的差示扫描量热法分析的图示描述。
具体实施方式
具有表面层和具有约150℃至约600℃之间Tg的核的聚合物纳米颗粒可通过以下步骤来制备:
(i)在液体烃介质中,使共轭二烯单体聚合,以生产聚(共轭二烯)嵌段;和
(ii)使所述聚(共轭二烯)嵌段与单乙烯基芳香族单体和多乙烯基芳香族单体的混合物共聚合,以生产芳香族嵌段。
将现有专利和公布如美国专利6,437,050(BridgestoneCorp.)和Macromol.Symp.118,143-148(1997)在此引入作为一般参考。
步骤(ii)发生时,足够量的包括聚(共轭二烯)嵌段和芳香族嵌段的共聚物可组装以形成胶束结构,典型地,与此同时,芳香族嵌段可通过多乙烯基芳香族单体交联。
具有表面层和具有约150℃至约600℃之间Tg的核的聚合物纳米颗粒通过分散聚合形成,虽然也可考虑乳液聚合。聚合可通过多阶段阴离子聚合来完成。已进行多阶段阴离子聚合来制备嵌段共聚物,例如在美国专利4,386,125中,在此将其引入以作参考。其他相关文献包括美国专利6,437,050和美国专利申请2004/0143064。
聚合物纳米颗粒可由包括聚(共轭二烯)嵌段和芳香族嵌段的二嵌段共聚物链形成。由于存在多乙烯基芳香族单体,芳香族嵌段典型地交联,至少部分地给出控制核的Tg的方式。聚合物纳米颗粒优选保持其彼此之间几乎没有或没有聚合的离散性。在优选的实施方案中,纳米颗粒基本是单分散的和形状均一的。
液体烃介质起到分散溶剂的作用,其可选自任何合适的脂族烃、脂环烃或其混合物,条件是在纳米颗粒形成步骤中,其以液体状态存在。示例性脂族烃包括但不限于戊烷、异戊烷、2,2-二甲基丁烷、己烷、庚烷、辛烷、壬烷和癸烷等。示例性脂环烃包括但不限于环戊烷、甲基环戊烷、环己烷、甲基环戊烷、环庚烷、环辛烷、环壬烷和环癸烷等。通常,不优选芳香烃和极性溶剂作为该液体介质。在示例性实施方案中,该液体烃介质包括己烷。
可将任何合适的共轭二烯或其混合物用作单体以生产聚(共轭二烯)嵌段。该共轭二烯单体的具体实例包括但不限于1,3-丁二烯、异戊二烯(2-甲基-1,3-丁二烯)、顺式-和反式-戊间二烯(1,3-戊二烯)、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、顺式-和反式-1,3-己二烯、顺式-和反式-2-甲基-1,3-戊二烯、顺式-和反式-3-甲基-1,3-戊二烯、4-甲基-1,3-戊二烯、2,4-二甲基-1,3-戊二烯等及其混合物。在优选的实施方案中,可将异戊二烯或1,3-丁二烯或其混合物用作该共轭二烯单体。
共轭二烯单体聚合成聚(共轭二烯)嵌段通过添加本领域已知的阴离子引发剂来引发。例如,阴离子引发剂可选自任何已知的有机锂化合物。合适的有机锂化合物由如下所示的式子来表示:
R(Li)x
其中R为具有1至x价的烃基。R通常每个R基团包含1至20个,优选2至8个碳原子,x为1至4的整数。典型地,x为1,并且R基团包括脂肪族基团和脂环族基团,如烷基、环烷基、环烷基烷基、烷基环烷基、链烯基以及芳基和烷芳基。
R基团的具体实例包括但不限于烷基如甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、正戊基、异戊基、正己基、正辛基和正癸基等;环烷基和烷基环烷基如环戊基、环己基、2,2,1-双环庚基、甲基环戊基、二甲基环戊基、乙基环戊基、甲基环己基、二甲基环己基、乙基环己基、异丙基环己基和4-丁基环己基等;环烷基烷基如环戊基-甲基、环己基-乙基、环戊基-乙基、甲基-环戊基乙基和4-环己基丁基等;链烯基如乙烯基和丙烯基等;芳烷基如4-苯基丁基;芳基和烷芳基如苯基、萘基、4-丁基苯基和对甲苯基等。
其他锂引发剂包括但不限于1,4-二锂代丁烷、1,5-二锂代戊烷、1,10-二锂代癸烷、1,20-二锂代二十烷、1,4-二锂代苯、1,4-二锂代萘、1,10-二锂代蒽、1,2-二锂代-1,2-二苯基乙烷、1,3,5-三锂代戊烷、1,5,15-三锂代二十烷、1,3,5-三锂代环己烷、1,3,5,8-四锂代癸烷、1,5,10,20-四锂代二十烷、1,2,4,6-四锂代环己烷和4,4′-二锂代联苯等。优选的锂引发剂包括正丁基锂、仲丁基锂、叔丁基锂、1,4-二锂代丁烷及其混合物。
可采用的其他锂引发剂为二烷基胺基锂(lithium dialkylamine)、二烷基膦锂(lithium dialkyl phosphine)、烷基芳基膦锂(lithium alkyl aryl phosphine)和二芳基膦锂(lithium diarylphosphine)。也可使用官能化锂引发剂。优选的官能团包括胺、甲酰基、羧酸、醇、锡、硅、甲硅烷基醚及其混合物。
在某些实施方案中,使用正丁基锂、仲丁基锂、叔丁基锂或其混合物来引发共轭二烯单体聚合成聚(共轭二烯)嵌段。
共轭二烯单体聚合成聚(共轭二烯)嵌段可尽需要长地持续,直到获得期望的单体转化率、聚合度(DP)和嵌段分子量。该步骤的聚合反应可持续约0.25小时至约10小时,或约0.5小时至约4小时,或约0.5小时至约2小时。该步骤的聚合反应可在约70°F至约350°F,或约74°F至约250°F,或约80°F至约200°F的温度下进行。在示例性实施方案中,聚合在65-195°F下持续约90分钟。
共轭二烯单体的阴离子聚合可在改性剂或1,2-微结构控制剂存在下进行,从而例如增大反应速率、平衡单体的反应比和/或控制共轭二烯单体中的1,2-微结构。合适的改性剂包括但不限于三乙胺、三正丁胺、六甲基磷酸三酰胺、N,N,N′,N′-四甲基乙二胺、乙二醇二甲醚、二甘醇二甲醚、三甘醇二甲醚、四甘醇二甲醚、四氢呋喃、1,4-二氮杂双环[2.2.2]辛烷、乙醚、三正丁基膦、对二噁烷、1,2-二甲氧基乙烷、二甲醚、甲乙醚、乙丙醚、二正丙醚、二正辛醚、苯甲醚、二苄醚、二苯醚、二甲基乙基胺、双氧杂环戊基(bix-oxalanyl)丙烷、三正丙胺、三甲胺、三乙胺、N,N-二甲基苯胺、N-乙基哌啶、N-甲基-N-乙基苯胺、N-甲基吗啉、四亚甲基二胺、低聚氧杂环戊基(oxolanyl)丙烷(OOPs)、2,2-双-(4-甲基二烷)和双四氢呋喃基丙烷等。
阴离子聚合也可在胺化合物如三乙胺、三甲胺、三丙胺、三异丙胺、三正丁胺等及其混合物存在下进行。
其他改性剂或1,2-微结构控制剂可为由结构式(IV)表示的线性氧杂环戊基低聚物和由结构式(V)表示的环状低聚物,如下所示:
Figure A20078004789500091
式(IV)
Figure A20078004789500092
式(V)
其中R14和R15独立地为氢或C1-C8烷基;R16、R17、R18和R19独立地为氢或C1-C6烷基;y为1至5的整数,以及z为3至5的整数。
改性剂或1,2-微结构控制剂的具体实例包括但不限于低聚氧杂环戊基丙烷(OOPs);2,2-双-(4-甲基二噁烷);双(2-氧杂环戊基)甲烷;1,1-双(2-氧杂环戊基)乙烷;双四氢呋喃基丙烷;2,2-双(2-氧杂环戊基)丙烷;2,2-双(5-甲基-2-氧杂环戊基)丙烷;2,2-双-(3,4,5-三甲基-2-氧杂环戊基)丙烷;2,5-双(2-氧杂环戊基-2-丙基)氧杂环戊烷(oxolane);八甲基全氢环四糠烯(octamethylperhydrocyclotetrafurfurylene)(环状四聚物);和2,2-双(2-氧杂环戊基)丁烷等。也可使用两种或多种改性剂或1,2-微结构控制剂的混合物。
任选地,聚(共轭二烯)嵌段具有包括共轭二烯单体和单乙烯基芳香族单体的无规化结构,所述共轭二烯单体和单乙烯基芳香族单体任选地在改性剂存在下使用阴离子引发剂共聚合。合适的单乙烯基芳香族单体包括但不限于苯乙烯、乙基乙烯基苯、α-甲基-苯乙烯、1-乙烯基萘、2-乙烯基萘、乙烯基甲苯、甲氧基苯乙烯和叔丁氧基苯乙烯等;以及其烷基、环烷基、芳基、烷芳基和芳烷基衍生物,其中在单体中的碳原子总数通常不大于约18;及其混合物。在示例性实施方案中,单乙烯基芳香族单体包括苯乙烯或乙基乙烯基苯或其混合物。如果聚(共轭二烯)嵌段具有包括共轭二烯单体和单乙烯基芳香族单体的无规化结构,则所得聚合物纳米颗粒将具有表面层,所述表面层具有包括共轭二烯单元和单乙烯基芳香族单元的共聚物。
然后,可将单乙烯基芳香族单体和多乙烯基芳香族单体的混合物与活性聚(共轭二烯)嵌段共聚合。单乙烯基芳香族单体和多乙烯基芳香族单体之间的重量比可在从约99.9∶0.01至约0.01∶99.9,优选从约99∶1至约1∶99,更优选从约90∶10至约10∶99的宽范围内。
可将包括一个乙烯基和芳香族基团的任何化合物用作单乙烯基芳香族单体。合适的单乙烯基芳香族单体包括但不限于苯乙烯、乙基乙烯基苯、α-甲基苯乙烯、1-乙烯基萘、2-乙烯基萘、乙烯基甲苯、甲氧基苯乙烯和叔丁氧基苯乙烯等;以及其烷基、环烷基、芳基、烷芳基和芳烷基衍生物,其中在单体中的碳原子总数通常不大于约18;及其混合物。在示例性实施方案中,单乙烯基芳香族单体包括苯乙烯或乙基乙烯基苯或其混合物。
可将任何包括两个或多个乙烯基和芳香族基团的化合物用作多乙烯基芳香族单体。合适的多乙烯基芳香族单体包括但不限于具有如下所示的通式的化合物:
Figure A20078004789500111
其中p为整数,且2≤p≤6,优选地,p为2或3,更优选地,p为2,即二乙烯基苯(DVB)。
在一个实施方案中,所述DVB可选自以下异构体的任何一种或其任意组合:
Figure A20078004789500112
当单乙烯基芳香族单体和多乙烯基芳香族单体的混合物与活性聚(共轭二烯)嵌段共聚合时,可添加另外的阴离子引发剂如锂引发剂。示例性阴离子引发剂可为如上所示的那些。在示例性实施方案中,使用正丁基锂、仲丁基锂、叔丁基锂或其混合物。聚合可尽需要长地持续,直到获得期望的核Tg、单体转化率、聚合度(DP)和嵌段分子量。该步骤的聚合反应可持续约0.5小时至约10小时,或约1小时至约6小时,或约1小时至约4小时。该步骤的聚合反应可在约70°F至约350°F,或约74°F至约250°F,或约80°F至约200°F的温度下进行。在示例性实施方案中,聚合步骤在165°F下持续3小时,然后在210°F下持续1小时。
应理解,由于使用单乙烯基芳香族单体和多乙烯基芳香族单体的混合物,胶束组装和芳香族嵌段的交联可以同时发生。
聚合物纳米颗粒由胶束状结构形成,所述胶束状结构具有由芳香族嵌段制成的核和由聚(共轭二烯)嵌段制成的表面层。
用于制备聚合物纳米颗粒的聚合反应可用终止剂终止。合适的终止剂包括但不限于醇如甲醇、乙醇、丙醇和异丙醇;胺、MeSiCl3、Me2SiCl2、Me3SiCl、SnCl4、MeSnCl3、Me2SnCl2和Me3SnCl等。在示例性实施方案中,将聚合反应混合物冷却并滴入任选地包含抗氧化剂如丁基化羟基甲苯(BHT)的异丙醇/丙酮溶液。异丙醇/丙酮溶液例如可通过混合1体积份异丙醇和4体积份丙酮来制备。
聚合物纳米颗粒可通过一种或多种机理来官能化,所述机理包括通过特定设计的引发剂而官能化;通过特定设计的终止剂而官能化;当产生表面层和/或核时通过官能化的可共聚单体的共聚合而官能化;或通过在聚(共轭二烯)表面层中的任何不饱和基团如乙烯基的改性而官能化。可引入聚合物纳米颗粒中的示例性官能团包括但不限于马来酰亚胺、羟基、羧基、甲酰基、偶氮羧基、环氧化物、氨基、氯化物(colonids)、溴化物等及其混合物。
在一个示例性实施方案中,根据以下方法制造聚合物纳米颗粒。首先,无规聚(共轭二烯)嵌段通过在己烷溶剂中使用丁基锂引发剂,和在无规化剂低聚氧杂环戊基丙烷(OOPs)存在下,共轭二烯单体和单乙烯基芳香族单体的溶液聚合来制备。共轭二烯单体可包括1,3-丁二烯,单芳香族单体可包括苯乙烯。其次,然后任选地使用额外量的丁基锂引发剂,使单乙烯基芳香族单体和多乙烯基芳香族单体的混合物与活性聚(共轭二烯)嵌段共聚合。单乙烯基芳香族单体可包括苯乙烯,多乙烯基芳香族单体可包括二乙烯基苯。反应用醇终止,然后干燥并去溶剂化。产物为具有交联核的星形聚合物纳米颗粒。
聚合物纳米颗粒可具有纳米球的形状。所述球的平均直径可在约5nm至约200nm,或约5nm至约100nm,或约10nm至约80nm,或约15nm至约60nm的范围内。
可将聚(共轭二烯)嵌段的分子量(Mn、Mw或Mp)控制在约1,000至约1,000,000的范围内,约1,000至约100,000的范围内,或约1,000至约80,000的范围内。
在很多示例性实施方案中,可将聚合物纳米颗粒的分子量(Mn、Mw或Mp)控制在约100,000至约1,000,000,000,或约1,000,000至约100,000,000的范围内。可将聚合物纳米颗粒的多分散性(重均分子量与数均分子量的比)控制在约1.01至约1.3的范围内,约1.01至约1.2的范围内,或约1.01至约1.1的范围内。
纳米颗粒可以以两个聚合步骤而不是三个步骤来生产,即,单乙烯基芳香族单体和多乙烯基芳香族单体作为混合物在一个步骤中或同时聚合,而不是单乙烯基芳香族单体首先聚合,然后多乙烯基芳香族单体共聚合或聚集以交联。该较简单的方法导致比三步骤方法更高的颗粒产率(80-98%相对40-85%)。该方法可有效地产生单体至高分子量纳米颗粒的高转化率(典型地,纳米颗粒的产率>90%)。
不像仅由乙烯基芳香族单体制得的颗粒那样,本发明的颗粒具有可硫化表面层如硫磺可硫化的表面层。可硫化表面层为硫磺或过氧化物可硫化表面层。合适的硫磺硫化剂的实例包括“橡胶制造者的(rubber maker’s)”可溶性硫磺;元素硫(单体硫);供硫硫化剂如有机硅烷多硫化物、二硫化胺、聚合多硫化物或硫磺烯烃加合物;以及不溶性聚合硫。
纳米颗粒具有充分交联的核,以致纳米颗粒核的Tg可在从约150℃至约600℃,从约200℃至约400℃,或从约250℃至约300℃的宽范围内。玻璃化转变温度可例如在10℃每分钟的加热速率下通过差示扫描量热计来测定。
将纳米颗粒配混入橡胶组合物如轮胎橡胶胎面组合物中。橡胶组合物可通过将橡胶和纳米颗粒与包括二氧化硅或炭黑或两者的混合物的补强填料、任选的加工助剂、任选的偶联剂、任选的硫化剂、其他期望或可接受的轮胎胎面组分和实现组合物满意硫化的有效量的硫磺混合来制备。
示例性橡胶包括共轭二烯聚合物、共轭二烯单体与单乙烯基芳香族单体的共聚物或三元聚合物。这些可用作在胎面胶料配混物中的100份橡胶,即组成该配混物的全部橡胶组分,或可将其与任何通常采用的胎面胶料橡胶共混,所述通常采用的胎面胶料橡胶包括天然橡胶、合成橡胶及其共混物。此类橡胶已被本领域熟练技术人员所公知,其包括合成聚异戊二烯橡胶、丁苯橡胶(SBR)、苯乙烯-异戊二烯橡胶、苯乙烯-异戊二烯-丁二烯橡胶、丁二烯-异戊二烯橡胶、聚丁二烯、丁基橡胶、氯丁橡胶、丁腈橡胶(NBR)、硅橡胶、氟弹性体、乙烯丙烯酸类橡胶、乙丙橡胶、乙烯-丙烯三元聚合物(EPDM)、乙烯乙酸乙烯酯共聚物、表氯醇橡胶、氯化聚乙烯-丙烯橡胶、氯磺化聚乙烯橡胶、氢化丁腈橡胶和四氟乙烯-丙烯橡胶等。
可用于可硫化弹性体组合物的补强二氧化硅填料的实例包括湿法二氧化硅(水合硅酸)、干法二氧化硅(无水硅酸)和硅酸钙等。其他合适的填料包括硅酸铝和硅酸镁等。其中,优选沉淀的无定形湿法、水合二氧化硅。可以每100份弹性体(phr)约1至约100份的量,优选以约5至80phr的量,更优选以约30至约80phrs的量使用二氧化硅。有用的上限范围受到由该类型填料赋予的高粘度的限制。可使用的一些商购可得的二氧化硅包括但不限于由PPG Industries(Pittsburgh,Pa.)生产的
Figure A20078004789500151
190、
Figure A20078004789500152
210、
Figure A20078004789500153
215、
Figure A20078004789500154
233和
Figure A20078004789500155
243等。许多有用的商品级不同的二氧化硅也可得自DeGussa Corporation(例如VN2、VN3)、Rhone Poulenc(例如
Figure A20078004789500156
1165MP0和J.M.Huber Corporation)。
可将橡胶与所有形式的炭黑,任选地另外与二氧化硅配混。炭黑可以约1至约100phr范围内的量存在。炭黑可包括任何通常可得的商业生产的炭黑,但优选具有表面积至少20m2/g,或优选至少35m2/g直到200m2/g以上的那些。在有用的炭黑中,为炉黑、槽黑和灯黑。可将上述炭黑的两种或多种的混合物用于制备本发明的炭黑产物。典型的合适的炭黑为由ASTMD-1765-82a指定的N-110、N-220、N-339、N-330,N-352、N-550、N-660。
可使用一些另外的填料,包括矿物填料如粘土、滑石、铝的水合物、氢氧化铝和云母。前述另外的填料是任选的,可以约0.5phr至约40phr的量使用。
已知许多偶联剂和相容剂用于组合二氧化硅和橡胶。在二氧化硅类偶联和相容剂中包括包含多硫化物组分或例如在多硫化物桥中包含约2至约8个硫原子的三烷氧基有机硅烷多硫化物如双-(3-三乙氧基甲硅烷基丙基)四硫化物(Si69)、双-(3-三乙氧基甲硅烷基丙基)二硫化物(Si75)等结构的硅烷偶联剂,以及如辛基三乙氧基硅烷和己基三甲氧基硅烷等的那些烷基烷氧基硅烷。
可将加工油添加至可硫化弹性体组合物中。可以0phr至约70phr的量使用加工油。可将加工油添加至组合物本身中,或可以充油弹性体的形式添加。示例性加工油包括芳香族的、脂环族的和低PCA油。合适的低PCA油包括具有通过IP346方法测定的低于3重量%的多环芳香族含量的那些。IP346方法的步骤可在由Institute of Petroleum,United Kingdom出版的StandardMethods for Analysis & Testing of Petroleum and RelatedProducts and British Standard 2000Parts,2003,第62版本中找到。合适的低PCA油包括适度提取溶剂化物(MES)、处理的馏出物芳香族提取物(TDAE)和重质环烷烃(heavy naphthenics)。合适的ME S油是商购可得的,如来自Shell的Catenex SNR、来自ExxonMobil的Prorex 15和Flexon 683、来自BP的VivaTec 200、来自TotalFinaElf的Plaxolene、来自Dahleke的Tudalen4160/4225、来自Repsol的ME S-H、来自Z8的ME S和来自Agip的Olio MESS 201。合适的TDAE油是商购可得的,如来自ExxonMobil的Tyrex 20、来自BP的VivaTec 500、VivaTec 180和Enerthene 1849和来自Repsol的Extensoil1996。合适的重质环烷油是可获得的,如Shellflex 794、Ergon Black Oil、Ergon H2000、Cross C2000、Cross C2400和San Joaquin 2000L。
本领域熟练技术人员容易理解,橡胶组合物可通过在橡胶配混领域中通常已知的方法如将橡胶与各种通常使用的添加剂材料混合来配混,所述添加剂材料例如硫化剂、活化剂、防焦剂和促进加工添加剂如油、包括增稠树脂的树脂、增塑剂、颜料、另外的填料、脂肪酸、氧化锌、蜡、抗氧化剂、抗臭氧剂和胶溶剂。如本领域熟练技术人员已知的,取决于橡胶组合物的预期用途,选择上述添加剂并以常规量使用。
在一个实施方案中,将纳米颗粒添加至包括至少一种橡胶的轮胎胎面中。示例性橡胶包括共轭二烯聚合物、共轭二烯单体与单乙烯基芳香族单体的共聚物或三元聚合物。这些可用作在胎面胶料配混物中的100份橡胶,即组成配混物的全部橡胶组分,或可将其与任何通常采用的胎面胶料橡胶共混,所述通常采用的胎面胶料橡胶包括天然橡胶、合成橡胶及其共混物。此类橡胶为本领域熟练技术人员所公知,其包括合成聚异戊二烯橡胶、丁苯橡胶(SBR)、苯乙烯-异戊二烯橡胶、苯乙烯-异戊二烯-丁二烯橡胶、丁二烯-异戊二烯橡胶、聚丁二烯、丁基橡胶、氯丁橡胶、丁腈橡胶(NBR)、硅橡胶、氟弹性体、乙烯丙烯酸类橡胶、乙丙橡胶、乙烯-丙烯三元聚合物(EPDM)、乙烯乙酸乙烯酯共聚物、表氯醇橡胶、氯化聚乙烯-丙烯橡胶、氯磺化聚乙烯橡胶、氢化丁腈橡胶和四氟乙烯-丙烯橡胶等。
在另一实施方案中,轮胎胎面包括至少两种橡胶,其各自包括至少一种共轭二烯单体单元和至少一种单乙烯基芳香族单体单元。示例性共轭二烯单体包括但不限于1,3-丁二烯、异戊二烯(2-甲基-1,3-丁二烯)、顺式-和反式-戊间二烯(1,3-戊二烯)、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、顺式-和反式-1,3-己二烯、顺式-和反式-2-甲基-1,3-戊二烯、顺式-和反式-3-甲基-1,3-戊二烯、4-甲基-1,3-戊二烯、2,4-二甲基-1,3-戊二烯等及其混合物。在优选的实施方案中,可将异戊二烯或1,3-丁二烯或其混合物用作该共轭二烯单体。示例性单乙烯基芳香族单元包括但不限于苯乙烯、乙基乙烯基苯、α-甲基-苯乙烯、1-乙烯基萘、2-乙烯基萘、乙烯基甲苯、甲氧基苯乙烯和叔丁氧基苯乙烯等;以及其烷基、环烷基、芳基、烷芳基和芳烷基衍生物,其中在单体中的碳原子总数通常不大于约18;及其混合物。
可使用纳米颗粒替换(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶,所述共聚物橡胶具有最密切匹配纳米颗粒表面层的单乙烯基芳香族含量的单乙烯基芳香族含量。纳米颗粒表面层的单乙烯基芳香族含量可为(链烯基苯-共轭二烯)共聚物之一的单乙烯基芳香族含量的约50%和约150%之间,或约75%和约125%之间,或约90%和约110%之间。这可使得将纳米颗粒组合入橡胶而没有明显影响橡胶基质的总的单乙烯基芳香族含量。
可将纳米颗粒以低于约50phr,低于约30phr,或低于约20phr的水平添加至橡胶组合物中。
纳米颗粒的核起到在橡胶中分散的填料的作用。填料效果归因于与橡胶基质相比的核的相对硬度。
实施例
使用示于表1的配方制备三种胶料。胶料2和3分别具有7phr和14phr的引入的本发明纳米颗粒,以代替具有最类似的苯乙烯含量的丁苯橡胶。使用的纳米颗粒的性质示于表2中。图1示出纳米颗粒的DSC分析。图1表明纳米颗粒表面层具有-37℃的Tg,而核的Tg不可检测出,这意味着核的Tg高于200℃。
三种硫化胶料的粘弹性示于表3中,其中结果从温度扫描实验获得。温度扫描实验使用分光光度计,在50Hz频率下,在对于-50℃至-5℃范围内的温度的0.2%应变下,和在对于-5℃至60℃范围内的温度的1%应变下进行。
包含纳米颗粒的橡胶配混物2和3分别显示在30℃下E′的11%和25%的增长,这表明转向性和驾驶响应性得到改进。尽管动态贮能模量显著增加,但是胶料2和3仅分别显示在60℃下tanδ的2%和10%的增大,这表明略高的滚动阻力。因而,纳米颗粒使动态贮能模量显著改进,而不明显影响配混物的滞后。
表1
Figure A20078004789500191
1溶液SBR(40.5%苯乙烯)
2乳液SBR(23.5%苯乙烯)
3示于表2的纳米颗粒性质
表2
Figure A20078004789500192
表3
Figure A20078004789500193
已描述示例性实施方案。显然,阅读和理解前述详细描述时,将发生对于其他的改进和改变。意图将示例性实施方案解释为包括所有此类改进和改变,只要它们包括在所附权利要求书或其等价物的范围内即可。

Claims (11)

1.一种组合物,其包括:
(a)至少两种(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶,和
(b)包含聚(单乙烯基芳香族)核和聚(单乙烯基芳香族化合物-共轭二烯)表面层的聚合物纳米颗粒;
其中所述聚合物纳米颗粒的核具有约150℃至约600℃之间的玻璃化转变温度(Tg),以及
所述聚合物纳米颗粒的聚(单乙烯基芳香族化合物-共轭二烯)表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基含量的约50%至约150%之间的单乙烯基芳香族含量。
2.根据权利要求1所述的组合物,其中所述聚合物纳米颗粒的表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基芳香族含量的约75%至约125%之间的单乙烯基芳香族含量。
3.根据权利要求1所述的组合物,其中所述聚合物纳米颗粒的表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基芳香族含量的约90%至约110%之间的单乙烯基芳香族含量。
4.根据权利要求1所述的组合物,其中所述聚(单乙烯基芳香族)核包括聚苯乙烯,以及所述聚(单乙烯基芳香族化合物-共轭二烯)表面层包括聚(苯乙烯-丁二烯)。
5.根据权利要求1所述的组合物,其中所述聚合物纳米颗粒具有约5至200纳米之间的平均直径。
6.一种包括胎面的轮胎,其中所述胎面包括:
(a)至少两种(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶,和
(b)包含聚(单乙烯基芳香族)核和聚(单乙烯基芳香族化合物-共轭二烯)表面层的聚合物纳米颗粒,
其中所述聚合物纳米颗粒的核具有约150℃至约600℃之间的玻璃化转变温度(Tg),以及
所述聚合物纳米颗粒的聚(单乙烯基芳香族化合物-共轭二烯)表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基含量的约50%至约150%之间的单乙烯基芳香族含量。
7.根据权利要求6所述的轮胎,其中所述橡胶包括至少两种(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶,所述聚合物纳米颗粒的表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基芳香族含量的约50%至约150%之间的单乙烯基芳香族含量。
8.根据权利要求6所述的轮胎,其中所述聚合物纳米颗粒的表面层包括所述(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶之一的单乙烯基芳香族含量的约75%至约125%之间的单乙烯基芳香族含量。
9.根据权利要求6所述的轮胎,其中所述至少两种(单乙烯基芳香族化合物-共轭二烯)共聚物橡胶分别为苯乙烯-丁二烯共聚物。
10.根据权利要求6所述的轮胎,其中所述聚(单乙烯基芳香族)核包括聚苯乙烯,以及所述聚(单乙烯基芳香族化合物-共轭二烯)表面层包括聚(苯乙烯-丁二烯)。
11.根据权利要求6所述的轮胎,其中所述聚合物纳米颗粒的核具有约200℃至约400℃之间的Tg。
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