CN117964804A - Carrier suspension for polyolefin catalyst component and preparation method and application thereof - Google Patents
Carrier suspension for polyolefin catalyst component and preparation method and application thereof Download PDFInfo
- Publication number
- CN117964804A CN117964804A CN202211305808.1A CN202211305808A CN117964804A CN 117964804 A CN117964804 A CN 117964804A CN 202211305808 A CN202211305808 A CN 202211305808A CN 117964804 A CN117964804 A CN 117964804A
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- Prior art keywords
- alcohol
- magnesium
- titanium
- compound
- alcohols
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000000725 suspension Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 23
- -1 magnesium alkoxide Chemical class 0.000 claims abstract description 91
- 239000011777 magnesium Substances 0.000 claims abstract description 66
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000002245 particle Substances 0.000 claims abstract description 58
- 150000001336 alkenes Chemical class 0.000 claims abstract description 34
- 239000010936 titanium Substances 0.000 claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000004820 halides Chemical class 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 230000002140 halogenating effect Effects 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- 150000002367 halogens Chemical class 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 103
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 44
- 150000001298 alcohols Chemical class 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- CNNRPFQICPFDPO-UHFFFAOYSA-N octacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCO CNNRPFQICPFDPO-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- JNBVLGDICHLLTN-DZUOILHNSA-N (2s)-2-acetamido-n-[(2s,3s)-4-[[[(2s)-2-acetamido-3-methylbutanoyl]amino]-(cyclohexylmethyl)amino]-3-hydroxy-1-phenylbutan-2-yl]-3-methylbutanamide Chemical compound C([C@H](NC(=O)[C@@H](NC(C)=O)C(C)C)[C@@H](O)CN(CC1CCCCC1)NC(=O)[C@@H](NC(C)=O)C(C)C)C1=CC=CC=C1 JNBVLGDICHLLTN-DZUOILHNSA-N 0.000 claims description 8
- 229960002666 1-octacosanol Drugs 0.000 claims description 8
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229960000735 docosanol Drugs 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 239000011630 iodine Substances 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 claims description 6
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 4
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001188 haloalkyl group Chemical group 0.000 claims description 4
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 4
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 4
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- DUAYDERMVQWIJD-UHFFFAOYSA-N 2-n,2-n,6-trimethyl-1,3,5-triazine-2,4-diamine Chemical compound CN(C)C1=NC(C)=NC(N)=N1 DUAYDERMVQWIJD-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 2
- FEXQDZTYJVXMOS-UHFFFAOYSA-N Isopropyl benzoate Chemical compound CC(C)OC(=O)C1=CC=CC=C1 FEXQDZTYJVXMOS-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- KYZHGEFMXZOSJN-UHFFFAOYSA-N benzoic acid isobutyl ester Natural products CC(C)COC(=O)C1=CC=CC=C1 KYZHGEFMXZOSJN-UHFFFAOYSA-N 0.000 claims description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001622 calcium bromide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 claims description 2
- 229910001640 calcium iodide Inorganic materials 0.000 claims description 2
- 229940046413 calcium iodide Drugs 0.000 claims description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 claims description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 claims description 2
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 claims description 2
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 claims description 2
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 claims description 2
- 239000002685 polymerization catalyst Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 14
- 239000011949 solid catalyst Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- NGDNVOAEIVQRFH-UHFFFAOYSA-N 2-nonanol Chemical compound CCCCCCCC(C)O NGDNVOAEIVQRFH-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-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
- BKQICAFAUMRYLZ-UHFFFAOYSA-N 4-methylheptan-3-ol Chemical compound CCCC(C)C(O)CC BKQICAFAUMRYLZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- KJWLAZDNFRTNJS-UHFFFAOYSA-N heptadecan-7-ol Chemical compound CCCCCCCCCCC(O)CCCCCC KJWLAZDNFRTNJS-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical class CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007962 solid dispersion Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 229940087291 tridecyl alcohol Drugs 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- ACUZDYFTRHEKOS-SNVBAGLBSA-N 2-Decanol Natural products CCCCCCCC[C@@H](C)O ACUZDYFTRHEKOS-SNVBAGLBSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ACUZDYFTRHEKOS-UHFFFAOYSA-N decan-2-ol Chemical compound CCCCCCCCC(C)O ACUZDYFTRHEKOS-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a carrier suspension for polyolefin catalyst components, a preparation method thereof, a Ziegler-Natta catalyst component, an olefin polymerization catalyst and an olefin polymerization method; wherein the carrier suspension comprises a titanium-containing magnesium alkoxide suspension obtained by dispersing magnesium alkoxide particles in an inert organic solvent and adding a first titanium-containing halide and an alcohol compound. The invention selects a small amount of halogen-containing mixture as halogenating agent, and when titanium halide and/or inert organic solvent are added in the reaction process, the reaction is easier to control, and the particle morphology is better maintained. The olefin polymerization catalyst adopts the treated alkoxy magnesium particles, and the obtained catalyst has large particle diameter, large pore volume, high activity during polymerization, good particle morphology, uniform distribution and good polymer flowability. The catalyst is suitable for a multi-kettle reaction process with prepolymerization in industrial application, has a long catalyst residence period, can copolymerize more ethylene to generate more rubber under the condition of the same melt index requirement, and keeps good fluidity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a carrier suspension for polyolefin catalyst components, a preparation method of the carrier suspension, a Ziegler-Natta catalyst component, an olefin polymerization catalyst and an olefin polymerization method.
Background
As the demand for polyolefin increases, so does the demand for olefin polymerization catalysts, the most widely used catalysts at present being magnesium chloride supported ziegler-natta catalysts. The preparation methods of the catalysts disclosed in Chinese patent CN85100997A and CN 1453298A generally comprise solid catalyst components composed of magnesium, titanium, halogen and electron-donating organic compounds. However, satisfying various properties such as proper particle size and shape, uniform particle distribution, minimization of fine particles, high bulk density, etc., and high catalyst activity and stereoregularity are not a catalyst capable of satisfying various demands. There have also been many studies on the preparation of olefin polymerization catalyst components using dialkoxymagnesium as a carrier. Patent EP0459009 discloses a catalyst component for the polymerization of olefins, which is prepared by forming a suspension of magnesium diethoxide in alkylbenzene, contacting this suspension with titanium tetrachloride and phthaloyl dichloride at a temperature between 80 and 125 ℃ and washing with alkylbenzene, and finally obtaining a titanium-containing catalyst component, from which the catalyst is obtained, although the activity is not sufficiently high during polymerization.
Patent EP0811639 discloses mainly a solid catalyst component for the polymerization of olefins, which is prepared by the reaction of a titanium halide, an aryl dicarboxylic acid ester and a magnesium alkoxide. By controlling the bulk density, average particle size and other indicators of the alkoxy magnesium and controlling the rate of rise from the temperature at which the titanium halide starts to contact with the alkoxy magnesium to the temperature at which the reaction takes place (the rate of rise is controlled to be between 0.5 and 20/min), a solid catalyst component is obtained, whereby a polyolefin having a high isotactic and high bulk density can be obtained, but the content of fine powder is too high, the activity is insufficient, the particles are too small, and the tackiness is liable to occur when producing a copolymer having a high rubber content.
At present, the supported catalyst taking the alkoxy magnesium as the carrier can have more excellent performance, is commonly used for developing high-end polypropylene products, and firstly needs to prepare the alkoxy magnesium carrier with excellent performance.
The preparation method of the circular particle alkoxy magnesium mainly comprises the following steps: 1) Firstly, preparing dialkoxy magnesium through alcohol and magnesium metal reaction, and then, adjusting the particle size through mechanical crushing; 2) In the reaction of magnesium metal and ethanol, the final adding proportion of magnesium/ethanol is controlled to be in the range of 9/1-1/15, and when ethanol and magnesium reflux, a manufacturing method of intermittently or continuously generating reaction is adopted (Japanese patent laid-open No. 3-74341); 3) A method for producing round fine particles by spray-drying an alcoholic solution of carboxylated magnesium carboxylate and continuing decarboxylation (Japanese patent application laid-open No. 6-87773); 4) A method for producing a catalyst wherein magnesium metal and ethanol react in the presence of saturated hydrocarbon (Japanese patent publication No. 63-4815); 5) A method for producing a round article represented by the chemical formula Mg (OR) 2 - & (OR ') was obtained by dispersing Mg (OR) 2 in R ' OH, then spray-drying the dispersed solid particles in ROH, and then distilling the suspension to remove R ' OH (Japanese patent application laid-open No. 62-51633).
In method 1), the shape of the particles is destroyed by comminution, and if particles with a complete surface morphology and particle size distribution are to be obtained, the yield has to be reduced. In method 2), although the final magnesium/ethanol addition ratio is defined to be 9/1 to 1/15, if the addition ratio is always fixed to 9/1 according to the results of the study and the test by the researchers, a sharp viscosity rise occurs in the latter half of the reaction, and if the reaction rate exceeds 80%, particles are aggregated without sufficient stirring, and uniform round particles cannot be obtained; if stirring is forced, the shape of the particles is destroyed (patent Hei 6-239521). On the other hand, if the initial addition ratio is set to 1/15, the reaction proceeds under the condition that the amount of ethanol is relatively large, and when the viscosity rises in the final stage of the reaction, stirring proceeds smoothly, but the obtained particles have a shape that is not round enough and a low volume density, and particles satisfying the condition cannot be obtained. Among the methods 3) to 5), mg and ROH require other raw materials and are complicated to handle, and therefore, they are not preferable as a method for producing desired fine particles. In addition, the shape, the diameter of the particles, and the like are not ideal manufacturing methods.
Thus, there is a need for preparing a support for polyolefin catalyst components having good particle morphology and capable of exhibiting excellent performance in olefin polymerization catalysts.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention proposes a carrier suspension for polyolefin catalyst component and a preparation method thereof, a Ziegler-Natta catalyst component and an olefin polymerization catalyst, an olefin polymerization method.
In a first aspect, the present invention provides a carrier suspension for a polyolefin catalyst component, the carrier suspension comprising a titanium-containing magnesium alkoxide suspension obtained by dispersing magnesium alkoxide particles in an inert organic solvent and adding a first titanium-containing halide and an alcohol compound; the magnesium alkoxide particles comprise the reaction product of: magnesium powder, mixed alcohol a, mixed alcohol b and halogenating agent;
as a specific embodiment of the invention, the preparation method of the alkoxy magnesium particles comprises the step of mixing magnesium powder, mixed alcohol a, mixed alcohol b and a halogenating agent to react under an inert atmosphere.
As a specific embodiment of the present invention, the inert atmosphere includes argon, nitrogen, helium, preferably nitrogen.
As a specific embodiment of the invention, preferably, the preparation method comprises the steps of firstly reacting metal magnesium, mixed alcohol a and halogenating agent, and then adding a certain amount of metal magnesium, mixed alcohol b and halogenating agent for reaction until the reaction progress exceeds 80%, thus obtaining the alkoxy magnesium carrier.
As a specific embodiment of the present invention, the reaction conditions include: the reaction temperature is 0-30 ℃, the reaction pressure is 0-0.3MPa, and the reaction time is 2-30h. Specifically, the reaction temperature of the invention can be carried out at the reflux temperature of 0-reaction system, the reflux temperature can be changed by small change of the reaction pressure, the higher the reaction temperature is selected, the faster the reaction is carried out, and the preferable pressure is 0-0.3 MPa. The reaction temperature may also be varied during the reaction, and the particle size and morphology may be varied by selecting the reaction temperature. The preferred reaction temperature of the present invention is from 30℃to the reflux temperature of the reaction system. The extent of progress of the reaction is judged by observing the amount of hydrogen gas discharged from the reaction, and the reaction time is usually 2 to 30 hours.
In the mixing method according to the present invention, the magnesium powder, the mixed alcohol a, the mixed alcohol b and the halogenating agent are added, and the reactants may be initially introduced at one time or may be selectively introduced in several times. The addition of the raw materials in several portions is preferable from the viewpoint of safety because it prevents the instantaneous generation of a large amount of hydrogen gas and prevents the entrainment of alcohol or halogen due to the instantaneous generation of a large amount of hydrogen gas. The number of divisions can be determined according to the size of the reaction tank and the amount of various materials. The order of addition of the reactive species may be determined as desired. Specifically, the method of adding the halogenating agent is not particularly limited, and the halogenating agent may be added by dissolving in ethanol, or may be added directly to magnesium powder and alcohol in solid or liquid form, or may be prepared by dropping an alcoholic solution of the halogenating agent during heating of the magnesium powder and alcoholic solution.
As a specific embodiment of the present invention, after the reaction, the product may be washed with an alcohol and/or a mixture of alcohols from which the magnesium alkoxide is prepared; washing with an inert organic solvent is also possible; the method and the number of times of the washing treatment are not particularly limited, and may be selected according to the circumstances.
As a specific embodiment of the invention, the average particle size of the magnesium powder is less than 360 mu m, preferably 300-100 mu m; specifically, the magnesium powder used may be any shape, for example, granular, ribbon-like or powder-like magnesium powder, in the case of good reactivity; in order to ensure that the average particle size of the produced magnesium alkoxide is maintained at 10 to 80. Mu.m, and that the morphology of the particles is excellent, it is desirable that the average particle size of the magnesium powder is preferably spherical particles of 360 μm or less, more preferably 300 to 100. Mu.m, so that relatively uniform reactivity can be maintained. The surface of the magnesium powder is not particularly limited, but the formation of a coating such as a hydroxide on the surface of the magnesium powder slows down the reaction, so that a magnesium powder having no coating such as a hydroxide on the surface is preferable.
As a specific embodiment of the present invention, the mixed alcohol a is a mixture of ethanol and an alcohol compound having more than 20 carbon atoms; the mixed alcohol b is an alcohol compound with carbon number not more than 10;
As a specific embodiment of the present invention, the alcohol compound having more than 20 carbon atoms is a linear or branched monohydric alcohol or a mixture of polyols, comprising: isomers of 1-di-undecanol and alcohols thereof, isomers of 1-docosanol and alcohols thereof, isomers of 1-di-tridecyl alcohol and alcohols thereof, isomers of 1-di-tetradecanol and alcohols thereof, isomers of 1-di-pentadecyl alcohol and alcohols thereof, isomers of 1-hexadecyl alcohol and alcohols thereof, isomers of 1-di-heptadecyl alcohol and alcohols thereof isomers of 1-octacosanol and alcohols thereof, isomers of 1-triacontanol and alcohols thereof, isomers of 4-methyl-3-ditridecanol and alcohols thereof, isomers of 4-methyl-3, 5-octacosanol and alcohols thereof, isomers of 6-methyl-3, 5, 7-heptadecanol and alcohols thereof.
As a specific embodiment of the invention, the mixed alcohol a is a mixture of ethanol and an alcohol compound with the carbon number of more than 20, preferably a mixture of ethanol and 1-behenyl alcohol and/or 1-octacosanol, wherein the ethanol accounts for 80-99.8wt% and the 1-behenyl alcohol and/or 1-octacosanol accounts for 0.1-15wt%.
As a specific embodiment of the present invention, in order to obtain good performance of the alkoxy magnesium, the lower the moisture content is required, the better; preferably, the water content of the mixed alcohol a is < 1000ppm, more preferably the water content is < 200ppm.
As a specific embodiment of the present invention, the mixed alcohol b is a linear or branched monohydric or polyhydric alcohol or a mixture of polyols, preferably selected from: methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 2-ethylbutanol, 2-ethylhexanol, 4-methyl-2-pentanol, 3, 5-trimethylpentanol, 4-methyl-3-heptanol, benzyl alcohol, 2-phenylethanol, 1-phenyl-1-propanol, ethylene glycol, glycerol, phenol;
Preferably, the mixed alcohol b is a mixture of ethanol and isooctyl alcohol and/or isopropyl alcohol and/or isobutyl alcohol, wherein the ethanol accounts for 80-99.8wt% and the isooctyl alcohol and/or isopropyl alcohol and/or isobutyl alcohol accounts for 0.2-20wt%;
As a specific embodiment of the present invention, in order to obtain good performance of the alkoxy magnesium, the lower the moisture content is required, the better; preferably, the water content of the mixed alcohol b is < 1000ppm, more preferably the water content is < 200ppm.
As a specific embodiment of the invention, the molar ratio of the mixed alcohol a to the magnesium powder is (2-50): 1, preferably (2.5-18): 1.
As a specific embodiment of the invention, the molar ratio of the mixed alcohol b to the magnesium powder is (2-50): 1, preferably (2.5-18): 1.
As a specific embodiment of the present invention, the halogenating agent is elemental halogen and/or an inorganic halide; preferably at least one selected from iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide and alkoxymagnesium halides; more preferably at least one selected from the group consisting of iodine, magnesium iodide, magnesium chloride and alkoxymagnesium halides, particularly preferably a mixture of iodine and magnesium chloride in which the molar ratio of iodine atoms to chlorine atoms is (0.01 to 99): 1, preferably (0.05 to 50): 1.
The molar ratio of the halogenating agent to magnesium powder is (0.0002-0.2): 1, preferably (0.0025-0.05): 1, based on halogen atoms. The inventors have found that the amount of halogen atoms added affects the particle morphology and particle size of the final magnesium alkoxide. When the amount of the halogen atom used is too small, the particle morphology of the obtained magnesium alkoxide is extremely poor; if the halogen atom is used in an excessive amount, not only the cost of preparing the alkoxy magnesium increases, but also the particle size of the alkoxy magnesium becomes very uneven, and the reaction is difficult to control.
As a specific embodiment of the present invention, the first titanium halide has a structure as shown in formula (I):
(R 1O)aTi(OR2)b(OR3)cXd formula (I)
In formula (I), R 1、R2 and R 3 are each independently selected from H and alkyl, especially C1-C10 alkyl, X is selected from chloro, bromo, iodo, a, b, C are each independently integers from 0 to 3, d is an integer from 1 to 4, and a+b+c+d=4;
preferably, the halide of the first titanium is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium chlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy, titanium monochlorotributoxy, titanium dichlorodibutoxy, titanium trichloromonobutoxy, their isomers;
as a specific embodiment of the present invention, the weight ratio of the halide of the first titanium to the alkoxymagnesium granule is (0.001-5): 1, preferably (0.002-2): 1.
As a specific embodiment of the invention, the chemical structure of the alcohol compound is shown as a formula (II):
R (OH) x formula (II)
In the formula (II), R is alkyl or halogenated alkyl more than C20, cycloalkyl or halogenated cycloalkyl more than C20, aryl or halogenated aryl more than C20, alkylaryl or halogenated aryl more than C20, aralkyl or halogenated aralkyl more than C20, x is an integer from 1 to 4;
As a specific embodiment of the present invention, the alcohol compound is an alcohol compound having more than 20 carbon atoms, and the alcohol compound having more than 20 carbon atoms is a linear or branched monohydric alcohol (or phenol) or polyhydric alcohol (or phenol); comprising the following steps: isomers of 1-di-undecanol and alcohols thereof, isomers of 1-docosanol and alcohols thereof, isomers of 1-di-tridecyl alcohol and alcohols thereof, isomers of 1-di-tetradecanol and alcohols thereof, isomers of 1-di-pentadecyl alcohol and alcohols thereof, isomers of 1-hexadecyl alcohol and alcohols thereof, isomers of 1-di-heptadecyl alcohol and alcohols thereof isomers of 1-octacosanol and alcohols thereof, isomers of 1-triacontanol and alcohols thereof, isomers of 4-methyl-3-ditridecanol and alcohols thereof, isomers of 4-methyl-3, 5-octacosanol and alcohols thereof, isomers of 6-methyl-3, 5, 7-heptadecanol and alcohols thereof;
as a specific embodiment of the present invention, the weight ratio of the alcohol compound to the alkoxymagnesium granule is (0.001-5): 1, preferably (0.002-2): 1.
In a second aspect, the present invention provides a method for preparing the support for polyolefin catalyst component, comprising the steps of:
s1: mixing magnesium powder, mixed alcohol a, mixed alcohol b and a halogenating agent to react in an inert atmosphere to obtain alkoxy magnesium particles;
s2: dispersing the alkoxy magnesium particles obtained in the step S1 by adopting an inert organic solvent to obtain an alkoxy magnesium suspension;
S3: and (2) adding a first titanium-containing halide and an alcohol compound into the magnesium alkoxide suspension obtained in the step (S2) to obtain a magnesium alkoxide suspension containing titanium, namely a carrier suspension for the polyolefin catalyst component.
As a specific embodiment of the present invention, in the step S1, the inert atmosphere includes argon, nitrogen, helium, preferably nitrogen; the reaction conditions include: the reaction temperature is 0-30 ℃, the reaction pressure is 0-0.3MPa, and the reaction time is 2-30h.
As a specific embodiment of the present invention, in the step S2, the inert organic solvent is at least one selected from pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene and derivatives thereof. The magnesium alkoxide must be properly treated with an inert organic solvent as a dispersant when reacting with a titanium halide and an alcohol. Preferred inert organic solvents are selected from at least one of pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene and derivatives thereof. The invention uses inert organic solvent, which can dilute the material and make the material in better stirring state, and can eliminate partial static, thus having certain effect on protecting the particle form of the product.
In a third aspect, the present invention provides a Ziegler-Natta catalyst component comprising the reaction product of:
A) A support suspension for a polyolefin catalyst component according to the first aspect;
b) A second titanium-containing halide;
c) Carboxylic acid ester electron donor compounds.
As a specific embodiment of the present invention, the component C) is selected from the group consisting of benzoic acid monoesters and phthalic acid ester compounds represented by formula (III),
In formula (III), R 4 and R 5 are each independently selected from substituted or unsubstituted alkyl of C 1-C8, cycloalkyl of C 3-C10, or aryl of C 6-C20; r 6-R9 are each independently selected from hydrogen, halogen, C 1-C4 alkyl or C 1-C4 alkoxy, preferably at least three of R 6-R9 are hydrogen, more preferably the carboxylate electron donor compound is selected from at least one of di-n-butyl phthalate, di-isobutyl phthalate, diethyl phthalate, dipentyl phthalate, dioctyl phthalate, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate and isobutyl benzoate
As a specific embodiment of the present invention, the molar ratio of the electron donor compound to magnesium in the alkoxymagnesium granule is (0.005 to 10): 1, preferably (0.01 to 2): 1;
As a specific embodiment of the present invention, the second titanium-containing halide is represented by formula (IV):
TiX n(OR10)4-n (IV)
In the formula (IV), X is halogen, R 10 is C 1-C20 alkyl, and n is an integer of 0-4;
As a specific embodiment of the present invention, the molar ratio of the second titanium-containing halide to magnesium in the alkoxy magnesium particles is (0.5 to 100): 1, preferably (1 to 50): 1.
As a specific embodiment of the present invention, the preparation of the Ziegler-Natta catalyst component may be carried out by methods conventional in the art for preparing olefin catalyst components; the solid catalyst component of the present invention is preferably prepared by the following method:
s1: the polyolefin catalyst component carrier suspension prepared by the preparation method of the first aspect or the second aspect is contacted with a second titanium-containing halide and a carboxylic ester electron donor compound to obtain a solid dispersion system, and the solid dispersion system is reacted to obtain a mother solution;
S2: filtering, washing and drying the mother liquor obtained in the step S1 to obtain the solid catalyst component.
As a specific embodiment of the present invention, in the step S2, the reaction temperature is-40-200 ℃, preferably-20-150 ℃, and the reaction time is 1min-20h, preferably 5min-8h.
In a fourth aspect, the present invention provides a catalyst for the polymerization of olefins comprising the reaction product of:
(1) A catalyst component according to the third aspect;
(2) An organoaluminum compound;
(3) Optionally, an external electron donor compound.
As a specific embodiment of the present invention, the organoaluminum compound is an organoaluminum compound represented by the formula AlR 'mX'3-m, wherein R' is selected from any one of hydrogen, an alkyl group of C 1-C20, and an aryl group of C 6-C20; x' is halogen, m is an integer from 1 to 3;
As a specific embodiment of the present invention, the external electron donor compound is an organosilicon compound represented by the formula R 4 pR5 qSi(OR6)4-p-q, wherein R 4 and R 5 are each independently selected from any one of halogen, a hydrogen atom, an alkyl group of C 1-C20, a cycloalkyl group of C 3-C20, an aryl group of C 6-C20, and a haloalkyl group of C 1-C20, and R 6 is selected from any one of an alkyl group of C 1-C20, a cycloalkyl group of C 3-C20, an aryl group of C 6-C20, and a haloalkyl group of C 1-C20; p and q are integers from 0 to 3, respectively, and p+q <4;
as a specific embodiment of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is (5-5000): 1, preferably (20-1000): 1, more preferably (50-500): 1; the molar ratio of aluminum in the organoaluminum compound to the external electron donor compound is (0.1 to 500): 1, preferably (1 to 300): 1, more preferably (3 to 100): 1.
In a fifth aspect, the present invention provides a process for the polymerization of olefins comprising contacting an olefin, at least one of which is represented by the general formula CH 2 =chr, wherein R is any one of hydrogen and an alkyl group of C 1-C6, with a catalyst according to the fourth aspect under olefin polymerization conditions.
As a specific embodiment of the present invention, the olefin polymerization method of the present invention can be used for homo-polymerization of olefins, and can also be used for copolymerizing a plurality of olefins. Specific examples of the α -olefin represented by the general formula CH 2 =chr are ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene, and more preferably, the olefin represented by the general formula CH 2 =chr is at least one selected from ethylene, propylene and 1-butene.
As a specific embodiment of the present invention, the olefin polymerization conditions are: the temperature is 0-150deg.C, preferably 60-130deg.C; the time is 0.1-5h, preferably 0.5-4h; the pressure is 0.01-10MPa, preferably 0.5-5MPa.
The above-mentioned raw materials in the present invention are all self-made or commercially available, and the present invention is not particularly limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention selects a small amount of halogen-containing mixture as halogenating agent, and when titanium halide and/or inert organic solvent are added in the reaction process, the reaction is easier to control, and the particle morphology is better maintained.
2. The alkoxy magnesium particles prepared by the invention are particularly suitable for preparing olefin polymerization catalysts, and the obtained catalysts have high activity, large particle size, good particle morphology and uniform distribution. The catalyst is suitable for a device with a long period of a multi-kettle reaction process in industrial application, can copolymerize more ethylene to generate more rubber under the condition of equal melt index requirement, and keeps good fluidity.
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting the invention in any way.
The evaluation of the magnesium alkoxide particles and polyolefin prepared in the examples of the present invention was performed by the following method:
1. the content of the organic matters in the magnesium alkoxide and olefin polymerization catalyst components was measured by using a Waters 600E type high performance liquid chromatograph manufactured by Waters corporation of America.
2. Particle size and particle size distribution of magnesium dialkoxide and catalyst were measured by Malvern Mastersizer TM < 2000 > n-hexane dispersant laser diffraction method, wherein span= (D90-D10)/D50.
3. The activity of the polymer is calculated by dividing the weight of the final polymer produced by the weight of the initial catalyst component added.
Examples 1 to 9
Examples 1-9 provide a support suspension for a polyolefin catalyst component and a process for preparing the same, a Ziegler-Natta catalyst component and an olefin polymerization catalyst, a process for polymerizing olefins, in particular as follows:
Preparation of magnesium alkoxide particles: in the reactor with stirrer, reflux condenser, thermometer and burette were installed. After sufficient displacement with nitrogen, 98ml of ethanol having a water content of less than 200ppm and a certain amount of higher alcohol having a carbon number of more than 20 (see Table 1) were added to the reactor, and 0.3g of elemental iodine and 0.2g of magnesium chloride were added to dissolve them. Then adding 8g of magnesium powder in total amount for 3 times, stirring, heating until the reflux temperature of the reaction system is reached, carrying out the reaction until the completion rate is 85%, and cooling to 30 ℃. 342ml of ethanol having a water content of less than 200ppm and 8ml of isooctanol having a water content of less than 200ppm were added to the reactor, and 1.2g of elemental iodine and 0.8g of magnesium chloride were added to dissolve the same. Then adding magnesium powder with the total amount of 24g for 4 times, stirring, heating until the reflux temperature of the reaction system is reached, and carrying out the reaction until the reaction is finished, namely, no more hydrogen is discharged. And then washing and drying. The specific addition amounts and results of the raw materials are shown in Table 1.
Preparation of a carrier suspension: 10g of the above-mentioned alkoxy magnesium particles were suspended in 50ml of toluene, then 0.5ml of titanium tetrachloride was added, the temperature was slowly raised to 80℃and a certain amount of higher alcohol having a carbon number of more than 20 was added, followed by stirring for 10 minutes, 1.5ml of a carboxylic acid ester compound (di-n-butyl phthalate DNBP was selected here to illustrate the performance of the examples, but this compound was not limiting), and after stirring for 5 minutes, the temperature was lowered to 25℃to prepare suspension X, ready for use.
Preparation of the solid catalyst component: adding 10mL of toluene and 90mL of titanium tetrachloride into a 300mL reaction kettle repeatedly replaced by high-purity nitrogen, cooling to-20 ℃, adding the suspension X, heating to 120 ℃, keeping the temperature for 2 hours, and then press-filtering the liquid. Then, 30mL of a mixed solution of titanium tetrachloride and 120mL of toluene is added, the temperature is raised to 110 ℃, 1.2mL of a carboxylic ester compound (di-n-butyl phthalate DNBP is selected to illustrate the performance of the embodiment, but not limited to the compound) is added dropwise, stirring treatment is carried out for 1 hour, and the liquid is filtered and filtered; then 60mL of titanium tetrachloride and 90mL of toluene are added, the temperature is raised to 110 ℃ and the mixture is stirred for 1 hour, the treatment is carried out for 2 times, the liquid is filtered off, the obtained solid is washed for 4 times by 150mL of hexane at 60 ℃, the liquid is filtered off and dried, and the solid powder is the solid catalyst component. The specific data are shown in Table 1.
Polymerization of propylene: in a 5 liter autoclave, a nitrogen stream was blown off at 70℃for 1 hour, and then 5mL of a hexane solution of triethylaluminum (triethylaluminum concentration: 0.5mmol/m 1), lmL mL of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (CHMMS concentration: 0.10mmol/m 1), 10mL of anhydrous hexane and 10mg of a solid catalyst component were introduced into the nitrogen stream at room temperature. The autoclave was closed and 1.0L (under normal conditions) of hydrogen and 2.0L of liquid propylene were introduced; the temperature was raised to 70 ℃ over 10 minutes with stirring. After polymerization at 70℃for 2 hours, stirring was stopped, unpolymerized propylene monomer was removed, and the polymer was collected and tested. The specific data are shown in Table 1.
Table 1 data on the preparation and evaluation of the supports and catalysts corresponding to examples 1-9
Comparative example 1
Preparation of an alkoxy magnesium carrier: in the reactor with stirrer, reflux condenser, thermometer and burette were installed. After sufficient displacement with nitrogen, 445ml of ethanol and 5ml of isooctanol are added into the reactor, 5g of elemental iodine is added to dissolve the isooctanol, then 32g of magnesium powder is added for 1 time, stirring is started, heating is carried out until the reflux temperature of the reaction system is reached, and the reaction is carried out until the reaction is completed, namely, no more hydrogen is discharged. Then washing and drying are carried out.
Preparation of a carrier suspension: as in example 1.
Solid catalyst component: as in example 1.
Polymerization of propylene: as in example 1.
The specific data are shown in Table 2.
Comparative example 2
Preparation of an alkoxy magnesium carrier: in the reactor with stirrer, reflux condenser, thermometer and burette were installed. After sufficient displacement with nitrogen, 445ml of ethanol and 5g of 1-octacosanol were added to the reactor, 5g of magnesium chloride were added to dissolve, then 32g of magnesium powder were added 5 times, stirring was started, and the temperature was raised until the reflux temperature of the reaction system was reached, and the reaction was carried out until the completion, i.e., no more hydrogen gas was discharged. Then washing and drying are carried out.
Preparation of a carrier suspension: as in example 1.
Solid catalyst component: as in example 1.
Polymerization of propylene: as in example 1.
The specific data are shown in Table 2.
Comparative example 3
Preparation of magnesium alkoxide particles: in the reactor with stirrer, reflux condenser, thermometer and burette were installed. After sufficient displacement with nitrogen, 30ml of ethanol and 70g of 1-octacosanol having a water content of less than 200ppm were added to the reactor, and after stirring, the temperature was raised, and 0.3g of elemental iodine and 0.2g of magnesium chloride were added to dissolve the same. Then adding 8g of magnesium powder in total amount for 3 times, heating until the reflux temperature of the reaction system is reached, carrying out the reaction until the completion rate is 85%, and cooling to 60 ℃. 342ml of ethanol having a water content of less than 200ppm and 8ml of isooctanol having a water content of less than 200ppm were added to the reactor, and 1.2g of elemental iodine and 0.8g of magnesium chloride were added to dissolve the same. Then adding magnesium powder with the total amount of 24g for 4 times, stirring, heating until the reflux temperature of the reaction system is reached, and carrying out the reaction until the reaction is finished, namely, no more hydrogen is discharged. And then washing and drying.
Preparation of a carrier suspension: as in example 1.
Solid catalyst component: as in example 1.
Polymerization of propylene: as in example 1.
The specific data are shown in Table 2.
Table 2 data on the preparation and evaluation of the supports and catalysts corresponding to comparative examples 1-3
As can be seen from the data in tables 1 and 2, the particle size of the magnesium alkoxide carrier of specific composition prepared by the invention is large and the distribution is narrow. The prepared catalyst has large pore diameter and large pore volume. When propylene polymerization is carried out, the polymerization activity is high. Is beneficial to improving the catalyst efficiency, and the polymer is not easy to be sticky. The catalyst has wide application prospect.
Any numerical value recited in this disclosure includes all values incremented by one unit from the lowest value to the highest value if there is only a two unit interval between any lowest value and any highest value. For example, if the amount of a component, or a process variable such as temperature, pressure, time, etc., is stated to be 50-90, it is meant in this specification that values such as 51-89, 52-88 … …, and 69-71, and 70-71 are specifically recited. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 units may be considered as appropriate. This is only a few examples of the specific designations. In a similar manner, all possible combinations of values between the lowest value and the highest value enumerated are to be considered to be disclosed.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (13)
1. A carrier suspension for polyolefin catalyst components, characterized in that the carrier suspension comprises a titanium-containing magnesium alkoxide suspension obtained by dispersing magnesium alkoxide particles in an inert organic solvent and adding a first titanium-containing halide and an alcohol compound; the magnesium alkoxide particles comprise the reaction product of: magnesium powder, mixed alcohol a, mixed alcohol b and halogenating agent.
2. The carrier for polyolefin catalyst components according to claim 1, wherein the preparation method of the alkoxy magnesium comprises mixing magnesium powder, mixed alcohol a, mixed alcohol b and halogenating agent under inert atmosphere to react;
the average particle size of the magnesium powder is less than 360 mu m, preferably 300-100 mu m;
The mixed alcohol a is a mixture of ethanol and an alcohol compound with carbon number more than 20; the mixed alcohol b is an alcohol compound with carbon number not more than 10;
Preferably, the mixed alcohol a is a mixture of ethanol and 1-behenyl alcohol and/or 1-octacosanol, wherein the ethanol accounts for 80-99.8wt% and the 1-behenyl alcohol and/or 1-octacosanol accounts for 0.1-15wt%;
Preferably, the water content of the mixed alcohol a is < 1000ppm, more preferably, the water content is < 200ppm;
Preferably, the mixed alcohol b is a mixture of linear or branched monohydric alcohol or polyhydric alcohol, more preferably, the mixed alcohol b is a mixture of ethanol and isooctyl alcohol and/or isopropyl alcohol and/or isobutyl alcohol, wherein the ethanol accounts for 80-99.8wt%, and the isooctyl alcohol and/or isopropyl alcohol and/or isobutyl alcohol accounts for 0.2-20wt%;
preferably, the water content of the mixed alcohol b is < 1000ppm, more preferably, the water content is < 200ppm;
The mol ratio of the mixed alcohol a to the magnesium powder is (2-50): 1, preferably (2.5-18): 1;
the mol ratio of the mixed alcohol b to the magnesium powder is (2-50): 1, preferably (2.5-18): 1;
The halogenating agent is halogen simple substance and/or inorganic halide; preferably at least one selected from iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide and alkoxymagnesium halides; more preferably at least one selected from the group consisting of iodine, magnesium iodide, magnesium chloride and alkoxymagnesium halides, particularly preferably a mixture of iodine and magnesium chloride in which the molar ratio of iodine atoms to chlorine atoms is (0.01 to 99): 1, preferably (0.05 to 50): 1, a step of;
The molar ratio of the halogenating agent to magnesium powder is (0.0002-0.2): 1, preferably (0.0025-0.05): 1, based on halogen atoms.
3. The support for polyolefin catalyst components according to claim 1 or 2, characterized in that the first titanium-containing halide has the structure represented by formula (I):
(R 1O)aTi(OR2)b(OR3)cXd formula (I)
In the formula (I), R 1、R2 and R 3 are independently selected from H and alkyl, wherein the alkyl is preferably C1-C10 alkyl, X is selected from chlorine, bromine and iodine, a, b and C are independently integers of 0-3, d is an integer of 1-4, and a+b+c+d=4;
Preferably, the first titanium-containing halide is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium chlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy, titanium monochlorotributoxy, titanium dichlorodibutoxy, titanium trichloromonobutoxy, and isomers thereof;
the weight ratio of the first titanium-containing halide to the alkoxy magnesium particles is (0.001-5): 1.
4. A support for polyolefin catalyst components according to any of claims 1 to 3, wherein the chemical structure of the alcohol compound is represented by formula (II):
R (OH) x formula (II)
In the formula (II), R is alkyl or halogenated alkyl more than C20, cycloalkyl or halogenated cycloalkyl more than C20, aryl or halogenated aryl more than C20, alkylaryl or halogenated aryl more than C20, aralkyl or halogenated aralkyl more than C20, x is an integer from 1 to 4;
Preferably, the alcohol compound is an alcohol compound with a carbon number greater than 20, and the alcohol compound with a carbon number greater than 20 is preferably a linear or branched monohydric alcohol (or phenol) or polyhydric alcohol (or phenol), preferably selected from the group consisting of an isomer of 1-di-undecanol and alcohols thereof, an isomer of 1-docosanol and alcohols thereof, an isomer of 1-di-tridecanol and alcohols thereof, an isomer of 1-twenty-four alcohol and alcohols thereof, an isomer of 1-twenty-five alcohol and alcohols thereof, an isomer of 1-twenty-four alcohol and alcohols thereof, an isomer of 1-twenty-eight alcohol and alcohols thereof, an isomer of 1-twenty-nine alcohol and alcohols thereof, an isomer of 1-thirty-one alcohol and alcohols thereof, an isomer of 4-methyl-3, 5-twenty-five alcohol and alcohols thereof, an isomer of 6-methyl-3, 7-di-heptadecanol and alcohols thereof;
The weight ratio of the alcohol compound to the alkoxy magnesium particles is (0.001-5): 1, preferably (0.002-2): 1.
5. A process for the preparation of a support suspension for polyolefin catalyst components according to claims 1 to 4, characterized in that it comprises the following steps:
s1: mixing magnesium powder, mixed alcohol a, mixed alcohol b and a halogenating agent to react in an inert atmosphere to obtain alkoxy magnesium particles;
s2: dispersing the alkoxy magnesium particles obtained in the step S1 by adopting an inert organic solvent to obtain an alkoxy magnesium suspension;
S3: and (2) adding a first titanium-containing halide and an alcohol compound into the magnesium alkoxide suspension obtained in the step (S2) to obtain a magnesium alkoxide suspension containing titanium, namely a carrier suspension for the polyolefin catalyst component.
6. The method according to claim 5, wherein in step S1, the inert atmosphere comprises argon, nitrogen, helium, preferably nitrogen; the reaction conditions include: the reaction temperature is 0-30 ℃, the reaction pressure is 0-0.3MPa, and the reaction time is 2-30h.
7. The method according to claim 5 or 6, wherein in the step S2, the inert organic solvent is at least one selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, and derivatives thereof.
8. A ziegler-natta catalyst component comprising the reaction product of:
A) A support for polyolefin catalyst components according to any of claims 1 to 4 or a support suspension for polyolefin catalyst components produced by the method according to any of claims 5 to 7;
b) A second titanium-containing halide;
c) Carboxylic acid ester electron donor compounds.
9. The Ziegler-Natta catalyst component according to claim 8, characterized in that said component C) carboxylate electron donor compound is selected from among the benzoic monoesters or the phthalic compounds according to formula (III),
In formula (III), R 4 and R 5 are each independently selected from substituted or unsubstituted alkyl of C 1-C8, cycloalkyl of C 3-C10, or aryl of C 6-C20; r 6-R9 is each independently selected from hydrogen, halogen, C 1-C4 alkyl or C 1-C4 alkoxy, preferably at least three of R 6-R9 are hydrogen, more preferably the carboxylate electron donor compound is selected from at least one of di-n-butyl phthalate, di-isobutyl phthalate, diethyl phthalate, dipentyl phthalate, dioctyl phthalate, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate and isobutyl benzoate;
The molar ratio of the carboxylate electron donor compound to magnesium in the alkoxy magnesium particles is (0.005-10) 1, preferably (0.01-2) 1;
the second titanium-containing halide is represented by formula (IV):
TiX n(OR10)4-n (IV)
In the formula (IV), X is halogen, R 10 is C 1-C20 alkyl, and n is an integer of 0-4;
The molar ratio of the halide containing the second titanium to magnesium in the alkoxy magnesium particles is (0.5 to 100): 1, preferably (1 to 50): 1.
10. A catalyst for the polymerization of olefins, characterized in that the catalyst comprises the reaction product of:
(1) A catalyst component according to any one of claims 1 to 7 or a catalyst component obtainable by the process of any one of claims 8 or 9;
(2) An organoaluminum compound;
(3) Optionally, an external electron donor compound.
11. The catalyst for olefin polymerization according to claim 10, wherein the organoaluminum compound is an organoaluminum compound represented by the formula AlR' mX'3-m,
Wherein R' is selected from any one of hydrogen, C 1-C20 alkyl and C 6-C20 aryl; x' is halogen, m is an integer from 1 to 3;
The external electron donor compound is an organosilicon compound shown in a formula R 4 pR5 qSi(OR6)4-p-q,
Wherein R 4 and R 5 are each independently selected from any one of halogen, a hydrogen atom, an alkyl group of C 1-C20, a cycloalkyl group of C 3-C20, an aryl group of C 6-C20, and a haloalkyl group of C 1-C20, and R 6 is selected from any one of an alkyl group of C 1-C20, a cycloalkyl group of C 3-C20, an aryl group of C 6-C20, and a haloalkyl group of C 1-C20; p and q are integers from 0 to 3, respectively, and p+q <4;
The molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is (5-5000): 1, preferably (20-1000): 1, more preferably (50-500): 1; the molar ratio of aluminum in the organoaluminum compound to the external electron donor compound is (0.1-500): 1, preferably (1-300): 1.
12. A process for the polymerization of olefins, characterized in that it comprises contacting an olefin under olefin polymerization conditions with a catalyst according to claim 10 or 11,
At least one of the olefins is represented by the general formula CH 2 =chr,
Wherein R is any one of hydrogen and alkyl of C 1-C6.
13. The olefin polymerization process of claim 12 wherein the olefin polymerization conditions are: the temperature is 0-150deg.C, preferably 60-130deg.C; the time is 0.1-5h, preferably 0.5-4h; the pressure is 0.01-10MPa, preferably 0.5-5MPa.
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