JPH02308803A - Production of ethylene-unsaturated carboxylic acid copolymer - Google Patents
Production of ethylene-unsaturated carboxylic acid copolymerInfo
- Publication number
- JPH02308803A JPH02308803A JP12788389A JP12788389A JPH02308803A JP H02308803 A JPH02308803 A JP H02308803A JP 12788389 A JP12788389 A JP 12788389A JP 12788389 A JP12788389 A JP 12788389A JP H02308803 A JPH02308803 A JP H02308803A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- copolymer
- chromium
- group
- unsaturated carboxylic
- 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.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000002841 Lewis acid Substances 0.000 claims abstract description 31
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 18
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 abstract description 3
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 abstract description 2
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 96
- -1 Polyethylene Polymers 0.000 description 54
- 229910052804 chromium Inorganic materials 0.000 description 47
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 150000001875 compounds Chemical class 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 11
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 150000002894 organic compounds Chemical class 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000005395 methacrylic acid group Chemical group 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000003003 phosphines Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910021559 Chromium(II) bromide Inorganic materials 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- XZQOHYZUWTWZBL-UHFFFAOYSA-L chromium(ii) bromide Chemical compound [Cr+2].[Br-].[Br-] XZQOHYZUWTWZBL-UHFFFAOYSA-L 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 4
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- IVKVYYVDZLZGGY-UHFFFAOYSA-K chromium(3+);octadecanoate Chemical compound [Cr+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O IVKVYYVDZLZGGY-UHFFFAOYSA-K 0.000 description 3
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 3
- UZDWIWGMKWZEPE-UHFFFAOYSA-K chromium(iii) bromide Chemical compound [Cr+3].[Br-].[Br-].[Br-] UZDWIWGMKWZEPE-UHFFFAOYSA-K 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical group CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical group CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 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
- 229910021564 Chromium(III) fluoride Inorganic materials 0.000 description 2
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-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
- 229940093499 ethyl acetate Drugs 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- XJAQAYFQGKTUNX-UHFFFAOYSA-N ethyl butanoate;methyl butanoate Chemical compound CCCC(=O)OC.CCCC(=O)OCC XJAQAYFQGKTUNX-UHFFFAOYSA-N 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- FTJATNSAFIFEDU-UHFFFAOYSA-N ethyl hept-6-enoate Chemical compound CCOC(=O)CCCCC=C FTJATNSAFIFEDU-UHFFFAOYSA-N 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- ZWNJJACKPNTXHY-UHFFFAOYSA-M ethylmagnesium chloride Chemical compound CC[Mg]Cl ZWNJJACKPNTXHY-UHFFFAOYSA-M 0.000 description 1
- JLHMVTORNNQCRM-UHFFFAOYSA-N ethylphosphine Chemical compound CCP JLHMVTORNNQCRM-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- NJVOZLGKTAPUTQ-UHFFFAOYSA-M fentin chloride Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 NJVOZLGKTAPUTQ-UHFFFAOYSA-M 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical group CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 150000002510 isobutyric acid esters Chemical class 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 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
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 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
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 1
- PWAJIGUTWKGVLP-UHFFFAOYSA-N methyl non-8-enoate Chemical compound COC(=O)CCCCCCC=C PWAJIGUTWKGVLP-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
- 229960001047 methyl salicylate Drugs 0.000 description 1
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- RIEABXYBQSLTFR-UHFFFAOYSA-N monobutyrin Chemical compound CCCC(=O)OCC(O)CO RIEABXYBQSLTFR-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- BVWUEIUNONATML-UHFFFAOYSA-N n-benzylethenamine Chemical compound C=CNCC1=CC=CC=C1 BVWUEIUNONATML-UHFFFAOYSA-N 0.000 description 1
- PMJFVKWBSWWAKT-UHFFFAOYSA-N n-cyclohexylprop-2-enamide Chemical compound C=CC(=O)NC1CCCCC1 PMJFVKWBSWWAKT-UHFFFAOYSA-N 0.000 description 1
- XNDDXSIFPSEJFS-UHFFFAOYSA-N n-ethenylcyclohexanamine Chemical compound C=CNC1CCCCC1 XNDDXSIFPSEJFS-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CNPHCSFIDKZQAK-UHFFFAOYSA-N n-prop-2-enylprop-2-enamide Chemical compound C=CCNC(=O)C=C CNPHCSFIDKZQAK-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-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
- PKLGTKSKHJFCIX-UHFFFAOYSA-N octyl undec-10-enoate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC=C PKLGTKSKHJFCIX-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- BTLSLHNLDQCWKS-UHFFFAOYSA-N oxocan-2-one Chemical compound O=C1CCCCCCO1 BTLSLHNLDQCWKS-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- RIYUQGWFHCLLDM-UHFFFAOYSA-N phenyl undec-10-enoate Chemical compound C=CCCCCCCCCC(=O)OC1=CC=CC=C1 RIYUQGWFHCLLDM-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- HHDLJTLPOGOXLR-UHFFFAOYSA-N propan-2-ylphosphane Chemical compound CC(C)P HHDLJTLPOGOXLR-UHFFFAOYSA-N 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WSIZDNPFIBZART-UHFFFAOYSA-N propyl undec-10-enoate Chemical compound CCCOC(=O)CCCCCCCCC=C WSIZDNPFIBZART-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- NNOBHPBYUHDMQF-UHFFFAOYSA-N propylphosphine Chemical compound CCCP NNOBHPBYUHDMQF-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- OIQCWAIEHVRCCG-UHFFFAOYSA-N tetrapropylstannane Chemical compound CCC[Sn](CCC)(CCC)CCC OIQCWAIEHVRCCG-UHFFFAOYSA-N 0.000 description 1
- 150000003573 thiols 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
- FPYOWXFLVWSKPS-UHFFFAOYSA-N triethylbismuthane Chemical compound CC[Bi](CC)CC FPYOWXFLVWSKPS-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
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- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
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- AYDYYQHYLJDCDQ-UHFFFAOYSA-N trimethylbismuthane Chemical compound C[Bi](C)C AYDYYQHYLJDCDQ-UHFFFAOYSA-N 0.000 description 1
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- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- NAPIXUWXWBJHOA-UHFFFAOYSA-N tris(2-methylpropyl)bismuthane Chemical compound CC(C)C[Bi](CC(C)C)CC(C)C NAPIXUWXWBJHOA-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
[産業上の利用分野]
本発明はエチレン−不飽和カルボン酸エステル共重合体
を特定の条件で熱jA理して得られるエチレン−不飽和
カルボン酸共重合体の製造法に関する。本発明の方法に
より得られるエチレン−不飽和カルボン酸共重合体は、
接着性、印刷性、低温柔軟性、低温耐衝撃性等の要求さ
れる用途に有効に利用される。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to the production of an ethylene-unsaturated carboxylic acid copolymer obtained by thermally treating an ethylene-unsaturated carboxylic acid ester copolymer under specific conditions. Regarding the law. The ethylene-unsaturated carboxylic acid copolymer obtained by the method of the present invention is
It is effectively used for applications requiring adhesion, printability, low-temperature flexibility, low-temperature impact resistance, etc.
[従来技術および発明が解決しようとする課題]従来よ
り、ポリエチレンは耐水性、耐薬品性。[Prior art and problems to be solved by the invention] Polyethylene has traditionally had water resistance and chemical resistance.
電気特性などに優れており、広汎な用途に使用されてい
る。しかし、化学的に不活性であるため、接着性や印刷
性、染色性に劣るという難点があり、これらの性質を要
求される用途への使用が制限されていた。It has excellent electrical properties and is used in a wide range of applications. However, because it is chemically inert, it has the disadvantage of poor adhesion, printability, and dyeability, which limits its use in applications that require these properties.
そこで、ポリエチレンのこのような性質を改善するため
、エチレンに不飽和カルボン酸を共重合させることが提
案されている(特公昭44−10275号、同44−2
228号、同48−377F16号公報)。Therefore, in order to improve these properties of polyethylene, it has been proposed to copolymerize ethylene with an unsaturated carboxylic acid (Japanese Patent Publication Nos. 44-10275 and 44-2).
No. 228, No. 48-377F16).
ところが、従来法においては、不飽和カルボン酸を用い
ているために装置の腐食が生じやすい。However, in the conventional method, since an unsaturated carboxylic acid is used, the equipment tends to be corroded.
さらに、不飽和カルボン酸の転化率が低い上に、得られ
る共重合体中の不飽和カルボン酸の含有率も低いもので
しかなかった。Furthermore, not only the conversion rate of unsaturated carboxylic acid was low, but also the content of unsaturated carboxylic acid in the obtained copolymer was only low.
また、エチレン−アクリル酸エチル共重合体を不活性雰
囲気でルイス酸触媒又は固体酸触媒の存在下に、2〜1
00kg/cm2の圧力で、200〜400℃の温度に
加熱することを特徴とする、二重結合を有する低分子量
のエチレン−アクリル酸共重合体の製造方法(特公昭5
7−56922号公報)が知られているが、該共重合体
が高温で熱分解するため、低分子量化し、力学的物性が
著しく低下する欠点がある。In addition, ethylene-ethyl acrylate copolymer was prepared in an inert atmosphere in the presence of a Lewis acid catalyst or a solid acid catalyst for 2 to 1
A method for producing a low molecular weight ethylene-acrylic acid copolymer having double bonds, characterized by heating to a temperature of 200 to 400°C at a pressure of 00 kg/cm2 (Japanese Patent Publication No. 5
No. 7-56922) is known, but since the copolymer is thermally decomposed at high temperatures, the molecular weight is reduced and the mechanical properties are significantly deteriorated.
さらに、本願出願人は先にエチレンと不飽和力る方法(
特開昭63−022807号公報)を提案した。Furthermore, the applicant has previously proposed a method of combining unsaturation with ethylene (
JP-A No. 63-022807).
しかし、この方法ではルイス酸、有機金属化合物の使用
量が多く、触媒効率が非常に悪く、分子量コントロール
も困難であり、装置の腐食も生じやすい欠点があった。However, this method has disadvantages in that large amounts of Lewis acids and organometallic compounds are used, the catalyst efficiency is very poor, molecular weight control is difficult, and equipment is easily corroded.
[課題を解決するための手段]
本発明者らは、上記従来の問題点を解消した極めて効率
の良いエチレン−不飽和カルボン酸共重合体の製造法を
開発すべく鋭意研究を重ねた。その結果、エチレンに直
接不飽和カルボン酸を反応させるのではなく、エチレン
と不飽和カルボン酸エステルとの共重合体をルイス酸の
存在下に熱処理することにより、低温で熱処理が可能と
なり、得られるエチレン−不飽和カルボン酸共重合体の
重合度低下が抑えられ、触媒効率を向上できることを見
い出し、この知見に基いて本発明を完成するに到った。[Means for Solving the Problems] The present inventors have conducted extensive research in order to develop an extremely efficient method for producing an ethylene-unsaturated carboxylic acid copolymer that solves the above-mentioned conventional problems. As a result, instead of reacting ethylene with an unsaturated carboxylic acid directly, by heat treating a copolymer of ethylene and an unsaturated carboxylic ester in the presence of a Lewis acid, heat treatment can be performed at a low temperature, and the resulting product can be obtained. It has been discovered that the decrease in the degree of polymerization of an ethylene-unsaturated carboxylic acid copolymer can be suppressed and the catalyst efficiency can be improved, and the present invention has been completed based on this knowledge.
すなわち、本発明はエチレン−不飽和カルボン酸エステ
ル共重合体をルイス酸の存在下、80〜150℃で熱処
理することを特徴とするエチレン−不飽和カルボン酸共
重合体の製造法を提供するものである。That is, the present invention provides a method for producing an ethylene-unsaturated carboxylic acid copolymer, which comprises heat-treating the ethylene-unsaturated carboxylic acid ester copolymer at 80 to 150°C in the presence of a Lewis acid. It is.
本発明で用いるエチレン−不飽和カルボン酸エステル共
重合体は
式
%式%[11
で表わされる繰返し単位[A]。The ethylene-unsaturated carboxylic acid ester copolymer used in the present invention has a repeating unit [A] represented by the formula % [11].
式
[式中、R1は炭素数1〜2oのアルキル基を示す。]
で表わされる繰返し単位[B]および
式
[式中、R2は水素原子、ハロゲン原子、炭素数1〜2
0のアルキル基、炭素数3〜2oのアルケニル基、炭素
数3〜2oのシクロアルキル基、炭素数6〜20のアリ
ール基または炭素数7〜2oのアラルキル基を示し、R
3は炭素数1〜2oのアルキル基、炭素数3〜2oのア
ルケニル基、炭素数3〜20のシクロアルキル基、炭素
数s〜2oのアリール基または炭素数7〜2oのアラル
キル基を示し、nはO〜20の整数である。コ
で表わされる繰返し単位[cコからなる共重合体を用い
る。Formula [wherein R1 represents an alkyl group having 1 to 2 carbon atoms]. ] and the repeating unit [B] represented by the formula [wherein R2 is a hydrogen atom, a halogen atom, and a carbon number of 1 to 2]
R
3 represents an alkyl group having 1 to 2 carbon atoms, an alkenyl group having 3 to 2 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having s to 2 carbon atoms, or an aralkyl group having 7 to 2 carbon atoms; n is an integer from 0 to 20. A copolymer consisting of repeating units represented by [c] is used.
なお、上記式[11]で表わされる繰返し単位[B]は
、R1の種類により様々であるが、このR′は炭素数1
〜20のアルキル基であり、具体的にはメチル基、エチ
ル基、n−プロピル基、i−プロピル基、n−ブチル基
、i−ブチル基、t−ブチル基、n−ペンチル基、n−
ヘキシル基、2−エチルヘキシル基、n−オクチル基な
どがある。Note that the repeating unit [B] represented by the above formula [11] varies depending on the type of R1, but this R' has 1 carbon number
~20 alkyl groups, specifically methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-
Examples include hexyl group, 2-ethylhexyl group, and n-octyl group.
また、上記式[m ]で表わされる繰返し単位[C]も
R2,R3の種類により様々であるが、具体的にはアク
リル酸単位、アクリル酸メチル単位。Further, the repeating unit [C] represented by the above formula [m] varies depending on the types of R2 and R3, but specifically, it is an acrylic acid unit or a methyl acrylate unit.
アクリル酸エチル単位、アクリル酸−n−プロピル単位
、アクリル酸−1−プロピル単位、アクリル酸−〇−ブ
チル単位、アクリル酸−1−ブチル単位、アクリル酸〜
t−ブチル単位、アクリル酸−n−ヘキシル単位、アク
リル酸−n−オクチル単位、アクリル酸−2−エチルヘ
キシル単位、アクリル酸ベンジル単位、メタクリル酸単
位、メタクリル酸メチル単位、メタクリル酸エチル単位
。Ethyl acrylate unit, n-propyl acrylate unit, 1-propyl acrylate unit, 〇-butyl acrylate unit, 1-butyl acrylate unit, acrylic acid ~
t-butyl unit, n-hexyl acrylate unit, n-octyl acrylate unit, 2-ethylhexyl acrylate unit, benzyl acrylate unit, methacrylic acid unit, methyl methacrylate unit, ethyl methacrylate unit.
メタクリル酸−n−プロピル単位、メタクリル酸−i−
プロピル単位、メタクリル酸−n−ブチル単位、メタク
リル酸−1−ブチル単位、メタクリル酸−七−ブチル単
位、メタクリル酸−2−エチルヘキシル単位、メタクリ
ル酸フェニル単位。methacrylic acid-n-propyl unit, methacrylic acid-i-
Propyl unit, n-butyl methacrylate unit, 1-butyl methacrylate unit, 7-butyl methacrylate unit, 2-ethylhexyl methacrylate unit, phenyl methacrylate unit.
α−タロロアクリル酸メチル単位、α−クロロアクリル
酸エチル単位あるいはα−フェニルアクリル酸メチル単
位などがある。Examples include methyl α-taloloacrylate unit, ethyl α-chloroacrylate unit, and methyl α-phenylacrylate unit.
この共重合体としては特に、繰返し単位[A]。In particular, this copolymer is a repeating unit [A].
[B]、[C]がランダムかつ直鎖状に配列されるとと
もに、上記、繰返し単位[B]の含有割合が0〜45モ
ル%、好ましくは0.1〜30モル%、繰返し単位[C
]の含有割合が0.001〜45モル%。[B] and [C] are arranged randomly and linearly, and the content of the repeating unit [B] is 0 to 45 mol%, preferably 0.1 to 30 mol%, and the repeating unit [C]
] The content ratio is 0.001 to 45 mol%.
好ましくは0.1〜30モル%のものであり、しかも、
その重l平均分子量は20.000以上、好ましくは5
0.000〜4,000,000のものを用いるのがよ
い。Preferably it is 0.1 to 30 mol%, and
Its weight average molecular weight is 20,000 or more, preferably 5
It is preferable to use 0.000 to 4,000,000.
このようなエチレン−不飽和カルボン酸エステル共重合
体は、クロム化合物と有機金属化合物を主成分とする触
媒を用い、ルイス酸の存在下でエヂレンと
式
[式中、R’、 R3,nは前記[1111式で示され
るものと同じ]
で表わされる不飽和カルボン酸エステルとを共重合し、
或いはさらに、必要に応じて
式゛
[式中、R1は前記[II ]式で示されるものと同じ
]
で表わされるα−オレフィンとを共重合して得られるも
のが好適である。Such an ethylene-unsaturated carboxylic acid ester copolymer is produced by using a catalyst mainly composed of a chromium compound and an organometallic compound, and in the presence of a Lewis acid, the ethylene and the formula [wherein R', R3, and n are Copolymerizing with an unsaturated carboxylic acid ester represented by the above [same as that shown by formula 1111],
Alternatively, those obtained by copolymerizing with an α-olefin represented by the formula (wherein R1 is the same as that shown in the formula [II] above), as necessary, are preferable.
ここで用いられる式[IV:]で表わされる不飽和カル
ボン酸エステルの具体例としては、アクリル酸メチル、
アクリル酸エチル、アクリル酸プロピル、アクリル酸ブ
チル、アクリル酸n−オクチル、アクリル酸2−エチル
ヘキシル、アクリル酸ベンジルなどのアクリル酸エステ
ル;メタクリル酸メチル、メタクリル酸エチル、メタク
リル酸ブチル、メタクリル酸2−エチルヘキシル、メタ
クリル酸フェニル、α−り四ロアクリル酸メチル。Specific examples of the unsaturated carboxylic acid ester represented by the formula [IV:] used here include methyl acrylate,
Acrylic acid esters such as ethyl acrylate, propyl acrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate , phenyl methacrylate, methyl alpha-tetraacrylate.
α−クロロアクリル酸エチルなどのα−置換アクリル酸
エステル;3−ブテン酸メチル、3−ブテン酸エチル、
4−ペンテン酸メチル、6−ヘプテン酸エチル、8−ノ
ネン酸メヂル、10−ウンデセン酸メチル、10−ウン
デセン酸プロピル、10−ウンデセン酸ブチル、10−
ウンデセン酸ヘキシル。α-substituted acrylic esters such as α-ethyl chloroacrylate; methyl 3-butenoate, ethyl 3-butenoate,
Methyl 4-pentenoate, ethyl 6-heptenoate, methyl 8-nonenoate, methyl 10-undecenoate, propyl 10-undecenoate, butyl 10-undecenoate, 10-
Hexyl undecenoate.
10−ウンデセン酸オクチル、10−ウンデセン酸デシ
ル、10−ウンデセン酸シクロヘキシル、10−ウンデ
セン酸フェニルなどの末端二重結合を有するカルボン酸
エステル等を挙げることができ、これらを単独であるい
は二種以上を混合して用いることができる。Examples include carboxylic acid esters having a terminal double bond such as octyl 10-undecenoate, decyl 10-undecenoate, cyclohexyl 10-undecenoate, and phenyl 10-undecenoate, and these may be used alone or in combination of two or more. They can be used in combination.
さらに、式[■]で表わされるα−オレフィンとしては
、プロピレン、1−ブテン11−ペンテン、1−ヘキセ
ン、1−オクテン、3−メチルブテン−1,4−メチル
ペンテン−1,1−デセン、ビニルシクロヘキセンなど
が挙げられる。Furthermore, as the α-olefin represented by the formula [■], propylene, 1-butene-11-pentene, 1-hexene, 1-octene, 3-methylbutene-1,4-methylpentene-1,1-decene, vinyl Examples include cyclohexene.
また、この重合の際に触媒の遷穆金属成分どして用いら
れるクロム化合物としては、様々なものがあり、例えば
クロムのカルボン酸塩類、クロムアルコキシ化合物、ク
ロムキレ−I・化合物、クロムπ−錯体、クロムアリー
ル化合物、ハロゲン化クロム、含酸素無機クロム化合物
、有機クロム化合物などが挙げられ、それらを具体的に
示すと次の通りである。In addition, there are various chromium compounds used as transition metal components of the catalyst during this polymerization, such as chromium carboxylates, chromium alkoxy compounds, chromium chelate-I compounds, and chromium π-complexes. , chromaryl compounds, chromium halides, oxygen-containing inorganic chromium compounds, organic chromium compounds, etc., and specific examples thereof are as follows.
まず、クロムのカルボン酸塩類としてはクロムのカルボ
ン酸塩およびクロムのカルボン酸塩の無水カルボン酸あ
るいはエステル、エーテル、ケトン付加物を用いる。First, as the chromium carboxylates, chromium carboxylates and carboxylic acid anhydrides, esters, ethers, and ketone adducts of chromium carboxylates are used.
ここで、クロムのカルホン酸塩どして通常は、一般式〇
r (OCOR’) 3 、 Cr (OCOR4)
3 ・(R”ORr′) 。、Cr(OCOR’)sl
R’coOR8)、Cr(OCOR’)3・R9(GO
ORIO)2、Cr (OCOR’ ) 3・[R”
2 CO] nあるいはCr(OCOR’:13・[(
R”Co)20]n [式中、++ 4〜n + 2
はそれぞれ炭素数1〜20のアルキル基、アルケニル基
、ビニル基、シクロアルキル基、アリール基、ハロアル
キル基、アラルキル基あるいは水素原子を示し、nは1
以上の実数である。]、で表わされる化合物が用いられ
る。具体的にはCr(C+7H35COO)3などの脂
肪族カルボン酸塩、Cr(CaHsCOO)3. Cr
(C)+3・C685COO)3などの芳香族カルボン
酸塩、および上記カルボン酸塩の無水カルボン酸付加物
、エステル付加物、エーテル付加物、ケトン付加物があ
げられる。これら付加物には、無水酢酸、無水プロピオ
ン酸、無水酪酸、無水イソ酪酸、無水吉草酸、無水イソ
吉草酸などの無水脂肪酸;無水安息香酸、無水トルイル
酸、無水桂皮酸、無水フタル酸1無水マレイン酸などの
無水芳香族酸;ギ酸メチル、ギ酸エチル、ギ酸プロピル
、ギ酸ブチル、酢酸メチル、酢酸エチル。Here, chromium carphonate usually has the general formula 〇r (OCOR') 3, Cr (OCOR4)
3 ・(R"ORr')., Cr(OCOR')sl
R'coOR8), Cr(OCOR')3・R9(GO
ORIO)2, Cr(OCOR')3・[R”
2 CO] n or Cr(OCOR':13・[(
R”Co)20]n [wherein, ++ 4 to n + 2
each represents an alkyl group, alkenyl group, vinyl group, cycloalkyl group, aryl group, haloalkyl group, aralkyl group or hydrogen atom having 1 to 20 carbon atoms, and n is 1
These are real numbers. ], is used. Specifically, aliphatic carboxylates such as Cr(C+7H35COO)3, Cr(CaHsCOO)3. Cr
Examples include aromatic carboxylic acid salts such as (C)+3.C685COO)3, and carboxylic anhydride adducts, ester adducts, ether adducts, and ketone adducts of the above carboxylic acid salts. These adducts include fatty acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, and isovaleric anhydride; benzoic anhydride, toluic anhydride, cinnamic anhydride, and phthalic anhydride. Aromatic acid anhydrides such as maleic acid; methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate.
酢酸プロピル、酢酸ブチル、酢酸ヘキシル、酢酸オクチ
ル、酢酸ベンジル、酢酸ビニル、酢酸フェニル、酢酸シ
クロヘキシル、プロピオン酸メチル、プロピオン酸エチ
ル、プロピオン酸プロピル、プロピオン酸ブチル、プロ
ピオン酸オクチル、プロピオン酸フェニル、プロピオン
酸ベンジル、酪酸メチル1酪酸エチル、酪酸プロピル、
酪酸ブチル、酪酸アミル、酪酸オクチル、吉草酸メチル
、吉草酸エチル、吉草酸プロピル、吉草酸ブチル、アク
リル酸メチル、アクリル酸エチル、アクリル酸ブチル、
アクリル酸2エチルヘキシル。Propyl acetate, butyl acetate, hexyl acetate, octyl acetate, benzyl acetate, vinyl acetate, phenyl acetate, cyclohexyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, octyl propionate, phenyl propionate, propionic acid Benzyl, methyl butyrate 1 ethyl butyrate, propyl butyrate,
Butyl butyrate, amyl butyrate, octyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, methyl acrylate, ethyl acrylate, butyl acrylate,
2-ethylhexyl acrylate.
メタクリル酸メチル、メタクリル酸エチル、メタクリル
酸ブチル、クロル酢酸メチル、ジクロロ酢酸エチル、ク
ロトン酸エチル、ピバリン酸エチル、マレイン酸ジメチ
ル、シクロヘキサンカルボン酸エチルなどの脂肪族エス
テル;安息香酸メチル、安息香酸エチル、安息香酸プロ
ピル、安息香酸ブチル、安息香酸オクチル、安息香酸シ
クロヘキシル、安息香酸ベンジル、トルイル酸メチル。Aliphatic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl chloroacetate, ethyl dichloroacetate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate; methyl benzoate, ethyl benzoate, Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzyl benzoate, methyl toluate.
トルイル酸エチル、エチル安息香酸エチル、アニス酸エ
チルなどの芳香族エステル:メチルエーテル、エチルエ
ーテル、イソプロピルエーテル。Aromatic esters such as ethyl toluate, ethyl ethylbenzoate, ethyl anisate: methyl ether, ethyl ether, isopropyl ether.
n−ブチルエーテル、アミルエーテル、テトラヒドロフ
ラン、アニソール、ジフェニルエーテルなどのエーテル
、アセトン、メチルエチルケトン。Ethers such as n-butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, acetone, methyl ethyl ketone.
メチルイソブチルケトン、アセトフェノン、ベンゾフェ
ノン、ベンゾキノンなどのケトンをあげることができる
。Examples include ketones such as methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone.
また、クロムアルコキシ化合物としては一般式%式%[
]
で表わされる化合物が用いられる。この一般式[Vl
]中のR1″は炭素数1〜20のアルキル基1アルケニ
ル基、シクロアルキル基、アリール基あるいはアラルキ
ル基を示す。HI3の具体例としてはメチル基、エチル
基、n−プロピル基、i−プロピル基、n−ブチル基、
i−ブチル基1ヘキシル基、2−エチルヘキシル基、フ
ェニル基などが挙げられる。また×1はハロゲン原子、
つまり塩素。In addition, as a chromium alkoxy compound, the general formula % formula % [
] A compound represented by these is used. This general formula [Vl
], R1'' represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Specific examples of HI3 include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. group, n-butyl group,
Examples include i-butyl group, 1-hexyl group, 2-ethylhexyl group, and phenyl group. Also, ×1 is a halogen atom,
In other words, chlorine.
臭素、沃素などを示す。mは0≦m<4を満たす実数で
ある。Indicates bromine, iodine, etc. m is a real number satisfying 0≦m<4.
上記一般式[Vl ]で表わされる化合物の具体例とし
ては、テトラメトキシクロム、テトラエトキシクロム、
テトラ−n−ブトキシクロム、テトラ−1−ブトキシク
ロム、テトラ−t−ブトキシクロム、テトラヘキシルオ
キシクロム、テトラステアリルオキシクロム、テトラフ
ェノキシクロム。Specific examples of the compound represented by the above general formula [Vl] include tetramethoxychromium, tetraethoxychromium,
Tetra-n-butoxychromium, tetra-1-butoxychromium, tetra-t-butoxychromium, tetrahexyloxychromium, tetrastearyloxychromium, tetraphenoxychromium.
トリエトキシクロムモノクロリト、ジェトキシクロムジ
クロリド、トリーn−ブトキシクロムモノクロリド、ト
リーt−ブトキシクロムモノクロリドなどが挙げられる
。Examples include triethoxychrome monochloride, jetoxychrome dichloride, tri-n-butoxychrome monochloride, tri-t-butoxychrome monochloride, and the like.
さらに、クロムキレート化合物としては、具体的には式
0r(acac)3で表わされるクロムトリスアセチル
アセトナート、 Cr (mbd) 3で表わされるク
ロムトリス(2−メチル−IJ−ブタンジオネート)
、 Cr(b’d)sで表わされるクロムトリス(1,
3−ブタンジオネート)などがあげられる。Furthermore, examples of chromium chelate compounds include chromium trisacetylacetonate represented by the formula 0r(acac)3, and chromium tris(2-methyl-IJ-butanedioate) represented by Cr(mbd)3.
, Cr(b'd)s (1,
3-butanedionate), etc.
ここで(acac)はアセチルアセトナート基を示し、
クロムトリスアセチルアセトナートは、の構造式で表わ
される。また、(mbd) は2−メチル−1,3−ブ
タンジオネート基を示し、クロムトリス(2−メチル−
1,3−ブタンジオネート)はの構造式で表わされる。Here (acac) represents an acetylacetonato group,
Chromium trisacetylacetonate is represented by the structural formula: In addition, (mbd) represents a 2-methyl-1,3-butanedioate group, and chromium tris(2-methyl-
1,3-butanedione) is represented by the structural formula.
さらに(bd)は1□3−ブタンジオネート基を示し、
クロムトリス(1,3−ブタンジオネート)は、
の構造式で表わされる。Furthermore, (bd) represents a 1□3-butanedioate group,
Chromium tris(1,3-butanedioate) is represented by the following structural formula.
クロムπ−錯体としては、(cp>20r ((cp
)はシクロペンタジニニル基を示す)で表わされるビス
シクロペンタジェニルクロム、(Cal[aLCrで表
わされるビスベンゼンクロム、 (2C6)1B>
(Cel+6) Crで表わされるジフェニルベンゼン
クロム、式で表わされるジムキサメチルベンゼンクロム
1式C1]3
C]]3
で表わされるπ−シクロペンタジエニルブロモクロミウ
ムアセチルアセテ−1−、式
で表わされるπ−シクロペンタジェニル(ベンゼン)ク
ロミウム1式
で表わされるπ−シクロペンタジェニル−π−シクロヘ
ブタジエニルクロミウムなどの芳香3]π−錯体、
l−リス(η−アリル)クロム、テトラキス(η−アリ
ル)クロムなどのπ−アリル錯体などがあげられる。As a chromium π-complex, (cp>20r ((cp
) represents a cyclopentazininyl group), bisbenzenechromium represented by (Cal[aLCr, (2C6)1B>
(Cel+6) Diphenylbenzene chromium represented by Cr, Dimxamethylbenzene chromium 1 represented by the formula C1]3 π-Cyclopentadienylbromochromium acetylacetate-1-, represented by the formula Aromatic 3]π-complexes such as π-cyclopentadienyl-π-cyclohebutadienylchromium represented by the formula π-cyclopentadienyl(benzene)chromium,
Examples include π-allyl complexes such as l-lis(η-allyl)chromium and tetrakis(η-allyl)chromium.
さらに、クロムアリール化合物としては、ジフェニルク
ロム、テトラフェニルトリステトラヒドロフランなどが
あげられる。Furthermore, examples of the chromaryl compound include diphenylchromium, tetraphenyltristetrahydrofuran, and the like.
また、ハロゲン化クロムとして好ましいものは一般式〇
rX”n (式中、×2はハロゲン原子を示し、nは
2.3または5を示す。)で表わされるものである。具
体的には三塩化クロム、三臭化クロム、三次化クロム、
二塩化クロム、三臭化クロム、工状化クロム、三弗化ク
ロム等が挙げられる。Preferred chromium halides are those represented by the general formula 〇rX''n (in the formula, x2 represents a halogen atom, and n represents 2.3 or 5). Chromium chloride, chromium tribromide, tertiary chromium,
Examples include chromium dichloride, chromium tribromide, modified chromium, and chromium trifluoride.
次に、含酸素無機クロム化合物としては酸化クロム、ハ
ロゲン含有クロム、クロム無機塩およびそれらの付加体
が用いられる。Next, as the oxygen-containing inorganic chromium compound, chromium oxide, halogen-containing chromium, chromium inorganic salts, and adducts thereof are used.
ここで酸化クロムとしては、例えばCrys。Here, as the chromium oxide, for example, Crys.
Cr2Ch、CrOなどが挙げられ、ハロゲン含有クロ
ムとしてはCr02C1!2 、 Cr (0)1)
CJ2 、 Cr (cpo4) 3などが挙げられる
。また、クロム無機塩としてはCr (NO3) 3.
Cr (PO4) 3.CrK (SO4)2 、Cr
2 (504) J2SO4。Examples include Cr2Ch, CrO, etc., and examples of halogen-containing chromium include Cr02C1!2, Cr(0)1)
Examples include CJ2, Cr(cpo4)3, and the like. Further, as the chromium inorganic salt, Cr (NO3) 3.
Cr (PO4) 3. CrK (SO4)2, Cr
2 (504) J2SO4.
CrNa(So、+)2. C52Cr04. CrL
iO2,CrBaJ。CrNa(So,+)2. C52Cr04. CrL
iO2, CrBaJ.
(Nl14) 2Gro、+ 、(旧+<) 2cr2
(h、 K2CrD、+、に3CrOa。(Nl14) 2Gro, +, (old +<) 2cr2
(h, K2CrD, +, 3CrOa.
Li2CrO4,Na2CrO4,PbCr0.、、
Pb2CrO4,Srl?ro、t。Li2CrO4, Na2CrO4, PbCr0. ,,
Pb2CrO4,Srl? ro,t.
C0Cr2O4,に2cr07. MgCr2O4,
MnCr2O4,++1cr204゜Na2Cr2O7
,2nCr204などを挙げることができる。C0Cr2O4, 2cr07. MgCr2O4,
MnCr2O4, ++1cr204゜Na2Cr2O7
, 2nCr204, etc.
さらに、上記含酸素無機クロム化合物の付加体としては
CrO3ピリジン錯体、 Cr03CJ−C1゜11g
N2錯体。Further, as an adduct of the oxygen-containing inorganic chromium compound, CrO3 pyridine complex, Cr03CJ-C1゜11g
N2 complex.
Cr0CJa・C1oH8N2錯体の他にCrN8(S
O,+)242H20゜Crに(504)2・12)1
20などの水和物などがある。In addition to the Cr0CJa・C1oH8N2 complex, CrN8(S
O, +)242H20°Cr(504)2・12)1
20 and other hydrates.
また、有機クロム化合物としては、一般式Cr LkX
3p−k (HD’) Aで表わされるものと、一般式
CrX’ 1 (ED) ’ Jで表わされるものがあ
る。In addition, as an organic chromium compound, general formula Cr LkX
There are those represented by 3p-k (HD') A and those represented by the general formula CrX' 1 (ED) ' J.
ここで前者は一般式
%式%[]
[式中、LはR”OCO,Co、(3+4またはNRI
4RI8を示しく但しR14,RIBはそねぞれ炭素数
1〜20のアルキル基、アルケニル基、シクロアルキル
基、アリール基またはアラルキル基を示し、同一であっ
ても或いは異なっていてもよい。)、×3はハロゲン原
子または水酸基を示す。また、EDは水、芳香環を有す
る炭化水素またはへテロ原子を有する有機化合物を示す
。さらに2は2.3.4または6を示し、kはO<k≦
pの式を満たす実数であり、では任意の正数を示す。但
し、k、pがともに3であり、かつLがR”OCOであ
る場合、pは1以上の正数を示す。]
で表わされるものである。ここでR14,II3の具体
例としてはメチル基、エチル基、n−プロピル基、i−
プロピル基、n−ブチル基、i−ブチル基、ヘキシル基
、2−エチルヘキシル基、フェニル基などが挙げられる
。Here, the former is the general formula % formula % [] [where L is R''OCO, Co, (3+4 or NRI
4RI8 where R14 and RIB each represent an alkyl group, alkenyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and may be the same or different. ), ×3 represents a halogen atom or a hydroxyl group. Further, ED represents water, a hydrocarbon having an aromatic ring, or an organic compound having a heteroatom. Furthermore, 2 indicates 2.3.4 or 6, and k is O<k≦
It is a real number that satisfies the expression of p, and indicates any positive number. However, when k and p are both 3 and L is R''OCO, p is a positive number of 1 or more.] Here, as a specific example of R14, II3, methyl group, ethyl group, n-propyl group, i-
Examples include propyl group, n-butyl group, i-butyl group, hexyl group, 2-ethylhexyl group, and phenyl group.
また、×3は塩素、臭素、沃素などのハロゲン原子また
は水酸基を示す。Moreover, x3 represents a halogen atom such as chlorine, bromine, or iodine, or a hydroxyl group.
さらに、EDは水、芳香環を有する炭化水素またはへテ
ロ原子を有する有機化合物を示す。芳香環を有する炭化
水素としてはトルエン、0−キシレン、m−キシレン、
p−キシレン、ナフチレン。Furthermore, ED indicates water, a hydrocarbon having an aromatic ring, or an organic compound having a heteroatom. Hydrocarbons having an aromatic ring include toluene, 0-xylene, m-xylene,
p-xylene, naphthylene.
インデン等が挙げられ、また、ペテロ原子を有する有機
化合物としてはエーテル類、エステル類。Examples include indene, and organic compounds having a petro atom include ethers and esters.
ケトン類、アミン類、ホスフィン類、ニトリル類、チオ
ール類、ピリジンなど、クロム化合物と錯体形成能を有
する有機化合物が挙げられる。Examples include organic compounds that have the ability to form a complex with chromium compounds, such as ketones, amines, phosphines, nitriles, thiols, and pyridine.
このような有機クロム化合物としては、例えば一般式[
■]のLがR”OCOの場合として、Cr(CH3f;
00)7/5(OH)2/3. Cr(CH3COO)
2(OH)。As such an organic chromium compound, for example, the general formula [
Cr(CH3f;
00)7/5(OH)2/3. Cr(CH3COO)
2 (OH).
Cr[C)13(CH2)+aCOO]21. Cr[
CH3(CH2:l+acOo]Cf2゜Cr[IBI
H23GOO]2C1l、 Cr(C目N25COO)
CJ2゜Cr(CHsCOO)2c#、 Cr(C2
i4sCOO)2c#。Cr[C)13(CH2)+aCOO]21. Cr[
CH3(CH2:l+acOo]Cf2゜Cr[IBI
H23GOO] 2C1l, Cr (C eye N25COO)
CJ2゜Cr(CHsCOO)2c#, Cr(C2
i4sCOO)2c#.
Cr(CH,、C00)C112,Cr(C21H43
COO)C#2゜Cr [CH3(CH2)14cOo
コ zc4. Cr[CH3(CL)zcOo]C
j!2などの脂肪酸塩およびCr [CI+3 (C1
12) l 6COO] CR2411F 。Cr(CH,,C00)C112,Cr(C21H43
COO) C#2゜Cr [CH3(CH2)14cOo
Ko zc4. Cr[CH3(CL)zcOo]C
j! Fatty acid salts such as 2 and Cr [CI+3 (C1
12) l6COO] CR2411F.
Cr[C1b(C1h)+4Coo]C,l!2・TH
F、 (Hr(c11++23coo)ci2・THF
、Cr(C2,843COO)fJ)2411Fなどの
上記化合物のTIIF (テトラヒドロフラン)付加
体や、鎮状エーテル、エステル、ケトンなどの付加体を
挙げることができる。Cr[C1b(C1h)+4Coo]C,l! 2.TH
F, (Hr(c11++23coo)ci2・THF
, Cr(C2,843COO)fJ)2411F, and other adducts of the above compounds such as TIIF (tetrahydrofuran), diluted ethers, esters, and ketones.
そして、LがR”OCOでp=に=3の場合として、C
r(CH3COO)a・R20,Cr(CH3COO)
3Pph3(但しphはフェニル基を示す。以下同じ)
。Then, as the case where L is R''OCO and p==3, C
r(CH3COO)a・R20,Cr(CH3COO)
3Pph3 (however, ph indicates a phenyl group. The same applies below)
.
Cr(CH3−1:OO)、・N(C113)3などが
挙げられる。Examples include Cr(CH3-1:OO), .N(C113)3, and the like.
また一般式[■]のLがCOの場合として、Cr(Go
)s 、 Cr(CD)sceHa、 Cr(GO)3
(II:H3OC0CaHs)。In addition, when L in the general formula [■] is CO, Cr(Go
)s, Cr(CD)sceHa, Cr(GO)3
(II:H3OC0CaHs).
Cr (Co) 3 (P−CIIaCallsCH3
) 、 Cr (Co) 3[P (Oph) 3]
3 。Cr(Co)3(P-CIIaCallsCH3
), Cr(Co)3[P(Oph)3]
3.
cr(co)5(pph、)、 CrtCo)3(Cs
lls)、 Cr(Go)s[p−c*c、n、cH3
] などを挙げることができる。cr(co)5(pph, ), CrtCo)3(Cs
lls), Cr(Go)s[p-c*c,n,cH3
] and so on.
さらに、一般式[■]のLがII4の場合として、[C
l2C(CHs)a]<、 Cr(CI−12C(CH
3)2phla。Furthermore, as a case where L in the general formula [■] is II4, [C
l2C(CHs)a]<, Cr(CI-12C(CHs)
3) 2phla.
Cr(CHs)4. Cr(CH2Cph3)4. C
r(C2Hs)4゜Cr(CaH7)4.Cr(C)1
2SlllIQ3)4(但しMeはメチル基を示す。以
下同じ)などが挙げられる。Cr(CHs)4. Cr(CH2Cph3)4. C
r(C2Hs)4°Cr(CaH7)4. Cr(C)1
2SllIQ3)4 (where Me represents a methyl group; the same applies hereinafter), and the like.
また、一般式[■]のLがNR14RI5の場合として
Cr (NEt2)4(但しEtはエチル基を示す。以
下同じ) 、 Or (NEt2) 3 、 Or (
NMQBII) 4 (但しBuはn−ブチル基を示
す。以下同じ) 、 Cr (NhleBu) 3゜C
r(NPr2)4(但しPrはn−プロピル基を示す。In addition, when L in the general formula [■] is NR14RI5, Cr (NEt2)4 (however, Et represents an ethyl group. The same applies hereinafter), Or (NEt2) 3, Or (
NMQBII) 4 (However, Bu represents an n-butyl group. The same applies hereinafter), Cr (NhleBu) 3°C
r(NPr2)4 (where Pr represents an n-propyl group.
以下同じ)、Cr(NPr2)3. Cr(NCsH+
o)4. Cr(NC511,、、)3゜Cr[NCH
(Ct13)z14. Cr[NCH(C113)z1
3. Cr(NMe2)、、。Same below), Cr(NPr2)3. Cr(NCsH+
o)4. Cr(NC511,,,)3゜Cr[NCH
(Ct13)z14. Cr[NCH(C113)z1
3. Cr(NMe2),.
Or [N (C[lHl l) 2] 4などが挙げ
られる。Examples include Or [N (C[lHl l) 2] 4 and the like.
これら有機クロム化合物のうちで特に好ましい化合物と
しては、酢酸クロムモノハライドやステアリン酸クロム
モノハライドなどのハロゲン化カルボン酸クロム系の化
合物、ネオペンチルクロムなどのアルキルクロム化合物
、トリス(ジシクロへキシルアミド)クロム[III
]やトリス(シーノルマルプロピルアミド)クロム[I
II ]なとのトリス(ジアルキルアミド)クロム[I
II ]系の化合物およびトリカルボニル(η−p−キ
シレン)クロム(0)などが挙げられる。Among these organic chromium compounds, particularly preferred compounds include chromium halogenated carboxylic acid compounds such as chromium acetate monohalide and chromium stearate monohalide, alkylchromium compounds such as neopentylchromium, and tris(dicyclohexylamide)chromium. [III
] and tris(s-normal propylamide)chromium [I
Tris(dialkylamide)chromium [I
II ] type compounds and tricarbonyl (η-p-xylene) chromium (0).
また、後者は一般式
%式%[]
[式中、×4はハロゲン原子を示し、(ED)’ は少
なくとも1つのへテロ原子を含む有機化合物を示す。ま
た、iは2.3または5であり、jは任意の正数を示す
。コ
で表わされるものである。ここで、×4は前記した如く
塩素、臭素1沃素、弗素などのハロゲン原子を示してい
る。Moreover, the latter has the general formula %[] [wherein x4 represents a halogen atom and (ED)' represents an organic compound containing at least one heteroatom. Further, i is 2.3 or 5, and j represents an arbitrary positive number. This is represented by ko. Here, x4 represents a halogen atom such as chlorine, bromine-iodine, or fluorine, as described above.
また、(ED) ’は少なくとも1つの炭素以外のへテ
ロ原子を含む有機化合物であって、ハロゲン化クロム(
CrX’+)と錯体形成可能な有機化合物である。さら
に、iは2.3または5であり、jは任意の正数を示し
、通常0.1−10、好ましくは2〜4を示している。(ED)' is an organic compound containing at least one heteroatom other than carbon, and chromium halide (
It is an organic compound that can form a complex with CrX'+). Further, i is 2.3 or 5, and j is any positive number, usually 0.1-10, preferably 2-4.
上記一般式[■コ中のハロゲン化クロム(εr″X’l
) としては、例えばCrC413,CrCJ2.
CrBr3゜CrF3. Crh、 CrL+、 Cr
F2. CrBr2. CrF3 などが挙げられ、特
にCrCρ3が好ましい。Chromium halide (εr″X'l) in the above general formula [■
), for example, CrC413, CrCJ2.
CrBr3゜CrF3. Crh, CrL+, Cr
F2. CrBr2. Examples include CrF3, and CrCρ3 is particularly preferred.
一方、このハロゲン化クロムとの錯体形成能を有する有
機化合物である(ED) ’ としては、エーテル、エ
ステル、ケトン、含窒素化合物、酸無水物、イオウ化合
物、ホスフィン、極性ビニル化合物などが挙げられる。On the other hand, organic compounds (ED) that have the ability to form complexes with chromium halides include ethers, esters, ketones, nitrogen-containing compounds, acid anhydrides, sulfur compounds, phosphines, polar vinyl compounds, etc. .
ここで、エーテルとして具体的にはジエチルエーテル、
ジプロピルエーテル、ジイソプロピルエーテル、ジブチ
ルエーテル、ジヘキシルエーテル、アニソール、フエネ
トール、ブチルフェニルエーテル、ペンチルフェニルエ
ーテル、メトキシトルエン、ペンシルエチルエーテル、
ジフェニルエーテル、ジベンジルエーテル、ベラトロー
ル。Specifically, the ether is diethyl ether,
Dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, phenetol, butylphenyl ether, pentylphenyl ether, methoxytoluene, pencil ethyl ether,
Diphenyl ether, dibenzyl ether, veratrol.
1.2−ジメトキシエタン、1,2−ジェトキシエタン
、1.2−ジブトキシエタン、ジエチレングリコールジ
メチルエーテル、アセタールなどの鎖状エーテルや芳香
族エーテル;プロピレンオキサイド、l、2−エポキシ
ブタン、ジオキサン、]・リリヤキサン。ラン、2−メ
チルフラン、テトラヒト口フラン、テトラヒドロビラン
、シネオール、総原子数9〜60個のクラウンエーテル
などの環状エーテルが挙げられる。Chain ethers and aromatic ethers such as 1,2-dimethoxyethane, 1,2-jethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, and acetal; propylene oxide, l,2-epoxybutane, dioxane, and lyryaxane . Examples include cyclic ethers such as ran, 2-methylfuran, tetrahydrofuran, tetrahydrobilane, cineol, and crown ethers having a total number of atoms of 9 to 60.
さらに、エステルとしては、アクリル酸メチル、アクリ
ル酸エチル、アクリル酸−2−エチルヘキシル等のアク
リル酸エステルやメタクリル酸メチル、メタクリル酸ノ
ニル、メタクリル酸トリデシル等のメタクリル酸エステ
ルをはじめ、ステアリン酸エステル、安息香酸エステル
、ケイ皮酸エチル1アビエチン酸エステル、アジピン酸
−ビス(2−エチルヘキシル)、γ−ブチロラクトン、
シュウ酸エステル、マロン酸ジエヂル、マレイン酸エス
テル、酒石酸ジブチル、クエン酸トリブチル、セバシン
酸エステル、フタル酸エステル、エチレングリコールモ
ノアセタート、二酢酸エチレン、エチレングリコールエ
ステル、ジエチレングリコールモノアセタート、トリア
セチン1モノブチリン、炭酸ジエチル、炭酸エチレン、
炭酸プロと1ノン、ホウ酸エステル、リン酸エステル、
ギ酸メチル、ギ酸エチル、ギ酸プロピル、ギ酸ブチル1
ギ酸インブチル、ギ酸ペンチル、酢酸メチル、酢酸エチ
ル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢
酸イソブチル、酢酸5ec−ブチル、酢酸ペンチル、酢
酸インペンチル。Furthermore, esters include acrylic esters such as methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate; methacrylic esters such as methyl methacrylate, nonyl methacrylate, and tridecyl methacrylate; stearic esters; and benzoic esters. acid ester, ethyl cinnamate 1-abietate ester, bis(2-ethylhexyl) adipic acid, γ-butyrolactone,
Oxalate ester, diethyl malonate, maleate ester, dibutyl tartrate, tributyl citrate, sebacate ester, phthalate ester, ethylene glycol monoacetate, ethylene diacetate, ethylene glycol ester, diethylene glycol monoacetate, triacetin monobutyrin, diethyl carbonate, ethylene carbonate,
carbonic acid pro and 1-non, boric acid ester, phosphoric acid ester,
Methyl formate, ethyl formate, propyl formate, butyl formate 1
Inbutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, 5ec-butyl acetate, pentyl acetate, impentyl acetate.
3−メトキシブチルアセタート、酢酸5ec−ヘキシル
、2−エチルブチルアセタート、2−エチルへキシルア
セター]・、酢酸シクロヘキシル、酢酸ベンジル、プロ
ピオン酸メチル、プロピオン酸エチル、プロピオン酸ブ
チル、プロピオン酸イソペンチル、酪酸エステル、イソ
酪酸エステル、イソ吉草酸エステルなどが挙げられる。3-methoxybutyl acetate, 5ec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate], cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate, butyric acid Examples include ester, isobutyric acid ester, isovaleric acid ester, and the like.
また、ケI・ンとしては、アセトン、メチルエチルケト
ン、2−ペンタノン、3−ペンタノン、2−ヘキサノン
、メチルイソブチルケトン、2−ヘプタノン、4−ヘプ
タノン、ジイソブチルケトン、アセトニルアセトン1メ
シチルオキシド、ホロン、イソホロン、シクロヘキサノ
ン、メチルシクロヘキサノン、アセトフェノン、ショウ
ノウなどが挙げられる。In addition, examples of carbon include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetonyl acetone 1 mesityl oxide, holone, Examples include isophorone, cyclohexanone, methylcyclohexanone, acetophenone, and camphor.
さらに、含窒素化合物どしては、アクリルアミド、N−
メチルアクリルアミド、N−イソプロピルアクリルアミ
ド、N−シクロヘキシルアクリルアミド、N−アリルア
クリルアミド、N、N−ジメチルアクリルアミド、 N
、N−ジシクロヘキシルアクリルアミドあるいはこれら
のメタクリル置換体などの(メタ)アクリルアミド:ア
クリロニI・リル、3−アセトキシアクリロニトリル、
2−イソプロピルアクリロニトリルあるいはこれらのメ
タクリル置換体などの(メタ)アクリルニトリル;ビニ
ルベンジルアミン、ビニルシクロヘキシルアミン、 N
、N−ジフェニルビニルアミンなどのビニルアミンやマ
レイミド、N−フェニルマレイミドヲハじめ、2−二I
・ロブロバン、ニトロベンゼン、二りロメタン、ニトロ
エタン、1−二l−ロブロバン、アセ1−二1−リル、
プロピオニトリル、スクシノニトリル、ブチロニトリル
、インブチロニトリル、バレロニトリル、ベンゾニトリ
ル1 α−トルニトリル、メチルアミン、ジメチルアミ
ン。Furthermore, examples of nitrogen-containing compounds include acrylamide, N-
Methylacrylamide, N-isopropylacrylamide, N-cyclohexylacrylamide, N-allylacrylamide, N,N-dimethylacrylamide, N
, (meth)acrylamides such as N-dicyclohexyl acrylamide or methacryl substituted products thereof: acrylonitrile, 3-acetoxyacrylonitrile,
(Meth)acrylonitrile such as 2-isopropylacrylonitrile or methacrylic substituted products thereof; vinylbenzylamine, vinylcyclohexylamine, N
, vinylamines such as N-diphenylvinylamine, maleimide, N-phenylmaleimide, etc., 2-2I
・Lobroban, nitrobenzene, dilomethane, nitroethane, 1-21-lobroban, ace1-21-lyl,
Propionitrile, succinonitrile, butyronitrile, inbutyronitrile, valeronitrile, benzonitrile 1 α-tolnitrile, methylamine, dimethylamine.
トリメチルアミン、エチルアミン、ジエチルアミン、ト
リエチルアミン、プロピルアミン、イソプロピルアミン
、ジプロピルアミン、ジイソプロピルアミン、ブチルア
ミン、イソブチルアミン1sec−ブチルアミン、 t
ert−ブチルアミン、ジブデルアミン、ジイソブチル
アミン、トリブチルアミン、ペンデルアミン、ジベンチ
ルアミン、トリペンチルアミン、2−エチルヘキシルア
ミン、アリルアミン、シクロヘキシルアミン、ジシクロ
ヘキシルアミン、エチレンジアミン、プロピレンジアミ
ン、ジエチレントリアミン、テトラエチレンペンタミン
、ポルムアミド、N−メチルホルムアミド、It、N−
ジメチルホルムアミド、 N、N−ジエチルホルムアミ
ド、アセトアミド、N−メチルアセトアミド、 N、N
−ジメチルアセトアミド、N−メチルプロピオンアミド
、 N、N、N’、N’ −テトラメチル尿素。C−カ
プロラクタム、カルバミド酸エステル、アニリン、N−
メチルアニリン、 N、N −ジメチルアニリン、 N
、N−ジエチルアニリン。Trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, butylamine, isobutylamine 1sec-butylamine, t
ert-butylamine, dibdelamine, diisobutylamine, tributylamine, pendelamine, dibentylamine, tripentylamine, 2-ethylhexylamine, allylamine, cyclohexylamine, dicyclohexylamine, ethylenediamine, propylene diamine, diethylenetriamine, tetraethylenepentamine, porumamide, N-methylformamide, It, N-
Dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N
-dimethylacetamide, N-methylpropionamide, N,N,N',N'-tetramethylurea. C-caprolactam, carbamic acid ester, aniline, N-
Methylaniline, N,N-dimethylaniline, N
, N-diethylaniline.
0−トルイジン、m−トルイジン、p−トルイジン、ピ
ロール、ピペリジン、ピリジン、4−ビニルピリジン、
α−ピコリン、β−ピコリン、γ−ピコリン、2.4−
ルチジン、2.6−ルチジン。0-toluidine, m-toluidine, p-toluidine, pyrrole, piperidine, pyridine, 4-vinylpyridine,
α-picoline, β-picoline, γ-picoline, 2.4-
Lutidine, 2,6-lutidine.
2−ピロリドン、N−メチルピロリドン、キノリン、イ
ンキノリンなどが挙げられる。Examples include 2-pyrrolidone, N-methylpyrrolidone, quinoline, inquinoline, and the like.
また、酸無水物としては無水マレイン酸、無水酢酸、プ
ロピオン酸無水物、酪酸無水物などが挙げられる。Further, examples of the acid anhydride include maleic anhydride, acetic anhydride, propionic anhydride, butyric anhydride, and the like.
さらに、イオウ化合物としては二硫化炭素、硫化ジメチ
ル、硫化ジエヂル、スルホラン、ヂオフェン、テトラヒ
ドロチオフェン、ジメチルスルホキシド、1,3−プロ
パンスルトンなどが挙げられる。Furthermore, examples of the sulfur compound include carbon disulfide, dimethyl sulfide, diethyl sulfide, sulfolane, diophene, tetrahydrothiophene, dimethyl sulfoxide, and 1,3-propane sultone.
また、ボスフィンとしてはメチルホスフィン。Also, methylphosphine is a bosphine.
エチルホスフィン、プロピルホスフィン、イソプロピル
ホスフィン、イソブチルホスフィン、フェニルホスフィ
ンなどの第1ホスフィン;ジメチルホスフィン、ジエチ
ルホスフィン、ジイソプロピルホスフィン、ジイソアミ
ルホスフィン、ジフェニルホスフィンなどの第2ホスフ
インニトリメチルホスフイン、トリエチルホスフィン、
トリフェニルホスフィン、メチルジフェニルホスフィン
。Primary phosphines such as ethylphosphine, propylphosphine, isopropylphosphine, isobutylphosphine, phenylphosphine; secondary phosphines such as dimethylphosphine, diethylphosphine, diisopropylphosphine, diisoamylphosphine, diphenylphosphine; nitrimethylphosphine, triethylphosphine;
Triphenylphosphine, methyldiphenylphosphine.
ジメチルフェニルポスフィンなどの第3ホスフイン等が
挙げられる。Examples include tertiary phosphines such as dimethylphenylphosphine.
さらに、極性ビニル化合物としてはメチルビニルエーテ
ル、エチルビニルエーテル1シクロヘキシルビニルエー
テル、イソプロペニルビニルエーテル、2−プロピニル
ビニルエーテル1ベンジルビニルエーテル、1−クロロ
エチルビニルエーテルなどのビニルエーテル;メチルビ
ニルケトン。Furthermore, as polar vinyl compounds, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether 1-cyclohexyl vinyl ether, isopropenyl vinyl ether, 2-propynyl vinyl ether 1-benzyl vinyl ether, and 1-chloroethyl vinyl ether; methyl vinyl ketone;
エチルビニルケトン、フェニルビニルケトン1メチルイ
ソプロペニルケトン、メチルプロペニルケトン、ジビニ
ルケトンなどのビニルケトンが挙げられる。Examples include vinyl ketones such as ethyl vinyl ketone, phenyl vinyl ketone, 1-methyl isopropenyl ketone, methyl propenyl ketone, and divinyl ketone.
また、この他に2−メトキシエタノール、2−エトキシ
エタノール、2−(メトキシメトキシ)エタノール、2
−インプロポキシエタノール。In addition, 2-methoxyethanol, 2-ethoxyethanol, 2-(methoxymethoxy)ethanol,
- Impropoxyethanol.
2−ブトキシェタノール、2−(イソペンチルオキシ)
エタノール、2−(ヘキシルオキシ)エタノール、2−
フェノキシエタノール、2−(ベンジルオキシ)エタノ
ール、フルフリルアルコール1テトラヒドロフルフリル
アルコール、ジエチレングリコール、ジエチレングリコ
ール千ツメチルエーテル、ジエチレングリコールモノエ
チルエーテル、ジエチレングリコールモノブチルエーテ
ル、トリエチレングリコール、トリエチレングリコール
モノメチルエーテル、テトラエチレングリコール、ポリ
エチレングリコール、1−メトキシ−2−プロパツール
、1−エトキシ−2−プロパツール、ジプロピレングリ
コール、ジプロピレングリコールモノメチルエーテル、
ジプロピレングリコールモノエチルエーテル、トリプロ
ピレングリコールモノメチルエーテル、ポリプロピレン
グリコール、ジアセトンアルコール、2−クロロエタノ
ール、1−クロロ−2−プロパツール13−クロロ−1
,2−プロパンジオール、乳酸エステル、サリチル酸メ
ヂル、2−メトキシエチルアセタート、2−エトキシエ
チルアセタート、2−ブトキシエチルアセタート、2−
フェノキシエチルアセタート、ジエチレングリコールモ
ノエチルエーテルアセタート、ジエチレングリコールモ
ツプチルエーテルアセター1・、アセト酢酸メチル。2-butoxyshetanol, 2-(isopentyloxy)
Ethanol, 2-(hexyloxy)ethanol, 2-
Phenoxyethanol, 2-(benzyloxy)ethanol, furfuryl alcohol 1 tetrahydrofurfuryl alcohol, diethylene glycol, diethylene glycol 1,000 methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, polyethylene Glycol, 1-methoxy-2-propatol, 1-ethoxy-2-propatol, dipropylene glycol, dipropylene glycol monomethyl ether,
Dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, polypropylene glycol, diacetone alcohol, 2-chloroethanol, 1-chloro-2-propatool 13-chloro-1
, 2-propanediol, lactic acid ester, methyl salicylate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-
Phenoxyethyl acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate 1., methyl acetoacetate.
アセト酢酸エチル、シアン酢酸メチル、シアン酢酸エチ
ル、3−ヒドロキシプロビオノニトリル。Ethyl acetoacetate, methyl cyanacetate, ethyl cyanacetate, 3-hydroxyprobiononitrile.
アセトンシアノヒドリン、2−アミノエタノール、2−
(ジエチルアミノ)エタノール、2−(ジエチルアミノ
)エタノール、ジェタノールアミン、N−ブチルジェタ
ノールアミン、トリエタノールアミン、トリイソプロパ
ツールアミン、インプロパツールアミン(混合物) 、
2.2’−チオジェタノール、フルフラール、ビス(
2−クロロエチル)エーテル、エビクロロヒドリン、0
−ニトロンアニソール、モルホリン、N−エチルモルホ
リン、N−フェニルモルホリン、水、アンモニア、液体
二酸化硫黄、ヒドラジン、塩化チオニル、塩化スルフリ
ルなども用いられる。Acetone cyanohydrin, 2-aminoethanol, 2-
(diethylamino)ethanol, 2-(diethylamino)ethanol, jetanolamine, N-butylgetanolamine, triethanolamine, triisopropanolamine, inpropanolamine (mixture),
2.2'-Thiogetanol, furfural, bis(
2-chloroethyl)ether, shrimp chlorohydrin, 0
-Nitrone anisole, morpholine, N-ethylmorpholine, N-phenylmorpholine, water, ammonia, liquid sulfur dioxide, hydrazine, thionyl chloride, sulfuryl chloride, and the like may also be used.
上記の如き一般式[■]で表わされるクロム化合物とし
て具体的には、CrCf12(ピリジン)、。Specifically, the chromium compound represented by the above general formula [■] is CrCf12 (pyridine).
CrBr2 (ピリジン)2. (r12 (ピリジン
)4. CrBr2(ピリジン)!1. Cr12(ピ
リジン)6. CrCR2(アセトニトリル
ルスルホキシド)2. CrBr2(ジメチルスルホキ
シド)3. CrI2 (ジメチルスルホキシドL.
CrCJ2(ヒドラジン)2. 0r12 (ヒドラジ
ン) 2 、 CrCf3(T)IF) s 。CrBr2 (pyridine)2. (r12 (pyridine) 4. CrBr2 (pyridine)! 1. Cr12 (pyridine) 6. CrCR2 (acetonitrile sulfoxide) 2. CrBr2 (dimethyl sulfoxide) 3. CrI2 (dimethyl sulfoxide L.
CrCJ2 (hydrazine)2. 0r12 (hydrazine) 2 , CrCf3(T)IF) s.
CrCffs(Nl13)3, CrCff3(NH3
)s. CrC#3(ピリジン)3。CrCffs(Nl13)3, CrCff3(NH3
) s. CrC#3 (pyridine)3.
CrC#3 (N,N−ジメチルホルムアミド)3.
0rC#3(s−カプロラクタム)3, crcz3(
エチレンジアミン)、。CrC#3 (N,N-dimethylformamide)3.
0rC#3 (s-caprolactam)3, crcz3(
ethylenediamine).
CrC#3 (2 、 2’−ジピリジルCrCff3
(EA) 2 、 Crl,I’s (アセトニド
リル)4 7、CrCff3(アセトン)26などが
挙げられ、これらの中でも特に三塩化クロム/アクリル
酸エチル錯体(CrCff3 (EA:l 3 やCr
C#s (EA) 2 ) 、 Crl3(アセトニ
トリル)4. t. CrCJ3(THF) 3, C
rCJa (アセトン)25などが好ましい。CrC#3 (2, 2'-dipyridyl CrCff3
(EA) 2 , Crl,I's (acetonidrile) 47, CrCff3 (acetone) 26, etc. Among these, chromium trichloride/ethyl acrylate complex (CrCff3 (EA:l 3 and Cr
C#s (EA) 2 ), Crl3 (acetonitrile)4. t. CrCJ3(THF) 3, C
rCJa (acetone) 25 and the like are preferred.
さらに、上記クロム化合物から選ばれる少なくとも1
fffiのクロム化合物を周期律表第1 −Ill族の
有機金属化合物で処.埋をして用いてもよい。Furthermore, at least one selected from the above chromium compounds
The chromium compound of fffi is treated with an organometallic compound of Group Ill of the periodic table. It may also be used buried.
次に、重合の際に触媒の有機金属成分として用いられる
有機金属化合物としては周期律表第1〜V族の有機金属
化合物が挙げられる。Next, examples of the organometallic compound used as an organometallic component of the catalyst during polymerization include organometallic compounds of Groups 1 to V of the periodic table.
このような有機金属化合物としては一般式%式%[]
で表わされる化合物が用いられる。この一般式[]X]
中のR16は炭素数1〜20のアルキル基,アルケニル
基,シクロアルキル基.アリール基あるいはアラルキル
基を示す RI8の具体例としてはメチル基.エチル基
,n−プロピル基,i−プロピル基,n−ブチル基,i
−ブチル基,ヘキシル基,2−エチルヘキシル基,フェ
ニル基などが挙げられる。また、Mはリチウム、す]・
リウム,カリウム、マグネシウム、亜鉛,カドミウム、
アルミニウム、ホウ素.ガリウム、ケイ素,スズ、アン
チモンあるいはビスマスを示す。さらに×5はハロゲン
原子、つまり塩素,臭素.沃素などを示す。gはMの原
子価であり、通常は1〜5の実数である。hはo<h≦
8の実数であって、種々の値を示す。As such an organometallic compound, a compound represented by the general formula % [] is used. This general formula []X]
R16 is an alkyl group, alkenyl group, or cycloalkyl group having 1 to 20 carbon atoms. A specific example of RI8 representing an aryl group or an aralkyl group is a methyl group. Ethyl group, n-propyl group, i-propyl group, n-butyl group, i
Examples include -butyl group, hexyl group, 2-ethylhexyl group, and phenyl group. Also, M is lithium]
lium, potassium, magnesium, zinc, cadmium,
Aluminum, boron. Indicates gallium, silicon, tin, antimony or bismuth. Furthermore, ×5 is a halogen atom, that is, chlorine or bromine. Indicates iodine, etc. g is the valence of M, and is usually a real number from 1 to 5. h is o<h≦
It is a real number of 8 and indicates various values.
上記一般式[IX]で表わされる化合物の具体例として
は、メチルリチウム、エチルリチウム、プロピルリチウ
ム、ブチルリチウム等のアルキルリチウムなど、ジエチ
ルマグネシウム、エチルブチルマグネシウム、ジノルマ
ルブチルマグネシウム、エチルクロロマグネシウムなど
のアルキルマグネシウム、ジメチル亜鉛.ジエチル亜鉛
,ジプロピル亜鉛、ジブチル亜鉛などのジアルキル亜鉛
、トリメチルガリウム、トリエチルガリウム。Specific examples of the compound represented by the above general formula [IX] include alkyllithiums such as methyllithium, ethyllithium, propyllithium, butyllithium, diethylmagnesium, ethylbutylmagnesium, di-n-butylmagnesium, ethylchloromagnesium, etc. Alkylmagnesium, dimethylzinc. Dialkyl zinc such as diethyl zinc, dipropyl zinc, dibutyl zinc, trimethyl gallium, triethyl gallium.
トリプロピルガリウム、トリブチルガリウムなどのアル
キルガリウム化合物、トリエチルホウ素。Alkyl gallium compounds such as tripropyl gallium and tributyl gallium, triethyl boron.
トリプロピルホウ素,]・リブチルホウ素などのアルキ
ルホウ素化合物、テトラエチルスズ、テトラプロピルス
ズ、トリブチルクロロスズ、テトラフェニルスズ、トリ
フェニルクロロスズなどのアルキルスズ化合物等が挙げ
られる。また、Mがアルミニウムである場合の化合物の
例としては様々なものがあり、具体的にはトリメチルア
ルミニウム、 l−リエチルアルミニウム. l−
リイソブロビルアルミニウム. l−リイソブチルア
ルミニウム.トリオクチルアルミニウム等のトリアルキ
ルアルミニウム化合物およびジエチルアルミニウムモノ
クロリド、ジエチルアルミニウムモノプロミド、ジエチ
ルアルミニウムモノアイオダイド、ジイソプロピルアル
ミニウムモノクロリド、ジイソブチルアルミニウムモノ
クロリド、ジオクチルアルミニウムモノクロリド等のジ
アルキルアルミニウムモノハライドあるいはメチルアル
ミニウムセスキクロリド、エチルアルミニウムセスキク
ロリド、エチルアルミニウムセスキプロミド、ブチルア
ルミニウムセスキクロリドなどのアルキルアルミニウム
セスキハライドが好適であり、またこれらの混合物も好
適なものとしてあげられる。さらに、アルキルアルミニ
ウムと水の反応により生成するアルキル基含有アルミノ
キサンも用いることがてきる。Examples thereof include alkylboron compounds such as tripropylboron,].butylboron, and alkyltin compounds such as tetraethyltin, tetrapropyltin, tributylchlorotin, tetraphenyltin, and triphenylchlorotin. In addition, there are various examples of compounds where M is aluminum, specifically trimethylaluminum, l-ethylaluminum. l-
Liisobrovir aluminum. l-lysobutylaluminum. Trialkylaluminum compounds such as trioctylaluminum, and dialkylaluminum monohalides or methylaluminum such as diethylaluminum monochloride, diethylaluminum monopromide, diethylaluminium monoiodide, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride, etc. Alkylaluminum sesquihalides such as sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquipromide, and butylaluminum sesquichloride are preferred, and mixtures thereof are also preferred. Furthermore, alkyl group-containing aluminoxane produced by the reaction of alkyl aluminum and water can also be used.
さらに、上記一般式[IX]で表わされる化合物の具体
例としては、トリフェニルビスマス、トリエチルビスマ
ス、トリメチルビスマス、トリイソブチルビスマスなど
のビスマス化合物が挙げられる。Furthermore, specific examples of the compound represented by the above general formula [IX] include bismuth compounds such as triphenylbismuth, triethylbismuth, trimethylbismuth, and triisobutylbismuth.
これらの中でも特にアルミニウム化合物が好適に用いら
れる。Among these, aluminum compounds are particularly preferably used.
ここで、上記クロム化合物と、有機金属化合物の使用比
率は特に制限はないが、通常は、前者中のクロム原子の
モル数を(a)、後者中の金属原子のモル数を(b)と
したとき、(b)/ (a)の値を0.1〜5000、
好ましくは1〜1000の割合とすれはよい。Here, the ratio of the chromium compound and the organometallic compound used is not particularly limited, but usually the number of moles of chromium atoms in the former is expressed as (a), and the number of moles of metal atoms in the latter is expressed as (b). Then, the value of (b)/(a) is 0.1 to 5000,
Preferably, the ratio is between 1 and 1000.
また、ルイス酸としては極性基の孤立電子対と錯体形成
可能なルイス酸化合物、例えば周期律表第■〜■族ある
いは■族のハロゲン化化合物が挙げられる。特にアルミ
ニウム、ポウ素、亜鉛、スズ、マグネシウム、アンチモ
ンなどのハロゲン化化合物、例えば塩化アルミニウム、
臭化アルミニウム、エチルアルミニウムジクロリド、ジ
エチルアルミニウムモノクロリド、三塩化ホウ素、塩化
亜鉛、四塩化スズ、アルキルスズハライド、塩化マグネ
シウム、五塩化アンチモン、三塩化アンチモンなどが好
ましいが、特に好ましくは塩化アルミニラム、臭化アル
ミニウム、エチルアルミニウムジクロリドなどである。Further, examples of the Lewis acid include Lewis acid compounds capable of forming a complex with a lone pair of electrons of a polar group, such as halogenated compounds of Groups (1) to (2) or (2) of the periodic table. In particular, halogenated compounds such as aluminum, boron, zinc, tin, magnesium, antimony, such as aluminum chloride,
Preferred are aluminum bromide, ethylaluminum dichloride, diethylaluminum monochloride, boron trichloride, zinc chloride, tin tetrachloride, alkyltin halide, magnesium chloride, antimony pentachloride, antimony trichloride, and particularly preferred are aluminum chloride, aluminum chloride, ethylaluminum dichloride, etc.
本発明に用いるエチレン−不飽和カルボン酸エステル共
重合体を製造するに際し、原料である不飽和カルボン酸
エステルのエチレンに対する使用割合は、目的とする共
重合体に要求される物性に応じて任意に選定すればよい
が、通常01〜45モル%の範囲で使用される。When producing the ethylene-unsaturated carboxylic acid ester copolymer used in the present invention, the ratio of the raw material unsaturated carboxylic ester to ethylene can be arbitrarily determined depending on the physical properties required of the desired copolymer. Although it may be selected, it is usually used in a range of 01 to 45 mol%.
また、前述のルイス酸と不飽和カルボン酸エステルの使
用割合は、不飽和カルボン酸エステル1に対して、ルイ
ス酸0.05〜2(モル比)、好ましくは0.2〜1
(モル比)である。Further, the ratio of the Lewis acid and the unsaturated carboxylic acid ester mentioned above is 0.05 to 2 (molar ratio), preferably 0.2 to 1 Lewis acid per 1 of the unsaturated carboxylic ester.
(molar ratio).
重合の形式は特に制限はなく、スラリー重合。There are no particular restrictions on the type of polymerization, and slurry polymerization is used.
溶液重合、気相重合等のいずれも可能であり、また連続
重合、非連続重合のいずれも可能である。Either solution polymerization, gas phase polymerization, etc. are possible, and both continuous polymerization and discontinuous polymerization are possible.
この場合、重合溶媒としては脂肪族炭化水素、脂環族炭
化水素、芳香族炭化水素、ハロゲン化炭化水素、ハロゲ
ン化炭素が用いられる。具体的にはペンタン、ヘキサン
、ヘプタン、オクタン、デカン、ドデカン、シクロヘキ
サン、ベンゼン、トルエン、キシレン、エチルベンゼン
、クロルベンゼン、二塩化エチレン、テトラクロルエチ
レン。In this case, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, and halogenated carbons are used as the polymerization solvent. Specifically, pentane, hexane, heptane, octane, decane, dodecane, cyclohexane, benzene, toluene, xylene, ethylbenzene, chlorobenzene, ethylene dichloride, and tetrachloroethylene.
灯油などが用いられる。重合条件としては反応圧力は常
圧〜200 kg/cm2G、好ましくは常圧〜100
kg/cm’Gであり、反応温度は一80〜70℃、
好ましくは一50〜60℃である。なお、反応時間は任
意であるが、通常1分間〜10時間の間で適宜選定すれ
ばよい。Kerosene etc. are used. As for the polymerization conditions, the reaction pressure is normal pressure to 200 kg/cm2G, preferably normal pressure to 100 kg/cm2G.
kg/cm'G, the reaction temperature is -80~70℃,
Preferably it is -50 to 60°C. Incidentally, the reaction time is arbitrary, but may be appropriately selected usually between 1 minute and 10 hours.
このようにして、エチレン−不飽和カルボン酸エステル
共重合体を得ることができる。In this way, an ethylene-unsaturated carboxylic acid ester copolymer can be obtained.
本発明においては、例えば上記のようにして得られたエ
チレン−不飽和カルボン酸エステル共重合体をルイス酸
と接触させ、熱処理を行なって、エチレン−不飽和カル
ボン酸共重合体を製造する。In the present invention, for example, the ethylene-unsaturated carboxylic acid ester copolymer obtained as described above is brought into contact with a Lewis acid and subjected to heat treatment to produce an ethylene-unsaturated carboxylic acid copolymer.
本発明はルイス酸の存在下に低温で熱処理を行なう点に
特色を有する。The present invention is characterized in that heat treatment is carried out at low temperature in the presence of a Lewis acid.
したがって、本発明においては上記の如く、既に製造さ
れたエチレン−不飽和カルボン酸エステル共重合体を用
いる場合たけでなく、ルイス酸を用いたエヂlノンー不
飽和カルボン酸エステル共重合体の製造と熱処理とを組
合わせた方法どすることもできる。Therefore, in the present invention, as mentioned above, not only the case where already produced ethylene-unsaturated carboxylic acid ester copolymer is used, but also the production of ethylene non-unsaturated carboxylic acid ester copolymer using Lewis acid. It is also possible to use a method in combination with heat treatment.
すなわち、前記の如きクロム化合物と有機金属化合物を
主成分とする触媒を用い、ルイス酸の存在下にエチレン
と不飽和カルボン酸エステルを共重合してエチレン一不
飽和カルボン酸エステル共重合体を得、次いで80〜1
50℃で熱処理してもよい。That is, an ethylene monounsaturated carboxylic ester copolymer is obtained by copolymerizing ethylene and an unsaturated carboxylic ester in the presence of a Lewis acid using a catalyst mainly composed of a chromium compound and an organometallic compound as described above. , then 80-1
Heat treatment may be performed at 50°C.
したがって、本発明におけるエチレン−不飽和カルボン
酸エステル共重合体とルイス酸の接触熱処理方法には以
下の如き態様が考えられる。Therefore, the following embodiments can be considered for the method of contact heat treatment of an ethylene-unsaturated carboxylic acid ester copolymer and a Lewis acid in the present invention.
まず第1に、エチレン−不飽和カルボン酸エステル共重
合体とルイス酸にさらに、トルエン、キシレンなどの溶
媒を加え、このルイス酸を含む共重合体を熱処理する方
法がある。これはスラリー状態で熱処理する方法である
。First, there is a method in which a solvent such as toluene or xylene is further added to an ethylene-unsaturated carboxylic acid ester copolymer and a Lewis acid, and the copolymer containing this Lewis acid is heat-treated. This is a method of heat treatment in a slurry state.
次に第2に、不活性7囲気下で反応容器あるいは押出機
にエチレン−不飽和カルボン酸エステルとルイス酸を加
えて直接熱処理する方法がある。Second, there is a method in which an ethylene-unsaturated carboxylic acid ester and a Lewis acid are added to a reaction vessel or an extruder under an inert atmosphere and the mixture is directly heat-treated.
さらに第3に、上記した如くクロム化合物と有機金属化
合物を主成分とする触媒を用い、ルイス酸の存在下にエ
チレンと不飽和カルボン酸エステルを共重合してエチレ
ン−不飽和カルボン酸エステル共重合体を得、エチレン
を脱圧し、アルゴンなどの不活性ガスで系内をパージし
て共重合反応を停止させた後、引き続いて80〜150
℃で熱処理を行なう方法がある。Thirdly, as mentioned above, ethylene and unsaturated carboxylic ester are copolymerized in the presence of a Lewis acid using a catalyst containing a chromium compound and an organometallic compound as main components. After the copolymerization was obtained, the ethylene was depressurized, and the system was purged with an inert gas such as argon to stop the copolymerization reaction.
There is a method of heat treatment at ℃.
上記第3の方法によねば、ルイス酸を有効に利用するこ
とができ、ルイス酸使用量を低減することができるため
触媒効率を向上させることができる。According to the third method, the Lewis acid can be used effectively and the amount of Lewis acid used can be reduced, so that the catalyst efficiency can be improved.
ここでルイス酸としては極性基の孤立電子対と錯体形成
可能なルイス酸化合物、例えば周期律表第1〜■族ある
いは■族のハロゲン化化合物が挙げられる。特にアルミ
ニウム、ホウ素、亜鉛、スズ、マグネシウム、アンチモ
ンなどのハロゲン化化合物、例えば塩化アルミニウム、
臭化アルミニウム、エチルアルミニウムジクロリド、ジ
エチルアルミニウムモノクロリド、三塩化ホウ素、塩化
亜鉛、四塩化スズ、アルキルスズハライF 、塩化マグ
ネシウム、五塩化アンチモン、三塩化アンチモンなどが
好ましいが、特に好ましくは塩化アルミニウム、臭化ア
ルミニウム2エチルアルミニウムジクロリドなどである
。Examples of the Lewis acid include Lewis acid compounds capable of forming a complex with a lone pair of electrons of a polar group, such as halogenated compounds of Groups 1 to 1 or Group 2 of the periodic table. Especially halogenated compounds such as aluminum, boron, zinc, tin, magnesium, antimony, e.g. aluminum chloride,
Aluminum bromide, ethylaluminum dichloride, diethylaluminium monochloride, boron trichloride, zinc chloride, tin tetrachloride, alkyltin halide F2, magnesium chloride, antimony pentachloride, antimony trichloride, etc. are preferred, but aluminum chloride, These include aluminum bromide, 2-ethylaluminum dichloride, and the like.
またルイス酸の使用量は、不飽和カルボン酸エステル単
位1モルに対し、0.05〜3モル、好ましくは0.2
〜1.5モル存在させる。ルイス酸の使用量が0.05
モル未満であると、カルボン酸の生成割合が低下する。The amount of Lewis acid used is 0.05 to 3 mol, preferably 0.2 mol, per 1 mol of unsaturated carboxylic acid ester unit.
~1.5 mol is present. The amount of Lewis acid used is 0.05
When the amount is less than mol, the production rate of carboxylic acid decreases.
一方、ルイス酸の使用量が3モルを超えると、ポリマー
の脱灰精製に大量の用役を必要とし、また低分子量化す
るため好ましくない。On the other hand, when the amount of Lewis acid used exceeds 3 moles, a large amount of use is required for demineralization and purification of the polymer, and the molecular weight becomes low, which is not preferable.
なお、熱処理条件は圧力は特に制限はなく、常圧でよい
が、温度は80〜150℃、好ましくは90〜140℃
で行なうことが必要である。熱処理温度が80℃未満で
あると反応が不十分であり、150℃を超えると、得ら
れる共重合体が低分子量化し、好ましくない。また、熱
処理時間は5分〜10時間。Note that the heat treatment conditions are not particularly limited in pressure and may be normal pressure, but the temperature is 80 to 150°C, preferably 90 to 140°C.
It is necessary to do so. If the heat treatment temperature is less than 80°C, the reaction will be insufficient, and if it exceeds 150°C, the resulting copolymer will have a low molecular weight, which is not preferred. Moreover, the heat treatment time is 5 minutes to 10 hours.
好ましくは10分〜5時間の間で適当な時間を選択すれ
ばよい。Preferably, an appropriate time may be selected between 10 minutes and 5 hours.
このようにして、本発明の目的とするエチレン−不飽和
カルボン酸共重合体が得られるが、この共重合体は次の
ような繰返し単位[A、]〜[D]
→C112−CIf□→−川[A]
F式中、Rl、、、 R3およびnは前記式[I]〜[
Ill mで示したものと同様である。]からなるもの
で繰返し単位[B]は共重合体全体の0〜45モル%、
繰返し単位[C] + [D]は0001〜45モル%
であり、
好ましくは0.4〜1である。In this way, an ethylene-unsaturated carboxylic acid copolymer, which is the object of the present invention, is obtained, and this copolymer has the following repeating units [A,] to [D] →C112-CIf□→ - River [A]
It is similar to that shown in Ill m. ], and the repeating unit [B] is 0 to 45 mol% of the entire copolymer,
Repeating unit [C] + [D] is 0001 to 45 mol%
and preferably 0.4 to 1.
また、得られる共重合体の分子量は2万以上、好ましく
は5万〜400万であり、原料に直鎖状ランダム構造の
エチレン−不飽和カルボン酸エステル共重合体を用いる
と同構造のエチレン−不飽和カルボン酸共重合体が得ら
れる。In addition, the molecular weight of the obtained copolymer is 20,000 or more, preferably 50,000 to 4,000,000, and when an ethylene-unsaturated carboxylic acid ester copolymer with a linear random structure is used as a raw material, an ethylene-unsaturated carboxylic acid ester copolymer with the same structure is used. An unsaturated carboxylic acid copolymer is obtained.
[実施例] 次に、本発明を実施例によりさらに詳しく説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
実施例1
(1)触媒成分[酢酸クロム(In)−トリエチルアル
ミニウム還元]の調製
市販の酢酸クロム(Ill )を120℃で減圧乾燥し
、吸着水を取り除いた。減圧乾燥後ボールミル粉砕を行
ないトノヒエンスラリーとした後、トリエチルアルミニ
ウム(クロム1 mobに対してトリエチルアルミニウ
ム0.33moρ)加えて触媒成分に用いた。スラリー
濃度はクロムとして0.40moR/fであった。Example 1 (1) Preparation of catalyst component [chromium (In) acetate-triethylaluminum reduction] Commercially available chromium acetate (Ill) was dried under reduced pressure at 120°C to remove adsorbed water. After drying under reduced pressure, the slurry was ground in a ball mill to obtain a tonohien slurry, and triethylaluminum (0.33 moρ of triethylaluminum per mob of chromium) was added thereto and used as a catalyst component. The slurry concentration was 0.40 moR/f as chromium.
(2)エチレン−アクリル酸2−エチルヘキシル共重合
体の製造
室温に保った1ftオートクレーブにアルゴン雰囲気下
でトルエン4QOmi+を入れ、オートクレーブ内を専
用の攪拌器を用いて20Orpmで攪拌した。次にアク
リル酸2−エチルヘキシル(EHA)とルイス酸として
三塩化アルミニウムをそれぞれ60ミリモル入れ、これ
にジエチルアルミニウムモノクロリド(DEAC)10
ミリモルを入れ、さらに上記(1)で調製したクロム触
媒成分をクロムとして0.6ミリモル入れた。(2) Production of ethylene-2-ethylhexyl acrylate copolymer Toluene 4QOmi+ was placed in a 1 ft autoclave kept at room temperature under an argon atmosphere, and the inside of the autoclave was stirred at 20 rpm using a special stirrer. Next, add 60 mmol each of 2-ethylhexyl acrylate (EHA) and aluminum trichloride as a Lewis acid, and add 10 mmol of diethylaluminum monochloride (DEAC).
In addition, 0.6 mmol of the chromium catalyst component prepared in (1) above was added as chromium.
次いで、アルゴンを止め、攪拌を500rpmとしたの
ち、重合温度50℃まで昇温し、オートクレーブ内の温
度が50℃に達したらエチレンを導入し、圧力を9.5
kg/cm2Gに保持して120分重合反応を行なっ
た。その後、未反応のエチレンを系外に脱圧し、系内を
アルゴンで充分置換して共重合反応を停止し、共重合体
を得た。Next, after stopping the argon gas and setting the stirring to 500 rpm, the temperature was raised to the polymerization temperature of 50°C. When the temperature inside the autoclave reached 50°C, ethylene was introduced and the pressure was increased to 9.5°C.
The polymerization reaction was carried out for 120 minutes while maintaining the pressure at kg/cm2G. Thereafter, unreacted ethylene was depressurized outside the system, and the inside of the system was sufficiently replaced with argon to stop the copolymerization reaction, thereby obtaining a copolymer.
(3)エチレン−アクリル酸共重合体の製造上記(2)
の操作に引続き、オートクレーブ内の温度を90℃に保
ち、1.5時間熱処理を行ない、室温まで降温した。生
成物をメタノール中に注入して沈殿させた固形分を、炉
別回収して塩酸−メタノール混合液で脱灰処理し、メタ
ノールで洗浄した。このようにして得た生成物を80℃
で2時間減圧乾燥し、白色の共重合体を得た。(3) Production of ethylene-acrylic acid copolymer (2) above
Following this operation, the temperature inside the autoclave was maintained at 90°C, heat treatment was performed for 1.5 hours, and the temperature was lowered to room temperature. The solid content precipitated by pouring the product into methanol was collected in a furnace, deashed with a hydrochloric acid-methanol mixture, and washed with methanol. The product thus obtained was heated at 80°C.
The mixture was dried under reduced pressure for 2 hours to obtain a white copolymer.
この共重合体を’ H−NMR分析により含有量を算出
したところ、アクリル酸含量5.9モル%、アクリル酸
2−エチルヘキシル含量0.3モル%であフた。また、
ゲルパーミェーションクロマトグラフィー(GPC)分
析より分子量(重量平均分子量)は65,000であっ
た。結果を第1表に示す。なお、GPCは溶媒としてト
リクロルベンゼンを用い、135℃で行なった。以下の
実施例、比較例においても同様である。When the content of this copolymer was calculated by 'H-NMR analysis, the acrylic acid content was 5.9 mol%, and the 2-ethylhexyl acrylate content was 0.3 mol%. Also,
Gel permeation chromatography (GPC) analysis revealed that the molecular weight (weight average molecular weight) was 65,000. The results are shown in Table 1. Note that GPC was performed at 135° C. using trichlorobenzene as a solvent. The same applies to the following Examples and Comparative Examples.
実施例2
実施例1において、実施例1の(3)の熱処理時間を4
.5時間に代えたこと以外は、実施例1と同様に行なっ
た。結果を第1表に示す。Example 2 In Example 1, the heat treatment time in (3) of Example 1 was increased to 4
.. The same procedure as in Example 1 was carried out except that the time was changed to 5 hours. The results are shown in Table 1.
比較例1
実施例1(2)で得られる共重合体を、一部取り出し、
熱処理を行なわずにメタノール中に注入して沈殿させた
固形分を炉別回収し、塩酸−メタノール混合液で脱灰処
理しメタノールで洗浄した。このようにして得た生成物
を80℃で2時間減圧乾燥し、白色の共重合体を得た。Comparative Example 1 A part of the copolymer obtained in Example 1 (2) was taken out,
The solids precipitated by pouring into methanol without heat treatment were recovered by furnace, deashed with a hydrochloric acid-methanol mixture, and washed with methanol. The product thus obtained was dried under reduced pressure at 80° C. for 2 hours to obtain a white copolymer.
この共重合体を’H−NMR分析により含有量を算出し
たところ、アクリル酸含量0.0モル%、アクリル酸2
−エチルヘキシル含量6.3モル%であフた。またGP
C分析により重量平均分子量は64,500であった。When the content of this copolymer was calculated by 'H-NMR analysis, the acrylic acid content was 0.0 mol%, and the acrylic acid content was 0.0 mol%.
-Ethylhexyl content was 6.3 mol%. Also GP
According to C analysis, the weight average molecular weight was 64,500.
結果を第1表に示す。The results are shown in Table 1.
比較例2
実施例1(2)で得られる共重合体を一部取り出し、メ
タノール中に注入して沈殿させた固形分を炉別回収し、
塩酸−メタノール混合液で脱灰処理しメタノールで洗浄
した。このようにして得た生成物を80℃で2時間減圧
乾燥し、メタノールを除去した。乾燥した生成物を、ト
ルエン400m1+を入れたオートクレーブ内に入れ、
オートクレーブ内を専用の攪拌器を用いて300rpm
で攪拌した。吹いで昇温しオー]・り1ノ−ブ内の温度
を90℃に保ち1.5時間熱処理を行ない、室温まで降
温した。生成物を取り出しメタノール中に注入して沈殿
させ、固形分をン戸別回収して80℃において2時間減
圧乾燥を行なった。得られた生成物を’)l−NMR分
析により含有量を算出したところ、アクリル酸含量0.
0モル%、アクリル酸2−エチルヘキシル含量6゜2モ
ル%であった。また、GPC分析により型出平均分子量
は64 、[10(lであった。結果を′kiJ1表に
示す。Comparative Example 2 A part of the copolymer obtained in Example 1 (2) was taken out, poured into methanol, and the precipitated solid content was recovered by furnace.
It was deashed with a hydrochloric acid-methanol mixture and washed with methanol. The product thus obtained was dried under reduced pressure at 80° C. for 2 hours to remove methanol. The dried product was placed in an autoclave containing 400 ml of toluene,
Inside the autoclave, use a special stirrer at 300 rpm.
It was stirred with Heat treatment was performed for 1.5 hours while the temperature inside the oven was maintained at 90° C., and the temperature was then lowered to room temperature. The product was taken out and poured into methanol to precipitate it, and the solid content was collected separately and dried under reduced pressure at 80° C. for 2 hours. When the content of the obtained product was calculated by ')l-NMR analysis, the acrylic acid content was 0.
The content of 2-ethylhexyl acrylate was 6.2 mol%. Furthermore, the average molecular weight of the molded product was found to be 64 and 10 (l) by GPC analysis. The results are shown in Table 'kiJ1.
実施例3
実施例1において、アクリル酸2−エチルヘキシルに代
えてアクリル酸イソブチル(i−BA)を用いたこと以
外は、実施例1と同様に行なった。結果を第1表に示す
。Example 3 The same procedure as in Example 1 was conducted except that isobutyl acrylate (i-BA) was used in place of 2-ethylhexyl acrylate. The results are shown in Table 1.
比較例3,4
実施例3(2)で得られる共重合体を、それぞれ比較例
1,2と同様に処理した。結果を第1表に示す。Comparative Examples 3 and 4 The copolymers obtained in Example 3 (2) were treated in the same manner as in Comparative Examples 1 and 2, respectively. The results are shown in Table 1.
実施例4
実施例1において、アクリル酸2−エチルヘキシルに代
えてアクリル酸エチル(EA)を用いたこと以外は、実
施例1と同様に行なった。結果を第1表に示す。Example 4 The same procedure as in Example 1 was conducted except that ethyl acrylate (EA) was used in place of 2-ethylhexyl acrylate. The results are shown in Table 1.
比較例5.6
実施例4(2)で得られる共重合体を、それぞれ比較例
1.2と同様に処理した。結果を第1表に示す。Comparative Example 5.6 The copolymers obtained in Example 4(2) were each treated in the same manner as in Comparative Example 1.2. The results are shown in Table 1.
比較例7
実施例4において、重合温度を70℃に代えたことおよ
び熱処理を行なわなかったこと以外は、実施例4と同様
に行なった。結果を第1表に示す。Comparative Example 7 The same procedure as in Example 4 was conducted except that the polymerization temperature was changed to 70° C. and no heat treatment was performed. The results are shown in Table 1.
比較例8
実施例4において、熱処理温度を20Q℃に代えたこと
以外は、実施例4と同様に行なった。結果を第1表に示
す。Comparative Example 8 The same procedure as in Example 4 was carried out except that the heat treatment temperature was changed to 20Q°C. The results are shown in Table 1.
比較例9
実施例4において、熱処理温度を70℃に代えたこと以
外は、実施例4と同様に行なった。結果を第1表に示す
。Comparative Example 9 The same procedure as in Example 4 was carried out except that the heat treatment temperature was changed to 70°C. The results are shown in Table 1.
実施例5
(1)触媒成分(ステアリン酸クロム)の調製ステアリ
ン酸クロムをボールミル粉砕した後、トルエンスラリー
として触媒成分として用いた。Example 5 (1) Preparation of catalyst component (chromium stearate) Chromium stearate was ground in a ball mill, and then used as a toluene slurry as a catalyst component.
スラリー濃度は0.40moI!/ρ (クロム単位)
であった。Slurry concentration is 0.40 moI! /ρ (chromium unit)
Met.
(2)エチレン−アクリル酸工+tル共重合体の製造
室温に保った4、5 、Qオートクレーブにアルゴンτ
囲気下でトルエン3j2を入れ、オートクレーブ内を専
用の攪拌器を用いて200rpmで攪拌した。次にアク
リル酸エチル(EA)と、ルイス酸として三塩化アルミ
ニウムをそれぞれ100ミリモル人ね、これにジエヂル
アルミニウムモノクロリド(DEAC)8ミリモルを人
ね、さらに上記(1)で調製したクロム触媒成分をクロ
ムとして0.8ミリモル入れた。(2) Production of ethylene-acrylic acid copolymer
Toluene 3j2 was added under ambient atmosphere, and the inside of the autoclave was stirred at 200 rpm using a special stirrer. Next, add 100 mmol each of ethyl acrylate (EA) and aluminum trichloride as a Lewis acid, add 8 mmol of diethyl aluminum monochloride (DEAC), and add the chromium catalyst component prepared in (1) above. 0.8 mmol of chromium was added.
次いで、アルゴンを止め、攪拌を50Orpmとしたの
ち、重合温度30℃まで昇温し、オートクレーブ内の温
度が30℃に達したらエチレンを導入し、圧力を9.S
J/am” Gに保持して180分重合反応を行なっ
た。その後、未反応のエチレンを系外に脱圧し、系内を
アルゴンで充分置換して共重合反応を停止し、共重合体
を得た。Next, the argon supply was stopped, the stirring was set to 50 rpm, and the temperature was raised to the polymerization temperature of 30°C. When the temperature inside the autoclave reached 30°C, ethylene was introduced and the pressure was increased to 9.5°C. S
The polymerization reaction was carried out for 180 minutes while maintaining the temperature at J/am” Obtained.
(3)エチレン−アクリル酸共重合体の製造実施例1(
3)と同様に行なった。結果を第1表に示す。(3) Production Example 1 of ethylene-acrylic acid copolymer (
The same procedure as 3) was carried out. The results are shown in Table 1.
比較例1O
実施例5(2)で得られる共重合体を、比較例1と同様
に処、理した。結果を第1表に示す。Comparative Example 1O The copolymer obtained in Example 5(2) was treated in the same manner as in Comparative Example 1. The results are shown in Table 1.
比較例11
室温に保った4、5 j2オーI・クレープに、アルゴ
ン7囲気下で]・ルエンスラリーにした塩化アルミニウ
ム150ミリモルを入れた後、トルエンを入れトルエン
全量が30DOml’となるように調製した後、オート
ウ1ノーブ内を専用の攪拌器を用いて20Orpmで攪
拌した。次にアクリル酸(AA)100 ミリモルを入
れてアルゴンを止めて3分間熟成した。次にオー1−ク
レープ内を再度アルゴンで置換した後アルゴン雰囲気下
でジエチルアルミニウムクロライド8ミリモル、実施例
5の(1)で得られたクロム触媒成分をクロムとして0
.8ミリモル入れた。Comparative Example 11 150 mmol of aluminum chloride made into a luene slurry was added to a 4,5 j2 O I crepe kept at room temperature under an atmosphere of 7 argon, and then toluene was added so that the total amount of toluene was 30 DOml'. After that, the inside of the Autoto 1 knob was stirred at 20 rpm using a special stirrer. Next, 100 mmol of acrylic acid (AA) was added, the argon supply was stopped, and the mixture was aged for 3 minutes. Next, after purging the inside of the O-1-crepe with argon again, 8 mmol of diethylaluminium chloride was added in an argon atmosphere, and the chromium catalyst component obtained in (1) of Example 5 was added to 0 as chromium.
.. 8 mmol was added.
次いでアルゴンを止め、攪拌を500rpmとしたのち
、重合温度30℃まで昇温し、オートクレーブ内の温度
が50℃に達したらエチレンを導入し、圧力を9.5
kg/cm2Gに保持して180分重合反応を行なった
。その後、室温まで降温し、未反応のエチレンを脱圧し
た。生成物をメタノール中に注入して沈殿させた固体共
重合体を、ン戸別回収して塩酸−メタノール混合液で脱
灰処理し、メタノールで洗浄した。この生成物を80℃
で2時間減圧乾燥し、白色の共重合体を得た。Next, the argon was stopped, the stirring was set to 500 rpm, and the temperature was raised to the polymerization temperature of 30°C. When the temperature inside the autoclave reached 50°C, ethylene was introduced and the pressure was increased to 9.5°C.
The polymerization reaction was carried out for 180 minutes while maintaining the pressure at kg/cm2G. Thereafter, the temperature was lowered to room temperature, and unreacted ethylene was depressurized. The solid copolymer precipitated by pouring the product into methanol was collected individually, deashed with a hydrochloric acid-methanol mixture, and washed with methanol. This product was heated at 80°C.
The mixture was dried under reduced pressure for 2 hours to obtain a white copolymer.
結果を第1表に示す。The results are shown in Table 1.
[発明の効果]
本発明の製造方法を用いれば、低温度で熱処理すること
により、共重合体の主鎖の切断反応が抑えられ、従って
、重合度の低下がほとんどない高分子量のエチレン−不
飽和カルボン酸共重合体が得られる。また、不飽和カル
ボン酸を直接使用しないために装置の腐食を生ぜず、さ
らに、エチレン−不飽和カルボン酸エステル共重合体の
製造と熱処理とを組合せることによりルイス酸の使用量
を低減することができ、また、触媒効率が向上し、産業
上極めて有用である。[Effects of the Invention] By using the production method of the present invention, the scission reaction of the main chain of the copolymer can be suppressed by heat treatment at a low temperature. A saturated carboxylic acid copolymer is obtained. In addition, since the unsaturated carboxylic acid is not used directly, equipment corrosion does not occur, and the amount of Lewis acid used can be reduced by combining the production of the ethylene-unsaturated carboxylic acid ester copolymer with heat treatment. It also improves catalyst efficiency, making it extremely useful industrially.
Claims (1)
イス酸の存在下、80〜150℃で熱処理することを特
徴とするエチレン−不飽和カルボン酸共重合体の製造法
。 2)クロム化合物と有機金属化合物を主成分とする触媒
を用い、ルイス酸の存在下にエチレンと不飽和カルボン
酸エステルを共重合してエチレン−不飽和カルボン酸エ
ステル共重合体を得、次いで80〜150℃で熱処理す
ることを特徴とするエチレン−不飽和カルボン酸共重合
体の製造法。 3)共重合を−80〜70℃で行なう請求項2記載の製
造法。[Claims] 1) A method for producing an ethylene-unsaturated carboxylic acid copolymer, which comprises heat-treating the ethylene-unsaturated carboxylic ester copolymer at 80 to 150°C in the presence of a Lewis acid. 2) Using a catalyst containing a chromium compound and an organometallic compound as main components, ethylene and an unsaturated carboxylic acid ester are copolymerized in the presence of a Lewis acid to obtain an ethylene-unsaturated carboxylic acid ester copolymer, and then 80% A method for producing an ethylene-unsaturated carboxylic acid copolymer, the method comprising heat-treating at ~150°C. 3) The manufacturing method according to claim 2, wherein the copolymerization is carried out at -80 to 70°C.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12788389A JPH02308803A (en) | 1989-05-23 | 1989-05-23 | Production of ethylene-unsaturated carboxylic acid copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12788389A JPH02308803A (en) | 1989-05-23 | 1989-05-23 | Production of ethylene-unsaturated carboxylic acid copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02308803A true JPH02308803A (en) | 1990-12-21 |
Family
ID=14971009
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12788389A Pending JPH02308803A (en) | 1989-05-23 | 1989-05-23 | Production of ethylene-unsaturated carboxylic acid copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02308803A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7884161B2 (en) | 2006-03-13 | 2011-02-08 | Lg Chem, Ltd. | Method for preparation of 1-alkene-acrylate based copolymer |
US7943709B2 (en) | 2007-03-30 | 2011-05-17 | Lg Chem, Ltd. | Copolymer comprising alkene, acrylate and unsaturated organic acid, and method for preparing the same |
WO2015115378A1 (en) * | 2014-01-28 | 2015-08-06 | 日本ポリエチレン株式会社 | Method for producing ethylene/unsaturated carboxylic acid copolymer, and said copolymer |
-
1989
- 1989-05-23 JP JP12788389A patent/JPH02308803A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7884161B2 (en) | 2006-03-13 | 2011-02-08 | Lg Chem, Ltd. | Method for preparation of 1-alkene-acrylate based copolymer |
EP2325216A1 (en) | 2006-03-13 | 2011-05-25 | LG Chem, Ltd. | Method for preparation of 1-alkene-acrylate based copolymer |
US8362178B2 (en) | 2006-03-13 | 2013-01-29 | Lg Chem, Ltd. | 1-alkene-acrylate based copolymer |
US8697825B2 (en) | 2006-03-13 | 2014-04-15 | Lg Chem, Ltd. | 1-alkene-acrylate based copolymer |
US7943709B2 (en) | 2007-03-30 | 2011-05-17 | Lg Chem, Ltd. | Copolymer comprising alkene, acrylate and unsaturated organic acid, and method for preparing the same |
US8163859B2 (en) | 2007-03-30 | 2012-04-24 | Lg Chem, Ltd. | Copolymer comprising alkene, acrylate and unsaturated organic acid, and method for preparing the same |
WO2015115378A1 (en) * | 2014-01-28 | 2015-08-06 | 日本ポリエチレン株式会社 | Method for producing ethylene/unsaturated carboxylic acid copolymer, and said copolymer |
JP2015163691A (en) * | 2014-01-28 | 2015-09-10 | 日本ポリエチレン株式会社 | Method for producing ethylene/unsaturated carboxylic acid copolymer and copolymer thereof |
US10550211B2 (en) | 2014-01-28 | 2020-02-04 | Japan Polyethylene Corporation | Process for producing ethylene/unsaturated carboxylic acid copolymer, and said copolymer |
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