JPWO2014069571A1 - ビニルアミン単位含有重合体溶液の製造方法 - Google Patents
ビニルアミン単位含有重合体溶液の製造方法 Download PDFInfo
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- JPWO2014069571A1 JPWO2014069571A1 JP2014544581A JP2014544581A JPWO2014069571A1 JP WO2014069571 A1 JPWO2014069571 A1 JP WO2014069571A1 JP 2014544581 A JP2014544581 A JP 2014544581A JP 2014544581 A JP2014544581 A JP 2014544581A JP WO2014069571 A1 JPWO2014069571 A1 JP WO2014069571A1
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- 229920000642 polymer Polymers 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical group NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 title claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 45
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 28
- 230000007062 hydrolysis Effects 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 13
- 239000011780 sodium chloride Substances 0.000 claims description 9
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 48
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000499 gel Substances 0.000 description 23
- 235000002639 sodium chloride Nutrition 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000003999 initiator Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 239000003349 gelling agent Substances 0.000 description 8
- 239000000123 paper Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 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 6
- -1 etc. Chemical compound 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910017053 inorganic salt Inorganic materials 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 235000013372 meat Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000036314 physical performance Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000012966 redox initiator Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 235000011148 calcium chloride Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000001641 gel filtration chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- VBZBISQOWJYWCC-UHFFFAOYSA-N 2-(2-carboxypropan-2-yldiazenyl)-2-methylpropanoic acid Chemical compound OC(=O)C(C)(C)N=NC(C)(C)C(O)=O VBZBISQOWJYWCC-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- DWSMBORYMHSAEA-UHFFFAOYSA-N 3-[(4-amino-4-iminobutan-2-yl)diazenyl]butanimidamide;dihydrochloride Chemical compound Cl.Cl.NC(=N)CC(C)N=NC(C)CC(N)=N DWSMBORYMHSAEA-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000567769 Isurus oxyrinchus Species 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
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- 239000004280 Sodium formate Substances 0.000 description 1
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- 241000376294 Tringa semipalmata Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
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- GYCUTPICSQQWKP-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 GYCUTPICSQQWKP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
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- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
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- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical compound O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
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- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- IUWVWLRMZQHYHL-UHFFFAOYSA-N n-ethenylpropanamide Chemical compound CCC(=O)NC=C IUWVWLRMZQHYHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明で使用されるN−ビニルカルボン酸アミドは、一般式:CH2=CH−NHCOR(式中、Rは水素原子または炭素数1〜6のアルキル基を表す)で示される。具体的にはN−ビニルホルムアミド(R=H)やN−ビニルアセトアミド(R=CH3)、その他、N−ビニルプロピオン酸アミド(R=C2H5)、N−ビニル酪酸アミド(R=C3H7)等が例示されるが、ポリビニルアミンへの誘導のし易さからN−ビニルホルムアミドが好ましい。
広い分子量分布を保ちつつ、還元粘度を前記の値に保つために、連鎖移動剤を用いてもよい。連鎖移動剤はMw/Mnを5より小さくしなければ特に制約は無い。
次いで、N−ビニルカルボン酸アミド(共)重合体の一部または全部を加水分解し、ポリビニルアミンに転換する。
加水分解が終了するとポリビニルアミンの水溶液となる。加水分解時の濃度により異なるが、1〜30質量%の水溶液が得られる。濃度は取り扱い性がよいように調節してもよい。好ましい濃度は(共)重合体の分子量にもよるが2〜25質量%より好ましくは3〜30質量%である。これより低濃度の場合、分子量分布にかかわらず、液粘性が低くなり取り扱い性は良くなるが、運搬等のコストが増大する。これより高い場合、重合体の分子量にもよるが分子量分布にかかわらず液粘性が高くなりすぎる。
ポリビニルアミンは各種分野に適用でき、特に製紙工業での抄紙薬剤、中でも歩留まり濾水剤、廃水処理での凝集剤などとして使用する場合には、高分子量のポリビニルアミンが有効であるとされているが、本発明によれば、従来より推奨されていた還元粘度9以上のポリビニルアミンを使用せずとも、同等以上の性能が得られる。さらに水溶液としての取り扱い性も良好である。
(共)重合体サンプルを1Nの食塩水中に、純分0.1g/dlの濃度に溶解し、25℃において、オストワルド粘度計を使用して流下時間を測定した。同様に、1N食塩水の流下時間を測定し、下記の式1によって還元粘度を求めた。
還元粘度 ηsp/C = (t−t0)/t0/0.1 [dl/g]・・・・(式1)
t:サンプル溶液の流下時間(秒)
t0:1N食塩水の流下時間(秒)
(共)重合体粉末をメタノール水で抽出し、残存単量体を液体クロマトグラフィーを使用して分析した。主たる不純物として、N−ビニルカルボン酸アミドと、N−ビニルカルボン酸アミドの水付加体が検出され、これらの合計をN−ビニルカルボン酸アミド換算で求めて残存モノマー量とし、別途求めた揮発分量を補正して転化率を算出した。
(共)重合体粉末を105℃で90分加熱し、減少分を重量法で求めた。
重合体水溶液の温度を25℃とし、ブルックフィールド粘度計、6rpm、ローターNo.4の条件にて測定した。なお、粘度は、mPa・sと表記した。
(重合体Aの合成及び性能評価;水溶液静置断熱重合法)
脱イオン水70質量部に対しポリエチレングリコール(平均分子量20000) 0.3質量部を溶解し、次いで、N−ビニルホルムアミド(純度99重量%)30質量部を混合した。更に、酢酸ソーダ0.1質量部を添加後リン酸により単量体水溶液がpH=6.3となるように調整し、単量体調製液を得た。
(重合体Bの合成及び性能評価;水溶液静置断熱重合法)
2,2’−アゾビス(2−アミジノプロパン)二塩酸塩を2000ppmに増量したほかは重合体Aと同様方法で重合を行い還元粘度5.8dl/gのN−ビニルホルムアミド重合体粉末を得た。重合転化率は99.8%、揮発分量は4.5質量%であった。GPC法により測定したMw/Mnは6.5であった。この製品を重合体Bとして、以下の重合体溶液の物性と性能評価を実施した。
2,2’−アゾビス(2−アミジノプロパン)二塩酸塩を2500ppmに増量したほかは重合体Aと同様方法で重合を行い還元粘度3.9dl/gのN−ビニルホルムアミド重合体粉末を得た。重合転化率は99.8%、揮発分量は4.5質量%であった。GPC法により測定したMw/Mnは5.1であった。この製品を重合体Cとした。
(重合体Dの調製及び性能評価)
前記重合体Cと重合体Aを70質量%/30質量%となるよう混合し、重合体Dとした。重合体Dを分析したところ、還元粘度6.4dl/g、重合転化率は99.8%、揮発分量は4.5質量%であった。GPC法により測定したMw/Mnは9.1であった。この重合体Dを以下の重合体溶液の物性と性能評価を実施した。
(重合体Eの合成及び性能評価;光重合法)
モノマーとしてN−ビニルホルムアミド333.3g(純度99%)、開始剤としてジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキサイド0.11g、塩化アンモニウム5.5g、「サニゾールB50」(花王製塩化ベンザルコニウム系界面活性剤、純度50%)0.55g、「AF108」(東邦化学製界面活性剤)0.055g、脱塩水210.5gを均一に溶解してモノマー溶液を調製し、窒素ガスを通気して溶存酸素を除去した。
(重合体Fの合成及び性能評価)
ジフェニル(2,4,6−トリメチルベンゾイル)ホスフィンオキサイドを0.55gに増量したほかは重合体Bと同様方法で重合を行い還元粘度8.3dl/gのN−ビニルホルムアミド重合体粉末を得た。重合転化率は99.0%、揮発分量は4質量%であった。GPC法により測定したMw/Mnは4.2であった。この製品を重合体Fとして、以下の重合体溶液の物性と性能評価を実施した。
攪拌機を有するガラス製セパラブルフラスコに、脱塩水275.2gを入れ、水酸化ナトリウム8.45g、ゲル化防止剤として亜二チオン酸ナトリウム0.75gを溶解し、ここに前記N−ビニルカルボン酸アミド重合体純分15gを撹拌下少しづつ加え、室温で1時間攪拌後、50℃に昇温した。2時間後、更に、80℃に昇温し、80℃で2時間保持して加水分解を行った。冷却後、内容物のポリビニルアミン溶液を取り出した。ポリビニルアミンの水溶液粘度を測定し、表1に示す。
段ボールを水に浸した後ビーターを使用して20分叩解して濃度を調節し、カナダ標準濾水量(CFS)=90、濃度1%、pH6.91の試験用スラリーを得た。そして、濾水性は、次のようにして評価した。すなわち、スラリー500mlに濾水剤として前記ポリビニルアミン溶液を重合体純分として200ppm(対段ボール)を添加し、パドル翼で900rpmで20秒撹拌、その後、ダイナミックドレネージジャー試験機(熊谷理機工業社製)にて10秒後の濾水量を測定した。一方、同一スラリーを使用して角型シートマシンを使用して手抄きにて抄紙、紙葉を濾布に挟み、0.4MPaプレス機で5分、更に、0.4MPaで2分プレス、その状態で含水率を調べ搾水性の目安とした。結果を表1に示す。
Claims (12)
- N−ビニルカルボン酸アミド単量体単位を含有する、重量平均分子量Mw/数平均分子量Mnの値が5以上である重合体を水溶液静置断熱重合法にて製造した後、前記重合体をアルカリ及びゲル化防止剤の存在下に水性溶媒中で加水分解を行うことを特徴とする、ビニルアミン単位含有重合体溶液の製造方法。
- ビニルアミン単位含有重合体溶液が製紙用内添薬剤である請求項1に記載の製造方法。
- 重合体中のN−ビニルカルボン酸アミド単量体単位が50モル%以上である請求項1又は2に記載の製造方法。
- N−ビニルカルボン酸アミド単量体単位がN−ビニルホルムアミド単量体単位である請求項1〜3の何れかに記載の製造方法。
- ゲル化防止剤が、亜二チオン酸塩、亜硫酸塩、重亜硫酸塩、二亜硫酸塩、ロンガリット、二酸化チオ尿素、水素化ホウ素ナトリウムの群から選ばれる少なくとも一つである請求項1〜4の何れかに記載の製造方法。
- ビニルアミン単位含有重合体溶液が製紙用歩留まり濾水剤である請求項1に記載の製造方法。
- 重合体の1N食塩水中0.1g/dlの還元粘度が2〜9である。請求項1〜6の何れかに記載の製造方法。
- 加水分解を行う際の水性溶媒中の重合体濃度が3質量%以上である請求項1〜7の何れかに記載の製造方法。
- 水性溶媒中の重合体濃度が3質量%以上である請求項1〜7の何れかに記載の製造方法。
- 水溶液静置断熱重合にてN−ビニルカルボン酸アミド単量体単位を含有する重合体を製造した後、乾燥粉末化して揮発分が0.1〜12質量%の重合体粉末を得、次いで、得られた前記粉末をアルカリ及びゲル化防止剤の存在下に水性溶媒中で加水分解を行う、請求項1に記載の重合体溶液の製造方法。
- 得られた重合体粉末を重合体溶液の使用場所に搬送し、当該使用場所において、重合体粉末をアルカリ及びゲル化防止剤の存在下に水性溶媒中で加水分解を行う、請求項10に記載の重合体溶液の製造方法。
- 重合体が還元粘度の異なる2種以上のN−ビニルカルボン酸アミド重合体の混合物である請求項1の方法。
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US6797785B1 (en) * | 1999-03-29 | 2004-09-28 | Snf S.A. | Methods for synthesizing polyvinyl amine (PVA) type flocculating and coagulating agents, novel agents thus obtained, uses thereof and improved paper types thus obtained |
JP2006257287A (ja) * | 2005-03-17 | 2006-09-28 | Daiyanitorikkusu Kk | 水溶性ビニルアミン重合体の製造方法 |
JP2010059220A (ja) * | 2008-09-01 | 2010-03-18 | Daiyanitorikkusu Kk | N−ビニルカルボン酸アミド系重合体の製造方法 |
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JP2004027015A (ja) * | 2002-06-25 | 2004-01-29 | Daiyanitorikkusu Kk | ポリビニルアミンの製造方法 |
JP2006257287A (ja) * | 2005-03-17 | 2006-09-28 | Daiyanitorikkusu Kk | 水溶性ビニルアミン重合体の製造方法 |
JP2010059220A (ja) * | 2008-09-01 | 2010-03-18 | Daiyanitorikkusu Kk | N−ビニルカルボン酸アミド系重合体の製造方法 |
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KR20170059012A (ko) | 2017-05-29 |
CA2890957A1 (en) | 2014-05-08 |
CN104768979A (zh) | 2015-07-08 |
JP6350286B2 (ja) | 2018-07-04 |
US20150259508A1 (en) | 2015-09-17 |
CN104768979B (zh) | 2017-08-25 |
US9745448B2 (en) | 2017-08-29 |
EP2915823A1 (en) | 2015-09-09 |
KR20150063123A (ko) | 2015-06-08 |
WO2014069571A1 (ja) | 2014-05-08 |
EP2915823B1 (en) | 2019-06-26 |
EP2915823A4 (en) | 2015-09-09 |
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