CN112694551B - Magnesium/titanium composite main catalyst for olefin polymerization, preparation method thereof, catalyst and application - Google Patents
Magnesium/titanium composite main catalyst for olefin polymerization, preparation method thereof, catalyst and application Download PDFInfo
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- CN112694551B CN112694551B CN201911008770.XA CN201911008770A CN112694551B CN 112694551 B CN112694551 B CN 112694551B CN 201911008770 A CN201911008770 A CN 201911008770A CN 112694551 B CN112694551 B CN 112694551B
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- Prior art keywords
- magnesium
- titanium
- compound
- olefin polymerization
- catalyst
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- 239000011777 magnesium Substances 0.000 title claims abstract description 112
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 112
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000010936 titanium Substances 0.000 title claims abstract description 82
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 81
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 74
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- -1 alcohol compound Chemical class 0.000 claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 19
- 150000004820 halides Chemical class 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 12
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 12
- 150000002430 hydrocarbons Chemical group 0.000 claims description 11
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 8
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 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
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000003701 inert diluent Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 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
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 235000011147 magnesium chloride Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Chemical group 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 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
- 238000001035 drying Methods 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
- 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004062 sedimentation Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims 3
- 239000002685 polymerization catalyst Substances 0.000 claims 2
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 235000019445 benzyl alcohol Nutrition 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 abstract description 12
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract description 8
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 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
- 239000011368 organic material Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 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 7
- 239000005049 silicon tetrachloride Substances 0.000 description 7
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002903 organophosphorus compounds Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 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
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 239000000047 product Substances 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
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- 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
- 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 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 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
- 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
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 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
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003921 oil Substances 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
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 230000002035 prolonged 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
- 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
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002904 solvent 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
- 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
- 150000003608 titanium Chemical class 0.000 description 1
- 150000003609 titanium compounds 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-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
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention relates to a magnesium/titanium composite main catalyst for olefin polymerization, a preparation method, a catalyst and application thereof. Firstly mixing a magnesium-containing compound, an aluminum-containing inorganic substance, stannic chloride and an alcohol compound, then mixing with an acyl halide compound, then reacting with a halide of titanium or a derivative thereof, and finally carrying out post-treatment to obtain the magnesium/titanium composite main catalyst. This was mixed with an aluminum-containing organic material to obtain a catalyst for polymerization. The magnesium/titanium composite main catalyst for olefin polymerization and the preparation method thereof avoid using phosphorus-containing compounds and phthalic anhydride with larger toxicity, and are more beneficial to environmental protection; meanwhile, the preparation method omits the dissolution reaction step of the precipitation aid, and shortens the preparation period of the magnesium/titanium composite main catalyst for olefin polymerization.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a magnesium/titanium composite main catalyst for olefin polymerization, in particular to a magnesium/titanium composite main catalyst for olefin polymerization, and a preparation method, a catalyst and application thereof.
Background
The development of the polyolefin industry is one of the important standards for measuring the national chemical production and the development level, and the catalyst is a core technology of key factors in the polyolefin industry. Among them, titanium-based catalysts have been widely used and developed because of high catalytic efficiency and low price.
Many studies and reports on catalyst performance improvement are currently focused on the following aspects: catalytic efficiency, particle morphology control, copolymerization capability, molecular weight distribution, and the like. However, in the preparation of the catalysts disclosed in the prior art, the use of environmental pollutants, such as organic phosphorus-containing compounds, phthalic anhydride, is mostly involved. Meanwhile, the catalyst preparation disclosed in the prior art also relates to the use of an auxiliary precipitation agent, so that the production period is prolonged, and the production efficiency is reduced.
For the production of general polyolefin resin, on the basis of further improving the catalyst performance, it is a development direction to simplify the catalyst preparation process, reduce the catalyst cost, develop an environmentally friendly technology to increase the benefit and enhance the competitiveness.
Disclosure of Invention
In order to develop an environment-friendly catalyst, the invention obtains an improved titanium-based polyethylene catalyst under the condition of avoiding the use of an organic phosphorus compound and an auxiliary precipitation agent, the catalyst prepared by the method has better performance than the existing catalyst, the dissolution reaction step of the auxiliary precipitation agent is omitted, and the raw materials are more environment-friendly than the organic phosphorus compound and phthalic anhydride system while shortening the preparation period of the catalyst.
It is an object of the present invention to provide a magnesium/titanium composite procatalyst for olefin polymerization, which is prepared from a raw material comprising a magnesium-containing compound, an aluminum-containing inorganic substance, tin tetrachloride, an alcohol compound, an acyl halide compound and a halide of titanium or a derivative thereof.
According to a preferred embodiment of the present invention, the magnesium-containing compound is selected from one or more of magnesium dihalide, water or alcohol complexes of magnesium dihalide, magnesium dihalide derivatives.
In a further preferred embodiment, the magnesium dihalide derivative is a derivative in which one of the halogen atoms in the magnesium dihalide molecule is replaced by a hydrocarbon or hydrocarbyloxy group.
In a still further preferred embodiment, the magnesium dihalide is selected from one or more of magnesium dichloride, magnesium dibromide, magnesium diiodide, preferably magnesium dichloride.
Wherein, when the magnesium-containing compound is dissolved, inert diluents such as: benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbon or halogenated hydrocarbon compounds, by inert is meant that the diluent should not participate in the reaction and not adversely affect the dissolution of the magnesium dihalide.
According to a preferred embodiment of the invention, the aluminium-containing mineral is selected from metallic aluminium and/or inorganic aluminium compounds.
In a further preferred embodiment, nano-aluminum powder is preferred when it is metallic aluminum, wherein the smaller the size of metallic aluminum, the more advantageous it is to disperse and shorten the reaction time.
In a further preferred embodiment, the inorganic aluminium compound is selected from the group consisting of anhydrous aluminium chloride, preferably finely powdered anhydrous aluminium chloride.
According to a preferred embodiment of the present invention, the aluminum-containing inorganic substance is used in an amount of 0.002 to 1mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the aluminum-containing inorganic substance is used in an amount of 0.005 to 0.5mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the aluminum-containing inorganic substance is calculated based on the molar amount of the aluminum element therein.
The inventor finds out through a great deal of experiments that the catalyst system formed by adding the aluminum-containing inorganic substance into the magnesium/titanium composite main catalyst for olefin polymerization has higher catalytic activity, and the analysis reasons are probably that after the aluminum-containing inorganic substance is added, the components have synergistic effect, so that the components in the magnesium/titanium composite main catalyst for olefin polymerization have synergistic effect, and the components are acted as a whole and cannot be subjected to fracture analysis.
According to a preferred embodiment of the present invention, the tin tetrachloride is used in an amount of 0.005 to 4mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the tin tetrachloride is used in an amount of 0.02 to 1mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is based on the molar amount of magnesium element therein.
The inventors have added tin tetrachloride to the magnesium/titanium composite main catalyst for olefin polymerization, which is equivalent to imparting a multi-metal component to the main catalyst, and have found that the addition of tin tetrachloride can promote precipitation of the main catalyst and increase bulk density.
According to a preferred embodiment of the invention, the alcohol compound is selected from C 1 ～C 12 Fatty alcohol, C 7 ～C 12 One or more of the aromatic alcohols and substituted alcohols derived therefrom, wherein the substituted alcohol derived therefrom is a compound selected from the group consisting of C 1 ～C 12 Fatty alcohol or C of (C) 7 ～C 12 Substituted alcohols derived from aromatic alcohols of (a).
In a further preferred embodiment, the alcohol compound is selected from at least one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol, phenethyl alcohol.
In a still further preferred embodiment, the alcohol compound is selected from at least one of ethanol, isooctanol, butanol, 2-ethylhexanol, benzyl alcohol, phenethyl alcohol. When two mixed alcohols are adopted, the molar ratio of the two is 1 to 50:1, 1 to 20:1 is preferred.
Wherein, the main function of the alcohol compound is to dissolve the magnesium-containing compound and form an alcohol compound with the magnesium-containing compound.
According to a preferred embodiment of the present invention, the alcohol compound is used in an amount of 0.1 to 10mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the alcohol compound is used in an amount of 0.2 to 6mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is based on the molar amount of magnesium element therein.
In the prior art, for example, chinese patent CN1229092a proposes a catalyst for ethylene polymerization or copolymerization and a method for preparing the same, wherein the catalyst is obtained by dissolving magnesium halide in an organic epoxy compound, adding an organic phosphorus compound to an electron donor to form a homogeneous solution, and reacting with at least one precipitation aid and a halide of titanium or a derivative thereof. For another example, chinese patent CN111516a discloses a process for the polymerization or copolymerization of ethylene, the titanium-containing component of the catalyst being prepared by the steps of: (1) Dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound to form a uniform solution; (2) Simultaneously or respectively carrying out contact reaction with at least one organic alcohol and at least one compound selected from C3-C5 cyclic ethers during or after complete dissolution; (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 anhydride to obtain the titanium-containing solid magnesium/titanium composite main catalyst for olefin polymerization.
In the preparation process of the catalyst disclosed in the prior art, in order to obtain a catalyst solid, an organic phosphorus compound is adopted in a dissolution system, and meanwhile, a method of adding an auxiliary precipitation agent is also adopted, especially phthalic anhydride is adopted as the auxiliary precipitation agent in the embodiment, and the phthalic anhydride is completely dissolved in a mixed solvent system, and then cooled and mixed with a titanium compound, so that the use of the auxiliary precipitation agent correspondingly prolongs the preparation period of the catalyst. In addition, the precipitation aid system has relatively high toxicity and high requirements on operation conditions.
In this application, the inventors avoided the use of organic phosphorus compounds; the inventors have also found that the dissolution effect of the magnesium-containing compound is better when two or more alcohol compounds are used. Meanwhile, different alcohols generate different titanium products in the later reaction with titanium-containing compounds, so that when more than two kinds of alcohol compounds are adopted, more than two kinds of titanium products are obtained, and when the titanium-containing compounds are applied to the preparation of polyolefin, a polymer with wider molecular weight distribution is obtained, thereby being beneficial to the processability of the polymer.
In a preferred embodiment, the acyl halide compound has the formula R (COX) a Wherein R is H, C 1 ～C 8 Aliphatic radical, C 1 ～C 8 Halogenated aliphatic hydrocarbon radicals, C 6 ～C 10 Aromatic hydrocarbon or C of (2) 6 ～C 10 X 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 benzoyl chloride, formyl chloride and dichloroacetyl chloride, for example benzoyl chloride.
In the invention, the acyl halide compound is adopted to prepare the magnesium/titanium composite main catalyst, wherein the acyl halide compound can be used as an electron donor to improve the hydrogen regulation sensitivity of the catalyst and can be used for providing chlorine for a reaction system, so that the use of titanium tetrachloride can be saved to a certain extent.
In a preferred embodiment, the acyl halide compound is used in an amount of 0.01 to 4.0mol based on 1mol of the magnesium compound.
In a further preferred embodiment, the acyl halide compound is used in an amount of 0.02 to 2.0mol based on 1mol of the magnesium compound.
According to a preferred embodiment of the invention, the titanium halide or derivative thereof has the general formula TiX n (OR) 4-n Wherein: x represents halogen, R represents C 1 ～C 14 Aliphatic hydrocarbon radicals or C 6 ～C 14 An aromatic hydrocarbon group, n is an integer of 0 to 4.
In a further preferred embodiment, the halide of titanium or derivative thereof is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy, for example titanium tetrachloride.
According to a preferred embodiment of the present invention, the halide of titanium or its derivative is used in an amount of 0.2 to 100mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the halide of titanium or derivative thereof is used in an amount of 1.0 to 20mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the halide of titanium or the derivative thereof is calculated based on the molar amount of the titanium element therein.
According to a preferred embodiment of the present invention, the preparation raw material of the magnesium/titanium composite procatalyst for olefin polymerization optionally further comprises an electron donor.
In a further preferred embodiment, the electron donor is selected from one or more of an organic ether, a silicon-containing compound and a boron-containing compound.
Preferably: (I) The organic ether is selected from one or more of methyl ether, diethyl ether, propyl ether, butyl ether, amyl ether and isoamyl ether; (II) the silicon-containing compound has the formula R 1 x R 2 y Si(OR 3 ) z The silicon compounds having no active hydrogen atoms, wherein R 1 And R is 2 R is a hydrocarbon group having 1 to 10 carbon atoms or halogen 3 Is a hydrocarbon group having 1 to 10 carbon atoms, wherein x, y and z are positive integers, x is 0.ltoreq.2, y is 0.ltoreq.2 and z is 0.ltoreq.4, and x+y+z=4. (III) boron compound of the formula R 1 x R 2 y B(OR 3 ) z Boron compounds without active hydrogen atoms, where R 1 And R is 2 R is a hydrocarbon group having 1 to 10 carbon atoms or halogen 3 Is hydrocarbon group with 1-10 carbon atoms, 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=3.
In a still further preferred embodiment, the silicon-containing compound is selected from one or more of silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and tetrakis (2-ethylhexyloxy) silane, preferably silicon tetrachloride, tetraethoxysilane; the boron-containing compound is selected from one or more of boron trichloride, trimethoxyborane, triethoxy borane, tripropoxy borane and tributoxy borane, preferably boron trichloride, triethoxy borane.
Wherein the electron donor is used as a Lewis base in a magnesium/titanium composite main catalyst for olefin polymerization, and provides electron pairs to metals in the catalyst.
According to a preferred embodiment of the present invention, the electron donor is used in an amount of 0 to 5mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the electron donor is used in an amount of 0 to 1mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is based on the molar amount of magnesium element therein.
In the present invention, most preferably, in the magnesium/titanium composite main catalyst, the aluminum-containing inorganic substance is 0.0075 to 0.4mol, the tin tetrachloride is 0.1 to 0.65mol, the alcohol compound is 3.5 to 6mol, the acyl halide compound is 0.05 to 1.25mol, the electron donor compound is 0 to 0.7mol, and the halide or derivative of titanium is 6.0 to 20mol, per mol of the magnesium-containing compound.
The second object of the present invention is to provide a method for preparing a magnesium/titanium composite main catalyst for olefin polymerization, which comprises the following steps:
step 1, mixing a magnesium-containing compound, an aluminum-containing inorganic substance, an alcohol compound and tin tetrachloride in the presence of an inert diluent to obtain a mixed solution;
step 2, cooling, then dripping the halide of titanium or the derivative thereof into the mixed solution, or dripping the mixed solution into the halide of titanium or the derivative thereof for reaction;
and step 3, heating, stirring and post-treating after the reaction to obtain the magnesium/titanium composite main catalyst for olefin polymerization.
According to a preferred embodiment of the invention, in step 1, the mixing is performed at a temperature of 0 to 170 ℃, preferably 40 to 140 ℃, more preferably the mixing is performed with stirring.
In a further preferred embodiment, in step 1, the inert diluent may be selected from one or more of benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbon or halogenated hydrocarbon compounds.
The term inert means that the diluent should not take part in the reaction and should not adversely affect the dissolution of the magnesium-containing compound.
According to a preferred embodiment of the invention, in step 2, the temperature is reduced to-35 to 60 ℃, preferably-30 to 20 ℃.
According to a preferred embodiment of the invention, in step 3, the temperature is raised to 10 to 150 ℃, preferably to 20 to 130 ℃.
In a further preferred embodiment, in step 3, the post-treatment comprises sedimentation, filtration, washing of the solids and drying.
Wherein the mother liquor is filtered off and the solids are preferably washed with a hydrocarbon solvent.
According to a preferred embodiment of the invention, an electron donor is optionally added in step 1 or step 2.
In the present invention, the magnesium/titanium composite main catalyst for olefin polymerization is obtained as powdery solid particles with an average particle diameter of about 2-50 microns, and the particle size can be controlled by changing the preparation conditions.
The third object of the present invention is to provide a catalyst for polymerization comprising a main catalyst and a cocatalyst, wherein the main catalyst is the magnesium/titanium composite main catalyst for olefin polymerization according to one of the objects of the present invention or the magnesium/titanium composite main catalyst for olefin polymerization obtained by the preparation method according to the second object of the present invention, and the cocatalyst is an organoaluminum compound.
According to a preferred embodiment of the invention, the organoaluminium compound has the general formula AlR n X 3-n Wherein: r is C 1 ～C 20 Preferably R is selected from alkyl, aralkyl or aryl; x is halogen, preferably chlorine or bromine; n is an integer of 0 < n.ltoreq.3.
In a further preferred embodiment, the organoaluminum compound is selected from one or more of trialkylaluminum, alkylaluminum hydride and alkylaluminum chloride.
Wherein the trialkylaluminum comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, and the like; the alkylaluminum hydride includes diethylaluminum monohydride, diisobutylaluminum monohydride and the like; the alkyl aluminum chloride comprises diethyl aluminum chloride, diisobutyl aluminum chloride, sesquiethyl aluminum chloride, ethyl aluminum dichloride and the like.
In a still further preferred embodiment, the organoaluminum compound is selected from triethylaluminum and/or triisobutylaluminum.
According to a preferred embodiment of the present invention, in the catalyst, the molar ratio of the organoaluminum compound to the magnesium/titanium composite main catalyst for olefin polymerization is (5 to 1000): 1, preferably (20 to 800): 1.
Wherein the molar amount of the magnesium/titanium composite procatalyst for olefin polymerization is calculated on the molar amount of the titanium element therein, and the molar amount of the organoaluminum compound is calculated on the molar amount of the aluminum element therein.
In the present invention, the magnesium/titanium composite procatalyst for olefin polymerization may be used in the form of a solid or suspension, and the magnesium/titanium composite procatalyst for olefin polymerization and the organoaluminum compound may be directly applied to the polymerization system or may be pre-complexed and then applied to the polymerization system.
It is a fourth object of the present invention to provide the use of the catalyst according to the third object of the present invention in the polymerization of olefins, both for the homo-and co-polymerization of olefins, preferably for the homo-polymerization of ethylene or for the co-polymerization of ethylene with alpha-olefins selected from one or more of propylene, butene, pentene, hexene, octene and 4-methyl 1-pentene.
Wherein, liquid phase polymerization or gas phase polymerization can be used in the polymerization. In the case of the liquid phase polymerization, an inert solvent such as saturated aliphatic hydrocarbon or aromatic hydrocarbon, e.g., propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., may be used as the reaction medium, and the polymerization may be performed before the polymerization. The polymerization may be carried out batchwise, semi-continuously or continuously.
In the polymerization, the polymerization temperature is preferably from 50℃to 100℃and is from room temperature to 150 ℃. 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 beneficial effects:
(1) The magnesium/titanium composite main catalyst for olefin polymerization and the preparation method thereof avoid using phosphorus-containing compounds and phthalic anhydride with larger toxicity, and are more beneficial to environmental protection;
(2) The magnesium/titanium composite main catalyst for olefin polymerization contains stannic chloride, is more favorable for precipitation of the main catalyst during preparation, and endows the main catalyst with more excellent bulk density;
(3) The preparation method omits the dissolution reaction step of the precipitation aid, and shortens the preparation period of the magnesium/titanium composite main catalyst for olefin polymerization;
(4) The catalyst of the invention has better activity and bulk density, and especially the polymerization activity of the catalyst is obviously improved after the acyl halide compound is added
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Example 1
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.0015mol of metallic aluminum, 0.4mol of n-decane, 0.0043mol of anhydrous stannic chloride, 0.13mol of isooctanol and 0.04mol of n-butanol are added, the temperature is raised to 130 ℃ for 1 hour, the temperature is lowered to 70 ℃, 0.002mol of benzoyl chloride is added, the temperature is lowered to-5 ℃, then 0.6mol of titanium tetrachloride is dripped into the mixture for half an hour, 0.015mol of silane is added for 1 hour, and then the temperature is raised to 110 ℃ for maintenanceAfter 1 hour, the mixture was filtered, washed with hexane for 4 times and dried in vacuo to give a magnesium/titanium composite main catalyst for olefin polymerization.
Example 2
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.006mol 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 ℃ for half an hour, 0.07mol of n-butanol is added, the mixture is maintained for half an hour, the temperature is lowered to 70 ℃, 0.010mol of benzoyl chloride is added, the temperature is lowered to-10 ℃, then 0.5mol of titanium tetrachloride is dripped into the mixture for 1 hour, the temperature is raised to 110 ℃ for 1 hour, the mixture is filtered, washed for 4 times by hexane, and the mixture is dried in vacuum, so that the magnesium/titanium composite main catalyst for olefin polymerization is obtained.
Example 3
In the warp of high purity N 2 In the fully replaced reactor, 0.03mol of anhydrous MgCl is added in sequence 2 0.012mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride and 0.017mol of anhydrous tin tetrachloride are added, the reaction is maintained for 5 minutes, 0.13mol of isooctanol is added, the temperature is raised to 130 ℃ for half an hour, 0.05mol of n-butanol is added, the reaction is maintained for half an hour, the temperature is lowered to 70 ℃, 0.020mol of benzoyl chloride is added, the reaction is lowered to-15 ℃, then 0.45mol of titanium tetrachloride is dripped into the reaction product, the reaction product is maintained for 1 hour, the reaction product is heated to 110 ℃ and maintained for 1 hour, and after filtration, the reaction product is washed for 4 times by hexane, and vacuum drying is carried out, thus obtaining the magnesium/titanium composite main catalyst for olefin polymerization.
Example 4
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.0003mol of anhydrous aluminum chloride and 0.6mol of toluene, 0.026mol of anhydrous tin tetrachloride and 0.09mol of n-butanol are added, 0.08mol of ethanol are added, the temperature is raised to 80 ℃ for 1 hour, 0.050mol of benzoyl chloride is added, the temperature is lowered to 0 ℃, 0.3mol of titanium tetrachloride is dripped into the mixture for half an hour, the temperature is raised to 85 ℃ for 1 hour, the mixture is filtered, washed for 4 times by hexane, and vacuum drying is carried out, so that the magnesium/titanium composite main catalyst for olefin polymerization is obtained.
Example 5
In the warp of high purity N 2 In the fully replaced reactor, 0.03mol of anhydrous MgCl is added in sequence 2 0.012mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride and 0.017mol of anhydrous tin tetrachloride are added, the reaction is maintained for 5 minutes, 0.13mol of isooctanol and 0.05mol of phenethyl alcohol are added, the temperature is raised to 130 ℃, the reaction is maintained for 1 hour, the temperature is lowered to 70 ℃, 0.020mol of benzoyl chloride is added, the temperature is lowered to-15 ℃, then 0.45mol of titanium tetrachloride is dripped into the reaction product, the reaction is maintained for 1 hour, the reaction product is filtered, washed for 4 times by hexane, and vacuum drying is carried out, so that the magnesium/titanium composite main catalyst for olefin polymerization is obtained.
Example 6
In the warp of high purity N 2 In the fully replaced reactor, 0.03mol of anhydrous MgCl is added in sequence 2 0.003mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.02mol of silicon tetrachloride and 0.017mol of anhydrous tin tetrachloride are added, the reaction is maintained for 5 minutes, 0.15mol of isooctanol is added, the temperature is raised to 130 ℃, the reaction is maintained for 1 hour, the temperature is lowered to 70 ℃, 0.020mol of benzoyl chloride is added, the temperature is lowered to-15 ℃, then 0.60mol of titanium tetrachloride is dripped into the reaction product for 1 hour, the reaction is raised to 110 ℃ and maintained for 1 hour, the reaction product is filtered, washed for 4 times by hexane, and vacuum drying is carried out, so that the magnesium/titanium composite main catalyst for olefin polymerization is obtained.
Comparative example 1
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.6mol of toluene, 0.03mol of epichlorohydrin, 0.02mol of tributyl phosphate and 0.06mol of ethanol are added under stirring, the temperature is raised to 60 ℃, the temperature is maintained for 1 hour, 0.0074mol of phthalic anhydride is added for half an hour, the solution is cooled to-15 ℃, 0.36mol of titanium tetrachloride is dripped into the solution for 1 hour, the temperature is raised to 60 ℃ for 1 hour, the filtration is carried out, the washing is carried out for 4 times by hexane, and the vacuum drying is carried out, thus obtaining the magnesium/titanium composite main catalyst for olefin polymerization.
Comparative example 2
Example 1 was repeated with the difference that: the phthalic anhydride was changed to 0.011mol only.
Comparative example 3
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.30mol of n-decane, adding 0.15mol of 2-ethylhexanol under stirring, heating to 115 ℃, maintaining the temperature for 1 hour, cooling to 50 ℃, adding 0.026mol of silicon tetrachloride, cooling the solution to-10 ℃, dripping 0.45mol of titanium tetrachloride into the solution, maintaining the temperature for 1 hour, heating to 120 ℃, maintaining the temperature for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the magnesium/titanium composite main catalyst for olefin polymerization.
Comparative examples 4 to 6
Comparative examples 4 to 6 are the procedures of examples 1 to 3, respectively, repeated except that benzoyl chloride was not used.
Experimental example ethylene polymerization
Stainless steel kettle with volume of 2 liters is subjected to H 2 After sufficient displacement, 1000mL of hexane, 1.0mL of a 1mol/L triethylaluminum hexane solution, and metered (9 to 12 mg) of the magnesium/titanium composite main catalysts for olefin polymerization prepared in examples 1 to 4 and comparative examples 1 to 6 were added thereto, the temperature was raised to 70℃and hydrogenated to 0.26MPa (gauge pressure), and ethylene was introduced into the reactor to 0.72MPa (gauge pressure), and polymerization was carried out at 80℃for 2 hours. The results are shown in Table 1.
Table 1:
as can be seen from the data in table 1, the catalysts of the present invention have better activity, bulk density and melt index under the same polymerization conditions than comparative examples 1 to 3; also, the polymerization activity was more excellent than comparative examples 4 to 6, indicating that the addition of the acid halide compound significantly improved the polymerization activity of the catalyst.
Claims (16)
1. The magnesium/titanium composite main catalyst for olefin polymerization is characterized in that the preparation raw materials of the magnesium/titanium composite main catalyst for olefin polymerization comprise magnesium-containing compounds, aluminum-containing inorganic substances, stannic chloride, alcohol compounds, acyl halide compounds and titanium halides or derivatives thereof; wherein the aluminum-containing inorganic substance is selected from at least one of metallic aluminum and/or an inorganic aluminum compound, based on 1mol of a magnesium-containing compound, the aluminum-containing inorganic substance is used in an amount of 0.002 to 1mol, the tin tetrachloride is used in an amount of 0.005 to 4mol, the alcohol compound is used in an amount of 0.1 to 10mol, the acid halide compound is used in an amount of 0.01 to 4.0mol, and the halide or derivative thereof is used in an amount of 0.2 to 100mol, wherein the molar amount of the magnesium-containing compound is calculated on the molar amount of magnesium element therein, the aluminum-containing inorganic substance is calculated on the molar amount of aluminum element therein, and the halide or derivative thereof is calculated on the molar amount of titanium element therein.
2. A magnesium/titanium composite main catalyst for olefin polymerization according to claim 1, wherein the catalyst is prepared by reacting, based on 1mol of a magnesium-containing compound,
the dosage of the aluminum-containing inorganic matters is 0.005-0.5 mol; and/or
The consumption of the stannic chloride is 0.02-1 mol;
wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the aluminum-containing inorganic substance is calculated based on the molar amount of the aluminum element therein.
3. The magnesium/titanium composite main catalyst for olefin polymerization according to claim 1, wherein,
the magnesium-containing compound is selected from one or more of magnesium dihalide, water or alcohol complex of magnesium dihalide and magnesium dihalide derivative, wherein the magnesium dihalide derivative is a derivative in which one halogen atom in a magnesium dihalide molecule is substituted by a hydrocarbon group or a hydrocarbyloxy group; and/or
The metal aluminum is nano aluminum powder; the inorganic aluminum compound is fine powder anhydrous aluminum chloride;
the acyl halide compound has the general formula of R (COX) a Wherein R is H, C 1 ～C 8 Aliphatic radical, C 1 ～C 8 Halogenated aliphatic hydrocarbon radicals, C 6 ～C 10 Aromatic hydrocarbon or C of (2) 6 ～C 10 X is halogen and a is 1 or 2.
4. A magnesium/titanium composite main catalyst for olefin polymerization according to claim 3, wherein,
the magnesium dihalide is selected from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide; and/or
The acyl halide compound is acyl chloride compound.
5. The magnesium/titanium composite procatalyst for olefin polymerization according to claim 4, wherein said acid halide compound is selected from at least one of benzoyl chloride, formyl chloride and dichloroacetyl chloride.
6. The magnesium/titanium composite main catalyst for olefin polymerization according to claim 1, wherein,
the alcohol compound is selected from C 1 ～C 12 Fatty alcohol, C 7 ～C 12 One or more of the aromatic alcohols and substituted alcohols, wherein the substituted alcohol is a compound selected from the group consisting of C 1 ～C 12 Fatty alcohol or C of (C) 7 ～C 12 Substituted alcohols derived from aromatic alcohols; and/or
The general formula of the halide or the derivative of the titanium is TiX n (OR) 4-n Wherein: x represents halogen, R represents C 1 ～C 14 Aliphatic hydrocarbon radicals or C 6 ～C 14 An aromatic hydrocarbon group, n is an integer of 0 to 4; and/or
The preparation raw material optionally further comprises an electron donor.
7. The magnesium/titanium composite main catalyst for olefin polymerization according to claim 6, wherein,
the alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol and phenethyl alcohol; and/or
The halide of titanium or the derivative thereof is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy and titanium trichloromonoethoxy; and/or
The electron donor is selected from one or more of an organic ether, a silicon-containing compound and a boron-containing compound.
8. The magnesium/titanium composite procatalyst for olefin polymerization according to claim 6, wherein the catalyst is prepared by reacting 1mol of the magnesium-containing compound,
the dosage of the alcohol compound is 0.2 to 6 mol; and/or
The usage amount of the acyl halide compound is 0.02-2.0 mol; and/or
The usage amount of the halide or the derivative of the titanium is 1.0 to 20mol; and/or
The dosage of the electron donor is 0-5 mol;
wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the halide of titanium or the derivative thereof is calculated based on the molar amount of the titanium element therein.
9. The method for preparing a magnesium/titanium composite main catalyst for olefin polymerization according to any one of claims 1 to 8, characterized in that the preparation method comprises the steps of:
step 1, mixing a magnesium-containing compound, an aluminum-containing inorganic substance, an alcohol compound and tin tetrachloride in the presence of an inert diluent, and then adding an acyl halide compound to obtain a mixed solution;
step 2, cooling, then dripping the halide of titanium or the derivative thereof into the mixed solution, or dripping the mixed solution into the halide of titanium or the derivative thereof for reaction;
and step 3, heating, stirring and post-treating after the reaction to obtain the magnesium/titanium composite main catalyst for olefin polymerization.
10. The method according to claim 9, wherein,
in the step 1, the mixing is carried out at a temperature of 0-170 ℃; and/or
In step 1, the inert diluent is selected from one or more of benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene, and other hydrocarbons or halogenated hydrocarbons; and/or
In the step 2, the temperature is reduced to minus 35 to 60 ℃; and/or
In the step 3, the temperature is raised to 10-150 ℃; and/or
In step 3, the post-treatment includes sedimentation, filtration, washing of solids and drying; and/or
Optionally, an electron donor is added in step 1 or step 2.
11. The method according to claim 10, wherein,
in the step 1, the mixing is carried out at 40-140 ℃; and/or
In the step 2, the temperature is reduced to minus 30 to 20 ℃; and/or
In step 3, the temperature is raised to 20-130 ℃.
12. A catalyst for polymerization comprising a main catalyst and a cocatalyst, wherein,
the main catalyst is the magnesium/titanium composite main catalyst for olefin polymerization according to one of claims 1 to 8 or the magnesium/titanium composite main catalyst for olefin polymerization obtained by the preparation method according to one of claims 9 to 11, and the cocatalyst is an organic aluminum compound.
13. The polymerization catalyst according to claim 12, wherein,
the general formula of the organic aluminum compound is AlR n X 3-n Wherein: r is C 1 ～C 20 Is a hydrocarbon group of (2); x is halogen; n is an integer of 0 < n.ltoreq.3; and/or
In the catalyst, the molar ratio of the organic aluminum compound to the magnesium/titanium composite main catalyst for olefin polymerization is (5-1000): 1, a step of; wherein the molar amount of the magnesium/titanium composite procatalyst for olefin polymerization is calculated on the molar amount of the titanium element therein, and the molar amount of the organoaluminum compound is calculated on the molar amount of the aluminum element therein.
14. The polymerization catalyst according to claim 13, wherein,
the general formula of the organic aluminum compound is AlR n X 3-n Wherein: r is selected from alkyl, aralkyl or aryl; x is chlorine and/or bromine; n is an integer of 0 < n.ltoreq.3; and/or
In the catalyst, the molar ratio of the organic aluminum compound to the magnesium/titanium composite main catalyst for olefin polymerization is (20-800): 1, a step of; wherein the molar amount of the magnesium/titanium composite procatalyst for olefin polymerization is calculated on the molar amount of the titanium element therein, and the molar amount of the organoaluminum compound is calculated on the molar amount of the aluminum element therein.
15. Use of the catalyst for polymerization according to claim 13 or 14 in olefin polymerization.
16. Use according to claim 15, in ethylene homo-or copolymerization.
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