CN1188481A - 基于含吡啶或喹啉部分的二齿配位体的过渡金属催化剂 - Google Patents

基于含吡啶或喹啉部分的二齿配位体的过渡金属催化剂 Download PDF

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CN1188481A
CN1188481A CN96194004A CN96194004A CN1188481A CN 1188481 A CN1188481 A CN 1188481A CN 96194004 A CN96194004 A CN 96194004A CN 96194004 A CN96194004 A CN 96194004A CN 1188481 A CN1188481 A CN 1188481A
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cyclopentadienyl
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S·纳吉
R·克里什纳莫蒂
J·A·泰里尔
L·V·克里伯斯
M·克克曼
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Lyondell Chemical Co
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Abstract

公开了一种助催化剂和通式(1)的二齿吡啶过渡金属催化剂的催化剂组合物,式中Y为O、S、NR、(2)或(3)。R各独立地选自氢或C1—6烷基,M为钛、锆或铪;X各独立地选自卤素、C1—6烷基、C1—6烷氧基或(4);L为X、环戊二烯基、C1—6烷基取代的环戊二烯基、茚基、芴基或(5);R′各独立地选自R、C1—6烷氧基、C6—16芳基、卤素或CF3;n为1—4。也公开了制备聚α－烯烃的方法,该方法包括用该催化剂组合物或具有下述通式(6)的催化剂的催化剂组合物聚合α－烯烃单体,式中Y、M、L、X和R′如前所定义。

Description

基于含吡啶或喹啉部分的二齿配位体的 过渡金属催化剂
本发明涉及用于聚合α-烯烃的催化剂，特别涉及使用含吡啶或喹啉部分的二齿配位体的过渡金属催化剂进行的乙烯聚合。
直到最近，聚烯烃的生产主要还是使用常规的齐格勒催化体系。典型的齐格勒催化剂是由含过渡金属的化合物和一种或多种有机金属化合物组成的。例如聚乙烯是用诸如三氯化钛和氯化二乙基铝，或四氯化钛、三氯氧化钒与三乙基铝的混合物之类的齐格勒催化剂生产的。这些种类的催化剂比较便宜，但是它们的活性低，必须以高浓度使用。残留于聚合物中的催化剂使聚合物产生黄或灰色，而且紫外线稳定性和长期稳定性差；再者，含氯的残留物能腐蚀聚合物加工设备。因此时常需要从聚合物里清除催化剂残留物或在聚合物中加中和剂和稳定剂，以克服残留物的有害作用，这样就增加了生产成本。另外，用齐格勒催化剂产生分子量分布较宽的聚合物，这是在许多应用中(诸如注射模塑)不希望有的。在掺入α-烯烃共聚单体时，它们也是较差的，这使聚合物密度控制产生困难。要达到某一密度可能要求大量过量的共聚单体。许多高级α-烯烃(诸如1-辛烯)，如果需要掺入，则只能掺入极低的量。
自从发现齐格勒催化体系以来，虽然已有了大量的改进，但这些催化剂现在已被近期发现的金属茂催化剂所代替。典型的金属茂催化剂是由具有一个或多个环戊二烯基环状配位体的过渡金属化合物组成的。当金属茂与和传统齐格勒催化剂一起使用的有机金属化合物(诸如烷基铝)一起使用时，其活性很低，但当与作为助催化剂的铝氧烷一起使用时，则有很高的活性。其活性一般很高而无须自聚合物中除去其残留物。再者，用它们生产的聚合物分子量很高并且分子量分布很窄。它们也能很好地掺入α-烯烃共聚单体。
然而，在较高的温度下，金属茂催化剂趋于生产分子量较低的聚合物。因此，它们能用于约在80-90℃下进行的乙烯气相和淤浆聚合，但一般在增加温度时它们不能很好地进行。于溶液中进行的乙烯聚合是理想的，因为它具有较大的灵活性以生产分子量范围和密度较宽同时又可以用各种不同种类的共聚单体的聚合物。溶液聚合可以生产能在许多不同应用中使用的聚合物。例如可生产用作食品包装隔离膜的高分子量和高密度聚乙烯(PE)薄膜，和韧性好和抗冲强度大的低密度乙烯共聚物。
现已发现了作为α-烯烃聚合催化剂其活性非常好的新颖二齿吡啶过渡金属化合物；也已发现至今为止无疑是具有任何催化性能的二齿喹啉过渡金属化合物，这些化合物也是优良的α-烯烃聚合催化剂。这些催化剂能生产性质与用金属茂催化剂生产的聚合物非常接近的聚合物，即聚合物有窄的分子量分布并均匀引入共聚单体。
含有二齿吡啶基配位体的本发明过渡金属催化剂的通式如下：
Figure A9619400400071
式中Y为O、S、NR、
Figure A9619400400072
R各独立地选自氢或C1-6烷基，R′各独立地选自C1-6烷基、C1-6烷氧基、C6-16芳基、卤素或CF3，M为钛、锆或铪，X各独立地选自氢、C1-6烷基、C1-6烷氧基或L为X、环戊二烯基、C1-6烷基取代的环戊二烯基、茚基、芴基或m为0-4，n为1-4。式中，基团Y最好是氧，因为这样的化合物较容易制备。同理，基团R最好是甲基，m最好是0。基团L最好是卤素，更优选氯，因为这样的催化剂有较优越的性能，并且容易制备。同理，基团X最好是卤素，特别是氯；基团M最好是钛。
二齿吡啶配合物的制备在实施例中说明，但一般它们能通过将具有酸式质子的取代吡啶前体与具有式MX3L的化合物在HX清除剂存在下进行反应而制备。反应是化学计量的，优选清除剂的化学计量。适合的清除剂的实例包括比取代吡啶碱性更强的化合物，诸如三乙胺、吡啶、氢化钠和丁基锂。如果清除剂是比取代吡啶更强的碱，就可制取取代吡啶的盐，并以取代吡啶盐为原料。当反应优选在溶剂中进行时，反应物只要求有部分的溶解度。可以使用非质子溶剂，诸如四氢呋喃(THF)、乙醚、甲苯、或二甲苯，浓度可用约0.2-20wt％固体，优选约5-10wt％固体。反应的发生温度约为-78℃至室温左右。反应进行时有沉淀形成，产物可用甲苯、二氯甲烷、乙醚或类似的提取剂进行提取。
本发明的二齿喹啉过渡金属催化剂具有如下的通式：式中R、R′、L、M、X和n如前所定义和p独立地选自0-3。
喹啉过渡金属催化剂的制取方法与吡啶过渡金属催化剂类似，只是以取代喹啉(诸如8-羟基喹啉)代替取代吡啶。也可在溶剂中使用丁基锂以制取8-羟基喹啉的锂盐，8-羟基喹啉的锂盐也可用作起始原料。
因为催化剂在正常情况下是与有机金属助催化剂结合使用的，所以最好是将催化剂溶于助催化剂也能溶解的溶剂中。例如，如果甲基铝氧烷(MAO)或聚甲基铝氧烷(PMAO)为助催化剂，那么可以使用甲苯、二甲苯、苯或乙苯作溶剂。优选的助催化剂是MAO，因为用它能得到高的活性和分子量分布较窄的聚合物。在聚合中使用的有机金属助催化剂与催化剂之摩尔比一般在0.01∶1-100,000∶1的范围，优选1∶1-10,000的范围。
可以替代的助催化剂是含非配位的惰性阴离子的酸式盐(见US 5,064,802)。酸式盐一般是非亲核化合物，它是由庞大的配位体连接在硼原子或铝原子上组成的，诸如四(五氟苯基)硼酸锂、四(五氟苯基)铝酸锂、四(五氟苯基)硼酸苯胺翁和它们的混合物。当这些化合物与催化剂反应时，所得到的阴离子相信是与含金属的阳离子成弱配位的。酸式盐与催化剂的摩尔比可在约0.01∶1-约1000∶1的范围，但最好是约1∶1-10∶1。从催从剂和酸式盐制备活性催化剂体系的方法没有限制，但优选的方法是在-78℃至约150℃的温度范围将它们在惰性溶剂中混合；需要时也可在单体的存在下进行混合。酸式盐可与上述的有机金属助催化剂结合使用。
催化剂和助催化剂可置于诸如硅胶、矾土、硅石、氧化镁或二氧化钛之类的载体上使用，但因它们对聚合物有污染，所以载体不是优选的。然而根据所使用的方法也可以需要载体。例如在气相聚合法和淤浆聚合法中一般需要有载体，以便控制所生产的聚合物的颗粒大小和阻止反应器壁结垢。使用载体时是将催化剂和助催化剂溶于溶剂，然后例如用蒸发溶剂的方法将其沉淀在载体材料上。助催化剂也可沉积在载体上或与载体化催化剂分别导入反应器。
催化剂是以常规方法用于烯属烃单体的聚合中。不饱和单体(诸如苯乙烯)可用本发明的催化剂来聚合，但它特别适用于聚合诸如丙烯、1-丁烯、1-己烯、1-辛烯、特别是乙烯之类的α-烯烃。
催化剂也可用常规方法用于诸如乙烯、丙烯、1-丁烯、1-己烯、1-辛烯等的不饱和单体混合物的共聚合，乙烯和诸如1，3-丁二烯、1，4-己二烯、1，5-己二烯等的二烯烃的混合物的共聚合；乙烯和诸如降冰片烯、亚乙基降冰片烯、乙烯基降冰片烯、降冰片二烯等的不饱和单体的混合物的共聚合。
本发明的催化剂可在各种不同的聚合方法中使用。它们可用于液相聚合法(淤浆、溶液、悬浮液、本体相聚合或其结合)，高压流体相或气相聚合法。这些方法可在系列或单级中使用。聚合反应区的压力可为约15psia至约50,000psia，温度可为约-78℃至约300℃。
实施例1
双(2-吡啶氧基)二氯化钛的合成
在0.02摩尔2-羟基吡啶和0.02摩尔三乙胺于50ml THF的溶液中在0℃下滴加0.01摩尔四氯化钛溶液，于室温下搅拌过夜。过滤后，蒸发THF溶液，从残留物中提取产物。产物结构如下：
实施例2
(环戊二烯基)(2-吡啶氧基)二氯化钛的制备
于0℃下将2-羟基吡啶(0.002摩尔)和三乙胺(0.002摩尔)于50ml乙醚中的溶液加入0.002摩尔环戊二烯基三氯化钛于50ml乙醚中的溶液，并搅拌过夜。从乙醚滤液中回收产物。产物结构如下：
实施例3
喹啉氧基过渡金属催化剂制各通法
在-78℃下将各种8-羟基喹啉衍生物的锂盐(用丁基锂制备)甲苯浆液与相应的钛或锆化合物(四氯化钛、四氯化锆、环戊二烯基三氯化钛或环戊二烯基三氯化锆)混合，并在室温下搅拌过夜。用甲苯或二氯甲烷提取，从反应混合物回收配合物。制备8-喹啉氧基三氯化钛(III)
Figure A9619400400112
是在-78℃下将0.01摩尔8-羟基喹啉的锂盐于30ml甲苯中的浆液(用1.45克(0.01摩尔)羟基喹啉和MeLi制备)加入1.9克(0.01摩尔)TiCl4于20ml甲苯中的溶液，并在室温下搅拌过夜。分离出沉淀，用甲苯洗涤，以100ml CH2Cl2提取。除去CH2Cl2后，分离得到棕色微晶状固体0.7克。
用类似方法由用2.28克(0.01摩尔)5，7-二氯-2-甲基-8-羟基喹啉制得的锂盐制备8-(2-甲基-5，7-二氯喹啉)氧基三氯化钛(IV)2.3克。
用类似的步骤由2.28克(0.01摩尔)5，7-二氯-2-甲基-8-羟基喹啉和1.165克(0.005摩尔)四氯化锆制备1.0克对比配合物双[8-(2-甲基-5，7-二氯喹啉)氧基]二氯化锆(V)
Figure A9619400400121
(环戊二烯基)(8-喹啉氧基)二氯化锆(VI)和(环戊二烯基)[8-(2-甲基-5，7-二氯喹啉)氧基]二氯化锆(VII)
Figure A9619400400123
的制备是用由1.45克(0.01摩尔)8-羟基喹啉或1.15克(0.005摩尔)5，7-二氯-2-甲基-8-羟基喹啉制得的锂盐在-78℃下与等摩尔量的环戊二烯基三氯化锆在甲苯中进行反应。在搅拌过夜和过滤后，从甲苯溶液分离到产物(0.62克VI和1.7克VII)。
实施例4
聚合反应
在研究中所有的聚合反应均在一个1.7升的反应器中进行。在进行聚合反应前反应器在用氮气吹扫下加热至130℃并保持在该温度30分钟进行“烘烤”。将乙烯、氢、己烯、丁烯和氮通过含13X分子筛的柱进行处理。在一典型的聚合反应中，反应器中加入0.850升己烷或甲苯，并用注射器加入要求体积的稀PMAO(AKZO公司)。监测盛氢的1升高压不锈钢容器的压力降(ΔP)将所需的氢加入反应器。用加压氮将催化剂的甲苯溶液加入反应器。在整个实验过程中反应器保持在等温条件下。在反应器中通入乙烯并通过调压器在需要时加入乙烯将压力控制在150psi。在反应器的温度和压力稳定后，将催化剂浆液加入反应器，聚合反应开始。用布洛克斯质流计(Brooks mass flow meter)监测乙烯流量。
使反应器放气终止聚合反应，聚合物经过滤而回收。加入约1000ppm丁基化羟甲苯/己烷(BHT)以稳定聚合物，并在80℃于真空炉中进一步脱挥发物2小时。按ASTM D-1238测定聚合物的熔体流动性。按ASTM D-150585在密度梯度柱中测压塑模制品的聚合物密度。
反应条件记录在下表中。
实验号 催化剂 温度(℃) 共聚单体 共聚单体(克) 催化剂(毫摩尔) 摩尔Al/M H2，ΔP 反应时间(分钟)
    1     I     80     无     0     9.5E·3     1897     0     15
    2     I     80     无     0     4.7E·3     3795     0     15
    3     I     80     无     0     4.7E·3     1897     20     15
    4     I     80     无     0     4.7E·3     1897     50     10
    5     I     80     丁烯     20     4.7E·3     1897     20     15
    6     II     80     无     0     9.0E·3     1001     0     60
    7     III     80     丁烯     10     8.4E·3     1074     10     30
    8     III     80     无     10     8.4E·3     1074     10     30
    9     IV     80     丁烯     0     6.6E·3     1324     0     30
    10     IV     80     丁烯     10     6.6E·3     1324     10     30
    11*     V     80     丁烯     10     1.14E·2     1175     0     10
    12*     V     80     丁烯     10     4.06E·3     1645     0     10
    13*     V     80     丁烯     10     8.12E·3     1645     0     10
    14     VI     80     丁烯     10     6.74E·3     991     0     15
    15     VI     80     丁烯     10     1.35E·2     991     0     15
    16     VI     80     丁烯     10     1.35E·2     1288     5     15
    17     VI     80     丁烯     10     1.89E·2     1132     15     15
    18     VI     110     丁烯     10     1.89E·2     1132     0     15
    19     VII     80     丁烯     10     1.10E·2     1212     0     15
    20     VII     80     丁烯     10     1.10E·2     1212     5     15
    21     VII     110     丁烯     10     1.54E·2     1126     15     15
    22     VII     80     丁烯     10     1.54E·2     1126     0     15
    23     VII     80     丁烯     10     1.54E·2     2078     0     15
表中“Al/M”为催化剂的PMAO中的铝对金属(钛或锆)的摩尔比
*对比实施例
下表为聚合反应结果
实验号   催化剂产率(kg/gm/h)       MI2       MI20     MFR     密度     Mw/Mn
    1     179.0     ＜0.01     ＜0.01     -
    2     153.2     ＜0.01     ＜0.01     -
    3     165.5     ＜0.01     1.8     -
    4     133.1     ＜0.01     2.47     -
    5     272.9     ＜0.01     0.964     -
    6     62.9     ＜0.01     ＜0.01     -
    7     99.2     0.90     16.9     18.9     0.9513     2.51
    8     167.9     0.41     4.2     10.2     3.67
    9     103.2     ＜0.01     -     -
    10     24.8     ＜0.01     -     -
    11*     低     -     -     -
    12*     无     -     -     -
    13*     无     -     -     -
    14     无     -     -     -
    15     98.1     ＜0.01     1.15     -
    16     177.7     0.93     21.4     23.1
    17     137.6     1.31     34.5     26.3
    18     159.0     0.81     16.1     19.8
    19     119.8     ＜0.01     .83     -
    20     198.7     0.46     11.4     24.7
    21     157.8     0.63     17.8     28.2
    22     160.1     0.06     12.8     -
    23     112.1     0.06     1.84     29.7
*对比实施例表中的Kg/gM/h为每克催化剂每小时生产的聚合物千克数。聚合物的熔体指数根据ASTM D-1238条件E和条件F测定。MI2是用2.16公斤重量(条件E)测定的熔体指数。MI20是用21.6公斤重量(条件F)测定的熔体指数。MFR是MI20/MI2比。聚合物密度根据ASTM D-1505测定。聚合物分子量分布的测定使用Wa-ters 150C凝胶渗透色谱仪，温度为135℃，溶剂为1，2，4-三氯苯。用重均分子量(Mw)和Mw/Mn(数均分子量)比表示分子量分布特征。
用本发明的催化剂可得到好的生产率和高分子量聚合物，由其极低的MI值可证实，甚至在较高温度(110℃)下催化剂VI和VII也是如此。

Claims (20)

1.一种通式如下的催化剂，
Figure A9619400400021
式中Y为O、S、NR、 或R各独立地选自氢或C1-6烷基，R′各独立地选自C1-6烷基、C1-6烷氧基、C6-16芳基、卤素或CF3；M为钛、锆或铪；X各独立地选自卤素、C1-6烷基、C1-6烷氧基或
Figure A9619400400023
；L为X、环戊二烯基、C1-6烷基取代的环戊二烯基、茚基、芴基或
Figure A9619400400024
m为0-4和n为1-4。
2.权利要求1的催化剂，其中Y为氧。
3.权利要求1的催化剂，其中X为卤素。
4.权利要求3的催化剂，其中X为氯。
5.权利要求1的催化剂，其中m为0。
6.权利要求1的催化剂，其中M为钛。
7.权利要求1的催化剂，其中M为锆。
8.权利要求1的催化剂，该催化剂为双(2-吡啶氧基)二氯化钛或(环己二烯基)(2-吡啶氧基)二氯化钛。
9.一种制取聚α-烯烃的方法，该方法包括使用如下通式的催化剂聚合α-烯烃单体，                   式中Y为O、S、NR、
Figure A9619400400032
R各独立地选自氢或C1-6烷基，R′各独立地选自R、C1-6烷氧基、C6-16芳基、卤素或CF3；M为钛、锆或铪；X各独立地选自卤素、C1-6烷基、C1-6烷氧基或
Figure A9619400400033
；L为X、环戊二烯基、C1-6烷基取代的环戊二烯基、茚基、芴基或 m为0-4和n为1-4，p独立地选自0-3。
10.权利要求9的方法，其中所说的催化剂具有通式
11.权利要求10的方法，其中Y为氧、X为卤素。
12.权利要求10的方法，其中M为钛。
13.权利要求10的方法，其中M为锆。
14.权利要求13的方法，其中Y为氧、X为卤素。
15.权利要求14的方法，其中X为氯。
16.权利要求15的方法，其中L为环戊二烯基。
17.权利要求16的方法，其中R′选自氯、甲基和它们的混合物。
18.权利要求9的方法，其中所说的催化剂选自8-喹啉氧基三氯化钛、8-(2-甲基-5，7-二氯喹啉)氧基三氯化钛、(环戊二烯基)(8-喹啉氧基)二氯化锆、(环戊二烯基)[8-(2-甲基-5，7-二氯喹啉)氧基]二氯化锆以及它们的混合物。
19.一种聚α-烯烃的制备方法，该方法包括在如下通式的催化剂存在下聚合α-烯烃单体，
Figure A9619400400041
式中Y为O、S、NR、
Figure A9619400400042
R各独立地选自氢或C1-6烷基，R′各独立地选自C1-6烷基、C1-6烷氧基、C6-16芳基、卤素或CF3；M为钛、锆或铪；X各独立地选自卤素、C1-6烷基、C1-6烷氧基或
Figure A9619400400043
；L为X、环戊二烯基、C1-6烷基取代的环戊二烯基、茚基、芴基或
Figure A9619400400044
m为0-2和n为1-4。
20.权利要求19的方法，其中所说的催化剂选自双(2-吡啶氧基)二氯化钛、(环戊二烯基)(2-吡啶氧基)二氯化钛以及它们的混合物。
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EP0832089B1 (en) 2001-09-26

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