JPS642121B2 - - Google Patents
Info
- Publication number
- JPS642121B2 JPS642121B2 JP13754880A JP13754880A JPS642121B2 JP S642121 B2 JPS642121 B2 JP S642121B2 JP 13754880 A JP13754880 A JP 13754880A JP 13754880 A JP13754880 A JP 13754880A JP S642121 B2 JPS642121 B2 JP S642121B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- carbon atoms
- catalyst
- polymerization
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- -1 organic acid ester compound Chemical class 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000011777 magnesium Substances 0.000 claims description 16
- 239000010936 titanium Substances 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000004711 α-olefin Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000006116 polymerization reaction Methods 0.000 description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 239000011949 solid catalyst Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 238000004737 colorimetric analysis Methods 0.000 description 4
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SHSGDXCJYVZFTP-UHFFFAOYSA-N 4-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C=C1 SHSGDXCJYVZFTP-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 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
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- YLYBTZIQSIBWLI-UHFFFAOYSA-N octyl acetate Chemical compound CCCCCCCCOC(C)=O YLYBTZIQSIBWLI-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-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
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- 229960002903 benzyl benzoate 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- LKRBKNPREDAJJQ-UHFFFAOYSA-M chloro-di(propan-2-yl)alumane Chemical compound [Cl-].CC(C)[Al+]C(C)C LKRBKNPREDAJJQ-UHFFFAOYSA-M 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- DQZKGSRJOUYVPL-UHFFFAOYSA-N cyclohexyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1CCCCC1 DQZKGSRJOUYVPL-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- IWYBVQLPTCMVFO-UHFFFAOYSA-N ethyl 2,2-dichloroacetate Chemical compound CCOC(=O)C(Cl)Cl IWYBVQLPTCMVFO-UHFFFAOYSA-N 0.000 description 1
- HHEIMYAXCOIQCJ-UHFFFAOYSA-N ethyl 2,2-dimethylpropanoate Chemical compound CCOC(=O)C(C)(C)C HHEIMYAXCOIQCJ-UHFFFAOYSA-N 0.000 description 1
- RETLCWPMLJPOTP-UHFFFAOYSA-N ethyl 2-chlorobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1Cl RETLCWPMLJPOTP-UHFFFAOYSA-N 0.000 description 1
- OUZCDRGUTZLAGO-UHFFFAOYSA-N ethyl 2-ethoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OCC OUZCDRGUTZLAGO-UHFFFAOYSA-N 0.000 description 1
- XSXVXSCMWUJXOS-UHFFFAOYSA-N ethyl 2-ethylbenzoate Chemical compound CCOC(=O)C1=CC=CC=C1CC XSXVXSCMWUJXOS-UHFFFAOYSA-N 0.000 description 1
- LMXMLKHKWPCFTG-UHFFFAOYSA-N ethyl 4-butoxybenzoate Chemical compound CCCCOC1=CC=C(C(=O)OCC)C=C1 LMXMLKHKWPCFTG-UHFFFAOYSA-N 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- HQKSINSCHCDMLS-UHFFFAOYSA-N ethyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCC)=CC=C21 HQKSINSCHCDMLS-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 1
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
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The present invention relates to a method for polymerizing α-olefin, in particular, polymerizing α-olefin having 3 to 8 carbon atoms using a specific activated titanium catalyst component, an organometallic compound, and an organic acid ester compound,
This invention relates to a method for obtaining highly stereoregular poly-α-olefins with high activity. Conventionally, α-
Methods for stereoregularly polymerizing olefins are known, for example, Japanese Patent Publication No. 1983-34098;
98076, and the method disclosed in Japanese Unexamined Patent Publication No. 53-2580. However, each method has advantages and disadvantages, and no method has yet been developed that satisfies various demands such as high activity, high stereoregularity, high bulk specific gravity, stability of the polymer, and ease of handling of the catalyst. In particular, there is an inverse correlation between the polymerization activity of the catalyst and the stereoregularity of the resulting polymer, and it has so far been extremely difficult to simultaneously maintain both of them at high levels. The present inventors have worked diligently to overcome the drawbacks of the above-mentioned conventional techniques and to develop a method for producing polyα-olefins with high bulk specific gravity while maintaining a high degree of both polymerization activity and stereoregularity of the resulting polymer. I did a lot of research. As a result, they discovered that the object could be achieved by using a specially treated magnesium compound with a titanium component supported thereon as a component of the catalyst, leading to the completion of the present invention. That is, the present invention provides (A) a compound having the general formula Mg(OR 1 ) 2 [wherein R 1 represents an alkyl group having 1 to 5 carbon atoms]. ] to a mixture of magnesium dialkoxide and magnesium chloride, a mixture of the general formula R 3 OH [wherein R 3 represents an alkyl group or cycloalkyl group having a straight chain or side chain having 1 to 10 carbon atoms] . ], then an organic acid ester compound is reacted, and further the general formula TiX 1 4 [in the formula,
X 1 represents a halogen atom. A solid product obtained by reacting titanium tetrahalide represented by (B) general formula AlR 4 n X 2 3-n [wherein R 4 is a carbon number of 1 to
5 alkyl group, m is a real number between 2 and 3, and X 2 represents a halogen atom. ] An α-olefin having 3 to 8 carbon atoms is polymerized using a catalyst containing an organoaluminum compound represented by the formula (C) and an organic acid ester compound (C).
A method for polymerizing olefins is provided. In the method of the present invention, a magnesium dialkoxide represented by the general formula Mg(OR 1 ) 2 is used. Here, R 1 represents an alkyl group having 1 to 5 carbon atoms as described above. Specific examples include magnesium dimethoxide, magnesium diethoxide, magnesium dipropoxide, and magnesium dibutoxide. Moreover, although commercially available magnesium dialkoxides can be used, those produced by the reaction of metallic magnesium and alcohol may also be used. The magnesium chloride used in the method of the present invention may be an anhydrous salt, but it is preferable to use an adduct of the alcohol. Such alcohol adducts are represented by the general formula MgCl 2 ·nR 2 OH, where R 2 is an alkyl group having 1 to 5 carbon atoms,
n is 0.1 to 10. Specifically, MgCl 2 .6C 2 H 5 OH and the like can be mentioned. When mixing the above-mentioned magnesium dialkoxide and the alcohol adduct of magnesium chloride, preferably the former: the latter = 1 to 4: 4 to 1
(molar ratio) of 100 to 200 under reduced pressure.
Heat to â and process for about 3 to 10 hours. During this heat treatment, a very small amount (above mixture 1) should be added to the system.
You can also add about 1 ml of alcohol per gram. The alcohol added here may be of the same type as the alcohol added during the alcohol treatment to be performed later, or may be of a different type. In the method of the present invention, the above-described mixture of magnesium dialkoxide and magnesium chloride is pulverized, and the resulting pulverized product is subjected to an alcohol treatment by reacting with an alcohol represented by the general formula R 3 OH. Here, R 3 represents an alkyl group or a cycloalkyl group having a straight chain or side chain having 1 to 10 carbon atoms, as described above. Suitable alcohols include primary, secondary or tertiary alcohols having 1 to 10 carbon atoms, more specifically methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, octanol. etc. can be given. The amount of the alcohol used in the alcohol treatment is not particularly limited and may be selected appropriately depending on various conditions, but it is usually 0.01 to 10 mol, preferably 0.1 to 10 mol, per 1 mol of magnesium in the above-mentioned pulverized material. It should be 5 moles. In addition, the temperature and time of this alcohol treatment may be determined as appropriate, but generally it should be in the range of 0 to 200°C for 5 minutes to 5 hours, preferably 20 to 100°C for 20 minutes to 3 hours. . Furthermore, in the present invention, after performing an alcohol treatment, the obtained product is reacted with an organic acid ester compound, and further a compound of the general formula TiX 1 4 [wherein X 1 represents a halogen atom] is formed. ] It is necessary to react titanium tetrahalide represented by: Examples of organic acid ester compounds used here include methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate,
Ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate , octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate,
Methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate,
Ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, Ύ-valerolactone, coumarin, phthalide,
Examples include esters having 2 to 18 carbon atoms such as ethylene carbonate. Particularly preferred are alkyl esters of aromatic carboxylic acids, such as alkyl esters of aromatic carboxylic acids having 1 to 4 carbon atoms, such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid. In addition, titanium tetrahalide has the general formula
It is represented by TiX 1 4 , where X 1 represents a halogen atom. Specifically, TiCl 4 , TiBr 4 ,
Examples include TiI 4 . These may be used alone or as a mixture. Among these, it is particularly preferable to use titanium tetrachloride (TiCl 4 ). The conditions for these reactions are not particularly limited and may be selected appropriately depending on various conditions, etc., but first, an organic acid ester compound is added to the product obtained by alcohol treatment to 1 mole of magnesium in the product. for
About 0.01 to 5 mol, preferably 0.1 to 1 mol, is added, and the reaction is usually carried out at 0 to 200°C for 5 minutes to 5 hours, preferably at 20 to 120°C for 20 minutes to 3 hours. Next, titanium tetrahalide is added to this reaction system in an amount of 0.5 to 100 mol, preferably 1 to 50 mol, per 1 mol of magnesium in the product.
The reaction is carried out at 200°C for 30 minutes to 10 hours, preferably at 50 to 150°C for 1 to 5 hours. In the reactions up to this point, it is also possible to use an inert solvent such as n-heptane, if necessary. After the reaction is completed, the solid product obtained is thoroughly washed with an inert solvent such as n-heptane. After the reaction, it is preferable to remove only the liquid and repeat the above-described addition of titanium tetrahalide and the reaction, since this improves the performance of the solid product as a catalyst. In the present invention, the solid product thus obtained is used as component (A) (solid catalyst component) of an α-olefin polymerization catalyst. According to the present invention, the above solid product is the component (A), and the organoaluminum compound is the component (B),
Furthermore, an organic acid ester compound was used as the (C) component,
α-olefin is polymerized using a catalyst consisting of three components (A), (B), and (C). When polymerizing α-olefin, the reaction system
A dispersion of the solid product as component (A), an organic acid ester compound as component (B), and an organic acid ester compound as component (C) are added, and then α
- Introducing olefin. The polymerization method and conditions are not particularly limited, and any of solution polymerization, suspension polymerization, gas phase polymerization, etc. is possible, and both continuous polymerization and discontinuous polymerization are possible. For example, in the case of solution polymerization or suspension polymerization, the amount of the catalyst component added is 0.001 to 1.0 mmol per titanium atom for component (A), and the amount of component (B) is 0.001 to 1.0 mmol per titanium atom. The amount is 1 to 1000 (molar ratio), preferably 5 to 500 (molar ratio) to titanium atoms. The amount of component (C) added should be 0.01 to 100 (mole ratio), preferably 0.1 to 50 (mole ratio), relative to the titanium atoms in component (A). The α-olefin pressure in the reaction system is preferably normal pressure to 50 kg/cm 2 , and the reaction temperature is 30 kg/cm 2 .
~200°C, preferably 50~150°C. Molecular weight adjustment during polymerization can be carried out by known means, such as hydrogen. The reaction time is 10 minutes ~
The time period may be appropriately selected from 10 hours, preferably from 30 minutes to 5 hours. Component (B) of the catalyst used in the method of the present invention is:
As mentioned above, it is an organoaluminum compound represented by the general formula AlR 4 n X 2 3-n . Here, R 4 represents an alkyl group having 1 to 5 carbon atoms, m is a real number between 2 and 3, and X 2 represents a halogen atom such as chlorine or bromine. Specifically, trimethylaluminum,
Trialkylaluminum compounds such as triethylaluminum, triisopropylaluminium, and triisobutylaluminum, and dialkylaluminum monohalides such as diethylaluminum monochloride, diisopropylaluminum monochloride, and diisobutylaluminum monochloride are preferred, and mixtures thereof are also preferred. It can be given as a thing. Furthermore, the organic acid ester compound which is the component (C) of the catalyst used in the method of the present invention is
The same material as used in the preparation of component (A) can be used. Furthermore, in this case, the organic acid ester compound as component (C) may be exactly the same compound as that used in the preparation of component (A) of the catalyst, or may be a different compound. In the method of the present invention, an α-olefin having 3 to 8 carbon atoms is polymerized using the catalyst described above. Such α-olefin has the general formula R 5 âCH=CH 2 (wherein,
R 5 represents an alkyl group having 1 to 6 carbon atoms. ), linear monoolefins such as propylene, butene-1, hexene-1, octene-1, branched monoolefins such as 4-methyl-pentene-1, dienes such as butadiene, and various others. The present invention can be effectively used for homopolymerization of these or copolymerization of various α-olefins. According to the method of the present invention, the activity of the catalyst used is extremely high, and the resulting polymer has great stereoregularity, resulting in extremely high product value. Therefore, since the method of the present invention is a method of highly active polymerization and a polymer with large stereoregularity is obtained, it is possible to simplify or omit the catalyst removal step and the amorphous polymer extraction step. , very efficient polymerization can be carried out. Next, examples of the present invention will be shown. Note that all operations in the following examples were performed under an argon stream. Further, the catalytic activity and isotactic yield (IY) determined in the examples were defined as follows. Catalyst activity: 70â, 2 hours, propylene partial pressure 7
Weight (Kg) of total polymer produced per 1g of titanium atom during polymerization under conditions of Kg/ cm2 . IY = Weight of polymer insoluble in boiling n-heptane/Weight of total polymer produced x 100 (%) Example 1 (1) Production of solid catalyst [Production of catalyst support (ClMgOR)] Average particle diameter of 10Ό pulverized with a ball mill of Mg
(OC 2 H 5 ) 2 10.4 g (91 mmol) and 33.7 g (91 mmol) of MgCl 2 6C 2 H 5 OH, which was produced by dissolving MgCl 2 in excess ethanol and distilling off the ethanol.
They were separated and both were mixed. Add a small amount (about 40ml)
Add ethanol, mix, and transfer to a flask.
The mixture was heat-treated at 160° C. for 4 hours under reduced pressure, and the resulting solid was pulverized to form a catalyst carrier. [Production of titanium-supported catalyst] 100 ml of heptane and 2 g of the above-mentioned support (19 mmol as Mg) were added to a 200 ml flask and stirred to suspend. Add 0.18g of ethanol to this suspension.
(3.8 mmol) and reacted at 80°C for 1 hour.
Next, 0.57 g (3.8 mmol) of benzoic acid ethyl ester was added and the reaction was carried out at 80°C for 1 hour, and then 36 g (190 mmol) of titanium tetrachloride was added dropwise at 80°C within 1 hour, and then refluxed for 3 hours. A time reaction was performed. After the reaction was completed, the supernatant liquid was removed by decanting, and 150 ml of heptane was added for washing. This operation was repeated until no chloride ions were detected in the heptane cleaning solution. The supported amount determined by colorimetric method is 20 mg.
-Ti/g- It was a carrier. (2) Polymerization of propylene 400 ml of heptane was added to the dry stainless steel autoclave in step 1. Add to this 2 mmol of triethylaluminum and 0.5 methyl paratoluate.
2 mmol of diethylaluminum chloride and 0.02 mmol of the solid catalyst as Ti were added, and the temperature was raised to 70°C. Add 0.2Kg/ cm2 of hydrogen,
By setting the propylene partial pressure to 7Kg/ cm2 and continuously introducing propylene, the total pressure is kept constant at 70â.
Polymerization was carried out for 2 hours. After the polymerization reaction, 70â
The insoluble polymer was separated by filtration. Furthermore, the filtered polymerization solvent was evaporated to dryness to recover the soluble polymer. The insoluble polymer was treated with boiling n-heptane for 6 hours to extract and separate the atactic polymer. The total polymer yield was 93.0 g and the catalyst activity was 97
Kg/g-Ti, isotactic yield (IY) is
It was 82.1%. Examples 2 to 9 Catalysts were produced in the same manner as in Example 1, except that the carrier produced in the same manner as in Example 1 was used and the type and amount of alcohol were changed in the production of the titanium catalyst. Further, propylene was polymerized using these catalysts under the same conditions as in Example 1. The results are shown in Table 1.
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ã第ïŒè¡šã«ç€ºãã[Table] Example 10 (1) Production of solid catalyst 200 ml of heptane in a 500 ml flask and Example 1
10 g (95 mmol as Mg) of the carrier prepared in the same manner as above was added and stirred to form a suspension. Add 1.8 g (24 mmol) of normal butanol to this suspension.
After the reaction was carried out for 1 hour under reflux, 180 g (950 mmol) of titanium tetrachloride was added dropwise within 1 hour, and the reaction was further carried out for 3 hours under reflux. After the reaction, the supernatant liquid was removed by decanting, and heptane was added.
200ml was added for washing. This operation was repeated until no chlorine ions were detected in the heptane cleaning solution. The supported amount determined by colorimetric method is 34 mg.
It was a Ti/g-carrier. (2) Polymerization of propylene Example 1 according to the method of Example 1 except that the amount of methyl paratoluate was changed to 0.5 mmol.
Polymerization of propylene was carried out under the same conditions as the method described above. The results are shown in Table 2. Examples 11 to 15 (1) Production of solid catalyst Catalysts were produced in the same manner as in Example 10, except that the amount of n-butanol and the amount of ethyl benzoate were changed. (2) Polymerization of propylene The catalyst prepared in (1) above was used, and the rest were as in Example 10.
Polymerization of propylene was carried out under the same conditions. The results are shown in Table 2.
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A.D.ã¯0.37ã§ãã€ãã[Table] Example 16 (1) Production of solid catalyst 180 g of titanium tetrachloride was added dropwise to the solid catalyst heptane slurry produced in Example 10 at room temperature, and after raising the temperature, the reaction was carried out under reflux for 3 hours. Thereafter, washing was carried out with heptane in the same manner as in Example 10, and a solid catalyst having a supported amount of 31 mg-Ti/g-carrier was obtained by colorimetric method. (2) Polymerization of propylene Example 1 according to the method of Example 1 except that the amount of methyl paratoluate was changed to 0.7 mmol.
Polymerization of propylene was carried out under the same conditions as the method described above. Catalytic activity is 136Kg/g-Ti, IY is 92.4%,
AD was 0.31. Example 17 (1) Production of solid catalyst 180 g of titanium tetrachloride was added dropwise to the solid catalyst heptane slurry produced in Example 14 at room temperature, and after raising the temperature, the mixture was reacted under reflux for 3 hours. Hereinafter, the same washing as in Example 10 was carried out with heptane, and the amount of support was determined by colorimetric method.
A solid catalyst of 34 mg-Ti/g-support was obtained. (2) Polymerization of propylene Example 1 according to the method of Example 1 except that the amount of methyl paratoluate was changed to 0.7 mmol.
Polymerization of propylene was carried out under the same conditions as the method described above. Catalytic activity is 164Kg/g-Ti, IY is 91.5%,
AD was 0.37.
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Claims (1)
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ã®ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã[Claims] 1 (A) General formula Mg(OR 1 ) 2 [wherein R 1 is a carbon number of 1 to
5 shows the alkyl group. ] A mixture of magnesium dialkoxide and magnesium chloride is added with the general formula R 3 OH [where R 3 is
Indicates an alkyl or cycloalkyl group having ~10 straight or side chains. ] is reacted, and then an organic acid ester compound is reacted, and further the general formula TiX 1 4 [wherein X 1 represents a halogen atom] is reacted. A solid product obtained by reacting titanium tetrahalide represented by (B) general formula AlR 4 n X 2 3-n [wherein R 4 represents an alkyl group having 1 to 5 carbon atoms, m is a real number between 2 and 3,
X 2 represents a halogen atom. A method for polymerizing an α-olefin, which comprises polymerizing an α-olefin having 3 to 8 carbon atoms using a catalyst containing an organoaluminum compound represented by the formula (C) and an organic acid ester compound (C). 2 α-olefin having 3 to 8 carbon atoms has the general formula R 5
âCH=CH 2 [In the formula, R 5 represents an alkyl group having 1 to 6 carbon atoms. ] The method according to claim 1, wherein the method is represented by:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13754880A JPS5763308A (en) | 1980-10-03 | 1980-10-03 | Polymerization of alpha-olefin |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13754880A JPS5763308A (en) | 1980-10-03 | 1980-10-03 | Polymerization of alpha-olefin |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5763308A JPS5763308A (en) | 1982-04-16 |
JPS642121B2 true JPS642121B2 (en) | 1989-01-13 |
Family
ID=15201265
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13754880A Granted JPS5763308A (en) | 1980-10-03 | 1980-10-03 | Polymerization of alpha-olefin |
Country Status (1)
Country | Link |
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JP (1) | JPS5763308A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61254610A (en) * | 1985-05-07 | 1986-11-12 | Mitsubishi Petrochem Co Ltd | Catalyst component for polymerizing olefin |
JPS623013U (en) * | 1985-06-24 | 1987-01-09 | ||
JP5077906B2 (en) * | 2005-12-28 | 2012-11-21 | æ±éŠãã¿ããŠã æ ªåŒäŒç€Ÿ | SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION, PROCESS FOR PRODUCING THE SAME, AND CATALYST AND METHOD FOR PRODUCING OLEFIN POLYMER USING THE SAME |
-
1980
- 1980-10-03 JP JP13754880A patent/JPS5763308A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5763308A (en) | 1982-04-16 |
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