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CN1113915C - 支化烯烃共聚物的热塑性弹性体组合物 - Google Patents

支化烯烃共聚物的热塑性弹性体组合物 Download PDF

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CN1113915C
CN1113915C CN98802252.4A CN98802252A CN1113915C CN 1113915 C CN1113915 C CN 1113915C CN 98802252 A CN98802252 A CN 98802252A CN 1113915 C CN1113915 C CN 1113915C
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ethene
thermoplastic elastomer
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equal
polymerization
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CN1259147A (zh
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E·J·马克尔
翁卫青
A·H·德克梅兹安
A·J·皮科克
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ExxonMobil Chemical Patents Inc
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Abstract

本发明涉及一种含有由可插入聚合的烯属不饱和单体得到的支化烯烃共聚物的热塑性弹性体组合物，其中该支化烯烃共聚物A)由DSC测定的Tg小于或等于10℃；B)Tm大于80℃；C)断裂伸长率大于或等于300%；D)拉伸强度大于或等于1500磅/平方英寸(10300kPa)；以及E)弹性回复大于或等于50%。本发明还涉及制备该组合物的方法，该方法包括：A)在一聚合反应中使乙烯或丙烯，以及任选地一种或多种可共聚合的单体进行聚合，聚合条件应足以形成具有大于40%链端基不饱和度的共聚物；B)使A)的产物与乙烯和一种或多种共聚单体进行共聚，以制备所述的支化烯烃共聚物。本发明的支化烯烃共聚物组合物适用于替代苯乙烯嵌段共聚物组合物，并适用于其它传统的热塑性弹性体应用领域。

Description

支化烯烃共聚物的热塑性弹性体组合物
发明领域
本发明涉及含有支化烯烃共聚物的热塑性弹性体组合物，该支化烯烃共聚物具有并入低结晶性聚乙烯主链的结晶性聚烯烃侧链。
背景技术
由于连接“硬”(可结晶的或玻璃态的)嵌段的“软”(弹性的)嵌段的存在，三嵌段和多嵌段共聚物在用作热塑性弹性体(“TPE”)组合物的弹性体聚合物领域是公知的。在典型的使用温度下，硬嵌段将聚合物网络连接在一起。然而，当加热至硬嵌段的熔融温度或玻璃化转变温度以上时，聚合物便易于流动，表现出热塑性行为。例如参见G.Holden和N.R.Legge，热塑性弹性体：综述(Thermoplastic Elastomers：A Comprehensive Review)，Oxford University Press(1987)。
商业上最常见的一类TPE聚合物为苯乙烯嵌段共聚物(SBC)，典型地为线性三嵌段聚合物，如苯乙烯-异戊二烯-苯乙烯和苯乙烯-丁二烯-苯乙烯，后者当氢化时实质上变为苯乙烯-(乙烯-丁烯)-苯乙烯嵌段共聚物。辐射型和星型支化的SBC共聚物也是公知的。典型地，这些共聚物是通过顺序阴离子聚合或线性二嵌段共聚物的化学偶联制备的。典型的SBC TPE的玻璃化转变温度(Tg)等于或低于约80～90℃，因此限制了这些共聚物在高温使用条件下的应用。例如参见，“嵌段聚合物及多相聚合物体系的结构和性能：目前态势及未来潜力纵览”(“Structure and Properties of Block Polymers and MultiphasePolymer System：An Overview of Present Status and FuturePotential”，)S.L.Aggarwal，Sixth Biennial Manchester PolymerSymposium(UMIST Manchester，March 1976)。
由于方法效率和原料成本的差异，烯烃的插入或配位聚合可经济性地提供更有效的制备共聚物产品的方式。因此已经发展了由烯属不饱和单体，如乙烯和C3～C8α烯烃得到的适用的TPE聚合物，并且这些聚合物也是公知的。其例子包括热塑性烯烃(“TPO”)如聚丙烯与乙烯-丙烯共聚物的物理共混物，以及类似的共混物，其中乙烯-丙烯，或乙烯-丙烯-二烯烃相被动态硫化，以使其在聚丙烯基质中保持良好分散的、呈分离的软相粒子的形式。例如参见，N.R.Legge，“热塑性弹性体等级：物理性能对比”(“Thermoplastice lastomercategories：a comparison of physical properties”)，ELASTOMERICS，14-20页(Sept.，1991)，这里将其引为参考。
金属茂催化剂在烯烃聚合中的使用在这一领域中带来了其它一些贡献。U.S.P.5391629公开了含有由乙烯和α-烯烃得到的递变和嵌段线性聚合物的热塑性弹性体配混料。据报道，可以用既可以制备硬片断又可以制备软片断的单点金属茂催化剂制备具有硬和软片断的聚合物。所提供的例子为具有高密度聚乙烯或全同立构聚丙烯的硬嵌段和乙丙橡胶软嵌段的线性热塑性弹性体。日本早期公开说明书H4-337308(1992)公开了称为聚烯烃共聚物的产物，该产物的制备是首先聚合丙烯形成全同立构聚丙烯，然后使聚丙烯与乙烯和丙烯共聚合，这两步聚合均是在有机铝化合物和硅桥连的双环戊二烯基二卤化锆化合物的存在下进行的。
Datta等(D.J.Lohse，S.Datta，and E.N.Kresge，大分子(Macromolecules)24，561(1991))公开了通过乙烯、丙烯和二烯烃的三元共聚合而用环二烯烃官能化的EP主链。然后在制备全同立构聚丙烯的催化剂的存在下，使统计官能化的EP“软嵌段”与丙烯进行共聚合。以这种方式，“硬”嵌段聚丙烯链中的一些在其形成时通过残余的烯属不饱和部分接枝到EP“软”嵌段上。例如参见EP-A-0366411。其中多官能度聚合物链用于随后反应中的这一类反应的缺点是，形成了不期望的高分子量物质，典型地，本领域中称其为凝胶。U.S.P.4999403公开了类似的接枝共聚物配混料，其中EPR主链中的官能团用于接枝具有反应性基团的全同立构聚丙烯。在这两种情况下，据称接枝共聚物适用作全同立构聚丙烯和乙丙橡胶共混物的相容剂配混料。
发明概述
本发明涉及含有由可插入聚合的烯属不饱和单体得到的支化烯烃共聚物的热塑性弹性体组合物，其中该支化烯烃共聚物A)由DSC测定的Tg小于或等于10℃；B)熔融温度(Tm)大于80℃；C)断裂伸长率大于或等于300％，优选大于500％；D)拉伸强度大于或等于1500磅/平方英寸(10300kPa)，优选大于2000磅/平方英寸(13800kPa)；以及E)弹性回复大于或等于50％。更特别地，该支化烯烃共聚物含有由烯烃，以及任选地一种或多种可共聚合的单体得到的结晶性侧链，使得其Tm大于80℃，并且数均分子量(Mn)大于1500，小于45000。本发明的热塑性弹性体组合物可通过含有下述步骤的方法制得：A)在一聚合反应中使一种烯烃，以及任选地一种或多种可共聚合的单体进行共聚合，聚合条件应足以形成具有大于40％链端基不饱和度的结晶性或玻璃态共聚物；B)使A)的产物与乙烯和一种或多种可共聚合的单体进行共聚，以制备所述的支化烯烃共聚物。该热塑性弹性体组合物具有与传统的重要的SBC共聚物可比的、或超过它们的弹性性能，因此对于这一重要类别的商业产品来说，提供了可供选择的原料来源和工业生产。
附图说明
图1说明的是本发明的支化烯烃共聚物与商品可得的苯乙烯嵌段共聚物热塑性弹性体，其测得的物理性能的比较。
发明详述
本发明的热塑性弹性体组合物含有支化的共聚物，其中共聚物主链和聚合物侧链均是使用活化的过渡金属有机金属催化剂，在配位或插入条件下，由单烯烃聚合得到。侧链是共聚合得到的，以使其具有适合于硬相区的结晶、半结晶或玻璃态性能，所谓“硬相区”是按照本领域对该术语的理解，并且侧链连接于结晶性或玻璃化状态低于侧链，优选基本上为无定形的，以使其适合于互补的热塑性弹性体组合物的软相区特性的聚合物主链。
结晶性侧链含有可在插入聚合条件下形成结晶或玻璃态聚合物片断的化学单元。符合该要求的公知单体为乙烯，丙烯，3-甲基-1-戊烯，以及它们的共聚物，包括乙烯与α-烯烃、环烯烃或苯乙烯系共聚单体的共聚物。优选的乙烯或丙烯共聚物侧链为，共聚单体的量不足以破坏结晶性使其Tm降至低于80℃。适宜的共聚单体包括C3～C20α-烯烃或偕二取代的单体，C5～C25环烯烃，苯乙烯系烯烃，及低碳数(C3～C8)烷基取代的环烯烃或苯乙烯系烯烃的同型物。因此典型地，侧链可含有85～100摩尔％的乙烯，0～15摩尔％的共聚单体，优选90～99摩尔％的乙烯和1～10摩尔％的共聚单体，最优选94～98摩尔％的乙烯和2～6摩尔％的共聚单体。或者是，侧链可含有90～100摩尔％的丙烯，0～10摩尔％的共聚单体，优选92～99摩尔％的丙烯和1～8摩尔％的共聚单体，最优选95～98摩尔％的丙烯和2～5摩尔％的共聚单体。特别地，当侧链Mn增至高于约3000时，优选引入少量的共聚单体以使脆性最小化，例如约0.2～4.0摩尔％的共聚单体。该共聚单体的选择可基于非结晶性破坏能力的其它一些性能，例如为提高聚乙烯膜的撕裂性，相对于短链的烯烃如1-丁烯，可优选长链烯烃共聚单体如1-辛烯。为提高聚乙烯膜的弹性或阻隔性能，相对于α-烯烃，可优选环状共聚单体，如降冰片烯或烷基取代的降冰片烯。
侧链可具有窄或宽的分子量分布(Mw/Mn)，例如1.1～30，典型地为2～8。此外，侧链可具有不同的共聚单体组成，例如包括公开于U.S.P.5382630(CDBI＞50％)的正交组成分布，这里将其引为参考。任选地，可使用具有不同分子量和/或组成的侧链的混合物。
侧链Mn的范围为大于或等于1500，小于或等于45000。优选侧链的Mn为1500～30000，更优选Mn为1500～25000。侧链的数目与侧链的Mn有关，使得侧链的重量与介于及出于并入的侧链的聚合物主链片断的总重量的总重量比为小于60％，优选40～50％。分子量这里是由凝胶渗透色谱(GPC)和差示折光指数(DRI)测量仪测定的。这一类别的优选支化烯烃共聚物，其由差示扫描量热法测定的熔融焓(ΔHf)为≤90cal/g(在≥80℃，≥5℃/min的扫描速度下，由记录的热流进行积分测定)。
当考虑侧链对主链结构的影响时，主链或主链聚合物片断的Tm(或者是Tg，若无Tm时)应低于侧链的。因此主链将优选含有测不出结晶性的化学单元的片断，或者Tg低于-10℃的化学单元的片断。结合起来，典型地，主链片断的Tm低于或等于80℃，Tg低于或等于-10℃。弹性主链将是特别适宜的，典型地，这样的主链将含有乙烯以及一种或多种C3～C12α-烯烃或二烯烃，特别是丙烯和1-丁烯。其它的共聚合单体包括偕二取代的烯烃如异丁烯，环烯烃如环戊烯，降冰片烯和烷基取代的降冰片烯，以及苯乙烯系单体如苯乙烯和烷基取代的苯乙烯。低结晶性的主链是适宜的，其例子为高共聚单体含量的乙烯共聚物(如前所述)，例如共聚单体含量大于8摩尔％。
如上所指出的，典型地，主链重量至少为聚合物总重量，即主链和侧链的总重量的40重量％。典型地，主链的公称重均分子量(Mw)至少等于或大于约50000。术语“公称”是指直接测定主链的Mn是基本不可能的，但共聚物产物的表征将显示与聚合物主链的非常近似的重量相关联的Mw测定值，该聚合物主链仅包括单烯烃单体单元衍生物和侧链的插入部分。
典型地，由实施例说明的通过GPC/DRI测定的、含有上述侧链和主链的支化烯烃共聚物的Mw等于或大于50000。典型地，Mw可超过300000，优选200000，上至500000或更大。
本发明的热塑性弹性体组合物可通过含有下述步骤的方法制得：A)在一聚合反应中使乙烯或丙烯，以及任选地一种或多种可共聚合的单体进行共聚合，聚合条件应足以形成具有大于40％链端基不饱和度的共聚物，其Tm≥80℃，Tg≤-10℃；B)使A)的产物与乙烯和一种或多种可共聚合的单体进行共聚，以制备所述的支化烯烃共聚物。对于步骤A)中制备的基于乙烯的大单体，优选其Tg低于-5℃，更优选低于-10℃。
有利地，方法中的步骤A)可以溶液法进行，其中所述的乙烯和任选地一种或多种可共聚合的单体，与被烷基铝氧烷助催化剂活化的过渡金属烯烃聚合催化剂相接触，铝与过渡金属的摩尔比小于约220∶1。如此形成的端不饱和共聚物，在从仅具有饱和端基的共聚物产物中分离或不分离的情况下，然后可与乙烯和可共聚合的单体在另一单独的反应中进行共聚合，该反应可以用活化的过渡金属插入聚合催化剂，特别是可以在所述支化烯烃共聚物中并入乙烯共聚物的催化剂，通过溶液、淤浆或气相乙烯聚合法进行。
或者是，方法步骤A)可以溶液法进行，其中使丙烯和任选地一种或多种可共聚合的单体，与由任何适宜的助催化剂活化的、立构严格的过渡金属烯烃聚合催化剂，即可以制得立构规整聚丙烯的催化剂相接触，反应保持在足够高的温度，以获得明显量的端不饱和聚合物链，反应温度例如高于约85℃，优选高于约90℃。如此形成的端不饱和共聚物，在从仅具有饱和端基的共聚物产物中分离或不分离的情况下，然后可与乙烯和可共聚合的单体，或者其它选择的适于制备低结晶性聚合物的单体，在另一单独的反应中进行共聚合，该反应使用活化的过渡金属插入聚合催化剂，特别是可以在所述具有低结晶性主链的支化烯烃共聚物中并入丙烯共聚物的催化剂，通过溶液、淤浆或气相乙烯聚合法进行。
足以形成侧链乙烯共聚物的条件包括，使用适宜的乙烯和共聚单体反应物摩尔比，以保证所述的侧链的衍生自烯烃的单元组成，以及可操作的催化剂和方法条件，以形成不饱和的链端。02/07/97提交的共同待审的临时申请U.S.系列No.60/037323的教导内容，特别适用于催化剂的选择，以及以高乙烯基不饱和度产率制备大单体共聚物链。在步骤A)中用于制备含不饱和部分的大单体的金属茂催化剂，实质上可以是任何可以进行乙烯的插入聚合的催化剂，它可以是具有高共聚单体并入能力的催化剂(见下述)，或者是低共聚单体并入能力的催化剂。典型地，低并入能力的催化剂为那些在金属配位位置上更加立构聚积的催化剂，因此特别适宜的为非桥连的和取代的非桥连的金属茂催化剂。还有在U.S.P.5498809、国际申请WO 94/19436和WO94/13715中公开了以高产率制备端亚乙烯基乙烯-1-丁烯共聚物的方式。还有1996.5.21提交的共同待审申请U.S.系列No.08/651030，其教导内容涉及制备具有高含量的亚乙烯基链端不饱和度的乙烯-异丁烯共聚物。在上述和下述部分中的短语“链端”或“端基”，当指不饱和度时，是指适于插入聚合的烯属不饱和度，而不论其是否精确地位于链端。还有U.S.P.5324801和5621054公开了结晶熔点为235℃和更高的交替乙烯-环烯烃共聚物，由这些公开内容的适宜的催化剂制得的大单体，将对用作本发明热塑性弹性体的硬相组分，具有玻璃态贡献作用。这一段中的所有文献并入本申请以作参考。
在一特别的实施方案中，可以在溶液聚合条件下，以优选的铝在烷基铝氧烷活化剂中的摩尔比，例如甲基铝氧烷(MAO)与过渡金属的摩尔比，制备适用作随后共聚合反应支链的含乙烯基、含乙烯的大单体聚合产物。优选的铝与烷基铝氧烷活化剂的摩尔比为≥20并≤175；更优选≥20并≤140；最优选≥20并≤100。温度、压力和反应时间与所选的方法有关，但通常它们在溶液法的正常范围内。因此温度的范围可为20～200℃，优选30～150℃，更优选50～140℃。反应压力通常为大气压至345MPa，优选至182MPa。对于典型溶液反应来说，温度范围为室温至190℃，压力为大气压至3.45MPa。反应可以间歇进行。适宜的淤浆型反应条件类似于溶液反应条件，不同的是反应温度受限在低于聚合物的熔融温度之下。此外还可以使用其它的反应方式，例如超临界液体介质法，其温度上至250℃，压力上至345MPa。在高温和高压反应条件下，典型地，生成低分子量，例如Mn为约1500的大单体产物。
在另一可选择的实施方案中，可以用适合于制备或者全同或者间同聚丙烯的金属茂催化剂，在溶液聚合条件下制备适用作随后共聚合反应支链的、含乙烯基含丙烯的大单体聚合产物。具有高含量端乙烯基不饱和度的丙烯大单体的优选反应方法，公开于Attorney DocketNo.97B075，1997.12.10提交的共同待审的美国申请60/067783。典型使用的催化剂为立构严格、手性或非对称的、桥连金属茂。例如参见U.S.P4892851、U.S.P.5017714、U.S.P.5132281、U.S.P.5155080、U.S.P.5296434、U.S.P.5278264、U.S.P.5318935、WO-A-(PCT/US92/10066)、WO-A-93/19103、EP-A2-0577581、EP-A1-0578838，以及科技文献“芳族取代基对桥连锆茂催化剂聚合特性的影响”(“The Influence of Aromatic Substituents on thePolymerization Behavior of Bridged Zirconocene Catalysts”)，Spaoeck，W.，等，有机金属(Organometallics)1994，13，954-963，和“ansa-Zirconocene Polymerization Catalysts withAnnelated Ring Ligands-Effects on Catalytic Activity andPolymer Chain Lengths”对催化活性具有增环反应环配体作用的柄型锆茂聚合催化剂和聚合物链长″，Brinzinger，H.，等，有机金属(Organometallics)1994，13，964-970，这里将这些文献引为参考。
优选地，对于全同聚丙烯来说，立构严格的过渡金属催化剂化合物选自桥连的双(茚基)锆茂或铪茂。在一优选的实施方案中，过渡金属催化剂化合物为二甲基甲硅烷基桥连的双(茚基)锆茂或铪茂。更优选地，过渡金属催化剂化合物为二甲基甲硅烷基(2-甲基-4-苯基茚基)二氯合锆、二氯合铪或二甲基锆、二甲基铪。在另一优选的实施方案中，过渡金属催化剂为二甲基甲硅烷基桥连的双(茚基)铪茂，如二甲基甲硅烷基双(茚基)二甲基铪或二氯合铪。制备高百分含量端乙烯基键合的、基于丙烯的大单体的方法包括：
a)约90～120℃下，于溶液中，使丙烯以及任选地少量可共聚合的单体，与含有立构严格的活化的过渡金属催化剂化合物的催化剂组合物相接触；和
b)回收数均分子量为约2000～50000的全同或间同聚丙烯链。
优选地，溶液中含有一种烃类溶剂。更优选地，烃类溶剂为芳香族的。同样，优选地，丙烯单体在95～115℃下接触。更优选地，所用温度为100～110℃。最优选地，丙烯单体在105～110℃下接触。通常反应压力可以为大气压至345MPa，优选至182MPa。反应可间歇或连续进行。适合于淤浆型反应的条件也同样适用，并且类似于溶液反应条件，典型地，聚合在适合的压力下于液态丙烯中进行。这里将所有文献引为参考。
此外，本发明的支化烯烃共聚物热塑性弹性体组合物，还可以在混合的催化剂体系存在下，由选定的烯烃直接同时制备，该混合的催化剂体系含有至少一种第一过渡金属烯烃聚合催化剂，该催化剂可制备链端基不饱和度大于40％的乙烯或丙烯共聚物，以及至少一种第二过渡金属烯烃聚合催化剂，该催化剂可在所述的支化烯烃共聚物中并入乙烯或丙烯均聚物或共聚物侧链。这种就地制备方法可以通过任何方法来进行，只要它能够制备具有结晶、半结晶或玻璃态性能的不饱和大单体，又能够使该大单体与构成低结晶性主链的共聚单体共聚合，从而制备支化的共聚物即可。可以在公知的适用于所述方法的温度和压力条件下，使用气相、淤浆和溶液法。
对于含高乙烯基或亚乙烯基的大单体的制备，特别地，当活化时可获得高链端不饱和度的适宜的第一催化剂包括上述说明的那些。优选地，如上所述对乙烯的均聚合呈活性、但不明显地并入高碳原子数的单体，或者是并入高碳原子数的单体而仅伴随Mn的降低的催化剂，在本发明热塑性共聚物组合物的同时或就地制备法中，对于结晶性或玻璃态侧链的制备将是特别适宜的，只要Mn可保持或提高至高于侧链的最小值。
适宜的第二催化剂化合物包括那些在所用的温度和压力条件下可以很好地并入共聚单体，而不明显降低聚合物主链Mn的催化剂。02/07/97提交的共同待审的临时申请U.S.系列No.60/037323的教导内容，特别适用于催化剂的选择，以及用以制备支化烯烃共聚物，并指出了适合于高共聚单体和大单体并入的催化剂化合物。如该申请所指出的，由含乙烯基或亚乙烯基的大单体、乙烯和可共聚合的共聚单体制备支化烯烃共聚物的优选的催化剂化合物包括，U.S.P.5198401、5270393、5324801、5444145、5475075、5635573、国际申请WO92/00333和WO96/00244所公开的桥连的双环戊二烯基和单环戊二烯基第4族金属化合物；10/20/95提交的共同待审的美国专利申请08/545973所提出的非桥连的单环戊二烯基第4族金属化合物，U.S.P.5318935和2/24/97提交的共同待审的申请08/803687所公开或提出的二酰胺基和二丙烯酰胺基过渡金属催化剂，以及WO96/23010所公开的α-二亚胺镍催化剂配合物。按照这些教导，典型地，过渡金属催化剂化合物与所述的活化助催化剂组分一起使用，助催化剂组分例如为可提供稳定化的非配位阴离子的烷基铝氧烷和离子化化合物。这一段中的每一篇文献均被并入本申请作为参考。工业实用性
本发明的热塑性弹性体组合物可用于其它热塑性弹性体组合物已应用的许多领域。这些应用包括但不限于苯乙烯嵌段共聚物，如苯乙烯-异戊二烯-苯乙烯和苯乙烯-丁二烯-苯乙烯共聚物，以及它们的加氢同系物的公知应用领域。这些应用包括许多，如粘合剂组合物和模塑制品的主链聚合物。这些应用将得益于提高的使用温度范围，典型地超过SBC共聚物组合物的80～90℃范围。本发明的组合物还适用作聚烯烃共混物的相容剂配料。此外，由于其固有的拉伸强度、弹性、和易于熔融加工的特性，本发明的热塑性弹性体组合物，任选地用通常的添加剂和辅助剂进行改性，可制备挤出膜、涂层和包装组合物。而且，由于优选的、使用易于得到的烯烃的插入聚合的制备方法，本发明的热塑性弹性体组合物可用低成本的石油化工原料，在低能量输入条件下制备(与低温阴离子聚合或者多步熔融加工条件相比，其中必须硫化以获得分离的热塑性弹性体形态)。
实施例
为进一步说明本发明，提供下列实施例。这些实施例不是以任何方式限制本发明，而仅仅是起到进一步说明的目的。
概述：所有的聚合反应在配有控温水夹套的1升密闭釜反应器中进行。用校正的视镜将液体计量注入到反应器中。首先经过高温下氮气中活化的碱性氧化铝，然后再经过高温下氮气中活化的13X分子筛，对高纯度(＞99.5％)己烷、甲苯和丁烯进料进行纯化。在氮气夹套管线中直接供应聚合级的乙烯，并且不用经进一步纯化使用。从Albemarle Inc.直接获得在不锈钢筒中的澄清的10％的甲基铝氧烷(在甲苯中)，将其分装入1升的玻璃容器中，室温下储存在实验室手套箱中。以所需量向反应器中加入乙烯，以维持总系统压力在所报道的水平上(半间歇操作)。用Matheson质量流量计(型号8272-0424)检测乙烯的流速。为确保反应介质混合良好，使用转速为750rpm的平浆搅拌器。
反应器的准备：首先用甲苯加热至150℃清洗反应器以溶解任何聚合物残余物，然后冷却并排掉。然后用110℃的夹套水对反应器进行加热，并用氮气流冲洗约30分钟。反应前，进一步将反应器用10氮气压力/出口循环(至100psi)和2乙烯压力/出口循环(至300psi)进行冲洗。该循环有三个目的：(1)彻底疏通所有的死点，如压力表，以冲洗掉不坚牢的污染物，(2)用乙烯置换体系中的氮气，(3)对反应器进行压力测试。
催化剂制备：所有的催化剂均是在水含量小于1.5ppm的惰性气氛下进行制备。为精确地计量少量的催化剂(常常低于1毫克)，在催化剂制备中使用新鲜制备的催化剂原液/稀释法。为使金属茂的溶解度最大化，使用甲苯作为溶剂。用MAO洗涤不锈钢转移管，以除去杂质，排掉，并用移液吸管加入活化剂和催化剂，首先加入MAO。
大单体合成：首先，在连续的氮气流下将催化剂转移管连接到反应器的一个端口上，以清除环境空气。然后如上所述清洗反应器并进行压力测试。接着向反应器中加入600ml溶剂并加热至所需的温度。然后加入共聚单体(若需要的话)，使温度达到平衡，并记录基本体系压力。除基本体系压力之外还要加上所需的乙烯的分压。使乙烯饱和体系(由0乙烯流率看出)后，用高压溶剂以脉冲形式注射入催化剂。通过从电子质量流量计上读取乙烯的摄入量来监视反应进程。当积累了所需量的大单体时，停止乙烯进料，并通过加热(～1分钟)至150℃30分钟使反应终止。在终止步骤的最后，将反应器冷却至LCB分段制备反应(下述)所需的温度，并取出大单体样品以作分析。
LCB分段结构的制备：在甲苯中用乙烯，100磅/平方英寸下，用MAO活化的(C5Me4SiMe2NC12H23)TiCl2催化剂，进行所有的长链支化(LCB)的烯烃共聚物的制备反应。在大多数的合成中用丁烯作共聚单体，但也使用降冰片烯作共聚单体进行选择性的反应，以制得用于使LCB含量定量化的样品。当生成所需量的聚合物(所有的聚积物)时，通过注入甲醇使反应终止。在约注入10秒钟内，观察到乙烯摄入量/反应器压力降停止。将产物倒入过量的异丙醇中，并使之蒸发以干燥。在另一实施例中(实施例3)，在一步法、混合金属茂的合成中，使用Cp2ZrCl2和(C5Me4SiMe2NC12H23)TiCl2催化剂，其中大单体与主链同时制备并并入到主链中。
催化剂匹配(配对)：对于混合金属茂的就地法实施例，选择金属茂催化剂配对，以使既使用具有良好并入性能的催化剂，又使用并入能力较差的催化剂。对该工艺来说，并入能力好的催化剂，其并入能力将是并入能力差的催化剂的3倍，更优选5倍。就本发明目的而言，对于每一催化剂化合物，使用如下定义的标准反应条件，通过并入的丁烯的重量百分数，来定义并测定共聚单体的并入能力。90℃下用高纯氮气冲洗1升高压釜2小时。接着用乙烯流冲洗体系的氮气。然后加入600ml甲苯和50ml液态丁烯。使体系在90℃平衡。然后以100磅/平方英寸加入乙烯，直至溶液饱和。在惰性气氛手套箱中，用不锈钢加料管将1毫克的催化剂加入到0.5毫升10重量％的MAO中。根据催化剂的活性，需要可多可少量的催化剂/MAO溶液，以保证实质水平的聚合反应而不产生过多的反应放热。用加压溶剂将催化剂注入到反应器中。通过加入所需量的乙烯将反应器压力保持在100磅/平方英寸。在反应器内的反应物组成有实质性改变之前(转化率＜20％，通过反应产物的分析确定)使反应终止。共聚单体并入量由1H NMR测定，并以每1000个碳原子的乙基数记。
实施例1
催化剂制备：如上所述制备不锈钢催化剂加料管。加入一等分的1毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入5毫升含16毫克(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
大单体合成：同时氮气清洗反应器中，并用两个乙烯充入/冲洗循环(至300磅/平方英寸)进行压力测试。然后将反应器的压力升至～40磅/平方英寸，以在初始操作过程中保持正反应器压力。夹套水温设定为90℃，并向反应器中加入600毫升甲苯和10毫升丁烯。搅拌器速率设定为750rpm。由于气相乙烯被吸收进溶液中，因此加入额外的乙烯以维持正反应器表压。反应器温度控制器设定为90℃，并使体系达到稳定状态。然后将乙烯压力控制器设定为100磅/平方英寸，并向体系中加入乙烯，直至乙烯摄入量测定为0，获得稳定状态为止。隔离反应器，用加压至300磅/平方英寸的甲苯迫使催化剂溶液从加料管中进入反应器。同时向反应器打开100磅/平方英寸的乙烯供料管线，目的是随着乙烯的反应消耗保持恒定的反应器压力。
反应进行15分钟后，将反应液迅速加热至150℃，保持30分钟，然后冷却至90℃。从反应器中取出预聚合的大单体样品。
LCB分段共聚物的合成：如上所述制备不锈钢催化剂加料管。加入一等分的0.5毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入1毫升每毫升含0.5毫克(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
反应器温度控制器设定为90℃。然后向含有大单体的反应器中加入70毫升丁烯，并使体系达到热平衡。接着以100磅/平方英寸(总的)向体系中加入乙烯。使乙烯饱和体系(由0乙烯流率看出)后，用高压溶剂以脉冲形式注射入催化剂。通过从电子质量流量计上读取乙烯的摄入量来监视反应进程。15分钟后通过注射入甲醇使反应终止。将产物倒入过量的异丙醇中，并蒸发干燥。LCB分段共聚物的总产量为42.6克。
实施例2
催化剂制备：如上所述制备不锈钢催化剂加料管。加入一等分的0.5毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入5毫升含8毫克Cp2ZrCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
大单体合成：同时清洗反应器中的氮气，并用两个乙烯充入/冲洗循环(至300磅/平方英寸)进行压力测试。然后将反应器的压力升至～20磅/平方英寸，以在初始操作过程中保持正反应器压力。夹套水温设定为90℃，并向反应器中加入600毫升甲苯和2毫升80.6重量％降冰片烯的甲苯溶液。搅拌器速率设定为750rpm。由于气相乙烯被吸收进溶液中，因此加入额外的乙烯以维持正反应器表压。反应器温度控制器设定为90℃，并使体系达到稳定状态。然后将乙烯压力控制器设定为30磅/平方英寸，并向体系中加入乙烯，直至乙烯摄入量测定为0，获得稳定状态为止。隔离反应器，用加压至300磅/平方英寸的甲苯迫使催化剂溶液从加料管中进入反应器。同时向反应器打开30磅/平方英寸的乙烯供料管线，目的是随着乙烯的反应消耗保持恒定的反应器压力。
反应进行15分钟后，将反应液迅速加热至150℃，保持30分钟，然后冷却至90℃。从反应器中取出预聚合的大单体样品。
LCB分段共聚物的合成：如上所述制备不锈钢催化剂加料管。加入一等分的0.5毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入1毫升每毫升含1毫克(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
反应器温度控制器设定为60℃。然后加入60毫升80.6重量％降冰片烯的甲苯溶液，并使体系达到热平衡。接着以100磅/平方英寸(总的)向体系中加入乙烯。使乙烯饱和体系(由0乙烯流率看出)后，用高压溶剂以脉冲形式注射入催化剂。通过从电子质量流量计上读取乙烯的摄入量来监视反应进程。5分钟后通过注射入甲醇使反应终止。将产物倒入过量的异丙醇中，并蒸发干燥。LCB分段共聚物的总产量为91.9克。
实施例3
催化剂制备：如上所述制备不锈钢催化剂加料管。加入一等分的1毫升10％甲基铝氧烷(MAO)的甲苯溶液，然后加入含0.25毫克(C5Me4SiMe2NC12H23)TiCl2和5微克Cp2ZrCl2的甲苯溶液。将密封管从手套箱中取出，并在连续的氮气流下连接到反应器的一个端口。在连续的氮气流下，将从反应器的供料管线引出的柔性不锈钢管线连接到加料管的另一端。
LCB分段共聚物的现场合成：同时氮气清洗反应器，并用两个乙烯充入/冲洗循环(至300磅/平方英寸)进行压力测试。然后将反应器的压力升至～40磅/平方英寸，以在初始操作过程中保持正反应器压力。夹套水温设定为90℃，并向反应器中加入600毫升甲苯和20毫升丁烯。搅拌器速率设定为750rpm。由于气相乙烯被吸收进溶液中，因此加入额外的乙烯以维持正反应器表压。反应器温度控制器设定为90℃，并使体系达到稳定状态。然后将乙烯压力控制器设定为100磅/平方英寸，并向体系中加入乙烯，直至乙烯摄入量测定为0，获得稳定状态为止。隔离反应器，用加压至300磅/平方英寸的甲苯迫使催化剂溶液从加料管中进入反应器。同时向反应器打开100磅/平方英寸的乙烯供料管线，目的是随着乙烯的反应消耗保持恒定的反应器压力。7分钟后通过注射入甲醇使反应终止。将产物倒入过量的异丙醇中，并蒸发干燥。LCB分段共聚物的总产量为18.5克。性能
表1中列出了选定物质的结构数据。头两个弹性体样品(1和2)中，将直接从反应器中取出的大单体作为样品，并用1H NMR和GPC表征，而对于实施例3(混合金属茂合成)，大单体和主链的性能是来自于相应的单一金属茂反应。
按照ASTM D-14的方法获得室温下和80℃的拉伸数据(图1中，室温下和80℃的断裂拉伸强度的单位是磅/平方英寸，断裂伸长率的单位是百分数)。使用与在ASTM D-14的测试方法中相同的样品在室温下测定回复率，所不同的是使样品伸长150％，然后释放10分钟，直接使用在试验样品上的参考标记测定相对于原始尺寸的回复百分率。选定样品的拉伸数据说明，统计支化的LCB分段共聚物配料，其拉伸强度等于或超过苯乙烯嵌段共聚物(Kraton)的拉伸强度，其弹性回复略微低于Kraton，但仍很好地保持在商业适用的范围内(见表1和图1)。降冰片烯LCB分段共聚物的断裂拉伸强度最大(4011磅/平方英寸)，而混合金属茂的丁烯LCB分段共聚物的弹性回复率最大(89％)。低分子量(10K，Cp2ZrCl2催化的)和高Mn(30-40K，(C5Me4SiMe2NC12H23)TiCl2催化的)的大单体，均使LCB分段共聚物具有适用的性能。
乙烯/丁烯LCB分段共聚物的弹性性能优于密度相近的EXACT4033(Exxon Chemical Company)乙烯/丁烯(E/B)无规共聚物，相当于或优于密度近似的ENGAGE8100(Dow Chemical Company)乙烯/辛烯(E/O)无规共聚物(表2)。对应的乙烯/降冰片烯(E/NB)线性和E/NB LCB分段共聚物的比较显示出，LCB分段共聚物在多数情况下有一定程度的缺陷，这部分是由于其降冰片烯含量太低。当然，所有的LCB分段共聚物与其线性对应物相比，在更高的温度下熔融，这是由于结晶性低分子量支链组分所致。值得注意的是，即使是当加热至其无定形组分的熔融温度之上，LCB分段共聚物仍保持相当的拉伸强度(参见80℃的拉伸数据)。所观察到的高温强度可能是缘于多嵌段型网络，其中无定形部分通过侧链固定在高密度、高熔融区。
产物表征：用配有DRI检测器、Shodex AT-806MS柱的高温系统Waters 150C GPC仪，在系统温度145℃下操作，分析支化烯烃共聚物产物样品。使用的溶剂为1，2，4-三氯苯，由该溶剂制备注射入的浓度为0.1mg/ml的聚合物样品溶液。总的溶剂流速为1.0ml/min，注射量为300微升。用一系列窄分布的聚苯乙烯(由Tosoh Corporation，Tokyo，1989获得)对GPC柱进行校正。为控制质量，使用了基于线性PE样品NBS-1475的宽标准校准物。用每一带有16个管形瓶的转盘进行标准的操作。每一批次的第一个样品注射两次。聚合物样品流出后，用Waters Expert Ease程序对所得谱图进行分析，计算分子量分布和平均Mn、Mw和Mz。
聚合物分析：表2中列出了反应产物的分子量、共聚单体含量和不饱和基团结构的分布。发现不饱和基团浓度(每1000个碳原子的总烯烃)和乙烯基的选择性随铝：金属比的降低而增加，其它因素相当。可通过减少溶液中乙烯的浓度(通过降低乙烯分压或提高温度)进一步增加所报道的烯烃共聚单体的浓度。
表2  支化共聚物与代表性的LLDPE的性能比较
    性能   支化共聚物E/B(#1)   支化共聚物E/NB(#2)   支化共聚物E/B(#3)   ENGAGE8100 E/O    EXACT4033 E/B
密度(g/ml)ASTM D-1505     0.887     ＞0.935     0.887     0.870     0.880
共聚单体(摩尔％ 1HNMR)     15.5     5.65     12.6     12.1     11.7
    熔点(℃，DSC)     119.2     115.5     123.5     60     63
    断裂拉伸强度磅/平方英寸(kPa)ASTM D-412     2401(16500)     4011(27700)     3054(21000)     1030(7100)     1780(12300)
   断裂伸长率(％)ASTM D-412     905     386     669     950     740
回复率(％)150％伸长     76     60     87     76     50
注：E＝乙烯，B＝丁烯，NB＝降冰片烯，O＝辛烯
表3  支化共聚物与商品三嵌段苯乙烯共聚物的性能比较(图1)
   实施例序号 反应器   拉伸嵌段(磅/平方英寸/kPa@25℃)  伸长率(％@25℃)  回复率(％@25℃)    拉伸强度(磅/平方英寸/kPa@80℃)  伸长率(％@80℃)
       1 二元   4011/27000     594     60     1544/10600     386
       2 单一   3054/21100     669     87     351/2400     505
 KratonG 1652   4002/276000     580     95     220/13500     86

Claims (7)

1.一种含有由可插入聚合的烯属不饱和单体得到的支化烯烃共聚物的热塑性弹性体组合物，该共聚物A)带数均分子量大于10000而小于45000的侧链，由DSC测定的Tg小于或等于10℃和Tm大于80℃；B)由DSC测定的Tg小于或等于-10℃的弹性体主链聚合链段；C)断裂伸长率大于或等于300％；D)拉伸强度大于或等于10300kPa；以及E)弹性回复大于或等于50％。
2.权利要求1的热塑性弹性体组合物，其中所述的支化烯烃共聚物含有由乙烯及任选地一种或多种可共聚合的单体得到的侧链，以使该侧链的Tg小于-10℃。
3.权利要求1的热塑性弹性体组合物，其中所述的支化烯烃共聚物含有由丙烯及任选地一种或多种可共聚合的单体得到的侧链，以使该侧链的Tg小于10℃，Tm大于或等于110℃。
4.权利要求1的热塑性弹性体组合物，该组合物由包含下述步骤的方法制备：A)在一聚合反应中使乙烯，以及任选地一种或多种可共聚合的单体进行共聚合，其中聚合反应包括(i)使乙烯、一种或多种α-烯烃单体和任选地一种或多种二烯单体在溶液中与活化的第4族金属茂化合物接触；和(ii)在50-150℃温度下进行该聚合反应；其中该共聚物具有大于40％链端基不饱和度；B)使A)的产物与乙烯和一种或多种可共聚合的单体进行共聚，以制备所述的支化烯烃共聚物。
5.权利要求4的热塑性弹性体组合物，其中步骤A)以溶液法进行，其中所述的乙烯和一种或多种可共聚合的单体，与被铝氧烷助催化剂活化的过渡金属烯烃聚合催化剂相接触，铝与过渡金属的摩尔比为20∶1至220∶1。
6.权利要求5的热塑性弹性体组合物，其中步骤B)用活化的过渡金属插入聚合催化剂，通过溶液、淤浆或气相乙烯聚合法，在一分离的反应中进行。
7.权利要求4的热塑性弹性体组合物，其中步骤A)和B)在混合的催化剂体系存在下同时进行，该混合的催化剂体系含有至少一种过渡金属烯烃聚合催化剂，该催化剂可制备链端基不饱和度大于40％的乙烯共聚物，以及至少一种过渡金属烯烃聚合催化剂，该催化剂可在所述的支化烯烃共聚物中并入乙烯共聚物。
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