CN1269852C - Loaded method of load type Non-metallocene catalyst-and polymerizing application - Google Patents
Loaded method of load type Non-metallocene catalyst-and polymerizing application Download PDFInfo
- Publication number
- CN1269852C CN1269852C CN 200310106156 CN200310106156A CN1269852C CN 1269852 C CN1269852 C CN 1269852C CN 200310106156 CN200310106156 CN 200310106156 CN 200310106156 A CN200310106156 A CN 200310106156A CN 1269852 C CN1269852 C CN 1269852C
- Authority
- CN
- China
- Prior art keywords
- group
- polymerization
- alkyl
- carrier
- catalyst
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000000379 polymerizing effect Effects 0.000 title abstract 2
- 150000001336 alkenes Chemical class 0.000 claims abstract description 53
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000004411 aluminium Substances 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 31
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 238000001994 activation Methods 0.000 claims abstract description 12
- 230000004913 activation Effects 0.000 claims abstract description 12
- 238000007725 thermal activation Methods 0.000 claims abstract description 12
- -1 metal oxide compound Chemical class 0.000 claims description 49
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 46
- 239000002904 solvent Substances 0.000 claims description 40
- 239000002685 polymerization catalyst Substances 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011574 phosphorus Substances 0.000 claims description 16
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000009969 flowable effect Effects 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 239000005046 Chlorosilane Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 150000003624 transition metals Chemical group 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 89
- 239000003054 catalyst Substances 0.000 abstract description 59
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 26
- 238000007334 copolymerization reaction Methods 0.000 abstract description 19
- 239000005977 Ethylene Substances 0.000 abstract description 17
- 239000007787 solid Substances 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 10
- 239000002002 slurry Substances 0.000 abstract description 10
- 230000003213 activating effect Effects 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 238000011068 loading method Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 112
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 84
- 238000006243 chemical reaction Methods 0.000 description 41
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- 239000010936 titanium Substances 0.000 description 27
- 239000000460 chlorine Substances 0.000 description 26
- 238000002156 mixing Methods 0.000 description 24
- 238000005406 washing Methods 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 19
- 229910052719 titanium Inorganic materials 0.000 description 19
- 238000005303 weighing Methods 0.000 description 18
- 239000004698 Polyethylene Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 16
- 229920000573 polyethylene Polymers 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 229920002554 vinyl polymer Polymers 0.000 description 14
- 229960001866 silicon dioxide Drugs 0.000 description 13
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 238000012993 chemical processing Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 238000005906 dihydroxylation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 3
- 229960003132 halothane Drugs 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 238000012725 vapour phase polymerization Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- QRDZSRWEULKVNW-UHFFFAOYSA-N 6-hydroxy-2-oxo-1h-quinoline-4-carboxylic acid Chemical compound C1=C(O)C=C2C(C(=O)O)=CC(=O)NC2=C1 QRDZSRWEULKVNW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910003902 SiCl 4 Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 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 2
- 125000005574 norbornylene group Chemical group 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 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
- 238000012797 qualification Methods 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 125000003375 sulfoxide group Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 1
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-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 compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910003691 SiBr Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 125000002433 cyclopentenyl group Chemical class C1(=CCCC1)* 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Abstract
The present invention provides a loading method and the polymerizing application thereof of a load type non-metallocene catalyst, which relates to the loading process of the non-metallocene catalyst for alkene polymerization in a novel structure and the application to the processes of olefinic polymerization and copolymerization, particularly to homopolymerization of ethylene or the copolymerization of the ethylene and other kinds of alpha-alkene, and belongs to the technical field of loading and organic polymerization of the catalyst. After the activating treatment, a porous carrier of the present invention is scoured, filtered, dried and extracted, and then the non-metallocene catalyst for the alkene polymerizationis is directly loaded. The activating treatment comprises thermal activation and/or chemical activation, and chemical treatment processes. The load type non-metallocene catalyst prepared by the loading process is a dry fluxible solid powder which can be used for carrying out slurry silting or homopolymerization in a gas-phase way or copolymerization of alkene or styrene from C2 to C10, particularly the ethylene or an organic monomer with functional groups. Homopolymerization products or copolymerization products with high melting points and favorable particle shapes can be obtained under the condition of lower dosage of alkane oxygen aluminium.
Description
Technical field
The invention relates to the load metallization processes of the non-metallocene olefin polymerization catalyst of a class novel texture, with and application in olefinic polymerization and copolymerization process, especially for the homopolymerization of ethene or the copolymerization of ethene and other alpha-olefin, belong to the loadization of catalyzer and the technical field of organic polymer.
Background technology
Known homogeneous transition-metal catalyst has very high catalytic activity in olefinic polymerization, as unsupported Ziegler one Natta catalyst, metallocene calalyst for polymerization of olefine, constrained geometry olefin polymerization catalysis or non-metallocene olefin polymerization catalyst.Wherein, Ziegler one Natta catalyst is many active centre olefin polymerization catalysis, and then three kinds are single active center's olefin polymerization catalysis.Metallocene calalyst for polymerization of olefine, the constrained geometry olefin polymerization catalysis all contains cyclopentadienyl ligands in catalyst structure, and the non-metallocene olefin polymerization catalyst ligating atom is an oxygen, nitrogen, sulphur and carbon etc., do not contain cyclopentadienyl group, be to find at the initial stage nineties and obtain launching to study, its catalytic activity can meet or exceed metallocene calalyst for polymerization of olefine, and kept the polymkeric substance of metallocene catalysis system controlled simultaneously, narrow molecular weight distribution, can carry out molecule to polymkeric substance cuts out, the polymericular weight and the degree of branching such as can regulate and control at advantage, and because a little less than this type of catalyzer oxytropism, can realize the copolymerization of polar monomer and alkene, thereby produce the functional polyolefin material of excellent performance.
During polymerization in homogeneous phase, the phenomenon that the polymkeric substance of formation can produce sticking still and twine stirring rake, this heat exchange to material in the normal operation of reactor and the reactor has bigger influence, is unfavorable for industrialized continuous production.In addition, need a large amount of promotor methylaluminoxane in the homogeneous catalysis system, polyolefinic production cost is increased, and because the introducing of a large amount of promotors, product performance have also been produced adverse influence, some in addition need in postorder processing, remove the aluminium of introducing in the polymerization process, further increased the cost of process.A kind of olefinic polymerization that patent WO03/010207 is prepared and copolymerization catalyst or catalyst system, have olefinic polymerization widely and copolymerization performance, be applicable to the polymerization technique of various ways, but when olefinic polymerization, need higher promotor consumption could obtain suitable olefin polymerizating activity, and polymerization process exist sticking still phenomenon.
Experience (Chem Rev, 2000,100:1347 according to the metallocene calalyst for polymerization of olefine industrial applications; Chem Rev, 2000,100:1377), the loadization of homogeneous phase non-metallocene olefin polymerization catalyst is very necessary.
The main purpose of catalyst cupportization is the granulating form for polymerization that improves catalyzer and polymkeric substance.It shows as the initial activity that has suitably reduced catalyzer to a certain extent, thereby reduces even avoided caking or the poly-cruelly phenomenon in the polymerization process; Catalyzer can improve the form of polymkeric substance after loadization, improve the apparent density of polymkeric substance, can make it satisfy more polymerization technique process, as vapour phase polymerization or slurry polymerization etc., the process of load simultaneously can reduce Preparation of catalysts and olefinic polymerization cost significantly, improve polymerization, prolong polymerization catalyst active lifetime etc.EP 0206794 use MAO is oxide support modified and use metallocenes subsequently, has objectively limited the controllability of the performance of solid support material to the polymer particles granularity.EP685494 acts on hydrophilic oxide with methylaluminoxane, with polyfunctionality organic crosslinking agent and the MAO/ of use activation subsequently metallocene complex, might reduce the tap density of polymerisate, is unfavorable for the industry use.
Patent CN 1352654 selects for use organoaluminum, organosilicon, organic-magnesium and organoboron compound to handle carrier, single site olefin polymerization catalysts of load heteroatom ligand then, and resulting loaded catalyst has high reactivity and long storage life.EP 295312 has described under the situation that the organic or inorganic bead-type substrate exists, and aluminoxanes solution is contacted with a kind of solvent that can not dissolve aikyiaiurnirsoxan beta, causes aikyiaiurnirsoxan beta to be deposited on the carrier.WO97/26285 describes the method for preparing carried metallocene catalyst under the high pressure, and the production cycle is long, and load efficiency is not high.And CN 1307065 handles carrier back loading metallocene catalyst with alkylaluminoxane under the ultra-sonic oscillation effect, and the load process is also uneconomical.
In order to improve the bonding strength between carrier and the catalyzer, CN 1162601 adopts the difunctionality linking agent to continue to handle the carrier of process aikyiaiurnirsoxan beta or alkylaluminium cpd processing.Patent CN 1174849 handles the silicon-dioxide of dehydroxylation in the toluene medium with MAO after, load metallocene catalyst does not more provide the polymerization activity data of loaded catalyst in the literary composition.Patent CN1120550 proposes a kind of method of catalyst cupportization, it is mainly with hydrophilic, macropore, inorganic carrier in small, broken bits, react with aikyiaiurnirsoxan beta after elder generation's thermal activation, then with multifunctional organic crosslinking agent reaction, mix with the reaction product of metallocenes and activator at last, thereby make carried type metallocene catalyst, but the consumption of aikyiaiurnirsoxan beta is higher in loading process.CN 1053673 adopts microwave action that catalyzer and the promotor that loads on the solid support material are contacted with each other in suspension, and then makes a kind of loaded catalyst of rock steady structure, but this method needs microwave device, and it is also remarkable to operate.CN1323319 adopts catalystic material to flood the porous particle carrier of mechanical flow state, the catalyst solution that is about to be equivalent to pore volume is sprayed onto on the carrier, and then drying makes loaded catalyst, this load method objectively requires the solubleness of catalyzer enough big, otherwise can not guarantee the homogeneity and the charge capacity of catalyst cupport.Patent WO96/00243 has described a kind of preparation method of supported catalyst compositions, be included in the two indenyl metallocenes and the aikyiaiurnirsoxan beta of mixing bridging in the solvent and form solution, described solution is combined with porous support, and the cumulative volume of wherein said solution is lower than the liquor capacity when forming slurries.
Summary of the invention
Technical problem: the objective of the invention is to provide on the basis of existing technology a kind of and have the longer polymerization activity life-span, have high stability, just with store and the load method and the aggregated application of the load type non-metallocene catalyst of transportation.
Technical scheme: the present invention relates to a class novel texture non-metallocene olefin polymerization catalyst the load metallization processes with and application in olefinic polymerization and copolymerization, the polymerization and ethene and the alpha-olefin that are particularly useful for ethene, comprise the copolymerization of the alpha-olefin of 3 or more carbon atoms, as with propylene, iso-butylene, butylene, amylene, hexene, octene and decene, diolefin such as divinyl, 1, the 7-octadiene, 1, the binary of 4-hexadiene or cycloolefin such as norbornylene etc., ternary or more polybasic copolymerization.
The load method method of load type non-metallocene catalyst of the present invention is characterized in that this method may further comprise the steps:
The carrier thermal activation and or chemical activation: carrier is under 100-1000 ℃, inert atmosphere or reduced pressure, and drying or roasting 1～24h carry out thermal activation; Carrier contacts with in metal halide, chlorosilane, aluminum alkyls, the aikyiaiurnirsoxan beta one or more and carries out chemical activation;
In the solvent, carrier is contacted with non-metallocene olefin polymerization catalyst, wash then, filter, dry with drain into flowable pressed powder.
Carrier is that porous organic material, IIA, IIIA, IVA family and IVB family metal oxide are at interior inorganic oxide, and oxidation mixture and mixed oxide, or the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or clay or molecular sieve or silica gel.
Described solvent is that catalyzer dissolves in mineral oil and different liquid hydrocarbons wherein, typical solvent is the varsol of from 5 to 12 carbon atoms, or the varsol that is replaced by the chlorine atom, or the aliphatic solvent of 6 to 10 carbon atoms, the cycloaliphatic solvent of 6 to 12 carbon atoms, preferred toluene or hexane; Non-metallocene olefin polymerization catalyst is the title complex with following structure:
Wherein:
M:1,2 or 3;
Q:0 or 1;
D:0 or 1;
N:1,2,3 or 4;
M: transition metal atoms;
X: be to comprise halogen atom, hydrogen atom, C
1-C
30Alkyl and C
1-C
30Replacement alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group at interior group, several X can be identical, also can be different, can also be each other in key Cheng Huan;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise X and polydentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom, R
21N or R
21P;
B: refer to nitrogen-containing group, phosphorus-containing groups or C
1-C
30Hydro carbons;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, contain C
1-C
30The nitrogen-containing group of alkyl, contain C
1-C
30The nitrogenous or C of alkyl
1-C
30Alkyl phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R
1, R
2, R
3, R
21, hydrogen, C
1-C
30Alkyl, halogen atom, C
1-C
30Substituted hydrocarbon radical or safing function group, R
1, R
2, R
3, R
21Group can be the same or different to each other, wherein adjacent group such as R
1, R
2, R
3Part can be each other in key Cheng Huan;
Alkyl refers to contain C
1-C
30Alkyl, C
1-C
30Cyclic hydrocarbon group, C
2-C
30Group, the C of carbon-carbon double bonds
2-C
30Carbon containing carbon triple-linked group, C
6-C
30Aryl radical, C
8-C
30Condensed ring alkyl or C
4-C
30Heterogeneous ring compound.
Adopt the olefin polymetiation process of load type non-metallocene catalyst, be to be Primary Catalysts with the carry type non-metallocene calalyst for polymerization of olefine, one of aikyiaiurnirsoxan beta, aluminum alkyls, Lewis acid or boron fluorine cpd are promotor, make polymerizable organic monomer under the condition that is enough to react, carry out slurry polymerization, vapour phase polymerization, letex polymerization, solution polymerization or copolymerization, slurry polymerization.The olefin polymetiation process of this loaded catalyst comprises the homopolymerization and the copolymerization process of alkene.
Polymerizable organic monomer is selected from the alkene of C2～C10, ethene especially, or contain the functional groups organic monomer.
In the present invention, element and metal be under the jurisdiction of certain gang all be meant by the family of this periodic table of elements and group corresponding to the family of IUPAC system marshalling or group as foundation.
Melting point polymer is determined on the TA-Q100 type differential scanning calorimetric analysis instrument (DSC) and carries out, and temperature rise rate is 5 ℃/min, and temperature range is 20～200 ℃.
The titanium elements Determination on content is carried out on OPTRMA-3000 type inductive coupling plasma emission spectrograph (ICP-AES) in the carry type non-metallocene calalyst for polymerization of olefine.
Beneficial effect: the present invention finds, adopts the prepared prepared polyethylene of carry type non-metallocene calalyst for polymerization of olefine of the present invention to have high fusing point.
The present invention finds that in starting polymerization or copolymerization stage, low mixing speed and low polymeric reaction temperature help to obtain the polymkeric substance of high reactivity and good particle shape.Here the initial action stage is meant the preceding 0.5h that feeds polymerization single polymerization monomer or comonomer.
The present invention finds that adopt the resulting carry type non-metallocene calalyst for polymerization of olefine of load method of the present invention to have the longer polymerization activity life-span, its active lifetime can reach 10h, the non-metallocene olefin polymerization catalyst that surpasses without load far away.
And the present invention also finds, adopts the resulting carry type non-metallocene calalyst for polymerization of olefine of load method of the present invention to have high stability, just with storage and transportation.Experimental result finds that under the anhydrous and oxygen-free environment, the carry type non-metallocene calalyst for polymerization of olefine of depositing 60 days still has identical olefin polymerizating activity.
Embodiment
The present invention discloses a kind of load method of non-metallocene olefin polymerization catalyst, and this method mainly comprises the following steps:
The carrier thermal activation and or chemical activation: carrier is under 100-1000 ℃, inert atmosphere or reduced pressure, and drying or roasting 1～24h carry out thermal activation; Carrier contacts with in metal halide, chlorosilane, aluminum alkyls, the aikyiaiurnirsoxan beta one or more and carries out chemical activation;
In solvent, carrier is contacted with non-metallocene olefin polymerization catalyst, wash then, filter, dry with drain into flowable pressed powder.
Resulting thus loaded catalyst, it mainly forms the middle layer that comprises that carrier, chemical activating agent and chemical processing agent are formed, and non-metallocene olefin polymerization catalyst.Non-metallocene olefin polymerization catalyst shape copying carrier form is a pulverulent solids that do, flowable.
The used carrier of the present invention can be arbitrarily, the surface has the porosu solid of functional group.It can be:
1, contain the organic materials of organo-functional group such as polyethylene, polypropylene, polybutene, polyvinyl alcohol, cyclodextrin and above-mentioned polymkeric substance based on monomeric multipolymer, polyester, polymeric amide, polyvinyl chloride, polyacrylic ester, polymethacrylate, polystyrene or partial cross-linked polymkeric substance, organo-functional group are selected from hydroxyl, primary amino, secondary amino group, sulfonic group, carboxyl, amide group, the mono-substituted amide group of N-, sulfonic acid amido, the mono-substituted sulfonic acid amido of N-, sulfydryl, acylimino and hydrazide group.Preferred partial cross-linked styrene polymer with surface hydroxyl functional group;
2, A, IIIA, IVA family and IVB family metal oxide are at interior solid inorganic oxide or halogenide, as silicon oxide (silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white, Thorotrast, magnesium chloride, and the mixture formed of inorganic oxide, functional group is selected from surface hydroxyl or carboxyl.Relatively suitable have oh group for the surface, comprise silicon oxide and with one or more IIA, IIIA family mixed oxide, as silicon oxide-magnesia mixed oxide, silica-alumina mixed oxide, the mixed oxide of the metal oxide of preferred silicon oxide, aluminum oxide and silicon oxide and one or more IIA, IIIA family is as solid support material.
3, the oxidation material for preparing by the pyrohydrolysis process of gaseous metal oxide compound or silicon compound.
Clay or molecular sieve are as mica, polynite, wilkinite, diatomite, ZSM-5, MCM-41.
The surface-area (BET method mensuration) that is fit to the carrier of wanting required for the present invention preferably from 10 to about 1000m
2/ g, more preferably from 100 to 600m
2/ g.Pore volume (determination of nitrogen adsorption) preferred 0.1 to 4cm
3Between/the g, more preferably 0.2 to 2cm
3/ g.The median size of carrier (laser particle analyzer mensuration) is from 1 to 500 μ m, more preferably from 1 to 100 μ m preferably.In above-mentioned solid support material, preferred IIA, IIIA, IVA family and IVB family metal oxide are at interior solid inorganic oxide or halide carrier with surface hydroxyl, most preferably silica gel.It can be any form, as granular, spherical, aggregate or other form.The content of hydroxyl can be measured with known technology, as infrared spectroscopy, nuclear magnetic resonance method, titanium tetrachloride method, metal alkylide or metal hydride titration technique.Suitable silica-gel carrier is arbitrarily can be by the commerical prod of buying, and as Grace955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid245, ES70, ES70X, ES757, Aerosil812, or CS-2133 and MS-3040.
Metal oxide surface generally all is by the tart surface hydroxyl, can makes it inactivation with catalyst reaction.Before using, carrier will experience the dehydroxylation process, and it can be under vacuum or inert atmosphere, calcination activation.Silica-gel carrier roasting 1～24h under 100-1000 ℃, inert atmosphere or reduced pressure finishes.Here said inert atmosphere be meant only contain in the gas and trace or do not contain can with the component of carrier reaction.Roasting condition is preferably at 500～800 ℃, N
2Or continuing 2～12h under the Ar atmosphere, optimum is 4～8h.Dehydroxylation silica gel through thermal activation need be preserved under inert atmosphere.
The purpose of the thermal activation of silica-gel carrier is to make carrier surface have highly active group, report (J AmChem Soc is arranged, 1996,118:401) point out, when drying temperature is 200 ℃～500 ℃, the oh group that is easy to remove is reversibly removed, produce the siloxane groups of low reaction activity, but surpass under 600 ℃ the situation at drying temperature, oh group forcibly is removed, change into water, produce and to have the high ring stress and the siloxane groups of high reaction activity very.Also can adopt chemical activating agent that the functional group of carrier surface is changed into other nonreactive siloxane groups.
Carrier also can be without the high-temperature roasting step, thus but the realization dehydroxylation process that directly contacts with chemical activating agent.Here said chemical activating agent, it can be the chemical reagent of any and carrier surface hydroxyl reaction, as chlorosilane, the halogenide of IIIA, IVB or VB metal, alkylate or halogenated alkyl compounds, dimethylchlorosilane, trimethylchlorosilane, aluminum alkyls are such as aluminium trimethide, aluminium triethyl, butyl aluminium; Aikyiaiurnirsoxan beta is such as methylaluminoxane and aikyiaiurnirsoxan beta, butyl aikyiaiurnirsoxan beta.For the temperature and time in this process, the present invention does not do strict the qualification, as at normal temperatures can be longer slightly, can lack under the high-temperature slightly, and generally between 0.5h～48h, preferred 1～10h.
Involved in the present invention to solvent can be mineral oil and different liquid hydrocarbons, the most basic requirement is that catalyzer can be dissolved in wherein, and both do not react.Typical solvent is the varsol of from 5 to 12 carbon atoms, or the varsol that is replaced by the chlorine atom, and as methylene dichloride or ether solvent such as ether or tetrahydrofuran (THF), acetone, ethyl acetate etc. also can use.Optimization aromatic solvent such as toluene and dimethylbenzene; Or the aliphatic solvent of 6 to 10 carbon atoms, as hexane, heptane, octane, nonane, decane and their isomer, the cycloaliphatic solvent of 6 to 12 carbon atoms is as hexane; Or their mixture.Most preferably toluene, hexane or methylene dichloride.
Carrier through thermal activation or chemical activation can directly contact with non-metallocene olefin polymerization catalyst solution, thereby load obtains carry type non-metallocene calalyst for polymerization of olefine.But discover that originally if obtain active more excellent carry type non-metallocene calalyst for polymerization of olefine, it is very crucial further handling.Compare with the extra activity that loaded catalyst is obtained, the cost of this treatment step is inappreciable.This process is that the carrier through thermal activation or chemical activation is contacted with chemical processing agent, incipient impregnation such as chemical processing agent solution spraying are on carrier, or solution impregnation, as carrier impregnation is stirred 0.5～72h in the chemical treatment agent solution, preferred 2～24h, most preferably 2～6h.Chemical processing agent is selected from one or more the polynary treatment agents formed in halogenide, alkylate, alkoxy compound or the halogenated alkyl compounds that chemical activating agent is selected from aikyiaiurnirsoxan beta, aluminum alkyls, borine, IVA, IVB or VB family metal.
Aikyiaiurnirsoxan beta adopts lienar for (I) particularly
R-(Al (R)-O) just
n-AlR
2
And/or the aikyiaiurnirsoxan beta of ring-type type aikyiaiurnirsoxan beta (II).
Just-(Al (R)-O-)
N+2
In structure (I) with (II), the R group can be identical or different, and be the C1-C8 alkyl, comprises methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, butyl aikyiaiurnirsoxan beta etc.Preferred R group is identical and is methyl, isobutyl-, phenyl or benzyl, most preferable, and n is the integer of 1-50, preferred 10～30.
Aluminum alkyls or boron alkyl are for having the compound of following general formula (III):
N(R)
3
Wherein: N is aluminium or boron, R and structure (I) and (II) in definition identical, each in three R groups can be identical, also can be different.Comprise alkyl metal cpd comprise trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-propyl aluminum, tri-butyl aluminum, dimethylaluminum chloride, triisopropylaluminiuand, three sec-butyl aluminium, three cyclopentyl aluminium, three amyl group aluminium, triisopentyl aluminium, three hexyl aluminium, ethyl dimethyl aluminium, methyl diethyl aluminum, three amyl group aluminium, three pairs-tolyl aluminium, dimethyl aluminium methylate, dimethyl aluminium ethylate, trimethyl-boron, triethyl-boron, tri-isobutyl-boron, tripropyl boron, tri butyl boron,
Halogenide, alkylate, alkoxy compound or the halogenated alkyl compounds of IVA, IVB or VB family metal are as SiCl
4, SiBr
4, Si (OC
2H
5)
3Cl, Si (OC
2H
5) Cl
3, S (OC
4H
9) Cl
3, Si (OC
4H
9)
3Cl, Si (OC
3H
7)
2Cl
2Deng; TiCl
4, TiBr
4, Ti (OC
2H
5)
3Cl, Ti (OC
2H
5) Cl
3, Ti (OC
4H
9) Cl
3, Ti (OC
4H
9)
3Cl, Ti (OC
3H
7)
2Cl
2, Ti (OC
6H
13)
2Cl
2, Ti (OC
8H
17)
2Br, Ti (OC
12H
25) Cl
3VCl
4, VBr
4, V (OC
2H
5)
3Cl, V (OC
2H
5) Cl
3, V (OC
4H
9) Cl
3, V (OC
4H
9)
3Cl, ZrCl
4, ZrBr
4, Zr (OC
2H
5)
3Cl, Zr (OC
2H
5) Cl
3, Zr (OC
4H
9) Cl
3, Zr (OC
4H
9)
3Cl, Zr (OC
3H
7)
2Cl
2, Zr (OC
6H
13)
2Cl
2, Zr (OC
8H
17)
2Br, Zr (OC
12H
25) Cl
3
Mentioned reagent can be used alone, but also also mix together.The halogen compounds of preferred aikyiaiurnirsoxan beta, titanium or zirconium, or contain the mixture of aikyiaiurnirsoxan beta, more preferably the binary chemical processing agent formed of methylaluminoxane and titanium tetrachloride.
The present invention is surprised to find that, directly adopts the halogenide of titanium, as TiCl
4As chemical processing agent, with independent employing methylaluminoxane or methylaluminoxane and TiCl
4The binary system of being formed is compared, and still can obtain very high polymerization activity and active lifetime, and is that the particle of polymkeric substance is a size uniform spherical particle more unexpectedly.
The adding of chemical processing agent can soon can be slow, preferably slowly adds, and helps dispersion process as dropping.
Washing, filtration, drying and the process of draining are to adopt method well known in the art, as drip washing, promptly under airtight or reactive atmosphere, can not be by the drip washing solid but can be at one by on the sand core funnel of solvent, by washing repeatedly of solvent to reach the purpose of washing and filtering; Or adopt Xian to wash, and promptly leave standstill and remove supernatant liquid, and then add solvent, so repeat these processes to reach the purpose of washing and filtering; Or the most usual method be will need washing and filtering system to going in the sand core funnel, take out by the suction filtration effect and desolvate, and then add solvent, suction filtration again, thereby reach the purpose of washing and filtering.The drip washing washing effect is best, but uneconomical, needs the time longer, and Xian washes simple, but effect is not thorough, the preferred suction filtration method of the present invention.The minimum triplicate that needs of washing and filtering process.The nature washing times is many more, and washing effect is just good more, but also can increase the consumption of solvent simultaneously.Preferred 3～5 times.Treatment temp and wash temperature are not subjected to strict restriction at this patent, can be 0 ℃～100 ℃.Preferred 20～80 ℃, between optimum 40 ℃～60 ℃.
Solid is about in temperature carries out drying under reduced pressure under 0～120 ℃, till obtaining mobile catalyst support powder.The length of this drying process time depends on used temperature, and the airtight situation of the ability of vacuum system and system is relevant.
Non-metallocene olefin polymerization catalyst involved in the present invention is the title complex (IV) with following structure
It mainly comprises the catalyst I VA and the IVB of following structure.
In order more to be expressly understood catalyst I VA, we can use IVA-1, and IVA-2, IVA-3 and IVA-4 come refinement to describe.
In order more to be expressly understood catalyst I VB, we can use IVB-1, and IVB-2, IVB-3 and IVB-4 come refinement to describe.
In all above-mentioned structures:
M:1,2 or 3;
Q:0 or 1;
D:0 or 1;
M: cross ripple atoms metal, especially titanium, zirconium, hafnium, chromium, iron, cobalt, nickel, palladium;
N:1,2,3 or 4;
X: be the alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, the boron-containing group that comprise the replacement of the alkyl of halogen atom, hydrogen atom, C1-C30 and C1-C30, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain the group of tin group, several X can be identical in the structural formula, also can be different, can also be each other in key Cheng Huan;
The halogen atom here comprises fluorine, chlorine, bromine or iodine;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise X and polydentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom,
-NR
23R
24,-N (O) R
25R
26,
-PR
28R
29,-P (O) R
30R
31, sulfuryl, sulfoxide group ,-Se (O) R
39
B: refer to nitrogen-containing group, phosphorus-containing groups or C
1-C
30Hydro carbons;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, contain C
1-C
30The nitrogen-containing group of alkyl, contain C
1-C
30The phosphorus-containing groups of alkyl, sulfuryl, sulfoxide group,
-N (O) R
25R
26,
-P (O) R
30R
31,-P (O) R
32(OR
33), wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
F: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
G: be inertia group, comprise or the safing function group, comprise C
1-C
30Alkyl, C
1-C
30The alkyl or the safing function group of replacement;
Y, Z: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R
1, R
2, R
3, R
4, R
5, R
10, R
11, R
12, R
13, R
14, R
15, R
16, R
17, R
18, R
19, R
20, R
21, R
22, R
23, R
24, R
27, R
28, R
29, R
30, R
31, R
32, R
33, R
34, R
35, R
36, R
38, R
39: hydrogen, C
1-C
30Alkyl, halogen atom, C
1-C
30Substituted hydrocarbon radical be meant halogenated alkyl especially, as-CH
2Cl ,-CH
2CH
2Cl or safing function group, above-mentioned group can be the same or different to each other, wherein adjacent group such as R
1With R
2, R
3, R
3With R
4, R
6, R
7, R
8, R
9And R
23With R
24Or R
25With R
26Deng can be each other in key Cheng Huan.
R
5Refer to lone-pair electron, hydrogen, C on the nitrogen
1-C
30Alkyl, C
1-C
30Alkyl, the oxy radical of replacement comprise hydroxyl, alkoxyl group-OR
34, the alkyl that has ether comprises-T-OR
34, sulfur-containing group comprises-SR
35,-T-SR
35, nitrogen-containing group comprises-NR
23R
24,-T-NR
23R
24, phosphorus-containing groups comprises-PR
28R
29,-T-PR
28R
29,-T-P (O) R
30R
31Work as R
5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group, phosphorus-containing groups, R
5In N, O, S, P, Se also can participate in coordination with metal.
T: be C
1-C
30Alkyl or C
1-C
30Substituted hydrocarbon radical or safing function group;
Such as following Nonmetallocene alkene olefin polymerization catalysis:
Preferred structure is to be the non-metallocene olefin polymerization catalyst shown in 1,3,6,16,23.Most preferred configuration is the non-metallocene olefin polymerization catalyst shown in 1 or 6.
Non-metallocene olefin polymerization catalyst is dissolved in the solvent, then the carrier with process step noted earlier contacts, here said contact both was meant and the carrier of flowable state can be joined in the solution of non-metallocene olefin polymerization catalyst, also the solution of non-metallocene olefin polymerization catalyst can be joined on the carrier of flowable state.Under agitation condition, react then.Temperature of reaction is not also done strict qualification in this patent, optionally temperature is as between 0 ℃～100 ℃, preferably between 20 ℃～60 ℃.
The chemical treating process of above-described carrier and the loading process of non-metallocene olefin polymerization catalysts all need carry out under the anhydrous and oxygen-free condition of strictness, here said anhydrous and oxygen-free condition is meant that the content of water and oxygen in the system continues less than 10ppm, and the anhydrous and oxygen-free condition is one of key factor that obtains highly active supported catalyst.
Carry type non-metallocene calalyst for polymerization of olefine having thus described the invention is a Primary Catalysts, aluminum alkyls, aikyiaiurnirsoxan beta or Lewis acid, boron fluothane, boron alkyl, boron alkyl ammonium salt are promotor, under the condition that is enough to react, carry out C2～C10 slurry olefin polymerization, vapour phase polymerization, letex polymerization, solution polymerization or copolymerization.
At the used C2 of polymkeric substance～C10 alkene with method preparation of the present invention, be selected from ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene or vinylbenzene, 1,4 divinyl, 2,5-pentadiene, 1, the 6-hexadiene, or contain the functional groups organic monomer, as the homopolymerization and the copolymerization process of vinyl acetate between to for plastic, methyl acrylate, ethyl propenoate, butyl acrylate.
Polyreaction can adopt technology well known in the art to carry out, preferred slurries polymerization and gaseous polymerization, polymerization single polymerization monomer with or comonomer and carry type non-metallocene calalyst for polymerization of olefine can under-40 ℃～120 ℃, normal pressure～10MPa, contact continuously or carry out off and on.Slurry polymerization process most preferably, especially for ethene, perhaps ethene and other alkene, the polymerization that contains the functional groups organic monomer and copolymerization process.
Polymer solvent can be to be selected from the solvent described in the front load process in the slurry polymerization process, preferred hexane solvent.
The promotor that can be used as this polymerization system has aluminum alkyls, aikyiaiurnirsoxan beta or Lewis acid, boron fluothane, boron alkyl, boron alkyl ammonium salt.Aluminum alkyls, aikyiaiurnirsoxan beta have been done detailed narration in front, and Lewis acid, boron fluothane, boron alkyl, boron alkyl ammonium salt then are meant the compound with following logical formula V:
[L-H]
+[NE
4]
-Or [L]
+[NE
4]
-
Wherein L is neutrality or male ionic Lewis acid, and H is a hydrogen atom, and N is aluminium or boron, and each E can be identical or different, for having the aryl of 6～12 carbon atoms, wherein have-individual above hydrogen replaced by halogen atom, alkoxyl group or phenoxy group.Comprise trimethyl ammonium tetraphenyl boron, trimethyl ammonium four (right-tolyl) boron, the basic boron of tributyl ammonium four (five fluorine boron), trimethyl-phosphine tetraphenyl boron, trimethyl ammonium tetraphenyl aluminium, tripropyl ammonium tetraphenyl aluminium, trimethyl ammonium four (right-tolyl) aluminium, triethyl ammonium four (neighbours, right-3,5-dimethylphenyl) aluminium, tributyl ammonium four (right-trifluoromethyl) aluminium, trimethyl ammonium four (right-trifluoromethyl) aluminium, tributyl ammonium four (pentafluorophenyl group) aluminium, N, N-Diethyl Aniline tetraphenyl aluminium, N, N-ethylaniline four (pentafluorophenyl group) aluminium, diethyl ammonium four (pentafluorophenyl group) aluminium etc.
The preferred aikyiaiurnirsoxan beta of promotor, the most preferable aikyiaiurnirsoxan beta.
Here the said condition that is enough to carry out polyreaction for slurry polymerization, then is meant temperature condition, pressure condition, mixing speed situation.
If desired, hydrogen can be used as the polymericular weight conditioning agent to be added, and its branch covers 0.01～5% of polymer monomer pressure, and preferred 0.1%～2%.
Polymerization pressure is at 0.1～10MPa, preferred 0.5～4MPa, optimum 1～3MPa.The raising of polymerization pressure can increase The Thermal Capacity of Gaseous, thereby helps heat passage in the reaction process.
The present invention finds that too high polymerization pressure can cause sticking still, can not obtain the good polymkeric substance of form.
Embodiment 1
1.1 the preparation of loaded catalyst
1.1.1 the activation of carrier
Get ES-70 type silica gel (Crosfield company product) roasting under nitrogen atmosphere.Its roasting condition is: 5 ℃/Min of temperature rise rate, and 200 ℃ of following constant temperature 0.5h, 400 ℃ of following constant temperature 0.5h are then at 600 ℃ of following constant temperature 4h, naturally cooling under nitrogen atmosphere at last.Be designated as the ES-70-600 carrier.
1.1.2 the chemical treatment of carrier
Under the nitrogen atmosphere of anhydrous and oxygen-free (content of water and oxygen all is lower than 5ppm), get 2.0413g ES-70-600 carrier, add the 20ml toluene solvant and stir formation suspension.Get the toluene solution (brief note for former MAO, MAO accounts for 15wt%, Witco company product) of 2ml methylaluminoxane (MAO), under 25 ℃ and agitation condition, slowly be added drop-wise in the above-mentioned suspension.Continue to stir 2h.Get titanium tetrachloride (TiCl again
4) hexane solution (titanium content is 0.41mol/L) 10ml, under 25 ℃ and agitation condition, slowly drip in above-mentioned mixed system, continue to stir 2h at last again.
1.1.3 washing, filter, dry and drain
With the suspension suction filtration, with the washing of 4 * 30ml toluene solvant, at last with gained solid decompressing and extracting Cheng Gan, flowable powder under vacuum condition.
1.1.4 the load of catalyzer
Take by weighing the non-metallocene olefin polymerization catalyst of 96.5mg structural formula shown in (6), join in the 20ml toluene,, and then join among the support powder, stir 12h 25 ℃ of following stirring and dissolving.
Adopt the washing of 1.1.3 method, filter, dry and drain, obtain doing, can flow, the loaded catalyst of orange.
1.2 polymerization
In the 0.5L autoclave of crossing with the exsiccant nitrogen purging, add 98.2mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent simultaneously, at ethylene pressure is that 1.04MPa, mixing speed are to carry out vinyl polymerization under 50 ℃ of 560rpm and the constant temperature, and the reaction times is 1h.Take out polymkeric substance, dry removing desolvated.
Output: 12.4g, DSC scanning curve show that polyethylene has 134.96 ℃ and 141.13 ℃ of two melting peaks.
Embodiment 2
2.1 Preparation of catalysts
Preparation of catalysts process similar embodiment 1.1 is got 2.048g ES-70-600 carrier, adds the 20ml toluene solvant.Slowly drip the toluene solution (former MAO and toluene solvant carry out dilution in 1: 9, note by abridging to be rare MAO) of 2ml MAO, slowly drip 10ml TiCl again
4Hexane solution (titanium content is 0.41mol/L), wash then, filter, dry and drain.
The non-metallocene olefin polymerization catalyst that takes by weighing 224mg is dissolved in the 40ml toluene solvant, so joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 2.4%.
2.2 polymerization
Adding 48.7mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 1.04MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 30 ℃, behind the 30min, increases mixing speed to 570rpm with improve temperature of reaction to 60 ℃, continues to react 1.5h.
Output: 21.72g, 140.56 ℃ of polyethylene fusing points.
Adding 40.9mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 200rpm, temperature of reaction is 30 ℃, behind the 30min, increases mixing speed to 600rpm with improve temperature of reaction to 50 ℃, continues to react 4.5h.
Output: 60.35g, 140.31 ℃ of polyethylene fusing points.
Adding 163.8mg loaded catalyst, the former MAO of 6ml and 260ml hexane solvent in the 2L autoclave simultaneously, is that 1.1MPa carries out vinyl polymerization at ethylene pressure.Mixing speed 300rpm, initial reaction temperature is 30 ℃, behind the 3.5h, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 48.80g, 140.31 ℃ of polyethylene fusing points.
2.3 copolymerization
Add 48.3mg loaded catalyst, the former MAO of 6ml and 500ml hexane solvent in the 2L autoclave simultaneously, opening mixing speed simultaneously is 300rpm.
Under 60 ℃, ethene and butylene are mixed according to mass ratio at 5: 1, in autoclave, provide interpolymer then, keep pressure 1.3MPa in the autoclave.Initial reaction temperature is 30 ℃, improves temperature of reaction to 50 ℃ behind the 30min, continues reaction 1.5h.
Output 23.74g, 127.81 ℃ of polyethylene fusing points.
Embodiment 3
Preparation of catalysts similar embodiment 1.1 is got 2.008g ES-70-600 carrier, adds the 20ml toluene solvant.Slowly drip 10ml TiCl
4Hexane solution (titanium content is 0.41mol/L), wash then, filter, dry and drain.Take by weighing the 191.4mg non-metallocene olefin polymerization catalyst and be dissolved in the 35ml toluene, join among the support powder, stir 12h.Wash at last, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 2.57%.
Polymerization process similar embodiment 1.2 is carried out.Adding 54.1mg loaded catalyst, the former MAO of 4ml and 250m1 hexane solvent in the 0.5L autoclave simultaneously, is that 1.04MPa, mixing speed are to carry out vinyl polymerization under 50 ℃ of 560rpm and the constant temperature at ethylene pressure.Reaction times is 2h.
Output: 13.45g, 136.88 ℃ of polyethylene fusing points.
Adding 44mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 25 ℃, behind the 30min, increases mixing speed to 590rpm with improve temperature of reaction to 50 ℃, continues to react 1.5h.
Output: 24.65g.
Embodiment 4
Preparation of catalysts similar embodiment 1.1 is got 1.6884g ES-70-600 carrier, adds the 20ml toluene solvant.Slowly drip 10ml SiCl
4Toluene solution (0.435mol/L), wash then, filter, dry and drain.Take by weighing the 137.5mg non-metallocene olefin polymerization catalyst and be dissolved in the 15ml toluene, join among the support powder, stir 12h.Wash at last, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 0.605%.
Polymerization similar embodiment 1.5 is carried out.In the 0.5L autoclave, add 92.1mg loaded catalyst, the former MAO of 4ml simultaneously) and the 250ml hexane solvent.Reaction times is 1h.
Output: 4.817g, DSC scanning curve show that polyethylene has 137.39 ℃ and 141.66 ℃ of two melting peaks.
Embodiment 5
The reactivation process of carrier is similar to the 1.1.1 among the embodiment.Get ES-70 type silica gel at 650 ℃ of following constant temperature 4h, be designated as the ES-70-650 carrier.
Preparation of catalysts process similar embodiment 3 is got 2.155g ES-70-650 carrier, adds the 20ml toluene solvant.Slowly drip 10ml TiCl
4Toluene solution (titanium content is 0.41mol/L), washing, filter, dry and take out.Take by weighing the non-metallocene olefin polymerization catalyst of 51.6mg structural formula shown in (16) and be dissolved in the 25ml toluene, join among the support powder, stir 24h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 137.1mg loaded catalyst, the former MAO of 6ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 1.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 25 ℃, behind the 30min, increases mixing speed to 590rpm with improve temperature of reaction to 50 ℃, continues to react 1.5h.
Output: 24.83g, 134.55 ℃ of polyethylene fusing points.
Embodiment 6
Preparation of catalysts process similar embodiment 1.1.Get 1.03g ES-70-650 carrier, add the 20ml toluene solvant, slowly drip the rare MAO of 2ml.Wash then, filter, dry and drain.Take by weighing the non-metallocene olefin polymerization catalyst of 106mg structural formula shown in (6), be dissolved in the 20ml toluene solvant, add 5ml TiCl
4Hexane solution (titanium content is 0.41mol/L), stir 2h after, join again among the support powder, stir 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 56.4mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 200rpm, temperature of reaction is 25 ℃, behind the 30min, increases mixing speed to 600rpm with improve temperature of reaction to 50 ℃, continues to react 1.5h.
Output: 12.30g, 137.97 ℃ of polyethylene fusing points.
Embodiment 7
Get ES-70 type silica gel at 300 ℃ of following constant temperature 6h, be designated as the ES-70-300 carrier.
Preparation of catalysts process similar embodiment 2.Get the 1gES-70-300 carrier, add the 20ml toluene solvant.Slowly drip the rare MAO of 4ml, slowly drip 10ml TiCl again
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h, wash then, filter, dry and drain.The non-metallocene olefin polymerization catalyst that takes by weighing 119mg is dissolved in the 20ml toluene, joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 30.6mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 25 ℃, behind the 30min, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 9.141g, 142.04 ℃ of polyethylene fusing points.
Embodiment 8
Preparation of catalysts process similar embodiment 3 takes by weighing 1.01g ES-70-300 carrier, adds the 20ml toluene solvant.Slowly drip 10mlTiCl
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h, wash then, filter, dry and drain.The non-metallocene olefin polymerization catalyst that takes by weighing 130mg is dissolved in the 20ml toluene, joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 36mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 25 ℃, behind the 30min, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 32.766g, 135.47 ℃ of polyethylene fusing points.
Embodiment 9
Preparation of catalysts similar embodiment 2 takes by weighing 1.071g ES-70-300 carrier, adds the 20ml toluene solvant.Slowly drip the toluene solution (1.01mol/L) of 1ml trimethyl aluminium (TMA), continue to stir 2h, slow again Dropwise 5 mlTiCl
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h.Through washing, filter, dry and drain into dried, flowable powder.The non-metallocene olefin polymerization catalyst that takes by weighing 104mg is dissolved in the 20ml toluene, and then joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 36.4mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 30 ℃, behind the 30min, improves temperature of reaction to 50 ℃, continues reaction 1.5h.
Output: 18.27g, 138.36 ℃ of polyethylene fusing points.
Embodiment 10
Preparation of catalysts similar embodiment 3 takes by weighing 1.077g ES-70-300 carrier, adds the 20ml toluene solvant.Slow Dropwise 5 ml TiCl
4Hexane solution (titanium content is 0.41mol/L), continue to stir 2h, wash then, filter, dry and drain.The non-metallocene olefin polymerization catalyst that takes by weighing 101mg is dissolved in the 20ml toluene, joins among the support powder, stirs 12h.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 36.3mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is 2.0MPa at ethylene pressure, and mixing speed is to carry out vinyl polymerization under the 600rpm condition.Initial reaction temperature is 30 ℃, behind the 30min, improves temperature of reaction to 40 ℃, continues reaction 1.5h.
Output: 34g, 137.32 ℃ of polyethylene fusing points.
Embodiment 11
The reactivation process of carrier is similar to the 1.1.1 among the embodiment.Get PQ-2133 type silica gel (Pq Corp.'s product) at 650 ℃ of following constant temperature 4h, be designated as the CS-2133-650 carrier.
Preparation of catalysts similar embodiment 3.Get 1.01g CS-2133-650 carrier, add the 20ml toluene solvant and stir formation suspension.Slow Dropwise 5 ml TiCl
4Hexane solution (titanium content is 0.41mol/L), wash then, filter, dry and drain.Take by weighing the non-metallocene olefin polymerization catalyst of 104mg structural formula shown in (16), join in the 25ml toluene,, and then join among the support powder, stir 24h 25 ℃ of following stirring and dissolving.Wash at last, filter, dry and drain.
Polymerization similar embodiment 1.2 is carried out.Adding 46.6mg loaded catalyst, the former MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 2.0MPa carries out vinyl polymerization at ethylene pressure.Initial mixing speed 150rpm, temperature of reaction is 30 ℃, behind the 30min, increases mixing speed to 600rpm with improve temperature of reaction to 50 ℃, continues to react 3h.
Output: 36g.
Embodiment 12
Take by weighing ES-70-300 silica-gel carrier 0.510g, add the 20ml toluene solvant, stir and form suspension, add 2.5ml dimethyldichlorosilane(DMCS) ((CH again
3)
2SiCl
2) toluene solution (contain (CH
3)
2SiCl
210%V/V).React 2h after scouring, filtration, drying, drain.And then the TiCl of adding 2.5ml
4Hexane solution (titanium content is 0.4lmol/L), wash again, filter, dry, drain.Take by weighing the non-metallocene olefin polymerization catalyst of 70mg structural formula shown in (16), be dissolved in the 20ml toluene, join among the support powder, stir 48h.Wash at last, filter, dry and drain.
Output: 24.2g.
Embodiment 13
Preparation of catalysts similar embodiment 1.1.Take by weighing 0.9858g crosslinked polystyrene carrier, add toluene 60ml, drip the former MAO of 8ml again, constant temperature stirs 1h down for 50 ℃, washing, filter, dry and drain.Take by weighing the 251.5g non-metallocene olefin polymerization catalyst, be dissolved in the 60ml toluene, above-mentioned solid is joined in the catalyst solution, stir 3h, and then washing, filter, dry and drain.
The titanium content of carry type non-metallocene calalyst for polymerization of olefine is 0.538%.
Polymerization similar embodiment 1.2 is carried out.Adding 114.7mg loaded catalyst, the former MAO of 6ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, is that 1.04MPa carries out vinyl polymerization at ethylene pressure.
Mixing speed 600rpm, temperature of reaction is 45 ℃, reaction 3h.
Output: 13.25g, 139.21 ℃ of polyethylene fusing points.
Claims (4)
1, a kind of load method of load type non-metallocene catalyst is characterized in that this method may further comprise the steps:
(1) the carrier thermal activation and or chemical activation: carrier is under 100～1000 ℃, inert atmosphere or reduced pressure, and drying or roasting 1～24h carry out thermal activation; Carrier contacts with in metal halide, chlorosilane, aluminum alkyls, the aikyiaiurnirsoxan beta one or more and carries out chemical activation;
(2) in solvent, carrier is contacted with non-metallocene olefin polymerization catalyst, wash then, filter, dry with drain into flowable pressed powder.
2, according to the load method of the described load type non-metallocene catalyst of claim 1, it is characterized in that carrier is that porous organic material, IIA, IIIA, IVA family and IVB family metal oxide are at interior inorganic oxide, and oxidation mixture and mixed oxide, or the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound, or clay or molecular sieve or silica gel.
3,, it is characterized in that described solvent is that catalyzer dissolves in mineral oil and different liquid hydrocarbons wherein according to the load method of the described load type non-metallocene catalyst of claim 1.
4, the load method of the described load type non-metallocene catalyst of claim 1 is characterized in that non-metallocene olefin polymerization catalyst is the title complex with following structure:
Wherein:
M:1,2 or 3;
Q:0 or 1;
D:0 or 1;
N:1,2,3 or 4;
M: transition metal atoms;
X: be to comprise halogen atom, hydrogen atom, C
1-C
30Alkyl and C
1-C
30Replacement alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group at interior group, several X can be identical, also can be different, can also be each other in key Cheng Huan;
In the structural formula all parts electronegative sum absolute value should with metal M in the structural formula positively charged absolute value identical, all parts comprise X and polydentate ligand;
A: Sauerstoffatom, sulphur atom, selenium atom, R
21N or R
21P;
B: refer to nitrogen-containing group, phosphorus-containing groups or C
1-C
30Hydro carbons;
D: refer to Sauerstoffatom, sulphur atom, selenium atom, contain C
1-C
30The nitrogen-containing group of alkyl, contain C
1-C
30The nitrogenous or C of alkyl
1-C
30Alkyl phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
E: refer to nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group, phosphorus-containing groups, wherein N, O, S, Se, P are ligating atom;
→: refer to singly-bound or two key;
...: refer to coordinate bond, covalent linkage or ionic linkage;
-: refer to covalent linkage or ionic linkage;
R
1, R
2, R
3, R
21, hydrogen, C
1-C
30Alkyl, halogen atom, C
1-C
30Substituted hydrocarbon radical or safing function group, R
1, R
2, R
3, R
21Group can be the same or different to each other, wherein adjacent group such as R
1, R
2, R
3Part can be each other in key Cheng Huan;
Alkyl refers to contain C
1-C
30Alkyl, C
1-C
30Cyclic hydrocarbon group, C
2-C
30Group, the C of carbon-carbon double bonds
2-C
30Carbon containing carbon triple-linked group, C
6-C
30Aryl radical, C
8-C
30Condensed ring alkyl or C
4-C
30Heterogeneous ring compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310106156 CN1269852C (en) | 2003-10-29 | 2003-10-29 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310106156 CN1269852C (en) | 2003-10-29 | 2003-10-29 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1539855A CN1539855A (en) | 2004-10-27 |
| CN1269852C true CN1269852C (en) | 2006-08-16 |
Family
ID=34333995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310106156 Expired - Lifetime CN1269852C (en) | 2003-10-29 | 2003-10-29 | Loaded method of load type Non-metallocene catalyst-and polymerizing application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1269852C (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101075404B1 (en) | 2004-12-17 | 2011-10-24 | 양지 페트로케미컬 컴퍼니 코., 리미티드. | Supported non-metallocene olefin polymerization catalyst, preparation and use thereof |
| CN100362024C (en) * | 2004-12-17 | 2008-01-16 | 扬子石油化工股份有限公司 | Highly active supporting method of non-metallocene catalyst |
| CN1962702B (en) * | 2005-11-10 | 2010-10-27 | 中国石化扬子石油化工有限公司 | Carry type non-metallocene calalyst for polymerization of olefine, its preparation method and uses |
| EP2202246B1 (en) | 2007-10-16 | 2016-06-15 | Sinopec Yangzi Petrochemical Company Ltd. | Non-metallocene catalyst supported on magnesium compound and its preparation method |
| KR101207294B1 (en) | 2007-10-16 | 2012-12-03 | 시노펙 양지 페트로케미컬 컴퍼니 엘티디. | Supported non-metallocene catalyst and its preparation method |
| JP5670460B2 (en) | 2009-10-26 | 2015-02-18 | 中国石油化工股▲ふん▼有限公司 | Supported nonmetallocene catalyst, process for its production and use thereof |
| WO2011050566A1 (en) | 2009-10-26 | 2011-05-05 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst, preparation method and uses thereof |
| EP2500365B1 (en) | 2009-11-13 | 2020-05-06 | China Petroleum & Chemical Corporation | Supported non-metallocene catalyst and preparation method and uses thereof |
| US8957169B2 (en) | 2009-11-13 | 2015-02-17 | China Petroleum & Chemical Corp. | Supported nonmetallocene catalyst, preparation and use thereof |
| CN102399320B (en) * | 2010-09-16 | 2014-02-26 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst and preparation method and application thereof |
| CN102399321B (en) * | 2010-09-16 | 2014-03-19 | 中国石油化工股份有限公司 | Supported non-metallocene catalyst, and its preparation method and application |
| CN102399322B (en) * | 2010-09-16 | 2014-02-26 | 中国石油化工股份有限公司 | Load-type non-metallocene catalyst, preparation method thereof, and application thereof |
| CN102399319B (en) * | 2010-09-16 | 2014-03-12 | 中国石油化工股份有限公司 | Load-type non-metallocene catalyst, preparation method thereof, and application thereof |
| CN102030843B (en) * | 2010-11-04 | 2012-05-30 | 中国石油天然气股份有限公司 | Olefinic polymerization non-metallocene metal catalyst system and preparation and application thereof |
| CN104059177B (en) * | 2013-03-21 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of load single metallocene catalyst for vinyl polymerization |
| CN104059181B (en) * | 2013-03-21 | 2016-09-28 | 中国石油化工股份有限公司 | A kind of supported non-metallocene metallic catalyst for vinyl polymerization |
| CN115838448B (en) * | 2021-09-18 | 2024-01-09 | 中国科学技术大学 | Supported catalyst and preparation method and application thereof |
-
2003
- 2003-10-29 CN CN 200310106156 patent/CN1269852C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1539855A (en) | 2004-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1281634C (en) | Loaded method of Non-metallocene catalyst loaded by composite carrier and polymerizing application | |
| CN1269852C (en) | Loaded method of load type Non-metallocene catalyst-and polymerizing application | |
| CN1149231C (en) | Supported olefin polymerization catalyst composition | |
| CN1094129C (en) | 3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process | |
| CN1133661C (en) | Catalyst composition and methods for its preparation and use in polymerization process | |
| CN1112370C (en) | Polymerization catalyst systems, their production and use | |
| CN1301271C (en) | Dual-site olefin polymerisation catalyst composition | |
| CN1691979A (en) | Bimetallic catalysts with higher activity | |
| CN1871264A (en) | Production of olefin polymerisation catalysts | |
| CN1805977A (en) | Polymerization process using a metallocene catalyst system | |
| CN1249760A (en) | New activator system for metallocene compounds | |
| CN1096517A (en) | Load catalyst system, its preparation and the application in olefinic polymerization thereof | |
| CN85108910A (en) | Polymerizing catalyst and preparation thereof and use | |
| CN1127524C (en) | Supported catalyst component, supported catalyst, their preparation and addition polymerization process | |
| CN1678643A (en) | Supported polymerisation catalysts | |
| CN1659193A (en) | Polymerization catalyst activators, method of preparing and their use in polymerization processes | |
| CN1475511A (en) | Catalyst for polymerizing olefin and process for polymerizing olefin by catalyst | |
| CN100349930C (en) | Olefin polymerization catalyst and olefin polymerization method using the same | |
| CN101080424A (en) | Organochromium/metallocene combination catalyst for producing bimodal resins | |
| CN1261221C (en) | Method for preparing catalyst cupport and polymerization with supported catalysts | |
| CN1321111A (en) | Transition metal catalysts and processes for producing alpha-olefin and vinyl compound polymer | |
| CN1789292A (en) | Application of supported non-metallocene catalyst in ethene polymerization process by slurry method | |
| CN1205235C (en) | Functionalized catalyst supports and supported catalyst system | |
| CN1789290A (en) | Highly active supporting method of non-metallocene catalyst | |
| CN101062959A (en) | Method of making mixed ziegler-natta/metallocece catalysts |
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 | ||
| C56 | Change in the name or address of the patentee |
Owner name: SINOPEC YANGZI PETROCHEMICAL CO.; SHANGHAI ORGANIC Free format text: FORMER NAME OR ADDRESS: YANGZI PETROCHEMICAL CO., LTD.; SHANGHAI ORGANIC CHEMISTRY INSTITUTE, CHINESE ACADEMY OF SCIENCES |
|
| CP03 | Change of name, title or address |
Address after: Block 777, Xinhua Road, Dachang District, Jiangsu, Nanjing: 210048 Co-patentee after: SHANGHAI INSTITUTE OF ORGANIC CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee after: SINOPEC YANGZI PETROCHEMICAL Co.,Ltd. Address before: No. 777, Dachang Xinhua Road, Liuhe District, Jiangsu, Nanjing Province, China: 210048 Co-patentee before: Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences Patentee before: Yangzi Petrochemical Co.,Ltd. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060816 |