CN1044821A - 烯烃聚合催化剂 - Google Patents

烯烃聚合催化剂 Download PDF

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CN1044821A
CN1044821A CN90101413A CN90101413A CN1044821A CN 1044821 A CN1044821 A CN 1044821A CN 90101413 A CN90101413 A CN 90101413A CN 90101413 A CN90101413 A CN 90101413A CN 1044821 A CN1044821 A CN 1044821A
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路易吉·雷斯科尼
翁贝托·詹尼尼
恩里科·阿尔比扎蒂
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Montedison SpA
Himont Inc
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Ausimont SpA
Himont Inc
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Abstract

由特殊二茂锆化合物和烷基铝化合物制得的烯 烃聚合催化剂。

Description

本发明涉及由二茂锆化合物和烷基铝化合物制得的烯烃聚合催化剂。
使用由二茂锆和三烷基铝制得的催化剂聚合乙烯是众所周知的。现有技术中所用的二茂锆可用下面通式表示：
（A）（C5RnH5-n）2ZrX2
式中R是含1-8个碳原子的烷基，n是0，1或2，X是卤原子，烷氧基、有机酸阴离子或无机酸阴离子。
这种催化剂的例子在美国专利2，924，593中有报导。
上述催化剂的活性在乙烯聚合中非常低，而在高级α-烯烃聚合中实际是零。
现已意外地发现，使用下述通式的化合物：
代替目前所用的二茂锆，与三烷基铝化合物或烷基氢化铝结合使用，可以得到在乙烯和CH2＝CHRα-烯烃（式中R是含1-8个碳原子的烷基）（共）聚合反应中具有高活性的催化剂。
在式A′中，（C5Rn′H5-n）和（C5Rm′H5-m）是环戊二烯基，它们也可以是相同的，其中R′是含有1到20个碳原子的烷基，链烯基，芳基，烷基芳基或芳基烷基，或是-CR2SiR3或-SiR3基团（R类似于R′的定义），要不就是同一环戊二烯基上的两个（或4个）R′取代基形成一个含4到6个碳原子的环;R″是一个二价基团，选自可以取代的含1到8个碳原子的亚烷基，
Figure 901014133_IMG3
SiR2
Figure 901014133_IMG4
PR或
Figure 901014133_IMG5
NR（其中R类似于R′的定义），所说的R″在两个环戊二烯基团之间形成一个连桥;x可是氢，卤素或-OH，-OZr（C5Rn′H5-n）（C5Rm′H5-m），-OR（R类似于R′的定义），或是R′含义的烃基。在式中当q是2时，X取代基也可以是不同的，当Zr是三价时，q是1，当Zr是四价时，q是2;p是0或1，n、m是0到5之间的数;在R′是烃基和P是0的情况下，（n+m）≥5;如果P＝1，（m+n）≥3;最后，当R′是-SiR3或-CR2SiR3时，如果P＝0或如果P＝1且R″是亚烷基时，（n+m）≥1;如果P＝1和R″是
Figure 901014133_IMG6
SiR2，
Figure 901014133_IMG7
PR或
Figure 901014133_IMG8
NR，（n+m）≥0
A′二茂锆的非限定性例子有：
[C5（CH3）3H2]2ZrCl2，[C5（CH3）4H]2ZrCl2，[C5（CH3）5]2ZrCl2，
[C5（CH3）5]2Zr（CH3）2，[C5（CH3）5]ZrH2，[C5（CH3）5]2Zr（OCH3）2
[C5（CH3）5]2Zr（OH）CL，[C5（CH3）5]2Zr（OH）2，
[C5（CH3）5]2Zr（C6H5）2，[C5（CH3）5]2Zr（CH3）Cl，
[C5（C2H5）（CH3）4]2ZrCl2，[C5（C6H5）（CH3）4]2ZrCl2，
[C5（C2H5）5]2ZrCl2，[C5（CH3）5]2Zr（C5H5）Cl，[C5（CH3）5]2ZrCl，
双（茚基）ZrCl2，双（茚基）Zr（CH3）2，
亚乙基双（茚基）ZrCl2，亚乙基双（茚基）Zr（CH3）2，
｛C5[Si（CH3）3]H4｝2ZrCl2，｛C5[Si（CH3）3]2H3｝2ZrCl2，
[C5（CH3）5]（C5H5）ZrCl2，[C5（CH3）5][C5（CH3）H4]ZrCl2，
（CH3）2Si（C5H4）2ZrCl2，（CH3）2Si[C5（CH3）4]2ZrCl2，
（CH3）2C[C5（CH3）4]2ZrCl2，（CH3）2C[C5（CH3）4（茚基）ZrCl2，
（CH3）2C（C5H4）（茚基）ZrCl2.
特别适用的化合物是那些化合物中的（C5Rn′H5-n）和（C5Rm′H5-m）基团是五甲基环戊二烯基环或是茚基，x取代基是氯原子，或是烷基（尤其是含1到5个碳原子的烷基），或是-OH基。
可以用式AlR3-ZHZ表示三烷基铝化合物或烷基单氢代铝，式中R是含1到10个碳原子的烷基、链烯基或烷基芳基，Z是0或1。
可以使用的烷基铝化合物非限定性例子是：
Al（CH3）3，Al（C2H5）3，AlH（C2H5）2，Al（isoC4H9）3，AlH（isoC4H9）2，
Al（C6H5）3，Al（CH2C6H5）3，Al[CH2C（CH3）3]3，Al[CH2Si（CH3）3]3，
Al（CH3）2（C2H5），Al（CH3）（C2H5）2，Al（CH3）2（isoC4H9）。
如上所示，本发明催化剂适用于乙烯和CH2＝CHRα烯烃或它们的混合物的聚合反应。
聚合反应是在惰性烃溶剂存在或不存在下的液相中进行，或是在气相中进行。聚合反应温度一般在0-150℃范围，最好是在40-80℃范围内。
烃溶剂可以是芳烃或脂肪烃，例如，甲苯，己烷，庚烷，或氯代烃如CH2Cl2或C2H4Cl2。
聚合物的分子量可以仅仅由聚合反应温度、催化剂组份的类型或浓度的变化而改变，也可使用分子量调节剂（如氢）来改变。
本发明的催化剂也可以在惰性载体上使用，这可通过将二茂锆或它与烷基铝化合物的反应产物或是烷基铝本身沉积在惰性载体上来完成，惰性载体的例子有二氧化硅，氧化铝，苯乙烯-二乙烯基苯共聚物或聚乙烯。
这样所得固体组份，如果需要的话，与再添加的烷基铝化合物结合使用，特别适用于气相聚合反应。
聚合反应前将催化剂组份进行相互间接触能获得特别优异的效果，接触的时间范围一般为1分钟到1小时，优选为5到10分钟，锆茂化合物的浓度范围为10-3到10-8摩尔/升;烷基铝的浓度范围为10到10-3摩尔/升。
给出下列实施例说明本发明，而对本发明没有限制作用。
实施例1
将1升装有热控制夹套，热电偶，氮气和乙烯供料阀，压力计和钢制磁力搅拌器，已在50℃恒温的高压釜在预先用氮气排空和充氮后处于真空状态下，然后，在保持内部温度为50℃的同时引入1大气压的乙烯和350毫升的甲苯。
在50毫升甲苯和氮气气氛下，2毫摩尔的三甲基铝和1毫克的[C5（CH3）5]2ZrCl2反应，5分钟后在环境温度下将该溶液注入到高压釜中，然后用乙烯加压到四个大气压，在保持乙烯压力恒定的同时，让聚合反应在50℃进行1小时。搅拌速率：1100转/分，其结果列于表1中。
实施例2-9
进行实施例1的相同操作过程，然而使用不同的烷基铝化合物和不同的二茂锆，所用的化合物和所得结果列于表1中。
实施例10
进行实施例1相同操作过程，不同的是用丙烯进行聚合，聚合反应温度保持在23℃，所溶解丙烯的量使压力保持在4个大气压的程度。
将18毫摩尔的ALMe3和4.4毫克的外消旋亚乙基双（茚基）ZrCl2（溶解在甲苯中）连续快速地注入到高压釜中，让聚合反应在23℃进行17小时，搅拌速率：1100转/分。
得到4.74克等规        立构聚丙烯：
[η]inh（THN;135℃）＝0.37
Mw＝29149
Mw/ Mn＝4.47
Tm＝134.20℃
产率：4942克聚合物/克Zr
表1（实施例1-9）
条件：400毫升甲苯，4大气压，50℃，1小时，Al＝5毫摩尔/升，在环境温度和无乙烯存在下各组份预接触5分钟。
实施例 二茂锆 Zr毫克 烷基铝 聚乙烯克 聚乙烯克/克Zr小时[η]inh
（dl/g）
1 CP★2ZrCl20.211 AlMe332.8 155，400 2.6
2 CP★2ZrCl20.211 AlEt329.7 140，700 5.2
3 CP★2ZrCL20.0211 AliBu317.4 824，600 8.4
4 CP★2ZrCl20.0211 AliBu2H 12.0 568，700 -
5 Ind2ZrCl20.023 AlMe35.8 252，100 4.8
6 Ind2ZrCl20.023 AlEt31.5 65，200 1.8
7 CP★2ZrMe20.023 AlMe39.8 426，000 3.2
8 CP★2ZrMe20.023 AlEt39.4 408，700 4.7
9 CP★2Zr（OH）20.0212 AliBu319.7 929，200 9.8
注：Me＝-CH3
Et＝-CH2CH3
iBu＝-CH2CH（CH3）2
CP＝环戊二烯基
CP★＝五甲基环戊二烯基
Ind＝茚基
MeCP＝甲基环戊二烯基
实施例11
进行实施例10的同样操作过程，不同的是使用200毫升CH2Cl2代替甲苯作溶剂。
将18毫摩尔ALMe3和2毫克外消旋亚乙基双（茚基）ZrCl2（溶解在2毫升甲苯中）迅速连续地注入到高压釜中，聚合反应在23℃进行17小时，搅拌速度：1100转/分。
得到2.74克等规立构聚丙烯;
ηinh（THN，135℃）＝0.33
产率：6284克聚合物/克Zr。
比较例1-4
进行实施例1的同样操作过程，不同的是使用表2中所示的锆化合物和烷基铝，表2中也列出了所得的结果。
表2（比较例1-4）
条件和注释如表1
比较例 二茂锆 毫克Zr 烷基铝 克PE 克PE/克Zr小时 ηi（dl/g）
1 CP2ZrCl20.212 AlMe38.2 38，700 2.6
2 CP2ZrCl20.212 AlEt30.45 2，100 1.4
3 CP2ZrCl20.312 AliBu32.15 6，900 -
4 （MeCP）2ZrCl20.028 AliBu31.55 55，300 -

Claims (5)

1、一种烯烃聚合反应催化剂，包括下述两组份间的反应产物：
A′)一种二茂锆化合物，其化学式为：
(C5Rn′H5-n)RP″(C5Rm′H5-m)ZrXq
式中(C5Rn′H5-n)和(C5Rn′H5-n)是环戊二烯基，它们可以是相同的，其中R′是含有1到20相碳原子的烷基、链烯基、芳基、烷基芳基或芳基烷基基团，也可以是CR2SiR3和SiR3基团(其中R类似于R′的定义)，还可以是同一环戊二烯基的2个或4个R′形成含4到6个碳原子的环；R″是二价基团，选自含1到8个碳原子的可取代的链烯基，
Figure 901014133_IMG1
(其中的R类似于R′的定义)，所说的R″在两个环戊二烯基之间形成一个连桥；X是氢，卤素，-OH，-OZr(C5Rm′H5-n)(C5Rm′H5-m)，-OR(其中的R类似于R′的定义)，或是具有R′含义的烃基；当q是2时，X取代基也可以是相互不同的；如果Zr是三价，则q是1，如果Zr是四价，则q是2；P是0或1，n，m是0到5之间的整数，在R′是烃基和P=0的情况下，(n+m)≥5；如果p=1(n+m)≥3，当R′是-SiR3或-CR2SiR3基团时，如果P=0或P=1和R″是亚烷基，则(n+m)≥1；如果p=1和R″是
Figure 901014133_IMG2
，则(n+m)≥0，
B′)一种三烷基铝化合物或烷基单氢化铝，其化学式为：
AlR3-2H2
式中R是含有1到10个碳原子的烷基，链烯基或烷基芳基，Z是0或1。
2、根据权利要求1的催化剂，其中（C5Rn′H5-n）和（C5Rm′H5-m）基团是五甲基环戊二烯基环或茚基环，X取代基是氯原子，-OH基或含有1-5个碳原子的烷基。
3、根据权利要求2的催化剂，其中烷基铝化合物是三烷基铝化合物和烷基单氢化铝。
4、根据权利要求1的催化剂，其中催化剂组份A′和B′在用于聚合相之前在无单体存在下相互之间进行接触。
5、根据权利要求2的催化剂，其中催化剂组份A′和B′或它们的反应产物载到惰性多孔的无机或有机载体上。
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