CN117924566A - Solid catalyst component for olefin polymerization, preparation method and application thereof - Google Patents
Solid catalyst component for olefin polymerization, preparation method and application thereof Download PDFInfo
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- CN117924566A CN117924566A CN202211321504.4A CN202211321504A CN117924566A CN 117924566 A CN117924566 A CN 117924566A CN 202211321504 A CN202211321504 A CN 202211321504A CN 117924566 A CN117924566 A CN 117924566A
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- China
- Prior art keywords
- catalyst component
- solid catalyst
- polymerization
- olefin
- succinate
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- Pending
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 142
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 42
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 239000011777 magnesium Substances 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 24
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920013639 polyalphaolefin Polymers 0.000 claims abstract description 16
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 145
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 145
- -1 polyethylene Polymers 0.000 claims description 85
- 238000000034 method Methods 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000004743 Polypropylene Substances 0.000 claims description 42
- 229920001155 polypropylene Polymers 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 25
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 22
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 239000004711 α-olefin Substances 0.000 claims description 16
- 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 14
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 12
- 239000012442 inert solvent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 9
- WGFNXLQURMLAGC-UHFFFAOYSA-N diethyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCC WGFNXLQURMLAGC-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 8
- 150000002681 magnesium compounds Chemical class 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 6
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-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
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 claims description 3
- DJHQJVJMROPIHP-UHFFFAOYSA-N diethyl 2-ethyl-2-methylbutanedioate Chemical compound CCOC(=O)CC(C)(CC)C(=O)OCC DJHQJVJMROPIHP-UHFFFAOYSA-N 0.000 claims description 3
- XDPQVTCYKCEWAT-UHFFFAOYSA-N dimethyl 2,2-dimethylbutanedioate Chemical compound COC(=O)CC(C)(C)C(=O)OC XDPQVTCYKCEWAT-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229940095102 methyl benzoate Drugs 0.000 claims description 3
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 claims description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 150000003900 succinic acid esters Chemical class 0.000 claims description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims 8
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 14
- 238000003860 storage Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 78
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 37
- 239000007788 liquid Substances 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 14
- 239000012265 solid product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 12
- 229910052801 chlorine Inorganic materials 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 9
- 102220043159 rs587780996 Human genes 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000007942 carboxylates Chemical class 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NTHKCSDJQGWPJY-UHFFFAOYSA-N CCCC[SiH](OC)OC Chemical compound CCCC[SiH](OC)OC NTHKCSDJQGWPJY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- WNVMVIYFKFGESM-UHFFFAOYSA-N bis(2-methylpropyl) 2,3-di(propan-2-yl)butanedioate Chemical compound CC(C)COC(=O)C(C(C)C)C(C(C)C)C(=O)OCC(C)C WNVMVIYFKFGESM-UHFFFAOYSA-N 0.000 description 1
- RQRAFBDBIOAJDS-UHFFFAOYSA-N bis(2-methylpropyl) 2-ethyl-2-methylbutanedioate Chemical compound CC(C)COC(=O)C(C)(CC)CC(=O)OCC(C)C RQRAFBDBIOAJDS-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- VTCHFSNTCCVHRC-UHFFFAOYSA-N dibutyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCCCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCCCC VTCHFSNTCCVHRC-UHFFFAOYSA-N 0.000 description 1
- YPENMAABQGWRBR-UHFFFAOYSA-N dibutyl(dimethoxy)silane Chemical compound CCCC[Si](OC)(OC)CCCC YPENMAABQGWRBR-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- AMMWFYKTZVIRFN-UHFFFAOYSA-N sodium 3-hydroxy-4-[(1-hydroxynaphthalen-2-yl)diazenyl]-7-nitronaphthalene-1-sulfonic acid Chemical compound [Na+].C1=CC=CC2=C(O)C(N=NC3=C4C=CC(=CC4=C(C=C3O)S(O)(=O)=O)[N+]([O-])=O)=CC=C21 AMMWFYKTZVIRFN-UHFFFAOYSA-N 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JAYPHJBLPAEMEX-UHFFFAOYSA-N trimethoxy(2-methylpentan-2-yl)silane Chemical compound CCCC(C)(C)[Si](OC)(OC)OC JAYPHJBLPAEMEX-UHFFFAOYSA-N 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the field of catalysts for olefin polymerization, and discloses a solid catalyst component for olefin polymerization, a preparation method and application thereof. The solid catalyst component comprises magnesium element, titanium element, halogen, poly alpha-olefin and carboxylic ester, wherein the carboxylic ester is at least one of mono-aliphatic carboxylic ester, di-aliphatic carboxylic ester, mono-aromatic carboxylic ester and di-aromatic carboxylic ester, and the Ti2p 3/2 electron binding energy of the titanium element is 456.10ev-454.90ev. The solid catalyst component is used for olefin polymerization and has the characteristics of slow activity decay along with the storage time and low content of obtained polymer fine powder.
Description
Technical Field
The invention relates to the field of catalysts for olefin polymerization, in particular to a solid catalyst component for olefin polymerization, a preparation method and application thereof.
Background
The Ziegler-Natta type spherical catalyst is widely applied to a loop polypropylene process device, is used for producing propylene homopolymers, propylene/ethylene (or butylene) random copolymers and impact copolymers, and has the characteristics of high polymerization activity, high stereospecificity, high polymer particle shape regularity and the like. The spherical catalyst is also used in gas phase polypropylene and polyethylene processes with a prepolymerization unit, such as SHPERIZONE and SHPERILENE process units, for the production of polypropylene and polyethylene. Although these process units are provided with a prepolymerization operation unit, the catalyst particles and polymer particles are broken up during the production of the resin, resulting in the presence of a certain amount of fines content in the polymer, especially in the production of propylene homopolymers with high melt flow index (MFR), which has a larger fines content, which affects the stability and long-term operation of the unit. Polypropylene units without a prepolymerization unit, such as UNIPOL process units, are not compatible with Ziegler-Natta type spherical catalysts because the catalyst or polymer particles are almost totally broken up during the polymerization process, producing a large amount of fines.
US9453088B2 discloses a prepolymerized catalyst for olefin polymerization, wherein the prepolymerized catalyst is a catalyst component which has an average particle diameter of less than 30 mu m, a prepolymerization multiple of less than 50g polymer/g catalyst and contains two electron donors of 1, 3-diether and aromatic ester, and the preparation method comprises the steps of firstly preparing a spherical catalyst containing two electron donors of 1, 3-diether and aromatic ester, and then prepolymerizing with olefin with 2-10 carbon atoms to obtain the prepolymerized catalyst. CN1421468a discloses a method for polymerizing or copolymerizing propylene, which is to prepolymerize Ziegler-Natta catalyst with ethylene or alpha-olefin at-10 ℃ to 80 ℃, the prepolymerization multiple is controlled to be 6-50000 times, and then propylene polymerization is carried out. US7329714B2 discloses a process for the prepolymerization of polypropylene comprising prepolymerizing a catalyst of the Ziegler-Zatta type with propylene or 4-methyl-1-pentene at a temperature of from 0 to 40 ℃ followed by propylene polymerization.
However, in the above-mentioned preparation method of the prepolymerized catalyst, when ethylene is used as a prepolymerized monomer to prepare the prepolymerized catalyst, the catalyst inevitably has a crushing phenomenon, and the content of polymer fine powder is also high when an olefin polymerization reaction is carried out; the pre-polymerized catalyst prepared by taking propylene or other alpha-olefins as pre-polymerized monomers has the advantages of quicker activity decay and lower commercial value along with the extension of the storage time. The polymerization activity of the prepolymerized catalyst prepared by either ethylene prepolymerization or propylene prepolymerization is attenuated along with the extension of the storage time, and the polymerization activity is unstable and cannot meet the requirements of industrial application.
Disclosure of Invention
Therefore, the invention aims to overcome the difficult problem that the storage time of the existing Ziegler-Zatta type prepolymerized catalyst is prolonged and the polymerization activity is fast in decay by changing the composition structure of the active center of the prepolymerized catalyst, and provides a solid catalyst component for olefin polymerization, a preparation method and application thereof.
According to a first aspect of the present invention, there is provided a solid catalyst component for olefin polymerization comprising magnesium element, titanium element, halogen, poly-alpha-olefin and carboxylic acid ester, wherein the carboxylic acid ester is at least one selected from the group consisting of mono-aliphatic carboxylic acid ester, di-aliphatic carboxylic acid ester, mono-aromatic carboxylic acid ester and di-aromatic carboxylic acid ester, and the Ti2p 3/2 electron binding energy of the titanium element is 456.10ev-454.90ev.
According to a second aspect of the present invention, there is provided a process for the preparation of a solid catalyst component for the polymerization of olefins, the process comprising the steps of:
(1) Contacting catalyst component A, alkyl aluminum and an external electron donor compound in the presence of an inert solvent; the catalyst component A contains carboxylic ester, titanium element, magnesium element and halogen, wherein the carboxylic ester is at least one of aliphatic carboxylic ester, aromatic carboxylic ester and succinate compound;
(2) Adding alpha-olefin into the reaction system obtained in the step (1) to carry out polymerization reaction;
(3) Removing unreacted alpha-olefin in the step (2), and adding hydrogen into the obtained reaction system to react;
The mass ratio of the alpha-olefin to the amount of the catalyst component A is 0.04:1-10:1, controlling the addition amount of the hydrogen to maintain the reaction pressure between 0.01 and 1.0MPa.
According to a third aspect of the present invention, there is provided a solid catalyst component prepared by the preparation method according to the second aspect of the present invention.
According to a fourth aspect of the present invention there is provided a catalyst for the polymerisation of olefins comprising a solid catalyst component according to the first or third aspect of the present invention, an alkyl aluminium and optionally an external electron donor compound or reaction product thereof.
According to a fifth aspect of the present invention there is provided a process for the polymerisation of olefins, the process comprising: the olefin is polymerized in the presence of the catalyst for olefin polymerization.
The solid catalyst component belongs to Ziegler-Zatta type prepolymerized catalyst, is used for olefin polymerization, has the advantage of slow polymerization activity attenuation along with the extension of storage time, and is not only suitable for olefin polymerization devices with prepolymerized operation units, but also suitable for polyolefin devices without prepolymerized operation units. In addition, the olefin polymer obtained by using the solid catalyst component for catalyzing olefin polymerization has better regularity and lower content of fine powder in the polymer.
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.
According to a first aspect of the present invention, there is provided a solid catalyst component for olefin polymerization comprising magnesium element, titanium element, halogen, poly-alpha-olefin and carboxylic acid ester, wherein the carboxylic acid ester is at least one selected from the group consisting of mono-aliphatic carboxylic acid ester, di-aliphatic carboxylic acid ester, mono-aromatic carboxylic acid ester and di-aromatic carboxylic acid ester, and the Ti2p 3/2 electron binding energy of the titanium element is 456.10ev-454.90ev.
The solid catalyst component provided according to the present invention, wherein the polyalphaolefin is selected from one or more of polyethylene, polypropylene, polybutene, polyoctene and polyisopentene, preferably polypropylene.
The solid catalyst component provided by the invention, wherein the content of magnesium element in the solid catalyst component is 1-18% by weight based on the total weight of the solid catalyst component; the content of titanium element is 0.1-3.5 wt%; halogen content of 2-65 wt%; the content of poly alpha-olefin is 0.1-89 wt%; the content of the carboxylic acid ester is 0.6-15 wt%.
In the present invention, the halogen is selected from one or more of fluorine, chlorine, bromine and iodine, preferably chlorine.
In some embodiments, the solid catalyst component comprises 0.1 to 89 weight percent polyalphaolefin, 0.1 to 3.5 weight percent titanium element, 1 to 18 weight percent magnesium element, 2 to 65 weight percent chlorine element, and 0.6 to 15 weight percent internal electron donor compound, based on the total mass of the solid catalyst component. Preferably, the poly alpha-olefin is contained in an amount of 1 to 50 wt%, the titanium element is contained in an amount of 0.5 to 2.5 wt%, the magnesium element is contained in an amount of 1 to 16 wt%, the chlorine element is contained in an amount of 2 to 55 wt%, and the internal electron donor compound is contained in an amount of 1 to 10 wt%, based on the total weight of the solid catalyst component.
In some embodiments, the polyalphaolefin is present in an amount of 9 to 35 weight percent, the titanium element is present in an amount of 2 to 2.5 weight percent, the magnesium element is present in an amount of 11 to 16 weight percent, the chlorine element is present in an amount of 35 to 55 weight percent, and the internal electron donor compound is present in an amount of 6 to 9 weight percent, based on the total weight of the solid catalyst component.
The solid catalyst component provided by the invention is spherical solid particles.
Preferably, the solid catalyst component has an average particle size D 50 to 150 μm. For example, the average particle size D 50 of the solid catalyst component may be 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 100 μm, 120 μm, 150 μm or a range consisting of them. In particular, the solid catalyst component may have an average particle size D 50 of 20 to 80 μm.
In the present invention, the average particle size D 50 was measured using a Master Sizer 2000 laser particle Sizer (manufactured by Malvern Instruments Ltd).
The solid catalyst component provided by the invention, wherein Ti2p electron binding energy of titanium element is measured by an X-ray photoelectron spectrometer (XPS). Specifically, a sample is stuck on a double-sided adhesive tape in a glove box, compacted and then stuck in a sensitive sample protection table for sealing and preservation, then the sample is quickly transferred into a sample preparation chamber of XPS for vacuumizing, a sealing cover of the sensitive sample protection table is opened after the vacuum degree of the preparation chamber is reduced to below 10 -6 bar, and the sample is transferred into an analysis chamber for XPS test after the vacuum degree of the preparation chamber is reduced to below 10 -7 bar. XPS uses a monochromator and an Al target (step size 0.05 eV) and charge correction was performed with a neutralization gun to sample over-neutralization. The charge of the unpolymerized catalyst was corrected based on the C1s of the alkyl carbon in the internal electron donor being 284.80 eV. The charge of the prepolymerized catalyst was corrected based on the C1s of polypropylene or polyethylene contained in the catalyst being 284.80 eV.
In some embodiments, the titanium element has a Ti2p 3/2 electron binding energy of 455.40eV-455.55eV, e.g., a Ti2p 3/2 electron binding energy of 455.42eV, 455.44eV, 455.45eV, 455.46eV, 455.47eV, 455.50eV, or 455.54 eV.
In some embodiments, the titanium element has a Ti2p 3/2 electron binding energy of 458.97eV-459.25eV and/or 457.53-458.00eV in addition to a Ti2p 3/2 electron binding energy of 456.10eV-454.90eV, preferably 455.40eV-455.55 eV.
The solid catalyst component provided by the invention is characterized in that the carboxylic acid ester is aliphatic carboxylic acid ester and/or aromatic carboxylic acid ester, and specifically at least one of mono-aliphatic carboxylic acid ester, di-aliphatic carboxylic acid ester, mono-aromatic carboxylic acid ester and di-aromatic carboxylic acid ester.
In the present invention, the aliphatic carboxylic acid ester means a carboxylic acid ester prepared from a mono (or di) aliphatic carboxylic acid and an aliphatic monohydric alcohol or an aromatic monohydric alcohol, and the aromatic carboxylic acid ester means a carboxylic acid ester prepared from a mono (or di) aromatic carboxylic acid and an aliphatic monohydric alcohol or an aromatic monohydric alcohol. Preferably, the carboxylic acid ester is selected from one or more of benzoate compounds, phthalate compounds and succinate compounds.
For example, the benzoate may be selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate.
For example, the phthalate compound may be selected from one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, and di-n-octyl phthalate.
For example, the succinate compound may be selected from one or more of diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate and diethyl 2-ethyl-2-methylsuccinate.
According to the solid catalyst component provided by the invention, the titanium content can be measured according to a colorimetric method. Specifically, 0.2-0.5g of the sample is dissolved by 50mL of 2N H 2SO4, the upper layer floating material is filtered, and clear liquid is taken for colorimetric; taking 2N H 2SO4 solution as blank, measuring the absorbance E1 of the cuvette with the thickness of 1cm under the wavelength of 410 mu m, then dripping 1 drop of 30% H 2O2, shaking uniformly, measuring the absorbance E2 of the cuvette, and calculating the titanium content Ti (%) according to the following formula:
Ti(％)＝[(E2-E1)×100)/(K·L·W·100)]×100
wherein: w-sample weight (g); l-cuvette thickness (cm); k-ratio extinction coefficient; e1-blank absorbance; e2-absorbance of sample.
The magnesium content can be measured by EDTA titration. Specifically, 0.2-0.5g of the sample is put into a 250mL conical flask, 20-30mL of 2N H 2SO4 solution is added for dissolution, 20mL of triethanolamine (1+2) standard solution is added, pH=10 is regulated by 20% NaOH solution, shaking is carried out, 10mL of buffer solution with pH=10 is added, 6 drops of H 2O2 with concentration of 30% and 30-50mL of distilled water are added, a small amount of chrome black T indicator is added, shaking is carried out uniformly, 0.02N EDTA solution is used for titration until the end point of changing from purple red to blue (disappearance of purple light), and the magnesium content Mg (%) is calculated according to the following formula:
Mg(％)＝[(VE·NE×24.31)/(G·1000)]×100
Wherein: g—sample mass (G); ve—the amount of EDTA consumed (mL); NE-EDTA solution equivalent; 24.31 atomic weight of magnesium.
The chlorine content can be measured according to silver nitrate titration. Specifically, weighing 0.04-0.1g of sample into a conical flask, adding 20mL of 2N H 2SO4 solution, and standing for 30 minutes; after multiple washes with distilled water, 20-30mL of 0.1N AgNO 3 solution was added dropwise, 3mL of 1:1HNO 3 solution was added, and the excess AgNO 3 solution was titrated with 0.1N NH 4 CNS standard solution. Titration to brick red did not disappear for two seconds as an end point, and chlorine content Cl (%) was calculated according to the following formula:
Cl(％)＝[(V1-V2×D)×N1×35.45/(G·1000)]×100
Wherein: v 1—AgNO3 amount of solution (mL); v 2 —amount of NH 4 CNS solution consumed (mL); volume ratio of D-AgNO 3/NH4 CNS solution; equivalent concentration of N 1—AgNO3; g-mass of sample (G); 35.45 atomic weight of chlorine.
The method for testing the content of the poly alpha-olefin in the solid catalyst component comprises the following steps: weighing a certain amount of samples of the (M1), dissolving the samples with ethanol and dilute hydrochloric acid, drying insoluble matters in vacuum at 80 ℃ to obtain solid matters (M2), tabletting 0.2g of the solid matters, measuring the poly alpha-olefin content (C1) of the solid matters by using an infrared spectrometer, and respectively calculating the mass percent of the poly alpha-olefin in the solid catalyst component according to the following formula:
CA＝M2×C1/M1
C A is the mass percent of poly-alpha-olefin in the solid catalyst component, M1 and M2 are the mass (g) of the sample and dry solids, respectively, and C1 is the mass percent of poly-alpha-olefin in the dry solids.
The method for testing the content of carboxylic ester in the solid catalyst component comprises the following steps: the sample was dissolved with ethyl acetate and hydrochloric acid solution (concentration: 2 mol/L), and extracted to obtain a carboxylic acid ester, the content of which was analyzed using a conventional liquid chromatograph.
The solid catalyst component provided by the invention further comprises aluminum alkyl and an external electron donor. The types and the contents of the aluminum alkyl and the external electron donor can be selected by referring to the existing olefin prepolymerization catalyst.
In addition, the solid catalyst component of the present invention may contain other components, such as an inert solvent, in addition to the above components.
According to a second aspect of the present invention, there is provided a process for the preparation of a solid catalyst component for the polymerization of olefins, the process comprising the steps of:
(1) Contacting catalyst component A, alkyl aluminum and an external electron donor compound in the presence of an inert solvent; the catalyst component A contains carboxylate, titanium element, magnesium element and halogen;
(2) Adding alpha-olefin into the reaction system obtained in the step (1) to carry out polymerization reaction;
(3) Removing the unreacted alpha-olefin in the step (2), and adding hydrogen into the obtained reaction system to react.
The preparation method provided by the invention further comprises the following steps: (4) And (3) sequentially carrying out solid-liquid separation and drying treatment on the system obtained in the step (3) to obtain the solid catalyst component. In some preferred embodiments, the drying process is performed by vacuum drying; the drying conditions include: the temperature is 40-50deg.C, and the time is 30-60min. In the present invention, the vacuum drying may be performed by a conventional vacuum pump, and there is no particular requirement for the present invention.
According to the production method of the present invention, in the step (1), the aluminum alkyl and the external electron donor compound may be selected with reference to the existing olefin prepolymerization catalyst, and the present invention is not particularly limited thereto.
Typically, the alkyl aluminum may be selected from one or more of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, and diethyl aluminum monochloride.
The external electron donor compound may be selected from one or more of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane and dicyclopentyldimethoxysilane.
In general, the molar ratio of the aluminum alkyl, the external electron donor compound and the catalyst component a used in terms of elemental titanium may be from 1 to 50:0.2-10:1. for example, the molar ratio of the aluminum alkyl, the external electron donor compound to the amount of the catalyst component A in terms of titanium element may be in the range of any numerical composition of the aluminum alkyl and the external electron donor compound in the ratio 1：0.2：1、5：0.2：1、10：0.2：1、15：0.2：1、20：0.2：1、30：0.2：1、40：0.2：1、50：0.2：1、15：0.3：1、15：0.5：1、15：1：1、15：2：1、15：3：1、15：4：1、15：5：1、15：20：1 or more.
According to the preparation method provided by the invention, the specific description of the carboxylic ester is as described in the first aspect of the invention, and is not repeated here.
According to the preparation method provided by the invention, in the step (1), the inert solvent can be selected by referring to the prior art. In general, the inert solvent may be selected from one or more of hexane, heptane and decane. The inert solvent is added in an amount such that the mass concentration of the catalyst component A in the inert solvent may be 5 to 50g/L.
The preparation method provided by the invention, wherein the conditions of the contact reaction comprise: the temperature may be 0-30 ℃, preferably 15-25 ℃; the time may be 1-30min, preferably 10-20min.
The preparation method provided by the invention, wherein in the step (2), the polymerization reaction conditions comprise: the temperature may be 0-50 ℃, preferably 15-25 ℃; the time may be 5-30min, preferably 10-20min.
In the present invention, after the polymerization reaction is completed, the unreacted α -olefin gas in step (2) is removed.
The preparation method provided by the invention, wherein in the step (3), the reaction conditions comprise: the temperature may be 0-50 ℃, preferably 15-25 ℃; the time may be 5-30min, preferably 10-20min.
The preparation method provided by the invention, wherein the step (3) further comprises a post-treatment step, and the post-treatment step generally comprises the following steps: filtering to remove liquid or optionally washing with hexane for 1-2 times to obtain solid product; the solid product is then dried under vacuum at 10-80 ℃ to obtain the solid catalyst component.
According to the preparation method provided by the invention, the alpha-olefin is preferably one or more selected from propylene, butene, octene and isoamylene, and the alpha-olefin is preferably propylene.
According to the preparation method provided by the invention, the mass ratio of the alpha-olefin to the dosage of the catalyst component A can be 0.04:1-10:1. for example, the mass ratio of the alpha-olefin to the amount of catalyst component a may be 0.04：1、0.05：1、0.08：1、0.1：1、0.2：1、0.3：1、0.4：1、0.5：1、0.6：1、0.7：1、0.8：1、0.9：1、1：1、2：1、3：1、4：1、5：1、6：1、7：1、8：1、9：1、10：1 or a range of compositions thereof.
According to the production method provided by the present invention, wherein the hydrogen gas in the step (3) is added to a reaction pressure of 0.01 to 1.0MPa, preferably 0.1 to 0.5MPa, more preferably 0.2 to 0.3MPa.
According to the preparation method provided by the invention, hydrogen can be added in the form of pure hydrogen or hydrogen mixed gas. Preferably, the hydrogen gas mixture is composed of hydrogen gas and an inert gas, and more preferably, the inert gas is selected from at least one of nitrogen, helium, neon, and argon. The invention has no special requirement on the concentration of the hydrogen in the hydrogen mixed gas, as long as the defined reaction pressure can be realized.
According to the preparation method provided by the present invention, wherein the catalyst component a can be prepared according to a conventional method of a main catalyst in an olefin polymerization catalyst in the art, the present invention is not particularly limited thereto, and for example, reference may be made to the methods disclosed in patent applications WO2012034357A1, WO2012097680A1 and patent nos. ZL03153152.0, ZL200410062291.3, ZL201310491641.7, ZL201310491393.6 and ZL 201310491648.9.
In the present invention, the catalyst component a may comprise or be the reaction product of titanium tetrachloride, a carrier, preferably a magnesium alkoxide carrier, a magnesium chloride alkoxide spherical carrier, or a spherical magnesium compound carrier, and an internal electron donor compound.
In the present invention, the average particle diameter of the carrier is 5 to 150. Mu.m, more preferably 20 to 80. Mu.m, still more preferably 30 to 60. Mu.m.
In some embodiments, the catalyst component a can be prepared by the methods disclosed in patents ZL03153152.0 and ZL 200410062291.3. More specifically, the support is a magnesium chloride alkoxide spherical support, and the catalyst component a is a reaction product of titanium tetrachloride, a spherical magnesium chloride alkoxide, and the internal electron donor compound such as a carboxylate.
The general formula of the spherical magnesium chloride alkoxide can be Mg (R 'OH) i(H2O)j, wherein R' is methyl, ethyl, n-propyl or isopropyl, i is 1.5-3.5, and j is 0-0.1.
The catalyst component A is prepared by a method comprising the following steps:
1) Reacting titanium tetrachloride with the magnesium chloride alkoxide spherical carrier for 20-120min at the temperature of minus 20 ℃ to 0 ℃ to obtain a mixture I;
2) Heating the mixture I to 100-120 ℃, adding the internal electron donor compound such as carboxylate in the heating process, and reacting for 20-200min at 100-120 ℃ to obtain a solid product II;
3) The solid product II was washed with titanium tetrachloride and hexane, respectively, and dried in vacuo.
In other embodiments, the catalyst component a may be prepared by the methods disclosed in patent WO2012034357A1 and WO2012097680 A1. More specifically, the carrier is an alkoxy magnesium carrier, and the catalyst component A is a reaction product of titanium tetrachloride, an alkoxy magnesium carrier and the internal electron donor compound in an inert solvent. The general formula of the alkoxy magnesium carrier is Mg (OEt) 2-k-l(OEH)k(OiPr)l, wherein Et is ethyl, EH is 2-ethylhexyl, iPr is isopropyl, and k and l are 0-0.5.
The catalyst component A can be prepared by the following steps: magnesium alkoxide is reacted with titanium tetrachloride and the internal electron donor compound, such as a carboxylate, in the presence of an inert solvent. The reaction temperature is generally-40 to 200 ℃, preferably-20 to 150 ℃; the reaction time is usually in the range of 1 minute to 20 hours, preferably 5 minutes to 8 hours. The solid obtained above is washed with an inert solvent, preferably toluene, to obtain a solid catalyst component. The washing is usually carried out for 1 to 24 hours, preferably 6 to 10 hours.
The solid catalyst component may be stored in a dry state or in an inert solvent.
In still other embodiments, the catalyst component a may be prepared by the methods disclosed in patents ZL201310491641.7, ZL201310491393.6, and ZL 201310491648.9. More specifically, the support is a spherical magnesium compound support, and the catalyst component a is a reaction product of titanium tetrachloride, a spherical magnesium compound support, and the internal electron donor compound, such as a carboxylate.
The spherical magnesium compound carrier is shown as a formula (3):
In formula (3), R 1 is a C 1-C12 linear or branched alkyl group; r 2 and R 3 are identical or different and are hydrogen or C 1-C5 linear or branched alkyl, wherein the hydrogen on the alkyl can be optionally substituted by halogen atoms; x is halogen; m is 0.1-1.9; n is 0.1-1.9; m+n=2.
The catalyst component A is prepared by a method comprising the following steps:
1) Reacting titanium tetrachloride with the spherical magnesium compound carrier for 20-120min at the temperature of minus 20 ℃ to 0 ℃ to obtain a mixture I;
2) Heating the mixture I to 100-120 ℃, adding the internal electron donor compound such as carboxylate in the heating process, and reacting for 20-200min at 100-120 ℃ to obtain a solid product II;
3) The solid product II was washed with titanium tetrachloride and hexane, respectively, and dried in vacuo.
The preparation method provided by the invention, wherein the vacuum drying conditions in the above operation comprise: the temperature is 40-50deg.C, and the time is 30-60min. In the present invention, the vacuum drying may be performed by a conventional vacuum pump, and there is no particular requirement for the present invention.
According to a third aspect of the present invention there is provided a solid catalyst component obtainable by the process according to the second aspect of the present invention.
According to a fourth aspect of the present invention there is provided a catalyst for the polymerization of olefins comprising a solid catalyst component according to the present invention, an alkyl aluminium and optionally an external electron donor compound or reaction product thereof.
The catalyst provided according to the invention, wherein the alkyl aluminum, the external electron donor compound and the respective contents can be selected according to the prior art.
In general, the alkyl aluminum may be selected from one or more of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, and diethyl aluminum monochloride.
The ratio of the molar amount of the aluminum alkyl in terms of aluminum element to the molar amount of the solid catalyst component in terms of titanium element may be 1 to 1000:1. for example, the ratio of the molar amount of the aluminum alkyl in terms of aluminum element to the molar amount of the solid catalyst component in terms of titanium element may be 1: 1.2: 1. 5: 1. 10: 1. 20: 1. 50: 1. 100: 1. 200: 1. 500: 1. 1000:1 or a range of compositions thereof.
In general, the external electron donor compound may be selected from at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and t-hexyltrimethoxysilane.
The ratio of the molar amount of the aluminum alkyl to the molar amount of the external electron donor compound to the silicon element may be 2 to 1000:1. for example, the ratio of the molar amount of the aluminum alkyl in terms of aluminum element to the molar amount of the external electron donor compound in terms of silicon element may be 2: 1. 5: 1. 10: 1. 20: 1. 50: 1. 100: 1. 200: 1. 500: 1. 1000:1 or a range of compositions thereof.
According to a fifth aspect of the present invention there is provided a process for the polymerisation of olefins, the process comprising: the olefin is subjected to a polymerization reaction in the presence of the catalyst for olefin polymerization according to the fourth aspect of the present invention.
The method provided by the invention, wherein the general formula of the olefin is CH 2 =chr, and R is hydrogen, alkyl of C 1-C6 or C 6-C10 aryl. Preferably, the olefin is selected from one or more of ethylene, propylene, butene, pentene and hexene.
The process according to the present invention, wherein the conditions of the polymerization reaction may be selected conventionally in the art, for example, the reaction temperature is 0 to 150 ℃, preferably the reaction temperature is 60 to 90 ℃, and the reaction pressure is normal pressure or higher.
Advantages of the technical solution of the present invention will be described in detail below by means of specific examples.
In the following examples and comparative examples,
The isotactic index of a polymer (polypropylene) refers to the mass percent of polypropylene insoluble in boiling n-heptane under the specified conditions, and is determined by heptane extraction (heptane boiling extraction for 6 hours), i.e., 2g of a dried polymer sample is taken, placed in an extractor and extracted with boiling heptane for 6 hours, after which the residue is dried to constant weight, and the ratio of the mass (g) of the obtained polymer to 2 is the isotactic index.
The melt index of the polymer was determined according to the method of ASTM D1238-99.
The particle size distribution of the polymer was screened through a standard sieve to calculate the mass percent of the fraction.
In the following embodiments, unless otherwise specified, the "vacuum" refers to the degree of vacuum achieved by a conventional vacuum pump.
The following preparation examples are given to illustrate the preparation of catalyst component A.
Preparation example 1
To a 3L glass reaction flask with stirring, 1.2L of titanium tetrachloride was added and cooled to-20℃and 100g of magnesium chloride alkoxide spherical carrier [ Mg (C 2H5OH)2.6 ] (average particle size D50=45 μm) was added under stirring, after reacting at-20℃for 0.5 hours, slowly heating to 120℃and adding 15g of diisobutylphthalate during heating, then reacting at 120℃for 0.5 hours, filtering off the liquid, adding 1L of titanium tetrachloride, after maintaining at 120℃for 2 hours, filtering off the liquid to obtain a solid product, washing the obtained solid product with hexane 5 times, and finally drying in vacuo to obtain catalyst component A (average particle size D50=40 μm, SPAN value 0.79), denoted as A-1.
Preparation example 2
To a 3L glass reaction flask with stirring, 1.2L of titanium tetrachloride was added and cooled to-20℃and 100g of magnesium chloride alkoxide spherical carrier [ Mg (C 2H5OH)2.6 ] (average particle size D50=45 μm) was added under stirring, after 0.5 hour reaction at-20℃the temperature was slowly raised to 120℃and 15g of diethyl 2, 3-diisopropylsuccinate was added during the temperature rise, then the reaction was carried out at 120℃for 0.5 hour, 1L of titanium tetrachloride was added, the liquid was filtered off after maintaining at 120℃for 2 hours to give a solid product, the obtained solid product was washed 5 times with hexane and finally dried under vacuum to give catalyst component A (average particle size D50=41 μm, SPAN value 0.80), which was designated as A-2.
Preparation example 3
650G of a magnesium diethoxide support (average particle size d50=47 μm), 3250ml of toluene and 65ml of di-n-butyl phthalate (DNBP) were taken and prepared into a suspension. Adding 2600mL of toluene and 3900mL of titanium tetrachloride into a 16L pressure-resistant reaction kettle repeatedly replaced by high-purity nitrogen, cooling to-5 ℃, adding the prepared suspension into the kettle, keeping the temperature for 1 hour, slowly heating to 110 ℃, adding 65mL of DNBP when the temperature is raised to 80 ℃, keeping the temperature for 2 hours, and then press-filtering the liquid clean. Then, a mixed solution of 5070mL of toluene and 3380mL of titanium tetrachloride was added, and the mixture was stirred at 110℃for 1 hour, thus treated 3 times, the liquid was filtered off, the obtained solid was washed 4 times with 150mL of hexane, the liquid was filtered off and dried to obtain a solid catalyst component (average particle size D50=42 μm, SPAN value 0.82), which was designated as A-3.
Preparation example 4
650G of a diethoxymagnesium support (average particle size d50=47 μm), 3250mL of toluene, 65mL of diethyl 2, 3-diisopropylsuccinate were taken and prepared into a suspension. Adding 2600mL of toluene and 3900mL of titanium tetrachloride into a 16L pressure-resistant reaction kettle repeatedly replaced by high-purity nitrogen, cooling to-5 ℃, adding the prepared suspension into the kettle, keeping the temperature for 1 hour, slowly heating to 110 ℃, adding 65mL of diethyl 2, 3-diisopropyl succinate when the temperature is raised to 80 ℃, keeping the temperature for 2 hours, and then press-filtering the liquid clean. Then, a mixed solution of 5070mL of toluene and 3380mL of titanium tetrachloride was added, and the mixture was stirred at 110℃for 1 hour, thus treated 3 times, the liquid was filtered off, the obtained solid was washed 4 times with 150mL of hexane, the liquid was filtered off and dried to obtain a solid catalyst component (average particle size D50=42 μm, SPAN value 0.82), which was designated as A-4.
Preparation example 5
To a 3L glass reaction flask with stirring, 1.2L of titanium tetrachloride was added and cooled to-20℃and then 100g of a spherical magnesium compound carrier (having a structure represented by formula (3) and an average particle size d50=46 μm) was added under stirring, after reacting at-20℃for 0.5 hours, the temperature was slowly raised to 120℃and 15g of diisobutylphthalate was added during the temperature rise, then reacting at 120℃for 0.5 hours, liquid was filtered off, 1L of titanium tetrachloride was added, after maintaining at 120℃for 2 hours, liquid was filtered off to obtain a solid product, the obtained solid product was washed 5 times with hexane and finally dried under vacuum to obtain catalyst component A (average particle size d50=41 μm, SPAN value 0.76) denoted as A-5.
Preparation example 6
To a 3L glass reaction flask with stirring, 1.2L of titanium tetrachloride was added and cooled to-20℃and then 100g of a spherical magnesium compound carrier (having a structure represented by formula (3) and an average particle size d50=46 μm) was added under stirring, after reacting at-20℃for 0.5 hours, the temperature was slowly raised to 120℃and 15g of diethyl 2, 3-diisopropylsuccinate was added during the temperature rise, then the reaction was carried out at 120℃for 0.5 hours, 1L of titanium tetrachloride was added, the liquid was filtered off after maintaining at 120℃for 2 hours to obtain a solid product, the obtained solid product was washed 5 times with hexane and finally dried under vacuum to obtain a catalyst component A (average particle size d50=42 μm, SPAN value 0.78) denoted as A-6.
The following examples are presented to illustrate the solid catalyst component of the present invention, its preparation method and the method of olefin polymerization.
Example 1
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-1 were added and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, hydrogen was added to a reaction vessel pressure of 0.3MPa, and the reaction was carried out at 15℃for 10 minutes, followed by purging of unreacted hydrogen. After filtering off the liquid in the reaction product, drying under vacuum gave a solid catalyst component (average particle size d50=41 μm, SPAN value 0.80), designated E-1. The composition of catalyst component E-1 is as follows: titanium 2.3 wt%, magnesium 15.5 wt%, chlorine 54.3 wt%, diisobutyl phthalate 8.7 wt% and 9.5 polyolefin%.
(2) Propylene polymerization A
Into a 5L autoclave, 5.0mmol of triethylaluminum, 0.2mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane and 15mg of solid catalyst component E-1 were charged, and after charging 1.5NL of hydrogen, 2.0kg of liquid propylene was added; raising the temperature to 70 ℃ under stirring and carrying out polymerization reaction for 1 hour at 70 ℃; the stirring was stopped and the unpolymerized propylene monomer was removed to give polypropylene, designated P-1A.
Propylene polymerization B
After the solid catalyst component E-1 was stored under nitrogen for 1 year, propylene polymerization was carried out according to the propylene polymerization A method, which was designated as P-1B.
Example 2
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size d50=42 μm, SPAN value 0.82), which was designated as E-2. The composition of catalyst component E-2 was as follows: 2.3 wt% of titanium, 15.1 wt% of magnesium, 54.9 wt% of chlorine, 8.5 wt% of diisobutyl phthalate and 9.4 wt% of polyolefin.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 1, except that the solid catalyst component E-1 was replaced with E-2, thereby producing polypropylene, which was designated as P-2A.
Propylene polymerization B
After the solid catalyst component E-2 was stored under nitrogen for 1 year, propylene polymerization was carried out in accordance with the propylene polymerization A method of example 1, and it was designated as P-2B.
Example 3
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 1 except that the catalyst component A2 was used in place of A1, thereby obtaining a solid catalyst component (average particle size D50=42 μm, SPAN value 0.81), designated as E-3. The composition of catalyst component E-3 was as follows: 2.2 wt% of titanium, 15.2 wt% of magnesium, 55.0 wt% of chlorine, 9.0 wt% of diethyl 2, 3-diisopropylsuccinate and 9.1 wt% of polyolefin.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 1, except that the solid catalyst component was replaced with E-3 from E-1 to obtain polypropylene, which was designated as P-3A.
Propylene polymerization B
After the solid catalyst component E-3 was stored under nitrogen for 1 year, propylene polymerization was carried out in accordance with the propylene polymerization A method of example 1, and it was designated as P-3B.
Example 4
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 15mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-2 were added and reacted at 15℃for 10 minutes; then 15g of propylene was added and reacted at 22℃for 10 minutes, the unreacted propylene was vented; the reaction kettle is replaced by nitrogen, mixed gas with the hydrogen content of 20 percent is added to the reaction pressure of 0.2MPa, the reaction is carried out for 10 minutes at 15 ℃, and unreacted hydrogen is discharged. After filtering off the liquid in the reaction product, drying under vacuum gave a solid catalyst component (average particle size d50=42 μm, SPAN value 0.82), designated E-4. The composition of catalyst component E-4 was as follows: 1.6 wt% of titanium, 11.9 wt% of magnesium, 39.3 wt% of chlorine, 6.0 wt% of diethyl 2, 3-diisopropylsuccinate and 32.5 wt% of polyolefin.
(2) Propylene polymerization A
Polymerization was carried out in the same manner as in propylene polymerization A of example 1 except that E-4 was used in place of E-1 to obtain polypropylene, which was designated as P-4A.
Propylene polymerization B
After the solid catalyst component E-4 was stored under nitrogen for 1 year, propylene was polymerized according to the method of propylene polymerization A, which was designated as P-4B.
Example 5
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-3 were added and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, hydrogen was added to a reaction vessel pressure of 0.3MPa, and the reaction was carried out at 15℃for 10 minutes, followed by purging of unreacted hydrogen. After filtering off the liquid in the reaction product, it was dried under vacuum to give a solid catalyst component (average particle size d50=43 μm, SPAN value 0.83), designated as E-5.
(2) Propylene polymerization A
Into a 5L autoclave, 5.0mmol of triethylaluminum, 0.2mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane and 15mg of solid catalyst component E-5 were charged, and after charging 1.5NL of hydrogen, 2.0kg of liquid propylene was added; raising the temperature to 70 ℃ under stirring and carrying out polymerization reaction for 1 hour at 70 ℃; the stirring was stopped and the unpolymerized propylene monomer was removed to give polypropylene, designated P-5A.
Propylene polymerization B
After the solid catalyst component E-5 was stored under nitrogen for 1 year, propylene polymerization was carried out according to the propylene polymerization A method, which was designated as P-5B.
Example 6
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 5 except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size d50=43 μm, SPAN value 0.83), which was designated as E-6.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 5, except that the solid catalyst component E-5 was replaced with E-6, thereby producing polypropylene, which was designated as P-6A.
Propylene polymerization B
After the solid catalyst component E-6 was stored under nitrogen for 1 year, propylene polymerization was carried out according to the propylene polymerization A method of example 5, which was designated as P-6B.
Example 7
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 5 except that the catalyst component A4 was used in place of A3, thereby obtaining a solid catalyst component (average particle size D50=43 μm, SPAN value 0.83), designated as E-7.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 5, except that the solid catalyst component was replaced with E-7 from E-5 to obtain polypropylene, designated as P-7A.
Propylene polymerization B
After the solid catalyst component E-7 was stored under nitrogen for 1 year, propylene polymerization was carried out according to the propylene polymerization A method of example 5, which was designated as P-7B.
Example 8
(1) Preparation of solid catalyst component
1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-5 were charged in a 5L autoclave and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, hydrogen was added to a reaction vessel pressure of 0.3MPa, and the reaction was carried out at 15℃for 10 minutes, followed by purging of unreacted hydrogen. After filtering off the liquid in the reaction product, drying under vacuum gave a solid catalyst component (average particle size d50=42 μm, SPAN value 0.77), designated E-8.
(2) Propylene polymerization A
Into a 5L autoclave, 5.0mmol of triethylaluminum, 0.2mmol of cyclohexylmethyldimethoxysilane, 10mL of hexane and 15mg of solid catalyst component E-8 were charged, and after charging 1.5NL of hydrogen, 2.0kg of liquid propylene was added; raising the temperature to 70 ℃ under stirring and carrying out polymerization reaction for 1 hour at 70 ℃; the stirring was stopped and the unpolymerized propylene monomer was removed to give polypropylene, designated P-8A.
Propylene polymerization B
After the solid catalyst component E-8 was stored under nitrogen for 1 year, propylene polymerization was carried out according to the propylene polymerization A method, which was designated as P-8B.
Example 9
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 8 except that ethylene was used instead of propylene, thereby obtaining a solid catalyst component (average particle size d50=42 μm, SPAN value 0.77), which was designated as E-9.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 8, except that the solid catalyst component E-8 was replaced with E-9, thereby producing polypropylene, which was designated as P-9A.
Propylene polymerization B
After the solid catalyst component E-9 was stored under nitrogen for 1 year, propylene polymerization was carried out according to the propylene polymerization A method of example 8, which was designated as P-9B.
Example 10
(1) Preparation of solid catalyst component
A solid catalyst component was prepared in the same manner as in example 8 except that the catalyst component A-6 was used in place of the catalyst component A-5, thereby obtaining a solid catalyst component (average particle size D50=43 μm, SPAN value 0.79), which was designated as E-10.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 8, except that the solid catalyst component was replaced with E-10 from E-8 to obtain polypropylene, designated as P-10A.
Propylene polymerization B
After the solid catalyst component E-10 was stored under nitrogen for 1 year, propylene polymerization was carried out according to the propylene polymerization A method of example 8, which was designated as P-10B.
Comparative example 1
Propylene polymerization A
The procedure of propylene polymerization A of example 1 was followed except that E-1 was replaced with catalyst component A-1 to give polypropylene, designated CP-1A.
Comparative example 2
Propylene polymerization A
The procedure of propylene polymerization A of example 3 was followed, except that E-2 was replaced with catalyst component A-2 to give polypropylene, designated CP-2A.
Comparative example 3
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-1 were added and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, and the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-3.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 1, except that E-1 was replaced with CE-3 as a solid catalyst component, thereby producing polypropylene, which was designated CP-3A.
Propylene polymerization B
Propylene polymerization was carried out according to the propylene polymerization B method of example 1, except that E-1 was replaced with CE-3 as a solid catalyst component, thereby producing polypropylene, which was designated CP-3B.
Comparative example 4
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-2 were added and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, and the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-4.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 1, except that E-1 was replaced with a solid catalyst component CE-4, thereby producing polypropylene, which was designated CP-4A.
Propylene polymerization B
Propylene polymerization was carried out in accordance with the propylene polymerization B method of example 1, except that E-1 was replaced with a solid catalyst component CE-4, thereby producing polypropylene, designated CP-4B.
Comparative example 5
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-1 were added and reacted at 22℃for 10 minutes; then 10g of ethylene and 2g of hydrogen are added, and the mixture is reacted for 10 minutes at 15 ℃ and the unreacted gas is vented; the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-5.
(2) Propylene polymerization A
Propylene was polymerized A in the same manner as in example 1 except that CE-5 was used in place of E-1 to obtain polypropylene, which was designated CP-5A.
Propylene polymerization B
Propylene was polymerized in the same manner as in example 1 except that CE-5 was used in place of E-1 to obtain polypropylene, which was designated CP-5B.
Comparative example 6
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-2 were added and reacted at 22℃for 10 minutes; then 10g of ethylene and 2g of hydrogen are added, and the mixture is reacted for 10 minutes at 15 ℃ and the unreacted gas is vented; the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-6.
(2) Propylene polymerization A
Propylene was polymerized A in the same manner as in example 1 except that CE-6 was used in place of E-1 to obtain polypropylene, which was designated CP-6A.
Propylene polymerization B
Propylene was polymerized in the same manner as in example 1 except that CE-6 was used in place of E-1 to obtain polypropylene, which was designated CP-6B.
Comparative example 7
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-1 were added and reacted at 22℃for 10 minutes; then 10g of propylene and 2g of hydrogen are added to react for 10 minutes at 15 ℃, and unreacted gas is vented; the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-7.
(2) Propylene polymerization A
Propylene was polymerized A in the same manner as in example 1 except that CE-7 was used in place of E-1 to obtain polypropylene, which was designated CP-7A.
Propylene polymerization B
Propylene was polymerized in the same manner as in example 1 except that CE-7 was used in place of E-1 to obtain polypropylene, which was designated CP-7B.
Comparative example 8
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-3 were added and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, and the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-8.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 5, except that the solid catalyst component was replaced with CE-8 from E-5, thereby producing polypropylene, designated CP-8A.
Propylene polymerization B
Propylene was polymerized in the same manner as in example 5 except that CE-8 was used in place of E-5 to obtain polypropylene, which was designated CP-8B.
Comparative example 9
(1) Preparation of solid catalyst component
In a 5L autoclave, 1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-4 were added and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, and the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-9.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 5, except that E-5 was replaced with a solid catalyst component CE-9, thereby producing polypropylene, which was designated CP-9A.
Propylene polymerization B
Propylene polymerization was carried out in accordance with the propylene polymerization B method of example 5, except that E-5 was replaced with a solid catalyst component CE-9, thereby producing polypropylene, designated CP-9B.
Comparative example 10
(1) Preparation of solid catalyst component
1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-5 were charged in a 5L autoclave and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, and the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-10.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 8, except that E-8 was replaced with CE-10 as a solid catalyst component, thereby producing polypropylene, which was designated CP-10A.
Propylene polymerization B
Propylene polymerization was carried out in accordance with the propylene polymerization B method of example 8, except that E-8 was replaced with a solid catalyst component CE-10, thereby producing polypropylene, designated CP-10B.
Comparative example 11
(1) Preparation of solid catalyst component
1.0L of hexane, 16mmol of triethylaluminum, 0.3mmol of cyclohexylmethyldimethoxysilane and 25.0g of catalyst component A-6 were charged in a 5L autoclave and reacted at 22℃for 10 minutes; then 10g of propylene was added and reacted at 15℃for 10 minutes, the unreacted propylene was vented; the reaction vessel was replaced with nitrogen, and the liquid in the reaction product was filtered off and dried under vacuum to give a solid catalyst component, designated CE-11.
(2) Propylene polymerization A
Propylene polymerization was carried out according to the propylene polymerization A method of example 10, except that E-10 was replaced with a solid catalyst component CE-11, thereby producing polypropylene, designated CP-11A.
Propylene polymerization B
Propylene polymerization was carried out in accordance with the propylene polymerization B method of example 10, except that E-10 was replaced with a solid catalyst component CE-11, thereby producing polypropylene, designated CP-11B.
TABLE 1 electronic binding energy of Ti2p 3/2 of titanium component of catalyst
TABLE 2 propylene polymerization results
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As can be seen from Table 1, the Ti2p 3/2 electron binding energy of the titanium component in the solid catalyst component prepared by the preparation method is changed, and the solid catalyst component has unique characteristics and can cause the olefin polymerization performance to be changed.
As can be seen from Table 2, the solid catalyst component of the present invention is used for olefin polymerization, has high polymerization activity, and can meet the requirements of industrial application. Compared with the prior art of the prepolymerized catalyst, as compared with comparative examples 1-11, the catalyst has greatly reduced attenuation of polymerization activity after being stored for 1 year, and can provide a prepolymerized catalyst with stable polymerization activity for the industrial production of polypropylene. The solid catalyst component is used for olefin polymerization and has the advantage of low content of polymer fine powder.
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 (12)
1. A solid catalyst component for olefin polymerization, comprising magnesium element, titanium element, halogen, poly-alpha-olefin and carboxylic acid ester, wherein the carboxylic acid ester is selected from at least one of mono-aliphatic carboxylic acid ester, di-aliphatic carboxylic acid ester, mono-aromatic carboxylic acid ester and di-aromatic carboxylic acid ester, and the Ti2p 3/2 electron binding energy of the titanium element is 456.10ev-454.90ev.
2. The solid catalyst component according to claim 1, characterized in that the polyalphaolefin is selected from one or more of polyethylene, polypropylene, polybutene, polyoctene and polyisopentene, preferably polypropylene;
And/or the solid catalyst component is a spherical solid particle, preferably the solid catalyst component has an average particle size D 50 to 150 μm, preferably 20 to 80 μm.
3. The solid catalyst component according to claim 1 or 2, wherein the content of magnesium element in the solid catalyst component is 1 to 18% by weight based on the total weight of the solid catalyst component; the content of titanium element is 0.1-3.5 wt%; halogen content of 2-65 wt%; the content of poly alpha-olefin is 0.1-89 wt%; the content of the carboxylic acid ester is 0.6-15 wt%.
4. A solid catalyst component according to any one of claims 1 to 3, wherein the carboxylic acid ester is one or more of benzoate, phthalate and succinate compounds;
Preferably, the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
And/or the phthalate compound is selected from one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate;
And/or the succinate compound is selected from one or more of diethyl 2, 3-diisopropyl succinate, diisobutyl 2, 3-diisopropyl succinate, di-n-butyl 2, 3-diisopropyl succinate, dimethyl 2, 2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate and diethyl 2-ethyl-2-methyl succinate.
5. A process for preparing a solid catalyst component for the polymerization of olefins, comprising:
(1) Contacting catalyst component A, alkyl aluminum and an external electron donor compound in the presence of an inert solvent; the catalyst component A contains carboxylic ester, titanium element, magnesium element and halogen, wherein the carboxylic ester is at least one of aliphatic carboxylic ester, aromatic carboxylic ester and succinate compound;
(2) Adding alpha-olefin into the reaction system obtained in the step (1) to carry out polymerization reaction;
(3) Removing unreacted alpha-olefin in the step (2), and adding hydrogen into the obtained reaction system to react;
The mass ratio of the alpha-olefin to the amount of the catalyst component A is 0.04:1-10:1, controlling the addition amount of the hydrogen to maintain the reaction pressure between 0.01 and 1.0MPa.
6. The production method according to claim 5, wherein in the step (1), the conditions of the contact reaction include: the temperature is 0-30deg.C, preferably 15-25deg.C; the time is 1-30min, preferably 10-20min;
and/or, in step (2), the polymerization conditions include: the temperature is 0-50deg.C, preferably 15-25deg.C; the time is 5-30min, preferably 10-20min;
and/or, in step (3), the reaction conditions include: the temperature is 0-50deg.C, preferably 15-25deg.C; the time is 5-30min, preferably 10-20min.
7. The process according to claim 5 or 6, wherein the alpha-olefin is selected from one or more of ethylene, propylene, butene, octene and isoamylene, preferably propylene.
8. The production method according to any one of claims 5 to 7, wherein the carboxylic acid ester is one or more of a benzoate compound, a phthalate compound and a succinate compound;
Preferably, the benzoate compound is selected from one or more of methyl benzoate, ethyl benzoate and n-butyl benzoate;
And/or the phthalate compound is selected from one or more of diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate and di-n-octyl phthalate;
And/or the succinate compound is selected from one or more of diethyl 2, 3-diisopropyl succinate, diisobutyl 2, 3-diisopropyl succinate, di-n-butyl 2, 3-diisopropyl succinate, dimethyl 2, 2-dimethyl succinate, diisobutyl 2-ethyl-2-methyl succinate and diethyl 2-ethyl-2-methyl succinate.
9. The production method according to any one of claims 5 to 8, wherein the catalyst component a is titanium tetrachloride, a carrier, and the carboxylic acid ester or a reaction product thereof;
Preferably, the general formula of the alkoxy magnesium carrier is Mg (OEt) 2-k-l(OEH)k(OiPr)l, wherein Et is ethyl, EH is 2-ethylhexyl, iPr is isopropyl, and k and l are 0-0.5;
Preferably, the general formula of the spherical magnesium chloride alkoxide can be Mg (R 'OH) i(H2O)j, wherein R' is methyl, ethyl, n-propyl or isopropyl, i is 1.5-3.5, and j is 0-0.1;
preferably, the spherical magnesium compound carrier is represented by formula (3):
In formula (3), R 1 is a C 1-C12 linear or branched alkyl group; r 2 and R 3 are identical or different and are hydrogen or C 1-C5 linear or branched alkyl, wherein the hydrogen on the alkyl can be optionally substituted by halogen atoms; x is halogen; m is 0.1-1.9; n is 0.1-1.9; m+n=2.
10. A solid catalyst component prepared by the preparation method according to any one of claims 5 to 9.
11. A catalyst for the polymerization of olefins comprising the solid catalyst component of any of claims 1 to 4 and 10, an alkyl aluminum and optionally an external electron donor compound or reaction product thereof.
12. A process for the polymerization of olefins, comprising: polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 11;
Preferably, the olefin has the general formula CH 2 =chr, R being hydrogen or an alkyl group of C 1-C6 or a C 6-C10 aryl group;
Preferably, the temperature of the polymerization reaction is 0 to 150 ℃, more preferably 60 to 90 ℃.
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| PCT/CN2023/126424 WO2024088298A1 (en) | 2022-10-26 | 2023-10-25 | Solid catalyst component for olefin polymerization, and preparation method therefor and use thereof |
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