JP5643671B2 - Polymerization method of carboxylic acid ester monomer - Google Patents
Polymerization method of carboxylic acid ester monomer Download PDFInfo
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- JP5643671B2 JP5643671B2 JP2011022904A JP2011022904A JP5643671B2 JP 5643671 B2 JP5643671 B2 JP 5643671B2 JP 2011022904 A JP2011022904 A JP 2011022904A JP 2011022904 A JP2011022904 A JP 2011022904A JP 5643671 B2 JP5643671 B2 JP 5643671B2
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- JP
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- Prior art keywords
- group
- general formula
- carbon atoms
- carboxylic acid
- represented
- Prior art date
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- 239000000178 monomer Substances 0.000 title claims description 44
- 238000006116 polymerization reaction Methods 0.000 title claims description 31
- 238000000034 method Methods 0.000 title claims description 25
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 30
- 125000003545 alkoxy group Chemical group 0.000 claims description 29
- 125000004104 aryloxy group Chemical group 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 26
- 125000005843 halogen group Chemical group 0.000 claims description 26
- -1 alcohol compound Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims description 22
- 150000004696 coordination complex Chemical class 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 17
- 125000004423 acyloxy group Chemical group 0.000 claims description 10
- 239000003463 adsorbent Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 229930195734 saturated hydrocarbon Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 150000002148 esters Chemical class 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 33
- 150000002430 hydrocarbons Chemical group 0.000 description 26
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000012535 impurity Substances 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 10
- 230000037048 polymerization activity Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- OCMNCWNTDDVHFK-UHFFFAOYSA-L dichloronickel;1,2-dimethoxyethane Chemical compound Cl[Ni]Cl.COCCOC OCMNCWNTDDVHFK-UHFFFAOYSA-L 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 125000004437 phosphorous atom Chemical group 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 3
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-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
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- QSABYDIVRXXXCV-UHFFFAOYSA-N 2-di(propan-2-yl)phosphanylbenzenesulfonic acid Chemical compound CC(C)P(C(C)C)C1=CC=CC=C1S(O)(=O)=O QSABYDIVRXXXCV-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- WLWNRAWQDZRXMB-YLFCFFPRSA-N (2r,3r,4r,5s)-n,3,4,5-tetrahydroxy-1-(4-phenoxyphenyl)sulfonylpiperidine-2-carboxamide Chemical compound ONC(=O)[C@H]1[C@@H](O)[C@H](O)[C@@H](O)CN1S(=O)(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 WLWNRAWQDZRXMB-YLFCFFPRSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 1
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- IRZVKYGINSGOOD-UHFFFAOYSA-N carbanide;palladium(2+) Chemical compound [CH3-].[CH3-].[Pd+2] IRZVKYGINSGOOD-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- JZPDBTOWHLZQFC-UHFFFAOYSA-N chloro-di(propan-2-yl)phosphane Chemical compound CC(C)P(Cl)C(C)C JZPDBTOWHLZQFC-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- PDXOPNHXAAQJJO-UHFFFAOYSA-N nickel;trifluoromethanesulfonic acid Chemical compound [Ni].OS(=O)(=O)C(F)(F)F PDXOPNHXAAQJJO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、カルボン酸エステルを含む重合体の製造方法に関する。さらに詳しく言えば、周期律表第１０族の金属錯体を触媒として用いカルボン酸エステルモノマーの単独重合体または共重合体を製造する方法において、高度に精製されたカルボン酸エステルモノマーを用いることを特徴とする触媒の重合活性が低下しない重合体の製造方法に関する。 The present invention relates to a method for producing a polymer containing a carboxylic acid ester. More specifically, in the method for producing a homopolymer or copolymer of a carboxylic acid ester monomer using a metal complex of Group 10 of the periodic table as a catalyst, a highly purified carboxylic acid ester monomer is used. The present invention relates to a method for producing a polymer in which the polymerization activity of the catalyst does not decrease.
ポリマー工業の進展において、製造コスト低減と省資源・省エネルギー化は、プロセス開発おいて、重要な課題となってきた。製造コスト低減は高活性触媒の開発による時間当たりのポリマー生産量を飛躍的に上げることでなされてきた。例えば、ポリエチレン、ポリプロピレン製造における無脱灰プロセス、気相プロセスへの転換はその例である。 In the progress of the polymer industry, reduction of manufacturing costs and resource / energy saving have become important issues in process development. Production cost reduction has been achieved by dramatically increasing the amount of polymer production per hour by developing highly active catalysts. For example, conversion to a non-deashing process and a gas phase process in the production of polyethylene and polypropylene are examples.
一方、近年、カルボン酸エステルモノマーなどの極性基含有モノマーを単独重合あるいはオレフィンと共重合可能な後周期遷移金属錯体触媒が注目されている。エチレン、プロピレンなどのα−オレフィンの重合において、極性基含有モノマーを共重合させて、無極性のポリエチレン、ポリプロピレンに染色性、接着性、エンジニアリングプラスティックとの相溶性など様々な機能を付加させる試みが行われている。 On the other hand, in recent years, late transition metal complex catalysts that can homopolymerize or copolymerize polar group-containing monomers such as carboxylic acid ester monomers with olefins have attracted attention. In the polymerization of α-olefins such as ethylene and propylene, there are attempts to add various functions such as dyeability, adhesion, compatibility with engineering plastics to nonpolar polyethylene and polypropylene by copolymerizing polar group-containing monomers. Has been done.
オレフィンと極性基含有モノマーを共重合できる重合触媒として、周期律表第１０族の金属錯体触媒を使用したブルックハルト（Brookhalt）（J. Am. Chem. Soc., 118, 267(1996)；非特許文献１）、野崎（J. Am. Chem. Soc., 131, 14606(2009)；非特許文献２）らの例が知られている。しかしながら、従来の後周期金属触媒系では、低活性な上に、長時間重合すると重合活性が低下していくため、高価な後周期遷移金属を使用するにも拘わらず、重合体製造に多量の触媒を必要とする。また、重合体中に多量の金属が残留し、劣化、着色等の原因となるため重合後に脱灰を行なう必要があり、無脱灰プロセス化が困難であるという工業的な問題点があった。 Brookhalt (J. Am. Chem. Soc., 118, 267 (1996)) using a metal complex catalyst of Group 10 of the periodic table as a polymerization catalyst capable of copolymerizing an olefin and a polar group-containing monomer; Examples of Patent Document 1) and Nozaki (J. Am. Chem. Soc., 131, 14606 (2009); Non-Patent Document 2) are known. However, in the conventional late cycle metal catalyst system, the polymerization activity decreases when polymerized for a long time in addition to the low activity, so that a large amount of polymer is produced in spite of using expensive late cycle transition metal. Requires a catalyst. In addition, since a large amount of metal remains in the polymer and causes deterioration, coloring, etc., it is necessary to perform deashing after polymerization, and there is an industrial problem that it is difficult to make a non-deashing process. .
本発明の課題は、周期律表第１０族の金属錯体触媒を用いたカルボン酸エステルモノマーを含む重合体の製造において、触媒の重合活性を飛躍的に向上させ、製造コストを大幅に低減できる重合体の製造方法を提供することにある。 An object of the present invention is to provide a polymer material that can dramatically improve the polymerization activity of a catalyst and greatly reduce the production cost in the production of a polymer containing a carboxylic acid ester monomer using a metal complex catalyst belonging to Group 10 of the periodic table. It is in providing the manufacturing method of coalescence.
本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、カルボン酸エステルモノマーを含む重合反応において、高度に精製されたカルボン酸エステルモノマーを用いることにより触媒の重合活性が飛躍的に向上することを見出し、本発明を完成するに至った。
すなわち、本発明は以下の［１］〜［８］に関する。
［１］ 一般式（Ｃ１）
で示される金属錯体を触媒として使用し、一般式（１）
で示されるカルボン酸エステルモノマーを単独であるいは２種以上を組み合わせて重合するか、または前記一般式（１）で示されるカルボン酸エステルモノマーとオレフィンとを共重合する方法において、重合系内の液相に含まれる、（Ａ）一般式（２）
で示されるアルコール化合物の濃度が５００ｗｔｐｐｍ以下、（Ｂ）一般式（３）
で示されるカルボン酸化合物の濃度が２００ｗｔｐｐｍ以下、（Ｃ）水の濃度が５０ｗｔｐｐｍ以下である、前記条件（Ａ）〜（Ｃ）の少なくとも１つを満足することを特徴とする重合体の製造方法。
［２］ 一般式（Ｃ１）で示される触媒が、一般式（Ｃ２）
で示される前項［１］に記載の重合体の製造方法。
［３］ 一般式（Ｃ２）で示される触媒が、一般式（Ｃ３）
で示される前項［２］に記載の重合体の製造方法。
［４］ 条件（Ａ）を満足することを必須とする前項［１］〜［３］のいずれかに記載の重合体の製造方法。
［５］ 条件（Ａ）および（Ｂ）を満足することを必須とする前項［１］〜［３］のいずれかに記載の重合体の製造方法。
［６］ 条件（Ａ）、（Ｂ）および（Ｃ）のすべてを満足することを必須とする前記［１］〜［３］のいずれかに記載の重合体の製造方法。
［７］ 蒸留または吸着剤による前処理により、前記一般式（２）で示されるアルコール化合物、前記一般式（３）で示されるカルボン酸化合物および水が除去された前記一般式（１）で示されるカルボン酸エステルモノマーを用いる前項［１］〜［６］のいずれかに記載の重合体の製造方法。
［８］ 前記一般式（１）で示されるカルボン酸エステルモノマーが酢酸アリルまたは酢酸ビニルである前項［１］〜［７］のいずれかに記載の重合体の製造方法。
As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have dramatically improved the polymerization activity of a catalyst by using a highly purified carboxylic acid ester monomer in a polymerization reaction including a carboxylic acid ester monomer. As a result, the present invention has been completed.
That is, the present invention relates to the following [1] to [8].
[1] General formula (C1)
As a catalyst, a metal complex represented by the general formula (1)
In the method of polymerizing the carboxylic acid ester monomer represented by the formula (1) alone or in combination of two or more, or copolymerizing the carboxylic acid ester monomer represented by the general formula (1) and the olefin, the liquid in the polymerization system (A) General formula (2) contained in the phase
(B) General formula (3)
And (C) the concentration of water is 50 wtppm or less, and satisfies the at least one of the above conditions (A) to (C). .
[2] The catalyst represented by the general formula (C1) is represented by the general formula (C2).
The manufacturing method of the polymer as described in the preceding clause [1] shown by these.
[3] The catalyst represented by the general formula (C2) is represented by the general formula (C3).
The manufacturing method of the polymer as described in the preceding item [2] shown by these.
[4] The method for producing a polymer as described in any one of [1] to [3] above, wherein it is essential to satisfy the condition (A).
[5] The method for producing a polymer as described in any one of [1] to [3] above, wherein it is essential to satisfy the conditions (A) and (B).
[6] The method for producing a polymer according to any one of [1] to [3], wherein it is essential to satisfy all of the conditions (A), (B), and (C).
[7] In the above general formula (1), the alcohol compound represented by the general formula (2), the carboxylic acid compound represented by the general formula (3), and water are removed by distillation or pretreatment with an adsorbent. The method for producing a polymer according to any one of [1] to [6], wherein the carboxylic acid ester monomer is used.
[8] The method for producing a polymer according to any one of [1] to [7], wherein the carboxylic acid ester monomer represented by the general formula (1) is allyl acetate or vinyl acetate.
高度に精製されたカルボン酸エステルモノマーを用いる本発明の重合方法によれば、従来、重合活性が低下するため製造コストが高く、工業的に製造することが困難であった周期律表第１０族の金属錯体触媒の重合活性を飛躍的に向上できるため、カルボン酸エステルを含むポリマーを低コストで製造することができる。 According to the polymerization method of the present invention using a highly purified carboxylic acid ester monomer, group 10 of the periodic table has heretofore been difficult to produce industrially because of high polymerization costs due to a decrease in polymerization activity. Since the polymerization activity of the metal complex catalyst can be dramatically improved, a polymer containing a carboxylic acid ester can be produced at a low cost.
以下、本発明に係る重合体の製造方法について、その好ましい形態を具体的に説明する。なお、特許請求の範囲を含む本明細書において「重合」は「共重合」を包含し、「重合体」は「共重合体」を包含する。また、「炭化水素」は特に断らない限り、飽和、不飽和の脂肪族および脂環族炭化水素、芳香族炭化水素を含む。「オレフィン」は、極性基の有無に関わらず、炭素−炭素二重結合を有する化合物（ただし、一般式（１）で示されるモノマーを除く。）を表す。 Hereinafter, the preferable form is demonstrated concretely about the manufacturing method of the polymer which concerns on this invention. In the present specification including claims, “polymerization” includes “copolymerization”, and “polymer” includes “copolymer”. Further, “hydrocarbon” includes saturated and unsaturated aliphatic and alicyclic hydrocarbons and aromatic hydrocarbons unless otherwise specified. “Olefin” represents a compound having a carbon-carbon double bond (excluding the monomer represented by the general formula (1)) regardless of the presence or absence of a polar group.
１．モノマー
本発明の重合体の製造方法では、一般式（１）
で示される少なくとも１つのカルボン酸エステルモノマーを重合するか、または一般式（１）で示されるカルボン酸エステルモノマーとオレフィンを共重合する。
1. Monomer In the method for producing a polymer of the present invention, the general formula (1)
Or at least one carboxylic acid ester monomer represented by the general formula (1) is copolymerized with an olefin.
Ｒ1、Ｒ2、Ｒ3は異なっていても、同一でもよい。水素原子または炭素原子数１〜５の飽和炭化水素基を表すＲ1、Ｒ2、Ｒ3としては水素原子または炭素数１または２のアルキル基が好ましい。炭素原子数１〜１８の飽和炭化水素基を表すＲ4としては、炭素数１〜５のアルキル基が好ましく、メチル基、エチル基がより好ましい。 R 1 , R 2 and R 3 may be different or the same. R 1 , R 2 and R 3 representing a hydrogen atom or a saturated hydrocarbon group having 1 to 5 carbon atoms are preferably a hydrogen atom or an alkyl group having 1 or 2 carbon atoms. R 4 representing a saturated hydrocarbon group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.
一般式（１）で示されるモノマーの具体例としては、酢酸ビニル、酢酸アリルが挙げられる。これら一般式（１）で示されるモノマーは１種を単独で、あるいは２種以上を組み合わせて用いることができる。 Specific examples of the monomer represented by the general formula (1) include vinyl acetate and allyl acetate. These monomers represented by the general formula (1) can be used alone or in combination of two or more.
一般式（１）で示されるモノマーと共重合させるオレフィンは炭素数２〜１２の鎖状オレフィンが好ましい。その具体例としては、エチレン、プロピレン、１−ブテン、１−ヘキセン、２−ヘキセン、４−メチル−１−ペンテン、１−オクテンが挙げられる。これらの中でも、特にエチレンおよびプロピレンが好ましい。これらは１種を単独で、あるいは２種以上を組み合わせて用いることができる。 The olefin copolymerized with the monomer represented by the general formula (1) is preferably a chain olefin having 2 to 12 carbon atoms. Specific examples thereof include ethylene, propylene, 1-butene, 1-hexene, 2-hexene, 4-methyl-1-pentene, and 1-octene. Among these, ethylene and propylene are particularly preferable. These can be used alone or in combination of two or more.
オレフィンと一般式（１）で示されるモノマーの組み合わせとしては、エチレンと酢酸アリル、エチレンと酢酸ビニル、プロピレンと酢酸アリル、プロピレンと酢酸ビニルなどが挙げられる。 Examples of the combination of the olefin and the monomer represented by the general formula (1) include ethylene and allyl acetate, ethylene and vinyl acetate, propylene and allyl acetate, and propylene and vinyl acetate.
２．重合系内不純物
本発明においては、重合系の液相内に含まれる不純物が、下記（Ａ）、（Ｂ）、および（Ｃ）の少なくとも１つを満足する必要がある。なお、各不純物の量は重合反応の開始時点での値である。
（Ａ）：一般式（２）
で示されるアルコール化合物の濃度が５００ｗｔｐｐｍ以下である、
（Ｂ）：一般式（３）
で示されるカルボン酸化合物の濃度が２００ｗｔｐｐｍ以下である、
（Ｃ）：水の濃度が５０ｗｔｐｐｍ以下である。
2. Impurities in polymerization system In the present invention, impurities contained in the liquid phase of the polymerization system must satisfy at least one of the following (A), (B), and (C). The amount of each impurity is a value at the start of the polymerization reaction.
(A): General formula (2)
The concentration of the alcohol compound represented by is 500 wtppm or less,
(B): General formula (3)
The concentration of the carboxylic acid compound represented by is 200 wtppm or less,
(C): The concentration of water is 50 wtppm or less.
一般式（２）で示されるアルコール化合物の濃度が５００ｗｔｐｐｍを超え、一般式（３）で示されるカルボン酸化合物の濃度が２００ｗｔｐｐｍを超え、および水濃度が５０ｗｔｐｐｍを超える場合、触媒の重合活性が低い上に長時間、重合反応が継続しないため、重合体の製造に多量の触媒が必要となる。好ましくは、一般式（２）で示されるアルコール化合物の濃度は１００ｗｔｐｐｍ以下、一般式（３）で示されるカルボン酸化合物の濃度は５０ｗｔｐｐｍ以下、または水の濃度は２０ｗｔｐｐｍ以下である。 When the concentration of the alcohol compound represented by the general formula (2) exceeds 500 wtppm, the concentration of the carboxylic acid compound represented by the general formula (3) exceeds 200 wtppm, and the water concentration exceeds 50 wtppm, the polymerization activity of the catalyst is low. In addition, since the polymerization reaction does not continue for a long time, a large amount of catalyst is required for the production of the polymer. Preferably, the concentration of the alcohol compound represented by the general formula (2) is 100 wtppm or less, the concentration of the carboxylic acid compound represented by the general formula (3) is 50 wtppm or less, or the concentration of water is 20 wtppm or less.
また、前記（Ａ）〜（Ｃ）のうち２つを満足することが好ましく、中でも（Ａ）および（Ｂ）の２つの条件を満足することがより好ましく、（Ａ）〜（Ｃ）の３条件のすべてを満足することがさらに好ましい。 Moreover, it is preferable to satisfy two of the above (A) to (C), and it is more preferable to satisfy the two conditions (A) and (B), and (A) to (C) 3 More preferably, all of the conditions are satisfied.
３．モノマー中の不純物
本発明において、重合系内の一般式（２）で示されるアルコール化合物の濃度、一般式（３）で示されるカルボン酸化合物の濃度、または水の濃度を低くするには、一般式（１）で示されるカルボン酸エステルモノマー中の上記濃度が低いものを使用するとよい。
3. In the present invention, in order to reduce the concentration of the alcohol compound represented by the general formula (2), the concentration of the carboxylic acid compound represented by the general formula (3), or the concentration of water in the polymerization system, What has a low said density | concentration in the carboxylic acid ester monomer shown by Formula (1) is good to use.
市販あるいは工業用原料として供給されている一般式（１）で示されるカルボン酸エステルモノマーは、種々の不純物を含んでいる。空気中で取り扱うとモノマー中の水分濃度が増加する可能性がある。水分が混入するとカルボン酸エステルモノマーの加水分解反応により、カルボン酸とアルコールが生成する可能性がある。これらカルボン酸エステルモノマーに含まれる不純物の中で、加水分解反応あるいは製造原料由来の不純物であるアルコール、カルボン酸と水は、本発明で使用する金属錯体触媒の重合活性を阻害する。また、触媒濃度の低い重合条件ではそれらの影響が大きくなる。 The carboxylic acid ester monomer represented by the general formula (1) supplied as a commercially available or industrial raw material contains various impurities. When handled in air, the moisture concentration in the monomer may increase. When moisture is mixed, there is a possibility that carboxylic acid and alcohol are generated by hydrolysis reaction of the carboxylic acid ester monomer. Among the impurities contained in these carboxylic acid ester monomers, alcohol, carboxylic acid and water, which are impurities derived from hydrolysis reaction or production raw materials, inhibit the polymerization activity of the metal complex catalyst used in the present invention. In addition, the influence of the polymerization increases under low polymerization conditions.
これらアルコール、カルボン酸および／または水を多量に含有したカルボン酸エステルモノマーを本発明で使用するには、これら不純物を除去するために精製する必要がある。
カルボン酸エステルモノマーの精製方法は、特に限定されるものではなく、種々の精製法を用いることができる。例えば、蒸留や吸着剤を利用する方法が挙げられる。吸着剤を使用して精製する場合、吸着剤として、ゼオライト、アルミナ、活性アルミナ、シリカ、活性炭、珪酸アルミニウム、珪藻土、活性白土等が挙げらる。吸着剤の性状等は特に制限されない。これらの吸着剤の中でも、ゼオライト、活性アルミナ、アルミナ、シリカが特に好ましい。これらは１種単独で、あるいは２種以上を組み合わせて用いることができる。カルボン酸エステルモノマーと吸着剤の接触処理条件は、種々の方法が利用できる。カルボン酸エステルモノマー中に吸着剤を投入して緩やかに撹拌あるいは静置する方法のほか、上記吸着剤をカラム等に充填し、これにカルボン酸エステルモノマーを通過させて行なうこともできる。
In order to use these carboxylic acid ester monomers containing a large amount of alcohol, carboxylic acid and / or water in the present invention, it is necessary to purify them in order to remove these impurities.
The purification method of the carboxylic acid ester monomer is not particularly limited, and various purification methods can be used. For example, a method using distillation or an adsorbent can be mentioned. In the case of purification using an adsorbent, examples of the adsorbent include zeolite, alumina, activated alumina, silica, activated carbon, aluminum silicate, diatomaceous earth, and activated clay. The properties of the adsorbent are not particularly limited. Among these adsorbents, zeolite, activated alumina, alumina, and silica are particularly preferable. These can be used alone or in combination of two or more. Various methods can be used for the contact treatment conditions of the carboxylic acid ester monomer and the adsorbent. In addition to a method in which an adsorbent is introduced into a carboxylic acid ester monomer and gently stirred or allowed to stand, the adsorbent can be packed in a column or the like, and the carboxylic acid ester monomer can be passed therethrough.
４．重合触媒
本発明で使用する重合触媒は、一般式（Ｃ１）で示される周期律表第１０族の遷移金属錯体である。
4). Polymerization catalyst The polymerization catalyst used in the present invention is a transition metal complex belonging to Group 10 of the periodic table represented by formula (C1).
一般式（Ｃ１）
以下、一般式（Ｃ１）の構造について説明する。
Ｍは周期律表第１０族の元素を表す。周期律表第１０族の元素としては、Ｎｉ、Ｐｄ、Ｐｔが挙げられるが、触媒活性や得られる分子量の観点からＮｉおよびＰｄが好ましく、Ｐｄがより好ましい。
Hereinafter, the structure of the general formula (C1) will be described.
M represents an element of Group 10 of the periodic table. Examples of the elements of Group 10 of the periodic table include Ni, Pd, and Pt, and Ni and Pd are preferable and Pd is more preferable from the viewpoint of catalytic activity and the obtained molecular weight.
Ｘはリン原子（Ｐ）または砒素原子（Ａｓ）であり、Ｍに２電子配位している。Ｘとしては入手が容易であることと触媒コストの面からリン原子（Ｐ）が好ましい。 X is a phosphorus atom (P) or an arsenic atom (As) and is coordinated to M by two electrons. X is preferably a phosphorus atom (P) from the viewpoint of easy availability and catalyst cost.
Ｒ5は、(1)水素原子、(2)アシロキシ基、または(3)ハロゲン原子、アルコキシ基、アリールオキシ基、およびアシロキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜３０の炭化水素基を表す。ハロゲン原子、アルコキシ基、アリールオキシ基、およびアシロキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜３０の炭化水素基において、炭素原子数１〜３０の炭化水素基としては、炭素原子数１〜６のアルキル基が好ましい。ハロゲン原子は塩素、臭素が好ましい。アルコキシ基としてはメトキシ基、エトキシ基が好ましい。アリールオキシ基としてはフェノキシ基が好ましい。アシロキシ基としてはアセトキシ基、ピバロキシ基が好ましい。Ｒ5の特に好ましい例として、水素原子、アセトキシ基、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、メトキシメチル基、フェノキシメチル基、１−アセトキシフェニル基、１−ピバロキシプロピル基などが挙げられる。 R 5 is (1) a hydrogen atom, (2) an acyloxy group, or (3) a carbon atom optionally substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group The hydrocarbon group of number 1-30 is represented. In the hydrocarbon group having 1 to 30 carbon atoms that may be substituted with one or more groups selected from a halogen atom, an alkoxy group, an aryloxy group, and an acyloxy group, a hydrocarbon group having 1 to 30 carbon atoms Is preferably an alkyl group having 1 to 6 carbon atoms. The halogen atom is preferably chlorine or bromine. The alkoxy group is preferably a methoxy group or an ethoxy group. The aryloxy group is preferably a phenoxy group. As the acyloxy group, an acetoxy group and a pivaloxy group are preferable. Particularly preferred examples of R 5 include a hydrogen atom, an acetoxy group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a methoxymethyl group, a phenoxymethyl group, a 1-acetoxyphenyl group, and a 1-pivaloxypropyl group. Is mentioned.
Ｙ、Ｒ6およびＲ7はそれぞれ独立して、(1)水素原子、(2)アルコキシ基、(3)アリールオキシ基、(4)シリル基、(5)アミノ基、または(6)ハロゲン原子、アルコキシ基、およびアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜３０の炭化水素基を表す。アルコキシ基としては炭素原子数１〜２０のものが好ましく、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基などが挙げられる。アリールオキシ基としては炭素原子数６〜２４のものが好ましく、フェノキシ基などが挙げられる。シリル基としてはトリメチルシリル基、アミノ基としてはアミノ基、メチルアミノ基、ジメチルアミノ基などが挙げられる。また、Ｒ6とＲ7は同じでも、異なっていてもよい。また、Ｒ6とＲ7は結合して環構造を形成してもよい。Ｒ6および／またはＲ7はＹと結合して環構造を形成してもよい。 Y, R 6 and R 7 are each independently (1) a hydrogen atom, (2) an alkoxy group, (3) an aryloxy group, (4) a silyl group, (5) an amino group, or (6) a halogen atom. , An hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from an alkoxy group and an aryloxy group. The alkoxy group is preferably one having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. As the aryloxy group, those having 6 to 24 carbon atoms are preferable, and examples thereof include a phenoxy group. Examples of the silyl group include a trimethylsilyl group, and examples of the amino group include an amino group, a methylamino group, and a dimethylamino group. R 6 and R 7 may be the same or different. R 6 and R 7 may combine to form a ring structure. R 6 and / or R 7 may combine with Y to form a ring structure.
Ｙ、Ｒ6、およびＲ7が表すハロゲン原子、アルコキシ基、およびアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜３０の炭化水素基における、炭素原子数１〜３０の炭化水素基としては、アルキル基、アリール基、シクロアルキル基、フリル基などが挙げられる。ハロゲン原子、アルコキシ基、およびアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜３０の炭化水素基における、アルコキシ基、アリールオキシ基の具体例としては前記Ｒ5と同様のものが挙げられる。ハロゲン原子はフッ素が好ましい。特に触媒活性の観点から、アルキル基およびアリール基が好ましい。 The number of carbon atoms in the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from the halogen atom, alkoxy group and aryloxy group represented by Y, R 6 and R 7 Examples of the hydrocarbon group having 1 to 30 include an alkyl group, an aryl group, a cycloalkyl group, and a furyl group. Specific examples of the alkoxy group and aryloxy group in the hydrocarbon group having 1 to 30 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group include the R The same thing as 5 is mentioned. The halogen atom is preferably fluorine. In particular, from the viewpoint of catalytic activity, an alkyl group and an aryl group are preferable.
以下、ＸがＰ（リン原子）の場合の、［Ｙ−Ｘ（Ｒ7）−Ｒ6］部位、すなわち
ＸがＡｓ（砒素原子）の場合の、［Ｙ−Ｘ（Ｒ7）−Ｒ6］部位、すなわち
Ｑは−Ｓ（＝Ｏ）2−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｐ（＝Ｏ）（−ＯＨ）−Ｏ−、または−Ｓ−で示される２価の基を表し、Ｍに１電子配位する部位である。前記各式の左側がＺに結合し、右側がＭに結合している。これらの中でも触媒活性の面から−Ｓ（＝Ｏ）2−Ｏ−が特に好ましい。 Q represents a divalent group represented by —S (═O) 2 —O—, —C (═O) —O—, —P (═O) (— OH) —O—, or —S—. , M is a site that coordinates one electron. The left side of each formula is bonded to Z, and the right side is bonded to M. Among these, -S (= O) 2- O- is particularly preferable from the viewpoint of catalytic activity.
Ｚは(1)水素原子、または(2)ハロゲン原子、アルコキシ基、およびアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜４０の炭化水素基を表す。ＹとＺは結合して環構造を形成してもよい。「ハロゲン原子、アルコキシ基、およびアリールオキシ基から選ばれる１つ以上の基で置換されていてもよい炭素原子数１〜４０の炭化水素基」におけるハロゲン原子、アルコキシ基、アリールオキシ基の具体例としては、Ｙ、Ｒ6、およびＲ7について述べたものが挙げられる。炭素原子数１〜４０の炭化水素基としては、メチル基、エチル基、イソプロピル基、ｔ−ブチル基、イソブチル基、シクロヘキシル基、シクロペンチル基、フェニル基、２−ｉ−プロピルフェニル基、２，６−ジ−ｉ−プロピルフェニル基などが挙げられる。 Z represents (1) a hydrogen atom, or (2) a hydrocarbon group having 1 to 40 carbon atoms which may be substituted with one or more groups selected from a halogen atom, an alkoxy group, and an aryloxy group. Y and Z may combine to form a ring structure. Specific examples of halogen atom, alkoxy group, and aryloxy group in “hydrocarbon group having 1 to 40 carbon atoms which may be substituted with one or more groups selected from halogen atom, alkoxy group, and aryloxy group” Include those described for Y, R 6 , and R 7 . Examples of the hydrocarbon group having 1 to 40 carbon atoms include methyl group, ethyl group, isopropyl group, t-butyl group, isobutyl group, cyclohexyl group, cyclopentyl group, phenyl group, 2-i-propylphenyl group, 2,6 -Di-i-propylphenyl group etc. are mentioned.
Ｚ−Ｑ部位は電気陰性度の大きい酸素原子または硫黄原子で金属原子Ｍに１電子配位している。Ｚ−Ｑ−Ｍ間の結合電子は、ＭからＺ−Ｑに移動しているため、形式上、Ｚ−Ｑをアニオン状態、Ｍをカチオン状態で表記することも可能である。 The ZQ site is an oxygen atom or sulfur atom having a high electronegativity and is coordinated with the metal atom M by one electron. Since the bond electrons between ZQM move from M to ZQ, it is possible to express ZQ as an anion state and M as a cation state.
一般式（Ｃ１）において、Ｙ部位とＺ部位は結合することができる。この場合、一般式（Ｃ１）は一般式（Ｃ２）で示される。一般式（Ｃ２）では、Ｙ−Ｚ部位を一体としてＹ1で示している。ここで、Ｙ1はＱとＸとの間の架橋構造を表すことになる。
Ｙ1におけるハロゲン原子、アルコキシ基、およびアリールオキシ基の具体例はＹで説明したものと同様である。炭素原子数１〜７０の炭化水素基としてはアルキレン基、アリーレン基等が挙げられる。特にアリーレン基が好ましい。 Specific examples of the halogen atom, alkoxy group and aryloxy group in Y 1 are the same as those described for Y. Examples of the hydrocarbon group having 1 to 70 carbon atoms include an alkylene group and an arylene group. An arylene group is particularly preferable.
ＸがＰ（リン原子）の場合、［（Ｒ6）（Ｒ7）Ｐ］部位としては、具体的に以下の構造が挙げられる。なお、下記の構造式ではＰとＭおよびＹ1との結合は省略している。
架橋構造Ｙ1はＸとＱ部位を結合する架橋部位である。ＸをＰ原子で示した架橋構造Ｙ1の具体例を以下に示す。ここで、複数のＲ9は、同じでも異なっていてもよく、水素原子、ハロゲン原子、炭素原子１〜２０の炭化水素基、またはハロゲン原子で置換された炭素原子数１〜２０の炭化水素基を表す。
置換基Ｒ6およびＲ7は、Ｙ1部位と結合して環構造を形成してもよい。具体的には以下の構造が挙げられる。
一般式（Ｃ２）で示される触媒の中でも、特に以下の一般式（Ｃ３）で示されるものが好ましい。
一般式（Ｃ３）においては、Ｒ5は炭素原子数１〜６のアルキル基が好ましく、メチル基が特に好ましい。Ｒ6およびＲ7は、ともにシクロヘキシル基、シクロペンチル基、またはイソプロピル基であることが好ましい。ＭはＰｄが好ましい。 In the general formula (C3), R 5 is preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. R 6 and R 7 are preferably both a cyclohexyl group, a cyclopentyl group, or an isopropyl group. M is preferably Pd.
一般式（Ｃ１）および（Ｃ２）で示される触媒の金属錯体は、公知の文献（例えば、J. Am. Chem. Soc. 2007, 129, 8948）に従って合成することができる。すなわち、０価あるいは２価のＭソースと一般式（Ｃ１）または（Ｃ２）中の配位子とを反応させて合成することができる。 The metal complex of the catalyst represented by the general formulas (C1) and (C2) can be synthesized according to known literature (for example, J. Am. Chem. Soc. 2007, 129, 8948). That is, it can be synthesized by reacting a zero-valent or divalent M source with a ligand in the general formula (C1) or (C2).
一般式（Ｃ３）で示される化合物は、一般式（Ｃ２）中のＹ1およびＱを、一般式（Ｃ３）に対応する特定の基にすることにより合成することができる。
０価のＭソースは、パラジウムソースとして、トリス（ジベンジリデンアセトン）ジパラジウムが挙げられ、ニッケルソースとして、テトラカルボニルニッケル（０）：Ｎｉ（ＣＯ）4、ビス（１，５−シクロオクタジエン）ニッケルが挙げられる。
The compound represented by the general formula (C3) can be synthesized by changing Y 1 and Q in the general formula (C2) to a specific group corresponding to the general formula (C3).
Examples of the zero-valent M source include tris (dibenzylideneacetone) dipalladium as a palladium source, and tetracarbonyl nickel (0): Ni (CO) 4 , bis (1,5-cyclooctadiene) as a nickel source. Nickel is mentioned.
２価のＭソースは、パラジウムソースとして、（１，５−シクロオクタジエン）（メチル）塩化パラジウム、酢酸パラジウム、ビス（アセトニトリル）ジクロロパラジウム：ＰｄＣｌ2（ＣＨ3ＣＮ）2、ビス（ベンゾニトリル）ジクロロパラジウム：ＰｄＣｌ2（ＰｈＣＮ）2、（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン）ジクロロパラジウム（II）：ＰｄＣｌ2（ＴＭＥＤＡ）、（Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン）ジメチルパラジウム（II）：ＰｄＭｅ2（ＴＭＥＤＡ）、ビス（アセチルアセトナト）パラジウム（II）：Ｐｄ（acac）2、トリフルオロメタンスルホン酸パラジウム（II）：Ｐｄ（ＯＣＯＣＦ3）2が、ニッケルソースとして、（アリル）塩化ニッケル、（アリル）臭化ニッケル、塩化ニッケル、酢酸ニッケル、ビス（アセチルアセトナト）ニッケル（II）：Ｎｉ（acac）2、（１，２−ジメトキシエタン）ジクロロニッケル（II）：ＮｉＣｌ2（ＤＭＥ）、トリフルオロメタンスルホン酸ニッケル（II）：Ｎｉ（ＯＳＯ2ＣＦ3）2が挙げられる。 The divalent M source is (1,5-cyclooctadiene) (methyl) palladium chloride, palladium acetate, bis (acetonitrile) dichloropalladium: PdCl 2 (CH 3 CN) 2 , bis (benzonitrile) as a palladium source. Dichloropalladium: PdCl 2 (PhCN) 2 , (N, N, N ′, N′-tetramethylethylenediamine) dichloropalladium (II): PdCl 2 (TMEDA), (N, N, N ′, N′-tetramethyl) Ethylenediamine) dimethyl palladium (II): PdMe 2 (TMEDA), bis (acetylacetonato) palladium (II): Pd (acac) 2 , palladium trifluoromethanesulfonate (II): Pd (OCOCF 3 ) 2 is a nickel source (Allyl) nickel chloride, (allyl) nickel bromide, nickel chloride, Acid nickel, bis (acetylacetonato) nickel (II): Ni (acac) 2, (1,2- dimethoxyethane) dichloro Nickel (II): NiCl 2 (DME), trifluoromethanesulfonic acid nickel (II): Ni (OSO 2 CF 3 ) 2 may be mentioned.
一般式（Ｃ１）または一般式（Ｃ２）で示される金属錯体は、単離して使用することができるが、錯体を単離することなくＭを含む金属ソースと配位子前駆体を反応系中で接触させて、これをそのまま重合（イン・サイチュ（in situ）重合）に供することもできる。特に一般式（Ｃ１）および（Ｃ２）中のＲ5が水素原子の場合、０価のＭを含む金属ソースと配位子前駆体とを反応させた後、錯体を単離することなくそのまま重合に供することが好ましい。 The metal complex represented by the general formula (C1) or the general formula (C2) can be isolated and used, but the metal source containing M and the ligand precursor can be used in the reaction system without isolating the complex. And can be directly subjected to polymerization (in situ polymerization). In particular, when R 5 in the general formulas (C1) and (C2) is a hydrogen atom, after reacting a metal source containing 0-valent M with a ligand precursor, polymerization is performed without isolation of the complex. It is preferable to use for.
この場合の配位子前駆体とは、一般式（Ｃ１）の場合、一般式（Ｃ１−１）
で示される。
The ligand precursor in this case is the general formula (C1-1) in the case of the general formula (C1).
Indicated by
一般式（Ｃ２）の場合、一般式（Ｃ２−１）
で示される。
In the case of the general formula (C2), the general formula (C2-1)
Indicated by
一般式（Ｃ１）におけるＭソース（Ｍ）と配位子前駆体（Ｃ１−１）（Ｘ）あるいは配位子前駆体（Ｃ１−２）（Ｚ）との比率（Ｘ／ＭあるいはＺ／Ｍ）またはＭソース（Ｍ）と配位子前駆体（Ｃ２−１）（Ｃ２配位子）との比率（（Ｃ２配位子）／Ｍ）は、０．５〜２．０の範囲で、さらには１．０〜１．５の範囲で選択することが好ましい。 Ratio (X / M or Z / M) of M source (M) and ligand precursor (C1-1) (X) or ligand precursor (C1-2) (Z) in the general formula (C1) ) Or M source (M) and the ligand precursor (C2-1) (C2 ligand) ratio ((C2 ligand) / M) is in the range of 0.5 to 2.0, Furthermore, it is preferable to select in the range of 1.0 to 1.5.
一般式（Ｃ１）あるいは一般式（Ｃ２）の金属錯体を単離する場合、予め電子供与性配位子（Ｌ）を配位させて安定化させたものを用いることもできる。この場合、ｑは１／２、１または２となる。ｑが１／２とは一つの２価の電子供与性配位子が２つの金属錯体に配位していることを意味する。ｑは金属錯体触媒を安定化する意味で１／２または１が好ましい。なお、ｑが０の場合は配位子がないことを意味する。 When isolating the metal complex of the general formula (C1) or the general formula (C2), it is possible to use one that has been previously stabilized by coordination with the electron donating ligand (L). In this case, q is 1/2, 1 or 2. When q is 1/2, it means that one divalent electron-donating ligand is coordinated to two metal complexes. q is preferably 1/2 or 1 in order to stabilize the metal complex catalyst. In addition, when q is 0, it means that there is no ligand.
Ｌの電子供与性配位子とは、電子供与性を有し、金属原子Ｍに配位して金属錯体を安定化させることのできる化合物である。電子供与性配位子（Ｌ）としては、硫黄原子を有するものとしてジメチルスルホキシド（ＤＭＳＯ）が挙げられる。窒素原子を有するものとして、炭素原子数１〜１０のトリアルキルアミン、炭素原子数１〜１０のジアルキルアミン、ピリジン、２，６−ジメチルピリジン（別名：ルチジン）、アニリン、２，６−ジメチルアニリン、２，６−ジイソプロピルアニリン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（ＴＭＥＤＡ）、４−（Ｎ，Ｎ−ジメチルアミノ）ピリジン（ＤＭＡＰ）、アセトニトリル、ベンゾニトリル、２−メチルキノリンなどが挙げられる。酸素原子を有するものとして、ジエチルエーテル、テトラヒドロフラン、１，２−ジメトキシエタンが挙げられる。 The L electron-donating ligand is a compound that has an electron-donating property and can coordinate to the metal atom M to stabilize the metal complex. As the electron donating ligand (L), dimethyl sulfoxide (DMSO) is exemplified as one having a sulfur atom. Those having a nitrogen atom include trialkylamines having 1 to 10 carbon atoms, dialkylamines having 1 to 10 carbon atoms, pyridine, 2,6-dimethylpyridine (also known as lutidine), aniline, and 2,6-dimethylaniline. 2,6-diisopropylaniline, N, N, N ′, N′-tetramethylethylenediamine (TMEDA), 4- (N, N-dimethylamino) pyridine (DMAP), acetonitrile, benzonitrile, 2-methylquinoline, etc. Is mentioned. Examples of those having an oxygen atom include diethyl ether, tetrahydrofuran, and 1,2-dimethoxyethane.
５．重合体の製造方法
本発明では、重合様式は特に制限されるものではなく、一般に使用される方法で重合可能である。すなわち、溶液重合法、気相重合法、バルク重合法などのプロセス法が可能であるが、特に溶液重合法、バルク重合法が好ましい。また、バッチ式、連続式のどちらでも可能であり、一段重合でも多段重合でも行うこともできる。
5. Production Method of Polymer In the present invention, the polymerization mode is not particularly limited, and polymerization can be performed by a generally used method. That is, process methods such as a solution polymerization method, a gas phase polymerization method, and a bulk polymerization method are possible, but a solution polymerization method and a bulk polymerization method are particularly preferable. Moreover, either batch type or continuous type is possible, and it can be carried out by single-stage polymerization or multi-stage polymerization.
一般式（Ｃ１）、（Ｃ２）または（Ｃ３）で示される金属錯体触媒とモノマーの総量のモル比は、モノマー／金属錯体の比で１〜１０，０００，０００の範囲、好ましくは１００〜１，０００，０００の範囲である。更に好ましくは１０００〜１００，０００の範囲である。 The molar ratio of the total amount of the metal complex catalyst represented by the general formula (C1), (C2) or (C3) and the monomer is in the range of 1 to 10,000,000, preferably 100 to 1 in terms of the monomer / metal complex ratio. In the range of 1,000,000. More preferably, it is the range of 1000-100,000.
重合温度は、特に限定されない。通常−３０〜２００℃の範囲で、好ましくは０〜１８０℃、より好ましくは２０〜１５０℃の範囲である。
重合圧力については原料モノマーの性状によるが、常圧から２０ＭＰａの範囲、好ましくは常圧から１０ＭＰａの範囲である。更に好ましくは常圧から５ＭＰａの範囲である。
重合時間は、バッチ式の場合、触媒の重合活性などにより適宜調整することができ、数分の短い時間も数百時間の長い反応時間も可能である。連続式の場合、滞留時間は数分の短い時間から数十時間の長い時間まで可能である。
The polymerization temperature is not particularly limited. Usually, it is in the range of -30 to 200 ° C, preferably 0 to 180 ° C, more preferably 20 to 150 ° C.
The polymerization pressure depends on the properties of the raw material monomers, but is in the range of normal pressure to 20 MPa, preferably in the range of normal pressure to 10 MPa. More preferably, it is in the range of normal pressure to 5 MPa.
In the case of a batch system, the polymerization time can be appropriately adjusted depending on the polymerization activity of the catalyst, and a short reaction time of several minutes or a long reaction time of several hundred hours is possible. In the case of a continuous system, the residence time can be as short as a few minutes or as long as several tens of hours.
重合は、触媒の活性低下を防ぐために不活性ガス雰囲気で行なうことが好ましい。また溶液重合の場合、モノマー以外に不活性溶媒を使用することが可能であるが、使用する場合はその不活性溶媒中の不純物にも注意する必要がある。一般式（２）で示されるアルコール、一般式（３）で示されるカルボン酸および／または水の濃度が高い不活性溶媒中を用いると、重合系内のそれらの濃度も高くなる。不活性溶媒の種類は特に限定されないが、イソブタン、ペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカンなどの脂肪族炭化水素、シクロペンタン、シクロヘキサン、メチルシクロペンタンなどの脂環族炭化水素、ベンゼン、トルエン、キシレンなどの芳香族炭化水素、クロロホルム、塩化メチレン、四塩化炭素、ジクロロエタン、テトラクロロエタン、クロロベンゼン、ジクロロベンゼン、トリクロロベンゼンなどのハロゲン化炭化水素、酢酸メチル、酢酸エチルなどの脂肪族エステル、安息香酸メチル、安息香酸エチルなどの芳香族エステルなどが挙げられる。これらは１種を単独で、あるいは２種以上を組み合わせて用いることができる。 The polymerization is preferably performed in an inert gas atmosphere in order to prevent a decrease in the activity of the catalyst. In addition, in the case of solution polymerization, it is possible to use an inert solvent in addition to the monomer. However, when used, it is necessary to pay attention to impurities in the inert solvent. When an alcohol represented by the general formula (2), a carboxylic acid represented by the general formula (3) and / or an inert solvent having a high concentration of water is used, their concentration in the polymerization system also increases. The type of the inert solvent is not particularly limited, but aliphatic hydrocarbons such as isobutane, pentane, hexane, heptane, octane, decane, and dodecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane, benzene, and toluene , Aromatic hydrocarbons such as xylene, chloroform, methylene chloride, carbon tetrachloride, dichloroethane, tetrachloroethane, halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, aliphatic esters such as methyl acetate and ethyl acetate, benzoic acid And aromatic esters such as methyl and ethyl benzoate. These can be used alone or in combination of two or more.
重合反応終了後、生成物である重合体は、公知の操作、処理方法（例えば、中和、溶媒抽出、水洗、分液、溶媒留去、再沈殿など）により後処理されて単離される。 After completion of the polymerization reaction, the product polymer is isolated by post-treatment by a known operation and treatment method (for example, neutralization, solvent extraction, water washing, liquid separation, solvent distillation, reprecipitation, etc.).
重合体の単離法は特に制限されるものではなく、公知の方法を用いることができる。特に、溶液重合またはバルク重合の場合には、生成した重合体が少なくとも冷却時に重合溶媒やモノマーに溶解せず、析出すると単離が容易である。この場合にはろ過などの簡単な操作で重合体と触媒が溶解している液（回収液）を分離することができる。生成した重合体が溶液に溶解したままであると再沈殿や溶媒や未反応モノマーの蒸発など重合体の分離工程が必要となる。 The method for isolating the polymer is not particularly limited, and a known method can be used. In particular, in the case of solution polymerization or bulk polymerization, the produced polymer does not dissolve in the polymerization solvent or monomer at least during cooling, and is easily isolated when precipitated. In this case, the liquid (recovered liquid) in which the polymer and the catalyst are dissolved can be separated by a simple operation such as filtration. If the produced polymer remains dissolved in the solution, a polymer separation step such as reprecipitation or evaporation of the solvent or unreacted monomer is required.
以下、合成例、実施例および比較例を挙げて本発明をより詳細に説明するが、本発明は下記の例に限定されるものではない。 EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to the following example.
［不純物量の測定方法］
（１）アリルコールおよび酢酸
アジレント・テクノロジー(株)製Ａｇｉｌｅｎｔ６８５０ガスクロマトグラフにより測定した。
測定条件は以下の通りである。
キャリアーガス：ヘリウム（１．２ｍＬ／分）、
注入液量：１μＬ、
スプリット比：２０、
カラム：ＤＢ−ＷＡＸＥＴＲ（長さ３０ｍ、内径０．３２ｍｍ、膜厚１．０μｍ）
カラム温度：４０℃、１０分→５℃／分→１２０℃、０分→１０℃／分→２２０℃、２４分、
検知器：ＦＩＤ。
内部標準を使用すると、内部標準自身やその不純物が試料中の成分と重なり、正確な定量が難しいので、反応に使用する酢酸アリルをそのまま測定した。不純物濃度は酢酸アリルの濃度を１００％と仮定し、面積比に感度比を乗じて求めた。この方法で求めた不純物は、蒸留などでは酢酸アリルと分離しにくい異性体である、酢酸イソプロペニル、１−酢酸プロペニル（ｃｉｓ体及びｔｒａｎｓ体）を含み、それらの濃度の合計は１％以下であった。
（２）水
三菱化学(株)製ＣＡ−２００型微量水分測定装置を用い、試料を５ｍＬ注入し測定した。
[Measurement method of impurities]
(1) Allylchol and acetic acid Measured with an Agilent 6850 gas chromatograph manufactured by Agilent Technologies.
The measurement conditions are as follows.
Carrier gas: helium (1.2 mL / min),
Injection volume: 1 μL,
Split ratio: 20,
Column: DB-WAXETR (length 30 m, inner diameter 0.32 mm, film thickness 1.0 μm)
Column temperature: 40 ° C., 10 minutes → 5 ° C./minute→120° C., 0 minute → 10 ° C./minute→220° C., 24 minutes,
Detector: FID.
When the internal standard was used, the internal standard itself and its impurities overlapped with the components in the sample, and accurate quantification was difficult. Therefore, allyl acetate used for the reaction was measured as it was. The impurity concentration was determined by multiplying the area ratio by the sensitivity ratio, assuming that the concentration of allyl acetate was 100%. Impurities determined by this method include isopropenyl acetate and 1-propenyl acetate (cis and trans isomers), which are isomers that are difficult to separate from allyl acetate by distillation or the like, and the total concentration thereof is 1% or less. there were.
(2) Water Using a CA-200 type trace moisture measuring device manufactured by Mitsubishi Chemical Corporation, 5 mL of the sample was injected and measured.
［試薬］
酢酸アリル：東京化成工業（株）製試薬を更に蒸留精製し、表１実施例１に示す濃度しか不純物を含まない酢酸アリルを得た。ただし、比較例２では東京化成工業（株）製試薬をそのまま使用した。
アリルアルコール：和光純薬工業（株）製試薬を使用した。
酢酸：和光純薬工業（株）製試薬を使用した。
水：和光純薬工業（株）製の蒸留水を使用した。
[reagent]
Allyl acetate: Reagents manufactured by Tokyo Chemical Industry Co., Ltd. were further purified by distillation to obtain allyl acetate containing impurities only at the concentrations shown in Table 1, Example 1. However, in Comparative Example 2, a reagent manufactured by Tokyo Chemical Industry Co., Ltd. was used as it was.
Allyl alcohol: A reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
Acetic acid: A reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
Water: Distilled water manufactured by Wako Pure Chemical Industries, Ltd. was used.
［重合体の構造の解析方法］
重合体中の一般式（１）で示されるモノマーに由来するモノマーユニットの含有率は、日本電子(株)製ＪＮＭ−ＥＸ４００を用い、1Ｈ−ＮＭＲにより求めた。溶媒として重ベンゼンを用い、８０℃において測定した。
平均分子量および重量平均分子量は、昭和電工(株)製，ＡＴ−８０６ＭＳカラム（２本直列）を備えた東ソー(株)製高温ＧＰＣ装置、ＨＬＣ−８１２１ＧＰＣ／ＨＴを用い、ポリスチレンを分子量の標準物質とするサイズ排除クロマトグラフィー（溶離液：１，２−ジクロロベンゼン、温度：１４５℃）により算出した。
[Method of analyzing polymer structure]
The content of the monomer unit derived from the monomer represented by the general formula (1) in the polymer was determined by 1 H-NMR using JNM-EX400 manufactured by JEOL Ltd. Measurement was performed at 80 ° C. using heavy benzene as a solvent.
The average molecular weight and the weight average molecular weight were measured by using a high-temperature GPC apparatus manufactured by Showa Denko KK, equipped with an AT-806MS column (two in series), HLC-8121GPC / HT, and polystyrene as a standard material for molecular weight. And size exclusion chromatography (eluent: 1,2-dichlorobenzene, temperature: 145 ° C.).
合成例１：
下記の反応スキームに従って金属錯体触媒１を合成した。
窒素雰囲気下、ベンゼンスルホン酸（Sigma−Aldrich社製、２１．７ｇ，１３７ｍｍｏｌ）のテトラヒドロフラン（ＴＨＦ）溶液（４００ｍＬ）に、ｎ−ブチルリチウム（関東化学(株)製、１．５７Ｍヘキサン溶液，１７４ｍＬ，２７４ｍｍｏｌ）を０℃で加え、室温で３時間撹拌した。反応容器を−７８℃に冷却した後にクロロジイソプロピルホスフィン（Sigma-Aldrich社製，１９．０ｇ，１２５ｍｍｏｌ）を−７８℃で加え、室温で２．５時間撹拌した。反応をトリフルオロ酢酸（東京化成工業(株)製、１５．６ｇ，１３７ｍｍｏｌ）で停止した後に、生じた沈殿をろ過によって回収し減圧下乾燥すると、２−（ジイソプロピルホスフィノ）ベンゼンスルホン酸：１ａが得られた。収量は２６．８ｇ（７８％）であった。
1Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）：δ 1.25 (d, J = 18.0 Hz, 6H), 1.53 (dd, J = 21.0, 6.6 Hz, 6H), 3.45 (br, 2H), 5.72 (br d, 1JPH = 380 Hz, 1H), 7.62-7.65 (m, 2H), 7.85 (br s, 1H), 8.29 (br s, 1H)。
Synthesis example 1:
Metal complex catalyst 1 was synthesized according to the following reaction scheme.
Under a nitrogen atmosphere, n-butyllithium (manufactured by Kanto Chemical Co., Ltd., 1.57 M hexane solution, 174 mL) was added to a tetrahydrofuran (THF) solution (400 mL) of benzenesulfonic acid (Sigma-Aldrich, 21.7 g, 137 mmol). , 274 mmol) at 0 ° C. and stirred at room temperature for 3 hours. After cooling the reaction vessel to −78 ° C., chlorodiisopropylphosphine (Sigma-Aldrich, 19.0 g, 125 mmol) was added at −78 ° C., and the mixture was stirred at room temperature for 2.5 hours. After stopping the reaction with trifluoroacetic acid (Tokyo Chemical Industry Co., Ltd., 15.6 g, 137 mmol), the resulting precipitate was collected by filtration and dried under reduced pressure to give 2- (diisopropylphosphino) benzenesulfonic acid: 1a was gotten. The yield was 26.8 g (78%).
1 H-NMR (400 MHz, CDCl 3 ): δ 1.25 (d, J = 18.0 Hz, 6H), 1.53 (dd, J = 21.0, 6.6 Hz, 6H), 3.45 (br, 2H), 5.72 (br d, 1 J PH = 380 Hz, 1H), 7.62-7.65 (m, 2H), 7.85 (br s, 1H), 8.29 (br s, 1H).
［化合物１ｂの合成］
アルゴン雰囲気下、２−（ジイソプロピルホスフィノ）ベンゼンスルホン酸（2-(diisopropylphosphino)benzenesulfonic acid）：１ａ（１６．３ｇ，５９．３ｍｍｏｌ）とジイソプロピルエチルアミン（和光純薬工業(株)製、３８．３ｇ，２９６ｍｍｏｌ）の塩化メチレン溶液（２００ｍＬ）に、(cod)ＰｄＭｅＣｌ（文献：Inorg. Chem., 1993, 32, 5769-5778に従って合成。cod＝１，５−シクロオクタジエン、１６．３ｇ，６１．５ｍｍｏｌ）の塩化メチレン溶液（７５ｍＬ）を加え、室温で２．５時間撹拌した。その後、溶液を濃縮した。1Ｈ−ＮＭＲスペクトルによりその残渣が化合物１ｂであると決定し、その質量は３３．７ｇ（＞９９％）であった。
1Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）：δ 0.69 (s, 3H, PdCH3), 1.19-1.45 (m, 27H), 2.53(sept, J = 7.1 Hz, 2H), 3.18 (br., 2H, HNCH2CH3), 3.82 (br., 2H, HNCH(CH3)2), 7.42-7.59 (m, 3H), 8.22 (d, J = 3.6 Hz, 1H), 9.37 (br s, 1H, NH)。
[Synthesis of Compound 1b]
Under an argon atmosphere, 2- (diisopropylphosphino) benzenesulfonic acid: 1a (16.3 g, 59.3 mmol) and diisopropylethylamine (manufactured by Wako Pure Chemical Industries, 38.3 g) , 296 mmol) in methylene chloride solution (200 mL), synthesized according to (cod) PdMeCl (literature: Inorg. Chem., 1993, 32, 5769-5778. Cod = 1,5-cyclooctadiene, 16.3 g, 61. 5 mmol) in methylene chloride (75 mL) was added and stirred at room temperature for 2.5 hours. The solution was then concentrated. The residue was determined to be compound 1b by 1 H-NMR spectrum and its mass was 33.7 g (> 99%).
1 H-NMR (400 MHz, CDCl 3 ): δ 0.69 (s, 3H, PdCH 3 ), 1.19-1.45 (m, 27H), 2.53 (sept, J = 7.1 Hz, 2H), 3.18 (br., 2H, HNCH 2 CH 3 ), 3.82 (br., 2H, HNCH (CH 3 ) 2 ), 7.42-7.59 (m, 3H), 8.22 (d, J = 3.6 Hz, 1H), 9.37 (br s, 1H, NH ).
［金属錯体触媒１の合成］
窒素雰囲気下、炭酸カリウム（８０．８ｇ，５８５ｍｍｏｌ）と２，６−ルチジン（東京化成工業(株)製、６２．７ｇ，５８５ｍｍｏｌ）の塩化メチレン懸濁液（５００ｍＬ）に、錯体１b（３３．７ｇ，５８．５ｍｍｏｌ）の塩化メチレン溶液（２００ｍＬ）を加え、室温で２．５時間撹拌した。溶媒を減圧下留去して残った固体を塩化メチレンで抽出した。抽出液をセライト（乾燥珪藻土）でろ過し、ゆっくりとヘキサン（２００ｍＬ）中に加えた。生じた金属錯体触媒１をろ過によって回収し、ヘキサンで洗浄した後に減圧下乾燥した。収量は２７．６ｇ（９４％）であった。
1Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ3）：δ 0.35 (s, 3H, PdCH3), 1.28 (dd, J = 14.8, 6.8 Hz, 6H), 1.36 (dd, J = 17.4, 6.6 Hz, 6H), 2.54-2.63 (m, 2H), 3.18 (s, 6H, CH3 of lutidine), 7.13 (d, J = 7.2 Hz, 2H), 7.45-7.61 (m, 4H), 8.31 (m, 1H)。
[Synthesis of Metal Complex Catalyst 1]
To a methylene chloride suspension (500 mL) of potassium carbonate (80.8 g, 585 mmol) and 2,6-lutidine (produced by Tokyo Chemical Industry Co., Ltd., 62.7 g, 585 mmol) in a nitrogen atmosphere, complex 1b (33. (7 g, 58.5 mmol) in methylene chloride (200 mL) was added, and the mixture was stirred at room temperature for 2.5 hours. The solvent was distilled off under reduced pressure, and the remaining solid was extracted with methylene chloride. The extract was filtered through celite (dry diatomaceous earth) and slowly added into hexane (200 mL). The resulting metal complex catalyst 1 was collected by filtration, washed with hexane, and then dried under reduced pressure. The yield was 27.6 g (94%).
1 H-NMR (400 MHz, CDCl 3 ): δ 0.35 (s, 3H, PdCH 3 ), 1.28 (dd, J = 14.8, 6.8 Hz, 6H), 1.36 (dd, J = 17.4, 6.6 Hz, 6H), 2.54-2.63 (m, 2H), 3.18 (s, 6H, CH 3 of lutidine), 7.13 (d, J = 7.2 Hz, 2H), 7.45-7.61 (m, 4H), 8.31 (m, 1H).
実施例１：
表１に示した濃度の酢酸、アリルアルコール、水を含む酢酸アリルを用いて、エチレンとの共重合反応を行なった。
窒素雰囲気下、金属錯体触媒１（０．０２０ｍｍｏｌ）を酢酸アリル（３００ｍＬ，２７９ｇ，２７８７ｍｍｏｌ）に溶解し、容器内部を十分乾燥し、窒素雰囲気下にした５００ｍＬオートクレーブに投入した。オートクレーブを撹拌し、温度８０℃で圧力が４．０ＭＰａで安定するまでエチレンを充填した後、２４時間共重合反応を行った。反応終了後、エチレンを脱圧し、重合反応液を室温まで冷却すると、重合体が反応液から析出した。重合体のスラリー溶液である反応液を、吸引ろ過することで、重合体を回収し、減圧下乾燥した。
重合体の収量は１７．８ｇ、触媒あたり、単位時間あたりの重合活性は、３７．１ｇ／（ｍｍｏｌ−ｃａｔ・ｈ）であった。また、重合体の酢酸アリル含有率は４．４ｍｏｌ％であり、数平均分子量１０，０００、重量平均分子量２１，０００であった。
Example 1:
A copolymerization reaction with ethylene was performed using acetic acid, allyl alcohol, and allyl acetate containing water at the concentrations shown in Table 1.
Under a nitrogen atmosphere, the metal complex catalyst 1 (0.020 mmol) was dissolved in allyl acetate (300 mL, 279 g, 2787 mmol), and the inside of the container was sufficiently dried and put into a 500 mL autoclave under a nitrogen atmosphere. The autoclave was stirred and charged with ethylene until the pressure was stabilized at 4.0 MPa at a temperature of 80 ° C., and then a copolymerization reaction was performed for 24 hours. After completion of the reaction, ethylene was depressurized and the polymerization reaction solution was cooled to room temperature, whereby a polymer was precipitated from the reaction solution. The polymer was recovered by suction filtration of the reaction solution, which was a slurry solution of the polymer, and dried under reduced pressure.
The yield of the polymer was 17.8 g, and the polymerization activity per unit time per unit time was 37.1 g / (mmol-cat · h). Further, the allyl acetate content of the polymer was 4.4 mol%, the number average molecular weight was 10,000, and the weight average molecular weight was 21,000.
実施例２〜５：
実施例１で用いた酢酸アリルに試薬のアリルアルコール、酢酸および／または水を加え、表１に示した濃度の酢酸、アリルアルコール、水を含む酢酸アリルを用いたこと以外は、実施例１と同様にして酢酸アリルとエチレンとの共重合反応を行なった。結果を表１に示す。
Examples 2-5:
Example 1 except that the reagents allyl alcohol, acetic acid and / or water were added to allyl acetate used in Example 1 and allyl acetate containing acetic acid, allyl alcohol and water having the concentrations shown in Table 1 was used. Similarly, a copolymerization reaction between allyl acetate and ethylene was carried out. The results are shown in Table 1.
実施例６：
実施例４で用いた、アリルアルコール、酢酸および水を含む酢酸アリル５００ｍＬにモレキュラシーブス１３Ｘを５０ｇ加え、適宜撹拌しながら、９日間放置した。放置後のアリルアルコール、酢酸および水の酢酸アリル中の濃度を表１に示す。アリルアルコール濃度は変化無いが、酢酸と水の濃度は低下した。このようにして前処理した酢酸アリルを用いた以外は、実施例４と同じようにしてエチレンとの共重合反応を行なった。結果は表１に示す。モレキュラシーブス１３Ｘにより前処理することにより、更に活性が高くなった。
Example 6:
50 g of molecular sieves 13X was added to 500 mL of allyl acetate containing allyl alcohol, acetic acid and water used in Example 4, and the mixture was allowed to stand for 9 days with appropriate stirring. Table 1 shows the concentrations of allyl alcohol, acetic acid and water in allyl acetate after standing. The allyl alcohol concentration did not change, but the acetic acid and water concentrations decreased. A copolymerization reaction with ethylene was performed in the same manner as in Example 4 except that allyl acetate pretreated in this way was used. The results are shown in Table 1. The activity was further increased by pretreatment with molecular sieves 13X.
比較例１：
実施例１で用いた酢酸アリルにアリルアルコール、酢酸および水をさらに加え、表１に示す濃度の酢酸、アリルアルコール、水を含む酢酸アリルを用いたこと以外は、実施例１と同じようにしてエチレンとの共重合反応を行なった。結果を表１に示す。
Comparative Example 1:
In the same manner as in Example 1, except that allyl alcohol, acetic acid and water were further added to allyl acetate used in Example 1, and allyl acetate containing acetic acid, allyl alcohol and water having the concentrations shown in Table 1 was used. A copolymerization reaction with ethylene was carried out. The results are shown in Table 1.
比較例２：
市販の酢酸アリル（東京化成工業(株)製，アリルアルコール、酢酸および水の濃度は表１に示す。）を用いたこと以外は、実施例１と同じようにしてエチレンとの共重合反応を行なった。結果を表１に示す。
Comparative Example 2:
A copolymerization reaction with ethylene was carried out in the same manner as in Example 1 except that commercially available allyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd., allyl alcohol, acetic acid and water concentrations are shown in Table 1) was used. I did it. The results are shown in Table 1.
Claims (7)
で示される金属錯体を触媒として使用し、一般式（１）
で示されるカルボン酸エステルモノマーを単独であるいは２種以上を組み合わせて重合するか、または前記一般式（１）で示されるカルボン酸エステルモノマーとオレフィンとを共重合する方法において、重合系内の液相に含まれる、（Ａ）一般式（２）
で示されるアルコール化合物の濃度が５００ｗｔｐｐｍ以下、（Ｂ）一般式（３）
で示されるカルボン酸化合物の濃度が２００ｗｔｐｐｍ以下、（Ｃ）水の濃度が５０ｗｔｐｐｍ以下である、前記条件（Ａ）〜（Ｃ）の少なくとも１つを満足することを特徴とする重合体の製造方法。 General formula (C3)
As a catalyst, a metal complex represented by the general formula (1)
In the method of polymerizing the carboxylic acid ester monomer represented by the formula (1) alone or in combination of two or more, or copolymerizing the carboxylic acid ester monomer represented by the general formula (1) and the olefin, the liquid in the polymerization system (A) General formula (2) contained in the phase
(B) General formula (3)
And (C) the concentration of water is 50 wtppm or less, and satisfies the at least one of the above conditions (A) to (C). .
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