CN1631922A - Catalyst for copolymerization of ethylene and styrene - Google Patents
Catalyst for copolymerization of ethylene and styrene Download PDFInfo
- Publication number
- CN1631922A CN1631922A CN 200310121872 CN200310121872A CN1631922A CN 1631922 A CN1631922 A CN 1631922A CN 200310121872 CN200310121872 CN 200310121872 CN 200310121872 A CN200310121872 A CN 200310121872A CN 1631922 A CN1631922 A CN 1631922A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- ethene
- styrene
- compound
- halide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 28
- 239000003054 catalyst Substances 0.000 title abstract description 22
- 238000007334 copolymerization reaction Methods 0.000 title description 11
- 239000005977 Ethylene Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000010936 titanium Substances 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004593 Epoxy Substances 0.000 claims abstract description 7
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 7
- -1 zinc halide Chemical class 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000003701 inert diluent Substances 0.000 claims description 7
- 239000011949 solid catalyst Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 5
- 150000002899 organoaluminium compounds Chemical class 0.000 claims description 5
- 239000012456 homogeneous solution Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 19
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 239000003085 diluting agent Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 63
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- 238000005406 washing Methods 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 229940091250 magnesium supplement Drugs 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 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 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- JHGDVEYCZZGUIW-UHFFFAOYSA-N ethene styrene Chemical compound C=C.C=C.C=CC1=CC=CC=C1 JHGDVEYCZZGUIW-UHFFFAOYSA-N 0.000 description 5
- 229940073589 magnesium chloride anhydrous Drugs 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000002798 neodymium compounds Chemical class 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 description 1
- 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
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-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
- 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
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- MNDMJXHHYVXIBJ-UHFFFAOYSA-N [Si].ClC=1C(=C(C=CC1)C1=CC=CC=C1)Cl Chemical compound [Si].ClC=1C(=C(C=CC1)C1=CC=CC=C1)Cl MNDMJXHHYVXIBJ-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 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
- 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
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- MCJUWBUSIQXMPY-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1 MCJUWBUSIQXMPY-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 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
- 238000012685 gas phase polymerization Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002680 magnesium Chemical class 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000035939 shock Effects 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
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- RJIFVNWOLLIBJV-UHFFFAOYSA-N tributyl benzene-1,2,4-tricarboxylate Chemical compound CCCCOC(=O)C1=CC=C(C(=O)OCCCC)C(C(=O)OCCCC)=C1 RJIFVNWOLLIBJV-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-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
- 210000001835 viscera Anatomy 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
the invention relates to a catalyst for synthesizing thylene and styrene, which contains component of titanium catalyst. The titanium catalyst is made through dissolving halogenide containing zinc into the solvment system comprising of organic epoxy compound, organic phosphorous compound and halogenide diluent, which is then mixed with titanium compound, with the existence of precipitating agent. In the polymerization, styrene monomer has high synthesizing activity, the polymer being made has good particle appearance and density, outstanding resisctance to impact performance as well as higher tensile strength and modulus.
Description
Technical field
The present invention relates to a kind of catalyzer and this Preparation of catalysts method thereof that is used for ethene and styrene copolymerisation.
Technical background
Polyvinyl resin occupies crucial status at polymeric material field, and its low price is widely used, but also exists defectives such as tensile strength is low, poor heat resistance, difficult bonding.Therefore the high performance of polyvinyl resin just becomes an important topic of current techniques development.And how on higher level, realize the balance of resin mechanical property and processing characteristics, the application class that improves material is an importance of polyethylene high performance.Wherein utilize the copolymerization technology for gold,, improve the content of styrene monomer in the polymkeric substance, make the technology of final polyvinyl resin high performance cause people's extensive concern more and more by the copolymerization of styrene-ethylene.
The current method for preparing high-performance ethylene copolymer alloy mainly contains two classes: i.e. post-treatment blending method and polymerization technique method.In these two kinds of methods, the post-treatment blending method is the simplest, and general plastic working factory can realize by the blend forcing machine.Disclosed a kind of resin material in the CN1292016 patent documentation, it is a kind of styren-based resin composition that comprises syndiotactic polystyrene, polyethylene, prepares with blending method.But document claims this resin to have good high speed flow ductility and coating.Be applicable to the molding extruding production line.But blending method process energy consumption height, and it is relative with quality relatively poor to obtain the homogeneity of resin.And the polymer alloy resin that the polymerization technique method obtains, because its different polymkeric substance and copolymer molecule chain can be realized the mixing of molecular level, so the quality of its gained polyethylene alloy resin is good and cost is also low.At present, employed catalyzer adopts griding reaction method preparation mostly in the technology of preparing of disclosed polyethylene-styrene resin alloy, and for example: Chinese patent CN1041763 and CN85102292 adopt openly that the griding reaction method prepares is used for ethene and styrene polymerization catalyzer.In Chinese patent CN1041763, disclosed a kind of high activated catalyst that relates to ethene gas-phase homopolymerization and copolymerization and preparation method thereof.It is with TiCl
4, Ti (OBU)
4With neodymium compound be compound primary catalysts, with MgCl
2, ZnCl
2And SiO
2Be complex carrier, add SiCl
2φ
2, SiCl
4, organic-magnesium complex compound and ethyl benzoate make the catalyst system of promotor.Adopt aluminum alkyl catalyst.This catalyzer is used for ethene gas-phase polymerization can make hydrogen transfer the molecular weight effect to significantly improve, and also can be used for ethene-styrene copolymerized and propylene high directionality polymerization simultaneously.Though the griding reaction time of this catalyzer, its catalytic activity was still not high greater than 35 hours.Being used for ethene-styrene copolymerisation, is that styrene content can reach 39～67% in the product in 0.5～2: 1 scope at 0.112MPa, 50 ℃, 2hr, styrene/ethylene (mol/mol), and catalytic efficiency only is 1100～1300 gram product/gram titaniums.
And for example: in Chinese patent CN85102292, described the catalyzer of a kind of styrene stereo directed polymerization or vinylbenzene and other alpha-olefinic copolymerization, by TiCl
4, MgCl
2, SiCl
2φ
2, (dichloro phenylbenzene silicon) and neodymium compound form, neodymium compound is generally NdCl
33C
2H
3OH or NdCl
33C
3H
7OH or NdCl
33C
4H
9OH.This catalyzer can make four indices such as styrene polymerization speed, catalytic efficiency, monomer conversion (being productive rate) and polystyrene degree of isotacticity be improved simultaneously.And this catalyzer also can be used for vinylbenzene and the copolymerization of general alkene (for example ethene) or the equal polymerization of alkene (for example ethene).This catalyzer adopts the griding reaction method to prepare total milling time and was generally 20～50 hours, is used for tactic polymerization under the atmospheric styrene, and catalytic efficiency reached as high as 2400 gram polystyrene/gram titaniums in 2 hours, but does not have the data of ethene-styrene copolymerisation.
The catalyzer of above-mentioned griding reaction method preparation has a common shortcoming to be, the bad control of resulting granules of catalyst form, and also size distribution is very wide, therefore polymerization products therefrom grain type is bad, fine powder is many, and apparent density is low, and activity of such catalysts is also unsatisfactory simultaneously.
Disclosed a kind of catalyzer that is used to prepare styrene-alpha olefin copolymer in Chinese patent CN1187502, this catalyzer contains cyclopentadiene titanium compound and alkylaluminoxane and aluminum alkyls.When using this catalyzer to carry out the styrene-alpha olefin copolymerization, can obtain having syndiotactic styrenic segmental segmented copolymer or have elasticity or the random copolymers of elasticity/plastic properties.But use MAO during this method polymerization, polymerization activity is lower, and polymerization activity is generally in 10 kg of polymer/below the gram titanium under 0.105MPa, 60 ℃, 2hr condition.
A kind of catalyst system that is used for olefinic polymerization is disclosed among the known again Chinese patent CN85100997, it is to be dissolved in organic epoxy compounds by magnesium halide, organo phosphorous compounds forms homogeneous solution, again with at least a precipitation additive, the halogenide and the derivative effect thereof of a kind of multi-carboxylate's electron donor and transition metals Ti prepare, when this catalyzer is used for propylene polymerization, high polymerization activity and stereospecificity have preferably been shown, but when being used for ethene and cinnamic copolymerization, the copolymerization activity is low, is difficult to form the multipolymer of higher styrene content.
Summary of the invention
The invention provides the catalyzer of a kind of alpha-olefinic copolymerization that is used for, particularly ethene and styrene copolymerisation, this catalyzer contains the reaction product of following component:
(1) a kind of titaniferous ingredient of solid catalyst, it is that zinciferous halogenide is dissolved in the solvent system of being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, mix with titanium compound after forming homogeneous solution, in the presence of precipitation additive, separate out solids; The monobasic or the polybasic carbonate of this solids by using aliphatic series or aromatics are handled, and it is attached on the solids, in case of necessity, with titanium compound and inert diluent solids are handled obtaining again;
(2) organo-aluminium compound;
(3) randomly, silicoorganic compound.
The ratio between ingredient of solid catalyst (1), organo-aluminium compound component (2) and the silicoorganic compound component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500.
Titaniferous ingredient of solid catalyst in the catalyzer of the present invention is prepared by the method that comprises following steps:
(1) zinciferous halogenide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, forms homogeneous solution;
(2) helping in the presence of the precipitation agent, is Ti (OR) with above-mentioned solution and at least a general formula
4-mX
mTitanium compound carry out contact reacts, and separate out titaniferous ingredient of solid catalyst, R is C in the formula
1～C
14Aliphatic group, X chooses from F, Cl, Br or its mixture, m is 1～4 integer,
In above-mentioned arbitrary step, introduce the monobasic or the polybasic carbonate of at least a aliphatic series or aromatics.
The preparation of above-mentioned steps (1) solution can be according to disclosed method among the Chinese patent CN85100997, and disclosed associated viscera is all introduced the present invention as a reference among the CN85100997.Wherein zinciferous halogenide is zinc halide or zinc halide and magnesium halide preferably.Described zinc halide is a zinc dihalide, and concrete compound is as zinc dichloride or dibrominated zinc.Described magnesium halide is selected from the complex compound, magnesium dihalide molecular formula of the water of magnesium dihalide, magnesium dihalide or alcohol one of them or two halogen atoms by alkyl or halogen-oxyl institute metathetical derivative.Concrete compound is as magnesium dichloride, dibrominated magnesium, chlorination phenoxy group magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium etc., wherein preferred magnesium dichloride.Mol ratio between zinc halide and the magnesium halide, in every mole of zinc halide, magnesium halide is the 0-10 mole, is preferably the 0.2-5 mole.
Described organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halo fat group alkene or diolefine of carbonatoms.Concrete as: oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether or tetrahydrofuran (THF).
Described organo phosphorous compounds is the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid.Concrete as: 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 or phosphorous acid benzene methyl.
Wherein in every mole of halogenide: organic epoxy compounds: 0.2-10mol, preferred 0.5～4mol; Organo phosphorous compounds: 0.1～5mol, preferred 0.3～1.0mol.
In order to make dissolving more abundant, in this solvent system, can randomly add inert diluent, common this inert diluent can adopt hexane, heptane, octane, benzene,toluene,xylene, 1,2-ethylene dichloride, chlorobenzene and other hydro carbons or halogenated hydrocarbon compound are as long as help the halogenide dissolved to use.Above-mentioned inert diluent can use separately, use also capable of being combined.
Solvent temperature is between 10-150 ℃, and upper temperature limit is no more than the boiling point of solvent.
Dissolution time is as the criterion to dissolve fully.
In the preparation of halide solution, each component of solution adds order in no particular order.
In the above-mentioned steps (2), helping in the presence of the precipitation agent, with the contact reacts of titanium compound and halide solution, its temperature of reaction is preferably :-40～0 ℃.Wherein precipitation additive is a kind of in organic acid anhydride, organic acid, ether, the 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.
In every mole of halogenide: the add-on of titanium compound is the 1-20 mole, and preferred: 4-10 mole, precipitation additive are 0.03～1.0 mole.
React in order to make the easier control of reaction, preferably titanium compound to be added in the halide solution, separate out solid catalyst particle in the reaction system temperature-rise period, temperature should be controlled at below the boiling point of solvent.
In the preparation of catalyst component of the present invention, also must add at least a electron donor compound, monobasic or polycarboxylic acid ester cpds as aliphatic series or aromatics, preferred monobasic or polynary aliphatic series or aromatic carboxylic acid's alkyl ester, concrete as: methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, diethyl malonate, Polycizer W 260, the phthalic ester diethyl ester, the phthalic ester diisobutyl ester, the phthalic ester di-n-butyl, the phthalic ester di-isooctyl, diethyl maleate, maleic acid n-butyl, the naphthalene dicarboxylic acids diethyl ester, the naphthalene dicarboxylic acids dibutylester, triethyl trimellitate, tributyl trimellitate, the benzene-1,2,3-tricarboxylic acid triethyl, the benzene-1,2,3-tricarboxylic acid tri-n-butyl, the pyromellitic acid tetra-ethyl ester, pyromellitic acid four butyl esters etc.
The electron donor compound can add reaction system in the arbitrary steps in the catalyst component preparation process, be preferably granules of catalyst and form the back adding.
Can obtain the solid powder th-1 catalyst of flowable state through conventional washing, drying and other steps for the catalyst component particle that forms.In order to regulate the content of titanium in the catalyzer, also can randomly adopt titanium compound that granules of catalyst is carried out one or many and handle.
In the solids containing titanium catalyst component of gained, titanium content is between 0.5～5%; Mg content is between 5～20%.
Organo-aluminium compound component in the catalyzer of the present invention is as general formula AlR
1 nX
3-nShown in, R in the formula
1Be identical or different C
1～C
20Alkyl can be a straight chain, and side chain or cyclic alkyl, X are halogen, n=1,2 or 3.Preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride etc.Can select for use one or more aluminum alkyls to mix use.
Silicoorganic compound component such as general formula R in the catalyzer of the present invention
nSi (OR ')
4-nShown in, 0≤n in the formula≤3, R is of the same race or different alkyl, cycloalkyl, aryl, haloalkyls with R ', R also can be halogen or hydrogen atom.Concrete as: trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane, phenylbenzene diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e, vinyltrimethoxy silane, cyclohexyl methyl dimethoxy silane, methyl-t-butyldimethoxysilane, preferred cyclohexyl methyl dimethoxy silane, dimethoxydiphenylsilane.
The catalyzer that the present invention relates to is applicable to polymerization or copolymerization, particularly ethene and the styrene copolymerisation reaction of alkene.Polyreaction is preferably carried out in inert solvent medium.Described inert solvent medium generally adopts hydrocarbon solvent, comprises aliphatic hydrocarbon, as propane, butane, Trimethylmethane, pentane, hexane, heptane, octane, decane, dodecane and kerosene etc.; Alicyclic hydrocarbon is as pentamethylene, hexanaphthene and methylcyclopentane etc.; Aromatic hydrocarbons is as benzene,toluene,xylene etc.; Halohydrocarbon as ethylene chloride and chlorobenzene etc., is advisable with aliphatic hydrocarbon solvent in these solvents.The scope of polymeric reaction temperature: 30---90 ℃, the scope of polymerization pressure: normal pressure---10MPa.
Catalyzer of the present invention is when being used for the reaction of ethene and styrene copolymerisation, has advantages of high catalytic activity, the polymerization activity of styrene monomer improves greatly, the polymkeric substance that obtains has good particle form and apparent density, the ethene and the styrene copolymer composite of gained have good particle form and apparent density, except possessing very good shock resistance simultaneously, also have higher tensile strength and modulus, the electrical insulation capability of material has also obtained tangible improvement.
Embodiment
Following Example is used for illustrating the present invention, is not to be used for limiting the scope of the invention.
Testing method:
1, the tensile strength of polymkeric substance and elongation at break: GB1040
2, the flexural strength of polymkeric substance and modulus in flexure: GB9341
3, notched Izod impact strength: GB/T 1043
One, catalyzer is synthetic:
In the reaction flask after high purity nitrogen purifies, add Zinc Chloride Anhydrous, Magnesium Chloride Anhydrous, toluene, epoxy chloropropane and tributyl phosphate (the add-on prescription is given) successively, be warming up to design temperature under stirring, being maintained until solid dissolves fully, add Tetra hydro Phthalic anhydride then, continue to keep for some time.To splash into TiCl after the solution cooling
4, separate out crystallization in the reaction system, temperature is slowly risen to 80 ℃, add dicarboxylic esters, and continue to keep 80 ℃ of for some time, use toluene wash twice later, adopt TiCl then
4Handle twice, and add the ethylene dichloride washing once, hexane wash gets solids, i.e. catalyzer four times.
Embodiment 1:
In the glass blender jar, under nitrogen protection, add Magnesium Chloride Anhydrous, 65mL toluene, 6.0mL epoxy chloropropane, 6.0mL tributyl phosphate, the 3.0gZnCl that 2.0g grinds
2, stir 120min down at 50 ℃, add the 1.0g Tetra hydro Phthalic anhydride then, continue to stir 1hr.Cool to-32 ℃ thereafter, splash into the 55mL titanium tetrachloride, be warmed up to 80 ℃ then, add DIBP2.4mL, keep 60min, leach mother liquor, with 40 ℃ of washings of 90mL toluene 2 times, filter back adding titanium tetrachloride 40mL, toluene 60mL and be warmed up to 100 ℃ of reaction 2hr, filter, with ethylene dichloride 90mL once, 80 ℃ of washings then with hexane respectively 60 ℃ of washings once, room temperature washing 3 times.Get the powdery solid catalyzer after the vacuum-drying.
Embodiment 2:
In the glass blender jar, under nitrogen protection, add Magnesium Chloride Anhydrous, 65mL toluene, 6.0mL epoxy chloropropane, 6.0mL tributyl phosphate, the 4.5gZnCl that 1.0g grinds
2, stir 120min down at 50 ℃, add the 1.0g Tetra hydro Phthalic anhydride then, continue to stir 1hr.Cool to-30 ℃ thereafter, splash into the 55mL titanium tetrachloride, be warmed up to 80 ℃ then, add DIBP2.8mL, keep 60min, leach mother liquor, with 40 ℃ of washings of 90mL toluene 2 times, filter back adding titanium tetrachloride 40mL, toluene 60mL and be warmed up to 100 ℃ of reaction 2hr, filter, with ethylene dichloride 90mL once, 80 ℃ of washings then with hexane respectively 60 ℃ of washings once, room temperature washing 3 times.Get the powdery solid catalyzer after the vacuum-drying.
Embodiment 3:
In the glass blender jar, under nitrogen protection, add 65mL toluene, 6.0mL epoxy chloropropane, 6.0mL tributyl phosphate, 6.0gZnCl
2, stir 120min down at 50 ℃, add the 1.0g Tetra hydro Phthalic anhydride then, continue to stir 1hr.Cool to-30 ℃ thereafter, splash into the 55mL titanium tetrachloride, be warmed up to 80 ℃ then, add DIBP2.8mL, keep 60min, leach mother liquor, with 40 ℃ of washings of 90mL toluene 2 times, filter back adding titanium tetrachloride 40mL, toluene 60mL and be warmed up to 100 ℃ of reaction 2hr, filter, with ethylene dichloride 90mL once, 80 ℃ of washings then with hexane respectively 60 ℃ of washings once, room temperature washing 3 times.Get the powdery solid catalyzer after the vacuum-drying.
Embodiment 4:
In the glass blender jar, under nitrogen protection, add Magnesium Chloride Anhydrous, 60mL toluene, 6.0mL epoxy chloropropane, 6.0mL tributyl phosphate, the 1.5gZnCl that 3.0g grinds
2, stir 120min down at 50 ℃, add the 1.0g Tetra hydro Phthalic anhydride then, continue to stir 1hr.Cool to-30 ℃ thereafter, splash into the 55mL titanium tetrachloride, be warmed up to 80 ℃ then, add DIBP2.0mL, keep 60min, leach mother liquor, with 40 ℃ of washings of 90mL toluene 2 times, filter back adding titanium tetrachloride 40mL, toluene 60mL and be warmed up to 100 ℃ of reaction 2hr, filter, with ethylene dichloride 90mL once, 80 ℃ of washings then with hexane respectively 60 ℃ of washings once, room temperature washing 3 times.Get the powdery solid catalyzer after the vacuum-drying.
Embodiment 5:
In the glass blender jar, under nitrogen protection, add Magnesium Chloride Anhydrous, 65mL toluene, 5.0mL epoxy chloropropane, 7.5mL tributyl phosphate, the 0.75gZnCl that 4.0g grinds
2, stir 120min down at 50 ℃, add the 1.0g Tetra hydro Phthalic anhydride then, continue to stir 1hr.Cool to-30 ℃ thereafter, splash into the 55mL titanium tetrachloride, be warmed up to 80 ℃ then, add DIBP4.5mL, keep 60min, leach mother liquor, with 40 ℃ of washings of 90mL toluene 2 times, filter back adding titanium tetrachloride 40mL, toluene 60mL and be warmed up to 100 ℃ of reaction 2hr, filter, with ethylene dichloride 90mL once, 80 ℃ of washings then with hexane respectively 60 ℃ of washings once, room temperature washing 3 times.Get the powdery solid catalyzer after the vacuum-drying.
Comparative Examples 1: the method according to embodiment 1 in the Chinese patent CN85100997 specification sheets prepares catalyzer.
Two, aggregation test:
(1) ethylene homo test
Equipment: 2 liters of stainless steel polymermaking autoclaves
Operate: after polymeric kettle is blown row with high pure nitrogen, vacuumize with ethene and blow row three times, logical ethene is to malleation; Add about the about 300mL of hexane, open and stir, add the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 10mg catalyst component, 5ml triethyl aluminum, rinse well, add H with the surplus hexane
2To 0.25MPa, heat up, feed ethene to 0.8MPa, 80 ℃ of polymerizations 2 hours stop polyreaction, obtain white polymer; Behind washing, suction filtration, use the vacuum drying oven drying treatment to constant weight, weighing test, calculated activity.
(2) vinylbenzene homopolymerization test
Equipment: 1000mL glass reaction still
Operate: after reactor is blown row with high pure nitrogen, keep malleation in the still, add hexane, add 10mg catalyst component, the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum and the hexane solution (concentration of DPMS is 0.1mmol/ml) of 1ml dimethoxydiphenylsilane (DPMS), rinse well with the surplus hexane, heating, while is drip styrene 200ml/ hexane solution (volume ratio 1: 1) at the uniform velocity, drips off in 30～60 minutes.Drip off back 80 ℃ and keep reaction 2 hours, system viscosity increases gradually, stops heating after then, stops stirring, and the polymers soln in the reactor is poured in the beaker that is added with methyl alcohol while hot, constantly stir, white powdery or thread polymkeric substance; Leave standstill suction filtration, to constant weight, weighing is tested with the vacuum drying oven drying treatment.
(3) ethene-styrene copolymerized test
Equipment: 2 liters of stainless steel polymermaking autoclaves
Operate: after polymeric kettle is blown row with high pure nitrogen, vacuumize with ethene and blow row three times, logical ethene is to malleation; Add about the about 300mL of hexane, vinylbenzene 70ml/ hexane solution (volume ratio 1: 1), open and stir, add 10mg catalyst component, the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum and the hexane solution (concentration of DPMS is 0.1mmol/ml) of 1ml dimethoxydiphenylsilane (DPMS), rinse well with the surplus hexane, add H
2To 0.05MPa, heat up, feed ethene to 0.8MPa, 80 ℃ of polymerizations 2 hours stop polyreaction, obtain white polymer; Behind washing, suction filtration, use the vacuum drying oven drying treatment to constant weight, weighing test, calculated activity.
Three, polymerization result:
Table 1
| Numbering | PE (polyethylene) | PS (polystyrene) | PES (ethylene-styrene copolymer composition) | |||
| ????AC ?gPE/gcat | ????BD ???g/cm 3 | ????AC ??gPE/gcat | Transformation efficiency % | ????AC ??gPE/gcat | ????BD ???g/cm 3 | |
| Example 1 | ????7807 | ????0.34 | ????27106 | ???54.5 | ????7600 | ????0.34 |
| Example 2 | ????5200 | ????0.38 | ??11386 | ????28.9 | ????5760 | ????0.36 |
| Example 3 | ????5100 | ????0.38 | ??10486 | ????30.0 | ????4520 | ????0.30 |
| Example 4 | ????4730 | ????0.37 | ??11890 | ????28.9 | ????2630 | ????0.29 |
| Example 5 | ????5810 | ????0.37 | ???/ | ????/ | ????6739 | ????0.40 |
| Contrast 1 | ????9020 | ????0.38 | Non-activity almost | ????------ | ????2380 | ????0.25 |
More as can be seen, adopt the polymerization activity of the equal polymerization of catalyzer vinylbenzene of the present invention, ethene-styrene copolymerisation higher, and the bulk density of resulting polymers is higher from the data of table 1, this will improve the performance of ethylene-styrene copolymer significantly.
Four, the The performance test results of multipolymer: the ethylene-styrene copolymer of embodiment 1 and 2 gained is carried out following performance test, the results are shown in Table 2:
Table 2
| Material property | Embodiment 1 | Embodiment 2 |
| Tensile strength (MPa) | ????38.8 | ????38.1 |
| Modulus in flexure (Gpa) | ????2.29 | ????2.30 |
| Notched Izod impact strength (KJ/m2) | Constantly (〉=49.7) | Constantly (〉=50.2) |
Claims (7)
1, the catalyzer that is used for ethene and styrene copolymerisation, this catalyzer contains the reaction product of following component:
(1) a kind of titaniferous ingredient of solid catalyst, it is that zinciferous halogenide is dissolved in the solvent system of being made up of organic epoxy compounds, organo phosphorous compounds and inert diluent, mix with titanium compound after forming homogeneous solution, in the presence of precipitation additive, separate out solids; The monobasic or the polycarboxylic acid ester cpds of this solids by using aliphatic series or aromatics are handled, and it is attached on the solids, in case of necessity, with titanium compound and inert diluent solids are handled obtaining again;
(2) organo-aluminium compound;
(3) randomly, silicoorganic compound.
The ratio between ingredient of solid catalyst (1), organo-aluminium compound component (2) and the silicoorganic compound component (3) wherein, with titanium: aluminium: the molar ratio computing between the silicon is 1: 5～1000: 0～500.
2, the catalyzer that is used for ethene and styrene copolymerisation according to claim 1 is characterized in that, described zinciferous halogenide is zinc halide or zinc halide and magnesium halide.
3, the catalyzer that is used for ethene and styrene copolymerisation according to claim 1 is characterized in that, described zinciferous halogenide is zinc halide and magnesium halide, and in every mole of zinc halide, magnesium halide is the 0.2-5 mole.
4, the catalyzer that is used for ethene and styrene copolymerisation according to claim 3 is characterized in that described zinc halide is a zinc dichloride.
5, the catalyzer that is used for ethene and styrene copolymerisation according to claim 1 is characterized in that described precipitation additive is an organic acid anhydride.
6, the catalyzer that is used for ethene and styrene copolymerisation according to claim 1 is characterized in that described polycarboxylic acid ester cpds is phthalic ester diisobutyl ester or phthalic ester di-n-butyl.
7, the application of the described catalyzer of one of claim 1-6 in ethene and styrene copolymerisation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310121872 CN1267464C (en) | 2003-12-24 | 2003-12-24 | Catalyst for copolymerization of ethylene and styrene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310121872 CN1267464C (en) | 2003-12-24 | 2003-12-24 | Catalyst for copolymerization of ethylene and styrene |
Publications (2)
| Publication Number | Publication Date |
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| CN1631922A true CN1631922A (en) | 2005-06-29 |
| CN1267464C CN1267464C (en) | 2006-08-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200310121872 Expired - Lifetime CN1267464C (en) | 2003-12-24 | 2003-12-24 | Catalyst for copolymerization of ethylene and styrene |
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| CN (1) | CN1267464C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173014B (en) * | 2006-10-31 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same |
| EP2712874A1 (en) | 2012-09-26 | 2014-04-02 | Basell Poliolefine Italia S.r.l. | Catalyst components for the polymerization of olefins |
| US9815918B2 (en) | 2012-03-19 | 2017-11-14 | Formosa Plastics Corporation, U.S.A. | Catalyst component for high activity and high stereoselectivity in olefin polymerization |
| CN111072804A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component and application thereof, olefin polymerization catalyst and olefin polymerization method |
-
2003
- 2003-12-24 CN CN 200310121872 patent/CN1267464C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173014B (en) * | 2006-10-31 | 2011-05-04 | 中国石油化工股份有限公司 | Catalyst for polymerization of ethylene or combined polymerization, producing method and application of the same |
| US9815918B2 (en) | 2012-03-19 | 2017-11-14 | Formosa Plastics Corporation, U.S.A. | Catalyst component for high activity and high stereoselectivity in olefin polymerization |
| EP2712874A1 (en) | 2012-09-26 | 2014-04-02 | Basell Poliolefine Italia S.r.l. | Catalyst components for the polymerization of olefins |
| WO2014048964A1 (en) | 2012-09-26 | 2014-04-03 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins and catalysts therefrom obtained |
| CN111072804A (en) * | 2018-10-19 | 2020-04-28 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component and application thereof, olefin polymerization catalyst and olefin polymerization method |
| CN111072804B (en) * | 2018-10-19 | 2022-07-12 | 中国石油化工股份有限公司 | Olefin polymerization catalyst component and application thereof, olefin polymerization catalyst and olefin polymerization method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1267464C (en) | 2006-08-02 |
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