CN1376167A - 有机金属催化剂组合物 - Google Patents

有机金属催化剂组合物 Download PDF

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CN1376167A
CN1376167A CN00813450A CN00813450A CN1376167A CN 1376167 A CN1376167 A CN 1376167A CN 00813450 A CN00813450 A CN 00813450A CN 00813450 A CN00813450 A CN 00813450A CN 1376167 A CN1376167 A CN 1376167A
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M·P·穆丹特尔
K·S·克林斯
A·P·伊顿
E·A·本哈姆
M·D·杰森
J·L·马丁
G·R·浩雷
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Phillips Petroleum Co
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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、和接触后的氟化氧化硅－氧化铝。

Description

有机金属催化剂组合物
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年发现一份水与一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，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、和氟化的氧化硅-氧化铝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)；
所述氟化的氧化硅-氧化铝包含氟化物、氧化硅和氧化铝。
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。
附图简述
附图中，图1示出所述催化剂组合物在不同氟化物载荷和焙烧温度下的活性曲线。
图2示出所述活性与加入NH4HF2的百分率的关系曲线。
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独立地选自脂族基、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US4 939 217；5 210 352；5 436 305；5 401 817；5 631 335；5 571 880；5 191132；5 480 848；5 399 636；5 565 592；5 347 026；5 594 078；5 498 581；5 496 781；5 563 284；5 554 795；5 420 320；5 451649；5 541 272；5 705 478；5 631 203；5 654 454；5 705 579；和5 668 230；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；
Figure A0081345000092
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；
Figure A0081345000103
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；
Figure A0081345000111
二氯·二甲基甲硅烷基-二(1-茚基)合锆；
Figure A0081345000112
二氯·辛基苯基甲硅烷基-二(1-茚基)合铪；
Figure A0081345000113
二氯·二甲基甲硅烷基-二(η5-4，5，6，7-四氢-1-茚基)合锆；
Figure A0081345000114
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；
Figure A0081345000121
一氯·二乙氧基·茚基合锆(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；
Figure A0081345000131
二氯·甲基辛基甲硅烷基-二(9-芴基)合锆；
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：
二氯·二(正丁基环戊二烯基)合锆；
二氯·二(茚基)合锆；
Figure A0081345000141
二氯·二甲基甲硅烷基-二(1-茚基)合锆；
Figure A0081345000142
二氯·甲基辛基甲硅烷基-二(9-芴基)合锆。
Figure A0081345000143
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；和
氯化二乙基铝。
目前优选TEA。
所述氟化的氧化硅-氧化铝包含氧化硅、氧化铝和氟化物。所述氟化的氧化硅-氧化铝为颗粒状固体形式。一般地，为生产所述氟化的氧化硅-氧化铝，用氟化剂处理氧化硅-氧化铝，以将氟化物加至所述氧化硅-氧化铝中。一般通过在氟化剂和适合的溶剂如醇或水的溶液中形成所述氧化硅-氧化铝的浆液将所述氟化物加至所述氧化硅-氧化铝中。特别适用的是1至3个碳原子的醇，因为它们的挥发性和低表面张力。使用适量的所述溶液以在干燥后在所述氧化硅-氧化铝上提供要求浓度的氟化物。干燥可通过本领域已知的任何方法进行。例如所述干燥可通过吸滤然后蒸发、真空干燥、或喷雾干燥完成。
可与氧化硅-氧化铝形成表面氟化物的任何有机或无机氟化剂均可用于本发明。适用的氟化剂包括但不限于氢氟酸(HF)、氟化铵(NH4F)、二氟化铵(NH4HF2)、氟硼酸铵(NH4BF4)、氟硅酸铵((NH4)2SiF6)、氟磷酸铵(NH4PF6)及其混合物。最优选的氟化剂是二氟化铵，因为它容易使用且易得。焙烧之前氟化物的存在量一般在约2至约50％(重)的范围内，优选约3至约25％(重)，最优选4至20％(重)氟化物，其中所述重量百分率是基于焙烧之前所述氟化的氧化硅-氧化铝的重量计。
焙烧所述氟化的氧化硅-氧化铝很重要。所述焙烧可在任何适合的环境中进行。一般地，此焙烧在环境气氛中(优选干燥的环境气氛)在约200至约900℃范围内的温度下进行约1分钟至约100小时范围内的时间。优选将所述氟化的氧化硅-氧化铝在约300至约600℃的温度下焙烧约1至约10小时，最优选在350至550℃的温度下焙烧1至10小时。
可选地，在焙烧过程中用氟化剂处理所述氧化硅-氧化铝。可使用能在所述焙烧步骤期间与所述氧化硅-氧化铝接触的任何氟化剂。除前面所述的那些氟化剂之外，高挥发性的有机氟化剂也特别适用。高挥发性的有机氟化剂可选自氟利昂、全氟己烷、全氟苯、氟代甲烷、三氟乙醇、及其混合物。可使用气态氟化氢或氟本身。与所述氧化硅-氧化铝接触的一种便利方法是在焙烧过程中使氟化剂汽化至用于使所述氧化硅-氧化铝流化的气流中。
所述氧化硅-氧化铝的孔体积应大于约0.5cc/g，优选大于约0.8cc/g，最优选大于1.0cc/g。
所述氧化硅-氧化铝的表面积应大于约100m2/g，优选大于约250m2/g，最优选大于350m2/g。
本发明的氧化硅-氧化铝中氧化铝含量为约5-95％，优选8-50％，最优选10-30％(重量)氧化铝。
本发明催化剂组合物可通过所述有机金属化合物、所述氟化的氧化硅-氧化铝、和所述有机铝化合物一起接触制备。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，一种方法是先使有机金属化合物与氟化的氧化硅-氧化铝在约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。
优选在注入反应器之前使所述有机金属化合物、所述有机铝化合物、和所述氟化的氧化硅-氧化铝在约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)以获得高活性。
所述催化剂组合物中有机铝化合物与所述氟化的氧化硅-氧化铝之重量比在约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的氧化硅-氧化铝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。这些比例是基于化合产生所述催化剂组合物的组分量。
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、和接触后的氟化的氧化硅-氧化铝。应注意所述接触后的氟化氧化硅-氧化铝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。
本发明催化剂组合物的活性高于如对照实施例3-7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未用氟化物浸渍的氧化铝、氧化硅或氧化硅-氧化铝的催化剂组合物。此外，本发明催化剂组合物的活性还高于如对照实施例9-10中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氟化的氧化硅或氟化的氧化铝的催化剂组合物。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。对比活性时，应在相同聚合条件下进行聚合试验。所述反应器没有任何壁垢、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氟化的氧化硅-氧化铝/hr，更优选大于2000，甚至更优选大于5000，最优选大于8000。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氧烷。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US4 424 341；4 501 885；4 613 484；4 737 280；和5 597 892；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制品。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)使氧化硅-氧化铝与含氟化氢铵(ammonium bifluoride)的水接触产生氟化的氧化硅-氧化铝；
(2)在350至550℃范围内的温度下焙烧所述氟化的氧化硅-氧化铝产生基于焙烧前所述氟化的氧化硅-氧化铝的重量有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。
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金属茂催化剂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”测定表面积和孔体积。该仪器来自QuantachromeCorporation，Syosset，N.Y.。
用于对照实施例3-7的氧化物复合物的制备
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所述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。然后收集所述氧化硅，保存在干氮气下。它未暴露于大气中。
氧化铝来自Akzo Nobel以Ketjen出售的B级氧化铝，孔体积为约1.78cc/g，表面积为约340m2/g。通过前面针对氧化硅所述的步骤制备氧化铝试样，但氧化铝试样在400℃、600℃和800℃下焙烧。
氧化硅-氧化铝来自W.R.Grace的MS 13-110，含13％氧化铝和87％氧化硅。所述氧化硅-氧化铝的孔体积为1.2cc/g，表面积为约400m2/g。如前面针对氧化硅所述制备氧化硅-氧化铝试样。
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，先将氧化物复合物或氟化的氧化硅-氧化铝在氮气下装入干燥的反应器中。然后用注射器加入2ml含有0.5g二氯二(正丁基环戊二烯基)合锆/100ml甲苯的溶液。然后，向反应器中加入1.2L异丁烷，将反应器加热至90℃。添加所述异丁烷的中间加入1ml或2ml TEA或二氯化乙基铝(EADC)。最后，向所述反应器中加入乙烯至等于550psig，试验期间保持此压力。继续搅拌所规定的时间，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，干燥和称重。
实施例1-2(对照)
此例说明有机金属化合物加入有TEA或EADC的反应器不提供任何活性。
如前面所述进行聚合试验，但不加氧化物复合物。加入乙烯，但未观察到活性。搅拌1小时后，使反应器卸压、打开，但都未发现聚合物。这些结果示于表1中。
实施例3-7(对照)
此例说明不同氧化物复合物、有机金属化合物和TEA的使用。
如前面所述将每种氧化物复合物加入反应器，然后加入前面所述方法中使用的有机金属化合物和TEA溶液。这些试验示于表1中。
氧化硅几乎未产生聚合物。公认比氧化硅酸性更强的氧化铝产生更多的聚合物，但活性仍非常低。三种不同活化温度试验中都如此。所述氧化硅-氧化铝也仅显示出极低的活性。
                表1(对照试验1-7)
实施例 氧化物复合物的类型   焙烧(℃) 氧化物复合物(g)   有机铝化合物(ml)   聚合物(g)  试验时间(min)   活性*
    1     无   0.0000   2(TEA)     0     61.1     0
    2     无   0.0000   2(EADC)     0     28.0     0
    3     氧化硅   600   0.5686   2(TEA)     0.65     63.0     1
    4     氧化铝   800   0.6948   1(TEA)     2.7     30.7     8
    5     氧化铝   600   0.2361   2(TEA)     6.9     60.9     29
    6     氧化铝   400   0.8475   1(TEA)     痕量     57.2     0
    7   氧化硅-氧化铝   600   0.3912   1(TEA)     8.3     40.0     32
*活性的单位是g聚合物/g加入的氧化物复合物/hr。
实施例8(对照和本发明试验)
在不同的氟化氢铵载荷和不同焙烧温度下生产以下催化剂组合物说明本发明。
将少量的氧化硅-氧化铝(W.R.Grace Company以MS 13-110出售，表面积400m2/g，孔体积1.2cc/g)用高于其重量两倍的含氟化氢铵的水溶液浸渍生产氟化的氧化硅-氧化铝。例如，用100ml含5g氟化氢铵的水溶液浸渍50g氧化硅-氧化铝，氟化氢铵的载荷为10％(重)。这产生湿砂稠度。
然后将所述氟化的氧化硅-氧化铝放在真空烘箱中，在半大气压的真空下于110℃干燥过夜。最后一步骤是将10g所述氟化的氧化硅-氧化铝在干燥的流化空气中在要求的温度下焙烧3小时。然后将所述氟化的氧化硅-氧化铝保存在氮气下直至如前面所述将少量的氟化氧化硅-氧化铝与有机金属化合物和TEA一起装入反应器中。
这些试验示于表2中，并绘于图1中。表3示出根据氟化氢铵载荷绘制的每种载荷(不管其焙烧温度)的最高活性试样。这些结果绘于图2中。
从表3的数据可见，在约300至约600℃的焙烧温度下氟化氢铵载荷为约5至约35％(重)时观察到极好的催化剂活性。
表2
  实施例   NH4HF2载荷(wt％) 氟化的氧化硅-氧化铝(g)   聚合物(g)  试验时间(min)   焙烧(℃)    活性*
    8-1     5     0.0293     140     69.0     450     4155
    8-2     5     0.0188     117     60.1     600     6213
    8-3     5     0.0353     60     37.0     750     2756
    8-4     5     0.2318     203     40.0     850     1312
    8-5     3     0.1266     205     45.7     800     2126
    8-6     10     0.0800     68     28.0     300     1816
    8-7     10     0.0248     163     67.7     350     5825
    8-8     10     0.0251     228     44.5     400     12248
    8-9     10     0.0183     175     48.0     400     11954
    8-10     10     0.0779     270     20.0     400     10398
    8-11     10     0.0109     165     60.0     450     15138
    8-12     10     0.0059     109     60.0     450     18475
    8-13     10     0.0200     224     60.1     500     11181
    8-14     10     0.0792     179     16.0     500     8485
    8-15     10     0.0249     175     60.0     550     7028
    8-16     10     0.0897     149     18.0     600     5537
    8-17     10     0.0346     113     60.2     650     3255
    8-18     10     0.0908     149     21.0     700     4688
    8-19     10     0.2336     288     50.0     750     1478
    8-20     10     0.0829     91     32.0     800     2057
    8-21     10     0.2185     183     55.0     850     916
    8-22     22     0.1773     319     30.0     200     3598
    8-23     22     0.2355     320     9.0     300     9068
    8-24     22     0.1456     250     21.0     400     4896
    8-25     22     0.0214     34     45.2     500     2109
    8-26     22     0.1715     146     31.0     600     1651
    8-27     22     0.1624     88     22.0     700     1474
    8-28     35     0.2944     336     10.0     300     6854
    8-29     35     0.0786     108     15.0     400     5471
    8-30     35     0.0725     160     39.0     450     2410
    8-31     35     0.0191     55     71.7     450     3395
    8-32     35     0.0832     58     20.0     500     2091
    8-33     35     0.1021     127     25.0     600     2989
    8-34     35     0.0715     21     26.0     700     689
    8-35     70     0.0175     0     92.3     450     0
    8-36     70     0.0446     0     40.0     450     0
*活性的单位是g聚合物/g加入的氟化氧化硅-氧化铝/hr。
表3
  实施例 NH4HF2载荷(wt％)   氟化的氧化硅-氧化铝(g)  聚合物(g) 试验时间(min)    焙烧(℃)   活性*
    7     0     0.3912   8.3    40.0     600     32
    8-5     3     0.1266   205    45.7     800     2126
    8-2     5     0.0188   117    60.1     600     6213
    8-11     10     0.0059   109    60.0     450     18475
    8-23     22     0.2355   320    9.0     300     9068
    8-28     35     0.2944   336    10.0     300     6854
    8-35     70     0.0175   0    92.3     450     0
*活性的单位是g聚合物/g加入的氟化氧化硅-氧化铝/hr。
实施例9(对照)
重复实施例8的步骤，但用氧化硅代替氧化硅-氧化铝。
如前面所述用10％氟化氢铵浸渍来自W.R.Grace的952级氧化硅产生氟化的氧化硅。所述氧化硅的表面积为约300m2/g，孔体积为约1.6cc/g。然后将所述氟化的氧化硅在干空气中于450℃焙烧3小时，测试聚合活性。它根本未显示出活性。
实施例10(对照)
重复实施例8的步骤，但用氧化铝代替氧化硅-氧化铝。
如前面所述用不同载荷的氟化氢铵浸渍来自Akzo Nobel的称为Ketjen grade B的氧化铝产生氟化的氧化铝。所述氧化铝的表面积为约400m2/g，孔体积为约1.6cc/g。然后将所述氟化的氧化铝试样在干空气中于450℃或500℃焙烧3小时，如前面所述测试聚合活性。结果见表4。所述氟化的氧化铝试样的活性明显低于使用氟化的氧化硅-氧化铝的本发明试验中显示的活性。
                        表4
  实施例 NH4HF2载荷(wt％) 氟化的氧化铝(g)   聚合物(g)  试验时间(min)   焙烧(℃)   活性*
  10-1     10  0.1086     17.6    40.0   500    243
  10-2     15  0.2563     243.9    60.0   500    952
  10-3     25  0.2542     164    55.0   450    704
  10-4     35  0.1157     37    30.0   500    640
*活性的单位是g聚合物/g加入的氟化氧化铝/hr。
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 (20)

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、和氟化的氧化硅-氧化铝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；
所述氟化的氧化硅-氧化铝包含氟化物、氧化硅和氧化铝。
2.权利要求1的方法，其中在加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、和所述氟化的氧化硅-氧化铝预接触约1分钟至约24小时。
3.一种催化剂组合物的生产方法，包括：
(1)使氧化硅-氧化铝与含氟化氢铵的水接触产生氟化的氧化硅-氧化铝；
(2)在350至550℃范围内的温度下焙烧所述氟化的氧化硅-氧化铝产生基于所述氟化的氧化硅-氧化铝的重量有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。
4.权利要求3的方法，其中所述方法主要由步骤(1)、(2)、(3)和(4)组成。
5.通过权利要求1的方法生产的催化剂组合物。
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550psig的乙烯压力下，所述催化剂组合物的活性大于约1000g聚合物/g氟化的氧化硅-氧化铝/hr。
7.权利要求6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550psig的乙烯压力下，所述催化剂组合物的活性大于8000g聚合物/g氟化的氧化硅-氧化铝/hr。
8.权利要求6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氧化硅-氧化铝之重量比在约3∶1至约1∶100的范围内。
9.权利要求8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氧化硅-氧化铝之重量比在1∶1至1∶50的范围内。
10.权利要求6的催化剂组合物，其中所述催化剂组合物中所述氟化的氧化硅-氧化铝与所述有机金属化合物之重量比在约1000∶1至约10∶1的范围内。
11.权利要求10的催化剂组合物，其中所述催化剂组合物中所述氟化的氧化硅-氧化铝与所述有机金属化合物之重量比在250∶1至20∶1的范围内。
12.权利要求11的催化剂组合物，其中基于焙烧前所述氟化的氧化硅-氧化铝的重量计，所述氟化的氧化硅-氧化铝包含10至30％(重)氧化铝、4至20％(重)氟化物，在350至550℃范围内的温度下焙烧。
13.一种催化剂组合物，包含接触后的有机金属化合物、接触后的有机铝化合物、和接触后的氟化氧化硅-氧化铝。
14.一种聚合方法，包括使至少一种单体和权利要求5所述催化剂组合物在聚合条件下接触生产聚合物。
15.权利要求14的方法，其中所述聚合条件包括淤浆聚合条件。
16.权利要求15的方法，其中所述接触在回路反应区中进行。
17.权利要求16的方法，其中所述接触在主要包含异丁烷的稀释剂存在下进行。
18.权利要求14的方法，其中至少一种单体是乙烯。
19.权利要求14的方法，其中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。
20.一种制品，包含按权利要求14生产的所述聚合物。
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