CN1643102A - 来自受控分布嵌段共聚物的粘合剂 - Google Patents

来自受控分布嵌段共聚物的粘合剂 Download PDF

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CN1643102A
CN1643102A CNA038074834A CN03807483A CN1643102A CN 1643102 A CN1643102 A CN 1643102A CN A038074834 A CNA038074834 A CN A038074834A CN 03807483 A CN03807483 A CN 03807483A CN 1643102 A CN1643102 A CN 1643102A
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D·L·小汉德林
C·L·威利斯
D·J·圣克莱尔
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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粘合剂和密封剂，和涉及这样嵌段共聚物与其它聚合物的共混物。嵌段共聚物被选择性氢化和具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。嵌段共聚物可以与增粘树脂，油和其它组分结合以形成本发明的粘合剂和密封剂。

Description

来自受控分布嵌段共聚物的粘合剂
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粘合剂和密封剂。
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。这些聚合物接着可以氢化以形成更稳定的嵌段共聚物，如在U.S.Pat.3595942和U.S.Re.27145中描述的那些。这样的聚合物宽广地称为苯乙烯类嵌段共聚物或SBC。
SBC长期以来用作粘合剂、密封剂和凝胶。例如，U.S.Pat.No.3239478(“Harlan”)公开了在粘合剂和密封剂中包括不饱和SIS和SBS聚合物的粘合剂。Harlan也广泛地公开了包括氢化S-B-S和S-I-S嵌段共聚物与增粘树脂和填充油用于各种粘合剂和密封剂的粘合剂，包括压敏粘合剂。在本领域已知的是与SBC橡胶链段相容的树脂在压敏粘合剂中引起粘性的发展。迄今为止，不可能制备SBC，其中橡胶链段的相容性特性可以由聚合物制造商控制。因此，树脂制造商已做了很多的工作以开发适合与不同类型SBC的每一种有最佳相容性的新树脂。例如，脂族树脂具有与SIS和SEBS类型SBC的良好相容性，但不与SBS类型具有良好相容性。已经开发新的脂族/芳族树脂，它具有与SBS类型SBC的良好相容性。本发明包括新类型的SBC’s，其中聚合物制造商可变化橡胶链段的相容性特性。
在文献中也已知不饱和SBS和SIS聚合物易于接受在热熔粘合剂和密封剂的加工期间发生的氧化降解和氢化的类似物在热熔体加工期间具有好得多的耐降解性。氢化SEBS和SEPS SBC中的橡胶链段比不饱和SBS和SIS聚合物中的橡胶链段有更高度缠结。因此，在恒定聚合物含量的配制剂中，基于氢化SBC的PSA一般比基于未氢化SBC的PSA具有更差的粘性。理想的是使用氢化和未氢化SBC的共混物以得到熔体稳定性和粘性的最好平衡。然而，由于相容性的差异，基于SEBS和SIS聚合物的共混物的粘合剂例如是不相容的。通常基于这些共混物的粘合剂初始是模糊的和在静置时相分离。基于这些共混物的粘合剂膜缺乏基于相容粘合剂的粘合剂高光泽和通常这些粘合剂的性能差。
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”。制备这样聚合物的方法详细描述于上述专利申请中。专利权人发现这些新聚合物的树脂相容性的确不同于常规的氢化SBC，它允许树脂制造商开发与这些新颖SBC相容的新树脂的机会。专利权人也发现可以通过使用不饱和SBC，特别是某些SIS聚合物，与这些新聚合物的共混物制备相稳定的清晰的粘合剂。这允许配制商开发热熔PSA，该热熔PSA具有对于氢化SBC发现的良好熔体稳定性但更好的粘性。
发明概述
在本发明的一个方面，我们发现一种新粘合剂组合物，该组合物包括100重量份至少一种具有单烯基芳烃和共轭二烯烃受控分布嵌段的氢化嵌段共聚物，25-300重量份至少一种增粘树脂，和0-200重量份填充油，其中该氢化嵌段共聚物含有至少一个聚合物嵌段A和至少一个聚合物嵌段B，和其中(a.)在氢化之前，每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地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.)在氢化之后已减少0-10％的芳烃双键，和已减少至少90％的共轭二烯烃双键；(c.)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000；(d.)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邻近A嵌段、富含单烯基芳烃单元的区域；(e.)氢化嵌段共聚物中单烯基芳烃的总数量是20-80wt％；和(f.)每个B嵌段中单烯基芳烃的重量百分比是10-75％。嵌段共聚物的通用构型是A-B、A-B-A、(A-B)n、(A-B)n-A、(A-B-A)nX或(A-B)nX，其中n是2-30，优选2-15，更优选2-6的整数，和X是偶合剂残基。本发明的粘合剂组合物包括热熔粘合剂、压敏粘合剂、溶剂基粘合剂等。
在本发明的另一方面，我们已表明可以采用与某些SIS类型SBC共混的受控分布嵌段共聚物，制备清晰的相稳定的粘合剂组合物。此粘合剂组合物包括100重量份受控分布嵌段共聚物，25-300重量份苯乙烯/异戊二烯未氢化嵌段共聚物，50-400重量份增粘树脂，和0-200重量份聚合物填充油。新颖聚合物可以加入到基于SIS聚合物的粘合剂中以改进稳定性或可以在基于新颖聚合物的粘合剂中包括SIS聚合物以改进粘性。
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(在此称为“受控分布”聚合，即导致“受控分布”结构的聚合)的某些特性分布，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仅仅单一玻璃化转变温度(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度如下：
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。
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和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。
在本发明的优选实施方案中，主题的受控分布共聚物嵌段含有三个不同的区域-在嵌段端部的共轭二烯烃富集区域和靠近嵌段中间或中心的单烯基芳烃富集区域。希望的是单烯基芳烃/共轭二烯烃受控分布共聚物嵌段，其中单烯基芳烃单元的比例逐渐增加到靠近嵌段中间或中心的最大值和然后逐渐降低，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。
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”具体地指“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B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，及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，该区域具有可测量地较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。对于受控分布嵌段B，单烯基芳烃的重量百分比是约10％-约75。
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第一嵌段及二烯烃和单烯基芳烃受控分布共聚物的第二嵌段。制备此热塑性嵌段共聚物的方法是通过对于嵌段聚合一般已知的任何方法。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。除线性的A-B-A构型以外，可以构造嵌段以形成星形(支化)聚合物(A-B)nX，或可以在混合物中结合两种类型的结构。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个或更多末端树脂状嵌段)以赋予强度。
也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。
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)聚合的共轭二烯烃。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30-70mol％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是它的组成单体Tg的中间。这样的Tg优选是至少-60℃，更优选-40～+30℃，和更优选-40～+10℃。第二Tg，即单烯基芳烃“玻璃性”嵌段的Tg优选大于80℃，更优选80-110℃。两个Tg的存在说明嵌段的微相分离，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。
选择性氢化嵌段共聚物。氢化可以通过现有技术已知的任何氢化或选择性氢化工艺进行。例如，已经使用方法如在如下文献中教导的那些完成这样的氢化：例如，U.S.专利3494942、3634594、3670054、3700633、和Re.27145。氢化可以在一定的条件下进行使得已减少至少90％的共轭二烯烃双键，和已减少0-10％的芳烃双键。优选的范围是减少至少95％的共轭二烯烃双键，和更优选减少98％的共轭二烯烃双键。或者，可以氢化聚合物使得芳族不饱和度也减少超过上述10％水平。在该情况下，共轭二烯烃和芳烃两者的双键可以减少90％或更多。
另外，可以采用许多方式官能化本发明的嵌段共聚物。一种方式是采用含有一个或多个官能团或它们衍生物，如羧酸基团和它们的盐、酸酐、酯、酰亚胺基团、酰胺基团、和酰氯的不饱和单体进行处理。要接枝到嵌段共聚物上的优选单体是马来酸酐、马来酸、富马酸、和它们的衍生物。官能化这样嵌段共聚物的进一步描述可以发现于Gergen等人，U.S.Pat.No.4578429和发现于U.S.Pat.No.5506299。在另一种方式中，可以通过将含硅或硼化合物接枝到聚合物上官能化本发明的选择性氢化嵌段共聚物，如在U.S.Pat.No.4882384中教导的那样。在仍然另一种方式中，可以将本发明的嵌段共聚物与烷氧基硅烷化合物接触，以形成硅烷改性的嵌段共聚物。在仍然另一种方式中，可以通过至少一个环氧乙烷分子反应到聚合物上，如在U.S.Pat.No.4898914中教导的那样，或通过聚合物与二氧化碳反应，如在U.S.Pat.No.4970265中教导的那样，官能化本发明的嵌段共聚物。仍然进一步地，可以金属化本发明的嵌段共聚物，如在U.S.Pat.No.5206300和5276101中教导的那样，其中将聚合物与烷基碱金属，如烷基锂接触。和仍然进一步地，可以通过磺酸类基团接枝到聚合物上官能化本发明的嵌段共聚物，如在U.S.5516831中教导的那样。
用于本发明粘合剂和密封剂的组分之一是增粘树脂。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两者。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。与氢化(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”，“WINGTACK”和“ARKON”销售。
用于本发明粘合剂和密封剂的另一种组分是聚合物填充油或增塑剂。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。这样的油包括链烷油和环烷油两者。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。
可用于本发明的另外增塑剂的例子是无规或顺序聚合的苯乙烯和共轭二烯烃的低聚物、共轭二烯烃如丁二烯或异戊二烯的低聚物、液体聚丁烯-1、和乙烯-丙烯-二烯烃橡胶，所有的分子量都为300-35,000，优选小于25,000mol重量。
采用的油或增塑剂数量从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。
配制压敏粘合剂以得到粘性，剥离，剪切和粘度的令人满意平衡。一般情况下，由于它们得到非常良好的粘性和良好的剪切，最广泛使用分子量为100,000-350,000和苯乙烯含量为12wt％-20wt％的SIS聚合物。然而，如果将它们混合和作为热熔体应用和，在最终的PSA带或标签中，它们不希望在高温下延长使用或当曝露于太阳光时，由于SIS聚合物会降解，必须保护它们以免降解。相反，当曝露于高温或太阳光时，SEBS聚合物具有优异的抗降解性，但一般情况下，它们在具有良好剪切的配制剂中得到具有有限粘性的粘合剂。已经发现，如果SEBS聚合物共混入基于SIS聚合物的PSA中以改进抗降解性，粘合剂通常变模糊和发生相分离。如果将SIS聚合物共混入基于SEBS聚合物的PSA中以改进粘性，再次粘合剂通常变模糊和发生相分离。已经发现新颖聚合物可以与优选的SIS聚合物共混和粘合剂是清晰的和在静置时不相分离。与优选SIS聚合物工作最好的新颖聚合物是那些物质，它们的分子量为25,000-150,000和端嵌段相中苯乙烯含量为15-25wt％和含有约25wt％共聚入橡胶链段的苯乙烯。
各种类型的填料和颜料可以包括在粘合剂配制剂中以着色粘合剂和降低成本。合适的填料包括碳酸钙、粘土、滑石、二氧化硅、氧化锌、二氧化钛等。依赖于使用的填料类型和粘合剂要用于的应用，填料的数量通常为0-30wt％，基于配制剂的无溶剂部分。特别优选的填料是二氧化钛。
如果要从溶剂溶液涂敷粘合剂，配制剂的有机部分会溶于溶剂或溶剂共混物。芳族烃溶剂如甲苯、二甲苯或Shell Cyclo Sol 53是合适的。脂族烃溶剂如己烷、石脑油或溶剂油也可以使用。如需要，可以使用由烃溶剂与极性溶剂组成的溶剂共混物。合适的极性溶剂包括酯如乙酸异丙酯，酮如甲基异丁基酮，和醇如异丙醇。使用的极性溶剂数量依赖于选择的特定极性溶剂和依赖于用于配制剂的特定聚合物结构。通常，使用的极性溶剂数量是溶剂共混物中的0-50wt％。
本发明的组合物可以由其它聚合物、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混炼成分的加入进一步改性而不背离本发明的范围。这样的组分描述于包括USPat.No.3239478和US Pat.No5777043的各种专利，其公开内容引入作为参考。
可以设计本发明的组合物用于很多种用途和应用。它们可以涂敷到纸、纸板、木材、金属箔、聚烯烃膜、聚氯乙烯膜、玻璃纸、毛毡、织造织物、非织造织物、玻璃等，和用于将两种或多种这样的材料粘合在一起。粘合剂用于压敏带，如掩蔽带、粘合片、其它粘合剂的底漆、粘合带、修补带、电绝缘带、层压材料、热熔粘合剂、乳香树脂、水泥、堵缝化合物、粘结剂、密封剂、延迟粘性粘合剂、粘合格、地毯衬垫、水泥等。
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A显示包括在本发明中的一些想象组合物。“CD聚合物”表示本发明的受控分布聚合物。
                  表A：应用，组合物和范围
应用 成分 组成，重量份
粘合剂 CD聚合物增粘树脂填充油 10025-3000-200
热熔粘合剂(优选的范围) CD聚合物增粘树脂端嵌段树脂填充油 10075-2000-500-150
溶剂基粘合剂(不包括溶剂) CD聚合物增粘树脂油 10025-3000-100
压敏粘合剂 CD聚合物苯乙烯/异戊二烯嵌段共聚物增粘树脂油 10025-30050-5000-200
建筑粘合剂或密封剂 CD聚合物增粘树脂端嵌段树脂碳酸钙 1000-2000-200100-800
防水涂料 CD聚合物沥青 100200-1000
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。用于实施例的测试方法是美国材料试验学会(ASTM)测试方法，和使用如下具体方法：
滚球粘性 ASTM D-3121
Polyken探针粘性 ASTM D-2979
回路粘性 ASTM D-6195
180°剥离 ASTM D-903
保持力 ASTM D-6463
SAFT ASTM D-4498
熔体粘度 ASTM D-3236
热老化粘度稳定性 ASTM D-4499
实施例1
根据以上提及的在先未决专利申请系列号60/355210包括同时提交的它的连续申请中公开的方法制备本发明的各种受控分布嵌段共聚物。所有的聚合物是选择性氢化AB或ABA嵌段共聚物，其中A嵌段是聚苯乙烯嵌段和在氢化之前的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富含丁二烯单元的末端区域和富含苯乙烯单元的中心区域。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。步骤I MW是第一A嵌段的分子量，步骤II MW是AB嵌段的分子量和步骤III MW是ABA嵌段的分子量。氢化聚合物使得减少大于约95％的二烯烃双键。
表1.受控分布聚合物
聚合物号   步骤IMW(k)  步骤IIMW(k)  步骤IIIMW(k)  步骤II中的％苯乙烯   苯乙烯嵌段度  1，2-BD   PSC
    (％)   (％)
    25     9.1     89     97     25     0     36   39
    27     7.5     70     77     25     3     36.1   40
    28     7.8     39     -     25     16     36   39
    26     7.3     43     50     37     0     36.7   47
其中“MW(k)”＝以千计的分子量和“PSC(％)”＝最终聚合物中苯乙烯的wt％。“苯乙烯嵌段度”仅用于B嵌段。
因此，聚合物#25是数均嵌段分子量为9500-80,000-9500的线性ABA三嵌段共聚物；聚合物#27是嵌段分子量为7500-62,600-7300的线性ABA三嵌段共聚物；聚合物#28是嵌段分子量为7800-31,500的AB二嵌段共聚物；和聚合物#26是嵌段分子量为7300-35,800-7300的线性ABA三嵌段共聚物。
实施例2
实施例2显示增粘树脂组合物对CD聚合物#25的橡胶中间嵌段链段相容性的影响。核磁共振(NMR)分析显示购自Goodyear的Wingtack树脂主要是脂族C5类型树脂但它们使用C5物流和芳族C9物流的混合物被聚合。它们主要的不同在于它们的芳族物质含量。NMR显示在Wingtack95、Plus、Extra、ET和86中的芳族质子分率分别是0、1.7、2.5、4.2和9.4。结果显示所有的树脂是此CD聚合物#25的有效增粘剂。具有最低芳族物质含量的树脂得到最好的Polyken探针粘性，而具有最高芳族物质含量的树脂得到最好的滚球粘性。Shellflex 371是Tg为-64℃的环烷类填充油。
表2
组成，phr #2-1 #2-2 #2-3 #2-4 #2-5
CD聚合物#25 100 100 100 100 100
WINGTACK 95 140
WINGTACK PLUS 140
WINGTACK EXTRA 140
WINGTACK ET 140
WINGTACK 86 140
SHELLFLEX 371 40 40 40 40 40
性能 a)
滚球粘性，cm ＞30 ＞30 ＞30 ＞30 25
Polyken探针粘性，kg 0.91 0.68 0.43 0.30 0.57
回路粘性，oz/in 51 44 41 50 46
180°剥离，pli 4.3 4.0 4.2 3.8 3.6
对钢(1×1，2kg)的HP，min ＞7000 ＞7000 ＞7000 ＞7000 ＞7000
对Mylar的SAFT(1×1，.5kg)，℃ 104 98 95 95 90
a)将PSA溶于甲苯和以1.8密耳干燥厚度在1密耳Mylar上流延。
实施例3
实施例3显示CD聚合物#25与氢化水白增粘树脂的相容性。购自Eastman的Regalite R91据信是通过聚合C9物流，随后由氢化消除几乎100％芳族部分制备。Regalrez系列树脂据信是通过聚合纯芳族单体如苯乙烯或乙烯基甲苯随后氢化而制备。氢化Regalrez 1094、6108和3102以分别消除约100％、60％和30％芳族部分。结果显示尽管含有70％芳族部分的Regalrez 3102是最不有效的增粘剂，所有四种树脂是CD聚合物#25的有效增粘剂。DRAKEOL 34购自Penreco和是Tg为-64℃的链烷类加工油。
表3
组成，％w  #3-1  #3-2  #3-3  #3-4
CD聚合物#25  35.0  35.0  35.0  35.0
REGALITE R91  44.0
REGALREZ 1094  41.5
REGALREZ 6108  41.5
REGALREZ 3102  41.5
DRAKEOL 34  21.0  23.5  23.5  23.5
性能 a)
滚球粘性，cm  6  4  9  26
Polyken探针粘性，kg  0.62  0.74  0.73  0.21
回路粘性，oz/in  32  63  69  47
180°剥离，pli  1.9  2.6  1.9  1.7
对Mylar的SAFT(1×1，.5kg)，℃  90  92  82  84
a)将PSA在甲苯中混合和以1.9密耳干燥厚度在1密耳Mylar上流延。
实施例4
实施例4显示使用CD聚合物#27与氢化树脂和水-白油粘合剂组合物对性能的影响。配制剂4-1、4-2和4-3显示聚合物含量的影响，保持采用Fox公式计算的玻璃化转变温度(Tg)恒定在-14℃。结果显示如下希望的倾向：增加的聚合物含量增加了SAFT和熔体粘度而没有对粘性和剥离有大的影响。配制剂4-3，4-4和4-5显示增加粘合剂Tg的效果，保持聚合物含量恒定在40wt％。结果显示如下希望的倾向：增加的Tg降低了粘性和增加了剥离而没有对SAFT或熔体粘度有大的影响。
表4
组成，％w  #4-1  #4-2  #4-3  #4-4  #4-5
CD聚合物#27  30.0  35.0  40.0  40.0  40.0
REGALITE R-91  46.0  44.0  42.1  45.2  48.1
DRAKEOL 34  24.0  21.0  17.9  14.8  11.9
计算的Tg，℃  -14  -14  -14  -10  -7
性能 a)
滚球粘性，cm  8  10  13  14  ＞30
Polyken探针粘性，kg  0.70  0.58  0.54  0.59  0.40
回路粘性，oz/in  55  64  65  79  69
180°剥离，pli  1.8  1.7  1.7  2.1  2.5
对Mylar的SAFT(1×1，.5kg)，℃  77  80  88  83  84
熔体粘度@177℃，Pa.s  8  15  29  35  39
将PSA混合为热熔体，溶于甲苯和以2密耳干燥厚度在1密耳Mylar上流延。
实施例5
实施例5显示聚合物结构对粘合剂性能的影响。样品#5-1和#5-2显示聚合物分子量的影响。结果显示较高的分子量得到较高的SAFT和较高的熔体粘度。样品#5-2到#5-6显示聚合物中三嵌段/二嵌段比例的影响。CD聚合物#28是AB二嵌段共聚物。结果显示当聚合物中三嵌段的分率降低时，熔体粘度降低。粘合剂性能不急剧变化直到聚合物的二嵌段含量接近100wt％，如在样品#5-6中那样。此样品的内聚强度足够低使得保持力样品内聚失败。
表5
组成，％w  #5-1  #5-2  #5-3  #5-4  #5-5  #5-6
CD聚合物#25  40
CD聚合物#27  40  30  20  10
CD聚合物#28  10  20  30  40
REGALITE R-91  45  45  45  45  45  45
DRAKEOL 34  15  15  15  15  15  15
性能 a)
滚球粘性，cm  7  15  7  7  6  3
Polyken探针粘性，kg  0.47  0.30  0.39  0.35  0.38  0.97
回路粘性，oz/in  34  75  77  76  72  110
180°剥离，pli  2.4  1.9  2.3  2.1  2.2  2.1
对钢(1×1，2kg)的HP，hr  ＞100  ＞100  ＞100  ＞100  ＞100  13cb)
对Mylar的SAFT(1×1，.5kg)，℃  94  82  85  82  76  70
熔体粘度@177℃，Pa.s  80  36  24  13  8  3
a)将PSA混合为热熔体，溶于甲苯和以2密耳干燥厚度在1密耳Mylar上流延。
b)c＝内聚失败
实施例6
实施例6显示包含如下物质共混物的溶剂基粘合剂的相稳定性：典型的SIS聚合物，SIS#1，与常规氢化SBC，SEBS#1，或与新颖CD聚合物#25。SIS#1的GPC峰值分子量为约245,000，聚苯乙烯端嵌段为约13,000和偶合效率为约44％。SEBS#1是聚苯乙烯端嵌段为约10,000和氢化聚丁二烯中间嵌段为约50,000的选择性氢化SBS嵌段共聚物。表6中显示的所有七种粘合剂在甲苯中以40wt％混合和然后允许包含粘合剂溶液的瓶子不受干扰地静置以测试它们是否相稳定。结果显示基于单个聚合物的所有三种样品，#6-1，6-4和6-7是初始清晰的和当允许不受干扰地静置时保持不变化。基于SIS#1和SEBS#1的共混物的样品#6-2和6-3是初始模糊的和在静置时相分离成两个清晰相。凝胶渗透色谱(GPC)分析显示顶部清晰层包含SEBS#1和底部清晰层包含SIS#1。相反，基于SIS#1和CD聚合物#25的共混物的样品#6-4和6-5是初始清晰的和甚至在不受干扰地静置之后保持清晰。靠近顶部取的样品和靠近溶液#6-4底部取的样品的GPC分析显示两个样品具有两种聚合物的数量，显示共混物的确是相稳定的。Piccotac 1095主要是从混合单体制备的脂族树脂和软化点为95℃。
表6
配制剂，％w  #6-1  #6-2  #6-3  #6-4  #6-5  #6-6  #6-7
SIS#1  35.0  23.4  11.7  23.4  11.7
SEBS#1  11.7  23.4  35.0
CD聚合物#25  11.7  23.4  35.0
PICCOTAC 1095  50.0  50.0  50.0  50.0  50.0  50.0  50.0
SHELLFLEX 371  15.0  15.0  15.0  15.0  15.0  15.0  15.0
粘合剂溶液
初始  清晰  模糊  模糊  清晰  清晰  清晰  清晰
在3天之后  清晰  分离的  分离的  清晰  清晰  清晰  清晰
实施例7
实施例7显示基于SIS#1与CD聚合物#25的共混物的粘合性的性能。将基于单个聚合物的粘合剂#7-1和#7-4，在sigma叶片混合机中混合为热熔粘合剂和然后以40wt％溶于甲苯。然后将溶液#7-1和#7-4以2/1或1/2比例共混在一起，得到溶液#7-2和#7-3。所有四个溶液是清晰和相稳定的。将它们以2密耳干燥厚度在1密耳聚酯衬垫上流延和测量粘合性能。样品#7-1和7-2上的结果显示至少1/3的SIS#1可以由CD聚合物#25替换而粘性降低较少。样品#7-2中氢化聚合物的存在预期向此粘合剂提供比#7-1更好的稳定性。样品#7-3和7-4上的结果显示由SIS#1替换1/3的CD聚合物#25得到粘性的显著改进，同时维持高保持力。
表7
配制剂，％w  #7-1  #7-2  #7-3  #7-4
SIS#1  35.0
CD聚合物#25  35.0
PICCOTAC 1095  45.0  45.0
SHELLFLEX 371  20.0  20.0
共混物#7-1  67  33
共混物#7-4  33  67
粘合剂性能
滚球粘性，cm  2  4  15  ＞30
回路粘性，oz/in  89  83  60  49
180°剥离，pli  6.1  3.5  2.2  2.0
对钢的HP，1×1，2kg，hr  19  30  ＞80  ＞80
SAFT，1×1，5kg，℃  75  80  88  97
实施例8
聚合物SIS#1具有44％的偶合效率，意味着它包含44％SIS三嵌段聚合物和56％未偶合SI二嵌段聚合物。人们可以通过以44/56比例共混CD聚合物#27，它是100％三嵌段聚合物，和CD聚合物#28，它是100％二嵌段聚合物，以模拟具有44％偶合效率的CD聚合物。实施例8显示基于如下物质的粘合剂的性能：SIS#1共混物与以44/56比例的CD聚合物#27和CD聚合物#28的共混物。粘合剂#8-1是基于SIS#1和粘合剂#8-4是基于CD聚合物#27和#28的共混物。在粘合剂#8-2中，1/3的SIS聚合物由CD聚合物替换和在粘合剂#8-3中，1/3的CD聚合物由SIS聚合物替换。结果显示采用CD聚合物替换粘合剂#8-1中1/3的SIS聚合物仅引起粘性的较少降低，和采用SIS聚合物替换1/3的CD聚合物得到粘性的显著改性。
通过在100ml烧杯中放置每种热熔粘合剂的50g样品，采用铝箔覆盖烧杯和在烘箱中在177℃下老化粘合剂，测定这四种粘合剂的热老化特性。所有四种粘合剂是清晰的和在热老化期间没有相分离，表明SIS#1和CD聚合物#27和#28具有良好的相容性。测量未老化的和在烘箱中8小时、24小时和48小时之后粘合剂的熔体粘度。粘合剂#8-1的结果显示SIS聚合物由于热老化而严重降解，在烘箱中老化48小时之后仅保持6％的它的初始粘度。粘合剂#8-4的结果显示CD聚合物具有良好的稳定性，在烘箱中老化48小时之后保持83％的它的初始粘度。粘合剂#8-2的结果显示采用CD聚合物替换1/3的SIS聚合物阻碍粘度损失的速率，因此改进粘合剂的热老化稳定性。
表8
配制剂，％w  #8-1  #8-2  #8-3  #8-4
SIS#1  35.0  23.3  11.7
CD聚合物#27  5.2  10.5  15.8
CD聚合物#28  6.4  12.8  19.3
REGALITE R91  45.0  45.0  45.0  45.0
DRAKEOL 34  20.0  20.0  20.0  20.0
粘合剂性能 a)
滚球粘性，cm  1.5  1.8  2.7  5.5
回路粘性，oz/in  95  81  53  47
180°剥离，pli  1.8  1.5  2.0  2.1
对钢的HP，1×1，2kg，hr  ＞100  ＞100  ＞100  ＞100
SAFT，1×1，5kg，℃  85  77  76  77
手指粘性  优异  优异  非常良好  良好
熔体粘度@177℃，Pa.s
初始  8460  6540  5200  6140
在8hr之后@177℃  5020  4620  4740  5360
在24hr之后@177℃  2700  2040  4320  5460
在48hr之后@177℃  520  1540  3020  5080
熔体粘度保留，％
初始  100  100  100  100
在8hr之后@177℃  59  71  91  87
在24hr之后@177℃  32  31  83  89
在48hr之后@177℃  6  24  58  83
a)将粘合剂混合为热熔体，溶于甲苯和以1.8密耳干燥厚度在2密耳Mylar上流延。
实施例9
实施例9比较了常规氢化SBC，SEBS#2，和CD聚合物#26在如下物质的混合物中的溶解度：烃溶剂，甲苯，与无VOC溶剂，以KESSCHEM 100购自Kessler Chemical的对氯苯并三氟化物(PCBTF)，或与乙酸叔丁酯(tBAc)，被预期很快变成无VOC溶剂。SEBS#2是聚苯乙烯端嵌段为约7,000和氢化聚丁二烯中间嵌段为约65,000的选择性氢化SBS嵌段共聚物。结果显示，如预期的那样，由于甲苯是聚苯乙烯端嵌段和两种聚合物橡胶中间嵌段两者的良溶剂，两种聚合物容易溶于甲苯。然而，由于对VOC的政府限制，严格限制烃溶剂的使用。表9中的结果显示，当由PCBTF替换甲苯时，粘度增加但聚合物仍然溶于包含至多80％PCBTF的共混物。然而，由于PCBTF不是橡胶链段的良溶剂，SEBS#2不溶于100％PCBTF。相反，PCBTF是CD聚合物#26橡胶嵌段的良溶剂和故它会溶于完全无VOC溶剂。
表9中的结果显示SEBS#2会溶于包含至多60wt％tBAc的甲苯与tBAc共混物。含有80％tBAc的共混物是清晰的凝胶和含有100％tBAc，溶剂太极性以至于不能溶解SEBS#2的橡胶嵌段。相反，如果必须满足VOC限制，CD聚合物#26会溶于100％tBAc。然而，由于它向CD聚合物#26的溶液提供低得多的粘度，包含20wt％甲苯和80wt％tBAc的溶剂共混物是更好的溶剂。
表9
    溶剂共混物，％w           粘度 a) ，cps
    甲苯     PCBTF     SEBS#2   CD聚合物#26
    100     0     500   160
    80     20     750   -
    60     40     1110   -
    40     60     2070   530
    20     80     5120   960
    0     100     清晰的凝胶   1980
    溶剂共混物，％w           粘度 a) ，cps
    甲苯     t-BAc     SEBS#2   CD聚合物#26
    100     0     500   160
    80     20     600   -
    60     40     1210   -
    40     60     12900   280
    20     80     清晰的凝胶   450
    0     100     不溶性   9300
a)布氏粘度@25℃@溶剂共混物中的20％聚合物。

Claims (8)

1.一种粘合剂组合物，包括100重量份至少一种具有单烯基芳烃和共轭二烯烃受控分布嵌段的氢化嵌段共聚物，25-300重量份至少一种增粘树脂，和0-200重量份填充油，其中该氢化嵌段共聚物含有至少一个聚合物嵌段A和至少一个聚合物嵌段B，和其中(a.)在氢化之前，每个A嵌段独立地是单烯基芳烃均聚物嵌段和每个B嵌段独立地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.)在氢化之后已减少0-10％的芳烃双键，和已减少至少90％的共轭二烯烃双键；(c.)每个A嵌段的数均分子量为3,000-60,000和每个B嵌段的数均分子量为30,000-300,000；(d.)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邻近A嵌段、富含单烯基芳烃单元的区域；(e.)氢化嵌段共聚物中单烯基芳烃的总数量是20-80wt％；和(f.)每个B嵌段中单烯基芳烃的重量百分比是10-75％。嵌段共聚物的通用构型是A-B、A-B-A、(A-B)n、(A-B)n-A、(A-B-A)nX或(A-B)nX，其中n是2-30，优选2-15，更优选2-6的整数，和X是偶合剂残基。本发明的粘合剂组合物包括热熔粘合剂、压敏粘合剂、溶剂基粘合剂等。
2.根据权利要求1的粘合剂组合物，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。
3.根据权利要求1或2的粘合剂组合物，其中该共轭二烯烃是丁二烯，和其中嵌段B中20-80mol％的缩合丁二烯单元具有1，2-构型。
4.根据权利要求1-3任意一项的粘合剂组合物，其中嵌段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。
5.根据权利要求1-4任意一项的粘合剂组合物，其中每个B嵌段中苯乙烯的重量百分比是10％-30％，和每个嵌段B的苯乙烯嵌段度指数小于10。
6.根据权利要求1-5任意一项的粘合剂组合物，其中该氢化嵌段共聚物是ABA、(A-B)n、(A-B)nA、或(A-B)aX嵌段共聚物，其中n是2-30的整数，X是偶合剂残基，该嵌段共聚物总分子量是40,000-140,000和其中每个B嵌段含有10-30wt％苯乙烯。
7.根据权利要求1-6任意一项的粘合剂组合物，其中该增粘树脂选自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，和/或选自苯并呋喃-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、聚苯醚及其混合物。
8.根据权利要求1-7任意一项的粘合剂组合物，包括100重量份至少一种该氢化嵌段共聚物，25-300重量份相容苯乙烯/异戊二烯未氢化嵌段共聚物，50-500重量份增粘树脂，和0-200重量份聚合物填充油。
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CN102757709A (zh) * 2011-04-26 2012-10-31 奇美实业股份有限公司 防湿绝缘涂料及其应用
CN102757709B (zh) * 2011-04-26 2014-11-26 奇美实业股份有限公司 防湿绝缘涂料及其应用
US9136038B2 (en) 2011-04-26 2015-09-15 Chi Mei Corporation Moisture-proof and insulating coating material and uses thereof
TWI561602B (en) * 2012-02-24 2016-12-11 Kraton Polymers Us Llc High flow, hydrogenated styrene-butadiene-styrene block copolymers and applications
CN104650687A (zh) * 2013-11-21 2015-05-27 奇美实业股份有限公司 防湿绝缘涂料及其应用

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