JPS62177008A - Production of copolymer - Google Patents
Production of copolymerInfo
- Publication number
- JPS62177008A JPS62177008A JP61017657A JP1765786A JPS62177008A JP S62177008 A JPS62177008 A JP S62177008A JP 61017657 A JP61017657 A JP 61017657A JP 1765786 A JP1765786 A JP 1765786A JP S62177008 A JPS62177008 A JP S62177008A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- reaction
- meth
- copolymer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 alkali metal salt Chemical group 0.000 claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 10
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 62
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 25
- 239000000178 monomer Substances 0.000 abstract description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 11
- 150000003839 salts Chemical class 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 5
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 4
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 abstract description 2
- JDSVWTAJRNTSSL-UHFFFAOYSA-M sodium;dodecyl hydrogen phosphate Chemical compound [Na+].CCCCCCCCCCCCOP(O)([O-])=O JDSVWTAJRNTSSL-UHFFFAOYSA-M 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 59
- 229920000642 polymer Polymers 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 15
- 235000002639 sodium chloride Nutrition 0.000 description 14
- 239000011734 sodium Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 230000008719 thickening Effects 0.000 description 9
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229920003169 water-soluble polymer Polymers 0.000 description 5
- 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 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004663 dialkyl amino group Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000007785 strong electrolyte Substances 0.000 description 3
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 230000009965 odorless effect Effects 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- VWXLCWNPSOUPPE-UHFFFAOYSA-N (1-amino-2-methylpropylidene)azanium;chloride Chemical compound Cl.CC(C)C(N)=N VWXLCWNPSOUPPE-UHFFFAOYSA-N 0.000 description 1
- YFZCNXJOYHYIGC-UHFFFAOYSA-N (2,2,2-trichloroacetyl) 2,2,2-trichloroethaneperoxoate Chemical compound ClC(Cl)(Cl)C(=O)OOC(=O)C(Cl)(Cl)Cl YFZCNXJOYHYIGC-UHFFFAOYSA-N 0.000 description 1
- NSYCJGRIGHDEMT-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(1,1,2,2,3,3,4,4,4-nonafluorobutylperoxy)butane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)OOC(F)(F)C(F)(F)C(F)(F)C(F)(F)F NSYCJGRIGHDEMT-UHFFFAOYSA-N 0.000 description 1
- KOWOGKUTCSIJFZ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl dihydrogen phosphate Chemical compound OP(O)(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KOWOGKUTCSIJFZ-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-UHFFFAOYSA-N 0.000 description 1
- CBQFBEBEBCHTBK-UHFFFAOYSA-N 1-phenylprop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)C(C=C)C1=CC=CC=C1 CBQFBEBEBCHTBK-UHFFFAOYSA-N 0.000 description 1
- WUPBHEBKORKMDB-UHFFFAOYSA-N 2,2-dimethyl-3-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)CNC(=O)C=C WUPBHEBKORKMDB-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- YPFIYMHYZDIPAR-UHFFFAOYSA-N 2-hexyldecyl dihydrogen phosphate Chemical compound CCCCCCCCC(COP(O)(O)=O)CCCCCC YPFIYMHYZDIPAR-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical class C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SYUYXOYNRMMOGW-UHFFFAOYSA-N n,n-dimethyl-3-phenylprop-2-en-1-amine Chemical compound CN(C)CC=CC1=CC=CC=C1 SYUYXOYNRMMOGW-UHFFFAOYSA-N 0.000 description 1
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000865 phosphorylative effect Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000003863 physical function Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- PBTSABBVLASENC-UHFFFAOYSA-N prop-2-enamide;trimethyl(propyl)azanium Chemical group NC(=O)C=C.CCC[N+](C)(C)C PBTSABBVLASENC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007717 redox polymerization reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はリン酸基を含有する共重合体の製造法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a copolymer containing phosphoric acid groups.
高分子化学の分野において種々の機能を高分子化合物に
付与させる研究が進められており、一つには化学的な機
能の付与、例えばリン酸酸性基の持つキレート能、帯電
防止能等の機能を高分子化合物に付与させる研究がある
。さらにもう一方においては物理的な機能、例えば界面
活性、即ち親木基と疎水基を有する両親媒性化合物特有
の自ら集合し組織化する性質（自己組織能）を高分子化
合物に付与させる研究や、高分子化合物に単に疎水性を
付与する研究がある。In the field of polymer chemistry, research is underway to impart various functions to polymer compounds. One example is the ability to impart chemical functions, such as the chelating ability and antistatic ability of phosphoric acid groups. There is research on imparting this to polymer compounds. Furthermore, on the other hand, research is being conducted to impart physical functions, such as surface activity, to polymeric compounds, such as the property of self-assembling and organizing (self-organizing ability) unique to amphiphilic compounds that have a parent group and a hydrophobic group. , there is research on simply imparting hydrophobicity to polymer compounds.
さらに、高分子化合物を工学ばかりでなく、医学、薬学
等の分野へ応用していく研究も最近盛んに行われてきて
おり、その場合には生体との適合性の良い化合物が望ま
れている。生体内にはリン脂質と呼ばれる一種のリン酸
エステルが多く存在し、従ってリン酸基を持つ化合物は
生体親和性に優れた性質が期待されており、例えば長鎖
アルキルアルコールのリン酸モノエステルのアルカリ金
属あるいはアルカノールアミン塩は皮膚に対する刺激が
少ない洗浄剤として広く用いられている。また、これら
リン酸エステルは先に述べた界面活性能という点におい
ても優れた性質を有している。リン酸基含有重合体はこ
れらリン酸基含有化合物の特徴ある性質のために新しい
機能を有する高分子化合物として種々研究されているが
、リン酸基を有する重合体を工業的に得ることは困難で
あり、工業的に容易に製造できる技術が望まれている。Furthermore, research has recently been actively conducted to apply polymer compounds not only to engineering, but also to fields such as medicine and pharmacy, and in such cases, compounds with good compatibility with living organisms are desired. . A type of phosphoric acid ester called phospholipid exists in large quantities in living organisms, and therefore compounds with a phosphoric acid group are expected to have excellent biocompatibility.For example, phosphoric acid monoesters of long-chain alkyl alcohols are Alkali metal or alkanolamine salts are widely used as cleansing agents that are less irritating to the skin. Furthermore, these phosphoric acid esters have excellent properties in terms of the above-mentioned surfactant ability. Phosphate group-containing polymers are being studied in various ways as polymer compounds with new functions due to the distinctive properties of these phosphate group-containing compounds, but it is difficult to industrially obtain polymers with phosphate groups. Therefore, a technology that can be easily manufactured industrially is desired.
また、高分子化合物の分野の一つに水溶性の高分子化合
物があり、水溶性高分子化合物はその水溶液において増
粘、ゲル化、乳化・分散安定化等の効果を示し、化粧品
、医薬品、食品、繊維、製紙工業等の分野において広く
利用されている。水溶性高分子化合物としては、澱粉類
等の天然系の高分子化合物、カルボキシメチルセルロー
ス等の天然系高分子化合物を化学修飾した半合成高分子
化合物、さらにポリビニルアルコールやポリアクリル酸
等の合成高分子化合物がある。とりわけ、化粧品類、医
薬品等の添加剤として用いる場合には、一定の品質のも
のを大量に供給できることから、合成高分子化合物が最
近盛んに用いられるようになってきた。In addition, one of the fields of polymer compounds is water-soluble polymer compounds, which exhibit effects such as thickening, gelling, emulsification and dispersion stabilization in aqueous solutions, and are used in cosmetics, pharmaceuticals, etc. It is widely used in fields such as food, textiles, and paper manufacturing. Water-soluble polymer compounds include natural polymers such as starches, semi-synthetic polymers that are chemically modified natural polymers such as carboxymethyl cellulose, and synthetic polymers such as polyvinyl alcohol and polyacrylic acid. There are compounds. In particular, when used as additives in cosmetics, pharmaceuticals, etc., synthetic polymer compounds have recently come into widespread use because they can be supplied in large quantities with a certain quality.
化粧品類に用いられる水溶性高分子化合物に要求される
性質としては、安全かつ皮膚に対する刺激が少ないこと
や、無色・無臭であることなどがあり、ポリアクリル酸
系の高分子化合物が良く用いられている。しかし、これ
ら従来の高分子化合物は、水溶性高分子化合物の性質で
ある増粘性をみた場合、洗浄剤基剤として用いられるポ
リオキシエチレンアルキルエーテル硫酸塩、α−オレフ
ィンスルホン酸塩等の強電解質水溶液や食塩等の無機塩
を含んだ水溶液においては溶解せず、しかも増粘効果も
示さないといった欠点があった。さらに、化粧品類にお
いてよく用いられるエタノール／水系において増粘効果
を示すものも少なかった。The properties required of water-soluble polymer compounds used in cosmetics include being safe and causing little irritation to the skin, and being colorless and odorless, and polyacrylic acid-based polymers are often used. ing. However, when looking at the thickening properties of water-soluble polymer compounds, these conventional polymer compounds are not compatible with strong electrolytes such as polyoxyethylene alkyl ether sulfates and α-olefin sulfonates, which are used as detergent bases. It has the disadvantage that it does not dissolve in aqueous solutions or aqueous solutions containing inorganic salts such as common salt, and does not exhibit a thickening effect. Furthermore, few products showed a thickening effect in the ethanol/water system often used in cosmetics.
従って、工業的に容易に製造でき、安全性にも問題の少
ないリン酸エステル系の重合体の開発が望まれている。Therefore, it is desired to develop a phosphate ester polymer that can be easily produced industrially and has fewer safety problems.
さらに、ポリオキシエチレンアルキルエーテル硫酸塩、
α−オレフィンスルホン酸塩等の強電解質水溶液や食塩
等の無機塩を含んだ水溶液においては溶解して増粘効果
を示し、さらにエタノール水を増粘させるような水溶性
高分子化合物の開発も望まれている。Furthermore, polyoxyethylene alkyl ether sulfate,
It is also desired to develop water-soluble polymer compounds that dissolve and exhibit a thickening effect in strong electrolyte aqueous solutions such as α-olefin sulfonates and aqueous solutions containing inorganic salts such as common salt, and that can also thicken ethanol water. It is rare.
斯かる実情において、本発明者らは鋭意検討を行った結
果、高純度のモノアルキルリン酸が優れた界面活性能を
有していること、及び、モノアルキルリン酸のモノアル
カリ金属塩とグリシジル（メタ）アクリレートのエポキ
シ基とが選択性よく反応すること、さらにこの反応で得
られた化合物が系内に存在するビニル系単量体との優れ
た共重合性を有しており、容易にリン酸基を含有する共
重合体が得られること、またこうして得られた共重合体
において特定の基を有する共重合体、あるいは特定の反
応条件で得られた共重合体が、水溶性で、かつポリオキ
シエチレンアルキルエーテル硫酸塩、α−オレフィンス
ルホン酸塩等の強電解質水溶液や食塩等の無機塩を含ん
だ水溶液においては溶解し増粘効果を示し、さらにエタ
ノール水を増粘させることを見出し、本発明を完成した
。Under these circumstances, the present inventors conducted intensive studies and found that highly purified monoalkyl phosphoric acid has excellent surfactant ability, and that monoalkyl metal salts of monoalkyl phosphoric acid and glycidyl The epoxy group of (meth)acrylate reacts with good selectivity, and the compound obtained by this reaction has excellent copolymerizability with vinyl monomers present in the system, making it easy to use. A copolymer containing a phosphoric acid group can be obtained, and the copolymer thus obtained has a specific group or a copolymer obtained under specific reaction conditions is water-soluble, It was also discovered that it dissolves in strong electrolyte aqueous solutions such as polyoxyethylene alkyl ether sulfates and α-olefin sulfonates, and in aqueous solutions containing inorganic salts such as common salt, exhibiting a thickening effect, and further increases the viscosity of ethanol water. , completed the invention.
すなわち本発明は、一般式（Ｉ）
（式中、Ｒ１は水素原子又はメチル基を示す）で表され
るグリシジル（メタ）アクリレートを、次の一般式（Ｉ
Ｉ）
ＨＯ−Ｐ−ＯＲ２（Ｉ１）
□
ＯＭ’
（式中、Ｒ２は炭素数１〜３６の直鎖もしくは分岐鎖の
アルキル基、又は含フツ素アルキル基を示し、Ｐはナト
リウム、カリウム等のアルカリ金属塩であることを示す
）
で表されるモノアルキルリン酸のモノアルカリ金属塩と
反応させた後、得られた反応混合物にさらにラジカル重
合開始剤を添加して重合させることを特徴とする次の一
般式（Ｉ［＋）１１ Ｉ ！
ＯＯＨＯＭ”
（式中、ｐｌ、 Ｒ２は前記の通りであり、Ｍ２は水素
原子、又はアルカリ金属、アルカリ土類金属、アルカノ
ールアミン、アルキルアミン或いはアンモニウム塩であ
ることを示す）
で表される構成基を有している共重合体の製造法を提供
するものである。That is, the present invention converts glycidyl (meth)acrylate represented by the general formula (I) (wherein R1 represents a hydrogen atom or a methyl group) into the glycidyl (meth)acrylate represented by the following general formula (I).
I) HO-P-OR2(I1) □ OM' (wherein, R2 represents a linear or branched alkyl group having 1 to 36 carbon atoms, or a fluorine-containing alkyl group, and P represents a fluorine-containing alkyl group such as sodium or potassium. After reacting with a monoalkali metal salt of monoalkyl phosphoric acid represented by (indicating that it is an alkali metal salt), a radical polymerization initiator is further added to the resulting reaction mixture for polymerization. The following general formula (I[+)11 I! OOHOM" (in the formula, pl and R2 are as described above, and M2 represents a hydrogen atom, an alkali metal, an alkaline earth metal, an alkanolamine, an alkylamine, or an ammonium salt) The present invention provides a method for producing a copolymer having the following properties.
前記式（Ｉ）で表される化合物と式（ＩＩ）で表される
化合物との反応は次の反応式に従い、式（ＩＶ）で表さ
れるリン酸エステルが生成するものであり、この化合物
は本発明者らの一部により既に確認され、提案されてい
る。The reaction between the compound represented by formula (I) and the compound represented by formula (II) produces a phosphoric acid ester represented by formula (IV) according to the following reaction formula, and this compound has already been confirmed and proposed by some of the present inventors.
１１ ＼／ Ｉ
ｏ ０ ０Ｍ’（Ｉ）
（ｎ）
０ ０ＨＯＭ’
（ＩＶ）
（式中、Ｒ１，Ｒ２，Ｍ＋は前記の通りである。）前記
の式（ＩＩ）で表されるモノアルキルリン酸のモノアル
カリ金属塩において、Ｒ２で表される炭素数１〜３６の
直鎖もしくは分岐鎖のアルキル基、又は含フツ素アルキ
ル基としては、メチル、エチル、ブチル、オクチル、デ
シル、ドデシル、テトラデシル、ヘキサデシル、オクタ
デシル、トコシル、トリアコンチル、２−エチルへキシ
ル、２−へキシルデシル、２−オクチルドデシル、２−
デシルテトラデシル、２−ドデシルヘキサデシル、２−
テトラデシルオクタデシル、モノメチル分岐イソステア
リル等のアルキル基；トリデカフルオロオクチル、ヘプ
タデカフルオロデシル、ヘンエイコサフルオロドデシル
、ペンタコサフルオロテトラデシル等の含フツ素アルキ
ル基等が挙げられるが、就中、界面活性能、自己組織能
の点では炭素数８〜３６のものが好ましい。11 \/ I o 0 0M'(I)
(n) 0 0 HOM' (IV) (In the formula, R1, R2, M+ are as described above.) In the monoalkali metal salt of monoalkyl phosphoric acid represented by the above formula (II), R2 represents Examples of linear or branched alkyl groups having 1 to 36 carbon atoms or fluorine-containing alkyl groups include methyl, ethyl, butyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, tocosyl, triacontyl, 2- Ethylhexyl, 2-hexyldecyl, 2-octyldodecyl, 2-
Decyltetradecyl, 2-dodecylhexadecyl, 2-
Alkyl groups such as tetradecyl octadecyl and monomethyl branched isostearyl; fluorine-containing alkyl groups such as tridecafluorooctyl, heptadecafluorodecyl, heneicosafluorododecyl, and pentacosafluorotetradecyl; among others, In terms of surface activity and self-assembly ability, those having 8 to 36 carbon atoms are preferred.
上記反応式中、式（ＩＩ）で表されるモノアルキルリン
酸のモノアルカリ金属塩は、対応するアルキル基を有す
る有機ヒドロキシ化合物に五酸化リン、オキシ塩化リン
、ポリリン酸等のリン酸化剤を反応させて、そのまま、
あるいは何らかの精製をしてモノアルキルリン酸を得た
後中和することにより得ることができ、そのいずれの方
法で得られたものでもよい。In the above reaction formula, the monoalkali metal salt of monoalkyl phosphoric acid represented by formula (II) is obtained by adding a phosphorylating agent such as phosphorus pentoxide, phosphorus oxychloride, or polyphosphoric acid to an organic hydroxy compound having a corresponding alkyl group. Let it react and leave it as is.
Alternatively, it can be obtained by performing some purification to obtain a monoalkyl phosphoric acid and then neutralizing it, and any of these methods may be used.
式（Ｉ）で表される化合物と、式（ＩＩ）で表される化
合物の反応の時に用いる溶剤としては特に限定はなく、
式（Ｉ）、（ＩＩ）で表される化合物が互いに溶解する
溶剤であればいずれでもよく、水、あるいはメタノール
、エタノール、イソプロパツール等の低級アルコール類
、あるいはｎ−ヘキサン、シクロヘキサン等の脂肪族炭
化水素類、あるいはベンゼン、トルエン、キシレン、ク
ロルベンゼン等の芳香族炭化水素類、あるいはジエチル
エーテル、ジイソプロピルエーテル、テトラヒドロフラ
ン等の有機エーテル類、あるいはジクロルメタン、クロ
ロホルム等のハロゲン化炭化水素類、あるいはアセトン
、メチルエチルケトン等のケトン類、あるいはジメチル
ホルムアミド、ジメチルアセトアミド等のアミド類、あ
るいはジメチルスルホキシド、スルホラン等のスルホキ
シド類が挙げられる。There are no particular limitations on the solvent used during the reaction of the compound represented by formula (I) and the compound represented by formula (II),
Any solvent may be used as long as the compounds represented by formulas (I) and (II) are mutually soluble, such as water, lower alcohols such as methanol, ethanol, and isopropanol, or fats such as n-hexane and cyclohexane. group hydrocarbons, or aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, or organic ethers such as diethyl ether, diisopropyl ether, and tetrahydrofuran, or halogenated hydrocarbons such as dichloromethane and chloroform, or acetone. and methyl ethyl ketone, amides such as dimethylformamide and dimethylacetamide, and sulfoxides such as dimethyl sulfoxide and sulfolane.
−上記反応の具体例を示すと、例えばモノドデシルリン
酸モノナトリウム（式（ＩＩ）で表される化合物におい
てＲ２＝Ｃ＋ｚＨｚｓ、Ｍ’＝Ｎａ）の水溶液にグリシ
ジル（メタ）アクリレートを加え、水に不溶のグリシジ
ル（メタ）アクリレートを乳化力のあるドデシルリン酸
モノナ１〜リウムで乳化させて反応させるとか、あるい
はモノ２−へキシルデシルリン酸ナトリウム（式（ＩＩ
）で表される化合物においてＲ２＝ＣｅＨ＋７−Ｃ１１
（Ｃ６）１＋＊）−ＣＨｚ、Ｍ’＝Ｎａ）のｎ−ヘキサ
ン溶液にグリシジル（メタ）アクリレートを加えて反応
することができる。また、上記溶剤は混合して用いても
良い。- To give a specific example of the above reaction, for example, glycidyl (meth)acrylate is added to an aqueous solution of monosodium monododecyl phosphate (R2=C+zHzs, M'=Na in the compound represented by formula (II)), and then added to water. Insoluble glycidyl (meth)acrylate may be emulsified and reacted with mono-mono-lium dodecyl phosphate having emulsifying power, or mono-2-hexyldecyl sodium phosphate (formula (II)
) in the compound represented by R2=CeH+7-C11
(C6)1+*)-CHz, M'=Na) can be reacted by adding glycidyl (meth)acrylate to an n-hexane solution. Further, the above solvents may be used in combination.
前記式（Ｉ）で表される化合物と式（ＩＩ）で表わされ
る化合物との反応モル比は任意に選ばれ、また、この反
応においてその反応条件により、式（Ｉ）で表される化
合物のエポキシ環の加水分解による次の式（Ｖ）
０ ０！（ＯＨ
（式中、ｉｌｌは前記の通りである）
で表される２、３−ジヒドロキシプロピル（メタ）アク
リレートの生成があり、従って反応終了時にはその反応
条件により、式（Ｉ）、（Ｉ［）、（ＩＶ）、（Ｖ）の
一部、あるいはすべての混合物になっている。また、こ
れらの混合物は必要により酸性化、更に塩基により中和
することもできる。The reaction molar ratio of the compound represented by formula (I) and the compound represented by formula (II) is arbitrarily selected, and the reaction conditions in this reaction are such that the molar ratio of the compound represented by formula (I) The following formula (V) by hydrolysis of the epoxy ring 0 0! 2,3-dihydroxypropyl (meth)acrylate represented by (OH (in the formula, ill is as described above) is produced. Therefore, at the end of the reaction, depending on the reaction conditions, the formula (I), (I[ ), (IV), and (V), or all of them. If necessary, these mixtures can be acidified and further neutralized with a base.
式（ｎ）で表される化合物をほぼ完全に反応させ、式（
ＩＶ）で表される化合物を得るためには、反応モル比ｒ
（ｒ一式（Ｉ）で表される化合物のモル数／式（Ｉ
Ｉ）で表される化合物のモル数）を３以上にすればよく
、本発明において、未反応の式（ＩＩ）で表されるモノ
アルキルリン酸塩の残存をできるだけ少なくするために
は、ｒ＝３以上で反応するのが好ましい。ただし、本発
明において、重合反応を行った後、重金属応には関与し
ない未反応モノアルキルリン酸塩は除去が可能であり、
本発明はこれに限定されるものではない。また、リン酸
エステルの機能を生かすためにはｒ−２０以下が好まし
い。The compound represented by formula (n) is almost completely reacted to form the formula (
In order to obtain the compound represented by IV), the reaction molar ratio r
(r: number of moles of compound represented by formula (I)/formula (I)
The number of moles of the compound represented by I) may be 3 or more. In the present invention, in order to minimize the residual unreacted monoalkyl phosphate represented by formula (II), r It is preferable to react with =3 or more. However, in the present invention, after the polymerization reaction, unreacted monoalkyl phosphates that do not participate in the heavy metal reaction can be removed.
The present invention is not limited to this. Further, in order to take advantage of the functions of the phosphoric acid ester, it is preferably r-20 or less.
また、反応条件により、式（Ｉ）で表される化合物も残
存するが、この化合物が残存したままラジカル重合開始
剤を加えて重合してもよいし、また反応系内に必要であ
れば水を加えてこの化合物のエポキシ環を完全に加水分
解して式（Ｖ）で表される化合物に転換したのちにラジ
カル重合開始剤を添加して重合しても良い。Furthermore, depending on the reaction conditions, the compound represented by formula (I) may also remain, but it is possible to polymerize by adding a radical polymerization initiator while this compound remains, or add water to the reaction system if necessary. may be added to completely hydrolyze the epoxy ring of this compound to convert it into a compound represented by formula (V), and then a radical polymerization initiator may be added for polymerization.
更に、本発明の効果を害さない範囲で式（Ｉ）、（Ｖｌ
で表される化合物以外の他のビニル系単量体を共重合す
ることもでき、共重合し得る他のビニル系単量体の量は
、通常、反応して得られた式（ＩＶ）で表される化合物
に対して ０．０１〜１０モル％である。これらビニル
系単量体としては、例えば陰イオン性の単量体としての
、（メタ）アクリル酸、クロトン酸、ビニル安息香酸、
ビニルスルホン酸、スチレンスルホン酸、３−アクリル
アミド−２，２−ジメチルプロパン−１−スルホン酸、
ビニルトルエンスルホン酸の如き不飽和−塩基酸、マレ
イン酸、フマール酸の如き不飽和二塩基酸及びこれらの
モノエステル、及び無水マレイン酸等のようなカルボン
酸、又はスルボン酸基を有する単量体が挙げられ、また
陽イオン性の単量体としての、ビニルピリジン、２−メ
チル−５−ビニルピリジンの如きモノビニルピリジン類
、Ｎ、Ｎ−ジメチルスチレン、Ｎ、Ｎ−ジメチルアミノ
メチルスチレン 、の如きジアルキルアミノ基を有する
スチレン類、Ｎ、Ｎ−ジメチルアミノエチル（メタ）ア
クリレート、Ｎ、Ｎ−ジエチルアミノプロピル（メタ）
アクリレートの如き（メタ）アクリル酸のジアルキルア
ミノ基を有するエステル類、Ｎ−（Ｎ”Ｎｌ＝ｌニジメ
チルアミノエチルメタ）アクリルアミド、Ｎ−（Ｎ’、
Ｎ’−ジエチルアミノプロピル）（メタ）アクリルアミ
ドの如きジアルキルアミノ基を有する（メタ）アクリル
アミド類、 （メタ）アリルジメチルアミンの如き不飽
和アミン、塩化（メタ）アクリロイロキシエチルトリメ
チルアンモニウム、塩化（メタ）アクリルアミドプロピ
ルトリメチルアンモニウムの如き不飽和基を有するアン
モニウム塩等が挙げられ、更にまた非イオン性の単量体
である（メタ）アクリル酸アルキルエステル（アルキル
基は直鎖もしくは分岐鎖で炭素数１ないし１８）、ポリ
エチレングリコール（メタ）アクリレート、アリルグリ
シジルエーテル、酢酸ビニル、アクリロニトリル、スチ
レン、アルキル置換スチレン（アルキル基の炭素数１な
いし１８）、（メタ）アクリルアミド、ビニルピロリド
ン等が挙げられる。また、これら共重合の相手モノマー
を二種類以上混合して使用することも可能である。Furthermore, formulas (I) and (Vl
It is also possible to copolymerize other vinyl monomers than the compound represented by the formula (IV), and the amount of the other vinyl monomers that can be copolymerized is usually determined by the formula (IV) obtained by reaction. It is 0.01 to 10 mol % based on the expressed compound. Examples of these vinyl monomers include (meth)acrylic acid, crotonic acid, vinylbenzoic acid as anionic monomers,
Vinyl sulfonic acid, styrene sulfonic acid, 3-acrylamido-2,2-dimethylpropane-1-sulfonic acid,
Unsaturated basic acids such as vinyltoluenesulfonic acid, unsaturated dibasic acids such as maleic acid, fumaric acid and their monoesters, and monomers having carboxylic acid or sulfonic acid groups such as maleic anhydride. and monovinylpyridines such as vinylpyridine, 2-methyl-5-vinylpyridine, N,N-dimethylstyrene, N,N-dimethylaminomethylstyrene, etc. as cationic monomers. Styrenes having a dialkylamino group, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminopropyl (meth)
Esters having a dialkylamino group of (meth)acrylic acid such as acrylate, N-(N"Nl=l dimethylaminoethylmeth)acrylamide, N-(N',
(meth)acrylamides having a dialkylamino group such as N'-diethylaminopropyl)(meth)acrylamide, unsaturated amines such as (meth)allyldimethylamine, (meth)acryloyloxyethyltrimethylammonium chloride, (meth)chloride Examples include ammonium salts with unsaturated groups such as acrylamide propyltrimethylammonium, and also nonionic monomers (meth)acrylic acid alkyl esters (alkyl groups are linear or branched and have 1 to 1 carbon atoms). 18), polyethylene glycol (meth)acrylate, allyl glycidyl ether, vinyl acetate, acrylonitrile, styrene, alkyl-substituted styrene (alkyl group having 1 to 18 carbon atoms), (meth)acrylamide, vinylpyrrolidone, and the like. It is also possible to use a mixture of two or more types of these copolymerization partner monomers.
重合時に用いる溶剤は特に限定はないが、反応時に用い
た溶剤を用いるのが時間的効率の点からも好ましい。し
かし、本発明はこれに限定されるものでなく、反応時に
用いた溶剤に他の溶剤を更に加えるか、または、反応時
に用いた溶剤を留去した後、上記溶剤を一種又はそれ以
上加えて重合反応を行っても何ら差し支えない。Although the solvent used during polymerization is not particularly limited, it is preferable to use the solvent used during the reaction from the viewpoint of time efficiency. However, the present invention is not limited thereto, and it is possible to further add another solvent to the solvent used during the reaction, or to add one or more of the above-mentioned solvents after distilling off the solvent used during the reaction. There is no problem in carrying out the polymerization reaction.
本発明で用いられるラジカル重合開始剤としては、重合
時に用いる溶剤により任意の既知のラジカル重合開始剤
を用いることができ、油溶性ラジカル重合開始剤として
、例えば、ジイソプロピルパーオキシジカーボネート、
ジー２−エチルヘキシルパーオキシジカーボネート、ベ
ンゾイルパーオキサイド、トリクロロアセチルパーオキ
サイド、パーフルオロブチルパーオキサイド等の過酸化
物、２，２゛−アゾビスイソブチロニトリル、２．２゛
−アゾビス（２，４−ジメチルバレロニトリル）等のア
ゾ化合物が挙げられ、また水溶性ラジカル重合開始剤と
しては、例えば、過酸化水素等のハイドロパーオキサイ
ド、過硫酸カリウム等の過酸化物あるいは２．２゛−ア
ゾビス（２−アミジノプロパン）塩酸塩等のアゾ化合物
等を用いることができる。これらの重合開始剤は二種類
以上を混合して使用することも可能であり、さらにはク
ロムイオン、亜硫酸イオン、ヒドロキシルアミン、ヒド
ラジン等を加えてレドックス系重合開始剤として使用す
ることも可能である。また、光重合も可能で光増感剤と
してベンゾインイソブチルエーテル等のカルボニル化合
物、過酸化ベンゾイル等の過酸化物、２，２゛−アゾビ
スイソブチロニトリル等のアゾ化合物も用いられる。ま
たこれらの触媒と共に促進剤として亜硫酸水素ナトリウ
ム、チオ硫酸ナトリウム、硫酸第一鉄アンモニウム等を
併用してもよい。As the radical polymerization initiator used in the present invention, any known radical polymerization initiator can be used depending on the solvent used during polymerization, and examples of the oil-soluble radical polymerization initiator include diisopropyl peroxydicarbonate,
Peroxides such as di-2-ethylhexyl peroxydicarbonate, benzoyl peroxide, trichloroacetyl peroxide, perfluorobutyl peroxide, 2,2゛-azobisisobutyronitrile, 2.2゛-azobis(2, Examples of water-soluble radical polymerization initiators include hydroperoxides such as hydrogen peroxide, peroxides such as potassium persulfate, or 2.2゛-azobis. Azo compounds such as (2-amidinopropane) hydrochloride and the like can be used. It is also possible to use two or more of these polymerization initiators in combination, and it is also possible to use them as a redox polymerization initiator by adding chromium ions, sulfite ions, hydroxylamine, hydrazine, etc. . Photopolymerization is also possible, and carbonyl compounds such as benzoin isobutyl ether, peroxides such as benzoyl peroxide, and azo compounds such as 2,2'-azobisisobutyronitrile are also used as photosensitizers. Further, in addition to these catalysts, sodium bisulfite, sodium thiosulfate, ferrous ammonium sulfate, etc. may be used in combination as a promoter.
重合開始剤の添加量は、通常、単量体に対し０．０５〜
５．０重量％が好ましい。The amount of the polymerization initiator added is usually 0.05 to 0.05 to the monomer.
5.0% by weight is preferred.
また、必要により架橋剤を添加してもよく、架橋剤とし
ては式（Ｉ） 、（ＩＶ） 、あるいは（Ｖ）で表され
る単量体と共重合する多官能のエチレン性不飽和単量体
が用いられ、例えばエチレングリコールジ（メタ）アク
リレート、ジエチレングリコールジ（メタ）アクリレー
ト、及びポリエチレングリコールのジ（メタ）アクリレ
ート、グリセリントリ （メタ）アクリレート、ジビニ
ルベンゼン、トリビニルベンゼン、Ｎ、Ｎ”メチレンビ
スアクリルアミド等を所望の量用いることが可能である
。In addition, a crosslinking agent may be added if necessary, and the crosslinking agent is a polyfunctional ethylenically unsaturated monomer that copolymerizes with the monomer represented by formula (I), (IV), or (V). For example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and di(meth)acrylate of polyethylene glycol, glycerin tri(meth)acrylate, divinylbenzene, trivinylbenzene, N,N”methylene Bisacrylamide and the like can be used in any desired amount.
重合するに際しての重合温度は、通常の重合の温度範囲
でよく、０〜１００℃、好ましくは２０〜８０℃が適当
である。The polymerization temperature during polymerization may be within the normal polymerization temperature range, and is suitably 0 to 100°C, preferably 20 to 80°C.
得られる重合体の分子量は特に限定はなく、液状の低分
子量のポリマーからプラスチック状の高分子量のポリマ
ーまで、重合条件をコントロールすることにより得るこ
とができ、場合によってはアルキルメルカプタン、芳香
族メルカプタン、チオグリコール酸、メルカプトエタノ
ールの如き連鎖移動剤を添加し、生成重合物の分子量を
制御することができる。The molecular weight of the resulting polymer is not particularly limited, and can be obtained by controlling the polymerization conditions, ranging from liquid low molecular weight polymers to plastic high molecular weight polymers. Chain transfer agents such as thioglycolic acid and mercaptoethanol can be added to control the molecular weight of the resulting polymer.
尚、本発明においてその反応条件により、本発明の一般
式（［１）で表される構成基の他、下記の一般式（Ｖｌ
）
０ ｃｏ、 ＯＭ２
（式中、Ｒ１，Ｒ２，Ｍ２は前記の通りである）で表さ
れる構成基を有することもある。In addition, in the present invention, depending on the reaction conditions, in addition to the constituent group represented by the general formula ([1) of the present invention, the following general formula (Vl
) 0 co, OM2 (in the formula, R1, R2, M2 are as described above).
本発明の製造法により得られる共重合体は、式（ＩＩＩ
）で表される構成基を有していることにより、高分子化
合物にリン酸基としての機能を容易に導入でき、リン酸
基のもつイオン交換能、キレート能、帯電防止能、生体
親和性等の機能を高分子化合物に付与させ、さらに式（
ｎ）で表される構成基においてＲ２が長鎖アルキル基の
場合には、高分子化合物に疎水基を導入すると共に高分
子化合物に界面活性剤的な性質を付与し、高分子界面活
性剤、乳化剤、分散剤として高分子化合物の用途を広げ
るものである。また、本発明において式（Ｉ［［）で表
される構成基を有する高分子化合物のうち特定の基を有
するものは、水やポリオキシエチレンアルキルエーテル
硫酸塩等の強電解質水溶液や食塩等の無機塩を含んだ水
溶液にも溶解し、その溶液を増粘させるものである。ま
た、エタノール水も増粘させる性質を有するものである
。The copolymer obtained by the production method of the present invention has the formula (III
), the function of a phosphate group can be easily introduced into a polymer compound, and the ion exchange ability, chelating ability, antistatic ability, and biocompatibility of the phosphate group can be easily introduced. By imparting functions such as
When R2 in the constituent group represented by n) is a long-chain alkyl group, a hydrophobic group is introduced into the polymer compound and surfactant-like properties are imparted to the polymer compound, and a polymer surfactant, This expands the uses of polymer compounds as emulsifiers and dispersants. In addition, in the present invention, among the polymer compounds having a constituent group represented by the formula (I [ It also dissolves in aqueous solutions containing inorganic salts and thickens the solution. Ethanol water also has the property of thickening.
本発明の方法はリン酸基、疎水基を含有する共重合体を
工業的に極めて有利に製造しうるちのである。従って、
工学、医学等の分野において幅広く利用しろるものであ
る。The method of the present invention makes it possible to industrially produce copolymers containing phosphoric acid groups and hydrophobic groups with great advantage. Therefore,
It can be widely used in fields such as engineering and medicine.
次に実施例を挙げて本発明を説明するが、本発明はこれ
らの実施例に限定されるものではない。Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.
実施例１
反応器に純度９７％のモノドデシルリン酸１００ｇ（０
，３６４モル、但しこの試料のＡＶＩ （本リン酸モノ
エステルの試料１ｇを第一当量点まで中和するのに必要
なＫＯＨのｍｇ数、以下も同様）−２１０，３、ＡＶ２
（本リン酸モノエステルの試料１ｇを第二当量点まで中
和するのに必要なＫＯＨのｍｇ数、以下も同様）−４２
０，８であった）を投入し、１規定水酸化ナトリウム水
溶液を３７５ｍ１加えて攪拌し、７０℃に昇温して均一
にした。この時反応系の酸価（試料１ｇを中和するのに
必要なＫＯＩＩのｍｇ数、以下も同様）は４２．９であ
った。次に反応系を７０°Ｃに保ちながら、メタクリル
酸グリシジル１６０ｇ（Ｉ，１３モル）を徐々に加え、
この温度で９時間攪拌した。この時の反応系の酸価はほ
ぼ０になり、反応が完結したことが分る。また、この時
の試料を、ＨＰＬＣ（高速液体クロマトグラフィー、以
下も同様）で分析したところ、新たな生成物のピークと
未反応のメタクリル酸グリシジルのピークとメタクリル
酸グリシジルのエポキシ環が加水分解された２、３−ジ
ヒドロキシプロピルメタクリレートのピークが認められ
た。さらに攪拌を続は合計２０時間反応したところでメ
タクリル酸グリシジルは完全に加水分解されなくなり、
生成物と２，３−ジヒドロキシプロピルメタクリレート
のみのピークが確認された。次に反応液を室温まで冷や
し、反応液から１２２ｇを攪拌機、還流冷却器、窒素ガ
ス導入管を付した別の反応器に移し、イオン交換水８７
８ｇを加え、窒素ガスを吹き込んで溶存酸素を追い出し
た。さらに通値酸カリウム５００ｍｇを添加溶解し７０
℃まで昇温した。５０℃近くで反応系の粘度が増してき
たが、さらに７０℃で４時間加熱攪拌した。この時の反
応系から採取した試料をＨＰＬＣで分析したところ、上
記反応で得られた生成物（式（ＩＶ）で表される化合物
においてＲ２＝Ｃ＋２Ｈｚｓ、Ｍ’＝Ｎａ）と２，３−
ジヒドロキシプロピルメタクリレートのピークは認めら
れず、単量体である化合物はほぼ全て重合したことがわ
かる。重合終了後、反応系を凍結させ凍結乾燥を行い、
得られた白色粉末の重合体をテトラヒドロフランで十分
洗浄し、さらに乾燥して約５０ｇの白色粉末を得た。Example 1 100 g of monododecyl phosphoric acid with a purity of 97% (0
, 364 mol, but the AVI of this sample (the number of mg of KOH required to neutralize 1 g of the sample of this phosphoric acid monoester to the first equivalence point, the same applies below) -210,3, AV2
(Number of mg of KOH required to neutralize 1 g of sample of this phosphoric acid monoester to the second equivalence point; the same applies below) -42
0.8), and 375 ml of 1N aqueous sodium hydroxide solution was added and stirred, and the temperature was raised to 70°C to make it uniform. At this time, the acid value (the number of mg of KOII required to neutralize 1 g of sample, hereinafter the same) of the reaction system was 42.9. Next, while maintaining the reaction system at 70°C, 160 g (I, 13 mol) of glycidyl methacrylate was gradually added.
Stirred at this temperature for 9 hours. At this time, the acid value of the reaction system became almost 0, indicating that the reaction was completed. In addition, when the sample at this time was analyzed by HPLC (high performance liquid chromatography, hereinafter the same applies), a new product peak, an unreacted glycidyl methacrylate peak, and the epoxy ring of glycidyl methacrylate were hydrolyzed. A peak of 2,3-dihydroxypropyl methacrylate was observed. After further stirring and reaction for a total of 20 hours, glycidyl methacrylate was no longer completely hydrolyzed.
Peaks of only the product and 2,3-dihydroxypropyl methacrylate were confirmed. Next, the reaction solution was cooled to room temperature, 122 g of the reaction solution was transferred to another reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas introduction tube, and 87 g of ion-exchanged water was
8 g was added and nitrogen gas was blown to drive out dissolved oxygen. Furthermore, add and dissolve 500 mg of common acid potassium and
The temperature was raised to ℃. Although the viscosity of the reaction system increased near 50°C, the mixture was further heated and stirred at 70°C for 4 hours. When a sample collected from the reaction system at this time was analyzed by HPLC, it was found that the product obtained in the above reaction (R2=C+2Hzs, M'=Na in the compound represented by formula (IV)) and 2,3-
No peak for dihydroxypropyl methacrylate was observed, indicating that almost all of the monomer compounds were polymerized. After the polymerization is completed, the reaction system is frozen and freeze-dried.
The obtained white powder polymer was thoroughly washed with tetrahydrofuran and further dried to obtain about 50 g of white powder.
この白色粉末の元素分析値は下表−１のようになり、上
記の反応において得られた化合物（式（ＩＶ）で表され
る化合物においてＲ２＝Ｃ＋２Ｈｚｓ、Ｍ’−Ｎａ）
１モルに対して、２，３−ジヒドロキシプロピルメタ
クリレート２モルの共重合体であるとしての計算値と一
致し、反応系にある単量体がほぼ全て重合したことがこ
のことからもわかる。The elemental analysis values of this white powder are as shown in Table 1 below, and the compound obtained in the above reaction (R2=C+2Hzs, M'-Na in the compound represented by formula (IV))
This agrees with the calculated value assuming that the copolymer contains 2 moles of 2,3-dihydroxypropyl methacrylate per 1 mole, and it can be seen from this that almost all the monomers in the reaction system were polymerized.
表−１
また、この重合体は、水に５重量％濃度で、ポリオキシ
エチレンラウリルエーテル硫酸ナトリウムの１５％水溶
液に３重量％濃度で、５℃から８０°Ｃの間で均一に溶
け、無色透明、無臭の粘性のある水溶液を与えた。また
、このポリオキシエチレンラウリルエーテル硫酸ナトリ
ウムの１５％水溶液に、この重合体を３重量％濃度で溶
解した水溶液に食塩を１％添加しても、透明な水溶液を
与えた。Table 1 In addition, this polymer dissolves uniformly between 5°C and 80°C at a concentration of 5% by weight in water and a concentration of 3% by weight in a 15% aqueous solution of sodium polyoxyethylene lauryl ether sulfate, and is colorless. A clear, odorless, viscous aqueous solution was obtained. Furthermore, even when 1% of common salt was added to a 15% aqueous solution of sodium polyoxyethylene lauryl ether sulfate in which this polymer was dissolved at a concentration of 3% by weight, a transparent aqueous solution was obtained.
さらに、この重合体を水に添加し、その粘度を東京計器
社製のＢ型粘度計を用いて測定したところ（ローター回
転数３０ｒｐｍ 、３０℃、以後の粘度測定も同様）、
下表−２に示す通りであり、これより重合体を添加する
ことによる増粘効果があることを示している。Furthermore, when this polymer was added to water and its viscosity was measured using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. (rotor rotation speed 30 rpm, 30°C, subsequent viscosity measurements were carried out in the same manner),
As shown in Table 2 below, this shows that the addition of the polymer has a thickening effect.
表−２
また、この重合体をポリオキシエチレンラウリルエーテ
ル硫酸ナトリウムの１５％水溶液に添加したところ、下
表−３のようになり、これも重合体を添加することによ
る増粘効果があることを示している。Table 2 In addition, when this polymer was added to a 15% aqueous solution of sodium polyoxyethylene lauryl ether sulfate, the results were as shown in Table 3 below, which also indicates that the addition of the polymer has a thickening effect. It shows.
表−３
また、この共重合体はエタノール／水の１／１溶液にも
熔解し、その溶液を増粘させた。Table 3 This copolymer was also dissolved in a 1/1 solution of ethanol/water to thicken the solution.
実施例２
攪拌機、還流冷却器を付した反応器に純度９３％のモノ
２−へキシルデシルリン酸７７．８ｇ（０，２２４モル
、但しコノ試料）ＡＶ１＝１７０．５ 、ＡＶ２＝３３
６．０であった）を投入し、１規定水酸化ナトリウム水
溶液２２４ｍ１を加えて攪拌し、７０°Ｃに昇温して均
一にした。次に反応系を７０℃に保ちながら、メタクリ
ル酸グリシジル１２７ｇ（０，８９６モル）を徐々に加
え、この温度で３０時間攪拌した。この時の反応系の酸
価はほぼ０であり、また、この時の試料を、ＨＰＬＣで
分析したところ、新たな生成物のピークとメタクリル酸
グリシジルのエポキシ環が加水分解された２、３−ジヒ
ドロキシプロピルメタクリレートのピークが認められた
。得られた反応混合物を攪拌機、還流冷却器、窒素ガス
導入管を付した別の反応器に移し、さらに反応系にイオ
ン交換水３６５０ ｇを加え溶解させ、窒素ガスを吹き
込んで溶存酸素を追い出した。さらに過硫酸カリウム２
ｇを添加溶解し７０℃まで昇温した。５０℃近くで反応
系の粘度が増してきたが、さらに７０℃で４時間加熱攪
拌した。この時の反応系から採取した試料をＨＰＬＣで
分析したところ、上記反応で得られた生成物（式（ＩＶ
）で表される化合物においてＲ２＝Ｃｌ１＋、−ＣＨ（
Ｃ６Ｈ＋１）−ＣＨｚ、Ｍ’＝Ｎａ） と２．３−ジヒ
ドロキシプロピルメタクリレートのピークは殆ど認めら
れず、単量体である化合物は殆ど重合したことがわかる
。重合終了後、反応系を凍結させ凍結乾燥を行い、さら
に得られた白色粉末の重合体をテトラヒドロフランで十
分洗浄し、さらに乾燥して白色粉末の重合体約２００ｇ
を得た。Example 2 77.8 g of mono-2-hexyldecyl phosphoric acid with a purity of 93% (0,224 mol, however, Kono sample) was placed in a reactor equipped with a stirrer and a reflux condenser, AV1 = 170.5, AV2 = 33
6.0), 224 ml of 1N aqueous sodium hydroxide solution was added and stirred, and the temperature was raised to 70°C to make it uniform. Next, while maintaining the reaction system at 70° C., 127 g (0,896 mol) of glycidyl methacrylate was gradually added, and the mixture was stirred at this temperature for 30 hours. The acid value of the reaction system at this time was almost 0, and when the sample at this time was analyzed by HPLC, a peak of a new product and a 2,3- A peak of dihydroxypropyl methacrylate was observed. The resulting reaction mixture was transferred to another reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas introduction tube, and 3,650 g of ion-exchanged water was added to the reaction system to dissolve it, and nitrogen gas was blown in to drive out dissolved oxygen. . In addition, potassium persulfate 2
g was added and dissolved, and the temperature was raised to 70°C. Although the viscosity of the reaction system increased near 50°C, the mixture was further heated and stirred at 70°C for 4 hours. HPLC analysis of a sample taken from the reaction system at this time revealed that the product obtained in the above reaction (formula (IV
) In the compound represented by R2=Cl1+, -CH(
C6H+1)-CHz, M'=Na) and 2,3-dihydroxypropyl methacrylate peaks were hardly observed, indicating that most of the monomeric compounds were polymerized. After the polymerization is completed, the reaction system is frozen and freeze-dried, and the obtained white powder polymer is thoroughly washed with tetrahydrofuran and further dried to obtain about 200 g of white powder polymer.
I got it.
この白色粉末の元素分析値は下表−４のようになり、上
記の反応において得られた化合物（式（ＩＶ）で表され
る化合物においてＲ２＝Ｃｌ１）１１？−ＣＨ（ＣａＨ
＋、１）−ＣＩ（ｚ 、Ｍ’ ＝Ｎａｌ １モルに対
して、２゜３−ジヒドロキシプロピルメタクリレート３
モルの共重合体であるとしての計算値と一致し、反応系
にある単量体がほぼ全て重合したことがこのことからも
わかる。The elemental analysis values of this white powder are as shown in Table 4 below, and the compound obtained in the above reaction (R2=Cl1 in the compound represented by formula (IV)) 11? -CH(CaH
+, 1) -CI(z, M' = 1 mole of Nal, 2°3-dihydroxypropyl methacrylate 3
This agrees with the calculated value assuming a molar copolymer, and it can be seen from this that almost all of the monomers in the reaction system were polymerized.
表−４
また、本実施例で得られた白色粉末のＩＲスペクトルを
第１図に示す。Table 4 Furthermore, the IR spectrum of the white powder obtained in this example is shown in FIG.
実施例３
攪拌機、還流冷却器を付した反応器に純度９３％のモノ
２−へキシルデシルリン酸モノナトリウム１７２ｇ（０
，４６６モル）をｎ−ヘキサン４００ｇに溶解した溶液
を仕込み（但しこの反応系の酸価−４６，５） 、さら
に反応系を６０℃に保ちながら、メタクリル酸グリシジ
ル３３１ｇ （２，３３モル）を徐々に加え、さらにｎ
−ヘキサンの還流下３０時間攪拌した。この時の反応系
の酸価は１４．５であり、リン酸エステルの反応率は、
この値よりほぼ７０％であることがわかる。この時、反
応系から採取した試料をＩＩ Ｐ Ｌ Ｃで分析したと
ころ、上記反応で得られた新たな生成物のピークとメタ
クリル酸グリシジルのピークが認められ、メタクリル酸
グリシジルのエポキシ環が加水分解されて生成する２、
３−ジヒドロキシプロピルメタクリレートのピークは僅
かしか認められなかった。次に反応液を室温まで冷やし
、反応混合物を攪拌機、還流冷却器、窒素ガス導入管を
付した別の反応器に移し、さらにｎ−ヘキサン１５００
ｇを加え窒素ガスを吹き込んで溶存酸素を追い出した。Example 3 In a reactor equipped with a stirrer and a reflux condenser, 172 g of monosodium mono-2-hexyldecyl phosphate with a purity of 93% (0
, 466 mol) dissolved in 400 g of n-hexane (however, the acid value of this reaction system is -46.5), and while keeping the reaction system at 60°C, 331 g (2.33 mol) of glycidyl methacrylate was added. Gradually add more n
-Stirred for 30 hours under reflux of hexane. The acid value of the reaction system at this time was 14.5, and the reaction rate of the phosphoric ester was:
It can be seen that this value is approximately 70%. At this time, when the sample collected from the reaction system was analyzed by II PLC, a peak of the new product obtained in the above reaction and a peak of glycidyl methacrylate were observed, indicating that the epoxy ring of glycidyl methacrylate was hydrolyzed. and generate 2,
Only a slight peak of 3-dihydroxypropyl methacrylate was observed. Next, the reaction solution was cooled to room temperature, and the reaction mixture was transferred to another reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and further heated with n-hexane 1500
g was added and nitrogen gas was blown in to drive out dissolved oxygen.
さらに２．２゛−アゾビス（２，４−ジメチルバレロニ
トリル）５゜７ｇを添加溶解し６０℃まで昇温した。昇
温すると同時に白色粉末が析出してきたが、さらにｎ−
ヘキサンの還流下で４時間加熱攪拌した。重合終了後、
得られた白色粉末を濾別し、さらに粉末をｎ−ヘキサン
で十分洗浄し、さらに乾燥して白色粉末の重合体約３６
０ｇを得た。Furthermore, 5.7 g of 2.2'-azobis(2,4-dimethylvaleronitrile) was added and dissolved, and the temperature was raised to 60°C. White powder precipitated as the temperature increased, but n-
The mixture was heated and stirred for 4 hours under refluxing hexane. After polymerization,
The obtained white powder was separated by filtration, and the powder was thoroughly washed with n-hexane and further dried to obtain a white powder polymer of about 36 cm.
Obtained 0g.
この白色粉末の元素分析値は下表−５のようになり、こ
の値より上記の反応において得られた化合物（式（ＩＶ
）で表される化合物においてＲ２＝ＣＢ＋’ｌ＋７−Ｃ
Ｈ（Ｃ６Ｈ１３）−ＣＨ２、Ｍ’ ＝Ｎａ） １モル
に対して、メタクリル酸グリシジル約１２モルの共重合
体であることがわかる。The elemental analysis value of this white powder is as shown in Table 5 below, and from this value, the compound obtained in the above reaction (formula (IV
) in the compound represented by R2=CB+'l+7-C
It can be seen that it is a copolymer of about 12 moles of glycidyl methacrylate per 1 mole of H(C6H13)-CH2, M'=Na).
表−５
また、本実施例で得られた白色粉末のＩＲスペクトルを
第２図に示す。このスペクトルから、３０４０ｃｍ−’
、及び９２０ｃｍ−’等のエポキシ環特有の吸収が見
られ、実施例２とは異なり、メタクリル酸グリシジルの
エポキシ環を残したままの共重合体が得られたことがわ
かる。Table 5 Furthermore, the IR spectrum of the white powder obtained in this example is shown in FIG. From this spectrum, 3040 cm-'
Absorption peculiar to the epoxy ring such as , and 920 cm-' was observed, indicating that, unlike Example 2, a copolymer was obtained in which the epoxy ring of glycidyl methacrylate remained.
実施例４
攪拌機、還流冷却器を付した反応器に純度９７％のモノ
（ヘプタデカフルオロデシル）リン酸９５．５ｇ（０
，１８モル、但しコノ試料）ＡＶ１＝１０８．９、ＡＶ
２ ＝２１７．０であった）を投入し、１規定水酸化ナ
トリウム水溶液１８５ｍ１を加えて攪拌し、７０℃に昇
温しで均一にした。次に反応系を７０℃に保ちながら、
メタクリル酸グリシジル１０５ｇ（０，７４モル）を徐
々に加え、この温度で４０時間攪拌した。この時の反応
系の酸価はほぼ０であり、また、この時の試料をＨＰＬ
Ｃで分析したところ、新たな生成物のピークとメタクリ
ル酸グリシジルのエポキシ環が加水分解された２、３−
ジヒドロキシプロピルメタクリレートのピークが認めら
れた。次に反応液を室温まで冷やし、反応混合物を攪拌
機、還流冷却器、窒素ガス導入管を付した別の反応器に
移し、さらに反応系にイオン交換水３７００ｇを加え溶
解させ、窒素ガスを吹き込んで溶存酸素を追い出した。Example 4 A reactor equipped with a stirrer and a reflux condenser was charged with 95.5 g of mono(heptadecafluorodecyl)phosphoric acid with a purity of 97%.
, 18 mol, however, Kono sample) AV1 = 108.9, AV
2 = 217.0), 185 ml of 1N aqueous sodium hydroxide solution was added, stirred, and heated to 70°C to make it uniform. Next, while keeping the reaction system at 70°C,
105 g (0.74 mol) of glycidyl methacrylate was gradually added and stirred at this temperature for 40 hours. The acid value of the reaction system at this time was almost 0, and the sample at this time was subjected to HPL
Analysis at C revealed that the new product peak and the 2,3-
A peak of dihydroxypropyl methacrylate was observed. Next, the reaction solution was cooled to room temperature, and the reaction mixture was transferred to another reactor equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube, and 3,700 g of ion-exchanged water was added to the reaction system to dissolve it, and nitrogen gas was blown into it. Dissolved oxygen was expelled.
さらに過硫酸カリウム２ｇを添加溶解し７０℃まで昇温
した。５０℃近くで反応系の粘度が増してきたが、さら
に７０℃で５時間加熱攪拌した。この時の反応系から採
取した試料を）ＩＰＬＣで分析したところ、上記反応で
得られた生成物（式（ＴＶ）で表される化合物において
Ｒ”＝Ｃｌ１ＦＩ？Ｃ２Ｈ４、Ｍ’＝Ｎａ） と２．３
−ジ。Furthermore, 2 g of potassium persulfate was added and dissolved, and the temperature was raised to 70°C. Although the viscosity of the reaction system increased near 50°C, the mixture was further heated and stirred at 70°C for 5 hours. When the sample collected from the reaction system at this time was analyzed by IPLC, it was found that the product obtained in the above reaction (in the compound represented by formula (TV), R''=Cl1FI?C2H4, M'=Na) and 2 .3
- Ji.
ヒドロキシプロピルメタクリレートのピークは殆ど認め
られず、単量体である化合物は殆ど重合したことがわか
る。重合終了後、反応系を凍結させ凍結乾燥を行い、さ
らに得られた白色粉末の重合体をテトラヒドロフランで
洗浄し、さらに乾燥して白色粉末の重合体約２００ｇを
得た。Almost no peak of hydroxypropyl methacrylate was observed, indicating that most of the monomer compounds were polymerized. After the polymerization was completed, the reaction system was frozen and freeze-dried, and the resulting white powder polymer was washed with tetrahydrofuran and further dried to obtain about 200 g of a white powder polymer.
この白色粉末の元素分析値は下表−６のようになり、上
記の反応において得られた化合物（式（ＩＶ）で表され
る化合物においてＲ２−ＣｅＦ＋ＪｚＨｔ 、Ｍ’ ＝
Ｎａ） １モルに対して、２，３−ジヒドロキシプロ
ピルメタクリレート３モルの共重合体であるとしての計
算値と一致し、反応系にある単量体はほぼ全て重合した
ことがこのことからもわかる。The elemental analysis values of this white powder are as shown in Table 6 below, and in the compound obtained in the above reaction (compound represented by formula (IV)), R2-CeF+JzHt, M' =
This agrees with the calculated value assuming a copolymer of 3 moles of 2,3-dihydroxypropyl methacrylate per 1 mole of Na), and it can be seen from this that almost all the monomers in the reaction system were polymerized. .
表−６Table-6
第１図は本発明の実施例２で得られた共重合体のＩＲス
ペクトルであり、第２図は本発明の実施例３で得られた
共重合体のＩＲスペクトルである。
手続主甫正書（自発）
昭和６１年３月５日
１、事件の表示
特願昭６１−１７６５７号
２、発明の名称
共重合体の製造法
３、補正をする者
事件との関係 特許出願人
（０９１）花 王 株 式 会 社４、代理
人
東京都中央区日本橋横山町１の３中井ビル明細書の発明
の詳細な説明の欄
６、補正の内容
（Ｉ） 明細書５頁６〜７行、６頁１５行及び１９頁
下から３行「強電解質水溶液や」を［強電（Ｉ）同２２
頁４行ｒＨＰＬｃＪの次に「（高速液体クロマトグラフ
ィー）」を挿入FIG. 1 is an IR spectrum of the copolymer obtained in Example 2 of the present invention, and FIG. 2 is an IR spectrum of the copolymer obtained in Example 3 of the present invention. Procedural author's letter (spontaneous) March 5, 1985 1, Indication of the case Patent Application No. 17657/1982 2, Name of the invention Method for producing copolymer 3, Relationship with the person making the amendment Patent application Person (091) Kao Co., Ltd. Company 4, Agent Nakai Building, 1-3 Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo Column 6 of detailed explanation of the invention in the specification, Contents of amendment (I) Specification page 5, 6- Line 7, page 6, line 15, and 3 lines from the bottom of page 19, ``Strong electrolyte aqueous solution.''
Insert "(High Performance Liquid Chromatography)" after page 4 line rHPLcJ
Claims (1)
れるグリシジル（メタ）アクリレートを、次の一般式（
II） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＾２は炭素数１〜３６の直鎖もしくは分岐鎖
のアルキル基、又は含フッ素アルキル基を示し、Ｍ＾１
はアルカリ金属塩であることを示す）で表されるモノア
ルキルリン酸のモノアルカリ金属塩と反応させた後、得
られた反応混合物にさらにラジカル重合開始剤を添加し
て重合させることを特徴とする次の一般式（III） ▲数式、化学式、表等があります▼（III） （式中、Ｒ＾１、Ｒ＾２は前記の通りであり、Ｍ＾２は
水素原子、又はアルカリ金属、アルカリ土類金属、アル
カノールアミン、アルキルアミン或いはアンモニウム塩
であることを示す） で表される構成基を有する共重合体の製造法。[Claims] Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 represents a hydrogen atom or a methyl group) glycidyl (meth)acrylate, The following general formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^2 represents a linear or branched alkyl group having 1 to 36 carbon atoms, or a fluorine-containing alkyl group, and M^1
is an alkali metal salt)), and then a radical polymerization initiator is further added to the resulting reaction mixture for polymerization. The following general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (III) (In the formula, R^1 and R^2 are as described above, and M^2 is a hydrogen atom or an alkali metal, A method for producing a copolymer having a constituent group represented by (indicating that it is an alkaline earth metal, an alkanolamine, an alkylamine, or an ammonium salt).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61017657A JPS62177008A (en) | 1986-01-29 | 1986-01-29 | Production of copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61017657A JPS62177008A (en) | 1986-01-29 | 1986-01-29 | Production of copolymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62177008A true JPS62177008A (en) | 1987-08-03 |
Family
ID=11949923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61017657A Pending JPS62177008A (en) | 1986-01-29 | 1986-01-29 | Production of copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62177008A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1305322A4 (en) * | 2000-08-03 | 2005-04-13 | Dpharm Ltd | Derivatives of branched-chain lipophilic molecules and uses thereof |
-
1986
- 1986-01-29 JP JP61017657A patent/JPS62177008A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1305322A4 (en) * | 2000-08-03 | 2005-04-13 | Dpharm Ltd | Derivatives of branched-chain lipophilic molecules and uses thereof |
| US7186703B2 (en) | 2000-08-03 | 2007-03-06 | D-Pharm Ltd. | Derivatives of branched-chain lipophilic molecules and uses thereof |
| US7687483B2 (en) | 2000-08-03 | 2010-03-30 | D-Pharm Ltd. | Derivatives of branch-chain lipophilic molecular and uses thereof |
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