CN1028641C - 用于链烯聚合的金属茂催化剂的制备 - Google Patents

用于链烯聚合的金属茂催化剂的制备 Download PDF

Info

Publication number
CN1028641C
CN1028641C CN90108884A CN90108884A CN1028641C CN 1028641 C CN1028641 C CN 1028641C CN 90108884 A CN90108884 A CN 90108884A CN 90108884 A CN90108884 A CN 90108884A CN 1028641 C CN1028641 C CN 1028641C
Authority
CN
China
Prior art keywords
metallocenes
ionic compound
ionize
charged ion
neutral
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN90108884A
Other languages
English (en)
Other versions
CN1051311A (zh
Inventor
约翰·尤恩
迈克尔·J·埃尔德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fina Technology Inc
Original Assignee
Fina Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=23660575&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1028641(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Fina Technology Inc filed Critical Fina Technology Inc
Publication of CN1051311A publication Critical patent/CN1051311A/zh
Application granted granted Critical
Publication of CN1028641C publication Critical patent/CN1028641C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/61927—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63908—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及用于链烯聚合反应的金属茂催化剂的制备。本方法使用一种使中性金属茂化合物电离的致电离剂。该致电离的离子化合物不含活性的质子，而含有碳鎓氧鎓或锍阳离子。它的阴离子不配位于或仅松散地配位于金属茂阳离子，且与该金属茂阳离子不发生化学反应。这类化合物之一是四(五氟苯基)合硼酸三苯基碳。
本发明可制得高活性的催化剂，并且不产生可能抑制催化剂活性的副产品。

Description

本发明涉及一种制备催化剂的方法;具体地说，它涉及用于链烯烃聚合的催化剂的制备方法。
链烯烃，尤其是丙烯，可以聚合形成各种形式的聚烯烃;全同立构的，间同立构的和无规立构的。全同立构的聚丙烯主要包含相同构型的重复单元，在链中只有少数无定的、短的倒位部分。全同立构聚丙烯的结构可表示为
全同立构聚丙烯可以是一种高结晶度的聚合物，它具有高的熔点和其它合乎需要的物理性能，这些性能与无定形（非晶态）聚合物显著不同。
间同立构聚合物主要包含精确地交替排列的立体异构体单元，其结构可表示为
Figure 901088846_IMG2
无规立构聚合物则在聚合物链中，重复单元的构型的次序是没有规则的。在工业应用中，一般总有若干百分比的无规立构的聚合物与全同立构形式一起制备出来。
链烯烃聚合主要使用Ziegler-Natta催化剂。一类Ziegler-Natta催化剂是以甲基铝噁烷（methyaluminoxane）作为助催化剂的Ⅳ族金属茂 化合物。已经证明，用于链烯烃聚合的Ziegler-Natta催化剂可以通过使Ⅳ族金属茂与一种离子化合物结合而形成。
Figure 901088846_IMG3
C＊p-五甲基环戊二烯基
M-Ⅳ族金属
R-烷基
L-配位体
[C]-阳离子
[A]-阴离子
所产生的化合物是一种具有催化剂作用的金属茂阳离子。离子化合物的阳离子[C]与金属茂反应产生一对离子对。阴离子[A]并不配位于金属茂阳离子，或者仅松散地配位于它。
下列各方法已用于产生上面的反应：
单电子氧化-这方法在“利用阳离子性的二（环戊二烯基）合锆（Ⅳ）的烷基配合物而进行的乙烯聚合”一文中已有说明，参看R.F.Jordan，C.S.Bajgur，R.Willett，B.Scott，J.Am.Chem.Soc.，p.7410-7411，Vol.108（1986）。这些早期实例使用路易斯碱来减小金属阳离子的亲电子性，阴离子是[BPh4]-，其中Ph是C6H5。反应发生在一种配位溶剂中。这些催化剂通常是低活性的。
质子化-这方法的说明见“阳离子性的烷基·二（环戊二烯基）合钛配合物的插入反应及其合成”（M.Bochmann，L.M.Wilson，J.Chem.Soc.Commun.，p.1610-1611，（1986））;“阳离子性的烷基·二（环戊二烯基）合钛配合物”（M.Bochmann，L.Wilson，Organometallics，p.2556-2563，Vol.6，（1987））;阳离子性的烷基·二（环戊二烯基）合钛配合物中腈的插入反应”（M.Bochmann，L.Wilson，Organometallics，p.1147-1154，Vol.7，（1987））。
欧洲专利申请0-277-003号涉及Turner用质子化方法以制备催化剂的工作。他将一种二（环戊二烯基）金属化合物与一种其阳离子能供给一个质子，而其阴离子含有许多硼原子的化合物相结合。该发明可以下列反应为例说明：
二甲基·二（环戊二烯基）合铪十
二（7，8-二碳十一硼烷）合钴（Ⅲ）酸N，N-二甲苯胺
→[Cp2HfMe][B]+CH4+N，N-二甲基苯胺
其中[B]是7，8-二碳十一硼烷
欧洲专利申请0-277-004号也涉及Turner用质子化方法制备催化剂的工作。他将一种二（环戊二烯基）金属化合物与一种离子化合物相结合，该离子化合物的阳离子将与金属化合物的一个配位体发生不可逆反应，而它的阴离子有许多亲脂性基团环绕在金属或准金属离子周围。该发明可以下列反应为例说明：
四（五氟苯基）合硼酸三（正丁基）铵
十二甲基·二（环戊二烯基）合锆
→[Cp2ZrMe][BPh4]+CH4+三正丁胺
质子化反应所产生的一种副产品是路易斯碱（胺），其中一些能与阳离子配位，因而抑制催化剂的活性。起始材料必须小心选择，以避免产生作为催化毒物的特定的胺类化合物。此外，上述催化剂和用该催化剂而制得的聚合物含有不希望有的有毒的剩留胺类。
配位体提取-配位体提取法的说明见“金属-碳的多重键”（R.R.Schrock，P.R.Sharp，J.Am.Chem.Soc.，P.2389-2399，Vol.100，No.8（April，1978）.）.
在大多数已知的方法中，都将甲基铝噁烷（MAO）随金属茂化合物一起加入作为助催化剂。MAO的作用是引发烷基化反应并促进金属茂化合物的电离。这助催化剂是一种清除剂，它减少使催化剂活性降低的毒物。目前已知的方法要求加入过量很多的MAO。而MAO的缺点是相当昂贵。因而使此催化剂系统成本高。
本发明的一个目的提供一种供烯烃聚合用的改进的催化剂的制备方法。
提供一种制造较高活性的催化剂的方法也是本发明的一个目的。
合成无路易斯碱作为副产品的金属茂阳离子，也是本发明的目的。
此外，本发明的目的是无需通过选择起始材料以控制可能成为催化毒物的副产品。
本发明的另一个目的是在聚丙烯的聚合反应中免除甲基铝噁烷（MAO）作为助催化剂。
另外，本发明的目的是制备不含氧化铝的聚合 物。
本发明还有一个目的是使制备的聚合物不含不希望的有的有毒胺类。
这些以及其它目的可通过以下方法来达到：将一种致电离剂（如四（五氟苯基）合硼酸三苯基碳与金属茂衍生物混合，然后将混合物加于链烯烃中。
本发明涉及制备用于链烯烃聚合的催化剂的方法，这方法用一种致电离剂来使金属茂电离。这种致电离剂不含活性的质子，且它的阴离子不配位于金属茂阳离子，或只松散地配位于该阳离子。而且这阴离子与该阳离子也无化学反应活性。
在这新的合成方法中，将致电离的离子化合物与金属茂的中性衍生物混合，产生以下反应：
其中Cp是环戊二烯基或被取代的环戊二烯基原子团，每一Cp可以相同或不同，M是Ⅲ，Ⅳ，Ⅴ或Ⅵ族金属，R是氢化物，卤素，酰胺或者烃基原子团，每一R可以相同或不同，如果R是氢化物，只能有一个R是氢化物，p等于1到4，C＊是碳鎓，氧鎓或锍阳离子，而A＊是一个阴离子，它不配位于或仅松散地配位于金属茂阳离子，而且与[Cp2MRp-1]不发生化学反应。
将每一反应剂置于不与金属茂阳离子配位或只与它松散地配位的溶剂中。这种溶剂的例子是甲苯和二氯甲烷。较好的是用甲苯。将两种反应物分别溶解于同一种溶剂中，然后在室温下混合在一起，摩尔比的范围是10∶1到1∶10（金属茂∶致电离化合物），较好在摩尔比是2∶1至1∶2，而最好的摩尔比是1∶1。混合后，在实施聚合反应的条件下将混合物加入到链烯中。较合意的链烯是乙烯和丙烯，最好是丙烯。
将一种含有碳鎓，氧鎓或锍离子的离子化合物（例如四（五氟苯基）合硼酸三苯基碳与金属茂中性衍生物混合。四（五氟苯基）合硼酸三苯基碳作为致电离剂，使金属茂电离。形成一种阳离子性的金属茂催化剂。
四（五氟苯基）合硼酸三苯基碳[Ph3C][BPh＊ 4]由下列反应制得：
其中Ph是苯基，而Ph＊是五氟苯基。三苯基碳鎓是阳离子。四（五氟苯基）合硼酸根是阴离子。
四（五氟苯基）合硼酸三苯基碳用下列实验室方法制得。将鲜黄色的27.1mmolePh3CCl在150cc二氯甲烷中的溶液在25℃下逐滴加入到25gmLiB（C6F5）4在350cc二氯甲烷的浆料中。将这橙色的浆料搅拌30分钟然后过滤。用二氯甲烷洗涤含有[Ph3C][BPh＊ 4]和LiCl的固体。将洗出液与滤液合并起来浓缩至75cc，然后在快速搅拌下用管加入（cannulated）到400cc戊烷中。用戊烷和少量甲苯将固体洗涤若干次，直至得到鲜黄色的[Ph3C][BPh＊ 4]粉末。产物有20克（75%）。
金属茂中性衍生物的通式为Cp2MRp，其中Cp是环戊二烯基或被取代的环戊二烯基原子团，每一Cp可以相同或不同，M是Ⅲ，Ⅳ，Ⅴ或Ⅵ族金属，最好是Ⅳ族金属，如钛、铪或锆，要得到较高的催化剂活性最好是锆，而要得到较高分子量则最好是铪，R是氢化物，卤素、酰胺或烃基（如含有1至20个碳原子的烷基，芳基，链烯基，烷芳基或芳烷基），每-R可以相同或不同，除非R是氢化物，只能有一个R是氢化物，而p等于1到4。较好的金属茂中性衍生物是二甲基·亚乙基二（四氢茚基）合锆，二甲基·亚乙基二（茚基）合锆和二甲基·异亚丙基（环戊二烯基-1-芴基）合锆。最好的金属茂中性衍生物是二甲基·亚乙基二（茚基）合锆。
链烯的聚合可以用任何已知的使用金属茂催化剂的链烯聚合方法来完成，例如本体聚合（inbulk），浆料聚合或气相聚合。对聚丙烯而言，聚合温度的范围为-80℃至150℃，更好为25℃至90℃，最好为50℃至80℃。
对本发明已作了大致的说明，以下的例子是本发明的具体实施，用来说明其实施方法和优点。应该理解，给出这些实施例是为了阐明说明书和下面的权利要求，而不是以任何方式限制它们。
实施例1
将55mg[Ph3C][BPh＊ 4]溶解于5cc甲苯中。将40mgEt（IndH4）2ZrMe2溶解于5cc甲苯中。将这两种溶液在室温下混合5分钟，得到一种清彻的黄色溶液。
用注射器将该混合物加入到一个2L的Zipperciave反应器内。在反应器内加入1.0L的丙烯。反应器温度置定在70℃。搅拌反应器内的物 质。在60分钟的聚合时间内温度保持在70℃，然后使丙烯从反应器中排出。用丙酮洗涤反应器内的物质，并在真空炉中干燥。
分析聚合物的熔点。熔点由差示扫描量热法（DSC）示得。结果见表1。
实施例2
重复实施例1中的过程，但使用40mg的[Ph3C][BPh＊ 4]和20mg的Et（IndH4）2ZrMe2。结果见表1。
实施例3
重复实施例1中的过程，但使用30mg的[Ph3C][BPh＊ 4]和15mg的Et（IndH4）2ZrMe2。反应器温度置定在80℃，且温度保持在80℃。结果见表1。
实施例4
重复实施例1中的过程，但使用60mg的[Ph3C][BPh＊ 4]和50mg的Et（IndH4）2ZrMe2。反应器温度置定在50℃，而温度保持在100℃。反应时间为10分钟。结果见表1。
实施例5
重复实施例1中的过程，但使用55mg的[Ph3C][BPh＊ 4]和50mg的Et（IndH4）2ZrMe2。反应器温度置定在50℃，而温度增加到168℃。反应时间为10分钟。结果见表1。
实施例6
重复实施例1的过程，但使用100mg的[Ph3C][BPh＊ 4]和60mg的Et（Ind）2ZrMe2。反应器温度置定在50℃，且温度保持在50℃。结果见表1。
实施例7
重复实施例1中的过程，但使用100mg的[Ph3C][BPh＊ 4]和60mg的Et（Ind）2ZrMe2。反应器温度置定在50℃，且温度保持在50℃。结果见表1。
实施例8
重复实施例1中的过程，但使用120mg的[Ph3C][BPh＊ 4]和80mg的iPr（Cp-1-Flu）ZrMe2。反应器温度置定在70℃，但温度升至100℃以上。结果见表1。
实施例9
重复实施例1中的过程，但使用100mg的[Ph3C][BPh＊ 4]和60mg的iPr（Cp-1-Flu）ZrMe2。反应器温度置定在70℃，但温度升至78℃。结果见表1。
实施例10
重复实施例1中的过程，但使用60mg的[Ph3C][BPh＊ 4]和40mg的iPr（Cp-1-Flu）ZrMe2。反应器温度置定在70℃。结果见表1。
以下是用本发明的方法所作的上述各次实验的结果。
表1见文后
本发明所述的方法可合成出在链烯聚合中用作催化剂的阳离子。使用本发明制备催化剂的方法可制得高活性的催化剂而不产生可能抑制催化剂活性的副产品。这种新的合成方法是一种不产生路易斯碱的洁净方法。这方法通过从Ⅳ族金属茂衍生物中移去一个甲基阴离子而产生活性的催化剂。
显而易见，利用以上所揭示的内容可以对本发明作许多修正和变化。因此应当理解，在所附权利要求的范围内，本发明能以这里所具体描述之外的其它方式实施。
表1
试验号    催化剂    致电离剂    试验时间
（mg）    （mg）    （分）
Et（IndH4）2ZrMe2[Ph3C][BPh＊ 4]
1    40    55    60
2    20    40    60
3    15    30    80
4    50    60    10
5    50    55    10
Et（Ind）2ZrMe2[Ph3C][BPh＊ 4]
6    60    100    60
7    60    100    30
iPr（Cp-1-Flu）Zr [Ph3C][BPh＊ 4]
Me2
8    80    120    5
9    60    100    60
10    40    60    60
Et（IndH4）2ZrMe2＝
二甲基·亚乙基二（四氢茚基）合锆
Et（Ind）2ZrMe2＝
二甲基·亚乙基二（茚基）合锆
iPr（Cp-1-Flu）ZrMe2＝
二甲基·异亚丙基（环戊二烯基-1-1芴基）合锆
[Ph3C][BPh＊ 4]＝
四（五氟苯基）合硼酸三苯基碳
表Ⅰ（续）
试验号    温度    产量    熔点
（℃）    （gm）    （℃）
1    70    9    138
2    50    55    138
3    80    45    131
4    50＊    74    134
5    50＊    135    -
6    50    19    137
7    50    11    134
8    70＊    224    115
9    70＊＊    51    -
10    70＊＊＊    186    119
＊反应失去控制;最高反应温度＞100℃
＊＊放热，最高反应温度78℃
＊＊＊放热反应

Claims (14)

1、一种制备催化剂的方法，其特征在于包括以下步骤：
a)将一种致电离的离子化合物与一种金属茂的中性衍生物混合；和
b)让该致电离的离子化合物与金属茂中性衍生物接触，使金属茂被致电离的离子化合物电离而形成离子对，其中的金属茂阳离子为催化剂；上述金属茂的中性衍生物的通式为
Cp2MPp；
其中Cp是环茂二烯基或被取代的环戊二烯基原子团，每一Cp可以相同或不同；M是Ⅳ族金属；R是氢化物，卤素，酰胺或烃基，每-R可以相同或不同，但只能有一个R是氢化物；P等于1到4；
其中致电离的离子化合物含有碳鎓阳离子，而致电离的离子化合物的阴离子与该金属茂阳离子不发生化学反应。
2、如权利要求1所述的方法，其特征在于在混合以前，致电离的离子化合物先溶解于一种溶剂中。
3、如权利要求2所述的方法，其特征在于在混合以前，金属茂的中性衍生物先分别地溶解于同一种溶剂中。
4、如权利要求3所述的方法，其特征在于其中金属茂中性衍生物与离子化合物的摩尔比的范围是从10∶1到1∶10。
5、如权利要求4所述的方法，其特征在于其中金属茂中性衍生物与离子化合物的摩尔比的范围是从2∶1到1∶2。
6、如权利要求5所述的方法，其特征在于其中金属茂中性衍生物与离子化合物的摩尔比是1∶1。
7、如权利要求4所述的方法，其特征在于其中的金属是选自钛，锆和铪的一种Ⅳ族金属。
8、如权利要求7所述的方法，其特征在于其中的金属是铪。
9、如权利要求7所述的方法，其特征在于其中的金属是锆。
10、如权利要求9所述的方法，其特征在于其中R是一种烃基，选自下列一组基团：含有1到20个碳原子的烷基、芳基、链烯基、烷芳基和芳烷基。
11、如权利要求10所述的方法，其特征在于其中金属茂中性衍生物选自下列一组物质：二甲基·亚乙基二（四氢茚基）合锆，二甲基·亚乙基二（茚基）合锆，二甲基·异亚亚基（环戊二烯基-1-芴基）合锆。
12、如权利要求11所述的方法，其特征在于其中金属茂中性衍生物是二甲基·亚乙基二（茚基）合锆。
13、如权利要求12所述的方法，其特征在于其中离子化合物是四（五氟苯基）合硼酸三苯基碳。
14、如权利要求13所述的方法，其特征在于其中的溶剂是甲苯。
CN90108884A 1989-10-30 1990-10-30 用于链烯聚合的金属茂催化剂的制备 Expired - Fee Related CN1028641C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41904689A 1989-10-30 1989-10-30
US419,046 1989-10-30

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN94118620A Division CN1033457C (zh) 1989-10-30 1994-11-23 一种链烯聚合的方法

Publications (2)

Publication Number Publication Date
CN1051311A CN1051311A (zh) 1991-05-15
CN1028641C true CN1028641C (zh) 1995-05-31

Family

ID=23660575

Family Applications (2)

Application Number Title Priority Date Filing Date
CN90108884A Expired - Fee Related CN1028641C (zh) 1989-10-30 1990-10-30 用于链烯聚合的金属茂催化剂的制备
CN94118620A Expired - Fee Related CN1033457C (zh) 1989-10-30 1994-11-23 一种链烯聚合的方法

Family Applications After (1)

Application Number Title Priority Date Filing Date
CN94118620A Expired - Fee Related CN1033457C (zh) 1989-10-30 1994-11-23 一种链烯聚合的方法

Country Status (10)

Country Link
EP (1) EP0426637B2 (zh)
JP (2) JP2943310B2 (zh)
KR (1) KR0165843B1 (zh)
CN (2) CN1028641C (zh)
AT (1) ATE120768T1 (zh)
CA (1) CA2027123C (zh)
DE (1) DE69018376T3 (zh)
DK (1) DK0426637T4 (zh)
ES (1) ES2071086T5 (zh)
GR (1) GR3015700T3 (zh)

Families Citing this family (295)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5198401A (en) * 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5384299A (en) * 1987-01-30 1995-01-24 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
US5153157A (en) * 1987-01-30 1992-10-06 Exxon Chemical Patents Inc. Catalyst system of enhanced productivity
US5763549A (en) * 1989-10-10 1998-06-09 Fina Technology, Inc. Cationic metallocene catalysts based on organoaluminum anions
CA2027122C (en) * 1989-10-30 2002-12-10 John A. Ewen Making metallocene catalysts using aluminum alkyls for controlled polymerization of olefins
US6294625B1 (en) 1990-03-20 2001-09-25 Exxonmobil Chemical Patents Inc. Catalyst system of enhanced productivity and its use in polymerization process
JP2545006B2 (ja) * 1990-07-03 1996-10-16 ザ ダウ ケミカル カンパニー 付加重合触媒
WO1992001723A1 (en) * 1990-07-24 1992-02-06 Mitsui Toatsu Chemicals, Incorporated CATALYST FOR α-OLEFIN POLYMERIZATION AND PRODUCTION OF POLY-α-OLEFIN THEREWITH
JPH06501047A (ja) * 1990-09-14 1994-01-27 エクソン・ケミカル・パテンツ・インク 制御されたタクチシティーのポリ−α−オレフィンを製造するためのイオン触媒
US5272003A (en) * 1990-10-26 1993-12-21 Exxon Chemical Patents Inc. Meso triad syndiotactic polypropylene fibers
EP0522581B1 (en) * 1991-07-11 1997-10-15 Idemitsu Kosan Company Limited Process for producing olefin based polymers and olefin polymerization catalyst
TW309523B (zh) * 1991-11-30 1997-07-01 Hoechst Ag
JP3194438B2 (ja) * 1992-01-08 2001-07-30 出光興産株式会社 スチレン系重合体の製造方法及びその触媒
US5296433A (en) * 1992-04-14 1994-03-22 Minnesota Mining And Manufacturing Company Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom
US5350723A (en) * 1992-05-15 1994-09-27 The Dow Chemical Company Process for preparation of monocyclopentadienyl metal complex compounds and method of use
US5317036A (en) * 1992-10-16 1994-05-31 Union Carbide Chemicals & Plastics Technology Corporation Gas phase polymerization reactions utilizing soluble unsupported catalysts
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.
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
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
US5514728A (en) * 1993-07-23 1996-05-07 Minnesota Mining And Manufacturing Company Catalysts and initiators for polymerization
US5498582A (en) * 1993-12-06 1996-03-12 Mobil Oil Corporation Supported metallocene catalysts for the production of polyolefins
DE4344689A1 (de) * 1993-12-27 1995-06-29 Hoechst Ag Metallocenverbindung
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
US6291389B1 (en) 1994-04-28 2001-09-18 Exxonmobil Chemical Patents Inc. Cationic polymerization catalysts
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
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
EP0710663A1 (en) 1994-11-01 1996-05-08 Japan Polyolefins Co., Ltd. Boron-containing compound, its polymer, catalyst comprising the polymer and metallocene compound, and process for producing polyolefin
ES2116188B1 (es) 1994-12-30 1999-04-01 Repsol Quimica Sa Proceso de obtencion de poliolefinas con distribuciones de pesos moleculares anchas, bimodales o multimodales.
US6143682A (en) * 1995-06-07 2000-11-07 Exxon Chemical Patents Inc. Bimetallocyclic transition metal catalyst systems
DK0848715T3 (da) * 1995-06-28 1999-12-13 Shell Int Research Katalysatorsammensætninger omfattende organomatalliske forbindelser
TW401445B (en) * 1995-07-13 2000-08-11 Mitsui Petrochemical Ind Polyamide resin composition
ES2120868B1 (es) * 1995-08-03 2000-09-16 Repsol Quimica Sa Sistema de catalizadores hetereogeneos tipo metalogeno, para procesos de obtencion de poliolefinas.
US5700748A (en) * 1995-09-29 1997-12-23 Union Carbide Chemicals & Plastics Technology Corporation Catalyst for the production of olefin polymers comprising a bridging allyl-cyclodienyl ligand on a metal atom
HUP9603449A3 (en) 1995-12-15 2000-03-28 Union Carbide Chem Plastic Process for production of long-chain branched polyolefins, polyethylene composition and product
US5856255A (en) * 1996-01-22 1999-01-05 Albemarle Corporation Preparation of supported auxiliary catalysts at elevated temperature and pressure in a closed vessel
US5786291A (en) * 1996-02-23 1998-07-28 Exxon Chemical Patents, Inc. Engineered catalyst systems and methods for their production and use
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)
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
EP0906343B1 (en) 1996-06-17 2001-04-18 Exxon Chemical Patents Inc. Mixed transition metal catalyst systems for olefin polymerization
CA2259582A1 (en) * 1996-07-23 1998-01-29 Stephan James Mclain Polymerization processes for olefins
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
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
WO1998016311A1 (en) * 1996-10-15 1998-04-23 Northwestern University Phenolate constrained geometry metallocene olefin polymerization catalyst, method of making, and method of using
PT839833E (pt) * 1996-10-30 2004-05-31 Repsol Quimica Sa Sistemas cataliticos para apolimerizacao e a copolimerizacao de alfa-olefinas
DE69705186T2 (de) 1996-10-30 2002-03-14 Repsol Quimica S.A., Madrid Katalysatorsysteme für die (Co)Polymerisation von Alpha-Olefinen
JP3955140B2 (ja) 1996-10-31 2007-08-08 レプソル・ケミカ・ソシエダ・アノニマ アルフアオレフインの重合及び共重合用触媒系
EP0856524A1 (en) 1997-02-01 1998-08-05 Repsol Quimica S.A. Heterogeneous catalyst components for olefins polymerization, preparation process and use thereof
BR9808578A (pt) 1997-02-07 2000-05-30 Exxon Chemical Patents Inc Polìmeros de propileno incorporando macrÈmeros de polietileno
EP0958309B2 (en) 1997-02-07 2013-10-09 ExxonMobil Chemical Patents Inc. Preparation of vinyl-containing macromers
TWI246520B (en) 1997-04-25 2006-01-01 Mitsui Chemicals Inc Processes for olefin polymerization
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
US6921794B2 (en) 1997-08-12 2005-07-26 Exxonmobil Chemical Patents Inc. Blends made from propylene ethylene polymers
US7026404B2 (en) 1997-08-12 2006-04-11 Exxonmobil Chemical Patents Inc. Articles made from 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
US6100224A (en) * 1997-10-01 2000-08-08 Exxon Chemical Patents Inc Copolymers of ethylene α-olefin macromers and dicarboxylic monomers and derivatives thereof, useful as additives in lubricating oils and in fuels
DE19744102A1 (de) 1997-10-06 1999-04-15 Targor Gmbh Katalysatorsystem
US6117962A (en) * 1997-12-10 2000-09-12 Exxon Chemical Patents Inc. Vinyl-containing stereospecific polypropylene macromers
US6197910B1 (en) 1997-12-10 2001-03-06 Exxon Chemical Patents, Inc. Propylene polymers incorporating macromers
US6184327B1 (en) 1997-12-10 2001-02-06 Exxon Chemical Patents, Inc. Elastomeric propylene polymers
DE19804970A1 (de) 1998-02-07 1999-08-12 Aventis Res & Tech Gmbh & Co Katalysatorsystem
TW562810B (en) 1998-04-16 2003-11-21 Mitsui Chemicals Inc Catalyst for olefinic polymerization and method for polymerizing olefine
ATE257490T1 (de) 1998-04-27 2004-01-15 Repsol Quimica Sa Katalysatorsysteme für die polymerisation und copolymerisation von alpha-olefinen
US6306960B1 (en) 1998-05-13 2001-10-23 Exxonmobil Chemical Patents Inc. Articles formed from foamable polypropylene polymer
US6784269B2 (en) 1998-05-13 2004-08-31 Exxonmobil Chemical Patents Inc. Polypropylene compositions methods of making the same
DE69918100T2 (de) 1998-05-13 2005-07-07 Exxonmobil Chemical Patents Inc., Baytown Propylenhomopolymere und herstellungsverfahren
US6245868B1 (en) 1998-05-29 2001-06-12 Univation Technologies Catalyst delivery method, a catalyst feeder and their use in a polymerization process
DE69935815T2 (de) 1998-07-01 2007-12-27 Exxonmobil Chemical Patents Inc., Baytown Elastische Mischung mit Kristallpolymeren und kristallisierbaren Polymeren des Propens
BR9913647B1 (pt) 1998-08-26 2008-11-18 polipropileno ramificado e processo para produzir o mesmo.
WO2000018808A1 (en) 1998-09-30 2000-04-06 Exxon Chemical Patents Inc. Cationic group 3 catalyst system
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
US6174930B1 (en) 1999-04-16 2001-01-16 Exxon Chemical Patents, Inc. Foamable polypropylene polymer
DE19917985A1 (de) 1999-04-21 2000-10-26 Targor Gmbh Katalysatorsystem
US6339134B1 (en) 1999-05-06 2002-01-15 Univation Technologies, Llc Polymerization process for producing easier processing polymers
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
US6479598B1 (en) 1999-07-20 2002-11-12 Exxonmobil Chemical Patents Inc. Petroleum resins and their production with BF3 catalyst
JP3808243B2 (ja) 1999-07-27 2006-08-09 三井化学株式会社 軟質樹脂組成物
US6403743B1 (en) 1999-09-14 2002-06-11 Exxonmobil Chemical Patents Inc. Petroleum resins and their production with supported catalyst
US6476164B1 (en) 1999-10-22 2002-11-05 Exxonmobil Chemical Patents Inc. Carbenium cationic complexes suitable for polymerization catalysts
US6475946B1 (en) 1999-10-22 2002-11-05 Exxonmobil Chemical Patents Inc. Olefin polymerization catalysis with aryl substituted carbenium cationic complexes
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
DE60006146T2 (de) 1999-11-04 2004-09-30 Exxonmobil Chemical Patents Inc., Baytown Propylencopolymerschäume und deren verwendung
US6822057B2 (en) 1999-12-09 2004-11-23 Exxon Mobil Chemical Patents Inc. Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them
US6281306B1 (en) 1999-12-16 2001-08-28 Univation Technologies, Llc Method of polymerization
MXPA02006199A (es) 1999-12-22 2003-10-15 Exxon Chemical Patents Inc Composiciones adhesivas a base de polipropileno.
KR100937175B1 (ko) 2000-01-26 2010-01-19 미쓰이 가가쿠 가부시키가이샤 올레핀 중합체
DE60114545T2 (de) 2000-03-31 2006-07-20 Mitsui Chemicals, Inc. Verfahren zur herstellung einer polyolefinzusammensetzung
DE10025412A1 (de) 2000-05-24 2001-11-29 Basell Polypropylen Gmbh Als Cokatalysator geeignete chemische Produkte, Verfahren zu ihrer Herstellung und ihre Verwendung in Katalysatorsystemen zur Herstellung von Polyolefinen
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
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
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
WO2002088200A1 (en) 2001-04-30 2002-11-07 W.R. Grace & Co.-Conn. Supported dual transition metal catalyst systems
US6734131B2 (en) 2001-04-30 2004-05-11 W. R. Grace & Co.-Conn. Heterogeneous chromium catalysts and processes of polymerization of olefins using same
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
KR100540049B1 (ko) 2001-04-30 2006-01-20 더블유.알. 그레이스 앤드 캄파니-콘. 지지된 전이 금속 중합 촉매의 제조 방법 및 이 방법으로형성된 조성물
JP2005522406A (ja) 2001-06-29 2005-07-28 エクソンモービル・ケミカル・パテンツ・インク メタロセン及び該メタロセン由来の触媒組成物
KR100440480B1 (ko) 2001-08-31 2004-07-14 주식회사 엘지화학 폴리올레핀 제조용 촉매 및 이를 이용한 폴리올레핀의제조방법
US6916892B2 (en) 2001-12-03 2005-07-12 Fina Technology, Inc. Method for transitioning between Ziegler-Natta and metallocene catalysts in a bulk loop reactor for the production of polypropylene
CA2368724C (en) 2002-01-21 2011-06-14 Bayer Inc. Process for preparing isobutylene-based polymers
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
US7943700B2 (en) 2002-10-01 2011-05-17 Exxonmobil Chemical Patents Inc. Enhanced ESCR of HDPE resins
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
EP2261292B1 (en) 2002-10-15 2014-07-23 ExxonMobil Chemical Patents Inc. Polyolefin adhesive compositions
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
US20040102311A1 (en) 2002-11-21 2004-05-27 Abbas Razavi Bridged metallocene catalyst component, method of making, polyolefin catalyst having C1, C2, or Cs symmetry, methods of making, methods of polymerizing, olefins and products made thereof
US7195806B2 (en) 2003-01-17 2007-03-27 Fina Technology, Inc. High gloss polyethylene articles
KR101004338B1 (ko) 2003-03-28 2010-12-28 미쓰이 가가쿠 가부시키가이샤 프로필렌／1―부텐 공중합체, 폴리프로필렌 조성물 및 그 용도, 및 폴리프로필렌 복합 필름
US6953764B2 (en) 2003-05-02 2005-10-11 Dow Global Technologies Inc. High activity olefin polymerization catalyst and process
US8158711B2 (en) 2003-08-25 2012-04-17 Dow Global Technologies Llc Aqueous dispersion, its production method, and its use
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
US8349929B2 (en) 2003-08-25 2013-01-08 Dow Global Technologies Llc Coating composition and articles made therefrom
US7763676B2 (en) 2003-08-25 2010-07-27 Dow Global Technologies Inc. Aqueous polymer dispersions and products from those dispersions
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
US8779053B2 (en) 2003-08-25 2014-07-15 Dow Global Technologies Llc Coating compositions
US8946329B2 (en) 2003-08-25 2015-02-03 Dow Global Technologies Llc Coating compositions
US8722787B2 (en) 2003-08-25 2014-05-13 Dow Global Technologies Llc Coating composition and articles made therefrom
US7803865B2 (en) 2003-08-25 2010-09-28 Dow Global Technologies Inc. Aqueous dispersion, its production method, and its use
WO2006031067A1 (en) 2004-09-16 2006-03-23 Lg Chem, Ltd. Catalyst system for polymerizing cyclic olefin having polar functional group, polymerizing method using the catalyst system, olefin polymer produced by the method and optical anisotropic film comprising the olefin polymer
JP2008516068A (ja) 2004-10-13 2008-05-15 エクソンモービル・ケミカル・パテンツ・インク エラストマー性反応ブレンド組成物
EP1805229A1 (en) 2004-10-28 2007-07-11 Dow Gloval Technologies Inc. Method of controlling a polymerization reactor
EP1805226A1 (en) 2004-10-29 2007-07-11 Exxonmobil Chemical Patents Inc. Catalyst compound containing divalent tridentate ligand
US7795194B2 (en) 2004-11-26 2010-09-14 Mitsui Chemicals, Inc. Synthetic lubricating oil and lubricating oil composition
US7588706B2 (en) 2004-12-16 2009-09-15 Exxonmobil Chemical Patents Inc. Multi-layer films with improved properties
KR20070087670A (ko) 2004-12-21 2007-08-28 다우 글로벌 테크놀로지스 인크. 폴리프로필렌-기재의 접착제 조성물
US7053163B1 (en) 2005-02-22 2006-05-30 Fina Technology, Inc. Controlled comonomer distribution along a reactor for copolymer production
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
US9644092B2 (en) 2005-06-22 2017-05-09 Exxonmobil Chemical Patents Inc. Heterogeneous in-situ polymer blend
US7935760B2 (en) 2005-06-22 2011-05-03 Exxonmobil Chemical Patents Inc. Process of making a heterogeneous polymer blend
US9745461B2 (en) 2005-06-22 2017-08-29 Exxonmobil Chemical Patents Inc. Vulcanized polymer blends
US7951872B2 (en) 2005-06-22 2011-05-31 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blend with continuous elastomeric phase and process of making the same
JP4991742B2 (ja) 2005-10-26 2012-08-01 ダウ グローバル テクノロジーズ エルエルシー 多層の、予備延伸された弾性製品
US7605208B2 (en) 2005-10-31 2009-10-20 Mitsui Chemicals, Inc. Process for producing thermoplastic resin composition
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
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
EP2024399B1 (en) 2006-05-17 2014-04-09 Dow Global Technologies LLC Ethylene/ alpha-olefin/ diene solution polymerization process
US7964680B2 (en) 2006-06-16 2011-06-21 Lg Chem, Ltd. Method for polymerizing cyclic olefin having polar functional group, olefin polymer produced thereby, optical anisotropic film comprising the same, and catalyst composition for polymerizing the cyclic olefin
KR101096836B1 (ko) 2006-07-31 2011-12-22 가부시키가이샤 프라임 폴리머 에틸렌계 수지 또는 에틸렌계 수지 조성물로 이루어지는 필름 또는 적층체
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
US7985804B2 (en) 2006-11-06 2011-07-26 Exxonmobil Chemical Patents Inc. Rubber toughened compositions, articles, films, and methods of making the same
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
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
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
CA2680181A1 (en) 2007-03-07 2008-09-12 Dow Global Technologies Inc. Tethered supported transition metal complex
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
TW200932762A (en) 2007-10-22 2009-08-01 Univation Tech Llc Polyethylene compositions having improved properties
US7906588B2 (en) 2007-10-26 2011-03-15 Exxonmobil Chemical Patents Inc. Soft heterogeneous isotactic polypropylene compositions
TW200936619A (en) 2007-11-15 2009-09-01 Univation Tech Llc Polymerization catalysts, methods of making, methods of using, and polyolefin products made therefrom
WO2009067337A1 (en) 2007-11-19 2009-05-28 Dow Global Technologies Inc. Long chain branched propylene-alpha-olefin copolymers
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
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
US8242198B2 (en) 2008-06-09 2012-08-14 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions
US8293856B2 (en) 2008-08-19 2012-10-23 Mitsui Chemicals, Inc. Process for preparing olefin polymer using mixed catalyst
US9168718B2 (en) 2009-04-21 2015-10-27 Exxonmobil Chemical Patents Inc. Method for producing temperature resistant nonwovens
US10161063B2 (en) 2008-09-30 2018-12-25 Exxonmobil Chemical Patents Inc. Polyolefin-based elastic meltblown fabrics
US8664129B2 (en) 2008-11-14 2014-03-04 Exxonmobil Chemical Patents Inc. Extensible nonwoven facing layer for elastic multilayer fabrics
US9498932B2 (en) 2008-09-30 2016-11-22 Exxonmobil Chemical Patents Inc. Multi-layered meltblown composite and methods for making same
EP2172490A1 (en) 2008-10-03 2010-04-07 Ineos Europe Limited Controlled polymerisation process
CN102245698B (zh) 2008-12-15 2014-01-08 埃克森美孚化学专利公司 热塑性烯烃组合物
KR101348060B1 (ko) 2009-02-27 2014-01-03 엑손모빌 케미칼 패턴츠 인코포레이티드 다층 부직 동일-공정계 라미네이트 및 이의 제조 방법
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
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
US9017593B2 (en) 2009-06-16 2015-04-28 Exxonmobil Chemical Patents Inc. Composite materials comprising propylene-based polymer blend coatings
US8791284B2 (en) 2009-07-01 2014-07-29 Mitsui Chemicals, Inc. Organometallic compound and production method thereof
US9005739B2 (en) 2009-07-23 2015-04-14 Exxonmobil Chemical Patents Inc. Laminated articles and their production
US20110020619A1 (en) 2009-07-23 2011-01-27 Van Den Bossche Linda M Polypropylene-Based Elastomer Coating Compositions
EP2483078B1 (en) 2009-10-02 2017-04-19 ExxonMobil Chemical Patents Inc. Multi-layered meltblown composite and methods for making same
MY149647A (en) 2009-10-19 2013-09-30 Sasol Tech Pty Ltd Oligomerisation of olefinic compounds with reduced polymer formation
WO2011053406A1 (en) 2009-10-29 2011-05-05 Exxonmobil Chemical Patents Inc. Pressure-sensitive hot melt adhesive compositions
US8668975B2 (en) 2009-11-24 2014-03-11 Exxonmobil Chemical Patents Inc. Fabric with discrete elastic and plastic regions and method for making same
CN102712701A (zh) 2009-12-07 2012-10-03 尤尼威蒂恩技术有限责任公司 减少催化剂的静电荷的方法和使用该催化剂生产聚烯烃的方法
KR101411182B1 (ko) 2009-12-21 2014-06-23 미쓰이 가가쿠 가부시키가이샤 신디오택틱 α-올레핀 중합체의 제조방법
EP2357035A1 (en) 2010-01-13 2011-08-17 Ineos Europe Limited Polymer powder storage and/or transport and/or degassing vessels
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
CN102791917B (zh) 2010-03-12 2014-11-05 埃克森美孚化学专利公司 制备耐热无纺织物的方法
EP2383301A1 (en) 2010-04-30 2011-11-02 Ineos Europe Limited Polymerization process
EP2383298A1 (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
SG186167A1 (en) 2010-07-28 2013-01-30 Exxonmobil Chem Patents Inc Ethylene based copolymer compositions as viscosity modifiers and methods for making them
CA2802109C (en) 2010-07-28 2015-04-07 Exxonmobil Chemical Patents Inc. Viscosity modifiers comprising blends of ethylene-based copolymers
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
JP5685317B2 (ja) 2010-10-15 2015-03-18 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 ポリプロピレンベース接着剤組成物
US9394381B2 (en) 2010-11-29 2016-07-19 Ineos Sales (Uk) Limited Polymerisation control process
WO2012097146A1 (en) 2011-01-14 2012-07-19 W. R. Grace & Co.-Conn. Process of making modified metallocene catalyst, catalyst produced and use thereof
WO2012134725A2 (en) 2011-03-25 2012-10-04 Exxonmobil Chemical Patent Inc. Amphiphilic block polymers prepared by alkene metathesis
WO2012134721A2 (en) 2011-03-25 2012-10-04 Exxonmobil Chemical Patents Inc. Vinyl terminated higher olefin polymers and methods to produce thereof
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
US8658556B2 (en) 2011-06-08 2014-02-25 Exxonmobil Chemical Patents Inc. Catalyst systems comprising multiple non-coordinating anion activators and methods for polymerization therewith
US8383740B1 (en) 2011-08-12 2013-02-26 Ineos Usa Llc Horizontal agitator
RU2608615C2 (ru) 2011-10-17 2017-01-23 Инеос Юроуп Аг Регулирование процесса дегазации полимеров
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
WO2013091836A1 (en) 2011-12-19 2013-06-27 Saudi Basic Industries Corporation (Sabic) Process for the preparation of metallocene complexes
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
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
CN104781628B (zh) 2012-11-12 2017-07-07 尤尼威蒂恩技术有限责任公司 用于气相聚合方法的再循环气体冷却器系统
KR101394943B1 (ko) 2012-11-19 2014-05-14 대림산업 주식회사 에틸렌과 알파-올레핀의 공중합체 및 그 제조방법
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
KR102038178B1 (ko) 2013-01-18 2019-10-29 다우 글로벌 테크놀로지스 엘엘씨 고분자량 폴리올레핀을 위한 중합 방법
US10548367B2 (en) 2013-01-29 2020-02-04 Exxonmobil Chemical Patents Inc. Footwear sole comprising a propylene-based elastomer, footwear comprising said sole, and methods of making them
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
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
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
KR101850233B1 (ko) 2014-03-28 2018-04-18 미쓰이 가가쿠 가부시키가이샤 올레핀계 수지, 그의 제조 방법 및 프로필렌계 수지 조성물
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
CN106715483B (zh) * 2014-10-03 2018-04-20 旭化成株式会社 乙烯聚合物和将其拉伸而得到的拉伸成形物以及乙烯聚合物的制造方法
CN107108777B (zh) 2014-11-12 2021-02-05 埃克森美孚化学专利公司 增塑剂的纯化及其在聚合物生产方法和装置中的用途
ES2784518T3 (es) 2014-12-09 2020-09-28 Mitsui Chemicals Inc Composición de resina a base de propileno
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
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
EP3279256A4 (en) 2015-03-31 2018-12-19 Mitsui Chemicals, Inc. Resin composition and use of same
US20180273669A1 (en) 2015-09-28 2018-09-27 Denka Company Limited Cross-copolymer and method for producing same
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
SG11201802756QA (en) 2015-12-16 2018-06-28 Exxonmobil Chemical Patents Inc Low crystalline polymer compositions
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
CA3018952C (en) 2016-03-31 2023-06-27 Exxonmobil Chemical Patents Inc. Low crystalline polymer compositions prepared in a dual reactor
US10647626B2 (en) 2016-07-12 2020-05-12 Chevron Phillips Chemical Company Lp Decene oligomers
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
US20190358928A1 (en) 2017-02-20 2019-11-28 Mitsui Chemicals, Inc. Laminate
MX2019009838A (es) 2017-02-20 2019-10-04 Mitsui Chemicals Inc Laminado.
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
WO2019027524A1 (en) 2017-08-02 2019-02-07 Exxonmobil Chemical Patents Inc. MULTILAYER FILMS AND METHODS OF MANUFACTURE
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.
ES2970673T3 (es) 2018-06-13 2024-05-30 Exxonmobil Chemical Patents Inc Composiciones de mezclas de poliolefinas
WO2020056119A1 (en) 2018-09-14 2020-03-19 Fina Technology, Inc. Polyethylene and controlled rheology polypropylene polymer blends and methods of use
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
WO2020172306A1 (en) 2019-02-20 2020-08-27 Fina Technology, Inc. Polymer compositions with low warpage
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
US20220169948A1 (en) 2019-03-26 2022-06-02 Mitsui Chemicals, Inc. Lubricating oil composition for compressor oils and method for producing the same
KR20210139401A (ko) 2019-03-26 2021-11-22 미쓰이 가가쿠 가부시키가이샤 윤활유 조성물 및 그의 제조 방법
KR20210139407A (ko) 2019-03-26 2021-11-22 미쓰이 가가쿠 가부시키가이샤 그리스 조성물 및 그의 제조 방법
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
US20220186133A1 (en) 2019-03-26 2022-06-16 Mitsui Chemicals, Inc. Lubricating oil composition for industrial gears and method for producing the same
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
EP3950899A4 (en) 2019-03-26 2022-08-17 Mitsui Chemicals, Inc. LUBRICATING OIL COMPOSITION, AND METHOD OF MAKING THE SAME
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
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
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
WO2022232123A1 (en) 2021-04-26 2022-11-03 Fina Technology, Inc. Thin single-site catalyzed polymer sheets
KR20230160903A (ko) 2021-05-20 2023-11-24 미쓰이 가가쿠 가부시키가이샤 수지 조성물, 및 그 용도 및 제조 방법
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL276385A1 (en) * 1987-01-30 1989-07-24 Exxon Chemical Patents Inc Method for polymerization of olefines,diolefins and acetylene unsaturated compounds
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

Also Published As

Publication number Publication date
CN1105673A (zh) 1995-07-26
ES2071086T3 (es) 1995-06-16
EP0426637A3 (en) 1991-08-07
GR3015700T3 (en) 1995-07-31
KR0165843B1 (ko) 1999-03-20
DK0426637T4 (da) 2002-01-14
DE69018376T2 (de) 1995-09-28
DK0426637T3 (da) 1995-07-10
JPH11315111A (ja) 1999-11-16
CN1033457C (zh) 1996-12-04
JPH03207703A (ja) 1991-09-11
EP0426637A2 (en) 1991-05-08
ATE120768T1 (de) 1995-04-15
EP0426637B2 (en) 2001-09-26
DE69018376D1 (de) 1995-05-11
KR910007970A (ko) 1991-05-30
ES2071086T5 (es) 2002-01-16
DE69018376T3 (de) 2002-05-16
CN1051311A (zh) 1991-05-15
EP0426637B1 (en) 1995-04-05
JP3224789B2 (ja) 2001-11-05
JP2943310B2 (ja) 1999-08-30
CA2027123A1 (en) 1991-05-01
CA2027123C (en) 2001-09-04

Similar Documents

Publication Publication Date Title
CN1028641C (zh) 用于链烯聚合的金属茂催化剂的制备
CN1037685C (zh) 一种金属茂催化剂体系
CN1028532C (zh) 生产半等规聚丙烯的催化剂
US5387568A (en) Preparation of metallocene catalysts for polymerization of olefins
CN1019579B (zh) 制备烯烃聚合催化剂的方法
CN1117770C (zh) 在高压下制备乙烯共聚物的方法
CN1130385C (zh) 氧化的茂金属聚烯烃蜡
CN87107013A (zh) 用金属茂催化剂体系改变聚烯烃熔点和分子量的方法
CN1304432C (zh) 生产聚烯烃共混物用的含催化剂组分混合物的催化剂体系
DE69225948T2 (de) Katalysator für Olefinpolymerisation und Verfahren zur Herstellung von Olefinpolymeren
CN1051322C (zh) 乙烯／丙烯共聚物、其制备方法、其弹性共聚物和由其制得的成形制品
CN1178949C (zh) 作为聚合催化剂的环戊二烯基过渡金属配合物
CN1255144A (zh) 用于α－烯烃聚合的催化剂溶液
CN1136239C (zh) 卤化镁/二氧化硅负载的半茂金属催化剂及其制备与应用
CN1127521C (zh) 链烯－1(共)聚合用催化剂的制备
CN1816576A (zh) 用于生产具有内部双键的聚烯烃的方法
CN1882613A (zh) 通过离子液体使聚合催化剂多相化
CN1211992A (zh) 通过悬浮聚合制备烯烃聚合物的方法
CN1184243C (zh) 一种长链支化聚乙烯弹性体的制备方法
CN1820032A (zh) 使用两台连续搅拌釜反应器以茂金属催化剂生产双模态聚烯烃的方法
CN1128825C (zh) 负载半茂金属的聚乙烯催化剂及其制备方法
CN1621423A (zh) 一种线性低密度聚乙烯的制备方法
CN1142195C (zh) 一种负载半茂金属的聚乙烯催化剂
CN1597710A (zh) 一种负载化双功能催化体系及制备方法和应用
CN1251842A (zh) 非茂类钛金属聚烯烃催化剂的制备及应用

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C15 Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993)
OR01 Other related matters
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee