CN112707978A - Magnesium-based catalyst component for olefin polymerization, preparation method thereof, catalyst and application thereof - Google Patents
Magnesium-based catalyst component for olefin polymerization, preparation method thereof, catalyst and application thereof Download PDFInfo
- Publication number
- CN112707978A CN112707978A CN201911020072.1A CN201911020072A CN112707978A CN 112707978 A CN112707978 A CN 112707978A CN 201911020072 A CN201911020072 A CN 201911020072A CN 112707978 A CN112707978 A CN 112707978A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- compound
- aluminum
- catalyst component
- based catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000011777 magnesium Substances 0.000 title claims abstract description 68
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 68
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- -1 aluminum compound Chemical class 0.000 claims abstract description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010936 titanium Substances 0.000 claims abstract description 24
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 19
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 17
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000012452 mother liquor Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 22
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 14
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 12
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 10
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002681 magnesium compounds Chemical class 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- FBCCMZVIWNDFMO-UHFFFAOYSA-N dichloroacetyl chloride Chemical compound ClC(Cl)C(Cl)=O FBCCMZVIWNDFMO-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims description 2
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 claims description 2
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002680 magnesium Chemical class 0.000 claims description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims description 2
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 238000001556 precipitation Methods 0.000 abstract description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 5
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000002903 organophosphorus compounds Chemical class 0.000 description 5
- 239000005049 silicon tetrachloride Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- OAFMYIADTCIEFV-UHFFFAOYSA-N hexane;triethylalumane Chemical compound CCCCCC.CC[Al](CC)CC OAFMYIADTCIEFV-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- LTEHWCSSIHAVOQ-UHFFFAOYSA-N tripropyl borate Chemical compound CCCOB(OCCC)OCCC LTEHWCSSIHAVOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a magnesium-based catalyst component for olefin polymerization, a preparation method, a catalyst and application thereof. The magnesium-based catalyst component comprises the reaction product of: (i) a magnesium-containing compound, (ii) an aluminum-containing substance, (iii) tin tetrachloride, (iv) an organic epoxy compound, (v) an organic alcohol, (vi) a titanium-containing compound, and optionally (vii) an electron donor. Mixing a magnesium-containing compound and a substance containing aluminum elements with tin tetrachloride, organic alcohol and an organic epoxy compound to form a mixed solution; cooling, namely dropping the titanium-containing compound into the mixed solution or dropping the mixed solution into the titanium-containing compound, and maintaining for a period of time; heating, stirring for a period of time, stopping stirring, settling, filtering, removing mother liquor, and washing solid with hydrocarbon solvent. The catalyst contains a magnesium-based catalyst component and an organic aluminum compound, has better activity and bulk density, and omits the step of dissolution reaction of a precipitation aid; avoids using phosphorus-containing compounds and phthalic anhydride with larger toxicity, and is beneficial to environmental protection.
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, and further relates to a magnesium-based catalyst component for olefin polymerization, a preparation method thereof, a catalyst and application thereof, in particular to an ethylene polymerization or copolymerization catalyst.
Background
In recent years, polyolefin polymer materials have long become one of the most important materials in today's society, and have been developed at a fast speed. Particularly, the rapid development of the polyolefin industry worldwide in recent decades indicates that the development and progress of the catalyst technology for olefin polymerization have promoted the development of the basic research of polyolefin and the industrialization technology thereof to the greatest extent.
In particular, the research of catalysts in the development of polyethylene has always been an important position in the synthesis and production of polyethylene. Among them, the titanium catalyst has been widely used and developed because of its high catalytic efficiency and low price.
Many studies and reports on the improvement of the catalyst performance are made, and the following aspects are mainly focused on: catalytic efficiency, particle morphology control, copolymerization ability, molecular weight distribution, and the like. For the production of general polyolefin resin, on the basis of further improving the catalyst performance, the catalyst preparation process is simplified, the catalyst cost is reduced, and an environment-friendly technology is developed to improve the benefit and enhance the competitiveness.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an olefin polymerization catalyst, and particularly relates to a magnesium-based catalyst component for olefin polymerization, and a preparation method and application thereof. The improved magnesium-based catalyst is prepared under the condition of avoiding the adoption of the organic phosphorus-containing compound and the precipitation aid, the catalyst prepared by the method has better performance than the catalyst disclosed by the prior art, the step of dissolution reaction of the precipitation aid is omitted, and the raw materials are more environment-friendly compared with a system containing the organic phosphorus-containing compound and phthalic anhydride while the preparation period of the catalyst is shortened.
It is an object of the present invention to provide a magnesium-based catalyst component for olefin polymerization comprising the reaction product of: (i) a magnesium compound, (ii) a substance containing an aluminum element, (iii) tin tetrachloride, (iv) an organic epoxy compound, (v) an organic alcohol, (vi) an acid halide compound, (vii) a titanium-containing compound, and optionally (viii) an electron donor.
In a preferred embodiment, the magnesium-containing compound is at least one selected from the group consisting of magnesium dihalides, water or alcohol complexes of magnesium dihalides, and derivatives of magnesium dihalides in which one halogen atom is substituted by a hydrocarbon or hydrocarbonoxy group in the molecule.
In a further preferred embodiment, the magnesium-containing compound is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, for example magnesium dichloride.
Wherein, inert diluents such as: benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbons or halogenated hydrocarbons, inert here means that the diluent should not take part in the reaction and should not adversely affect the dissolution of the magnesium compound.
In a preferred embodiment, the aluminum element-containing substance is at least one selected from the group consisting of metallic aluminum and inorganic aluminum compounds.
In a further preferred embodiment, the smaller the size of the metal aluminum, the more favorable the dispersion and the shorter the reaction time, and the nano aluminum powder is preferred; the inorganic aluminum compound is aluminum chloride, preferably anhydrous aluminum chloride in the form of fine powder.
In the invention, a compound carrier formed by compounding an aluminum-containing substance and a magnesium-containing compound is adopted, and after a great deal of experiments, the inventor finds that a catalyst system formed by adding the aluminum-containing substance has higher catalytic activity, and the analysis reason is probably that after the aluminum-containing substance is added, a synergistic effect exists among the components, so that the invention emphasizes that the components in the catalyst component are synergistic and act as a whole, and cannot be cleaved and analyzed.
In a preferred embodiment, the organic alcohol comprises C1～C12Fatty alcohol or C7～C12Or substituted alcohols derived therefrom.
In a further preferred embodiment, the organic alcohol is selected from at least one of methanol, ethanol, propanol, isooctanol, n-butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol, phenethyl alcohol.
In a still further preferred embodiment, the organic alcohol is selected from at least one of ethanol, isooctanol, n-butanol, 2-ethylhexanol, benzyl alcohol, phenethyl alcohol. When two mixed alcohols are adopted, the molar ratio of the two mixed alcohols is 1-50: 1, 1-20: preferably 1.
In the application, the inventor successfully realizes the complete dissolution of the magnesium-containing compound by using the alcohol compound and the epoxy compound together, thereby avoiding the use of an organic phosphorus compound; the inventors have also surprisingly found that the dissolving effect of the magnesium-containing compound is better when two or more alcohol compounds are used. Meanwhile, different alcohols generate different titanium products when reacting with the titanium-containing compound at the later stage, so that more than two titanium products are obtained when more than two alcohol compounds are adopted, and a polymer with wider molecular weight distribution can be obtained when the alcohol compounds are applied to the preparation of polyolefin, thereby being beneficial to the processability of the polymer.
In a preferred embodiment, the organic epoxy compound comprises C2～C8Oxide of an aliphatic olefin, oxide of an aliphatic diolefin, oxide of a halogenated aliphatic olefin, oxide of a halogenated aliphatic diolefin, glycidyl ether and internal ether.
In a further preferred embodiment, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran.
In a further preferred embodiment, the organic epoxide is selected from at least one of ethylene oxide, propylene oxide, epichlorohydrin, tetrahydrofuran, for example tetrahydrofuran and/or epichlorohydrin.
In the invention, the organic alcohol is adopted to dissolve the magnesium-containing compound, and the organic epoxy compound is also adopted to further promote the dissolution of the magnesium-containing compound.
In the prior art, chinese patent CN111516A discloses a method for ethylene polymerization or copolymerization, the titanium-containing component of the catalyst is prepared by the following steps: (1) dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound to form a uniform solution; (2) during or after the dissolution, simultaneously or respectively carrying out contact reaction with at least one organic alcohol and at least one compound selected from C3-C5 cyclic ethers; (3) and (3) carrying out contact reaction on the mixture obtained in the step (2) and at least one Ti-containing compound in the presence of at least one organic acid anhydride to obtain the titanium-containing solid catalyst component. When the catalyst system is used for ethylene polymerization, the defect of low apparent density of the obtained polymer is obvious. Chinese patent CN1229092A proposes a catalyst for ethylene polymerization or copolymerization and its preparation method, wherein the catalyst is obtained by dissolving magnesium halide in organic epoxy compound, organic phosphorus compound, adding electron donor to form a uniform solution, reacting with at least one precipitation aid and halide of transition metal titanium or its derivative, and combining with organic aluminum compound during polymerization. The catalyst shows higher activity when used for ethylene polymerization, and the obtained polymer has higher apparent density.
In the preparation process of the two catalysts disclosed in the patent, in order to obtain catalyst solids, both a dissolving system adopts an organic phosphorus compound and a method for adding a precipitation aid is adopted, particularly phthalic anhydride is adopted as the precipitation aid in the embodiment, and the phthalic anhydride is completely dissolved in a mixed solvent system and then cooled to be mixed with a titanium compound, so that the use of the precipitation aid correspondingly prolongs the preparation period of the catalyst. In addition, the auxiliary precipitating agent system has relatively high toxicity and high requirement on operation conditions.
However, in the present invention, it has been found that, in view of the above-mentioned one of the objects of the present invention, an organic phosphorus compound is not added, and an organic alcohol and an organic epoxy compound are used in appropriate amounts, and a benzoic anhydride-based precipitant is not used.
In a preferred embodiment, the acyl halide compound is of the formula R (COX)aWherein R is H, C1～C8Aliphatic radical of (A), C1～C8Halogenated aliphatic hydrocarbon group of (2), C6～C10Aryl or C6～C10X is halogen and a is 1 or 2.
In a further preferred embodiment, the acid halide compound is an acid chloride compound, preferably at least one selected from the group consisting of benzoyl chloride, formyl chloride and dichloroacetyl chloride, such as benzoyl chloride.
In the invention, the magnesium-based catalyst component is prepared by adopting the acyl halide compound, wherein the acyl halide compound can be used as an electron donor to improve the hydrogen regulation sensitivity of the catalyst on one hand, and can provide chlorine for a reaction system on the other hand, so that the use of titanium tetrachloride can be saved to a certain extent.
In a preferred embodiment, the titanium-containing compound has the formula TiXn(OR)4-nWherein: x is halogen and R is C1～C14Aliphatic hydrocarbon group of (C)6～C14An aromatic hydrocarbon group, and n is an integer of 0 to 4.
In a further preferred embodiment, the titanium-containing compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, for example titanium tetrachloride.
The electron donors of the present invention are compounds known to those skilled in the art, such as: at least one of organic ether, silicon-containing compound and boron-containing compound.
Wherein:
the organic ether is at least one of methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether and isoamyl ether;
the silicon-containing compound is of the general formula R1 xR2 ySi(OR3)zSilicon compounds having no active hydrogen atom shown, wherein R1And R2Each is a C1-10 alkyl group or halogen, R3The carbon atom number of the alkyl is 1-10, wherein x, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 4, and x + y + z is 4; among them, at least one of silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetrakis (2-ethylhexyloxy) silane is preferable, and silicon tetrachloride and/or tetraethoxysilane is most preferable;
the boron-containing compound is shown as the general formula R1 xR2 yB(OR3)zBoron compounds having no active hydrogen atom shown, wherein R1And R2Each is a C1-10 alkyl group or halogen, R3The carbon atom number is 1-10 alkyl, wherein x, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 3, and x + y + z is 3; among them, at least one of boron trichloride, trimethoxyborane, triethoxyborane, tripropoxyborane and tributoxyborane is preferable, and boron trichloride and/or triethoxyborane are most preferable.
In a preferred embodiment, in the magnesium-based catalyst component, per mole of magnesium-containing compound, the amount of the aluminum-containing substance is 0.002 to 1mol, the amount of the tin tetrachloride is 0.005 to 4.0mol, the amount of the organic alcohol is 0.1 to 10mol, the amount of the organic epoxy compound is 0.01 to 5mol, the amount of the acyl halide compound is 0.01 to 4.0mol, the amount of the electron donor compound is 0 to 5mol, and the amount of the titanium-containing compound is 0.2 to 100 mol.
In a further preferred embodiment, the magnesium-based catalyst component comprises 0.005 to 0.5mol of aluminum-containing substance, 0.02 to 1.0mol of tin tetrachloride, 0.2 to 6mol of organic alcohol, 0.02 to 2mol of organic epoxy compound, 0.02 to 2.0mol of acid halide compound, 0 to 1mol of electron donor compound, and 1.0 to 20mol of titanium-containing compound per mol of magnesium-containing compound.
In a further preferred embodiment, in the magnesium-based catalyst component, the amount of the aluminum-containing material is 0.0075 to 0.4mol, the amount of the tin tetrachloride is 0.1 to 0.65mol, the amount of the organic alcohol is 3.5 to 6.0mol, the amount of the organic epoxy compound is 0.25 to 1.5mol, the amount of the acid halide compound is 0.05 to 1.25mol, the amount of the electron donor compound is 0 to 0.5mol, and the amount of the titanium-containing compound is 6.0 to 20mol per mol of the magnesium-containing compound.
It is another object of the present invention to provide a process for the preparation of a magnesium-based catalyst component for the polymerization of olefins as described in one of the objects of the present invention.
In a preferred embodiment, the preparation process is as follows: (1) mixing a magnesium-containing compound and an aluminum-containing substance with tin tetrachloride, organic alcohol and an organic epoxy compound, and then adding an acyl halide compound to form a mixed solution; (2) cooling, namely dropping the titanium-containing compound into the mixed solution or dropping the mixed solution into the titanium-containing compound, preferably maintaining the mixed solution for a certain period of time after the dropping is finished; (3) heating, stirring for a while, stopping stirring, settling, filtering, removing mother liquor, washing solid with hydrocarbon solvent, and getting magnesium-base catalyst component for olefin polymerization.
In a further preferred embodiment, an electron donor compound may also be added during the preparation, preferably in step (1) or step (2).
In a further preferred embodiment, the step (1) is carried out at 0 to 170 ℃, preferably 40 to 140 ℃; the step (2) is carried out at-35 to 60 ℃, preferably at-30 to 20 ℃.
The magnesium-based catalyst component obtained by the preparation method is powdery solid particles, the average particle size is about 2-50 microns, and the particle size can be controlled by changing the preparation conditions.
The invention also aims to provide a catalyst for olefin polymerization, which comprises the following components:
A) a magnesium-based catalyst component, preferably a magnesium-based catalyst component according to one of the objects of the present invention or a magnesium-based catalyst component obtained by the preparation method according to the second object of the present invention;
B) general formula is AlRnX3-nWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 0 < n.ltoreq.3.
Wherein, the general formula is AlRnX3-nWherein R is an alkyl group, an aralkyl group or an aryl group; x is chlorine or bromine. Preferably, the organoaluminum compound comprises a trialkylaluminum, an alkylaluminum chloride; more preferably, the organoaluminium compound is selected from at least one of trimethylaluminium, triethylaluminium, triisobutylaluminium, trioctylaluminium, diethylaluminium monochloride, diisobutylaluminium monochloride, ethylaluminium sesquichloride, ethylaluminium dichloride, for example from triethylaluminium and/or triisobutylaluminium.
In a preferred embodiment, the molar ratio of component B) to component A) is (5-1000): 1, preferably (20 to 800): 1.
wherein the molar amount of the component B) is calculated by the molar amount of the aluminum element therein, and the molar amount of the component A) is calculated by the molar amount of the titanium element therein.
The component A) of the catalyst system of the invention can be used in the form of a solid or a suspension, and the components A) and B) of the catalyst system of the invention can be directly applied to the polymerization system or can be pre-complexed and then applied to the polymerization system.
The fourth object of the present invention is to provide the use of the catalyst for olefin polymerization in the homopolymerization or copolymerization of olefins, especially in the homopolymerization of ethylene and the copolymerization of ethylene and alpha-olefins, wherein the comonomer can be propylene, butene, pentene, hexene, octene, or 4-methyl-1-pentene.
When the polymerization is carried out, liquid phase polymerization or gas phase polymerization may be employed. In the liquid phase polymerization, an inert solvent such as a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc. may be used as a reaction medium, and a prepolymerization may be carried out before the polymerization. The polymerization may be carried out in a batch, semi-continuous or continuous manner.
When the polymer is applied to polymerization, the polymerization temperature is between room temperature and 150 ℃, preferably between 50 and 100 ℃. In order to regulate the molecular weight of the polymer, hydrogen is used as a molecular weight regulator.
Compared with the prior art, the invention has the following obvious advantages: the catalyst prepared by the method has better activity and bulk density, and particularly, the use amount of titanium tetrachloride is obviously reduced after the acyl halide compound is added; the dissolution reaction step of the precipitation aid is omitted, and the preparation period of the catalyst is shortened; meanwhile, the method avoids using phosphorus-containing compounds and phthalic anhydride with larger toxicity, thereby being more beneficial to environmental protection; in addition, the magnesium-based catalyst component for polymerization contains tin tetrachloride, so that the magnesium-based catalyst component is more favorably precipitated during preparation, and the magnesium-based catalyst component is endowed with more excellent bulk density.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
Example 1
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.0015mol of metallic aluminum and 0.4mol of n-decane, 0.0043mol of anhydrous tin tetrachloride is added, 0.13mol of isooctanol and 0.02mol of n-butanol are added, the temperature is raised to 130 ℃, the temperature is maintained for 1 hour, the temperature is lowered to 70 ℃, 0.03mol of epichlorohydrin is added, the temperature is maintained for half an hour, 0.002mol of benzoyl chloride is added, the temperature is lowered to-5 ℃, 0.5mol of titanium tetrachloride is dripped into the titanium tetrachloride, the temperature is maintained for half an hour, 0.015mol of tetraethoxysilane is added, the temperature is maintained for 1 hour, the temperature is raised to 110 ℃, the temperature is maintained for 1 hour, the mixture is washed by hexane for 4 times after being filtered, and the mixture is.
(2) Homopolymerization reaction
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity hydrogen, 1L of hexane and 1.0mL of triethylaluminum hexane solution with the concentration of 1M are added, 9-12 mg of the magnesium-based catalyst component A) prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to enable the pressure in the kettle to reach 0.26MPa (gauge pressure), ethylene is introduced to enable the total pressure in the kettle to reach 0.72MPa (gauge pressure), and polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the polymerization result is shown in Table 1.
Example 2
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.006mol of metallic aluminum and 0.4mol of n-decane, 0.009mol of silicon tetrachloride and 0.0086mol of anhydrous tin tetrachloride are added, the mixture is maintained for 5 minutes, 0.13mol of isooctanol is added, the temperature is raised to 130 ℃, the mixture is maintained for half an hour, 0.04mol of n-butanol is added, the mixture is maintained for half an hour, the temperature is reduced to 70 ℃, 0.03mol of epoxy chloropropane is added, the mixture is maintained for half an hour, 0.010mol of benzoyl chloride is added, the temperature is reduced to-10 ℃, 0.45mol of titanium tetrachloride is added in the mixture and maintained for 1 hour, then the temperature is raised to 110 ℃, the mixture is maintained for 1 hour, the mixture is filtered, washed for 4 times by hexane, and vacuum.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 3
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2In the fully displaced reactor, 0.03mol of anhydrous MgCl was added in succession20.012mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride is added, 0.017mol of anhydrous stannic chloride is added, the reaction is maintained for 5 minutes, 0.13mol of isooctanol is added, the temperature is raised to 130 ℃, the reaction is maintained for half an hour, 0.04mol of n-butanol is added, the reaction is maintained for half an hour, the temperature is lowered to 70 ℃, 0.0075mol of epoxy chloropropane is added, the reaction is maintained for half an hour, 0.020mol of benzoyl chloride is added, the temperature is lowered to-15 ℃, 0.35mol of titanium tetrachloride is dripped into the reaction, the reaction is maintained for 1 hour, the reaction is raised to 110 ℃, the reaction is maintained for 1 hour, the mixture is washed for 4 times by hexane.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 4
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.0003mol of anhydrous aluminum chloride and 0.6mol of toluene, 0.026mol of anhydrous stannic chloride, 0.07mol of n-butyl alcohol, 0.07mol of ethanol and 0.06mol of epoxy chloropropane are added, the temperature is raised to 80 ℃, the reaction is maintained for 1 hour, 0.050mol of benzoyl chloride is added, the temperature is lowered to 20 ℃, 0.3mol of titanium tetrachloride is dripped into the reaction, the reaction is maintained for half an hour, the temperature is raised to 85 ℃, the reaction is maintained for 1 hour, the reaction product is washed for 4 times by hexane after being filtered, and the reaction product is dried in vacuum, so that the magnesium-based catalyst component is obtained.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 5
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.0003mol of anhydrous aluminum chloride and 0.6mol of toluene, 0.026mol of anhydrous stannic chloride, 0.07mol of n-butyl alcohol, 0.07mol of phenethyl alcohol and 0.04mol of epoxy chloropropane are added, the temperature is raised to 80 ℃, the reaction is maintained for 1 hour, 0.050mol of benzoyl chloride is added, the temperature is lowered to 20 ℃, 0.3mol of titanium tetrachloride is dripped into the reaction, the reaction is maintained for half an hour, the temperature is raised to 85 ℃, the reaction is maintained for 1 hour, the reaction product is filtered, washed for 4 times by hexane and dried in vacuum, and the magnesium-based catalyst component is obtained.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 6
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.0004mol of anhydrous aluminum chloride and 0.6mol of toluene, 0.026mol of anhydrous stannic chloride, 0.16mol of n-butanol, heating to 110 ℃, maintaining for 1 hour, cooling to 60 ℃, adding 0.04mol of epichlorohydrin, maintaining for half an hour, adding 0.050mol of epichlorohydrinBenzoyl chloride is cooled to 20 ℃, 0.3mol of titanium tetrachloride is dripped into the benzoyl chloride for half an hour, then the benzoyl chloride is heated to 85 ℃ for 1 hour, and the benzoyl chloride is washed with hexane for 4 times after being filtered and dried in vacuum, thus obtaining the magnesium-based catalyst component.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative example 1
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.6mol of toluene, adding 0.03mol of epoxy chloropropane, 0.02mol of tributyl phosphate and 0.06mol of ethanol under stirring, heating to 60 ℃, maintaining for 1 hour, adding 0.0074mol of phthalic anhydride, maintaining for half an hour, cooling the solution to-15 ℃, dripping 0.60mol of titanium tetrachloride into the solution, maintaining for 1 hour, heating to 60 ℃, maintaining for 1 hour, filtering, washing with hexane for 4 times, and drying in vacuum to obtain the magnesium-based catalyst component A).
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative example 2
(1) Preparation of magnesium-based catalyst component: like comparative example 1, only the phthalic anhydride was changed to 0.011 mol.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative example 3
(1) Preparation of magnesium-based catalyst component A)
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.30mol of n-decane, 0.15mol of 2-ethylhexanol is added under stirring, the temperature is raised to 115 ℃, the temperature is maintained for 1 hour, the temperature is lowered to 50 ℃, 0.026mol of silicon tetrachloride is added, the solution is cooled to-10 ℃, 0.45mol of titanium tetrachloride is dripped into the solution, the solution is maintained for 1 hour, then the temperature is raised to 120 ℃, the solution is maintained for 1 hour, the mixture is filtered, washed by hexane for 4 times and dried in vacuum, and the magnesium-based catalyst component A) is obtained.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative examples 4 to 6
Comparative examples 4 to 6 the procedure of example 1 and examples 3 and 4 were repeated, respectively, except that benzoyl chloride was not added and the polymerization results were as shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the catalyst of the present invention has better activity and bulk density under the same polymerization conditions than those of comparative examples 1 to 3, and at the same time, the catalyst of the present invention has more excellent hydrogen regulation performance under the same polymerization conditions than those of comparative examples 4 to 6.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A magnesium-based catalyst component for the polymerization of olefins, said magnesium-based catalyst component comprising the reaction product of: (i) magnesium-containing compound, (ii) aluminum-containing substance, (iii) tin tetrachloride, (iv) organic epoxy compound, (v) organic alcohol, (vi) acyl halide compound, (vii) titanium-containing compound, and optionally (viii) electron donor compound.
2. The magnesium-based catalyst component for olefin polymerization of claim 1, characterized in that:
the organic epoxy compound comprises C2～C8Oxides of aliphatic olefins, oxides of aliphatic diolefins, oxides of halogenated aliphatic olefins, oxides of halogenated aliphatic diolefins, glycidyl ethers and internal ethers of (a); preferably, the organic epoxy compound is selected from ethylene oxideAt least one of alkane, propylene oxide, epichlorohydrin and tetrahydrofuran; and/or
The organic alcohol comprises C1～C12Fatty alcohol or C7～C12The aromatic alcohol of (a) or a substituted alcohol derived therefrom, preferably at least one selected from the group consisting of methanol, ethanol, propanol, isooctanol, n-butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol, and phenethyl alcohol, more preferably at least one selected from the group consisting of ethanol, isooctanol, n-butanol, 2-ethylhexanol, benzyl alcohol, and phenethyl alcohol; and/or
The acyl halide compound has the general formula of R (COX)aWherein R is H, C1～C8Aliphatic radical of (A), C1～C8Halogenated aliphatic hydrocarbon group of (2), C6～C10Aryl or C6～C10X is halogen, a is 1 or 2; preferably, the acid halide compound is an acid chloride compound, and more preferably, the acid halide compound is at least one selected from the group consisting of benzoyl chloride, formyl chloride and dichloroacetyl chloride.
3. The magnesium-based catalyst component for olefin polymerization of claim 2, characterized in that: on a per mole basis of the magnesium compound,
the using amount of the stannic chloride is 0.005-4.0 mol, preferably 0.02-1.0 mol; and/or
The using amount of the organic alcohol is 0.1-10 mol, preferably 0.2-6 mol; and/or
The dosage of the organic epoxy compound is 0.01-5 mol, preferably 0.02-2 mol; and/or
The amount of the acid halide compound is 0.01 to 4.0mol, preferably 0.02 to 2.0 mol.
4. The magnesium-based catalyst component for olefin polymerization of claim 1, characterized in that:
the aluminum-containing substance is at least one selected from metallic aluminum and inorganic aluminum compounds; preferably, the metal aluminum is nano aluminum powder, and the inorganic aluminum compound is aluminum chloride; and/or
The magnesium-containing compound is selected from at least one of magnesium dihalide, a water or alcohol complex of magnesium dihalide, and a derivative of magnesium dihalide, wherein one halogen atom in a molecule is substituted by a hydrocarbon group or a hydrocarbonoxy group, and is preferably selected from at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide; and/or
The amount of the aluminum-containing substance is 0.002 to 1.0mol, preferably 0.005 to 0.5mol, per mol of the magnesium compound.
5. The magnesium-based catalyst component for the polymerization of olefins according to one of the claims 1 to 4, characterized in that:
the general formula of the titanium-containing compound is TiXn(OR)4-nWherein: x is halogen and R is C1～C14Aliphatic hydrocarbon group of (C)6～C14An aromatic hydrocarbon group, n is an integer of 0 to 4; preferably at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium; and/or
The electron donor is at least one of organic ether, silicon-containing compound and boron-containing compound; and/or
The amount of the titanium-containing compound is 0.2-100 mol, preferably 1.0-20 mol, per mol of the magnesium compound; and/or the dosage of the electron donor is 0-5 mol, preferably 0-1 mol.
6. Process for the preparation of a magnesium based catalyst component for the polymerization of olefins according to one of the claims 1 to 5, carried out as follows: (1) mixing a magnesium-containing compound and an aluminum-containing substance with tin tetrachloride, organic alcohol and an organic epoxy compound, and then adding an acyl halide compound to form a mixed solution; (2) cooling, namely dripping a titanium-containing compound into the mixed solution or dripping the mixed solution into the titanium-containing compound; (3) heating, stirring, stopping stirring, settling, filtering, removing mother liquor, washing solid with hydrocarbon solvent to obtain magnesium-base catalyst component for olefin polymerization.
7. The production method according to claim 6, wherein,
an electron donor compound can also be added, preferably in the step (1) or the step (2); and/or
The step (1) is carried out at 0-170 ℃, preferably at 40-140 ℃; and/or
The step (2) is carried out at-35 to 60 ℃, preferably at-30 to 20 ℃.
8. A catalyst for olefin polymerization, the catalyst comprising:
A) a magnesium-based catalyst component, preferably a magnesium-based catalyst component for olefin polymerization as defined in any one of claims 1 to 5 or a magnesium-based catalyst component for olefin polymerization prepared according to the preparation process of any one of claims 6 to 7;
B) general formula is AlRnX3-nWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 0 < n.ltoreq.3; preferably, R is alkyl, aralkyl or aryl; x is chlorine or bromine.
9. The catalyst for olefin polymerization according to claim 8, wherein,
the organic aluminum compound comprises trialkyl aluminum and alkyl aluminum chloride; preferably, the organic aluminum compound is at least one selected from trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride; and/or
The molar ratio of the component B) to the component A) is (5-1000): 1, preferably (20 to 800): 1; wherein the molar amount of the component B) is calculated by the molar amount of the aluminum element therein, and the molar amount of the component A) is calculated by the molar amount of the titanium element therein.
10. Use of the catalyst for olefin polymerization according to claim 8 or 9 in homopolymerization or copolymerization of olefins.
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