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

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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
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约翰·尤恩
迈克尔·J·埃尔德
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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。
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CN1033457C (zh) 1996-12-04
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DE69018376T2 (de) 1995-09-28
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ES2071086T3 (es) 1995-06-16
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