CN1040217C - 新的丙烯结晶共聚物的制备方法 - Google Patents

新的丙烯结晶共聚物的制备方法 Download PDF

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CN1040217C
CN1040217C CN88109197A CN88109197A CN1040217C CN 1040217 C CN1040217 C CN 1040217C CN 88109197 A CN88109197 A CN 88109197A CN 88109197 A CN88109197 A CN 88109197A CN 1040217 C CN1040217 C CN 1040217C
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moles
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路易吉·马丽亚·雷斯康尼
恩里科·阿尔比扎蒂
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    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • 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
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Abstract

制备具有少量乙烯和/或α-烯烃的新的丙烯结晶共聚物的方法，该共聚物具有良好的机械性能、较低的熔点和在25℃二甲苯中有限的溶解度。制备此聚合物的方法为聚合适当组成的丙烯与乙烯和/或α-烯烃的混合物，使用得自立体刚性和手性锆化合物和甲基铝氧烷化合物的催化剂。

Description

新的丙烯结晶共聚物的制备方法
本发明涉及的是新的丙烯结晶共聚物及其制备方法。
本领域的普通技术人员都知道，在聚合反应过程中，加入少量的共聚单体，主要是乙烯和1-丁烯可以对聚丙烯改性。这种改性的目的是降低聚合物的熔点，由此而使得薄膜显示出改进的可焊接性。
但是，迄今已知方法获得的共聚物却有共聚单体分布不均匀的缺点，这将使聚合物在冷的二甲苯中显示较高的溶解性，并使由此而得制品的机械性能下降。
由欧洲专利申请0185918号得知使用立体有择催化剂进行丙烯聚合，其中这些立体有择聚合催化剂是由立体刚性和手性锆化合物，例如：乙烯-双-茚基-二氯化锆和乙烯-双(4，5，6，7-四氢茚基)二氯化锆，以及甲基铝氧烷(methylalumoxanic)化合物而得到的。
这些催化剂还可以用于丙烯与乙烯或其它烯烃的混合物的聚合，以及丙烯与那些实例中的富含乙烯、可溶于二甲苯，显示出丙烯序列的等规立构构型的共聚物混合物的聚合。
本申请人现已意外地发现通过使用如下催化体系，如果各单体的聚合能够在那种所形成的共聚物的组成具有类似于存在气相中各单体的组成的条件下进行，则可以获得具有少量乙烯和/或α-烯烃的丙烯共聚物，这里α-烯烃的分子式如下：CH2＝CHR
式中R是从2至20个C原子的烷基。共聚物具有高结晶性及良好的机械性能(非常类似于丙烯均聚物)，并且熔点在从110℃至140℃的范围内，在冷二甲苯中显示出有限的溶解度(在25℃二甲苯中可溶的聚合物部分少于10％)。
上述催化体系可由以下方法得到：
a)分子式如下的立体刚性和手性锆化合物：
Figure C8810919700051
其中：R1和R2是卤素或1至6个C原子的烷基；
X和Y是不对称单环或多环有机基团；
R3是1至4个C原子的线性基团或含有3至6个C原子的环状基团；
b)分子式如下的铝氧烷化合物
Figure C8810919700052
具有n在从2至25的范围之内；或具有n在从1至25的范围之内。本申请人已经发现，并且这也是本发明完全意外的一个方面，共聚物的组成当各单体(不是所说混合物的丙烯)的含量在从2至10摩尔％的范围之内时类似于存在于气相中的各单体混合物的组成。
尤其是，在有乙烯的共聚物情况下，处于气相混合物中乙烯的含量在从2至6摩尔％的范围内；而在丙烯-乙烯-丁烯三元共聚物的情况下，乙烯和丁烯的含量在从2至10摩尔％的范围之内。
由在上述条件下的操作所得到的共聚物，其共聚单体的分布是非常均匀的。在有乙烯的共聚物情况下，这可以由采用13C核磁共振的方法的分析(如在《macromolecules》10(3)536(1977)中说明的)来证明：观察不到多于一个乙烯单元的序列的特征信号。
使用上述催化剂制备共聚物不但可在气相操作而且也可在液相操作(在含惰性烃溶剂存在下，或在液体丙烯中)下进行。气相的组成，包括在上述临界范围之内，在聚合过程中保持不变。例如：在液体丙烯中操作的丙烯-乙烯混合物聚合情况中，应保持乙烯的过压不变。
反之，在气相进行聚合的情况下，或在惰性烃溶剂存在下，则加入组成不变的气体单体混合物。聚合在低于20℃的温度下进行，最好在从0℃至10℃的范围内。
由在上述条件下的操作所得到的共聚物，其特性粘度(在1，2，3，4四氢化萘中，135℃下)高于0.2分升/克。正如已经说明的，此共聚物主要用于薄膜领域，这是由于由此制得薄膜的可焊接性的缘故。
下面的实施例其目的仅在于说明本发明，而不是限制它。
实施例1-8聚甲基铝氧烷的合成
将44.5克的Al2(SO4)3·18H2O和200ml的甲苯在氮气氛下加入容积为500ml的烧瓶中，该烧瓶装有温度计、带有连到气体计量计旋塞的泡状冷凝器、100ml的滴液漏斗、氮气旋塞和磁力搅拌器；并将60ml纯三甲基铝加入滴液漏斗。
中断氮气供应，打开与气体计量计的连通，在室温下将三甲基铝迅速滴加到Al2(SO4)3·18H2O的悬浮液中，与此同时保持强烈的搅拌。
温度升至55℃，通过热浴的方法再增至60℃，并保持该值不变，反应在4小时后完成。过滤悬浮液，并干燥溶液：得到15.8克的产品，相应于44％的收率。
冰点平均分子量1160；平均齐聚度20。锆化合物合成
乙烯-双-茚基-二氯化锆(EBIZ)和乙-双(四氢茚基)-二氯化锆(EBTHIZ)的合成根据(Journal of Orga-nometallic chemistry》(1985)288，63进行。聚合
所有的操作都在氮气下进行。
将含有45mg的聚甲基铝氧烷和0.8mg的锆化合物的20ml甲苯溶液加入三颈瓶，该瓶装有泡管、温度计和气体排放旋塞及机械搅拌装置，保持所控温度为0℃。
在排掉氮气之后，连续加入气体混合物，其组成列于下表中，流速为20升/小时。
聚合时间、催化剂类型和聚合物性质如表中所示。
对比例1
在丙烯物流下将含350mg的聚甲基铝氧烷的150ml甲苯溶液加入300ml的玻璃高压釜，高压釜的温度被调至0℃的控制值，然后注入5mg的溶解在甲苯中的EBTHIZ，高压釜内的压力增至4个大气压，在0℃下使聚合继续进行4小时，得到30.5g的聚合物，数据记在表中。
对比例2
方法按照例1进行，除了锆化合物之外，这里使用的是EBIZ(相应的聚合物数据记在表中)。
对比例3
重复EP0185938的例7，所得的20g聚合物含有47摩尔％的乙烯，具有〔η〕＝0.15分升/克，在20℃可溶于二甲苯的部分为81.3％。
在13C核磁共振试验中，聚合物显示多个乙烯序列。
                          表1
                气体组成        时间    收率      共聚物组成             η                   T        在20℃可溶于二
     锆化合物   (摩尔％)                                                                      甲苯的部分例子
                C2   C4   C3 (小时)  (克)    C2   C4   C3   (分升/分克)    (℃)         (％重量)对比例1   EBTHIZ    -     -    100    5      30.5    -     -    100       1.25         147             0对比例2   EBIZ      -     -    100    3      4.7     -     -    100       0.68         144             01       EBTHIZ    2     -    98     2      1.40    2.6                  1.34         134.9           0.162       EBIZ      2     -    98     2      0.75    2.8                  0.72         132.3           0.03       EBTHIZ    3.5   -    96.5   2      3.10    3.5                  1.6          129.6           2.54       EBIZ      3.5   -    96.5   2      1.90    3.2                  0.9          128.1           2.05       EBTHIZ    5     -    95     2      1.40    5.46       EBIZ      5     -    95     2      5.25    4.4                  0.60         123             2.227       EBTHIZ    -     5    95     2      0.48    5.4                  1.40         125             5.58       EBIZ      -     5    95     2      1.25    5.9                  0.46         125             5.3

Claims (2)

1.一种制备具有乙烯或1-丁烯的丙烯结晶共聚物的方法，该结晶共聚物含有2.6至5.4摩尔％的乙烯或5.4-5.9摩尔％的1-丁烯，熔点在110℃至140℃的范围内，并且在25℃二甲苯中溶解度低于10重量％；所述方法包括将丙烯与乙烯或1-丁烯的混合物进行聚合，并使用由下列化合物形成的催化剂：
-立体刚性和手性锆化合物，其分子式为：
式中：
R1和R2是卤素或1至6个C原子的烷基，
X和Y是不对称单环或多环有机基团，
R3是1至4个C原子的线性基团，或含有3至6个C原子的环状基团；以及
-铝氧烷化合物，分子式为
Figure C8810919700022
式中n是在2至25范围内的数，或分子式为
式中n是在1至25范围内的数；
聚合反应是在下述条件下进行操作的：将在气相混合物中存在的乙烯或1-丁烯的含量分别保持在2至5摩尔％和5摩尔％范围内，且聚合温度低于20℃。
2.根据权利要求1的方法，其中所得到的丙烯/乙烯的结晶共聚物含有2.6至5.4摩尔％的乙烯，而所述共聚物的熔点在123℃至134.9℃的范围内，将在气相混合物中存在的乙烯含量保持在2至5摩尔％范围内。
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NO885281L (no) 1989-05-29
IT8741012A0 (it) 1987-11-27
AU2595288A (en) 1989-06-01
BR8806244A (pt) 1989-08-15
ES2031986T3 (es) 1993-01-01
FI885462A (fi) 1989-05-28
US5516866A (en) 1996-05-14
EP0318049A1 (en) 1989-05-31
CA1338368C (en) 1996-06-04
ZA888859B (en) 1989-08-30
FI96770C (fi) 1996-08-26
EP0318049B2 (en) 2003-07-16
DE3869921D1 (de) 1992-05-14
NO171791B (no) 1993-01-25
US6355758B1 (en) 2002-03-12
NO171791C (no) 1993-05-05
JPH01266116A (ja) 1989-10-24
KR890008188A (ko) 1989-07-10
FI96770B (fi) 1996-05-15
AU604582B2 (en) 1990-12-20
KR950013682B1 (ko) 1995-11-13
FI885462A0 (fi) 1988-11-24
IT1221653B (it) 1990-07-12
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