CN1070652A - 减活化及再活化的金属茂催化剂体系 - Google Patents
减活化及再活化的金属茂催化剂体系 Download PDFInfo
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 41
- 230000009849 deactivation Effects 0.000 title claims abstract description 31
- -1 aluminium alkoxide compound Chemical class 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- 239000004480 active ingredient Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001728 carbonyl compounds Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical class Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004429 atom Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XFBYPTDICTYNBZ-UHFFFAOYSA-L CC1=C[C@@](C)([Zr](Cl)Cl)C=C1 Chemical class CC1=C[C@@](C)([Zr](Cl)Cl)C=C1 XFBYPTDICTYNBZ-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- VNVUTMPEJGCDNY-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C(CC)=CC2=C1 Chemical class [Cl-].[Cl-].C1=CC=C2C([Zr+2])C(CC)=CC2=C1 VNVUTMPEJGCDNY-UHFFFAOYSA-L 0.000 description 1
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical class [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 1
- FRDRZJBEQBTXMF-UHFFFAOYSA-L [Cl-].[Cl-].CCC1([Zr++])C=CC(C)=C1 Chemical class [Cl-].[Cl-].CCC1([Zr++])C=CC(C)=C1 FRDRZJBEQBTXMF-UHFFFAOYSA-L 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- 150000005524 benzylchlorides Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
用于C2—C10链烯烃聚合的金属茂催化剂体系，
其可由一种预活化的金属茂催化剂体系经过减活而
得到。该预活化金属茂催化剂体系的活性组分含有
一种周期表IV或V副族金属的金属茂配合物，以及一
种低聚的铝氧烷化合物。在需要时，可以将该体系再
活化。
Description
本发明涉及用于C2-C10链烯烃聚合的金属茂催化剂体系，该体系可由预活化的金属茂催化剂体系经减活化而得到，所述预活化金属茂催化剂体系的活性组分含有一种元素周期表Ⅳ或Ⅴ副族金属的金属茂配合物，以及一种低聚的铝氧烷（alumoxane）化合物。
本发明还涉及可由减活的金属茂体系的再活化而得到的金属茂催化剂体系，还涉及该减活及再活化金属茂催化剂体系的制备方法，以及该催化剂在制备聚烯烃中的应用，以及借助于此等金属茂催化剂制备聚烯烃的方法，以及所得到的聚烯烃。
由于金属茂催化剂在用铝化合物预活化之后可达到最优的聚合活性，会发生工艺工程问题，例如在该催化剂进行计量时由于早期聚合作用而堵塞计量系统。通过将催化剂体系减活，可以避免上述问题，但所说的减活必须是可逆的。
本发明的目的之一是将预活化的金属茂催化剂减活，然后将之再活化。
业已发现，借助于本文开端所定义的金属茂催化剂体系而达到本发明的上述目的。还发现了制备该等减活和再活化金属茂催化剂体系的方法、它们用于制备聚烯烃的用途、借助于此等金属茂催化剂体系制备聚烯烃的方法、以及所得到的聚烯烃。
适于减活的金属茂催化剂体系的活性组分中含有一种周期表Ⅳ或Ⅴ副族金属的配合物，特别是钛、锆、铪、钒、铌或钽的配合物。优选使用的配合物是该金属原子通过π键与不饱和环碳原子相键接的情况，例如与环戊二烯基、芴基或茚基键接。此外，在优选使用的配合物中，该金属原子还可以键接到其他配位体，特别是氟、氯、溴、碘、氢或C1-C10烷基，例如甲基、乙基、丙基或丁基。特别适用的配合物是含有氯的品种。
可以举出参考的例如有EP-A-129368，EP-A-407870，EP-A-413326，EP-A-399347，DE-A-3929693所述的适用的金属茂催化剂体系。
已证实的优选的金属茂催化剂体系是含有下列的活性组分的体系：
a）通式Ⅰ的金属茂配合物
其中R1至R3和R5至R7各自是氢、C1-C10烷基、5员至7员的环烷基并可被C1-C6烷基所取代、或者C6-C15芳基或芳烷基，其中两个相邻的基即R1和R2、R2和R3、R5和R6或R6和R7可以一起形成一个C4-C15的环状基团;R4和R8各自是氢或C1-C10烷基;R9是C1-C10烷基、C3-C10环烷基或C6-C10芳基;M是钛、锆、铪、钒、铌或钽;Y是硅、锗、锡或碳;X是氢、氟、氯、溴、碘或C1-C10烷基;n为0、1或2;以及
b）通式Ⅱ或Ⅲ的开链或环状铝氧烷化合物
其中R10为C1-C4烷基，m为5至30。
式Ⅰ的优选的金属茂配合物是R1和R5相同并且是氢或C1-C10烷基;R4与R8相同并且是氢、甲基、乙基、异丙基或叔丁基;R3和R7各自是C1-C4烷基;R2和R6各自是氢;或者两个相邻的基R2和R3以及R6和R7一起形成C4-C12不饱和环状基团;R9是C1-C8烷基;M为锆或铪;Y为硅或碳;X为氯。
特别优选的配合物举例如下：
二甲基甲硅烷二基双（3-叔丁基-5-甲基环戊二烯基）二氯化锆，
二乙基甲硅烷二基双（3-叔丁基-5-甲基环戊二烯基）二氯化锆，
甲基乙基甲硅烷二基双（3-叔丁基-5-甲基环戊二烯基）二氯化锆，
二甲基甲硅烷二基双（3-叔丁基-5-乙基环戊二烯基）二氯化锆，
二甲基甲硅烷二基双（3-叔丁基-5-甲基环戊二烯基）二甲基锆，
二甲基甲硅烷二基双（2-甲基茚基）二氯化锆，
二乙基甲硅烷二基双（2-甲基茚基）二氯化锆，
二甲基甲硅烷二基双（2-乙基茚基）二氯化锆，
二甲基甲硅烷二基双（2-异丙基茚基）二氯化锆，
二甲基甲硅烷二基双（2-叔丁基茚基）二氯化锆，
二乙基甲硅烷二基双（2-甲基茚基）二溴化锆，
二甲基硫化物双（2-甲基茚基）二氯化锆，
二甲基甲硅烷二基双（2-甲基-5-甲基环戊二烯基）二氯化锆，
二甲基甲硅烷二基双（2-甲基-5-乙基环戊二烯基）二氯化锆，
二甲基甲硅烷二基双（2-乙基-5-异丙基环戊二烯基）二氯化锆，
二甲基甲硅烷二基双（2-甲基茚基）二氯化锆，
二甲基甲硅烷二基双（2-甲基苯并茚基）二氯化锆，
二甲基甲硅烷二基双（2-甲基茚基）二氯化铪。
此等配合物可以用常规方法合成，优选将相应取代的环状烃阴离子与钛、锆、铪、钒、或钽的卤化物进行反应。特别是刊载于J.Organome tal.Chem.369（1989），359-370的相应制备方法。
该金属茂催化剂体系除含有该配合物之外，还含有通式Ⅰ或Ⅱ的低聚铝氧烷化合物，其中R10优选为甲基或乙基，m优选为10至25。
此等低聚铝氧烷化合物通常由三烷基铝溶液与水反应来制备，特别是EP-A-284708和US-A-4794096所描述的制备方法。
一般的规律，所得低聚铝氧烷的存在方式是不同长度的链状和环状分子的混合物，于是其中的m是一个平均值。该铝氧烷化合物还可含有C1-C8的三烷基铝化合物，例如三甲基-、三乙基-、或甲基二乙基铝，或者是其中一些有机基团被氢原子取代的三烷基铝化合物。
业已证实，周期表Ⅳ或Ⅴ副族金属的配合物与该低聚铝氧烷化合物为如下的含量比率是有利的，即该低聚铝氧烷化合物中的铝对该配合物中的过渡金属的比率为10∶1至106∶1，特别是10∶1至104∶1。
首先，将该周期表Ⅳ或Ⅴ副族金属的配合物与该低聚铝氧烷化合物混合，结果即得到一种活化的催化剂体系。此一活化步骤的时间通常为1至120分钟，特别是10至100分钟。优选的混合方式是使该配合物与该低聚铝氧烷化合物在惰性溶剂中的溶液于0至50℃进行接触，所述溶剂例如苯、甲苯、己烷、庚烷或其混合物。
业已证实，亲电子试剂特别适用于减活此等预活化的金属茂催化剂体系，其中优选的有有机卤化物，例如C1-10烷基卤化物和C6-C12芳基卤化物，这些物质又可以被C1-C10烷基或卤素所单取代至五取代，特别是苄基氯、C1-C10醇、C3-C12酮、C2-C10醛、以及NO、CO2，或者上述化合物的混合物。业已证实，苄基氯和CO2是特别优选的。
一般规律，用于减活的化合物用量为0.1至5000，优选1至500，特别是1至200倍量，按过渡金属的摩尔当量计。
从原则上讲，该预活化的金属茂催化剂体系进行减活时的温度和压力并不重要。一般规律，所用温度为-70℃至+100℃，压力为0.1至3000巴。减活进行时间通常为0.1至100分钟。
然后，可将已减活的金属茂催化剂系计量并送入反应器中，并在该反应器中再活化。
对于将该等减活的金属茂催化剂体系再活化而言，业已证实有机金属化合物特别适用。优选的是有机基铝，特别是铝氧烷。
具体实例是按式Ⅱ或式Ⅲ的开链或环状的铝氧烷化合物。
通常将该等低聚铝氧烷化合物溶解于惰性溶剂中，例如苯、甲苯、己烷或庚烷或其混合物，然后加入到已减活的金属茂催化剂体系中。此处，从原则上讲，反应所用的温度、压力以及时间也是并不重要;通常，该反应是在-70℃至+100℃，压力0.1至3000巴，进行0.1至100分钟。
一般规律，用于减活的化合物的用量为10至105倍，优选102至104倍，特别是102至103倍，按过渡金属的摩尔当量计。
以此方式再活化的金属茂催化剂体系可以用于制备聚烯烃。
不言而喻，对于C2-C10链烯的均聚物和共聚物而言，优选的单体是乙烯、丙烯、丁烯、戊烯、己烯。此种新型催化剂体系优选适用于制备聚丙烯以及丙烯与少量其他C2-C10链烯（特别是乙烯和丁烯）的共聚物。
这些聚合物的制备可以在常规用于链烯聚合的反应器中以分批方式或优选以连续方式进行。适用的反应器包括连续操作的带搅拌的反应釜，也可以采用多个搅拌釜串联连接的方式。
进行聚合是在1至3000巴压力，优选1至2500巴，0℃至300℃温度，优选0至150℃。聚合时间通常为0.5至10小时。
借助此种新型催化剂体系的聚合反应可以以气相、以悬浮液、在液态单体中和在惰性溶剂中进行。在溶剂中进行聚合时，特别应用液态烃，例如苯或甲苯。以气相、以悬浮液以及在液态单体中进行聚合，也可得到具体优良性能特性的聚合物。
所形成的聚合物的平均分子量可以用聚合技术中通常采用的方法来控制，例如，借助于加入调节剂，例如用氢，或借助于变化反应条件来控制。
所得的C2-C10链烯聚合物特别可以用于生产纤维、薄膜以及模制件。
此种新型减活和再活化的金属茂催化剂体系特别容易操作和管理，并且具有优良生产率。
实施例 丙烯聚合物的制备
实例1
a）预活化金属茂催化剂体系的制备
将9毫克（≌0.02毫摩尔）二甲基甲硅烷二基双（1-茚基）二氯化锆
溶解于5毫升1.6摩尔浓度的甲基铝氧烷/甲苯溶液中，室温搅拌15分钟（摩尔比率Al∶Zr＝400∶1）。
b）该预活化金属茂催化剂体系的减活
将0.1摩尔浓度的苄基氯/甲苯溶液（含≌3毫摩尔苄基氯）于室温加入到a）步骤所制备的预活化的金属茂催化剂体系中，将此混合物搅拌10分钟。
然后，将按b）步骤减活的金属茂催化剂体系加入到有效容积为1升的带搅拌的容器中。
c）该减活金属茂催化剂体系的再活化
然后，将10毫升1.6摩尔浓度的甲基铝氧烷/甲苯溶液（≌16毫摩尔甲基铝氧烷）加入到该反应器中，从而加入到按b）步骤减活的金属茂催化剂体系中，于室温将该混合物搅拌5分钟。
d）聚合
将150毫升甲苯加入到按c）步骤再活化的金属茂催化剂体系中，然后于50℃和1巴压力通入丙烯，历时30分钟。然后，将反应产物搅拌下加入到850毫升甲醇和盐酸的混合物中（摩尔比率16∶1），过滤分出沉淀物，于90℃干燥4小时。
生产率：2023克聚丙烯/克Zr化合物。
实例2
按实例1的步骤，不同之处是减活（步骤b））是用78毫升CO2（≌3.5毫摩尔），CO2是于室温经过流量计通入该预活化的金属茂催化剂溶液中。
生产率：223克聚丙烯/克Zr化合物。
对比实例V1和V2
按实例1和2的步骤，不同之处是不采用减活金属茂催化剂体系的再活化步骤（步骤c））。
这些催化剂在聚合时没有活性，亦即对比实例V1和V1的生产率均为0克聚丙烯/克Zr化合物。
Claims (10)
1、一种用于C2-C10链烯聚合的金属茂催化剂体系，该催化剂体系是通过将一种预活化的金属茂催化剂体系减活而得，该预活化金属茂催化剂体系含有作为活性组分的一种周期表Ⅳ或Ⅴ副族金属的金属茂配合物，以及一种低聚的铝氧烷化合物。
2、权利要求1的金属茂催化剂体系，其为通过将该减活的金属茂催化剂体系再活化而得。
3、权利要求1的金属茂催化剂体系，其中该减活作用是使用一种亲电子试剂。
4、权利要求2的金属茂催化剂体系，其中该再活化作用是使用一种有机金属化合物。
5、权利要求1的金属茂催化剂体系的制备方法，其中包括将一种预活化的金属茂催化剂体系用一种亲电子试剂进行减活。
6、权利要求5的方法，其中所用的亲电子试剂是一种有机卤化物、一种醇、一种羰基化合物、NO、CO2，或它们的混合物。
7、权利要求2的金属茂催化剂体系的制备方法，其中包括将一种减活的金属茂催化剂体系用一种有机金属化合物再活化。
8、权利要求1至4中任一项的金属茂催化剂体系的用途，用于制备一种聚烯烃。
9、一种借助于一种金属茂催化剂体系制备C2-C10链烯烃聚合物的方法，其中使用了权利要求1-4中任一项的金属茂催化剂体系。
10、一种C2-C10链烯烃的聚合物，该聚合物是通过权利要求9的方法而制得。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4130352A DE4130352A1 (de) | 1991-09-12 | 1991-09-12 | Des- und reaktivierte metallocenkatalysatorsysteme |
| DEP4130352.0 | 1991-09-12 |
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| CN1070652A true CN1070652A (zh) | 1993-04-07 |
| CN1073120C CN1073120C (zh) | 2001-10-17 |
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| CN92110661A Expired - Fee Related CN1073120C (zh) | 1991-09-12 | 1992-09-11 | 减活及再活化的金属茂催化剂体系及其制法和应用 |
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| US (1) | US5474961A (zh) |
| EP (1) | EP0603224B1 (zh) |
| JP (1) | JPH06510807A (zh) |
| CN (1) | CN1073120C (zh) |
| DE (2) | DE4130352A1 (zh) |
| ES (1) | ES2117673T3 (zh) |
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| WO (1) | WO1993005079A1 (zh) |
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| EP0630910A1 (en) * | 1993-06-28 | 1994-12-28 | Union Carbide Chemicals & Plastics Technology Corporation | Use of Lewis Bases for activity reduction in metallocene catalyzed olefin polymerization reactions |
| US5804678A (en) * | 1993-07-13 | 1998-09-08 | Mitsui Petrochemical Industries, Ltd. | Process for gas phase polymerization of olefin |
| US5733988A (en) * | 1994-06-29 | 1998-03-31 | Union Carbide Chemicals & Plastics Technology Corporation | Process for reducing polymer build-up in recycle lines and heat exchangers during polymerizations employing butadiene, isoprene, and/or styrene |
| DE19527047A1 (de) * | 1995-07-25 | 1997-01-30 | Danubia Petrochem Deutschland | Metallocene mit silylsubstituierten Brücken und deren Einsatz für die Olefinpolymerisation |
| US5731381A (en) * | 1996-11-01 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Termination of gas phase polymerizations of conjugated dienes, vinyl-substituted aromatic compounds and mixtures thereof |
| US6998449B2 (en) | 2001-09-14 | 2006-02-14 | Bp Corporation North America | Latent metallocene catalyst systems for olefin polymerization |
| KR102301007B1 (ko) * | 2016-06-23 | 2021-09-10 | 보레알리스 아게 | 촉매 비활성화 방법 |
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| US3173770A (en) * | 1960-12-23 | 1965-03-16 | Eastman Kodak Co | Metal deactivators for organic materials |
| US3202491A (en) * | 1962-05-24 | 1965-08-24 | Eastman Kodak Co | Hydrocarbon oil sludging inhibitor composition |
| FR2566781B1 (fr) * | 1984-06-28 | 1986-11-14 | Bp Chimie Sa | Procede de polymerisation ou de copolymerisation d'alpha-olefines en lit fluidise, en presence d'un systeme catalytique ziegler-natta |
| JPS61151211A (ja) * | 1984-12-24 | 1986-07-09 | Toa Nenryo Kogyo Kk | エチレンの共重合方法 |
| JPS61151208A (ja) * | 1984-12-26 | 1986-07-09 | Toa Nenryo Kogyo Kk | ブテン−１の重合方法 |
| US4871375A (en) * | 1987-07-30 | 1989-10-03 | Basf Aktiensellschaft | Fuels for Otto engines |
| US4931417A (en) * | 1987-11-09 | 1990-06-05 | Chisso Corporation | Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure |
| DE3826074A1 (de) * | 1988-07-30 | 1990-02-01 | Hoechst Ag | Propylen-isoblockpolymer und verfahren zu seiner herstellung |
| US4942147A (en) * | 1989-05-08 | 1990-07-17 | Union Carbide Chemicals And Plastics Company, Inc. | Catalyst system containing an autoacceleration inhibitor |
| DE3916366A1 (de) * | 1989-05-19 | 1990-11-22 | Basf Ag | Neue umsetzungsprodukte von aminoalkylenpolycarbonsaeuren mit sekundaeren aminen und erdoelmitteldestillatzusammensetzungen, die diese enthalten |
| DE3916555A1 (de) * | 1989-05-20 | 1990-11-22 | Hoechst Ag | Verfahren zur herstellung von ethylenpolymeren |
-
1991
- 1991-09-12 DE DE4130352A patent/DE4130352A1/de not_active Withdrawn
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1992
- 1992-09-02 US US08/204,273 patent/US5474961A/en not_active Expired - Fee Related
- 1992-09-02 WO PCT/EP1992/002016 patent/WO1993005079A1/de active IP Right Grant
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- 1992-09-02 JP JP5504946A patent/JPH06510807A/ja active Pending
- 1992-09-02 DE DE59209397T patent/DE59209397D1/de not_active Expired - Lifetime
- 1992-09-02 EP EP92918310A patent/EP0603224B1/de not_active Expired - Lifetime
- 1992-09-07 TW TW081107057A patent/TW235967B/zh active
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| Publication number | Publication date |
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| US5474961A (en) | 1995-12-12 |
| DE59209397D1 (de) | 1998-08-06 |
| EP0603224A1 (de) | 1994-06-29 |
| TW235967B (zh) | 1994-12-11 |
| JPH06510807A (ja) | 1994-12-01 |
| EP0603224B1 (de) | 1998-07-01 |
| CN1073120C (zh) | 2001-10-17 |
| WO1993005079A1 (de) | 1993-03-18 |
| ES2117673T3 (es) | 1998-08-16 |
| DE4130352A1 (de) | 1993-03-18 |
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