JPH0356507A - Preparation of hydrophilic hydrazide polymer - Google Patents
Preparation of hydrophilic hydrazide polymerInfo
- Publication number
- JPH0356507A JPH0356507A JP19228989A JP19228989A JPH0356507A JP H0356507 A JPH0356507 A JP H0356507A JP 19228989 A JP19228989 A JP 19228989A JP 19228989 A JP19228989 A JP 19228989A JP H0356507 A JPH0356507 A JP H0356507A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- hydrazide
- solution
- water
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001868 water Inorganic materials 0.000 claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000003960 organic solvent Substances 0.000 abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 5
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000008096 xylene Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 64
- 238000000034 method Methods 0.000 description 23
- 235000002639 sodium chloride Nutrition 0.000 description 22
- 239000007787 solid Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 20
- -1 ethoxyethylene glycol-propylene glycol acrylate Chemical compound 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000000178 monomer Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- 229920006243 acrylic copolymer Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004185 ester group Chemical group 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 229940049920 malate Drugs 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 3
- 125000004018 acid anhydride group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000001509 sodium citrate Substances 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- YHYCMHWTYHPIQS-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol Chemical compound COC(O)COCCO YHYCMHWTYHPIQS-UHFFFAOYSA-N 0.000 description 2
- 229940093475 2-ethoxyethanol Drugs 0.000 description 2
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-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
- 239000000843 powder Substances 0.000 description 2
- 229920013730 reactive polymer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- LXEBRZVXSJOUGN-UHFFFAOYSA-N 1-ethoxy-2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(O)COCCOCCOCCOCCOCCOCCOCCOCCO LXEBRZVXSJOUGN-UHFFFAOYSA-N 0.000 description 1
- PCJTZWIMKYXOAJ-UHFFFAOYSA-N 1-ethoxy-3-(1-hydroxypropan-2-yloxy)propan-2-ol Chemical compound CCOCC(O)COC(C)CO PCJTZWIMKYXOAJ-UHFFFAOYSA-N 0.000 description 1
- ZDTLUUIYCAMIMQ-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(O)COCCO ZDTLUUIYCAMIMQ-UHFFFAOYSA-N 0.000 description 1
- CMCLUJRFBZBVSW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCO CMCLUJRFBZBVSW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JQCWCBBBJXQKDE-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]-1-methoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(O)COCCOCCO JQCWCBBBJXQKDE-UHFFFAOYSA-N 0.000 description 1
- COORVRSSRBIIFJ-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]-1-methoxyethanol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(O)COCCOCCO COORVRSSRBIIFJ-UHFFFAOYSA-N 0.000 description 1
- WBSXINVZPSZFFL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]-1-methoxyethanol Chemical compound COC(O)COCCOCCOCCOCCOCCOCCOCCOCCO WBSXINVZPSZFFL-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- AVANZZDGIRLSLM-UHFFFAOYSA-N 2-butoxypropyl prop-2-enoate Chemical compound CCCCOC(C)COC(=O)C=C AVANZZDGIRLSLM-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- RIIRGXOHHAMBRJ-UHFFFAOYSA-N 2-ethoxypropyl 2-methylprop-2-enoate Chemical compound CCOC(C)COC(=O)C(C)=C RIIRGXOHHAMBRJ-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- JQUWCYSGSDOZOO-UHFFFAOYSA-N 2-methoxypropane-1,2-diol Chemical compound COC(C)(O)CO JQUWCYSGSDOZOO-UHFFFAOYSA-N 0.000 description 1
- KRYUTHZTBZVTDA-UHFFFAOYSA-N 2-methoxypropane-1,2-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(C)(O)CO KRYUTHZTBZVTDA-UHFFFAOYSA-N 0.000 description 1
- XZIMDXCGDMCMLT-UHFFFAOYSA-N 2-methoxypropyl prop-2-enoate Chemical compound COC(C)COC(=O)C=C XZIMDXCGDMCMLT-UHFFFAOYSA-N 0.000 description 1
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical class OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- XHEAXONBJSHBKK-UHFFFAOYSA-N C(CCC)OC(COCCOCCOCCOCCOCCOCCOCCOCCO)O Chemical compound C(CCC)OC(COCCOCCOCCOCCOCCOCCOCCOCCO)O XHEAXONBJSHBKK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000243251 Hydra Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons 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
- 150000001408 amides Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- PPISOKQRPRDLMC-UHFFFAOYSA-M azanium;sodium;sulfate Chemical compound [NH4+].[Na+].[O-]S([O-])(=O)=O PPISOKQRPRDLMC-UHFFFAOYSA-M 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940018560 citraconate Drugs 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 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
- 239000012528 membrane Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229960004109 potassium acetate Drugs 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 235000007715 potassium iodide Nutrition 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
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- OTNVGWMVOULBFZ-UHFFFAOYSA-N sodium;hydrochloride Chemical compound [Na].Cl OTNVGWMVOULBFZ-UHFFFAOYSA-N 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
【産業上の利用分野］
本発明は親水性ヒドラジド化重合体の製造方法に関する
ものである。さらに詳しくいえば、本発明は、反応性高
分子重合体として、種々の用途に好適に用いられる高純
度の親水性ヒドラジド化重合体を効率よく製造する方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a hydrophilic hydrazide polymer. More specifically, the present invention relates to a method for efficiently producing a highly pure hydrophilic hydrazide polymer that is suitably used for various purposes as a reactive polymer.
［従来の技術〕
従来、分子鎖中に酸ヒドラジド基を有する重合体は、水
溶液中でカチオン性高分子重合体としての挙動を示すと
ともに、該基の反応性により反応性高分子重合体として
も作用することから、種々の用途、例えば金属捕集剤、
紙力増強剤、ホルマリン吸収剤、水溶性塗料などの材料
や耐熱材料、還元材料などとして極めて有用であること
が知られている。[Prior Art] Conventionally, polymers having acid hydrazide groups in their molecular chains behave as cationic polymers in aqueous solutions, and also as reactive polymers due to the reactivity of the groups. Because of its action, it has various uses, such as metal scavengers,
It is known to be extremely useful as a material for paper strength enhancers, formalin absorbents, water-soluble paints, heat-resistant materials, reducing materials, etc.
このようなヒドラジド化重合体は、通常重合体中の酸ア
ミド、酸無水物、エステルなどにヒドラジンやヒドラジ
ンヒドラートなどのヒドラジド化剤を作用させることに
より製造されている。しかしながら、このヒドラジド化
反応においては、目的とするヒドラジド化に必要なｍｏ
ｌｔ数の当量よりも過剰にヒドラジド化剤を加えなけれ
ばならず、したがって反応終了後過剰に加えたヒドラジ
ド化剤を除去して、ヒドラジド化重合体を精製するため
に、これまで種々の方法が試みられてきた。Such hydrazidated polymers are usually produced by reacting acid amides, acid anhydrides, esters, etc. in the polymer with a hydrazidizing agent such as hydrazine or hydrazine hydrate. However, in this hydrazidation reaction, the mo amount required for the desired hydrazidation is
The hydrazidating agent must be added in excess of the equivalent amount of lt number, and therefore various methods have been used to purify the hydrazidated polymer by removing the excess hydraziding agent after the reaction is completed. It has been tried.
例えば、反応終了液を大量のメタノールなどの有機溶媒
中に注ぎ、ヒドラジド化重合体を析出させてろ別する方
法（特公昭５２−２２８７８号公報）、反応終了液中に
過酸化物の溶液を滴下して、ヒドラジド化剤を窒素ガス
、アンモニア、水などに分解したのち、これらを留去さ
せ、ヒドラジド化重合体を精製する方法（特開昭６２−
１４６９０３号公報）などが提案されている。For example, a method in which the reaction completed liquid is poured into a large amount of an organic solvent such as methanol to precipitate the hydrazide polymer and then filtered (Japanese Patent Publication No. 52-22878), or a peroxide solution is dropped into the reaction completed liquid. The hydrazidation agent is decomposed into nitrogen gas, ammonia, water, etc., and then these are distilled off to purify the hydrazidation polymer.
146903) and the like have been proposed.
しかしながら前者の有機溶媒中に反応終了液を注ぐ方法
においては、精製に使用されたヒドラジド化剤を含む有
機溶剤の回収が困難なため、製造コストが極めて高くつ
くのを免れず、また、特に生成したヒドラジド化重合体
が親水性溶媒（例えばイングロパノール）などにも溶け
る場合には、反応終了液を疎水性溶媒（例えばヘキサン
など）中に投入してヒドラジド化重合体を析出させなけ
ればならないが、ヒドラジド化剤が親水性のため、その
除去効率が著しく低いなどの欠点がある。However, in the former method of pouring the reaction-finished liquid into an organic solvent, it is difficult to recover the organic solvent containing the hydrazidating agent used for purification, so the production cost is extremely high. If the hydrazidated polymer is also soluble in a hydrophilic solvent (e.g., ingropanol), the reaction completed solution must be poured into a hydrophobic solvent (e.g., hexane, etc.) to precipitate the hydrazidated polymer. However, since the hydrazidating agent is hydrophilic, it has drawbacks such as extremely low removal efficiency.
一方、過酸化物を用いてヒドラジド化剤を分解する方法
は、かなり危険を伴う精製法であって、大量生産するた
めには厳重な安全設備を必要とするなどの欠点を有し、
必ずしも工業的方法とはいえない。On the other hand, the method of decomposing a hydrazidating agent using peroxide is a very dangerous purification method, and has drawbacks such as requiring strict safety equipment for mass production.
This is not necessarily an industrial method.
本発明は、このような事情のもとで、無着色で高純度の
ヒドラジド化重合体を、安全かつ安価に、極めて効率よ
く製造するための工業的に実施可能な方法を提供するこ
とを目的としてなされたものである。Under these circumstances, the purpose of the present invention is to provide an industrially viable method for safely, inexpensively, and extremely efficiently producing an uncolored, highly pure hydrazide polymer. This was done as a.
本発明者らは、前記目的を達成するために鋭意研究を重
ねた結果、生成したヒドラジド化重合体が水に分解又は
溶解可能な場合、ヒドラジド化反応終了液から残存ヒド
ラジド化剤を除去するには、反応終了液を塩類と接触さ
せて、該ヒドラジド化重合体を析出又は高濃度溶液層と
して分離するのが極めて有利であることを見い出し、こ
の知見に基づいて本発明を完戊するに至った。As a result of extensive research to achieve the above object, the present inventors have found that if the produced hydrazidation polymer can be decomposed or dissolved in water, it is possible to remove the residual hydrazidation agent from the hydrazidation reaction finished liquid. found that it is extremely advantageous to bring the reaction-completed liquid into contact with salts to separate the hydrazide polymer as a precipitate or a highly concentrated solution layer, and based on this knowledge, they completed the present invention. Ta.
すなわち、本発明は、ヒドラジド或形性官能基を有する
重合体とヒドラジド化剤とを反応させてヒドラジド化重
合体を製造するに当たり、生或したヒドラジド化重合体
のＬｏｇＰ値（ただし、Ｐは水とれ−オクタノールに対
する分配係数である）が１．１０以下の場合、反応終了
液を塩類と接触させて、該ヒドラジド化重合体を析出又
は高濃度溶液層として分離することを特徴とする親水性
ヒドラジド化重合体の製造方法を提供するものである。That is, in producing a hydrazidated polymer by reacting a hydrazide-forming functional group-containing polymer with a hydrazidating agent, the present invention provides the LogP value (where P is A hydrophilic hydrazide characterized in that when the partition coefficient (partition coefficient for octanol) is 1.10 or less, the hydrazided polymer is separated as a precipitate or a highly concentrated solution layer by contacting the reaction-completed liquid with a salt. The present invention provides a method for producing a chemical polymer.
以下、本発明を詳細に説明する。The present invention will be explained in detail below.
本発明においては、ヒドラジド化重合体の原料として、
ヒドラジド形戊性官能基を有する重合体が用いられる。In the present invention, as raw materials for the hydrazide polymer,
A polymer having a hydrazide type hollow functional group is used.
この重合体については、エステル基、酸アミド基、酸無
水物基などのヒドラジド形戊性官能基を有するものであ
ればよく、特に制限はない。このようなものとしては、
例えば分子内にエステル基、酸アミド基、酸無水物基な
どのヒドラジド形戊性官能基を有するビニル型単量体を
１種重合させて戊る単独重合体、前記単量体２種以上を
組み合わせて共重合させて成る共重合体、前記単量体１
種又は２種以上と、これらと共重合可能な分子内にヒド
ラジド形成性官能基を有しないビニル型単量体の少なく
とも１種とを共重合させて成る共重合体が挙げられる。This polymer is not particularly limited as long as it has a hydrazide-type basic functional group such as an ester group, an acid amide group, or an acid anhydride group. As such,
For example, a homopolymer obtained by polymerizing one type of vinyl monomer having a hydrazide-type functional group such as an ester group, an acid amide group, or an acid anhydride group in the molecule, or a homopolymer obtained by polymerizing two or more of the above monomers. A copolymer formed by copolymerizing in combination, the above monomer 1
Examples include copolymers formed by copolymerizing a species or two or more species and at least one vinyl monomer that does not have a hydrazide-forming functional group in the molecule that can be copolymerized with these.
分子内にエステル基を有するビニル型単量体としては、
例えばメチルアクリレート、エチルアクリレート、ｎ−
プチルアクリレート、インブチルアクリレート、ｔ−プ
チルアクリレート、２−エチルへキシルアクリレート、
７エニルアクリレート、シクロヘキシルアクリレート、
メチルメタクリレート、エチルメタクリレート、ｎ−プ
チルメタクリレート、インブチルメタクリレート、１−
プチルメタクリレート、２−エチルへキシルメタクリレ
ート、フェニルメタクリレート、シクロヘキシルメタク
リレートなどが挙げられる。As a vinyl monomer having an ester group in the molecule,
For example, methyl acrylate, ethyl acrylate, n-
butyl acrylate, imbutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate,
7-enyl acrylate, cyclohexyl acrylate,
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, 1-
Examples include butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, and cyclohexyl methacrylate.
また、一般式（Ｉ）
Ｒ１
■
ＣＨ２−Ｃ
一
Ｃ−０
１
０イＡ’−０｝−Ｘ
・・・ （Ｉ）
（式中のＲｌは水素原子又はメチル基、Ａ１はエチレン
基、プロピレン基及びブチレン基の中から選ばれた少な
くとも１種のアルキレン基、Ｘは水素原子又は炭素数１
〜４のアルキル基、ｍは１〜３０の整数である）
で表される単量体、例えば２−ヒドロキシェチルアクリ
レート、２−ヒドロキシプロビルアクリレート、２−メ
トキシエチルアクリレート、２−メトキシプ口ピルアク
リレート、２−エトキシエチルアクリレート、２−エト
キシブロビルアクリレート、２−プトキシエチルアクリ
レート、２−ブトキシプ口ピルアクリレート、メトキシ
ジエチレングリコールアクリレート、エトキシエチレン
グリコーループロピレングリコールアクリレート、２−
メトキシプロピレングリコールアクリレート、メトキシ
トリエチレングリコールアクリレート、２−メトキシト
リプロピレングリコールアクリレート、メトキシジエチ
レングリコーループロピレングリコールアクリレート、
エトキシノナエチレングリコールアクリレート、エトキ
シエイコサエチレングリコールアクリレート、２−ブト
キシトリアコンタプロピレングリコールアクリレート、
２−ヒドロキシエチルメタクリレート、２−ヒドロキシ
ブ口ピルメタクリレート、２−メトキシエチルメタクリ
レート、２−メトキシグロビルメタクリレート、２−エ
トキシエチルメタクリレート、２−エトキシプロビルメ
タクリレート、２−ブトキシエチルメタクリレート、２
−プトキシプ口ピルメタクリレート、メトキシジエチレ
ングリコールメタクリレート、メトキシエチレングリコ
ーループロピレングリコールメタクリレート、２〜メト
キシジプロピレングリコールメタクリレート、メトキシ
トリエチレングリコールメタクリレート、２−メトキシ
トリプロピレングリコールメタクリレート、メトキシジ
エチレングリコーループロピレングリコールメタクリレ
ート、エトキシノナエチレングリコールメタクリレート
、エトキシェイコサエチレングリコールメタクリレート
、２−ブトキシトリアコンタプロピレングリコールメタ
クリレートなどが挙げられる。In addition, general formula (I) R1 ■ CH2-C -C-0 1 0iA'-0}-X (I) (Rl in the formula is a hydrogen atom or a methyl group, A1 is an ethylene group, a propylene group, and at least one alkylene group selected from butylene groups, X is a hydrogen atom or has 1 carbon number
-4 alkyl group, m is an integer of 1 to 30), such as 2-hydroxyethyl acrylate, 2-hydroxypropylacrylate, 2-methoxyethyl acrylate, 2-methoxypropyl Acrylate, 2-ethoxyethyl acrylate, 2-ethoxybrobyl acrylate, 2-ptoxyethyl acrylate, 2-butoxypropyl acrylate, methoxydiethylene glycol acrylate, ethoxyethylene glycol-propylene glycol acrylate, 2-
Methoxypropylene glycol acrylate, methoxytriethylene glycol acrylate, 2-methoxytripropylene glycol acrylate, methoxydiethylene glycol-propylene glycol acrylate,
Ethoxynonaethylene glycol acrylate, ethoxyeicosaethylene glycol acrylate, 2-butoxytriacontapropylene glycol acrylate,
2-hydroxyethyl methacrylate, 2-hydroxybutopyr methacrylate, 2-methoxyethyl methacrylate, 2-methoxyglobil methacrylate, 2-ethoxyethyl methacrylate, 2-ethoxypropyl methacrylate, 2-butoxyethyl methacrylate, 2
-Ptoxypropylene glycol methacrylate, methoxydiethylene glycol methacrylate, methoxyethylene glycol-propylene glycol methacrylate, 2-methoxydipropylene glycol methacrylate, methoxytriethylene glycol methacrylate, 2-methoxytripropylene glycol methacrylate, methoxydiethylene glycol-propylene glycol methacrylate, ethoxynonaethylene Examples include glycol methacrylate, ethoxyceicosaethylene glycol methacrylate, 2-butoxytriacontapropylene glycol methacrylate, and the like.
さらに、
一般式（Ｉ［）
ｏ−ｃ ｃ−ｏ
〔式中のＲ２及びＲ３はそのいずれか一方が水素原子で
他方が水素原子又はメチル基、Ａ２はエチレン基、プロ
ピレン基及びブチレン基の中から選ばれた少なくとも１
種のアルキレン基、Ｙは水素原子又は炭素数１〜４のア
ルキル基、２は炭素数１〜４のアルキル基又は式
→Ａ３−０｝ＴＱ
（ Ａ Ｓはエチレン基、プロピレン基及びプチレン基
の中から選ばれた少なくとも１種のアルキレン基、Ｑは
水素原子、炭素数１〜４のアルキル基又はアシル基、ｋ
は０又は１〜３０の整数）で示される基、ｎはＯ又は１
〜３０の整数である〕で表される単量体、例えばジ（２
−メトキシエチル）マレート、シ（メトキシジエチレン
クリコール）マレート、ジ（メトキシトリエチレングリ
コ一ル）マレート、ジ（ブトキシノナエチレングリコー
ル）マレート、ジ（エトキシトリコサエチレングリコー
ル）マレート、ジ（２−メトキシプロピレングリコール
）マレート、ジ（２−エトキシジプロピレングリコール
）マレート、ジ（ｌ−ブトキシトリプロピレングリコー
ル）マレート、２−メトキシエチルメチルマレート、メ
トキシジエチレングリコールエチルマレート、メトキシ
トリプロピレングリコールドデシルマレート、ジ（２−
メトキシエチル）７マレート、ジ（メトキシジエチレン
グリコール）フマレート、シ（メトキシノナエチレング
リコール）フマレート、ジ（エトキシトリコサエチレン
グリコール）フマレート、メトキシジエチレングリコー
ルエチルフマレート、ジ（２−メトキシエチル）シトラ
コネート、ジ（メトキシエチル）メサコネートなどが挙
げられる。Furthermore, general formula (I [) oc c-o [In the formula, one of R2 and R3 is a hydrogen atom and the other is a hydrogen atom or a methyl group, and A2 is an ethylene group, a propylene group, or a butylene group. at least one selected from
species alkylene group, Y is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 2 is an alkyl group having 1 to 4 carbon atoms, or the formula →A3-0}TQ (AS is an ethylene group, a propylene group, and a butylene group) at least one alkylene group selected from among, Q is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group, k
is 0 or an integer of 1 to 30), n is O or 1
an integer of ~30], such as di(2
-methoxyethyl)malate, cy(methoxydiethylene glycol)malate, di(methoxytriethyleneglycol)malate, di(butoxynonaethyleneglycol)malate, di(ethoxytricosaethyleneglycol)malate, di(2-methoxy propylene glycol) maleate, di(2-ethoxydipropylene glycol) maleate, di(l-butoxytripropylene glycol) maleate, 2-methoxyethyl methyl maleate, methoxy diethylene glycol ethyl maleate, methoxy tripropylene glycol decyl maleate, (2-
methoxyethyl) 7-malate, di(methoxydiethylene glycol) fumarate, di(methoxynonaethylene glycol) fumarate, di(ethoxytricosaethylene glycol) fumarate, methoxydiethylene glycol ethyl fumarate, di(2-methoxyethyl) citraconate, di(methoxyethyl) (ethyl) mesaconate, etc.
次に、分子内に酸アミド基を有するビニル型単量体とし
ては、例えばアクリルアミド、メタクリルアミド、Ｎ−
ヒドロキシメチルアクリルアミド、Ｎ−ヒドロキシメチ
ルメタクリルアミド、２−アクリルアミドグリコーリッ
クアシド、２−メタクリルアミドグリコーリックアシド
、２−アクリルアミドー２−メチルプロパンスルホン酸
ナトリウム、２−メタクリルアミド−２−メチルプロパ
ンスルホン酸ナトリウムなどが挙げられる。Next, examples of vinyl monomers having an acid amide group in the molecule include acrylamide, methacrylamide, N-
Hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, 2-acrylamideglycolic acid, 2-methacrylamideglycolic acid, sodium 2-acrylamide-2-methylpropanesulfonate, sodium 2-methacrylamide-2-methylpropanesulfonate Examples include.
また、酸無水物基を有するビニル基単量体としては、例
えば無水マレイン酸、無水イタコン酸、無水シトラコン
酸などが挙げられる。Furthermore, examples of the vinyl group monomer having an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
これらのヒドラジド形戊性官能基を有するビニル型単量
体は１種用いてもよいし、２種以上を組み合わせて用い
てもよい。One type of these vinyl monomers having a hydrazide type hollow functional group may be used, or two or more types may be used in combination.
さらに、前記単量体と共重合可能な分子内にヒドラシド
形成性官能基を有しない単量体としては、例えばスチレ
ン、α−メチルスチレン、アクリル酸、メタクリル酸、
マレイン酸、フマール酸、酢酸ビニル、アクリロニトリ
ル、ブタジエン、ビニルブチルエーテルなどが挙げられ
る。これらの共重合可能な単量体は１種用いてもよいし
、２種以上を組み合わせて用いてもよい。Furthermore, examples of monomers that do not have a hydraside-forming functional group in the molecule that can be copolymerized with the monomers include styrene, α-methylstyrene, acrylic acid, methacrylic acid,
Examples include maleic acid, fumaric acid, vinyl acetate, acrylonitrile, butadiene, vinyl butyl ether, and the like. One type of these copolymerizable monomers may be used, or two or more types may be used in combination.
本発明方法は、生或するヒドラジド化重合体が水に溶解
又は分散可能、すなわちＬｏｇＰ値が１．ＩＯ以下の場
合に適用される。このＬｏｇＰ値とは、水と有機溶媒（
ｎ−オクタノール）とに対する分配係数Ｐの対数であり
、物質の疎水性及び親水性度合の指標となる。ＬｏｇＰ
値は実測可能な値であるが、分子の構或因子ごとに疎水
性７ラグメント定数ｆを帰属し、その総和Σｆとして算
出することができる［「ジャーナル・オブ・メディスナ
ル・ケミストリー（Ｊ．Ｍｅ ｄ．Ｃｈ ｅｍ．）Ｊ第
１８巻、′＠８ ６ ５ヘーシ（１ ９ ７ ５年）
］ ． コの値は実測値とかなりよく一致し、本発明に
おいては、各七ノマー単位のＬｏｇＰ値を前記方法で算
出し、モル分率をかけて総和しｔ；ものを該ヒドラジド
化重合体のＬｏｇＰ値として算出した。該７ラグメント
のｆ定数は、次の第１表に示されるとおりである。また
、第２表に前記分子内にヒドラジド形威性官能基を有す
るビニル型単量体の中で代表的なもののＬｏｇＰ値を示
す。In the method of the present invention, the raw hydrazide polymer is soluble or dispersible in water, that is, the LogP value is 1. Applies to cases below IO. This LogP value is the difference between water and organic solvent (
It is the logarithm of the partition coefficient P with respect to n-octanol), and is an index of the degree of hydrophobicity and hydrophilicity of a substance. LogP
The value is a measurable value, but it can be calculated as the sum Σf by assigning a hydrophobic 7-lagment constant f to each structural factor of the molecule [Journal of Medical Chemistry (J. Med. .Ch em.) J Volume 18, '@865 Hesi (1975)
] ． In the present invention, the LogP value of each heptanomer unit is calculated by the method described above, multiplied by the mole fraction, and summed. Calculated as a value. The f-constants of the seven fragments are shown in Table 1 below. Furthermore, Table 2 shows the LogP values of typical vinyl monomers having a hydrazide functional group in the molecule.
生或したヒドラジド化重合体のＬｏｇＰ値が１．１０よ
りも大きい場合、ヒドラジド化重合体は水に分散不可能
となり塩を添加することなく析出あるいは高濃度溶液と
して分離することが可能で、必ずしも本発明に従った方
法を用いなくとも製造することができる。したがって、
本発明は生成したヒドラジド化重合体のｔ．ｏｇｐ値が
１．１０以下である親水性ヒドラジド化重合体において
適用される。When the LogP value of the raw hydrazide polymer is greater than 1.10, the hydrazide polymer cannot be dispersed in water and can be separated as a precipitate or a highly concentrated solution without adding salt. It can also be produced without using the method according to the invention. therefore,
The present invention provides a t. Applicable to hydrophilic hydrazidated polymers having an ogp value of 1.10 or less.
（以下余白）
第
ｌ
表
ｌ）鎖状化合物における値
２）ベンゼン系化合物における値
３）７ラグメント間の結合数より１−を差し引いた数と
かけ合わせて用いる
４）炭素数の枝分かれの因子
（以下余白）
本発明において、原料として用いるヒドラジド形成性官
能基を有する単独重合体又は共重合体の分子量について
は特に制限はないが、重合体としての物性上適当な範囲
に限定されていることが望ましい。この範囲は単量体の
種類によって左右され、一概に定めることができないが
、一般に重量平均分子量として、１ ，５ ０ ０〜２
００，０００の範囲にある重合体が用いられる。(Leaving space below) Table 1) Values for chain compounds 2) Values for benzene compounds 3) Used by multiplying by the number of bonds between 7 fragments minus 1-4) Branching factor of carbon number ( In the present invention, there is no particular restriction on the molecular weight of the homopolymer or copolymer having a hydrazide-forming functional group used as a raw material, but it may be limited to an appropriate range in view of the physical properties of the polymer. desirable. This range depends on the type of monomer and cannot be determined unconditionally, but generally the weight average molecular weight is 1,500 to 2.
Polymers in the range of 0.00,000 are used.
本発明におけるヒドラジド化反応は、ヒドラジド形戊性
官能基を有する単独重合体又は共重合体を直接か又は有
機溶媒に溶解させたのちに、ヒドラジド化剤を反応させ
る方法が用いられる。この際使用する有機溶媒としては
、例えばメタノール、工５／−ル、インプロパノール、
ｎ−フロパノール、ｎ−ブタノール、ｓｅｃ−ブタノー
ル、インフタノール、ｔ−ブタノール、シクロヘキサノ
ールなどのアルコール系溶剤、ベンゼン、トルエン、キ
シレンなどの芳香族炭化水素、ヘキサン、ミネラルスピ
リットなどの脂肪族炭化水素、エチレングリコールモノ
メチルエーテル、エチレングリコ−ルモノエチルエーテ
ル、ジエチレンクリコールモノメチルエーテルなどのエ
ーテルアルコール類、Ｎ，Ｎ−ジメチルホルムアミド（
ＤＭＦ） 、ジオキサンなどが挙げられ、これらは１種
用いてもよいし、２種以上を混合して用いることもでき
る。In the hydrazidation reaction in the present invention, a method is used in which a homopolymer or copolymer having a hydrazide-type hollow functional group is reacted with a hydrazidating agent either directly or after dissolving it in an organic solvent. Examples of organic solvents used at this time include methanol, alcohol, inpropanol,
Alcohol solvents such as n-furopanol, n-butanol, sec-butanol, inftanol, t-butanol, and cyclohexanol; aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and mineral spirits; Ether alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, N,N-dimethylformamide (
DMF), dioxane, etc., and these may be used alone or in combination of two or more.
また、該溶液中の重合体濃度は溶液粘度が２５℃の温度
で０．２〜３０ボイズとなるような範囲で選ばれる。ま
た、ヒドラジド化剤の種類については特に制限はなく、
従来のヒドラジド化剤として慣用されているもの、例え
ばヒドラジンやヒドラジンヒドラートなどを用いること
ができる。これらのヒドラジド化剤は水溶液の状態で用
いてもよいし、水を含まない１００％試剤として用いて
もよく、また単独で用いてもよいし、２種以上を組み合
わせて用いてもよい。さらにその使用量は、所望のヒド
ラジド化率を得るための理論量以上、好ましくは理論量
の１．２〜５倍量の範囲で選ばれる。Further, the polymer concentration in the solution is selected within a range such that the solution viscosity is 0.2 to 30 voids at a temperature of 25°C. In addition, there are no particular restrictions on the type of hydrazidating agent;
Conventional hydrazidizing agents, such as hydrazine and hydrazine hydrate, can be used. These hydrazidating agents may be used in the form of an aqueous solution or as a 100% water-free reagent, and may be used alone or in combination of two or more. Furthermore, the amount used is selected within the range of at least the theoretical amount for obtaining the desired hydrazidation rate, preferably from 1.2 to 5 times the theoretical amount.
該ヒドラジド化反応における反応温度は使用する重合体
の種類などに左右され一概に定めることはできないが、
通常３０〜１２０℃の範囲において重合体の種類に応じ
て適宜選ばれる。また、反応時間は重合体の種類、ヒド
ラジド化剤の量、所望ヒドラジド化率、反応温度などに
よって左右され一概に定めることができないが一般的に
は０．５〜１０時間程度で十分である。The reaction temperature in the hydrazidation reaction depends on the type of polymer used and cannot be determined unconditionally.
Usually, the temperature is appropriately selected in the range of 30 to 120°C depending on the type of polymer. Further, the reaction time depends on the type of polymer, the amount of hydrazidating agent, the desired hydrazidation rate, the reaction temperature, etc., and cannot be determined unconditionally, but generally about 0.5 to 10 hours is sufficient.
このようにしてヒドラジド化反応が終了した反応溶液に
は生成したヒドラジド化重合体とともに過剰のヒドラジ
ド化剤が存在しているので、これを除去する必要がある
。In the reaction solution in which the hydrazidation reaction has been completed in this manner, an excess of the hydrazidation agent is present together with the produced hydrazidation polymer, and this must be removed.
本発明においては、塩類を溶解させた溶液中に反応終了
液を投入するか、あるいは反応終了液を希釈後塩類を加
えてヒドラジド化重合体を析出又は高濃度溶液として分
離し、残存するヒドラジド化剤を除去する。In the present invention, the reaction completed solution is poured into a solution in which salts have been dissolved, or salts are added after diluting the reaction completed solution to precipitate the hydrazided polymer or separate it as a highly concentrated solution, and the remaining hydrazided polymer is separated. remove the agent.
この際塩類を溶解させるための溶媒や反応終了液を希釈
するための溶媒は、いずれも通常水が用いられるが、水
と相溶する有機溶媒、例えばアルコール類、セロンルブ
類、ＤＭＦ，ジオキサンなどの溶媒の１種又は２種以上
と水との混合溶媒も用いることができる。At this time, water is usually used as the solvent for dissolving the salts and the solvent for diluting the reaction-completed solution, but organic solvents that are compatible with water, such as alcohols, seronlubes, DMF, dioxane, etc. A mixed solvent of one or more solvents and water can also be used.
またこの際用いる塩類としては、例えば硫酸バリウム、
塩化バリウム、硝酸バリウム、塩化カルシウム、リン酸
水素カルシウム、硝酸カリウム、ヨウ化カリウム、リン
酸カリウム、硫酸カリウム、塩化リチウム、ヨウ化リチ
ウム、炭酸マグネシウム、塩化マグネシウム、ヨウ化マ
グネシウム、硝酸マグネシウム、炭酸アンモニウム、塩
化アンモニウム、リン酸水素アンモニウム、硝酸アンモ
ニウム，ｉｓアンモニウム、硫酸ナトリウムアンモニウ
ム、塩化ナトリウム、炭酸水素ナトリウム、リン酸水素
ナトリウムなどの無機塩類、クエン酸カリウム、クエン
酸カルシウム、クエン酸アンモニウム、クエン酸ナトリ
ウム、クエン酸マグネシウムなどのクエン酸塩、酢酸ア
ンモニウム、酢酸カリウム、酢酸ナトリウム、酢酸マグ
ネシウムなどの酢酸塩、シュウ酸ナトリウムなどのシュ
ウ酸塩、コハク酸ナトリウムなどのコハク酸塩、酒石酸
ナトリウムなどの酒石酸塩、フタル酸水素ナトリウムな
どの７タル酸塩などの有機塩類が挙げられ、これらの１
種を用いてもよいし、２種以上を混合して用いてもよい
。In addition, the salts used at this time include, for example, barium sulfate,
Barium chloride, barium nitrate, calcium chloride, calcium hydrogen phosphate, potassium nitrate, potassium iodide, potassium phosphate, potassium sulfate, lithium chloride, lithium iodide, magnesium carbonate, magnesium chloride, magnesium iodide, magnesium nitrate, ammonium carbonate, Inorganic salts such as ammonium chloride, ammonium hydrogen phosphate, ammonium nitrate, is ammonium, sodium ammonium sulfate, sodium chloride, sodium hydrogen carbonate, sodium hydrogen phosphate, potassium citrate, calcium citrate, ammonium citrate, sodium citrate, citric acid Citrates such as magnesium acid, acetates such as ammonium acetate, potassium acetate, sodium acetate, magnesium acetate, oxalates such as sodium oxalate, succinates such as sodium succinate, tartrates such as sodium tartrate, phthalates. These include organic salts such as 7-talates such as sodium hydrogen chloride;
Seeds may be used or a mixture of two or more types may be used.
本発明においては、ヒドラジド化重合体を分離する方法
として、例えば次に示す（１）及び（２）の方法が好ま
しく用いられる。In the present invention, the following methods (1) and (2), for example, are preferably used as a method for separating the hydrazide polymer.
すなわち、（１）の方法は、まず塩類を水単独又は水と
有機溶媒との混合溶媒に溶解させ、この塩溶液中にヒド
ラジド化反応終了液を徐々に加えて、重合体を析出させ
るか、又は高濃度溶液として分離する。この際使用する
塩類の量は、塩の種類やヒドラジド化重合体の性質、反
応溶液の種類などによって異なるが、一般的には塩類溶
液と反応終了液との合計量に対し、６０重量％以下にな
るように選ばれる。まｔ；塩類溶液の量は、反応終了液
に対して３００重量倍までの範囲で選ぶのが適当である
。得られた重合体が固形の場合はろ過、遠心分離法、デ
カンテーションなどにより析出物を分離する。また、得
られた重合体が高濃度溶液又は溶液状の場合には、静置
して２層に分液したのち、公知の手段によって重合体層
を分離する。That is, in method (1), salts are first dissolved in water alone or in a mixed solvent of water and an organic solvent, and the hydrazidation reaction completed liquid is gradually added to this salt solution to precipitate the polymer, or Or separate as a highly concentrated solution. The amount of salts used at this time varies depending on the type of salt, the properties of the hydrazide polymer, the type of reaction solution, etc., but generally it is 60% by weight or less based on the total amount of the salt solution and the reaction completed liquid. chosen to be. It is appropriate to select the amount of the salt solution within a range of up to 300 times the weight of the reaction-completed solution. If the obtained polymer is solid, the precipitate is separated by filtration, centrifugation, decantation, or the like. When the obtained polymer is in the form of a highly concentrated solution or solution, it is left to stand and separated into two layers, and then the polymer layers are separated by known means.
一方、（２）の方法は、まずヒドラジド化反応終了液を
水単独又は水と有機溶媒との混合溶媒で希釈したのち、
この希釈液に、撹拌しながら塩をそのまま、あるいは有
機溶媒に溶解させて加え、ヒドラジド化重合体を析出又
は高濃度溶液として分離する。この際ヒドラジド化反応
終了液を希釈する希釈剤の量は、ヒドラジド化反応終了
液の１００重量倍以下の範囲から選ぶのが適当である。On the other hand, in method (2), the hydrazidation reaction completed solution is first diluted with water alone or a mixed solvent of water and an organic solvent, and then
The salt is added as it is or dissolved in an organic solvent to this diluted solution while stirring, and the hydrazide polymer is separated as a precipitate or a highly concentrated solution. At this time, the amount of diluent used to dilute the hydrazidation reaction completed liquid is appropriately selected from a range of 100 times or less by weight of the hydrazidation reaction completed liquid.
また塩類の量は、通常ヒドラジド化反応終了液、希釈剤
、塩類とを合わせた合計量の６０重量％以下になるよう
に選ばれる。析出したヒドラジド化重合体又は高濃度溶
液状のヒドラジド化重合体は、前記（１）の場合と同様
に処理して分離する。The amount of salts is usually selected to be 60% by weight or less of the total amount of the hydrazidation reaction finished liquid, diluent, and salts. The precipitated hydrazide polymer or the hydrazide polymer in the form of a highly concentrated solution is treated and separated in the same manner as in the case of (1) above.
次に、前記（１）及び（２・）の方法により分離された
固形状又は高濃度溶液状ヒドラジド化重合体は、必要な
らば、さらに水単独又は水と有機溶媒との混合溶媒で希
釈後、塩類を添加して、ヒドラジド化重合体を固形状又
は高濃度溶液として分離する。このような操作を数回繰
り返すことによって、ヒドラジド化剤をほぼ完全に除去
することができる。Next, the solid or highly concentrated solution hydrazide polymer separated by the methods (1) and (2) above is diluted with water alone or with a mixed solvent of water and an organic solvent, if necessary. , salts are added to separate the hydrazided polymer as a solid or a highly concentrated solution. By repeating this operation several times, the hydrazidizing agent can be almost completely removed.
また、前記（１）、（２）の方法においては、必要に応
じ、透析、電気透析、限外ろ過などの方法により脱塩処
理を施すこともできる。Furthermore, in the methods (1) and (2) above, desalination treatment can also be performed by methods such as dialysis, electrodialysis, and ultrafiltration, if necessary.
［実施例］
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.
実施例１
２１Ｉの五つ口フラスコに２−エトキシエタノール３２
０ｇ、キシレン８０ｇを仕込み、撹拌しなからｌ ４
０ ’Ｏに加熱した。次にエチルアクリレート１００ｇ
、ｎ−プチルメタクリレート４００ｇから或る単量体混
合物にバーブチルＤ［ジーｔ−プチルペルオキシド、日
本油脂（株）商品名］２．５ｇを溶解し、この溶液を前
記の加熱フラスコ中へ２時間かけて滴下した。撹拌しな
がら４時間前記の温度に保持したのち、これを２−エト
キシエタノール８０ｇ、キシレン２０９で希釈して原料
のアクリル共重合体溶液９９８ｇを得た。このようにし
て得られたアクリル共重合体溶液は固形分が５０重量％
、粘度が８ポイズ／２５゜Ｃであり、また共重合体の重
量平均分子量が５６，０００で無色透明であった。Example 1 32 2-ethoxyethanol was added to a 21I five-necked flask.
0g, xylene 80g, stir, then l 4
Heated to 0'O. Next, 100g of ethyl acrylate
, 2.5 g of barbutyl D [di-t-butyl peroxide, trade name of NOF Corporation] was dissolved in a certain monomer mixture from 400 g of n-butyl methacrylate, and this solution was poured into the above heating flask for 2 hours. dripped. After maintaining the above temperature for 4 hours with stirring, this was diluted with 80 g of 2-ethoxyethanol and 209 g of xylene to obtain 998 g of a raw material acrylic copolymer solution. The acrylic copolymer solution thus obtained has a solid content of 50% by weight.
The copolymer had a viscosity of 8 poise/25°C, a weight average molecular weight of 56,000, and was colorless and transparent.
次に、このアクリル共重合体溶液に、その中のアクリル
共重合体全量をヒドラジド化するために１００％ヒドラ
ジンヒドラー１−１２５９ （前記ビニル型単量体中
のエチルアクリレートのエステル基だけをヒドラジド化
するのに要する理論量の２．５倍′！ｋ）を加え、撹拌
しなから１２０゜Ｃで３時間反応させｔ；。その後反応
溶液を５，０００，の水中に投入して撹拌希釈し溶液が
均一（白色乳化状態）になった時点で、硫酸アンモニウ
ム２．５００９を粉末のまま徐々に添加した。硫酸アン
モニウムを完全に添加し終わったのち、１０分間撹拌し
その後一夜静置した。塩を加えることによって析出した
固形樹脂は、徐々に沈み白色の沈澱が生じた。これをろ
別し真空乾燥を行って白色固形樹脂を得た。その後この
固形樹脂に、水５．０００９を加え再溶解させたのち、
硫酸アンモニウム２ ．５ ０ ０９を加え樹脂を再び
沈澱させた。この沈澱をろ別乾燥し白色固形樹脂を得た
。その後水５．０００９及び硫酸アンモニウム２，５０
０９を用いて同じ操作を行った（計３回）。Next, in order to hydrazide the entire amount of the acrylic copolymer in this acrylic copolymer solution, 100% hydrazine hydra 1-1259 (hydrazide only the ester group of ethyl acrylate in the vinyl monomer) is added. 2.5 times the theoretical amount required for the reaction was added, and the reaction was carried out at 120°C for 3 hours without stirring. Thereafter, the reaction solution was poured into 5,000 ml of water and diluted with stirring. When the solution became homogeneous (white emulsified state), 2.500 ml of ammonium sulfate was gradually added as a powder. After complete addition of ammonium sulfate, the mixture was stirred for 10 minutes and then allowed to stand overnight. The solid resin precipitated by adding salt gradually sank to form a white precipitate. This was filtered and vacuum dried to obtain a white solid resin. After that, 5.000% of water was added to this solid resin to redissolve it, and then
Ammonium sulfate 2. 5009 was added to precipitate the resin again. This precipitate was filtered and dried to obtain a white solid resin. Then water 5.0009 and ammonium sulfate 2.50
The same operation was performed using 09 (3 times in total).
このようにして得られた白色樹脂を少量の水で２〜３回
洗い流し、真空乾燥させて目的とするヒドラジド化樹脂
４２５ｇを得た。The white resin thus obtained was washed two to three times with a small amount of water and dried under vacuum to obtain 425 g of the desired hydrazide resin.
実施例２
２Ｑの五つ口フラスコにｎ−ブタノール３００９を仕込
み、撹拌しながら１１０℃まで加熱した。Example 2 N-butanol 3009 was charged into a 2Q five-necked flask and heated to 110° C. with stirring.
その後２−ヒドロキシエチルアクリレート９６９、ｎ−
プチルアクリレート３８４ｇから或る単量体混合物にパ
ーブチル０〔ｔ−プチルパーオキシ−２−エチルヘキサ
ノエート、日本油脂（株）商品名〕２０９を溶解し、こ
の溶液を前記の加熱フラスコ中へ２時間かけて滴下した
。撹拌しながら１時間前記の温度に保持したのち、これ
にｎ−プタノール５０９にパープチル０ ２９を溶解
した溶液を３０分かけて滴下した。その後１時間前記の
温度に保持したのち、これにｎ−プタノール１５０ｇを
加えて希釈し、原料のアクリル共重合体溶液９９５ｇを
得た。得られたアクリル共重合体溶液は固形分が５０重
量％、粘度が０．２ボイズ／２５℃であり、また共重合
体の重量平均分子量がｓ，ｏｏｏで無色透明であった。Then 2-hydroxyethyl acrylate 969, n-
Perbutyl 0 [t-butyl peroxy-2-ethylhexanoate, trade name of NOF Corporation] 209 was dissolved in a certain monomer mixture from 384 g of butyl acrylate, and this solution was poured into the heating flask described above. It dripped over time. After maintaining the above temperature for 1 hour while stirring, a solution of Purptyl 029 in n-butanol 509 was added dropwise over 30 minutes. Thereafter, the temperature was maintained at the above temperature for 1 hour, and then 150 g of n-butanol was added to dilute the solution to obtain 995 g of a raw material acrylic copolymer solution. The obtained acrylic copolymer solution had a solid content of 50% by weight, a viscosity of 0.2 voids/25°C, a weight average molecular weight of s,ooo, and was colorless and transparent.
次に、このアクリル共重合体溶液に、その中のアクリル
共重合体全量をヒドラジド化するｔ；めに１００％ヒド
ラジンヒドラート７５ｇ （前記ビニル型単量体中の２
−ヒドロキシエチルアクリレートのエステル基だけをヒ
ドラジド化するのに要する理論量の１．８＠量）及び２
８重量％アンモニア水１００ｇを加え、撹拌しながら９
０℃で６時間反応させた。水７．０００９に塩化ナトリ
ウム２１０９を溶解させた溶液を用意し、前記反応終了
液をこの溶液中に撹拌しながら徐々に加えた。Next, to this acrylic copolymer solution, 75 g of 100% hydrazine hydrate (75 g of 100% hydrazine hydrate
- the theoretical amount required to hydrazide only the ester group of hydroxyethyl acrylate) and 2
Add 100g of 8% by weight ammonia water and add 9% by weight while stirring.
The reaction was carried out at 0°C for 6 hours. A solution of sodium chloride 2109 dissolved in water 7.0009 was prepared, and the reaction-completed solution was gradually added to this solution while stirring.
その後１時間撹拌を行い一夜静置しＩ；。After that, it was stirred for 1 hour and left to stand overnight.
このように一夜靜置して青白色粘調樹脂溶液を下層に沈
降させデカンテーションにより下層の濃厚樹脂溶液を得
た。その後この樹脂溶液を水５ ，０ ０ ０ｇで希釈
したのち、塩化ナトリウム１００９を用いて前記と同様
に濃厚樹脂溶液を得た。同様の操作を水３．０００９及
び塩化ナトリウム１００９を用いて行った。このように
して得られた下層樹脂溶液は収量が１ ．０ ３ ２９
で樹脂濃度が４２重量％、粘度が２０ポイズ／２５℃で
あった。In this manner, the mixture was allowed to stand overnight, and the bluish-white viscous resin solution was precipitated into the lower layer, followed by decantation to obtain a lower layer of a concentrated resin solution. Thereafter, this resin solution was diluted with 5,000 g of water, and then sodium chloride 1009 was used to obtain a concentrated resin solution in the same manner as above. A similar operation was carried out using 3.0009 g of water and 100 g of sodium chloride. The yield of the lower layer resin solution obtained in this way is 1. 0 3 29
The resin concentration was 42% by weight and the viscosity was 20 poise/25°C.
実施例３
実施例１において、溶媒としてトルエン３００９、単量
体混合物としてｎ−プチルアクリレート１００ｇ、スチ
レン１００ｇ、重合開始剤としてペンゾイルバーオキサ
イド３ｇをそれぞれ使用し、かつ重合条件を１１０℃で
３時間とした以外は、実施例１と同様にしてアクリル共
重合体溶液５０２ｇを得た。得られた共重合体溶液は固
形分が４０重量％、粘度が３．４ポイズ／２５℃であり
、また共重合体の重量平均分子量が２１，０００で無色
透明であった。Example 3 In Example 1, 3009 toluene was used as the solvent, 100 g of n-butyl acrylate and 100 g of styrene were used as the monomer mixture, and 3 g of penzoyl peroxide was used as the polymerization initiator, and the polymerization conditions were 110° C. for 3 hours. Except for the above, 502 g of an acrylic copolymer solution was obtained in the same manner as in Example 1. The obtained copolymer solution had a solid content of 40% by weight, a viscosity of 3.4 poise/25° C., a weight average molecular weight of 21,000, and was colorless and transparent.
次に、このアクリル共重合体溶液に、その中のアクリル
共重合体全量をヒドラジド化するためにＤＭＦ２００９
を加えたのち、８０重量％ヒドラジンヒドラート１４６
ｇ （前記ビニル型単量体中のｎ−プチルアクリレート
のエステル基をヒドラジド化するのに要する理論量の５
倍量）を加え、撹拌しながら９８゜０で６時間反応させ
た。その後反応溶液を水７００９とメタノール３００９
で希釈したのち、３５重量％塩化カルシウム水溶液２０
９を徐々に滴下した。滴下後３０分撹拌し一夜放置して
白色固形沈澱を生じさせたのち、デヵンテーションによ
り上層液を取り去った。この白色固形物に水７００ｇと
メタノール３００９を加えて再溶解し、３５重量％塩化
カルシウム水溶液２００ｇを徐々に滴下し、白色固形物
をデカンテーションで分離する操作を続けて計４回行っ
た。Next, DMF2009 was added to this acrylic copolymer solution in order to hydrazide the entire amount of the acrylic copolymer therein.
After adding 80% by weight hydrazine hydrate 146
g (the theoretical amount required to hydrazide the ester group of n-butyl acrylate in the vinyl monomer)
double the amount) was added, and the mixture was reacted at 98°0 for 6 hours with stirring. After that, the reaction solution was mixed with water 7009 and methanol 3009
After diluting with 35% by weight calcium chloride aqueous solution 20
9 was gradually added dropwise. After the dropwise addition, the mixture was stirred for 30 minutes, left overnight to form a white solid precipitate, and the upper layer liquid was removed by decantation. This white solid was redissolved by adding 700 g of water and methanol 3009, 200 g of a 35% by weight aqueous calcium chloride solution was gradually added dropwise, and the white solid was separated by decantation, which was repeated four times in total.
このようにして得られた白色固形物を真空乾燥して目的
とするヒドラジド化重合体４４２ｇを得た。The thus obtained white solid was vacuum dried to obtain 442 g of the desired hydrazide polymer.
実施例４
１０１の四つ口フラスコに水４，４５０９、イソプロパ
ノール５０ｇ、過硫酸カリウム０．９５９を仕込み均一
にし、これにアクリルアミド５００９を加えて撹拌し均
一な溶液とした。Example 4 4,4509 g of water, 50 g of isopropanol, and 0.959 g of potassium persulfate were charged into a 101 four-necked flask and made uniform. Acrylamide 5009 was added thereto and stirred to form a uniform solution.
この溶液を８０’Ｏに昇温し２時間重合反応させたのち
、室温に冷却しポリアクリルアミド溶液４．９５０９を
得た。得られた溶液は固形分が１０重量％、粘度が２２
．７ポイズ／２５°Ｃであった。またこの重合体の重量
平均分子量は、１０１，０００で無色透明であった。This solution was heated to 80'O and subjected to a polymerization reaction for 2 hours, and then cooled to room temperature to obtain polyacrylamide solution 4.9509. The resulting solution had a solid content of 10% by weight and a viscosity of 22
．． The temperature was 7 poise/25°C. The weight average molecular weight of this polymer was 101,000, and it was colorless and transparent.
得られたポリアクリルアミド溶液全量に８０重量％ヒド
ラジンヒドラート水溶液１ ．２ ３ ８９（ヒドラジ
ド化するのに要する理論量の３．５倍量）を加え、撹拌
しながら９０℃で３時間反応させた。この反応終了液に
、固形のクエン酸ナトリウム４．９５０９を徐々に加え
、３０分撹拌を続けたのち、一夜靜置した。一夜靜置す
ると白色固形沈澱物が生成したので、これをろ別した。80% by weight aqueous hydrazine hydrate solution 1. 2 3 89 (3.5 times the theoretical amount required for hydrazidation) was added, and the mixture was reacted at 90° C. for 3 hours with stirring. Solid sodium citrate (4.9509 g) was gradually added to this reaction-completed solution, stirring was continued for 30 minutes, and then left overnight. After standing overnight, a white solid precipitate was formed, which was filtered.
ろ別した白色固形物に水４，８００９を加え再び溶解さ
せたのち、この再溶解した樹脂溶液にクエン酸ナトリウ
ム４．８００９を加えて白色樹脂を析出させ、これをろ
別した。その後少量の水で３回程度白色固形物を洗った
のち、真空乾燥を行って目的とするヒドラジド化重合体
４５３ｇを得た。After adding 4,8009 g of water to the filtered white solid and dissolving it again, 4,800 g of sodium citrate was added to this redissolved resin solution to precipitate a white resin, which was filtered. Thereafter, the white solid was washed three times with a small amount of water, and then vacuum dried to obtain 453 g of the desired hydrazide polymer.
比較例１
実施例２と同じ方法で原料重合体の製造及びヒドラジド
化を行った。ヒドラジド化後の溶液に過酸化水素水（磯
度３１重量％）１４７．４９とインプロパノール２．５
００９の混合液を６０℃１時間で滴下した。その後反応
液を撹拌しながら８２℃に昇温し溶媒の一部と共に水、
窒素ガス及びアンモニアを留去して精製ヒドラジド化重
合体溶液１．１７０９を得た。この溶液は固形分が４０
重量％、粘度が１．６５ポイズ／２５°Ｃであった。Comparative Example 1 A raw material polymer was produced and hydrazidated in the same manner as in Example 2. The solution after hydrazidation is 147.49% hydrogen peroxide solution (31% by weight) and 2.5% impropanol.
A mixed solution of 009 was added dropwise at 60° C. for 1 hour. Thereafter, the temperature of the reaction solution was raised to 82°C while stirring, and water and part of the solvent were added.
Nitrogen gas and ammonia were distilled off to obtain purified hydrazide polymer solution 1.1709. This solution has a solid content of 40
The weight percent and viscosity were 1.65 poise/25°C.
比較例２
実施例４と同じ方法で原料重合体を重合し、得られたポ
リアクリルアミド溶液ｓ，ｏｏｏ９をメタノール５０ａ
中に注いで重合体を沈澱させ６０℃で減圧乾燥して、重
量平均分子量１０２，５００の白色粉末ポリアクリルア
ミド４２０９を得た。Comparative Example 2 The raw material polymer was polymerized in the same manner as in Example 4, and the obtained polyacrylamide solution s,ooo9 was mixed with methanol 50a
The polymer was poured into the solution to precipitate it and dried under reduced pressure at 60° C. to obtain white powder polyacrylamide 4209 having a weight average molecular weight of 102,500.
次にこのポリアクリルアミド２５０９と８０重量％ヒド
ラジンヒドラート水溶液２．５００９とをフラスコに入
れ撹拌しなから９０”Ｃで３時間反応させたのち、反応
液を氷酢酸５０ｃｃを含むメタノール２５ｌ中に注いで
沈澱物を生或させた。これをさらに水２，０００，で再
溶解させＩ；ノチ、氷酢酸５０ｃｃを含むメタノール２
Ｏｆｉ中に注ぎ沈澱物を生威させ、真空乾燥して白色固
形樹脂２０９ｇを得ｌ；。Next, this polyacrylamide 2509 and 80% by weight hydrazine hydrate aqueous solution 2.5009 were placed in a flask and reacted at 90"C for 3 hours without stirring, and then the reaction solution was poured into 25 liters of methanol containing 50 cc of glacial acetic acid. A precipitate was formed.The precipitate was further dissolved in 2,000 ml of water, and 2,000 ml of methanol containing 50 cc of glacial acetic acid was added.
The precipitate was poured into Ofi and dried under vacuum to obtain 209 g of a white solid resin.
以上、実施例１〜４、比較例１，２で得られたヒドラジ
ド化重合体の性状、残留ヒドラジン量、ＬｏｇＰ値を第
３表に示した。なお残留ヒドラジン量の定量は、それぞ
れの樹脂に、濃度が１０重量％になるまで水を加え、ア
ルパックサービス（株）社製高分子電解質膜（Ｇ−０１
Ｔ）を用いてＭＣ − ４ Ａ＠外ろ過器で３ ． ５
ｋｇ／ ｃｍ”の圧力でろ過したろ液を、ＪＩＳＢ−
８２２４の方法に従ってヒドラジン量を求め、固形樹脂
中のヒドラジン含量を算出した。The properties, residual hydrazine amounts, and LogP values of the hydrazide polymers obtained in Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 3. To quantify the amount of residual hydrazine, add water to each resin until the concentration is 10% by weight, and use a polymer electrolyte membrane (G-01 manufactured by Alpac Service Co., Ltd.).
3. Using T) with MC-4A@external filter. 5
The filtrate filtered at a pressure of "kg/cm" is
The amount of hydrazine was determined according to the method of 8224, and the hydrazine content in the solid resin was calculated.
第
３
表
第３表から分かるように実施例１〜４における残留ヒド
ラジン量は０．００３重量％以下で、比較例１〜２に比
べて明らかに少なく、数十分の１ないし千分のｌ程度で
あった。特に同一組戊で精製法のみ異なる実施例２と比
較例ｌを比較すると実施例２の残留ヒドラジン量は比較
例１の約５００分の１であった。また比較例１の場合に
は還元力の強いヒドラジンを酸化剤である過酸化水素で
分解するので著しい発泡を伴い危険であるばかりか得ら
れた精製樹脂溶液が黄変するという欠点も有していた。Table 3 As can be seen from Table 3, the amount of residual hydrazine in Examples 1 to 4 was 0.003% by weight or less, clearly smaller than that in Comparative Examples 1 to 2, ranging from several tenths to thousandths of a liter. It was about. In particular, when comparing Example 2 and Comparative Example 1, which had the same structure but differed only in the purification method, the amount of residual hydrazine in Example 2 was about 1/500 of that in Comparative Example 1. In addition, in the case of Comparative Example 1, hydrazine, which has a strong reducing power, is decomposed with hydrogen peroxide, which is an oxidizing agent, which is not only dangerous due to significant foaming, but also has the disadvantage that the obtained purified resin solution turns yellow. Ta.
これに比べて実施例１〜４は黄色着色もなくまた安全な
方法であった。In comparison, Examples 1 to 4 did not cause any yellowing and were a safe method.
以上のことから本発明によるヒドラジド化重合体の精製
方法は、従来の方法より優れていることが分かる。From the above, it can be seen that the method for purifying hydrazide polymers according to the present invention is superior to conventional methods.
［発明の効果］
本発明によると、ヒドラジド化反応終了液を塩類と接触
させて、生或したヒドラジド化重合体を析出又は高濃度
溶液層として分離することによって、無着色で高純度の
親水性ヒドラジド化重合体（ヒドラジド化剤含量０．０
０３重量％以下）を、安全かつ安価に極めて効率よく製
造することができる。[Effects of the Invention] According to the present invention, by bringing the hydrazidation reaction completed liquid into contact with salts and separating the formed hydrazidated polymer as a precipitate or a highly concentrated solution layer, a colorless and highly pure hydrophilic polymer can be produced. Hydrazized polymer (hydrazidating agent content 0.0
03% by weight or less) can be produced safely, inexpensively, and extremely efficiently.
本発明の方法で得られるヒドラジド化重合体は、例えば
金属捕集剤、紙力増強剤、ホルマリン吸収剤、水溶性塗
料などの材料や耐熱材料、還元材料などとして好適に用
いられる。The hydrazide polymer obtained by the method of the present invention is suitably used as, for example, a metal collector, a paper strength enhancer, a formalin absorbent, a water-soluble paint, a heat-resistant material, a reducing material, and the like.
Claims (1)
ド化剤とを反応させてヒドラジド化重合体を製造するに
当たり、生成したヒドラジド化重合体のＬｏｇＰ値（た
だし、Ｐは水とｎ−オクタノールに対する分配係数であ
る）が１．１０以下の場合、反応終了液を塩類と接触さ
せて、該ヒドラジド化重合体を析出又は高濃度溶液層と
して分離することを特徴とする親水性ヒドラジド化重合
体の製造方法。1. When producing a hydrazide polymer by reacting a polymer having a hydrazide-forming functional group with a hydrazide agent, the LogP value of the produced hydrazide polymer (where P is the distribution coefficient between water and n-octanol) ) is 1.10 or less, a method for producing a hydrophilic hydrazided polymer, which comprises contacting the reaction-completed liquid with a salt to separate the hydrazided polymer as a precipitate or a highly concentrated solution layer. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19228989A JPH0356507A (en) | 1989-07-25 | 1989-07-25 | Preparation of hydrophilic hydrazide polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19228989A JPH0356507A (en) | 1989-07-25 | 1989-07-25 | Preparation of hydrophilic hydrazide polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0356507A true JPH0356507A (en) | 1991-03-12 |
Family
ID=16288805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19228989A Pending JPH0356507A (en) | 1989-07-25 | 1989-07-25 | Preparation of hydrophilic hydrazide polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0356507A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593046A (en) * | 1994-05-09 | 1997-01-14 | Nikko Kogyo Kabushiki Kaisha | Collapsible housing frame |
| JP2007046062A (en) * | 2003-11-12 | 2007-02-22 | Otsuka Chemical Co Ltd | Polyacrylic hydrazide and crosslinking or curing agent for resin |
| WO2008007650A1 (en) * | 2006-07-14 | 2008-01-17 | Otsuka Chemical Co., Ltd. | Hydrazine storage resin |
-
1989
- 1989-07-25 JP JP19228989A patent/JPH0356507A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5593046A (en) * | 1994-05-09 | 1997-01-14 | Nikko Kogyo Kabushiki Kaisha | Collapsible housing frame |
| JP2007046062A (en) * | 2003-11-12 | 2007-02-22 | Otsuka Chemical Co Ltd | Polyacrylic hydrazide and crosslinking or curing agent for resin |
| WO2008007650A1 (en) * | 2006-07-14 | 2008-01-17 | Otsuka Chemical Co., Ltd. | Hydrazine storage resin |
| JP5398261B2 (en) * | 2006-07-14 | 2014-01-29 | 大塚化学株式会社 | How to store hydrazine |
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