CN1643058B - 从受控分布嵌段共聚物制备的制品 - Google Patents
从受控分布嵌段共聚物制备的制品 Download PDFInfo
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Abstract
本发明涉及从单烯基芳烃和共轭二烯烃的新颖阴离子嵌段共聚物制备的制品,和涉及这样的嵌段共聚物与其它聚合物的共混物。嵌段共聚物含有单烯基芳烃端嵌段及单烯基芳烃和共轭二烯烃的受控分布嵌段。嵌段共聚物可以与选自如下的至少一种其它聚合物共混:烯烃聚合物、苯乙烯聚合物、无定形树脂和工程热塑性树脂。
Description
发明领域
本发明涉及从单烯基芳烃和共轭二烯烃的新颖阴离子嵌段共聚物制备的制品,和涉及这样的嵌段共聚物与其它聚合物的共混物。本发明也涉及成形制品和从这样的新颖嵌段共聚物形成制品的方法。
技术背景
单烯基芳烃和共轭二烯烃嵌段共聚物的制备是公知的。采用苯乙烯和丁二烯制备线性ABA嵌段共聚物的前几篇专利之一是U.S.Pat.3149182。在最近四十多年内,已经开发大量新苯乙烯二烯烃聚合物。现在已经发现基于单烯基芳烃端嵌段以及单烯基芳烃和共轭二烯烃受控分布中间嵌段的新颖阴离子嵌段共聚物,该新颖阴离子嵌段共聚物描述于在先未决、通常受让的U.S.专利申请系列号60/355210,题目为“新颖嵌段共聚物及其制备方法”,和它的连续申请。制备这样的聚合物的方法详细描述于上述专利申请中。
现在已发现的在于这些新颖嵌段共聚物与加工油和其它聚合物的共混物或复合物具有令人惊奇的性能优点,和显示各种最终用途应用中的有希望功用,该应用包括注塑、挤出商品和聚合物改性。
发明概述
在本发明的一个方面,我们发现包括至少一种嵌段共聚物和非必要地包括另一种组分的新颖组合物具有对许多应用的优异性能,该嵌段共聚物含有单烯基芳烃和共轭二烯烃的受控分布嵌段。我们也发现这些组合物可用于各种成形工艺,和它们也在加工中具有许多优点。
因此,本发明的宽广方面是一种制品,该制品包括至少一种嵌段共聚物和非必要地至少一种选自如下的其它组分:烯烃聚合物、苯乙烯聚合物、增粘树脂、聚合物填充油和工程热塑性树脂,其中该嵌段共聚物含有至少一个A嵌段和至少一个B嵌段,和其中(a.)每个A嵌段是单烯基芳烃均聚物嵌段和每个B嵌段是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段;(b.)每个A嵌段的平均分子量为3,000-60,000和每个B嵌段的平均分子量为30,000-300,000;(c.)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域;(d.)嵌段共聚物中单烯基芳烃的总数量是20-80wt%;和(e.)B嵌段中单烯基芳烃的重量百分比是10-75%。
在本发明的另一方面,我们显示可以以很多种工艺形成制品,该工艺包括注塑、压缩模塑、重叠模塑、浸渍、挤出、旋转模塑、搪塑、纤维纺丝、吹塑、聚合物改性、流延成膜、吹胀成膜和发泡。
在本发明的仍然另一方面,可以将制品加工成如下形式:膜、片材、多层层压材料、涂层、带、条、型材、模塑件、泡沫、带子、织物、丝线、长丝、带状物、纤维、多个纤维、或纤维性纤网。
至于本发明的优点,长期需要具有仍然是弹性体的、具有高聚苯乙烯含量的聚合物.在此描述的本发明由聚苯乙烯含量为35%-80%及具有弹性体性能的苯乙烯类嵌段共聚物组成.弹性体性能由不存在清楚屈服点以及在施加的负荷释放时产生恢复指示.这样聚合物的一个特征是与相对低杨氏模量结合的高橡胶模量.例如,可以生产具有相对刚性的橡胶响应的聚合物,该聚合物仍然相对柔软.由于受控分布向本发明的聚合物提供改进的弹性,柔软度,和透明度,与现有技术聚合物相比这是独特的.这样聚合物的另一个特征在于它具有不使结合的粘合剂降解的倾向.这是由于油和增粘树脂在聚合物自身中的更低溶解度,得到使这样的复合成分从相邻粘合剂中分离的更低倾向.这种与高刚度,高流动,和良好弹性结合的属性使此聚合物可用于个人卫生应用.也需要可以与大量聚苯乙烯共混和对于低成本弹性体复合技术解决方案保持弹性体的聚合物.包含至多50%聚苯乙烯的复合物显示高橡胶刚度和弹性体行为.这样聚合物的另一特征是比现有技术低的硬度,它与改进的橡胶刚度结合,使此聚合物可用于模塑和挤出商品以及用于重叠模塑.这样聚合物的仍然另一特征是依赖于引入到橡胶中间嵌段中的苯乙烯的量而调谐橡胶Tg的能力.这种属性可用于声音和振动阻尼应用中,其中能量耗散必须可对声音或振动的频率调谐.具有高橡胶Tg的聚合物也可用于某些包装应用如收缩-包裹膜或糖果包裹膜.具有苯乙烯含量至少为75%的弹性体的一个益处在于弹性体会通过“塑料”的FDA批准,故会被批准用于包括脂肪食品的直接食品接触.此因素,与低O2和CO2渗透率一起将使聚合物也可用于食品包裹膜。
本发明的受控分布共聚物提供另外的优点在于它们使用一般设计用于加工热塑性聚苯乙烯的设备容易加工的能力,该聚苯乙烯是最广泛公知和使用的烯基芳烃聚合物之一。可以通过挤出或注塑,使用热塑性塑料工业通常的单螺杆或双螺杆技术完成熔体加工。如果适当,也可以使用溶液或纺丝流延技术。
最后,本发明的共聚物可以与不会有害影响共聚物性能的其它组分配混。可以用作另外组分的例示材料非限制性地包括颜料、抗氧剂、稳定剂、表面活性剂、蜡、和流动促进剂。本发明的聚合物可用于很多种应用,该应用包括例如模塑和挤出商品如玩具、把手、手柄、鞋底、管材、运动商品、密封剂、垫片、和油凝胶。组合物也发现作为如下物质橡胶增韧剂的用途:聚烯烃、聚氯乙烯、聚苯乙烯、聚酰胺、聚氨酯、聚酯、聚碳酸酯和环氧树脂。本发明的聚合物也可用于合金和共混物,和用作各种聚合物和其它材料的增容剂。
优选实施方案的详细描述
本发明的关键组分是新颖嵌段共聚物,该共聚物包含单烯基芳烃端嵌段以及单烯基芳烃和共轭二烯烃的独特中间嵌段.令人惊奇地,(1)单体加入的独特控制和(2)乙醚或其它改性剂作为溶剂组分(它以下称为“分布剂”)的使用的结合导致两种单体的某些特性分布(在此称为“受控分布”聚合,即导致“受控分布”结构的聚合),和也导致在聚合物嵌段中某些单烯基芳烃富集区域和某些共轭二烯烃富集区域的存在.对于在此的目的,“受控分布”定义为表示具有如下属性的分子结构:(1)邻近单烯基芳烃均聚物(“A”)嵌段的末端区域,该区域富含(即含有大于平均数量的)共轭二烯烃单元;(2)一个或多个不邻近A嵌段的区域,该区域富含(即含有大于平均数量的)单烯基芳烃单元;和(3)具有相对低嵌段度的总体结构.对于在此的目的,“富含”定义为大于平均数量,优选大于平均数量5%.此相对低嵌段度可以由对于受控分布嵌段中间体的单一(“Tg”)的存在显示,当使用差示扫描量热法(“DSC”)热方法或通过机械方法分析时,该单一玻璃化转变温度在单独的任一单体的Tg之间,或如通过质子核磁共振(“H-NMR”)方法显示.也可以在B嵌段聚合期间适于聚苯乙烯基锂端基检测的波长范围内,从UV-可见吸光度的测量推断嵌段度的可能性.此数值的急剧和显著增加指示聚苯乙烯基锂链端的显著增加.在此方法中,这仅在共轭二烯烃浓度下降到临界水平以下才发生,以保持受控分布聚合.在此点存在的任何苯乙烯单体以嵌段的形式加入.由本领域技术人员使用质子NMR测量的术语“苯乙烯嵌段度”定义为在聚合物链上含有两个S最近邻接部分的聚合物中S单元的比例.在使用H-1 NMR测量两个试验数量之后测量苯乙烯嵌段如下:
首先,通过在7.5-6.2ppm的H-1 NMR光谱中积分总苯乙烯芳族信号和将此数量除以5以解释每个苯乙烯芳族环上的5个芳族氢,测定苯乙烯单元(即当成比例时任意仪器单位抵消)的总数目。
其次,通过从6.88和6.80之间的信号最小值到6.2ppm的H-1 NMR光谱中积分芳族信号部分和将此数量除以2以解释每个嵌段苯乙烯芳族环上的2个邻位氢,测定嵌段苯乙烯单元。此信号对那些苯乙烯单元的环上两个邻位氢的指定报导于F.A.Bovey,大分子的高分辩率NMR(Academic Press,纽约和伦敦,1972),第6章,该苯乙烯单元含有两个苯乙烯最近邻接部分。
苯乙烯嵌段度简单地是嵌段苯乙烯对总苯乙烯单元的百分比:
嵌段%=100乘(嵌段苯乙烯单元/总苯乙烯单元)
这样表达的聚合物-Bd-S-(S)n-S-Bd-聚合物,其中n大于零,定义为嵌段苯乙烯。例如,如果在以上例子中n等于8,则嵌段度指数是80%。优选嵌段度指数小于40。对于苯乙烯含量为10wt%-40wt%的一些聚合物,优选嵌段度指数小于10。
本发明的一个实施方案中,例如,嵌段B的苯乙烯嵌段度小于40mol%,该苯乙烯嵌段度指数定义为在聚合物链上含有两个苯乙烯邻接部分的嵌段B中苯乙烯单元的比例。例如,B嵌段中苯乙烯的重量百分比是10%-40%,和嵌段B的苯乙烯嵌段度指数小于10。
此受控分布结构在控制所得共聚物的强度和Tg中非常重要,这是由于受控分布结构保证实质上没有两种单体的相分离,即与如下嵌段共聚物形成对照:其中单体实际保持为具有不同Tg的单独“微相”,但实际上化学结合在一起。此受控分布结构保证仅存在一个Tg和因此所得共聚物的热性能是可预测的并事实上是预先确定的。此外,当具有这样受控分布结构的共聚物然后用作二嵌段、三嵌段或多嵌段共聚物中的一个嵌段时,通过适当构成的受控分布共聚物区域的存在变成可能的相对更高Tg倾向于改进流动和加工性能。也可以达到某些其它性能的改进。
制备本发明新颖受控分布共聚物的开始材料包括初始单体。烯基芳烃可以选自苯乙烯、α-甲基苯乙烯、对甲基苯乙烯、乙烯基甲苯、乙烯基萘、和对丁基苯乙烯或其混合物。在这些物质中,苯乙烯是最优选的和可购自各个制造商和相对便宜。在此使用的共轭二烯烃是1,3-丁二烯和取代丁二烯如异戊二烯、戊间二烯、2,3-二甲基-2,3-丁二烯、和1-苯基-1,3-丁二烯、或其混合物。在这些物质中,最优选是1,3-丁二烯。在此使用的和在权利要求中使用的“丁二烯”具体地表示“1,3-丁二烯”。
如上所讨论的那样,受控分布聚合物嵌段含有邻近A嵌段的二烯烃富集区域和不邻近A嵌段、和典型地靠近嵌段中心的芳烃富集区域.典型地邻近A嵌段的区域包括嵌段的前15-25%和包括二烯烃富集区域,而剩余部分被认为富集芳烃.术语“二烯烃富集”表示与芳烃富集区域相比,该区域具有可测量的更高的二烯烃对芳烃比例.表达此的另一种方式是单烯基芳烃单元的比例沿聚合物链逐渐增加到靠近嵌段中间或中心的最大值(如果我们描述ABA结构)和然后逐渐降低直到聚合物嵌段完全聚合.此结构是显著的和不同于现有技术中讨论的渐变和/或无规结构.
对于受控分布嵌段B,在每一B嵌段中单烯基芳烃的重量百分比是约10%-约75%,优选20-75%。对于总体总聚合物,单烯基芳烃重量百分比是20-80%,优选35-80%。
在此使用的“热塑性嵌段共聚物”定义为含有如下嵌段的嵌段共聚物:至少一个单烯基芳烃,如苯乙烯的嵌段及至少一个二烯烃和单烯基芳烃受控分布共聚物的嵌段。制备此热塑性嵌段共聚物的方法是通过嵌段聚合一般已知的任何方法。关于制备本申请中所用的嵌段共聚物的细节可参考在先未决专利申请序列号60/355,210和它的继续申请。本发明包括作为实施方案的热塑性共聚物组合物,它们可以是二嵌段、三嵌段共聚物或多嵌段组合物。在二嵌段共聚物组合物的情况下,一个嵌段是烯基芳烃基均聚物嵌段和与其聚合的是二烯烃和烯基芳烃受控分布共聚物的第二嵌段。在三嵌段组合物的情况下,它包括作为端嵌段的玻璃性烯基芳烃基均聚物和作为中间嵌段的二烯烃和烯基芳烃受控分布共聚物。在制备三嵌段共聚物组合物的情况下,受控分布二烯烃/烯基芳烃共聚物可以在此指定为“B”和烯基芳烃基均聚物指定为“A”。A-B-A三嵌段组合物可以由顺序聚合或偶合制备。在顺序溶液聚合技术中,首先将单烯基芳烃引入以生产相对硬的芳族嵌段,随后引入受控分布二烯烃/烯基芳烃混合物以形成中间嵌段,和然后随后引入单烯基芳烃以形成末端嵌段。除线性A-B-A构型以外,可以构造各嵌段以形成星形(支化)聚合物,(A-B)nX或(A-B-A)nX,或可以在混合物中结合各种类型的结构。例如当使用硅烷例如四乙氧基硅烷作为偶合剂时,所得聚合物典型地是线性偶合产物即(A-B)2X和10-30%重量三臂星形聚合物即(A-B)3X的混合物。一些A-B二嵌段聚合物可以存在,但优选至少约30wt%嵌段共聚物是A-B-A或星形的(或另外支化的以每个分子含有2个或更多末端树脂性嵌段)以赋予强度。
还重要的是控制各个嵌段的分子量。对于AB二嵌段,所需的嵌段重量对于单烯基芳烃A嵌段为3,000-60,000,和对于受控分布共轭二烯烃/单烯基芳烃B嵌段为30,000-300,000。优选的范围是对于A嵌段为5000-45,000和对于B嵌段为50,000-250,000。对于三嵌段,它可以是顺序ABA或偶合(AB)2X嵌段共聚物,A嵌段应当是3,000-60,000,优选5000-45,000,而对于顺序嵌段的B嵌段应当是约30,000-300,000,和对于偶合聚合物的B嵌段(两个)为该数量的一半。三嵌段共聚物的总平均分子量应当为40,000-400,000,和对于星形共聚物为60,000-600,000。这些分子量最精确地由光散射测量测定,和表达为数均分子量。
在一个特别的具体实施方案中,该嵌段共聚物具有通用构型A-B-A、(A-B)n、(A-B-A)n、或(A-B)nX或其混合,其中n是2-30的整数,X是偶合剂残基,每个A嵌段的数均分子量为5,000-20,000,每个B嵌段的数均分子量为30,000-100,000,和总分子量是50,000-140,000。
本发明的另一个重要方面是控制受控分布共聚物嵌段中共轭二烯烃的微结构或乙烯基含量.术语“乙烯基含量”表示通过1,2-加成(在丁二烯的情况下-在异戊二烯的情况下它是3,4-加成)聚合共轭二烯烃.尽管纯“乙烯基”仅在1,3-丁二烯的1,2-加聚情况下形成,异戊二烯3,4-加聚(和对于其它共轭二烯烃的相似加成)对嵌段共聚物最终性能的影响相似.术语“乙烯基”表示聚合物链上侧乙烯基的存在.当指丁二烯作为共轭二烯烃的应用时,优选共聚物嵌段中20-80mol%的缩合丁二烯单元具有由质子NMR分析测定的1,2乙烯基构型,优选20-40mol%的缩合丁二烯单元应当具有1,2乙烯基构型.这有效地通过改变分布剂的相对数量而控制.如理解的那样,分布剂起两个目的-它产生单烯基芳烃和共轭二烯烃的受控分布,和也控制共轭二烯烃的微结构.分布剂对锂的合适比例公开和教导于US Pat.Re27145,它的公开内容引入作为参考。
本发明热塑性弹性体二嵌段和三嵌段聚合物包括一个或多个受控分布二烯烃/烯基芳烃共聚物嵌段和一个或多个单烯基芳烃嵌段,该聚合物的重要特征在于它们具有至少两个Tg,低值是受控共聚物嵌段的结合Tg,该Tg是它的构成单体Tg的中间。这样的Tg优选是至少-60℃,更优选-40~+30℃。第二Tg,单烯基芳烃“玻璃性”嵌段的Tg优选大于70℃,更优选75-110℃。两个Tg的存在,说明了嵌段的微相分离,在很多种应用中引起显著的弹性和强度,和它的易加工性和所需的熔体流动特性。
本发明的一种令人惊奇组合物是嵌段共聚物和聚合物填充油的结合物。尽管在油不存在下,这些聚合物比传统三嵌段聚合物显示更刚性的弹性体行为,在油的存在下它们显示更软的弹性体行为。特别优选是与嵌段共聚物弹性体链段相容的类型油。尽管更高芳族物质含量的油是令人满意的,优选的是具有低挥发性和小于50%芳族物质含量的那些石油基白油。典型的链烷烃加工油可用于软化和填充本发明的聚合物;然而,具有更高环烷烃含量的加工油更与受控分布橡胶嵌段相容。优选的是环烷类含量为40%-55%和芳族类含量小于10%的加工油。油应当另外具有低挥发性,优选具有大于260℃(500°F)的初始沸点。采用的油数量从0到300重量份变化,相对于每一百重量份橡胶,或嵌段共聚物,优选20-150重量份。
本发明的嵌段共聚物可以与很多种其它聚合物共混,该其它聚合物包括烯烃聚合物、苯乙烯聚合物、增粘树脂、和工程热塑性树脂。
例如,根据本发明的一个具体实施方案,所述制品包括100重量份该嵌段共聚物和(i)5-100重量份烯烃聚合物,和/或(ii)5-200重量份苯乙烯聚合物,和/或(iii)5-50重量份增粘树脂,和/或5-150重量份聚合物填充油和/或80-95重量份工程热塑性树脂,基于该嵌段共聚物和该工程热塑性树脂的重量。
此外,本发明的受控分布聚合物可以与常规苯乙烯/二烯烃和氢化苯乙烯/二烯烃嵌段共聚物,如购自KRATON Polymers的嵌段共聚物共混。这些嵌段共聚物包括线性S-B-S、S-I-S、S-EB-S、S-EP-S嵌段共聚物。也包括的是基于苯乙烯以及异戊二烯和/或丁二烯和的星形嵌段共聚物和选择性氢化的星形嵌段共聚物。
烯烃聚合物包括,例如乙烯均聚物、乙烯/α-烯烃共聚物、丙烯均聚物、丙烯/α-烯烃共聚物、高抗冲聚丙烯、丁烯均聚物、丁烯/α-烯烃共聚物、和其它α-烯烃共聚物或共聚体.代表性聚烯烃包括,例如但不限于,基本线性乙烯聚合物、均匀支化的线性乙烯聚合物、不均匀支化乙烯聚合物,包括线性低密度聚乙烯(LLDPE)、极低或超低密度聚乙烯(ULDPE或VLDPE)、中等密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)和高压低密度聚乙烯(LDPE).其中包括的其它聚合物是乙烯/丙烯酸(EEA)共聚物、乙烯/甲基丙烯酸(EMAA)离聚物、乙烯/醋酸乙烯酯(EVA)共聚物、乙烯/乙烯醇(EVOH)共聚物、乙烯/环烯烃共聚物、聚丙烯均聚物和共聚物、丙烯/苯乙烯共聚物、乙烯/丙烯共聚物、聚丁烯、乙烯一氧化碳共聚体(例如,乙烯/一氧化碳(ECO)共聚物、乙烯/丙烯酸/一氧化碳三元共聚物等.其中包括的仍然其它聚合物是聚氯乙烯(PVC)和PVC与其它材料的共混物.
苯乙烯聚合物包括,例如晶体聚苯乙烯、高抗冲聚苯乙烯、中等抗冲聚苯乙烯、苯乙烯/丙烯腈共聚物、苯乙烯/丙烯腈/丁二烯(ABS)聚合物、间同立构聚苯乙烯、苯乙烯/甲基丙烯酸甲酯共聚物和苯乙烯/烯烃共聚物。代表性苯乙烯/烯烃共聚物是优选包含至少10wt%,更优选等于或大于25wt%共聚苯乙烯单体的基本无规乙烯/苯乙烯共聚物。也包括的是苯乙烯接枝聚丙烯聚合物,如以商品名聚合物提供,最初由Himot,Inc.(现在Basell)开发的那些。
对于说明书和权利要求书的目的,术语“工程热塑性树脂”包括在下表A中列出类别中发现的,和进一步在US专利No.4107131中定义的各种聚合物,该文献的公开内容在此引入作为参考。
表A
1.热塑性聚酯 |
2.热塑性聚氨酯 |
3.聚(芳基醚)和聚(芳基砜) |
4.聚碳酸酯 |
5.缩醛树脂 |
6.聚酰胺 |
7.卤代热塑性塑料 |
8.腈屏蔽物树脂 |
9.聚(甲基丙烯酸甲酯) |
10.环烯烃共聚物 |
增粘树脂包括聚苯乙烯嵌段相容树脂和中间嵌段相容树脂.聚苯乙烯嵌段相容树脂可以选自苯并呋喃-茚树脂、聚茚树脂、聚(甲基茚)树脂、聚苯乙烯树脂、乙烯基甲苯-α甲基苯乙烯树脂、α甲基苯乙烯树脂、聚苯醚,特别地聚(2,6-二甲基-1,4-亚苯基醚).这样的树脂是如以商标“HERCURES”,“ENDEX”,“KRISTALEX”,“NEVCHEM”和“PICCOTEX”销售.与(中间)嵌段相容的树脂可以选自相容C5烃树脂、氢化C5烃树脂、苯乙烯改性C5树脂、C5/C9树脂、苯乙烯改性萜烯树脂、完全氢化或部分氢化C9烃树脂、松香树脂、松香衍生物及其混合物.这些树脂如以商标“REGALITE”,“REGALREZ”,“ESCOREZ”,和“ARKON”销售.
本发明的聚合物共混物可以进一步与其它聚合物、油、填料、增强剂、抗氧剂、稳定剂、阻燃剂、和防粘连剂、润滑剂和其它橡胶和塑料配混成分进一步配混而不背离本发明的范围。
可以采用的各种填料的例子见于1971-1972年现代塑料百科全书,240-247页。增强剂可以简单定义为加入到树脂状基体中以改进聚合物强度的材料。大多数这些增强材料是高分子量的无机或有机产物。各种例子包括玻璃纤维、石棉、硼纤维、碳和石墨纤维、晶须、石英和二氧化硅纤维、陶瓷纤维、金属纤维、天然有机纤维、和合成有机纤维。特别优选是包含2-80wt%玻璃纤维的本发明增强聚合物共混物,基于获得的增强共混物的总重量。偶合剂如各种硅烷可用于增强共混物的制备。
关于各种成分的相对数量,这会部分依赖于特定的最终用途和依赖于选择用于特定最终用途的特定嵌段共聚物。下表B显示以重量百分比表达的一些想象组合物,它们包括在本发明中。对于“聚合物”数量,一部分可包括常规苯乙烯嵌段共聚物:
表B:应用,组合物和范围
本发明的聚合物可用于大量应用,作为净聚合物或在复合物中。如下各种最终用途和/或过程用于说明性的,和不限制本发明:
·聚合物改性应用
·玩具、医疗器具的注塑
·挤出膜、管材、型材
·用于个人护理的重叠模塑应用、把手、软触摸应用,用于汽车部分,如气囊、方向盘等
·浸渍商品,如手套
·热固性应用,如在用于托盘的片材模塑复合物或本体模塑复合物中
·用于玩具和其它制品的旋转模塑
·汽车皮层的搪塑
·用于涂层的热喷涂
·用于医疗器具的吹制膜
·具有改进耐扭结性的医疗目的用透明管材
·用于汽车/工业部件的吹塑件
·用于个人卫生应用的膜和纤维
实施例
提供如下实施例以说明本发明。实施例不用于限制本发明的范围和它们不应当这样解释。除非另外说明,数量为重量份或重量百分比。
实施例1
根据以上提及并与本申请同时提时提交的连续和在先未决专利申请系列号60/355210的例示实施方案#III中公开的方法制备本发明的各种受控分布嵌段共聚物。所有的聚合物是不饱和嵌段共聚物,其中A嵌段是聚苯乙烯嵌段和B嵌段是苯乙烯/丁二烯受控分布嵌段,该受控分布嵌段含有邻近A嵌段、富含丁二烯单元的末端区域和不邻近A嵌段、富含苯乙烯单元的其它区域。所有的聚合物是偶合聚合物,其中偶合剂是四乙氧基硅烷。尽管也形成10-30wt%的三臂星形产物,(A-B)3X,以及一些未偶合嵌段,即A-B,在聚合条件下,占优势的物质是线性产物,即(A-B)2X。对于在此的目的,可以忽略偶合剂残基或剩余部分。在下表1中显示各种聚合物。这些聚合物然后用于其它实施例中描述的各种应用。表1和1a中列出了对于不饱和聚合物的各种分析结果。嵌段I MW是以1000为单位的第一A或聚苯乙烯嵌段的分子量,嵌段II MW是以1000为单位的B或受控分布嵌段的累积分子量和嵌段III MW是以1000为单位的最终A或聚苯乙烯嵌段的分子量。关于步骤II MW,第一个数字是1,3-丁二烯部分和第二个数字是苯乙烯部分。例如,在聚合物#16中,B嵌段具有85,000丁二烯和31,000苯乙烯的分子量,总计116,000。1,2-乙烯基构型给定为23.5mol%,以及整个聚合物中和中间嵌段中的重量百分比苯乙烯。例如,对于聚合物#16,整个聚合物含有约42wt%苯乙烯和中间嵌段含有约27wt%苯乙烯(表1a中的“计算的中间PSC”)。对于每种聚合物给出偶合效率(或CE)。将对于每一种聚合物的苯乙烯嵌段度计算和显示于表1a(“计算的中间嵌段”)。最后对于一些聚合物给出熔体流动速率。
实施例2
在此实施例中,将一种受控分布嵌段共聚物(聚合物#17)与BX6105的商业样品,购自BASF的不饱和SBS嵌段共聚物对比,它含有无规苯乙烯/丁二烯中间嵌段。根据本发明采用受控分布苯乙烯/丁二烯中间嵌段制备聚合物#17。两者具有相似的总体苯乙烯含量,如表2所示。如表2所示,聚合物#17具有在200℃/5此条件下测量的更大改进的熔体流动。分别采用对于Styroflex和聚合物#17的204℃/1000psi和190℃/800psi的熔体温度/注射压力,对注塑试片测量硬度和雾度。聚合物#17的shore A硬度比Styroflex低大约20点和雾度低57%。对在175℃和1250psi下压制的压缩模塑试片测量机械性能。尽管拉伸强度几乎相同,聚合物#17具有更高的断裂伸长率。聚合物#17也比Styroflex更适应,如由25%-500%的一致更低模量所示。在循环加载条件下,由于它比Styroflex恢复两倍的能量及一半的永久变形,聚合物#17是更为弹性的。
与Styroflex,一种具有相似总苯乙烯含量的无规化中间嵌段聚合物现有技术典型的聚合物相比,受控分布聚合物#17清楚地显示在低伸长率下低得多的应力。在低伸长率下的刚度典型地由拉伸模量,或杨氏模量表征。例如聚合物#17的杨氏模量仅为1,400psi(10MPa),而对于Styroflex是5,000psi(35MPa)。与对于Styroflex为90psi(0.62MPa)相比,聚合物#17在100和300%伸长率之间的橡胶模量,或斜率稍微更高,为94psi(0.65MPa)。因此受控分布聚合物在高伸长率下保持坚硬拉伸和无规聚合物的高拉伸强度,但在低伸长率下更为弹性行为的增加益处。
实施例3
在此实施例中,将两种不同的受控分布嵌段共聚物(聚合物#19和聚合物#17)在线共混(包括100%聚合物#19的复合物3-1和包括70%聚合物#17和30wt%KRATON D-1403的复合物3-2,KRATON D-1403是75wt%苯乙烯含量的苯乙烯/丁二烯嵌段共聚物)和使用流延膜生产线挤出成膜。两种复合物具有高水平的聚苯乙烯(大于约70wt%)。在表3中显示测试结果。由于加工诱导的取向,复合物3-1在机器方向和横向两者中显示不同的屈服点和相似于聚烯烃的机械响应,而复合物3-2是更为弹性的。两种膜复合物具有高拉伸强度,使它们适用于食品包裹和柔性包装膜应用。复合物3-2也展示良好的粘附特性。在其中PSC大于70%的情况下,依赖于加工条件可以获得具有不同屈服点的聚合物。使用此属性可以制备半刚性或柔性膜。
实施例4
在此实施例中,将一种受控分布嵌段共聚物(聚合物#17)从10wt%甲苯溶液制备成溶剂流延膜。在表4中显示氧气和二氧化碳渗透率系数以及LDPE(0.914密度)和聚苯乙烯的报导数值。单位是1013cm3×cm/cm2×S×Pa。如表4所示,本发明的受控分布聚合物的渗透率系数与对LDPE和PS报导的那些具有相同的数量级。
实施例5
采用具有13熔融指数的均聚苯乙烯,Chevron-Phillips MC3600制备受控分布聚合物#17的共混物(包含63%总聚苯乙烯)。在表5中实施例5-2到5-6显示,令人惊奇地至多40wt%均聚苯乙烯的加入仍然导致具有良好恢复和低永久变形的弹性膜。膜5-5的总苯乙烯含量几乎是78%。本领域公知的是具有大部分聚苯乙烯含量的嵌段共聚物膜是塑性的而不是弹性的。在Brabender混合头中制备实施例5-2到5-6。特别注意的是对于小于50%的均聚苯乙烯含量,在伸长到100%之后大于50%应变能量的恢复和仅14%永久变形。共混物5-7显示油的加入可用于降低共混物的模量和改进它的恢复。
也在表5中显示的是聚(氯乙烯)(“PVC”)的数据。复合物5-3,5-4和5-5与PVC的性能相似而具有相似硬度,改进拉伸强度,和改进滞后与可比刚度。
此外共混物的高苯乙烯含量允许它们直接涂漆和印刷而没有预处理。
实施例6
在实施例6中,将受控分布嵌段共聚物#17,19和20与变化数量的聚丙烯均聚物(PP 5A15H),聚苯乙烯均聚物(Chevron-PhillipsMC3600),链烷油(34),和环烷油(471)配混,如表6所示。使用Brabender混合头制备复合物随后在175℃下压缩模塑。如表6所示,可以采用聚苯乙烯和聚丙烯,采用或不采用油制备复合物以具有高拉伸强度和各种硬度。
实施例7
在实施例7中,在单螺杆挤出机膜生产线中将Chevron-PhillipsMC3600均聚苯乙烯与受控分布聚合物配混。将受控分布聚合物#17与均聚苯乙烯粒料翻滚和将混合物加入到在成膜标准条件下操作的挤出机中。挤出机中的螺杆是没有混合元件的正常压缩螺杆。根据ASTM D412在机器方向和横向两者中测试膜。在这些共混物中,取向在机器是显然的,导致非常刚性的膜。然而在横向中,膜保持弹性的并有良好的恢复。这些膜的高苯乙烯含量也允许对膜使用粘合剂而没有粘合剂性能的劣化。为展示此特征,与由25%SIS聚合物,60%增粘树脂和15%油组成的粘合剂接触,将样品7-3的膜在65℃下老化两周。在老化之后的剥离强度从4.2pli降到2.9pli。其后分析粘合剂和发现粘合剂包含大约39%SIS聚合物和61%结合的增粘树脂和油。这表明一些增粘树脂和油已经吸收入7-2膜中,从而可解释粘合力的损失。通过比较,在与相同粘合剂接触在65℃下老化两周之后,基于传统SEBS嵌段共聚物的典型弹性体膜损失所有它的粘合力。在老化之后,发现粘合剂包含83%SIS聚合物和17%增粘树脂和油。这表明几乎所有增粘树脂和油迁移入弹性体膜中,破坏了粘合。
实施例8
在此实施例中,在装配有急冷辊,压料辊,和涂层悬挂膜模头的单螺杆挤出机上,将一种受控分布嵌段共聚物(聚合物#19)制备成流延膜。样品用以30rpm操作的急冷辊和以50rpm操作的压料辊制备。然后在25℃和/或50℃下将样品拉伸到100%或200%应变,如下表8中所示。在浸入40℃水中30秒之前,允许拉伸样品在25℃下平衡两小时。在浸入水中之前,在样品上加标线使得可以将收缩百分比测量为((浸入之后的长度-浸入之前的长度)/浸入之前的长度)。在40℃水中30秒之后,流延的、未拉伸对照物显示6%的收缩。在40℃下30秒之后,在25℃下拉伸到200%应变的膜显示大约38%收缩。也对在25℃下拉伸到200%应变的膜评价收缩温度的影响。在70℃水中浸入30秒之后观察到大约54%的收缩。在机器方向发生收缩时,也在横向发生34%的膨胀。最后,通过拉伸流延膜到100%应变和在25℃下对未受约束的膜测量收缩,测量膜的自然收缩。在60分钟之后,膜显示大约37%的自然收缩。
实施例9
当用作苯乙烯单体基热固性应用的改性剂时,本发明的受控分布苯乙烯类嵌段共聚物提供加工优点。如表9所示,与对比S-B-S聚合物I(“CP I”),一种线性苯乙烯-丁二烯-苯乙烯三嵌段共聚物相比,受控分布聚合物#17和#19在苯乙烯单体中提供更低粘度的溶液(15wt%聚合物,25℃);这和受控分布聚合物无关而分子量高75%。当与更大尺寸的线性S-B-S聚合物,对比S-B-S聚合物II(“CP II”)相比,聚合物#17和#19提供的溶液粘度低于常规聚合物的25%。清楚地,与从对比S-B-S聚合物II制备的相似溶液相比,聚合物#17和#19的苯乙烯溶液容易处理,更自由流动。在表9中,采用转轴21在100rpm下测量布氏粘度,和PSC是嵌段共聚物的聚苯乙烯含量。
说明性实施方案聚合物#20具有比聚合物#17和#19低得多的苯乙烯含量。尽管聚合物#20的MW低于聚合物#17或#19,聚合物#20苯乙烯溶液的粘度比更大聚合物任一种的苯乙烯溶液粘度大两倍。这些结果支持如下假设:具有更高苯乙烯水平的本发明聚合物优于苯乙烯水平低于50wt%的聚合物。与苯乙烯含量低于50wt%的类似聚合物相比,苯乙烯含量越高,受控分布聚合物越容易在苯乙烯基热固性体系中加工。
考虑到苯乙烯单体中的粘度性能,可预期本发明的受控分布聚合物是片材模塑复合物(SMC)和本体模塑复合物(BMC)应用的良好侯选物。参见,如,US专利No.4400478,它在此引入作为参考,它公开了在SMC和BMC应用中采用嵌段共聚物的配方和技术。
实施例10
在实施例10中,将本发明的受控分布聚合物(聚合物#17)与聚丙烯均聚物(Novolene 100 UC)配混以确定它在搪塑应用中的合适性(数量是重量份)。将复合物(10-2)与基于Styroflex BX-6105的复合物(10-1)比较。如表10所示,两种复合物的性能相似,但基于受控分布聚合物的复合物的熔体流动显著更高,使得它是搪塑应用的更好侯选物。
实施例11
在实施例11中,受控分布共聚物用于在各种基材上重叠模塑的复合物,和用作重叠模塑的净聚合物,并与用于重叠模塑的商业配制剂比较。用于测试的基材是尼龙6(N6),高抗冲聚苯乙烯(HIPS)和丙烯腈丁二烯苯乙烯三元共聚物(ABS)。
在复合物11-1中,将马来化氢化嵌段共聚物(KRATON 1901X)与受控分布共聚物#17,Renoil 471油和碳酸钙配混。复合物11-2是基于KRATON 1901X和选择性氢化SBS嵌段的商业重叠模塑复合物。
使用Krauss Maffai模塑机注塑基材。在模塑之前在真空下在180F下将尼龙6干燥24小时。在模塑之前在真空下在180F下将ABS干燥2小时。然后使用Krauss Maffai模塑机将选择的材料重叠模塑到基材上。
将重叠模塑试片切成1英寸条。从基材剥离出大约1/2英寸重叠模塑材料。将基材的剥离部分然后在加热的压挤机中弯曲到90度角。使用Instron 1120拉伸测试仪,测试每种材料五个条的90度剥离强度。在2英寸每分钟下运行测试。在表12中显示平均初始剥离强度。
结果表明对于ABS和HIPS基材,净不饱和聚合物#17比商业重叠模塑复合物表现甚至更好和比11-1复合物表现好得多。采用尼龙6的结果显示与商业重叠模塑复合物几乎相等的性能。相对于商业复合物和11-1复合物共混物两者,净聚合物#17也保持优异的透明度。
实施例12
在实施例12中,将三种不同的受控分布聚合物与变化数量的聚苯乙烯(PS)和苯乙烯/甲基丙烯酸甲酯(SMMA)聚合物配混,以确定对总体性能的影响。三种受控分布聚合物是聚合物17,19和20。聚苯乙烯是购自Chevron Phillips的EB 3300和SMMA是购自Resirene的CET-130。也使用KRATON D 1403,一种PSC为约75wt%的高苯乙烯含量苯乙烯/丁二烯嵌段共聚物;KR03,一种苯乙烯含量为约75wt%购自ChevronPhillips的高苯乙烯嵌段共聚物;苯乙烯含量为约73%购自Fina的Finaclear 520;和购自BASF的Styrolux 3G55,其苯乙烯含量也为约75wt%。首先将各种组分干混,和在Engel注塑机中注塑共混物。根据ASTM D-638测试拉伸性能,和根据ASTM D-1003测试光学性能。在表13中列出结果和各种配制剂(表达为重量百分比)。
关于100%聚合物比较物,所有的聚合物具有大约相同的苯乙烯含量。然而,根据本发明的聚合物#19比D1403,KR03,和Styrolux 3G55具有高的伸长率。关于50/50共混物,含有聚合物#19的共混物具有最高的伸长率,即,比PS与常规高苯乙烯含量SBS嵌段共聚物-D 1403的共混物的伸长率大10倍,和高于对比共混物。
在含有SMMA聚合物的70/30共混物中,含有聚合物#19的共混物的仲长率几乎是含有D-1403的共混物的两倍。
这些比较物显示聚合物#19在改性PS和SMMA中具有更高的效率,以制备刚性包装产品和模塑商品,即,当使用本发明的受控分布聚合物时,你需要更少的苯乙烯嵌段共聚物去改性PS或SMMA。
实施例13
本发明的一些聚合物可用作阻尼材料。对于阻尼应用,重要的是由动态机械测试测量的玻璃化转变温度为-10℃~+30℃。也重要的是能够容易调节玻璃化转变温度以达到选择频率的阻尼或在选择的温度下。表14显示聚合物#17的Tg是4.6℃,它是通常用于阻尼的范围。实施例14-2和14-3显示Tg可以容易由中间嵌段树脂如Regalrez 1085或端嵌段树脂如Kristallex 1120的加入而增加。实施例14-4和14-5显示油的加入降低聚合物的Tg,而不管是否存在均聚苯乙烯。Tg的增加伴随着增加的刚度和相反地降低的Tg伴随着降低的刚度。在所有的情况下,都保持良好的强度和伸长率。
表1.不饱和S/Bd中间嵌段聚合物的分析结果
聚合物号 | 嵌段IMW | 嵌段II MW | 嵌段III MW | 分布剂 | 1,2-BD | PSC(%) | CE(%) | MFR(200C/5kg)(g/10min) |
16 | 15.5 | 85/31 | 15.5 | DBE | 23.5 | 42 | >90 | 0.6 |
17 | 15.6 | 50/50 | 15.6 | DEB | 24.6 | 63 | >90 | 17.6 |
18 | 11.7 | 75/25 | 11.7 | nBE | 22.8 | 40 | 70 | 10.8 |
19 | 21 | 38/69 | 21 | DEB | 24.3 | 76 | 95 | 11.7 |
20 | 12.5 | 78/25 | 12.5 | ODMB | 23.7 | 38.8 | 92 | |
21 | 21.2 | 36/65 | 21.2 | DEB | 32.6 | 76 | 95 | |
22 | 20.1 | 30/65 | 20.1 | ODMB | 30 | 74 | 94 |
聚合物号 | 嵌段IMW | 嵌段II MW | 嵌段III MW | 分布剂 | 1,2-BD | PSC(%) | CE(%) | MFR(200C/5kg)(g/10min) |
23 | 14.8 | 49/49 | 14.8 | ODMB | 25 | 64.5 | 90 |
表1a.在步骤II结束时聚合物的NMR结果
聚合物号 | 预期的NMRPSC | 预期的NMR嵌段 | 计算的中间PSC | 计算的中间嵌段 |
16 | 42.3 | 56 | 26.9 | 12 |
17 | 61.8 | 45 | 49.9 | 11 |
18 | 40.0 | 59 | 26.0 | 22 |
19 | 75.4 | 56 | 65.7 | 30 |
20 | 38.7 | 57 | 23.8 | 13 |
21 | 76.9 | 55 | 67.1 | 27 |
22 | 74.3 | 59 | 63.4 | 32 |
23 | 64.5 | 57 | 53.8 | 33 |
表2 | 聚合物#17 | Styroflex BX6105 |
PSC(%) | 63 | 66 |
MFR(g/10min) | 17.7 | 10.5 |
Shore A硬度(10s) | 62 | 84 |
雾度(%) | 21.8 | 51.3 |
拉伸 |
表2 | 聚合物#17 | Styroflex BX6105 |
TS(psi) | 4298 | 4338 |
伸长率(%) | 950 | 734 |
25%模量(psi) | 152 | 429 |
50%模量(psi) | 203 | 465 |
100%模量(psi) | 255 | 524 |
200%模量(psi) | 366 | 760 |
300%模量(psi) | 517 | 1122 |
500%模量(psi) | 917 | 2125 |
150%滞后 | ||
恢复的能量(%) | 59.1 | 30.7 |
永久变形(%) | 18.9 | 38.9 |
表3 | ||
复合物号 | 3-1 | 3-2 |
聚合物#19 | 100 | |
聚合物#17 | 70 | |
D1403 | 30 | |
拉伸(MD) | ||
拉伸强度(psi) | 3785 | 3685 |
伸长率(%) | 397 | 464 |
100%模量(psi) | 1577 | 988 |
300%模量(psi) | 2929 | 1918 |
拉伸(PMD) |
表2 | 聚合物#17 | Styroflex BX6105 |
拉伸强度(psi) | 3650 | 4020 |
伸长率(%) | 390 | 560 |
100%模量(psi) | 1545 | 455 |
300%模量(psi) | 2846 | 1170 |
100%滞后(MD) | ||
恢复的能量(%) | 4.7 | 18 |
永久变形(%) | 86 | 45 |
100%滞后(PMD) | ||
恢复的能量(%) | 4.6 | 36 |
永久变形(%) | 86 | 21 |
200%滞后(MD) | ||
恢复的能量(%) | 5.2 | 15 |
永久变形(%) | 168 | 102 |
200%滞后(PMD) | ||
恢复的能量(%) | 5.1 | 34 |
永久变形(%) | 168 | 41 |
MD=机器方向,PMD=垂直于机器方向(也称为横向,TD)
表4 | 二氧化碳渗透率系数 | 氧气渗透率系数 |
聚合物#17 | 15.6 | 2.0 |
LDPE | 9.5 | 2.2 |
PS | 7.9 | 1.9 |
表5 | |||||||||
复合物号 | 5-1 | 5-2 | 5-3 | 5-4 | 5-5 | 5-6 | 5-7 | 5-8 | PVC |
聚合物#17 | 100 | 90 | 80 | 68 | 60 | 50 | 61.2 | 61.2 | |
PS(MC3600) | 10 | 20 | 32 | 40 | 50 | 28.8 | 28.8 | ||
Drakeol 34 | 10 | ||||||||
Renoil 471 | 10 | ||||||||
拉伸 | |||||||||
拉伸强度(psi) | 4298 | 3492 | 3780 | 4088 | 3251 | 2192 | 2992 | 2888 | 2168 |
伸长率(%) | 950 | 770 | 604 | 534 | 404 | 229 | 713 | 657 | 409 |
50%模量(psi) | 203 | 236 | 286 | 360 | 450 | 956 | 178 | 207 | 488 |
100%模量(psi) | 255 | 309 | 418 | 577 | 789 | 1372 | 273 | 308 | 751 |
200%模量(psi) | 366 | 491 | 816 | 1213 | 1620 | 2055 | 534 | 606 | 1196 |
100%滞后(MD) | |||||||||
峰值应力(psi) | 281 | 352 | 498 | 691 | 1229 | 288 | 252 | ||
恢复的能量(%) | 58.9 | 57.5 | 55.5 | 50.5 | 27.3 | 63.7 | 65.6 | 26 | |
永久变形(%) | 16.2 | 14.5 | 14.3 | 14.6 | 20.2 | 11.1 | 11.1 | 37 | |
Shore A硬度(108) | 71 | 73 | 75 | 70 |
表8 | 聚合物#19流延膜的收缩性能 |
在25℃下的自然收缩(%) | |
30分钟 | 34.4 |
60分钟 | 36.7 |
在40℃下的30s MD收缩(%) | |
未拉伸对照物 | 6.3 |
在25℃下拉伸到100%应变 | 23.3 |
在50℃下拉伸到100%应变 | 28.8 |
在25℃下拉伸到200%应变 | 37.7 |
表8 | 聚合物#19流延膜的收缩性能 |
拉伸到200%应变 | 40℃ 70℃ |
30s MD收缩(%) | 37.7 53.6 |
30s PMD收缩(%) | 20 34 |
表9-在苯乙烯中15wt%下的溶液粘度(25℃)
材料 | PSC | MW(10<sup>3</sup>) | 粘度(cps) |
聚合物#20 | 40% | 120 | 378 |
聚合物#17 | 63% | 128 | 153 |
聚合物#19 | 75% | 135 | 126 |
CP I | 30% | 72 | 162 |
CP II | 35% | 140 | 648 |
表10:聚合物#17与PP配制剂中的Styroflex BX6105对比
表11
表12
材料和基材 | 平均初始剥离强度(pli) |
11-1 ABS | 1.5 |
11-1 N6 | 1.8 |
11-1 HIPS | 9.1 |
聚合物17-ABS | 13.8 |
聚合物17-N6 | 2.9 |
聚合物17-HIPS | 20 |
11-2 ABS | 10.1 |
11-2 N6 | 3.6 |
11-2 HIPS | 13.3 |
表13
表14 | |||||
化合物号 | 14-1 | 14-2 | 14-3 | 14-4 | 14-5 |
聚合物#17 | 100 | 80 | 80 | 87 | 61.2 |
Regalrez 1085 | 20 | ||||
Kristalex 1120 | 20 | ||||
Renoil 471 | 13 | 10 | |||
PS(MC3600) | 28.8 | ||||
拉伸 |
表14 | |||||
拉伸强度(psi) | 4298 | 3826 | 3601 | 3394 | 2888 |
伸长率(%) | 950 | 972 | 859 | 1070 | 657 |
50%模量(psi) | 203 | 164 | 323 | 138 | 207 |
100%模量(psi) | 255 | 216 | 356 | 170 | 308 |
200模量(psi) | 366 | 327 | 488 | 225 | 606 |
TG(℃) | 4.6 | 12.0 | 47.4 | -4.0 | -3.9 |
Claims (10)
1.一种制品,所述制品是如下形式的制品:膜、片材、涂层、带材、条、型材、模塑件、泡沫、带子、织物、丝线、带状物、纤维、多个纤维或纤维性纤网,和所述制品包括至少一种嵌段共聚物和非必要地至少一种选自如下的其它组分:烯烃聚合物、苯乙烯聚合物、增粘树脂、聚合物填充油和工程热塑性树脂,其中该嵌段共聚物含有至少一个A嵌段和至少一个B嵌段,和其中(a.)每个A嵌段是单烯基芳烃均聚物嵌段和每个B嵌段是至少一种共轭二烯烃和至少一种单烯基芳烃的受控分布共聚物嵌段;(b.)每个A嵌段的平均分子量为3,000-60,000和每个B嵌段的平均分子量为30,000-300,000;(c.)每个B嵌段包括邻近A嵌段、富含共轭二烯烃单元的末端区域和一个或多个不邻近A嵌段、富含单烯基芳烃单元的区域,其中富含共轭二烯烃单元的末端区域包括B嵌段的前15-25%;(d.)嵌段共聚物中单烯基芳烃单体单元的总数量是20-80wt%;和(e.)B嵌段中单烯基芳烃的重量百分比是10-75%。
2.根据权利要求1的制品,其中所述制品是长丝形式的制品。
3.根据权利要求1或2的制品,其中该单烯基芳烃是苯乙烯和该共轭二烯烃选自异戊二烯和丁二烯。
4.根据权利要求3的制品,其中该共轭二烯烃是丁二烯,和其中嵌段B中20-80mol%的丁二烯单元具有1,2-构型。
5.根据权利要求3的制品,其中嵌段B的苯乙烯嵌段度指数小于40%,该苯乙烯嵌段度指数定义为在聚合物链上含有两个苯乙烯单体单元邻接部分的嵌段B中苯乙烯单元的比例。
6.根据权利要求5的制品,其中B嵌段中苯乙烯单体单元的重量百分比是10%-40%,和嵌段B的苯乙烯嵌段度指数小于10%。
7.根据权利要求1或2的制品,其中该嵌段共聚物具有通用构型A-B-A、(A-B)n、(A-B-A)n、或(A-B)nX或其混合,其中n是2-30的整数,X是偶合剂残基,每个A嵌段的数均分子量为5,000-20,000,每个B嵌段的数均分子量为30,000-100,000,和总分子量是50,000-140,000。
8.根据权利要求1或2的制品,包括100重量份该嵌段共聚物和(i)5-100重量份烯烃聚合物,和/或(ii)5-200重量份苯乙烯聚合物,和/或(iii)5-50重量份增粘树脂,和/或5-150重量份聚合物填充油和/或80-95重量份工程热塑性树脂,基于该嵌段共聚物和该工程热塑性树脂的重量。
9.根据权利要求1或2的制品,其中该制品以选自如下的方法形成:注塑、重叠模塑、浸渍、挤出、旋转模塑、纤维纺丝或成膜。
10.根据权利要求1或2的制品,其中该制品以选自如下的方法形成:搪塑或发泡。
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Patent Citations (2)
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EP0796871B1 (en) * | 1996-03-18 | 2000-02-16 | Shell Internationale Researchmaatschappij B.V. | Process for the polymerisation of conjugated diene monomers |
EP0879836B1 (en) * | 1997-05-22 | 2003-09-24 | Nippon Zeon Co., Ltd. | Aromatic vinyl-conjugated diene block copolymer and production process thereof |
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