CN1051684A - 含路易斯酸和烷基铝的金属茂催化剂 - Google Patents

含路易斯酸和烷基铝的金属茂催化剂 Download PDF

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CN1051684A
CN1051684A CN90109368A CN90109368A CN1051684A CN 1051684 A CN1051684 A CN 1051684A CN 90109368 A CN90109368 A CN 90109368A CN 90109368 A CN90109368 A CN 90109368A CN 1051684 A CN1051684 A CN 1051684A
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aluminum alkyls
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约翰·尤恩
迈克尔·J·埃尔德
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Abstract

本发明是关于一种催化剂体系，它含有中性的金 属茂化合物，烷基铝和路易斯酸。路易斯酸的酸度必 须足以使中性的金属茂化合物离介生成阳离子金属 茂催化剂。路易斯酸的配位体应当是不与金属茂阳 离子反应的。任何一种有与一个过渡金属相连的两 个环戊二烯环的金属茂催化剂化合物均对本发明有 用。
本发明也是关于使用该催化剂体系聚合烯烃的 方法。该方法是将金属茂与路易斯酸接触，将烷基铝 与烯烃接触，再将这两种混合物在聚合反应条件下互 相接触。

Description

本发明一般说是关于一种改进的催化剂体系以及使用该催化剂体系的方法，具体地说，是关于一种含路易斯酸和烷基铝的金属茂化合物的催化剂体系以及该改进的催化剂体系用于烯烃聚合，主要是用于丙烯聚合的方法。
用金属茂化合物作为烯烃聚合的催化剂是众所周知的。德国专利申请No.2608863公开了一种用于乙烯聚合的催化剂体系，它由二烷基双（环戊二烯基）钛、三烷基铝和水组成。德国专利申请No.2608933公开了一种乙烯聚合的催化剂体系，它由通式为（环戊二烯基）nZrY4-n′的锆金属茂组成，式中Y代表R1CH2AlR2、CH2CH2AlR2和CH2CH（AlR2）2其中R为烷基或金属取代的烷基，n是1-4的数;该金属茂催化剂与三烷基铝助催化剂和水结合起来使用。
用金属茂作为乙烯和其它α-烯烃共聚合的催化剂也是现有技术中众所周知的。美国专利No.4542199中Kaminsky等人公开了一种烯烃的聚合方法，特别是聚乙烯的制备方法以及乙烯和其它α-烯烃共聚物的制备方法。所公开的催化剂体系包括通式为（环戊二烯基）2meRHal的一种催化剂，式中R为卤素，环戊二烯基或C1-C6的烷基，me是过渡金属，特别是锆，Hal是卤素，特别是氯。该催化剂体系也包括一种铝氧烷，其通式（对线型分子）为Al2OR4（Al（R）-O）n和/或（对环状分子）为（Al（R）-O）n+2，式中n是4～20的一个数，R是甲基或乙基。在美国专利4404344中也公开了一种类似的催化剂体系。
美国专利No.4530914公开了一种具有宽分子量分布，特别是双峰值或多峰值分子量分布的乙烯-聚乙烯聚合的催化剂体系。该催化剂体系至少含有两种不同的金属茂和一种铝氧烷。该专利所公开的金属茂在两个环戊二烯基的环之间可以有一个桥，这个桥使那些环具有立体刚性。
欧洲专利公开No 0185918公开了一种用于烯烃聚合的立体刚性的手性锆金属茂催化剂。该申请中没有说明铪可以代替锆用来生产有用的聚合产品。该申请所公开的两个环戊二烯基之间的桥是一种C1-4的线型烃或C3-6的环型烃。
烯烃的聚合主要是用Zeigler-Natta催化剂。有一类Zeigler-Natta催化剂是周期表第Ⅳ族金属的金属茂化合物，并用甲基铝氧烷（MAO）作为助催化剂。用钛或锆的金属茂催化剂和铝氧烷助催化剂生产全同立构聚丙烯的一种体系，已在J.Am.Chem.Soc.Vol，106，PP6355-64，1984“在用可溶性4B族金属茂/甲基铝氧烷催化剂的丙烯聚合中立体化学控制机理”一文中作了阐述。该文章指出，用乙烯-桥茚基衍生物的外消旋对映体的手性催化剂所得的是按常规结构的等规立构聚丙烯，这种结构可用对映位置的立体化学控制模型予测。然而，用内消旋非手性型乙烯-桥接的钛茚基非对映体和非手性的锆茂衍生物所生产的聚丙烯具有纯无规结构。
MAO使金属茂活化而使其能促进α-烯烃的聚合。其它铝的有机金属化合物，例如三甲基铝（TMA）或二甲基卤化铝，都是众所周知它们自己不会促进聚合反应的。不管是烷基铝还是二甲基卤化铝，它们都不能单独作为有效的助催化剂。
将TMA和二甲基氟化铝（DMF）组合起来作为一种助催化剂来代替MAO，现在已被证明是有效的。DMF是一种路易斯酸。这样的组合，在以下这篇文章中有报导，即“丙烯的等规聚合：以4族金属的茂化合物为基础没有甲基铝氧烷的均相催化剂”，A  Zambelli.P.Longo和A.Grassi.Macromolecules，Vol.22.P.2186-2189，1989。用TMA/DMF制备的聚合物，其立体化学结构与用MAO制备的聚合物很相似。但是用TMA/DMF混合物所得到的聚合产率均大大低于用MAO所得的产率。
含氯化镁的金属茂化合物所形成的一种催化剂体系具有二甲基双（环戊二烯基）钍，它对乙烯聚合是有效的这也已有报导。这样的组合，报导在下面这篇文章中，即“〔（CH3）5C5〕2Th（CH3）2表面化学和催化。在mgcl2上表面烷基化和乙烯插入/聚合的NMR光谱直接观察”，D.Heddin和T.J.Marks，J，Am，Chem.Soc，Vol.110，No.5.1988。从环戊二烯基化合物中提取甲基形成阳离子。甲基与镁配位形成镁阴离子。氯化镁是一种路易斯酸。
在没有清除剂（如甲基铝氧烷）存在的情况下，金属茂催化剂很易中毒。聚合反应要求高的离子浓度，并常常发生反应失控或根本没有生成聚合物而终止的情况。
本发明提供一种有路易斯酸和烷基铝的金属茂化合物的催化剂体系，以及一种使用该改进的催化剂体系进行链烯烃聚合的方法。按照本发明，可以生产由α-烯烃聚合得到的均聚物或共聚物。聚合物链的增长是在金属茂化合物的中性烷基衍生物存在下进行的，该金属茂化合物已经与路易斯酸和烷基铝接触。任何金属茂催化剂化合物只要有两个与过渡金属配位的环戊二烯环，都可用于本发明。
将该催化剂与路易斯酸接触，烷基铝与烯烃接触。这两种混合物在聚合条件下相互接触。
本发明是关于一种含金属茂催化剂，路易斯酸和烷基铝的催化剂体系，以及使用该催化剂体系进行烯烃聚合的方法。
金属茂催化剂的通式是：
其中CP是环戊二烯基或取代的环戊二烯基，每个CP是相同的或不相同的，M是Ⅲ.Ⅳ.Ⅴ或Ⅵ族金属，R是氢化物，卤素，酰胺或烃基，每个R相同或不相同（除了只有一个R是氢化物之外），而P是1-4。M优选的是Ⅳ族金属，如钛、锆或铪，最好是锆。R优选的是有20个以下碳原子的烷基、芳基、链烯基、烷芳基或芳烷基。R最好是6个以下碳原子的烷基或烷氧基，或者10个以下碳原子的芳基。金属茂的中性衍生物优选的是二甲基双（四氢茚基）锆或二甲基乙烯双（茚基）锆，最好是二甲基乙烯双（茚基）锆。
本发明用的路易斯酸是能接受电子对的任何物质，其酸度要足以使中性的金属茂离解成阳性金属茂催化剂。另外，路易斯酸的配位体不能与金属茂的阳离子反应。优选的路易酸是含硼的或是氯化镁（mgcl2），最好是三（五氟苯基）硼。
烷基铝的通式是AlR3，其中R是卤素、氧、氢化物、烷基、烷氧基或芳基，每个R是相同或不相同的，而且至少一个R是烷基。较佳的烷基铝是三甲基铝（TMA）或三乙基铝（TEAL），最佳的烷基铝是三乙基铝。
本发明在实施时，烷基铝与烯烃是混合的。将路易斯酸溶解在非极性溶剂中，或在非极性溶剂中拌成浆。将中性的金属茂催化剂分开溶解在相同的溶剂中。再将该路易斯酸混合物和催化剂混合物合并。合并后的混合物与烯烃和烷基铝的共混物相接触。金属茂∶路易斯酸∶烷基铝的摩尔比范围从0.01∶1∶0.1至5∶1∶350，较佳的是从0.5∶1∶0.5至4∶1∶25，最佳的摩尔比范围，对于溶解在非极性溶剂中的路易斯酸是0.02∶1∶1，对于在非极性溶剂中形成浆状的路易斯酸是0.01∶1∶1。
用金属茂催化剂对烯烃的聚合可通过任何已知的烯烃聚合方法来完成，例如本体聚合，淤浆聚合或气相聚合。对于聚丙烯，聚合温度范围从-80℃到150℃，优选25°～90℃，最优选50℃～80℃。
在加和不加烷基铝以及加和不加路易斯酸的条件下对以下的催化剂体系进行了评价。
1.ipr（CP-1-Flu）ZrMe2/F15/TEAl（TMA）
2.ipr（CP-1-Flu）ZrMe2/MgCl2/TEAl
3.Et（Ind）2ZrMe2/F-15/TEAl
4.Et（Ind）2ZrMe2/MgCl2/TEAl
Et（Ind）2ZrMe2是二甲基乙烯双（茚基）锆，
ipr（CP-1-Flu）ZrMe2是二甲基异亚丙基（环戊二烯基-1-芴基）锆和F15是三（五氟苯基）硼。
烷基铝和路易斯酸结合起来使用，这对于聚合反应的再现，控制及提高效率来说，均是必要的。
以上已对本发明作了一般的说明，现给出以下一些例子作为本发明的具体实施方案，用它们来证明本发明的可行性和优点。当然这是以举例说明本发明的方式来给出实施例，而不是想把说明书或权利要求限制到一定要按什么方式实施。
第一组  例1
将0.16毫摩尔三乙基铝（TEAl）溶解在5ml的甲苯中并在5psig的氮压下将它加到2升的Zipperclave反应器中。反应器的温度调到70℃，将1升的丙烯泵入反应器。该混合物在1200rpm速度下搅拌10分钟。
将35毫克ipr（Cp-1-Flu）Zrme2溶解在10毫升的二甲苯中。将该催化剂加到一个每端都装球形阀的40毫升不锈钢弹状储气瓶中。把400毫升丙烯通过此瓶泵入反应器内。该反应器的温度维持在70℃并对反应器内的物料搅拌30分钟。聚合反应结束后，冷却反应器并从反应器中排出未反应的丙烯。此实施例中没有反应产物。结果示于表Ⅰ。
例2
将0.33毫摩尔的三乙基铝（TEAl）溶解在5毫升甲苯中并加到一个Zipperclave反应器中。反应器温度调至70℃时加入1.0升丙烯。将该混合物在1200rpm速度下搅拌15分钟。
在5毫升二甲苯中溶解78.6毫克三（五氟苯基）硼使之形成无色溶解。将60毫克ipr（CP-1-Flu）ZrMe2溶解在10毫升二甲苯中形成黄色溶液。这两种溶液混合在一起形成红色的溶液，该溶液在室温下混合5分钟。
将该催化剂混合物加到一个50毫升不锈钢弹状储气瓶中。把200毫升丙烯通过此瓶泵入反应器内。反应器内的物料搅拌30分钟。反应器温度升至90℃。
将未反应的丙烯从反应器中排出，用丙酮洗涤反应产物并在真空中干燥。
分析测定聚合物的溶点和分子量。熔点是由差示扫描量热法（DCS）测得。用凝胶渗透色谱（GPC）分析法计算得到分子量。结果示于表Ⅰ。
例3
重复例2的方法，使用0.33毫摩尔三乙基铝（TEAl），27毫克三（五氟苯基）硼和20毫克ipr（CP-1-Flu）-ZrMe2。反应器中的物料搅拌30分钟，结果示于表Ⅰ。
例4
重复例2的方法，使用0.16毫摩尔三乙基铝（TEAL），46毫克三（五氟苯基）硼和15毫克ipr（CP-1-Flu）-ZrMe2。反应器中的物料搅拌30分钟。结果示于表Ⅰ。
例5
重复例2的方法，使用0.10毫摩尔三乙基铝（TEAL），46毫克三（五氟苯基）硼和35毫克ipr（CP-1-Flu）ZrMe2。反应器中的物料搅拌30分钟。结果示于表Ⅰ。
例6
重复例2的方法，使用0.16毫摩尔三乙基铝（TEAL），46毫克三（五氟苯基）硼和35毫克ipr（CP-1-Flu）-ZrMe2。反应器的物料搅拌30分钟。结果示于表Ⅰ。
例7
重复例2的方法，使用0.33毫摩尔三乙基铝（TEAL），46毫克三（五氟苯基）硼和35毫克ipr（CP-1-Flu）-ZrMe2。反应器的物料搅拌30分钟。未反应的丙烯从反应器中排出。没有反应产物。结果示于表Ⅰ。
例8
重复例2的方法，使用0.16毫摩尔三乙基铝（TEAL），46毫克三（五氟苯基）硼和35毫克ipr（CP-1-Flu）-ZrMe2。反应器中的物料搅拌30分钟。结果示于表Ⅰ。
第2组  例9
将0.16毫摩尔三乙基铝（TEAL）溶解在5毫升甲苯中，并在5psig氮压下将它加到一个2升的Zipperclave反应器中。
反应器温度调到60℃后泵入1升丙烯。该混合物在1200rpm速度下搅拌10分钟。
将86毫克MgCl2在5毫升甲苯中调成浆。将18毫克ipr（CP-1-Flu）ZrMe2通入MgCl2浆液中。将该混合物搅拌12小时得到一种暗紫色的悬浮液。
将该催化剂混合物加到一个50毫升的不锈钢弹状储气瓶中，将200毫升丙烯通过该瓶泵入反应器中。反应器内物料搅拌30分钟。将未反应的丙烯从反应器中排出，然后用稀HCl的甲醇溶液洗涤反应产物，再在真空烘箱中干燥。
分析测定该聚合物的熔点和分子量。熔点是从差示扫描量热法（DCS）测得。分子量用凝胶渗透色谱（GPC）分析法计算得到。结果示于表Ⅰ。
第3组  例10
将1升丙烯加到Eipperclave反应器中。反应温度调至70℃。将78.6毫克三（五氟苯基）硼溶解在5毫升甲苯中，58毫克Et（Ind）2ZrMe2溶介在18毫升甲苯中。把这两种溶液混合在一起在室温下混合5分钟。
将该催化剂混合物加到一个50毫升不锈钢弹状储气瓶中。通过该瓶泵入反应器200毫升丙烯。反应器温度保持在70℃，并搅拌反应器中物料35分钟。将未反应的丙烯从反应器中排出。没有反应产物。结果列于表Ⅰ。
例11
将0.33毫摩尔三乙基铝（TEAL）溶解在5毫升非配位溶剂中并把它加到一个Zipperclave反应器中。反应器定点温度调到70℃并往反应器加入1.0升丙烯。将该混合物在1200rpm转速下搅拌10分钟。
将78.6毫克三（五氟苯基）硼溶解在5毫升甲苯中形成无色溶液。58毫克Et（Ind）2ZrMe2溶解在10毫升甲苯中形成淡黄色溶液。将这两种溶液混在一起形成透明的暗黄溶液，在室温下混合5分钟。
将该催化剂混合物加到一个50毫升不锈钢弹状储气瓶中。通过此瓶往反应器中泵入200毫升丙烯。把反应器温度升至95℃以上并将反应器内物料搅拌6分钟。从反应器排出未反应的丙烯。用丙酮洗涤反应产物并在真空中干燥。
分析测定该聚丙烯反应产物的熔点和分子量。熔点是从差示扫描量热法（DCS）测得。分子量用凝胶渗透色谱（GPC）分析法计算得到。结果示于表Ⅰ。
例12
重复例11的方法，使用0.66毫摩尔TEAL，27毫克三（五氟苯基）硼和20毫克Et（Ind）2ZrMe2。反应器中物料搅拌22分钟。结果示于表Ⅰ。
例13
重复例11的方法，使用0.33毫摩尔TEAL，2.5毫克三（五氟苯基）硼和2.5毫克Et（Ind）2ZrMe2。反应器内物料搅拌30分钟。结果示于表Ⅰ。
例14
重复例11的方法，使用0.66毫摩尔TEAL，102毫克三（五氟苯基）硼和2.5毫克Et（Ind）2ZrMe2。将反应器中物料搅拌30分钟。结果示于表Ⅰ。
例15
重复例11的方法，使用0.66毫摩尔TEAL，154毫克三（五氟苯基）硼和2.5毫克Et（Ind）2ZrMe2。反应器中物料搅拌30分钟。结果示于表Ⅰ
例16
重复例11的方法，使用0.66毫摩尔TEAL，308毫克三（五氟苯基）硼和2.5毫克Et（Ind）2ZrMe2。反应器的物料搅拌30分钟。结果示于表Ⅰ。
第4组  例17
重复例9的方法，用352毫克氯化镁，40毫克Et（Ind）2ZrMe2，0.66毫摩尔TEAL，搅拌时间30分钟。结果示于表Ⅰ。
例18
重复例9的方法，用352毫克氯化镁，10毫克Et（Ind）2ZrMe2，0.66毫摩尔TEAL，搅拌时间30分钟。结果列于表Ⅰ。
例19
重复例9的方法，用124毫克氯化镁，40毫克Et（Iad）2ZrMe2，0.66毫摩尔TEAL，搅拌时间30分钟。结果示于表Ⅰ。
对于F15催化剂体系，将B∶Zr摩尔比提高到大大超过1∶1时，得到较高催化效率。这意味着低效率的部分原因是由于没有被F15完全离子化。
从以上的认识，本发明的许多改进和各种各样的变更显然都是可能的。因此可以理解到，本发明所提的权利要求范围之内，除了在说明书中特别说明之外，都是可以实施的。
Figure 901093688_IMG1
Figure 901093688_IMG2
例号  聚合温度  产量  熔点  分子量  分子量
＃  ℃  ℃  X1000  分布
1  70  0  -  -  -
2  70  123  57.6  1.9
3  70  7  110  64.3  2.0
4  70  58
5  70  5  105  39  2.0
6  70  168  105  61  1.9
7  70  110  123  55  2.0
8  70  167
9  60  6  131  57  2.0
10  70  0  -  -  -
11  70  117  113  15  4.2
12  70  70  122  17.5  3.5
13  70  0
14  70  1  127  26  2.8
15  70  90  130  20  5.1
16  70  33  129  25  3.7
17  70  49  133  31  1.9
18  70  47  130  29  2.4
19  70  8  130  30  2.0

Claims (27)

1、一种催化剂体系，含有：
a)一种中性金属茂化合物；
b)一种烷基铝；
c)一种路易斯酸；
其中烷基铝的通式是AlR3，式中R是卤素，氧、氢化物、烷基、烷氧基或芳基，每个R是相同或不相同的，并且至少一个R是烷基，
其中中性金属茂化合物的通式：
式中Cp是环戊二烯基或取代的环戊二烯基，每个Cp相同或不相同，M是Ⅲ、Ⅳ、Ⅴ或Ⅵ族金属，R是氢化物，卤素，酰胺或烃基，除了只有一个R是氢化物之外，每个R相同或不相同，P是1-4。
其中路易斯酸的酸度是足以将中性金属茂化合物离介形成阳离子金属茂催化剂，以及，
其中路易斯酸的配位体是不与金属茂阳离子反应的。
2、一种如权利要求1所述的催化剂，其中R是选自由烷基、芳基、链烯基、烷芳基和芳烷基组成的组中有20个以下碳原子的烃基。
3、一种如权利要求2所述的催化剂，其中R是6个以下碳原子的烷基或烷氧基，或者10个以下碳原子的芳基。
4、一种如权利要求1所述的催化剂，其中M是Ⅳ族金属选自由钛、锆和铪组成的组。
5、一种如权利要求4所述的催化剂，其中金属茂的中性甲基衍生物选自由二甲基乙烯双（茚基）锆和二甲基异亚丙基（环戊二烯基-1-芴基）锆组成的组。
6、一种如权利要求1所述的催化剂，其中烷基铝选自三乙基铝和三甲基铝。
7、一种如权利要求6所述的催化剂，其中烷基铝是三乙基铝。
8、一种如权利要求1所述的催化剂，其中路易斯酸选自所有含硼和含氯化镁的路易斯酸。
9、一种如权利要求8所述的催化剂，其中路易斯酸是三（五氟苯基）硼。
10、一种制备催化剂的方法，该方法包括：
a）将一种路易斯酸与一种中性金属茂化合物混合;和
b）使离子化的离子化合物与中性的金属茂化合物之间进行接触;其中金属茂的中性衍生物的通式为：
式中CP是环戊二烯基或取代的环戊二烯基，每个CP相同或不相同，M是Ⅲ，Ⅳ，Ⅴ或Ⅵ族金属，R是氢化物，卤素，酰胺或烃基，除了只有一个R是氢化物之外每个R相同或不相同，P是1-4。
11、如权利要求10所述的方法，其中的烯烃是丙烯。
12、如权利要求10所述的方法，其中R是选自由烷基、芳基、链烯基，烷芳基和芳烷基组成的组中有20个以下碳原子的烃基。
13、如权利要求10所述的方法，其中M是选自由钛、锆和铪组成的组中的第Ⅳ族金属。
14、如权利要求13所述的方法，其中M是锆。
15、如权利要求14所述的方法，其中金属茂的中性衍生物是从二甲基乙烯双（茚基）锆和二甲基异亚丙基（环戊二烯基-1-芴基）锆中选择。
16、如权利要求10所述的方法，其中路易斯酸是从含硼和含氯化镁的所有路易斯酸中选择。
17、如权利要求16所述的方法，其中路易斯酸是三（五氟苯基）硼。
18、一种烯烃的聚合方法，包括：
a）将烷基铝与烯烃混合;
b）将中性金属茂化合物与路易斯酸混合;
c）将金属茂-路易斯酸混合物与烷基铝-烯烃混合物混合;
其中烷基铝的通式为AlR3，式中R是卤素，氧、氢化物、烷基、烷氧基或芳基、每个R相同或不相同并且至少一个R是烷基;以及
其中中性金属茂化合物的通式为：
式中CP是环戊二烯基或取代的环戊二烯基，每个CP相同或不相同，M是第Ⅲ、Ⅳ、Ⅴ或Ⅵ族金属，R是氢化物，卤素、酰胺或烃基，除了只有一个R是氢化物之外每个R相同或不相同，P是1-4。
19、如权利要求18所述的方法，其中R是6个碳以下的烷基或烷氧基，或者是10个碳以下的芳基。
20、如权利要求19所述的方法，其中金属茂∶路易斯酸∶烷基铝的摩尔比范围是从0.01∶1∶0.1至5∶1∶350。
21、如权利要求20所述的方法，其中金属茂∶路易斯酸∶烷基铝的摩尔比范围是从0.5∶1∶0.5至4∶1∶25。
22、如权利要求21所述的方法，其中金属茂∶路易斯酸∶烷基铝的摩尔比是0.02∶1∶1。
23、如权利要求21所述的方法。其中金属茂∶路易斯酸∶烷基铝的摩尔比是0.01∶1∶1。
24、如权利要求16所述的方法，其中烷基铝选自三乙基铝和三甲基铝。
25、如权利要求21所述的方法，其中烷基铝是三乙基铝。
26、如权利要求18所述的方法，其中路易斯酸是从含硼和含氯化镁的所有路易斯酸中选择。
27、如权利要求23所述的方法，其中路易斯酸是三（五氟苯基）硼。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1090638C (zh) * 1996-07-26 2002-09-11 中国石油化工总公司 用于烯烃聚合与共聚合的催化剂及其制法和应用
CN108126753A (zh) * 2017-12-26 2018-06-08 华东理工大学 一类茂金属化合物在制备烯丙基端基丙烯齐聚物中的应用

Families Citing this family (292)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5153157A (en) * 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5198401A (en) * 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5391629A (en) * 1987-01-30 1995-02-21 Exxon Chemical Patents Inc. Block copolymers from ionic catalysts
US5241025A (en) * 1987-01-30 1993-08-31 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5384299A (en) * 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US6294625B1 (en) 1990-03-20 2001-09-25 Exxonmobil Chemical Patents Inc. Catalyst system of enhanced productivity and its use in polymerization process
WO1992001723A1 (en) * 1990-07-24 1992-02-06 Mitsui Toatsu Chemicals, Incorporated CATALYST FOR α-OLEFIN POLYMERIZATION AND PRODUCTION OF POLY-α-OLEFIN THEREWITH
JP3117231B2 (ja) * 1991-03-11 2000-12-11 三井化学株式会社 幅広い分子量分布を有するシンジオタクチックポリ−α−オレフィンの製造方法
US5721185A (en) * 1991-06-24 1998-02-24 The Dow Chemical Company Homogeneous olefin polymerization catalyst by abstraction with lewis acids
TW300901B (zh) 1991-08-26 1997-03-21 Hoechst Ag
NL9101502A (nl) * 1991-09-06 1993-04-01 Dsm Nv Werkwijze voor het bereiden van een gebrugde metalloceenverbinding alsmede een katalysatorcomponent en een werkwijze voor de polymerisatie van een olefinen.
TW309523B (zh) * 1991-11-30 1997-07-01 Hoechst Ag
TW304963B (zh) * 1992-01-27 1997-05-11 Hoechst Ag
US5374696A (en) * 1992-03-26 1994-12-20 The Dow Chemical Company Addition polymerization process using stabilized reduced metal catalysts
US5330948A (en) * 1992-03-31 1994-07-19 Northwestern University Homogeneous catalysts for stereoregular olefin polymerization
US5296433A (en) * 1992-04-14 1994-03-22 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
EP0572034A2 (en) * 1992-05-29 1993-12-01 Idemitsu Kosan Company Limited Ethylenic copolymer and ethylenic copolymer composition
JP3153000B2 (ja) * 1992-06-11 2001-04-03 三菱化学株式会社 α‐オレフィン重合体の製造法
JPH061803A (ja) * 1992-06-18 1994-01-11 Mitsubishi Petrochem Co Ltd オレフィンの重合法
US5710222A (en) 1992-06-22 1998-01-20 Fina Technology, Inc. Method for controlling the melting points and molecular weights of syndiotactic polyolefins using metallocene catalyst systems
JP3398381B2 (ja) * 1992-07-01 2003-04-21 エクソンモービル・ケミカル・パテンツ・インク 遷移金属オレフィン重合触媒
US5317036A (en) * 1992-10-16 1994-05-31 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization reactions utilizing soluble unsupported catalysts
NL9201970A (nl) * 1992-11-11 1994-06-01 Dsm Nv Indenylverbindingen en katalysatorcomponenten voor de polymerisatie van olefinen.
DE69310101T2 (de) * 1992-11-18 1997-09-25 Mitsui Petrochemical Ind Katalysator für Olefinpolymerisation und Verfahren für Olefinpolymerisation unter Anwendung desselben
BE1006438A3 (fr) * 1992-12-17 1994-08-30 Solvay Systeme catalytique, utilisation de ce systeme catalytique pour la (co)polymerisation d'olefines, procede de preparation de ce systeme catalytique et procede de (co)polymerisation d'olefines.
GB9226905D0 (en) * 1992-12-24 1993-02-17 Wellcome Found Pharmaceutical preparation
BE1006880A3 (fr) * 1993-03-01 1995-01-17 Solvay Precurseur solide d'un systeme catalytique pour la polymerisation d'olefines, procede pour sa preparation, systeme catalytique comprenant ce precurseur solide et procede de polymerisation d'olefines en presence de ce systeme catalytique.
JP3473955B2 (ja) * 1993-03-31 2003-12-08 出光興産株式会社 ビニル系重合体製造用の触媒及びビニル芳香族系重合体の製造方法
CA2125247C (en) * 1993-06-07 2001-02-20 Daisuke Fukuoka Transition metal compound, olefin polymerization catalyst component comprising said compound, olefin polymerization catalyst containing said catalyst component, process for olefinpolymerization using said catalyst , propylene homopolymer, propylene copolymer and propylene elastomer
DE69434709T2 (de) * 1993-06-07 2006-10-19 Mitsui Chemicals, Inc. Propylenelastomere
US6462154B1 (en) 1993-06-15 2002-10-08 Idemitsu Kosan Co., Ltd. Process for preparing olefin polymer and catalyst for polymerization of olefin
JPH0733812A (ja) * 1993-07-02 1995-02-03 Idemitsu Kosan Co Ltd スチレン系重合体製造触媒及びそれを用いたスチレン系重合体の製造方法
US5455214A (en) * 1993-09-09 1995-10-03 Mobil Oil Corporation Metallocenes supported on ion exchange resins
US5631202A (en) * 1993-09-24 1997-05-20 Montell Technology Company B.V. Stereospecific metallocene catalysts with stereolocking α-CP substituents
FI945959A (fi) * 1993-12-21 1995-06-22 Hoechst Ag Metalloseenejä ja niiden käyttö katalyytteinä
US5594080A (en) * 1994-03-24 1997-01-14 Leland Stanford, Jr. University Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor
JP4026846B2 (ja) 1994-04-11 2007-12-26 三井化学株式会社 プロピレン系重合体組成物の製造方法およびプロピレン系重合体組成物
CA2157400C (en) * 1994-04-11 2003-07-29 Takashi Ueda Process for preparing propylene polymer composition, and propylene polymer composition
DE4420456A1 (de) * 1994-06-13 1995-12-14 Hoechst Ag Übergangsmetallverbindung
WO1996004319A1 (en) * 1994-08-03 1996-02-15 Exxon Chemical Patents Inc. Supported ionic catalyst composition
US6143686A (en) * 1994-08-03 2000-11-07 Exxon Chemical Patents, Inc. Supported ionic catalyst compositions
US5643847A (en) * 1994-08-03 1997-07-01 Exxon Chemical Patents Inc. Supported ionic catalyst composition
DE4431838A1 (de) * 1994-09-07 1996-03-14 Basf Ag Geträgerte Metallocen-Katalysatorsysteme
TW369547B (en) 1994-09-21 1999-09-11 Mitsui Chemicals Inc Olefin polymerization catalyst and process for olefin polymerization
DE4434640C1 (de) 1994-09-28 1996-02-01 Hoechst Ag Verfahren zur Herstellung verbrückter Metallocene
DE4436113A1 (de) 1994-10-10 1996-04-11 Hoechst Ag Metallocenverbindung
US5500398A (en) * 1994-11-09 1996-03-19 Northwestern University Homogeneous α-olefin dimerization catalysts
EP0745615B1 (en) * 1994-12-20 2004-07-28 Mitsui Chemicals, Inc. Process for the preparation of ethylene polymer and ethylene polymer
US5888636A (en) * 1995-01-19 1999-03-30 Mitsui Chemicals, Inc. Multi-layer blow molded article of polypropylene
CN1076282C (zh) 1995-03-02 2001-12-19 三井化学株式会社 聚丙烯复合膜
DE59600760D1 (de) * 1995-06-12 1998-12-10 Targor Gmbh Übergangsmetallverbindung
TW401445B (en) * 1995-07-13 2000-08-11 Mitsui Petrochemical Ind Polyamide resin composition
US6403772B1 (en) * 1995-09-11 2002-06-11 Montell Technology Company, Bv Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom
KR100254936B1 (ko) * 1995-10-18 2000-05-01 고토 기치 올레핀(공)중합체 조성물과 그 제조방법 및 올레핀(공)중합용 촉매와 그 제조방법
US6787618B1 (en) 1995-12-01 2004-09-07 Basell Polypropylen Gmbh Metallocene compound and high molecular weight copolymers of propylene and olefins having two or four to thirty-two carbon atoms
DE19546500A1 (de) 1995-12-13 1997-06-19 Hoechst Ag Verfahren zur Herstellung eines Cycloolefincopolymeren
DE19546501A1 (de) 1995-12-13 1997-06-19 Hoechst Ag Metallocenverbindung
HUP9603449A3 (en) 1995-12-15 2000-03-28 Union Carbide Chem Plastic Process for production of long-chain branched polyolefins, polyethylene composition and product
EP0786466B1 (en) * 1996-01-25 2003-04-16 Tosoh Corporation Olefin polymerisation process which comprises a transition metal catalyst.
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
US6225426B1 (en) * 1996-04-10 2001-05-01 Uniroyal Chemical Company, Inc. Process for producing polyolefin elastomer employing a metallocene catalyst
EP0906343B1 (en) 1996-06-17 2001-04-18 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)
US6207608B1 (en) 1996-08-09 2001-03-27 University Of Iowa Research Foundation Olefin polymerization with direct use of ansa-metallocene amide complexes as catalysts
US6130302A (en) * 1996-08-19 2000-10-10 Northwestern University Synthesis and use of (polyfluoroaryl)fluoroanions of aluminum, gallium and indium
US6262200B1 (en) 1996-08-19 2001-07-17 Northwestern University (Polyfluoroaryl)fluoroanions of aluminum, gallium, and indium of enhanced utility, uses thereof, and products based thereon
US5854166A (en) * 1996-08-19 1998-12-29 Northwestern University Synthesis and use of (perfluoroaryl) fluoro-aluminate anion
JPH10101727A (ja) * 1996-09-24 1998-04-21 Shell Internatl Res Maatschappij Bv オレフィン又はポリマーを水素化するための触媒及び方法
CA2271861C (en) 1996-11-15 2007-09-04 Montell Technology Company B.V. Heterocyclic metallocenes and polymerization catalysts
TW425414B (en) * 1997-02-18 2001-03-11 Chisso Corp Preactivated catalyst for olefin (co)polymerization, catalyst for olefin (co)polymerization and olefin (co)polymer composition and their manufacturing method
EP0972800A4 (en) 1997-04-02 2004-06-16 Chisso Corp MODIFIED OLEFIN (CO) POLYMER COMPOSITION, METHOD FOR THE PRODUCTION THEREOF AND MODIFIED OLEFIN (CO) POLYMER MOLD
US6303696B1 (en) 1997-04-11 2001-10-16 Chisso Corporation Propylene (co)polymer composition using metallocene catalyst
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
TWI246520B (en) 1997-04-25 2006-01-01 Mitsui Chemicals Inc Processes for olefin polymerization
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
US6228795B1 (en) 1997-06-05 2001-05-08 Exxon Chemical Patents, Inc. Polymeric supported catalysts
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
DE19732804A1 (de) 1997-07-30 1999-02-04 Bayer Ag Katalysatoren auf Basis von Fulven-Metallkomplexen
DE19733017A1 (de) 1997-07-31 1999-02-04 Hoechst Ag Chemische Verbindung
TW504515B (en) 1997-08-07 2002-10-01 Chisso Corp Olefin (co)polymer composition
US6635715B1 (en) 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
US7026404B2 (en) 1997-08-12 2006-04-11 Exxonmobil Chemical Patents Inc. Articles made from blends made from propylene ethylene polymers
US6921794B2 (en) 1997-08-12 2005-07-26 Exxonmobil Chemical Patents Inc. Blends made from propylene ethylene polymers
FR2769245B1 (fr) 1997-10-02 1999-10-29 Atochem Elf Sa Support solide activateur des catalyseurs metallocenes en polymerisation des olefines, son procede de preparation, systeme catalytique et procede de polymerisation correspondants
DE19744102A1 (de) 1997-10-06 1999-04-15 Targor Gmbh Katalysatorsystem
DE19808253A1 (de) 1998-02-27 1999-09-02 Aventis Res & Tech Gmbh & Co Katalysatorsystem, Verfahren zu seiner Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE19808254A1 (de) 1998-02-27 1999-09-02 Aventis Res & Tech Gmbh & Co Chemische Verbindung
TW562810B (en) 1998-04-16 2003-11-21 Mitsui Chemicals Inc Catalyst for olefinic polymerization and method for polymerizing olefine
DE69935815T2 (de) 1998-07-01 2007-12-27 Exxonmobil Chemical Patents Inc., Baytown Elastische Mischung mit Kristallpolymeren und kristallisierbaren Polymeren des Propens
GB9816940D0 (en) * 1998-08-05 1998-09-30 Bp Chem Int Ltd Polymerisation catalysts
WO2000018808A1 (en) 1998-09-30 2000-04-06 Exxon Chemical Patents Inc. Cationic group 3 catalyst system
US6225427B1 (en) 1998-10-15 2001-05-01 Uniroyal Chemical Company, Inc. Olefin polymerization process employing metallocene catalyst provided by cocatalyst activation of a metallocene procatalyst
US6147173A (en) * 1998-11-13 2000-11-14 Univation Technologies, Llc Nitrogen-containing group 13 anionic complexes for olefin polymerization
TW576843B (en) 1998-12-25 2004-02-21 Mitsui Chemicals Inc Olefin polymerization catalyst and process for olefin polymerization using the olefin polymerization catalyst
US6469188B1 (en) 1999-01-20 2002-10-22 California Institute Of Technology Catalyst system for the polymerization of alkenes to polyolefins
EP1171480B1 (de) 1999-03-29 2005-05-25 Basell Polyolefine GmbH Verfahren zur polymerisation von olefinen
JP2000351813A (ja) 1999-04-09 2000-12-19 Mitsui Chemicals Inc エチレン・α−オレフィン共重合体およびその製造方法ならびにその用途
US6632885B2 (en) 1999-04-13 2003-10-14 Mitsui Chemicals, Inc. Soft syndiotactic polypropylene composition and molded product
WO2000068276A1 (fr) * 1999-05-10 2000-11-16 Japan As Represented By Director General Of The Agency Of Industrial Science And Technology Procede de production de polymere d'olefine vivant
US6303718B1 (en) 1999-09-17 2001-10-16 Bayer Aktiengesellschaft Composition based on fluorine-containing metal complexes
JP3808243B2 (ja) 1999-07-27 2006-08-09 三井化学株式会社 軟質樹脂組成物
DE19935592A1 (de) 1999-08-02 2001-02-08 Elenac Gmbh Imidochromverbindungen in Katalysatorsystemen für die Olefinpolymerisation
IT1313599B1 (it) * 1999-08-05 2002-09-09 Enichem Spa Complessi metallici utilizzabili nella catalisi per la (co)polimerizzazione delle alfa-olefine
BR0013271A (pt) 1999-08-13 2002-04-16 Basell Polyolefine Gmbh Copolìmeros de etileno com c3-ci2, alfa-olefinas, processo de prepraração de copolìmeros de etileno, mistura de polìmeros, utilização de copolìmeros de etileno com c3-ci2 alfa-olefinas, e, fibras, lâminas e corpos moldados
US6475947B1 (en) 1999-09-10 2002-11-05 Phillips Petroleum Company Oligomeric metallocenes and their use
US6667274B1 (en) * 1999-12-30 2003-12-23 Phillips Petroleum Company Polymerization catalysts
KR100937175B1 (ko) 2000-01-26 2010-01-19 미쓰이 가가쿠 가부시키가이샤 올레핀 중합체
KR20010082913A (ko) * 2000-02-22 2001-08-31 박찬구 아미도계 ｉｖ족 금속 착화합물을 이용한 폴리이소부텐의제조방법
US20040072975A1 (en) 2000-03-17 2004-04-15 Jorg Schottek Salt-like chemical compound, its preparation and its use in catalyst systems for preparing polyolefins
DE60114545T2 (de) 2000-03-31 2006-07-20 Mitsui Chemicals, Inc. Verfahren zur herstellung einer polyolefinzusammensetzung
US6846943B2 (en) 2000-05-23 2005-01-25 Chisso Corporation Metallocene compound, olefin polymerization catalyst containing the compound, and method for producing an olefin polymer by use of the catalyst
US6635733B2 (en) 2000-05-23 2003-10-21 Chisso Corporation Elastomeric polypropylene
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
BR0107037A (pt) 2000-07-26 2003-06-10 Mitsui Chemicals Inc Polìmero de poliolefina ramificada e método de preparação da mesma
NO20013880L (no) 2000-08-22 2002-02-25 Rohm & Haas Matriks og fremgangsmåte for fremstilling av polyolefiner
SG102636A1 (en) 2000-09-07 2004-03-26 Mitsui Chemicals Inc Polar group-containing olefin copolymer, process for preparing the same, thermoplatic resin composition containing the copolymer, and uses thereof
KR100844062B1 (ko) 2001-02-21 2008-07-07 미쓰이 가가쿠 가부시키가이샤 올레핀 중합용 촉매 및 이 촉매를 사용하는 올레핀중합체의 제조방법
JP5156167B2 (ja) 2001-04-12 2013-03-06 エクソンモービル・ケミカル・パテンツ・インク プロピレン−エチレンポリマー及び製造法
WO2003000790A1 (en) 2001-06-22 2003-01-03 Exxonmobil Chemical Patents, Inc. Metallocene-produced very low density polyethylenes or linear lowdensity polyethylenes as impact modifiers
US7019157B2 (en) 2001-08-06 2006-03-28 Chisso Corporation Metallocene compounds, production process for olefin polymers using catalysts containing them and olefin polymers produced by the production process
FR2830868B1 (fr) * 2001-10-11 2004-12-03 Atofina Composition a base de polypropylene isotactique obtenu par catalyse metallocene et de polypropylene isotactique obtenu par catalyse ziegler natta, greffe
JP3865314B2 (ja) 2001-10-19 2007-01-10 旭化成ケミカルズ株式会社 オレフィンの重合方法
CN100484975C (zh) 2002-07-31 2009-05-06 埃克森美孚化学专利公司 硅烷可交联的聚乙烯
US6995279B2 (en) 2002-08-02 2006-02-07 Chisso Corporation Metallocene compounds, processes for the production of olefin polymers using catalysts containing the compounds, and olefin polymers produced by the processes
EP1550693B1 (en) 2002-08-27 2007-07-11 Mitsui Chemicals, Inc. Thermoplastic elastomer and molded object thereof
ES2306884T3 (es) 2002-09-05 2008-11-16 Exxonmobil Chemical Patents Inc. Pelicula contraible.
JP2005538218A (ja) 2002-09-05 2005-12-15 エクソンモービル・ケミカル・パテンツ・インク 延伸フィルム
EP2465878B1 (en) 2002-09-27 2020-04-01 Mitsui Chemicals, Inc. Bridged metallocene compound for olefin polymerization and method of polymerizing olefin using the same
EP2261292B1 (en) 2002-10-15 2014-07-23 ExxonMobil Chemical Patents Inc. Polyolefin adhesive compositions
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
KR100662836B1 (ko) 2002-10-23 2006-12-28 미쓰이 가가쿠 가부시키가이샤 마그네슘을 함유하는 담체 성분 및 올레핀 중합에의 응용
DE10251513A1 (de) 2002-11-04 2004-05-19 Basf Ag Übergangsmetallkatalysatoren für (Co)Polymerisation von olefinischen Monomeren
JP4574550B2 (ja) 2003-02-14 2010-11-04 三井化学株式会社 シンジオタクティックプロピレン系重合体組成物
KR101004338B1 (ko) 2003-03-28 2010-12-28 미쓰이 가가쿠 가부시키가이샤 프로필렌／1―부텐 공중합체, 폴리프로필렌 조성물 및 그 용도, 및 폴리프로필렌 복합 필름
US7803865B2 (en) 2003-08-25 2010-09-28 Dow Global Technologies Inc. Aqueous dispersion, its production method, and its use
TW200517426A (en) 2003-08-25 2005-06-01 Dow Global Technologies Inc Aqueous dispersion, its production method, and its use
US9169406B2 (en) 2003-08-25 2015-10-27 Dow Global Technologies Llc Coating compositions
US7763676B2 (en) 2003-08-25 2010-07-27 Dow Global Technologies Inc. Aqueous polymer dispersions and products from those dispersions
US8779053B2 (en) 2003-08-25 2014-07-15 Dow Global Technologies Llc Coating compositions
US8349929B2 (en) 2003-08-25 2013-01-08 Dow Global Technologies Llc Coating composition and articles made therefrom
US8158711B2 (en) 2003-08-25 2012-04-17 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
US8722787B2 (en) 2003-08-25 2014-05-13 Dow Global Technologies Llc Coating composition and articles made therefrom
US8946329B2 (en) 2003-08-25 2015-02-03 Dow Global Technologies Llc Coating compositions
US8357749B2 (en) 2003-08-25 2013-01-22 Dow Global Technologies Llc Coating composition and articles made therefrom
US7947776B2 (en) 2003-08-25 2011-05-24 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
EP1697428B1 (en) 2003-12-23 2014-01-15 Basell Polyolefine GmbH Catalyst system for olefin polymerization
US7119153B2 (en) 2004-01-21 2006-10-10 Jensen Michael D Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength
GB0411742D0 (en) 2004-05-26 2004-06-30 Exxonmobil Chem Patents Inc Transition metal compounds for olefin polymerization and oligomerization
AU2005275740A1 (en) 2004-08-27 2006-03-02 Mitsui Chemicals, Inc. Catalysts for olefin polymerization, process for production of olefin polymers, olefin copolymers, novel transition metal compounds, and process for production of transition metal compounds
US20060057351A1 (en) * 2004-09-10 2006-03-16 Alain Yang Method for curing a binder on insulation fibers
EP1805229A1 (en) 2004-10-28 2007-07-11 Dow Gloval Technologies Inc. Method of controlling a polymerization reactor
US7795194B2 (en) 2004-11-26 2010-09-14 Mitsui Chemicals, Inc. Synthetic lubricating oil and lubricating oil composition
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
SG162743A1 (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
US20070225423A1 (en) * 2005-10-07 2007-09-27 Mitsui Chemicals, Inc. Process for producing blow molded product by blow molding
US20070080483A1 (en) * 2005-10-07 2007-04-12 Mitsui Chemicals, Inc. Process for producing injection molded product
US7605208B2 (en) 2005-10-31 2009-10-20 Mitsui Chemicals, Inc. Process for producing thermoplastic resin composition
EP1963347B1 (en) 2005-12-14 2011-10-19 ExxonMobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US20090127751A1 (en) 2006-03-10 2009-05-21 Mitsui Chemicals, Inc. Process for Producing Molded Product by Inflation Molding
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
WO2007114009A1 (ja) 2006-03-30 2007-10-11 Mitsui Chemicals, Inc. 射出成形による成形体の製造方法
US7951873B2 (en) 2006-05-05 2011-05-31 Exxonmobil Chemical Patents Inc. Linear low density polymer blends and articles made therefrom
KR101096836B1 (ko) 2006-07-31 2011-12-22 가부시키가이샤 프라임 폴리머 에틸렌계 수지 또는 에틸렌계 수지 조성물로 이루어지는 필름 또는 적층체
EP2065439B1 (en) 2006-09-20 2012-03-28 Mitsui Chemicals, Inc. Polyolefin composition
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
DE102006057822A1 (de) 2006-12-06 2008-06-26 Basell Poliolefine Italia S.R.L. Mehrschichtiges Verbundmaterial mit inhärent latentem Schutz gegenüber Verformung unter Temperatureinwirkung als Ausgleich des Bi-Metalleffektes
US7713636B2 (en) * 2006-12-15 2010-05-11 Exxonmobil Chemical Patents Inc. Multi-layer films comprising propylene-based polymers
DE102006060459A1 (de) * 2006-12-19 2008-06-26 Basell Poliolefine Italia S.R.L. Mehrschichtiges Verbundmaterial mit mindestens einer Glasschicht
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
WO2008087945A1 (ja) 2007-01-16 2008-07-24 Prime Polymer Co., Ltd. 中空成形体用エチレン系樹脂組成物及びそれからなる中空成形体
CN101679702B (zh) 2007-06-14 2012-07-04 三井化学株式会社 热塑性弹性体组合物
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
JP5126993B2 (ja) 2007-07-04 2013-01-23 三井化学株式会社 遷移金属錯体化合物、該化合物を含むオレフィン多量化用触媒および該触媒存在下で行うオレフィン多量体の製造方法
MX2010002085A (es) * 2007-08-29 2010-03-26 Albemarle Corp Activaciones de catalizador de aluminoxano derivados de agentes precursores de cation dialquilaluminio, procesos para su elaboracion, y su uso en catalizadores y polimerizacion de olefinas.
US7906588B2 (en) 2007-10-26 2011-03-15 Exxonmobil Chemical Patents Inc. Soft heterogeneous isotactic polypropylene compositions
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
DE102007057606A1 (de) 2007-11-28 2009-06-04 Basell Polyolefine Gmbh Modular aufgebaute Rotationstrommel für Elektro- und Haushaltsgeräte
EP2112173A1 (en) 2008-04-16 2009-10-28 ExxonMobil Chemical Patents Inc. Catalyst compounds and use thereof
ATE524500T1 (de) 2008-01-31 2011-09-15 Exxonmobil Chem Patents Inc Verbesserte verwendung linearer alpha-olefine bei der herstellung von metallocen-katalysierten poly-alpha-olefinen
EP2103634A1 (en) 2008-03-20 2009-09-23 ExxonMobil Chemical Patents Inc. Production of propylene-based polymers
JP5473898B2 (ja) 2008-03-27 2014-04-16 三井化学株式会社 樹脂組成物およびその用途
JPWO2009122967A1 (ja) 2008-03-31 2011-07-28 三井化学株式会社 樹脂組成物および溶融袋
US9938400B2 (en) 2008-04-23 2018-04-10 Exxonmobil Chemical Patents Inc. Propylene copolymers in soft thermoplastic blends
US8293856B2 (en) 2008-08-19 2012-10-23 Mitsui Chemicals, Inc. Process for preparing olefin polymer using mixed catalyst
JP5557835B2 (ja) 2009-03-30 2014-07-23 三井化学株式会社 オレフィンと共役ジエンとの共重合体、およびその製造方法
JP5615807B2 (ja) 2009-04-21 2014-10-29 三井化学株式会社 オレフィン重合体の製造方法
US9127151B2 (en) 2009-04-28 2015-09-08 Exxonmobil Chemical Patents Inc. Polymer compositions having improved properties as viscosity index improvers and use thereof in lubricating oils
US8378042B2 (en) 2009-04-28 2013-02-19 Exxonmobil Chemical Patents Inc. Finishing process for amorphous polymers
US20120028865A1 (en) 2010-07-28 2012-02-02 Sudhin Datta Viscosity Modifiers Comprising Blends of Ethylene-Based Copolymers
US8791284B2 (en) 2009-07-01 2014-07-29 Mitsui Chemicals, Inc. Organometallic compound and production method thereof
KR20120052990A (ko) 2009-08-18 2012-05-24 바젤 폴리올레핀 게엠베하 전기 구동 자동차에서의 전력 전지용 하우징
WO2011020582A1 (en) 2009-08-18 2011-02-24 Basell Polyolefine Gmbh Plastic fuel container for motor bikes or automotive hybrid cars
KR101411182B1 (ko) 2009-12-21 2014-06-23 미쓰이 가가쿠 가부시키가이샤 신디오택틱 α-올레핀 중합체의 제조방법
CN105061644B (zh) 2009-12-24 2017-10-27 埃克森美孚化学专利公司 用于生产新型合成基础油料的方法
US9416206B2 (en) 2010-01-22 2016-08-16 Exxonmobil Chemical Patents Inc. Lubricating oil compositions and method for making them
CN102725319B (zh) 2010-01-27 2014-10-15 埃克森美孚化学专利公司 共聚物、其组合物及制造它们的方法
US8058461B2 (en) 2010-03-01 2011-11-15 Exxonmobil Chemical Patents Inc. Mono-indenyl transition metal compounds and polymerization therewith
US20120135903A1 (en) 2010-05-11 2012-05-31 Mitsui Chemicals, Inc. Lubricating oil composition
CN103025819B (zh) 2010-07-28 2015-07-22 埃克森美孚化学专利公司 含乙烯-基共聚物的共混物的粘度改性剂
CA2802109C (en) 2010-07-28 2015-04-07 Exxonmobil Chemical Patents Inc. Viscosity modifiers comprising blends of ethylene-based copolymers
SG186167A1 (en) 2010-07-28 2013-01-30 Exxonmobil Chem Patents Inc Ethylene based copolymer compositions as viscosity modifiers and methods for making them
EP2711380A4 (en) 2011-05-18 2014-11-05 Mitsui Chemicals Inc PROPYLENE COPOLYMER AND PROPYLENE COPOLYMER COMPOSITION, FORM AND FOAM FOR THIS, AND METHOD FOR THE PRODUCTION THEREOF AND THIS FOAM
WO2013091836A1 (en) 2011-12-19 2013-06-27 Saudi Basic Industries Corporation (Sabic) Process for the preparation of metallocene complexes
CN104080792A (zh) 2011-12-19 2014-10-01 沙特基础工业公司 用于制备茂金属络合物的方法
JP5769821B2 (ja) 2011-12-27 2015-08-26 三井化学株式会社 ４−メチル−１−ペンテン（共）重合体組成物、該組成物からなるフィルムおよび中空成形体
EP2799486B1 (en) 2011-12-28 2017-08-23 Mitsui Chemicals, Inc. Ethylene-based polymer composition, and molded body obtained from same
US10316176B2 (en) 2012-02-03 2019-06-11 Exxonmobil Chemical Patents Inc. Polymer compositions and methods of making them
US9139794B2 (en) 2012-02-03 2015-09-22 Exxonmobil Chemical Patents Inc. Process for the production of polymeric compositions useful as oil modifiers
JP6088548B2 (ja) 2012-02-03 2017-03-01 エクソンモービル ケミカル パテンツ インコーポレイテッド 油改質剤として有用なポリマー組成物を製造する方法
SG11201405812VA (en) 2012-03-21 2014-10-30 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
WO2013158225A1 (en) 2012-04-18 2013-10-24 Exxonmobil Chemical Patents Inc. Polyolefin compositions and methods of production thereof
CN104661751B (zh) 2012-09-24 2017-02-22 埃克森美孚化学专利公司 乙烯基封端的聚乙烯的生产
SG11201502294RA (en) 2012-09-25 2015-05-28 Mitsui Chemicals Inc Transition Metal Compound, Olefin Polymerization Catalyst, And Olefin Polymer Production Process
EP2902419B1 (en) 2012-09-25 2020-08-19 Mitsui Chemicals, Inc. Method for producing olefin polymer, and olefin polymer
KR101394943B1 (ko) 2012-11-19 2014-05-14 대림산업 주식회사 에틸렌과 알파-올레핀의 공중합체 및 그 제조방법
ITMI20122206A1 (it) 2012-12-20 2014-06-21 Versalis Spa Procedimento per la preparazione di (co)polimeri di dieni coniugati in presenza di un sistema catalitico comprendente un complesso bis-immino-piridinico di cobalto
ITMI20122201A1 (it) 2012-12-20 2014-06-21 Versalis Spa Complesso osso-azotato di cobalto, sistema catalitico comprendente detto complesso osso-azotato e procedimento per la (co)polimerizzazione di dieni coniugati
ITMI20122199A1 (it) 2012-12-20 2014-06-21 Versalis Spa Procedimento per la preparazione di (co)polimeri di dieni coniugati in presenza di un sistema catalitico comprendente un complesso bis-imminico di cobalto
ITMI20122203A1 (it) 2012-12-20 2014-06-21 Versalis Spa Procedimento per la preparazione di (co)polimeri di dieni coniugati in presenza di un sistema catalitico comprendente un complesso osso-azotato di cobalto
CN109824802A (zh) 2012-12-21 2019-05-31 埃克森美孚化学专利公司 桥联的金属茂化合物、催化剂体系和使用它们的聚合方法
CN110551424B (zh) 2012-12-28 2022-07-29 陶氏环球技术有限责任公司 涂料组合物和由其制成的物品
EP2922925B1 (en) 2012-12-28 2019-12-04 Dow Global Technologies LLC Coating compositions
CN105008439B (zh) 2013-02-20 2018-01-09 普瑞曼聚合物株式会社 双轴拉伸膜和乙烯系聚合物组合物
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
CN105143279B (zh) 2013-03-12 2017-10-27 三井化学株式会社 烯烃聚合物的制造方法及烯烃聚合用催化剂
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
ITMI20131830A1 (it) 2013-11-05 2015-05-06 Versalis Spa Polibutadieni di-blocco stereoregolari a struttura 1,4-cis/1,2 sindiotattica da polimerizzazione stereospecifica
ITMI20131828A1 (it) 2013-11-05 2015-05-06 Versalis Spa Polibutadieni di-blocco stereoregolari a struttura 1,4-cis/1,2 sindiotattica da polimerizzazione stereospecifica
SG11201606561WA (en) 2014-02-13 2016-09-29 Mitsui Chemicals Inc PROCESS FOR PRODUCING ETHYLENE/α-OLEFIN COPOLYMER
KR101862960B1 (ko) 2014-02-13 2018-05-31 미쓰이 가가쿠 가부시키가이샤 에틸렌·α-올레핀·비공액 폴리엔 공중합체 및 그의 용도, 및 그의 제조 방법
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
JP6702854B2 (ja) 2014-02-28 2020-06-03 三井化学株式会社 架橋体とその製造方法および用途、ならびにエチレン系共重合体
JP6618891B2 (ja) 2014-03-28 2019-12-11 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
KR101850233B1 (ko) 2014-03-28 2018-04-18 미쓰이 가가쿠 가부시키가이샤 올레핀계 수지, 그의 제조 방법 및 프로필렌계 수지 조성물
CN106133005B (zh) 2014-03-28 2018-08-24 三井化学株式会社 烯烃系树脂及其制造方法
KR101970078B1 (ko) 2014-09-10 2019-04-17 미쓰이 가가쿠 가부시키가이샤 윤활유 조성물
US9944728B2 (en) 2014-09-11 2018-04-17 Mitsui Chemicals, Inc. Production method of olefin (co)polymer containing constituent unit derived from 1-butene
PL3194409T3 (pl) 2014-09-17 2020-06-01 Versalis S.P.A. Kompleks pirydynowy cyrkonu, wkład katalityczny zawierający ten kompleks pirydynowy cyrkonu i sposób (ko)polimeryzacji sprzężonych dienów
ES2784518T3 (es) 2014-12-09 2020-09-28 Mitsui Chemicals Inc Composición de resina a base de propileno
BR112017020142B1 (pt) 2015-03-20 2022-04-12 Mitsui Chemicals, Inc Composição de elastômero termoplástico, métodos para produzir a mesma, artigo moldado, peça de automóvel, mangueira de automóvel e porta-mala de automóvel compreendendo a referida composição
CN107429011B (zh) 2015-03-20 2020-06-19 三井化学株式会社 热塑性弹性体组合物及其制造方法
EP3279256A4 (en) 2015-03-31 2018-12-19 Mitsui Chemicals, Inc. Resin composition and use of same
ITUB20152581A1 (it) 2015-07-29 2017-01-29 Versalis Spa Complesso azotato di titanio, sistema catalitico comprendente detto complesso azotato di titanio e procedimento per la (co)polimerizzazione di dieni coniugati
US20180320102A1 (en) 2015-11-09 2018-11-08 Mitsui Chemicals, Inc. Viscosity modifier for lubricating oils, additive composition for lubricating oils, and lubricating oil compositions
KR20170090977A (ko) * 2016-01-29 2017-08-08 삼성전자주식회사 편광 필름, 광학 필름 및 표시 장치
JP6703093B2 (ja) 2016-03-04 2020-06-03 三井化学株式会社 積層体およびその用途
ITUA20163932A1 (it) 2016-05-30 2017-11-30 Versalis Spa Complesso osso-azotato di ferro, sistema catalitico comprendente detto complesso osso-azotato di ferro e procedimento per la (co)polimerizzazione di dieni coniugati
US10647626B2 (en) 2016-07-12 2020-05-12 Chevron Phillips Chemical Company Lp Decene oligomers
WO2018124070A1 (ja) 2016-12-27 2018-07-05 三井化学株式会社 潤滑油組成物、潤滑油用粘度調整剤、および潤滑油用添加剤組成物
JP6741790B2 (ja) 2017-01-16 2020-08-19 三井化学株式会社 自動車ギア用潤滑油組成物
MX2019009838A (es) 2017-02-20 2019-10-04 Mitsui Chemicals Inc Laminado.
US20190358928A1 (en) 2017-02-20 2019-11-28 Mitsui Chemicals, Inc. Laminate
CA3068805C (en) 2017-07-06 2023-05-16 Mitsui Chemicals, Inc. Olefin oligomerization catalyst and method for producing olefin oligomer in the presence of the same catalyst
IT201700109176A1 (it) 2017-09-29 2019-03-29 Versalis Spa Complesso bis-imminico di titanio, sistema catalitico comprendente detto complesso bis-imminico di titanio e procedimento per la (co)polimerizzazione di dieni coniugati
MX2020009404A (es) 2018-03-20 2020-10-01 Mitsui Chemicals Inc Copolimero de etileno/alfa-olefina/polieno no conjugado, metodo para producir el mismo y uso del mismo.
JP7182644B2 (ja) 2018-12-04 2022-12-02 三井化学株式会社 ４－メチル－１－ペンテン共重合体を含有する樹脂組成物、およびキャパシタ用フィルム
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
CN113574147A (zh) 2019-03-26 2021-10-29 三井化学株式会社 汽车齿轮用润滑油组合物及其制造方法
KR20210139401A (ko) 2019-03-26 2021-11-22 미쓰이 가가쿠 가부시키가이샤 윤활유 조성물 및 그의 제조 방법
CN113574150A (zh) 2019-03-26 2021-10-29 三井化学株式会社 汽车变速箱油用润滑油组合物及其制造方法
EP3950900A4 (en) 2019-03-26 2022-08-10 Mitsui Chemicals, Inc. COMPOSITION OF LUBRICATING OIL FOR INTERNAL COMBUSTION ENGINE, AND METHOD OF MAKING THE SAME
US20220177798A1 (en) 2019-03-26 2022-06-09 Mitsui Chemicals, Inc. Lubricating oil composition for hydraulic 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
KR20210139407A (ko) 2019-03-26 2021-11-22 미쓰이 가가쿠 가부시키가이샤 그리스 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
US20220169948A1 (en) 2019-03-26 2022-06-02 Mitsui Chemicals, Inc. Lubricating oil composition for compressor oils and method for producing the same
EP3950899A4 (en) 2019-03-26 2022-08-17 Mitsui Chemicals, Inc. LUBRICATING OIL COMPOSITION, AND METHOD OF MAKING THE SAME
KR102580620B1 (ko) 2019-03-29 2023-09-19 미쓰이 가가쿠 가부시키가이샤 수지 조성물
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
EP4023737A4 (en) 2019-08-29 2023-08-30 Mitsui Chemicals, Inc. LUBRICATING OIL COMPOSITION
KR102707199B1 (ko) 2019-10-07 2024-09-13 미쓰이 가가쿠 가부시키가이샤 에틸렌·α-올레핀 공중합체 조성물 및 그 용도
JP7369200B2 (ja) 2019-10-29 2023-10-25 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
JP7341256B2 (ja) 2020-01-30 2023-09-08 三井化学株式会社 ポリアミド組成物
US20230365794A1 (en) 2020-10-06 2023-11-16 Mitsui Chemicals, Inc. Resin composition
JPWO2022154126A1 (zh) 2021-01-18 2022-07-21
JPWO2022186053A1 (zh) 2021-03-05 2022-09-09
WO2022210843A1 (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、フィルムおよび積層体
JPWO2022210844A1 (zh) 2021-03-31 2022-10-06
US20240191068A1 (en) 2021-03-31 2024-06-13 Mitsui Chemicals, Inc. Ethylene resin composition and shaped article
KR20230160903A (ko) 2021-05-20 2023-11-24 미쓰이 가가쿠 가부시키가이샤 수지 조성물, 및 그 용도 및 제조 방법
EP4426804A1 (en) 2021-11-05 2024-09-11 ExxonMobil Chemical Patents Inc. Polypropylene viscosity modifiers and lubricating oils thereof
WO2023081327A1 (en) 2021-11-05 2023-05-11 Chevron Oronite Company Llc Lubricating oil composition with viscosity modifier based on syndiotactic propylene-based ethylene-propylene copolymers with improved properties
KR20240096736A (ko) 2021-11-05 2024-06-26 엑손모빌 케미컬 패튼츠, 아이엔씨. 신디오택틱 프로필렌계 에틸렌-프로필렌 공중합체
CN118251454A (zh) 2021-11-16 2024-06-25 三井化学株式会社 树脂组合物及其用途
KR20240127475A (ko) 2022-03-24 2024-08-22 미쓰이 가가쿠 가부시키가이샤 에틸렌·α-올레핀·5-바이닐-2-노보넨 공중합체, 당해 공중합체를 포함하는 조성물, 및 가교체

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242099A (en) * 1964-03-27 1966-03-22 Union Carbide Corp Olefin polymerization catalysts
US3756998A (en) * 1968-10-14 1973-09-04 Union Carbide Corp L catalysts polymerization of olefins using supported pi arenechromium tricarbony
US3709853A (en) * 1971-04-29 1973-01-09 Union Carbide Corp Polymerization of ethylene using supported bis-(cyclopentadienyl)chromium(ii)catalysts
US4808561A (en) * 1985-06-21 1989-02-28 Exxon Chemical Patents Inc. Supported polymerization catalyst
PL276385A1 (en) * 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
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
US5155080A (en) * 1988-07-15 1992-10-13 Fina Technology, Inc. Process and catalyst for producing syndiotactic polyolefins
US5162278A (en) * 1988-07-15 1992-11-10 Fina Technology, Inc. Non-bridged syndiospecific metallocene catalysts and polymerization process
US5387568A (en) * 1989-10-30 1995-02-07 Fina Technology, Inc. Preparation of metallocene catalysts for polymerization of olefins

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1090638C (zh) * 1996-07-26 2002-09-11 中国石油化工总公司 用于烯烃聚合与共聚合的催化剂及其制法和应用
CN108126753A (zh) * 2017-12-26 2018-06-08 华东理工大学 一类茂金属化合物在制备烯丙基端基丙烯齐聚物中的应用

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