CN1997681A - 具有高流动性和高弹性的嵌段共聚物 - Google Patents

具有高流动性和高弹性的嵌段共聚物 Download PDF

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CN1997681A
CN1997681A CNA2005800117461A CN200580011746A CN1997681A CN 1997681 A CN1997681 A CN 1997681A CN A2005800117461 A CNA2005800117461 A CN A2005800117461A CN 200580011746 A CN200580011746 A CN 200580011746A CN 1997681 A CN1997681 A CN 1997681A
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segmented copolymer
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D·小汉德林
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Abstract

披露了一种能够借助于最少的添加剂直接挤出或者模塑并且具有高的弹性和低的永久变形性的弹性体氢化嵌段共聚物。该氢化嵌段共聚物具有高的熔体流动性，这使得在熔融加工例如挤出和模塑中容易加工该氢化嵌段共聚物。

Description

具有高流动性和高弹性的嵌段共聚物
相关申请的交叉引用
本申请要求于2004年3月3日提交的题目为“具有高流动性和高弹性的嵌段共聚物”的美国临时专利申请60/549,570的优先权。
发明背景
1.发明领域
本发明涉及单链烯基芳烃和共轭二烯烃的氢化阴离子嵌段共聚物，并且涉及由该嵌段共聚物制备的制品。本发明特别涉及苯乙烯和丁二烯或异戊二烯的氢化嵌段共聚物。
2.技术背景
单链烯基芳烃和共轭二烯烃的嵌段共聚物的制备是非常公知的。最初的由苯乙烯和丁二烯制备的线型ABA嵌段共聚物的专利之一是美国专利No.3,149,182。该嵌段共聚物的应用包括注塑、挤出、吹塑、粘合剂等。这些聚合物还被用于例如将用于制造屋顶和路面的沥青改性的应用。该嵌段共聚物的其它应用包括制备薄膜、纤维和无纺织物。
这类嵌段共聚物的一个例子在Holden等的美国专利No.4,188,432中。其中披露了基本由包含不超过约55％苯乙烯均聚物的高抗冲苯乙烯-丁二烯接枝共聚物或其混合物组成的抵抗脂肪类物质侵蚀的成型制品。该成型制品还包含小比例的聚乙烯或聚丙烯和X-Y-X嵌段共聚物，其中每一X是分子量约5,000-10,000的聚苯乙烯嵌段，Y是分子量为25,000-50,000的氢化聚丁二烯嵌段。
嵌段共聚物的另一个例子可在Djiauw等的美国专利No.5,705,556中找到。在该参考文献中，披露了可以使用弹性体嵌段共聚物、聚苯醚、聚烯烃和增粘树脂制备用于制造弹性纤维或薄膜的可挤出的弹性体组合物。进一步描述了包含25-75wt％嵌段共聚物的制品，该嵌段共聚物包含至少两个被氢化共轭二烯烃嵌段隔开的单链烯基芳烃嵌段。
在本领域中公知的是采用注塑、挤出和纤维纺丝由聚合物制备制品，使用加工助剂以减少所使用的聚合物不希望的性能。例如，在Newkirk等的美国专利No.4,273,946中披露了在纤维挤出之后在机械和热处理操作中在升高的温度下在使用条件下的对发烟具有优良稳定性的纤维润滑剂。
以上引述的嵌段共聚物和现今其它常规的高弹性嵌段共聚物尽管具有许多所希望的性能，但它们特别是在挤出、模塑和纤维纺丝应用中难以加工。例如，通常实践使用大量的聚烯烃、增量油、增粘树脂和蜡和/或其它加工助剂以将常规嵌段共聚物挤出。这些添加剂难以添加、通常导致了弹性性能降低并且会造成所不希望的加工问题例如发烟和模头咬模(build up)。另一方面，可以制得具有优良加工性的常规的嵌段共聚物，然而它们的机械性能差以致于它们通常不能用于模塑和挤出的制品。在由嵌段共聚物制备模塑、挤出和纺丝制品的领域中，将希望的是使用不需要如此多的加工助剂或者甚至不需要任何加工助剂并且仍然具有优良弹性的嵌段共聚物制备这些制品。
发明概述
在一个方面中，本发明是一种包含S嵌段和E或E1嵌段并且具有以下通式的选择性氢化的嵌段共聚物或其混合物：
S-E-S，(S-E1)n，(S-E1)nS，(S-E1)nX
其中：(a)在氢化之前，S嵌段是聚苯乙烯嵌段；(b)在氢化之前，E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段；(c)在氢化之前，E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；(d)n具有2-6的值，X为偶联剂残基；(e)该嵌段共聚物的苯乙烯含量为13-25％；(f)氢化之前该聚二烯烃嵌段的乙烯基含量为60-85mol％；(g)该嵌段共聚物包含少于15wt％的具有以下通式的较低分子量单元：
S-E或S-E1
其中S、E和E1如同已经定义的那样；(h)在氢化之后，约0-10％的苯乙烯双键被氢化并且至少80％的共轭二烯烃双键被氢化；(i)每一S嵌段的分子量为5,000-7,000；和(j)根据ASTM D1238在230℃和2.16kg重量下，该嵌段共聚物的熔体指数大于或等于12克/10分钟。
在仍然另一个方面中，本发明是一种选自以下物质的制品：薄膜、片材、涂料、带、条、型材、管、模制品、泡沫塑料、带材、织物、线、长丝、丝带(ribbon)、纤维、纤维束和纤维网；其中该制品采用一种包含S嵌段和E或E1嵌段并且具有以下通式的选择性氢化的嵌段共聚物或其混合物而制备：
S-E-S，(S-E1)n，(S-E1)nS，(S-E1)nX
其中：(a)在氢化之前，S嵌段是聚苯乙烯嵌段；(b)在氢化之前，E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段；(c)在氢化之前，E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；(d)n具有2-6的值，X为偶联剂残基；(e)该嵌段共聚物的苯乙烯含量为13-25％；(f)氢化之前该聚二烯烃嵌段的乙烯基含量为60-85mol％；(g)该嵌段共聚物包含少于15wt％的具有以下通式的较低分子量单元：
S-E或S-E1
其中S、E和E1如同已经定义的那样；(h)在氢化之后，约0-10％的苯乙烯双键被氢化并且至少80％的共轭二烯烃双键被氢化；(i)每一S嵌段的分子量为5,000-7,000；和(j)根据ASTM D1238在230℃和2.16kg重量下，该嵌段共聚物的熔体指数大于或等于12克/10分钟。
本发明的另一方面是一种选自通过直接挤出制备的薄膜、带材、管、条、纤维或长丝的制品，其能够单独使用或处于具有多个其它层的层压结构中；或者该制品选自通过选自注塑、搪塑、滚塑、压塑和浸渍的方法制备的透明的挠性部件；其中该制品采用一种包含S嵌段和E或E1嵌段并且具有以下通式的选择性氢化的嵌段共聚物或其混合物而制备：
S-E-S，(S-E1)n，(S-E1)nS，(S-E1)nX
其中：(a)在氢化之前，S嵌段是聚苯乙烯嵌段；(b)在氢化之前，E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段；(c)在氢化之前，E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；(d)n具有2-6的值，X为偶联剂残基；(e)该嵌段共聚物的苯乙烯含量为13-25％；(f)氢化之前该聚二烯烃嵌段的乙烯基含量为60-85mol％；(g)该嵌段共聚物包含少于15wt％的具有以下通式的较低分子量单元：
S-E或S-E1
其中S、E和E1如同已经定义的那样；(h)在氢化之后，约0-10％的苯乙烯双键被氢化并且至少80％的共轭二烯烃双键被氢化；(i)每一S嵌段的分子量为5,000-7,000；并且其中该氢化嵌段共聚物的熔体指数大于50，滞后恢复率大于60％。
在仍然另一个方面中，本发明是一种包含S嵌段和E或E1嵌段并且具有以下通式的嵌段共聚物或其混合物：
S-E-S，(S-E1)n，(S-E1)nS，(S-E1)nX
其中：(a)S嵌段是聚苯乙烯嵌段；(b)E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段；(c)E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；(d)n具有2-6的值，X为偶联剂残基；(e)该嵌段共聚物的苯乙烯含量为13-25％；(f)氢化之前该聚二烯烃嵌段的乙烯基含量为60-85mol％；(g)该嵌段共聚物包含少于15wt％的具有以下通式的较低分子量单元：
S-E或S-E1
其中S、E和E1如同已经定义的那样；和(h)每一S嵌段的分子量为5,000-7,000。
优选实施方案的详细描述
在一个实施方案中，本发明是一种包含S嵌段和E或E1嵌段并且具有以下通式的选择性氢化的嵌段共聚物或其混合物：
S-E-S，(S-E1)n，(S-E1)nS，(S-E1)nX
其中：(a)在氢化之前，S嵌段是聚苯乙烯嵌段；(b)在氢化之前，E嵌段或E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的聚二烯烃嵌段。该嵌段共聚物可以是线型的、或者是具有3-6个臂的星形的。线型构造的通式包括：
S-E-S和/或(S-E1)n和/或(S-E1)nS
其中E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段；E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；n具有2-6，优选2-4，更优选平均约为3的值。星形构造的通式包括：
Figure A20058001174600091
和
其中E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；X是偶联剂残基。
本文中使用的术语“分子量”是指以克/摩尔计的聚合物或共聚物的嵌段的真实分子量。在本说明书和权利要求书中引用的分子量可以借助于例如根据ASTM 3536进行的使用聚苯乙烯校正标准的凝胶渗透色谱法(GPC)测量。GPC是一种非常公知的方法，其中根据分子大小(最大的分子首先洗脱)而将聚合物分开。使用可商购获得的聚苯乙烯分子量标准来校正色谱图。采用如此校正的GPC测量的聚合物分子量是苯乙烯当量分子量。当获知了聚合物的苯乙烯含量和二烯烃链段的乙烯基含量时，可以将苯乙烯当量分子量转化成真实分子量。使用的检测器优选是组合的紫外线和折射率检测器。本文中所述的分子量在GPC轨迹的峰处测量、其被转化成真实分子量，并且通常被称作“峰值分子量”。
本发明的嵌段共聚物通过苯乙烯和选自丁二烯、异戊二烯及其混合物的二烯烃的阴离子聚合而制备。通过在约-150℃至约300℃的温度下，优选在约0℃-约100℃的温度下在合适的溶剂中将苯乙烯和二烯烃单体与有机碱金属化合物接触而实现该聚合。特别有效的阴离子聚合引发剂是具有通式RLin的有机锂化合物，其中R是含有1-20个碳原子的脂族烃基、脂环族烃基、芳族烃基或烷基取代的芳族烃基，n具有1-4的值。优选的引发剂包括正丁基锂和仲丁基锂。用于阴离子聚合的方法是非常公知的并且可以在例如美国专利No.4,039,593和美国重新颁发的专利No.Re27,145的一些参考文献中找到。
本发明的嵌段共聚物可以是线型的、线型偶联的，或者是具有2-6个“臂”的混合物的星形嵌段共聚物。线型嵌段共聚物可以通过将苯乙烯聚合以形成第一S嵌段、加入丁二烯以形成E嵌段、然后加入另外的苯乙烯以形成第二S嵌段而制备。线型偶联的嵌段共聚物通过形成第一S嵌段和E嵌段，然后将该二嵌段与双官能偶联剂接触而制备。星形嵌段共聚物通过使用至少三官能的偶联剂而制备。
可用于制备线型嵌段共聚物的双官能偶联剂包括，例如披露于美国专利No.3,766,301中的苯甲酸甲酯。其它可用于形成星形嵌段共聚物的具有两个、三个或四个官能团的偶联剂包括，例如披露于美国专利No s.3,244,664、3,692,874、4,076,915、5,075,377、5,272,214和5,681,895中的四氯化硅和烷氧基硅烷；披露于美国专利No.3,281,383中的聚环氧化物、聚异氰酸酯、聚亚胺、聚醛、聚酮、聚酐、聚酯、多卤化物；披露于美国专利No.3,594,452中的二酯；披露于美国专利No.3,880,954中的甲氧基硅烷；披露于美国专利3,985,830中的二乙烯基苯；披露于美国专利No.4,104,332中的1，3，5-苯三羧酸三氯化物；披露于美国专利No.4,185,042中的环氧丙氧基三甲氧基硅烷；和披露于美国专利No.4,379,891中的氧基二丙基双(三甲氧基硅烷)。
在本发明的一个实施方案中，使用的偶联剂是通式为Rx-Si-(OR’)y的烷氧基硅烷，其中x为0或1，x+y＝3或4，R和R’相同或不同，R选自芳基、线型烷基和支化的烷基烃基，R’选自线型和支化的烷基烃基。芳基优选含有6-12个碳原子。烷基优选含有1-12个碳原子，更优选1-4个碳原子。在熔融条件下，这些烷氧基硅烷偶联剂可以进一步偶联以产生大于4的官能度。优选的四烷氧基硅烷是四甲氧基硅烷(“TMSi”)、四乙氧基硅烷(“TESi”)、四丁氧基硅烷(“TBSi”)和四(2-乙基己氧基)硅烷(“TEHSi”)。优选的三烷氧基硅烷是甲基三甲氧基硅烷(“MTMS”)、甲基三乙氧基硅烷(“MTES”)、异丁基三甲氧基硅烷(“IBTMO”)和苯基三甲氧基硅烷(“PhTMO”)。在这些当中，更优选的是四乙氧基硅烷和甲基三甲氧基硅烷。
本发明的一个重要方面是聚合物的微观结构。与本发明相关的微观结构是E和/或E1嵌段中高含量的乙烯基。该构造可以通过在二烯烃的聚合期间使用控制剂而获得。典型的试剂是二乙醚。参见美国专利No.Re 27,145和美国专利No.5,777,031，其披露内容在此引入作为参考。对于在制备嵌段共聚物领域中的那些普通技术人员而言所公知的可以使用的任何微观结构控制剂可用于制备本发明的嵌段共聚物。
在本发明的实践中，制备嵌段共聚物以使得它们在氢化之前在E和/或E1嵌段中具有约60-约85mol％的乙烯基。在另一个实施方案中，制备嵌段共聚物以使得它们具有约65-约85mol％的乙烯基含量。在仍然另一个实施方案中，制备嵌段共聚物以使得它们具有约70-约85mol％的乙烯基含量。本发明的另一个实施方案包括以使得它们在E和/或E1嵌段中具有约73-约83mol％的乙烯基含量而制备的嵌段共聚物。
在一个实施方案中，本发明是一种氢化的嵌段共聚物。采用本领域公知的几种氢化方法的任何一种而将本发明的氢化嵌段共聚物选择性氢化。例如，可以采用如在美国专利Nos.3,494,942；3,634,594；3,670,054；3,700,633和Re.27,145中教导的那些方法实现氢化，这些专利的披露内容在此引入作为参考。选择性地用于共轭聚二烯烃嵌段中的双键、而将聚苯乙烯嵌段中的芳族不饱和度基本保持完整的任何氢化方法可用于制备本发明的氢化嵌段共聚物。
在现有技术中公知的并且可用于制备本发明的氢化嵌段共聚物的方法涉及到使用合适的催化剂，特别是包含铁族金属原子(特别是镍或钴)和合适的还原剂(例如，烷基铝)的催化剂或催化剂前体。还可以使用的是钛基催化剂体系。一般而言，氢化可以在合适的溶剂中在约20℃-约100℃的温度下和在约100psig(689kPa)-约5,000psig(34，473kPa)的氢气分压下完成。通常采用基于全部溶液以重量计约10ppm-约500ppm的铁族金属的催化剂浓度，并且通常在氢化条件下使接触持续约60-约240分钟的时间。在氢化结束后，将通常使氢化催化剂和催化剂残余物与聚合物分离。
在本发明的实践中，该氢化嵌段共聚物的氢化度大于80％。这意味着E或E1嵌段中超过80％的共轭二烯烃双键从烯烃被氢化至烷烃。在一个实施方案中，E或E1嵌段的氢化度大于约90％。在另一个实施方案中，E或E1嵌段的氢化度大于约95％。
在本发明的实践中，嵌段共聚物的苯乙烯含量约为13-约25wt％。在一个实施方案中，嵌段共聚物的苯乙烯含量约为15-约24％。处于这些范围内的任何苯乙烯含量可用于本发明。在本发明的实践中，在氢化之后，S嵌段中0-10％的苯乙烯双键被氢化。
在本发明的嵌段共聚物中，每一S嵌段的分子量约为5,000-约7,000。在一个实施方案中，每一S嵌段的分子量约为5,800-约6,600。本发明的嵌段共聚物的S嵌段可以是具有处于这些范围内的任何分子量的聚苯乙烯嵌段。
在本发明的实践中，E嵌段是单个聚二烯烃嵌段。这些聚二烯烃嵌段可以具有约40,000-约70,000的分子量。E1嵌段是分子量约20,000-约35,000的聚二烯烃嵌段。在一个实施方案中，E嵌段的分子量范围约为45,000-约60,000，并且在被偶联之前，偶联的嵌段共聚物的每一E1嵌段的分子量范围约为22,500-约30,000。
本发明优于常规的氢化嵌段共聚物的一个优点在于它们具有高的熔体流动性，这使得它们能够容易地被模塑或者被连续地挤出成成型体或薄膜或者被纺丝成纤维。该性能使得最终使用者避免或者至少限制了使用使性能退化、造成区域污染、发烟并且甚至在模子和模头上形成积聚的添加剂。但是，本发明氢化的嵌段共聚物的会造成这些所不希望的效应的杂质，例如得自于不充分偶联的二嵌段同样非常少。本发明的嵌段共聚物和氢化嵌段共聚物具有少于15wt％的二嵌段含量，例如具有以下通式的二嵌段：
SE或SE1
其中S、E和E1如前所定义。在一个实施方案中，二嵌段含量少于10％，在另一个实施方案中少于8％。例如，在氢化嵌段共聚物的结构为(S-E1)2X的情况下，该嵌段共聚物含有少于10％的S-E1类物质。所有百分比以重量计。
本发明氢化的嵌段共聚物的一个特征在于它们具有低的有序-无序温度。本发明氢化的嵌段共聚物的有序-无序温度(ODT)通常小于约250℃。高于250℃，聚合物更难以加工，尽管对于一些应用而言在某些情况下可以采用大于250℃的ODT。一种这样的情形是当将嵌段共聚物与其它组分结合以改进加工性时。这些其它的组分可以是热塑性聚合物、油、树脂、蜡等。在一个实施方案中，ODT小于约240℃。优选地，本发明氢化的嵌段共聚物的ODT约为210℃-约240℃。在某些应用中该性能可能是重要的，因为当ODT低于210℃时，嵌段共聚物可能展现出令人不希望地过多或低强度的蠕变。出于本发明的目的，将“有序-无序温度”定义为在其上可以通过毛细管流变学或动态流变学测量零剪切粘度的温度。
出于本发明的目的，术语“熔体指数”是根据ASTM D1238在230℃和2.16kg重量下聚合物熔体流动性的量度。其以10分钟内通过熔体流变仪孔口的聚合物克数为单位表示。本发明氢化的嵌段共聚物具有所希望的高熔体指数，这使得其与具有较高熔体指数的类似的氢化嵌段共聚物相比更容易加工。在一个实施方案中，本发明氢化的嵌段共聚物的熔体指数大于或等于12。在另一个实施方案中，本发明氢化的嵌段共聚物的熔体指数大于或等于20。在仍然另一个实施方案中，本发明氢化的嵌段共聚物的熔体指数大于或等于40。本发明的另一个实施方案包括熔体指数约为20-约100的氢化的嵌段共聚物。本发明的仍然另一个实施方案包括熔体指数约为50-约85的氢化的嵌段共聚物。
本发明的氢化嵌段共聚物尤其适用于制备需要基于熔体的加工的制品。例如，本发明的氢化嵌段共聚物可用于选自注塑、重叠注塑、镶嵌模塑、浸渍、挤出、滚塑、搪塑、纤维纺丝、制膜和发泡的方法。采用这些方法制备的制品包括：薄膜、片材、涂料、带、条、型材、管、模制品、泡沫塑料、带材、织物、线、长丝、丝带、纤维、纤维束、纤维网和包含多层薄膜和/或纤维层的层压制品。
尽管本发明的氢化共聚物具有如此低的有序-无序温度和高的熔体指数，以致于可以在不使用加工助剂的条件下将它们用于制备制品，但有时还希望使用一些助剂和其它添加剂。这些添加剂的例子是选自以下的物质：其它的嵌段共聚物、烯烃聚合物、苯乙烯聚合物、增粘树脂、封端树脂、聚合物增量油、蜡、填料、增强剂、润滑剂、稳定剂、工程热塑性树脂、和其混合物。
当添加剂是烯烃聚合物时，典型的聚合物包括，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、和其它的α-烯烃共聚物或互聚物。代表性的聚烯烃包括例如，但不限于，基本线型的乙烯聚合物、均匀支化的线型乙烯聚合物、非均匀支化的线型乙烯聚合物，包括线型低密度聚乙烯(LLDPE)、超低或甚低密度聚乙烯(ULDPE或VLDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)和高压低密度聚乙烯(LDPE)。下面包括的其它聚合物是乙烯/丙烯酸(EAA)共聚物、乙烯/甲基丙烯酸(EMAA)离聚物、乙烯/乙酸乙烯酯(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/一氧化碳互聚物(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)。优选的是高透明性的软质烯烃聚合物，例如聚乙烯和聚丙烯共聚物、塑性体、弹性体和互聚物。例子包括得自于Dow Chemical的Affinity、Engage和Versify聚合物与得自于Exxon Mobil的Exact和Vistamaxx聚合物。下面包括的仍然另一些聚合物是聚氯乙烯(PVC)和PVC与其它材料的共混物。
还可以将本发明的氢化共聚物与苯乙烯类聚合物混合。苯乙烯类聚合物包括，例如结晶聚苯乙烯、高抗冲聚苯乙烯、中抗冲聚苯乙烯、苯乙烯/丙烯腈共聚物、苯乙烯/丙烯腈/丁二烯(ABS)聚合物、间同立构聚苯乙烯和苯乙烯/烯烃共聚物。代表性的苯乙烯/烯烃共聚物是优选含有至少20wt％共聚的苯乙烯单体的基本无规的乙烯/苯乙烯或丙烯/苯乙烯共聚物。还包括的是苯乙烯接枝的聚丙烯聚合物，例如以商品名Interloy提供的、最初由Himont，Inc.(如今为Basell)开发的那些。还可以将本发明的氢化共聚物与其它嵌段共聚物例如苯乙烯-二烯烃-苯乙烯三嵌段、辐射状或星型的嵌段聚合物、苯乙烯-二烯烃二嵌段聚合物和这些聚合物的氢化变体混合。可以使用的高乙烯基含量聚合物的例子包括得自于Kurraray的Hybrar和得自于JSR的Dynaron。
出于本发明的说明书和权利要求书的目的，术语“工程热塑性树脂”包括了在下表A中列出的种类中发现的、并且进一步在美国专利No.4,107,131中定义的多种聚合物，该专利的披露内容在此引入作为参考。
表A
    热塑性聚酯
    热塑性聚氨酯
    聚(芳基醚)和聚(芳基砜)
    聚碳酸酯
    缩醛树脂
    聚酰胺
    氢化热塑性塑料
    腈类阻透性树脂
    聚(甲基丙烯酸甲酯)
    环烯烃共聚物
当与本发明的氢化嵌段共聚物一起使用的添加剂是增粘树脂时，典型的树脂包括聚苯乙烯嵌段相容性树脂和中间嵌段相容性树脂。聚苯乙烯嵌段相容性树脂可以选自香豆酮-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-甲基苯乙烯树脂和聚苯醚，特别是聚(2，6-二甲基-1，4-亚苯基醚)。这些树脂例如以商标名“HERCURES”、“ENDEX”、“KRISTALEX”、“NEVCHEM”和“PICCOTEX”出售。与氢化(中间)嵌段相容的树脂可以选自相容性C5烃树脂、氢化C5烃树脂、苯乙烯化的C5树脂、C5/C9树脂、苯乙烯化的萜烯树脂、完全氢化或部分氢化的C9烃树脂、松香酯、松香衍生物和其混合物。这些树脂例如以商标名“REGALITE”、“REGALREZ”、“ESCOREZ”和“ARKON”出售。我们还可以使用聚苯乙烯嵌段相容性树脂和中间嵌段相容性树脂两者。
当添加剂是弹性体聚乙烯或聚丙烯共聚物时，例子包括得自于DowChemical的Affinity、Engage和Versify聚合物以及得自于ExxonMobil的Exact和Vistamaxx聚合物。
尽管可以使用以上所提及的添加剂，但通常希望的是限制它们的使用以避免其固有的问题，这些问题包括，但不限于发烟、模头咬模、模具咬模、区域污染等。在一个实施方案中，在用本发明的氢化嵌段共聚物制备的制品中存在的添加剂的总浓度约为0.001-约25wt％。在另一个实施方案中，在用本发明的氢化嵌段共聚物制备的制品中存在的添加剂的总浓度约为0.001-约10wt％。在仍然另一个实施方案中，在用本发明的氢化嵌段共聚物制备的制品中存在的添加剂的总浓度约为0.001-约5wt％。本发明的另一个实施方案包括其中在用本发明的氢化嵌段共聚物制备的制品中存在的添加剂的总浓度约为0.001-约1wt％的情况。
可以将本发明的聚合物作为纯的聚合物或者以处于配混料中的形式而用于大量的应用。以下的各种最终用途和/或工艺意在说明，并不限制本发明：
·聚合物改性应用
·玩具、医疗器械的注塑
·挤出的薄膜、管材、型材
·重叠注塑应用，用于个人护理、夹子、软接触应用，用于汽车部件例如气囊、方向盘等
·浸渍的物品，例如手套
·热固性应用，例如用于盘子的片状模塑料或整块(bulk)模塑料
·用于玩具和其它制品的滚塑
·汽车外壳的搪塑
·用于涂料的热喷涂
·用于医疗器械的吹塑薄膜
·热熔粘合剂
·用于汽车/工业部件的吹塑
·用于个人卫生应用的薄膜和纤维
·官能化聚合物的粘结层
·屋顶片材
·土工用膜应用
本发明的氢化嵌段共聚物具有非常弹性的性能，并且还有非常高的熔体指数。在一个实施方案中，本发明的氢化嵌段共聚物的滞后恢复率大于50％，并且在伸长至300％之后在第一次回缩周期时的永久变形率小于20％。例如，本发明的一个优选实施方案是熔体指数大于50并且滞后恢复率大于60％的氢化嵌段共聚物。该实施方案特别可用于制备选自通过直接挤出制备的薄膜、带材、管、条、纤维或长丝的制品，其能够单独使用或处于具有多个其它层的层压结构中；或者通过选自注塑、搪塑、滚塑、压塑和浸渍的方法制备的透明的挠性部件。
可以任选地包含0.001-10wt％的选自稳定剂、增量油、蜡、增粘树脂、封端树脂、表面改性剂和聚烯烃的添加剂来制备这些制品，以增强流动性、刚性或弹性。当存在时，该一种或多种添加剂可以包括聚乙烯或聚丙烯均聚物或共聚物。在一个实施方案中，该聚乙烯或聚丙烯均聚物或共聚物是高透明性聚丙烯共聚物，该共聚物可以是聚乙烯或聚丙烯塑性体、弹性体或互聚物。
实施例
提供以下实施例以阐述本发明。这些实施例并不旨在限制本发明的范围，并且不应该将它们如此理解。除非另外说明，数量以重量份或重量百分比计。
实施例1
通过以下方式制备氢化的嵌段共聚物：在微观结构控制剂的存在下苯乙烯阴离子聚合和之后丁二烯阴离子聚合，随后偶联并且然后氢化：二嵌段聚合物阴离子，S-B-Li，通过将361kg环己烷和16.7kg苯乙烯装入反应器制备。将反应器温度升至约40℃。通过加入少量等分量的仲丁基锂直到初次出现颜色而将杂质除去。加入1,900ml约12wt％的于环己烷中的仲丁基锂溶液，并且在约60℃下将苯乙烯完全聚合。以该反应制得的聚苯乙烯的分子量通过GPC测量为6,400。加入320g1，2-二乙氧基丙烷，然后在一定速率下加入72.6kg丁二烯以使得温度保持约60℃。在丁二烯聚合结束时收集的样品基于1H NMR的苯乙烯含量为21.3wt％，乙烯基含量为69％，并且通过GPC测量的总的分子量为35,000。在大部分丁二烯聚合之后，加入623g异戊二烯。将异戊二烯聚合，然后加入257g TESi，并且在60℃下使偶联反应进行60分钟。加入甲醇(8.5g，0.1mol/mol Li)以终止反应。最终产物具有91％的偶联率，并且72％的偶联类物质是线型的，剩余的28％是3-臂星形的。
在按照[Co]为20ppm的新癸酸钴-三乙基铝催化剂溶液(Al/Co＝1.7mol/mol)的存在下将聚合物样品氢化至残余烯烃浓度为0.09meq/g。在这些条件下氢化之后，聚合物保持91％是偶联的。通过用磷酸水溶液清洗而将催化剂除去，并且在通常用于氢化聚合物的条件下通过蒸汽汽提将聚合物回收。
以使得可以测量苯乙烯嵌段和丁二烯/异戊二烯嵌段的分子量这样的方式取得样品。还测量氢化之前1，2-构造的丁二烯含量和偶联率。测试该氢化嵌段共聚物的熔体流动性和ODT。测试结果在下面示于表1中。
实施例2
通过以下方式制备氢化的嵌段共聚物：在微观结构控制剂的存在下苯乙烯阴离子聚合和之后丁二烯阴离子聚合，随后偶联，然后氢化：二嵌段聚合物阴离子，S-B-Li，通过将348kg环己烷和26kg苯乙烯装入反应器制备。将反应器温度升至约40℃。通过加入少量等分量的仲丁基锂直到初次出现颜色而将杂质除去。加入3,160ml约12wt％的于环己烷中的仲丁基锂溶液，并且在约60℃下将苯乙烯完全聚合。以该反应制得的聚苯乙烯的分子量通过GPC测量为6,200。将温度保持在60℃，加入450g 1，2-二乙氧基丙烷，然后在一定速率下加入90kg丁二烯以使得温度保持约60℃。在丁二烯聚合结束时收集的样品基于1HNMR的苯乙烯含量为22wt％，乙烯基含量为81％，并且通过GPC测量的总的分子量为30,200。将丁二烯聚合，然后加入363g TESi，并且在60℃下使偶联反应进行60分钟。加入甲醇(15g，0.1mol/mol Li)以终止反应。最终产物具有89％的偶联率，并且65％的偶联类物质是线型的，剩余的35％是3-臂星形的。
在20ppmNi/辛酸镍-三乙基铝催化剂溶液(Al/Ni＝2.1mol/mol)的存在下将聚合物样品氢化至残余烯烃浓度为0.17meq/g。在这些条件下氢化之后，聚合物89％是偶联的。通过用磷酸水溶液清洗而将催化剂除去，并且在通常用于氢化聚合物的条件下通过蒸汽汽提将聚合物回收。
以使得可以测量苯乙烯嵌段和丁二烯嵌段的分子量这样的方式取得样品。还测量氢化之前1，2-构造的丁二烯含量和偶联率。测试该氢化嵌段共聚物的熔体流动性和ODT。测试结果在下面示于表1中。
实施例3
通过以下方式制备氢化的嵌段共聚物：在微观结构控制剂的存在下苯乙烯阴离子聚合和之后丁二烯阴离子聚合，随后偶联，然后氢化：二嵌段聚合物阴离子，S-B-Li，通过将243kg环己烷和20kg苯乙烯装入反应器制备。将反应器温度升至约40℃。通过加入少量等分量的仲丁基锂直到初次出现颜色而将杂质除去。加入2,500ml约12wt％的于环己烷中的仲丁基锂溶液，并且在约60℃下将苯乙烯完全聚合。以该反应制得的聚苯乙烯的分子量通过GPC测量为6,100。将温度保持在60℃，加入210g 1，2-二乙氧基丙烷，然后在一定速率下加入60kg丁二烯以使得温度保持约60℃。在丁二烯聚合结束时收集的样品基于1HNMR的苯乙烯含量为22wt％，乙烯基含量为76％，并且通过GPC测量的总的分子量为27,700。将丁二烯聚合，然后加入243g TESi，并且在60℃下使偶联反应进行60分钟。最终产物具有94％的偶联率，并且62％的偶联类物质是线型的，剩余的38％是3-臂星形的。
在10ppmNi/辛酸镍-三乙基铝催化剂溶液(Al/Ni＝2.1mol/mol)的存在下将聚合物样品氢化至残余烯烃浓度为0.17meq/g。在这些条件下氢化之后，聚合物保持89％是偶联的。通过用磷酸水溶液清洗而将催化剂除去，并且在通常用于氢化聚合物的条件下通过蒸汽汽提将聚合物回收。
以使得可以测量苯乙烯嵌段和丁二烯嵌段的分子量这样的方式取得样品。还测量氢化之前1，2-构造的丁二烯含量和偶联率。测试该氢化嵌段共聚物的熔体流动性和ODT。测试结果在下面示于表1中。
实施例4
通过实施例2和3的方法制备聚合物，其中以使得苯乙烯嵌段的分子量为6,200、偶联之前总的分子量为33,200、乙烯基含量为78％并且偶联度为97％这样的方式改变苯乙烯和丁二烯进料量。在氢化之后，偶联率为96％，残余不饱和度为0.1meq/g。
实施例5
通过实施例2和3的方法制备聚合物，除了将甲基三甲氧基硅烷用作偶联剂。苯乙烯和丁二烯进料量为使得苯乙烯嵌段的分子量为6,200、偶联之前总的分子量为32,800、乙烯基含量为76％，并且偶联度为94％。
实施例6
通过实施例2和3的方法制备聚合物，除了将四甲氧基硅烷用作偶联剂。苯乙烯和丁二烯进料量为使得苯乙烯嵌段的分子量为6,100、偶联之前的分子量为34,500、乙烯基含量为76％，并且偶联度为95％。
比较例I、II和III
基本上采取与实施例2相同的方式制备和测试比较的氢化嵌段共聚物I和II，除了苯乙烯嵌段分子量大于本发明的最大分子量。通过将苯乙烯然后丁二烯然后苯乙烯序列(sequential)聚合，随后氢化而制备比较例III。测试结果在下面示于表1中。
表1
实施例号 S嵌段mwt(k)   E嵌段mwt(k)   偶联率   E嵌段中1，2-丁二烯％   ODT℃ 熔体指数
    1     6.4     27.7     91     68   250     18
    2     6.2     24.0     89     81   230     81
    3     6.1     21.6     94     76   230     72
    4     6.2     27.0     97     78   240     17
    5     6.2     26.6     94     76   ＜250     31
    6     6.1     28.5     95     76   ＜250     20
    I     7.5     30.8     84     67   260     10
    II     7.9     26.8     92     69   300+     6
    III     7.2     55.8     8.5*     68   300+     7
列出的分子量值是采用凝胶渗透色谱法和聚苯乙烯标准测量的真实分子量。
ODT采用Bohlin VOR流变仪测量。
熔体指数测试方法[230℃，2.16KG，ASTM D-1238]。
实施例1-4和比较例I-III表明S嵌段的分子量会对熔体指数和/或ODT具有显著作用。
实施例5-7
通过加入0.15％脱模剂和0.02％Ethanox 330稳定剂，随后在230℃下在Davis Standard流延薄膜生产线上挤出，而由表1中的一些聚合物制备薄膜。聚合物2和3产生了低的挤出压力，并且由于它们高的流动性而形成了光滑、透明的薄膜。比较例III形成了具有高的挤出背压的较粗糙薄膜。根据ASTM D412在挤出方向上测量的这些薄膜的拉伸和滞后性能在表2中示出。所有这些表现出优良的强度和弹性，这由在伸长至300％之后高的第一周期恢复率和低的永久变形率来说明。
表2
实施例号     5     6     7
聚合物     2     3     III
性能     MD     MD     MD
2英寸/分钟下的应力-应变
断裂下的最大应力(psi)     1887     1584     2044
断裂下的应变(％)     970     938     922
100％下的应力，psi     206     177     205
300％下的应力，psi     440     382     429
滞后至300％，3个周期
周期1恢复率     74     75     81
永久变形率(％)     9     8     10
最大应力(psi)     404     358     346
实施例8-16
在220℃下采用Brabender混合机—在约65RPM下运行的混合机以表3中示出的比例将实施例3的聚合物与熔体流动指数为30的聚丙烯共聚物—Dow Chemical 6D43、低分子量聚丙烯均聚物—得自于Eastman1 Chemical的Estaflex P1010、可作为REGALREZ 1126从Eastman Chemical商购获得的氢化烃类树脂和可作为NOVA 555从NovaChemical商购获得的聚苯乙烯配混。如上测试该配混的氢化共聚物，结果在下面示于表3中。
表3
实施例    8      9     10     11     12     13     14     15     16
 分数     分数     分数     分数     分数     分数     分数     分数     分数
聚合物3  1     0.95     0.9     0.8     0.9     0.9     0.8     0.8     0.8
Dow 6D43 PP     0.05     0.1     0.2     0.07
Regalrez 1126     0.1     0.1     0.13     0.13
EastoflexP1010     0.1     0.07
Nova 555 PS     0.1
Ethanox 330  0.0002     0.0002     0.0002     0.0002     0.0002     0.0002     0.0002     0.0002     0.0002
总计(g)  43.2     43.2     43.2     43.2     43.2     42.43     42.43     43.2     43.2
性能
透明性  透明     透明     透明     模糊     透明     透明     模糊     透明     透明
2英寸/分钟下的应力-应变
断裂下的最大应力，psi  1678     1406     1401     1239     1152     1350     1304     1266     1336
断裂下的应变，％  936     915     932     747     951     1028     832     1082     1032
100％下的应力，psi  224450     233451     244465     321666     180359     178348     132327     130272     175
300％下的应力，psi     356
滞后至300％，3个周期
周期1恢复率  73     65     60     52     68     70     84     75     65
永久变形率(％) 16 20 21 26     20     20     20     18     22
最大应力(psi) 338 348 329 497 302 281 220     212     289
实施例9、10和11表明可以加入聚丙烯以提高刚性，这如同以滞后恢复率为代价在100和300％伸长率下的模量所表现出的那样。实施例12表明，加入较少的结晶P1010聚丙烯如同加入增粘树脂Regalrez1126那样降低了模量。可以将增粘树脂和PS或PP的组合用于提高流动性或刚性并同时保持透明性，然而，没有改性的基础聚合物与大多数配混料相比保持了优良的性能平衡性。这说明了在实际加工中使用含有最少量添加剂的纯聚合物制备制品的重要性。

Claims (11)

1.一种包含S嵌段和E或E1嵌段并且具有以下通式的选择性氢化的嵌段共聚物或其混合物：
S-E-S，(S-E1)n，(S-E1)nS，(S-E1)nX
其中：
(a)在氢化之前，S嵌段是聚苯乙烯嵌段；
(b)在氢化之前，E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段；
(c)在氢化之前，E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；
(d)n为具有2-6的值的整数，X为偶联剂残基；
(e)该嵌段共聚物的苯乙烯含量为13-25wt％；
(f)氢化之前该聚二烯烃嵌段的乙烯基含量为70-85mol％；
(g)该嵌段共聚物包含少于15wt％的具有以下通式的较低分子量单元：
S-E或S-E1
其中S、E和E1如同已经定义的那样；
(h)在氢化之后，约0-10％的苯乙烯双键被氢化，并且至少80％的共轭二烯烃双键被氢化；
(i)每一S嵌段的分子量为5,000-7,000；和
(j)根据ASTM D1238在230℃和2.16kg重量下，该嵌段共聚物的熔体指数大于或等于12克/10分钟。
2.根据权利要求1的嵌段共聚物，其中该嵌段共聚物的有序-无序温度(ODT)小于250℃。
3.根据权利要求1或2的嵌段共聚物，其中该嵌段共聚物的苯乙烯含量为15-24wt％，并且该聚二烯烃嵌段的乙烯基含量为73-83mol％。
4.根据权利要求1-3任一项的嵌段共聚物，其中每一S嵌段的分子量为5,800-6,600。
5.根据权利要求1-4任一项的嵌段共聚物，其中E或E1嵌段的氢化度大于90％。
6.根据权利要求1-5任一项的嵌段共聚物，其具有的有序-无序温度为210℃-240℃。
7.根据权利要求1-6任一项的嵌段共聚物，其具有的滞后恢复率大于50％，并且在伸长至300％之后在第一次回缩周期的永久变形率小于20％。
8.一种选自以下物质的制品：薄膜、片材、涂料、带、条、型材、管、模制品、泡沫塑料、带材、织物、线、长丝、丝带、纤维、纤维束和纤维网；其中该制品通过选自注塑、镶嵌模塑、重叠注塑、浸渍、挤出、滚塑、搪塑、纤维纺丝、制膜和发泡的方法制备，并且其中该制品采用权利要求1-7任一项的氢化的嵌段共聚物制备。
9.根据权利要求8的制品，其中该氢化的嵌段共聚物另外包含至多约25wt％的一种或多种选自以下物质的添加剂：烯烃聚合物、苯乙烯聚合物、增粘树脂、聚合物增量油、填料、增强剂、润滑剂、工程热塑性树脂、和其混合物。
10.根据权利要求9的制品，其中该添加剂选自聚乙烯或聚丙烯均聚物或共聚物，该聚乙烯或聚丙烯均聚物或共聚物是塑性体、弹性体或互聚物或者高透明性聚丙烯共聚物。
11.一种包含S嵌段和E或E1嵌段并且具有以下通式的嵌段共聚物或其混合物：
S-E-S，(S-E1)n，(S-E1)nS，(S-E1)nX
其中：
(a)S嵌段是聚苯乙烯嵌段；
(b)E嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为40,000-70,000的聚二烯烃嵌段；
(c)E1嵌段是选自聚丁二烯、聚异戊二烯和其混合物的分子量为20,000-35,000的聚二烯烃嵌段；
(d)n为具有2-6的值的整数，X为偶联剂残基；
(e)该嵌段共聚物的苯乙烯含量为13-25％；
(f)该聚二烯烃嵌段的乙烯基含量为70-85％；
(g)该嵌段共聚物包含少于15wt％的具有以下通式的较低分子量单元：
S-E或S-E1
其中S、E和E1如同已经定义的那样；和
(h)每一S嵌段的分子量为5,000-7,000。
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CN102617970A (zh) * 2012-04-26 2012-08-01 湖南汇中新材料有限公司 一种氢化嵌段共聚物弹性体-尼龙6的组合物
CN102617970B (zh) * 2012-04-26 2014-03-05 湖南汇中新材料有限公司 一种氢化嵌段共聚物弹性体-尼龙6的组合物

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