CN100363389C - Catalyst used for ethylene polymerization or copolymerization and its preparation method - Google Patents
Catalyst used for ethylene polymerization or copolymerization and its preparation method Download PDFInfo
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- CN100363389C CN100363389C CNB2004100782804A CN200410078280A CN100363389C CN 100363389 C CN100363389 C CN 100363389C CN B2004100782804 A CNB2004100782804 A CN B2004100782804A CN 200410078280 A CN200410078280 A CN 200410078280A CN 100363389 C CN100363389 C CN 100363389C
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- Prior art keywords
- titanium
- catalyzer
- component
- catalyst
- vinyl polymerization
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 31
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract description 12
- 239000005977 Ethylene Substances 0.000 title description 2
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- -1 magnesium halide Chemical class 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 239000003701 inert diluent Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000012456 homogeneous solution Substances 0.000 claims abstract description 11
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 229920002554 vinyl polymer Polymers 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 16
- 239000004615 ingredient Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 235000011007 phosphoric acid Nutrition 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000011949 solid catalyst Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 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 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000005049 silicon tetrachloride Substances 0.000 claims description 6
- 150000003609 titanium compounds Chemical class 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- KNOXYHBCQYPISX-UHFFFAOYSA-N butoxysilicon Chemical compound CCCCO[Si] KNOXYHBCQYPISX-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 2
- CADAOKXOWMHTKV-UHFFFAOYSA-N C(C)O[Ti](OCC)OCC.[Cl] Chemical compound C(C)O[Ti](OCC)OCC.[Cl] CADAOKXOWMHTKV-UHFFFAOYSA-N 0.000 claims description 2
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 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
- UFCXHBIETZKGHB-UHFFFAOYSA-N dichloro(diethoxy)silane Chemical compound CCO[Si](Cl)(Cl)OCC UFCXHBIETZKGHB-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
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 2
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 2
- PTVDYMGQGCNETM-UHFFFAOYSA-N trityl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OC(=O)C(=C)C)C1=CC=CC=C1 PTVDYMGQGCNETM-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 239000000470 constituent Substances 0.000 abstract 1
- 150000002118 epoxides Chemical class 0.000 abstract 1
- 238000012685 gas phase polymerization Methods 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000035945 sensitivity Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 235000011147 magnesium chloride Nutrition 0.000 description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical class Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- DIQFNLWXHNEONM-UHFFFAOYSA-N 2-chloroethoxysilicon Chemical compound [Si]OCCCl DIQFNLWXHNEONM-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JSQIOVKHLRAROY-UHFFFAOYSA-N C(CC)O[Si](OCCC)OCCC.[Cl] Chemical compound C(CC)O[Si](OCCC)OCCC.[Cl] JSQIOVKHLRAROY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WZBHHSQKLRFBQY-UHFFFAOYSA-N O(C)[Si](OC)OC.[Cl] Chemical compound O(C)[Si](OC)OC.[Cl] WZBHHSQKLRFBQY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000004067 aliphatic alkene group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HRYDYCUCHYGDBK-UHFFFAOYSA-N dibutoxy(dichloro)silane Chemical compound CCCCO[Si](Cl)(Cl)OCCCC HRYDYCUCHYGDBK-UHFFFAOYSA-N 0.000 description 1
- QEHKWLKYFXJVLL-UHFFFAOYSA-N dichloro(dimethoxy)silane Chemical compound CO[Si](Cl)(Cl)OC QEHKWLKYFXJVLL-UHFFFAOYSA-N 0.000 description 1
- LQGVEVWCWJGLAL-UHFFFAOYSA-N dichloro(dipropoxy)silane Chemical compound CCCO[Si](Cl)(Cl)OCCC LQGVEVWCWJGLAL-UHFFFAOYSA-N 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical class [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- DRNMMRVXQPVSNE-UHFFFAOYSA-N propoxysilicon Chemical compound CCCO[Si] DRNMMRVXQPVSNE-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 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
- 239000004711 α-olefin Substances 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention provides a catalyst for ethene polymerization or copolymerization and a preparation method thereof. The active constituent of the catalyst is a catalyst component containing titanium and formed by dissolving magnesium halide in an organic epoxide, an organic phosphorus compound, organic alcohol and an inert diluent to form a homogeneous solution, using the halide of titanium or a derivate thereof to separate a solid precipitate containing magnesium/titanium in the existence of a separation assisting agent and adopting at least one hydrogen regulation performance improver for treatment. When used for the ethene polymerization, the catalyst shows high activity and high hydrogen regulation sensitivity; simultaneously, the obtained polymer has good particle shape and high apparent density and is suitable for ethene slurry and gas-phase polymerization technologies.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for vinyl polymerization or copolymerization.
Background technology
In the polyreaction of alkene, particularly in the copolymerization of the polymerization of ethene or ethene and alpha-olefin, adopt with magnesium, titanium, halogen and electron donor basal component mostly as catalyzer.A kind of catalyzer that is used for vinyl polymerization or copolymerization is disclosed among the Chinese patent CN1229092A, it is to add a kind of low-carbon alcohol again as electron donor stimulator formation homogeneous solution by magnesium halide being dissolved in organic epoxy compounds, organo phosphorous compounds, halogenide and derivative effect thereof with at least a precipitation additive and transition metals Ti prepares again, this catalyzer has shown very high activity when being used for the slurry polymerization of ethene, the particle form of resulting polymers is better simultaneously, and apparent density is also higher.But this catalyzer hydrogen response is bad.When the resin of synthetic high fusion index, its activity is with the improve of hydrogen add-on, and it is very big to descend.To be unfavorable for polymkeric substance like this with a kind of Catalyst Production wide molecular weight distribution.
A kind of Primary Catalysts that is used to produce ethylene polymer is disclosed in Chinese patent CN1158136A, this catalyzer comprises a kind of inorganic carrier, preferred active silica carrier, a kind of chlorine compound on the carrier, a kind of magnesium compound on the carrier, a kind of titanium compound that is carried on the carrier of being carried on of being carried on.The characteristics of this catalyzer are: hydrogen response is good, and polymerization activity is with the raising of hydrogen add-on, and it is less to descend, and is suitable for the polyvinyl resin of production wide molecular weight distribution.But the complex manufacturing of this catalyzer, production cost is higher.
Summary of the invention
In order to overcome the deficiency of above-mentioned catalyst system, the purpose of this invention is to provide a kind of slurry polymerization that is suitable for ethene, be specially adapted to the polyvinyl catalyzer of production wide molecular weight distribution.This catalyzer is compared its advantage with existing catalyzer be the catalytic activity height, and copolymerization performance is good, and hydrogen response is good, and production technique is simple, and production cost is lower.
The present invention is used for the catalyzer of vinyl polymerization or copolymerization, comprises following component:
A, titaniferous ingredient of solid catalyst, it is by magnesium halide being dissolved in organic epoxy compounds, organo phosphorous compounds, organic alcohol compound and the inert diluent, form homogeneous solution, halogenide or derivatives thereof with titanium in the presence of precipitation additive is separated out the precipitation of solid material that contains magnesium/titanium, adopt at least a hydrogen regulation performance improving agent to handle solid ingredient, after washing, drying, obtain the particulate solid catalyzer;
B, organo-aluminium compound;
Ratio between B component and the component A is 5～1000 with aluminium and titanium molar ratio computing.
Magnesium halide described in the catalyst component A of the present invention is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in alkyl or the-oxyl institute metathetical derivative of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.Above-mentioned magnesium dihalide is specially: magnesium dichloride, dibrominated magnesium, two magnesium iodides, preferred magnesium dichloride.
Organic epoxy compounds described in the catalyst A component of the present invention is selected from and comprises the compounds such as oxide compound, glycidyl ether and inner ether of carbonatoms at 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, tetrahydrofuran (THF) etc.
Organo phosphorous compounds described in the catalyst A component of the present invention is selected from the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, for example: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, phosphorous acid benzene methyl etc.
Precipitation additive described in the catalyst A component of the present invention is selected from a kind of in organic acid, organic acid anhydride, organic ether, the organic ketone or their mixture.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, pyromellitic acid anhydride, acetic acid, propionic acid, butyric acid, vinylformic acid, methacrylic acid, acetone, methylethylketone, benzophenone, methyl ether, ether, propyl ether, butyl ether, amyl ether etc.
Organic alcohol is the straight chain alcohol or the isomery alcohol of 1～8 carbon atom among the catalyst component A of the present invention, for example: a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, octanol, the 2-Ethylhexyl Alcohol, or their mixture.
The general formula of the compound of the transition metals Ti described in the catalyst component A of the present invention is Ti (OR) 4-nXn, R is aliphatic hydrocarbyl or the aromatic hydrocarbyl of C1～C14 in the formula, X is a halogen atom, n is 1 to 4 integer, specifically can select a kind of in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, trichlorine one ethanolato-titanium or their mixture for use, preferred titanium tetrachloride.
The described hydrogen regulation performance improving agent of catalyst component A of the present invention is the silicon compounds, and its general formula is Si (OR)
aX
b, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0 to 4 integer, b is 0 to 4 integer, a+b=4.Concrete as trichlorine methoxyl group silicon, three chloroethoxy silicon, trichlorine propoxy-silicon, trichlorine butoxy silicon, dichloro dimethoxy silicon, dichloro diethoxy silicon, dichloro dipropoxy silicon, dichloro dibutoxy silicon, one chlorine trimethoxy silicon, a chlorine triethoxysilicane, a chlorine tripropoxy silicon, one chlorine, three butoxy silicon, tetramethoxy-silicane, tetraethoxy-silicane, tetrapropoxy-silicane, four butoxy silicon, silicon tetrachloride etc., preferred silicon tetrachloride, tetraethoxy-silicane.
Inert diluent described in the catalyst component A of the present invention is pentane, hexane, heptane, octane, decane, benzene, toluene, dimethylbenzene and derivative thereof.
Mol ratio between described each component of catalyst component A of the present invention is in every mole of magnesium halide, 0.01～10 mole of organic epoxy compounds, with 0.02～4 mole for well; 0.01～10 mole of organo phosphorous compounds, with 0.02～4 mole for well; 0.02～0.8 mole of precipitation additive, with 0.03～0.5 mole for well; Organic pure 0.005～15 mole, with 0.05～10 mole for well; 0.2～20 mole of the compound of transition metals Ti, with 1～15 mole for well; 0.005～15 mole of hydrogen regulation performance improving agent, with 0.06～10 mole for well.
Its chemical ingredients of catalyst component A of the present invention is mainly titaniferous 1～10%, magnesium 10～20%, and chlorine 40～70%, hydrogen regulation performance improving agent 5～25%, organic pure 0.01～5%, inert diluent 0～10%.
The described alkylaluminium cpd of catalyst component B of the present invention, its general formula is AlRnX3-n, in the formula R can for hydrogen, and carbonatoms be 1～20 alkyl, particularly alkyl, aralkyl, aryl; X is particularly chlorine and a bromine of halogen; N is the number of 0＜n≤3.Particular compound is as aluminum alkyl halides such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, sesquialter ethyl aluminum chloride, two different aluminium triethyl, wherein with triethyl aluminum, triisobutyl aluminium for well.
In the catalyst system of the present invention, in the B component among aluminium and the component A mol ratio of titanium be 5～1000, be preferably 100～800.
The preparation method of catalyst component A of the present invention is: (1) under agitation is dissolved in magnesium halide organic epoxy compounds, organo phosphorous compounds, organic alcohol compound and and inert diluent in, form homogeneous solution, in the presence of precipitation additive, under-30～60 ℃ of temperature, be preferably-30～5 ℃, titanium compound is splashed into above-mentioned magnesium halide homogeneous solution or the magnesium halide homogeneous solution is splashed in the titanium compound, reaction mixture is warming up to 60～110 ℃ again, suspension was stirred under this temperature 0.1～10 hour, the elimination mother liquor, after the inert diluent washing, filter, adding inert diluent and hydrogen regulation performance improving agent reacted 0.5～8 hour down at 50～100 ℃, through the inert diluent washing, filter, obtain titaniferous ingredient of solid catalyst after the drying.
The present invention compares with prior art, has following obvious advantage: the invention provides a kind of slurry polymerization that is suitable for ethene, be specially adapted to the polyvinyl catalyzer of production wide molecular weight distribution.This catalyzer is compared its advantage with existing catalyzer be the catalytic activity height, copolymerization performance is good, hydrogen response is good, catalyzer and polymer beads form are good, characteristics such as fine powder content is low, be highly suitable for ethylene thick liquid polymerizing technology, be particularly suitable for adopting the polyvinyl production technique of double-reactor production wide molecular weight distribution; And production technique is simple, and production cost is lower.
Embodiment
Further describe the present invention below in conjunction with embodiment, scope of the present invention is not subjected to the restriction of these embodiment.Scope of the present invention proposes in claims.
Embodiment 1
Preparation of Catalyst:
With 4.8 gram magnesium chlorides, 40 milliliters of toluene, 3.0 milliliter epoxy chloropropane, 3.6 milliliter tributyl phosphate, 10.0 milliliter ethanol joins in the reactor, at mixing speed 450rpm, temperature is under 60 ℃ the condition, reacted two hours, add 0.7 gram Tetra hydro Phthalic anhydride, continue reaction one hour, be cooled to-5 ℃, drip 22 milliliters of titanium tetrachlorides, be warming up to 80 ℃ gradually, constant temperature one hour, the elimination mother liquor after 4 washings of hexane, filters, add 150 milliliters of hexanes again, drip 10.0 milliliters of silicon tetrachlorides at 60 ℃, constant temperature one hour is after 2 washings of hexane obtain ingredient of solid catalyst after the drying.
Polymerization:
Condition 1: 2 liter polymeric kettles are filled hydrogen hocket three times with vacuumizing, add 1 liter normal hexane, 2mmol triethyl aluminum and 10 milligrams of solid catalysts, be warming up to 70 ℃ of hydrogen that add 0.28MPa, arrive 0.73MPa with the ethene ftercompction then, reacted 2 hours down at 80 ℃, after reaction finishes, cooling separated and collected polymkeric substance.
Condition 2: 2 liter polymeric kettles are filled hydrogen hocket three times, add 1 liter normal hexane, 2mmol triethyl aluminum and 40 milligrams of solid catalysts with vacuumizing.Be warming up to 70 ℃ of hydrogen that add 0.58MPa, arrive 0.73MPa with the ethene ftercompction then, reacted 2 hours down at 80 ℃, after reaction finished, the separated and collected of lowering the temperature polymkeric substance carried out performance test to polyvinyl resin, the results are shown in Table 1.
Embodiment 2
Preparation of Catalyst:
With 4.8 gram magnesium chlorides, 40 milliliters of toluene, 3.0 milliliter epoxy chloropropane, 3.6 milliliter tributyl phosphate, 7.0 milliliter ethanol joins in the reactor, at mixing speed 450rpm, temperature is under 60 ℃ the condition, reacted two hours, add 0.7 gram Tetra hydro Phthalic anhydride, continue reaction one hour, be cooled to-5 ℃, drip 22 milliliters of titanium tetrachlorides, be warming up to 80 ℃ gradually, constant temperature one hour, the elimination mother liquor, through 4 washings of hexane, after the filtration, add 150 milliliters of hexanes again, drip 2 milliliters of silicon tetrachlorides at 60 ℃, constant temperature one hour is after 2 washings of hexane obtain ingredient of solid catalyst after the drying.
Polymerization
With embodiment 1, the results are shown in Table 1.
Embodiment 3
Preparation of Catalyst
Other condition is with embodiment 1, and the silicon tetrachloride consumption changes 5 milliliters into.
Polymerization
With embodiment 1, the results are shown in Table 1.
Embodiment 4
Preparation of Catalyst
Other condition is with embodiment 1, and the silicon tetrachloride consumption changes 8 milliliters into.
Polymerization
With embodiment 1, the results are shown in Table 1.
Embodiment 5
Preparation of Catalyst
Other condition is with embodiment 1, and the silicon tetrachloride consumption changes 15 milliliters into.
Polymerization
With embodiment 1, the results are shown in Table 1.
Embodiment 6
Preparation of Catalyst
Other condition drips 5 milliliters of silicon tetrachlorides and changes 3.3 milliliters of dropping tetraethoxy-silicanes into embodiment 1.
Polymerization
With embodiment 1, the results are shown in Table 1.
Comparative example
Comparative example 1
4.8 gram magnesium chlorides, 40 milliliters of toluene, 3.0 milliliters of epoxy chloropropane, 3.6 milliliters of tributyl phosphates, 7.0 milliliters of ethanol are joined in the reactor, be under 60 ℃ the condition in mixing speed 450rpm, temperature, reacted two hours, add 0.7 gram Tetra hydro Phthalic anhydride, continue reaction one hour, be cooled to-5 ℃, drip 22 milliliters of titanium tetrachlorides, be warming up to 80 ℃ gradually, constant temperature one hour, the elimination mother liquor repeatedly washs after drying through inert diluent toluene and organic solvent hexane, obtains ingredient of solid catalyst.
Carry out polymerization with above-mentioned catalyst component as Primary Catalysts, polymerizing condition the results are shown in Table 1 with embodiment 1.
Table 1: polymerization result
| Embodiment | Condition 1 | Condition 2 | ||||
| Active (gPE/gCat) | BD (g/cm 3) | MI (g/10min) | Active (gPE/gCat) | BD (g/cm 3) | MI (g/10min) | |
| 1 | 45000 | 0.32 | 0.78 | 5010 | 0.33 | 177 |
| 2 | 42200 | 0.32 | 0.42 | 4380 | 0.34 | 68.9 |
| 3 | 41560 | 0.33 | 0.45 | 4107 | 0.36 | 75.8 |
| 4 | 43560 | 0.31 | 0.59 | 4585 | 0.37 | 95.0 |
| 5 | 41950 | 0.33 | 0.63 | 4830 | 0.35 | 86.5 |
| 6 | 45200 | 0.33 | 0.68 | 2392 | 0.33 | 105 |
| Comparative example | - | - | - | - | - | - |
| 1 | 39800 | 0.31 | 0.42 | 5210 | 0.32 | 55.9 |
Claims (14)
1. a catalyzer that is used for vinyl polymerization or copolymerization is characterized in that, comprises following component:
A, titaniferous ingredient of solid catalyst, it is by magnesium halide being dissolved in organic epoxy compounds, organo phosphorous compounds, organic alcohol compound and the inert diluent, form homogeneous solution, halogenide or derivatives thereof with titanium in the presence of precipitation additive is separated out the precipitation of solid material that contains magnesium/titanium, adopt at least a hydrogen regulation performance improving agent to handle solid ingredient, after washing, drying, obtain the particulate solid catalyzer; Hydrogen regulation performance improving agent wherein is the silicon compounds, and its general formula is Si (OR)
aX
b, R is C in the formula
1～C
14Aliphatic hydrocarbyl or aromatic hydrocarbyl, X is a halogen, a is 0 to 4 integer, b is 0 to 4 integer, a+b=4;
B, organo-aluminium compound;
Ratio between B component and the component A is 5～1000 with aluminium and titanium molar ratio computing.
2. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that, magnesium halide described in the component A is a magnesium dihalide, the complex compound of the water of magnesium dihalide and alcohol, a kind of by in the derivative that alkyl or-oxyl replaced of one of them halogen atom in the magnesium dihalide molecular formula, or their mixture.
3. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that, organic epoxy compounds described in the catalyst A component is selected from oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, a kind of in butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, the diglycidylether or their mixture.
4. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that the organo phosphorous compounds described in the catalyst A component is selected from a kind of in ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, the phosphorous acid benzene methyl or their mixture.
5. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, the organic alcohol compound described in the catalyst A component is straight chain alcohol or the isomery alcohol of C1～C8.
6. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that the described organic alcohol compound of component A is a kind of in methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, the 2-Ethylhexyl Alcohol or their mixture.
7. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, the described inert diluent of component A is pentane, hexane, heptane, octane, decane, benzene, toluene, dimethylbenzene and derivative thereof.
8. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1, it is characterized in that, the compound of the described transition metals Ti of component A is a titanium tetrahalide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro diethoxy titanium, a kind of in the three chloro-ethanolato-titaniums, or their mixture.
9. the catalyzer that is used for vinyl polymerization or copolymerization described in according to Claim 8, the compound that it is characterized in that the transition metals Ti described in the component A is a titanium tetrachloride.
10. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, the described hydrogen regulation performance properties-correcting agent of component A is silicon tetrachloride, tetraethoxy-silicane, four butoxy silicon, a chlorine triethoxysilicane, dichloro diethoxy silicon.
11. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, the consumption mol ratio of magnesium halide and hydrogen regulation performance improving agent is: 1: 0.005～15.
12. the catalyzer that is used for vinyl polymerization or copolymerization according to claim 1 is characterized in that, the consumption mol ratio of magnesium halide and organic alcohol is: 1: 0.005～15.
13. the preparation method of the described catalyst component A of one of claim 1～12 is: (1) under agitation is dissolved in magnesium halide organic epoxy compounds, organo phosphorous compounds, organic alcohol compound and and inert diluent in, form homogeneous solution, in the presence of precipitation additive, under-30～60 ℃ of temperature, titanium compound is splashed into above-mentioned magnesium halide homogeneous solution or the magnesium halide homogeneous solution is splashed in the titanium compound, reaction mixture is warming up to 60～110 ℃ again, suspension was stirred under this temperature 0.1～10 hour, the elimination mother liquor, after the inert diluent washing, filter, adding inert diluent and hydrogen regulation performance improving agent reacted 0.5～8 hour down at 50～100 ℃, through the inert diluent washing, filter, obtain titaniferous ingredient of solid catalyst after the drying.
14. the preparation method of catalyst component A according to claim 13, the temperature that titanium compound is splashed into the magnesium halide homogeneous solution is-30～5 ℃.
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| CN101274967B (en) * | 2007-03-28 | 2010-05-19 | 中国石油化工股份有限公司 | Catalyst for ethylene polymerization and components thereof |
| CN102977232B (en) * | 2011-09-02 | 2015-08-19 | 中国石油化工股份有限公司 | A kind of catalyst system for vinyl polymerization |
| CN103772546B (en) * | 2012-10-23 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of catalyst component for polymerization of ethylene and catalyst thereof |
| CN104974279B (en) * | 2014-04-11 | 2017-08-25 | 中国石油化工股份有限公司 | Catalytic component and its catalyst and preparation method for ethylene polymerization |
| CN105199022B (en) * | 2014-06-18 | 2019-06-28 | 中国石油化工股份有限公司 | For ethylene homo conjunction or catalyst and its application of combined polymerization |
| CN112724287A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and preparation method and application thereof |
| CN111333755A (en) * | 2020-04-29 | 2020-06-26 | 江苏扬农化工集团有限公司 | Catalyst for preparing ultra-high molecular weight polyethylene and preparation method and application thereof |
| CN115975080B (en) * | 2021-10-14 | 2024-09-17 | 中国石油化工股份有限公司 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
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| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| WO2002038620A1 (en) * | 2000-11-10 | 2002-05-16 | Samsung General Chemicals Co., Ltd. | Method for producing a catalyst for homo- or co-polymerization of ethylene |
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| CN1298887A (en) * | 1999-12-06 | 2001-06-13 | 中国石油化工集团公司 | Catalyst system for polymerization or copolymerization of olefine |
| WO2002038620A1 (en) * | 2000-11-10 | 2002-05-16 | Samsung General Chemicals Co., Ltd. | Method for producing a catalyst for homo- or co-polymerization of ethylene |
| EP1349878A1 (en) * | 2000-11-10 | 2003-10-08 | Samsung General Chemicals Co., Ltd. | Method for producing a catalyst for homo- or co-polymerization of ethylene |
| CN1531558A (en) * | 2000-11-10 | 2004-09-22 | ������ѧ��ʽ���� | Method for producing catalyst for homo-or co-polymerization of ethylene |
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