CN1281634C - Loaded method of Non-metallocene catalyst loaded by composite carrier and polymerizing application - Google Patents
Loaded method of Non-metallocene catalyst loaded by composite carrier and polymerizing application Download PDFInfo
- Publication number
- CN1281634C CN1281634C CN 200310106157 CN200310106157A CN1281634C CN 1281634 C CN1281634 C CN 1281634C CN 200310106157 CN200310106157 CN 200310106157 CN 200310106157 A CN200310106157 A CN 200310106157A CN 1281634 C CN1281634 C CN 1281634C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- load
- group
- metallocene
- 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 65
- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 230000000379 polymerizing effect Effects 0.000 title claims 2
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 150000001336 alkenes Chemical class 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000008569 process Effects 0.000 claims abstract description 31
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 24
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 18
- 239000000741 silica gel Substances 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 92
- -1 metal oxide compound Chemical class 0.000 claims description 57
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 41
- 229910052782 aluminium Inorganic materials 0.000 claims description 33
- 239000004411 aluminium Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 19
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 238000007725 thermal activation Methods 0.000 claims description 12
- 150000002681 magnesium compounds Chemical class 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
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- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
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- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 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 4
- 150000003624 transition metals Chemical group 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 230000002508 compound effect Effects 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
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- 239000011368 organic material Substances 0.000 claims description 3
- 238000009991 scouring Methods 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 65
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 18
- 238000007334 copolymerization reaction Methods 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 18
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 10
- 239000000178 monomer Substances 0.000 abstract description 9
- 239000002002 slurry Substances 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004711 α-olefin Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- FCAJYRVEBULFKS-UHFFFAOYSA-N 2-(oxolan-2-yl)ethanol Chemical compound OCCC1CCCO1 FCAJYRVEBULFKS-UHFFFAOYSA-N 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 74
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 239000000460 chlorine Substances 0.000 description 30
- 229960001866 silicon dioxide Drugs 0.000 description 20
- 239000010936 titanium Substances 0.000 description 15
- 229960002337 magnesium chloride Drugs 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 13
- 229940091250 magnesium supplement Drugs 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- 229920000573 polyethylene Polymers 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 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
- 125000004429 atom Chemical group 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 238000012993 chemical processing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
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- 230000009969 flowable effect Effects 0.000 description 3
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 3
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- 238000011068 loading method 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
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- 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
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 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
- 230000001476 alcoholic effect 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
- 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
- 230000015572 biosynthetic process Effects 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 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
- 230000001186 cumulative effect Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000002433 cyclopentenyl group Chemical class C1(=CCCC1)* 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
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000010520 ghee 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
- 239000012456 homogeneous solution Substances 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
- 230000000977 initiatory 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
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 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
- 238000001465 metallisation Methods 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
- 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
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage 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
- 238000012360 testing method Methods 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 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
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A carrying method of a non-metallocene catalyst carried by a composite carrier and a polymerization application relate to a preparation method of a non-metallocene olefin polymerization catalyst carried by a composite carrier, and an application of the catalyst in the polymerization process and the copolymerization process of olefin; especially, the catalyst is used for the homopolymerization of ethylene or the copolymerization of ethylene and other alpha-olefin. The method comprises: after being thermally activated, silica gel reacts with the tetrahydrofuran-ethanol solution of magnesium chloride to prepare the composite carrier; then, the composite carrier reacts with a chemical treating agent to prepare a modified composite catalyst; finally, the non-metallocene olefin polymerisation catalyst is carried by a solution method or an equivolume immersion method. The carried non-metallocene catalyst prepared by the carrying process is dry fluxible solid powder and can be used for the slurry or gas phase homopolymerization or copolymerization of C2 to C10 olefin or phenylethylene, especially ethylene, or organic monomers comprising functional groups. Copolymerization products with a high melting point and a good particle shape can be obtained under the condition of low aluminoxane consumption.
Description
Technical field
The present invention is the preparation method of the non-metallocene olefin polymerization catalyst of composite carrier load, 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 load technology of catalyzer and the technical field of olefinic polymerization.
Background technology
Known homogeneous transition-metal catalyst has very high catalytic activity in olefinic polymerization, as unsupported Ziegler-Natta catalyst, metallocene calalyst for polymerization of olefine, constrained geometry olefin polymerization catalysis or non-metallocene olefin polymerization catalyst.Wherein, Ziegler-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 CN1352654 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 CN1307065 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, CN1162601 adopts the difunctionality linking agent to continue to handle the carrier of process aikyiaiurnirsoxan beta or alkylaluminium cpd processing.Patent CN1174849 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.
The catalyzer that with the Magnesium Chloride Anhydrous is carrier demonstrates advantages of high catalytic activity in olefin polymerization process, but this type of catalyzer is highly brittle, and is broken easily in polymerization reactor, thereby causes polymer morphology bad.Silicon dioxide carried catalyzer has good flowability, can be used for gas fluidised bed polymerisation, but silicon dioxide carried metallocene and non cyclopentadienyl catalyst then show lower catalytic activity.Therefore, just may prepare and have high catalytic activity, the catalyzer of the controlled and good abrasion strength resistance of globule size if magnesium chloride and silicon-dioxide are well organically combined.
People such as K.Soga are at J.Polym.Sci., Polym.Chem.Ed.35, the polymerization that the cyclopentadiene titanous chloride is carried on the catalyzer that makes on the magnesium chloride support discussed in 291～311 articles of delivering, this catalyzer and triisobutyl aluminum cocatalyst are used and can prepare polypropylene, and have high polymerization activity.
EP 0878484 has reported the MgCl with low content of magnesium chloride (less than 3%)
2/ SiO
2The catalyzer of two carrier loaded zirconium metallocene-prepared can be used for the homopolymerization or the copolymerization of ethene, has catalytic activity preferably.
Patent CN 1364817 discloses magnesium chloride/silicon dioxide carried beta-diketon half metallocene-titanium metal Preparation of catalysts method and aggregated application, and its ethylene polymerization activity reaches 7.42 * 10
6Gram polyethylene/mole titanium hour, but in the patent less than concrete data about polymkeric substance granulating aspect of performance.
Summary of the invention
Technical problem: the load method that the objective of the invention is to provide on the basis of existing technology a kind of non-metallocene olefin polymerization catalyst.
Technical scheme: the load metallization processes of non-metallocene olefin polymerization catalyst on complex carrier that the present invention relates to a class novel texture, with and application in olefinic polymerization and copolymerization, the homopolymerization and ethene and other 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 of the non-metallocene catalyst of composite carrier load of the present invention may further comprise the steps:
1, will be under 100-1000 ℃, inert atmosphere or reduced pressure as the porosu solid of carrier, drying or roasting 1～24h carry out thermal activation;
2, magnesium compound is dissolved in tetrahydrofuran (THF)-pure mixed system and forms solution, the porosu solid with thermal activation joins in this solution again, and fully reaction forms transparent system under 0～60 ℃ of agitation condition; Washing after filtration, dry and drain after make complex carrier; Perhaps this clear solution adding non-polar organic solvent is made it precipitation and fully separate out, filtration washing, drying are drained and are made complex carrier then; Make complex carrier;
3, with arbitrarily can with one or more chemical reagent of complex carrier surface functional group effect, halogenide, alkylate or halogenated alkyl compounds, methylaluminoxane or titanium tetrachloride or both mixtures as aikyiaiurnirsoxan beta, IIIA, IVB or VB metal carry out chemically modified to complex carrier, obtain modifying complex carrier;
4, non-metallocene olefin polymerization catalyst is dissolved in the solvent, contacts 12～72 hours after scouring filtrations, dryings with complex carrier or modification complex carrier then and drains into load type non-metallocene catalyst.
Wherein step 3 is optional steps.
Porosu solid as carrier is: 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, silica gel.
Magnesium compound is magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium in the load method, or their mixture or magnesium chloride.In the process with the porosu solid of thermal activation and magnesium compound effect, described tetrahydrofuran (THF)-pure mixed solvent is tetrahydrofuran (THF)-Fatty Alcohol(C12-C14 and C12-C18), tetrahydrofuran (THF)-cyclic alcohol or tetrahydrofuran (THF)-aromatic alcohol, tetrahydrofuran-ethyl alcohol.Porosu solid is a silica gel, and magnesium compound is a magnesium halide, and magnesium halide and silica gel mass ratio are 1: 0.1～40, and the best is 1: 1～10.Non-metallocene olefin polymerization catalyst solution is dissolved in used solvent is mineral oil or different liquid hydrocarbons in the solvent, 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, or tetrahydrofuran (THF), 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.
The olefin polymetiation process of the non-metallocene catalyst of composite carrier load of the present invention is a Primary Catalysts with the non-metallocene catalyst of composite carrier load, with one of aikyiaiurnirsoxan beta, aluminum alkyls, Lewis acid or boron fluorine cpd is promotor, makes polymerizable organic monomer carry out slurry polymerization, vapour phase polymerization, letex polymerization, solution polymerization or copolymerization under the condition that is enough to react.Polymerizable organic monomer is the alkene of C2～C10, especially ethene, or contains 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.
Beneficial effect: adopt load method disclosed by the invention, can obtain very high non-metallocene olefin polymerization catalyst content, its mass ratio can reach 1/3rd of whole loaded catalyst, still can obtain the good olefin polymer of particle shape.
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 very high fusing point.
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 good particle shape.
Description of drawings
Fig. 1 is sample of the present invention (embodiment 1) size-grade distribution (average 409.7 μ m).
Fig. 2 is another kind of sample (embodiment 4) size-grade distribution (average 689.8 μ m) of the present invention.
Fig. 3 is sample of the present invention (embodiment 1) fusing point test figure as a result.
Embodiment
The load method of the non-metallocene catalyst of composite carrier load of the present invention may further comprise the steps:
1, be the porosu solid of carrier under 100-1000 ℃, inert atmosphere or reduced pressure, drying or roasting 1～24h carry out thermal activation;
2, magnesium compound is dissolved in tetrahydrofuran (THF)-pure mixed system and forms solution, and the porosu solid with thermal activation joins in this solution again, and fully reaction forms transparent system under 0～60 ℃ of agitation condition; Washing after filtration, dry and drain after make complex carrier; Perhaps this clear solution adding non-polar organic solvent is made it precipitation and fully separate out, filtration washing, drying are drained and are made complex carrier then;
3, adopt arbitrarily can with one or more chemical reagent of complex carrier surface functional group effect, halogenide, alkylate or halogenated alkyl compounds, methylaluminoxane or titanium tetrachloride or both mixtures as aikyiaiurnirsoxan beta, IIIA, IVB or VB metal carry out chemically modified to complex carrier, obtain modifying complex carrier;
4, metallocene calalyst for polymerization of olefine is dissolved in the solvent, contacts 12～72 hours after scouring filtrations, dryings with complex carrier or modification complex carrier then and drains into load type non-metallocene catalyst.
Wherein step (3) is an optional step.
Resulting thus complex carrier, modification complex carrier and load type non-metallocene catalyst replicating vector form all are pressed powders that do, flowable.
The used porosu solid of the present invention can be arbitrarily, the surface has the porosu solid of functional group.It can be:
A, the organic materials that contains 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;
B, IIA, 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, most preferably silica gel.
C, the oxidation material for preparing by the pyrohydrolysis process by gaseous metal oxide compound or silicon compound.
D, 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 is preferably from 10～1000m
2/ g is more preferably from 100～600m
2/ g.Preferred 0.1～the 4cm of pore volume (determination of nitrogen adsorption)
3Between/the g, more preferably at 0.2～2cm
3/ g.The median size of carrier (laser particle analyzer mensuration) is preferably from 1～500 μ m, more preferably from 1～100 μ m.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 Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245, ES70, ES70X, ES757, Aerosil812, or CS-2133 and MS-3040.
Metal oxide surface generally all is the tart surface hydroxyl is arranged, can to make 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.
Involved in the present invention to solvent can be mineral oil and different liquid hydrocarbons.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, acetate second clarified butter 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 tetrahydrofuran (THF), toluene or hexane.
Porosu solid through thermal activation needs further to make complex carrier with the magnesium compound effect.Magnesium compound comprises magnesium halide, as MgCl
2, MgBr
2, MgI
2The alkoxyl group magnesium halide, as Mg (OMe) Cl, Mg (OEt) Cl, Mg (OPr) Cl, Mg (OBu) Cl; Alkoxyl magnesium is as Mg (OEt)
2, Mg (OiPr)
2, Mg (OBu)
2, and their mixture.Preferred magnesium halide, most preferably magnesium chloride.The magnesium chloride water content should be less than 1% of quality, and median size is 1～100 μ m, preferred 20～40 μ m; Specific surface area is 5～100m
2/ g, preferred 5～30m
2/ g.
Magnesium Chloride Anhydrous joined in tetrahydrofuran (THF)-pure mixed solvent to stir form solution, improve whipping temp and help to shorten dissolution process, temperature range is from 0～60 ℃, preferred 40～50 ℃.Here the alcohol in said tetrahydrofuran (THF)-pure mixed solvent can be Fatty Alcohol(C12-C14 and C12-C18), as methyl alcohol, ethanol, Virahol, butanols, hexanol, 2-methyl amyl alcohol, the basic butanols of 2-, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol etc., cycloalkanol, as hexalin, methyl-cyclohexanol; Aromatic alcohol, as Bian alcohol, methyl Bian alcohol, sec.-propyl Bian alcohol etc., preferred fat alcohol, most preferred ethanol.
Silica gel is joined in this solution, fully reaction forms transparent system under 0～60 ℃ of agitation condition again.Time is 1～48 hour, preferred 4～24 hours.Magnesium chloride and silica gel mass ratio are 1: 0.1～40, preferred 1: 1～10.Tetrahydrofuran (THF) described here-pure mixed solvent can be tetrahydrofuran (THF)-Fatty Alcohol(C12-C14 and C12-C18) or tetrahydrofuran (THF)-aromatic alcohol, preferred tetrahydrofuran-ethyl alcohol.Magnesium halide and silica gel mass ratio are 1: 0.1～40, preferred 1: 1～10.The mass ratio of magnesium chloride and tetrahydrofuran (THF) is 1: 5～25, preferred 1: 10～20.Magnesium chloride and alcoholic acid mass ratio are 1: 1～5, preferred 1: 1～3.If the consumption of alcohol solvent is very little, then magnesium chloride be difficult for to form homogeneous solution, and if the alcohol solvent consumption is too many, then economic aspect is unfavorable, and the catalyst performance that makes is also undesirable.Above-mentioned transparent system is filtered, adopt the toluene solvant washing repeatedly, drain then and obtain complex carrier, perhaps in system, add non-polar organic solvent,, place precipitation and fully separate out as hexane, filter, adopt the hexane solvent washing repeatedly, final drying obtains complex carrier with draining.
Complex carrier can directly contact with non-metallocene olefin polymerization catalyst solution, thereby load obtains carry type non-metallocene calalyst for polymerization of olefine.But originally discover if obtain active more excellent carry type non-metallocene calalyst for polymerization of olefine, further handle making that to modify complex carrier be very crucial.Compare with the extra activity that loaded catalyst is obtained, the cost of this treatment step is inappreciable.
This process is that complex carrier is contacted with chemical processing agent, adopts solution dipping method, 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 methylaluminoxane or titanium tetrachloride or binary chemical processing agent that both formed.
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: transition metal atoms, 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, Cl-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, and employing solution dipping method or equi-volume impregnating are with complex carrier or modify compound contacting, and make the non-metallocene olefin polymerization catalyst of composite carrier load.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 incipient impregnation process is that non-metallocene catalyst is dissolved in the solvent with the saturated absorption corresponding amount of carrier, drains behind confined reaction 12～72h.Equi-volume impregnating need have the solvent of high solubleness to non-metallocene olefin polymerization catalyst, in the present invention, and preferred tetrahydrofuran solvent.
The chemical treating process of above-described carrier and the loading process of non-metallocene olefin polymerization catalyst 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.
Washing and filtering, drying are drained the key that process also is acquisition high reactivity and good particle shape polymkeric substance fully.The washing and filtering process is removed the material of free state, and drying is drained the good combination power that can obtain reactive material.
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 has more than one hydrogen to be 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.
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 polymer particle size measure of spread is carried out on Beckman Coulter LS230 type laser particle analyzer.
1.1 the preparation of loaded catalyst
1.1.1 the activation of carrier
Get ES70 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 ES70-650 carrier.
1.1.2 the preparation of Magnesium Chloride Anhydrous
Calcining 3h under 500 ℃, air atmosphere makes Magnesium Chloride Anhydrous with the analytical pure magnesium chloride.
1.1.3 the preparation of complex carrier
Under the nitrogen atmosphere of anhydrous and oxygen-free (content of water and oxygen all is lower than 5ppm), take by weighing 1.064 gram Magnesium Chloride Anhydrouss, add 30ml tetrahydrofuran (THF) (THF), 30 ℃ are stirred 16h down, drip 2.5ml dehydrated alcohol (the 4A molecular sieve soaks more than 4 days) then, adding 530mg ES70-650 carrier, 25 ℃ are stirred the 4h after-filtration, with 4 * 30ml toluene wash, filtration, final drying and draining.
1.1.4 modify the preparation of complex carrier
Take by weighing the 510mg complex carrier, add 20mg toluene and form suspension, drip 1ml methylaluminoxane (MAO successively, concentration is 1.5wt%, and Witco company product abbreviates rare MAO as) and the hexane solution of 2.5ml titanium tetrachloride (volume ratio is 5%, titanium content is 0.41mol/L), after stirring 2h, with 4 * 30ml toluene wash, filtration, final drying with drain.
1.1.5 the load of catalyzer
Take by weighing the non-metallocene olefin polymerization catalyst of 50mg structural formula shown in (6), join in the 20ml toluene,, and then join among the modification complex carrier, stir 16h 25 ℃ of following stirring and dissolving.
And then with 4 * 30ml toluene wash, filtration, drying with drain, obtain doing, can flow, the loaded catalyst of orange.
1.2 polymerization
(concentration is 15wt% to add the toluene solution of 13.5mg loaded catalyst, 3ml MAO in the 0.5L autoclave of crossing with the exsiccant nitrogen purging simultaneously, abbreviate dense MAO as) and the 250ml hexane solvent, at ethylene pressure is that 3.0MPa, mixing speed are to carry out vinyl polymerization under 50 ℃ of 600rpm and the constant temperature, and the reaction times is 1h.Take out polymkeric substance, dry removing desolvated.
Output: 32.7g, 142.80 ℃ of polyethylene fusing points.
2.1 Preparation of catalysts
Preparation of catalysts process similar embodiment 1.1 is got complex carrier 507mg among the 1.1.3, only slow Dropwise 5 ml TiCl
4Hexane solution.Carry out solution impregnation in the 25ml of 70mg non-metallocene olefin polymerization catalyst toluene solution, wash at last, filter, dry and drain.
2.2 polymerization
In the 0.5L autoclave, add 12mg loaded catalyst, the dense MAO of 3ml simultaneously, and the 250ml hexane solvent, be that 3.0MPa carries out vinyl polymerization at ethylene pressure.Mixing speed 540rpm, temperature of reaction is 60 ℃, the continuation reaction times is 1.5h.
Output: 61.52g.
(removing) adds 35.3mg loaded catalyst, the dense MAO of 3ml and 580ml hexane solvent simultaneously in the 2L autoclave, be that 2.0MPa carries out vinyl polymerization at ethylene pressure.Mixing speed 300rpm, temperature of reaction is 50 ℃, the reaction times is 1h.
Output: 45.6g.
2.3 copolymerization
Add 24.3mg loaded catalyst, the dense MAO of 3ml and 550ml hexane solvent in the 2L autoclave simultaneously, the unlatching mixing speed is 300rpm.Under 60 ℃, ethene and butylene are mixed according to mass ratio at 20: 1, in autoclave, provide interpolymer then, keep pressure 1.3MPa in the autoclave.Temperature of reaction is 50 ℃, and the reaction times is 1h.
Output 27.5g, 139.02 ℃ of polyethylene fusing points.
Embodiment 3
Get ES-70 type silica gel at 300 ℃ of following constant temperature 6h, be designated as the E870-300 carrier.
Preparation of catalysts similar embodiment 1.1.Wherein only be to change 530mg ES70-650 into the 1.0gES70-300 carrier, make complex carrier.Get wherein 0.5g then, use 10mlTiCl
4Hexane solution handle.Take by weighing the 48mg catalyzer at last and add the dissolving of 30ml toluene, adopt the solution dipping method supported catalyst.
Polymerization process similar embodiment 1.2 is carried out.13.6mg loaded catalyst, the dense MAO of 3ml and 250ml hexane solvent are that 2.0MPa, mixing speed are to carry out vinyl polymerization under 510rpm and 50 ℃ at ethylene pressure.Reaction times is 1h.
Output: 25.18g, 142.33 ℃ of polyethylene fusing points.
Embodiment 4
Preparation of catalysts similar embodiment 1.1.Wherein only be to change 530mg E870-650 into the 1.0gES70-650 carrier, make complex carrier.Get 0.5g then, only handle with the rare MAO of 8ml.Get at last and modify complex carrier 520mg, the 2mlTHF solution of incipient impregnation 111mg catalyzer.
Polymerization similar embodiment 1.2 is carried out.In the 0.5L autoclave, add 25.9mg loaded catalyst, the dense MAO of 4ml and 250ml hexane solvent simultaneously.
Output: 28.46g.
Modify complex carrier with embodiment 4.Get at last and modify complex carrier 492mg, the 1.5mlTHF solution of incipient impregnation 153mg catalyzer.
Polymeric type is like (changing into: 1) carry out.In the 0.5L autoclave, add 13mg loaded catalyst, the dense MAO of 4ml and 250ml hexane solvent simultaneously.
Output: 14.51g.
Modify complex carrier with embodiment 4.Get at last and modify complex carrier 500mg, incipient impregnation 97.5mg catalyzer and 0.8mlTiCl
4THF solution (TiCl
4Volume content is 2%).
Polymerization similar embodiment 1 is carried out.Add 17mg loaded catalyst, the dense MAO of 4ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, the reaction times is 0.5h.
Output: 31.75g, 141.33 ℃ of polyethylene fusing points.
Take by weighing the 1g Magnesium Chloride Anhydrous, add 25mlTHF and 2.5ml dehydrated alcohol, after the dissolving, add 2g ES70-650 carrier again, add the 50ml hexane behind the 5h and make it to separate out, with 4 * 30ml hexane wash, filtration, final drying with drain.Take by weighing the 0.5g complex carrier, add 20ml toluene and 5mlTiCl
4Hexane solution (volume ratio is 5%, and titanium content is 0.41mol/L), stir 12h after-filtration washing drying and drain to such an extent that modify complex carrier, drain behind the 0.8mlTHF incipient impregnation 16h with the 100mg catalyzer.
Polymerization similar embodiment 1.2 is carried out.Add 8.6mg loaded catalyst, the dense MAO of 3ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, the reaction times is 1h.
Output: 35.28g, 141.47 ℃ of polyethylene fusing points.
Embodiment 8
Take by weighing the modification complex carrier 2g among the embodiment 7, continue to handle with the rare MAO of 8ml.Get this and modify complex carrier 500mg, with draining behind 97mg catalyzer and the 0.8mlTHF incipient impregnation 16h.
Polymerization similar embodiment 1 is carried out.Add 8mg loaded catalyst, the dense MAO of 3ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, the reaction times is 40min.
Output: 12g.
Embodiment 9
Take by weighing the 1g Magnesium Chloride Anhydrous, add 25mlTHF and 2.5ml dehydrated alcohol, after the dissolving, add 2g ES70-650 carrier again, add TiCl behind the 5h
4Hexane solution (volume ratio 1%) make it to separate out, with 4 * 30ml hexane wash, filtration, final drying and draining.Take by weighing the 0.5g complex carrier, drain behind the 0.8mlTHF incipient impregnation 16h with the 125mg catalyzer.
Polymerization similar embodiment 1 is carried out.Add 11.5mg loaded catalyst, the dense MAO of 3ml and 250ml hexane solvent in the 0.5L autoclave simultaneously, the reaction times is 1.5h.
Output: 26g
Claims (8)
1. the load method of the non-metallocene catalyst of a composite carrier load is characterized in that this method may further comprise the steps:
(1) will be under 100～1000 ℃, inert atmosphere or reduced pressure as the porosu solid of carrier, drying or roasting 1～24h carry out thermal activation;
(2) magnesium compound is dissolved in tetrahydrofuran (THF)-pure mixed system and forms solution, the porosu solid with thermal activation joins in this solution again, and fully reaction forms transparent system under 0～60 ℃ of agitation condition; Washing after filtration, dry and drain after make complex carrier; Perhaps this clear solution adding non-polar organic solvent is made it precipitation and fully separate out, filtration washing, drying are drained and are made complex carrier then;
(3) non-metallocene olefin polymerization catalyst is dissolved in the polar solvent, contacts 12～72 hours after scouring filtrations, dryings with complex carrier or modification complex carrier then and drain, become load type non-metallocene catalyst.
2. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that as the porosu solid of carrier being: 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.
3. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that magnesium compound is magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium in the load method, or their mixture.
4. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that described tetrahydrofuran (THF)-pure mixed solvent is tetrahydrofuran (THF)-Fatty Alcohol(C12-C14 and C12-C18), tetrahydrofuran (THF)-cyclic alcohol or tetrahydrofuran (THF)-aromatic alcohol, tetrahydrofuran (THF)-ethanol in the process with the porosu solid of thermal activation and magnesium compound effect.
5. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that porosu solid is a silica gel, magnesium compound is a magnesium halide, and magnesium halide and silica gel mass ratio are 1: 0.1～40.
6. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that modifying complex carrier and be adopt arbitrarily can with one or more chemical reagent of complex carrier surface functional group effect.
7. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that non-metallocene olefin polymerization catalyst is dissolved in the solvent, used solvent is to dissolve the mineral oil of this non-metallocene catalyst or different liquid hydrocarbons.
8. according to the load method of the non-metallocene catalyst of the described composite carrier load of claim 1, it is characterized in that described Nonmetallocene polymerizing catalyst, it is characterized in that this catalyzer has the title complex of 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:
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