CN1059448C - 一种用于生产间规聚烯烃的金属茂催化剂及其制备方法 - Google Patents

一种用于生产间规聚烯烃的金属茂催化剂及其制备方法 Download PDF

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CN1059448C
CN1059448C CN89104461A CN89104461A CN1059448C CN 1059448 C CN1059448 C CN 1059448C CN 89104461 A CN89104461 A CN 89104461A CN 89104461 A CN89104461 A CN 89104461A CN 1059448 C CN1059448 C CN 1059448C
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约翰A·依文
阿巴士·拉什夫
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Abstract

本发明提供一种用于制备间规聚烯烃的金属茂催化剂。该催化剂一般地由下式表达：R″(CpRn)(CpR′m)Me Qk式中每个Cp为环戊二烯基或取代的环戊二烯基环；每一个Rn和R′m为相同或不同的并为具有1-20个碳原子的烃基；R″为二个Cp之间的赋于催化剂立体刚性的结构桥；Me为元素周期表中ⅣB、ⅤB或ⅥB族的金属；每一Q为具有1-20个碳原子的烃基或为卤素；0≤K≤3；0≤n≤4；1≤m≤4；以及R′m选自(Cp R′m)为空间上不同于(Cp Rn)的环。

Description

一种用于生产间规聚烯烃的金属茂催化剂及其制备方法
本发明涉及用于制备间规聚烯烃的金属茂催化剂。该催化剂包括桥接的金属茂在一个与其它环不同方式的取代的环戊二烯基环中。本发明进一步包括用一种或多种所揭示的催化剂制备间规聚烯烃的方法，同时包括该催化剂的制备方法。
本发明提供一种具有三个或更多个碳原子的烯烃聚合以生产具有间规立体化学构型的聚合物的催化剂和方法。该催化剂和方法在聚合丙烯以形成高结晶性、间规聚丙烯的新型显微结构中是特别有用的。
在已知技术中已知间规聚合物具有独特的立体化学结构，在其单体单元中在大分子主链中具有不对称碳原子彼此交替和规则的对映构型。在Natta等的美国专利号3,258,455中首先揭示了间规聚丙烯。Natta等通过用三氯化钛和二乙基铝单氯化物制备的催化剂得到间规聚丙烯。在Natta等然后的美国专利号3,305,538中，揭示用三乙酰基丙酮酸钒或卤化的钒化合物与有机铝化合物结合来生产间规聚丙烯。Emrick的美国专利号3,364,190中揭示由细分散的钛或钒三氯化物、铝氯化物、三烷基铝和含三价磷的路易士碱组合的催化剂系统来生产间规聚丙烯。
如在这些专利中所揭示的资料以及已知技术中所熟知的，间规聚丙烯的结构和性质与等规聚丙烯是明显不同的。等规结构一般被描述为甲基基团连结至连续的单体单元的叔碳原子通过聚合物的主链在假设平面的同一面上，即：甲基基团全部在平面的上面或下面。利用费歇尔(Fischer)投影公式，等规聚丙烯的立体化学顺序描述如下：
Figure C8910446100051
另一种描述该结构的途径是通过NMR的应用。Bovey’s的NMR命名规则对等规五价基表述为：……mmmm……，对每一个“m”代表一个“内消旋”二价基或在该平面同一边的连续的甲基基团。如在已知技术中所熟知的，在链结构中任何偏差或反转会降低聚合物的等规度和结晶度。
与等规结构相反，间规聚合物是那些甲基基团连结至连续的单体单元的叔碳原子在聚合物平面不同面的链中。间规聚丙烯显示为如下表示的锯齿形曲折：用费歇尔投影公式间规聚合物的结构表示如下：
Figure C8910446100053
在NMR命名原则中，该五价基被描述为：……rrrr……每一个“r”表示一个“外消旋”二价基，即：连续的甲基基团在平面的不同侧面上。在链中r二价基的百分数决定聚合物的间规度。间规聚合物为结晶状，并类似等规聚合物在二甲苯中不溶解。间规和等规聚合物两者的结晶性区别在于二甲苯中溶解的无规聚合物。无规聚合物显示在聚合物链中重复的单元的无规则程度并基本上形成蜡状产物。
而一种催化剂可能产生所有的三种类型的聚合物。所希望的催化剂是一种仅形成少量无规聚合物而主要是等规或间觌聚合物的催化剂。生产等规聚烯烃的催化剂在共同待批的1987.4.3日申请的美国专利申请号034,472,1987.9.11日申请的096,075，以及1987.9.11日申请的095,755中被揭示，这些申请揭示手性的、立体刚性金属茂催化剂来聚合烯烃以形成等规聚合物，并在高等规聚丙烯的聚合中特别有用的。然而，本发明是采用不同级的金属茂催化剂用于问规聚烯烃的聚合中，以及更具体地是用于间规聚丙烯中。
除了新揭示的催化剂外，本发明同时提供具有新的显微结构的间规聚丙烯。发现该催化剂的结构不仅影响与等规聚合物相对的间规聚合物的形成，而且也显示影响在聚合物链中从主要的重复单元偏离的类型和数量。上述用于生产间规聚丙烯的催化剂被认为使用链端来控制整个聚合反应机制。这些上述已知的催化剂，诸如：Natta等在参考文献中提及，生产具有以下结构为主的间规聚合物：
Figure C8910446100061
或在NMR命名规则中具有……rrrrrmrrrrr……。该间规聚丙烯结构的NMR分析揭示在Zambelli等的Macromolecules，Vol，13，p267-270(1980)中，Zambelli′s分析表明主要的单个内消旋二价基遍布于在链中的任何其它的偏离。然而，发现此处揭示的催化剂产生与先前所知和揭示的带有不同显微结构的聚合物，另外还在结构中具有高百分数的外消旋二价基。
本发明提供一种催化剂并用于制备间规聚烯烃，以及更具体地为间规聚丙烯的方法。该催化剂和方法产生具有高间规度和具有新型的间规的显微结构的聚合物。进一步地，本发明包括通过催化剂结构变化得到具有宽的分子量分布的和单一特性(诸如：熔点)的聚合物的方法。
本发明提供的该新型催化剂是通过用下式描述的立体刚性金属茂催化剂得到的：
R″(CpRn)(CpR′m)MeQk式中每一个Cp为环戊二烯基或取代的环戊二烯基环：每一个R和R′为具有1-20个碳原子的烃基； R″为赋于Cp环以立体刚性的二个Cp环之间的结构桥； Me为过渡金属；以及每一个Q为烃基或为卤素。进一步地，R′m为选自导致(CpR′m)与(CpRn)立体上不同的取代的环戊二烯基环。发现用如上述的带有立体上不同的环戊二烯基环的金属茂催化剂产生一种主要是间规聚合物而不是等规聚合物。
本发明进一步提供一种间规聚烯烃，以及具体地为间规聚丙烯的生产方法，它包括使用至少一种上述结构式的催化剂并导入包含烯烃单体的反应区域中。另外，在反应区域中可以导入电子供体化合物和/或一种助催化剂诸如：铝噁烷。进一步地，该催化剂在导入反应区域前和/或在反应器中的反应条件稳定化前也可以预聚合。
本发明同时包括生产具有宽分子量分布的间规聚烯烃的一种方法。该方法包括在聚合过程中使用至少二种上述结构式的不同的催化剂。进一步发现通过此处所述的聚合方法产生的聚合物的特性可随聚合温度或催化剂的结构不同加以控制。尤其是我们发现较高的聚合温度导致在间规聚合物中带有混合的显微构造。同时，我们发现通过反应温度、催化剂一助催化剂的比例以及催化剂结构以影响聚合物的熔点，较高的反应温度一般地产生具有较低熔点的较小结晶度的聚合物。进一步地用不同结构的催化剂可以得到具有不同熔点的聚合物产物。
本发明进一步包括一种桥接的金属茂催化剂的制备方法，它包括环戊二烯或取代的环戊二烯和亚甲基环戊二烯或取代的亚甲基环戊二烯在反应条件下充分接触以产生一种桥接的二环戊二烯或取代的二环戊二烯。该方法进一步包括桥接的二环戊二烯和结构式为MeQk的金属化合物充分接触络合桥接的二环戊二烯以产生桥接的金属茂。
图1为本发明的较佳催化剂结构的说明，并具体表示异-丙基(环戊二烯基)(芴基)铪二氯化物；
图2，在实施例1中为用异-丙基(环戊二烯基)(芴基)锆二氯化物催化剂产生的聚合物的NMR谱图。该聚合物在二甲苯中重结晶一次；
图3和图4，为在实施例7和8中产生的聚合物在二甲苯中重结晶三次的聚合物的IR谱图。
本发明提供一种催化剂并用于制备间规聚烯烃、具体地为间规聚丙烯的方法。不仅本发明的催化剂产生间规聚丙烯，而且它们产生的聚合物具有新型的显微结构。
当丙烯或其它α-烯烃用含有过渡金属化合物的催化剂被聚合时，该聚合产物典型地包括无定形的、无规的和结晶的在二甲苯中不溶部分的混合物。该结晶状组份既可以含有等规或间规的聚合物，也可以是它们二者的混合物。共同待批的美国专利申请号034,472；096,075和095,775中揭示了高的等规级金属茂催化剂。与这些申请所揭示的催化剂相反，用于本发明生产的聚合物的催化剂为间规级并产生具有高间规指数的聚合物。我们发现间规聚丙烯比相应的等规聚合物具有较低的结晶热。另外，在聚合物链中具有同样数量的缺陷，间规聚合物比等规聚合物具有较高的熔点。
本发明的金属茂催化剂可以用以下结构式描述
R″(CpRn)(CpR′m)MeQk
式中每一个Cp为环戊二烯基或取代的环戊二烯基环：R和R′为具有1-20个碳原子的烃基；每一个R可以为相同或不同的，以及每一个R′也可以为相同或不同的；R″为二个Cp环之间赋于Cp催化剂中的环立体刚性的结构桥，以及R″较佳地选自包括具有1-4个碳原子的烷基或含有硅、锗、磷、氮、硼或铝的烷基；Me为元素周期表中IVB、VB或VIB族金属；每一个Q为具有1-20个碳原子的烷基或为卤素；0≤k≤3； 0≤n≤4；以及1≤m≤4。为了成为间规级，我们发现在金属茂催化剂中的Cp环必须基本上以不同方式取代的，导致在二个Cp环之间存在立体性的不同，由选择在(Cp R′m)中的R′m基本上区别于取代(Cp Rn)的环。为了产生间规聚合物，在环戊二烯基环上直接取代的基团的特性被认为是重要的。于是，如用此处的“立体上不同”或“立体地不同”意味着Cp环立体特性之间的不同，这是控制每一连续单体单元被引入Cp环之间的立体障碍的不同起阻止以随意的方式引入单体的作用，并且控制单体被加至聚合物链或间规构型的方式。
如在权利要求书中说明的不希望受本发明范围的限制，认方在聚合反应中催化剂和引入的单体单元与添加至聚合物链的单体异构化、单体的同分异构化通过不同的取代的Cp环的立体障碍来控制的，导致间规聚合物的不同构型特性而与此相反Natta等揭示的催化剂是链端控制。反应机制的不同导致聚合物不同的结构。
用于本发明的生产聚合物的较佳催化剂中，Me为钛、锆或铪；Q较佳为卤素以及最佳为氯；以及K较佳2，但它可以随金属原子价的不同而不同。作为例子的烷基包括甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、异戊基、己基、庚基、辛基、壬基、癸基、十六烷基苯基以及诸如此类。其它的用于金属茂催化剂的烃基基团包括其它的烷基、芳基、链烯基、烷基芳基或芳基烷基。进一步地，Rn和R′m可以包括烷基连结在Cp环中单一碳原子，也可以连结在环中的二个碳原子。图1表示较佳催化剂异-丙基(芴基)(环戊二烯基)铪二氯化物的结构。在图1中表示的锆类似物的催化剂同样是较佳的。
该催化剂可以通过已知技术中任意的方法制备，以下揭示两种制备催化剂的方法，用第二种方法产生较稳定和更大活性的催化剂是较佳的。重要的是通常因为采用不纯的催化剂会产生低分子量无定形的聚合物，所以催化剂配位化合物应是“纯净”的。通常催化剂配位化合物的制备包括形成和分离Cp或取代的Cp配位体，然后它们与卤代金属反应以形成配位化合物。
本发明的金属茂催化剂在已知技术的等规聚丙烯制备的许多聚合过程中是有用的。当本发明的催化剂用于这些类型的方法时，与其说产生等规聚合物倒不如说产生间规聚合物。通过本发明说明的用于聚合物制备的聚合方法的进一步的例子包括在美国专利申请于009,712(申请日1987.2.2，)以及095,755(申请日1987.9.11.)中所揭示的，这些披露作为此处参考。这些较佳的聚合过程包括在催化剂导入反应区域之前，催化剂的预聚合和/或催化剂和助催化剂和烯烃单体的预接触。
与先前披露的生产等规聚合物的金属茂催化剂一样，本发明的间规级催化剂和铝助催化剂相结合，较佳地与铝噁烷、烷基铝或其混合物结合是特别有用的。另外，根据欧洲专利公开号226,463(1987.6.24.公开的)由Howard Turner等发明者转让给Exxon ChemicalPatents Inc所给出的配位化合物，在此处描述为金属茂催化剂和过量的铝催化剂之间可以进行分离。如在此处所揭示的，金属茂在合适的溶剂存在下与过量的铝噁烷反应。金属茂配位化合物和铝噁烷可以被分离并用作本发明的催化剂。
用于和本发明的催化剂结合的铝噁烷，既可以用于聚合反应中也可以形成由Turner揭示的配位化合物，可以用通式(R-Al-O)表示成环状以及用通式R(R-Al-O)n-Al R2表示成线状，式中R为1至5个碳原子的烷基以及n约为1至20的整数。最佳的R为甲基。铝噁烷可以用已知技术中多种已知方法制备。较佳地，它们通过水与三烷基铝溶液，诸如：三甲基铝，在一合适的溶剂中诸如苯中接触制备。另一较佳的方法包括在美国专利号4,404,344中说明的在水合硫酸铜的存在下制备铝噁烷，该揭示作为此处参考。该方法包括用硫酸铜处理三甲基铝在甲苯中的稀溶液。用于本发明的其它铝助催化剂的制备可以通过本技术领域中的已知方法制备。
以下将通过具体实施例进一步详细说明本发明的各种优点和有效之处。在方法A和B中说明锆和铪金属茂催化剂的两种不同合成过程。两种合成过程均在惰性气氛下采用Vaccum Atmospheres Glovebox或Schlenk技术完成的。该合成方法通常包括以下步骤：1)制备卤代的或烷基化的金属化合物，2)制备配位体，3)合成配位化合物，以及4)提纯该配位化合物，架桥的取代的二环戊二烯配位体的合成是通过亚甲基环戊二烯或取代的亚甲基环戊二烯与环戊二烯或取代的环戊二烯在反应条件下充分接触完成，以产生架桥的二环戊二烯或取代的二环戊二烯。如在已知技术中所熟知的，在亚甲基环戊二烯中的Cp-C，碳原子通过双键连结到环戊二烯基环的。用于此处的取代的亚甲基环戊二烯为(Cp Ra)＝CR′b式中亚甲基环戊二烯既取代Cp环或在末端碳原子上取代或取代二者。Ra和Rb为烃基基团，由于每一个Ra和Rb可以是相同或不同的，而0≤a≤4以及0≤b≤2。合成的其它三步可以由以下所示或在已知技术中所熟知的方法完成。通过这些方法产生的催化剂的一般的结构式为异-丙基(芴基)(环戊二烯基)Me Cl2，式中的Me既可以为锆也可以为铪，取决于实施例。图1表示铪催化剂的结构，而锆催化剂基本上具有用锆代替铪原子位置的相同结构。
催化剂的制备-方法A：
在方法A中，卤代的金属化合物用四氢呋喃(“THF”)作为溶剂制备的，导致THF键合在最终的催化剂配位化合物中。具体地，Me Cl4 THT按Manzer L.，“Inorg，Synth”.，21，135-36(1982)的说明制备的。在以下的实施例中，Me为锆和铪，但也可以包括钛或其它过渡金属。
取代的环戊二烯基配位体可以采用已知技术中的各种方法根据具体的桥或环取代基选择制备。较佳的具体例子在以下的实施例中说明，该配位体是2，2-异丙基-(芴)环戊二烯。为了制备该配位体，在装备有侧管和滴液漏斗的圆底烧瓶中将44克(0.25摩尔)的芴溶解在350毫升THF中。该滴液漏斗中装有在1.4M乙醚中的0.25摩尔的甲基锂(CH3Li)，将CH3Li滴加入芴溶液并将深橙-红色溶液搅拌几个小时。气体挥发殆尽后，将溶液冷却至-78℃并在溶液中滴加入含有26.5克(0.25摩尔)的6，6-二甲基亚甲基环戊二烯的100毫升THF。将红色溶液逐步热至室温并搅拌过夜。该溶液用200毫升水处理并搅拌10分钟。该溶液的有机组份用每分100毫升的乙醚萃取几次，以及合并的有机相用硫酸镁干燥。从有机相除去醚，得到黄色固体将其溶解在500毫升氯仿中，并通过加入过量的甲醇于2℃进行重结晶得到白色粉末。
配位体的元素分析表明碳为化合物重量的91.8％以及氢为化合物重量的7.4％。相应于C21H2的重量百分数，碳为92.6％以及氢为7.4％。由配位体的NMR谱建立的结构包括一个环戊二烯基环通过异丙基桥连结经取代，以形成芴基基团的第二个环戊二烯基环。间规类催化剂配位化合物是用配位体和金属四氯化物-THF配位化合物合成的。该催化剂通过将在己烷(1.6M)中的0.05摩尔的N-.丁基锂滴加至含有6.8克(0.025摩尔)的上述Cp配位体的100毫升的THF溶液中。该溶液于35℃搅拌12小时，然后将含在200毫升THF中的9.4克(0.025摩尔)的Zr Cl4-2THF快速地在强烈搅拌下，加至在500毫升的圆底烧瓶中的配位体溶液中。该深橙-红色溶液在回流下搅拌12小时。LiCl和红色固体的混合物通过在真空下除去溶剂而分离。
按方法A产生的催化剂配位化合物说明，某些不纯物和过度的空气和潮气的敏感性。在以下实施例作为一种结果，方法A催化剂采用一种或多种以下纯化方法纯化。
1.用戊烷萃取：含在固体红色催化剂配位化合物中痕量黄色杂质用戊烷重复地萃取，直至戊烷成为无色。
2.组分的重结晶：该红色配位化合物通过溶解在100毫升的甲苯中，通过细孔烧结玻璃过滤与白色的LiCl分离，并加入戊烷形成饱和溶液，采用在-20℃结晶分离红色锆配位化合物。
3.在苯乙烯-二乙烯苯交联共聚物上层析：将50克苯乙烯-二乙烯苯交联共聚物SM-2(20-50目球形大网状的苯乙烯-二乙烯苯共聚物，购自BiO-Rad实验室)以30×1.5厘米的柱于70℃在真空下干燥48小时。然后该小球装入甲苯经几小时平衡，在甲苯中的红色催化剂配位化合物的浓溶液用150-200毫升甲苯从柱向下洗提，配位化合物通过在真空下蒸发甲苯回收
催化剂的合成工艺-方法B
作为一种变通的合成工艺，方法B提供的催化剂是更为空气稳定、更为活性并产生较高百分数间规聚丙烯的催化剂。在该方法中，二氯甲烷用作非一配位溶剂。该方法如以下说明的用过渡金属铪，但该工艺也可采用锆、钛或其它过渡金属。取代的环戊二烯基配位体以上述方法A中相同方法在THF中合成。该红色的配位体二锂盐(0.025摩尔)如在方法A中揭示的通过在真空下除去溶剂被分离并用戊烷洗涤。分离的红色二锂盐溶解在125毫升冷的二氯甲烷以及等当量(0.025摩尔)的Hf Cl4于-78℃在125毫升二氯甲烷中独立地调成淤浆。将Hf Cl4淤浆迅速地注入含有配位体溶液的烧瓶中。该混合物于-78℃搅拌2小时，让其缓慢热至25℃并搅拌附加的12小时。过滤除去不溶解的白色盐(LiCl)，过冷却该棕/黄色二氯甲烷溶液至-20℃12小时并除去上清液得到一种中等空气敏感的黄色粉末。亮黄色的产物在烧结玻璃过滤器上洗涤重复过滤去除冷的反复返回过滤器上的上清液。该催化剂配位化合物采用真空脱除溶剂被分离，并贮藏在干的脱氧的氩气中。该方法得到5.5克的催化剂配位化合物。
采用方法B制备的铪催化剂配位化合物的元素分析表明，该催化剂含有48.79％(重量)的碳、3.4％氢、15.14％氯以及33.2％铪。与C12H18Hf Cl2理论分析相比较的百分比为48.39％C、3.45％。H、13.59％Cl以及34.11％铪。同样，用方法B制备的锆催化剂的元素分析显示接近于期待值或理论值。进一步地，在以下的实施例中说明某些铪配位化合物采用96%纯度的Hf Cl4同时含约4％Zr Cl4的Hf Cl4制备的。还有以99.99纯度的Hf Cl4制备的其它催化剂试样。可以看到用纯的Hf催化剂和那些用含有少量百分量的锆产生的催化剂在聚合物分子量分布中的不同。混合的催化剂生产的聚合物比纯催化剂系统具有较宽的分子量分布。
以的实施例详细地说明本发明的聚合物的制备以及它们的各种优点。在表1中表示实施例1-17以及在表2中表示实施例18-33的聚合物的聚合工艺和分析的结果。
实施例1)
丙烯的聚合是用按上述方法A生产的0.16毫克异丙基(环戊二烯基)(芴)锆二氯化物进行的。该催化剂用分级重结晶法纯化。该催化剂与含有10.7％(重量)的具有平均分子量约为1300的甲基铝噁烷(MAO)的甲苯熔液预接触20分钟。该铝噁烷在聚合反应中起助催化剂作用。10毫升的MAO溶液用于聚合中。将催化剂和助催化剂溶液于室温加至密闭反应器(Zipperclave reactor)，接着添加1.2立升的液体丙烯。然后加热反应器的内容物至如在表1和表2中所示的聚合温度T于20℃少于约5分钟。在这期间，催化剂发生聚合。聚合反应让其进行60分钟，在这期间反应器保持聚合温度。聚合终了快速排出单体。用50％甲醇的稀盐酸溶液洗涤反应器中内容物并以真空干燥。聚合产出14克聚丙烯，为“聚合的”产率，即：没有进一步分离或提纯的。
聚合物的分析：
聚合物分析测定熔点Tm、结晶热Hc、分子量Mp、Mw和Mn、二甲苯中不溶物的X1百分数以及间规指数S.I.除了另有说明外，分析是在包括产生的间规部分和任何等规聚合物的在二甲苯中不溶部分的聚合物上进行的。通过在热的二甲苯中溶解，聚合产物除去无规聚合物，冷却溶液至0℃析出在二甲苯中不溶物。用该方法连续重结晶导致基本上从二甲苯不溶部分除去所有无规聚合物。
熔点Tm是采用已知技术差示扫描量热法(DSC)测定得出的数据。列于表1和表2的熔点，Tm1和Tm2并不是真实的平衡的熔点点，而是DCS峰值温度。在聚丙烯中，通常得到一较上的和较下的峰温度，即：两个峰，该两者熔点在表1和表2中以较低的熔点作为Tm1而较高的点为Tm2。真实的平衡的熔点要经几个小时以上才能得到，极大多数将比DSC较低峰熔点高几度。如在已知技术中，聚丙烯的熔点通过聚合物的二甲苯不溶部分的结晶度来测定。所表明的是通过DSC熔点操作之前和聚合物的二甲苯可溶物或无规形去除之后的真实熔点。其结果表明去除大部分无规聚合物后的熔点仅相差1-2℃。如在表1中表示的，在实施例1中生产的聚合物所测得的熔点为145℃和150℃。DSC数据也用于测定结晶热，如表1和表2所示，以J/g测定-HC。熔点和-HC是在无规聚合物去除前以“聚合的”试样测定的。
聚合物的分子量的计算采用凝胶渗透色谱法(GPC)分析，在带有Jordi凝胶柱和超高分子量混合床的Waters 150C型仪器上完成的，该溶剂为三氯苯以及操作温度为140℃。由GPC得出有关所得聚合物的二甲苯不溶部分的峰分子量Mp、数均分子量Mn以及重均分子量Mw。分子量分布MWD通常由Mw除以Mn测定。在表1中表示试样测定的值。GPC分析也用于测定间规指数S.I.％，表示在表1和表2中，间规指数是在聚合反应中产生的间规结构的百分数的测量并从“作为聚合的”试样的分子量数据测定的。
NMR分析用于聚合物的显微结构的测定。上述产生的聚合物试样被溶解在20％的1，2，4-三氯化苯/6b-苯中，并在Bruke AMWB300型波谱仪用负门广谱去耦方法测定。实验条件为：发射频率为75.47MHz；去耦频率为300.3MHz；脉冲重复时间为12秒；捕获时间为1.38秒；脉冲角为90°(11.5微秒脉冲宽度)；存储规模为74k点；频谱为12195HZ累积由7千个瞬变值以及探针温度置于133℃。在图2中显示产生的聚合物并在二甲苯中重结晶一次的NMR谱图。在表3中该计算的和观察的谱值表示实施例1的试样在二甲苯中重结晶一次的和实施例1-A的试样在二甲苯中重结晶三次的相应的数据，计算值采用Inone等的Polymer，Vol25，p-1640(1984)中的Bernoullian概率方程以及已知技术中导出。
在二甲苯中重结晶一次的样品其结果显示外消旋二价基(r)的百分数为95％，在二甲苯中重结晶三次，r二价基的百分数为98％(表明聚合物含有2％或少于2％的内消旋(m)二价基)。进一步地，NMR谱图显示内消旋二价基主要地以成对存在，即：mm三价基，与先前所知的在链中单一m二价基结构相反。这样，本发明的催化剂制得一种聚合物，该聚合物具有一种新型的显微结构。
实施例2
除了用500毫升甲苯用作聚合反应中的助溶剂外重复实施例1的过程。另外，在聚合中用1克MAO以及反应温度为50℃。得到15克油状的聚合物产物。该聚合物按上述给出的方法分析以及其结果示于表1中。
实施例3
除了铪作为过渡金属用于催化剂外重复实施例2的过程。其它反应条件示于表1中，以及产生的聚合物的分析的成分同时示于表1中。
图4和图5表示分别由实施例7和8产生的聚合物的IR谱图。间规聚丙烯的特征波带为977和962cm-1是显而易见的。这些波的存在再次证实聚合物的间规结构。相应的等规聚丙烯的波带分别为995和974cm-1。
实施例4至8
除了示于表1中的不同反应条件外，重复实施例1的过程。另外，实施例4用色谱法作为纯化方法而实施例5不采用纯化过程。聚合结果和聚合物的分析示于表1中。
图3和图4分别表示实施例7和8产生的重结晶三次的聚合物的IR谱图。
实施例9至16
除了示于表1中的催化剂和助催化剂量的变化外重复实施例1的过程。另外，在实施例9-13和15中的催化剂采用戊烷萃取和分级重结晶纯化。实施例14用戊烷萃取和色谱纯化方法。实施例16不用任何纯化方法。
实施例17
除了铪作为过渡金属用于催化剂外重复实施例1的过程。其它反应条件示于表1。该催化剂用戊烷萃取和分级重结晶方法纯化。聚合的结果示于表1。
实施例18和19
用上述方法B并用含约4％Zr Cl4的95％纯度的Hf Cl4合成的铪金属茂催化剂。该聚合采用示于表2的条件以实施例1的聚合方法进行。该聚合物按在实施例1所述的方法分析，其结果示于表2。
实施例20-31
锆金属茂催化剂用方法B的合成方法制备，以及丙烯的聚合以表2中每一实施例的条件进行。聚合产物按实施例1的方法进行分析，以及其结果示于表2。需注意实施例20-22的间规指数：S.I.是测定二甲苯不溶级分得到。这些级分的间规指数几乎为100％。实施例20和22的观察的(obsd.)NM R谱数据示于表4中。该数据在实施例20和22中分别产生的聚合物并从二甲苯中为重结晶一次的实施例20和22给出的数据。实施例22-A为实施例22在二甲苯中重结晶三次的聚合物。
实施例32-33
铪金属茂催化剂用方法B的合成方法制备。实施例32的催化剂用99％纯度的Hf Cl4制备而在实施例33中的催化剂用含有约4％Zr CCl4的95％纯度的Hf Cl4制备。聚合按实施例1的方法在表2中实施例32和33所示的条件下进行。在这些实施例中所制得的聚合物的分析法果也列示在表2中。实施例33的NMR数据示于表4中(实施例33，样品从二甲苯中重结晶一次)以及(实施例33A，样品从二甲苯中重结晶三次)。
示于表1-4中的数据以及在图2和图3中所示的本发明的聚合物主要为具有高结晶性和新型显微结构的间规聚丙烯。尤其是在表3和4中所示的NMR数据证实即使带有很少产生的等规聚合物，在二甲苯不溶部分含有非常高百分数的间规聚合物。另外，间规聚合物含有高百分数的“r”基团和“rrrr”五价基，它说明仅有少量百分数从聚合物链中的“rrrr”结构偏离，该偏离主要地以“mm”类型存在。事实上，在表3中实施例1-A所示的结果，偏离在链中仅为“mm”类型。其它的NMR试样显示“mm”偏离与“m”偏离相比占主要地位。于是，业已发现一种新型显微结构的间规聚丙烯。
在表1和表2中的数据表明聚合产物的高的结晶性，相对高的熔点、TM和TM以及相对高的结晶热、-Hc说明聚合物为高度结晶的。该数据进一步说明在聚合反应温度T和熔点、分子量以及聚合物结晶热之间的相关性。当反应温度增加时，所有这三个性能均相应降低。同时看出聚合物得率最多的温度范围内。该温度范围随所用的催化剂类型不同而不同但典型地为50-70℃。甲基铝噁烷(MAO)的浓度也显示影响聚合物的收率。数据表明MAO的浓度越高，聚合物的收率越高。同时看到MAO的浓度对无规聚合物产生的数量有某些影响。MAO显示出类似净化剂对杂质的纯化作用，并有助于降低所得的无规聚合物的数量。该数据进一步表明在本发明的锆催化剂和铪催化剂之间的不同。用铪催化剂产生的聚合物比锆催化剂产生的聚合物趋向于有较少的结晶度和具有较低的熔点。在表4中的数据同时表明铪催化剂在聚合物链中产生较高百分数的等规嵌段，如用存在的等规五价基mmmm所反映的那样。
实施例18、19和33说明通过使用本发明所述的催化剂的混合物，能获得较宽分子量分布MWD＝Mw/Mn。在这些实施例中的催化剂是用含有约4％Zr Cl4的Hf Cl4制备的。在这些实施例中聚合物的MWD显著地高于基本上用纯的锆催化剂生产的聚合物的MWD(参见实施例32)。于是，可用两种不同催化剂的混合物生产具有宽的分子量分布的聚合物。
列举的实施例仅为了进一步理解本发明的间规类催化剂，而不是限定它的具体结构，而通过给出的结构式来描述催化剂，在结构式中一个Cp环是一个以立体的不同方式取代的。在上述实施例中，该环包括一个非取代的Cp环和一个形成基和取代的Cp环，但是通过使用含有桥接的Cp环的其它的配位体能获得类似的结果，其中所述的桥接的Cp环是一个以基本上不同的方式从另一个Cp环上取代的Cp环，即茚基和Cp环，四甲基取代的Cp环和Cp环，一个二烷基取代的Cp环和一个单烷基取代的Cp环等等。
从本发明的详细阐述，恰好给出本发明提供的一种催化剂和制备间规聚丙烯的方法，这是明显的。由于本发明的详细说明，而不是几个例子，在本技术领域的技术人员在不脱离本发明的范围对催化剂和方法作出各种改进将是显而易见的。
                                     表1  方法A
            催化剂     MAO           得量                   -Hc实施例   金属    (mg)     (∝)    T℃    (g)     Tm1℃   Tr2℃  J/g   Mp/1000  Mw/Mn    间规率％1         Zr    10.0     10.0     20     14      145     150    43    119       2.5      622         Zr    10.3     1g       50     26      129     137    45    57        1.9      633         Hf    10.3     1g       50     12              104    17   1222                464         Zr    5.0      10.0     50     130     132     138    37    61                 875         Zr    5.1      10.0     50     83      131     138    35    62                 846         Zr    5.0      0.3g     70     22      115     127    34    71                 837         Zr    5.1      5.0      50     63      131     140    37    60                 388         Zr    5.1      10.0     50     110     132     140    38    60                 429         Zr    5.1      1.0      50     14      114     125    21    53                 2410        Zr    5.0      2.5      50     34      111     122    14    60                 23
      Zr    5.1      5.0      50     63      119     130    21    60                 3812        Zr    5.0      10.0     50     73      125     137    32    64                 6513        Zr    5.0      1.0      50     83      121     132    22    59                 4214        Zr    2.6      10.0     50     85      134     140    40    62                 8915        Zr    5.1      10.0     50     110     125     134    29    60                 4216        Zr    5.1      10.0     50     115     131     133    38    62                 8417        Hf    13.3     1g       60     55      63      108          223                52
                                        表2  方法B
             催化剂        MAO            得量                     -Hc实施例    金属    (mg)        (∝)    T℃     (g)     Tm1℃    Tm2℃    J/g    Mw/1000    Mw/Mn    间规率％18        Hf     10.0         10      50       58     115      125      24      644       5.419        Hf     5.0          10      50       60     117      124      24      774       4.820        Zr     0.6          10      50       162    134      140      40      69        1.8         9321        Zr     1.5          10      29       49     142      146      45      106       1.9         9522        Zr     0.6          10      70       119             134      39      54        2.0         9523        Zr     0.2          10      50       27     135      140      39      69        1.924        Zr     0.6          10      50       162    134      140      40      69        1.825        Zr     0.6          10      25       26              145      44      133       1.926        Zr     0.6          10      70       119             134      39      54        2.027        Zr     1.5          10      29       49     143      145      45      105       1.928        Zr     2.5          10      50       141    135      141      40      70        1.929        Zr     5.0          10      23       152    123      137      43      88        2.130        Zr     0.5          10      60       165    123      137      37      52        1.831        Zr     0.5          5       70       153    120      134      36      55        2.432        Hf     2.5          10      70       95     103               19      474       2.633        Hf     10.0         10      50       27     114               25      777       5.3
                     表3
               实施例1     实施例1A
          测量的％    计算的％    测量的％   计算的％％              95          95         98          98mm              0.3         0.2        0           0mmmr            0.3         0.6        0           0rmmr            1.5         1.4        1.3         1.0mmrr            2.4         2.9        1.9         2.1rrmr+mmrm            1.5         1.6        0           0mrmr            1.6         0.8        0           0rrrr            88.0        89.1       94.7        94.7mrrr            3.9         3.1        2.2         2.1mrrm            0.4         0.4        0           0O3V.                        0.2                    0.1
                                表4
     实施例20    实施例22    实施例22-A    实施例33   实施例33-A
     测量的％    测量的％     测量的％     测量的％    测量的％mmmm       0          0.77         0.51         2.34        2.04mmmr       0.23       0.45         0.31         0.73        0.76rmmr       1.67       1.82         1.81         2.72        2.96mmrr       3.58       4.25         4.06         5.72        6.44mrmm+rmrr       2.27       3.23         3.57         2.87        3.12mrmr       1.51       2.06         1.70         1.37        1.53rrrr       82.71      77.58        78.12        75.7        74.55mrrr       6.45       7.75         9.02         7.4         8.01mrrm       0.68       0.73         0.93         1.08        0.55

Claims (9)

1.一种用于制备间规聚烯烃的金属茂催化剂，所述的催化剂由下式表述：R″(CpRn)(CpR′m)MeQk，其特征在于式中每一个Cp为环戊二烯基或取代的环戊二烯基环；每一个R为相同或不同的并为具有1-20个碳原子的烃基；每一个R′为相同或不同的并为具有1-20个碳原子的烃基；R″为二个Cp环之间的赋于催化剂中Cp环立体刚性的结构桥；Me为元素周期表中IVB、VB、VIB族的金属；每一Q为具有1-20个碳原子的烷基或为卤素；0≤k≤3；0≤n≤4；1≤m≤4；以及式中R′选自(CpR′m)为空间上不同于(CpRn)的环，以及该催化剂进一步包括一种助催化剂。
2.如权利要求1所述的催化剂，其特征在于所述的催化剂是异丙基(环戊二烯基)(芴基)锆二氯化物。
3.如权利要求1所述的催化剂，其特征在于式中Me为钛、锆或铪。
4.如权利要求1所述的催化剂，其特征在于R″选自包括具有1-4个碳原子的烷基、硅烷基、锗烷基、磷烷基、氮烷基、硼烷基以及铝烷基的组。
5.如权利要求1所述的催化剂，其特征在于所述的催化剂是异丙基(环戊二烯基)(芴基)铪二氯化物。
6.如权利要求1所述的催化剂，其特征在于进一步包括一种助催化剂选自铝噁烷、烷基铝及其混合物的组的铝化合物。
7.如权利要求6所述的催化剂，其特征在于包括金属茂催化剂和铝噁烷的配位化合物。
8.一种制备桥接的金属茂催化剂的方法，其特征包括：
(a)在反应条件下使环戊二烯或取代的环戊二烯与亚甲基环戊二烯或取代的亚甲基环戊二烯充分接触以制备桥接的二环戊二烯或取代的二环戊二烯；
(b)在反应条件下使该桥接的二环戊二烯或取代的二环戊二烯与式子为MeQk的金属化合物充分接触使二环戊二烯或取代的二环戊二烯与金属化合物络合制得一桥接的金属茂，其中Me为元素周期表中IVB、VB或VIB族的金属；每一个Q为具有1-20个碳原子的烃基或为卤素以及0≤k≤3。
9.如权利要求8所述的方法，其特征在于步骤(b)的接触在一种非配位的溶剂中完成。
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CZ365589A3 (en) 1997-12-17
NO892330D0 (no) 1989-06-07
EP0351392A3 (en) 1993-11-18
FI97894C (fi) 1997-03-10
EP0351392A2 (en) 1990-01-17
US5334677A (en) 1994-08-02
DD300545A5 (de) 1992-06-17
KR0145313B1 (ko) 1998-07-15
JP2851867B2 (ja) 1999-01-27
EP0351392B2 (en) 2005-03-02
ES2157194T3 (es) 2001-08-16
NO172588B (no) 1993-05-03
NO892330L (no) 1990-01-16
FI893140A0 (fi) 1989-06-28
ES2157194T5 (es) 2005-07-16
ATE200902T1 (de) 2001-05-15
AU3660589A (en) 1990-01-18
US4892851A (en) 1990-01-09
DE68929293T3 (de) 2005-11-17
RU2077541C1 (ru) 1997-04-20
KR900001728A (ko) 1990-02-27
AU610731B2 (en) 1991-05-23
FI97894B (fi) 1996-11-29
DD290200A5 (de) 1991-05-23
DE68929293T2 (de) 2001-09-20
EP0351392B1 (en) 2001-05-02
DE68929293D1 (de) 2001-06-07
NO172588C (no) 1993-08-11
SK280700B6 (sk) 2000-06-12
CN1040036A (zh) 1990-02-28
CA1338600C (en) 1996-09-17
JPH0241303A (ja) 1990-02-09
SK365589A3 (en) 2000-06-12
FI893140A (fi) 1990-01-16
RU2017519C1 (ru) 1994-08-15
CZ283418B6 (cs) 1998-04-15

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