CN87106984A - 用于烯烃聚合的铪金属茂催化剂 - Google Patents

用于烯烃聚合的铪金属茂催化剂 Download PDF

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CN87106984A
CN87106984A CN87106984.9A CN87106984A CN87106984A CN 87106984 A CN87106984 A CN 87106984A CN 87106984 A CN87106984 A CN 87106984A CN 87106984 A CN87106984 A CN 87106984A
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约翰A·尤厄
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Abstract

本发明提供了一种用于烯烃聚合和共聚的催化剂体系，该体系包括手性、立体刚性的铪金属茂催化剂与铝化合物合用。铝化合物优先采用 烷铝，也可以是熔铝和三甲基铝的混合物。这种混合物会引起催化剂超时衰变。催化剂体系还可能包含一种能增加金属茂催化剂溶解度的溶剂。这种催化剂体系所产生的有用聚合物产品的分子量大于10,000。

Description

本发明涉及用于烯烃聚合和共聚的催化剂体系，更确切地说，它是一种包含手性、立体刚性的铪金属茂催化剂与铝化合物混合的体系。现已发现，使用这种催化剂体系后，聚合物产品的分子量大于10，000。
本发明是申请号为034，341，1987年4月3日提出申请的发明的部分继续申请。
本发明提供了一种用于烯烃聚合，尤其是丙烯和高级α-烯烃聚合以及烯烃共聚，尤其是乙烯和丙烯共聚的铪金属茂催化剂。
金属茂用作乙烯聚合时的催化剂是已有技术。申请号为2，068，863的德国专利中发明了一种用于乙烯聚合的催化剂体系，包括双环戊二烷基钛，三烷基铝和水。申请号为2，608，933的德国专利中发明了一种用于乙烯聚合的催化剂体系，包括锆金属茂催化剂体系，化学通式为（环戊二烯基）nZrY4-n，这里Y代表R1CH2AlR2或CH2CH2AlR2或CH2CH（AlR2）2，R则代表烷基或金属取代后的烷基，n的数值为1～4;金属茂催化剂与三烷基铝助催化剂结合并与水混合后使用。
金属茂催化剂用于乙烯聚合和其它的α-烯烃共聚是在本技术领域中所熟知的。专利号为4，542，199的美国专利中，Kaminsky等发明了一种烯烃聚合，尤其是聚乙烯制备以及聚乙烯和其它α-烯烃的共聚的方法。所发明的催化剂体系包括分子式为（环戊二烯基）2MeRHal的催化剂体系，这里R代表卤素，或环戊二烯基或C1～C6的烷基;Me是过渡金属，尤其是锆;Hal是一种卤素，尤其是氯。该催化剂体系也包含一种噁烷铝，化学通式为Al2OR4[Al（R）-O]n的线性分子或[Al（R）-O]n+2的环状分子，n的数值为4～20，R是甲基或乙基。一近似的催化剂体系在美国专利4，404，344中揭示过。
美国专利4，530，914中发明了一种用于从乙烯聚合成聚乙烯的催化剂体系，所得到的聚乙烯具有较宽的分子量分布，尤其是双峰和多峰的分子量分布范围。该催化剂体系至少包括两种不同的金属茂和一种噁烷铝。该专利揭示了一种带有桥链结构的金属茂，桥可架于两个环戊二烯基环之间，形成立体刚性结构的环。
欧洲专利0，185，918中揭示了一种手性的、立体刚性结构的锆金属茂作为烯烃聚合催化剂。该案中未提出铪可以取代锆并用于有用的聚合物生产中。在环戊二烯基基团之间的桥是1～4个碳原子组成的线性烃，或是具3～6个碳原子的环状烃。
在该领域的普通技术人员都知道，聚烯烃，主要是聚丙烯，可能被制造成不同的形式：等规立构的、间规立构的、无规立构的和等规一无规立体嵌段的。等规立构的聚丙烯具有有规则的重复相同构型的单元，在链上只有少数不规则的倒位。等规立构的聚丙烯可能表示如下：
Figure 87106984_IMG1
等规立构的聚丙烯能够形成一高晶态聚合物，所形成的晶体聚合物，具有晶体的熔点和其它所需的物理性能，这些性能不同于在非晶态或无晶态下，同样的聚合物所具有的性能。
间规立构的聚合物主要是具有有规则的交替构型单元，可以用如下结构表示：
Figure 87106984_IMG2
聚合物链中没有规则的单元构型重复的称无规立构聚合物。在工业应用上，在生成等规立构形式的聚合物时，带有一定百分率的无规立构聚合物。这种聚合物具有倒位构型的循环单元，是一种等规立构规正嵌段聚合物，可表示如下：
Figure 87106984_IMG3
后一种类型的立体规正嵌段聚合物，已经用在美国专利4，522，982中所揭示的金属茂催化剂成功地生产出来了。
用于生产等规立构的聚丙烯的催化剂体系采用钛金属茂或锆金属茂催化剂和噁烷铝助催化剂，这种噁烷铝在美国化学杂志，106卷，6355～64页，（1984年）的文章：“用可溶基团4B金属茂/甲基噁烷铝作催化剂时，丙烯聚合中的立体结构化学控制的机理”中已描述过了。这篇文章描述了由乙烯桥茚基衍生物的外消旋对映体得到的手性催化剂，产生了等规立构的聚丙烯，它的结构符合对映位立构化学控制模型。但是，乙烯桥茚基钛非对映体的内消旋非手性形式和非手性锆茂衍生物作催化剂时，产生的聚丙烯是纯的无规立体结构。
上述有关资料一般描述的金属茂催化剂都是两个环戊二烯环与过渡期金属相连接。这种一般的描述中应该包括铪金属茂，但是，有关的资料只是提到了钛金属茂和锆金属茂已被证实可用，本发明最先提到了用铪金属茂作为催化剂。因此，铪金属茂催化剂以前尚没有在有用的聚丙烯产品的生产，尤其是产品的分子量低于10，000的产品生产上应用过。在众所周知的金属茂体系中，铪不能简单地取代锆和钛并产生积极的效果。
本发明包括一种新型铪金属茂催化剂的发明，这在已有技术中尚未出现过。在相似的条件和相似的结构下，这种催化剂显示的特性和产生的效果优于锆金属茂和钛金属茂催化剂所显示的效果。
本发明提供了一种用于烯烃聚合的催化剂体系，包括手性、立体刚性的铪金属茂催化剂，其化学通式为R″[C5（R′）4]2HfQp和一个铝化合物，这里，[C5（R′）4]代表环戊二烯基或被取代后的环茂二烯基环;R′代表氢或烃基，烃基的碳原子数目为1～20，每个R′可以是相同的，也可以是不同的;R″是一有机或无机的基团，在两个[C5（R′）4]环之间提供桥链结构，赋予了所述催化剂的立体刚性;Q是烃基，如芳基、烷基、链烯基，烷基芳香基或芳香基烷基，它们的碳原子数目为1～20，Q也可代表一卤素，且0≤p≤3。
本发明所描述的铪金属茂催化剂是一种立体有择催化剂，它所产生的聚合物分子量高于先前所谈到的催化剂所产生的。聚合物分子量可以恒定在10，000以上。这些聚合物同时也是有规的立体聚合物，具有很高的晶体熔点和光学活性。本发明的催化剂也显示了很高的效率。
本发明的铪金属茂催化剂也可用于聚烯烃，尤其是可用于丙烯和乙烯的共聚中。
本发明也包括了噁烷铝和三甲基铝的混合物对铪金属茂催化剂的效应。噁烷铝和三甲基铝的混合物会引起催化剂超时衰变，衰变后的催化剂产生的聚合物产品分子量较低。分子量的分布很窄，但是，新的催化剂维持着与原始的催化剂相同的有规立体性能。
在本发明的另一个具体实施例中，一种溶剂被加入催化剂体系中，增加了催化剂在烯烃溶液中的溶解性。所选择的溶剂可以是甲苯、二甲苯或二氯甲烷。
下面，将结合附图，对最佳实施例加以描述。
附图显示了三甲基铝对于分子式为Et（Ind）2HfCl2的铪金属茂的催化剂，且有噁烷铝存在下的影响。附图举出了双峰值随时间变化的分布曲线。
本发明提供了一种用于烯烃聚合和共聚的铪金属茂催化剂体系，它所得到的有用产品的分子量高于先前揭示的采用铪催化剂的。用铪金属茂催化剂产生的聚合物，与用锆金属茂作催化剂所得到的聚合物相比，具有较高的有规立体结构和较高的分子量。本发明中这种或其它的优越性将从下列详细描述和附例中变得更加明显。
本发明的铪金属茂催化剂可用下列分子式来表示：
R″[C5（R′）4]2HfQp
这里：[C5（R′）4]是环茂二烯基或被取代的环戊二烯基基团;R′是氢或是碳原子为1～20的烃基，每个R′可以是相同的，也可以是不同的;R″是一有机或无机的基团，它至少有一部分可以在两个[C5（R′）4]基团之间起桥链的作用，并因此形成立体刚性的催化剂;Q可以是烃基，如具有1～20个碳原子的烷基，芳基，链烯基，烷基芳香基或芳香基烷基，Q也可以是一卤素，且0≤p≤3。用于丙烯和高级α-烯烃聚合时，该催化剂应该是手性的，即是非镜象重叠的，而用于乙烯的聚合或主要是乙烯共聚的催化剂则不必是手性的或立体刚性结构的。
典型的烷基，如甲基、乙基、丙基、丁基、戊基、异戊基、己基、异丁基、庚基、辛基、壬基、癸基、十六烷基、苯基、亚甲基、亚乙基丙烯基等可能组成如上描述的催化剂的一个部分。典型的卤素原子，包括氯、溴和碘，优先采用氯。Q可代表一卤素，p的最佳值为2。[C5（R′）4]中的取代基R′优先采用茚基（Ind），也可以是茚基水合物（IndH4）。如前所述，其它的烃基也能加入到环戊二烯基环中。
R″是一稳定的组分，它是两个[C5（R′）4]环之间的桥，它的作用是使催化剂成为立体刚性。R″可以是无机基团或有机基团或包括可以作为桥的组分。R″的例子包括碳原子数1～4的亚烃基、烃基硅，烃基锗，烃基膦，烃基胺，硼，氮、硫、亚磷，铝或含有这些元素的基团。R″优先组分是亚甲基（-CH2-），亚乙基（-C2H4-），烃基硅和成环烷基硅，如：环丙基硅等。本发明中，桥R″和取代基R′可以变化，从而提供不同特性的聚合物产品。
在本发明中，铪金属茂催化剂和铝化合物结合使用。铝化合物优先采用噁烷铝，化学通式为（R-Al-O）的代表环结构，（R-Al-O）nAlR2则代表线性结构。上式中，R是碳原子数为1～5的烷基组分。n是1～20的整数。大多数情况下，R是甲基。通常，在噁烷铝制备中，例如从三甲基铝和水制备噁烷铝时，可得到线性和环状的混合物。
噁烷铝可以通过不同的途径制备，优先采用水和三甲基铝溶液接触制备，例如，将三甲基铝溶于一合适的溶剂，如苯中。最好是，噁烷铝的制备如美国专利4.404，344中揭示的，在水合硫酸铜存在下制备，这样的描述被纳入参考资料。这种方法包括将三甲基铝溶于例如甲苯的稀溶液，再用分子式为CuSO4·5H2O的硫酸铜处理，甲烷的产生确证了已发生反应。
作为本发明的一个部分，揭示了三甲基铝和噁烷铝混合物和铪金属茂催化剂结合使用会引起催化剂的衰变。只混有痕量三甲基铝（TMA）的噁烷铝，与铪金属茂催化剂结合，得到的聚合物产品分子量都很高，并显示了相当好的对称性的分子量分布。（见图曲线a）。将约1毫摩尔的TMA加入到16毫摩尔的噁烷铝中，经2小时后才引起催化剂的衰变，这样所形成的新的催化剂使产生的聚合物分子量较低，分布很窄，但有规立构性和原来的一样（见图曲线“b～d”）。当聚合反应进行了一段较长时间时，在分子量分布中，较低分子量的峰值随间的增加而增加，如在图中所表示的。
本发明也包括了一种可增加催化剂在单体中溶解度的溶剂的使用。在这一个较佳实施例中，金属茂催化剂和烯烃单体一样，配成液态应用。溶剂可预先混合于催化剂中或和单体一起加入。优先采用的溶剂包括有：甲苯，二甲苯和二氯甲烷，但是，溶剂可以是任何的有机溶剂。由于催化剂通常略带极性，故所考虑的溶剂也都带有一定的极性，溶剂的选择取决于催化剂，某一特殊的溶剂对于某一催化剂的相容性可能要比其它溶剂好。
本发明的金属茂催化剂的制备方法是本领域的普通技术人员公知的。典型的过程包括上面描述的HfQ基团和R″基团加入到一些初始的化合物，如茚基或其它基团取代后的双环戊二烯基环。铪金属茂催化剂的一个制备例子在如下实施例1中使用。
本发明的应用催化剂的聚合过程包括该领域内的任何过程。优先采用的一种方法是共同待批申请，编号009，712的申请中所揭示的，因此，该申请也被纳入有关资料中，它描述了一种在把催化剂加入到聚合反应区之前的催化剂预聚合。另一种优先采用的过程将在下列实施例中举出。
下列实施例更详细地列举了本发明和它的各种优点，包括在这些例子中，以使用铪催化剂为实施例，用锆金属茂催化剂作为比较例，以说明分子量的增加和其它性能的改进。结果概括于表1中。
实施例1
催化剂的制备
分子式为Et（Ind）2HfCl2的铪金属茂催化剂制备的方法是这样的，将38毫摩尔的正丁基锂己烷溶液加入到预冷却至-91℃，150ml四氢呋喃溶液中，该四氢呋喃溶液中含有5克（19mmol）的双茚基乙烷。整个溶液再加热至50℃，搅拌3小时，然后在150℃下滴加到HfCl4/THF加合溶液（19毫摩尔HfCl4溶于150ml THF中）中。搅拌过夜，热量被去除并且将氯化氢气体通入溶液中鼓泡，鼓泡15分钟，可得到黄色的溶液，四气呋喃被旋转蒸发，固体中加入少量二氯甲烷。溶剂慢慢地倾出，并旋转蒸发得到亮黄色的固体，在真空中进行干燥。黄色固体被溶于100ml二氯甲烷中时，不溶性的氯化锂可被过滤去除。再加入冷的戊烷，有若干克亮黄色粉末析出。所得复合物经过滤后，干燥并在0℃的干燥甲苯中分步重结晶而进一步纯化。
丙烯的聚合（聚合过程1）
在一个容积为75毫升的不锈钢样品钢瓶中充满氩气，将含有0.14毫克Et（Ind）2HfCl2的溶液和甲苯，溶液和甲苯在钢瓶中预先与10毫升甲基噁烷铝甲苯溶液接触5分钟。随后将钢瓶中的物质用针管注射到一只2升的带有密闭阀的密闭的反应器中，再加入1升丙烯，维持在反应温度50℃，将反应器内的溶液搅拌1小时。然后排气放出丙烯，反应器内的物质用50%甲醇盐酸稀溶液清洗并真空干燥。
聚合物分析
然后对聚合物产品进行熔点和分子量的分析。表1中的熔点是用DSC（差示扫描量热仪）测得的数据，该测定方法是本技术领域内的技术人员公知的。熔点不是真正的平衡熔点，但它是DSC测定的峰值温度。真正的平衡熔点高于DSC测出的值。聚丙烯的熔点是由聚合物的等规立构部分的结晶度所决定，结果发现，大多数无规立构聚合物被去除，而等规立构聚合物被保留下来后，所测出的熔点差异仅为1～2℃。这就说明，不管是二甲苯可溶物或无规聚合物被移去前还是移去后，所测得的结果用DSC熔点测定证明均是可信的。当等规立构聚合物为主时，能产生较鲜明的、较清淅的熔点峰值。
聚合物的分子量用GPC（凝胶渗透色层分离法）测定。测定在Waters    150.C装置中，用Jordi凝胶柱进行。溶剂为三氯苯，操作温度为140℃，Mn和Mw以及Mw/Wn，的值已列于表1中。
实施例2
实施例1的过程在这里重复，催化剂用量为1.42mg，反应温度为80℃，结果见表1。
比较例3及4
实施例1的过程也在这里重复，但应用了锆金属茂催化剂，与使用铪催化剂的结果进行比较。
实施例5～7
实施例1的过程这里进行了重复，但催化剂是使用氢化的铪金属茂催化剂，结构式为：Et（IndH4）2HfCl2，采用下列所述聚合过程2的方法。该过程不同于实施例1中（聚合过程1）的方法，本过程中，在加入催化剂和助催化剂混合物之前先行加入丙烯。反应温度的变化形式列于表1中。
比较例8-10
这些比较例与实施例5～7是平行的，使用的操作手续相同，但使用分子式为：Et（IndH4）2ZrCl2的锆金属茂催化剂，结果列于表1。比较表1中的结果，在同样情况下，本发明的铪金属茂催化剂所产生聚合物分子量比应用锆金属茂催化剂所得的聚合物分子量要高。
实施例11～16，20
实施例1中Et（Ind）2HfCl2催化剂的制备过程在这里进行了重复。聚合过程NO·3，与过程NO·2相同，除了它是将500ml甲苯和800ml丙烯加入反应器，200ml丙烯被用来将催化剂和助催化剂注入反应器中。其它的聚合条件在表中已列出。
实施例17～19
在这些实施例中，下述的聚合过程4，与过程3相同，除了甲苯的加入量为1000ml，丙烯为1800ml，一起投入4立升的反应器中，200ml丙烯把催化剂/助催化剂注入反应器。
这里要注意：在实施例1～2，5～7，11～14，和在附图中表示的实施例中，所用的铪催化剂都是由纯度为98%，并沾染了一些锆杂质的HfCl4溶液制备的。在实施例15～20中的铪催化剂则用纯度为99.99%的HfCl4制备。
实施例11～20的结果表明，所得的聚合物产品具有很高的分子量。该结果还表明了体系中铪的浓度和聚合物分子量之间的关系。实施例19和20表明：在较低的聚合温度下，聚合物产品的分子量较高。
作为本发明的一部分，也表明了在催化剂体系中使用噁烷铝和三甲基铝的混合物会引起催化剂的超时衰变。这种衰变在图中有所显示，表明了分子量分布随时间而变化的关系。在图中，曲线“a”是实施例1～2中所得到的聚合物典型分子量的分布曲线。曲线“b～d”表明了在相似的催化剂，含有三甲基铝体系中依次0.5小时，1小时，2小时的分布曲线。这些曲线反映了双峰分布和从0.5小时的高分子量聚合物到2小时后较低分子量的聚合物的催化剂衰变过程。
取决于某一特殊的催化剂，三甲基铝可以用不同的量与噁烷铝合用。优先采用的方法是：三甲基铝的加量为噁烷铝与三甲铝混合物的0～20摩尔百分数。如图所示，体系包含1摩尔的三甲基铝和16摩尔的噁烷铝。这里，已对本发明的几个实施例进行了描述，但可以理解，在不背离本发明的范围内，是能够作些改进和修改的。
Figure 87106984_IMG4

Claims (20)

1、一种用于烯烃聚合和烯烃共聚的催化剂体系，其特征在于主要包括：
(a)一种手性的、立体刚性的铪金属茂催化剂，可以用下列分子式来描述：R″[C5(R′)4]2HfQp，这里，[C5(R′)4]是环戊二烯基或被取代的环戊二烯基环，每个R′可以是氢或碳原子数1～20的烃基；R″是一有机或无机的基团，其作用是在两个[C5(R′)4]环之间提供一桥结构，可赋予所述催化剂的立体刚性；Q可以是碳原子数1～20的烃基或一种卤素；且0≤p≤3；
(b)一种铝化合物。
2、如权利要求1所述的催化剂体系，其特征在于所述[C5（R′）4]是含有茚基或水合茚基的基团。
3、如权利要求1所述的催化剂体系，其特征在于所述R″可以是下列基团中的一种：碳原子数为1～4的亚烃基，烃基硅，烃基锗，烷基膦，烃基胺，硼，氮，硫，亚磷，铝和其它含有这些元素的基团。
4、如权利要求1所述的催化剂体系，其特征在于R″包括乙烯桥。
5、如权利要求1所述的催化剂体系，其特征在于所述Q可以是氯。
6、如权利要求1所述的催化剂体系，其特征在于所述铝化合物可以是噁烷铝或噁烷铝与三甲基铝的混合物。
7、如权利要求1所述的催化剂体系，其特征在于所得到的聚合物分子量大于10，000。
8、如权利要求1所述的催化剂体系，其特征在于进一步包括（c），一种溶剂。
9、如权利要求8所述的催化剂体系，其特征在于所述溶剂可以是甲苯或二甲苯或二氯甲烷。
10、一种用于三个或三个以上碳原子的烯烃聚合和共聚的催化剂体系，其特征在于所述体系包括：
（a）一种手性的、立体刚性的铪金属茂催化剂，可以用下列分子式来描述：R″[C5（R′）4]2HfQp，这里，[C5（R′）4]是环戊二烯基或被取代的环戊二烯基环;每个R′可以是氢或碳原子数1～20的烃基;R″是一有机或无机的组份，其作用是在两个[C5（R′）4]环之间提供一桥结构，可赋予所述催化剂的立体刚性;Q可以是碳原子数1～20的烃基或一种卤素;且0≤p≤3;
（b）一种铝化合物。
11、如权利要求10所述的催化剂体系，其特征在于所述[C5（R′）4]是从茚基及水合茚基基团中选出的。
12、如权利要求10所述的催化剂体系，其特征在于所述R″可以是下列基团中的一种：碳原子数为1～4的亚烃基，烃基硅，烃基锗，烷基膦，烷基胺，硼，氮，硫，亚磷，铝和其它含有这些元素的基团。
13、如权利要求10所述的催化剂体系，其特征在于R″包括乙烯桥。
14、如权利要求10所述的催化剂体系，其特征在于Q是氯。
15、如权利要求10所述的催化剂体系，其特征在于所述铝化合物可以是噁烷铝或噁烷铝与三甲基铝的混合物。
16、如权利要求10所述的催化剂体系，其特征在于所述铝化合物由约0～20摩尔百分数的三甲基铝和约80～100摩尔百分数的铝所组成。
17、如权利要求16所述的催化剂体系，其特征在于该体系显示了催化剂的超时衰变。
18、如权利要求17所述的催化剂体系，其特征在于催化剂的这种衰变是以产生较低分子量的聚合物产品为特征的。
19、如权利要求10所述的催化剂体系，其特征在于还包括（c），一种溶剂。
20、如权利要求19所述的催化剂体系，其特征在于所述溶剂可以是甲苯或二甲苯或二氯甲烷。
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