CN117924549A - Ziegler-Natta catalyst component, process for preparing the same, olefin polymerization catalyst and process for polymerizing olefin - Google Patents
Ziegler-Natta catalyst component, process for preparing the same, olefin polymerization catalyst and process for polymerizing olefin Download PDFInfo
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- CN117924549A CN117924549A CN202211305183.9A CN202211305183A CN117924549A CN 117924549 A CN117924549 A CN 117924549A CN 202211305183 A CN202211305183 A CN 202211305183A CN 117924549 A CN117924549 A CN 117924549A
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- China
- Prior art keywords
- alcohol
- compound
- alkyl
- titanium
- cyano
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 39
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000011954 Ziegler–Natta catalyst Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000002685 polymerization catalyst Substances 0.000 title abstract description 12
- 230000000379 polymerizing effect Effects 0.000 title description 2
- -1 magnesium alkoxide Chemical class 0.000 claims abstract description 135
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 51
- 239000011777 magnesium Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 150000004820 halides Chemical class 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 79
- 125000000217 alkyl group Chemical group 0.000 claims description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 32
- 150000001298 alcohols Chemical class 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000011949 solid catalyst Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical group 0.000 claims description 14
- CNNRPFQICPFDPO-UHFFFAOYSA-N octacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCO CNNRPFQICPFDPO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 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
- 229960000735 docosanol Drugs 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229960002666 1-octacosanol Drugs 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 230000002140 halogenating effect Effects 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- MISPJWXLQJXWHM-UHFFFAOYSA-N (5-benzoyloxy-4-ethylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)C(CC)C(CC)OC(=O)C1=CC=CC=C1 MISPJWXLQJXWHM-UHFFFAOYSA-N 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 claims description 4
- ASFLIXVTLOHGHE-UHFFFAOYSA-N 5-benzoyloxyheptan-3-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(CC)OC(=O)C1=CC=CC=C1 ASFLIXVTLOHGHE-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 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
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 claims description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical class CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-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
- 229940035429 isobutyl alcohol Drugs 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
- 239000000126 substance Substances 0.000 claims description 4
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontan-1-ol Chemical class CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- CHPIWTZSNIMWMZ-UHFFFAOYSA-N (3-benzoyloxy-2,3-dimethylbutyl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)(C)C(C)COC(=O)C1=CC=CC=C1 CHPIWTZSNIMWMZ-UHFFFAOYSA-N 0.000 claims description 2
- IIYIECVYGJTMQU-UHFFFAOYSA-N (5-benzoyloxy-6-methylheptan-3-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(C(C)C)OC(=O)C1=CC=CC=C1 IIYIECVYGJTMQU-UHFFFAOYSA-N 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- QCCJUUZWWCHCPY-UHFFFAOYSA-N 2-(benzoyloxymethyl)butyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(CC)COC(=O)C1=CC=CC=C1 QCCJUUZWWCHCPY-UHFFFAOYSA-N 0.000 claims description 2
- MSFBANCBVHDEJG-UHFFFAOYSA-N 2-(benzoyloxymethyl)pentyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(CCC)COC(=O)C1=CC=CC=C1 MSFBANCBVHDEJG-UHFFFAOYSA-N 0.000 claims description 2
- GNBPEYCZELNJMS-UHFFFAOYSA-N 2-methylbutane-1,3-diol Chemical compound CC(O)C(C)CO GNBPEYCZELNJMS-UHFFFAOYSA-N 0.000 claims description 2
- SPXWGAHNKXLXAP-UHFFFAOYSA-N 2-methylpentane-1,3-diol Chemical compound CCC(O)C(C)CO SPXWGAHNKXLXAP-UHFFFAOYSA-N 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
- YDVICEZKBCWZLM-UHFFFAOYSA-N 3-(2,2-dimethylpropanoyloxy)pentyl 2,2-dimethylpropanoate Chemical compound CCC(CCOC(=O)C(C)(C)C)OC(=O)C(C)(C)C YDVICEZKBCWZLM-UHFFFAOYSA-N 0.000 claims description 2
- QYKAQVPHBTYMDQ-UHFFFAOYSA-N 4-benzoyloxyheptan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CCC)CC(C)OC(=O)C1=CC=CC=C1 QYKAQVPHBTYMDQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-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
- GMIJLGFPOXCNBC-UHFFFAOYSA-N [2-(benzoyloxymethyl)-5-methyl-2-propan-2-ylhexyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C(C)C)(CCC(C)C)COC(=O)C1=CC=CC=C1 GMIJLGFPOXCNBC-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- SUNRWLABUWCFLP-UHFFFAOYSA-N butane-1,3-diol;2,3-dimethylbenzoic acid Chemical compound CC(O)CCO.CC1=CC=CC(C(O)=O)=C1C SUNRWLABUWCFLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229940114081 cinnamate Drugs 0.000 claims description 2
- 125000004122 cyclic group Chemical group 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
- 125000005843 halogen group Chemical group 0.000 claims description 2
- KJWLAZDNFRTNJS-UHFFFAOYSA-N heptadecan-7-ol Chemical compound CCCCCCCCCCC(O)CCCCCC KJWLAZDNFRTNJS-UHFFFAOYSA-N 0.000 claims description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical class CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000003701 inert diluent Substances 0.000 claims description 2
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 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
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- 239000007962 solid dispersion Substances 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
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- 229940087291 tridecyl alcohol Drugs 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 150000002899 organoaluminium compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 38
- 238000009826 distribution Methods 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 230000037048 polymerization activity Effects 0.000 abstract description 5
- 238000009827 uniform distribution Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 22
- 238000010992 reflux Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 229910001629 magnesium chloride Inorganic materials 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 10
- 229910052740 iodine Inorganic materials 0.000 description 10
- 239000011630 iodine Substances 0.000 description 10
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006073 displacement reaction Methods 0.000 description 8
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 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
- 230000009286 beneficial effect Effects 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002994 raw material 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
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- ZPYVAEKBXKGWCX-UHFFFAOYSA-N diethyl 2-cyano-2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C#N)(C(C)C)C(=O)OCC ZPYVAEKBXKGWCX-UHFFFAOYSA-N 0.000 description 2
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-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
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer 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
- 239000003960 organic solvent Substances 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- PAIWFVCLHYBMAO-UHFFFAOYSA-N 1-O-ethyl 4-O-methyl 2,3-di(butan-2-yl)-2-cyanobutanedioate Chemical compound CCOC(=O)C(C#N)(C(C)CC)C(C(C)CC)C(=O)OC PAIWFVCLHYBMAO-UHFFFAOYSA-N 0.000 description 1
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- PRHXCGXOCGMYQB-UHFFFAOYSA-N diethyl 2-cyano-3-ethyl-2-methylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CC)C PRHXCGXOCGMYQB-UHFFFAOYSA-N 0.000 description 1
- AKTPRFYUYYRKDG-UHFFFAOYSA-N diethyl 2-cyano-3-ethyl-2-pentylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CC)CCCCC AKTPRFYUYYRKDG-UHFFFAOYSA-N 0.000 description 1
- DRYRGLKXIYTIFV-UHFFFAOYSA-N diethyl 2-cyano-3-ethyl-2-propan-2-ylbutanedioate Chemical compound CCOC(=O)C(CC)C(C#N)(C(C)C)C(=O)OCC DRYRGLKXIYTIFV-UHFFFAOYSA-N 0.000 description 1
- TWQLYTZYDBLIJZ-UHFFFAOYSA-N diethyl 2-cyano-3-ethyl-2-propylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CC)CCC TWQLYTZYDBLIJZ-UHFFFAOYSA-N 0.000 description 1
- CCTSOAZOULXVHA-UHFFFAOYSA-N diethyl 2-cyano-3-methyl-2-propan-2-ylbutanedioate Chemical compound CCOC(=O)C(C)C(C#N)(C(C)C)C(=O)OCC CCTSOAZOULXVHA-UHFFFAOYSA-N 0.000 description 1
- WSURKOJRNKLJHY-UHFFFAOYSA-N diethyl 2-cyano-3-pentyl-2-propan-2-ylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCCC)C(C)C WSURKOJRNKLJHY-UHFFFAOYSA-N 0.000 description 1
- VIKNFQVDJYRNMC-UHFFFAOYSA-N diethyl 2-cyano-3-pentyl-2-propylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCCC)CCC VIKNFQVDJYRNMC-UHFFFAOYSA-N 0.000 description 1
- MCHAXEKAPXJCCJ-UHFFFAOYSA-N diethyl 2-cyano-3-propan-2-yl-2-propylbutanedioate Chemical compound C(C)OC(C(C(C(=O)OCC)C(C)C)(CCC)C#N)=O MCHAXEKAPXJCCJ-UHFFFAOYSA-N 0.000 description 1
- YVORWCAUMHDOJD-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-(2-methylpropyl)butanedioate Chemical compound C(C)OC(C(C(C(=O)OCC)CCCC)(CC(C)C)C#N)=O YVORWCAUMHDOJD-UHFFFAOYSA-N 0.000 description 1
- WPMRCWWQLMETLB-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-(3-methylbutyl)butanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCC)CCC(C)C WPMRCWWQLMETLB-UHFFFAOYSA-N 0.000 description 1
- BBCHAANPBADBAS-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-(4-methylpentyl)butanedioate Chemical compound C(C)OC(C(C(C(=O)OCC)CCCC)(CCCC(C)C)C#N)=O BBCHAANPBADBAS-UHFFFAOYSA-N 0.000 description 1
- VTHNTEMGIKZTQA-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-cyclopentylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCC)C1CCCC1 VTHNTEMGIKZTQA-UHFFFAOYSA-N 0.000 description 1
- DACSIQINUUMUAK-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-ethylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCC)CC DACSIQINUUMUAK-UHFFFAOYSA-N 0.000 description 1
- FSRRILBGCBNUAN-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-hexylbutanedioate Chemical compound C(C)OC(C(C(C(=O)OCC)CCCC)(CCCCCC)C#N)=O FSRRILBGCBNUAN-UHFFFAOYSA-N 0.000 description 1
- BASDPBWBENFDQR-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-methylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCC)C BASDPBWBENFDQR-UHFFFAOYSA-N 0.000 description 1
- VPMIEQGVKHKHPW-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-pentylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCC)CCCCC VPMIEQGVKHKHPW-UHFFFAOYSA-N 0.000 description 1
- YJGUCSUYROZWNI-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-propan-2-ylbutanedioate Chemical compound CCCCC(C(=O)OCC)C(C#N)(C(C)C)C(=O)OCC YJGUCSUYROZWNI-UHFFFAOYSA-N 0.000 description 1
- WSJUDNCHJKDIHB-UHFFFAOYSA-N diethyl 3-butyl-2-cyano-2-propylbutanedioate Chemical compound C(#N)C(C(=O)OCC)(C(C(=O)OCC)CCCC)CCC WSJUDNCHJKDIHB-UHFFFAOYSA-N 0.000 description 1
- QKBDUXBABMMGAU-UHFFFAOYSA-N dimethyl 2,3-di(butan-2-yl)-2-cyanobutanedioate Chemical compound CCC(C)C(C(=O)OC)C(C#N)(C(C)CC)C(=O)OC QKBDUXBABMMGAU-UHFFFAOYSA-N 0.000 description 1
- PYDGWDGSWQNNKU-UHFFFAOYSA-N dimethyl 2-cyano-2,3-bis(2-methylpropyl)butanedioate Chemical compound COC(=O)C(CC(C)C)C(CC(C)C)(C#N)C(=O)OC PYDGWDGSWQNNKU-UHFFFAOYSA-N 0.000 description 1
- LIGXYBPUNRYXOY-UHFFFAOYSA-N dimethyl 2-cyano-2,3-dicyclopentylbutanedioate Chemical compound COC(=O)C(C1CCCC1)C(C#N)(C1CCCC1)C(=O)OC LIGXYBPUNRYXOY-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MRGHYZZLRRXSIY-UHFFFAOYSA-N dipropan-2-yl 2,3-di(butan-2-yl)-2-cyanobutanedioate Chemical compound CCC(C)C(C(=O)OC(C)C)C(C#N)(C(C)CC)C(=O)OC(C)C MRGHYZZLRRXSIY-UHFFFAOYSA-N 0.000 description 1
- YQVXBEBKTIADMC-UHFFFAOYSA-N dipropan-2-yl 2-cyano-2,3-bis(2-methylpropyl)butanedioate Chemical compound CC(C)CC(C(=O)OC(C)C)C(CC(C)C)(C#N)C(=O)OC(C)C YQVXBEBKTIADMC-UHFFFAOYSA-N 0.000 description 1
- AKKNNYCIGSDJSO-UHFFFAOYSA-N dipropan-2-yl 2-cyano-2,3-dicyclopentylbutanedioate Chemical compound CC(C)OC(=O)C(C1CCCC1)C(C#N)(C1CCCC1)C(=O)OC(C)C AKKNNYCIGSDJSO-UHFFFAOYSA-N 0.000 description 1
- WCSOKBKWPOWXCY-UHFFFAOYSA-N dipropyl 2,3-di(butan-2-yl)-2-cyanobutanedioate Chemical compound CCCOC(=O)C(C(C)CC)C(C#N)(C(C)CC)C(=O)OCCC WCSOKBKWPOWXCY-UHFFFAOYSA-N 0.000 description 1
- LNSGRDSHLZQYNP-UHFFFAOYSA-N dipropyl 2-cyano-2,3-bis(2-methylpropyl)butanedioate Chemical compound CCCOC(=O)C(CC(C)C)C(CC(C)C)(C#N)C(=O)OCCC LNSGRDSHLZQYNP-UHFFFAOYSA-N 0.000 description 1
- HUBLDEBYTMTKSZ-UHFFFAOYSA-N dipropyl 2-cyano-2,3-di(propan-2-yl)butanedioate Chemical compound CCCOC(=O)C(C(C)C)C(C#N)(C(C)C)C(=O)OCCC HUBLDEBYTMTKSZ-UHFFFAOYSA-N 0.000 description 1
- PBGDYZVBEZENQL-UHFFFAOYSA-N dipropyl 2-cyano-2,3-dicyclopentylbutanedioate Chemical compound CCCOC(=O)C(C1CCCC1)C(C#N)(C1CCCC1)C(=O)OCCC PBGDYZVBEZENQL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 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
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-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
- 150000003077 polyols Chemical class 0.000 description 1
- 230000035484 reaction time 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 Ziegler-Natta catalyst component, a preparation method thereof, an olefin polymerization catalyst and an olefin polymerization method. A ziegler-natta catalyst component comprising the reaction product of: a) Particles of magnesium alkoxide; b) Carboxylic acid ester electron donor compounds; c) A polyol ester compound; d) A first titanium-containing halide; e) An internal electron donor. Catalyst for the polymerization of olefins comprising the reaction product of: (1) the aforementioned catalyst component; (2) an organoaluminum compound; (3) optionally, an external electron donor compound. The alkoxy magnesium particles prepared by the invention are particularly suitable for preparing olefin polymerization catalysts, and the obtained catalysts have large particle size, uniform distribution, high polymerization activity, slow activity attenuation, high isotactic index of the obtained polymer, wide molecular weight distribution and excellent fluidity. The catalyst is suitable for a device with a long period of a multi-kettle reaction process in industrial application, and the obtained polymer has obvious isotacticity index and molecular weight distribution characteristics.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a Ziegler-Natta catalyst component, a preparation method thereof, 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 to obtain a titanium-containing catalyst component, from which a catalyst having a high activity and an insufficient duration of activity is obtained, although it is polymerized.
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 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 high isotacticity and high bulk density can be obtained, but the content of fine powder thereof is high, the durability of the activity is insufficient, the isotacticity index is not high enough, and the molecular weight distribution is not wide enough.
Therefore, there is a need for a Ziegler-Natta catalyst component and an olefin polymerization catalyst having a large particle size and a uniform distribution and high polymerization activity for use in olefin polymerization.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention proposes a Ziegler-Natta catalyst component and a preparation method thereof, an olefin polymerization catalyst and an olefin polymerization method. In a first aspect, the present invention provides a Ziegler-Natta catalyst component characterized by the reaction product of:
A) Particles of magnesium alkoxide;
b) A first titanium-containing halide;
C) Carboxylic acid ester electron donor compounds;
D) A polyol ester compound;
e) An internal electron donor.
As a specific embodiment of the present invention, the magnesium alkoxide particles comprise the reaction product of: magnesium powder, mixed alcohol a, mixed alcohol b and halogenating agent;
the average particle size of the magnesium powder is less than 360 mu m, preferably 300-100 mu m; and/or the number of the groups of groups,
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; the mixed alcohol a is a mixture of ethanol and the alcohol compound with the carbon number 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%; the mixed alcohol b is a linear or branched monohydric alcohol or a mixture of polyols, preferably at least two 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; 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%;
the mol ratio of the mixed alcohol a to the magnesium powder is (2-50): 1, preferably (2.5-18): 1; and/or the number of the groups of groups,
The mol ratio of the mixed alcohol b to the magnesium powder is (2-50): 1, preferably (2.5-18): 1; and/or the number of the groups of groups,
The halogenating agent is halogen simple substance and/or inorganic halide; and/or the number of the groups of groups,
The molar ratio of the halogenating agent to magnesium powder is (0.0002-0.2): 1, preferably (0.0025-0.05): 1, calculated on halogen atom;
The magnesium alkoxide particles further include a second titanium-containing halide and alcohol treatment;
the second titanium-containing halide has a structure as shown in formula (I):
(R 1O)aTi(OR2)b(OR3)cXd formula (I)
In the formula (I), R 1、R2 and R 3 are the same or different and are selected from H and alkyl, especially C1-C10 alkyl, X is selected from chlorine, bromine and iodine, a, b and C are independently integers of 0-4, d is independently an integer of 1-4, and a+b+c+d=4;
Preferably, the second 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, their isomers;
the weight ratio of the second titanium-containing halide to the alkoxy magnesium is (0.001-5) 1, preferably (0.002-2) 1;
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;
Preferably, the alcohol compound is an alcohol compound with a carbon number of more than 20, and the alcohol compound with a carbon number of more than 20 is a monohydric alcohol (or phenol) or a polyhydric alcohol (or phenol) which is linear or branched; more preferably, it comprises: 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;
The weight ratio of the alcohol compound to the alkoxy magnesium is (0.001-5): 1, preferably (0.002-2): 1.
As a specific embodiment of the present invention, the carboxylic acid ester electron donor compound is selected from benzoic acid monoesters or 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 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 electron donor compound to magnesium in the alkoxymagnesium particles is (0.005-10): 1, preferably (0.01-2): 1.
As a specific embodiment of the present invention, the polyol ester compound is selected from the group consisting of a glycol ester compound represented by the formula (IV),
In the formula (IV), R 1-R2 are the same or different and are each independently a substituted or unsubstituted straight-chain C1-C20 alkyl group, a substituted or unsubstituted branched-chain C3-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 alkylaryl group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C2-C10 alkylene group or a substituted or unsubstituted C10-C20 condensed ring aryl group;
R 3-R8 are identical or different and are each independently hydrogen, halogen, substituted or unsubstituted, straight-chain C1-C20-alkyl, substituted or unsubstituted, branched C3-C20-alkyl, substituted or unsubstituted, C3-C20-cycloalkyl, substituted or unsubstituted, C6-C20-aryl, substituted or unsubstituted, C7-C20-alkylaryl, substituted or unsubstituted, C7-C20-arylalkyl, substituted or unsubstituted, C2-C10-alkylene or substituted or unsubstituted, C10-C20-fused-ring aryl; or at least one of R 3-R6 is cyclic with at least one of R 7-R8;
Preferably, the polyol ester compound is at least one of 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 1, 3-butanediol dimethylbenzoate, 2-methyl-1, 3-butanediol diisochlorobenzoate, 2, 3-dimethyl-1, 3-butanediol dibenzoate, 1, 3-pentanediol dipivalate, 2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol benzoic cinnamate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, and the like, preferably at least one of 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 2, 4-pentanediol dibenzoate;
The molar ratio of the polyol ester electron donor compound to magnesium in the magnesium alkoxide particles is (0.01-5): 1, preferably (0.02-2): 1.
As a specific embodiment of the invention, the internal electron donor is a cyano succinate compound shown in a general formula (V);
In formula (V), R 1 'and R 2', which may be the same or different, are each independently selected from hydrogen, C 1-C14 straight-chain alkyl, C 3-C10 branched alkyl, C 3-C10 cycloalkyl, C 6-C10 aryl, C 7-C10 alkylaryl, and C 7-C10 arylalkyl; r 3 'and R 4', which may be the same or different, are each independently selected from the group consisting of C 1-C14 straight-chain alkyl, C 3-C10 branched-chain alkyl, C 3-C10 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl, and C 7-C20 arylalkyl;
Preferably, R 1 'and R 2' are each independently selected from hydrogen, C 1-C8 straight chain alkyl and C 3-C8 branched alkyl;
Preferably, R 3 'and R 4' are each independently selected from C 1-C6 straight chain alkyl and C 3-C6 branched alkyl;
as a specific embodiment of the present invention, the internal electron donor is selected from:
2-cyano-2, 3-diisopropylbutanedioic acid diethyl ester, 2-cyano-2, 3-dimethylbutanedioic acid diethyl ester, 2-cyano-2, 3-diethylbutanedioic acid diethyl ester, 2-cyano-2, 3-di-n-propylbutanedioic acid diethyl ester, 2-cyano-2, 3-di-n-pentylsuccinic acid diethyl ester, 2-cyano-2, 3-diisopentylsuccinic acid diethyl ester, 2-cyano-2, 3-di-n-hexylbutanedioic acid diethyl ester, 2-cyano-2, 3-diisohexylbutanedioic acid diethyl ester, 2-cyano-2, 3-diisopropylbutanedioic acid di-n-propyl ester, 2-cyano-2, 3-diisopropylbutanedioic acid diisopropyl ester, 2-cyano-2, 3-diisopropylbutanedioic acid diisobutyl ester, 2-cyano-2, 3-diisopropylbutanedioic acid diethyl ester, 2-cyano-2, 3-diisopropylbutanedioic acid methyl ester (r=4%), r3=ethyl), 2-cyano-2, 3-diisopropylbutanedioic acid-1-ethyl-4-methyl ester (r4=ethyl, r3=methyl), 2-cyano-2, 3-diisopropylbutanedioic acid-1-n-butyl-4-ethyl ester (r4=n-butyl, r3=ethyl), 2-cyano-2, 3-diisopropylbutanedioic acid-1-ethyl-4-n-butyl ester (r4=ethyl, r3=n-butyl), 2-cyano-2, 3-diisobutylbutanedioic acid dimethyl ester, 2-cyano-2, 3-diisobutylbutanedioic acid diethyl ester, 2-cyano-2, 3-diisobutylbutanedioic acid di-n-propyl ester, 2-cyano-2, 3-diisobutylbutanedioic acid diisopropyl ester, 2-cyano-2, 3-diisobutylbutanedioic acid di-n-butyl ester, 2-cyano-2, 3-diisobutylbutanedioic acid-1-methyl ester-4-ethyl ester (r4=methyl, r3=ethyl), 2-isobutyl-2, 3-diisobutylbutanedioic acid-1-ethyl-4-methyl ester (r4=ethyl, r3=methyl), 2-cyano-2, 3-diisobutylbutanedioic acid-1-n-butyl-4-ethyl ester (r4=n-butyl, r3=ethyl), 2-cyano-2, 3-diisobutylbutanedioic acid-1-ethyl-4-n-butyl ester (r4=ethyl, r3=n-butyl), 2-cyano-2, 3-di-sec-butylbutanedioic acid dimethyl ester, 2-cyano-2, 3-di-sec-butylbutanedioic acid diethyl ester, 2-cyano-2, 3-di-sec-butylbutanedioic acid di-n-propyl ester, 2-cyano-2, 3-di-sec-butylbutanedioic acid diisopropyl ester, 2-cyano-2, 3-di-sec-butylbutanedioic acid di-n-butyl ester, 2-cyano-2, 3-di-sec-butylbutanedioic acid diisobutyl ester, 2-cyano-2, 3-di-sec-butylbutanedioic acid-1-methyl ester-4-ethyl ester (r4=methyl, r3=ethyl), 2-cyano-2, 3-di-sec-butylbutanedioic acid-1-ethyl ester-4-methyl ester (r4=ethyl, r3=methyl), 2-cyano-2, 3-di-sec-butylbutanedioic acid-1-ethyl ester-4-n-butyl ester (r4=ethyl), r3=n-butyl), dimethyl 2-cyano-2, 3-dicyclopentylsuccinate, diethyl 2-cyano-2, 3-dicyclopentylsuccinate, di-n-propyl 2-cyano-2, 3-dicyclopentylsuccinate, diisopropyl 2-cyano-2, 3-dicyclopentylsuccinate, di-n-butyl 2-cyano-2, 3-dicyclopentylsuccinate, diisobutyl 2-cyano-2, 3-dicyclopentylsuccinate, 1-methyl 2-ethyl 2-cyano-2, 3-dicyclopentylsuccinate (r4=methyl, r3=ethyl), 2-cyano-2, 3-dicyclopentylsuccinic acid-1-ethyl-4-methyl ester (r4=ethyl, r3=methyl), 2-cyano-2, 3-dicyclopentylsuccinic acid-1-n-butyl-4-ethyl ester (r4=n-butyl, r3=ethyl), 2-cyano-2, 3-dicyclopentylsuccinic acid-1-ethyl-4-n-butyl ester (r4=ethyl, r3=n-butyl), dimethyl 2-cyano-2, 3-dicyclohexyl succinate, diethyl 2-cyano-2, 3-dicyclohexyl succinate, di-n-propyl 2-cyano-2, 3-dicyclohexyl succinate, diisopropyl 2-cyano-2, 3-dicyclohexyl succinate, di-n-butyl 2-cyano-2, 3-dicyclohexyl succinate, diisobutyl 2-cyano-2, 3-dicyclohexyl succinate, 1-methyl 2, 3-dicyclohexyl succinate-4-ethyl 2-cyano-2, 3-dicyclohexyl succinate-1-ethyl 4-methyl (r4=methyl, r3=ethyl), 1-ethyl 2-cyano-2, 3-dicyclohexyl succinate-4-methyl (r4=ethyl, r3=methyl), 1-n-butyl 2, 3-dicyclohexyl succinate-4-ethyl (r4=n-butyl, r3=ethyl), 2-cyano-2, 3-dicyclohexylsuccinic acid-1-ethyl-4-n-butyl ester (r4=ethyl, r3=n-butyl);
Diethyl 2-cyano-2-methyl-3-ethylsuccinate, diethyl 2-cyano-2-methyl-3-n-propylsuccinate, diethyl 2-cyano-2-methyl-3-isopropyl succinate, diethyl 2-cyano-2-methyl-3-n-butylsuccinate, diethyl 2-cyano-2-methyl-3-isobutyl succinate, diethyl 2-cyano-2-methyl-3-n-pentylsuccinate, diethyl 2-cyano-2-methyl-3-isopentylsuccinate, diethyl 2-cyano-2-methyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-methyl-3-n-hexylsuccinate, diethyl 2-cyano-2-methyl-3-isohexylsuccinate;
Diethyl 2-cyano-2-ethyl-3-methylsuccinate, diethyl 2-cyano-2-ethyl-3-n-propylsuccinate, diethyl 2-cyano-2-ethyl-3-isopropylsuccinate, diethyl 2-cyano-2-ethyl-3-n-butylsuccinate, diethyl 2-cyano-2-ethyl-3-isobutylsuccinate, diethyl 2-cyano-2-ethyl-3-n-pentylsuccinate, diethyl 2-cyano-2-ethyl-3-isopentylsuccinate, diethyl 2-cyano-2-ethyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-ethyl-3-n-hexylsuccinate, diethyl 2-cyano-2-ethyl-3-isohexylsuccinate;
Diethyl 2-cyano-2-n-propyl-3-methylsuccinate, diethyl 2-cyano-2-n-propyl-3-ethylsuccinate, diethyl 2-cyano-2-n-propyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-propyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-propyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-propyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-propyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-propyl-3-hexylsuccinate, diethyl 2-cyano-2-n-propyl-3-isohexylsuccinate;
Diethyl 2-cyano-2-isopropyl-3-methylsuccinate, diethyl 2-cyano-2-isopropyl-3-ethylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-propylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-butylsuccinate, diethyl 2-cyano-2-isopropyl-3-isobutyl succinate, diethyl 2-cyano-2-isopropyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isopropyl-3-isopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isopropyl-3-isohexylsuccinate;
diethyl 2-cyano-2-n-butyl-3-methylsuccinate, diethyl 2-cyano-2-n-butyl-3-ethylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-butyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-butyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-pentylsuccinate, diethyl 2-cyano-2-n-butyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-hexylsuccinate, diethyl 2-cyano-2-n-butyl-3-isohexylsuccinate;
Diethyl 2-cyano-2-isobutyl-3-methylsuccinate, diethyl 2-cyano-2-isobutyl-3-ethylsuccinate, monoethyl 2-syringyl-2-isobutyl-3-n-propylsuccinate, diethyl 2-cyano-2-isobutyl-3-isopropylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-butylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isobutyl-3-isopentylsuccinate, diethyl 2-cyano-2-isobutyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isobutyl-3-isohexylsuccinate;
diethyl 2-cyano-2-n-pentyl-3-methylsuccinate, diethyl 2-cyano-2-n-pentyl-3-ethylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-propylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isopropylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-butylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-pentyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-pentyl-3-hexylsuccinate, diethyl 2-cyano-2-n-pentyl-3-isohexylsuccinate;
Diethyl 2-cyano-2-isopentyl-3-methylsuccinate, diethyl 2-cyano-2-isopentyl-3-ethylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-propylsuccinate, diethyl 2-cyano-2-isopentyl-3-isopropyl succinate, diethyl 2-cyano-2-isopentyl-3-n-butylsuccinate, diethyl 2-cyano-2-isopentyl-3-isobutylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isopentyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isopentyl-3-n-hexylsuccinate, diethyl 2-cyano-2-isopentyl-3-isohexylsuccinate;
Diethyl 2-cyano-2-cyclopentyl-3-methylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-ethylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-propylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isopropyl succinate, diethyl 2-cyano-2-cyclopentyl-3-n-butylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isobutyl succinate, diethyl 2-cyano-2-cyclopentyl-3-n-pentylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isopentylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-n-hexylsuccinate, diethyl 2-cyano-2-cyclopentyl-3-isohexylsuccinate;
2-cyano-2-n-hexyl-3-methylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-ethylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-n-propylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-isopropylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-n-butylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-isobutylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-n-pentylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-isopentylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-cyclopentylsuccinic acid diethyl ester, 2-cyano-2-n-hexyl-3-isohexylsuccinic acid diethyl ester;
At least one of diethyl 2-cyano-2-isohexyl-3-methylsuccinate, diethyl 2-cyano-2-isohexyl-3-ethylsuccinate, diethyl 2-cyano-2-isohexyl-3-n-propylsuccinate, diethyl 2-cyano-2-isohexyl-3-isopropyl succinate, diethyl 2-cyano-2-isohexyl-3-n-butylsuccinate, diethyl 2-cyano-2-isohexyl-3-isobutyl succinate, diethyl 2-cyano-2-isohexyl-3-n-pentylsuccinate, diethyl 2-cyano-2-isohexyl-3-isopentylsuccinate, diethyl 2-cyano-2-isohexyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isohexyl-3-n-hexylsuccinate.
The molar ratio of the internal electron donor to magnesium in the alkoxy magnesium particles is (0.005-10) 1, preferably (0.01-2) 1.
As a specific embodiment of the present invention, the first titanium-containing halide is represented by formula (VI):
TiX n(OR10)4-n (VI)
In the formula (VI), X is halogen, R 10 is C 1-C20 alkyl, and n is an integer of 0-4;
The molar ratio of the first titanium-containing halide to magnesium in the magnesium alkoxide particles is from (0.5 to 100): 1, preferably from (1 to 50): 1.
In a second aspect, the present invention provides a process for the preparation of said Ziegler-Natta catalyst component comprising the steps of:
s1: suspending the magnesium alkoxide particles in an inert diluent to form a suspension,
S2: contacting the suspension obtained in the step S1 with a first titanium-containing halide, a carboxylate electron donor compound, a polyol ester compound and an internal electron donor to obtain a solid dispersion system, and reacting to obtain a mother solution;
S3: filtering, washing and drying the mother liquor obtained in the step S2 to obtain the solid catalyst component.
As a specific embodiment of the present invention, the magnesium alkoxide particles in the step S1 are dispersed by using an inert organic solvent to obtain a magnesium alkoxide suspension; adding a first titanium-containing halide and an alcohol compound into the alkoxy magnesium suspension to obtain treated alkoxy magnesium particles; the suspension in step S1 is preferably a suspension containing titanium alkoxymagnesium.
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 third aspect, the present invention provides a catalyst for the polymerization of olefins comprising the reaction product of:
(1) A catalyst component according to claims 1 to 6 or a catalyst component obtained by the production process according to claim 7;
(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, C 1-C20 alkyl and C 6-C20 aryl; x' is halogen, and m is an integer of 1-3.
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 independently selected from any one of halogen, hydrogen atom, alkyl of C 1-C20, cycloalkyl of C 3-C20, aryl of C 6-C20 and halogenated alkyl of C 1-C20, and R 6 is selected from any one of alkyl of C 1-C20, cycloalkyl of C 3-C20, aryl of C 6-C20 and halogenated alkyl 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 fourth 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 third 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 propylene polymerization catalyst obtained by the invention has large particle size, uniform distribution, high polymerization activity, slow activity decay, and the obtained polymer has high isotactic index, wide molecular weight distribution and good fluidity. The catalyst is suitable for a multi-kettle reaction process with prepolymerization in industrial application, and has long residence time, and has wide application prospect.
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.
4. The method for testing the Isotactic Index (II) of the polymer comprises the following steps: after 2 g of the dried polymer sample was placed in an extractor and extracted with boiling heptane for 6 hours, the residue was dried to constant weight and the isotactic index was calculated by the following formula: isotactic index II = mass of polymer after extraction/2 x 100%.
Examples 1 to 9
Examples 1-9 provide Ziegler-Natta catalyst components and methods of making the same, olefin polymerization catalysts and olefin polymerization processes, with the following details:
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 the solid catalyst component: 10g of the above-mentioned alkoxy magnesium particles are suspended in 50ml of toluene, then 0.5ml of titanium tetrachloride is added, the temperature is slowly raised to 80 ℃, a certain amount of higher alcohol with carbon number more than 20 is added, stirring is carried out for 10 minutes, 1.5ml of carboxylic ester compound (di-n-butyl phthalate DNBP is selected here to illustrate the performance of the example, but not limited to the compound) is added as an internal electron donor, stirring is carried out for 5 minutes, and then the temperature is reduced to 25 ℃, so that a suspension X is prepared for later use. 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 adding 30mL of mixed solution of titanium tetrachloride and 120mL of toluene, heating to 110 ℃, dropwise adding a certain amount of dihydric alcohol ester compound (see table 1), stirring for 1 hour, and filtering and pressing the liquid cleanly; 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 1 to 3 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, 438ml of ethanol and 12ml of isooctanol were added to the reactor, 6g of elemental iodine was added to dissolve the same, then 32g of magnesium powder was added 2 times, stirring was started, and then the temperature was raised until the reflux temperature of the reaction system was reached, and the reaction was allowed to proceed until completion, i.e., no more hydrogen was discharged. Then washing and drying are carried out.
Solid catalyst component: example 1 was repeated except that the diol ester compound was not added.
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, 438ml of ethanol and 12g of 1-behenyl alcohol were added to the reactor, 6g of magnesium chloride was added to dissolve the mixture, then 32g of magnesium powder was 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 completed, i.e., no more hydrogen gas was discharged. Then washing and drying are carried out.
Solid catalyst component: example 1 was repeated except that the diol ester compound was not added.
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-behenyl alcohol 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 magnesium powder with the total amount of 6g for 2 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 26g of magnesium powder in total amount for 3 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.
Solid catalyst component: example 1 was repeated except that the carboxylic acid ester compound was not added.
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
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As can be seen from the data in tables 1 and 2, the specific composition of the magnesium alkoxide carrier prepared by the invention has large particle size, narrow distribution and composition. The prepared catalyst has uniform size, high polymerization activity, long activity period and high isotactic index when propylene polymerization is carried out. Is beneficial to developing long-period high-rigidity brand products on a large propylene polymerization device with long catalyst residence time. The catalyst has wide application prospect.
Examples 10 to 17
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 amounts and results of the raw materials are shown in Table 3.
Preparation of the solid catalyst component: 10g of the alkoxy magnesium particles are taken and suspended in 50ml of toluene, then 0.5ml of titanium tetrachloride is added, the temperature is slowly raised to 80 ℃, a certain amount of higher alcohol with carbon number more than 20 is added, the mixture is stirred for 10 minutes, the temperature is reduced to 25 ℃, and a suspension X is prepared for later use. In a 300mL reaction kettle repeatedly replaced by high-purity nitrogen, 10mL of toluene and 90mL of titanium tetrachloride are added, the temperature is raised to 60 ℃, the suspension X is added, the temperature is raised to 110 ℃, the temperature is kept for 2 hours, and then the liquid is subjected to filter pressing cleanly. Then adding 30mL of mixed solution of titanium tetrachloride and 120mL of toluene, heating to 100 ℃, dropwise adding a certain amount of cyano succinate compound as an internal electron donor (see table 1), stirring for 1 hour, and filtering and pressing the liquid cleanly; 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 3.
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 1 to 3 hours, stirring was stopped, unpolymerized propylene monomer was removed, and the polymer was collected and tested. The specific data are shown in Table 3.
TABLE 3 data on the preparation and evaluation of the supports and catalysts corresponding to examples 10-17
Comparative example 4
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, 6g of elemental iodine is added to dissolve the isooctanol, then 32g of magnesium powder is added for 2 times, 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.
Solid catalyst component: example 10 was repeated except that di-n-butyl phthalate (DNBP) was added instead of the cyano succinate compound.
Polymerization of propylene: as in example 10.
The specific data are shown in Table 4.
Comparative example 5
Preparation of an alkoxy magnesium carrier: in the reactor with stirrer, reflux condenser, thermometer and burette were installed. After sufficient displacement with nitrogen, 440ml of ethanol and 10g of 1-hexacosanol were added to the reactor, 5g of magnesium chloride was added to dissolve, then 32g of magnesium powder was 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.
Solid catalyst component: example 10 was repeated except that di-n-butyl phthalate (DNBP) was added instead of the cyano succinate compound.
Polymerization of propylene: as in example 10.
The specific data are shown in Table 4.
Comparative example 6
Preparation of magnesium alkoxide particles: in the reactor with stirrer, reflux condenser, thermometer and burette were installed. After sufficient displacement with nitrogen, 32ml of ethanol having a water content of less than 200ppm and 68g of 1-octacosanol 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.
Solid catalyst component: example 10 was repeated except that di-n-ethyl phthalate (DEP) was added instead of the cyano succinate compound.
Polymerization of propylene: as in example 10.
The specific data are shown in Table 4.
Table 4 data on support and catalyst preparation and evaluation corresponding to comparative examples 4-6
As can be seen from the data in tables 3 and 4, 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 uniform size, high polymerization activity, long activity period and wide molecular weight distribution when propylene polymerization is carried out. Is beneficial to developing the product with long period and wide molecular weight distribution on a large propylene polymerization device with long catalyst residence time. 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 ziegler-natta catalyst component comprising the following components and/or reaction products thereof:
A) Particles of magnesium alkoxide;
b) A first titanium-containing halide;
C) Carboxylic acid ester electron donor compounds;
D) A polyol ester compound;
e) An internal electron donor.
2. The ziegler-natta catalyst component according to claim 1 wherein said magnesium alkoxide particles comprise the reaction product of: magnesium powder, mixed alcohol a, mixed alcohol b and halogenating agent;
the average particle size of the magnesium powder is less than 360 mu m, preferably 300-100 mu m; and/or the number of the groups of groups,
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; the mixed alcohol a is a mixture of ethanol and the alcohol compound with the carbon number 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%; 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%; and/or the number of the groups of groups,
The mol ratio of the mixed alcohol a to the magnesium powder is (2-50): 1, preferably (2.5-18): 1; and/or the number of the groups of groups,
The mol ratio of the mixed alcohol b to the magnesium powder is (2-50): 1, preferably (2.5-18): 1; and/or the number of the groups of groups,
The halogenating agent is halogen simple substance and/or inorganic halide; and/or the number of the groups of groups,
The molar ratio of the halogenating agent to magnesium powder is (0.0002-0.2): 1, preferably (0.0025-0.05): 1, calculated on halogen atom;
the magnesium alkoxide particles further include a second titanium-containing halide treatment, and an alcohol treatment;
the second titanium-containing halide has a structure as shown in formula (I):
(R 1O)aTi(OR2)b(OR3)cXd formula (I)
In the formula (I), R 1、R2 and R 3 are the same or different and are selected from H and alkyl, especially C1-C10 alkyl, X is selected from chlorine, bromine and iodine, a, b and C are independently integers of 0-3, d is independently an integer of 1-4, and a+b+c+d=4;
Preferably, the second 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, their isomers;
the weight ratio of the second titanium-containing halide to the alkoxy magnesium is (0.001-5) 1, preferably (0.002-2) 1;
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;
Preferably, the alcohol compound is an alcohol compound with a carbon number of more than 20, and the alcohol compound with a carbon number of more than 20 is a monohydric alcohol (or phenol) or a polyhydric alcohol (or phenol) which is linear or branched; more preferably, it comprises: 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;
The weight ratio of the alcohol compound to the alkoxy magnesium is (0.001-5): 1, preferably (0.002-2): 1.
3. The Ziegler-Natta catalyst component according to claim 1 or 2, characterized in that said carboxylic acid ester electron donor compound is selected from among benzoic acid monoesters or phthalic acid ester 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 electron donor compound to magnesium in the alkoxymagnesium particles is (0.005-10): 1, preferably (0.01-2): 1.
4. A Ziegler-Natta catalyst component according to any of claims 1-3, wherein said polyol ester compound is selected from the group consisting of the glycol ester compounds of formula (IV),
In the formula (IV), R 1-R2 are the same or different and are each independently a substituted or unsubstituted straight-chain C1-C20 alkyl group, a substituted or unsubstituted branched-chain C3-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 alkylaryl group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C2-C10 alkylene group or a substituted or unsubstituted C10-C20 condensed ring aryl group;
R 3-R8 are identical or different and are each independently hydrogen, halogen, substituted or unsubstituted, straight-chain C1-C20-alkyl, substituted or unsubstituted, branched C3-C20-alkyl, substituted or unsubstituted, C3-C20-cycloalkyl, substituted or unsubstituted, C6-C20-aryl, substituted or unsubstituted, C7-C20-alkylaryl, substituted or unsubstituted, C7-C20-arylalkyl, substituted or unsubstituted, C2-C10-alkylene or substituted or unsubstituted, C10-C20-fused-ring aryl; or at least one of R 3-R6 is cyclic with at least one of R 7-R8;
Preferably, the polyol ester compound is at least one of 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 1, 3-butanediol dimethylbenzoate, 2-methyl-1, 3-butanediol diisochlorobenzoate, 2, 3-dimethyl-1, 3-butanediol dibenzoate, 1, 3-pentanediol dipivalate, 2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol benzoic cinnamate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, and the like, preferably at least one of 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 2, 4-pentanediol dibenzoate;
The molar ratio of the polyol ester electron donor compound to magnesium in the magnesium alkoxide particles is (0.01-5): 1, preferably (0.02-2): 1.
5. The ziegler-natta catalyst component according to any of claims 1 to 4 wherein said internal electron donor is a cyano succinate compound of formula (V);
In formula (V), R 1 'and R 2', which may be the same or different, are each independently selected from hydrogen, C 1-C14 straight-chain alkyl, C 3-C10 branched alkyl, C 3-C10 cycloalkyl, C 6-C10 aryl, C 7-C10 alkylaryl, and C 7-C10 arylalkyl; r 3 'and R 4', which may be the same or different, are each independently selected from the group consisting of C 1-C14 straight-chain alkyl, C 3-C10 branched-chain alkyl, C 3-C10 cycloalkyl, C 6-C20 aryl, C 7-C20 alkylaryl, and C 7-C20 arylalkyl;
Preferably, R 1 'and R 2' are each independently selected from hydrogen, C 1-C8 straight chain alkyl and C 3-C8 branched alkyl;
Preferably, R 3 'and R 4' are each independently selected from C 1-C6 straight chain alkyl and C 3-C6 branched alkyl;
the molar ratio of the internal electron donor to magnesium in the alkoxy magnesium particles is (0.005-10) 1, preferably (0.01-2) 1.
6. The ziegler-natta catalyst component according to any of claims 1 to 5 wherein said first titanium-containing halide is represented by formula (VI):
TiX n(OR10)4-n (VI)
In the formula (VI), X is halogen, R 10 is C 1-C20 alkyl, and n is an integer of 0-4;
The molar ratio of the first titanium-containing halide to magnesium in the magnesium alkoxide particles is from (0.5 to 100): 1, preferably from (1 to 50): 1.
7. A process for the preparation of a ziegler-natta catalyst component according to any of claims 1 to 6 comprising the steps of:
s1: suspending the magnesium alkoxide particles in an inert diluent to form a suspension,
S2: contacting the suspension obtained in the step S1 with a first titanium-containing halide, a carboxylate electron donor compound, a polyol ester compound and an internal electron donor to obtain a solid dispersion system, and reacting to obtain a mother solution;
S3: filtering, washing and drying the mother liquor obtained in the step S2 to obtain the solid catalyst component.
8. A catalyst for the polymerization of olefins, characterized in that the catalyst comprises the reaction product of:
(1) A catalyst component according to claims 1 to 6 or a catalyst component obtained by the production process according to claim 7;
(2) An organoaluminum compound;
(3) Optionally, an external electron donor compound.
9. The catalyst for olefin polymerization according to claim 8, 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, and m is an integer of 1-3.
10. The catalyst for olefin polymerization according to claim 8 or 9, wherein 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 independently selected from any one of halogen, hydrogen atom, alkyl of C 1-C20, cycloalkyl of C 3-C20, aryl of C 6-C20 and halogenated alkyl of C 1-C20, and R 6 is selected from any one of alkyl of C 1-C20, cycloalkyl of C 3-C20, aryl of C 6-C20 and halogenated alkyl of C 1-C20; p and q are integers from 0 to 3, respectively, and p+q <4.
11. The catalyst for the polymerization of olefins according to any of the claims 8 to 10 characterized in that the molar ratio of aluminium in the organoaluminium compound to titanium in the catalyst component is in the range of (5 to 5000): 1, preferably in the range of (20 to 1000): 1, more preferably in the range of (50 to 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.
12. 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 the catalyst of any one of claims 8-11 under olefin polymerization conditions.
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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