CN1297575C - 用于乙烯聚合或共聚合的催化剂组分及其催化剂 - Google Patents
用于乙烯聚合或共聚合的催化剂组分及其催化剂 Download PDFInfo
- Publication number
- CN1297575C CN1297575C CNB2004100311280A CN200410031128A CN1297575C CN 1297575 C CN1297575 C CN 1297575C CN B2004100311280 A CNB2004100311280 A CN B2004100311280A CN 200410031128 A CN200410031128 A CN 200410031128A CN 1297575 C CN1297575 C CN 1297575C
- Authority
- CN
- China
- Prior art keywords
- compound
- catalyst component
- magnesium
- catalyst
- mole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000005977 Ethylene Substances 0.000 title abstract description 11
- -1 magnesium halide Chemical class 0.000 claims abstract description 30
- 239000011777 magnesium Substances 0.000 claims abstract description 27
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 9
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011949 solid catalyst Substances 0.000 claims description 4
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001399 aluminium compounds Chemical class 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 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 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 125000004067 aliphatic alkene group Chemical group 0.000 claims 1
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 12
- 239000004411 aluminium Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002002 slurry Substances 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002681 magnesium compounds Chemical class 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 abstract 1
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 235000011147 magnesium chloride Nutrition 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003701 inert diluent Substances 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 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 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- CADAOKXOWMHTKV-UHFFFAOYSA-N C(C)O[Ti](OCC)OCC.[Cl] Chemical compound C(C)O[Ti](OCC)OCC.[Cl] CADAOKXOWMHTKV-UHFFFAOYSA-N 0.000 description 1
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 description 1
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 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 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 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
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-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
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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Abstract
本发明提供了一种用于乙烯聚合或共聚合的催化剂组分,该催化剂组分的制备方法和含该催化剂组分的催化剂,其中所述的催化剂组分包含负载在无机氧化物载体上的镁复合物、至少一种钛化合物,至少一种有机醇化合物和至少一种有机铝的反应产物,所述的镁复合物是将卤化镁溶解在含有机环氧化合物和有机磷化合物的体系中。本发明的催化剂非常适用于乙烯的淤浆聚合工艺,所得聚合物的粒径均匀、粒径分布窄,并且催化剂具有较高的催化活性和较好的氢调敏感性。
Description
技术领域
本发明涉及一种用于乙烯聚合或共聚合的催化剂组分,该催化剂组分的制备方法和该催化剂组分的催化剂。
技术背景
众所周知,含Ti/Mg复合物的催化剂体系在聚乙烯的工业化生产中占主导地位,其研究核心不外乎在于催化剂的聚合活性、催化剂的颗粒形态和粒径分布、催化剂的氢调敏感性和共聚性能等等。而在乙烯的淤浆聚合工艺中,除要求催化剂应具有较高的催化活性外,控制所生产的乙烯聚合物的粒径大小和粒径分布是十分重要的。在乙烯聚合,特别是乙烯的淤浆法聚合过程中,很容易产生较细的聚合物例子,这种细粉易产生静电、造成“扬尘”现象,有时易结块,造成设备管道的堵塞。而控制聚合物的粒径大小和粒径分布最有效的方法是控制催化剂的粒径和粒径分布。
在现有技术中,为了得到具有均匀颗粒直径和较好颗粒形态的催化剂,人们通常采用以下的两类方法来制备催化剂。
第一种是将氯化镁等镁化合物溶解在某些溶剂中得到均匀溶液,然后再将该溶液与钛化合物和任选地给电子体混合,通过沉淀的方法得到含镁、钛和任选的给电子体的固体物,并将该固体物用过量的液态钛化合物进行处理后得到催化剂颗粒。例如中国专利CN1099041A、CN1229092、CN85100997等中所公开的。这种传统方法的缺点是催化剂颗粒的粒径和粒径分布完全是通过沉淀过程来控制的,其稳定性的控制比较困难,而且由于大量液态钛化合物的使用,给回收系统和环保方面带来很大问题,催化剂成本较高。同时,所得聚合物的颗粒分布较宽,粒径分布较难控制。
例如,在专利CN1229092中,以氯化镁为载体,四氯化钛为活性组分,催化剂的制备方法如下:先将MgCl2溶解在溶剂体系中,形成均匀透明溶液,然后在助析出剂存在下,低温下与TiCl4反应,通过缓慢升温析出固体催化剂。制得的催化剂组分用于乙烯聚合时,虽然聚合物的颗粒形态较好,但催化剂的氢调敏感性和催化活性还不令人满意。同时,在合成该催化剂时需采用具有一定毒性的苯酐等有机物作为助析出剂,不仅催化剂的成本较高,而且会造成一定的环境污染。
第二种是将催化剂活性组分直接负载于惰性载体,如硅胶等之上,由于硅胶的颗粒直径容易控制,而且颗粒形态较好,因此可得到颗粒均匀的催化剂粒子。但由于载体上活性组分的负载量受到限制,因此这种方法制得的催化剂中钛含量较低,聚合活性不高。例如:在专利CN1268520中,以氯化镁、二氧化硅为载体,四氯化钛为活性组分,催化剂的制备方法如下:将MgCl2在THF中与TiCl4反应,再与经烷基铝处理过的SiO2混合,除去THF后制得催化剂组分,在用于乙烯聚合时,由于催化剂中的钛含量较低,因此聚合活性较低。因此,这种催化剂体系虽然可用于乙烯的气相流化床聚合工艺,但由于较低的催化活性很难适用于乙烯的淤浆聚合工艺中。
同时,在乙烯的淤浆聚合工艺中,除要求催化剂应具有较高的催化活性和较好的颗粒分布外,为了生产具有较好性能的乙烯均聚物或共聚物,还要求催化剂应具有较好的氢调敏感性,即很容易地通过聚合过程中氢分压来调节最终聚合物的熔融指数,以得到不同商业牌号的聚乙烯树脂。而上述的催化剂体系的氢调敏感性还不令人满意。
因此,非常需要提供一种适用于乙烯的淤浆聚合工艺,催化活性高、粒径均匀、粒径分布窄,并且具有较好的氢调敏感性的催化剂。
发明内容
本发明提供了一种用于乙烯聚合或共聚合的催化剂组分,包含负载在无机氧化物载体上的镁复合物、至少一种钛化合物,至少一种有机醇化合物和至少一种有机铝的反应产物;
其中所述的镁复合物是将卤化镁溶解在含有机环氧化合物和有机磷化合物的溶剂体系中,
所述的有机醇化合物是碳原子数为1-10的直链、支链或环烷基的醇,
所述的有机铝化合物的通式为AlR1 nX1 3-n,式中R1为氢,碳原子数为1~20的烃基,X1为卤素,n为1<n≤3的数
所述的钛化合物通式为Ti(OR2)aX2 b,式中R2为C1~C14的脂族烃基或芳族烃基,X2为卤素,a是0、1或2,b是1至4的整数,a+b=3或4。。
在本发明所述的用于乙烯聚合或共聚合的催化剂组分中,对于所述的载体来说,一些无机氧化物都是适用的,但优选的是硅、铝、钛、铬和锆氧化物或它们的混合物,最优选二氧化硅材料、三氧化铝材料或它们的混合物。一般地,二氧化硅载体的形态呈球形,其平均粒径为1-50μm,优选5-30μm。其表面积≥200m2/g,优选≥250m2/g。平均孔隙度优选为1.4-1.8ml/g。这种载体物质应是干燥的,即不吸水的,优选在使用将其在≥600℃下进行活化,或者任选地采用烷基铝进行活化处理。
本发明所述的镁复合物是将二卤化镁溶解在含有机环氧化合物和有机磷化合物的溶剂体系中形成的复合物。通常这种复合物应是一均匀透明的溶液。
其中所述的卤化镁选自二卤化镁、二卤化镁的水或醇的络合物、二卤化镁分子式中其中一个或两个卤原子被烃基或卤烃氧基所置换的衍生物。具体的化合物如:二氯化镁、二溴化镁、氯化苯氧基镁、氯化异丙氧基镁、氯化丁氧基镁等,其中优选二氯化镁。所述卤化镁化合物可以单独或混合使用。
溶剂体系中所述的有机环氧化合物选自碳原子数在2~8的脂肪族烯烃、二烯烃或卤代脂肪组烯烃或二烯烃的氧化物、缩水甘油醚和内醚中的至少一种。例如但不局限于:环氧乙烷、环氧丙烷、环氧丁烷、丁二烯氧化物,丁二烯双氧化物、环氧氯丙烷、甲基缩水甘油醚、二缩水甘油醚。
溶剂体系中所述的有机磷化合物为正磷酸或亚磷酸的烃基酯或卤代烃基酯。具体如:正磷酸三甲酯、正磷酸三乙酯、正磷酸三丁酯、正磷酸三苯酯、亚磷酸三甲酯、亚磷酸三乙酯、亚磷酸三丁酯或亚磷酸苯甲酯。其中以每摩尔卤化镁计:有机环氧化合物:0.2-10mol,优选0.5~4mol;有机磷化合物:0.1~10mol,优选0.2~4mol mol。
为了使溶解更加充分,在该溶剂体系中可任选地加入惰性稀释剂,通常这种惰性稀释剂包括芳烃类化合物或烷烃类化合物,芳烃类化合物包括苯、甲苯、二甲苯、一氯代苯、二氯代苯、三氯代苯、一氯甲苯及其衍生物;烷烃包括3~20个碳的直链烷烃、支链烷烃或环烷烃中的一种或它们的混合物,如丁烷,戊烷,己烷,环己烷,庚烷等,只要有助于卤化镁溶解的都可以使用。上述的惰性稀释剂可单独使用,也可组合使用。
所述的有机醇化合物包括碳原子数为1-10的直链、支链或环烷基的醇,例如:甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、丙三醇,己醇,2-甲基戊醇,2-乙基丁醇,正庚醇,2-乙基己醇,正辛醇,癸醇等;环烷醇,如环己醇,甲基环己醇;优选乙醇、丁醇、2-乙基己醇、丙三醇。
所述的有机铝化合物的通式为AlR1 nX1 3-n,式中R1独立地为氢或碳原子数为1~20的烃基,,特别是烷基、芳烷基或芳基;X1为卤素,特别是氯和溴;n为0<n≤3的数。其中优选n不等于3。具体化合物如:三甲基铝、三乙基铝、三异丁基铝、三辛基铝、一氢二乙基铝、一氢二异丁基铝、一氯二乙基铝、一氯二异丁基铝、倍半乙基氯化铝、二氯乙基铝等烷基铝卤化物,其中优选烷基铝的卤化物,优以一氯二乙基铝为最好。
所述的钛化合物通式为Ti(OR2)aX2 b,式中R2为C1~C14的脂族烃基或芳族烃基,X2为卤素,a是0、1或2,b是1至4的整数,a+b=3或4。优选四氯化钛、四溴化钛、四碘化钛、四丁氧基钛、四乙氧基钛、一氯三乙氧基钛、三氯化钛、二氯二乙氧基钛、三氯一乙氧基钛中的一种或其混合物。
在本发明所述的用于乙烯聚合或共聚合的催化剂组分中,以每摩尔卤化镁计,有机醇化合物为:0.1-10摩尔,优选1-4摩尔;有机铝化合物为0.05~5摩尔,优选0.1-0.5摩尔。钛化合物为1~15摩尔,优选2~10摩尔。,无机氧化物载体用量为10-200g,优选为30~80g。
本发明上述的催化剂组分可采用以下的方法制备:
(1)将卤化镁溶解于含有机环氧化合物和有机磷化合物的溶剂体系中,优选地在溶剂体系中加入惰性稀释剂,形成均匀溶液,溶解温度:50-90℃;在形成溶液的过程中或溶液形成后加入有机醇化合物;在溶液形成后加入有机铝化合物,有机醇化合物和有机铝化合物可同时加入也可分别加入,优选先加入有机醇化合物,反应一定的时间。
(2)在无机氧化物载体存在下,较低的温度下,优选-40℃-20℃内,将上述溶液与钛化合物进行接触反应,无机氧化物载体可在溶液与钛化合物进行接触反应之前或之后加入,并将混合物缓慢升温至60℃-100℃,固体物逐渐析出在载体上,反应一定的时间后,除去未反应物和溶剂,并采用惰性稀释剂洗涤,得到本发明的催化剂组分。
本发明还提供了一种用于乙烯的均聚合反应或乙烯与其它α-烯烃的共聚合反应的催化剂,其中的α-烯烃包括丙烯、丁烯-1、4-甲基戊烯-1、己烯-1、辛烯-1、苯乙烯、甲基苯乙烯等;该催化剂包含:(1)上述的本发明的催化剂组分与(2)通式为AlR3 nX3 3-n的有机铝化合物的反应产物,式中R3可以为氢、碳原子数为1~20的烃基,特别是烷基、芳烷基、芳基;X3为卤素,特别是氯和溴;n为0<n≤3的数。具体化合物如:三甲基铝、三乙基铝、三异丁基铝、三辛基铝、一氢二乙基铝、一氢二异丁基铝、一氯二乙基铝、一氯二异丁基铝、倍半乙基氯化铝、二氯乙基铝等烷基铝卤化物,其中优选三烷基铝化合物,具体选自三乙基铝、三异丁基铝、三正丁基铝、三正己基铝和三正辛基铝。优以三乙基铝、三异丁基铝为好。其中组份(2)中铝与组分(1)中钛的摩尔比为5~500,优选20-200。
聚合时可采用液相聚合,也可以采用气相聚合。
液相聚合介质包括:己烷、庚烷、环己烷、石脑油、抽余油、加氢汽油、煤油、苯、甲苯、二甲苯等饱和脂肪烃或芳香烃等惰性溶剂。聚合前可以先进行预聚合,聚合方式可以采用间歇式、半连续式或连续式。
聚合温度为0~150℃,以40~100℃为好。
为了调节最终聚合物的分子量,采用氢气作分子量调节剂。
具体实施方式
下面以实施例来说明本发明,但并非限制发明范围。
实例1
(1)催化剂组分的制备:在经过高纯氮气充分置换过的反应器中,依次加入4.0g二氯化镁,经分子筛处理过的甲苯100ml、环氧氯丙烷3.0ml、磷酸三丁酯2.8ml、乙醇6.4ml,搅拌下升温至80℃,当固体完全溶解形成均一的溶液后80℃条件下反应0.5小时。降温至30℃,滴加4.8ml浓度为2.2M的一氯二乙基铝,并在30℃维持反应1小时。加入经干燥处理的硅胶2.5g,将该体系冷却至-25℃,缓慢滴加40ml四氯化钛,然后缓慢升温至80℃,反应2小时。停止搅拌,静置,悬浮液很快分层,抽除上层清夜,甲苯洗涤两遍、己烷洗涤四遍,高纯氮气吹干,得到流动性好、粒径分布窄的固体催化剂组分。其中Ti含量为6.21%,Mg含量为10.38%,Cl含量为43.52%,乙氧基含量为4.7%,Al含量为0.19%,Si含量为4.85%,有机膦含量为4.75%。(均为重量含量)
(2)乙烯聚合
容积为2L的不锈钢反应釜,经高纯氮气充分置换后,加入己烷1L,浓度1M的三乙基铝1.0ml,加入上述制备的催化剂(含0.25毫克钛),升温至75℃,通入氢气使釜内压力达到0.28Mpa,再通入乙烯使釜内总压达到0.73Mpa(表压),在80℃条件下聚合2小时,聚合结果见表1,表2。
实施例2
(1)催化剂的合成同实施例1。只是乙醇用量由6.4ml改为5.9ml。
(2)乙烯聚合同实施例1。聚合结果见表1。
实施例3
(1)催化剂的合成同实施例2。只是一氯二乙基铝用量由4.8ml改为4.4ml。
(2)乙烯聚合同实施例1。聚合结果见表1。
实施例4
(1)催化剂的合成同实施例2。只是一氯二乙基铝用量改为3.8ml。
(2)乙烯聚合同实施例1。聚合结果见表1。
实施例5
(1)催化剂的合成同实施例1。只是一氯二乙基铝改为三乙基铝浓度为1.0M用量为4.6ml。
(2)乙烯聚合同实施例1。聚合结果见表1。
实施例6
(1)催化剂的合成同实施例1。只是乙醇用量改为9.8ml。
(2)乙烯聚合同实施例1。聚合结果见表1。
实施例7
(1)催化剂的合成同实施例1。
(2)乙烯聚合同实施例1,只是氢气/乙烯压力比为0.18/0.55。聚合结果见表2。
实施例8
(1)催化剂的合成同实施例1。
(2)乙烯聚合同实施例1,只是氢气/乙烯压力比为0.38/0.35。聚合结果见表2。
实施例9
(1)催化剂的合成同实施例1。
(2)乙烯聚合同实施例1,只是氢气/乙烯压力比为0.45/0.28。聚合结果见表2。
实施例10
(1)催化剂的合成同实施例1。
(2)乙烯聚合同实施例1,只是氢气/乙烯压力比为0.58/0.15。聚合结果见表2。
对比例1
(1)催化剂的合成同实施例1。只是不加一氯二乙基铝。
(2)乙烯聚合同实施例1。聚合结果见表1。
对比例2
(1)催化剂组分的合成按CN1229092实施例1所述方法制备。
在经高纯氮气充分置换的反应器中,依次加入0.042mol无水MgCl2(约4g)、60ml甲苯、0.032mol环氧氯丙烷、0.022mol磷酸三丁酯、0.017mol乙醇,搅拌下升温至80℃,并维持15分钟固体完全溶解,形成均匀溶液,然后加入邻苯二甲酸酐0.0074mol,再维持1小时,将该溶液冷却至-25℃,再将0.5mol四氯化钛(约55ml)滴入其内,然后缓慢升温至80℃,反应3小时,过滤后分别用甲苯和己烷洗涤3次,真空干燥,得到固体催化剂。
(2)乙烯聚合条件同实施例1,聚合结果见表1。
从表1和表2的聚合数据可以看出,在同样的聚合条件下,本发明的催化剂可得到更高熔融指数的聚乙烯树脂,而且通过调节聚合过程中的氢分压,可以很容易地得到不同熔融指数的树脂,即熔融指数随氢分压的变化非常明显。而且由于在本发明的催化剂中引入了无机氧化物载体,因此所得聚合的粒径分布要窄于对比例2(以苯酐作为析出剂),在所得的聚合物中过粗或过细的粒子均较少。
表1
编号 | C2H5OHml | Et2AlClml | Et3Alml | 硅胶g | 活性gPE/gcat | BDg/cm-3 | MI2.16g/10min | 粒径分布(目) | |||||||
<20 | 20-40 | 40-60 | 60-80 | 80-100 | 100-140 | 140-200 | >200 | ||||||||
实施例1实施例2实施例3实施例4实施例5实施例6对比例1对比例2 | 6.45.95.95.96.49.86.4 | 4.84.84.43.86.4 | 4.6 | 2.52.52.52.52.52.52.50 | 4002037113423734107120300258003464021100 | 0.310.320.310.330.320.330.320.31 | 0.340.280.240.220.180.19 | 3.75.99.72.20.4512.3 | 17.470.016.925.315.022.5 | 54.111.827.859.369.725.2 | 13.94.928.99.16.916.9 | 5.03.39.31.82.412.1 | 3.52.45.91.22.28.4 | 1.61.31.10.92.25.7 | 0.70.60.70.31.221.9 |
表2
编号 | H2/C= 2MPa/MPa | 活性gPE/gcat | MI2.16g/10min |
实施例1实施例7实施例8实施例9实施例10 | 0.28/0.450.18/0.550.38/0.350.45/0.280.58/0.15 | 400205168023330158106860 | 0.340.050.852.6925.05 |
Claims (8)
1、一种用于乙烯聚合或共聚合的催化剂组分,包含负载在无机氧化物载体上的镁复合物、至少一种钛化合物,至少一种有机醇化合物和至少一种有机铝的反应产物;
其中所述的镁复合物是将卤化镁溶解在含有机环氧化合物和有机磷化合物的溶剂体系中,
所述的有机醇化合物是碳原子数为1-10的直链、支链或环烷基的醇,
所述的有机铝化合物的通式为AlR1 nX1 3-n,式中R为氢,碳原子数为1~20的烃基,X1为卤素,n为1<n≤3的数;
所述的钛化合物通式为Ti(OR2)aX2 b,式中R2为C1~C14的脂族烃基或芳族烃基,X2为卤素,a是0、1或2,b是1至4的整数,a+b=3或4;
其中,以每摩尔卤化镁计,有机醇化合物为:0.1-10摩尔,有机铝化合物为0.05~5摩尔,钛化合物为1~15摩尔。
2、根据权利要求1所述的用于乙烯聚合或共聚合的催化剂组分,在镁复合物的制备中,所述的有机环氧化合物选自碳原子数在2~8的脂肪族烯烃、二烯烃或卤代脂肪族烯烃或二烯烃的氧化物、缩水甘油醚中的至少一种。
3、根据权利要求1所述的用于乙烯聚合或共聚合的催化剂组分,在镁复合物的制备中,所述的有机磷化合物为正磷酸或亚磷酸的烃基酯或卤代烃基酯。
4、根据权利要求1所述的用于乙烯聚合或共聚合的催化剂组分,在镁复合物的制备中,以每摩尔卤化镁计:有机环氧化合物:0.2-10mol,有机磷化合物:0.1~10mol。
5、根据权利要求1所述的用于乙烯聚合或共聚合的催化剂组分,其中以每摩尔卤化镁计,无机氧化物载体用量为10~200g。
6、一种用于乙烯聚合或共聚合的催化剂,包括以下物质反应的产物:
(a)权利要求1-5中任一项所述的固体催化剂组分;
(b)至少一种通式为AlR3 nX3 3-n的有机铝化合物,式中R3可以为氢、碳原子数为1~20的烃基,X3为卤素,n为0<n≤3的数。
7、权利要求6所述的催化剂,其中烷基铝化合物(b)为一种三烷基铝化合物。
8、权利要求7所述的催化剂,其中三烷基铝化合物选自三乙基铝、三异丁基铝、三正丁基铝、三正己基铝、三正辛基铝。
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PCT/CN2005/000469 WO2005100409A1 (fr) | 2004-04-12 | 2005-04-08 | Composant catalytique pour la polymerisation d'ethylene, son procede de preparation et catalyseur le contenant |
KR1020067023457A KR20070061481A (ko) | 2004-04-12 | 2005-04-08 | 에틸렌 중합용 촉매 성분, 그의 제조 방법 및 이를포함하는 촉매 |
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CN101838352B (zh) * | 2009-03-20 | 2013-11-06 | 中国石油化工股份有限公司 | 用于乙烯聚合或共聚合的催化剂组分及其催化剂 |
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CN103059171B (zh) * | 2011-10-18 | 2015-06-17 | 中国石油化工股份有限公司 | 一种用于烯烃聚合的催化剂组分和催化剂 |
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