CN1643016B - 新型嵌段共聚物及其制备方法 - Google Patents
新型嵌段共聚物及其制备方法 Download PDFInfo
- Publication number
- CN1643016B CN1643016B CN038074842A CN03807484A CN1643016B CN 1643016 B CN1643016 B CN 1643016B CN 038074842 A CN038074842 A CN 038074842A CN 03807484 A CN03807484 A CN 03807484A CN 1643016 B CN1643016 B CN 1643016B
- Authority
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- China
- Prior art keywords
- block
- monomer
- copolymer
- segmented copolymer
- alkenyl arene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000000178 monomer Substances 0.000 claims description 102
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 99
- 229920000642 polymer Polymers 0.000 claims description 72
- 238000006116 polymerization reaction Methods 0.000 claims description 64
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- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 19
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229920001519 homopolymer Polymers 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 11
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Abstract
本发明涉及新型嵌段共聚物,它含有共轭二烯和单烯基芳烃的控制分布共聚物嵌段,其中控制分布共聚物嵌段具有富含共轭二烯单元的末端区和富含单烯基芳烃单元的中心区。还描述了该嵌段共聚物的制备方法。
Description
技术领域
本发明涉及单烯基芳烃和共轭二烯的新型阴离子嵌段共聚物,以及该嵌段共聚物的制备方法。尤其是,本发明涉及阴离子嵌段共聚物,其中嵌段之一是在该共聚物嵌段中具有特定单体排列的共轭二烯和单烯基芳烃的控制分布共聚物。
背景技术
嵌段共聚物的制备是众所周知的。在具有代表性的合成方法中,利用引发剂化合物开始一种单体的聚合。进行反应直至消耗完所有单体,得到活性均聚物。向该活性均聚物中加入化学上与第一单体不同的第二单体。第一聚合物的活性端作为继续聚合的点,从而将第二单体以不同的嵌段结合到线型聚合物上。这样生长的嵌段共聚物直到封端之前都是活性的。
封端将嵌段共聚物的活性端转变为不增长的物质,因此使聚合物对单体或偶联剂不具有反应性。这样封端的聚合物通常称作二嵌段共聚物。如果聚合物没有封端,那么活性嵌段共聚物能够与其它单体反应形成顺序的线型嵌段共聚物。或者,活性嵌段共聚物与通常称作偶联剂的多官能团试剂接触。将两个活性端连接起来形成具有两倍于起始的活性二嵌段共聚物分子量的线型三嵌段共聚物。连接两个以上活性二嵌段共聚物区得到具有至少三个臂的星形嵌段共聚物结构。
关于由苯乙烯和丁二烯制成的线型ABA嵌段共聚物的第一批专利之一是美国专利3,149,182。这些聚合物反过来能够氢化形成更稳定的嵌段共聚物,如美国专利3,595,942和Re 27,145所述的那些。有时所希望的是无规共聚物如SBR而不是嵌段共聚物。无规苯乙烯丁二烯共聚物或SBR描述于美国专利2,975,160、4,547,560、4,367,325和5,336,737中。
希望嵌段共聚物具有低熔融粘度的发明人考虑了利用无规苯乙烯和丁二烯嵌段,如美国专利3,700,633所述。使嵌段共聚物具有透明性的方法之一也是对无规嵌段共聚物进行的,如美国专利4,089,913、4,122,134和4,267,284。
当制备苯乙烯和丁二烯的无规嵌段时,由于丁二烯共聚合速率比苯乙烯更快,因此将形成所谓的“递变”嵌段。参见美国专利5,191,024、5,306,779和5,346,964。因此在美国专利4,603,155中,专利人制备了包括多个递变嵌段的嵌段以得到更无规的共聚物。但是多种情况下,专利人依赖于连续加入两种单体或使用无规化试剂以实现更无规的结构。这些技术描述于美国专利3,700,633和4,412,087以及德国专利申请DE4420952、DE19615533、DE19621688、DE195003944、DE19523585和DE19638254。然而,有些无规化试剂将毒化氢化催化剂,使得难于或不可能进行聚合物的随后氢化,因此必须避免使用这种无规化试剂。含有N原子的无规化试剂特别容易出现这种问题。
尽管性能上已经作出了一些改进,但是如果能够增加苯乙烯/丁二烯嵌段共聚物的拉伸刚性而不增加塑性,那将是有意义的。还希望的是具有增加的极性、同时还具有明显降低的熔融和溶液粘度的聚合物。申请人发现,通过设计在二烯嵌段中具有不同结构的聚合物能够实现这些改进,其中避免了不可取的嵌段指数(blockiness),同时还降低或避免了后聚合氢化处理过程中出现的不利作用。
发明概述
广义上说,本发明包括具有至少一个A嵌段和至少一个B嵌段的嵌段共聚物,其中:
a.每个A嵌段独立地为单烯基芳烃聚合物嵌段,每个B嵌段独立地为至少一种共轭二烯和至少一种单烯基芳烃的控制分布共聚物嵌段;
b.每个A嵌段的数均分子量为3,000至60,000,每个B嵌段的数均分子量为30,000至300,000;
c.每个B嵌段包括邻接A嵌段的末端区域和不邻接A嵌段的一个或多个区域,其中邻接A嵌段的末端区域富含共轭二烯单元,不邻接A嵌段的一个或多个区域富含单烯基芳烃单元;
d.嵌段共聚物中单烯基芳烃的总量为20wt%至80wt%;和
e.每个B嵌段中单烯基芳烃的重量百分数为10%至75%。
该嵌段共聚物可以部分地、选择地或全部地氢化。在优选实施方案中,嵌段共聚物的杨氏模量低于2,800psi(20MPa),100-300%伸长的橡胶模量或斜率大于70psi(0.5MPa)。这些性能在现有技术聚合物中没有发现。
因此,一方面,本发明涉及一般构型为A-B,A-B-A,(A-B)n,(A-B)n-A,(A-B-A)nX或(A-B)nX的嵌段共聚物,其中n为2至约30的整数,X是偶联剂残基,其中A和B与上面定义相同。例如,这一方面的实施方案中,本发明涉及具有结构A1-B1-A2-B2的四嵌段共聚物,其中:
a.每个A1和A2嵌段是单烯基芳烃聚合物嵌段,每个B1嵌段是至少一个共轭二烯和至少一个单烯基芳烃的控制分布共聚物嵌段,并且每个B2嵌段选自:(i)至少一种共轭二烯和至少一种单烯基芳烃的控制分布共聚物嵌段;(ii)共轭二烯的均聚物嵌段;和(iii)两种或多种不同共轭二烯的共聚物嵌段;
b.每个A1和A2嵌段的平均分子量为3,000至60,000,每个B1嵌段的平均分子量为30,000至300,000,并且每个B2嵌段的平均分子量为2,000至40,000;
c.每个B1嵌段包括邻接A嵌段的末端区域和不邻接A嵌段的一个或多个区域,其中邻接A嵌段的末端区域富含共轭二烯单元,不邻接A嵌段的一个或多个区域富含单烯基芳烃单元;
d.嵌段共聚物中单烯基芳烃的总量为20wt%至80wt%;和
e.每个B1嵌段中单烯基芳烃的重量百分数为10%至75%。
另一方面,本发明涉及进一步包括至少一个C嵌段的上述嵌段共聚物,其中每个C嵌段是一种或多种共轭二烯的聚合物嵌段,其数均分子量为2,000至200,000。
又一方面,本发明包括至少部分经过氢化的所述嵌段共聚物。例如,二烯嵌段的不饱和度可以被还原,使得25至95%或者优选至少90%的二烯双键还原,而低于10%或没有单烯基芳烃双键的氢化(所谓的“选择性氢化”)。如果需要,A嵌段还可以全部饱和,以降低至少约90%的芳烃双键。还有,还可以仅仅使具有乙烯基连接的那些双键饱和。
再另一方面,本发明包括其上连接了至少一种官能团的上述嵌段共聚物。
申请人还要求保护制备这些聚合物的发明方法。方法之一包括:
a.在惰性烃溶剂和有机锂引发剂存在下,在第一反应器中聚合单烯基芳烃,从而形成了用锂离子封端的活性聚合物嵌段A1;
b.向第二反应器中加入惰性烃溶剂、80至100%的共聚物嵌段B1中所需要的单烯基芳烃单体,10至60%的共聚物嵌段B1中所需要的共轭二烯单体,和分布试剂(distribution agent);
c.将活性均聚物嵌段A1转移到第二反应器中并开始聚合步骤b中加入的单烯基芳烃单体和共轭二烯单体;和
d.在5至60mol%的步骤c的单体聚合后,以使共轭二烯单体的浓度不低于0.1wt%的速率,向第二反应器中连续加入剩余量的共轭二烯单体和单烯基芳烃,直至嵌段B1中90%的单体被聚合。
优选地是,连续加入结束时,低于20wt%,最优选低于15%的未反应单体由单烯基芳烃组成从而形成了活性嵌段共聚物A1B1。
本发明的另一种方法包括:
a.在惰性烃溶剂和有机锂引发剂存在下,在第一反应器中聚合单烯基芳烃,从而形成了用锂离子封端的活性聚合物嵌段A1;
b.在步骤a的聚合完成之前,向反应器中加入共聚物嵌段B1所需要的40至60%的共轭二烯单体的一等分试样和有效量的分布试剂,并继续单烯基芳烃单体和共轭二烯单体的聚合;
c.在步骤b的10至60mol%单体聚合后,以使共轭二烯单体的浓度不低于0.1wt%的速率,向反应器中逐渐加入剩余量的共轭二烯单体和单烯基芳烃,直至嵌段B1中90%的单体被聚合,由此形成了活性共聚物嵌段A1B1;和
d.向反应器中加入附加的单烯基芳烃单体,由此形成了活性共聚物A1B1A2,其中A1嵌段和A2嵌段的平均分子量分别为3,000至60,000,B1嵌段的平均分子量为30,000至300,000。
在可供选择的实施方案中,嵌段A1中的单烯基芳烃单体被聚合到完成,同时加入单烯基芳烃单体和共轭二烯单体,但是以更快的速度加入单烯基芳烃单体。
附图的简要说明
图1、2和3示出在三个单独S-S/Bd-S嵌段共聚物的中间嵌段中,苯乙烯(“S”)和丁二烯(“Bd”)的分布。如图所示,本发明控制分布的嵌段共聚物的特征在于,在控制分布嵌段的嵌段末端存在富含丁二烯的区域和接近中间或中心存在富含苯乙烯的区域。图4是本发明嵌段共聚物的拉伸性能图,所述嵌段共聚物在中间嵌段含有苯乙烯,并且与普通和高含量乙烯基聚合物相比具有控制的分布。图4中的所有聚合物都具有10,000-80,000-10,000的公称嵌段分子量。图5比较了本发明控制分布聚合物与市售产品的应力-应变曲线,其中市售产品具有相似的苯乙烯含量,但不是控制分布的。
发明详述
本发明涉及新型组合物,以及共聚作为单烯基芳烃/共轭二烯嵌段共聚物一部分的烯基芳烃和二烯的制备方法。令人惊奇地是,将(1)独特控制单体的加入和(2)使用二乙醚或其它改性剂作为溶剂组分(称作“分布试剂”)的组合导致了两种单体的某些特征分布(本文中称作“控制分布”聚合,即形成“控制分布”结构的聚合),还导致在聚合物嵌段中出现了富含某些单烯基芳烃的区域和富含某些共轭二烯的区域。鉴于此,将“控制分布”定义为具有下述属性的分子结构:(1)富含(即比平均含量更高)共轭二烯单元的末端区邻接单烯基芳烃均聚物(“A”)嵌段;(2)一个或多个富含(即比平均含量更高)单烯基芳烃单元的区域不邻接A嵌段;(3)整个结构具有较低的嵌段指数(blockiness)。为此,“富含”定义为比平均量更高,例如优选比平均量高5%。该较低的嵌段指数可以从所述控制分布聚合物嵌段仅仅存在一个单一的玻璃化转变温度(“Tg”)看出,或者通过质子核磁共振(“H-NMR”)方法看出,当通过差示扫描量热计(“DSC”)热方法或通过机械方法分析时,所述Tg为两个单体单独时的Tg的中间值。B嵌段共聚过程中,在适合检测聚苯乙烯基锂端基的波长范围内,由UV可见吸光度检测也能够推测出潜在的嵌段指数。该数值的急剧和明显增加说明了聚苯乙烯基锂链末端的明显增加。该方法中,这种情况仅仅出现在当共轭二烯浓度降低到维持控制分布聚合的临界值以下。此时存在的任何苯乙烯单体将以嵌段的(blocky)形式加成。本领域技术人员利用质子NMR测试的“苯乙烯嵌段指数”定义为聚合物中S单元的比例,所述聚合物在聚合物链上具有两个S最近邻接。苯乙烯嵌段指数是在利用H-1NMR按照下述方法测试两个实验量之后确定的:
首先,通过积分H-1NMR谱图从7.5至6.2ppm的总苯乙烯芳基信号,并将该数值除以5以说明每个苯乙烯芳环上的5个芳族氢,来确定苯乙烯单元的总数(即当求比值时排除任意仪器组)。
第二,通过积分H-1NMR谱图从6.88和6.80至6.2ppm之间的信号最小值那部分的芳基信号,并将该数值除以2以说明每个嵌段的苯乙烯芳环上有2个邻位氢来确定嵌段的苯乙烯单元。对那些苯乙烯单元环上两个邻位氢的信号的说明报道在F.A.Bovey,High Resolution NMRof Macromolecules(Academic Press,New York and London,1972),Chapter 6,所述苯乙烯单元具有两个最近邻接的苯乙烯。
简单地说,苯乙烯嵌段指数就是嵌段的苯乙烯与总的苯乙烯单元的百分比。
嵌段%=100×(嵌段的苯乙烯单元/总苯乙烯单元)
这样表达的聚合物-Bd-S-(S)n-S-Bd-聚合物定义为嵌段的苯乙烯,其中n大于0。例如,如果上述实例中n等于8,那么嵌段指数为80%。优选的是,嵌段指数小于约40。对于苯乙烯含量为10wt%至40wt%的一些聚合物来说,优选的是,嵌段指数小于约10。
在控制所得共聚物的强度和Tg方面,这种控制分布结构非常重要,因为控制分布结构确保了基本上没有两种单体的相分离,即与其中单体实际上保持为单独“微相”的嵌段共聚物相反,所述“微相”具有不同Tg但实际上化学连接在一起。该控制分布结构确保了所述嵌段只有一个Tg,因此所得共聚物的热性能是可以预测的,实际上是可以预先确定的。此外,当具有这种控制分布结构的共聚物作为二嵌段、三嵌段或多嵌段共聚物中的一个嵌段时,通过适当设计的控制分布共聚物区域的存在使之成为可能的较高Tg将往往提高流动性和加工性。某些其它性能的改性也能达到。
在本发明的优选实施方案中,主题控制分布共聚物嵌段具有三个不同的区域,其中富含共轭二烯的区域在嵌段末端,富含单烯基芳烃的区域靠近嵌段中间或中心。所希望的是单烯基芳烃/共轭二烯控制分布共聚物嵌段,其中单烯基芳烃单元的百分比逐渐增加至接近嵌段的中间和中心的最大值,然后逐渐降低直到聚合物嵌段全部聚合。这种结构与现有技术中所描述的递变和/或无规结构不同。
最大程度上利用已知的和以前采用的方法和材料,能够实施阴离子溶液共聚以形成本发明的控制分布共聚物。通常,在作为本发明关键特征的某些分布试剂存在下,利用助剂材料包括聚合引发剂、溶剂、促进剂和结构改性剂的已知选择,实现阴离子性的共聚。在优选实施方案中,该分布试剂是非螯合醚。这种醚化合物的实例是环状醚如四氢呋喃和四氢吡喃,和脂肪族单醚如二乙醚和二丁醚。有时,特别是当共轭二烯的乙烯基含量高于50%时,有必要使用螯合剂,包括乙二醇的二烷基醚和脂肪族聚醚如二乙二醇二甲醚和二乙二醇二乙醚。其它分布试剂包括例如邻二甲氧基苯或“ODMB”,它有时称作螯合剂。优选的醚是脂肪族单醚,更优选的是二乙醚。这种聚合可以间歇、半间歇或连续进行,最优选间歇进行,但是不管怎样,重要的是,在开始共聚之前或同时,在选择的溶剂中存在无规化试剂。
分布试剂的引入抵消了生长链末端将一个单体结合到另一个上的优先权。例如,对于苯乙烯和二烯,优先权应当是针对二烯。这种分布试剂促进了两种单体更有效地“控制分布”共聚,因为活性链末端“看到”一种单体几乎是与“看到”另一种单体一样的容易。因此,聚合方法使每种单体以几乎相同的速率进入到聚合物中。这种方法形成了没有任何一种单体组分“长链(long runs)”的聚合物,即上面定义的控制分布共聚物。在优选方法中,单烯基芳烃单体将在第二等分二烯的缓慢加入完成时几乎消耗完,因此聚合末端富含共轭二烯。整个聚合过程中将形成共轭二烯单体的短嵌段,而且单烯基芳烃单体嵌段仅仅在共轭二烯单体的浓度相当低时才形成。在优选条件下,B嵌段中单烯基芳烃单体的累积百分比在约40%至60%总转化率时达到峰值,但是仅仅超过最终数值约25%至30%。单体比较均匀分布的结果是得到具有单一Tg的产品,该Tg是两个对应均聚物Tg的加权平均值。
如上所述,分布试剂优选非螯合醚。“非螯合”表示,这种醚不与增长的聚合物螯合,也就是说,它们不与由引发剂化合物(例如锂离子)衍生的链末端形成特殊的相互作用。因为本发明中所用的非螯合醚是通过改变整个聚合物料的极性而起作用,因此优选使用较大浓度。当选择优选的二乙醚时,以聚合物料(溶剂和单体)的重量计,优选浓度为约0.5至约10wt%,优选约1至约10wt%,更优选约3至约6wt%。另外,可以使用更高浓度的这种单醚,但是看上去在没有增加效率的情况下反而增加了费用。当分布试剂是ODMB时,基于总反应器内容物,其用量通常为20至400PPMW(百万分之重量份数),对于低乙烯基含量产品来说优选20至40PPMW,对于高乙烯基含量产品来说优选100至200PPMW。
本发明的重要方面是控制在控制分布共聚物嵌段中的共轭二烯的微结构或乙烯基含量。术语“乙烯基含量”是指通过1,2-加成聚合共轭二烯的事实(对于丁二烯来说是这样,对于异戊二烯来说是3,4-加成)。尽管仅仅在1,3-丁二烯的1,2-加成聚合时才形成了纯“乙烯基”,但是异戊二烯的3,4-加成聚合(和其它共轭二烯的类似加成)对嵌段共聚物最终性能的影响是类似的。术语“乙烯基”是指聚合物链上存在侧挂乙烯基。当丁二烯用作共轭二烯时,优选地是,共聚物嵌段中20至80mol%的缩聚丁二烯单元具有根据质子NMR分析测定的1,2-乙烯基构型。对于选择性氢化的嵌段共聚物来说,优选30至70mol%的缩聚丁二烯单元应该具有1,2-构型。对于不饱和的嵌段共聚物来说,优选20至40mol%的缩聚丁二烯单元应该具有1,2-乙烯基构型。这可以通过改变分布试剂的相对含量进行有效地控制。应当可以理解,分布试剂有两种用途:它产生单烯基芳烃和共轭二烯的控制分布,还控制共轭二烯的微结构。分布试剂与锂的合适比例描述并报道于美国专利Re27,145,其公开内容被引入以供参考。
用作聚合载体的溶剂可以是任何不与所形成聚合物的活性阴离子链末端反应的烃,其应在商业化聚合单元中易于处理,并且使产物聚合物具有合适的溶解度特性。例如,通常缺可离子化氢的非极性脂肪族烃是特别合适的溶剂。通常使用的是环状烷烃如环戊烷、环己烷、环庚烷和环辛烷,所有这些都是相对性地非极性。当将温度作为考虑的主要因素之一时,其它合适的溶剂对于本领域技术人员来说也是已知的,并且能够选择以在给定的工艺条件下有效地发挥作用。
制备本发明新型控制分布共聚物的原料包括起始单体。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、和对丁基苯乙烯或它们的混合物。其中,苯乙烯是最优选的,且可从多个制造商那里商购,并且较便宜。本发明所用的共轭二烯是1,3-丁二烯和取代丁二烯如异戊二烯、1,3-戊二烯、2,3-二甲基-1,3-丁二烯和1-苯基-1,3-丁二烯、或它们的混合物。其中,最优选1,3-丁二烯。本文中以及权利要求书中所用的“丁二烯”专门指“1,3-丁二烯”。
对于阴离子共聚反应来说,其它重要的原料包括一种或多种聚合引发剂。本发明中的引发剂包括例如烷基锂化合物和其它有机锂化合物如仲丁基锂、正丁基锂、叔丁基锂、戊基锂等,所述有机锂化合物包括二-引发剂如间二异丙烯基苯的二仲丁基锂加成物。其它这种二-引发剂描述在美国专利6,492,469中。各种聚合引发剂中,优选仲丁基锂。聚合混合物(包括单体和溶剂)中可以使用的引发剂的量是基于每个所需的聚合物链一个引发剂分子计算出来的。锂引发剂工艺是众所周知的,描述在如美国专利4,039,593和Re27,145中,它们的公开内容被引入本文以供参考。
制备本发明新型共聚物的聚合条件通常类似于阴离子聚合中通常使用的那些。本发明中,聚合优选在-30至150℃、更优选10至100℃下进行,并且鉴于工业限制最优选在30至90℃下进行。反应是在惰性气氛优选氮气中进行,并且也可以在0.5至10bar的压力范围内进行。取决于所用温度、单体组分的浓度、聚合物的分子量和分布试剂的含量,该共聚通常少于12小时,并且能够在5分钟至5小时内完成。
如上所述,本发明的重要发现是在控制分布嵌段的聚合过程中,控制单体加料。为了将嵌段指数降低至最小,理想的是在丁二烯的存在下尽可能多地聚合苯乙烯。为此,优选的方法是尽可能快地加入苯乙烯料,同时缓慢加入丁二烯,以尽可能长地将丁二烯的浓度保持在不低于0.1wt%,优选直到苯乙烯接近消耗完。如果丁二烯低于该水平,存在此时将形成苯乙烯嵌段的危险。通常不可取的是,反应的丁二烯加料部分过程中形成了苯乙烯嵌段。
在两个反应器的聚合流程中,最容易完成的是与加入10至60%共轭二烯一起向第二反应器中加入80至100%单烯基芳烃。然后,通过从第一反应器转移活性聚合物,使单体开始聚合。在5至60mol%的单体聚合后,加入剩余部分的单烯基芳烃(如果存在的话),并且以将共轭二烯单体浓度保持在不低于0.1wt%的速率下,加入剩余的共轭二烯单体。加入二烯单体的速率是根据中间嵌段的苯乙烯含量、所用的反应温度以及分布控制剂的类型和浓度决定的。在6%至10%二乙醚存在下,反应速率较快。该体系中,二烯通常在15至60分钟内加完。在0.5%至1%二乙醚或35至40PPM邻二甲氧基苯存在下,两种单体的速率都更慢。在该溶剂体系中,最典型地是在60至90分钟内加完二烯。中间嵌段的苯乙烯含量越高,缓慢加入二烯就越有利。如果以完全顺序方法制备聚合物,那么优选的是确保连续加入丁二烯直到嵌段B1中90%的单体聚合,并且在未反应的单体池(pool)中,单烯基芳烃单体的百分含量降低至低于20wt%,优选低于15wt%。以此方式,在大部分聚合过程中阻止形成苯乙烯嵌段,在聚合结束时就剩下了足够的共轭二烯,确保了B1嵌段的末端区更富含二烯单体。所得聚合物嵌段在接近嵌段的开始和结尾处存在富含二烯的区域,在接近嵌段中心存在富含芳烃的区域。优选方法的产品中,通常嵌段的头15至25%以及最后的75%至85%富含二烯,剩下的部分被认为富含芳烃。术语“富含二烯”意指该区域比中心区域的二烯与芳烃比例明显高。表达这一意思的另一种方法是,单烯基芳烃单元的百分比沿着聚合物链逐渐增加,直到接近嵌段的中间或中心达到最大值,然后逐渐降低直到聚合物嵌段充分聚合。在优选实施方案中,向反应器中加入全部的单烯基芳烃和10至20%的共轭二烯,在约5至约10%的起始单体聚合后,加入剩余的共轭二烯。
如果使用相当高含量的分布控制剂,那么利用上述方法通常能够实现芳烃单体在最终产物中的理想分布。在更高的中间嵌段苯乙烯含量和低含量分布控制剂下,一些嵌段指数是不可避免的。优选通过偶联来制备这些产物。这确保形成的任何嵌段苯乙烯位于与末端嵌段有一定距离的位置。当通过偶联制备本发明聚合物时,优选地是保留5%至10%的二烯单体,并且在芳烃单体聚合完成时立即加入这些物料。这确保了所有的链末端是二烯单元。活性二烯链末端通常更有效地与偶联剂反应。
如果本发明的产物是在单反应器方法中制备的(其中,所有的B1单体被加入到含有活性A嵌段的反应器中),那么优选的是,开始加入芳烃单体之前1分钟开始加入二烯单体。还优选的是,起初快速加入两种单体,然后当大部分芳烃单体加入时降低二烯加入速率。该方法确保了B1嵌段的初始区域富含二烯单体,并形成了足够大的池(pool),避免了在工艺步骤的早期缺乏二烯单体。如上所述,最佳速率取决于中间嵌段的苯乙烯含量、反应温度和所用分布控制剂的类型和浓度。
对于控制分布或B嵌段来说,每个B嵌段中单烯基芳烃的重量百分比为10wt%至75wt%,对于选择性氢化的聚合物来说,优选25wt%至50%。
本文中所用的“热塑性嵌段共聚物”定义为,至少具有一种或多种单烯基芳烃如苯乙烯的第一嵌段和二烯和单烯基芳烃的控制分布共聚物的第二嵌段的嵌段共聚物。这种热塑性嵌段共聚物的制备方法是通过通常所知道的用于嵌段聚合的任何方法。作为实施方案,本发明包括为二嵌段、三嵌段共聚物、四嵌段共聚物或多嵌段组合物的热塑性共聚物组合物。对于二嵌段共聚物组合物来说,一个嵌段是基于烯基芳烃的均聚物嵌段,与它聚合的是二烯和烯基芳烃的控制分布共聚物的第二嵌段。对于三嵌段组合物来说,它包括玻璃化烯基芳烃基均聚物作为末端嵌段,以及二烯和烯基芳烃的控制分布共聚物作为中间嵌段。当制备三嵌段共聚物组合物时,本发明中控制分布的二烯/烯基芳烃共聚物可以称作“B”,而基于烯基芳烃的均聚物称作“A”。A-B-A三嵌段组合物可以通过顺序聚合或偶联来制备。在顺序溶液聚合技术中,首先加入单烯基芳烃制成较硬的芳烃嵌段,随后加入控制分布的二烯/烯基芳烃混合物形成中间嵌段,然后加入单烯基芳烃形成末端嵌段。除了线型A-B-A构型外,嵌段可以构造成形成星形(支化)聚合物、(A-B)nX或两种类型结构的混合物。另外考虑了包括不对称的多模态(polymodal)嵌段共聚物,其中一些A嵌段比一些其它的A嵌段具有更高的分子量,例如这种聚合物具有结构:(A1-B)d-X-e(B-A2),其中d为1至30,e为1至30,A1和A2嵌段的分子量至少相差20%。可以存在一些A-B二嵌段聚合物,但是优选的是至少70wt%的嵌段共聚物是A-B-A或星形(或者其它方式的支链,以使每个分子中具有2或多个末端树脂嵌段)以赋予强度。
星形(支化)聚合物的制备需要称作“偶联”的后聚合步骤。上述星形式子中,n为2至30的整数,优选2至15,X是偶联剂的残留物或残基。本领域已知多种偶联剂,包括如二卤代烷烃、卤化硅、硅氧烷、多官能团环氧化物、氧化硅化合物、一元醇与羧酸的酯(如己二酸二甲酯)和环氧化油。合适的多烯基偶联剂包括二乙烯基苯,优选间二乙烯基苯。优选四烷氧基硅烷如四乙氧基硅烷(TEOS),脂肪族二酯如己二酸二甲酯和己二酸二乙酯,和二缩水甘油基芳族环氧化合物如双酚A和表氯醇反应得到的二缩水甘油醚。
能够用于进一步改变聚合物构型并由此改变它们的性能的其它可能的后聚合处理包括封端和链终止。封端剂如环氧乙烷、二氧化碳或它们的混合物用于在链末端接上官能团,然后该官能团能够用作进一步改变性能反应的反应位。相反,链终止简单地阻止了进一步聚合,因此防止分子量增长超过一期望值。当所有的单体已经聚合时,这通过剩下的活性金属原子的失活,特别是活性碱金属原子的失活,更优选通过活性锂原子的失活来完成。有效的链终止剂包括水,醇如甲醇、乙醇、异丙醇、2-乙基己醇、它们的混合物等,和羧酸如甲酸、乙酸、马来酸、它们的混合物等。参见如美国专利4,788,361,其说明书被引入本文以供参考。现有技术中,使活性或活的金属原子位失活的其它化合物是已知的,并且任何这些已知的化合物都可以使用。或者,活的共聚物可以经过简单地氢化来使金属位失活。
可以在一定固体含量范围内,优选约5至约80wt%的溶剂和单体,更优选约10至约40wt%范围内进行本发明上述聚合方法,所述方法包括制备二烯/烯基芳烃共聚物和由它们制成的二嵌段和多嵌段共聚物。对于高固体聚合来说,优选按照避免超过期望的聚合温度的增量加入如上所述的任何给定单体,包括上述预先制备的均聚物或共聚物。最终三嵌段聚合物的性能很大程度上取决于所得的烯基含量和二烯含量。为了确保具有显著的弹性性能同时理想地保持高Tg和强度性能,以及令人期望的透明性,优选三嵌段和多嵌段聚合物的烯基芳烃含量高于20wt%,优选20至80wt%。这表明,基本上所有的剩余含量是二烯,所述剩余含量是二烯/烯基芳烃嵌段的一部分。
控制各嵌段的分子量也很重要。对于AB二嵌段来说,单烯基芳烃A嵌段的所需嵌段分子量是3,000至60,000,而控制分布共轭二烯/单烯基芳烃B嵌段为30,000至300,000。对于A嵌段的优选范围是5000至45,000,对于B嵌段为50,000至250,000。对于可能为顺序ABA或偶联的(AB)2X嵌段共聚物的三嵌段共聚物来说,A嵌段应当为3,000至60,000,优选5000至45,000,而对于顺序嵌段的B嵌段应当为30,000至300,000,对于偶联的聚合物的B嵌段(2个)为上述值的一半。三嵌段共聚物的总平均分子量应当为40,000至400,000,对于星形共聚物应当为60,000至600,000。对于四嵌段共聚物ABAB来说,末端B嵌段的嵌段大小应当为2,000至40,000,其它嵌段与顺序三嵌段共聚物的类似。通过光散射测量方法最准确地测定这些分子量,并用数均分子量表示。
本发明热塑性弹性二嵌段、三嵌段和四嵌段聚合物的重要特征在于,它们具有至少两个Tg,较低的Tg是控制分布共聚物嵌段的单一Tg,它是组成单体Tg的中间值,其中所述嵌段聚合物包括一种或多种控制分布的二烯/烯基芳烃共聚物嵌段和一种或多种单烯基芳烃嵌段。该Tg优选至少-60℃,更优选-40至+30℃,最优选-40至+10℃。第二Tg是单烯基芳烃“玻璃化”嵌段的Tg,优选+80至+110℃,更优选+80至+105℃。说明嵌段微相分离的两个Tg的存在对多种应用中材料显著的弹性和强度以及易于加工和理想的熔体流动特性有帮助。
应当注意,在本发明又一个实施方案中,本发明组合物的其它性能改进可以通过另一种后聚合处理来达到,即嵌段共聚物的氢化。优选的氢化是最终嵌段共聚物的二烯部分的选择性氢化。另外,B嵌段和A嵌段都可以氢化,或者仅仅部分B嵌段氢化。通常,氢化提高了热稳定性、紫外光稳定性、氧化稳定性,由此提高了最终聚合物的耐候性。本发明的主要优点在于,存在于起始聚合工艺过程中的分布试剂如非螯合一元醚不干涉或者以另外的方式“毒化”氢化催化剂,因此任何附加的除去步骤都是不必要的。
氢化可以通过现有技术已知的几种氢化或选择性氢化方法来进行。例如,这种氢化可以利用如美国专利3,595,942、3,634,549、3,670,054、3,700,633和Re27,145中所教导的方法完成,上述专利公开内容被引入本文以供参考。这些方法用于氢化含有芳族或烯属不饱和度的聚合物,并基于利用合适的催化剂。该催化剂或催化促进剂优选包括第VIII族金属如镍或钴,其与合适的还原剂如烷基铝或选自元素周期表第I-A、II-A和III-B的金属、特别是锂、镁或铝的氢化物组合。在合适溶剂或稀释剂中,在20至80℃下能够完成该反应。其它有用的催化剂包括基于钛的催化剂体系。
可在使得至少90%的共轭二烯双键和0至10%的芳烃双键被还原的条件下进行氢化。优选范围是还原了至少95%的共轭二烯双键,更优选还原了98%的共轭二烯双键。或者,可以氢化聚合物,以使上述芳族不饱和度还原了超过10%。这样的过度氢化通常是在较高温度下达到的。此时,共轭二烯和芳烃的总双键还原了90%或更多。
氢化一完成,优选用较大量含水酸(优选20-30wt%)和聚合物溶液通过搅拌提取催化剂,其中体积比为0.5份含水酸对应1份聚合物溶液。合适的酸包括磷酸、硫酸和有机酸。50℃下连续搅拌30至60分钟,同时喷射氧气和氮气混合物。必须注意,执行这一步骤时要避免形成氧气和烃的爆炸性混合物。
另外,本发明的嵌段共聚物可以用多种方法官能化。一种方法是用具有一个或多个官能团的不饱和单体或它们的衍生物处理,所述官能团或它们的衍生物如羧酸基团和它们的盐、酸酐、酯、酰亚胺基团、酰胺基团和酰氯。接枝到嵌段共聚物上的优选单体是马来酸酐、马来酸、氟马酸、和它们的衍生物。官能化这种嵌段共聚物的更详细描述可以参见Ger gen等的美国专利4,578,429和5,506,299。另一种方法,如美国专利4,882,384所教导的那样,通过将含硅或硼化合物接枝到聚合物上可以官能化本发明的选择性氢化嵌段共聚物。又一种方法中,本发明的嵌段共聚物与烷氧基硅烷化合物接触,形成硅烷改性的嵌段共聚物。再一个方法中,如美国专利4,898,914所教导的那样,将至少一个环氧乙烷分子接枝到聚合物上,或者如美国专利4,970,265所教导的那样,使聚合物与二氧化碳反应,来官能化本发明的嵌段共聚物。此外,如美国专利5,206,300和5,276,101所教导的那样,金属化本发明的嵌段共聚物,其中聚合物与碱金属烷基化物如烷基锂接触。再还有,如美国专利5,516,831所教导的那样,通过在聚合物上接枝磺酸基来官能化本发明的嵌段共聚物。这一段中提到的所有专利都被引入本文以供参考。
所有的聚合以及任何所需的后处理方法的最后一步是整理处理,将最终聚合物从溶剂中取出。本领域技术人员已知多种方法,包括利用蒸气蒸发溶剂,凝聚聚合物接着过滤。最终结果是获得根据其性能用于多种具有挑战性应用的“清洁”嵌段共聚物。这些性能包括例如最终聚合物的应力-应变响应,其表明本发明的组合物对应变具有更刚性的橡胶响应,因此延伸相同的长度需要更大的应力。这是一个非常有用的性能,其允许在给定产品中可以利用更少的材料达到相同的力。弹性性能也改变了,随着伸长的增加模量增加,并减少了橡胶平台区的出现,其中在该平台区需要较大地增加伸长以增加应力。另一个令人惊奇的性能是增加的撕裂强度。在利用通常设计用于加工热塑性聚苯乙烯的设备容易加工的能力方面,本发明的控制分布共聚物具有附加的优点,所述热塑性聚苯乙烯是最众所周知的材料之一并且利用了烯基芳烃聚合物。利用热塑性塑料工业通用的单螺杆或双螺杆技术,通过挤出或注射成型可以实现熔体加工。如果合适,也可以使用溶液或旋转浇注技术。
本发明的聚合物可以用于多种应用中,包括例如模塑制品或挤出制品如玩具、把手、柄、鞋底、管材、体育用品、密封剂、垫圈、和油凝胶(oil gels)。还发现该组合物可以用作聚烯烃、聚酰胺、聚酯和环氧树脂的橡胶增韧剂。当与常规苯乙烯嵌段共聚物相比,提高的弹性使得这些共聚物特别适用于粘合剂,包括压敏粘合剂和热熔粘合剂。
特别令人感兴趣的应用是热塑性膜,它保留了苯乙烯嵌段共聚物的加工性,而且具有与弹力聚氨酯相类似的较高“弹力”。当与聚乙烯复合,或与粘性树脂和聚乙烯的混合物复合时,本发明的控制分布共聚物能够满足这些性能期望。与常规苯乙烯/乙烯-丁烯嵌段共聚物相比,所得膜在耐刺穿和强度方面明显提高,并降低了粘度。同样的控制分布苯乙烯/丁二烯共聚物(20/80wt/wt)还可以与油和聚苯乙烯配制成膜复合物,其中当与基于苯乙烯/乙烯-丁烯/苯乙烯嵌段共聚物的对比配方相比,它具有更高的强度并提高了能量恢复性和透明性。在用油和聚丙烯配制的模塑应用中,降低的粘度和摩擦系数也使应用如管帽密封具有膨胀性,所述管帽密封也可以不用使内容物起霜和污染的不受欢迎的滑爽剂制成。
最后,本发明的共聚物也可以与不反面影响共聚物性能的其它组分复合。可以用作其它组分的示范性材料包括但不限于颜料、抗氧剂、稳定剂、表面活性剂、蜡、流动促进剂、溶剂、微粒、和为提高组合物加工性和料粒加工的材料。
下面的实施例仅仅希望作为说明,不想也不应当以任何方式解释为对本发明范围的限制。
说明性实施方案I
在说明性实施方案I中,根据本发明所要求保护的方法制备了本发明的多种控制分布的共聚物。所有的聚合物都是选择性氢化的ABA嵌段共聚物,其中A嵌段是聚苯乙烯嵌段,B嵌段在氢化之前是苯乙烯/丁二烯控制分布的嵌段共聚物,它具有富含丁二烯单元的末端区和富含苯乙烯单元的中心区。在标准条件下氢化聚合物,以使B嵌段中95%以上的二烯双键被还原。
下面描述在二乙醚(DEE)存在下,在1,3-丁二烯(Bd)和苯乙烯(S)的阴离子共聚中,用于有效控制共聚单体分布的一般方法。在环己烷中逐步合成了大量三嵌段共聚物。利用DEE控制橡胶中间嵌段中的苯乙烯和丁二烯共聚分布。共聚过程中,随着反应进行收集了多个样品,以进行共聚单体分布程度的H-NMR表征。
步骤I中,30℃下,将合适量的聚合级环己烷加入到充分混合的227L不锈钢反应容器中。用氮气控制反应容器中的压力。30℃下向反应器中加入苯乙烯单体。向反应器中加入10mL增量的仲丁基锂(12wt%)来滴定环己烷和苯乙烯单体混合物。用在线比色计确定滴定终点。滴定后,向反应器中加入仲丁基锂来引发活性聚苯乙烯嵌段的阴离子聚合。使温度增加至55℃,并继续反应至99.9%苯乙烯转化率。这完成了该嵌段共聚物的第一苯乙烯嵌段,即(S)-。
步骤II中,30℃下,将合适量的聚合级环己烷加入到充分混合的492L不锈钢反应容器中。首先,向反应器中加入步骤II反应中所需要的全部苯乙烯单体。其次,向反应器中加入步骤II反应中所需要的一半丁二烯单体。第三,向反应器中加入合适量的DEE。第四,向反应器中加入10mL增量的仲丁基锂(12wt%)来滴定环己烷、苯乙烯单体、丁二烯单体和二乙醚混合物。用在线比色计确定滴定终点。步骤II的反应物滴定后,30℃下,通过氮气压力将活性聚苯乙烯链从步骤I的反应容器转移至步骤II的反应容器,来引发苯乙烯和丁二烯在步骤II中的共聚反应。引发共聚10分钟后,以保持整个聚合速率几乎恒定的速率,向步骤II的反应器中加入剩下的一半丁二烯单体。使温度升高至55℃,继续反应至基于丁二烯动力学达到99.9%转化率。这完成了苯乙烯-丁二烯无规化中间嵌段加成到步骤I的聚苯乙烯嵌段上。此时聚合物的结构为(S)-(S/Bd)-。
步骤III中,55℃下,向步骤II的反应容器中加入更多的苯乙烯单体以与活性(S)-(S/Bd)-聚合物链反应。步骤III的反应保持在接近等温条件下直至达到99.9%的苯乙烯转化率。向最终反应溶液中加入合适量(过量约10mol%)的高纯度甲醇来终止活性聚合物链。最终的聚合物结构为(S)-(S/Bd)-(S)。然后选择性氢化所有聚合物生成线型ABA嵌段共聚物,其中A嵌段是聚苯乙烯嵌段,氢化之前的B嵌段是苯乙烯丁二烯控制分布的嵌段,它具有富含丁二烯单元的末端区和富含苯乙烯单元的中心区。下面表1表示了多种聚合物。步骤I MW是第一A嵌段的分子量,步骤II MW是AB嵌段的分子量,步骤III MW是ABA嵌段的分子量。氢化聚合物,使约95%以上的二烯双键被还原。
在一系列改变苯乙烯-丁二烯中间嵌段组成的基础上进行该实验19次。对19个实验的分析结果(聚合物1至15和24至27)在表1和表1a中示出。头8个实验的聚合条件在表2中示出。其它11个聚合物的聚合条件与头8个类似。表3示出了各种聚合物的聚合物结构。聚合物28是选择性氢化的AB二嵌段共聚物。其中,聚苯乙烯A嵌段是首先聚合的,接着是要求聚合控制分布苯乙烯/丁二烯B嵌段,再接着是二烯双键的氢化。
下面描述用于表征聚合物中间或“B”嵌段的方法。聚合的本性就是在起始的苯乙烯嵌段后形成聚合物中间嵌段。由于在步骤II中形成的聚合物的中间嵌段不能单独分析,因此它必须与步骤I的苯乙烯嵌段一起分析,必须从总数中减去步骤I的苯乙烯嵌段份额来确定表征聚合物中间嵌段的参数。利用四个实验量来计算聚合物中间嵌段中的苯乙烯百分含量(Mid PSC)和聚合物中间嵌段的嵌段苯乙烯百分含量(MidBlocky)。(注意:中间嵌段的%BD12是直接测量的,不需要校正步骤I的苯乙烯嵌段中的BD份额)。用聚合物实施例15说明实验量和计算方法。对于聚合物实施例15来说,四个关键的实验量为:
GPC步骤I MW:9.0k
GPC步骤II MW:86.8k
NMR步骤II PSC:33.4wt%
NMR步骤II嵌段苯乙烯:33%
其中,步骤I由步骤I的苯乙烯嵌段组成,而步骤II是步骤I的苯乙烯嵌段和苯乙烯/丁二烯中间嵌段的混合物。
步骤II的总苯乙烯量为:
86.8k×33.4wt%=29.0k步骤II的苯乙烯。
中间嵌段的苯乙烯量为从步骤II的苯乙烯中减去步骤I的苯乙烯量得出:
29.0k-9.0k=20.0k中间嵌段的苯乙烯。
中间嵌段的质量为从步骤II的MW中减去步骤I的MW得出:
86.8k-9.0k=77.8k中间嵌段的质量。
“Mid PSC”是中间嵌段苯乙烯相对于中间嵌段质量的百分比:100×20.0k中间嵌段苯乙烯/77.8k中间嵌段质量=25.7wt%。
由嵌段苯乙烯%和步骤I I的苯乙烯质量得出嵌段苯乙烯的质量:33%×29.0k=9.6k步骤II的嵌段苯乙烯。
从步骤II的嵌段苯乙烯质量中减去步骤I的苯乙烯嵌段得出中间嵌段中的嵌段苯乙烯质量:
9.6k步骤II的嵌段苯乙烯-9.0k的步骤I苯乙烯嵌段=0.6k。
“Mid Blocky”是中间嵌段中的嵌段苯乙烯相对于中间嵌段中的苯乙烯的百分比:
100×0.6k中间嵌段的嵌段苯乙烯/20.0k中间嵌段的苯乙烯=3%。
表1a示出了该说明性实施方案所描述的所有聚合物的B中间嵌段中苯乙烯嵌段指数的计算值(“Mid Blocky”)。还示出了每个B中间嵌段中计算的苯乙烯百分含量(“计算的Mid PSC”)。
图1、2和3描述了该实施方案中制备的3个聚合物的Bd/S嵌段中的单体分布。在步骤II的S-S/Bd-S嵌段的制备过程中,即嵌段共聚物制备方法中丁二烯和苯乙烯部分的控制分布共聚过程中,通过在不同时间取出活性聚合溶液的等分试样得出这些附图中的数据。利用H-NMR技术测试这些等分试样中每个的聚丁二烯和聚苯乙烯组成。通过从等分试样的累积聚苯乙烯含量中减去步骤I的聚苯乙烯嵌段中的聚苯乙烯组分来调整这些“原始数据”。对于每个等分试样来说,差值是步骤II嵌段的聚苯乙烯组分。将聚丁二烯含量与聚苯乙烯含量的摩尔比(用该方法计算的)对每个实验中的每个等分试样的转化率作图。对于每个等分试样来说,步骤II嵌段的分子量是从等分试样的分子量中减去步骤I嵌段的分子量得出的。最终等分试样的步骤II嵌段的分子量被认为是该区域(100%转化率)的总分子量。每个等分试样的转化率是通过该等分试样的步骤II的分子量与聚合的最终步骤II的等分试样的分子量之比来计算的。
这些图清楚地说明了本发明的有益效果。所有情况下,控制分布聚合都是从较高比例的丁二烯与苯乙烯混合比(富含丁二烯)开始和结束的。显然,在步骤II区域的两个末端都没有聚苯乙烯链,因此仅仅通过步骤I和步骤III苯乙烯加料的多少以及这些聚合步骤中活性链末端的数目,就能够控制末端嵌段的分子量。步骤I和步骤III聚苯乙烯嵌段的大小都不会由于步骤II开始或结束时加入聚苯乙烯而增大。
重要的是注意,根据H-NMR的分析,尽管在每次聚合中,步骤II区域的中心部分苯乙烯更多(具有更低的Bd/S比),但是在该阶段的聚合过程中,仍然只有少量(如果有的话)结合到聚合物链上的苯乙烯多重谱线(<10mol%的苯乙烯)。尽管苯乙烯与丁二烯的相对引入速率在这部分聚合过程(步骤II聚合的40%至60%转化率)中增加,但是仍然观察到苯乙烯单体控制分布地引入到聚合物链上。对于在选择性氢化的S-S/Bd-S(还已知作为S-S/E/B-S或苯乙烯-苯乙烯/乙烯/丁二烯-苯乙烯)嵌段共聚物中,实现所需的更刚性的拉伸性能来说,这些共聚反应中苯乙烯的这种控制分布引入是必要的。
说明性实施方案II
在说明性实施方案II中,将本发明的各种聚合物与现有技术中的聚合物进行了比较。所有聚合物都是用苯乙烯和丁二烯单体制成的线型选择性氢化的ABA嵌段共聚物,并且每个A末端嵌段的公称或目标分子量为10,000,B中间嵌段的分子量为80,000。该实施例利用了说明性实施方案I中的聚合物2和3。聚合物C-1和C-2是用于比较的,在B中间嵌段中不含有任何苯乙烯。C-1具有更高的乙烯基1,2含量,为68%,而C-2的乙烯基1,2含量为38%。用B中间嵌段中约23wt%苯乙烯制备了聚合物C-3。聚合物C-3是用常规聚合方法制备的,其中中间嵌段是利用螯合剂通过共聚丁二烯和苯乙烯制备的,而不是控制加入丁二烯和苯乙烯单体。此外,所有的丁二烯和苯乙烯都是在中间嵌段聚合开始的时候与微结构改性剂(1,2-二乙氧基丙烷)一起加入到反应器中。因此,聚合物C-3不具有“控制分布”的结构。关于嵌段分子量和乙烯基1,2含量的细节在表4中示出。
用聚合物制备了膜并根据ASTM D412测试了拉伸性能,结果表示在表5中。本发明的目的之一是制备比聚合物C-2具有更刚性的弹性响应的聚合物,其中聚合物C-2是现有技术众所周知的聚合物。本发明的目的是增加在伸长率超过100%时的橡胶刚性,由此增加弹力,同时有限增加杨氏模量和无限小伸长时的刚性。增加杨氏模量损害了弹性性能,因为它预示着增加了塑性。如聚合物C-1所示,在不是将苯乙烯控制加成到嵌段B上的情况下,增加乙烯基含量在低和高伸长率下降低了刚性,如图4所示。表5定量表示了,增加乙烯基含量既降低了杨氏模量、无限小伸长时的刚性,又降低了橡胶模量、在100至300%的更高伸长时的橡胶刚性。然而如图4和表5所示,在控制分布中向中间嵌段中加入苯乙烯增加了橡胶刚性,少量增加了杨氏模量。聚合物C-3说明了在B中间嵌段中控制苯乙烯分布的重要性。尽管与聚合物3的组成类似,但是与现有技术中的标准C-2相比,其橡胶模量没有增加,而其杨氏模量明显增加,因此它既表现了更低的弹力又表现了更大的塑性。表5中,500%时的模量也说明了这一响应。如图4和图5中的500%模量所示,本发明聚合物2和3具有更刚性的弹性行为。
说明性实施方案III
说明性实施方案III中,在二乙醚(DEE)、二正丁基醚(nBE)或邻二甲氧基苯(ODMB)存在下,在1,3-丁二烯(Bd)和苯乙烯(S)阴离子聚合过程中,采用说明性实施方案I的一般方法有效地控制苯乙烯分布,同时保持足够低的乙烯基含量以制备有用的不饱和产物。用四乙氧基硅烷(TEOS)偶联活性S-S/BdLi二嵌段合成了多个(S-S/Bd)nX线型/星形嵌段共聚物的混合物。有些时候,随着共聚反应的进行收集几个样品,以H-NMR表征单体的分布。对应于特定反应的工艺数据归纳在表6中。
步骤II中,利用多种分布试剂代替DEE。剩余苯乙烯聚合后约10分钟内发生,聚合阴离子或者如上所述进行偶联,或者加入少量丁二烯(1-2kg)封端。如期望的那样,加入丁二烯后,来自比色计的信号急剧下降,说明链末端转变为聚丁二烯基锂。这完成了苯乙烯-丁二烯无规化中间链段加成到步骤I的聚苯乙烯嵌段上。随着远离步骤I的嵌段,该链段含有的苯乙烯更多,直至形成短末端丁二烯嵌段。
用四乙氧基硅烷偶联制成了最终产物。每摩尔聚合物阴离子加入约0.4至0.5摩尔硅烷。在这样的条件下,尽管也形成了约10%至30%的三臂星形聚合物,但是绝大部分的偶联物是线型产物。通常,用丁二烯封端提高了偶联效率,所述偶联效率定义为根据GPC面积确定的偶联物与偶联物加上二嵌段的比值。这些实施例中达到了高于90%的偶联效率。向最终反应器溶液中加入合适量的高纯度甲醇终止了所有的活性聚合物链。如果由于递变(tapering)在共聚结束时形成了短的苯乙烯嵌段,则该方法确保了它将位于中间嵌段链段的中心区。表7示出了该实施例中制备的多种不饱和嵌段共聚物。
如表7中的聚合物21所示,该普通方法还能够制备高中间嵌段苯乙烯/高乙烯基聚合物,除了二乙醚浓度增加到6wt%,并且增加丁二烯加入速率以反映出在更高醚含量下反应速率更快之外,基本上与上述方法相同制备该聚合物21。为了确保适当过量丁二烯,在开始的几分钟,丁二烯的加入速率约0.24kg/min,随后降低速率。平均加料速率约0.2kg/min。
表7和1a列出了不饱和聚合物(不饱和聚合物是聚合物16至23)的多个分析结果。嵌段I MW是用1000作单位表示的第一A或聚苯乙烯嵌段的分子量,嵌段II MW是以1000作单位表示的B或控制分布嵌段的累积分子量,而嵌段III MW是以1000作单位表示的最后A或聚苯乙烯嵌段的分子量。对于步骤II MW,第一个数值是1,3-丁二烯部分,第二个数值是苯乙烯部分。例如,聚合物16中的B嵌段中,丁二烯分子量为85,000,苯乙烯分子量为31,000,总分子量为116,000。中间嵌段中,苯乙烯重量百分比约26%。与整个聚合物和中间嵌段中的苯乙烯百分含量一起给出1,2-乙烯基构型。例如,对于聚合物16,整个聚合物含有约42wt%苯乙烯,中间嵌段含有约26wt%苯乙烯(表1a中的“计算Mid PSC”)。对每个聚合物都给出了偶联效率(或CE)。计算出每个聚合物的苯乙烯嵌段指数,并表示在表1a(“计算的Mid Blocky”)。最后,给出一些聚合物的熔体流动速率。
说明性实施方案IV
该实施例中,将一种控制分布的嵌段共聚物(聚合物17)与市售样品BX6105进行了比较,后者是来自BASF的不饱和SBS嵌段共聚物,具有无规的苯乙烯/丁二烯中间嵌段。聚合物17是根据本发明用控制分布的苯乙烯/丁二烯中间嵌段制成的。如表8所示,这两种聚合物具有类似的总苯乙烯含量。如表8所示,聚合物17具有提高的在200℃/5kg条件下测试的熔体流动速率。分别对Styroflex和聚合物17采用熔融温度/注射压力为204℃/1000psi(6.9MPa)和190℃/800psi(5.5MPa)的条件,对注射模塑小片测试硬度和浊度。聚合物17比Styroflex具有低约20个点的肖氏A硬度和低57%的浊度。对在175℃和1250psi(8.6MPa)下压制的模压成型小片测试机械性能。虽然拉伸强度几乎相同,但是聚合物17具有更高的断裂伸长率。如在25%至500%之间恒定的较低模量所示,聚合物17比Styroflex更柔顺。在循环载荷条件下,聚合物17具有更高的弹性,因为它以为Styroflex的一半的永久变形恢复了为其两倍的能量。
图5说明了本发明弹性体的有益效果。与具有更高的初始力的塑性材料相反,弹性体通常以低变形如低于25%伸长下的低初始力为特征。与Styroflex相比,控制分布聚合物17在低伸长下明显具有低得多的力,其中所述Styroflex是现有技术中具有类似总苯乙烯含量的无规化中间嵌段聚合物的典型聚合物。低伸长下的刚性通常用拉伸模量或杨氏模量表征,所述拉伸模量或杨氏模量是无限小拉伸下的应力-应变曲线的斜率。例如,聚合物17的杨氏模量仅为1,400psi(10MPa),而Styroflex的为5,000psi(35MPa)。对于100至300%伸长率间的橡胶模量或斜率,聚合物17的比Styroflex的稍高,分别为94psi(0.65MPa)和90psi(0.62MPa)。因此,控制分布聚合物在高的伸长率下保持了刚性拉伸,而无规聚合物的高拉伸强度在低拉伸率下增加了更高弹性行为的效果。参见表10,它也示出了各个聚合物的B中间嵌段的玻璃化转变温度(Tg)。聚合物19*和20*的Tg是在氢化后测试的。
说明性实施方案V
该实施例中,将为与尼龙6,6(Zytel 101)混合物形式的两种不同的控制分布嵌段共聚物(15和15FG)与KRATON GF-1901进行了比较,其中所述混合物是在双螺杆挤出机中混合了15和20wt%的尼龙6,6。聚合物15FG是在Berstorff双螺杆挤出机中,通过马来酸化聚合物15至结合的马来酸酐含量为1.7wt%的方法制备的。KRATON FG1901是被马来酸化至类似1.7wt%含量的S-EB-S嵌段共聚物。将混合物注射成型,并利用悬臂梁冲击实验机测试冲击强度。从模具的封闭端和入口端提取样品以最小化成型作用。
如图9所示,马来酸酐的加入大大提高了聚合物15FG增韧尼龙6,6的能力。与可得材料相比,马来酸化聚合物15FG提供的韧性越大,达到相同韧性所需要的改性剂越少。
表1:控制分布聚合物
其中,“MW(k)”是以千为单位的真正的分子量,“1,2-BD,%”是聚合物丁二烯部分的乙烯基含量,“PSC%”是最终聚合物中的苯乙烯wt%。分子量是链段的累积分子量,步骤II MW是步骤I和步骤II的链段MW,步骤III MW是三嵌段共聚物的最终MW。
表1a:步骤II结束时聚合物的NMR结果
表2:S/B中间嵌段共聚物的聚合条件
表3:A1-B-A2聚合物的聚合物结构
表4:A1-B-A2聚合物的聚合物结构
*在这三个聚合物合成后没有测量实际嵌段大小,并且仅仅给出了目标嵌段分子量。
表5:拉伸性能
表6:低乙烯基S/Bd中间嵌段共聚物的聚合条件
表7:不饱和S/Bd中间嵌段聚合物的分析结果
表8:
聚合物17 | Styroflex BX6105 | |
PSC(%) | 63 | 66 |
MFR(g/10min) | 17.7 | 10.5 |
肖氏A硬度(10s) | 62 | 84 |
浊度(%) | 21.8 | 51.3 |
拉伸性能 | ||
TS(psi) | 4298 | 4338 |
伸长率(%) | 950 | 734 |
25%的模量(psi) | 152 | 429 |
50%的模量(psi) | 203 | 465 |
100%的模量(psi) | 255 | 524 |
200%的模量(psi) | 366 | 760 |
300%的模量(psi) | 517 | 1122 |
500%的模量(psi) | 917 | 2125 |
150%滞后效应 | ||
恢复的能量(%) | 59.1 | 30.7 |
永久变形(%) | 18.9 | 38.9 |
表9
表10
聚合物 | 杨氏模量(MPa) | 橡胶模量(MPa) | 中间嵌段的Tg |
2 | 4.7 | 0.54 | -31.3 |
3 | 5.8 | 0.67 | -22.7 |
5 | -12.6 | ||
C-1 | 2.3 | 0.32 | -31.8 |
C-2 | 4.4 | 0.45 | -37.4 |
C-3 | 7.7 | 0.37 | |
17 | 10 | 0.65 | +4.6 |
Styroflex | 35 | 0.62 | |
19 | +26 |
19* | +11.5 | ||
20* | +20.3 |
Claims (20)
1.一种嵌段共聚物,它在氢化之前具有至少一个聚合物嵌段A和至少一个聚合物嵌段B,其中:
a.每个A嵌段独立地为单烯基芳烃均聚物嵌段,每个B嵌段独立地为至少一种共轭二烯和至少一种单烯基芳烃的控制分布共聚物嵌段;
b.每个A嵌段的数均分子量为3,000至60,000,每个B嵌段的数均分子量为30,000至300,000;
c.每个B嵌段包括邻近A嵌段的末端区域和不邻近A嵌段的一个或多个区域,其中邻近A嵌段的末端区域富含共轭二烯单元,不邻近A嵌段的一个或多个区域富含单烯基芳烃单元,且嵌段的头15-25%以及最后的75-85%被认为富含二烯,剩下的部分被认为富含芳烃;
d.嵌段共聚物中单烯基芳烃的总量为20wt%至80wt%;和
e.每个B嵌段中单烯基芳烃的重量百分比为10%至75%;
其中所述嵌段共聚物具有一般构型A-B-A,(A-B)n,(A-B)n-A,(A-B-A)nX或(A-B)nX,其中n为2至30的整数,X是偶联剂残基。
2.根据权利要求1的嵌段共聚物,其中所述单烯基芳烃是苯乙烯,所述共轭二烯选自异戊二烯和丁二烯。
3.根据权利要求1或2的嵌段共聚物,其中所述共轭二烯是丁二烯,和其中嵌段B中20至80mol%的丁二烯单元具有1,2-构型。
4.根据权利要求1或2的嵌段共聚物,其中嵌段B的苯乙烯嵌段指数小于40%,所述苯乙烯嵌段指数是在聚合物链上具有两个苯乙烯单元邻接的嵌段B中苯乙烯单元的比例。
5.根据权利要求4的嵌段共聚物,其中B嵌段中的苯乙烯单元重量百分含量为10wt%至40wt%,嵌段B的苯乙烯嵌段指数低于10%。
6.根据权利要求1或2的嵌段共聚物,其中嵌段共聚物被部分、选择性或全部氢化。
7.根据权利要求6的嵌段共聚物,其中氢化后,0至10%的芳烃双键被还原,和至少90%的共轭二烯双键被还原。
8.根据权利要求1或2的嵌段共聚物,还包括至少一种C嵌段,其中每个C嵌段是一种或多种共轭二烯的聚合物嵌段,其数均分子量为2,000至200,000。
9.根据权利要求1或2的嵌段共聚物,其上接枝了酸化合物或它的衍生物,和/或其已与含硅或含硼化合物反应,与至少一个环氧乙烷分子反应,与至少一个二氧化碳分子反应,和/或它用碱金属烷基化物金属化。
10.根据权利要求1或2的嵌段共聚物,其中所述A嵌段的玻璃化转变温度为+80℃至+110℃,所述B嵌段的玻璃化转变温度为高于-60℃至低于所述A嵌段的玻璃化转变温度。
11.根据权利要求1或2的嵌段共聚物,其在低于25%伸长率下的杨氏模量为低于20MPa,在100至300%伸长率下的橡胶模量为大于0.5MPa。
12.一种制备权利要求1至11中任一项的嵌段共聚物的方法,包括下述步骤:
a.在惰性烃溶剂和有机锂引发剂存在下,在第一反应器中聚合单烯基芳烃,从而形成了用锂离子封端的活性聚合物嵌段A1;
b.向第二反应器中加入惰性烃溶剂、80至100mol%共聚物嵌段B1中所需要的单烯基芳烃单体、30至60mol%共聚物嵌段B1中所需要的共轭二烯单体和有效量的分布试剂;
c.将活性均聚物嵌段A1转移到第二反应器中并开始聚合步骤b中加入的单烯基芳烃单体和共轭二烯单体;和
d.在10至60mol%步骤c的单体已聚合后,以保持共轭二烯单体的浓度不低于0.1wt%的速率,向第二反应器中连续加入剩余量的共轭二烯单体和单烯基芳烃,直至嵌段B1中90mol%的单体已被聚合,由此形成了活性嵌段共聚物A1B1。
13.根据权利要求12的方法,其中步骤b中,向反应器中加入了100%的单烯基芳烃单体和50%的共轭二烯单体。
14.根据权利要求12或13的方法,包括向第二反应器中加入附加的单烯基芳烃单体,从而形成活性嵌段共聚物A1B1A2的附加步骤,其中A1嵌段和A2嵌段的数均分子量均为3,000至60,000,B1嵌段的数均分子量为30,000至300,000,该方法还包括使所述活性嵌段共聚物A1B1A2与封端剂接触以形成封端的共聚物的任选步骤。
15.根据权利要求12或13的方法,包括使活性嵌段共聚物A1B1与偶联剂接触以形成嵌段共聚物(A1B1)nX的附加步骤,其中n为2至30的整数,X是偶联剂残基。
16.一种制备权利要求1至11中任一项的嵌段共聚物的方法,包括下述步骤:
a.在惰性烃溶剂和有机锂引发剂存在下,在一个反应器中聚合单烯基芳烃,从而形成了用锂离子封端的活性聚合物嵌段A1;
b.在步骤a的聚合完成之前,向反应器中加入共聚物嵌段B1所需要的40至60mol%的共轭二烯单体的一等分试样和分布试剂,并继续单烯基芳烃单体和共轭二烯单体的聚合;
c.在步骤b中的20至60mol%的单体已聚合后,以保持共轭二烯的浓度不低于0.1wt%的速率,向反应器中逐渐加入剩余量的共轭二烯单体和单烯基芳烃单体,直至嵌段B1中90mol%的单体已被聚合,由此形成了活性嵌段共聚物A1B1;和
d.向反应器中加入附加的单烯基芳烃单体,从而形成了活性共聚物A1B1A2,其中A1嵌段和A2嵌段的数均分子量均为3,000至60,000,B1嵌段的数均分子量为30,000至300,000,并且包括使所述活性嵌段共聚物A1B1A2与封端剂接触以形成封端的共聚物的任选步骤。
17.根据权利要求12的方法,其中所述嵌段共聚物被氢化。
18.根据权利要求12的方法,其中所述分布试剂选自环状醚和脂肪族单醚。
19.根据权利要求18的方法,其中所述脂肪族单醚是二乙醚。
20.权利要求1至11中任一项的嵌段共聚物在模塑制品或挤出制品中、作为橡胶增韧剂或在粘合剂中的应用。
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