JP7447485B2 - Method for producing highly polymerizable N-vinylcarboxylic acid amide monomer - Google Patents
Method for producing highly polymerizable N-vinylcarboxylic acid amide monomer Download PDFInfo
- Publication number
- JP7447485B2 JP7447485B2 JP2019236147A JP2019236147A JP7447485B2 JP 7447485 B2 JP7447485 B2 JP 7447485B2 JP 2019236147 A JP2019236147 A JP 2019236147A JP 2019236147 A JP2019236147 A JP 2019236147A JP 7447485 B2 JP7447485 B2 JP 7447485B2
- Authority
- JP
- Japan
- Prior art keywords
- acid amide
- vinylcarboxylic acid
- amide monomer
- mass
- monomer
- 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.)
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- 239000000178 monomer Substances 0.000 title claims description 133
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 title claims description 95
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 69
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 claims description 42
- 238000002425 crystallisation Methods 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 31
- 230000008025 crystallization Effects 0.000 claims description 30
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 21
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- GORGQKRVQGXVEB-UHFFFAOYSA-N n-ethenyl-n-ethylacetamide Chemical compound CCN(C=C)C(C)=O GORGQKRVQGXVEB-UHFFFAOYSA-N 0.000 claims description 2
- DFMIMUDDPBAKFS-UHFFFAOYSA-N n-ethenyl-n-ethylformamide Chemical compound CCN(C=C)C=O DFMIMUDDPBAKFS-UHFFFAOYSA-N 0.000 claims description 2
- PNLUGRYDUHRLOF-UHFFFAOYSA-N n-ethenyl-n-methylacetamide Chemical compound C=CN(C)C(C)=O PNLUGRYDUHRLOF-UHFFFAOYSA-N 0.000 claims description 2
- OFESGEKAXKKFQT-UHFFFAOYSA-N n-ethenyl-n-methylformamide Chemical compound C=CN(C)C=O OFESGEKAXKKFQT-UHFFFAOYSA-N 0.000 claims description 2
- XHLDCMPNOQBZQH-UHFFFAOYSA-N n-ethenylbenzamide Chemical compound C=CNC(=O)C1=CC=CC=C1 XHLDCMPNOQBZQH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000001953 recrystallisation Methods 0.000 description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 239000003505 polymerization initiator Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 239000012264 purified product Substances 0.000 description 8
- -1 2-ethylhexyl Chemical group 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- RYGPJMDKDKHOTB-UHFFFAOYSA-N n-(1-methoxyethyl)acetamide Chemical compound COC(C)NC(C)=O RYGPJMDKDKHOTB-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- KMLONCKJQMYVCO-UHFFFAOYSA-N n-buta-1,3-dienylacetamide Chemical compound CC(=O)NC=CC=C KMLONCKJQMYVCO-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000013268 sustained release Methods 0.000 description 2
- 239000012730 sustained-release form Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- BOVQCIDBZXNFEJ-UHFFFAOYSA-N 1-chloro-3-ethenylbenzene Chemical compound ClC1=CC=CC(C=C)=C1 BOVQCIDBZXNFEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- CGRKYGKHZOCPSZ-UHFFFAOYSA-N 2-methylpropanediamide Chemical compound NC(=O)C(C)C(N)=O CGRKYGKHZOCPSZ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QJCAFILOSPAUEZ-UHFFFAOYSA-N 3-methylidenepent-4-enamide Chemical compound NC(=O)CC(=C)C=C QJCAFILOSPAUEZ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 241000792859 Enema Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- LBSPZZSGTIBOFG-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;dihydrochloride Chemical compound Cl.Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 LBSPZZSGTIBOFG-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013267 controlled drug release Methods 0.000 description 1
- 239000003405 delayed action preparation Substances 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229940039227 diagnostic agent Drugs 0.000 description 1
- 239000000032 diagnostic agent Substances 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000007920 enema Substances 0.000 description 1
- 229940095399 enema Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000002979 fabric softener Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 238000005259 measurement Methods 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- NZGMXBADPHMBCL-UHFFFAOYSA-N n-buta-1,3-dienylformamide Chemical compound C=CC=CNC=O NZGMXBADPHMBCL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-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
- 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
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法に関する。さらに詳しくは、重合性が改善されたＮ－ビニルカルボン酸アミド単量体の生産性を高く製造する方法に関する。 The present invention relates to a method for producing a highly polymerizable N-vinylcarboxylic acid amide monomer. More specifically, the present invention relates to a highly productive method for producing N-vinylcarboxylic acid amide monomers with improved polymerizability.
Ｎ－ビニルカルボン酸アミドから誘導されるＮ－ビニルカルボン酸アミドポリマーは水溶性高分子であり、水だけでなく、アルコールやジメチルスルホキシド（ＤＭＳＯ）といった極性溶媒にも溶解する。そして、非イオン性ポリマーであるため塩やｐＨの影響を受けず、また耐候性が高く、特に熱に対する安定性が高いという特性を有する。これらの特性を活かし、工業的には、バインダーや分散剤、粘着剤・接着剤、増粘剤、凝集剤などに応用されている。 N-vinylcarboxylic acid amide polymers derived from N-vinylcarboxylic acid amide are water-soluble polymers and are soluble not only in water but also in polar solvents such as alcohol and dimethyl sulfoxide (DMSO). Since it is a nonionic polymer, it is not affected by salt or pH, has high weather resistance, and has particularly high stability against heat. Taking advantage of these properties, it is applied industrially to binders, dispersants, pressure-sensitive adhesives, thickeners, flocculants, etc.
Ｎ－ビニルカルボン酸アミドの製造方法については、これまで多くの方法が提案されている。例えば、カルボン酸アミド、アセトアルデヒド、アルコールを原料として中間体となるＮ－（１－アルコキシエチル）カルボン酸アミドを製造し、その後、熱分解または接触分解により合成する方法などである。
このＮ－ビニルカルボン酸アミドの合成反応中には、Ｎ－ビニルカルボン酸アミドの他に、未反応のＮ－（１－アルコキシエチル）カルボン酸アミドやカルボン酸アミドなどの中間体が含まれる。これらの化合物は沸点、蒸気圧、溶解度などの物性がＮ－ビニルカルボン酸アミドと近く、Ｎ－ビニルカルボン酸アミドを蒸留精製することは困難であった。そこで、Ｎ－ビニルカルボン酸アミドの精製方法についても、提案がされている。
Many methods have been proposed so far for producing N-vinylcarboxylic acid amide. For example, there is a method in which N-(1-alkoxyethyl)carboxylic acid amide is produced as an intermediate using carboxylic acid amide, acetaldehyde, and alcohol as raw materials, and then synthesized by thermal decomposition or catalytic decomposition.
During the synthesis reaction of N-vinylcarboxylic acid amide, intermediates such as unreacted N-(1-alkoxyethyl)carboxylic acid amide and carboxylic acid amide are included in addition to N-vinylcarboxylic acid amide. These compounds have physical properties such as boiling point, vapor pressure, and solubility that are close to those of N-vinylcarboxylic acid amide, and it has been difficult to purify N-vinylcarboxylic acid amide by distillation. Therefore, methods for purifying N-vinylcarboxylic acid amide have also been proposed.
特許２６１９２０４号では、圧力晶析による精製方法が開示されており、高重合性を示すＮ－ビニルカルボン酸アミドが比較的高純度で得られる。しかし、この方法は設備投資が大きく、工業的には大規模生産でないと安価に製品を提供できない問題がある。また、特許５１２６７６４号では、アルコールと脂肪族炭化水素による溶媒晶析法が開示されている。しかし、この溶媒の組み合わせは貧溶媒の使用量が多く、容積効率が低いため生産性が悪い。
またＮ－ビニルカルボン酸アミドの重合阻害物質として、特許第４０９９８３１号公報ではＮ－１，３－ブタジエニルカルボン酸アミドが、国際公開第１７／１４５５６９号では不飽和アルデヒドが特定されているが、上記を取り除いてもなお良好な重合性が得られないケースがあった。
Japanese Patent No. 2619204 discloses a purification method using pressure crystallization, and N-vinylcarboxylic acid amide exhibiting high polymerizability can be obtained with relatively high purity. However, this method requires a large investment in equipment, and there is a problem in that industrially, the product cannot be provided at a low price unless it is produced on a large scale. Furthermore, Japanese Patent No. 5126764 discloses a solvent crystallization method using an alcohol and an aliphatic hydrocarbon. However, this combination of solvents requires a large amount of poor solvent and has low volumetric efficiency, resulting in poor productivity.
Furthermore, as polymerization inhibitors for N-vinylcarboxylic acid amide, N-1,3-butadienylcarboxylic acid amide is specified in Japanese Patent No. 4099831, and unsaturated aldehyde is specified in WO 17/145569. However, even if the above-mentioned factors were removed, there were cases in which good polymerizability could not be obtained.
本発明の課題は、効率的にＮ－ビニルカルボン酸アミドを精製して、高重合性のＮ－ビニルカルボン酸アミド単量体を製造しうる方法を提供することにある。さらには、製造されたＮ－ビニルカルボン酸アミド単量体を用いて高分子量のＮ－ビニルカルボン酸アミドポリマーを製造することにある。 An object of the present invention is to provide a method for efficiently purifying N-vinylcarboxylic acid amide and producing a highly polymerizable N-vinylcarboxylic acid amide monomer. Another object of the present invention is to produce a high molecular weight N-vinylcarboxylic acid amide polymer using the produced N-vinylcarboxylic acid amide monomer.
高重合性のＮ－ビニルカルボン酸アミド単量体の製造方法について鋭意検討した結果、メチルエチルケトンと炭素数６～７の脂肪族炭化水素を用いた溶媒晶析により、高重合性のＮ－ビニルカルボン酸アミド単量体を製造することが可能となることを見出し、本発明を完成するに至った。 As a result of intensive studies on the production method of highly polymerizable N-vinylcarboxylic acid amide monomer, we found that highly polymerizable N-vinylcarboxylic The inventors have discovered that it is possible to produce acid amide monomers, and have completed the present invention.
すなわち、本発明の構成は以下の通りである。
［１］Ｎ－ビニルカルボン酸アミド単量体を８５～９９質量％で含む粗Ｎ－ビニルカルボン酸アミド単量体結晶に、メチルエチルケトンと炭素数６～７の脂肪族炭化水素との混合溶媒に溶解させたのち、溶媒晶析を行い、固液分離して、Ｎ－ビニルカルボン酸アミド単量体精製物を回収する工程を含む、
高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。
［２］前記溶媒晶析工程におけるメチルエチルケトン／Ｎ－ビニルカルボン酸アミド単量体結晶の質量比が、０．０１以上０．５以下であり、
前記溶媒晶析工程における炭素数６～７の脂肪族炭化水素／Ｎ－ビニルカルボン酸アミド単量体結晶の質量比が０．５以上３．０以下であることを特徴とする、［１］に記載の高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。
［３］前記メチルエチルケトンの質量は、前記炭素数６～７の脂肪族炭化水素の質量に対して０．００３～１．０であることを特徴とする、［１］または［２］に記載の高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。
［４］ 前記溶媒晶析が、Ｎ－ビニルカルボン酸アミド単量体結晶をメチルエチルケトンと炭素数６～７の脂肪族炭化水素との混合溶媒に、３０℃～８０℃で溶解した後、－２０℃～２０℃に冷却することで行われる、［１］～［３］のいずれか１項に記載の高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。
［５］ 前記溶媒晶析で使用する炭素数６～７の脂肪族炭化水素が、ノルマルヘキサン、シクロヘキサン、ノルマルヘプタン、シクロへプタンおよびメチルシクロヘキサンから選ばれる少なくとも１つであることを特徴とする、［１］～［４］のいずれか１項に記載の高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。
［６］ 前記溶媒晶析工程で固液分離する方法が、ろ過分離であることを特徴とする、［１］～［５］のいずれか１項に記載の高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。
［７］ 前記Ｎ－ビニルカルボン酸アミド単量体がＮ－ビニルアセトアミド単量体であることを特徴とする、［１］～［５］のいずれか１項に記載の高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。
That is, the configuration of the present invention is as follows.
[1] Crude N-vinylcarboxylic acid amide monomer crystals containing 85 to 99% by mass of N-vinylcarboxylic acid amide monomer are added to a mixed solvent of methyl ethyl ketone and an aliphatic hydrocarbon having 6 to 7 carbon atoms. After dissolving, performing solvent crystallization, solid-liquid separation, and recovering a purified N-vinylcarboxylic acid amide monomer,
A method for producing a highly polymerizable N-vinylcarboxylic acid amide monomer.
[2] The mass ratio of methyl ethyl ketone/N-vinylcarboxylic acid amide monomer crystals in the solvent crystallization step is 0.01 or more and 0.5 or less,
[1] characterized in that the mass ratio of aliphatic hydrocarbon having 6 to 7 carbon atoms/N-vinylcarboxylic acid amide monomer crystals in the solvent crystallization step is 0.5 or more and 3.0 or less. A method for producing a highly polymerizable N-vinylcarboxylic acid amide monomer as described in .
[3] The method according to [1] or [2], wherein the mass of the methyl ethyl ketone is 0.003 to 1.0 with respect to the mass of the aliphatic hydrocarbon having 6 to 7 carbon atoms. A method for producing a highly polymerizable N-vinylcarboxylic acid amide monomer.
[4] In the solvent crystallization, N-vinylcarboxylic acid amide monomer crystals are dissolved in a mixed solvent of methyl ethyl ketone and an aliphatic hydrocarbon having 6 to 7 carbon atoms at 30 to 80 °C, and then -20 The method for producing a highly polymerizable N-vinylcarboxylic acid amide monomer according to any one of [1] to [3], which is carried out by cooling to 20°C to 20°C.
[5] The aliphatic hydrocarbon having 6 to 7 carbon atoms used in the solvent crystallization is at least one selected from normal hexane, cyclohexane, normal heptane, cycloheptane, and methylcyclohexane, The method for producing a highly polymerizable N-vinylcarboxylic acid amide monomer according to any one of [1] to [4].
[6] The highly polymerizable N-vinylcarboxylic acid amide according to any one of [1] to [5], wherein the solid-liquid separation method in the solvent crystallization step is filtration separation. Method for producing monomers.
[7] The highly polymerizable N-vinyl according to any one of [1] to [5], wherein the N-vinylcarboxylic acid amide monomer is an N-vinylacetamide monomer. A method for producing a carboxylic acid amide monomer.
本発明によれば、従来よりも生産性に優れた高重合性Ｎ－ビニルカルボン酸アミド単量体を製造することが出来る。 According to the present invention, a highly polymerizable N-vinylcarboxylic acid amide monomer can be produced with higher productivity than ever before.
本発明を実施するための方法は、次の工程を含む。
Ｎ－ビニルカルボン酸アミド単量体を８５～９９質量％で含む粗Ｎ－ビニルカルボン酸アミド単量体結晶に、メチルエチルケトンと炭素数６～７の脂肪族炭化水素との混合溶媒に溶解させたのち、溶媒晶析を行い、固液分離して、Ｎ－ビニルカルボン酸アミド単量体精製物を回収する工程。
A method for carrying out the invention includes the following steps.
A crude N-vinylcarboxylic acid amide monomer crystal containing 85 to 99% by mass of N-vinylcarboxylic acid amide monomer was dissolved in a mixed solvent of methyl ethyl ketone and an aliphatic hydrocarbon having 6 to 7 carbon atoms. Thereafter, a step of performing solvent crystallization and solid-liquid separation to recover a purified N-vinylcarboxylic acid amide monomer.
なお、本明細書において、「粗Ｎ－ビニルカルボン酸アミド単量体」とは、Ｎ－ビニルカルボン酸アミド単量体からなる成分とともに、不純物を含むことを意味し、すなわち「精製されていない」Ｎ－ビニルカルボン酸アミド単量体である。 In addition, in this specification, "crude N-vinylcarboxylic acid amide monomer" means that it contains impurities as well as a component consisting of N-vinylcarboxylic acid amide monomer, that is, "crude N-vinylcarboxylic acid amide monomer" ” is an N-vinylcarboxylic acid amide monomer.
Ｎ－ビニルカルボン酸アミド単量体は、例えばＮ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－メチル－Ｎ－ビニルアセトアミド、Ｎ－ビニルベンズアミド、Ｎ－ビニル－Ｎ－メチルホルムアミド、Ｎ－ビニル－Ｎ－エチルホルムアミド、Ｎ－ビニル－Ｎ－エチルアセトアミド、Ｎ－ビニルピロリドンが挙げられる。好ましくは、Ｎ－ビニルアセトアミドである。 N-vinylcarboxylic acid amide monomers include, for example, N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylbenzamide, N-vinyl-N-methylformamide, N-vinyl-N -ethylformamide, N-vinyl-N-ethylacetamide, and N-vinylpyrrolidone. Preferably it is N-vinylacetamide.
上記粗Ｎ－ビニルカルボン酸アミド単量体は、いずれの製造方法によって得たものでもよい。例えば、カルボン酸アミド、アセトアルデヒドおよびアルコールからＮ－(１－アルコキシエチル)カルボン酸アミドを合成し、これを熱分解または接触分解して得たものであってもよい（特開昭５０－７６０１５号公報参照）。また、カルボン酸アミドとアセトアルデヒドとからエチリデンビスカルボン酸アミドを合成し、これを熱分解して得たものであってもよい（特開昭６１－１０６５４６号公報参照）。
粗Ｎ－ビニルカルボン酸アミド単量体に含まれるＮ－ビニルカルボン酸アミド単量体以外のものとしては、主に、Ｎ－（１－アルコキシエチル）カルボン酸アミド、カルボン酸アミド、炭素数１～５のアルコールなどが含まれ、これらは、Ｎ－ビニルカルボン酸アミド単量体の製造方法などに由来する不純物である。
The crude N-vinylcarboxylic acid amide monomer may be obtained by any production method. For example, it may be obtained by synthesizing N-(1-alkoxyethyl)carboxylic acid amide from carboxylic acid amide, acetaldehyde and alcohol, and then thermally decomposing or catalytically decomposing it (JP-A-50-76015). (see official bulletin). Alternatively, it may be obtained by synthesizing ethylidene biscarboxylic acid amide from carboxylic acid amide and acetaldehyde and thermally decomposing it (see JP-A-61-106546).
Other than N-vinylcarboxylic acid amide monomer contained in the crude N-vinylcarboxylic acid amide monomer, N-(1-alkoxyethyl)carboxylic acid amide, carboxylic acid amide, carbon number 1 -5 alcohols are included, and these are impurities derived from the manufacturing method of N-vinylcarboxylic acid amide monomer.
上記粗Ｎ－ビニルカルボン酸アミド単量体は、Ｎ－ビニルカルボン酸アミド単量体を８５～９９質量％の量で含み、好ましくは９０～９８質量％で含み、より好ましくは９２～９８質量％で含むことが望ましい。Ｎ－ビニルカルボン酸アミド単量体がこの範囲で含まれている場合は、Ｎ－ビニルカルボン酸アミド単量体の回収率を高くでき、得られたＮ－ビニルカルボン酸アミド単量体は純度が高く、優れた重合性を示すために望ましい。上記粗Ｎ－ビニルカルボン酸アミド単量体に含まれるＮ－ビニルカルボン酸アミド単量体の量が５０～８５質量％の範囲の場合は、適宜、晶析、蒸留、抽出などの操作によって、Ｎ－ビニルカルボン酸アミド単量体の含有量を調整してもよい。またこのような操作で、粗Ｎ－ビニルカルボン酸アミド単量体中の不溶成分を予め除去することもできる。 The crude N-vinylcarboxylic acid amide monomer contains N-vinylcarboxylic acid amide monomer in an amount of 85 to 99% by weight, preferably 90 to 98% by weight, more preferably 92 to 98% by weight. It is desirable to include it in %. When the N-vinylcarboxylic acid amide monomer is contained within this range, the recovery rate of the N-vinylcarboxylic acid amide monomer can be increased, and the obtained N-vinylcarboxylic acid amide monomer has a high purity. is desirable because it has a high polymerizability and exhibits excellent polymerizability. When the amount of N-vinylcarboxylic acid amide monomer contained in the above-mentioned crude N-vinylcarboxylic acid amide monomer is in the range of 50 to 85% by mass, it can be prepared by appropriate operations such as crystallization, distillation, extraction, etc. The content of N-vinylcarboxylic acid amide monomer may be adjusted. In addition, insoluble components in the crude N-vinylcarboxylic acid amide monomer can also be removed in advance by such an operation.
通常、公知の製造方法で得られる粗Ｎ－ビニルカルボン酸アミド単量体中のＮ－ビニルカルボン酸アミド単量体の含有量の上限は、前記範囲にあるが、この上限より高い粗Ｎ－ビニルカルボン酸アミド単量体を本発明の製造方法で処理しても、Ｎ－ビニルカルボン酸アミド単量体の精製物を得ることは可能である。 Usually, the upper limit of the content of N-vinylcarboxylic acid amide monomer in the crude N-vinylcarboxylic acid amide monomer obtained by a known production method is within the above range, but the content of crude N- Even if vinylcarboxylic acid amide monomer is treated by the production method of the present invention, it is possible to obtain a purified product of N-vinylcarboxylic acid amide monomer.
溶媒晶析工程
溶媒晶析工程では、回収したＮ－ビニルカルボン酸アミド単量体結晶を、晶析溶媒であるメチルエチルケトンに、貧溶媒である炭素数６～７の脂肪族炭化水素の存在下に溶解させたのち、晶析させる。回収したＮ－ビニルカルボン酸アミド単量体結晶は、Ｎ－ビニルカルボン酸アミド単量体を８８質量％以上の量で含み、好ましくは９０質量％以上、さらに好ましくは９２質量％以上の量で含むものが望ましい。Ｎ－ビニルカルボン酸アミド単量体結晶は、Ｎ－ビニルカルボン酸アミド単量体以外に、前記晶析母液や、リンズに用いた母液を含むことがある。
Solvent crystallization process In the solvent crystallization process, the recovered N-vinylcarboxylic acid amide monomer crystals are added to methyl ethyl ketone, which is a crystallization solvent, in the presence of an aliphatic hydrocarbon having 6 to 7 carbon atoms, which is a poor solvent. After dissolving, crystallize. The recovered N-vinylcarboxylic acid amide monomer crystals contain N-vinylcarboxylic acid amide monomer in an amount of 88% by mass or more, preferably 90% by mass or more, more preferably 92% by mass or more. It is desirable to include. The N-vinylcarboxylic acid amide monomer crystals may contain, in addition to the N-vinylcarboxylic acid amide monomer, the crystallization mother liquor or the mother liquor used in the rinse.
使用するメチルエチルケトンの質量は、使用するＮ－ビニルカルボン酸アミド単量体結晶の質量に対し、好ましくは０．０１以上０．５以下の比率であり、より好ましくは、０．０２～０．４、更に好ましくは０．０３～０．３である。
また、使用する炭素数６～７の脂肪族炭化水素としては、ノルマルヘキサン、シクロヘキサン、メチルシクロヘキサン、ノルマルヘプタン、シクロヘプタンが好ましく、さらに好ましくは、シクロヘキサン、メチルシクロヘキサンが挙げられる。炭素数が５以下の脂肪族炭化水素は沸点が低いため取扱いが難しく、炭素数が８以上の脂肪族炭化水素は沸点が高くなり、結晶から除去しきれない場合がある。また、炭素数６～７の脂肪族炭化水素の質量は、使用するＮ－ビニルカルボン酸アミド単量体結晶の質量に対し、好ましくは０．５以上３．０以下の比率であり、より好ましくは０．５～２．０であることが好ましい。この比率の範囲にあると、Ｎ－ビニルカルボン酸アミド単量体の再結晶が充分に析出するとともに、溶媒使用量が多くならず、晶析装置の容積効率を高くできるので望ましい。
使用するメチルエチルケトンの質量は、使用する炭素数６～７の脂肪族炭化水素の質量に対して０．００３～１．０が好ましく、０．００５～０．８がより好ましく、０．０１～０．５がさらに好ましい。
The mass of methyl ethyl ketone used is preferably in a ratio of 0.01 to 0.5, more preferably 0.02 to 0.4, to the mass of the N-vinylcarboxylic acid amide monomer crystal used. , more preferably from 0.03 to 0.3.
The aliphatic hydrocarbon having 6 to 7 carbon atoms to be used is preferably normal hexane, cyclohexane, methylcyclohexane, normal heptane, or cycloheptane, and more preferably cyclohexane or methylcyclohexane. Aliphatic hydrocarbons with carbon numbers of 5 or less have low boiling points and are difficult to handle, while aliphatic hydrocarbons with carbon numbers of 8 or more have high boiling points and may not be completely removed from the crystals. Furthermore, the mass of the aliphatic hydrocarbon having 6 to 7 carbon atoms is preferably in a ratio of 0.5 to 3.0, more preferably 0.5 to 3.0, to the mass of the N-vinylcarboxylic acid amide monomer crystal used. is preferably 0.5 to 2.0. When the ratio is within this range, the N-vinylcarboxylic acid amide monomer is sufficiently recrystallized, the amount of solvent used is not increased, and the volumetric efficiency of the crystallizer can be increased, which is desirable.
The mass of methyl ethyl ketone used is preferably 0.003 to 1.0, more preferably 0.005 to 0.8, and more preferably 0.01 to 0, relative to the mass of the aliphatic hydrocarbon having 6 to 7 carbon atoms. .5 is more preferred.
Ｎ－ビニルカルボン酸アミド単量体結晶を溶解する温度は３０～８０℃が好ましく、より好ましくは３０～６０℃、さらに好ましくは３５～４５℃である。この温度範囲では、Ｎ－ビニルカルボン酸アミドが変性することなく、十分に溶解するため望ましい。
次いで、溶解したＮ－ビニルカルボン酸アミド単量体を冷却して再結晶を析出させる。この冷却温度は－２０℃～２０℃が好ましく、より好ましくは－１５～１５℃、さらに好ましくは－１０℃～１０℃である。この温度範囲にあれば、設備的なコストが小さく、かつ晶析収率が十分となり、望ましい。
Ｎ－ビニルカルボン酸アミド単量体の再結晶を回収して、Ｎ－ビニルカルボン酸アミド単量体精製物が製造される。
The temperature at which the N-vinylcarboxylic acid amide monomer crystals are dissolved is preferably 30 to 80°C, more preferably 30 to 60°C, and still more preferably 35 to 45°C. This temperature range is desirable because the N-vinylcarboxylic acid amide is sufficiently dissolved without being denatured.
Next, the dissolved N-vinylcarboxylic acid amide monomer is cooled to precipitate recrystallization. The cooling temperature is preferably -20°C to 20°C, more preferably -15°C to 15°C, even more preferably -10°C to 10°C. This temperature range is desirable because equipment costs are low and the crystallization yield is sufficient.
The recrystallized N-vinylcarboxylic acid amide monomer is recovered to produce a purified N-vinylcarboxylic acid amide monomer.
溶媒晶析工程で析出したＮ－ビニルカルボン酸アミド単量体の再結晶を効率よく分離する方法としては、ろ過による分離が好ましい。ろ過による方法に制限はないが、晶析母液との分離や生産性の観点で、遠心分離ろ過や加圧ろ過などが好ましい。また、ろ過後にリンズを行うことも母液との分離性を向上させる上で好ましい。リンズに用いる溶媒としては、晶析溶媒と同様のメチルエチルケトンと炭素数６～７の脂肪族炭化水素が好ましい。リンズに使用するメチルエチルケトンの質量は、工程（Ａ）から回収したＮ－ビニルカルボン酸アミド単量体結晶の質量に対し、０．０１～０．３の比率で使用することが好ましく、より好ましくは０．０１～０．２、さらに好ましくは０．０２～０．１である。また、リンズに使用する炭素数６～７の脂肪族炭化水素の質量は工程（Ａ）から回収したＮ－ビニルカルボン酸アミド単量体結晶の質量に対し、０．１～３．０の比率で使用することが好ましく、より好ましくは０．１～２．０、さらに好ましくは０．１～１．５が好ましい。 As a method for efficiently separating the recrystallized N-vinylcarboxylic acid amide monomer precipitated in the solvent crystallization step, separation by filtration is preferred. Although there are no restrictions on the method of filtration, centrifugal filtration, pressure filtration, etc. are preferred from the viewpoint of separation from the crystallization mother liquor and productivity. It is also preferable to perform rinsing after filtration in order to improve separation from the mother liquor. As the solvent used for the rinse, methyl ethyl ketone, which is the same as the crystallization solvent, and aliphatic hydrocarbons having 6 to 7 carbon atoms are preferred. The mass of methyl ethyl ketone used in the rinse is preferably used in a ratio of 0.01 to 0.3, more preferably It is 0.01 to 0.2, more preferably 0.02 to 0.1. In addition, the mass of the aliphatic hydrocarbon having 6 to 7 carbon atoms used for the rinds is in a ratio of 0.1 to 3.0 to the mass of the N-vinylcarboxylic acid amide monomer crystals recovered from step (A). It is preferable to use it, more preferably from 0.1 to 2.0, even more preferably from 0.1 to 1.5.
こうして製造された高重合性Ｎ－ビニルカルボン酸アミド単量体は、純度が高く、高い重合性を備えている。 The highly polymerizable N-vinylcarboxylic acid amide monomer thus produced has high purity and high polymerizability.
溶媒晶析工程で回収された母液には、アルコール、カルボン酸アミド、Ｎ－(１－アルコキシエチル)カルボン酸アミドなど、Ｎ－ビニルカルボン酸アミド単量体の合成原料が含まれている。これらを粗Ｎ－ビニルカルボン酸アミド単量体の製造工程、例えば、Ｎ－(１－アルコキシエチル)カルボン酸アミドの合成工程などに回送して再利用してもよい。
こうして製造された高重合性Ｎ－ビニルカルボン酸アミド単量体は、適宜重合されて使用できる。たとえば、上記の製造方法によって得られた高純度Ｎ－ビニルカルボン酸アミド単量体を含む単量体を重合して得られる単独重合体、またはＮ－ビニルカルボン酸アミド単量体と他の単量体とを重合して得られる共重合体などとして利用できる。これらの（共）重合体は水溶性であり、種々の用途に用いられる。
The mother liquor recovered in the solvent crystallization step contains raw materials for the synthesis of N-vinylcarboxylic acid amide monomers, such as alcohol, carboxylic acid amide, and N-(1-alkoxyethyl)carboxylic acid amide. These may be reused by being sent to the production process of crude N-vinylcarboxylic acid amide monomer, for example, the synthesis process of N-(1-alkoxyethyl)carboxylic acid amide.
The highly polymerizable N-vinylcarboxylic acid amide monomer thus produced can be appropriately polymerized and used. For example, a homopolymer obtained by polymerizing a monomer containing a high-purity N-vinylcarboxylic acid amide monomer obtained by the above production method, or a homopolymer obtained by polymerizing a monomer containing a high-purity N-vinylcarboxylic acid amide monomer and other monomers. It can be used as a copolymer obtained by polymerizing with a polymer. These (co)polymers are water-soluble and are used for various purposes.
上記他の単量体としては、(メタ)アクリル酸またはその塩、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸（イソ）プロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸オクチル、(メタ)アクリル酸２－エチルヘキシル、(メタ)アクリル酸メトキシエチル、２－ヒドロキシエチル(メタ)アクリレート、２－ヒドロキシプロピル(メタ)アクリレート、ポリオキシアルキレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸系単量体；(メタ)アクリルアミド、Ｎ，Ｎ－ジメチル(メタ)アクリルアミド、Ｎ，Ｎ－ジエチル(メタ)アクリルアミド、Ｎ－メチロール(メタ)アクリルアミド、２－(メタ)アクリルアミド－２－メチルプロパンスルホン酸またはその塩、Ｎ－イソプロピル(メタ)アクリルアミド等の(メタ)アクリルアミド系単量体；酢酸ビニル、酪酸ビニル、吉草酸ビニル等のビニルエステル系単量体；スチレン、α－メチルスチレン、p－メチルスチレン、p－メトキシスチレン、ｍ－クロロスチレン等のスチレン系単量体；メチルビニルエーテル、ブチルビニルエーテル、ビニルベンジルエーテル等のビニルエーテル系単量体；無水マレイン酸、マレイン酸またはその塩、フマル酸またはその塩、マレイン酸ジメチルエステル、フマル酸ジエチルエステル等のジカルボン酸系単量体；アリルアルコール、アリルフェニルエーテル、アリルアセテート等のアリル系単量体；(メタ)アクリロニトリル、塩化ビニル、エチレン、プロピレン等の単量体などが挙げられる。 Other monomers mentioned above include (meth)acrylic acid or its salt, methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, butyl (meth)acrylate, ( Octyl meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polyoxyalkylene glycol mono(meth)acrylate (meth)acrylic acid monomers such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methylol(meth)acrylamide, 2-(meth)acrylamide (meth)acrylamide monomers such as acrylamide-2-methylpropanesulfonic acid or its salts, N-isopropyl (meth)acrylamide; vinyl ester monomers such as vinyl acetate, vinyl butyrate, and vinyl valerate; styrene; Styrenic monomers such as α-methylstyrene, p-methylstyrene, p-methoxystyrene, m-chlorostyrene; Vinyl ether monomers such as methyl vinyl ether, butyl vinyl ether, vinyl benzyl ether; maleic anhydride, maleic acid or its salts, dicarboxylic acid monomers such as fumaric acid or its salts, maleic acid dimethyl ester, fumaric acid diethyl ester; allyl monomers such as allyl alcohol, allyl phenyl ether, allyl acetate; (meth)acrylonitrile, Examples include monomers such as vinyl chloride, ethylene, and propylene.
また、上記他の単量体は、単独で用いても、２種類以上組み合わせて用いてもよい。上記他の単量体の量は、共重合体の用途によって適宜決めればよいが、全単量体中、通常６０質量％以下、好ましくは４０質量％以下の量で用いることが望ましい。 Further, the other monomers mentioned above may be used alone or in combination of two or more types. The amount of the above-mentioned other monomers may be appropriately determined depending on the use of the copolymer, but it is desirable to use them in an amount of usually 60% by mass or less, preferably 40% by mass or less based on the total monomers.
本発明の高重合性Ｎ－ビニルカルボン酸アミド単量体を重合する際に、重合開始剤を用いても良い。重合開始剤としては、ビニル化合物のラジカル重合に一般的に使用されるものを限定することなく使用できる。例えば、レドックス系重合開始剤、アゾ化合物系重合開始剤、過酸化物系重合開始剤があげられる。
これらは、１種を単独で使用してもよいし、２種以上を併用してもよい。
上記（共）重合体は、増粘効果、分散効果などの機能を利用して広い分野に好適に用いられる。以下に具体例を例示するが、この限りでない。
A polymerization initiator may be used when polymerizing the highly polymerizable N-vinylcarboxylic acid amide monomer of the present invention. As the polymerization initiator, those commonly used for radical polymerization of vinyl compounds can be used without limitation. Examples include redox polymerization initiators, azo compound polymerization initiators, and peroxide polymerization initiators.
These may be used alone or in combination of two or more.
The above (co)polymers are suitably used in a wide range of fields by utilizing functions such as thickening effect and dispersion effect. Specific examples are illustrated below, but are not limited thereto.
（１）工業用分散剤
例えば、無機・有機の各種粉末の分散剤として用いられる。より具体的には、例えば、シリカ、アルミナ、チタニア、炭酸カルシウム等の無機粉末；タルク、カオリン等の鉱物系粉末；カーボンブラック等の各種顔料粉末；ポリウレタン、ポリアクリル酸エステル、ポリエチレン等の樹脂粉末；ステアリン酸塩等の有機粉末などについて、水などの各種極性溶媒に対する分散剤として用いられる。
(1) Industrial dispersant For example, it is used as a dispersant for various inorganic and organic powders. More specifically, for example, inorganic powders such as silica, alumina, titania, and calcium carbonate; mineral powders such as talc and kaolin; various pigment powders such as carbon black; resin powders such as polyurethane, polyacrylate, and polyethylene. ; Used as a dispersant for various polar solvents such as water for organic powders such as stearate.
（２）塗料、インキなどに用いる増粘剤・分散剤
例えば、塗料、インキなどについて、添料分散剤；粘度、レベリングなどの調整剤；濡れ性改良剤として用いられる。
(2) Thickeners/dispersants used in paints, inks, etc. For example, in paints, inks, etc., they are used as additive dispersants; regulators for viscosity, leveling, etc.; and wettability improvers.
（３）水および油に用いる処理剤・採取剤
（４）化粧品
例えば、シャンプー、リンズ、ローションなどの化粧品について、乳化安定剤、潤滑剤、乳化型化粧料（乳化剤として使用）、皮膜型パック剤、セット剤に用いられる。
(3) Treatment agents and collection agents used for water and oil (4) Cosmetics For example, for cosmetics such as shampoos, rinses, and lotions, emulsion stabilizers, lubricants, emulsion type cosmetics (used as emulsifiers), film type pack agents , used as a setting agent.
（５）トイレタリー製品
例えば、液体洗剤（衣料用、台所用、トイレ・タイル用）、歯磨き、クレンザー、柔軟仕上げ剤、工業用洗浄剤などの増粘剤として用いられる。
(5) Toiletry products For example, it is used as a thickener for liquid detergents (for clothing, kitchen, toilets and tiles), toothpaste, cleansers, fabric softeners, industrial cleaning agents, etc.
（６）粘着剤およびその助剤
（７）メディカル分野
例えば、錠剤（徐放性薬剤）、腸溶性薬剤、パップ剤、プラスター剤等の貼付剤用の基材、外用軟膏剤、薬剤放出制御製剤、胃内浮遊徐放性製剤、粘膜投与製剤、外皮用組成物（医療用フィルム）、創傷被覆保護材、歯科用材料、口腔用吸収剤、歯間清掃具等において、薬剤の保持・徐放のために用いられるほか、消毒用オートクレーブで加熱されて反復使用される尿道カテーテル・浣腸器等の医療器具用潤滑剤、診断薬の粘度調整剤として用いられる。
(6) Adhesives and their auxiliaries (7) Medical field For example, base materials for patches such as tablets (sustained release drugs), enteric-coated drugs, poultices, and plasters, external ointments, and controlled drug release preparations. Retention and sustained release of drugs in gastric floating sustained release preparations, mucosal administration preparations, skin compositions (medical films), wound dressings, dental materials, oral absorbents, interdental cleaning tools, etc. In addition, it is used as a lubricant for medical instruments such as urinary catheters and enema devices that are heated repeatedly in disinfection autoclaves, and as a viscosity adjuster for diagnostic agents.
（８）吸水材、保水剤、シーリング剤、保冷剤
（９）その他
例えば、製紙用処理剤；芳香消臭剤；乾燥剤；発酵助剤；パッキン用材料、古壁等の剥離剤に用いられるほか、玩具、汗取り装身具、超音波探傷用接触媒質、超音波探触子、電池・センサー等の電解質支持体などの増粘剤として用いられる。
(8) Water-absorbing materials, water-retaining agents, sealing agents, cold-packing agents (9) Others For example, used as paper processing agents; aromatic deodorizers; desiccants; fermentation aids; packing materials, stripping agents for old walls, etc. It is also used as a thickener for toys, sweat-removing accessories, couplants for ultrasonic flaw detection, ultrasonic probes, electrolyte supports for batteries, sensors, etc.
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
本発明の製造方法で得られた高重合性Ｎ－ビニルアセトアミド単量体の分析方法を以下に示す。なお分析方法は以下に限定されず、公知の方法を採用することが可能である。
EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.
A method for analyzing the highly polymerizable N-vinylacetamide monomer obtained by the production method of the present invention is shown below. Note that the analysis method is not limited to the following, and any known method may be employed.
・組成分析
実施例・比較例で得られたＮ－ビニルアセトアミド単量体の純度は、以下の条件のＧＣ分析で定量する。
装置：高性能汎用ガスクロマトグラフ「ＧＣ－２０１４」（株式会社島津製作所製）
カラム：ＤＢ－ＷＡＸ（φ０．２５ｍｍ × ３０ｍ、Ａｇｉｌｅｎｔ Ｔｅｃｈｎｏｌｏｇｉｅｓ社製）
キャリアガス種類：Ｈｅ
キャリアガス流量：１ｍＬ／分
スプリット比：４０
カラム温度：４０℃（７分）→昇温（２５℃／分）→１３０℃（１５分）→昇温（３０℃／分）→２２０℃（７分）の順で昇温プログラムを設定
インジェクション温度：２００℃
検出器：水素炎イオン化検出器（ＦＩＤ）
検出器温度：２３０℃
また、Ｎ－ビニルアセトアミド単量体は、高速液体カラムクロマトグラフィー（ＨＰＬＣ）法により、紫外可視分光吸収スペクトルにより確認・同定した。測定条件は次のとおりである。
カラム：昭和電工株式会社製：Ｓｈｏｄｅｘ（登録商標） ＳＩＬ－５Ｂ
溶離液：イソプロピルアルコール（ＩＰＡ）／Ｎ－ヘキサン＝１／９（質量比）
カラム温度：４０℃
流量：１．０ｍＬ／分
検出器：紫外可視分光検出器、２５４ｎｍ
- Composition analysis The purity of the N-vinylacetamide monomer obtained in the Examples and Comparative Examples is determined by GC analysis under the following conditions.
Equipment: High-performance general-purpose gas chromatograph “GC-2014” (manufactured by Shimadzu Corporation)
Column: DB-WAX (φ0.25mm x 30m, manufactured by Agilent Technologies)
Carrier gas type: He
Carrier gas flow rate: 1mL/min Split ratio: 40
Column temperature: Set the temperature increase program in the following order: 40℃ (7 minutes) → Temperature increase (25℃/min) → 130℃ (15 minutes) → Temperature increase (30℃/minute) → 220℃ (7 minutes) Injection Temperature: 200℃
Detector: Flame ionization detector (FID)
Detector temperature: 230℃
Further, the N-vinylacetamide monomer was confirmed and identified by ultraviolet-visible absorption spectrum using high performance liquid column chromatography (HPLC) method. The measurement conditions are as follows.
Column: Showa Denko Co., Ltd.: Shodex (registered trademark) SIL-5B
Eluent: Isopropyl alcohol (IPA)/N-hexane = 1/9 (mass ratio)
Column temperature: 40℃
Flow rate: 1.0 mL/min Detector: UV-visible spectrophotometer, 254 nm
・重合性試験
また、得られたＮ－ビニルアセトアミド単量体精製物の重合性については、次に示す重合性試験により評価を行う。
-Polymerizability test In addition, the polymerizability of the obtained purified N-vinylacetamide monomer is evaluated by the following polymerizability test.
［１］触媒注入管、窒素ガス吹込管、窒素ガス排気管、温度計を備えた、１００ｍｌガラス容器を準備する。
［２］［１］のガラス容器にＮ－ビニルアセトアミド単量体精製物 ２０ｇ、イオン交換水 ５８ｇを秤取る。
［３］窒素ガス５０ｃｍ３／分でバブリングしながらウォーターバスで３０℃に加温する。窒素ガスは重合終了まで通気する。
［４］重合開始剤として、２，２`－アゾビス［２－（２－イミダゾリン―２－イル）プロパン］二塩酸塩（富士フイルム和光純薬株式会社製 Ｖ－０４４）１．６ｇにイオン交換水４８．４ｇを加えて溶解する。
［５］重合開始剤として２，２`－アゾビス（２－メチルプロピオンアミジン）二塩酸塩（富士フイルム和光純薬株式会社製 Ｖ－５０）４．０ｇにイオン交換水４６．０ｇを加えて溶解する。
［６］窒素ガス通気が１時間経過したところで、［４］の重合開始剤溶液 １．０ｇを、続けて［５］の重合開始剤溶液 １．０ｇを注射器により添加する。
［７］ガラス容器をウォーターバスから取り出し、ガラス表面の水分をペーパーで除去してから断熱容器に移し重合を継続させる。
［８］重合温度を監視し、［６］の重合開始剤添加から、標準温度ピーク到達時間（重合開始剤注入から温度ピーク到達までの時間）を重合性の指標とした。重合性の良・不可の判断は、標準温度ピーク到達時間で判断し、１２０分未満を良とする。
[1] Prepare a 100ml glass container equipped with a catalyst injection pipe, a nitrogen gas blowing pipe, a nitrogen gas exhaust pipe, and a thermometer.
[2] Weigh out 20 g of purified N-vinylacetamide monomer and 58 g of ion-exchanged water into the glass container from [1].
[3] Heat to 30° C. in a water bath while bubbling nitrogen gas at 50 cm 3 /min. Nitrogen gas is passed through until the polymerization is completed.
[4] As a polymerization initiator, 1.6 g of 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. V-044) was ion-exchanged. Add 48.4 g of water and dissolve.
[5] As a polymerization initiator, 46.0 g of ion-exchanged water was added to 4.0 g of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-50) and dissolved. do.
[6] After one hour of nitrogen gas aeration, add 1.0 g of the polymerization initiator solution from [4], followed by 1.0 g of the polymerization initiator solution from [5], using a syringe.
[7] Remove the glass container from the water bath, remove moisture on the glass surface with paper, and then transfer to a heat-insulating container to continue polymerization.
[8] The polymerization temperature was monitored, and the time from the addition of the polymerization initiator in [6] to the standard temperature peak arrival time (the time from the polymerization initiator injection to the temperature peak arrival) was used as an index of polymerizability. The judgment of whether the polymerizability is good or bad is made based on the standard temperature peak reaching time, and a time of less than 120 minutes is considered good.
［合成例１］
アセトアルデヒド２２４ｇ、メタノール３２５ｇ、アセトアミド１００ｇを硫酸触媒下、４０℃にて反応させてｐＨ１．２のＮ－（１－メトキシエチル）アセトアミドを合成した。その反応液に４８質量％水酸化ナトリウム水溶液を加えてｐＨ８．３に調整した。その後、単蒸留装置にて温度６０～７０℃、圧力３３ｋＰａ（絶対圧力）で低沸点成分を留去後、温度７０℃、圧力０．３ｋＰａ（絶対圧力）で水及びメタノールを留去し、純度９２質量％のＮ－（１－メトキシエチル）アセトアミドを１５１ｇ得た。
続いて、Ｎ－（１－メトキシエチル）アセトアミドを４００℃、２０ｋＰａ（絶対圧力）に保たれた反応器（内径２０ｍｍ、長さ２４０ｍｍのチューブ型反応器）に、１．５ｇ／分の割合で供給した。反応器出口に設置された冷却管で、熱分解反応で生成したＮ－ビニルアセトアミドとメタノールの混合物を凝縮して、粗Ｎ－ビニルアセトアミド回収物を得た。Ｎ－（１－メトキシエチル）アセトアミドの転化率は９０％であった。
[Synthesis example 1]
N-(1-methoxyethyl)acetamide having a pH of 1.2 was synthesized by reacting 224 g of acetaldehyde, 325 g of methanol, and 100 g of acetamide at 40° C. under a sulfuric acid catalyst. A 48% by mass aqueous sodium hydroxide solution was added to the reaction solution to adjust the pH to 8.3. After that, low boiling point components are distilled off at a temperature of 60 to 70°C and a pressure of 33 kPa (absolute pressure) using a simple distillation apparatus, and then water and methanol are distilled off at a temperature of 70°C and a pressure of 0.3 kPa (absolute pressure) to achieve purity. 151 g of 92% by mass N-(1-methoxyethyl)acetamide was obtained.
Subsequently, N-(1-methoxyethyl)acetamide was added at a rate of 1.5 g/min to a reactor (tubular reactor with an inner diameter of 20 mm and a length of 240 mm) maintained at 400°C and 20 kPa (absolute pressure). supplied. A mixture of N-vinylacetamide and methanol produced by the thermal decomposition reaction was condensed in a cooling pipe installed at the outlet of the reactor to obtain a crude N-vinylacetamide recovery product. The conversion rate of N-(1-methoxyethyl)acetamide was 90%.
次いで０．３％Ｐｄ－Ａｌ２Ｏ３触媒をカラムに充填した（充填量は粗Ｎ－ビニルアセトアミド回収物２０ｇに対して触媒量１ｍｌになる量とした）のち、反応温度４０℃、水素ガス圧力０．０３ＭＰａ（ゲージ圧）、触媒充填カラムでの空間速度（ＳＶ値）が１００／時間になるよう粗Ｎ－ビニルアセトアミド回収物を循環流通し、熱分解反応で副生したＮ－１，３－ブタジエニルアセトアミドを水素化して低減した。
反応時間はＮ－１，３－ブタジエニルアセトアミド量が３０質量ｐｐｍ以下となるまで実施した。Ｎ－１，３－ブタジエニルアセトアミドが低減された粗Ｎ－ビニルアセトアミド回収物を、単蒸留装置を用いて真空度０．３ｋＰａ（絶対圧力）以下、ボトム温度６０℃以下の条件下蒸留しメタノールを除去して、粗Ｎ－ビニルアセトアミド単量体を１２０ｇ得た。この粗Ｎ－ビニルアセトアミド単量体中のＮ－ビニルアセトアミド単量体純度は７５質量％であった。
Next, the column was filled with 0.3% Pd-Al 2 O 3 catalyst (the packing amount was such that the amount of catalyst was 1 ml for 20 g of recovered crude N-vinylacetamide), and then the reaction temperature was 40°C and hydrogen gas was added. The crude N-vinylacetamide recovered product was circulated so that the pressure was 0.03 MPa (gauge pressure) and the space velocity (SV value) in the catalyst-packed column was 100/hour. 3-Butadienylacetamide was reduced by hydrogenation.
The reaction time was continued until the amount of N-1,3-butadienyl acetamide became 30 mass ppm or less. The recovered crude N-vinylacetamide with reduced N-1,3-butadienyl acetamide is distilled using a simple distillation device under the conditions of a degree of vacuum of 0.3 kPa (absolute pressure) or less and a bottom temperature of 60° C. or less. Methanol was removed to obtain 120 g of crude N-vinylacetamide monomer. The N-vinylacetamide monomer purity in this crude N-vinylacetamide monomer was 75% by mass.
［合成例２］
合成例１で得た粗Ｎ－ビニルアセトアミド単量体を晶析装置により４０℃に昇温し融解させ、４０℃から１０℃まで６時間で冷却晶析し、遠心分離ろ過器へ移送し、遠心分離ろ過器を用い固液分離を行い、その後にメチルエチルケトン４ｇ／メチルシクロヘキサン７７ｇにてリンズを行い、Ｎ－ビニルアセトアミド単量体の結晶を５２ｇ得た。この時のＮ－ビニルアセトアミドは純度９５質量％であった。
[Synthesis example 2]
The crude N-vinylacetamide monomer obtained in Synthesis Example 1 was heated to 40°C in a crystallizer and melted, cooled from 40°C to 10°C for 6 hours, crystallized, and transferred to a centrifugal filter. Solid-liquid separation was performed using a centrifugal filter, followed by rinsing with 4 g of methyl ethyl ketone/77 g of methylcyclohexane to obtain 52 g of N-vinylacetamide monomer crystals. The purity of N-vinylacetamide at this time was 95% by mass.
［実施例１］
合成例２で得たＮ－ビニルアセトアミド単量体結晶５２ｇに、メチルエチルケトン２．６ｇ、メチルシクロヘキサン５７ｇを加え、４０℃に加熱して溶解後、７時間で５℃に冷却することで溶媒晶析して、Ｎ－ビニルアセトアミド単量体の再結晶を析出させた。その後、再結晶を含むスラリーを遠心分離ろ過器へ移送し、遠心分離ろ過器を用い固液分離を行い、その後にメチルエチルケトン１ｇ／メチルシクロヘキサン２５ｇにてリンズを行い、再結晶を回収して、Ｎ－ビニルアセトアミド単量体の精製物を得た。得られた精製物は４６ｇで、Ｎ－ビニルアセトアミド単量体の純度は９９．８質量％であった。
得られたＮ－ビニルアセトアミド単量体精製物について、重合性試験を行った。その結果は、１０６分であった。
[Example 1]
To 52 g of N-vinylacetamide monomer crystals obtained in Synthesis Example 2, 2.6 g of methyl ethyl ketone and 57 g of methyl cyclohexane were added, heated to 40°C to dissolve, and then cooled to 5°C for 7 hours to perform solvent crystallization. Then, recrystallization of N-vinylacetamide monomer was precipitated. Thereafter, the slurry containing recrystallization is transferred to a centrifugal filter, solid-liquid separation is performed using the centrifugal filter, and then rinsing is performed with 1 g of methyl ethyl ketone/25 g of methyl cyclohexane to collect the recrystallization. - A purified vinyl acetamide monomer was obtained. The amount of purified product obtained was 46 g, and the purity of the N-vinylacetamide monomer was 99.8% by mass.
A polymerization test was conducted on the obtained purified N-vinylacetamide monomer. The result was 106 minutes.
［実施例２］
溶媒晶析において、使用量をメチルエチルケトン１０ｇ、メチルシクロヘキサン５７ｇとした以外は、実施例１と同様にしてＮ－ビニルアセトアミド単量体の再結晶を析出させた。その後、再結晶を含むスラリーを遠心分離ろ過器へ送液し、固液分離を行い、リンズを行ったのち再結晶を回収して、Ｎ－ビニルアセトアミド単量体の精製物を得た。得られた精製物は４１ｇで、純度が９９．８質量％であった。重合性試験の結果は、９８分であった。
[Example 2]
Recrystallization of N-vinylacetamide monomer was performed in the same manner as in Example 1, except that in the solvent crystallization, the amounts used were 10 g of methyl ethyl ketone and 57 g of methyl cyclohexane. Thereafter, the slurry containing the recrystallization was sent to a centrifugal filter, solid-liquid separation was performed, and after rinsing, the recrystallization was collected to obtain a purified N-vinylacetamide monomer. The obtained purified product weighed 41 g and had a purity of 99.8% by mass. The result of the polymerization test was 98 minutes.
［実施例３］
溶媒晶析およびリンズにおいて、メチルシクロヘキサンの代わりにノルマルヘキサンを用いた以外は、実施例２と同様にしてＮ－ビニルアセトアミド単量体の再結晶を析出させた。その後、再結晶を含むスラリーを遠心分離ろ過器へ送液し、固液分離を行い、リンズを行ったのち再結晶を回収して、Ｎ－ビニルアセトアミド単量体の精製物を得た。得られた精製物は４２ｇで、純度が９９．８質量％であった。重合性試験の結果は、１０８分であった。
[Example 3]
Recrystallization of N-vinylacetamide monomer was performed in the same manner as in Example 2, except that n-hexane was used instead of methylcyclohexane in the solvent crystallization and rinsing. Thereafter, the slurry containing the recrystallization was sent to a centrifugal filter, solid-liquid separation was performed, and after rinsing, the recrystallization was collected to obtain a purified N-vinylacetamide monomer. The obtained purified product weighed 42 g and had a purity of 99.8% by mass. The result of the polymerization test was 108 minutes.
［実施例４］
溶媒晶析およびリンズにおいて、メチルシクロヘキサンの代わりにシクロヘキサンを用いた以外は、実施例２と同様にしてＮ－ビニルアセトアミド単量体の再結晶を析出させた。その後、再結晶を含むスラリーを遠心分離ろ過器へ送液し、遠心分離ろ過器を用い固液分離を行い、リンズを行ったのち、再結晶を回収して、Ｎ－ビニルアセトアミド単量体を得た。得られた精製物は４１ｇで、純度が９９．７質量％であった。重合性試験の結果は、１０６分であった。
[Example 4]
N-vinylacetamide monomer was recrystallized in the same manner as in Example 2, except that cyclohexane was used instead of methylcyclohexane in the solvent crystallization and rinsing. Thereafter, the slurry containing the recrystallization is sent to a centrifugal filter, solid-liquid separation is performed using the centrifugal filter, and after rinsing, the recrystallization is collected and the N-vinylacetamide monomer is extracted. Obtained. The obtained purified product weighed 41 g and had a purity of 99.7% by mass. The result of the polymerization test was 106 minutes.
［実施例５］
合成例１、合成例２および実施例１と同様の操作を行い、純度が９９．７質量％、重合性試験が１０６分であったＮ－ビニルアセトアミド単量体を、２０℃にて１．５年間保管した。保管後の純度は９７．２質量％、重合性試験結果が１３０分であった。このＮ－ビニルアセトアミド単量体５２ｇを、実施例２と同様にしてＮ－ビニルアセトアミド単量体の精製物を得た。得られた精製物は４１ｇで、純度が９９．７質量％であった。重合性試験の結果は、１００分であった。
[Example 5]
The same operations as in Synthesis Example 1, Synthesis Example 2, and Example 1 were performed, and N-vinylacetamide monomer, which had a purity of 99.7% by mass and a polymerization test of 106 minutes, was treated at 20°C for 1. Stored for 5 years. The purity after storage was 97.2% by mass, and the polymerization test result was 130 minutes. A purified N-vinylacetamide monomer was obtained from 52 g of this N-vinylacetamide monomer in the same manner as in Example 2. The obtained purified product weighed 41 g and had a purity of 99.7% by mass. The result of the polymerization test was 100 minutes.
［比較例１］
合成例２で得られたＮ－ビニルアセトアミド単量体の結晶５２ｇ（純度９５質量％）について、重合性試験を実施の結果、１６０分となり重合性不良の結果であった。
[Comparative example 1]
A polymerization test was performed on 52 g of N-vinylacetamide monomer crystals (purity 95% by mass) obtained in Synthesis Example 2, and the polymerization time was 160 minutes, indicating poor polymerization.
［比較例２］
合成例１と同様にして得られたメタノールを除去した後の粗Ｎ－ビニルアセトアミド単量体１００ｇに対して、冷却晶析を実施せずに、メチルエチルケトン２０ｇ、メチルシクロヘキサン１１０ｇを加えて４０℃に加熱して溶解後、７時間で５℃に冷却することで溶媒晶析を実施したが、さらに１時間掛けて０℃に冷却しても結晶の析出が見られず、Ｎ－ビニルアセトアミド単量体を得ることが出来なかった。
[Comparative example 2]
20 g of methyl ethyl ketone and 110 g of methyl cyclohexane were added to 100 g of the crude N-vinylacetamide monomer obtained in the same manner as in Synthesis Example 1 after removing methanol without performing cooling crystallization, and the mixture was heated to 40°C. After heating and dissolving, solvent crystallization was carried out by cooling to 5°C over 7 hours, but no crystal precipitation was observed even after cooling to 0°C over 1 hour, and N-vinylacetamide monomer I couldn't get the body.
［比較例３］
溶媒晶析において、メチルエチルケトンを２０ｇ用い、メチルシクロヘキサンを使用しない以外は、実施例１と同様にしてＮ－ビニルアセトアミド単量体の再結晶を析出させた。溶媒量が少なく、スラリーの流動性がかなり悪化したが、Ｎ－ビニルアセトアミド単量体の再結晶を遠心分離ろ過器へ移送し、遠心分離ろ過器を用い固液分離を行い、その後にメチルエチルケトン１ｇ／メチルシクロヘキサン２５ｇにてリンズを行い、再結晶を回収した。得られた精製物は２９ｇで、純度が９９．７質量％であった。重合性試験の結果は、１１４分であった。
[Comparative example 3]
Recrystallization of N-vinylacetamide monomer was performed in the same manner as in Example 1 except that 20 g of methyl ethyl ketone was used and methyl cyclohexane was not used in the solvent crystallization. Although the fluidity of the slurry was considerably deteriorated due to the small amount of solvent, the recrystallized N-vinylacetamide monomer was transferred to a centrifugal filter, solid-liquid separation was performed using the centrifugal filter, and then 1 g of methyl ethyl ketone was added. Rinsing was performed with 25 g of /methylcyclohexane to collect recrystallization. The obtained purified product weighed 29 g and had a purity of 99.7% by mass. The result of the polymerization test was 114 minutes.
［比較例４］
溶媒晶析において、使用量をメチルエチルケトン３１ｇ、メチルシクロヘキサン２０８ｇを使用したため、晶析装置を大きくする必要が生じて、容積効率が４分の１に大きく低下した。それ以外は、実施例１と同様にしてＮ－ビニルアセトアミド単量体の再結晶を析出させた。溶媒使用量が多いため、Ｎ－ビニルアセトアミド単量体の再結晶を含む析出液を遠心分離ろ過器へ分割投入して、遠心分離ろ過器を用い固液分離を行い、その後にメチルエチルケトン１ｇ／メチルシクロヘキサン２５ｇにてリンズを行い、再結晶を回収した。得られた精製物は３４ｇ、純度９９．７質量％であった。重合性試験の結果は、９６分であった。
晶析条件および評価結果を合わせて表１に示す。
[Comparative example 4]
In the solvent crystallization, since 31 g of methyl ethyl ketone and 208 g of methyl cyclohexane were used, it was necessary to enlarge the crystallizer, and the volumetric efficiency was significantly reduced to one-fourth. Other than that, N-vinylacetamide monomer was recrystallized in the same manner as in Example 1. Since the amount of solvent used is large, the precipitate containing the recrystallized N-vinylacetamide monomer is divided into a centrifugal filter and solid-liquid separation is performed using the centrifugal filter, and then 1 g of methyl ethyl ketone/methyl Rinsing was performed with 25 g of cyclohexane to collect recrystallization. The obtained purified product weighed 34 g and had a purity of 99.7% by mass. The result of the polymerization test was 96 minutes.
Table 1 shows the crystallization conditions and evaluation results.
本発明によって得られたＮ－ビニルカルボン酸アミド単量体を使用することにより、凝集剤、増粘剤、分散剤、粘着剤などに利用されるＮ－ビニルカルボン酸アミドポリマーの製造に利用される。
By using the N-vinylcarboxylic acid amide monomer obtained by the present invention, it can be used in the production of N-vinylcarboxylic acid amide polymers used as flocculants, thickeners, dispersants, adhesives, etc. Ru.
Claims (6)
前記メチルエチルケトンの質量は、前記粗Ｎ－ビニルカルボン酸アミド単量体結晶の質量に対し、０．０１以上０．５以下の比率であり、
前記炭素数６～７の脂肪族炭化水素の質量は、前記粗Ｎ－ビニルカルボン酸アミド単量体結晶の質量に対し、０．５以上３．０以下の比率であり、
前記Ｎ－ビニルカルボン酸アミド単量体は、Ｎ－ビニルホルムアミド、Ｎ－ビニルアセトアミド、Ｎ－メチル－Ｎ－ビニルアセトアミド、Ｎ－ビニルベンズアミド、Ｎ－ビニル－Ｎ－メチルホルムアミド、Ｎ－ビニル－Ｎ－エチルホルムアミド、Ｎ－ビニル－Ｎ－エチルアセトアミド、またはＮ－ビニルピロリドンである、
高重合性Ｎ－ビニルカルボン酸アミド単量体の製造方法。 A crude N-vinylcarboxylic acid amide monomer having an N-vinylcarboxylic acid amide monomer content of 50 to 85% by mass is distilled or melted and then cooled and crystallized. A step of adjusting the content, and a crude N-vinylcarboxylic acid amide monomer crystal containing 85 to 99% by mass of N-vinylcarboxylic acid amide monomer obtained in the above step , and methyl ethyl ketone and carbon number 6 After dissolving in a mixed solvent with an aliphatic hydrocarbon of ~7, performing solvent crystallization, solid-liquid separation, and recovering a purified N-vinylcarboxylic acid amide monomer,
The mass of the methyl ethyl ketone is in a ratio of 0.01 to 0.5 with respect to the mass of the crude N-vinylcarboxylic acid amide monomer crystal,
The mass of the aliphatic hydrocarbon having 6 to 7 carbon atoms is in a ratio of 0.5 to 3.0 with respect to the mass of the crude N-vinylcarboxylic acid amide monomer crystal,
The N-vinylcarboxylic acid amide monomer includes N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, N-vinylbenzamide, N-vinyl-N-methylformamide, N-vinyl-N - ethylformamide, N-vinyl-N-ethylacetamide, or N-vinylpyrrolidone,
A method for producing a highly polymerizable N-vinylcarboxylic acid amide monomer.
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