CN1057845A - 具有氧化活性的加聚催化剂 - Google Patents

具有氧化活性的加聚催化剂 Download PDF

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CN1057845A
CN1057845A CN91104485A CN91104485A CN1057845A CN 1057845 A CN1057845 A CN 1057845A CN 91104485 A CN91104485 A CN 91104485A CN 91104485 A CN91104485 A CN 91104485A CN 1057845 A CN1057845 A CN 1057845A
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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 LlMX+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LlMX2的4族或镧系金属 衍生物，其中各符号如说明书所定义。

Description

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付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付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;1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：
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Ⅱ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或其它Ⅱ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Ⅱ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 91104485X_IMG2
其中：M是钛或锆;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：
Figure 91104485X_IMG3
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 91104485X_IMG4
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-联二亚乙基二辛基钛，（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（环己基环戊二烯基）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，（环己基甲基环戊二烯基）环戊二烯基二苄基锆，二[（环己基）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，Hg+2 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使用。
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）。需要的话，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，如环己烷、环庚烷、甲基环己烷、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-己二烯、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。或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-己二烯。
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（Isopar ETM）和300ml1-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 (18)

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，具有20个以下碳、硅或锗原子的烃基、甲硅烷基或甲锗烷基，
1是大于或等于1的整数；以及
A-是一价相容的非配位阴离子，该方法包括使式LlMX2表示的4族或镧系金属衍生物(其中L，1，M和各X分别定义如上)与一种在还原态下不干扰所得催化剂的氧化剂接触，所述氧化剂表示为
(Ox+a)b(A-)d
其中：Ox+a是一种具有能氧化Ⅳ族或镧系金属的衍生物的电荷(+a)的非质子酸阳离子氧化剂；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，其中阳离子氧化剂具有至少+0.20V的氧化电位。
3、根据权利要求2所述的方法，其中阳离子氧化剂具有至少+0.25V的氧化电位。
4、根据前述权利要求中任一项所述的方法，其中O +ax选自二茂铁鎓;二茚Fe（Ⅲ）;取代的二茂铁鎓的阳离子衍生物;以及金属阳离子。
5、根据权利要求4所述的方法，其中O +ax是二茂铁鎓或Ag+1。
6、根据前述权利要求中任一项所述的方法，其中A-是
[BX1X2X3X4]-
其中：B是3价态硼，X1-X4是相同或不同的、含6-20个碳或硅原子的非反应性有机基团或甲硅烷基且视情况两个或多个X1-X4可通过稳定的桥基相互连接。
7、根据权利要求6所述的方法，其中X1，X2，X3和X4是含6-20个碳原子全氟烃基。
8、根据前述权利要求中任一项所述的方法，其中M是钛或锆。
9、根据前述权利要求中任一项所述的方法，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的阴离子配位体，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C2-10亚烷基，以及
m是0-10O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。
10、一种选自根据前述权利要求中任一项所述的方法其中L是将受限几何形状赋予给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衍生物。
11、根据权利要求10所述的方法，其中LiMX2具有下式结构：
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。
12、根据权利要求11所述的方法，其中各X相互无关地为氢化物，C10以下的烷基或芳基;Y是NR′，且Z是（ER′2）m，其中各R′相互无关地是氢，含10个碳或硅原子的甲硅烷基、烷基、芳基或其组合。
13、根据前述权利要求中任一项所述的方法，其中Z是氢化物或C1-C10烃基。
14、根据权利要求13所述的方法，其中X是苄基。
15、一种加聚催化剂，它基本上无胺或膦付产物并具有以下结构式：
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族金属或镧系金属;
X是氢化物或含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1的整数
A是一价相容的非配位阴离子。
16、根据权利要求15所述的催化剂，其中L，l，M，X和A-按权利要求1-14中任一项所定义。
17、用权利要求15或16所述的催化剂或权利要求1-14中任一项所述的方法得到催化剂作为加聚催化剂。
18、一种催化加聚的方法，其特征在于催化剂是按权利要求15或16所定义的或按权利要求1-14中任一项所述的方法制取的。
CN91104485A 1990-07-03 1991-07-02 加聚催化剂的制备方法 Expired - Fee Related CN1032008C (zh)

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Families Citing this family (376)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE37788E1 (en) * 1987-01-30 2002-07-09 Exxon Chemical Patents, Inc. Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
US5384299A (en) * 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5264405A (en) * 1989-09-13 1993-11-23 Exxon Chemical Patents Inc. Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalysts
US7163907B1 (en) * 1987-01-30 2007-01-16 Exxonmobil Chemical Patents Inc. Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization
US5198401A (en) * 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5621126A (en) * 1987-01-30 1997-04-15 Exxon Chemical Patents Inc. Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
US5763547A (en) * 1992-10-02 1998-06-09 The Dow Chemical Company Supported catalyst complexes for olefin in polymerization
US6825369B1 (en) * 1989-09-14 2004-11-30 The Dow Chemical Company Metal complex compounds
US5801113A (en) * 1990-06-22 1998-09-01 Exxon Chemical Patents, Inc. Polymerization catalyst systems, their production and use
US5272003A (en) * 1990-10-26 1993-12-21 Exxon Chemical Patents Inc. Meso triad syndiotactic polypropylene fibers
US5189192A (en) * 1991-01-16 1993-02-23 The Dow Chemical Company Process for preparing addition polymerization catalysts via metal center oxidation
GB9107378D0 (en) * 1991-04-08 1991-05-22 Ici Plc Olefin polymerisation
US6545088B1 (en) 1991-12-30 2003-04-08 Dow Global Technologies Inc. Metallocene-catalyzed process for the manufacture of EP and EPDM polymers
FR2688783A1 (fr) * 1992-03-23 1993-09-24 Rhone Poulenc Chimie Nouveaux borates d'onium ou de complexe organometallique amorceurs cationiques de polymerisation.
US6147184A (en) * 1992-03-23 2000-11-14 Rhone-Poulenc Chimie Onium borates/borates of organometallic complexes and cationic initiation of polymerization therewith
US5374696A (en) * 1992-03-26 1994-12-20 The Dow Chemical Company Addition polymerization process using stabilized reduced metal catalysts
US6143854A (en) 1993-08-06 2000-11-07 Exxon Chemical Patents, Inc. Polymerization catalysts, their production and use
JP3332051B2 (ja) * 1992-12-18 2002-10-07 出光興産株式会社 重合用触媒及び該触媒系を用いる重合体の製造方法
GB9226905D0 (en) 1992-12-24 1993-02-17 Wellcome Found Pharmaceutical preparation
FR2702485B1 (fr) * 1993-03-10 1995-04-14 Rhone Poulenc Chimie Compositions à base de polyorganosiloxanes réticulables par voie cationique et leur utilisation dans le domaine de l'antiadhérence papier, de la protection des fibres optiques et des circuits imprimés.
EP0812854B2 (en) * 1993-06-07 2011-04-20 Mitsui Chemicals, Inc. Novel transition metal compound, olefin polymerization catalyst comprising said compound, process for olefin polymerization using said catalyst and propylene homo- and copolymer
EP0629631B1 (en) * 1993-06-07 2002-08-28 Mitsui Chemicals, Inc. Novel transition metal compound, and polymerization catalyst containing it
US5470993A (en) * 1993-06-24 1995-11-28 The Dow Chemical Company Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom
US5514728A (en) * 1993-07-23 1996-05-07 Minnesota Mining And Manufacturing Company Catalysts and initiators for polymerization
US5455333A (en) * 1993-08-16 1995-10-03 Albemarle Corporation Preparation of metallocenes
US5504223A (en) * 1994-01-25 1996-04-02 The Dow Chemical Company Synthesis of cyclopentadienyl metal coordination complexes from metal hydrocarbyloxides
CN1104444C (zh) * 1994-04-11 2003-04-02 三井化学株式会社 丙烯聚合物组合物的制备方法
CA2157400C (en) * 1994-04-11 2003-07-29 Takashi Ueda Process for preparing propylene polymer composition, and propylene polymer composition
US6160066A (en) * 1994-06-24 2000-12-12 Exxon Chemical Patents, Inc. Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
US5955625A (en) * 1995-01-31 1999-09-21 Exxon Chemical Patents Inc Monocyclopentadienyl metal compounds for ethylene-α-olefin-copolymer production catalysts
US5543480A (en) * 1994-06-28 1996-08-06 The Dow Chemical Company Polymerization process using diene containing catalysts
US5486632A (en) * 1994-06-28 1996-01-23 The Dow Chemical Company Group 4 metal diene complexes and addition polymerization catalysts therefrom
US5972822A (en) * 1994-08-02 1999-10-26 The Dow Chemical Company Biscyclopentadienyldiene complex containing addition polymerization catalysts
US6111020A (en) * 1994-09-02 2000-08-29 The Dow Chemical Company Crosslinked foams from blends of ethylene vinyl acetate and ethylene-styrene interpolymers
US5495036A (en) * 1994-09-12 1996-02-27 The Dow Chemical Company Metal (III) complexes containing conjugated, non-aromatic anionic II-bound groups and addition polymerization catalysts therefrom
US5541349A (en) * 1994-09-12 1996-07-30 The Dow Chemical Company Metal complexes containing partially delocalized II-bound groups and addition polymerization catalysts therefrom
TW369547B (en) 1994-09-21 1999-09-11 Mitsui Chemicals Inc Olefin polymerization catalyst and process for olefin polymerization
US5536797A (en) * 1994-10-03 1996-07-16 The Dow Chemical Company Syndiotactic prochiral olefin polymerization process
US7153909B2 (en) 1994-11-17 2006-12-26 Dow Global Technologies Inc. High density ethylene homopolymers and blend compositions
US5464906A (en) * 1994-11-21 1995-11-07 The Dow Chemical Company Ethylene homopolymerization using group 3 metal complexes
WO1996016094A1 (en) * 1994-11-23 1996-05-30 The Dow Chemical Company Preparation of syndiotactic polyolefins from prochiral olefins
US5625015A (en) 1994-11-23 1997-04-29 Exxon Chemical Patents Inc. Method for making supported catalyst systems and catalyst systems therefrom
US5512693A (en) * 1994-12-07 1996-04-30 The Dow Chemical Company Preparation of titanium (II) or zirconium (II) complexes
JP3375780B2 (ja) * 1995-03-29 2003-02-10 三井化学株式会社 重包装袋用ポリエチレン樹脂組成物およびその組成物からなる重包装袋用ポリエチレン樹脂フィルム
TW401445B (en) * 1995-07-13 2000-08-11 Mitsui Petrochemical Ind Polyamide resin composition
KR100414757B1 (ko) 1995-07-14 2004-06-04 스미또모 가가꾸 고오교오 가부시끼가이샤 전이금속착체,그것의제조방법,그전이금속착체를함유하는올레핀중합촉매,및올레핀중합체의제조방법
CN1080724C (zh) * 1995-08-31 2002-03-13 住友化学工业株式会社 过渡金属配合物,烯烃聚合催化剂及生产烯烃聚合物的方法
IT1276070B1 (it) 1995-10-31 1997-10-24 Siac It Additivi Carburanti Processo per la preparazione di polimeri a base di etilene a basso peso molecolare
AU717137B2 (en) * 1995-11-24 2000-03-16 Ciba Specialty Chemicals Holding Inc. Borate coinitiators for photopolymerization
US5854362A (en) * 1995-12-11 1998-12-29 The Dow Chemical Company Supported biscyclopentadienyl metal complexes
US5856256A (en) * 1996-02-20 1999-01-05 Northwestern University Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations
US6291695B1 (en) 1996-02-20 2001-09-18 Northwestern University Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon
US6274752B1 (en) 1996-02-20 2001-08-14 Northwestern University Organo-Lewis acid as cocatalyst for cationic homogeneous Ziegler-Natta olefin polymerizations
IT1282666B1 (it) 1996-02-22 1998-03-31 Enichem Spa Catalizzatore metallocenico sostituito per la (co) polimerizzazione delle olefine
CN1216554A (zh) * 1996-05-07 1999-05-12 陶氏化学公司 改进的亚乙烯基芳烃的间同立构聚合方法
JPH10152509A (ja) * 1996-05-14 1998-06-09 Mitsui Chem Inc 気相重合方法及びそのための気相重合装置ならびにブロワー
JPH09309926A (ja) 1996-05-17 1997-12-02 Dow Chem Co:The エチレン共重合体の製造方法
AU718884B2 (en) 1996-06-17 2000-04-20 Exxon Chemical Patents Inc. Mixed transition metal catalyst systems for olefin polymerization
US6066603A (en) * 1996-06-17 2000-05-23 Exxon Chemical Patents Inc. Polar monomer containing copolymers derived from olefins useful as lubricant and useful as lubricant and fuel oil additivies process for preparation of such copolymers and additives and use thereof
US5811379A (en) 1996-06-17 1998-09-22 Exxon Chemical Patents Inc. Polymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such polymers and additives and use thereof (PT-1267)
CA2260985A1 (en) * 1996-07-22 1998-01-29 Richard D. Ernst Metal complexes containing bridged, non-aromatic, anionic, dienyl groups and addition polymerization catalysts therefrom
DE69730718T2 (de) 1996-08-08 2005-09-22 Dow Global Technologies, Inc., Midland Metallkomplexe enthaltend ein an position 3 substituierte cyclopentadienylgruppe und ein olefinpolymerisationsverfahren
TW412560B (en) 1996-09-04 2000-11-21 Dow Chemical Co Compositions and adhesives comprising a substantially random interpolymer of at least one vinylidene and at least one vinylidene aromatic monomer or hindered aliphatic vinylidene monomer, and coextruded or laminated multilayer film and tape
EP0927288B1 (en) 1996-09-04 2002-03-13 The Dow Chemical Company Floor, wall or ceiling covering
US6015868A (en) * 1996-10-03 2000-01-18 The Dow Chemical Company Substituted indenyl containing metal complexes and olefin polymerization process
US6812289B2 (en) 1996-12-12 2004-11-02 Dow Global Technologies Inc. Cast stretch film of interpolymer compositions
US6184319B1 (en) 1996-12-20 2001-02-06 Sumitomo Chemical Company, Limited Olefin polymer, films or sheets made therefrom, and process for the production of olefin polymer
WO1998030587A2 (en) 1997-01-08 1998-07-16 Hercules Incorporated Metal halide solid acids and supported metal halides as catalysts for the preparation of hydrocarbon resins
WO1998033872A1 (fr) 1997-01-31 1998-08-06 Mitsui Chemicals, Inc. Huile lubrifiante ou composition d'huile lubrifiante et composition de fioul
AR012582A1 (es) 1997-04-14 2000-11-08 Dow Global Technologies Inc Composiciones polimericas de elongacion mejorada y formulaciones adhesivas de fusion en caliente que incluyen dicha composicion
JP3817015B2 (ja) * 1997-04-14 2006-08-30 三井化学株式会社 環状オレフィン系共重合体およびその用途
TW420693B (en) 1997-04-25 2001-02-01 Mitsui Chemicals Inc Olefin polymerization catalysts, transition metal compounds, and <alpha>-olefin/conjugated diene copolymers
US6420507B1 (en) 1997-05-01 2002-07-16 The Dow Chemical Company Olefin polymers prepared with substituted indenyl containing metal complexes
US6319969B1 (en) 1997-06-26 2001-11-20 The Dow Chemical Company Interpolymer compositions for use in sound management
US6262161B1 (en) 1997-06-26 2001-07-17 The Dow Chemical Company Compositions having improved ignition resistance
US6172015B1 (en) 1997-07-21 2001-01-09 Exxon Chemical Patents, Inc Polar monomer containing copolymers derived from olefins useful as lubricant and fuel oil additives, processes for preparation of such copolymers and additives and use thereof
KR20010022700A (ko) 1997-08-08 2001-03-26 그래햄 이. 테일러 바닥, 벽 또는 천장 피복재로 사용하기에 적합한 시이트재, 및 그를 제조하기 위한 방법 및 중간체
US7232871B2 (en) 1997-08-12 2007-06-19 Exxonmobil Chemical Patents Inc. Propylene ethylene polymers and production process
US6921794B2 (en) 1997-08-12 2005-07-26 Exxonmobil Chemical Patents Inc. Blends made from propylene ethylene polymers
US6635715B1 (en) 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
DE69828975T2 (de) 1997-08-15 2006-01-12 Dow Global Technologies, Inc., Midland Filme aus im wesentlichen homogenen linearen olefinischen polymerzusammensetzungen
KR20010023332A (ko) 1997-08-27 2001-03-26 그래햄 이. 테일러 가공성이 개선된 탄성중합체
US6150297A (en) 1997-09-15 2000-11-21 The Dow Chemical Company Cyclopentaphenanthrenyl metal complexes and polymerization process
US6630545B2 (en) 1997-09-15 2003-10-07 The Dow Chemical Company Polymerization process
HUP0004603A2 (hu) 1997-10-17 2001-04-28 The Dow Chemical Company Alfa-olefin monomerek egy vagy több vinil- vagy vinilidén-aromás monomerrel és/vagy egy vagy több gátolt alifás vagy cikloalifás vinil vagy vinilidén monomerrel alkotott interpolimerjét és vezetőképes adalékanyagokat tartalmazó elegyek
US6716786B1 (en) 1998-02-20 2004-04-06 The Dow Chemical Company Supported catalyst comprising expanded anions
ES2196835T3 (es) 1998-02-20 2003-12-16 Dow Global Technologies Inc Activadores cataliticos que comprenden aniones expandidos.
US6699573B1 (en) 1998-03-16 2004-03-02 Dow Global Technologies Inc. Liner compositions
TW568829B (en) 1998-03-26 2004-01-01 Mitsui Chemicals Inc Laminated film
TW562810B (en) 1998-04-16 2003-11-21 Mitsui Chemicals Inc Catalyst for olefinic polymerization and method for polymerizing olefine
CA2334908A1 (en) 1998-06-12 1999-12-16 Avery Dennison Corporation Multilayered thermoplastic film and sign cutting method using the same
KR100581789B1 (ko) 1998-07-01 2006-05-23 엑손모빌 케미칼 패턴츠 인코포레이티드 프로필렌의 결정성 중합체 및 결정화가능한 중합체를포함하는 탄성 블렌드 조성물
US6403773B1 (en) 1998-09-30 2002-06-11 Exxon Mobil Chemical Patents Inc. Cationic group 3 catalyst system
CN1134467C (zh) 1998-11-02 2004-01-14 杜邦唐弹性体公司 剪切稀化的乙烯/α-烯烃共聚体及它们的制备
US5993707A (en) * 1998-12-04 1999-11-30 The Dow Chemical Company Enlarged cell size foams made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers
US6048909A (en) * 1998-12-04 2000-04-11 The Dow Chemical Company Foams having increased heat distortion temperature made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers
US6187232B1 (en) * 1998-12-04 2001-02-13 The Dow Chemical Company Acoustical insulation foams
US6231795B1 (en) 1998-12-04 2001-05-15 The Dow Chemical Company Soft and flexible foams made from blends of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic and/or sterically hindered aliphatic or cycloaliphatic vinyl or vinylidene interpolymers
JP2002531721A (ja) 1998-12-08 2002-09-24 ザ ダウ ケミカル カンパニー 熔融接合可能なポリプロピレン／エチレン重合体の繊維および該繊維製造用組成物
TW576843B (en) 1998-12-25 2004-02-21 Mitsui Chemicals Inc Olefin polymerization catalyst and process for olefin polymerization using the olefin polymerization catalyst
US6632885B2 (en) 1999-04-13 2003-10-14 Mitsui Chemicals, Inc. Soft syndiotactic polypropylene composition and molded product
US6339134B1 (en) 1999-05-06 2002-01-15 Univation Technologies, Llc Polymerization process for producing easier processing polymers
US6555634B1 (en) 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
WO2000069870A1 (en) 1999-05-13 2000-11-23 The Dow Chemical Company Metal complexes containing bridging heteroatom for olefin-polymerization-process
JP3808243B2 (ja) 1999-07-27 2006-08-09 三井化学株式会社 軟質樹脂組成物
US6331597B1 (en) 1999-08-09 2001-12-18 The Dow Chemical Company Azidosilane-modified, moisture-curable polyolefin polymers, process for making, and articles obtained therefrom
US6524702B1 (en) 1999-08-12 2003-02-25 Dow Global Technologies Inc. Electrical devices having polymeric members
US6362270B1 (en) 1999-08-12 2002-03-26 The Dow Chemical Company Thermoplastic compositions for durable goods applications
ES2646296T3 (es) 1999-08-17 2017-12-13 Dow Global Technologies Llc Composición polimérica fluida
US6559090B1 (en) 1999-11-01 2003-05-06 W. R. Grace & Co.-Conn. Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation
US6399535B1 (en) 1999-11-01 2002-06-04 W. R. Grace & Co.-Conn. Coordination catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation
EP1242471B1 (en) 1999-12-10 2012-02-29 Dow Global Technologies LLC Substituted group 4 metal complexes, catalysts and olefin polymerization process
US6281306B1 (en) 1999-12-16 2001-08-28 Univation Technologies, Llc Method of polymerization
AU2731701A (en) 2000-01-07 2001-07-24 Dow Global Technologies Inc. Thermoformable ethylene/styrene interpolymer-based polymer blend film for three-dimensional transfer finish foil
SG147271A1 (en) * 2000-01-26 2008-11-28 Mitsui Chemical Inc 22 51 56 D Olefin polymer and process for preparing the same
ATE409192T1 (de) * 2000-03-01 2008-10-15 Shell Int Research Selektive, katalytische und thermische funktionalisierung von sekundären oder aromatischen c-h bindungen in zyklischen kohlenwasserstoffen
US6451937B1 (en) 2000-03-01 2002-09-17 Shell Oil Company Selective, catalytic, thermal functionalization of primary C-H hydrocarbon bonds
US6160029A (en) * 2000-03-08 2000-12-12 The Dow Chemical Company Olefin polymer and α-olefin/vinyl or α-olefin/vinylidene interpolymer blend foams
US6649671B2 (en) 2000-03-13 2003-11-18 Dow Global Technologies Inc. Concrete and process to make same
EP1209179B1 (en) 2000-03-31 2005-11-02 Mitsui Chemicals, Inc. Processes for producing polyolefin composition
US6613921B2 (en) 2000-06-30 2003-09-02 Dow Global Technologies Inc. Polycyclic, fused ring compounds, metal complexes and polymerization process
US6806327B2 (en) 2000-06-30 2004-10-19 Dow Global Technologies Inc. Substituted polycyclic, fused ring compounds, metal complexes and polymerization process
JP2002020417A (ja) 2000-07-04 2002-01-23 Mitsui Chemicals Inc オレフィンの重合方法
KR100443766B1 (ko) * 2000-07-04 2004-08-09 미쓰이 가가쿠 가부시키가이샤 극성올레핀 공중합체의 제조방법 및 이 방법에 의하여얻어진 극성올레핀 공중합체
US6767931B2 (en) 2000-07-20 2004-07-27 Dow Global Technologies Inc. Foam compositions from blend of alkenyl aromatic polymers and alpha-olefin/vinyl or vinylidene aromatic interpolymers
US6627573B2 (en) * 2000-07-20 2003-09-30 The Dow Chemical Company Expanded anionic compounds comprising hydroxyl or quiescent reactive functionality and catalyst activators therefrom
US6995229B2 (en) 2000-07-26 2006-02-07 Mitsui Chemicals, Inc. Polymer and process for producing the same
ES2276731T3 (es) * 2000-09-07 2007-07-01 Mitsui Chemicals, Inc. Copolimero de olefina que contiene un grupo polar, procedimiento para preparar el mismo, composicion de resina termoplastica que contiene el copolimero y usos de los mismos.
US6943133B2 (en) * 2000-10-20 2005-09-13 Univation Technologies, Llc Diene functionalized catalyst supports and supported catalyst compositions
KR100844062B1 (ko) 2001-02-21 2008-07-07 미쓰이 가가쿠 가부시키가이샤 올레핀 중합용 촉매 및 이 촉매를 사용하는 올레핀중합체의 제조방법
EP1370607A2 (en) * 2001-02-27 2003-12-17 Dow Global Technologies Inc. Fabricated articles prepared from blends of substantially random ethylene/propylene/vinyl aromatic interpolymers with polypropylene
ATE485319T1 (de) 2001-04-12 2010-11-15 Exxonmobil Chem Patents Inc Verfahren zur polymerisation von propylen und ethylen in lösung
WO2002102859A2 (en) 2001-04-30 2002-12-27 W. R. Grace & Co.-Conn. Coordination catalyst systems employing chromium support-agglomerate and method of their preparation
KR100628620B1 (ko) 2001-04-30 2006-09-26 더블유.알. 그레이스 앤드 캄파니-콘. 이종 크롬 촉매 및 이를 사용하는 올레핀의 중합 방법
DE60214172T2 (de) 2001-04-30 2007-07-12 W.R. Grace & Co.-Conn. Geträgerte dualübergangsmetallkatalysatorsysteme
ATE470682T1 (de) 2001-04-30 2010-06-15 Grace W R & Co Verfahren zur herstellung von geträgerten übergangsmetallpolymerisationskatalysatoren und daraus gebildete zusammensetzungen
US6943224B2 (en) 2001-04-30 2005-09-13 W. R. Grace & Co.-Conn. Process for preparing supported transition metal catalyst systems and catalyst systems prepared thereby
MXPA03010095A (es) * 2001-05-04 2004-03-16 Dow Global Technologies Inc Copolimeros o terpolimeros aleatorios o de bloques, producidos usando catalizadores de complejo metalico.
CA2446116A1 (en) * 2001-05-14 2002-11-21 Dow Global Technologies Inc. 3-aryl-substituted cyclopentadienyl metal complexes and polymerization process
US6946531B2 (en) * 2001-05-14 2005-09-20 Dow Global Technologies Inc. Low molecular weight ethylene interpolymers and polymerization process
ATE384086T1 (de) * 2001-06-15 2008-02-15 Dow Global Technologies Inc Verzweigte polymere auf alpha-olefin basis
AU2002310315A1 (en) * 2001-07-23 2003-02-17 Dow Global Technologies, Inc. Salt of lewis acid/acid adducts and catalyst activators therefrom
WO2003013806A1 (en) 2001-08-10 2003-02-20 Dow Global Technologies Inc. Wood treatment composition and method of use
MY139205A (en) 2001-08-31 2009-08-28 Pennzoil Quaker State Co Synthesis of poly-alpha olefin and use thereof
WO2003033545A2 (en) * 2001-10-12 2003-04-24 Dow Global Technologies Inc. Metal complex compositions and their use as catalysts to produce polydienes
EP1444276A1 (en) 2001-11-06 2004-08-11 Dow Global Technologies, Inc. Isotactic propylene copolymers, their preparation and use
US6927256B2 (en) 2001-11-06 2005-08-09 Dow Global Technologies Inc. Crystallization of polypropylene using a semi-crystalline, branched or coupled nucleating agent
US6943215B2 (en) 2001-11-06 2005-09-13 Dow Global Technologies Inc. Impact resistant polymer blends of crystalline polypropylene and partially crystalline, low molecular weight impact modifiers
JP2005515277A (ja) 2002-01-22 2005-05-26 ダウ グローバル テクノロジーズ インコーポレーテッド 高い溶融流動性をもつビニル芳香族ポリマー
US20040106739A1 (en) * 2002-02-19 2004-06-03 Cheung Yunwa Wilson Blends of substantially random interpolymers with enhanced thermal performance
KR101002620B1 (ko) * 2002-03-14 2010-12-21 다우 글로벌 테크놀로지스 인크. 치환된 인데닐 금속 착물 및 중합방법
US20050010039A1 (en) * 2002-03-14 2005-01-13 Graf David D Polycyclic fused heteroring compounds metal complexes and polymerization process
CN100595202C (zh) 2002-09-27 2010-03-24 三井化学株式会社 烯烃聚合用交联金属茂化合物及使用该化合物的烯烃聚合方法
EP1554320B2 (en) 2002-10-02 2011-07-13 Dow Global Technologies LLC Liquid and gel-like low molecular weight ethylene polymers
ES2394304T3 (es) 2002-10-15 2013-01-30 Exxonmobil Chemical Patents, Inc. Sistema de múltiples catalizadores para la polimerización de olefinas y polímeros producidos a partir de éstos
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
EP1964884A1 (en) 2002-10-17 2008-09-03 Dow Global Technologies Inc. Highly filled polymer compositions
EP1555272B1 (en) 2002-10-23 2010-12-08 Mitsui Chemicals, Inc. Supported olefin polymerisation catalyst
DE10251513A1 (de) * 2002-11-04 2004-05-19 Basf Ag Übergangsmetallkatalysatoren für (Co)Polymerisation von olefinischen Monomeren
CA2807874A1 (en) * 2003-02-21 2004-09-10 Styron Europe Gmbh Process for homo- or copolymerization of conjugated olefines
JP4742221B2 (ja) 2003-03-21 2011-08-10 ダウ グローバル テクノロジーズ エルエルシー モルホロジー制御オレフィン重合プロセス
US7084219B2 (en) 2003-03-25 2006-08-01 Sumitomo Chemical Company, Limited Contact product, and catalyst component and catalyst for addition polymerization, and process for producing addition polymer
EP1985638B1 (en) 2003-03-28 2010-02-17 Mitsui Chemicals, Inc. Propylene copolymer, polypropylene composition, use thereof, transition metal compounds, and catalysts for olefin polymerization
FI20030610A0 (fi) * 2003-04-22 2003-04-22 Raisio Benecol Oy Syötävä tuote
US6927264B2 (en) * 2003-05-28 2005-08-09 Dow Global Technologies Inc. Metal complexes and polymerization process using same
JP4090389B2 (ja) * 2003-06-10 2008-05-28 株式会社日立製作所 核磁気共鳴装置
CA2536339C (en) 2003-08-19 2013-01-08 Dow Global Technologies Inc. Interpolymers suitable for use in hot melt adhesives and processes to prepare same
US20070073012A1 (en) * 2005-09-28 2007-03-29 Pannell Richard B Method for seed bed treatment before a polymerization reaction
US20050148742A1 (en) * 2004-01-02 2005-07-07 Hagerty Robert O. Method for controlling sheeting in gas phase reactors
US7985811B2 (en) * 2004-01-02 2011-07-26 Univation Technologies, Llc Method for controlling sheeting in gas phase reactors
ATE446304T1 (de) 2004-01-28 2009-11-15 Idemitsu Kosan Co Übergangsmetallverbindung und katalysator zur olefinpolymerisierung
ES2342895T3 (es) 2004-03-17 2010-07-16 Dow Global Technologies Inc. Composicion catalitica que comprende agente de transferencia para la formacion de copolimero de multiples bloques de etileno.
SG151302A1 (en) 2004-03-17 2009-04-30 Dow Global Technologies Inc Catalyst composition comprising shuttling agent for higher olefin multi- block copolymer formation
AR048817A1 (es) 2004-03-17 2006-05-31 Dow Global Technologies Inc Composicion catalizadora que comprende agente de enlace para la formacion de copolimeros de multiples bloques de etileno
CN102321201B (zh) 2004-06-16 2013-06-26 陶氏环球技术有限责任公司 选择聚合改性剂的方法
CA2790012A1 (en) * 2004-06-28 2006-01-12 Dow Global Technologies Llc Adhesion promoters for multistructural laminates
KR101195320B1 (ko) * 2004-08-09 2012-10-29 다우 글로벌 테크놀로지스 엘엘씨 중합체를 제조하기 위한 지지된비스(하이드록시아릴아릴옥시) 촉매
KR20090021399A (ko) 2004-08-27 2009-03-03 미쓰이 가가쿠 가부시키가이샤 올레핀 중합체
EP1805229A1 (en) 2004-10-28 2007-07-11 Dow Gloval Technologies Inc. Method of controlling a polymerization reactor
BRPI0516675A (pt) * 2004-11-05 2008-09-16 Dow Global Technologies Inc composto de ferrocênio substituìdo, processo para a polimerização por adição de um ou mais monÈmeros olefìnicos e processo para a sìntese de um composto organometálico de grupo 3-10
CN100390256C (zh) 2004-11-26 2008-05-28 三井化学株式会社 合成润滑油和润滑油组合物
EP1829903B1 (en) * 2004-12-22 2013-02-13 Mitsui Chemicals, Inc. Propylene polymer, composition containing the polymer, and molded objects obtained from these
JP2008533276A (ja) 2005-03-17 2008-08-21 ダウ グローバル テクノロジーズ インコーポレイティド タクチック／アタクチックマルチブロックコポリマー形成用の可逆的移動剤を含む触媒組成物
WO2006101595A1 (en) * 2005-03-17 2006-09-28 Dow Global Technologies Inc. Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation
US9410009B2 (en) 2005-03-17 2016-08-09 Dow Global Technologies Llc Catalyst composition comprising shuttling agent for tactic/ atactic multi-block copolymer formation
JP5438256B2 (ja) 2006-11-17 2014-03-12 三井化学株式会社 ポリプロピレン系樹脂フィルムおよびその用途
SG162742A1 (en) 2005-05-18 2010-07-29 Mitsui Chemicals Inc Catalyst for olefin polymerization, method for producing olefin polymer, method for producing propylene copolymer, propylene polymer, propylene polymer composition, and use of those
JP5551360B2 (ja) 2005-07-11 2014-07-16 ダウ グローバル テクノロジーズ エルエルシー シラングラフトオレフィンポリマー、それらから調製される組成物および物品、ならびにそれらの製造方法
ES2526056T3 (es) 2005-09-15 2015-01-05 Dow Global Technologies Llc Copolímeros de bloque de olefinas catalíticos por medio de agente de transporte polimerizable
BRPI0617041B1 (pt) * 2005-09-15 2018-01-30 Dow Global Technologies Inc. PROCESSO PARA PREPARAR UM POLÍMERO DIFUNCIONAL EM a, ?"
US20070082998A1 (en) * 2005-10-07 2007-04-12 Mitsui Chemicals, Inc. Process for producing injection molded product
US20070080483A1 (en) * 2005-10-07 2007-04-12 Mitsui Chemicals, Inc. Process for producing injection molded product
US20070225423A1 (en) * 2005-10-07 2007-09-27 Mitsui Chemicals, Inc. Process for producing blow molded product by blow molding
US20070100056A1 (en) * 2005-10-31 2007-05-03 Mitsui Chemicals, Inc. Process for producing thermoplastic resin composition
US7605208B2 (en) * 2005-10-31 2009-10-20 Mitsui Chemicals, Inc. Process for producing thermoplastic resin composition
US8153243B2 (en) 2005-12-09 2012-04-10 Dow Global Technologies Llc Interpolymers suitable for multilayer films
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
EP1992649A4 (en) * 2006-02-15 2009-04-22 Mitsui Chemicals Inc ETHYLENE RESIN AND EXTRUSION-BLOW MOLDED ARTICLE COMPRISING THE SAME
US20090036584A1 (en) * 2006-02-15 2009-02-05 Mitsui Chemicals, Inc. Environmental Stress Cracking Resistance Improver, and Resin Composition With Improved Environmental Stress Cracking Resistance Properties Containing the Same
WO2007105483A1 (ja) 2006-03-10 2007-09-20 Mitsui Chemicals, Inc. インフレーション成形による成形体の製造方法
EP2006071B1 (en) 2006-03-27 2012-02-22 Mitsui Chemicals, Inc. Process for producing shaped article by t-die molding
JP2007261201A (ja) 2006-03-29 2007-10-11 Mitsui Chemicals Inc ブロー成形による成形体の製造方法
EP2002955A4 (en) 2006-03-30 2009-09-16 Mitsui Chemicals Inc METHOD FOR PRODUCING A MOLDED OBJECT BY INJECTION MOLDING
CN102786619B (zh) * 2006-05-17 2015-01-07 陶氏环球技术有限责任公司 乙烯/α-烯烃/二烯溶液聚合法
US9120888B2 (en) 2006-06-15 2015-09-01 Dow Global Technologies Llc Functionalized olefin interpolymers, compositions and articles prepared therefrom and methods for making the same
WO2008015984A1 (fr) 2006-07-31 2008-02-07 Mitsui Chemicals, Inc. Composition de résine thermoplastique pour scellement de cellule solaire, feuille pour scellement de cellule solaire et cellule solaire
WO2008016059A1 (fr) 2006-07-31 2008-02-07 Mitsui Chemicals, Inc. Film ou stratifié comprenant une résine d'éthylène ou une composition de résine d'éthylène
JPWO2008047878A1 (ja) 2006-10-20 2010-02-25 三井化学株式会社 共重合体、潤滑油粘度調整剤および潤滑油組成物
US7863368B2 (en) * 2006-11-17 2011-01-04 Mitsui Chemicals, Inc. Propylene resin composition, process for producing propylene resin composition, propylene polymer composition, shaped article produced of the propylene resin composition, and electric wire
US20100048820A1 (en) * 2006-11-17 2010-02-25 Mitsui Chemicals, Inc. Process for producing syndiotactic propylene polymer
EP2096126A1 (en) 2006-12-19 2009-09-02 Mitsui Chemicals, Inc. Solid catalyst for olefin polymerization, olefin polymerization method, and olefin polymer particle produced by the method
BRPI0806778B1 (pt) 2007-01-16 2019-03-26 Prime Polymer Co., Ltd Composição de resina de etileno moldada a sopro, artigo moldado a sopro e tanque de combustível
ITMI20070877A1 (it) 2007-05-02 2008-11-03 Dow Global Technologies Inc Processo per la produzione di copolimeri a blocchi multipli con l'utilizzo di solventi polari
ITMI20070878A1 (it) 2007-05-02 2008-11-03 Dow Global Technologies Inc Processo per la polimerizzazine di polimeri tattici con l'uso di catalizzatori chirali
US8063146B2 (en) 2007-06-14 2011-11-22 Mitsui Chemicals, Inc. Thermoplastic elastomer composition
JP5226973B2 (ja) 2007-06-15 2013-07-03 三井化学株式会社 エチレン系共重合体、該共重合体を含む組成物ならびにその用途
CN101687776B (zh) * 2007-07-04 2015-07-01 三井化学株式会社 过渡金属配位化合物、含有该化合物的烯烃聚合用催化剂以及在该催化剂存在下进行的烯烃聚合物的制造方法
TW200932762A (en) 2007-10-22 2009-08-01 Univation Tech Llc Polyethylene compositions having improved properties
US20100292421A1 (en) 2007-11-19 2010-11-18 Mitsui Chemicals, Inc. Bridged metallocene compound, olefin polymerization catalyst containing the same, and ethylene polymer obtained with the catalyst
RU2479593C2 (ru) 2007-12-18 2013-04-20 Юнивейшн Текнолоджиз, Ллк Способ регулирования активности бимодального катализатора в процессе полимеризации
US8459525B2 (en) 2008-02-14 2013-06-11 Ethicon Endo-Sugery, Inc. Motorized surgical cutting and fastening instrument having a magnetic drive train torque limiting device
ES2407851T3 (es) * 2008-03-27 2013-06-14 Mitsui Chemicals, Inc. Composición de resina y uso de la misma
CN104059283B (zh) * 2008-03-31 2017-04-12 三井化学株式会社 树脂组合物和熔融袋
JP5754940B2 (ja) * 2008-08-19 2015-07-29 三井化学株式会社 混合触媒によるプロピレン重合体の製造方法
EP2172490A1 (en) 2008-10-03 2010-04-07 Ineos Europe Limited Controlled polymerisation process
JP5789195B2 (ja) 2008-12-08 2015-10-07 シリコンバレー メディカル インスツルメンツ インコーポレイテッド 画像誘導のためのカテーテルのシステム
WO2010102163A2 (en) 2009-03-06 2010-09-10 Dow Global Technologies Inc. Catalysts, processes for making catalysts, processes for making polyolefin compositions and polyolefin compositions
KR101359198B1 (ko) 2009-03-30 2014-02-05 미쓰이 가가쿠 가부시키가이샤 올레핀과 공액 다이엔의 공중합체, 및 그의 제조 방법
KR101327598B1 (ko) 2009-04-21 2013-11-12 가부시키가이샤 프라임 폴리머 올레핀 중합체의 제조 방법
CN102803280A (zh) 2009-06-11 2012-11-28 格雷斯公司 制造铝氧烷的方法和包括由此制备的铝氧烷的催化剂
US8318874B2 (en) 2009-06-26 2012-11-27 Dow Global Technologies Llc Process of selectively polymerizing ethylene and catalyst therefor
JP5675609B2 (ja) 2009-07-01 2015-02-25 三井化学株式会社 有機金属化合物およびその製造方法
BR112012001948B1 (pt) 2009-07-29 2019-08-20 Dow Global Technologies Llc Agente de translado de cadeia, processo para a polimerização de pelo menos um monômero polimerizável por adição, copolímero em multi-bloco e composição de catalisador
BR112012001942B1 (pt) 2009-07-29 2019-10-22 Dow Global Technologies Llc agente de permuta de cadeia multifuncional, processo para preparar um agente de permuta de cadeia multifuncional, processo para preparar uma composição multifuncional, composição multifuncional, processo para preparar um agente de permuta de cadeia multifuncional contendo poli-radical poliolefina, poliolefina telequélica, processo para preparar uma poliolefina com funcionalidade terminal e separador de bateria
WO2011016992A2 (en) 2009-07-29 2011-02-10 Dow Global Technologies Inc. Polymeric chain transfer/shuttling agents
US20110054122A1 (en) * 2009-08-31 2011-03-03 Jerzy Klosin Catalyst and process for polymerizing an olefin and polyolefin prepared thereby
EP2518089B1 (en) 2009-12-21 2014-11-26 Mitsui Chemicals, Inc. Process for production of syndiotactic alpha-olefin polymer
EP2357035A1 (en) 2010-01-13 2011-08-17 Ineos Europe Limited Polymer powder storage and/or transport and/or degassing vessels
CN102781981B (zh) 2010-02-19 2015-09-16 陶氏环球技术有限责任公司 烯烃单体聚合方法及其催化剂
ES2691727T3 (es) 2010-02-19 2018-11-28 Dow Global Technologies Llc Complejos metal-ligando y catalizadores
EP2383298A1 (en) 2010-04-30 2011-11-02 Ineos Europe Limited Polymerization process
EP2383301A1 (en) 2010-04-30 2011-11-02 Ineos Europe Limited Polymerization process
US20120135903A1 (en) 2010-05-11 2012-05-31 Mitsui Chemicals, Inc. Lubricating oil composition
WO2011146291A1 (en) 2010-05-17 2011-11-24 Dow Global Technologies Llc Process for selectively polymerizing ethylene and catalyst therefor
EP2609123B1 (en) 2010-08-25 2017-12-13 Dow Global Technologies LLC Process for polymerizing a polymerizable olefin and catalyst therefor
WO2012061706A1 (en) 2010-11-04 2012-05-10 Dow Global Technologies Llc Double shuttling of polyolefin polymeryl chains
US9464181B2 (en) 2010-11-24 2016-10-11 Exxonmobil Chemical Patents Inc. High filler loaded polymer composition
SG190835A1 (en) 2010-11-29 2013-07-31 Ineos Commercial Services Uk Polymerisation control process
EP2663400A4 (en) 2011-01-14 2014-07-30 Grace W R & Co PROCESS FOR THE PREPARATION OF A MODIFIED METALLOCENE CATALYST, CATALYST THUS PRODUCED AND USE THEREOF
WO2012103080A1 (en) 2011-01-26 2012-08-02 Dow Global Technologies Llc Process for making a polyolefin-polysiloxane block copolymer
US9296836B2 (en) 2011-05-12 2016-03-29 Dow Global Technologies Llc Non-cyclopentadienyl-based chromium catalysts for olefin polymerization
JP5697747B2 (ja) 2011-05-18 2015-04-08 三井化学株式会社 プロピレン系共重合体、プロピレン系共重合体組成物、その成形体およびその発泡体、およびそれらの製造方法
US8383740B1 (en) 2011-08-12 2013-02-26 Ineos Usa Llc Horizontal agitator
US9181367B2 (en) 2011-10-17 2015-11-10 Ineos Europe Ag Polymer degassing process control
EP2799488B1 (en) 2011-12-27 2016-07-20 Mitsui Chemicals, Inc. 4-methyl-1-pentene (co)polymer composition, and film and hollow molded body, each of which is formed from 4-methyl-1-pentene (co)polymer composition
CN104024326B (zh) 2011-12-28 2016-11-23 三井化学株式会社 乙烯类聚合物组合物和由其得到的成形体
JP6188715B2 (ja) 2011-12-29 2017-08-30 ダウ グローバル テクノロジーズ エルエルシー 低分子量エチレン系材料及びアルファ−オレフィン系材料を製造するためのプロセス
CN104024285B (zh) 2011-12-29 2017-03-22 陶氏环球技术有限责任公司 基于超支化的烯烃油的介电流体
US9315602B2 (en) 2012-03-21 2016-04-19 Mitsui Chemicals, Inc. Method for producing olefin polymer
SG11201406117PA (en) 2012-03-28 2014-11-27 Mitsui Chemicals Inc Encapsulating material for solar cell and solar cell module
EP2671639B1 (en) 2012-06-04 2017-01-11 Sasol Performance Chemicals GmbH Guanidinate complexes and their use as chain transfer polymerization catalysts
SG11201502294RA (en) 2012-09-25 2015-05-28 Mitsui Chemicals Inc Transition Metal Compound, Olefin Polymerization Catalyst, And Olefin Polymer Production Process
WO2014050817A1 (ja) 2012-09-25 2014-04-03 三井化学株式会社 オレフィン重合体の製造方法およびオレフィン重合体
KR101394943B1 (ko) 2012-11-19 2014-05-14 대림산업 주식회사 에틸렌과 알파-올레핀의 공중합체 및 그 제조방법
JP2016506444A (ja) 2012-12-27 2016-03-03 ダウ グローバル テクノロジーズ エルエルシー エチレン系ポリマー
CN104884484B (zh) 2012-12-27 2018-09-14 陶氏环球技术有限责任公司 用于产生乙烯类聚合物的聚合方法
CN104870489B (zh) 2012-12-27 2018-03-09 陶氏环球技术有限责任公司 用于烯烃聚合的催化剂系统
EP2938645B1 (en) 2012-12-27 2019-05-15 Dow Global Technologies LLC An ethylene based polymer
WO2014105414A1 (en) 2012-12-27 2014-07-03 Dow Global Technologies Llc A polymerization process for producing ethylene based polymers
PL2960270T3 (pl) 2013-02-20 2018-04-30 Prime Polymer Co Ltd Folia rozciągana dwuosiowo oraz kompozycja polimerów etylenowych
CN104994948B (zh) 2013-02-27 2017-11-24 三井化学株式会社 烯烃多聚化用催化剂以及在该催化剂存在下进行的烯烃多聚体的制造方法
EP2975069B1 (en) 2013-03-12 2018-09-05 Mitsui Chemicals, Inc. Method for producing olefin polymer and catalyst for olefin polymerization
EP3013871B1 (en) 2013-06-28 2022-10-19 Dow Global Technologies LLC Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts
WO2015056787A1 (ja) 2013-10-18 2015-04-23 三井化学株式会社 エチレン・α－オレフィン共重合体を含有する接着剤
CN105813742B (zh) 2013-12-19 2020-05-15 陶氏环球技术有限责任公司 金属-配位体络合物、由其衍生的烯烃聚合催化剂以及利用所述催化剂的烯烃聚合方法
EP3106475B1 (en) 2014-02-13 2019-08-28 Mitsui Chemicals, Inc. Method for producing ethylene/alpha-olefin copolymer
BR112016016900B8 (pt) 2014-02-13 2022-05-17 Mitsui Chemicals Inc Copolímero de etileno-alfa-olefina-polieno não conjugado, artigo moldado, composição, método de fabricação deste copolímero, composição para uma junta de vedação, junta de vedação, composição para formação de uma mangueira e mangueira
TWI679214B (zh) 2014-02-14 2019-12-11 日商三井化學股份有限公司 乙烯．α-烯烴．非共軛多烯共聚合體、其製造方法暨用途
KR101909799B1 (ko) 2014-02-28 2018-10-18 미쓰이 가가쿠 가부시키가이샤 가교체와 그의 제조 방법 및 용도, 및 에틸렌계 공중합체
WO2015147215A1 (ja) 2014-03-28 2015-10-01 三井化学株式会社 エチレン／α－オレフィン共重合体および潤滑油
RU2647310C1 (ru) 2014-03-28 2018-03-15 Митсуи Кемикалс, Инк. Смола на основе олефина, способ ее получения и композиция на основе пропиленовой смолы
EP3124506B1 (en) 2014-03-28 2022-06-22 Mitsui Chemicals, Inc. Olefin resin and method for producing same
US20170152377A1 (en) 2014-06-26 2017-06-01 Dow Global Technologies Llc Breathable films and articles incorporating same
US20170129229A1 (en) 2014-06-26 2017-05-11 Dow Global Technologies Llc Blown films with improved toughness
MX2016016600A (es) 2014-06-26 2017-04-27 Dow Global Technologies Llc Peliculas fundidas con rugosidad mejorada.
JP6985015B2 (ja) 2014-06-30 2021-12-22 ダウ グローバル テクノロジーズ エルエルシー オレフィン重合用の触媒系
BR112016029439B1 (pt) 2014-06-30 2022-01-04 Dow Global Technologies Llc Processo para formar um polímero à base de olefina
SG11201700372SA (en) 2014-07-24 2017-02-27 Dow Global Technologies Llc Bis-biphenylphenoxy catalysts for polymerization of low molecular weight ethylene-based polymers
CN106795449B (zh) 2014-09-10 2020-08-07 三井化学株式会社 润滑油组合物
WO2016039416A1 (ja) 2014-09-11 2016-03-17 三井化学株式会社 １－ブテン由来の構成単位を含むオレフィン（共）重合体の製造方法
EP3224287B1 (en) 2014-11-25 2019-05-01 Univation Technologies, LLC Methods of controlling polyolefin melt index
WO2016089935A1 (en) 2014-12-04 2016-06-09 Dow Global Technologies Llc Five-coordinate bis-phenylphenoxy catalysts for the preparation of ethylene-based polymers
US9670346B2 (en) 2014-12-09 2017-06-06 Mitsui Chemicals, Inc. Propylene-based resin composition
US10351646B2 (en) 2014-12-31 2019-07-16 Dow Global Technologies Llc Polyolefin composition and method of producing the same
CN107548385B (zh) 2015-03-13 2022-01-21 陶氏环球技术有限责任公司 利用包含具有含有磷环的配体的铬络合物的催化剂的烯烃低聚反应方法
JP6439039B2 (ja) 2015-03-20 2018-12-19 三井化学株式会社 熱可塑性エラストマー組成物、その用途、その製造方法、エチレン・α−オレフィン・非共役ポリエン共重合体およびその用途
US10280293B2 (en) 2015-03-20 2019-05-07 Mitsui Chemicals, Inc. Thermoplastic elastomer composition and method for producing same
KR101913992B1 (ko) 2015-03-31 2018-10-31 미쓰이 가가쿠 가부시키가이샤 수지 조성물 및 그의 용도
EP3093280A1 (en) 2015-05-13 2016-11-16 Sasol Performance Chemicals GmbH Process for the oligomerisation of olefins by coordinative chain transfer polymerisation and catalyst synthesis
WO2017004462A1 (en) 2015-06-30 2017-01-05 Dow Global Technologies Llc A polymerization process for producing ethylene based polymers
JP6895393B2 (ja) 2015-06-30 2021-06-30 ダウ グローバル テクノロジーズ エルエルシー エチレン系ポリマーを生成するための重合プロセス
CN108350121B (zh) 2015-09-30 2021-10-01 陶氏环球技术有限责任公司 主催化剂和使用其的聚合方法
BR112018005909B1 (pt) 2015-09-30 2022-05-03 Dow Global Technologies Llc Pró-catalisador para a polimerização de etileno e processo de polimerização para a produção de polímeros à base de etileno
JP6832348B2 (ja) 2015-09-30 2021-02-24 ダウ グローバル テクノロジーズ エルエルシー 連鎖シャトリングに有用な多頭性または二頭性組成物、及びそれを調製するためのプロセス
WO2017082182A1 (ja) 2015-11-09 2017-05-18 三井化学株式会社 潤滑油用粘度調整剤、潤滑油用添加剤組成物および潤滑油組成物
EP3214124B2 (en) 2016-03-02 2022-06-08 Dow Global Technologies LLC An ethylene/alpha-olefin copolymer composition, and articles comprising the same
EP3214116B1 (en) 2016-03-03 2021-06-23 Dow Global Technologies LLC Breathable films and method of making the same
EP3214211B1 (en) 2016-03-03 2020-12-30 Dow Global Technologies LLC Artificial turfs and method of making the same
ES2703602T3 (es) 2016-03-03 2019-03-11 Dow Global Technologies Llc Composición de polietileno, método para fabricar la misma, y películas fabricadas a partir de la misma
WO2017150612A1 (ja) 2016-03-04 2017-09-08 三井化学株式会社 積層体およびその用途
SG11201808185XA (en) 2016-03-31 2018-10-30 Dow Global Technologies Llc Olefin polymerization catalyst systems and methods of use thereof
SG10202009722UA (en) 2016-03-31 2020-11-27 Dow Global Technologies Llc An olefin polymerization catalyst
BR112018069231B1 (pt) 2016-03-31 2022-08-30 Dow Global Technologies Llc Sistema catalisador de polimerização de olefina e processo para polimerizar um ou mais polímeros à base de olefina
KR102174575B1 (ko) 2016-07-21 2020-11-05 미쓰이 가가쿠 가부시키가이샤 폴리프로필렌계 수지 조성물, 및 단층 및 다층 필름
WO2018022871A1 (en) 2016-07-29 2018-02-01 Dow Global Technologies Llc SYNTHESIS OF m-TERPHENYL PENDANT BIS-ETHER LIGANDS AND METAL COMPLEX AND THEIR USE IN OLEFIN POLYMERIZATION
MX2019003247A (es) 2016-09-28 2019-08-05 Dow Global Technologies Llc Peliculas sopladas con propiedades mejoradas.
KR102444560B1 (ko) 2016-09-30 2022-09-20 다우 글로벌 테크놀로지스 엘엘씨 체인 셔틀링에 유용한 다중 또는 이중 헤드 구성 요소 및 이를 준비하는 과정
KR102459739B1 (ko) 2016-09-30 2022-10-28 다우 글로벌 테크놀로지스 엘엘씨 이중 연결 포스포구아니딘 4족 금속 착체 및 이로부터 생성된 올레핀 중합 촉매
EP3519467B1 (en) 2016-09-30 2021-03-17 Dow Global Technologies LLC Bis-phosphaguanidine and poly-phosphaguanidine ligands with group iv metal catalysts produced therefrom
BR112019006150B1 (pt) 2016-09-30 2023-02-28 Dow Global Technologies Llc Composição e processo para preparar a composição
CN109963886B (zh) 2016-09-30 2023-01-06 陶氏环球技术有限责任公司 磷杂胍iv族金属烯烃聚合催化剂
US11359035B2 (en) 2016-09-30 2022-06-14 Dow Global Technologies Llc Multi- or dual-headed compositions useful for chain shuttling and process to prepare the same
CN109906144B (zh) 2016-09-30 2021-08-10 陶氏环球技术有限责任公司 用作多层膜中的连接层的树脂以及包含其的多层膜
EP3312007B1 (en) 2016-10-18 2023-12-27 Dow Global Technologies LLC Multilayer stretch hood compositions and structures
CN110072981B (zh) 2017-01-16 2022-02-25 三井化学株式会社 汽车齿轮用润滑油组合物
KR102276516B1 (ko) 2017-02-20 2021-07-12 미쓰이 가가쿠 가부시키가이샤 적층체
US20190358928A1 (en) 2017-02-20 2019-11-28 Mitsui Chemicals, Inc. Laminate
EP3596142B1 (en) 2017-03-15 2023-05-24 Dow Global Technologies LLC Catalyst system for multi-block copolymer formation
BR112019019130B1 (pt) 2017-03-15 2023-03-28 Dow Global Technologies Llc Sistema catalisador de polimerização de olefina e processo para preparar um copolímero de múltiplos blocos
ES2946762T3 (es) 2017-03-15 2023-07-25 Dow Global Technologies Llc Sistema de catalizador para la formación de copolímero multibloque
US20200247936A1 (en) 2017-03-15 2020-08-06 Dow Global Technologies Llc Catalyst system for multi-block copolymer formation
KR20190123340A (ko) 2017-03-15 2019-10-31 다우 글로벌 테크놀로지스 엘엘씨 다중-블록 공중합체 형성을 위한 촉매 시스템
AR111718A1 (es) 2017-04-19 2019-08-14 Dow Global Technologies Llc Estructuras de laminados y materiales de empaque flexibles que las incluyen
AR112359A1 (es) 2017-06-30 2019-10-23 Dow Global Technologies Llc Laminados de polietileno para usar en materiales de embalaje flexibles
AR112245A1 (es) 2017-06-30 2019-10-09 Dow Global Technologies Llc Laminados y películas de polietileno multicapa para usar en materiales de envasado flexibles
CN115872822A (zh) 2017-07-06 2023-03-31 三井化学株式会社 烯烃多聚化用催化剂及在该催化剂存在下进行的烯烃多聚体的制造方法
WO2019060387A1 (en) 2017-09-22 2019-03-28 Dow Global Technologies Llc THERMOFORMED FILM COMPOSITIONS HAVING ENHANCED TENACITY AFTER THERMOFORMING PROCESSES
JP7221948B2 (ja) 2017-09-29 2023-02-14 ダウ グローバル テクノロジーズ エルエルシー 溶解性を改善させるために金属上にメチレントリアルキルシリコン配位子を有するビスフェニルフェノキシポリオレフィン触媒
WO2019067274A1 (en) 2017-09-29 2019-04-04 Dow Global Technologies Llc BIS-PHENYL-PHENOXY-POLYOLEFIN CATALYSTS HAVING TWO METHYLENETRIALKYLSILICIUM-TYPE LIGANDS ON METAL FOR ENHANCED SOLUBILITY
KR102590973B1 (ko) 2017-09-29 2023-10-19 다우 글로벌 테크놀로지스 엘엘씨 개선된 용해도를 위한 금속 상에 알콕시 리간드 또는 아미도 리간드를 갖는 비스-페닐-페녹시 폴리올레핀 촉매
US11905348B2 (en) 2018-03-20 2024-02-20 Mitsui Chemicals, Inc. Ethylene/alpha-olefin/non-conjugated polyene copolymer, method for producing the same, and use thereof
US20220041847A1 (en) 2018-12-04 2022-02-10 Mitsui Chemicals, Inc. Resin composition containing 4-methyl-1-pentene copolymer, and film for capacitors
US20220073658A1 (en) 2018-12-28 2022-03-10 Dow Global Technologies Llc Telechelic polyolefins and processes for preparing the same
KR20210121028A (ko) 2018-12-28 2021-10-07 다우 글로벌 테크놀로지스 엘엘씨 유기금속 사슬 이동제
WO2020140067A1 (en) 2018-12-28 2020-07-02 Dow Global Technologies Llc Curable compositions comprising unsaturated polyolefins
CN113498414A (zh) 2018-12-28 2021-10-12 陶氏环球技术有限责任公司 包括遥爪聚烯烃的可固化组合物
WO2020135681A1 (en) 2018-12-28 2020-07-02 Dow Global Technologies Llc Curable compositions comprising unsaturated polyolefins
WO2020189676A1 (ja) 2019-03-19 2020-09-24 三井化学株式会社 プロピレン系樹脂組成物、成形体およびプロピレン重合体
WO2020194542A1 (ja) 2019-03-26 2020-10-01 三井化学株式会社 潤滑油組成物およびその製造方法
KR20210139400A (ko) 2019-03-26 2021-11-22 미쓰이 가가쿠 가부시키가이샤 자동차 기어용 윤활유 조성물 및 그의 제조 방법
US20220169939A1 (en) 2019-03-26 2022-06-02 Mitsui Chemicals, Inc. Lubricating oil and method for producing the same
KR20210139402A (ko) 2019-03-26 2021-11-22 미쓰이 가가쿠 가부시키가이샤 내연 기관용 윤활유 조성물 및 그의 제조 방법
US20220186133A1 (en) 2019-03-26 2022-06-16 Mitsui Chemicals, Inc. Lubricating oil composition for industrial gears and method for producing the same
KR20210141610A (ko) 2019-03-26 2021-11-23 미쓰이 가가쿠 가부시키가이샤 자동차 변속기유용 윤활유 조성물 및 그의 제조 방법
US20220169942A1 (en) 2019-03-26 2022-06-02 Mitsui Chemicals, Inc. Lubricating oil composition for internal combustion engines and method for producing the same
KR20210139408A (ko) 2019-03-26 2021-11-22 미쓰이 가가쿠 가부시키가이샤 압축기유용 윤활유 조성물 및 그의 제조 방법
US20220177798A1 (en) 2019-03-26 2022-06-09 Mitsui Chemicals, Inc. Lubricating oil composition for hydraulic oil and method for producing the same
WO2020194550A1 (ja) 2019-03-26 2020-10-01 三井化学株式会社 グリース組成物およびその製造方法
US20220118750A1 (en) 2019-03-26 2022-04-21 Dow Global Technologies Llc Multilayer films, laminates, and articles comprising multilayer films
US20220153978A1 (en) 2019-03-29 2022-05-19 Mitsui Chemicals, Inc. Resin compositions
CN114127169B (zh) 2019-08-08 2023-08-01 普瑞曼聚合物株式会社 丙烯系聚合物组合物和成型体
US20220411659A1 (en) 2019-10-07 2022-12-29 Mitsui Chemicals, Inc. ETHYLENE/alpha-OLEFIN COPOLYMER COMPOSITION AND APPLICATION THEREOF
WO2021085225A1 (ja) 2019-10-29 2021-05-06 三井化学株式会社 エチレン系共重合体組成物およびその用途
KR20220123062A (ko) 2020-01-30 2022-09-05 미쓰이 가가쿠 가부시키가이샤 폴리아마이드 조성물
BR112022023903A2 (pt) 2020-05-27 2022-12-27 Dow Global Technologies Llc Formulações de polímero e tubulação de irrigação incluindo formulações de polímero
CN116194492A (zh) 2020-07-17 2023-05-30 陶氏环球技术有限责任公司 用于限制几何构型主催化剂的烃基改性的甲基铝氧烷助催化剂
JPWO2022075350A1 (zh) 2020-10-06 2022-04-14
US20230382929A1 (en) 2020-10-15 2023-11-30 Dow Global Technologies Llc Olefin polymerization catalysts bearing a 6-amino-n-aryl azaindole ligand
US20240101737A1 (en) 2021-01-18 2024-03-28 Mitsui Chemicals, Inc. WATER DISPERSION COMPOSITION, METHOD FOR PRODUCING THE WATER DISPERSION COMPOSITION, AND ETHYLENE alpha-OLEFIN COPOLYMER ACID-MODIFIED SUBSTANCE
JPWO2022186053A1 (zh) 2021-03-05 2022-09-09
WO2022210844A1 (ja) 2021-03-31 2022-10-06 三井化学株式会社 エチレン－α－オレフィン共重合体、熱可塑性樹脂組成物、およびフィルム
EP4317215A1 (en) 2021-03-31 2024-02-07 Mitsui Chemicals, Inc. Ethylene resin composition and molded body
EP4316833A1 (en) 2021-03-31 2024-02-07 Mitsui Chemicals, Inc. ETHYLENE-a-OLEFIN COPOLYMER, THERMOPLASTIC RESIN COMPOSITION, FILM, AND LAMINATE
WO2022232760A1 (en) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Processes for transitioning between different polymerization catalysts in a polymerization reactor
JPWO2022244879A1 (zh) 2021-05-20 2022-11-24
WO2023002947A1 (ja) 2021-07-20 2023-01-26 三井化学株式会社 潤滑油用粘度調整剤および作動油用潤滑油組成物

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0780930B2 (ja) * 1985-12-26 1995-08-30 三井石油化学工業株式会社 α−オレフインの重合方法
US5055438A (en) * 1989-09-13 1991-10-08 Exxon Chemical Patents, Inc. Olefin polymerization catalysts
US5096867A (en) * 1990-06-04 1992-03-17 Exxon Chemical Patents Inc. Monocyclopentadienyl transition metal olefin polymerization catalysts
US5153157A (en) * 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
IL85097A (en) 1987-01-30 1992-02-16 Exxon Chemical Patents Inc Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes
US4931417A (en) * 1987-11-09 1990-06-05 Chisso Corporation Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure
US5026798A (en) * 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5064802A (en) * 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5066741A (en) * 1990-03-22 1991-11-19 The Dow Chemical Company Process for preparation of syndiotactic vinyl aromatic polymers
CA2024830A1 (en) * 1989-09-29 1991-03-30 Richard E. Campbell, Jr. Process for preparation of syndiotactic vinyl aromatic polymers
DE69018376T3 (de) * 1989-10-30 2002-05-16 Fina Technology Herstellung von Metallocenkatalysatoren für Olefinpolymerisation.
US5034034A (en) * 1990-08-28 1991-07-23 The Dow Chemical Company Novel aryl carbonate cyanoaryl ether gas separation membranes

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