CN100371351C - 有机金属催化剂组合物 - Google Patents
有机金属催化剂组合物 Download PDFInfo
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- CN100371351C CN100371351C CNB008135924A CN00813592A CN100371351C CN 100371351 C CN100371351 C CN 100371351C CN B008135924 A CNB008135924 A CN B008135924A CN 00813592 A CN00813592 A CN 00813592A CN 100371351 C CN100371351 C CN 100371351C
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Abstract
本发明提供适用于聚合至少一种单体生产聚合物的催化剂组合物。本发明还提供适用于聚合至少一种单体生产聚合物的催化剂组合物，其中所述催化剂组合物包含接触后的有机金属化合物、接触后的有机铝化合物、和接触后的氟化固体氧化物复合物。
Description
发明领域
本发明涉及有机金属催化剂组合物领域。
发明背景
本文中“基本上由…组成”意指此短语之后的工艺步骤、物质或物质的混合物不包括对所述工艺的功能或通过所述工艺生产的或此短语后所述物质或物质组合的性能有重大影响的任何其它步骤或组分。
聚合物的生产是数十亿美元的行业。此行业每年生产几十亿磅聚合物。在开发可使该行业增值的技术方面已花费数百万美元。
这些技术之一称为金属茂催化剂技术。自从约1960年就已经知道金属茂催化剂。然而，它们的低产率使之未能商业化。约在1975年发现一份水与两份三甲基铝接触生成甲基铝氧烷，然后使这种甲基铝氧烷与金属茂化合物接触，形成活性更高的金属茂催化剂。然而，不久就认识到形成活性金属茂催化剂需要大量昂贵的甲基铝氧烷。这已成为金属茂催化剂商业化的重大障碍。
已用硼酸盐化合物代替大量的甲基铝氧烷。但这也不令人满意，因为硼酸盐化合物非常容易中毒和分解，而且也很贵。
还应注意到多相催化剂很重要。这是因为大多数现代工业聚合过程都需要多相催化剂。此外，多相催化剂可导致形成堆积密度高的基本上均匀的聚合物粒子。这些类型的基本上均匀的粒子是理想的，因为它们改善聚合物生产和运输的效率。为生产多相金属茂催化剂已付出很多努力；但这些催化剂尚不完全令人满意。
因此，聚合物工业仍需要提供使金属茂催化剂活化的经济材料，还需要有效的多相金属茂催化剂。本发明人提供本发明帮助解决这些问题。
发明概述
希望提供一种可用于聚合至少一种单体以生产聚合物的催化剂组合物的生产方法。
还希望提供所述催化剂组合物。
还希望提供一种方法，包括使至少一种单体与所述催化剂组合物在聚合条件下接触生产所述聚合物。
还希望提供包含用本发明催化剂组合物生产的聚合物的制品。
根据本发明一实施方案，提供一种催化剂组合物的生产方法。所述方法包括(或可选地“基本上由以下步骤组成”、或“由以下步骤组成”)：使有机金属化合物、有机铝化合物、和氟化的固体氧化物复合物接触；
其中所述有机金属化合物有以下通式：
(X1)(X2)(X3)(X4)M1
其中M1选自钛、锆、和铪；
(X1)独立地选自环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基、和取代的芴基；
其中(X1)的取代的环戊二烯基、取代的茚基和取代的芴基上的取代基选自脂族基、环状基团、脂族和环状基团的组合、甲硅烷基、卤代烷基、卤离子、有机金属基、磷基、氮基、硅、磷、硼、锗、和氢；
(X1)上至少一个取代基可以是连接(X1)和(X2)的桥连基；
(X3)和(X4)独立地选自卤离子、脂族基、取代的脂族基、环状基团、取代的环状基团、脂族基和环状基团的组合、取代的脂族基和环状基团的组合、脂族基和取代的环状基团的组合、取代的脂族基和取代的环状基团的组合、氨基、取代的氨基、膦基、取代的膦基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基、和取代的有机金属基；
(X2)选自环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基、取代的芴基、卤离子、脂族基、取代的脂族基、环状基团、取代的环状基团、脂族基和环状基团的组合、取代的脂族基和环状基团的组合、脂族基和取代的环状基团的组合、取代的脂族基和取代的环状基团的组合、氨基、取代的氨基、膦基、取代的膦基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基、和取代的有机金属基；
(X2)上的取代基选自脂族基团、环状基团、脂族和环状基团的组合、甲硅烷基、卤代烷基、卤离子、有机金属基、磷基、氮基、硅、磷、硼、锗、和氢；
(X2)上至少一个取代基可以是连接(X1)和(X2)的桥连基；
所述有机铝化合物有以下通式：
Al(X5)n(X6)3-n
其中(X5)为有1至约20个碳原子的烃基；
(X6)为卤离子、氢负离子、或醇根；和
“n”为1至3的数(包括端值)；
所述氟化固体氧化物复合物包含氟化物和固体氧化物复合物；
其中所述固体氧化物复合物选自氧化硅-氧化钛和氧化硅-氧化锆。
根据本发明另一实施方案，提供一种方法，包括使至少一种单体和所述催化剂组合物在聚合条件下接触生产聚合物。
根据本发明另一实施方案，提供一种制品。所述制品包含按本发明生产的聚合物。
阅读本文后，这些目的和其它目的对于本领域普通技术人员将更显而易见。
发明详述
本发明所用有机金属化合物有以下通式：
(X1)(X2)(X3)(X4)M1
式中，M1选自钛、锆、和铪。目前，最优选M1为锆。
式中，(X1)独立地选自(以下称为“OMC-I组”)环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基例如四氢茚基、和取代的芴基例如八氢芴基。
(X1)的取代的环戊二烯基、取代的茚基和取代的芴基上的取代基可选自脂族基、环状基团、脂族和环状基团的组合、甲硅烷基、卤代烷基、卤离子、有机金属基、磷基、氮基、硅、磷、硼、锗、和氢，只要这些基团对所述催化剂组合物的聚合活性无显著的不利影响。
适用的脂族基的例子是烃基，例如链烷烃和烯烃。适用的环状基团的例子是环烷烃、环烯烃、环炔烃、和芳烃。取代的甲硅烷基包括但不限于烷基甲硅烷基(其中每个烷基含1至约12个碳原子)、芳基甲硅烷基、和芳基烷基甲硅烷基。适用的卤代烷基有1至约12个碳原子的烷基。适用的有机金属基包括但不限于取代的甲硅烷基衍生物、取代的锡基、取代的锗基、和取代的硼基。
适用的此取代基的例子是甲基、乙基、丙基、丁基、叔丁基、异丁基、戊基、异戊基、己基、环己基、庚基、辛基、壬基、癸基、十二烷基、2-乙基己基、戊烯基、丁烯基、苯基、氯基、溴基、碘基、三甲基甲硅烷基、和苯基辛基甲硅烷基。
式中，(X3)和(X4)独立地选自(以下称为“OMC-II组”)卤离子、脂族基、取代的脂族基、环状基团、取代的环状基团、脂族基和环状基团的组合、取代的脂族基和环状基团的组合、脂族基和取代的环状基团的组合、取代的脂族基和取代的环状基团的组合、氨基、取代的氨基、膦基、取代的膦基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基、和取代的有机金属基，只要这些基团对催化剂组合物的聚合活性无显著的不利影响。
适用的脂族基的例子是烃基，例如链烷烃和烯烃。适用的环状基团的例子是环烷烃、环烯烃、环炔烃、和芳烃。目前，优选(X3)和(X4)选自卤离子和有1至约10个碳原子的烃基。但最优选(X3)和(X4)选自氟、氯和甲基。
式中，(X2)可选自OMC-I组或OMC-II组。
(X1)或(X2)上至少一个取代基可以是连接(X1)和(X2)的桥连基，只要所述桥连基对催化剂组合物的活性无显著的不利影响。适用的桥连基包括但不限于脂族基、环状基团、脂族基和环状基团的组合、磷基、氮基、有机金属基、硅、磷、硼、和锗。
适用的脂族基的例子是烃基，例如链烷烃和烯烃。适用的环状基团的例子是环烷烃、环烯烃、环炔烃、和芳烃。适用的有机金属基包括但不限于取代的甲硅烷基衍生物、取代的锡基、取代的锗基、和取代的硼基。
已知许多制备这些有机金属化合物的方法。参见例如US4939217；5210352；5436305；5401817；5631335；5571880；5191132；5480848；5399636；5565592；5347026；5594078；5498581；5496781；5563284；5554795；5420320；545l649；5541272；5705478；5631203；5654454；5705579；和5668230；其内容引入本文供参考。
这种有机金属化合物的具体实例如下：
二氯·二(环戊二烯基)合铪；
二氯·二(环戊二烯基)合锆；
二正丁氧基·1，2-亚乙基-二(η5-1-茚基)合铪；
二甲基·1，2-亚乙基-二(η5-1-茚基)合锆；
二氯·3，3-亚戊基-二(η5-4，5，6，7-四氢-1-茚基)合铪；
二氯·甲基苯基甲硅烷基-二(η5-4，5，6，7-四氢-1-茚基)合锆；
二(二叔丁氨基)·二(正丁基环戊二烯基)合铪；
二氯·二(正丁基环戊二烯基)合锆；
二氯·二甲基甲硅烷基-二(1-茚基)合锆；
二氯·辛基苯基甲硅烷基-二(1-茚基)·合铪；
二氯·二甲基甲硅烷基-二(η5-4，5，6，7-四氢-1-茚基)合锆；
二氯·二甲基甲硅烷基-二(2-甲基-1-茚基)合锆；
二氯·1，2-亚乙基-二(9-芴基)合锆；
一氯·二乙氧基·茚基合钛(IV)；
二氯·(异丙氨基二甲基甲硅烷基)环戊二烯基合钛；
二氯·二(五甲基环戊二烯基)合锆；
二氯·二(茚基)合锆；
二氯·甲基辛基甲硅烷基-二(9-芴基)合锆；
和
一氢·三氟甲磺酸根·二-[1-(N，N-二异丙氨基)硼杂苯]合锆。
优选所述有机金属化合物选自：
二氧·二(正丁基环戊二烯基)合锆；
二氯·二(茚基)合锆；
二氯·二甲基甲硅烷基-二(1-茚基)合锆；
二氯·甲基辛基甲硅烷基-二(9-芴基)合锆。
有机铝化合物有以下通式：
Al(X5)n(X6)3-n
该式中，(X5)为有1至约20个碳原子的烃基。目前，优选(X5)为有1至10个碳原子的烷基。但最优选(X5)选自甲基、乙基、丙基、丁基和异丁基。
该式中，(X6)为卤离子、氢负离子、或醇根。目前，优选(X6)独立地选自氟和氯。但最优选(X6)为氯。
该式中，“n”为1至3的数(包括端值)。但优选“n”为3。
这种化合物的例子如下：
三甲基铝；
三乙基铝(TEA)；
三丙基铝；
乙醇二乙基铝；
三丁基铝；
氢化三异丁基铝；
三异丁基铝；
氢化二异丁基铝；和
氯化二乙基铝。
目前优选TEA。
所述氟化固体氧化物复合物包含氟化物和固体氧化物复合物。所述固体氧化物复合物选自氧化硅-氧化钛和氧化硅-氧化锆。氧化硅是所述固体氧化物复合物的主要组分。
所述氧化硅-氧化钛的氧化钛含量一般在约0.5至约30％(重)钛的范围内，优选约2.5至约15％(重)钛，最优选4至10％(重)钛。
所述氧化硅-氧化锆的氧化锆含量一般在约1至约40％(重)锆的范围内，优选约5至约30％(重)锆，最优选8至20％(重)锆。
所述固体氧化物复合物的孔体积应大于约0.5cc/g.，优选大于约0.8cc/g，最优选大于1cc/g。
所述固体氧化物复合物的表面积应为约100至约1000m2/g，优选约200至约800m2/g，最优选200至800m2/g。
所述固体氧化物复合物可通过本领域已知的任何方法制备。第一种方法是通过含水材料的共凝胶制备所述固体氧化物复合物，如US3887494；3119569；4405501；4436882；4436883；4392990；4081470；4981831；和4152503中所述，其内容引入本文供参考。该方法中，使钛或锆盐如硫酸氧钛溶于酸如硫酸中，加入硅酸钠直至在中性pH下发生胶凝作用。在约pH 7至10和约60至约90℃下老化几小时，然后清洗和干燥。可通过本领域已知的任何手段如共沸蒸馏、喷雾干燥、急骤干燥、真空干燥等完成干燥。
第二种方法是通过在有机或无水溶液中共凝胶制备所述固体氧化物复合物，以US4301034；4547557；和4339559为代表，其内容引入本文供参考。这些技术中，使有机硅酸酯例如原硅酸四乙酯和有机钛酸酯或有机锆酸酯例如四异丙氧基钛或锆溶于有机溶液例如醇中，将少量的水与酸或碱一起加入其中使所述固体氧化物复合物水解和胶凝。可改变这些成分的添加次序，每种成分的添加过程可分步进行以获得特殊性质。老化和干燥通常产生高孔隙率的固体氧化物复合物。
第三种方法是用氧化钛或氧化锆层涂布氧化硅表面制备所述固体氧化物复合物，以US4424320；4405768；4402864；4382022；4368303；和4294724为例，其内容引入本文供参考。可采用本领域已知的任何技术。一种特别常用的方法是用烷氧基钛或锆(例如异丙氧基钛)或卤化钛或锆(例如四氯化钛)的有机溶液处理氧化硅，所述氧化硅已在约200℃下干燥除去吸附水。然后干燥和在空气中高温焙烧使所述钛或锆转化成氧化钛或氧化锆，基本保持分散。如果使所述钛或锆化合物汽化至气流中，然后使之与氧化硅接触，此反应也可在气相中进行。
本领域已知的用含氟化合物使所述固体氧化物复合物氟化的任何方法都可用于本发明。一种常用方法是用含氟盐如氟化铵(NH4F)、氟化氢铵(NH4HF2)、氢氟酸(HF)、氟硅酸铵((NH4)2SiF6)、氟硼酸铵(NH4BF4)、氟磷酸铵(NH4PF6)、氟硼酸(HBF4)及其混合物的水溶液浸渍所述固体氧化物复合物。或者，可使所述含氟化合物溶于有机溶剂如醇，用于浸渍所述固体氧化物复合物以减少干燥过程中孔的收缩至最低。干燥可通过本领域已知的任何方法如真空干燥、喷雾干燥、急骤干燥等方法进行。
也可通过将含氟化合物加至胶凝之前的含水材料之一中使含氟化合物掺入凝胶中。这些含水材料公开在前面所述制备固体氧化物复合物的第一和第二种方法中。
也可在干燥之前将所述含氟化合物加至含凝胶的浆液中。凝胶的形成公开在前面所述制备固体氧化物复合物的第一和第二种方法中。
也可在焙烧的过程中加入所述含氟化合物。此技术中，使所述含氟化合物汽化进入用于使所述固体氧化物复合物流化的气流中以使所述固体氧化物复合物被所述气流氟化。除上述一些含氟化合物之外，挥发性有机氟化物也可在高于其分解温度的温度下或在足以导致反应的温度下使用。例如，可在空气或氮气中在约300至约600℃下使全氟己烷、全氟苯、三氟乙酸、三氟乙酸酐、六氟乙酰丙酮化物等汽化并与所述固体氧化物复合物接触。也可使用含无机氟化物的蒸气，例如氟化氢或元素氟气体。
还可在氟化之前在约100至约900℃范围内的温度下焙烧所述固体氧化物复合物。
焙烧之前氟化物的存在量基于焙烧之前所述氟化固体氧化物复合物的重量为约2至约50％(重)氟化物。优选为约3至约25％(重)，最优选4至20％(重)氟化物，基于焙烧之前所述氟化固体氧化物复合物的重量。
焙烧所述氟化固体氧化物复合物很重要。一般地，此焙烧在约200至约900℃范围内的温度下进行，时间在约1分钟至约100小时的范围内。优选在约300至约700℃的温度下焙烧所述氟化固体氧化物复合物，时间在约1至约50小时的范围内；最优选在350至600℃的温度下焙烧，时间在3至20小时的范围内。
焙烧可在任何适合的气氛中完成。一般地，所述焙烧在惰性气氛中完成。所述焙烧也可在氧化气氛(如氧气或空气)或还原气氛(如氢气或一氧化碳)中完成。焙烧还可分段进行，例如在较低温度下在气相中进行氟化，然后在较高温度下焙烧。或者可先在氧化气氛中进行焙烧，然后在不同温度下在还原气氛中进行焙烧，反之亦然。
可选地，在所述焙烧处理之中或之后可包含少量氯化物以在某些情况下获得更高的活性，或增强所述钛或锆的作用。
本发明催化剂组合物可通过所述有机金属化合物、所述有机铝化合物、和所述氟化固体氧化物复合物一起接触制备。此接触可以多种方式进行，例如共混。此外，这些化合物可分开地供入反应器中，或者在所述反应器中进一步接触之前使这些化合物的各种组合先接触，或者可在加入所述反应器之前使所有三种化合物先接触。
目前，一种方法是先使所述有机金属化合物与所述氟化固体氧化物复合物在约10至约200℃(优选15至80℃)的温度下接触约1分钟至约24小时(优选1分钟至1小时)形成第一混合物，然后使此第一混合物与有机铝化合物接触形成所述催化剂组合物。
另一种方法是在注入聚合反应器之前使所述有机金属化合物、所述有机铝化合物、和所述氟化固体氧化物复合物在约10至约200℃(优选20至80℃)的温度下预接触约1分钟至约24小时(优选1分钟至1小时)。
所述催化剂组合物中有机铝化合物与所述氟化固体氧化物复合物之重量比在约5∶1至约1∶1000的范围内，优选约3∶1至约1∶100，最优选1∶1至1∶50。
所述催化剂组合物中所述氟化固体氧化物复合物与所述有机金属化合物之重量比在约10000∶1至约1∶1的范围内，优选约1000∶1至约10∶1，最优选250∶1至20∶1。所述比例是基于化合产生所述催化剂组合物的组分量计。
接触之后，所述催化剂组合物包含接触后的有机金属化合物、接触后的有机铝化合物、和接触后的氟化固体氧化物复合物。应注意所述接触后的氟化固体氧化物复合物占所述催化剂组合物的大多数(重量)。通常不知道催化剂的确切组分，因而本发明将所述催化剂组合物描述为包含接触后的化合物。
所述催化剂组合物中所述接触后的有机铝化合物与所述接触后的氟化固体氧化物复合物之重量比在约5∶1至约1∶1000的范围内，优选约3∶1至约1∶100，最优选1∶1至1∶50。
所述催化剂组合物中所述接触后的氟化固体氧化物复合物与所述接触后的有机金属化合物之重量比在约10000∶1至约1∶1的范围内，优选约1000∶1至约10∶1，最优选250∶1至20∶1。
本发明催化剂组合物的活性高于如对比实施例4和5所示使用相同有机金属化合物和相同有机铝化合物但使用用氟化物浸渍的氧化硅或氧化钛的催化剂组合物。此活性是在淤浆聚合条件下、用异丁烷作稀释剂、在约50至约150℃的聚合温度和约400至约800psig的乙烯压力下测量的。所述反应器基本上没有任何壁垢、涂层或其它形式污垢的明显迹象。
但优选所述活性大于约1000g聚合物/g氟化固体氧化物复合物/hr，更优选大于2000，最优选大于2500。此活性是在淤浆聚合条件下、用异丁烷作稀释剂、在90℃的聚合温度和550psig的乙烯压力下测量的。所述反应器基本上没有任何壁垢、涂层或其它形式污垢的明显迹象。
本发明的重要方面之一是形成所述催化剂组合物不必使用铝烷氧。铝氧烷是很昂贵的化合物，极大地增加聚合物的生产成本。这还意味着不需要水帮助形成此铝氧烷。这是有益的，因为水有时可能破坏聚合过程。此外，还应注意到形成所述催化剂组合物不需硼酸盐化合物。总之，这意味着可容易且以低成本生产可用于聚合单体或单体与一或多种共聚单体的多相的催化剂组合物，因为不存在任何铝氧烷化合物或硼酸盐化合物。此外，本发明中既不必加入有机铬化合物，也不必加入任何MgCl2。虽然所述优选实施方案中不需铝氧烷、硼酸盐化合物、有机铬化合物或MgCl2，但这些化合物可用于本发明的其它实施方案中。
本发明另一实施方案中，提供一种方法，包括使至少一种单体与所述催化剂组合物接触生产至少一种聚合物。本文所用术语聚合物”包括均聚物和共聚物。所述催化剂组合物可用于聚合至少一种单体生产均聚物或共聚物。均聚物通常由每分子有2至约20个碳原子、优选每分子有2至约10个碳原子的单体残余组成。目前，优选至少一种单体选自乙烯、丙烯、1-丁烯、3-甲基-1-丁烯、1-戊烯、3-甲基-1-戊烯、4-甲基-1-戊烯、1-己烯、3-乙基-1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、及其混合物。
想要均聚物时，最优选聚合乙烯或丙烯。想要共聚物时，所述共聚物包含单体残余和一或多种共聚单体残余，每分子有约2至约20个碳原子。适用的共聚单体包括但不限于每分子有3至20个碳原子的脂族1-烯烃，例如丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-辛烯和其它烯烃，及共轭或非共轭的二烯烃如1，3-丁二烯、异戊二烯、戊间二烯、2，3-二甲基-1，3-丁二烯、1，4-戊二烯、1，7-己二烯、和其它二烯烃及其混合物。想要共聚物时，优选聚合乙烯和至少一种选自1-丁烯、1-戊烯、1-己烯、1-辛烯和1-癸烯的共聚单体。引入反应区生产共聚物的共聚单体量基于所述单体和共聚单体的总重一般为约0.01至约10％(重)，优选约0.01至约5％(重)，最优选0.1至4％(重)。或者可使用足以在所产生的共聚物中获得上述浓度(重量)的量。
可使至少一种单体聚合产生聚合物的方法为本领域已知，例如淤浆聚合、气相聚合、和溶液聚合。优选在回路反应区进行淤浆聚合。适用于淤浆聚合的稀释剂为本领域公知，包括在反应条件下为液体的烃。本文所用术语稀释剂”未必意指惰性物质；稀释剂可对聚合有贡献。适用的烃包括但不限于环己烷、异丁烷、正丁烷、丙烷、正戊烷、异戊烷、新戊烷、和正己烷。此外，最优选用异丁烷作为淤浆聚合中的稀释剂。此技术的例子可参见US4424341；4501885；4613484；4737280；和5597892；其内容引入本文供参考。
在该方法中使用所述催化剂组合物在反应器基本不结垢的情况下产生良好品质的聚合物颗粒。在回路反应区在淤浆聚合条件下使用所述催化剂组合物时，优选所述固体氧化物复合物的粒度在约10至约1000μm的范围内，优选约25至约500μm，最优选50至200μm，以在聚合过程中最好控制。
本发明一具体实施方案中，提供一种催化剂组合物的生产方法，所述方法包括(可选地“主要由以下步骤组成”或“由以下步骤组成”)：
(1)使固体氧化物复合物与含氟化氢铵的水接触产生氟化固体氧化物复合物；
其中所述固体氧化物复合物选自氧化硅-氧化钛和氧化硅-氧化锆；
(2)在350至600℃范围内的温度下焙烧所述氟化固体氧化物复合物产生基于焙烧前所述氟化固体氧化物复合物的重量有4至20％(重)氟化物的焙烧后组合物；
(3)使所述焙烧后组合物与二氯·二(正丁基环戊二烯基)合锆在15至80℃范围内的温度下混合产生混合物；和
(4)在1分钟和1小时之间的时间后，使所述混合物与三乙基铝混合产生所述催化剂组合物。
本发明中可在聚合过程中用氢气控制聚合物分子量。
本发明的特征之一是所述氟化固体氧化物复合物比单独使用氧化硅、氧化硅-氧化钛、或氧化硅-氧化锆更有效地使所述有机金属化合物活化。因此，氧化钛或氧化锆有助于有机金属化合物活化。本发明的第二个特征在于所述氧化钛或氧化锆本身是弱聚合催化剂，给通过所述有机金属化合物生产的对称分子量分布的聚合物提供高分子量组分。此高分子量组分或歪斜的分子量分布使所述聚合物具有比由典型的有机金属化合物得到的聚合物更高的熔体强度和剪切特性。这些聚合物的分子量分布可随所用有机金属化合物和所述钛或锆的相对贡献改变。因此，本发明的特征之一是可由有机金属化合物产生约2.5至约4.0的多分散性和约25至约50的HLMI/MI值，否则将产生约2.1至约2.5的多分散性和小于约20的HLMI/MI值。
产生所述聚合物之后，可制成各种制品，例如家用容器和器具、膜产品、转鼓、燃料罐、管、地膜、和衬里。可用各种方法形成这些制品。通常向所述聚合物中加入添加剂和改性剂以提供要求的效果。相信用本发明可在保持用有机金属化合物生产的聚合物的大多数特性的情况下以更低的成本生产制品。
实施例
测试方法
用“Quantachrome Autosorb-6 Nitrogen Pore Size DistributionInstrument”测定载体的表面积和孔体积。该仪器来自QuantachromeCorporation，Syosset，N.Y.。
按ASTM D1505和ASTM D1928，Procedure C在以约15℃/小时冷却并在室温下调整约40小时的模压试样上测量聚合物密度(g/cc)。
高载荷熔体指数(HLMI，g/10min)按ASTM D1238在190℃下用21600g载荷测量。
熔体指数(MI，g/10min)按ASTM D1238在190℃下用2160g载荷测量。
聚合试验的描述
聚合试验在配有以400转/分钟(rpm)运转的marine搅拌器的2.2L钢反应器中进行。所述反应器由与钢冷凝器相连的装有沸甲醇的钢夹套包围。通过改变施加给所述冷凝器和夹套的氮气压力控制甲醇的沸点，借助电子控制仪器使精确温度控制在0.5℃内。
除非另有说明，先将少量的(通常0.01-0.10g)氧化物复合物或本发明氟化固体氧化物复合物在氮气下装入干燥的反应器中。然后用注射器加入2ml有机金属化合物溶液，该溶液含有0.5g有机金属化合物(通常为二氯·二(正丁基环戊二烯基)合锆)/100ml甲苯。然后，向反应器中加入1.2L异丁烷液体，将反应器加热至90℃。添加所述异丁烷的中间加入1ml或2ml 15wt％(1M)庚烷溶液形式的TEA或25wt％(1.5M)庚烷溶液形式的二氯化乙基铝(EADC)。最后，向所述反应器中加入乙烯至等于试验期间保持的固定压力(通常为550psig)。继续搅拌所规定的时间(通常约1小时)，记录为保持压力加入反应器的乙烯流量指示所述活性。
分配时间后，停止乙烯流，使反应器缓慢卸压，打开反应器回收颗粒状聚合物。所有情况下，所述反应器都很干净，没有任何壁垢、涂层或其它形式污垢的迹象。然后取出所述聚合物，称重。
对比实施例1和2(无氧化物复合物)
此例说明有机金属化合物溶液加入有有机铝化合物而没有氧化物复合物的反应器不提供任何活性。如前面所述进行聚合试验。先加入2ml二氯·二(正丁基环戊二烯基)合锆溶液(0.5g二氯·二(正丁基环戊二烯基)合锆/100ml甲苯)。然后加入所述1L异丁烷的一半(0.5L)，然后在例1中加入2ml 15wt％TEA或在例2中加入2ml 25wt％二氯化乙基铝(EADC)。加入另一半异丁烷，最后加入乙烯。未观察到活性。搅拌1小时后，使反应器卸压，打开，但均未发现聚合物。
这些结果示于表1中。
对比实施例3(氧化硅)
此例说明用氧化硅作为与有机铝化合物一起使用的有机金属化合物的活化剂。
氧化硅来自W.R.Grace，952级，孔体积约1.6cc/g，表面积约300m2/g。将约10g氧化硅放在底部配有烧结石英盘的1.75in.石英管中。使所述氧化硅载于所述盘上，使干空气以约1.6-1.8标准立方英尺/小时的线速通过所述盘向上吹。然后打开石英管周围的电炉，使温度以400℃/小时的速度升至600℃。在此温度下使所述氧化硅在干空气中流化3小时产生焙烧氧化硅。然后收集所述氧化硅，保存在干氮气下。它未暴露于大气中。
然后将所述焙烧氧化硅加至反应器中，然后加入如前所述有机金属化合物溶液和TEA溶液。这些试验示于表1中，列出焙烧氧化硅的加入量，试验时间(分钟)、和产生的聚合物的量。所述焙烧氧化硅几乎未产生聚合物。
对比实施例4(氟化氧化硅)
将50g上述952级氧化硅用100ml含5g溶解的氟化氢铵的水溶液浸渍产生氟化氧化硅。得到湿砂稠度的试样，然后在半大气压的真空下于110℃干燥过夜。再通过例3中所述方法将所述氟化氧化硅在干空气中于600℃焙烧。所述氟化氧化硅的表面积为约192m2/g，孔体积约1.29cc/g。
然后测试少量的此氟化氧化硅在聚合试验中作为有机金属化合物和有机铝化合物的活化剂。如表1中所示，它未产生活性。
对比实施例5(氟化氧化钛)
从Degussa，Inc.得到5g Aerosil氧化钛试样，如例3中所述在干空气中于600℃焙烧3小时。焙烧过程中，将1ml全氟己烷注入所述氧化钛床上游的气流中。随着所述全氟己烷蒸气升入所述600℃的床中，它分解，因而使氟化物沉淀在所述氧化钛表面上。产生氟化氧化钛。
然后测试少量的此氟化氧化钛在聚合试验中作为有机金属化合物的活化剂。如表1中所示，它几乎未产生活性。
对比实施例6(氧化硅-氧化钛)
如Deitz在US3887494中所述通过共凝胶制备氧化硅-氧化钛。使硫酸氧钛溶于浓硫酸中，在剧烈搅拌下缓慢加入硅酸钠溶液。pH达到约6时，所述混合物胶凝成均质透明物。然后在pH 7下于80℃老化3小时，水洗九遍，用1％(重)硝酸铵洗两遍。然后使该凝胶在乙酸乙酯中共沸干燥产生氧化硅-氧化钛。所述氧化硅-氧化钛含有约8％钛，表面积约450m2/g，孔体积约2.0cc/g。然后将10g所述氧化硅-氧化钛试样在流化干空气中于600℃焙烧3小时。然后测试少量所述氧化硅-氧化钛试样与有机金属化合物溶液一起的聚合活性。如表1中所示，未显示出明显的活性。
发明实施例7(在600℃焙烧的氟化的氧化硅-氧化钛)
将8.51g来自实施例6的氧化硅-氧化钛试样通过在干空气中流化在600℃焙烧3小时。然后用35ml通过2.50g氟化氢铵溶于100ml甲醇制备的溶液浸渍。这使所述氧化硅-氧化钛初湿，构成约3.9mmol氟化物/g的当量，产生氟化的氧化硅-氧化钛。然后使甲醇蒸发，将氟化的氧化硅-氧化钛如上所述再在空气中于600℃焙烧3小时。
然后先将0.1166g所述氟化的氧化硅-氧化钛在氮气下装入干燥的反应器中。然后用注射器加入2ml含0.5g二氯·二(正丁基环戊二烯基)合锆/100ml甲苯的有机金属化合物溶液。再加入1.2L异丁烷液体，将反应器加热至90℃。添加异丁烷的过程中间加入1ml 15％TEA。最后，加入乙烯使反应器压力等于550psig，试验过程中保持此压力。继续搅拌1小时，通过记录为保持压力加入反应器的乙烯流量指示所述活性。
分配时间后，停止乙烯流，使反应器缓慢卸压，打开反应器回收颗粒状聚合物。所述反应器很干净，没有任何壁垢、涂层或其它形式污垢的迹象。然后取出所述聚合物，称重为137.5g。因此，活性为1164g产生的聚合物/g装入的氟化氧化硅-氧化钛/hr。此数据示于表1中。
该聚合物的分子量分布比用典型的有机金属化合物生产的聚合物更宽。熔体指数为0.04g/10min，高载荷熔体指数为1.72g/10min，得到剪切比(shear ratio)为42.5，高于由典型有机金属化合物得到的通常为16-17的比率。数均分子量为66000，重均分子量为178000，得到多分散性(Mw/Mn)为2.7。这些数据示于表2中。
本发明实施例8和9(在450℃焙烧的氟化的氧化硅-氧化钛)
将实施例7中所述氟化的氧化硅-氧化钛的另一试样在450℃下焙烧代替在600℃下焙烧。也在聚合试验中测试，测得活性增至1834g产生的聚合物/g装入的氟化氧化硅-氧化钛/hr(表1，实施例8)。
再测试此在450℃下焙烧的氟化氧化硅-氧化钛，但在加入乙烯之前使之在反应器中与TEA和有机金属化合物在90℃下反应20分钟。此步骤使测得的活性增至2837g聚合物/g氟化氧化硅-氧化钛/hr(表1，实施例9)。
对比实施例10和11(氧化硅-氢化锆)
如下制备氧化硅-氧化锆。获得来自W.R.Grace的952级氧化硅，其表面积为约300m2/g，孔体积为约1.6cc/g。将26.3g氧化硅试样在流化氮气中于200℃干燥3小时。然后将50ml含11.72g丙氧基锆的庚烷溶液加至所述试样中。在氮气下于60℃下使庚烷蒸发至试样变干产生氧化硅-氧化锆。然后在空气中于600℃焙烧3小时。两次试验中，此氧化硅-氧化锆的聚合活性为产生35和78g聚合物/g氧化硅-氧化锆/hr。
本发明实施例12(氟化的氧化硅-氧化锆)
通过以下步骤使用于实施例10和11的氧化硅-氧化锆氟化。将14.3g已在600℃焙烧过的氧化硅-氧化锆用含0.82g氟化氢铵的水溶液饱和，产生湿砂稠度的氟化氧化硅-氧化锆。使所述氟化氧化硅-氧化锆在120℃下真空干燥过夜，然后在干空气中于500℃焙烧3小时，然后进行活性试验。所述活性增至465g产生的聚合物/g氧化硅-氧化锆/hr。
对比实施例13(氢化硅-氧化锆)
如下所述通过无水胶凝制备含10％(重)锆的氧化硅-氧化锆。将1mol(约200ml)原硅酸四乙酯加至500ml正丙醇中。然后将1ml硫酸与30ml水一起加入，这是完全水解所需量的约85％。将此溶液搅拌30分钟使之反应。温度微升，表明发生水解。然后，加入70ml丙氧基锆，但未产生氧化锆沉淀，表明与所述原硅酸四乙酯反应已消耗掉基本上所有水。将此溶液搅拌15分钟，再加入50ml水，也没有氧化锆沉淀，表明已结合至氧化硅中。将溶液再搅拌15分钟，然后加入氢氧化铵直至发生胶凝形成透明凝胶。使凝胶在真空烘箱中于120℃干燥过夜，然后将试样在干空气中于600℃焙烧3小时。此试样与有机金属化合物和有机铝化合物一起用于聚合活性试验时产生230g聚合物/g氧化硅-氧化锆/hr的活性。
本发明实施例14和15(氟化的氧化硅-氧化锆)
将实施例13中所述氧化硅-氧化锆的两试样(一个在600℃下焙烧之前获得(实施例14)，另一个在焙烧之后获得(实施例15))用含足以等于试样的10％(重)的氟化氢铵的甲醇溶液浸渍。两试样都在120℃下真空干燥过夜，然后在空气中于500℃焙烧3小时。与有机金属化合物和有机铝化合物一起用于聚合活性试验时，都产生在3000和5000g聚合物/g氟化的氧化硅-氧化锆/hr的高活性。
表1：聚合结果
| 实施例 | 测试化合物<sup>*</sup> | 焙烧温度(℃) | 测试化合物的加入量(g) | 有机铝化合物(mmol) | 聚合物(g) | 试验时间(min) | 活性*(g/g/h) |
| 1-对照 | 无氧化物复合物 | 0.0000 | 2TEA | 0 | 61.1 | 0 | |
| 2-对照 | 无氧化物复合物 | 0.0000 | 2EADC | 0 | 28.0 | 0 | |
| 3-对照 | 氧化硅 | 600 | 0.5686 | 2TEA | 0.7 | 63.0 | 1 |
| 4-对照 | 氟化的氧化硅 | 600 | 0.4350 | 1TEA | 0 | 24.5 | 0 |
| 5-对照 | 氟化的氧化钛 | 600 | 0.1461 | 1TEA | 0.2 | 34.1 | 2 |
| 6-对照 | 氧化硅-氧化钛 | 600 | 0.1392 | 2TEA | 0 | 60.0 | 0 |
| 7-本发明 | 氟化的氧化硅-氧化钛 | 600 | 0.1166 | 1TEA | 135.7 | 60.0 | 1164 |
| 8-本发明 | 氟化的氧化硅-氧化钛 | 450 | 0.0090 | 1TEA | 17.0 | 61.8 | 1834 |
| 9-本发明 | 氟化的氧化硅-氧化钛 | 450 | 0.1893 | 1TEA | 179.0 | 20.0 | 2837 |
| 10-对照 | 氧化硅-氧化锆 | 600 | 0.1663 | 1TEA | 13.0 | 60.0 | 78 |
| 11-对照 | 氧化硅-氧化锆 | 600 | 0.2493 | 1TEA | 6.0 | 41.5 | 35 |
| 12-本发明 | 氟化的氧化硅-氧化锆 | 500 | 0.2108 | 1TEA | 98.0 | 60.0 | 465 |
| 13-对照 | 氧化硅-氧化锆 | 600 | 0.2229 | 1TEA | 67.8 | 58.0 | 230 |
| 14-本发明 | 氟化的氧化硅-氧化锆 | 500 | 0.0277 | 1TEA | 98.0 | 70.0 | 3033 |
| 15-本发明 | 氟化的氧化硅-氧化锆 | 500 | 0.1129 | 1TEA | 257.0 | 30.9 | 4420 |
| 在90℃、550psig和1.2L异丁烷下聚合；有机金属化合物＝25μmol二氯·二(正丁基环戊二烯基)合锆，或2.3mg Zr有机铝化合物＝1或2ml TEA或2ml EADC | |||||||
*测试化合物＝氧化物复合物或氟化的固体氧化物复合物
*活性＝g聚合物/g氧化物复合物或氟化的固体氧化物复合物/hr(g/g/h)
表2
| 测试化合物 | HLMI(g/10min) | HLMI/MI | 数均分子量(Mn) | 重均分子量(Mn) | Mw/Mn |
| 氟化的氧化硅-氧化钛 | 1.72 | 42.5 | 66000 | 178000 | 2.7 |
虽然已对本发明进行了详细的描述，但本发明不应限于此，而要包括在其精神和范围内的所有改变和修改。
Claims (17)
1.一种催化剂组合物的生产方法，所述方法包括使有机金属化合物、有机铝化合物、和氟化的固体氧化物复合物接触产生所述催化剂组合物，
其中所述有机金属化合物有以下通式：
(X1)(X2)(X3)(X4)M1
其中M1是钛、锆或铪；
(X1)独立地选自环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基或取代的芴基；
其中(X1)的取代的环戊二烯基、取代的茚基和取代的芴基上的取代基选自脂族基、环状基团、脂族和环状基团的组合、甲硅烷基、卤代烷基、卤离子、有机金属基、磷基、氮基、硅、磷、硼、锗或氢；
(X1)上至少一个取代基可以是连接(X1)和(X2)的桥连基；
(X3)和(X4)独立地选自卤离子、脂族基、取代的脂族基、环状基团、取代的环状基团、脂族基和环状基团的组合、取代的脂族基和环状基团的组合、脂族基和取代的环状基团的组合、取代的脂族基和取代的环状基团的组合、氨基、取代的氨基、膦基、取代的膦基烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基或取代的有机金属基；
(X2)选自环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基、取代的芴基、卤离子、脂族基、取代的脂族基、环状基团、取代的环状基团、脂族基和环状基团的组合、取代的脂族基和环状基团的组合、脂族基和取代的环状基团的组合、取代的脂族基和取代的环状基团的组合、氨基、取代的氨基、膦基、取代的膦基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基、或取代的有机金属基；
(X2)上的取代基选自脂族基团、环状基团、脂族和环状基团的组合、甲硅烷基、卤代烷基、卤离子、有机金属基、磷基、氮基、硅、磷、硼、锗或氢；
(X2)上至少一个取代基可以是连接(X1)和(X2)的桥连基；
所述有机铝化合物有以下通式：
Al(X5)n(X6)3-n
其中(X5)为有1至20个碳原子的烃基；
(X6)为卤离子、氢负离子、或醇根；和
“n”为1至3的数，包括端值；
所述氟化的固体氧化物复合物包含氟化物和固体氧化物复合物；
其中所述固体氧化物复合物选自氧化硅-氧化钛或氧化硅-氧化锆；和
其中所述催化剂组合物在基本不存在有机硼酸盐和铝氧烷的情况下是有活性的。
2.权利要求1的方法，包括：
(1)使所述固体氧化物复合物与含氟化氢铵的水接触产生氟化的固体氧化物复合物；
(2)在350至600℃范围内的温度下焙烧所述氟化的固体氧化物复合物产生基于焙烧前所述氟化的固体氧化物复合物的重量有4至20％重量氟化物的焙烧后组合物；
(3)使所述焙烧后组合物与二氯·二(正丁基环戊二烯基)合锆在15至80℃范围内的温度下混合产生混合物；和
(4)在1分钟和1小时之间的时间后，使所述混合物与三乙基铝混合产生所述催化剂组合物。
3.权利要求2的方法，其中所述方法主要由步骤(1)、(2)、(3)和(4)组成。
4.一种催化剂组合物，所述组合物包括有机金属化合物、有机铝化合物、和氟化的固体氧化物复合物的接触产物，
其中所述有机金属化合物有以下通式：
(X1)(X2)(X3)(X4)M1
其中M1选自钛、锆或铪；
(X1)独立地选自环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基或取代的芴基；
其中(X1)的取代的环戊二烯基、取代的茚基和取代的芴基上的取代基选自脂族基、环状基团、脂族和环状基团的组合、甲硅烷基、卤代烷基、卤离子、有机金属基、磷基、氮基、硅、磷、硼、锗或氢；
(X1)上至少一个取代基可以是连接(X1)和(X2)的桥连基；
(X3)和(X4)独立地选自卤离子、脂族基、取代的脂族基、环状基团、取代的环状基团、脂族基和环状基团的组合、取代的脂族基和环状基团的组合、脂族基和取代的环状基团的组合、取代的脂族基和取代的环状基团的组合、氨基、取代的氨基、膦基、取代的膦基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基或取代的有机金属基；
(X2)选自环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基、取代的芴基、卤离子、脂族基、取代的脂族基、环状基团、取代的环状基团、脂族基和环状基团的组合、取代的脂族基和环状基团的组合、脂族基和取代的环状基团的组合、取代的脂族基和取代的环状基团的组合、氨基、取代的氨基、膦基、取代的膦基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基、或取代的有机金属基；
(X2)上的取代基选自脂族基团、环状基团、脂族和环状基团的组合、甲硅烷基、卤代烷基、卤离子、有机金属基、磷基、氮基、硅、磷、硼、锗或氢；
(X2)上至少一个取代基可以是连接(X1)和(X2)的桥连基；
所述有机铝化合物有以下通式：
Al(X5)n(X6)3-n
其中(X5)为有1至20个碳原子的烃基；
(X6)为卤离子、氢负离子、或醇根；和
“ n”为1至3的数，包括端值；
所述氟化的固体氧化物复合物包含氟化物和固体氧化物复合物；
其中所述固体氧化物复合物选自氧化硅-氧化钛或氧化硅-氧化锆和
其中所述催化剂组合物在基本不存在有机硼酸盐和铝氧烷的情况下是有活性的。
5.权利要求4的催化剂组合物，其中在淤浆聚合条件下、用异丁烷作稀释剂、在90℃的聚合温度和3893kPa的乙烯压力下，所述催化剂组合物的活性大于1000g聚合物/g氟化的固体氧化物复合物/小时。
6.权利要求5的催化剂组合物，其中在淤浆聚合条件下、用异丁烷作稀释剂、在90℃的聚合温度和3893kPa的乙烯压力下，所述催化剂组合物的活性大于2500g聚合物/g氟化的固体氧化物复合物/小时。
7.权利要求5的催化剂组合物，其中所述催化剂组合物中所述有机铝化合物与所述氟化的固体氧化物复合物之重量比在3∶1至1∶100的范围内。
8.权利要求7的催化剂组合物，其中所述催化剂组合物中所述有机铝化合物与所述氟化的固体氧化物复合物之重量比在1∶1至1∶50的范围内。
9.权利要求5的催化剂组合物，其中所述催化剂组合物中所述氟化的固体氧化物复合物与所述有机金属化合物之重量比在1000∶1至10∶1的范围内。
10.权利要求9的催化剂组合物，其中所述催化剂组合物中所述氟化的固体氧化物复合物与所述有机金属化合物之重量比在250∶1至20∶1的范围内。
11.一种催化剂组合物，包含接触后的有机金属化合物、接触后的有机铝化合物、和接触后的氟化固体氧化物复合物。
12.权利要求4的催化剂组合物在一种聚合方法中的用途，该聚合方法包括使至少一种单体和所述催化剂组合物在聚合条件下接触产生至少一种聚合物。
13.权利要求12的用途，其中所述聚合条件包括淤浆聚合条件。
14.权利要求13的用途，其中所述接触在回路反应区中进行。
15.权利要求14的用途，其中所述接触在主要包含异丁烷的稀释剂存在下进行。
16.权利要求12的用途，其中所述至少一种单体是乙烯。
17.权利要求12的用途，其中所述至少一种单体包括乙烯和每分子有3至20个碳原子的脂族1-烯烃。
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| US09/408,904 US6395666B1 (en) | 1999-09-29 | 1999-09-29 | Organometal catalyst compositions |
| US09/408,904 | 1999-09-29 |
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| ES2484766T3 (es) | 2014-08-12 |
| MXPA02003245A (es) | 2002-09-30 |
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| ZA200202086B (en) | 2003-08-27 |
| EP1230274A1 (en) | 2002-08-14 |
| HK1049019A1 (en) | 2003-04-25 |
| US20040024147A1 (en) | 2004-02-05 |
| AU7729100A (en) | 2001-04-30 |
| EP1230274A4 (en) | 2005-07-06 |
| CA2384654A1 (en) | 2001-04-05 |
| NO20021411L (no) | 2002-05-23 |
| RU2235100C2 (ru) | 2004-08-27 |
| NO20021411D0 (no) | 2002-03-21 |
| US20020128404A1 (en) | 2002-09-12 |
| US6992032B2 (en) | 2006-01-31 |
| TWI283604B (en) | 2007-07-11 |
| KR20020034196A (ko) | 2002-05-08 |
| US6653416B2 (en) | 2003-11-25 |
| WO2001023434A1 (en) | 2001-04-05 |
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