CN102344506A - Catalyst component for vinyl polymerization and catalyst comprising the same - Google Patents
Catalyst component for vinyl polymerization and catalyst comprising the same Download PDFInfo
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- CN102344506A CN102344506A CN2010102403761A CN201010240376A CN102344506A CN 102344506 A CN102344506 A CN 102344506A CN 2010102403761 A CN2010102403761 A CN 2010102403761A CN 201010240376 A CN201010240376 A CN 201010240376A CN 102344506 A CN102344506 A CN 102344506A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 39
- 229920002554 vinyl polymer Polymers 0.000 title abstract description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 23
- 150000002681 magnesium compounds Chemical class 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 17
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 229910000085 borane Inorganic materials 0.000 claims description 63
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 63
- -1 alcohol compound Chemical class 0.000 claims description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000004411 aluminium Substances 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 14
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000003701 inert diluent Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000002685 polymerization catalyst Substances 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 4
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 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 3
- 239000000376 reactant Substances 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation 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
- 239000000047 product Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 15
- 239000002002 slurry Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 235000011147 magnesium chloride Nutrition 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000011218 segmentation Effects 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-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
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 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
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- YACCECLVHQLZQK-UHFFFAOYSA-N methoxyperoxyethane Chemical compound CCOOOC YACCECLVHQLZQK-UHFFFAOYSA-N 0.000 description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229960005222 phenazone Drugs 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 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
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-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
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYZZHQUICKTJHD-UHFFFAOYSA-N C(C)[Ti](OC)(OC)CC Chemical compound C(C)[Ti](OC)(OC)CC RYZZHQUICKTJHD-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005336 allyloxy group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 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
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000001276 controlling effect Effects 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005558 fluorometry Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- KGZLFTWMCMEEJR-UHFFFAOYSA-N heptane;hydrochloride Chemical compound Cl.CCCCCCC KGZLFTWMCMEEJR-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient 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
- 239000007788 liquid Substances 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical class [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 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
- JBIASUUIWKZOJM-UHFFFAOYSA-N n-ethyl-n-phenoxyethanamine Chemical compound CCN(CC)OC1=CC=CC=C1 JBIASUUIWKZOJM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 229910001961 silver nitrate Inorganic materials 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
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000004448 titration Methods 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
- 238000012725 vapour phase polymerization Methods 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a catalyst component for vinyl polymerization, a catalyst containing the component, and a preparation method of the component. The catalyst component is prepared by the following steps: (1)reacting a magnesium compound, an organic alcoholic compound, at least an organic titanium compound with at least a boron compound to obtain a reaction product A; (2) reacting the reaction product A with at least an organo-aluminum compound to obtain a reaction product B; (3) reacting the reaction product B with at least an inorganic titanium compound to obtain the final catalyst component. The catalyst disclosed herein has high catalytic activity, good hydrogen response, narrow polymer particle size distribution and the like, and is very suitable for being applied in vinyl slurry polymerization technology and composite polymerization technology that requiring a high catalytic activity catalyst.
Description
Technical field
The present invention relates to a kind of catalyst component that is used for ethylene polymerization, the preparation method of this catalyst component and this catalyzer.
Technical background
As everyone knows; The catalyst body that contains the Ti/Mg mixture ties up in the poly suitability for industrialized production occupies an leading position, and its research core is nothing more than the hydrogen response of the particle form of the polymerization activity that is catalyzer, catalyzer and size distribution, catalyzer and copolymerization performance or the like.And in slurry polymerization process of ethylene, except that requiring catalyzer should have the advantages of high catalytic activity, polyvinyl size and size distribution that control is produced are crucial.At vinyl polymerization, particularly in the slurry polymerization process of ethene, be easy to produce fine polymer powder, this fine powder is prone to produce static, is prone to caking, causes the obstruction of equipment pipe.And the effective means of the size of controlling polymers and size distribution is the particle diameter and the size distribution of control catalyst.
In the prior art, in order to obtain having the catalyzer of single-size diameter and better particle form, people adopt two following class methods to prepare catalyzer usually.
First kind is magnesium compounds such as magnesium chloride to be dissolved in obtain homogeneous solution in some solvent; And then with this solution and titanium compound and randomly electron donor mix; Obtain containing the solids of magnesium, titanium and optional electron donor through sedimentary method, and obtain granules of catalyst after this solids handled with excessive liquid titanium compound.For example disclosed among Chinese patent CN1099041A, the CN1229092 etc.The shortcoming of this traditional method is that the particle diameter and the size distribution of granules of catalyst controlled through precipitation process fully, and this is the recrystallization process of magnesium carrier composition, and its stable control ratio is difficulty.
For example, in patent CN1229092, be carrier with the magnesium chloride, titanium tetrachloride is an active ingredient, the Preparation of catalysts method is following: earlier with MgCl
2Be dissolved in the solvent system, form homogeneous transparent solution, then the precipitation additive phthalic anhydride exist and low temperature under and TiCl
4Reaction is separated out solid catalyst through slow intensification.When the catalyst component that makes was used for vinyl polymerization, though the particle form of polymkeric substance is better, the fine polymer powder that catalyzer prepares in industrial production was still more, and the hydrogen response and the catalytic activity of catalyzer are also unsatisfactory simultaneously.Simultaneously, when synthetic this catalyzer, need adopt organism such as phthalic anhydride to promote sedimentary separating out, and need to add a large amount of titanium tetrachlorides as precipitation additive.Therefore not only the existence of acid anhydrides produces adverse influence to catalyzer, and the use of simultaneously a large amount of titanium tetrachlorides also can cause a large amount of wastes and pollution.
Second kind is the carrier that preparation earlier has good particle form, carries titanium then, and prepared in reaction obtains highly active polyolefin catalyst.Chinese patent CN85105150 for example, patents such as CN101300278.
Chinese patent CN85105150 at first adopts magnesium halide and titan-alkoxide reaction; Generate solid magnesium-containing carrier with the aluminum alkyls reaction then with better particle form; This carrier and titanium tetrachloride reaction obtain solid catalyst at last, and the polyethylene polymer of this Preparation of Catalyst has characteristics such as tap density height, active height.But magnesium halide and titan-alkoxide reaction product fail to form solution in this Preparation of catalysts process when reacting with aluminum alkyls; The magnesium-containing carrier particle form that obtains is not ideal enough; The polymkeric substance segmentation content of preparation is still more, and the hydrogen regulation performance of this catalyzer is slightly poor simultaneously.
As everyone knows; In slurry polymerization process of ethylene; Except that requiring catalyzer should have advantages of high catalytic activity and preferably the size distribution; In order to produce Alathon or multipolymer with better performance; Also require catalyzer should have better hydrogen regulation sensitivity; I.e. melting index of regulating final polymkeric substance through hydrogen dividing potential drop in the polymerization process at an easy rate is to obtain the polyvinyl resin of the different commercial trades mark.And the hydrogen response of above-mentioned catalyst system is also unsatisfactory.
Therefore; Being starved of provides a kind of catalyzer that is applicable to slurry polymerization process of ethylene; Not only catalytic activity is high for it, particle diameter evenly, narrow diameter distribution, and have better hydrogen regulation sensitivity, the polymkeric substance of its preparation has advantages such as uniform particles, narrow diameter distribution, segmentation content are few.
Summary of the invention
The technical problem that the present invention will solve provides a kind of catalyzer that is used for ethylene polymerization; This catalyst activity is high, particle diameter is even, narrow diameter distribution; And have better hydrogen regulation sensitivity, the polymer beads of its preparation evenly, narrow diameter distribution, segmentation content be few.
The catalyst component that is used for ethylene polymerization, it obtains through comprising following reactions step:
(1) a kind of magnesium compound, a kind of organic alcohol compound, at least a organic titanic compound and the reaction of at least a boron compound are obtained reaction product A; Described magnesium compound is the hydrate of magnesium dihalide or magnesium dihalide; It is 1～10 Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol or halogenated alcohol that described organic alcohol compound is selected from carbonatoms; Described organic titanic compound general formula is Ti (OR
1)
aX
1 b, R wherein
1For carbonatoms is 1～14 aliphatic alkyl or aromatic hydrocarbyl, X
1Be halogen, a is 1,2,3 or 4, and b is 0,1,2,3, a+b=4; The general formula of described boron compound is R
2 xR
3 yB (OR
4)
z, R wherein
2And R
3Be respectively carbonatoms and be 1～10 alkyl or halogen, R
4For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3; In every mole of magnesium compound, organic alcohol compound is 0～6 mole, and organic titanic compound is 1～10 mole, and boron compound is 0.1～2 mole;
(2) reaction product A and the reaction of at least a organo-aluminium compound are obtained reaction product B; Described organo-aluminium compound general formula is AlR
5 nX
2 3-n, R wherein
5For hydrogen or carbonatoms are 1～20 alkyl, X
2Be halogen, n is 1,2 or 3; In every mole of magnesium compound, organo-aluminium compound is 0.5～10 mole;
(3) reaction product B and the reaction of at least a inorganic titanium compound are obtained the final catalyst component; The general formula of described inorganic titanium compound is TiX
3 n, X
3Be halogen, n=4; In every mole of magnesium compound, inorganic titanium compound is 0.5～10 mole.
Wherein magnesium dihalide is selected from magnesium dichloride, dibrominated magnesium, bifluoride magnesium, two magnesium iodides etc., preferred magnesium dichloride, and said halogenated magnesium compound can separately or mix and use.
It is 1～10 Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol and halogenated alcohol that described organic alcohol compound is selected from carbonatoms; Fatty Alcohol(C12-C14 and C12-C18) is like methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, glycerin, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, 2-Ethylhexyl Alcohol, n-Octanol, decyl alcohol, hexalin, methyl-cyclohexanol; Aromatic alcohol is like phenylcarbinol, methylbenzyl alcohol, α-Jia Jibenjiachun, α, alpha-alpha-dimethyl phenylcarbinol, isopropyl benzene methyl alcohol, phenylethyl alcohol; Halogenated alcohol is like in trichlorine methyl alcohol, ethapon and three Mecorals etc. one or more; One or more in preferred alcohol, butanols, 2-Ethylhexyl Alcohol, the glycerin wherein; When using alcohol mixture, various alcohol can add simultaneously or separately add, and each pure ratio in the alcohol composition is had no particular limits; In 1 mole of magnesium compound, the consumption of alcohol is generally 0～6 mole, preferred 0.1～2 mole.
Described organic titanic compound general formula is Ti (OR
1)
aX
1 b, R wherein
1For carbonatoms is 1～14 aliphatic alkyl or aromatic hydrocarbyl, X
1Be halogen, a is 1,2 or 3, and b is 0,1,2,3 or 4, a+b=3 or 4; Preferred four titanium alkoxides, like purity titanium tetraethoxide, four titanium butoxide, the tetramethoxy titanium, dimethoxy diethyl titanium, four hexyloxy titaniums, four the last of the ten Heavenly stems oxygen base titanium, benzyloxy-4 titanium, four phenoxide titaniums etc.; Most preferably general formula is Ti (OR
1)
aX
1 bOrganic titanic compound, R wherein
1For carbonatoms is 1～14 aliphatic alkyl, X
1Be halogen, a is 2,3 or 4, and b is 4-a, purity titanium tetraethoxide for example, four titanium butoxide; In 1 mole of magnesium compound, the consumption of organic titanic compound is generally 1～10 mole, preferred 1～4 mole.
Its general formula of described boron compound is R
2 xR
3 yB (OR
4)
z, R wherein
2And R
3Be respectively carbonatoms and be 1～10 alkyl or halogen, R
4For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3; Preferred its general formula of alkoxyl group borine is R
2 xR
3 yB (OR
4)
z, R wherein
2And R
3Be respectively carbonatoms and be 1～10 alkyl or halogen, R
4For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3.
Concrete compound is like the trimethoxy borine; The triethoxy borine; The tripropoxy borine; Tributoxy-boron alkane; Ethyl dimethoxy borine; Ethyl diethoxy borine; Methyl dimethoxy oxygen base borine; Methyl diethoxy borine; N-propyl diethoxy borine; N-propyl dimethoxy borine; Decyl dimethoxy borine; Decyl diethoxy borine; Cyclopentyl dimethoxy borine; Cyclopentyl diethoxy borine; 2-methylcyclopentyl dimethoxy borine; 2,3-dimethylcyclopentyl dimethoxy borine; Cyclohexyl dimethoxy borine; Cyclohexyl diethoxy borine; Methyl dimethoxy oxygen base borine; Methyl diethoxy borine; Ethyl diethoxy borine; Vinyl-dimethyl oxygen base borine; Vinyl diethoxy borine; Tertiary butyl diethoxy borine; Normal-butyl dimethoxy borine; Normal-butyl diethoxy borine; Isobutyl-dimethoxy borine; Isobutyl-diethoxy borine; Cyclohexyl diethoxy borine; Cyclohexyl dimethoxy borine; Phenyl dimethoxy borine; Diethylamino phenyl oxygen base borine; One chlorine dimethoxy borine; One chlorine diethoxy borine; Ethyl diisopropoxy borine; Vinyl dibutoxy borine; The dimethyl phenoxy borine; Methyl two allyloxy borines; Dimethyl one methoxyl group borine; Dimethyl one oxyethyl group borine; Di-isopropyl one methoxyl group borine; Di-isopropyl one oxyethyl group borine; Tertiary butyl methyl one methoxyl group borine; Tertiary butyl methyl one oxyethyl group borine; Tert-pentyl methyl one oxyethyl group borine; Two cyclopentyl, one methoxyl group borine; Two cyclopentyl, one oxyethyl group borine; Methylcyclopentyl one oxyethyl group borine; Methylcyclopentyl one methoxyl group borine; Phenylbenzene one methoxyl group borine; Phenylbenzene one oxyethyl group borine; Aminomethyl phenyl one oxyethyl group borine; Aminomethyl phenyl one methoxyl group borine; Two o-tolyl one methoxyl group borines; Two o-tolyl one oxyethyl group borines; Tolyl one methoxyl group borine between two; Tolyl one oxyethyl group borine between two; Biconjugate tolyl one methoxyl group borine; One or more mixing wherein such as biconjugate tolyl one oxyethyl group borine are used; Wherein preferred trimethoxy borine, triethoxy borine, tripropoxy borine and tributoxy-boron alkane, most preferably triethoxy borine; In 1 mole of magnesium compound, the consumption of boron compound is generally 0.1～2 mole, preferred 0.1～1 mole.
Among the present invention, the boron compound that in the solid titanium catalyst component that finally obtains, should contain q.s is to improve the over-all properties of catalyzer, and boron compound also plays the effect of the precipitation additive that promotes the moulding of granules of catalyst precipitating simultaneously.In addition, also can adopt other the compound that in preparation process, can generate above-mentioned boron compound.
In order to make dissolving more abundant; In this solvent system, can randomly add inert diluent; Common this inert diluent comprises arene compounds or alkane derivative, and arene compounds comprises benzene,toluene,xylene, monochloro-benzene, dichlorobenzene, trichloro-benzene, monochlorotoluene and derivative thereof; Alkane comprises a kind of in straight-chain paraffin, branched paraffin or the naphthenic hydrocarbon of 3～20 carbon or their mixture, like butane, and pentane, hexane, hexanaphthene, heptane etc. are as long as help the magnesium halide dissolved to use.Above-mentioned inert diluent can use separately, use also capable of being combined.
The general formula of described organo-aluminium compound is AlR
5 nX
2 3-n, R in the formula
5For hydrogen or carbonatoms are 1～20 alkyl, these groups can be the same or different, X
2Be halogen; Can be that the same halogen atom also can be different halogen atom, these compounds comprise, triethyl aluminum; Aluminium diethyl monochloride; Dichloro one aluminium triethyl, sesquialter aluminium triethyl, dichloro aluminium isobutyl; Triisobutyl aluminium; One chlorine di-isopropyl aluminium, a chloromethyl n-propyl aluminium, a chlorodiphenyl base aluminium etc.; Wherein preferred sesquialter aluminium triethyl, aluminium diethyl monochloride, dichloro one aluminium triethyl; In 1 mole of magnesium compound, the consumption of organo-aluminium compound is generally 0.5～10 mole, preferred 1～5 mole.
The preferred halogenated titanium of described inorganic titanium compound is like a kind of or its mixture in titanium tetrachloride, titanium tetrabromide, the titanium tetra iodide; In 1 mole of magnesium compound, the consumption of described titanium compound is generally 0.5～10 mole, preferred 1～5 mole.
The above-mentioned catalyst component of the present invention can adopt following method preparation:
(1) with magnesium compound and organic titanic compound, organic alcohol compound and boron compound reaction, in the presence of inert diluent, form clear solution, preferred 50～90 ℃ of solvent temperature, obtains reaction product A at the reaction regular hour;
(2) under suitable temperature; In preferred 0 ℃～70 ℃; Reaction product A and organo-aluminium compound are carried out contact reacts under agitation condition; Reaction generates solid chemical compound; After the organo-aluminium compound adding finishes; After continuing the reaction certain hour, obtaining reaction product B with the inert diluent washing is the good carrier granule of particle form;
(3) under suitable temperature; In preferred 0 ℃～100 ℃; Reaction product B and inorganic titanium compound are carried out contact reacts; And mixture is warming up to 60 ℃～110 ℃; After the reaction regular hour; Remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain catalyst component of the present invention (1).
The present invention also provides the catalyzer of the copolymerization of a kind of equal polymerization reaction that is used for ethene or ethene and other alpha-olefin, and alpha-olefin wherein comprises propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, vinylbenzene, vinyl toluene etc.; It is that general formula is AlR with catalyst component (2) that this catalyzer comprises above-mentioned catalyst component of the present invention (1)
6 nX
4 3-nThe reaction product of organo-aluminium compound, R in the formula
6Can be the alkyl of l～20, particularly alkyl, aralkyl, aryl for hydrogen or carbonatoms; X
4Be halogen, particularly chlorine and bromine; N is the integer of 0＜n≤3.Particular compound is selected from 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, ethyl aluminum dichloride etc., wherein preferred triethyl aluminum, triisobutyl aluminium.Wherein the mol ratio of the middle titanium of aluminium and catalyst component (1) is 5～500 in the catalyst component (2), preferred 20～200.
Slurry polymerization can be adopted during polymerization, also vapour phase polymerization can be adopted.
The slurry polymerization medium comprises: Trimethylmethane, hexane, heptane, hexanaphthene, petroleum naphtha, raffinate oil, inert solvent such as aliphatic saturated hydrocarbon such as hydrogenated gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon.
In order to regulate the molecular weight of final polymkeric substance, adopt hydrogen to make molecular weight regulator.
Catalyzer of the present invention has advantages such as advantages of high catalytic activity, better hydrogen regulation sensitivity and narrow grain size distribution of polymers, segmentation content are few, is highly suitable for slurry polymerization process of ethylene and needs in the polymerization mix technology of high activated catalyst.
Embodiment
Testing method:
1, the size-grade distribution of catalyzer: MASTERSIZE particles distribution instrument, normal hexane be as dispersion agent, useful range 0.02～2000 μ m
2, the relative weight per-cent of element (Mg, Ti) in the catalyst system: plasma emission spectrum (ICP)
3, the relative weight per-cent of chlorine element in the catalyst system: silver nitrate titration method
4, the relative weight per-cent of element silicon in the catalyst system: X-ray fluorometry
5, the mensuration of melting index: ASTM-D 1238
6, the mensuration of tap density: DIN-53194
With embodiment the present invention is described below, but and unrestricted invention scope.
Embodiment 1
(1) preparation of catalyst component: in the reactor of fully replacing through high pure nitrogen; Add 4.0g magnesium dichloride (0.042mol), 60ml toluene, 19.2g (0.084mol) purity titanium tetraethoxide, 6.9ml (0.1176mol) ethanol, 2.1ml (0.0126mol) triethoxy borine successively; Stir down and be warming up to 70 ℃ of reactions, dissolve fully when solid behind the solution that forms homogeneous and reacted 1 hour under 70 ℃ of conditions.Be cooled to 65 ℃, slowly dripping 21ml concentration is the aluminium diethyl monochloride n-heptane solution of 2M, and keeps reaction 1 hour at 65 ℃, after be warmed up to 90 ℃ of continued reaction 1 hour.This system is cooled to 30 ℃, allows solid precipitation, filter out filtrating, and, in solids, add the 60ml hexane and stir, slowly drip the 60ml titanium tetrachloride, 30 ℃ of reactions 1 hour with 60ml hexane wash solid twice.Stop to stir, leave standstill, the very fast layering of suspension-s extracts the upper strata stillness of night, hexane wash four times, and high pure nitrogen dries up, and obtains the ingredient of solid catalyst of good fluidity, narrow diameter distribution.The catalyzer composition is seen table 1.
(2) vinyl polymerization
Volume is the stainless steel cauldron of 2L; After high pure nitrogen is fully replaced; Add hexane 1L; The triethyl aluminum 1.0ml of concentration 1M adds the solid catalyst of above-mentioned preparation, is warming up to 70 ℃; Feeding hydrogen makes the still internal pressure reach 0.50Mpa; Feed ethene again and make the interior stagnation pressure of still reach 1.0Mpa (gauge pressure), polymerization is 2 hours under 90 ℃ of conditions, and polymerization result is seen table 1.
Embodiment 2
(1) catalyzer is synthetic with embodiment 1.Just amount of ethanol changes 4.9ml into by 6.9ml.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Embodiment 3
(1) catalyzer is synthetic with embodiment 2.Just aluminium diethyl monochloride changes the dichloro aluminium isobutyl into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Embodiment 4
(1) catalyzer is synthetic with embodiment 2.Just aluminium diethyl monochloride changes dichloro one aluminium triethyl into.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Embodiment 5
(1) catalyzer is synthetic with embodiment 2.Just the triethoxy borine changes tributoxy-boron alkane into, and consumption is 3.4ml (0.0126mol).
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Comparative Examples 1
(1) the synthetic CN85105150 embodiment 1 said method of pressing of catalyst component prepares.
(2) the vinyl polymerization condition is with embodiment 1, and polymerization result is seen table 1.
Comparative Examples 2
(1) catalyzer is synthetic with embodiment 2.Just do not add the triethoxy borine.
(2) vinyl polymerization is with embodiment 1.Catalyzer is formed and polymerization result is seen table 1.
Can find out that from the aggregated data of table 1 under same polymerizing condition, catalyst activity of the present invention is higher, hydrogen regulation performance is better, and gained polymeric size distribution is narrower, and it is all less to cross thick or meticulous particle in the polymkeric substance.
Claims (11)
1. the catalyst component that is used for ethylene polymerization, it obtains through comprising following reactions step:
(1) a kind of magnesium compound, a kind of organic alcohol compound, at least a organic titanic compound and the reaction of at least a boron compound are obtained reaction product A;
Described magnesium compound is the hydrate of magnesium dihalide or magnesium dihalide;
It is 1～10 Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol or halogenated alcohol that described organic alcohol compound is selected from carbonatoms;
Described organic titanic compound general formula is Ti (OR
1)
aX
1 b, R wherein
1For carbonatoms is 1～14 aliphatic alkyl or aromatic hydrocarbyl, X
1Be halogen, a is 1,2,3 or 4, and b is 0,1,2,3, a+b=4;
The general formula of described boron compound is R
2 xR
3 yB (OR
4)
z, R wherein
2And R
3Be respectively carbonatoms and be 1～10 alkyl or halogen, R
4For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3;
In every mole of magnesium compound, organic alcohol compound is 0～6 mole, and organic titanic compound is 1～10 mole, and boron compound is 0.1～2 mole;
(2) reaction product A and the reaction of at least a organo-aluminium compound are obtained reaction product B; Described organo-aluminium compound general formula is AlR
5 nX
2 3-n, R wherein
5For hydrogen or carbonatoms are 1～20 alkyl, X
2Be halogen, n is 1,2 or 3; In every mole of magnesium compound, organo-aluminium compound is 0.5～10 mole;
(3) reaction product B and the reaction of at least a inorganic titanium compound are obtained the final catalyst component; The general formula of described inorganic titanium compound is TiX
3 n, X
3Be halogen, n=4; In every mole of magnesium compound, inorganic titanium compound is 0.5～10 mole.
2. the catalyst component that is used for ethylene polymerization according to claim 1; The consumption that it is characterized in that each reactant is in every mole of magnesium compound; Organic alcohol compound is 0.1～2 mole; Organic titanic compound is 1～4 mole; Boron compound is 0.1～1 mole; Organo-aluminium compound is 1～5 mole, and inorganic titanium compound is 1～5 mole.
3. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described organic titanic compound general formula is Ti (OR
1)
aX
1 b, R wherein
1For carbonatoms is 1～14 aliphatic alkyl, X
1Be halogen, a is 2,3 or 4, and b is 4-a.
4. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described organic titanic compound is selected from purity titanium tetraethoxide or four titanium butoxide.
5. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described inorganic titanium compound is selected from least a in titanium tetrachloride, titanium tetrabromide and the titanium tetra iodide.
6. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described boron compound general formula is R
2 xR
3 yB (OR
4)
z, R wherein
2And R
3Be respectively carbonatoms and be 1～10 alkyl or halogen, R
4For carbonatoms is 1～10 alkyl, x wherein, y, z are positive integer, 0≤x≤2,0≤y≤1 and 0≤z≤3, and x+y+z=3.
7. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described boron compound is selected from least a in trimethoxy borine, triethoxy borine, tripropoxy borine and the tributoxy-boron alkane.
8. the ethylene polymerization catalysts component that is used for according to claim 1 is characterized in that described organo-aluminium compound is selected from aluminium diethyl monochloride, dichloro one aluminium triethyl or sesquialter aluminium triethyl.
9. the described preparation method who is used for the ethylene polymerization catalysts component of claim 1, it may further comprise the steps:
(1) with magnesium compound and organic titanic compound, organic alcohol compound and boron compound reaction, in the presence of inert diluent, form clear solution, solvent temperature is 50～90 ℃, obtains reaction product A;
(2), reaction product A and organo-aluminium compound are reacted under agitation condition, with obtaining reaction product B after the inert diluent washing at 0 ℃～70 ℃;
(3) at 0 ℃～100 ℃, reaction product B and inorganic titanium compound are reacted, and mixture is warming up to 60 ℃～110 ℃, remove unreacted reactant and solvent, and adopt the inert diluent washing, obtain final reacting product.
10. the catalyzer that is used for ethylene polymerization, it comprises the reaction product of following component:
(1) the described catalyst component of one of claim 1-8;
(2) general formula is AlR
6 nX
4 3-nOrgano-aluminium compound, R wherein
6For hydrogen or carbonatoms are 1～20 alkyl, X
4Be halogen, n is 1,2 or 3.
11. the catalyzer that is used for ethylene polymerization according to claim 10, wherein the mol ratio of the middle titanium of aluminium and component (1) is 20～200 in the component (2).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104418961B (en) * | 2013-09-03 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization reaction as well as catalyst and preparation method of catalyst component |
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Application publication date: 20120208 |