CN1051321C - 乙烯聚合物的悬浮聚合生产方法 - Google Patents
乙烯聚合物的悬浮聚合生产方法 Download PDFInfo
- Publication number
- CN1051321C CN1051321C CN94194653A CN94194653A CN1051321C CN 1051321 C CN1051321 C CN 1051321C CN 94194653 A CN94194653 A CN 94194653A CN 94194653 A CN94194653 A CN 94194653A CN 1051321 C CN1051321 C CN 1051321C
- Authority
- CN
- China
- Prior art keywords
- alkyl
- aryl
- cycloalkyl
- component
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000725 suspension Substances 0.000 title abstract description 7
- 229920000573 polyethylene Polymers 0.000 title abstract 2
- -1 cyclic aluminium oxane compound Chemical class 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000004411 aluminium Substances 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 150000001721 carbon Chemical group 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 239000000460 chlorine Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Chemical group 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical group [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910052715 tantalum Chemical group 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052790 beryllium Inorganic materials 0.000 claims description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000004407 fluoroaryl group Chemical group 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- 229910052705 radium Inorganic materials 0.000 claims 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 229920001519 homopolymer Polymers 0.000 abstract description 2
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 19
- 239000002585 base Substances 0.000 description 16
- UPFLRGQIBJZJFH-UHFFFAOYSA-N C[SiH2]C.Cl.Cl Chemical compound C[SiH2]C.Cl.Cl UPFLRGQIBJZJFH-UHFFFAOYSA-N 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- NKKALSOFYFMKGW-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] Chemical compound [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] NKKALSOFYFMKGW-UHFFFAOYSA-L 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical class CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- UJDJZYLJEVRQNN-UHFFFAOYSA-N CC=C1C(C(C2=CC=CC=C22)C3=C2C(C)=C(C)C(C)=C3C)=CC=C1.Cl.Cl Chemical compound CC=C1C(C(C2=CC=CC=C22)C3=C2C(C)=C(C)C(C)=C3C)=CC=C1.Cl.Cl UJDJZYLJEVRQNN-UHFFFAOYSA-N 0.000 description 1
- PRQXONWMWVCAEW-UHFFFAOYSA-L CCC1(C=CC=C1)[Zr](Cl)Cl Chemical compound CCC1(C=CC=C1)[Zr](Cl)Cl PRQXONWMWVCAEW-UHFFFAOYSA-L 0.000 description 1
- NZDLIIBVQQCHBI-UHFFFAOYSA-L Cl[Zr]Cl.CC1=C[CH]C=C1 Chemical compound Cl[Zr]Cl.CC1=C[CH]C=C1 NZDLIIBVQQCHBI-UHFFFAOYSA-L 0.000 description 1
- ZBKJVVTWGPHNSC-UHFFFAOYSA-L Cl[Zr]Cl.C[C]1C(C)=C(C)C(C)=C1C Chemical compound Cl[Zr]Cl.C[C]1C(C)=C(C)C(C)=C1C ZBKJVVTWGPHNSC-UHFFFAOYSA-L 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- LREUFPOQFXNWRE-UHFFFAOYSA-N [Zr].C1(C=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 Chemical compound [Zr].C1(C=CC=C1)C1=C(C=CC=C1)C1=CC=CC=C1 LREUFPOQFXNWRE-UHFFFAOYSA-N 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical class CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000375 suspending agent Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
一种在下述催化剂体系存在下,通过悬浮聚合制备乙烯均聚物或乙烯与其它烯烃或其混合物的共聚物的方法,其中所用的催化剂体系是含有下列活性组分的催化剂体系;A)用三烷基铝处理过的一种微细载体,B)一种金属茂催化剂配合物,C)一种开链或环状的铝氧烷化合物,和D)一种烷基碱金属或烷基碱土金属化合物或其混合物。
Description
本发明涉及在催化剂体系存在下用悬浮聚合法制备乙烯均聚物或乙烯与其它烯烃或其混合物的共聚物的方法。
例如,据EP-A 294 942披露,为了得到具有改善形态的聚合物可将金属茂催化剂载于载体上。但是,这样做一方面会降低生产率,另一方面在聚合过程中会在器壁上产生沉积并形成结块。
制备乙烯聚合物的一种方法是悬浮聚合法。这可采用菲利普的PF(颗粒形成)法在连续操作的环形反应器中进行,如US-A3 242 150和US-A3 248 179所述。但是这种方法制得的产品分子量分布宽。
本发明的一个目的是提供一种通过悬浮聚合来制备乙烯均聚物或乙烯与其它烯烃或其混合物的共聚物的方法,该方法没有上述缺点。
我们已经发现,这个目的可通过下述方法达到,即在如下催化剂体系存在下,用悬浮聚合制备乙烯均聚物或乙烯与其它烯烃或其混合物的共聚物的方法,其中所用的催化剂体系是含有下列活性组分的催化剂体系:
A)用三烷基铝处理过的一种微细载体,
B)一种金属茂催化剂配合物,
C)一种开链或环状的铝氧烷化合物,和
D)一种烷基碱金属或烷基碱土金属化合物或其混合物。
我们还发现,乙烯均聚物或乙烯与其它烯烃或其混合物的共聚物,均可通过上述方法制得。
本新方法可用于制备乙烯均聚物或乙烯与其它烯烃或其混合物的共聚物。优选的共聚物是其中用1-链烯,优选直链不支化的C3-C51-链烯,特别是用1-丁烯和1-己烯作为共聚单体的那类共聚物。也可以使用多种不同的共聚单体。按单体总量计,共聚单体的用量为0.1-80%(重量),优选5-50%(重量)。
在该新方法中,乙烯的均聚物或共聚物是在一种催化剂体系存在下,用悬浮聚合法制备的。
该催化剂体系含有作为组分A)的一种用三烷基铝处理过的微细载体,其粒径较好为1-200微米,更好为30-70微米。适用的载体材料是,例如通式为SiO·aAl2O3的硅胶,其中a为0-2,优选0-0.5;因此这些硅胶是铝硅酸盐或二氧化硅。这类产品是可从市场上购得的,例如Grace公司的Silica Gel 332。水含量为2-12%(重量)的硅胶(按照以10K/分的速度加热至200℃时的重量损失测定)是比较好的。
其它无机氧化物,如Al2O3、TiO2或ThO2也可用作载体。
用三烷基铝处理载体时其用量为0.1-3,较好为0.3-1.2,更好为0.5-0.8mol/(载体kg数×%水含量)。优选使用三甲基铝。
该催化剂体系含有作为组分B)的一种金属茂配合物,较好是周期表中第IV和V副族的金属的金属茂配合物。
其中:
M是钛、锆、铪、钒、铌或钽,
X是氟、氯、溴、碘、氢、C1-C10-烷基、C6-C15-芳基或-OR6,
R6是C1-C10-烷基、C6-C15-芳基、烷芳基、芳烷基、氟烷基或氟芳基,每个烷基含有1-10个碳原子,每个芳基含有6-20个碳原子。
R1-R5各是氢、C1-C10-烷基、可带有一个C1-C6-烷基作为取代基的5-至7-元的环烷基、C6-C15-芳基或芳烷基,其中两个相邻的基团合在一起可进一步形成一个4-15,较好8-15个碳原子的环状基团,或Si(R7)3,
R7是C1-C10-烷基,C6-C15-芳基或C3-C10-环烷基,
Z是X或
R8-R12各是氢、C1-C10-烷基、可带有一个C1-C10-烷基作为取代基的5-至7-元环烷基、C6-C15-芳基或芳烷基,其中两个相邻基团合在一起可进一步形成一个4-15,较好8-15个碳原子的环状基团,或Si(R13)3,
R13是C1-C10-烷基、C6-C15-芳基或C3-C10-环烷基,或者
R4和Z含在一起形成一个-[Y(R14)2]n-E-基团,
Y是硅、锗、锡或碳,
R14是C1-C10-烷基、C3-C10-环烷基或C6-C10-芳基,
A是-O-、-S-、>NR15或>PR15,
R15是C1-C10-烷基、C6-C15-芳基、C3-C10-环烷基、烷芳基或Si(R16)3,
R16是C1-C10-烷基、C6-C15-芳基、C3-C10-环烷基或烷芳基。
因此金属茂这一术语的含义应理解为不仅仅是双(η-环戊二烯基)-金属配合物。
式Ia中特别优选的化合物是下面所定义的化合物,其中:
M是钛、锆或铪,
X是氯,
R1-R5各是氢或C1-C4烷基。
优选的式Ib的化合物是下面所定义的化合物,其中
M是钛、锆或铪,
X是氯、C1-C4-烷基或苯基,
R1-R5各是氢、C1-C4-烷基或Si(R7)3,
R8-R12各是氢、C1-C4-烷基或Si(R13)3。
式Ib中特别适用的化合物是其中两个环戊二烯基相同的那些化合物。
特别适用的化合物的例子包括:
氯化双(环戊二烯基)锆,
二氯化双(五甲基环戊二烯基)锆,
双(环戊二烯基)二苯基锆,
二氯化双(甲基环戊二烯基)锆,
二氯化双(乙基环戊二烯基)锆,
二氯化双(正丁基环戊二烯基)锆,和
二氯化双(三甲基甲硅烷基环戊二烯基)锆以及相应的二甲基锆化合物。
式Ic中特别优选的化合物是下面所定义的化合物,其中:
R1和R8是相同的,且可为氢或C1-C10-烷基,
R5和R12是相同的,且可为氢、甲基、乙基、异丙基或叔丁基,
R3和R10各是C1-C4-烷基,
R2和R9各是氢,或者两个相邻的基团R2和R3,以及R9和R10可合在一起形成一个4-12个碳原子的环状基团,
R14是C1-C8-烷基,
M是钛、锆或铪,
Y是硅、锗、锡或碳,
X是氯或C1-C4-烷基。
特别适用的配合物的例子包括:
二氯化二甲基硅烷二基双(环戊二烯基)锆,
二氯化二甲基硅烷二基双(茚基)锆,
二氯化二甲基硅烷二基双(四氢化茚基)锆,
二氯化亚乙基双(环戊二烯基)锆,
二氯化亚乙基双(茚基)锆,
二氯化亚乙基双(四氢化茚基)锆,
二氯化四甲基亚乙基-9-芴基环戊二烯基锆,
二氯化二甲基硅烷二基双(3-叔丁基-5-甲基环戊二烯基)锆,
二氯化二甲基硅烷二基双(3-叔丁基-5-乙基环戊二烯基)锆,
二甲基硅烷二基双(3-叔丁基-5-甲基环戊二烯基)二甲基锆,
二氯化二甲基硅烷二基双(2-甲基茚基)锆,
二氯化二甲基硅烷二基双(2-异丙基茚基)锆,
二氯化二甲基硅烷二基双(2-叔丁基茚基)锆,
二溴化二乙基硅烷二基双(2-甲基茚基)锆,
二氯化二甲基硅烷二基双(2-甲基-5-甲基环戊二烯基)锆,
二氯化二甲基硅烷二基双(2-乙基-5-异丙基环戊二烯基)锆,
二氯化二甲基硅烷二基双(2-甲基茚基)锆,
二氯化二甲基硅烷二基双(2-甲基苯并茚基)锆,和
二氯化二甲基硅烷二基双(2-甲基茚基)铪。
通式Id中特别适用的化合物是下面所定义的化合物,其中:
M是钛或锆,
X是氯或C1-C10-烷基
Y当n=1时是硅或碳,当n=2时是碳,
R14是C1-C8-烷基,C5-C6-环烷基或C6-C10-芳基,
A是-O-、-S-、或>NR15,和
R1-R3和R5各是氢、C1-C10-烷基,C3-C10-环烷基、C6-C15-芳基,或Si(R7)3,或者两个相邻的基团形成一个4-12个碳原子的环状基团。
通式I中特别优选的金属茂配合物是其中基团R1-R5中至少有一个不是氢,且特别是C1-C10-烷基的那种化合物,优选使用式Ib的化合物,特别是二氯化双(正丁基环戊二烯基)锆。
这类配合物可按本身已知的方法合成,优选的方法是让相应取代的环烃阴离子与钛、锆、铪、钒、铌或钽的卤化物反应。
相应的制备方法的例子可参阅,特别是Journal oforganometallic Chemistry,369(1989),359-370。
μ-氧代双(氯代双环戊二烯基)锆也可用作金属茂配合物。
该催化剂体系还含有开链或环状铝氧烷化合物作为组分C)。
例如下面通式II或III的开链或环状铝氧烷化合物是适用的:
其中:
R17是C1-C4-烷基,优选甲基或乙基,m是5-30的整数,优选10-25。
这类齐聚铝氧烷化合物的制备通常是通过使三烷基铝溶液与水反应来实现的,可参阅特别是EP-A 284 708和US-A 4,794,096。
通常,所得到的齐聚铝氧烷化合物是以不同长度的直链或环状链两种分子的混合物形式存在的,所以m应看成是一个平均值。该铝氧烷化合物也可以与其它烷基金属化合物,较好是与烷基铝的混合物形式存在。
该催化剂体系含有作为组分D)的一种烷基碱金属或烷基碱土金属化合物或其混合物。通式IV或V所示的烷基碱金属或碱土金属化合物是较好的:
M1R18 IV
M2(R19)2 V其中:M1是锂、钠、钾、铷或铯,M2是铍、镁、钙、锶或钡,和R18和R19是C1-C8-烷基。
M1较好是锂,M2是镁,R18和R19各自较好是直链的C1-C8-烷基,特别是C1-C4-烷基。正丁基锂是特别合适的。
在制备该催化剂体系的一个优选的程序中,将金属茂配合物涂布到用三烷基预处理过的载体上。经预处理的载体较好是用金属茂配合物(组分B)和铝氧烷化合物(组分C)的溶液浸渍,较好用芳烃,尤其是甲苯作为溶剂。然后将该混合物蒸发至干或过滤,并进行干燥。铝氧烷化合物中的Al与金属茂配合物中的金属M的摩尔比为50∶1-2000∶1,较好为100∶1-1000∶1,更好为200∶1-600∶1。浸渍液的用量要加以选择,以便使得用金属茂配合物和铝氧烷化合物的溶液浸渍后的载体在干燥每克含有5-50微摩尔的金属茂。
组分D)是以无载体催化剂组分的形式加入到聚合反应中的。每克有载体的催化剂中D)的用量为0.2-10,较好0.5-5,更好1-3毫摩尔。
悬浮聚合方法本身是已知的。聚合反应通常是在一种悬浮剂中,较好在一种链烷烃中进行的。聚合温度为-20-115℃,压力为105-107Pa。悬浮液中的固含量通常为10-80%。该方法可以以间歇方式,例如在带搅拌的高压釜中进行,也可以以连续方式,例如在管式反应器中,更好是在环形反应器中进行。特别可以采用US-A3 242 150和US-A 3 248 179中所述的菲利蓄PF法。
在该新方法中,完全不会发生器壁沉积和形成结块的问题。此外,乙烯聚合物的分子量分布窄,在乙烯共聚物的情况下,得到了窄的均匀的共聚单体分布和低的密度。
实例
实例1
有载体的催化剂的制备
在一个用氮气冲洗过干燥反应器中,将4.0kg SiO2(Grace,SG332,平均粒径为50微米,水含量5%(重量))悬浮于30升庚烷中,并使其恒温在18℃。在60分钟时间内滴加11.2升1摩尔三甲基铝(TMA)的庚烷溶液,并使温度保持在30℃以下。在TMA滴加完毕后,继续搅拌7小时。将悬浮液过滤,残留物用10升庚烷洗涤2次。在减压下于50℃干燥后,得到一种铝含量为6.6%(重量)的呈自由流动粉末形式的改性载体。
在室温下将6.80g(16.81mmol)二氯化双(正丁基环戊二烯基)锆在4.92升1.53摩尔甲基铝氧烷的甲苯溶液中的溶液搅拌20分钟,然后加入0.94kg上述的改性载体,再继续搅拌60分钟。在减压下于50℃脱除溶剂。形成一种黄色的自由流动粉末(1.34kg),其铝含量为15.9%(重量),锆含量为0.10%(重量)。因此,总摩尔比Al∶Zr为540∶1。
实例2-6
乙烯均聚物的间歇悬浮聚合制备方法
实例2
先将4.5升异丁烷和60mg正丁基锂放入到用氮气小心地冲洗过的带搅拌的10升不锈钢高压釜中,并使其恒温在70℃的聚合温度。然后将489mg有载体的催化剂(由实例1得到)与另外0.5升异丁烷一起冲入到高压釜中,再压入乙烯使总压达到38×105Pa。继续计量加入乙烯使高压釜中压力保持恒定。90分钟后,通过排放高压釜使聚合反应终止。得到自由流动颗粒形式的聚合物1820g。
分析数据列于表1。
实例3
制备过程如实例2,所不同的是使用521mg有载体的催化剂,且聚合温度是60℃。产量是2400g。进一步的数据列于表1。
实例4
制备过程如实例2,所不同的是使用503mg有载体的催化剂,且聚合温度是80℃。产量是1600g。进一步的数据列于表1。
实例5
制备过程如实例2,所不同的是使用518mg有载体的催化剂,且聚合温度是90℃。产量是1590g。进一步的数据列于表1。
实例6
制备过程如实例2,所不同的是使用519mg有载体的催化剂,且聚合温度是100℃。产量是630g。进一步的数据列于表1。
在实例3-6的任一实例中均未发生器壁沉积和结块。
对比实例VI
制备过程如实例2,所不同的是使用511mg有载体的催化剂,且不加入正丁基锂。经过20分钟后,由于搅拌器严重爆震使聚合反应不得不终止。高压釜内含有580g大量器壁沉积形式和少量结块形式的产物。表1实例2-6的乙烯均聚物的分析数据实例 载体催 聚合 产量 粘度 堆密度 Mw Mn Mw/Mn
化剂 温度 η
[mg] [℃] [g] [dl/g] [g/l] [103g/mol][103g/mol]2 489 70 1820 3.49 290 225 92 2.443 521 60 2400 3.69 315 293 105 2.804 503 80 1600 3.18 243 224 97 2.305 518 90 1590 3.00 254 164 77 2.146 519 100 630 2.59 209 170 73 2.34
实例7-11
乙烯-1-丁烯共聚物的间歇悬浮聚合制备方法
实例7
制备过程如实例2,所不同的是使用498mg有载体的催化剂,且开始时除加入异丁烯外还加入50ml 1-丁烯。产量是l250g。进一步的数据列于表2。
实例8
制备过程如实例2,所不同的是使用508mg有载体的催化剂,且开始时除加入异丁烯外还加入100ml 1-丁烯。产量是1350g。进一步的数据列于表2。
实例9
制备过程如实例2,所不同的是使用513mg有载体的催化剂,且开始时除加入异丁烯外还加入200ml 1-丁烯。产量是1520g。进一步的数据列于表2。
实例10
制备过程如实例2,所不同的是使用529mg有载体的催化剂,且开始时除了加入异丁烯外还加入400ml 1-丁烯。产量是1250g。进一步的数据列于表2。
实例11
制备过程如实例2,所不同的是使用527mg有载体的催化剂,且开始时除了加入异丁烯外还加入400ml 1-丁烯,聚合温度是80℃。产量是1380g。进一步的数据列于表2。
在实例7-11的任一实例中均未发生器壁沉积和结块。表2实例7-11的乙烯/1-丁烯共聚物的分析数据实例 载体催 聚合 1-丁烯 产量 粘度 密度 1-丁烯 堆密度 Mw Mn Mw/Mn
化剂 温度 η 含量 [103g/ [103g/
[mg] [℃] [ml] [g] [dl/g] [g/cm3] [%重量] [g/l] mol] mol]7 489 70 50 1250 2.42 0.9381 未测定 247 138 66 2.088 508 70 100 1350 2.02 0.9318 未测定 285 124 59 2.109 513 70 200 1520 1.88 0.9293 2.4 263 104 54 1.9410 529 70 400 1250 1.96 0.9240 3.7 281 103 50 2.0411 527 80 400 1380 2.03 0.9203 4.4 269 118 55 2.14
实例12
乙烯均聚物的连续悬浮聚合制备方法
聚合反应是在连续操作的环形反应器中,即在一个用电弧方法封闭管式反应器中进行的,其中所形成的聚合物的异丁烯悬浮液借助于配置在管路中的泵在管中循环。这类反应器的原理可参阅例如US-A3 242 150和US-A3 248 179。反应器的容积为0.18米3。
进行这种聚合反应时,将15kg/h(千克/小时)乙烯、35kg/h异丁烯、5.8g/h有载体的催化剂(从实例1得到)及0.4g/h正丁基锂连续地计量加入到反应器中。在40巴和70℃的聚合温度下,所形成的液相中的乙烯含量为24%(体积),悬浮液中的固含量为240kg/m3。聚合物产率为14.5kg/h。所得产物的分析数据列于表3。
实例13
乙烯-1-丁烯共聚物的连续悬浮聚合制备方法
制备过程如实例12,所不同的是将16kg/h乙烯、1.6kg/h 1-丁烯、34kg/h异丁烯、4.9g/h有载体的催化剂和0.4g/h正丁基锂计量加入到反应器中。所形成的液相中的乙烯含量为26%(体积),液相中1-丁烯含量为10%(体积)。悬浮液中固含量为230kg/m3。聚合物产率为15kg/h。所得产物的分析数据列于表3。
共聚单体掺入的均匀性由ATREF(分析温度提升洗脱分级)法证实。附图说明洗出的物质对洗脱温度的依赖性。洗脱曲线为单模式,且比较窄。特别是,未发现任何HDPE组分(在约100℃洗脱)。有关该方法可参阅L.Wild,Adv.Polym.Sci.98,1-47(1990),第13页以后。所用的洗脱液是1,2,4-三氯苯。
表3
由连续聚合制得聚合物的分析数据
实例12 实例13生产率(聚合物克数/催化剂体系总克数) 2400 2800MFI[克/10分钟] 0.2 1.0HLMI[克/10分钟] 3.6 16密度[克/厘米3] 0.945 0.9111-丁烯含量[%,重量] - 7.9堆密度[克/升] 260 240粘度η[分升/克] 3.28 1.95Mw[103克/摩尔] 219 121Mn[103克/摩尔] 79 63Mw/Mn 2.77 1.92冷庚烷提取物[%,重量] 0.1 0.1落镖指数[克](40微米膜) - 1100落镖指数[克](25微米膜) - 790
下列方法用于测定产物的特性:
MFI和HLMI:DIN 53 735,所加重量2.16或21.6kg,
η值:DIN 53 733,
堆密度:DIN 53 468,
密度:DIN 53 479,
重均分子量Mw和数均分子量Mn:凝胶渗透色谱法。
1-丁烯含量:用13C-NMR和IR光谱法测定。
冷庚烷提取物:100克聚合物在1升庚烷中于25℃搅拌2小时,然后过滤。将滤液蒸发至干,称重。
落镖指数:按照ASTM D1709用吹塑膜测定。
Claims (6)
1.一种在下述催化剂体系存在下,通过悬浮聚合制备乙烯均聚物或乙烯与其它烯烃或其混合物的共聚物的方法,其中所用的催化剂体系是含有下列活性组分的催化剂体系:
A)用三烷基铝处理过的一种微细载体,
B)一种金属茂催化剂配合物,
C)一种开链或环状的铝氧烷化合物,和
D)一种烷基碱金属或烷基碱土金属化合物或其混合物。
2.如权利要求1所要求的方法,其中用一种粒径为1-200微米的载体作为组分A)。
3.如权利要求1或2中任一项所要求的方法,其中用一种用三烷基铝处理过的硅胶作为组分A)。
4.如权利要求1或2中任一项所要求的方法,其中用一种下面通式I所示的金属茂配合物作为组分B):其中:M是钛、锆、铪、钒、铌或钽,X是氟、氯、溴、碘、氢、C1-C10-烷基、C6-C15-芳基或-OR6,
R6是C1-C10-烷基、C6-C15-芳基、烷芳基、芳烷基、氟烷基或氟芳基,每个烷基含有1-10个碳原子,每个芳基含有6-20个碳原子,
R1-R5各是氢、C1-C10-烷基、可带有一个C1-C6-烷基作为取代基的5-至7-元的环烷基、C6-C15-芳基或芳烷基,其中两个相邻的基团合在一起可进一步形成一个4-15个碳原子的环状基团,或Si(R7)3,
R7是C1-C10-烷基,C6-C15-芳基或C3-C10-环烷基,
R8-R12各是氢、C1-C10-烷基、可带有一个C1-C10-烷基作为取代基的5-至7-元环烷基、C6-C15-芳基或芳烷基,其中两个相邻基团合在一起可进一步形成一个4-15个碳原子的环状基团,或Si(R13)3,
R13是C1-C10-烷基、C6-C15-芳基或C3-C10-环烷基,或者
R4和Z合在一起形成一个-[Y(R14)2]n-E-基团,
Y是硅、锗、锡或碳,
R14是C1-C10-烷基、C3-C10-环烷基或C6-C10-芳基,
n是1、2、3或4,
A是-O-、-S-、>NR15或>PR15,
R15是C1-C10-烷基、C6-C15-芳基、C3-C10-环烷基、烷芳基或Si(R16)3,
R16是C1-C10-烷基、C6-C15-芳基、C3-C10-环烷基或烷芳基。
5.如权利要求1或2中任一项所要求的方法,其中用通式II或III所示的一种开链或环状铝氧烷化合物作为组分C):其中:
R17是C1-C4烷基,m是5-30的整数。
6.如权利要求1或2中任一项所要求的方法,其中用通式IV或V所示的一种烷基碱金属或烷基碱土金属化合物或其混合物作为组分D):
M1R18 IV
M2(R19)2 V其中:M1是锂、钠、钾、铷或铯,M2是铍、镁、钙、锶、钡或镭,和R18和R19是C1-C8-烷基。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4344672A DE4344672C1 (de) | 1993-12-27 | 1993-12-27 | Verfahren zur Herstellung von Polymerisaten des Ethylens durch Suspensionspolymerisation |
DEP4344672.8 | 1993-12-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1139439A CN1139439A (zh) | 1997-01-01 |
CN1051321C true CN1051321C (zh) | 2000-04-12 |
Family
ID=6506364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN94194653A Expired - Fee Related CN1051321C (zh) | 1993-12-27 | 1994-12-13 | 乙烯聚合物的悬浮聚合生产方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US5756607A (zh) |
EP (1) | EP0737213B1 (zh) |
JP (1) | JP3785423B2 (zh) |
KR (1) | KR100354725B1 (zh) |
CN (1) | CN1051321C (zh) |
AT (1) | ATE159956T1 (zh) |
DE (2) | DE4344672C1 (zh) |
ES (1) | ES2108563T3 (zh) |
FI (1) | FI114712B (zh) |
NO (1) | NO309193B1 (zh) |
WO (1) | WO1995018160A1 (zh) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994021691A1 (en) * | 1993-03-25 | 1994-09-29 | Mobil Oil Corporation | Process for forming a granular resin |
DE4431838A1 (de) * | 1994-09-07 | 1996-03-14 | Basf Ag | Geträgerte Metallocen-Katalysatorsysteme |
US6506866B2 (en) * | 1994-11-17 | 2003-01-14 | Dow Global Technologies Inc. | Ethylene copolymer compositions |
US7153909B2 (en) | 1994-11-17 | 2006-12-26 | Dow Global Technologies Inc. | High density ethylene homopolymers and blend compositions |
CA2186696A1 (en) * | 1995-09-29 | 1997-03-30 | Takashi Seki | Catalyst component and catalyst |
DE19606166A1 (de) * | 1996-02-20 | 1997-08-21 | Basf Ag | Verfahren zur Herstellung von Polymerisaten von Alkenen durch Suspensionspolymerisation |
JPH09309926A (ja) * | 1996-05-17 | 1997-12-02 | Dow Chem Co:The | エチレン共重合体の製造方法 |
DE19621969A1 (de) * | 1996-05-31 | 1997-12-04 | Basf Ag | Verfahren zur Herstellung von kristallinen Polymerisaten durch Dispersionspolymerisation in Gegenwart von Metallocenkatalysatorsystemen |
DE69831819T2 (de) * | 1997-01-30 | 2006-07-06 | Total Petrochemicals Research Feluy, Seneffe | Selektive Wirkung von Metallocen-Katalysatoren für die Herstellung von isotaktischen Polyolefinen |
US6441116B1 (en) | 1997-09-03 | 2002-08-27 | Idemitsu Kosan Co., Ltd. | Ethylenic copolymer, composition containing said copolymer, and ethylenic copolymer film |
US20030236365A1 (en) * | 2002-06-24 | 2003-12-25 | Fina Technology, Inc. | Polyolefin production with a high performance support for a metallocene catalyst system |
EP2440564A4 (en) | 2009-06-11 | 2014-07-09 | Grace W R & Co | PROCESS FOR PRODUCING ALUMINOXANE AND CATALYSTS COMPRISING ALUMINOXANE THUS PREPARED |
US9127096B2 (en) * | 2010-10-18 | 2015-09-08 | California Institute Of Technology | Methods and systems for synthesis of an ultra high molecular weight polymer |
US11028192B2 (en) | 2017-03-27 | 2021-06-08 | Exxonmobil Chemical Patents Inc. | Solution process to make ethylene copolymers |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5032562A (en) * | 1989-12-27 | 1991-07-16 | Mobil Oil Corporation | Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution |
EP0447722A2 (en) * | 1989-12-26 | 1991-09-25 | Mobil Oil Corporation | Zirconium-based catalyst composition for polymerizing olefins |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3242150A (en) * | 1960-03-31 | 1966-03-22 | Phillips Petroleum Co | Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone |
US3248179A (en) * | 1962-02-26 | 1966-04-26 | Phillips Petroleum Co | Method and apparatus for the production of solid polymers of olefins |
CA1268754A (en) * | 1985-06-21 | 1990-05-08 | Howard Curtis Welborn, Jr. | Supported polymerization catalyst |
US4659685A (en) * | 1986-03-17 | 1987-04-21 | The Dow Chemical Company | Heterogeneous organometallic catalysts containing a supported titanium compound and at least one other supported organometallic compound |
US5077255A (en) * | 1986-09-09 | 1991-12-31 | Exxon Chemical Patents Inc. | New supported polymerization catalyst |
JPH072794B2 (ja) * | 1986-12-29 | 1995-01-18 | 昭和電工株式会社 | ポリオレフインの製造方法 |
JP2538595B2 (ja) * | 1987-05-13 | 1996-09-25 | 三井石油化学工業株式会社 | オレフイン重合用固体触媒 |
US4925821A (en) * | 1987-12-17 | 1990-05-15 | Exxon Chemical Patents Inc. | Method for utilizing triethyaluminum to prepare an alumoxane support for an active metallocene catalyst |
DD267986A1 (de) * | 1988-01-06 | 1989-05-17 | Tech Hochschule C Schorlemmer | Verfahren zur katalytischen homo- und copolymerisation von ethylen |
US4935397A (en) * | 1988-09-28 | 1990-06-19 | Exxon Chemical Patents Inc. | Supported metallocene-alumoxane catalyst for high pressure polymerization of olefins and a method of preparing and using the same |
US5145818A (en) * | 1989-12-29 | 1992-09-08 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for the polymerization of olefins |
JP2826362B2 (ja) * | 1990-02-13 | 1998-11-18 | 三井化学株式会社 | オレフィン重合用固体触媒の製造方法、オレフィン重合用固体触媒およびオレフィンの重合方法 |
DE4024421A1 (de) * | 1990-08-01 | 1992-02-06 | Basf Ag | Ziegler-natta-katalysatorsysteme mit metallorganischen verbindungen |
EP0474391B1 (en) * | 1990-08-21 | 1995-10-25 | Nippon Oil Co. Ltd. | Polyolefins |
EP0490269B1 (en) * | 1990-12-10 | 1996-02-28 | Idemitsu Kosan Company Limited | Graft copolymer and process for producing the same |
DE69219206T2 (de) * | 1991-05-31 | 1997-08-28 | Mitsui Petrochemical Ind | Fester Katalysatorbestandteil, Katalysator und Verfahren für Olefinpolymerisation |
DE4139262A1 (de) * | 1991-11-29 | 1993-06-03 | Basf Ag | Getraegerte katalysatorsysteme zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alkenen |
US5391660A (en) * | 1992-01-14 | 1995-02-21 | Nippon Oil Company, Limited | Process for preparing polyolefines |
FI112233B (fi) * | 1992-04-01 | 2003-11-14 | Basell Polyolefine Gmbh | Katalyytti olefiinipolymerointia varten, menetelmä sen valmistamiseksi ja sen käyttö |
US5459217A (en) * | 1993-04-09 | 1995-10-17 | Mitsui Petrochemical Industries, Ltd. | Ethylene/alpha-olefin copolymer |
US5525678A (en) * | 1994-09-22 | 1996-06-11 | Mobil Oil Corporation | Process for controlling the MWD of a broad/bimodal resin produced in a single reactor |
-
1993
- 1993-12-27 DE DE4344672A patent/DE4344672C1/de not_active Expired - Lifetime
-
1994
- 1994-12-13 CN CN94194653A patent/CN1051321C/zh not_active Expired - Fee Related
- 1994-12-13 KR KR1019960703455A patent/KR100354725B1/ko not_active IP Right Cessation
- 1994-12-13 EP EP95904458A patent/EP0737213B1/de not_active Expired - Lifetime
- 1994-12-13 WO PCT/EP1994/004125 patent/WO1995018160A1/de active IP Right Grant
- 1994-12-13 JP JP51765295A patent/JP3785423B2/ja not_active Expired - Fee Related
- 1994-12-13 AT AT95904458T patent/ATE159956T1/de not_active IP Right Cessation
- 1994-12-13 ES ES95904458T patent/ES2108563T3/es not_active Expired - Lifetime
- 1994-12-13 US US08/666,409 patent/US5756607A/en not_active Expired - Fee Related
- 1994-12-13 DE DE59404553T patent/DE59404553D1/de not_active Expired - Fee Related
-
1996
- 1996-06-25 FI FI962620A patent/FI114712B/fi active
- 1996-06-26 NO NO962696A patent/NO309193B1/no not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0447722A2 (en) * | 1989-12-26 | 1991-09-25 | Mobil Oil Corporation | Zirconium-based catalyst composition for polymerizing olefins |
US5032562A (en) * | 1989-12-27 | 1991-07-16 | Mobil Oil Corporation | Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution |
Also Published As
Publication number | Publication date |
---|---|
JPH09507093A (ja) | 1997-07-15 |
FI962620A (fi) | 1996-06-25 |
KR100354725B1 (ko) | 2003-01-06 |
DE59404553D1 (de) | 1997-12-11 |
ES2108563T3 (es) | 1997-12-16 |
FI114712B (fi) | 2004-12-15 |
EP0737213A1 (de) | 1996-10-16 |
DE4344672C1 (de) | 1995-06-14 |
CN1139439A (zh) | 1997-01-01 |
JP3785423B2 (ja) | 2006-06-14 |
FI962620A0 (fi) | 1996-06-25 |
NO309193B1 (no) | 2000-12-27 |
EP0737213B1 (de) | 1997-11-05 |
NO962696L (no) | 1996-06-26 |
NO962696D0 (no) | 1996-06-26 |
WO1995018160A1 (de) | 1995-07-06 |
US5756607A (en) | 1998-05-26 |
ATE159956T1 (de) | 1997-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1087300C (zh) | 在单反应器中生产宽/双峰分子量分布树脂的控制方法 | |
CN1048255C (zh) | 烯烃聚合的固体催化剂与烯烃的聚合方法 | |
CN1051321C (zh) | 乙烯聚合物的悬浮聚合生产方法 | |
CN1092206C (zh) | 防止反应器结垢的方法 | |
CN1053673C (zh) | 负载催化剂体系、它的制备及其在烯烃聚合中的应用 | |
CN1234739C (zh) | 支化半结晶乙烯―丙烯组合物 | |
CN1301271C (zh) | 双位烯烃聚合催化剂组合物 | |
CN1117101C (zh) | 催化剂载体的制法和担载的聚烯烃催化剂及它们在制备聚烯烃的用途 | |
CN1037106C (zh) | α烯烃聚合的方法 | |
CN1077113C (zh) | 催化剂组合物 | |
CN1044822A (zh) | 烯烃聚合催化剂 | |
CN1107859A (zh) | 烯烃聚合方法 | |
CN1053433A (zh) | 用于制备聚烯烃类的催化剂和预聚物 | |
CN1055742A (zh) | 烯烃气相聚合方法 | |
CN1137905C (zh) | 茂金属化合物及其在烯烃聚合中的应用 | |
KR20110043464A (ko) | 혼성 담지 메탈로센 촉매의 제조방법 및 이를 이용하여 제조된 혼성 담지 메탈로센 촉매 | |
CN1053432A (zh) | 用于制备聚烯烃类的催化剂和预聚物 | |
CN1930193A (zh) | 金属茂类和生产聚乙烯的方法 | |
CN1062271C (zh) | 金属茂化合物 | |
CN1264393A (zh) | 高活性聚乙烯催化剂 | |
CN1054775A (zh) | 用于烯烃聚合的催化剂和预聚物以及由其制得的乙烯(共)聚合物 | |
CN1035297A (zh) | 烯烃聚合催化剂及其聚合方法 | |
CN1314920A (zh) | 在载体上的金属茂催化剂和使用该催化剂的烯烃聚合法 | |
CN1789292A (zh) | 负载型非茂金属催化剂在淤浆法乙烯聚合工艺中的应用方法 | |
CN1142192C (zh) | 含有液态硅氧烷和多胺的反应产物的催化剂体系 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
ASS | Succession or assignment of patent right |
Owner name: BASEL POLYOLEFINE CO., LTD. Free format text: FORMER OWNER: BASF COMPANY Effective date: 20060310 |
|
C41 | Transfer of patent application or patent right or utility model | ||
TR01 | Transfer of patent right |
Effective date of registration: 20060310 Address after: Federal Republic of Germany Wessel Ning Patentee after: Basel poly hydrocarbon Limited by Share Ltd Address before: Ludwigshafen, Federal Republic of Germany Patentee before: BASF AG |
|
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |