CN1188431C - 有机金属化合物催化剂 - Google Patents
有机金属化合物催化剂 Download PDFInfo
- Publication number
- CN1188431C CN1188431C CNB008178437A CN00817843A CN1188431C CN 1188431 C CN1188431 C CN 1188431C CN B008178437 A CNB008178437 A CN B008178437A CN 00817843 A CN00817843 A CN 00817843A CN 1188431 C CN1188431 C CN 1188431C
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- China
- Prior art keywords
- group
- replaces
- zirconium
- replacement
- cyclic group
- Prior art date
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- 229910052726 zirconium Inorganic materials 0.000 claims description 116
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 112
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 85
- 125000001931 aliphatic group Chemical group 0.000 claims description 63
- 125000004122 cyclic group Chemical group 0.000 claims description 61
- 239000000126 substance Substances 0.000 claims description 47
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- 238000000034 method Methods 0.000 claims description 41
- 238000001354 calcination Methods 0.000 claims description 39
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- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 3
- 150000002739 metals Chemical class 0.000 claims 3
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 2
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- 238000009835 boiling Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
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- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
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- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- AHBPBADERZDJKT-UHFFFAOYSA-N pentane-2,3-dione zirconium Chemical compound [Zr].C(C)C(=O)C(=O)C AHBPBADERZDJKT-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
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Abstract
本发明提供适用于使至少一种单体聚合以生产聚合物的催化剂组合物。本发明还提供适用于使至少一种单体聚合以生产聚合物的催化剂组合物，其中所述催化剂组合物包括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处理过的固体氧化物。
Description
发明领域
本发明涉及有机金属化合物催化剂领域。
发明背景
聚合物的生产是数十亿美元的行业。此行业每年生产数十亿磅聚合物。在开发可增加此行业价值的技术方面已花费几百万美元。
这些技术之一称为金属茂催化剂技术。大约自1958年开始已经知道金属茂催化剂。但其低生产率使之未商业化。大约在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，生成有较高活性的金属茂催化剂。然而，不久即认识到要形成活性的金属茂催化剂需要大量昂贵的甲基铝氧烷。这明显地妨碍了金属茂催化剂的商业化。
氟有机硼酸盐化合物已用于代替大量的甲基铝氧烷。但因这样的硼酸盐化合物非常容易中毒和分解而不令人满意，而且可能也很贵。
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颗粒。这些类型的基本上均匀的颗粒是理想的，因为它们改善了聚合物生产和输送的效率。人们已付出许多努力试图生产多相金属茂催化剂；但这些催化剂尚不完全令人满意。
因此，本发明人提出本发明以有助于解决这些问题。
发明概述
本发明提供一种催化剂组合物的生产方法，所述催化剂可用于聚合至少一种单体以生产聚合物。
本发明还提供一种催化剂组合物。
本发明提供一种方法，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以生产聚合物。
本发明提供一种制品，该制品包含用本发明的催化剂组合物生产的聚合物。
根据本发明的一个实施方案，提供一种催化剂组合物的生产方法。该方法包括(或任选地“主要由以下步骤组成”或“由以下步骤组成”)：使有机金属化合物、有机铝化合物和处理过的固体氧化物接触以生产所述催化剂组合物，
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；
其中(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；
其中在(X1)的所述取代的环戊二烯基、取代的茚基和取代的芴基上的取代基选自脂族基团、环状基团、脂族和环状基团的组合、甲硅烷基、烷基卤化物基团(alkyl halide groups)、卤基(halides)、有机金属基团、磷基、氮基、硅、磷、硼、锗和氢；
其中在(X1)上至少一个取代基可以是连接(X1)和(X2)的桥连基团；
其中(X3)和(X4)独立地选自卤基、脂族基团、取代的脂族基团、环状基团、取代的环状基团、脂族基团和环状基团的组合、取代的脂族基团和环状基团的组合、脂族基团和取代的环状基团的组合、取代的脂族基团和取代的环状基团的组合、氨基、取代的氨基、磷基(phosphido)、取代的磷基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基团和取代的有机金属基团；
其中(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、卤基、脂族基团、取代的脂族基团、环状基团、取代的环状基团、脂族基团和环状基团的组合、取代的脂族基团和环状基团的组合、脂族基团和取代的环状基团的组合、取代的脂族基团和取代的环状基团的组合、氨基、取代的氨基、磷基、取代的磷基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基团和取代的有机金属基团；
其中在(X2)上的取代基选自脂族基团、环状基团、脂族基团和环状基团的组合、甲硅烷基、烷基卤化物基团、卤基、有机金属基团、磷基、氮基、硅、磷、硼、锗和氢；
其中在(X2)上的至少一个取代基可以是连接(X1)和(X2)的桥连基团；
其中所述有机铝化合物有以下通式：
Al(X5)n(X6)3-n
其中(X5)为有1-20个碳原子的烃基；
其中(X6)为卤离子、氢负离子、或醇根离子；
其中“n”为1至3的数；并且
其中所述处理过的固体氧化物包含至少一种卤素、锆和固体氧化物；
其中所述卤素是选自氯、溴和氟中至少之一；
其中所述固体氧化物选自氧化铝、磷铝酸盐、硅铝酸盐及其混合物。
采用术语“主要由以下步骤组成”是指所述方法不包括任何所列举步骤以外的对本发明希望的目的有负面影响的其它的步骤。
根据本发明的另一个实施方案，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以生产聚合物。
根据本发明的另一个实施方案，提供一种制品。所述制品包含根据本发明生产的聚合物。
本领域普通技术人员在阅读了本说明书后，将更清楚地了解这些目的和其它目的。
发明详述
用于本发明的有机金属化合物有以下通式：
(X1)(X2)(X3)(X4)M1
此式中，M1选自钛、锆和铪。通常最优选M1为锆。
此式中，(X1)独立地选自(下文中称为“Group OMC-I”)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)。
在(X1)的所述取代的环戊二烯基、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团、环状基团、脂族和环状基团的组合、甲硅烷基、烷基卤化物基团、卤基、有机金属基团、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明显的不利影响。
适合的脂族基团的例子是烃基如烷属烃和烯烃。适合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每个烷基含有1至约12个碳原子的烷基甲硅烷基、芳基甲硅烷基和芳基烷基甲硅烷基。适合的烷基卤化物基团有含1至约12个碳原子的烷基。适合的有机金属基团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。
适合的这种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。
此式中，(X3)和(X4)独立地选自(下文中称为“Group OMC-II”)卤基、脂族基团、取代的脂族基团、环状基团、取代的环状基团、脂族基团和环状基团的组合、取代的脂族基团和环状基团的组合、脂族基团和取代的环状基团的组合、取代的脂族基团和取代的环状基团的组合、氨基、取代的氨基、磷基、取代的磷基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基团和取代的有机金属基团，只要这些基团对所述催化剂组合物的聚合活性无明显的不利影响。
适合的脂族基团的例子是烃基如烷属烃和烯烃。适合的环状基团的例子是环烷烃、环烯烃、环炔烃和芳烃。通常优选(X3)和(X4)选自卤基和有1至约10个碳原子的烃基。但最优选(X3)和(X4)选自氟基、氯基和甲基。
此式中，(X2)可选自Group OMC-I或Group OMC-II。
(X1)或(X2)上至少一个取代基可以是连接(X1)和(X2)的桥连基团，只要所述桥连基团对所述催化剂组合物的活性无明显的不利影响。适合的桥连基团包括但不限于脂族基团、环状基团、脂族基团和环状基团的组合、磷基、氮基、有机金属基团、硅、磷、硼和锗。
适合的脂族基团的例子是烃基如烷属烃和烯烃。适合的环状基团的例子是环烷烃、环烯烃、环炔烃和芳烃。适合的有机金属基团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USP 4 939217；5 210 352；5 436 305；5 401 817；5 631 335；5 571 880；5191 132；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；5 451 649；5 541 272；5 705 478；5 631 203；5 654 454；5 705 579和5 668230。
这类有机金属化合物的具体实例如下：
二氯·双(环戊二烯基)合铪；
二氯·双(环戊二烯基)合锆；
1，2-亚乙基-双(η5-1-茚基)·二-正丁氧基合铪；
1，2-亚乙基-双(η5-1-茚基)·二甲基合锆；
二氯·3，3-亚戊基-双(η5-4，5，6，7-四氢-1-茚基)合铪；
二氯·甲基苯基甲硅烷基-双(η5-4，5，6，7-四氢-1-茚基)合锆；
双(正丁基环戊二烯基)·双(二叔丁氨基)合铪；
二氯·双(正丁基环戊二烯基)合锆；
二氯·二甲基甲硅烷基-双(1-茚基)合锆；
二氯·辛基苯基甲硅烷基-双(1-茚基)合铪；
二氯·二甲基甲硅烷基-双(η5-4，5，6，7-四氢-1-茚基)合锆；
二氯·二甲基甲硅烷基-双(2-甲基-1-茚基)合锆；
二氯·1，2-亚乙基-双(9-芴基)合锆；
一氯·茚基·二乙氧基合钛(IV)；
二氯·(异丙氨基二甲基甲硅烷基)环戊二烯基合钛；
二氯·双(五甲基环戊二烯基)合锆；
二氯·双(茚基)合锆；
二氯·甲基辛基甲硅烷基-双(9-芴基)合锆；
和
(三氟甲基磺酸根)·双-[1-(N，N-二异丙氨基)硼杂苯]·氢根
合锆
优选地，所述有机金属化合物选自：
二氯·双(正丁基环戊二烯基)合锆；
二氯·双(茚基)合锆；
二氯·二甲基甲硅烷基-双(1-茚基)合锆；
和
二氯·甲基辛基甲硅烷基-双(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。通常，优选(X5)为有1至约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、氢负离子或醇根离子。通常优选(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。但优选“n”为3。
这类化合物的例子如下：
三甲基铝；
三乙基铝(TEA)；
三丙基铝；
乙氧基二乙基铝；
三丁基铝；
氢化二异丁基铝；
氢化三异丁基铝；
三异丁基铝；和
氯化二乙基铝。
通常，优选TEA。
所述处理过的固体氧化物包括至少一种卤素、锆和固体氧化物。所述卤素是选自氯、溴和氟中至少之一。一般地，所述固体氧化物选自氧化铝、二氧化硅、磷铝酸盐、硅铝酸盐及其混合物。优选地，所述固体氧化物是氧化铝。所述固体氧化物可以通过本领域已知的任何方法生产，例如通过凝胶、共凝胶、一种化合物在另一种化合物上的浸渍和火焰水解。
一般地，所述固体氧化物在500℃煅烧后的表面积为约100～约1000m2/g，优选约200～约800m2/g，最优选250～600m2/g。
所述固体氧化物的孔体积通常大于约0.5cc/g，优选大于约0.8cc/g，最优选大于1.0cc/g。
为制备所述处理过的固体氧化物，可采用任何本领域已知的制备含锆固体氧化物的方法，使至少一种含锆化合物与所述固体氧化物接触。可以在煅烧前，或者在煅烧固体氧化物后的单独的步骤中，将锆加入到固体氧化物中。
一般地，在煅烧前，所述固体氧化物与含锆化合物的水溶液或有机溶液接触。例如，可以通过在含锆化合物和合适的溶剂例如醇或水的溶液中形成固体氧化物的淤浆而将锆加入到固体氧化物中。因为其挥发性和低表面张力，1～3个碳原子的醇是特别合适的。使用合适量溶液以在干燥后提供期望的锆浓度。任何可溶于水或可溶于有机溶剂的锆化合物都适合在固体氧化物上浸渍锆。实例包括但不限于四丙氧基锆、硝酸氧锆、乙酰丙酮锆及其混合物。干燥可以用任何本领域已知的方法完成。例如，可以通过抽滤然后蒸发、真空干燥、喷雾干燥或急剧干燥来完成所述干燥。
如果在煅烧后加入锆，一种优选的方法是用含锆化合物的烃溶液浸渍所述固体氧化物，所述锆化合物优选是锆烷氧化物或卤化物，例如ZrCl4，Zr(OR)4等，其中R是含有1～约12个碳的烷基或芳基。锆烷氧化物的实例包括但不限于四丙氧基锆、四丁氧基锆等。
一般地，在含锆固体氧化物中锆的存在量为约0.1～约30％重量的锆，其中重量百分比是基于煅烧前含锆固体氧化物的重量，或将该量加入到预先煅烧过的固体氧化物中。优选地，在含锆固体氧化物中锆的存在量为约0.5～约20％重量的锆，基于煅烧前含锆固体氧化物的重量，或将该量加入到预先煅烧过的固体氧化物中。最优选地，在含锆固体氧化物中锆的存在量为1～10％重量的锆，基于煅烧前含锆固体氧化物的重量，或将该量加入到预先煅烧过的固体氧化物中。
在所述固体氧化物与含锆化合物结合以制备含锆固体氧化物之前或之后，将固体氧化物煅烧约1分钟～约100小时，优选约1小时～约50小时，最优选3小时～20小时。一般地，煅烧在约200℃～约900℃的温度进行，优选约300℃～约700℃，最优选350℃～600℃。煅烧可以在任何合适的气氛中进行。一般地，煅烧可以在惰性气氛中完成。或者，煅烧可以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。
煅烧后或煅烧期间，所述含锆固体氧化物与至少一种含卤化合物接触。含卤化合物选自含氯化合物、含溴化合物和含氟化合物。含卤化合物可以呈液相，或优选地呈蒸气相。任选地，所述固体氧化物在与含卤化合物接触前，可以在100～900℃煅烧。
任何本领域已知的使固体氧化物与含氟化合物接触的方法都可以用于本发明。一种常规的方法是在煅烧前，用含氟盐的水溶液浸渍固体氧化物，所述含氟盐是例如氟化铵[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]及其混合物。
在第二种方法中，可以将含氟化合物溶解在有机化合物例如醇中，并加入到固体氧化物中，以使在干燥过程中孔的收缩最小。干燥可以通过本领域已知的方法完成，例如真空干燥、喷雾干燥、急剧干燥等。
在第三种方法中，所述含氟化合物也可在煅烧期间加入。在此技术中，使所述含氟化合物汽化进入用于流化固体氧化物的气流中，使所述固体氧化物氟化。除以上所述一些含氟化合物之外，还可在高于有机氟化物的分解点的温度下或在高至足以导致反应的温度下使用挥发性有机氟化物。例如可在空气或氮气中在约300～约600℃下，使全氟己烷、全氟代苯、三氟乙酸、三氟乙酸酐、六氟乙酰丙酮化物及其混合物汽化，并与所述固体氧化物接触。也可使用无机含氟化合物，例如氟化氢或甚至元素氟。
在处理过的固体氧化物上的氟的量为约2～约50％重量氟，基于煅烧前处理过的固体氧化物的重量，或将该量加入到预先煅烧过的固体氧化物中。在处理过的固体氧化物上的氟的量优选为约3～约25％重量，最优选为4～20％重量氟，基于煅烧前处理过的固体氧化物的重量，或将该量加入到预先煅烧过的固体氧化物中。
任何本领域已知的使固体氧化物与含氯化合物或含溴化合物接触的方法都可以用于本发明。一般地，在煅烧期间或煅烧后进行接触，优选在煅烧期间进行接触。可以使用任何能够在固体氧化物上沉积氯或溴或二者的合适的含氯化合物或含溴化合物。合适的含氯化合物和含溴化合物包括挥发性的或液体有机氯化物或溴化物和无机氯化物或溴化物。有机氯化物或溴化物可选自四氯化碳、氯仿、二氯乙烷、六氯代苯、三氯乙酸、溴仿、二溴甲烷、全溴丙烷、光气，及其混合物。无机氯化物或溴化物可选自气态的氯化氢、四氯化硅、四氯化锡、四氯化钛、三氯化铝、三氯化硼、亚硫酰氯、磺酰氯、溴化氢、三溴化硼、四溴化硅，及其混合物。另外，可以使用氯气或溴气。任选地，在某些情况下，当使所述含锆固体氧化物与含氯化合物或含溴化合物接触时，也可以包括含氟化合物，以实现更高的活性。
如果使用无机含氯化合物或含溴化合物，例如四氯化钛、三氯化铝或三氯化硼，还可以通过蒸气相沉积或甚至通过使用无水溶剂，在煅烧后使含氯化合物或含溴化合物与含锆固体氧化物接触。
使用的氯或溴的量为煅烧前处理过的固体氧化物重量的约0.01～约10倍，或将该量加入到预先煅烧过的固体氧化物中。优选使用的氯或溴的量为煅烧前处理过的固体氧化物重量的约0.05～约5倍，最优选为0.05～1倍，或将该量加入到预先煅烧过的固体氧化物中。
在本发明的另一个实施方案中，可以向处理过的固体氧化物中加入除锆以外的其它金属以提高有机金属化合物的活性。例如，可以加入金属如锌、银、铜、锑、镓、锡、镍、钨及其混合物。如果所述固体氧化物将在煅烧期间被氯化，这将特别有用。
可通过使所述有机金属化合物、所述有机铝化合物和所述处理过的固体氧化物一起接触来生产本发明的催化剂组合物。此接触可以以各种方式如共混进行。此外，这些化合物的每一种都可分别地加入反应器中，或者可使这些化合物的各种组合一起接触，然后在反应器内进一步接触，或者可在进入反应器之前使所有这三种化合物一起接触。
通常，一种方法是：先使所述有机金属化合物和所述处理过的固体氧化物在约10℃～约200℃，优选15℃～80℃的温度下一起接触约1分钟～约24小时，优选1分钟～1小时，而形成第一混合物，然后使所述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：在注入聚合反应器中之前，使所述有机金属化合物、所述有机铝化合物和所述处理过的固体氧化物在约10℃～约200℃，优选20℃～80℃的温度下，预接触约1分钟～约24小时，优选1分钟～1小时。
所述催化剂组合物中，所述有机铝化合物与所述处理过的固体氧化物之重量比为约5∶1～约1∶1000，优选约3∶1～约1∶100，最优选1∶1～1∶50。
所述催化剂组合物中，所述处理过的固体氧化物与所述有机金属化合物之重量比为约10,000∶1～约1∶1，优选约1000∶1～约10∶1，最优选250∶1～20∶1这些比例是基于混合得到所述催化剂组合物的组分的量。
接触后，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处理过的固体氧化物。优选地，所述接触后的处理过的固体氧化物占所述催化剂组合物的半数以上(重量)。通常，催化剂的具体组分是未知的，因而，本发明将所述催化剂组合物描述成包含接触后的化合物。
在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处理过的固体氧化物之重量比为约5∶1～约1∶1000，优选约3：1～约1∶100，最优选1∶1～1∶50。
所述催化剂组合物中，所述接触后的处理过的固体氧化物与所述接触后的有机金属化合物之重量比为约10,000∶1～约1∶1，优选约1000∶1～约10∶1，最优选250∶1～20∶1。这些比例是基于为给出催化剂组合物而结合的所述组分的量。
本发明的催化剂组合物的活性大于100g聚合物/g处理过的固体氧化物/hr，优选大于500，最优选大于约1,000。此活性是在淤浆聚合条件下测量，用异丁烷作为稀释剂，聚合温度为90℃，乙烯压力为550psig。所述反应器应基本上没有任何壁垢、涂层或其它形式的污垢的迹象。
本发明的重要方面之一是形成所述催化剂组合物的过程中不需使用铝氧烷。铝氧烷是昂贵的化合物，使聚合物生产成本显著增加。这还意味着不需要水帮助以形成这种铝氧烷。这是有益的，因为水有时可终止聚合过程。此外，应注意到形成所述催化剂组合物的过程中不需使用氟代有机硼酸盐化合物。当处理过的固体氧化物形成后，本发明的处理过的固体氧化物是无机性的，在有机聚合介质中是非均相的，并且可以容易而且便宜地生产，因为基本上不存在任何铝氧烷化合物或氟代有机硼酸盐化合物。还应指出，为了形成所述催化剂组合物，不需加入有机铬化合物和MgCl2。虽然在优选的实施方案中不需要铝氧烷、氟代有机硼酸盐化合物、有机铬化合物和MgCl2，但这些化合物也可用于本发明的其它实施方案。
本发明的另一实施方案中，提供一种方法，包括使至少一种单体和所述催化剂组合物接触以生产聚合物。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使至少一种单体聚合以生产均聚物或共聚物。通常，均聚物由每分子有2至约20个碳原子、优选每分子有2至约10个碳原子的单体残基组成。一般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。
要求均聚物时，最优选使乙烯或丙烯聚合。要求共聚物时，所述共聚物包括单体残基和一种或多种共聚单体残基，每一种都含有约2至约20个碳原子/分子。适合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，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；及共轭或非共轭二烯烃，如1，3-丁二烯、异戊二烯、1，3-戊二烯、2，3-二甲基-1，3-丁二烯、1，4-戊二烯、1，7-己二烯和其它的这样的二烯烃及其混合物。要求共聚物时，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。基于单体和共聚单体的总重，加入反应区用于生产共聚物的共聚单体量一般为约0.01～约10％重量的共聚单体，优选约0.01～约5％重量，最优选0.1～4％重量。或者，使用足以在所生产的共聚物中得到上述重量浓度的量。
聚合至少一种单体生产聚合物的工艺为本领域已知，例如淤浆聚合、气相聚合和溶液聚合。优选在环管反应区中进行淤浆聚合。适用于淤浆聚合的稀释剂为本领域所熟知，包括在反应条件下为液态的烃。本文所用术语“稀释剂”未必指惰性材料；稀释剂可对聚合有贡献。适合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，最优选使用异丁烷作为淤浆聚合中的稀释剂。该技术的例子可见USP 4 424 341；4 501 885；4 613 484；4 737 280和5 597 892。
所述催化剂组合物用于此工艺可生产高质量的聚合物颗粒，基本上不会污染反应器。当所述催化剂组合物在淤浆聚合条件下用于环管反应区时，为在聚合期间最好控制，优选所述固体氧化物的粒度为约10～约1000μm，优选约25～约500μm，最优选50～200μm。
在本发明更具体的实施方案中，提供一种催化剂组合物的生产方法，所述方法包括(任选地“主要由以下步骤组成”或“由以下步骤组成”)：
(1)使氧化铝与含有四烷氧基锆，即Zr(OR)4，其中R是含有1～12个碳的脂肪基的溶液接触，产生含锆的氧化铝，含有1～10％重量的锆，基于煅烧前含锆氧化铝的重量；
(2)在350～600℃的温度下，将所述含锆氧化铝煅烧3～20小时以生产煅烧过的组合物；
(3)使所述煅烧过的组合物与四氯化碳接触10分钟～30分钟以生产氯化的含锆氧化铝，四氯化碳的量为煅烧前氧化铝重量的0.05～1倍；
(4)在15～80℃的温度下，使所述氯化的含锆氧化铝与二氯·双(正丁基环戊二烯基)合锆混合约1分钟～1小时以生产一种混合物；和
(5)使所述混合物与三乙基铝混合以生产催化剂组合物。
本发明聚合过程中可用氢气控制聚合物的分子量。
本发明的一个特征是：所述含锆固体氧化物本身是聚合催化剂，在有机金属化合物的通常对称的分子量分布上，提供高分子量组分。此组分或偏斜的分子量分布，使聚合物具有比由有机金属化合物单独得到的聚合物更高的熔体强度和剪切响应。根据含锆固体氧化物和有机金属化合物的相对贡献，可以得到双峰聚合物分布。
生产所述聚合物之后，可将其制成各种制品，如家用容器和用具、薄膜产品、桶、燃料箱、管、地膜和衬里。各种方法可形成这些制品。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。相信采用在此所述的发明可以以更低的成本生产制品，同时保持用金属茂催化剂生产的聚合物的大多数特性(如果不是所有特性的话)。
实施例
测试方法
用“ Quantachrome Autosorb-6 Nitrogen Pore Size DistributionInstrument”测定表面积和孔体积。此仪器可购自QuantachromeCorporation，Syosset，N.Y.。
熔体指数(MI)(g/10min)采用ASTM D1238-95，在190℃下用2,160g重量的载荷测量。
高载荷熔体指数(HLMI)(g/10min)采用ASTM D1238，条件E，在190℃下用21,600g重量的载荷测量。
固体氧化物
由W.R.Grace得到952级二氧化硅，孔体积为约1.6cc/g，表面积为约300m2/g。
由Akzo Nobel Chemical得到以Ketjen B级氧化铝名义出售的工业氧化铝，孔体积为约1.78cc/g，表面积为约350m2/g。
煅烧
为煅烧固体氧化物，将约10g样品放在底部配有烧结的石英片的1.75英寸石英管中。在所述固体氧化物载于所述石英片上的情况下，吹入干燥空气，以约1.6至约1.8标准立方英尺/小时的线速向上通过所述石英片。然后打开所述石英管周围的电炉，使温度以400℃/小时的速度升至指定温度，例如600℃。在此温度下，使固体氧化物在所述干燥空气中流化3小时。然后将固体氧化物收集并储存在干燥氮气下，在该气氛下保护固体氧化物不接触大气直到准备进行测试。它不再允许有任何的暴露于大气的情况。
聚合试验
聚合试验在配有以400转/分钟(rpm)转动的marine搅拌器的2.2L钢反应器中进行。该反应器周围有钢夹套，夹套内含有沸腾的甲醇，与钢冷凝器相连。甲醇的沸点通过改变施于所述冷凝器和夹套的氮气压力控制，借助于电子控制仪器可使温度控制精确在0.5℃内。
首先将少量(通常为0.1～1.0g)卤化的固体氧化物或本发明处理过的固体氧化物在氮气下装入干燥的反应器中。然后，加入2.0ml含有0.5％重量的二氯·双(正丁基环戊二烯基)合锆的甲苯溶液，接着加入0.6L异丁烷液体。然后加入1.0ml 1.0M的三乙基铝(TEA)溶液，接着加入另外的0.6L异丁烷液体。然后将反应器加热到指定的温度，典型地为90℃，最后，向反应器中加入乙烯至等于550psig的固定压力(除非另外说明)。搅拌该反应混合物最长达1小时。随着乙烯的消耗，流入更多的乙烯以维持所述压力。通过记录为保持设定的压力而进入反应器的乙烯流量来记录活性。
在规定的时间之后，停止乙烯流，使反应器缓慢降压，打开反应器回收颗粒状聚合物。在所有例子中，反应器都是清洁的，没有任何壁垢、涂层或其它形式的污垢的迹象。然后取出聚合物并称重。活性表示为每克投入的卤化的固体氧化物或处理过的固体氧化物每小时产生的聚合物的克数(g/g/hr)。
结果
本发明的具体实施例描述如下。这些聚合试验的结果列于表1。
实施例1
1-A(对照样-氯化的氧化铝)
将Ketjen B级氧化铝在600℃下于干燥空气中煅烧3小时。9.3g重的该材料的一份样品于干燥氮气中加热到600℃，并在该温度再保持3小时。然后，将2.3ml四氯化碳注入到氧化铝下的氮气流中，在此四氯化碳汽化并被携带向上通过氧化铝床以生产氯化的氧化铝。在所有四氯化碳蒸发后，将所述氯化的氧化铝在氮气氛下冷却到室温，然后储存在密封的玻璃容器中，直到用于聚合试验。当与有机金属化合物和TEA加入到反应器中时，发现其活性为1066g聚合物/g氯化的氧化铝/hr。聚合物的MI为0.17g/10min，HLMI为2.8g/10min，HLMI/MI比值为16.5，反映出窄的分子量分布，这是典型的金属茂生产的聚合物。
1-B(对照样-氯化的含锆氧化铝)
将Ketjen B级氧化铝在600℃下于干燥空气中煅烧3小时。用含有9.0ml在丁醇中的80wt％的四丁氧基锆(1.049g/ml)和31ml干燥庚烷的溶液浸渍19.7g重的该材料的一份样品，以制备含锆的氧化铝。在约80℃，在干燥氮气流下使过量的溶剂蒸发掉。然后在500℃，在氮气氛下煅烧所述含锆的氧化铝，在该过程中，向气流中注入3.0ml四氯化碳以制备氯化的含锆氧化铝。在基本上所有的四氯化碳都汽化并向上通过处于500℃的含锆氧化铝床后，将氯化的含锆氧化铝在氮气氛下储存。
然后在有三乙基铝存在但无有机金属化合物存在的情况下，测试所述氯化的含锆氧化铝的聚合活性。得到862g聚合物/g氯化的含锆氧化铝/hr，表明处理过的固体氧化物本身具有内在的活性。聚合物的MI为0，HLMI为0，表明由这样的锆催化剂得到极高的分子量。
1-C(本发明-氯化的含锆氧化铝)
按照前述程序，但是在有机金属化合物存在下，再测试实施例1-B的同样的氯化的含锆氧化铝的聚合活性。得到1484g聚合物/g氯化的含锆氧化铝/hr，表明了有机金属化合物的另外的贡献。这样，氯化的含锆氧化铝表现出与实施例1-A的氯化的氧化铝对照样相当的活性，但是聚合物却大大不同。所述聚合物的MI为0，HLMI为0，表明锆对高分子量的贡献。
实施例2
2-A(对照样-氯化的二氧化硅)
将Davison 952级二氧化硅在600℃下于干燥空气中煅烧3小时。约10.0g重的该材料的一份样品于干燥氮气中加热到600℃，然后将2.3ml四氯化碳注入到二氧化硅下的氮气流中(如实施例1)，在此四氯化碳汽化并被携带向上通过二氧化硅床以生产氯化的二氧化硅。在所有四氯化碳蒸发后，将所述氯化的二氧化硅在氮气氛下冷却到室温，然后储存在密封的玻璃容器中，直到用于聚合试验。当与有机金属化合物和TEA一起加入到反应器中时，发现无聚合物产生。
2-B(本发明-氯化的含锆二氧化硅)
用75ml 80％的四丁氧基锆丁醇溶液浸渍50g重的Davison 952级二氧化硅样品，以制备含锆的二氧化硅。然后，加入由25ml水和25ml丙醇配成的另外50ml溶液，以水解所述丁氧基锆。该混合物在真空下于120℃干燥16小时。将重15.90g的所述含锆二氧化硅的样品在干燥氮气中加热到600℃，维持2小时。然后，向氮气流中注入1.0ml四氯化碳以氯化所述含锆的二氧化硅，从而制备氯化的含锆二氧化硅。在基本上所有的四氯化碳都汽化后，将氯化的含锆二氧化硅在氮气氛下储存。
然后如前所述，在三乙基铝和有机金属化合物存在下，测试所述氯化的含锆二氧化硅的聚合活性。得到123g聚合物/g氯化的含锆二氧化硅/hr。尽管该数值低，但它比根本不产生聚合物的实施例2-A中的氯化二氧化硅对照样试验有相当大的改进。这表明所述氯化的含锆二氧化硅能够活化有机金属化合物。而且，该聚合物的MI为0，HLMI为0，显示了锆的贡献。
2-C(本发明-氯化的含锆二氧化硅)
再测试实施例2-B的氯化的含锆二氧化硅与有机金属化合物和三乙基铝一起的聚合活性，只是还向反应器中加入20psig的氢气以降低制备的聚合物的分子量。该试验得到相当的活性，但是分子量没有降低到足以产生很大的变化的程度。MI仍然为0，而HLMI仅增加到0.02。再次地，这表明了锆的贡献。
2-D(本发明-氯化的含锆二氧化硅)
再测试实施例2-B的氯化的含锆二氧化硅与有机金属化合物和三乙基铝一起的聚合活性，只是向反应器中加入50psig的氢气以进一步降低制备的聚合物的分子量。该试验又得到相当的活性，并且分子量降低到足以产生0.14的MI和8.94的HLMI。如HLMI/MI的比值为64.8所表明，该试验给出了宽的分子量分布，大大宽于实施例1-A中的有机金属化合物对照样。所述宽的分子量分布是由于有机金属化合物和氯化的含锆二氧化硅的贡献。
2-E(本发明-氯化的含锆二氧化硅)
再测试实施例2-B的氯化的含锆二氧化硅与有机金属化合物和三乙基铝一起的聚合活性，如实施例2-D又加入50psig的氢气。该试验又得到相当的活性，并且分子量降低到足以产生0.18的MI和10.9的HLMI。如HLMI/MI的比值为59.6所表明，该试验给出了宽的分子量分布，大大宽于实施例1-A中的有机金属化合物对照样。所述宽的分子量分布又是由于有机金属化合物和氯化的含锆二氧化硅的贡献。
实施例3
3-A(对照样-氟化的氧化铝)
将Ketjen B级氧化铝在600℃下于干燥空气中煅烧3小时。用含有1.25g溶解的氟化氢铵的25ml水溶液浸渍12.3g重的该氧化铝样品，并在真空烘箱中于120℃干燥过夜，以制备氟化的氧化铝。然后将其于干燥氮气中加热到600℃，并在该温度保持3小时。然后，将所述氟化的氧化铝在氮气氛下冷却到室温，并储存在密封的玻璃容器中，直到用于聚合试验。当与有机金属化合物和TEA一起加入到反应器中时，发现其活性为1250g聚合物/g氟化的氧化铝/hr。聚合物的MI为0.21，HLMI为3.48，HLMI/MI比值为16.6，反映出窄的分子量分布，这是典型的金属茂生产的聚合物。
3-B(对照样-氟化的含锆氧化铝)
将Ketjen B级氧化铝在600℃下于干燥空气中煅烧3小时。用含有9.0ml在丁醇中的80wt％的四丁氧基锆(1.049g/ml)和31ml干燥庚烷的溶液浸渍19.7g重的该氧化铝样品，以制备含锆的氧化铝。在约80℃，在干燥氮气流下使过量的溶剂蒸发掉。然后在600℃，在氮气氛下煅烧16.80g重的所述含锆的氧化铝样品，在该过程中，向气流中注入3.0ml全氟己烷以制备氟化的含锆氧化铝。在基本上所有的全氟己烷都汽化并向上通过处于600℃的含锆氧化铝床后，将气流切换为干燥空气，通40分钟。最后，将氟化的含锆氧化铝在氮气氛下储存。
然后在有TEA存在但无有机金属化合物存在的情况下，测试所述氟化的含锆氧化铝的聚合活性。得到35g聚合物/g氟化的含锆氧化铝/hr，表明所述的氟化的含锆氧化铝的活性比实施例1-B中的氯化的含锆氧化铝的活性低得多。得到的聚合物的MI为0，HLMI为0，表明氟化的含锆氧化铝也产生极高分子量的聚合物。
3-C(本发明-氟化的含锆氧化铝)
按照聚合程序所述，再测试实施例3-B的氟化的含锆氧化铝的聚合活性，但是这次在有机金属化合物存在下进行。这次氟化的含锆氧化铝产生高得多的活性，为1382g聚合物/g氟化的含锆氧化铝，表明所述氟化的含锆氧化铝也具有活化有机金属化合物的能力。所述聚合物的MI为0，HLMI为1.74，这处于实施例3-A的有机金属化合物和实施例3-B的氟化的含锆氧化铝之间。这样，得到更宽的分子量分布。
实施例4
4-A(本发明-氟化的含锆氧化铝)
用由20ml异丙醇和24ml在丁醇中的80wt％的四丁氧基锆溶液(1.049g/ml)配成的40ml溶液浸渍Ketjen B级氧化铝(100-200目，未煅烧)，以制备含锆的氧化铝。该含锆的氧化铝在真空烘箱中于120℃干燥过夜。然后在600℃，在干燥空气中煅烧11.17g所述含锆的氧化铝3小时。然后，向空气流中注入5.0ml全氟己烷以氟化所述含锆氧化铝，从而制备氟化的含锆氧化铝。在所有的全氟己烷都已汽化并向上通过所述含锆氧化铝床后，将氟化的含锆氧化铝冷却并储存在干燥氮气氛下。
然后在有机金属化合物和三乙基铝存在下，测试所述氟化的含锆氧化铝的聚合活性。其活性为924g聚合物/g氟化的含锆氧化铝/hr。聚合物的MI为0.03，HLMI为2.26，这样HLMI/MI的比值为83.6，它比实施例3-A的纯有机金属化合物对照样高很多。更高的剪切比表明了由氟化的含锆氧化铝的另外的贡献所造成的更宽的分子量分布。所述氟化的含锆氧化铝引入了少量但具有极高分子量的聚合物组分，该组分占本实施例的整个聚合物分子量分布的约4％。
4-B(本发明-氟化的含锆氧化铝)
为进一步降低得到的聚合物的分子量，在有机金属化合物和三乙基铝存在下，再次测试实施例4-A的氟化的含锆氧化铝的聚合活性，只是将乙烯压力从通常的550psig降低到450psig，并且还加入25ml 1-己烯以制备乙烯-己烯共聚物。在这些条件下，所述氟化的含锆氧化铝的活性为523g聚合物/g氟化的含锆氧化铝/hr。由于所使用的乙烯浓度低，该活性比实施例4-A低。发现聚合物的MI为0.30，HLMI为6.38，这样HLMI/MI的比值为21.1。再次地，更高的剪切比表明了由于氟化的含锆氧化铝的另外的贡献，分子量分布比由实施例3-A的有机金属化合物得到的分子量分布更宽。所述氟化的含锆氧化铝引入了少量但具有极高分子量的聚合物组分，该组分占本实施例的整个聚合物分子量分布的约7％。
| 表1实施例 试验化合物 有机金属 试验 聚合物 运转时间 活性 注释 MI HLMI HLMI/MI化合物 化合物 产率 (minutes) g/g/hr (g/10(g/10(g) (g) min)min)1A对照样 Cl-氧化铝 是 1.1281 100.2 5.0 1066 0.17 2.8 16.51B对照样 Cl-Zr/氧化铝 否 0.4585 247.0 37.5 862 0.00 0.001C发明 Cl-Zr/氧化铝 是 0.0874 110.0 50.9 1484 0.00 0.002A对照样 Cl-二氧化硅 是 0.4414 0 60.0 02B发明 Cl-Zr/二氧化硅 是 0.3608 31.3 42.2 123 0.00 0.002C发明 Cl-Zr/二氧化硅 是 0.2826 30.6 60.9 107 20psig H2 0.00 0.022D发明 Cl-Zr/二氧化硅 是 0.4136 43.5 62.0 102 50psig H2 0.14 8.94 64.82E发明 Cl-Zr/二氧化硅 是 0.4503 43.2 60.0 96 50psig H2 0.18 10.90 59.63A对照样 F-氧化铝 是 0.2253 281.6 60.0 1250 0.21 3.48 16.63B对照样 F-Zr/氧化铝 否 0.1522 3.0 33.4 35 0.00 0.003C发明 F-Zr/氧化铝 是 0.0832 120.0 62.6 1382 0.00 1.744A发明 F-Zr/氧化铝 是 0.5510 331.0 39.0 924 0.03 2.26 83.64B发明 F-Zr/氧化铝 是 0.0960 50.5 60.3 523 450psig 乙烯 0.30 6.38 21.120mls 己烯 |
*活性＝g聚合物/g试验化合物/hr
虽然为了说明已详细地描述了本发明，但不是要限制本发明而是要包括在本发明的精神和范围内的所有改变和修改。
Claims (18)
1.一种催化剂组合物的生产方法，所述方法包括使至少一种有机金属化合物、至少一种有机铝化合物和至少一种处理过的固体氧化物接触以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；
其中(X1)独立地为环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基或取代的芴基；
其中在(X1)的所述取代的环戊二烯基、取代的茚基或取代的芴基上的各取代基是脂族基团、环状基团、脂族和环状基团的组合、甲硅烷基、烷基卤化物基团、卤基、有机金属基团、磷基、氮基、硅、磷、硼、锗或氢；
其中(X1)上至少一个取代基任选是连接(X1)和(X2)的桥连基团；
其中(X3)和(X4)独立地为卤基、脂族基团、取代的脂族基团、环状基团、取代的环状基团、脂族基团和环状基团的组合、取代的脂族基团和环状基团的组合、脂族基团和取代的环状基团的组合、取代的脂族基团和取代的环状基团的组合、氨基、取代的氨基、磷基、取代的磷基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基团或取代的有机金属基团；
其中(X2)是环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基、取代的芴基、卤基、脂族基团、取代的脂族基团、环状基团、取代的环状基团、脂族基团和环状基团的组合、取代的脂族基团和环状基团的组合、脂族基团和取代的环状基团的组合、取代的脂族基团和取代的环状基团的组合、氨基、取代的氨基、磷基、取代的磷基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基团或取代的有机金属基团；
其中在(X2)上的各取代基是脂族基团、环状基团、脂族基团和环状基团的组合、甲硅烷基、烷基卤化物基团、卤基、有机金属基团、磷基、氮基、硅、磷、硼、锗或氢；
其中(X2)上至少一个取代基任选是连接(X1)和(X2)的桥连基团；
其中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；
其中(X6)为卤离子、氢负离子或醇根离子；和
其中“n”为1至3的数；
其中所述处理过的固体氧化物包含至少一种卤素、锆和固体氧化物；
其中所述卤素是氯、溴或氟中至少之一；
其中所述固体氧化物是氧化铝、铝磷酸盐、硅铝酸盐或任何两种或多种所述固体氧化物的混合物；
其中基本上不存在铝氧烷。
2.权利要求1的方法，其中所述处理过的固体氧化物与至少一种另外的金属接触。
3.权利要求2的方法，其中所述至少一种另外的金属是锌、银、铜、锑、镓、锡、镍、钨或任何两种或多种所述金属的混合物。
4.权利要求1的方法，其中这样制备的催化剂组合物在淤浆聚合条件下的活性大于500，所述淤浆聚合条件为：使用异丁烷作为稀释剂，聚合温度为90℃，乙烯压力为3.89MPa。
5.权利要求4的方法，其中所述催化剂组合物在淤浆聚合条件下的活性大于1000，所述淤浆聚合条件为：使用异丁烷作为稀释剂，聚合温度为90℃，乙烯压力为3.89MPa。
6.权利要求1的方法，其中在所述催化剂组合物中，所述有机铝化合物与所述处理过的固体氧化物之重量比在3∶1至1∶100的范围内。
7.权利要求6的方法，其中在所述催化剂组合物中，所述有机铝化合物与所述处理过的固体氧化物之所述重量比在1∶1至1∶50的范围内。
8.权利要求1的方法，其中在所述催化剂组合物中，所述处理过的固体氧化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。
9.权利要求8的方法，其中在所述催化剂组合物中，所述处理过的固体氧化物与所述有机金属化合物之所述重量比在250∶1至20∶1的范围内。
10.权利要求1的方法，其中所述处理过的固体氧化物包括氧化铝，1～10％重量的锆/克煅烧前所述处理过的固体氧化物，基于煅烧前所述处理过的固体氧化物重量的4～20％重量的氟，并且在350～600℃温度下煅烧3～20小时。
11.一种制备催化剂组合物的方法，所述方法包括：
(1)使氧化铝与含有四烷氧基锆，即Zr(OR)4，其中R是含有1～12个碳的脂肪基的溶液接触，产生含锆的氧化铝，含有1～10％重量的锆，基于煅烧前含锆氧化铝的重量；
(2)在350～600℃的温度下，将所述含锆氧化铝煅烧3～20小时以制备煅烧过的组合物；
(3)使所述煅烧过的组合物与四氯化碳接触10分钟～30分钟以制备氯化的含锆氧化铝，四氯化碳的量为煅烧前氧化铝重量的0.05～1倍；
(4)在15～80℃的温度下，使所述氯化的含锆氧化铝与二氯·双(正丁基环戊二烯基)合锆混合1分钟～1小时以生产一种混合物；和
(5)使所述混合物与三乙基铝混合以制备催化剂组合物。
12.一种基本上不含铝氧烷的催化剂组合物，包括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处理过的固体氧化物；
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；
其中(X1)独立地为环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基或取代的芴基；
其中在(X1)的所述取代的环戊二烯基、取代的茚基或取代的芴基上的各取代基是脂族基团、环状基团、脂族和环状基团的组合、甲硅烷基、烷基卤化物基团、卤基、有机金属基团、磷基、氮基、硅、磷、硼、锗或氢；
其中(X1)上至少一个取代基任选是连接(X1)和(X2)的桥连基团；
其中(X3)和(X4)独立地为卤基、脂族基团、取代的脂族基团、环状基团、取代的环状基团、脂族基团和环状基团的组合、取代的脂族基团和环状基团的组合、脂族基团和取代的环状基团的组合、取代的脂族基团和取代的环状基团的组合、氨基、取代的氨基、磷基、取代的磷基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基团或取代的有机金属基团；
其中(X2)是环戊二烯基、茚基、芴基、取代的环戊二烯基、取代的茚基、取代的芴基、卤基、脂族基团、取代的脂族基团、环状基团、取代的环状基团、脂族基团和环状基团的组合、取代的脂族基团和环状基团的组合、脂族基团和取代的环状基团的组合、取代的脂族基团和取代的环状基团的组合、氨基、取代的氨基、磷基、取代的磷基、烷氧基、取代的烷氧基、芳氧基、取代的芳氧基、有机金属基团或取代的有机金属基团；
其中在(X2)上的各取代基是脂族基团、环状基团、脂族基团和环状基团的组合、甲硅烷基、烷基卤化物基团、卤基、有机金属基团、磷基、氮基、硅、磷、硼、锗或氢；
其中(X2)上至少一个取代基任选是连接(X1)和(X2)的桥连基团；
其中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；
其中(X6)为卤离子、氢负离子或醇根离子；和
其中“n”为1至3的数；
其中所述处理过的固体氧化物包含至少一种卤素、锆和固体氧化物；
其中所述卤素是氯、溴或氟；
其中所述固体氧化物是氧化铝、铝磷酸盐、硅铝酸盐或任何两种或多种所述固体氧化物的混合物。
13.一种聚合方法，包括使至少一种单体与权利要求12的催化剂组合物或按照权利要求1-11中任意一项的方法制备的催化剂组合物在聚合条件下接触以生产聚合物。
14.权利要求13的方法，其中所述聚合条件包括淤浆聚合条件。
15.权利要求14的方法，其中所述接触在环管反应区中进行。
16.权利要求15的方法，其中所述接触在包含异丁烷作为主要部分的稀释剂存在下进行。
17.权利要求13的方法，其中所述至少一种单体为乙烯。
18.权利要求13的方法，其中所述至少一种单体包括乙烯和每分子有3～20个碳原子的脂族1-烯烃。
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| JP2006522189A (ja) | 2003-04-03 | 2006-09-28 | バーゼル・ポリオレフィン・ゲーエムベーハー | 気相流動床反応器内における有機遷移金属化合物存在下での高分子量ポリオレフィンの製造 |
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| US11845814B2 (en) | 2022-02-01 | 2023-12-19 | Chevron Phillips Chemical Company Lp | Ethylene polymerization processes and reactor systems for the production of multimodal polymers using combinations of a loop reactor and a fluidized bed reactor |
| US20230331875A1 (en) | 2022-04-19 | 2023-10-19 | Chevron Phillips Chemical Company Lp | Loop slurry periodogram control to prevent reactor fouling and reactor shutdowns |
| US11753488B1 (en) | 2022-06-24 | 2023-09-12 | Chevron Phillips Chemical Company Lp | Processes for preparing metallocene-based catalyst systems with an alcohol compound |
| US20240301099A1 (en) | 2023-03-09 | 2024-09-12 | Chevron Phillips Chemical Company Lp | Dual metallocene polyethylene with improved escr for rotomolded, injection molded, and related products |
| US20250066274A1 (en) | 2023-08-22 | 2025-02-27 | Chevron Phillips Chemical Company Lp | Integrated processes utilizing water electrolysis and oxidative dehydrogenation of ethane |
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-
1999
- 1999-12-03 US US09/454,975 patent/US6548442B1/en not_active Expired - Lifetime
-
2000
- 2000-12-01 ES ES00992600T patent/ES2252091T3/es not_active Expired - Lifetime
- 2000-12-01 WO PCT/US2000/042496 patent/WO2001041920A1/en active IP Right Grant
- 2000-12-01 DE DE60022909T patent/DE60022909T2/de not_active Expired - Lifetime
- 2000-12-01 CA CA002394693A patent/CA2394693A1/en not_active Abandoned
- 2000-12-01 HU HU0203595A patent/HUP0203595A3/hu unknown
- 2000-12-01 AU AU45141/01A patent/AU770747B2/en not_active Ceased
- 2000-12-01 CN CNB008178437A patent/CN1188431C/zh not_active Expired - Fee Related
- 2000-12-01 DK DK00992600T patent/DK1250190T3/da active
- 2000-12-01 AT AT00992600T patent/ATE305332T1/de not_active IP Right Cessation
- 2000-12-01 EP EP00992600A patent/EP1250190B1/en not_active Expired - Lifetime
-
2002
- 2002-06-03 NO NO20022631A patent/NO20022631L/no not_active Application Discontinuation
-
2003
- 2003-02-26 HK HK03101438.5A patent/HK1049294B/zh not_active IP Right Cessation
- 2003-03-17 US US10/390,497 patent/US6878785B2/en not_active Expired - Fee Related
-
2004
- 2004-11-19 US US10/993,958 patent/US20050137366A1/en not_active Abandoned
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|---|---|
| HUP0203595A3 (en) | 2004-06-28 |
| US20030171511A1 (en) | 2003-09-11 |
| US20050137366A1 (en) | 2005-06-23 |
| CN1414880A (zh) | 2003-04-30 |
| AU4514101A (en) | 2001-06-18 |
| CA2394693A1 (en) | 2001-06-14 |
| HUP0203595A2 (hu) | 2003-01-28 |
| US6548442B1 (en) | 2003-04-15 |
| EP1250190A4 (en) | 2003-06-25 |
| DK1250190T3 (da) | 2005-10-17 |
| EP1250190A1 (en) | 2002-10-23 |
| HK1049294B (zh) | 2006-03-17 |
| US6878785B2 (en) | 2005-04-12 |
| DE60022909T2 (de) | 2006-06-22 |
| DE60022909D1 (de) | 2006-02-09 |
| ES2252091T3 (es) | 2006-05-16 |
| WO2001041920A1 (en) | 2001-06-14 |
| AU770747B2 (en) | 2004-03-04 |
| HK1049294A1 (en) | 2003-05-09 |
| NO20022631D0 (no) | 2002-06-03 |
| ATE305332T1 (de) | 2005-10-15 |
| EP1250190B1 (en) | 2005-09-28 |
| NO20022631L (no) | 2002-07-10 |
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