CN1032008C - 加聚催化剂的制备方法 - Google Patents

加聚催化剂的制备方法 Download PDF

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CN1032008C
CN1032008C CN91104485A CN91104485A CN1032008C CN 1032008 C CN1032008 C CN 1032008C CN 91104485 A CN91104485 A CN 91104485A CN 91104485 A CN91104485 A CN 91104485A CN 1032008 C CN1032008 C CN 1032008C
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罗·E·拉泊影特
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Abstract

公开了一类无干扰性胺或膦副产物的式L1MX+A的加聚催化剂，其制备方法是用式(Ox+a)b(A-)d的氧化剂氧化式L1MX2的4族或镧系金属衍生物，其中各符号如说明书所定义。

Description

加聚催化剂的制备方法
本发明涉及可用作催化剂物质的组合物，这些催化剂组合物的制备方法，和用这类组合物作为加聚催化剂的方法。更具体地说，本发明涉及催化剂组合物及其制备方法和用这些催化剂聚合烯烃、二烯烃和/或炔属不饱和单体的方法。
当然，用齐格勒-纳塔型催化剂聚合可加聚单体是本技术领域中公知的。一般来说，这些可溶性系统含4族或镧系金属化合物和金属烷基化物助催化剂，特别是烷基铝助催化剂。
EP-A-0277,004公开了某类二(环戊二烯基)金属化合物，它是通过二(环戊二烯基)金属配合物与含非配位相容阴离子的质子酸(Bronsted acid)盐反应形成的。该文献公开了这样的配合物可用作聚合烯烃的催化剂。上述EP-A-0277,004所述内容在此援引以供参考。
遗憾的是，现已发现按上述技术制得的催化剂受所含的副产物胺或由形成催化剂产生的膦化合物的不利影响。也就是说，EP-A-0277,004方法涉及金属化合物的配位体和质子酸盐的阳离子之间的不可逆反应。实际上，这种阳离子一般是在催化剂形成过程上由质子专移到配位体上形成叔胺或膦的三烷基铵或膦离子。这种胺或膦化合物因对加聚反应有抑制作用，所以是所得催化剂的不需要的组分。
如果提供一种能以只形成非干扰性和惰性副产物的方式而活化的加聚催化剂，则是很理想的。
美国化学学会杂志109，4111—413(1987)公开了一种通过d°有机金属化合物的一个电子氧化制备阳离子锆(IV)苄基配合物的方法。用于制备茂锆的溶剂是四氢呋喃或二氯甲烷，这两种物质均干扰所需催化剂的形成和(或)对后序烯烃聚合选成不利影响。另外，该文献使用了一种含四苯基硼酸根的氧化剂。现已发现，这种阴离子用于制备加聚催化剂的氧化活化法时是不能接受的。
现已发现，采用本发明的方法可以避免或至少可以降低现有技术的烯烃离子聚合催化剂的前述和其它缺点。另外，本发明提供了一种改进的催化剂活化工序和改进的加聚方法。所以，本发明一个目的是提供可用于聚合包括烯烃、二烯烃和/或炔属不饱和单体在内的可加聚单体的改进的离子催化剂系统。本发明的另一目的是提供这种改进的催化剂的制备方法。本发明的又一个目的是提供一种用这种改进的催化剂的改进的聚合方法。本发明的又一个目的是提供一种不形成干扰化合物的改进的催化剂。本发明最后一个目的是提供一种可更好地控制聚合产物分子量和分子量分布的改进的催化剂。
本发明提供一种可用于加聚反应的催化剂，这种催化剂基本上无胺付产物，其结构式如下：
LlMX+A-
其中：L各次出现相互无关地是一配位体或配位系，M是元素周期表4族金属或镧系金属；X是氢化物或具有20个以下的碳、硅或锗原子的烃基、甲硅烷基或甲锗烷基；l是大于或等于
优选M是元素周期表的4族金属，最优选是钛或锆。而且，优选X是氢化物或C1—C10烃基。
此外，本发明提供了一种制备上述加聚催化剂的方法，该方法包括使一种符合下式的4族金属或镧系金属的衍生物
             LlMX2(式中L，l，M和X定义如上)与一种在还原态不干扰所得催化剂的氧化剂接触，所述氧化剂含有一种阳离子氧化剂和相容的非配位阴离子。
该氯化剂具有以下结构式：
(Ox+a)b(A-)d             (I)其中：Ox +a是一种非质子酸、具有能氧化4族或镧系金属的衍生物的(+a)电荷的阳离子氧化剂，A-定义如前；以及b和d选自能提供电荷平衡的整数。
根据情况可在一种惰性稀释剂(如有机液)中使4族或镧系金属的衍生物与上述氧化剂接触而制取催化剂。
这里所用的元素周期表均指由CRC新闻有限公司1989年出版和具有版权的元素周期表。还有，所述族指的是采用IUPAC命名系统在元素周期表中反映的族。
术语“配位体或配位系”指的是辅助供电子或共享电子部分。这样的配位体包括阴离子配位体和中性供体配位体。
合适的阴离子的配位体的典型但非限制例有：R，-R′(OR′)mOR，(OR′)mOR，-PR2，-SR，-OR，-NR2氢化物和含14族元素的有机准金属基，其中在所述有机准金属的有机部分中所含的各烃基相互无关地含有1—20个碳原子。在这些配位体中：
R是烃基，甲硅烷基，甲锗烷基，或具有1—24个碳、硅或锗原子的取代的烃基、甲硅烷基或甲锗烷基；R′是C2-10亚烷基，以及m是整数0—10。
合适的中性供体配位体(L′)的典型但非限制例有：ROR，NR3，PR3和SR2，其中R定义如上。
这里所用的术语“阳离子氧化剂”指的是具有足以使4族金属或镧系金属衍生物分子氧化成催化物质的氧化电位的有机或无机离子。一般且优选衍生物的4族或镧系金属已是最高原子氧化态。本发明的方法包括分子氧化。大多数优选的阳离子氧化剂具有至少+0.20V，最好至少+0.25V的氧化电位。阳离子氧化剂不是质子酸。
这里所用的术语“相容的非配位阴离子”意指这样的阴离子，当它在本发明催化剂系统中起着电荷平衡阴离子的作用时不将其阴离子取代基或链段转移给任何阳离子物形成中性的4族或镧系金属的产物。“相容阴离子”是在催化剂的制备或使用过程中不降鲜成中性的阴离子。
这里所用的术语“准金属”包括那些显示出半金属特性的非金属，如硼、磷等等。
进一步优选的衍生物以式L″MX2表示，其中L″是将受限几何形状给与金属活性部位并含有20个以下的非氢原子的取代的环戊二烯基或类似的非定域П键基的衍生物，以及M和X定义如上。
这里所用的术语“受限几何形状”意指因环戊二烯基或取代的环戊二烯基上的一个或多个取代基形成了部分环状结构，金属原子被迫很大程度上露出活性金属，环状结构金属连到相邻的共价部分上并通过η5其它П键相互作用保持与环戊二烯基或取代二环戊二烯基缔合。可以理解，金属原子和环戊二烯基或取代的环戊二烯基的构原子之间的各个键不必是相同的。也就是说，金属可对称或不对称地П键合到环戊二烯或取代的环戊二烯基上。
以下进一步定义活性金属部位的几何形状。环戊二烯基或取代的环戊二烯基的重心可定义为构成环戊二烯基或取代的环戊二烯基原子中心的各X、Y和Z坐标的平均值。在环戊二烯基或取代的环戊二烯基的重心与金属配合物的相互配位体之间的金属中心处形成的角Q通过单一晶体X-射线衍射的标准技术容易地计算出。每个这样的角可依受限金属配合物的分子结构的不同而提高或降低。这样的配合物，即其中一个或多个角Q比类似相当的配合物(不同的只是氢取代了受限诱导取代基)中的小，具有本发明所要求的受限几何形状。与相当的配合物相比，优选一个或多个上述角Q降低至少5％，更优选降低7.5％。特别优选的是，所有键角的平均值也比相当的配合物中低。
本发明的4族金属或镧系金属的单环戊二烯基金属配位配合物最好具有受限几何结构，以便最小的角Q低于115℃，更好低于110℃，最佳低于105℃。
特别优选的衍生物化合物是下式I表示的单环戊二烯基化合物：
Figure C9110448500101
其中：M是钛或锆；Cp *是以η5合方式键合到M上的环戊二烯基或取代的环戊二烯基；Z是含氧、硼或元素周期14族元素的二价部分；Y的含氮、磷、氧或硫的连接基，或Z和Y一起构成一稠合环系；以及X定义如前。
在分子氧化之后，本发明特别优选的催化剂由下式II表示：其中：Cp *，Z，M，X和A-定义如前。
环戊二烯基中的各碳原子可以被选自烃基、取代的烃基(其中一个或多个氢原子被卤素原子所取代)、烃取代的准金属基(其中准金属选自元素周期表14族元素)和卤素基团的相同或不同的基团取代或未取代。另外，两个或多个这样的取代基可一起构成稠合环系。可用于取代环戊二烯基中至少一个氢原子的合适的烃基和烃取代基含有1—20个碳原子，包括直链或支化烷基、环烃基、烷基取代的环烃基、芳基和烷基取代的芳基。合适的有机准金属基包括14族元素的一-，二-和三-取代的有机准金属基，其中各烃基含有1—20个碳原子。更具体地说，合适的有机准金属基包括三甲基甲硅烷基，三乙基甲硅烷基，乙基二甲基甲硅烷基，甲基二乙基甲硅烷基，三苯基甲锗烷基，三甲基甲锗烷基等等。
最优选的衍生物化合物是下式表示的酰氨基硅烷或酰氨基联二亚烷基(alkanediyl)化合物：
Figure C9110448500111
其中；M是键合到η5-环戊二烯基上的钛或锆；R′每次出现相互无关地选自氢、具有10个以下碳或硅原子的甲硅烷基、烷基、芳基和它们的混合物；E是硅或碳；X每次出现相互无关地是氢化物、C10以下的烷基或芳基；和m是1或2。
上述最优选的金属的配位化合物的例子包括这样的化合物，其中酰氨基上的R′是甲基、乙基、丙基、戊基、己基(包括其异构体在内)、降冰片基、苄基、苯基等等；该环戊二烯基是环戊二烯基、茚基、四氢茚基、芴基、八氢芴基、等等；上述环戊二烯基上的R′每次出现分别是氢、甲基、乙基、丙基、丁基、戊基、己基(包括异构体在内)、降冰片基、苄基、等等；且X是甲基、新戊基、三甲基甲硅烷基、降冰片基、苄基、甲基苄基、苯基等等。具体化合物有(叔丁酰氨基)(四甲基η5-环戊二烯基)-1，2-联二亚乙基二甲基锆，(叔丁酰氨基)甲基-η5-环戊二烯基)-1，2-联二亚乙基二甲基苄基钛，(甲酰氨基)(四甲基-η5-环戊二烯基)-1，2-联二亚乙基二苯甲基锆，(甲酰氨基)(四甲基-η5-环戊二烯基)-1，2-联二亚乙基三辛基钛，(乙酰氨基)(四甲基-η5-环戊二烯基-亚甲基二苯基钛，(叔丁酰氨基)二苄基(四甲基-η5-环戊二烯基)硅烷二苄基锆，(苄酰氨基二甲基)(四甲基-η5-环戊二烯基)硅烷二(三甲基甲硅烷基)钛，以及(苯基磷酰基)二甲基(四甲基-η5-环戊二烯基)硅烷二苄基锆。
在最优选的方案中，-Z-Y-是具有10个以下非氢原子的酰氨基硅烷或酰氨基烷基，即：(叔丁酰氨基)(二甲基甲硅烷基)，(叔丁酰氨基)-1-乙烷-2-基，等等。
可用于制备本发明改进的催化剂的衍生物化合物是无活性氢(除氢化物离去基X之外)或其中可能的活性氢被大的保护基保护住的共价键合的金属化合物。在这类金属衍生物化合物上合适的有机取代基有降冰片基，新戊基，三甲基甲硅烷基和二苯基甲基。合适的衍生物化合物的典型但非限制例有：四降冰片基钛，四苄基锆，四新戊基钛，二苯氧基二(三甲基甲硅烷基)锆，二(2，6-二异丙基-4-甲基)苯氧基二苄基钛，三(叔丁基硅氧基)三甲基锆，二甲氧基二苯甲基钛，二(2，4，6-三甲基苯氧基)二苄基钛，丁氧基三[(三甲基甲硅烷基)甲基]锆，二降冰片基二甲基钛，三苄基氢化钛等等；环戊二烯基和二(环戊二烯基)金属化合物，例如二(环戊二烯基)二甲基锆，环戊二烯基三苄基锆，环戊二烯基三甲基钛，环戊二烯基三甲基锆，二(环戊二烯基)二新戊基钛，环戊二烯基三(二苯基甲基)锆，二(环戊二烯基)二苯基锆，环戊二烯基三新戊基钛，二(环戊二烯基)二(间甲苯基)锆，二环戊二烯基二(对甲苯基)锆；烃基取代的环戊二烯基或二(环戊二烯基)化合物，例如五甲基环戊二烯基)-(环戊二烯基)二甲基锆，二(乙基环戊二烯基)二甲基锆，(五甲基环戊二烯基)三苄基锆，(正丁基环戊二烯基)三新戊基钛，环戊二烯基二甲基氢化钛，二(环戊二烯基)二(二苯基甲基)锆，二(叔丁基环戊二烯基)二(三甲基甲硅烷基甲基)锆，二(环已基环戊二烯基)二甲基锆，(苄基环戊二烯基)二(间甲苯基)甲基钛，(二苯基环戊二烯基)二降冰片基甲基锆，二甲基环戊二烯基)二苯基锆，(四乙基环戊二烯基)三苄基锆，(丙基环戊二烯基)(环戊二烯基)二甲基锆，二(丙基环戊二烯基)二甲基锆，(正丁基环戊二烯基)二甲基(正丁氧基)钛，环戊二烯基二苯基异丙氧基锆，(环已基甲基环戊二烯基)环戊二烯基二苄基锆，二[(环已基)甲基环戊二烯基]二苄基锆，二(环戊二烯基)二氢化锆，苄基环戊二烯基二甲基铪，二(茚基)二苄基锆，(叔丁酰氨基)二甲基(四甲基-η5-环戊二烯基硅烷二苄基锆，(苄酰氨基)二甲基(四乙基-η5-环戊二烯基)硅烷二丁基钛等等；金属烃基取代的环戊二烯基金属化合物，如[(三甲基甲硅烷基)环戊二烯基]三甲基锆，二[(三甲基甲锗烷基)环戊二烯基]二甲基钛，[(三甲基甲锡烷基)环戊二烯基]三苄基锆，[(五-三甲基甲硅烷基)环戊二烯基](环戊二烯基)二甲基锆，二[(三甲基甲硅烷基)环戊二烯基]二甲基锆，五[(三甲基甲硅烷基)环戊二烯基]三苄基钛，二[三甲基甲锗烷基)环戊二烯基]二苄基铪，卤代环戊二烯基化合物，如[三氟甲基)环戊二烯基](环戊二烯基)二甲基锆，二[(三氟甲基)环戊二烯基]二降冰片基锆，[(三氟甲基)环戊二烯基]三苄基锆；甲硅烷基取代的(环戊二烯基)金属化合物，如二(环戊二烯基)二(三甲基甲硅烷基)锆，环戊二烯基三(苯基二甲基甲硅烷基)锆；桥基环戊二烯基金属化合物，如亚甲基二[(环戊二烯基)二甲基锆]，亚乙基-二[(环戊二烯基)二苄基锆]，(二甲基亚甲硅烷基)-二-[(环戊二烯基)二甲基钛]，亚甲基-二-(环戊二烯基)二(三甲基甲硅烷基)锆，(二甲基亚甲硅烷基)-二-(环戊二烯基二辛戊二烯基铪)，亚乙基-二-(四氢茚基)二苄基锆和二甲基亚甲硅烷基(芴基)(环戊二烯基)二甲基钛。
当然，可应用于本发明催化剂组合物的其它化合物、特别是含有其它4族或镧系金属的化合物对于本技术领域专业人员来说是很明显的。在制备本发明化合物中可用作氧化剂的化合物包含一种阳离子氧化剂和前述一种或多种相容的非配位阴离子。
在优选方案中，前式(I)的A-c包括一种含多个亲油基的单一配位配合物，所述亲油基共价键合到并屏蔽住带有中心形成电荷的金属或准金属原子，其阴离子很大，在氧化条件和随后聚合条件下是稳定的，并与所得的含4族金属或镧系金属的催化剂相容且不与其发生配合。所用的阴离子只提供电荷平衡而不干扰O的氧化能力或所得催化剂的催化性质。能形成在本发明反应条件下稳定的配位配合物的任何金属或准金属均可包含在阴离子中。合适的金属包括但不局限层于铝、金和铂。合适的准金属包括但不限于硼、磷和硅。最优选含阴离子的氧化剂，包括含单一硼原子的配位配合物。
特别适用于制备本发明催化剂的含硼阴离子由以下通式表示：
             [BX1X2X3X4]-其中：B是3价态硼；X1-X4是含6—20个碳或硅原子的相同或不同的非反应性有机或甲硅烷基。另外，两个或多个X1-X4可通过一稳定的桥基相互连接。优选X1-X4无活性氢部分。也就是说，这些基团无氢、只在非活性部位中含氢或含有足够的位阻来保护潜在的活性氢部位。X1-X4合适的基团的例子是含6-20个碳原子的全氟烃基，3，4，5-三氟苯基等等。
最优选的相容的非配位阴离子是四(五氟苯基)硼根(borate)。
本发明所用的合适的有机阳离子氯化剂包括二茂铁鎓离子，二茚基Fe(III)离子和取代的二茂铁的阳离子衍生物，以及类似的分子物。合适的金属阳离子氧化剂包括Ag+1，Pd+2，Pt+2，Hg+2，Hg2 +2，Ag+和Cu+。最优选的阳离子氧化剂是二茂铁鎓和Ag+1阳离子。
在制备本发明改进的催化剂中用的氧化剂的典型但非限制例是四(五氟苯基)硼化二茂铁，四-3，4，5-三氟苯基硼化金(I)，四(五氟苯基)硼化银和四-3，5-双三氟甲基苯基硼化1，1-二甲基二茂铁。
可以列出类似的含有其它金属和准金属用作氯化剂的合适的化合物，但为了公开而列出这样的化合物是没有必要的。在这方面应指出，列出所有化合物不仅不能完全，而且从前面通式本领域专业人员很容易发现适用的其它硼化合物以及含有其它金属如准金属的有用的化合物。
不希望受任何具体操作理论的束缚，据信阳离子氧化剂使4族或镧系金属衍生物的分子氧化，在本方法中成为中性物。氧化的金属衍生物通过单分子脱除反应丢掉氢或烃基(·R)。两个或多个这样的烃基形成氢分子或式Rx的中性有机物(其中x是大于或等于2的整数)。这些付产物当然是中性的，不会干扰后面的聚合反应，而且还可从反应混合物中除掉。这种结果远比会形成胺或类似反应付产物的前面公知的催化剂活化法要好。
应指出，必须选择这两种用于制备活性催化剂的结合的化合物，以避免阴离子链段、特别是芳基转移到金属阳离子上形成催化惰性物。这可通过位阻，即在连接4族或镧系金属的基因上进行取代或在阴离子的芳碳原子上进行取代而实现。然后，含有例如全烃取代的环戊二烯基的4族金属和镧系金属化合物(第一种组分)可有效地与比第一种组分范围更宽的第二种化合物一起使用。但是，由于金属取代基的含量和尺寸下降，用含有更耐降解的阴离子的第二种化合物(例如在苯环的间位和/或对位上有取代基的化合物，得到了更有效的催化剂。使阴离子更耐降解的另一种方法是在阴离子中进行氟取代，特别是全氟取代。这样，含氟取代的稳定阴离子的第二种组分可与范围更宽的第一种组分一起便用。
一般来说，在-100℃-300℃的某一温度及在一种合适的溶剂中合并这两种组分可制取催化剂。
可使用这种催化剂聚合单独的或混合物形式的α-烯烃和／或C2-C18炔属不饱和单体和/或C4-C18二烯烃。催化剂也可用于聚合α-烯烃、二烯烃和/或炔属不饱单体与其它不饱和单体。一般来说，聚合可在本领域公知的齐格勒一纳塔型或Kaminsky—Sinn型聚合反应条件下进行，也就是说，温度为0—250℃，压力为大气压-1000大气压(100MPa)。需要的活，可采用悬浮液溶液、淤浆或其它工艺条件。可使用载体，但最好以均相方式使用催化剂。当然，如果直接将组分加到聚合工艺中而且在所述聚合工艺中使用合适的溶剂或稀释剂(包括浓缩单体在内)，不用说催化剂系统将就地形成。但是，优先选择在加到聚合混合物之前，在合适的溶剂及单独步骤中形成催化剂。
如上所述，本发明改进的催化剂最好在一合适的溶剂如稀释剂中制备。合适的溶剂如稀释剂包括现有技术中公知的、能用作聚合烯烃、二烯烃和炔属不饱和单体的溶剂的任何溶剂。合适的溶剂包括直链和支链的烃，如异丁烷，丁烷、戊烷、己烷、庚烷、辛烷、以及它们的混合物，环烃或脂环烃，如环已烷、环庚烷、甲基环已烷、甲基环庚烷；全氟烃，如全氟C4-10烷和芳基和烷基取代的芳基化合物，如苯，甲苯和二甲苯。合适的溶剂还包括液体烯烃，它们可起着单体或共聚用单体的作用，其例子有乙烯、丙烯、丁二烯、环戊烯、1-己烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1，4-已二烯、1-辛烯、1-癸烯、苯乙烯、二乙烯、二乙基苯、烯丙基苯和乙烯基甲苯(包括全部单独或混合物形式的异构体在内)。
据信，本发明活性催化剂物质含有一个金属中心，它仍保持阳离子性、不饱和性和具有与烯烃、二烯烃和炔属不饱和化合物反应的全属碳键。式A-的电荷平衡的阴离子残余也与该金属中心缔合。
按本发明方法形成的催化剂可保持在溶液中，或从溶剂中分出、隔离和贮藏，便于以后使用。如前指出，催化剂也可在聚合反应中就地加以制备，即将各组分加入到聚合反应器中，在此各组分接触和反应，得到本发明改进的催化剂。
4族金属或镧系金属化合物衍生物与所用的氧化剂的当量比优选为0.1∶1—10∶1，更优选为0.75∶1—2∶1，最佳1.0∶1.0。在大多数聚合反应中，催化剂与所用的可聚合化合物的当量比为10-12∶1—10-1∶1，更优选10∶1—10-3∶1。
某些本发明催化剂(特别是那些以单环戊二烯基取代的钛化合物为基础并结合含硼氧化剂的催化剂)的有利特点是，当本发明的催化剂用于单独共聚合α-烯烃类、或共聚合α-烯烯与二烯烃的混合物时，与用比较普通的齐格勒-纳塔型催化剂制得的共聚物相比，结合到共聚物中的较高分子量的烯烃或二烯烃的量显著提高。乙烯和较高级α-烯烃与前述本发明钛基催化剂反应的相对速率如此相似，以至在用本发明催化剂制得的共聚均中的单体分布可通过单体反应物之比得以控制。
按照本发明通常可聚合的“可加聚单体”的例子有烯属不饱和单体，炔属化合物，共轭或非共轭二烯烃，多烯，一氧化碳，等等。优选单体包括C2-10α-烯烃，特别是乙烯、丙烯、异丁烯、1-丁烯、1-己烯、4-甲基-1-戊烯和1-辛烯。其它优选单体包括苯乙烯、卤代-或烷基取代的苯乙烯，四氟乙烯，乙烯基苯并环丁烷和1，4-已二烯。
一般来说，可以选择催化剂，以便得到的聚合物产物中无某些微量的杂质，例如在用齐格勒纳塔型催化剂制得的聚合物中常见的铝、镁和氯化物。因此，用来发明催化剂制得的聚合物产物应具有比比较常用的、含金属烷基化物(如烷基铝)的齐格勒-纳塔型催化剂制得的聚合物更宽的应用范围。
在对本发明进行了介绍之后，以下用实施例进一步说明本发明，但这些实施例并不意味着限制本发明。所有份数和百分数均以重量计，除非另外注明。
实施例1
通过在50ml纯化脱气的甲苯中合并50毫摩尔二(环戊二烯基)二苄基锆和50毫摩尔全氟四苯基硼化二茂铁，制备催化剂混合物。搅拌混合物约30秒，直至放出蓝色二茂铁鎓。聚合反应
在4升反应器中，将催化剂与含有2升混合的烷烃溶剂(Isopar ETM，Exxon化学有限公司产)、75ml氢(于50psi，350kPa)和乙烯(31大气压，3.1MPa)的混合物合并。反应物预先脱气和纯化，并将反应器中的物料加热到170℃。加入10ml实施例1的催化剂。乙烯立即迅速地被摄取且反应器内的温度显著上升(乙烯摄取率高于每分钟100克，温度升高大于17℃)。反应10分钟后，将反应器中的物料取出并脱挥发份，得到46克高密度聚乙烯。
实施例2
往25ml脱气纯化的甲苯中加入25毫摩尔(叔丁酰氨基)二甲基(四甲基-η5-环戊二烯基)硅烷二苄基锆和25毫摩尔全氟四苯基硼化二茂铁。搅拌混合物约1分钟，直至排出蓝色固体二茂铁鎓。聚合反应
往4反应器中加入2升混合烷烃溶剂(IsoparETM)和300ml 1-辛烯，加热到150℃并用乙烯加压到31大气压(3.1MPa)。所有组分预先脱气和纯化。加入2ml上述催化剂溶液后乙烯立即迅速地被摄取，且反应器温度大幅度上升(乙烯摄取率为每分钟50克，温升26℃)。10分钟后，将反应器中的物料取出并脱挥发份，剩下78克乙烯/1-辛烯共聚物。根据物料衡算测定，聚合物的1-辛烯含量为7.5摩尔％。
实施例3
在5毫升甲苯中混合各为10毫摩尔的(叔丁酰氨基)二甲基(η5-2，3，4，5-四甲基环戊二烯基)硅烷二苄基钛和全氟四苯基硼化二茂铁，以制备催化剂溶液，搅拌30秒后，消耗了蓝色二茂铁并形成了褐绿色溶液。聚合反应
在130℃下将该催化剂溶液加到搅拌着的(500rpm)含Isopar-E(1000ml)、1-辛烯(200ml)、氢(于50psi下50ml，350kPa)和乙烯(于450psi下饱和，3MPa)的2升反应器中，从而温升了45℃。催化剂溶液加到反应器中10分钟后，从反应器中取出反应器内的物料，汽提挥发物，得到104克线型低密度聚乙烯。
实施例4
在5ml甲苯中，用各为10毫摩尔的全氟四苯基硼化二茂铁和2-(η5-环戊二烯基)-2-(η5-芴基)丙烷二苄基锆制备催化剂混合物。搅拌1分钟后，得到浅绿色溶液。聚合反应
在50℃下，将该催化剂溶液加到搅拌着的(500rpm)内含丙烯(200克)、Isopar-E(600ml)和1-苯烯(200ml)的反应器中。加入催化剂后温升了10℃，尽管-10℃的乙二醇/水混合物通过反应器内冷却盘管循环，仍维持了3分钟。30分钟后，取出反应器内的物料，脱挥发份，得到167克透明的橡胶状间规丙烯/1-辛烯共聚物。

Claims (7)

1.一种制备下式加聚催化剂的方法：
          LlMX+A-其中：
L每次出现相互无关地是一配位体或配位体系；
M是元素周期表4族金属或镧系元素；
X是氢化物，至多20个碳、硅或锗原子的烃基、甲硅烷基或甲锗烷基，
l是大于或等于1的整数；以及
A-是四(五氟苯基)硼酸根、四(3，4，5—三氟苯基)硼酸根或四(3，5—双三氟甲基苯基)硼酸根，该方法包括使式LlMX2表示的4族或镧系金属衍生物(其中L，l，M和各X分别定义如上)与一种满足下式的氧化剂接触，
              (Ox +a)b(A-)d其中：Ox +a是二茂铁鎓基或Ag+；A-定义如上；以及b和d选自能提供电荷平衡的整数。
2.根据权利要求1所述的方法，其中M是钛或锆。
3.根据权利要求1所述的方法，其中L是
a)一种选自R、-R′(OR′)mOR、(OR′)mOR、-PR2、-SR、-OR、-NR2、氢化物和含有一个14族元素的有机准金属基，其中有机准金属的有机部分中所含的各烃取代基相互无关地含有1—20个碳原子，其中
R是烃基，甲硅烷基，甲锗烷基或含1—24个碳、硅或锗原子的取代的烃基、甲硅烷基或甲锗烷基；
R′是C2-20亚烷基，以及
m是0—10的整数；或
b)一种选自ROR、NR3、PR3、和SR2的中性供体配位体，其中R定义如上。
4.根据权利要求1所述的方法，其中LlMX2具有下式结构：
Figure C9110448500031
其中：
M是钛或锆；
X如权利要求1定义，
Cp*是以η5结合方式键合到M上的环戊二烯基或取代的环戊二烯基；
Z是含氧、硼或元素周期表14族元素的二价部分；以及
Y是含氮、磷、氧或硫的连接基，Z和Y也可一起构成稠合环系。
5.根据权利要求4所述的方法，其中各X相互无关地为氢化物，至多C10的烷基或芳基；Y是NR′，且Z是(ER2′)m，其中E是硅或碳，各R′相互无关地是氢，含至多10个碳或硅原子的甲硅烷基、烷基、芳基或其组合。
6.根据权利要求4所述的方法，其中X是氢化物或C1—C10烃基。
7.根据权利要求6所述的方法，其中X是苄基。
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