CN1246127A - 含乙烯基的大分子单体的制备 - Google Patents

含乙烯基的大分子单体的制备 Download PDF

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CN1246127A
CN1246127A CN98802127A CN98802127A CN1246127A CN 1246127 A CN1246127 A CN 1246127A CN 98802127 A CN98802127 A CN 98802127A CN 98802127 A CN98802127 A CN 98802127A CN 1246127 A CN1246127 A CN 1246127A
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E·J·马克尔
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Abstract

本发明描述一种聚合物组合物,包括Mn为约400至75000的烯烃聚合物链,乙烯基与总烯属基团之比满足式(1),其中a=－0.24和b=0.8,和每1000个碳原子的乙烯基总数大于或等于8000÷Mn。本发明包括这些聚合产物的制备方法,包括使一或多种烯烃共聚单体与含有过渡金属催化剂化合物和铝氧烷的催化剂溶液体系接触,其中铝与过渡金属之比为10∶1至低于或等于200∶1(Al∶Me)。本发明的工艺条件可预计大分子单体的分子量和乙烯基不饱和特征。乙烯基/烯属基团≥[共聚单体的摩尔百分率+0.1]a×10a×b (1)。

Description

含乙烯基的大分子单体的制备
发明领域
本发明涉及用过渡金属催化剂化合物与铝氧烷助催化剂活化剂由烯烃制备含乙烯基的大分子单体的方法。
发明背景
已知乙烯基封端的聚合物(对于本申请而言包括由两或多种单体合成的低聚物、均聚物和共聚物)，由于在聚合物链的一端或两端有可利用的乙烯属不饱和，而适用于后聚合(或后低聚)反应。这种反应包括加成反应如用于接枝其它乙烯属不饱和部分的那些反应，和插入聚合，其中乙烯基封端的聚合物与其它单体如α-烯烃和/或其它可插入聚合的单体共聚。在后一种情况中，乙烯基封端的聚合物通常称为大分子单体。
早期研究用烷基铝氧烷如甲基铝氧烷活化的金属茂过渡金属催化剂化合物观察到：它们用于烯烃聚合时产生的不饱和端基比典型的用传统的前金属茂齐格勒-纳塔催化剂进行的插入聚合所产生的不饱和端基占聚合物的百分率更高。参见EP-A-0 129 638及其同族专利US5324 800。后来，Resconi等在“在双(五甲基环戊二烯基)锆和-铪中心的烯烃聚合：链转移机理”，美国化学会志(J.Am.Chem.Soc.)，1992，114，1025-1032中报道观察到在丙烯低聚中使用双(五甲基环戊二烯基)锆茂或铪茂利于消去β-甲基，超过通常更期望的消去β-氢负离子，作为链转移或聚合物链终止方法。这是根据观察到乙烯基端基与亚乙烯基端基之比对于锆茂在92至8的范围内，对于铪茂在98至2的范围内。
除这些观察之外，WO94/07930研究了将乙烯基封端的大分子单体掺入聚乙烯链中使聚乙烯中包括长支链的优点，其中所述大分子单体有大于3800的临界分子量，或者，换言之含有250或更多的碳原子。据说利于形成乙烯基封端的聚合物的条件是高温、无共聚单体、无链转移剂、和非溶液法或用链烷烃稀释剂的分散相。还说在聚合期间升高温度产生消去β-氢负离子的产品，例如加入乙烯以形成乙烯“封端”。该文献接着描述了一大类用铝氧烷或提供稳定的非配位阴离子的电离化合物活化时适用于该发明的单环戊二烯基和双环戊二烯基金属茂。实施例均说明路易斯酸活化剂三(全氟苯基)硼与二甲基·双(环戊二烯基)合锆在90℃的聚合温度下的应用。乙烯分别与这两种大分子单体进行共聚，使用与形成所述大分子单体所用的催化剂体系相同的催化剂体系。
WO95/11931中描述了支化的乙烯大分子单体。根据该公开，乙烯基应大于总不饱和基的75％(摩尔)、更优选大于80％(摩尔)，据说重均分子量在100至20000的范围内。据说产生所述大分子单体的方法是用含有第3至10族金属的过渡金属化合物，据说第4、5、和6族的环戊二烯基衍生物在此有令人满意的实用性。还说这些过渡金属化合物与离子化合物、铝氧烷或路易期酸反应能形成适用于聚合的离子配合物。据说过渡金属组分与铝氧烷组分之比为1/10至1/10000是理想的，或更优选为1/30至1/2000。实施例1和7说明在铝氧烷化合物与过渡金属化合物之比分别为240和2000的情况下制备乙烯大分子单体。
许多专利涉及金属茂催化剂与不同量的活化铝氧烷助催化剂的应用。其一是US4 752 597，其中在适合的溶剂中使金属茂和铝氧烷以铝金属与过渡金属之比为12∶1至100∶1的摩尔比反应制备金属茂和铝氧烷的相对不溶于烃的固体反应产物。然后分离出所述固体反应产物。据说该固体反应产物适用于气相、淤浆和溶液聚合。
现有技术还涉及在各种条件下用各种金属茂制备链端不饱和聚合物，所报道的方法产生乙烯基-、亚乙烯基-、1，2-亚乙烯基-和三取代-不饱和。通过标准的表征方法(1H-NMR或13C-NMR)难以测定不饱和链端的总量导致本领域中接受通过各类不饱和占总不饱和端的分数表征不饱和端基。然而，工业上有效的生产方法得益于不饱和端基占总端基(即包括饱和端)的浓度高。因此，所报道的分子量分布不同和不能精确地测量或预计所得链端类型、或不利于生产非乙烯基的不饱和链端限制了现有技术的实用性。一般认为乙烯基链端对于后续聚合反应中的链端官能化作用和插入作用比其它类型的反应性更高，更优选。因此，致力于改善乙烯基端链聚合物的制备方法、其预见性及其在制备支化聚合物中的用途。
发明概述
本发明包括有主要为乙烯基的烯属不饱和的烯烃聚合反应产物。在这些反应产物组合物中，乙烯基的摩尔浓度大于或等于总聚合物链摩尔浓度的50％。更具体地，由凝胶渗透色谱法(GPC)和差示折光指数(DRI)的测量结果计算，本发明是一种聚合反应产物组合物，包括数均分子量(“Mn”)为约400至约75 000的烯烃聚合物链，乙烯基与总烯属基团之比满足下式：
(1)乙烯基/烯属基团≥[共聚单体的摩尔百分率+0.1]a×10a×b
其中a＝-0.24和b＝0.8，
和每1000个碳原子的乙烯基总数大于或等于8000÷Mn。本发明还包括有高含量乙烯基不饱和的聚合物的意外而有效的制备方法，包括使一或多种烯烃单体与含有过渡金属催化剂化合物和铝氧烷的催化剂溶液组合物接触，其中铝与过渡金属之比为10∶1至220∶1。可产生大于总不饱和链的70％的含乙烯基链，同时由GPC和NMR计算总聚合物链中不饱和链的产量高。因此，用本发明的工艺条件可预计大分子单体的分子量和乙烯基不饱和特征，进一步能制备有适用于改善工艺应用的特制特性的支化聚合物，例如需要或工业上优选熔融工艺时，和在聚合物共混物中大分子单体或共聚单体组分的选择可能导致改善聚合物共混物的相容性或其它特性时。
附图简述
图1说明本发明的实施例1-24，以聚合产物中总烯属基的百分率示出乙烯基产率及其按下面式(1)的关系曲线。如本申请中所述按1H(NMR)法表征乙烯基。
发明详述
本发明的聚合性大分子单体组合物是烯烃单体的插入或配位聚合的聚合物链反应产物。有效地获得相对于聚合反应产物中不饱和链总数高比例的含乙烯基链的方法，达到高于80％含乙烯基链、甚至高于90％。对于乙烯均聚物，最高含量高于90％、甚至95％。对于共聚物，乙烯基链的含量取决于乙烯与共聚单体之比，如式(1)所定义。该聚合物组合物或反应产物含有窄多分散性的链，多分散性为1.5至约6、典型地2至4、甚至2至3.5。
本发明聚合性大分子单体的数均分子量(Mn)典型地在大于或等于400道尔顿至小于80000道尔顿的范围内，更优选小于60000道尔顿，最优选小于或等于50000道尔顿。
在前面的式(1)中，a和b的值在表A所示优选范围内。
      表A
    a     b
  -0.20    0.8
  -0.18    0.83
  -0.15    0.83
  -0.10    0.85
该聚合反应产物的每1000个碳原子的乙烯基总数典型地大于0.13且小于9.85。
如此所述物质的聚合物组成对于总聚合反应产物(包括有饱和基的聚合物链和有不饱和基的聚合物链)表现出含乙烯基链的数量较高。因此，这些聚合产物可有效地用于需要反应性乙烯基的后续反应。本发明聚合产物的此有效性的量度由所观察到的反应效率说明，即官能化反应或大分子单体共聚反应的所要反应产物的产率。总乙烯基含量越高，官能化聚合物的产率或含大分子单体支化的共聚物产率越高。
用本发明的催化剂组合物可合成各种本发明含乙烯基大分子单体的聚合反应产物，包括均聚物、共聚物和含三或多种单体的聚合物。因此，用这些催化剂聚合的单体包括但不限于：乙烯，C3-C18α-烯烃，异丁烯；环烯烃，例如降冰片烯、甲基降冰片烯、环戊烯；苯乙烯，非共轭二烯烃和环二烯烃。如上列所暗示的，可通过配位或插入聚合与乙烯共聚的任何共聚单体均适用于本发明。这还包括：内烯烃，如1-丁烯；取代的烯烃，如3-甲基-1-戊烯；多取代的烯烃，如3，3-二甲基-1-己烯和芳族烯烃。聚合反应产物中单体的组合不仅限于无规共聚物或无规共聚物的混合物。本领域中已知可用各种方法(例如不断变化的催化剂或顺序聚合法)控制链中单体和共聚单体的次序以赋予适用的性能。
本发明含乙烯基大分子单体聚合产物的制备方法涉及使一或多种烯烃单体与含有优选的铝与过渡金属之比的过渡金属催化剂化合物和铝氧烷的催化剂溶液组合物接触。该催化剂溶液的制备典型地包括使铝氧烷活化剂与过渡金属化合物在适合的溶剂中接触形成活化的催化剂溶液。甲苯是优选用于催化剂溶液的溶剂，因为铝氧烷和许多在其中活化时适用作催化剂的过渡金属化合物的溶解度高。能在很大程度上使活化剂和过渡金属化合物均溶剂化的其它溶剂也适用，可容易地经验确定。脂族和芳族溶剂均适用，只要过渡金属化合物和铝氧烷活化剂在所用混合温度下显著地溶解。
本发明含乙烯基大分子单体聚合产物的制备方法主要取决于烷基铝氧烷活化剂中铝与过渡金属之摩尔比。优选该比值≥20且≤175；更优选≥20且≤140；最优选≥20且≤100。反应的温度、压力和时间取决于所选方法，但一般在所选方法的正常范围内。因此，温度可在20至200℃的范围内，优选30至150℃，更优选50至140℃，最优选在55和135℃之间。反应压力一般可为大气压至305×103kPa，优选182×103kPa。对于典型的溶液反应，温度典型地在环境温度至250℃的范围内，压力从环境压力至3450kPa。反应可间歇进行。淤浆型反应的条件与溶液法条件相似，但反应温度限于聚合物的熔融温度。在某些反应构型中，可使用超临界流体介质，温度高达250℃，压力高达345×103kPa。在高温反应条件下，典型地产生较低分子量范围的大分子单体产物。
间歇反应时间可为1分钟至10小时，更优选5分钟至6小时，最典型地为45分钟至90分钟。反应也可连续进行。在连续法中，平均停留时间同样可在1分钟至10小时内改变，更优选5分钟至6小时，最典型地为45分钟至90分钟。
适用于本发明方法用于制备含乙烯基大分子单体反应产物的过渡金属催化剂包括一或多种过渡金属催化剂前体化合物，它有1)辅助稳定配体和2)与铝氧烷活化剂反应产生活性过渡金属催化剂配合物的附加配体。优选的化合物包括含至少一种辅助取代的或未取代的环戊二烯基(“Cp”)环作为过渡金属的配体的金属茂化合物。此处“取代”意指与一或两个Cp环的环碳原子键合的一或多个氢原子被一或多个能与所述环碳原子σ-键合的一价基取代。例子包括C1-C30烃基及其一或多个碳原子被另一第14族原子如Si或Ge取代的对应物。术语“取代”包括1)与两个不同的Cp配体或一个Cp配体和另一过渡金属配体如第15或16族杂原子配体键合的桥连或连接基，和2)稠环构型，其中两个Cp环原子通过取代基共价键连如在茚基和芴基配体中，其本身可进一步被取代和/或桥连。例子包括本领域已知适用于烯烃聚合的那些单环戊二烯基和双环戊二烯基第4-6族化合物。关于双环戊二烯基化合物，参见例如US5 324 800、5 324 801、5 441 920和5 502124。关于单环戊二烯基金属茂化合物的例子，参见US5 055 038、5 264505、和1995年10月20日申请的共同待审美国专利申请No.08/545973和1995年6月7日申请的No.08/487 25 5(由WO96/00244公开)。
本发明金属茂的定义中还包括那些环戊二烯基类似物，其中一或多个环碳原子被第14或15族杂原子取代，或在稠环体系如茚基和芴基中，其中任何稠环中的一或多种碳原子如此取代。适用的金属茂基本上包括专利文献如以上所列专利文献和关于烯烃聚合(包括涉及无定形、半结晶和结晶均聚物和多于一种单体的共聚物的那些)的学术文献中任何可用的金属茂。特别地，涉及聚乙烯聚合物和共聚物的那些文献和涉及有规立构高级烯烃如全同立构和间同立构聚丙烯聚合物和共聚物的那些文献含有适合的描述。
本领域已知能用铝氧烷活化的任何其它过渡金属烯烃聚合催化剂前体化合物特别是第4、5、6、7、8、9和10族金属的那些也适用，参见例如WO96/23010、US5 504 049、5 318 935、和共同待审美国专利申请No.08/473 693(1995年6月7日申请)和60/019 626(1996年6月17日申请)。这些文献均引入本文供参考。
适用于本发明的反应器构型包括连续、间歇和半间歇的反应器。溶液相、淤浆相、和超临界相条件适用于使用这些催化剂的烯烃聚合。此外还明确倾向于多个串联的上述类型反应器和/或多个反应条件和/或多种催化剂构型组合。
根据聚合物的溶解度、挥发性和安全/健康考虑选择优选用于溶液相反应的溶剂。优选非极性链烷烃或芳烃。对于超临界流体反应，反应介质一般由聚合物、单体、和共聚单体及可选的适合的超临界助溶剂组成。对于淤浆反应，稀释剂可为惰性液体或本体液相共聚单体。溶剂、助溶剂和共聚单体典型地通过吸附剂材料包括氧化铝和分子筛处理纯化。也可通过加入本领域公知的适合净化剂(包括但不限于烷基金属和铝氧烷)使杂质钝化。
工业实用性
其中至少一些支链由本发明含乙烯基大分子单体产品衍生的支化聚合物特别适用于例如有大分子单体衍生的支链的加工性改善的乙烯共聚物。将本发明聚合产物加入有能掺入庞大单体的催化剂化合物的插入聚合环境中可实现乙烯基大分子单体的掺入制备支化聚合物。所述催化剂包括适用于庞大的共聚单体如1-十八烯、3-甲基-1-戊烯和环烯烃如降冰片烯的插入聚合的桥连单和双环戊二烯基金属茂催化剂化合物。参见例如US5 324 801、5 444 145、5 475 075、和5 635573和WO96/000244。其它适用于本发明含乙烯基大分子单体聚合产物的催化剂体系包括但不限于上述文献中所述第4、5、6、7、8、9、和10族金属的酰氨基和亚氨基衍生物。而且，在背景部分中提及的WO94/07930描述了掺入大分子单体的优点及方法。这些文献均引入本文供参考。
对于乙烯基大分子单体产物和支化共聚物的制备，已知许多方法和大分子单体和单体物质加入反应器的次序变换是可能的，有些比其它的更有利。例如，本领域公知加入连续溶液相反应器之前用铝氧烷使金属茂预活化产生比金属茂和活化剂以两股分开的物流连续加入时有更高的活性。此外，控制预接触时间使催化剂效率最大可能是有利的，例如避免活性催化剂组合物过度老化。
本发明优选的支化共聚物是乙烯均聚物和乙烯与两或多种共聚单体的共聚物。最易得到的共聚单体是烯烃，特别是丙烯、1-丁烯、异丁烯、1-己烯、和1-辛烯。其它适用的共聚单体包括但不限于：内烯烃、环烯烃、取代的烯烃、多取代的烯烃、和芳族烯烃，如前面对于乙烯基大分子单体产物所描述的那些。根据所要聚合产物性能选择所用共聚单体，所用金属茂根据其掺入要求量烯烃的能力选择。参见描述适用于乙烯-降冰片烯共聚物的各种金属茂的US5 635 573和描述适用于乙烯-异丁烯共聚物的单环戊二烯基金属茂的共同待审美国专利申请No.08/651 030(5/21/96申请)。这些文献引入本文供参考。
为改善聚乙烯薄膜的撕裂性，较长的烯烃共聚单体如1-辛烯比较短的烯烃如丁烯更优选。为改善聚乙烯薄膜的弹性或防护性能，环状共聚单体如降冰片烯比烯烃更优选。选择反应器中共聚单体的浓度使聚合物中有要求量的共聚单体，最优选0至50％(摩尔)。
此外，可使两或多种有相同或不同共聚单体和/或相同或不同分子量的聚合性大分子单体链反应产生有理想性能的新聚合物组合物。我们发现通过接合这些大分子单体链衍生的支化/嵌段分子的统计混合物或配制混合物表现出商业适用性。可选地，可用二烯烃控制不饱和链掺入其它不饱和链。
含乙烯基的低分子量聚合产物的官能化反应包括基于含乙烯基化合物和乙烯属不饱和化合物的热或自由基加成或接枝的那些反应。工业上适用的典型实例是与马来酸、马来酐或乙烯基酸或酸酯如丙烯酸、丙烯酸甲酯等的后接枝反应。加入这些基团可通过酰胺化、酰亚胺化(immidization)、酯化等附加官能化。例如，参见US5 498 809和WO94/19436和WO94/13715。这些文献均涉及有亚乙烯基末端的乙烯-1-丁烯聚合物及其官能化成润滑油组合物中的有效分散剂。也参见EPO 513 211B1，其在用于燃料组合物的有效蜡晶体改性剂组合物中描述了类似的共聚物。适用于此的本发明聚合产物典型地有约1500至10000的Mn，优选约2000至5000Mn。这些文献均引入本文供参考。
优选使用高乙烯基不饱和的本发明聚合产物，从而在制备后它们迅速官能化或共聚。高反应性的乙烯基似乎易与外来杂质发生副反应，甚至与含其它不饱和基的聚合物链发生二聚或加成反应。因此制备后以稀浓度保持在冷却的惰性环境中和立即应用将使本发明乙烯基大分子单体产物的应用效率最佳。因此利用串联反应器或并联反应器的连续法是有效的，在一个反应器中制备乙烯基大分子单体产物，并连续地加入另一反应器。
实施例
总则：所有聚合均在配有控制温度的水夹套的1升Zipperclave反应器中进行。用校准视镜计量液体加入反应器。高纯度(＞99.5％)己烷、甲苯和丁烯进料先通过在高温氮气中活化的碱式氧化铝，然后通过在高温氮气中活化的13x分子筛纯化。聚合级乙烯直接在有氮气夹套的管线中供应，使用时不进一步纯化。来自Albemarle Inc.的10％甲基铝氧烷(MAO)的甲苯溶液接收在不锈钢筒中，分入1升玻璃容器中，储存在环境温度下的实验室手套箱中。根据需要向反应器加入乙烯保持系统总压在所报告的水平(半间歇操作)。乙烯的流速用Matheson质量流量计(型号8272-0424)监测。为确保反应介质充分混合，使用以750rpm旋转的平桨式搅拌器。
反应器的准备：首先清洁反应器，在甲苯中加热至150℃使任何聚合物残余溶解，然后冷却并排放。然后用110℃的夹套水加热反应器，并用流动的氮气吹扫反应器～30分钟。反应前，用10次氮气加压/放空循环(至100psi)和2次乙烯加压/放空循环(至300psi)进一步吹扫反应器。循环有三个目的：(1)彻底渗透所有死端如压力表以清除短效污染物，(2)用乙烯置换系统中的氮气，和(3)对反应器压力试验。
催化剂的制备：所有催化剂制备均在水含量＜1.5ppm的惰性气氛中进行。为精确测量很小量的催化剂(通常低于1mg)，在催化剂制备中使用新制备的催化剂原料溶液/稀释法。为使金属茂的溶解度最大，用甲苯作为溶剂。用MAO洗涤不锈钢移送管去除杂质，排放，并通过移液吸管(MAO在前)加入活化剂和催化剂。
大分子单体的合成：首先，使催化剂移送管与反应器口相连，在连续氮气流下清除环境空气。然后，如上所述对反应器进行吹扫和压力试验。然后，将600ml溶剂装入反应器，加热至所要温度。然后加入共聚单体(如果有)，使温度平衡，记录系统的基本压力。在系统基本压力之上加入所要分压的乙烯。使乙烯饱和该系统后(由乙烯流量为0指示)，用高压力溶剂脉冲注射催化剂。由电子质量流量计读乙烯的摄入监视反应进程。已积累要求量的大分子单体时，终止乙烯流，通过迅速冷却(～1分钟)和加入过量甲醇使聚合产物沉淀终止反应。聚合物/溶剂混合物在流动的环境空气中干燥。
产品的表征：用配有DRI检测仪、Showdex AT-806MS柱的Waters150℃高温系统，在145℃的系统温度下操作，通过凝胶渗透色谱法分析聚合产物试样。所用溶剂为1，2，4-三氯代苯，由其制备0.1mg/ml浓度的聚合物试样溶液用于注射。总溶剂流速为1.0ml/min，注射器尺寸为300微升。用一系列窄聚苯乙烯(来自TosohCorporation，Tokyo，1989)校准GPC柱。为控制质量，用基于线性PE试样NBS-1475的宽标准标定。用16-瓶圆盘传送带进行标定。每批的第一试样注射两次。聚合物试样洗脱后，用Waters Expert Fuse程序分析所得色谱计算分子量分布和Mn、Mw和Mz均值之一或多个。用Randall方法，大分子化学物理评述(Rev.Macromo.Chem.Phys.)，C29，(2&3)，p.285-297使长链支化定量化。用500mHz Varian Unity模型，在125℃操作，用d2-四氯乙烷作溶剂，进行1H-NMR分析。用100mHz频率的Varian Unity Plus模型在相同条件下进行13C-NMR分析。
实施例1
催化剂的制备
如上所述准备不锈钢催化剂加料管。加入一等分0.25ml 10％甲基铝氧烷(MAO)的甲苯溶液，然后加入0.5ml含1mg Cp2ZrCl2(二氯·双环戊二烯基合锆)/ml的甲苯溶液。从手套箱中取出密封管，在连续氮气流下与反应器口相连。在连续氮气流下将来自反应器供应歧管的软不锈钢管线与加料管的另一端相连。
均聚
对反应器同时进行氮气吹扫和用2次乙烯填充/清除循环(至300psig)(2170kPa)的压力试验。然后使反应器压力升至～40psig(377kPa)以在开始操作期间保持正反应器压力。夹套水温设在90℃，向反应器加入600ml甲苯。搅拌器设置在750rpm。随着气相乙烯被吸收至溶液中，加入附加乙烯以保持正反应器表压。反应器温控器设置在90℃，使系统达到稳态。再将乙烯压力调节器设置在100psig(791kPa)，向系统加乙烯直至通过乙烯摄入量为0测量达到稳态。隔离该反应器，用加压至300psig(2170kPa)的甲苯脉冲迫使催化剂溶液从加料管移至反应器。立即将100psig(791kPa)的乙烯供应歧管开向反应器以在反应消耗乙烯时保持反应器压力恒定。反应30分钟后，将反应溶液迅速冷却，加入200ml甲醇终止反应并使聚合物沉淀。将产物移至2升的敞口盆中，在环境空气中干燥，产生38g聚乙烯均聚物。表1中概括了实施例1的反应条件。
实施例2-7
催化剂的制备
实施例2-7的MAO活化的Cp2ZrCl2催化剂与实施例1的相同，但催化剂溶液(含1mg Cp2ZrCl2/ml的甲苯)的用量和10％MAO的甲苯溶液的用量不同。这些催化剂配方示于表1中。
均聚
实施例2-7所用反应条件仅与实施例1中所用条件有微小改变。这些改变示于表1中。
实施例8
催化剂的制备
以与实施例1相似的方式制备催化剂，区别仅在于Cp2ZrCl2和MAO活化剂的用量不同。表1中概括了这些催化剂的制备。
共聚
如实施例1中准备反应器，但在添加液体之前用氮气填充反应器。加入甲苯后，加入50ml丁烯，使反应器温度平衡在90℃。记录基本压力为25psig(273kPa)。加入乙烯使系统的总平衡压力达125psig(963kPa)，或者说产生100psia(688kPa)的乙烯分压。注射催化剂后10分钟，通过冷却和加入甲醇终止反应。干燥后分离出64g乙烯/丁烯共聚物。
实施例9-10
催化剂的制备
实施例9-10中Cp2ZrCl2催化剂和MAO活化剂的用量示于表1中。用实施例1的方法准备加料管和催化剂溶液。
共聚
按实施例8的方法，将氮气、溶剂和丁烯加入反应器，加热至90℃。记录基本压力，设置乙烯压力调节器添加乙烯使乙烯的平衡分压升至100psia(689kPa)。用乙烯饱和该系统(通过乙烯摄入量为0测量)后，注射催化剂。表1所示持续时间后加入甲醇终止反应。
实施例11
催化剂的制备
将一等分2.5ml 10％MAO的甲苯溶液加至如上准备的不锈钢催化剂加料管中。然后将2ml含0.5mg(C5Me4SiMe2NC12H23)TiCl2(二氯·(四甲基环戊二烯基)二甲基甲硅烷基(环十二碳氨基)合钛)/ml的甲苯溶液加至加料管。
均聚
用与实施例1基本相同的步骤进行聚合，但用表1所示条件。干燥后，得到17g均聚物。
实施例12-15
催化剂的制备
用实施例11的步骤准备催化剂和活化剂。区别仅在于催化剂溶液和MAO活化剂的量不同(见表1)。
均聚
实施例12-15中所用步骤与实施例1 1相同，但条件稍微不同示于表1中。
实施例16-19
催化剂的制备
用实施例11的方法制备催化剂和活化剂。活化剂和催化剂的用量见表1。
共聚
向充满氮气的反应器中加入溶剂，然后加入1-丁烯。将反应器加热至所要反应温度(见表1)，记录压力。调节乙烯供应调节器在保持表中所列乙烯绝对分压所需压力下供应乙烯。然后将乙烯供应开向反应器直至达到平衡，由乙烯流量为0指示。密封该反应器，用高压溶剂(甲苯或己烷，取决于反应所用溶剂)注射催化剂。所示反应时间后，使产物迅速冷却、用甲醇终止，在环境空气中干燥。
实施例20-22
催化剂的制备
含1mg((CH3)2Si(C9H6)2)HfCl2(二氯·二甲基甲硅烷基双茚基合铪)/ml的甲苯溶液加至10％MAO甲苯溶液中配制催化剂。用量示于表1中。
共聚
所用共聚反应方法与实施例16-19相同，但在实施例21中，将氢气加至反应器。如下供应氢气：将甲苯和丁烯加至含有氮气的洁净反应器。将反应器加热至90℃，记录(基本)压力为30psig(308kPa)。加入氢气使系统压力升至130psig(998kPa)(氢气分压100psia(689kPa))。然后将乙烯调节器设置在230psig(1687kPa)，使系统的乙烯分压为100psia(689kPa)。然后以与实施例20相似的方式进行反应。
实施例23&24
催化剂的制备
分别使用实施例1和11中所述Cp2ZrCl2和(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。先将MAO(10％甲苯溶液)加入催化剂加料管，然后加入(C5Me4SiMe2NC12H23)TiCl2的溶液和Cp2ZrCl2的溶液。
均聚
使用与实施例1基本相同的步骤。只是条件不同(表1)。
聚合物分析
表2中报告了反应产物的分子量、共聚单体含量、和不饱和基结构分布。发现不饱和基浓度(每1000个碳原子的总烯烃)以及乙烯基选择性随铝∶金属之比的降低而增加，所有其它因素相同。降低溶液中乙烯浓度(通过降低乙烯分压或增加温度)可进一步增加烯烃浓度(共聚单体)。
表1.反应条件
实施例 催化剂* 催化剂量(mg) 乙烯分压(psi) 反应温度(℃) MAO**(ml) Al/金属比 己烷(ml) 甲苯(ml) 1-丁烯(ml) 氢气分压(psi) 时间(min) 产量(g)
 1c  a  0.5  100  90  0.25  172  0  600  30  38
 2  a  4  100  90  0.25  21.5  0  600  30  34
 3  a  8  100  90  0.5  21.5  0  600  18  58
 4  a  32  20  90  2  21.5  0  600  30
 5c  a  0.5  100  90  0.25  172  600  0  30  11
 6  a  8  100  90  0.5  21.5  600  0  30  19
 7  a  32  15  90  2  21.5  600  0  30  2
 8c  a  0.5  100  90  0.25  172  0  600  50  10  64
 9c  a  1  100  90  0.5  172  600  0  50  30
 10  a  32  100  90  2  21.5  600  0  50  10  31
 11c  b  1  100  90  2.5  1375  0  600  30  17
 12  b  8  20  90  0.5  34.4  0  600  5
 13c  b  1  100  90  2.5  1375  600  0  30  12
 14  b  32  17  90  2  34.4  600  0  30
 15c  b  10  30  90  6  1375  600  0  20
 16c  b  1  100  90  1.5  825  0  600  10  30  15
 17c  b  1  100  90  1.5  825  0  600  50  30  22
 18  b  16  100  90  1  34.4  0  600  10  30
 19c  b  1  100  60  2.5  1375  600  0  50  30  21
 20c  c  1  100  90  0.5  316  0  600  50  30  6.5
 21  c  5  130  90  1.25  158  0  600  50  100  30  36
 22c  c  1  100  90  0.5  316  600  0  50  30  5
 23  a+b  32+1.5  60  90  3  31.4  600  0  60  47
 24c  a+b  1+1  30  90  1  212  0  600  30
*a＝Cp2ZrCl2    b＝(C5Me4SiMe2NC12H23)TiCl2    c＝((CH3)2Si(C9H6)2)HfCl2
**MAO＝10wt.％甲基铝氧烷的甲苯溶液
表2.聚合物分析
实施例#   Mn   Mw   Mw/Mn   ％烯烃按乙烯基计   每1000C乙烯基  每1000C1，2-亚乙烯基 每1000C亚乙烯基 每1000C三取代 mole％丁烯 wt.％丁烯 每1000CLCB
  1c   47184   101961   2.161   51.5   0.17   0.08   0.03   0.05
  2   25154   55516   2.207   91.4   0.32   0.03   0   0
  3   24619   54085   2.197   94.6   0.35   0.02   0   0
  4   5657   14916   2.637   88.4   2.05   0.15   0.12   0
  5c   39544   102041   2.580   76.0   0.19   0.04   0.02   0
  6   12933   46941   3.630   89.5   0.77   0.09   0   0
  7   1744   4710   2.701   85.4   10.16   0.36   0.74   0.63
  8c   10222   35513   3.474   18.5   0.17   0.08   0.02   0.65   4.4   8.5
  9c   10315   33214   3.220   36.1   0.35   0.09   0.36   0.17   2   3.9
  10   6964   35992   5.168   64.3   2.96   0.06   0.07   1.51   3.9   7.5
  11c   110000   332087   3.019
  12   22124   125359   5.666   89.6   0.43   0.03   0.02   0
  13c   99900   288000   2.883
  14   3655   13117   3.589   86.1   2.48   0.12   0.11   0.17
  15c   14087   37966   2.695   64.3   0.36   0.10   0.05   0.05   0.21
  16c   57187   134710   2.356   63.2   0.12   0.02   0.05   0
  17c   62704   153163   2.443   14.3   0.03   0.07   0.01   0.1   35.9   52.8
  18   48611   173905   3.577   84.6   0.22   0   0   0.04   5.8   10.9
  19c   190105   402985   2.120   5.9   0.01   0.02   0   0.14   31.7   48.1
  20c   81835   211882   2.589   6.7   0.02   0.09   0.05   0.14   16.8   28.7
  21   7014   23431   3.341   56.3   0.09   0.02   0.04   0.01   12.5   22.2
  22c   63906   148475   2.323   14.6   0.06   0.11   0.06   0.18   16.1   27.7
  23   4396   17467   3.973   90.0   2.71   0.12   0.18   0
  24c   27359   56997   2.083   59.3   0.32   0.16   0.03   0.03
以下实施例说明本发明大分子单体的制备和它们与可共聚单体共聚形成长链支化的共聚物。
实施例I
催化剂的制备
如上所述准备不锈钢催化剂加料管。加入一等分1ml 10％甲基铝氧烷(MAO)的甲苯溶液，然后加入16mg Cp2ZrCl2的甲苯溶液。从手套箱中取出密封管，在连续氮气流下与反应器口相连。在氮气流下使来自反应器供应岐管的软不锈钢管线与加料管的另一端相连。
大分子单体的合成
对1升反应器同时进行氮气吹扫和用2次乙烯填充/清除循环(至300psig)(2170kPa)的压力试验。然后使反应器压力升至～20psig(239kPa)以在开始操作期间保持正反应器压力。夹套水温设在90℃，向反应器加入600ml甲苯。搅拌器设置在750rpm。随着气相乙烯被吸收至溶液中，加入附加乙烯以保持正反应器表压。反应器温控器设置在90℃，使系统达到稳态。再将乙烯压力调节器设置在20psig，向系统加乙烯直至通过乙烯摄入量为0测量达到稳态。隔离该反应器，用加压至300psig(2170kPa)的甲苯脉冲迫使催化剂溶液从加料管移至反应器。立即将20psig(239kPa)的乙烯供应歧管开向反应器以在反应消耗乙烯时保持反应器压力恒定。反应8分钟后，将反应溶液迅速加热至150℃30分钟以杀伤催化剂，然后冷却至90℃。由加料口取少量大分子单体试样。通过13C-NMR分析显示大分子单体中不存在可测量的长支链。大分子单体的数均和重均分子量分别为9268和23587道尔顿，81.7％的烯烃为乙烯基。
实施例II
支化聚合物的制备
取完大分子单体试样后立即将25g 80.7％降冰片烯的甲苯溶液加至实施例I反应器的内容物中。使含有0.5ml 10％MAO的甲苯溶液和1mgCpCp*ZrCl2的催化剂加料管与加料口相连。通过调节乙烯供应调节器并使系统达到平衡(由流入反应器的乙烯为0指示)，使90℃反应器的总压升至100psig(791kPa)。用300psig(2170kPa)的甲苯脉冲注射催化剂。反应20分钟后，迅速使系统放空和冷却。用过量甲醇熄灭试样并蒸发至干。分离出42g乙烯-降冰片烯共聚产物，含有均聚乙烯支链和乙烯-降冰片烯主链的支化聚合物。该产物的13C-NMR分析显示存在每1000个碳原子0.085个长支链。
实施例III
催化剂的制备
如上所述准备不锈钢催化剂加料管。加入一等分2ml 10％甲基铝氧烷(MAO)的甲苯溶液，然后加入32mg(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液。从手套箱中取出密封管，在连续氮气流下与反应器口相连。在氮气流下使来自反应器供应岐管的软不锈钢管线与加料管的另一端相连。
大分子单体的合成
对2升反应器同时进行氮气吹扫和用2次乙烯填充/清除循环(至300psig)(2170kPa)的压力试验。然后使反应器压力升至约40psig(377kPa)以在开始操作期间保持正反应器压力。夹套水温设在90℃，向反应器加入1200ml甲苯和20ml丁烯。搅拌器设置在750rpm。随着气相乙烯被吸收至溶液中，加入附加乙烯以保持正反应器表压。反应器温控器设置在90℃，使系统达到稳态。再将乙烯压力调节器设置在40psig(377kPa)，向系统加乙烯直至通过乙烯摄入量为0测量达到稳态。隔离该反应器，用加压至300psig(2170kPa)的甲苯脉冲迫使催化剂溶液从加料管移至反应器。立即将40psig(377kPa)的乙烯供应歧管开向反应器以在反应消耗乙烯时保持反应器压力恒定。反应25分钟后，将反应溶液迅速加热至147℃15分钟以杀伤催化剂，然后冷却至90℃。将系统连续排空并用氮气吹扫至干以除去溶剂和乙烯及丁烯单体。然后加入1200ml甲苯，使系统在90℃下平衡。由加料口取乙烯-丁烯大分子单体试样。该大分子单体的数均和重均分子量分别为22394和58119。通过FTIR测量获得大分子单体的共聚单体含量为6.6％(摩尔)丁烯。
实施例IV
支化聚合物的制备
通过调节乙烯供应调节器并使系统达到平衡(由流入反应器的乙烯为0指示)，使实施例III的反应器(在90℃)的内容物加压至100psig。使含有2ml 10％MAO的甲苯溶液和2mg(C5Me4SiMe2NC12H23)TiCl2的甲苯溶液的催化剂加料管与加料口相连。用300psi的甲苯脉冲注射催化剂。反应10分钟后，使系统压力升至300psig(2170kPa)。反应23分钟后，迅速使系统放空和冷却。用过量甲醇熄灭试样并蒸发至干。分离出69.5g产物，通过FTIR分析，均聚乙烯主链有56％(重)实施例III的乙烯-丁烯大分子单体支链。
用GPC法使高分子量的支化物质与低分子量的大分子单体分离，然后通过FTIR确定大分子单体和高分子量支化聚合物中丁烯的量，测量链支化。高分子量的支化物质中丁烯的平均含量为3.7％(摩尔)，而大分子单体产物中为6.6％(摩尔)。支化水平由下式计算：
表1.反应条件
参考号 催化剂* 催化剂量(mg) 乙烯分压(psi) 反应温度(℃) MAO**(ml) Al/金属比 甲苯(ml) 1-丁烯(ml) 降冰片烯(80.7％甲苯溶液) 时间(min) 产量(g)
 I  a  16  20  90  1  34.4  600  -  -  8  -
 II  b  1  100  90  0.5  275  600  -  25g  20  42
 III  c  32  40  90  2  34.4  1200  20  -  25  -
 IV  c  2  100/300  90  2  550  1200  -  -  23  69.5
*a＝Cp2ZrCl2；b＝Cp((Me5)Cp)ZrCl2；c＝(C5Me4SiMe2NC12H23)TiCl2
**MAO＝10wt.％甲基铝氧烷的甲苯溶液

Claims (11)

1.一种组合物，包括Mn为约1500至75000的烯烃聚合物链，乙烯基与总烯属基团之比满足下式：
(1)乙烯基/烯属基团≥[共聚单体的摩尔百分率+0.1]a×10a×b
其中a＝-0.24和b＝0.8，和每1000个碳原子的乙烯基总数大于或等于8000÷Mn。
2.权利要求1的组合物，其中a＝-0.20。
3.权利要求1的组合物，其中a＝-0.18和b＝0.83。
4.权利要求1的组合物，其中a＝-0.15和b＝0.83。
5.权利要求1的组合物，其中所述烯烃聚合物包括一或多种由乙烯、C3-C12α-烯烃、异丁烯和降冰片烯组成的基团。
6.有高含量乙烯基不饱和的聚合物的制备方法，包括使一或多种烯烃单体与含有过渡金属催化剂化合物和铝氧烷的催化剂溶液组合物接触，其中铝与过渡金属之比为10∶1至220∶1。
7.权利要求6的方法，其中铝与过渡金属之比为20∶1至140∶1。
8.权利要求6的方法，其中铝与过渡金属之比为20∶1至100∶1。
9.权利要求6的方法，其中所述过渡金属催化剂化合物为能用铝氧烷活化用于烯烃聚合的第4、5、6、7、8、9、10族金属之一。
10.权利要求9的方法，其中所述过渡金属催化剂化合物为双环戊二烯基第4族金属化合物。
11.权利要求9的方法，其中所述过渡金属催化剂化合物为单环戊二烯基第4族金属化合物。
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CN103443139A (zh) * 2011-03-25 2013-12-11 埃克森美孚化学专利公司 乙烯基封端的高级烯烃聚合物及其生产方法
CN103443139B (zh) * 2011-03-25 2016-10-12 埃克森美孚化学专利公司 乙烯基封端的高级烯烃聚合物及其生产方法
CN104428326A (zh) * 2012-09-27 2015-03-18 埃克森美孚化学专利公司 乙烯基封端聚合物及其制造方法
CN111788238A (zh) * 2017-11-07 2020-10-16 诺瓦化学品(国际)股份有限公司 乙烯互聚物产品和膜
CN111788238B (zh) * 2017-11-07 2023-01-24 诺瓦化学品(国际)股份有限公司 乙烯互聚物产品和膜

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BR9806952A (pt) 2000-03-21
WO1998034965A1 (en) 1998-08-13
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CA2276214A1 (en) 1998-08-13
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EP0958309A1 (en) 1999-11-24
US6555635B2 (en) 2003-04-29
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DE69836415T3 (de) 2014-03-27
US20020077434A1 (en) 2002-06-20
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