JP6107417B2 - Zwitterion-containing polymer gel - Google Patents
Zwitterion-containing polymer gel Download PDFInfo
- Publication number
- JP6107417B2 JP6107417B2 JP2013108862A JP2013108862A JP6107417B2 JP 6107417 B2 JP6107417 B2 JP 6107417B2 JP 2013108862 A JP2013108862 A JP 2013108862A JP 2013108862 A JP2013108862 A JP 2013108862A JP 6107417 B2 JP6107417 B2 JP 6107417B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- zwitterion
- polymer gel
- monomer
- swelling
- 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.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims description 107
- 239000000178 monomer Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000002734 clay mineral Substances 0.000 claims description 41
- -1 acryloyloxy group Chemical group 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical group C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 10
- 229940117986 sulfobetaine Drugs 0.000 claims description 10
- 239000000499 gel Substances 0.000 description 89
- 230000008961 swelling Effects 0.000 description 50
- 239000007864 aqueous solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 27
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 150000003839 salts Chemical class 0.000 description 20
- 239000012266 salt solution Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 15
- 230000004043 responsiveness Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910017053 inorganic salt Inorganic materials 0.000 description 9
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 9
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 238000009864 tensile test Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011557 critical solution Substances 0.000 description 6
- 230000002522 swelling effect Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 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
- 238000004132 cross linking Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229940094522 laponite Drugs 0.000 description 3
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- SFPNZPQIIAJXGL-UHFFFAOYSA-N 2-ethoxyethyl 2-methylprop-2-enoate Chemical compound CCOCCOC(=O)C(C)=C SFPNZPQIIAJXGL-UHFFFAOYSA-N 0.000 description 2
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VPWUMUULHWRAII-UHFFFAOYSA-N S(=O)(=O)([O-])[O-].CCC.C[NH+](C)CCCNC(C=C)=O.C[NH+](C)CCCNC(C=C)=O Chemical compound S(=O)(=O)([O-])[O-].CCC.C[NH+](C)CCCNC(C=C)=O.C[NH+](C)CCCNC(C=C)=O VPWUMUULHWRAII-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002504 physiological saline solution Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- MGNVWUDMMXZUDI-UHFFFAOYSA-N propane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CCCS(O)(=O)=O MGNVWUDMMXZUDI-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- KGFNCEVZZDDBTR-UHFFFAOYSA-N 1-piperazin-1-ylbut-3-en-2-one Chemical compound C=CC(=O)CN1CCNCC1 KGFNCEVZZDDBTR-UHFFFAOYSA-N 0.000 description 1
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-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
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- YQIGLEFUZMIVHU-UHFFFAOYSA-N 2-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C(C)=C YQIGLEFUZMIVHU-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- MTPJEFOSTIKRSS-UHFFFAOYSA-N 3-(dimethylamino)propanenitrile Chemical compound CN(C)CCC#N MTPJEFOSTIKRSS-UHFFFAOYSA-N 0.000 description 1
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- AREPZLLNBMJORV-UHFFFAOYSA-N C(=O)(C=C)C1=C(C=CC=C1)S(=O)(=O)O Chemical compound C(=O)(C=C)C1=C(C=CC=C1)S(=O)(=O)O AREPZLLNBMJORV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000871495 Heeria argentea Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- ZRKLEAHGBNDKHM-UHFFFAOYSA-N N,n'-diallyl-2,3-dihydroxysuccinamide Chemical compound C=CCNC(=O)C(O)C(O)C(=O)NCC=C ZRKLEAHGBNDKHM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZVCSFBVPPUDEHN-UHFFFAOYSA-N S(=O)(=O)([O-])[O-].CCCC.C[NH+](C)CCCNC(C=C)=O.C[NH+](C)CCCNC(C=C)=O Chemical compound S(=O)(=O)([O-])[O-].CCCC.C[NH+](C)CCCNC(C=C)=O.C[NH+](C)CCCNC(C=C)=O ZVCSFBVPPUDEHN-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229940048053 acrylate Drugs 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 239000012935 ammoniumperoxodisulfate Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 1
- FOGSDLLFGSNQCW-UHFFFAOYSA-N n-[(prop-2-enoylamino)methoxymethyl]prop-2-enamide Chemical compound C=CC(=O)NCOCNC(=O)C=C FOGSDLLFGSNQCW-UHFFFAOYSA-N 0.000 description 1
- UBTYFVJZTZYJHZ-UHFFFAOYSA-N n-[2-(prop-2-enoylamino)propyl]prop-2-enamide Chemical compound C=CC(=O)NC(C)CNC(=O)C=C UBTYFVJZTZYJHZ-UHFFFAOYSA-N 0.000 description 1
- DJVKJGIZQFBFGS-UHFFFAOYSA-N n-[2-[2-(prop-2-enoylamino)ethyldisulfanyl]ethyl]prop-2-enamide Chemical compound C=CC(=O)NCCSSCCNC(=O)C=C DJVKJGIZQFBFGS-UHFFFAOYSA-N 0.000 description 1
- FIBUWQFQYAAXHD-UHFFFAOYSA-N n-cyclopropyl-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NC1CC1 FIBUWQFQYAAXHD-UHFFFAOYSA-N 0.000 description 1
- LCXIFAOALNZGDO-UHFFFAOYSA-N n-cyclopropylprop-2-enamide Chemical compound C=CC(=O)NC1CC1 LCXIFAOALNZGDO-UHFFFAOYSA-N 0.000 description 1
- ZOTWHNWBICCBPC-UHFFFAOYSA-N n-ethyl-n-methylprop-2-enamide Chemical compound CCN(C)C(=O)C=C ZOTWHNWBICCBPC-UHFFFAOYSA-N 0.000 description 1
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 1
- COYVWKMZTCAFHO-UHFFFAOYSA-N n-methyl-n-propan-2-ylprop-2-enamide Chemical compound CC(C)N(C)C(=O)C=C COYVWKMZTCAFHO-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920005787 opaque polymer Polymers 0.000 description 1
- PZXHOJFANUNWGC-UHFFFAOYSA-N phenyl 2-oxoacetate Chemical class O=CC(=O)OC1=CC=CC=C1 PZXHOJFANUNWGC-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001988 small-angle X-ray diffraction Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- AZJYLVAUMGUUBL-UHFFFAOYSA-A u1qj22mc8e Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O=[Si]=O.O=[Si]=O.O=[Si]=O.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 AZJYLVAUMGUUBL-UHFFFAOYSA-A 0.000 description 1
Description
本発明は、双性イオン含有有機高分子と粘土鉱物とが三次元網目を形成してなる高分子ゲルに関するものである。 The present invention relates to a polymer gel in which a zwitterion-containing organic polymer and a clay mineral form a three-dimensional network.
高分子ゲルは有機高分子の三次元架橋物が水または有機溶媒を含んで膨潤したものであり、膨潤性やゴム状弾性を有するソフトマテリアルとして、医療・医薬、食品、土木、バイオエンジニアリング、スポーツ関連などの分野で広く用いられている（例えば、非特許文献１参照）。しかし、従来のランダムな化学架橋により形成された高分子ゲルは膨潤性が低く、また、力学的にも脆弱で取り扱いが困難な場合が多かった。これに対して、本発明者らはこれまでに、水溶性有機モノマーの重合体と層状粘土鉱物とが複合化して形成された三次元網目を有する高分子ゲル（有機無機複合ゲル）が、優れた吸水性や極めて高い伸張性などの特徴を有することについて報告した（例えば特許文献１参照）。 Polymer gel is a three-dimensional cross-linked organic polymer that contains water or an organic solvent and swells. As a soft material with swelling and rubbery elasticity, it can be used for medical / medicine, food, civil engineering, bioengineering, sports. Widely used in related fields (for example, see Non-Patent Document 1). However, conventional polymer gels formed by random chemical cross-linking have low swelling properties and are often fragile and difficult to handle. On the other hand, the present inventors have so far provided a polymer gel (organic-inorganic composite gel) having a three-dimensional network formed by combining a polymer of a water-soluble organic monomer and a layered clay mineral. It has been reported that it has characteristics such as water absorption and extremely high extensibility (see, for example, Patent Document 1).
しかし、高分子ゲルに対する要求性能は更に高まり、ゲルの吸収性についてもより優れた性能が求められるようになってきている。例えば、高い膨潤性（即ち、高吸収性）を無機塩水溶液中で、具体的には生理食塩水や海水中またはそれ以上の濃度の無機塩水溶液中で、実現することが求められている。一般に、高分子ゲルの水中での膨潤度は次の三つの因子で決まることが知られている。即ち、架橋密度、高分子の溶媒親和性、および高分子に含まれるイオン性基濃度である。このことから、高吸水性を実現するためには、親水性の高いイオン性高分子を低密度架橋（例えば、ポリアクリル酸ナトリウム架橋体）することが有効とわかる。実際、高吸水性ゲルと呼ばれるものがポリアクリル酸ナトリウム架橋体ゲルで実用化されている。しかし、膨潤液が無機塩を含む水溶液である場合は、その膨潤性が極端に低下してしまうことが問題として知られている。また、上で述べた有機無機複合ゲルの場合も無機塩水溶液中での膨潤性は低下することが知られている。その他の高分子ゲルとして、例えば、双性イオンを含有する高分子ゲルについては学術的にいくつかの報告（例えば、非特許文献２および非特許文献３）があるが、双性イオン高分子のみからなる高分子ゲルでは、（ゲルに吸収された水溶液量／ゲルの固形分量）で定義される質量比（膨潤度に相当）が３以下と極めて低かったり、また、双性イオンモノマーとイオン性モノマーや中性モノマーとの共重合高分子ゲルでは、塩濃度の増加と共に吸収量が低下するなど、上記問題を解決できるものではなかった。従って、かかる塩化ナトリウムなどの無機塩を含む水溶液中で、大きく膨潤（即ち、水溶液を多量に吸収）する高分子ゲル、また、優れた力学物性や機能性（温度応答性など）を併せ持つ高分子ゲルの開発が望まれていた。 However, the required performance for the polymer gel is further increased, and more excellent performance is required for the absorbability of the gel. For example, it is required to achieve high swellability (that is, high absorbency) in an inorganic salt aqueous solution, specifically, in a physiological saline solution, seawater, or an inorganic salt aqueous solution having a higher concentration. In general, it is known that the degree of swelling of a polymer gel in water is determined by the following three factors. That is, the crosslinking density, the solvent affinity of the polymer, and the ionic group concentration contained in the polymer. From this, in order to realize high water absorption, it is effective to carry out low density crosslinking (for example, sodium polyacrylate cross-linked body) of an ionic polymer having high hydrophilicity. In fact, what is called a superabsorbent gel is put into practical use as a sodium polyacrylate crosslinked gel. However, when the swelling liquid is an aqueous solution containing an inorganic salt, it is known as a problem that the swelling property is extremely lowered. Also, it is known that the swelling property in an inorganic salt aqueous solution is reduced in the case of the organic-inorganic composite gel described above. As other polymer gels, for example, there are some academic reports on polymer gels containing zwitterions (for example, Non-Patent Document 2 and Non-Patent Document 3), but only zwitterionic polymers. In the polymer gel consisting of, the mass ratio (corresponding to the degree of swelling) defined by (amount of aqueous solution absorbed in the gel / solid content of the gel) is very low as 3 or less, and the zwitterionic monomer and ionicity Copolymer polymer gels with monomers and neutral monomers have not been able to solve the above problems, for example, the amount of absorption decreases with increasing salt concentration. Therefore, a polymer gel that swells greatly (that is, absorbs a large amount of the aqueous solution) in an aqueous solution containing an inorganic salt such as sodium chloride, and a polymer that has excellent mechanical properties and functionality (temperature responsiveness, etc.). The development of a gel was desired.
本発明が解決しようとする課題は、塩水溶液中で高い膨潤性（吸収性）を示し、より好ましくは、更に、高い強度や力学的タフネスの優れた力学物性、及び／または、温度応答性などの機能を併せ持つ高分子ゲル材料を提供することにある。 The problem to be solved by the present invention shows high swellability (absorbability) in an aqueous salt solution, and more preferably, mechanical properties having high strength and mechanical toughness, and / or temperature responsiveness, etc. The object is to provide a polymer gel material having both functions.
本発明者らは、上記課題を解決すべく鋭意研究に取り組んだ結果、双性イオンを有するモノマーの重合体または共重合体と水中で層状剥離した水膨潤性粘土鉱物とが三次元網目を形成してなる双性イオン含有高分子ゲルが、高い塩水溶液の吸収性（膨潤性）を有すること、更には、高吸収性と共に優れた力学物性および/または温度応答性を併せ持つことができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the inventors of the present invention formed a three-dimensional network of a polymer or copolymer of a monomer having zwitterions and a water-swellable clay mineral exfoliated in water. It is found that the zwitterion-containing polymer gel thus obtained has a high salt solution absorbability (swellability), and also has excellent mechanical properties and / or temperature responsiveness in addition to high absorbency. The present invention has been completed.
すなわち、本発明は、双性イオンを有するモノマー（Ａ）の重合体と水中で層状剥離した水膨潤性粘土鉱物（Ｂ）とが三次元網目を形成してなる双性イオン含有高分子ゲルであって、双性イオンを有するモノマー（Ａ）の双性イオンがスルフォベタインであることを特徴とする双性イオン含有高分子ゲルを提供する。 That is, the present invention is a zwitterion- containing polymer gel in which a polymer of a monomer (A) having zwitterions and a water-swellable clay mineral (B) exfoliated in water form a three-dimensional network. The zwitterion-containing polymer gel is characterized in that the zwitterion of the monomer (A) having zwitterions is sulfobetaine .
また、本発明は、双性イオンを有するモノマー（Ａ）と（メタ）アクリルアミド基又は（メタ）アクリロイルオキシ基を有する水溶性ラジカル重合性モノマー（Ｃ）との共重合体が水中で層状剥離した水膨潤性粘土鉱物（Ｂ）と三次元網目を形成してなる双性イオン含有高分子ゲルであって、双性イオンを有するモノマー（Ａ）の双性イオンがスルフォベタインであることを特徴とする双性イオン含有高分子ゲルを提供する。 In the present invention, the copolymer of the monomer (A) having zwitterions and the water-soluble radical polymerizable monomer (C) having a (meth) acrylamide group or a (meth) acryloyloxy group is peeled off in water. A zwitterion-containing polymer gel formed by forming a three-dimensional network with a water-swellable clay mineral (B) , wherein the zwitterion of the monomer (A) having zwitterions is sulfobetaine A zwitterion-containing polymer gel is provided.
また、本発明は、双性イオンを有するモノマー（Ａ）が、双性イオンと共にアクリルアミド基又はアクリロイルオキシ基を有することを特徴とする双性イオン含有高分子ゲルを提供する。 In addition, the present invention provides a zwitterion-containing polymer gel, wherein the monomer (A) having zwitterions has an acrylamide group or an acryloyloxy group together with the zwitterions.
さらに本発明は、双性イオン含有高分子ゲルにおける水膨潤性粘土鉱物（Ｂ）の量が、双性イオンを有するモノマーの重合体または共重合体に対して、０．０５〜５の質量比の範囲であることを特徴とする双性イオン含有高分子ゲルを提供する。 Further, in the present invention, the amount of the water-swellable clay mineral (B) in the zwitterion-containing polymer gel is such that the mass ratio of 0.05 to 5 with respect to the polymer or copolymer of the monomer having zwitterions. The zwitterion-containing polymer gel is characterized by being in the range of
本発明の双性イオン含有高分子ゲルは、NaClなどの無機塩水溶液中での高い膨潤性（水溶液吸収性）を有する。特に、無機塩濃度の高い水溶液で優れた膨潤性（水溶液吸収性）を示す。また、本発明の双性イオン含有高分子ゲルは、優れた力学物性及び／または上限臨界共溶温度を示す温度応答性の機能を併せ持つことも可能である。本発明の双性イオン含有高分子ゲルは均一で透明性を有し、取り扱い性に優れたゲル材料である。また、各種形状および大きさで調製することが可能である。このように、本発明の双性イオン含有高分子ゲルは、無機塩水溶液の高吸収性、優れた力学物性、温度応答性にくわえて、成分として用いた粘土鉱物や双性イオン（共）重合体の特徴を生かして、医療関連部材用途、医薬品関連部材用途、美容関連部材用途、生活用品部材用途、電子部材用途、工業製品部材用途、土木・建築関連部材用途、農業用製品部材用途など多くの用途へ適用できる。 The zwitterion-containing polymer gel of the present invention has high swellability (aqueous solution absorbability) in an aqueous inorganic salt solution such as NaCl. In particular, it exhibits excellent swellability (aqueous solution absorbability) with an aqueous solution having a high inorganic salt concentration. In addition, the zwitterion-containing polymer gel of the present invention can also have an excellent mechanical property and / or a temperature responsive function exhibiting an upper critical eutectic temperature. The zwitterion-containing polymer gel of the present invention is a gel material that is uniform, transparent, and excellent in handleability. It can also be prepared in various shapes and sizes. As described above, the zwitterion-containing polymer gel of the present invention is not limited to the superabsorbency, excellent mechanical properties, and temperature responsiveness of the inorganic salt aqueous solution. Utilizing the characteristics of coalescence, medical-related materials use, pharmaceutical-related materials usage, beauty-related materials usage, daily life materials usage, electronic materials usage, industrial product materials usage, civil engineering / architecture materials usage, agricultural product materials usage, etc. It can be applied to any use.
本発明の双性イオン含有高分子ゲルは、双性イオンを有するモノマー（A）の重合体または共重合体と水膨潤性粘土鉱物（B）とが分子レベルで複合化することによりなる三次元網目を形成してなるものである。より具体的には、双性イオンを有するモノマーの重合体または共重合体が水中で層状に剥離した水膨潤性粘土鉱物と水素結合またはイオン結合により相互作用して架橋され、三次元網目を形成しているものである。このことは該双性イオン含有高分子ゲルが水又は無機塩水溶液中で溶解することなく膨潤すること、且つ該ゲルを長時間（例えば、５００時間以上）保持しても構成成分である水膨潤性粘土鉱物及び双性イオンを有する重合体または共重合体が抽出されないことや、延伸や圧縮の力学試験において、大きな可逆的伸張性や圧縮性を示すことから支持される。更に、分析的は、双性イオン含有高分子ゲル乾燥物の超泊切片の電子顕微鏡観察において、粘土鉱物が層状剥離して、高分子マトリックスの中に均一に分散していることや、Ｘ線回折において粘土鉱物の層間距離に対応するブラック反射が観測されないことからも確認される。 The zwitterion-containing polymer gel of the present invention has a three-dimensional structure obtained by complexing a polymer or copolymer of a monomer (A) having zwitterions with a water-swellable clay mineral (B) at a molecular level. A mesh is formed. More specifically, a polymer or copolymer of monomers having zwitterions interacts with a water-swellable clay mineral separated in layers in water by hydrogen bonds or ionic bonds, and forms a three-dimensional network. It is what you are doing. This means that the zwitterion-containing polymer gel swells without dissolving in water or an aqueous inorganic salt solution, and the water swell is a constituent even if the gel is held for a long time (for example, 500 hours or more). This is supported by the fact that a polymer or copolymer having a water-soluble clay mineral and a zwitterion is not extracted, and exhibits a large reversible stretchability and compressibility in a mechanical test of stretching and compression. Furthermore, analytically, in the electron microscope observation of the ultra-night section of the dried zwitterion-containing polymer gel, the clay mineral is delaminated and uniformly dispersed in the polymer matrix, This is also confirmed by the fact that no black reflection corresponding to the interlayer distance of the clay mineral is observed in the diffraction.
本発明における双性イオンを有するモノマー（A）としては、正電荷を持つカチオンおよび負電荷を持つアニオンの両方を１モノマーの中に一つずつ含むものであって、水に溶解する性質を有するものがより好ましい。より好ましくは、双性イオンと共に、モノマー中にアクリルアミド基またはアクリロイルオキシ基を有するものである。双性イオンの種類としては、カチオンとして４級アンモニウム基、アニオンとしてスルホン酸基、カルボン酸基、リン酸基などを含むものであり、特に好ましくは、カチオンとして４級アンモニウム基、アニオンとしてスルホン酸基を有するものである。なお、これらの双性イオンは、それぞれアニオン基の種類に応じて、スルフォベタイン、カルボベタイン、ホスフォベタインと呼ばれる。スルフォベタインの場合は、層状剥離した粘土鉱物と複合して得られた高分子ゲルの力学物性が、他の双性イオン基より優れていること、また、上限臨界共溶温度を有する温度応答性を示すことが特長となる。具体的には、より好ましい双性イオンを有するモノマーとして、モノマー中にアクリルアミド基またはアクリロイルオキシ基を有するスルフォベタインモノマーである。より具体的な例としては、好ましくは化１〜化３で示されるスルフォベタインモノマーが、特に好ましくは化１および化３で示されるスルフォベタインモノマーが用いられる。化１：N,N-ジメチル（アクリルアミドプロピル）アンモニウムプロパンサルフェイト、化２：N,N-ジメチル（アクリルアミドプロピル）アンモニウムブタンサルフェイト、化３：N.N-ジメチル（アクリロイルオキシエチル）アンモニウムプロパンサルフェイト The monomer (A) having a zwitterion in the present invention contains both a positively charged cation and a negatively charged anion in one monomer, and has a property of dissolving in water. Those are more preferred. More preferably, it has an acrylamide group or an acryloyloxy group in the monomer together with the zwitterion. Zwitterions include quaternary ammonium groups as cations, sulfonic acid groups, carboxylic acid groups, and phosphate groups as anions, and particularly preferably quaternary ammonium groups as cations and sulfonic acids as anions. It has a group. These zwitterions are called sulfobetaine, carbobetaine, and phosphobetaine, depending on the type of anion group. In the case of sulfobetaine, the mechanical properties of the polymer gel obtained by complexing with the layered exfoliated clay mineral are superior to other zwitterionic groups, and the temperature response has an upper critical solution temperature. It is a feature to show the property. Specifically, as a monomer having a more preferable zwitterion, a sulfobetaine monomer having an acrylamide group or an acryloyloxy group in the monomer. As a more specific example, a sulfobetaine monomer represented by Chemical Formulas 1 to 3 is preferably used, and a sulfobetaine monomer represented by Chemical Formulas 1 and 3 is particularly preferably used. Formula 1: N, N-dimethyl (acrylamidopropyl) ammonium propane sulfate, Formula 2: N, N-dimethyl (acrylamidopropyl) ammonium butane sulfate, Formula 3: N.N-dimethyl (acryloyloxyethyl) ammonium propane sulfate
本発明で用いられる双性イオンを有するモノマー（A）と共重合するモノマー（C）としては、（A）と共重合できる水溶性ラジカル重合性モノマーが用いられるが、好ましくは（メタ）アクリルアミド基または（メタ）アクリロイルオキシ基を有する水溶性ラジカル重合性モノマーであり、特に好ましくは（メタ）アクリルアミド基である。（メタ）アクリルアミド基を有する水溶性ラジカル重合性モノマーの具体例としては、Ｎ−アルキルアクリルアミド、Ｎ，Ｎ−ジアルキルアクリルアミド、アクリルアミド等のアクリルアミド類、または、Ｎ−アルキルメタクリルアミド、Ｎ，Ｎ−ジアルキルメタクリルアミド、メタクリルアミド等のメタクリルアミド類が挙げられる。ここでアルキル基としては炭素数が１〜４のものが特に好ましく選択される。一方、（メタ）アクリロイルオキシ基を有する水溶性ラジカル重合性モノマーの具体例としては、メトキシエチルアクリレート、エトキシエチルアクリレート、メトキシエチルメタクリレート、エトキシエチルメタクリレートなどがあげられる。より具体的には、例えば、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド、Ｎ−シクロプロピルアクリルアミド、Ｎ−イソプロピルアクリルアミド、アクリロイルモルフォリン、メタクリルアミド、Ｎ−メチルメタクリルアミド、Ｎ−シクロプロピルメタクリルアミド、Ｎ−イソプロピルメタクリルアミド、Ｎ,Ｎ−ジメチルアクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリルアミド、Ｎ−メチル−Ｎ−エチルアクリルアミド、Ｎ−メチル−Ｎ−イソプロピルアクリルアミド、Ｎ−メチル−Ｎ−ｎ−プロピルアクリルアミド、Ｎ,Ｎ−ジエチルアクリルアミド、Ｎ−アクリロイルピロリディン、Ｎ−アクリロイルピペリディン、Ｎ−アクリロイルメチルホモピペラディン、Ｎ−アクリロイルメチルピペラディン、アクリルアミド、ヒドロキシエチルアクリレート、メトキシエチルアクリレート、エトキジエチルアクリレート、メトキシエチルメタクリレート、エトキシエチルメタクリレートが例示される。以上の例示にも含まれるように、（C）のポリマーとして例えば下限臨界共溶温度を持つような温度応答性を示すもの（例えば、Ｎ−イソプロピルアクリルアミド）は、本発明における高分子ゲルの温度応答性をより的確なものとするために有効に用いられる。また水溶性ラジカル重合性モノマーとしては、これらから選ばれる一つまたは複数が用いられる。更に、上記水溶性ラジカル重合性モノマー（C）として、上記のモノマーに加えて、他の水溶性ラジカル重合性モノマーを一緒に用いることも可能である。特に、アニオンまたはカチオンを一つだけ有するイオン性モノマーを合わせて用いることは膨潤性の制御などに有効である。イオン性モノマーの例としては、アクリル酸、アクリルベンゼンスルフォン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、３−メタクリルアミド−プロピルトリメチルアンモニウムなどが挙げられる。 As the monomer (C) that is copolymerized with the monomer (A) having zwitterion used in the present invention, a water-soluble radical polymerizable monomer that can be copolymerized with (A) is used, preferably a (meth) acrylamide group. Or it is a water-soluble radically polymerizable monomer which has a (meth) acryloyloxy group, Especially preferably, it is a (meth) acrylamide group. Specific examples of the water-soluble radically polymerizable monomer having a (meth) acrylamide group include acrylamides such as N-alkylacrylamide, N, N-dialkylacrylamide and acrylamide, or N-alkylmethacrylamide and N, N-dialkyl. And methacrylamides such as methacrylamide and methacrylamide. Here, an alkyl group having 1 to 4 carbon atoms is particularly preferably selected. On the other hand, specific examples of the water-soluble radical polymerizable monomer having a (meth) acryloyloxy group include methoxyethyl acrylate, ethoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate and the like. More specifically, for example, N-methylacrylamide, N-ethylacrylamide, N-cyclopropylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylmethacrylamide, N-cyclopropylmethacrylamide, N -Isopropylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-isopropylacrylamide, N-methyl-Nn-propylacrylamide, N, N-diethylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmethylhomopiperadine, N-acryloylmethylpiperazine, acrylami , Hydroxyethyl acrylate, methoxyethyl acrylate, ethoxy diethyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate and the like. As also included in the above examples, the polymer (C) having a temperature responsiveness having a lower critical eutectic temperature (for example, N-isopropylacrylamide) is the temperature of the polymer gel in the present invention. Effectively used to make the responsiveness more accurate. As the water-soluble radical polymerizable monomer, one or more selected from these are used. Further, as the water-soluble radical polymerizable monomer (C), in addition to the above monomers, other water-soluble radical polymerizable monomers can be used together. In particular, using an ionic monomer having only one anion or cation in combination is effective for controlling the swelling property. Examples of the ionic monomer include acrylic acid, acrylbenzene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 3-methacrylamide-propyltrimethylammonium.
本発明で用いられる双性イオンを有するモノマー（A）と共重合するモノマー（C）の割合としては、（A）：（C）のモル比が９９：１〜１：９９の中から選択できるが、好ましくは９８：２〜１０：９０、より好ましくは９５：５〜３０：７０、特に好ましくは９０：１０〜５０：５０である。この範囲とすることで、双性イオンとしての膨潤性または温度応答性を保ちつつ、優れた力学物性を有することができる。 本発明の双性イオン含有高分子ゲルに用いる粘土鉱物としては、水に膨潤性を有するものであり、好ましくは水によって層間が膨潤するものが用いられる。より好ましくは少なくとも一部が水中で層状に剥離して分散できるものであり、特に好ましくは水中で１ないし１０層以内の厚みの層状に剥離して均一分散できる層状粘土鉱物である。例えば、水膨潤性スメクタイトや水膨潤性雲母などが用いられ、より具体的には、ナトリウムを層間イオンとして含む水膨潤性ヘクトライト、水膨潤性モンモリロナイト、水膨潤性サポナイト、水膨潤性合成雲母などが挙げられる。 As a ratio of the monomer (C) copolymerized with the monomer (A) having a zwitterion used in the present invention, the molar ratio of (A) :( C) can be selected from 99: 1 to 1:99. However, it is preferably 98: 2 to 10:90, more preferably 95: 5 to 30:70, and particularly preferably 90:10 to 50:50. By setting it as this range, it is possible to have excellent mechanical properties while maintaining swellability or temperature responsiveness as zwitterions. The clay mineral used in the zwitterion-containing polymer gel of the present invention is one that has a swelling property in water, and preferably one that swells between layers by water. More preferably, it is a layered clay mineral that can be at least partially exfoliated and dispersed in layers in water, and particularly preferably a lamellar clay mineral that can be exfoliated and dispersed uniformly in water with a thickness of 1 to 10 layers. For example, water-swellable smectite or water-swellable mica is used. More specifically, water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable saponite, water-swellable synthetic mica, etc. Is mentioned.
本発明において用いられる水膨潤性粘土鉱物の量は、双性イオンを有するモノマーの重合体または共重合体に対して、０．０５〜５の質量比の範囲が好ましく、より好ましくは０．１〜３、特に好ましくは０．２〜２である。質量比が０．０５以下では、有効な三次元網目を形成しづらく、５以上では均一な粘土鉱物の分散が困難となる場合がある。 The amount of the water-swellable clay mineral used in the present invention is preferably in the range of mass ratio of 0.05 to 5, more preferably 0.1 to the polymer or copolymer of monomers having zwitterions. -3, particularly preferably 0.2-2. If the mass ratio is 0.05 or less, it is difficult to form an effective three-dimensional network, and if it is 5 or more, it may be difficult to uniformly disperse the clay mineral.
本発明の双性イオン含有高分子ゲルが吸収できる媒体としては、水の他、無機塩を含む水溶液、無機水酸化物を含む水溶液、有機塩を含む水溶液、その他、各種溶質を含む水溶液、水と混和する有機溶剤または水との混合溶媒などが用いられる。特に、塩化ナトリウム、塩化リチウム、塩化カルシウム、塩化アルミニウムを始めとする無機塩を含む水溶液は好ましく用いられる。水と混和する有機溶剤としては、メタノール、エタノール、プロパノール、アセトン、メチルエチルケトン、メチルイソブチルケトン、テトラヒドロフラン、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシド及びそれらの混合溶媒が挙げられる。 The medium that can be absorbed by the zwitterion-containing polymer gel of the present invention includes water, aqueous solutions containing inorganic salts, aqueous solutions containing inorganic hydroxides, aqueous solutions containing organic salts, other aqueous solutions containing various solutes, water An organic solvent miscible with water or a mixed solvent with water is used. In particular, an aqueous solution containing inorganic salts such as sodium chloride, lithium chloride, calcium chloride, and aluminum chloride is preferably used. Examples of the organic solvent miscible with water include methanol, ethanol, propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, and a mixed solvent thereof.
本発明の双性イオン含有高分子ゲルでは、水中で層状剥離した水膨潤性粘土鉱物のみを架橋剤として用いることが最も有効である。ただし、力学物性の制御や過度の膨潤性を抑制するなどのため、水膨潤性粘土鉱物と共に一般に用いられている有機架橋剤（例：ビスアクリルアミド）を少量併用することも可能である。このような有機架橋剤の例としては、Ｎ，Ｎ’−メチレンビスアクリルアミド、Ｎ，Ｎ’−プロピレンビスアクリルアミド、ジ（アクリルアミドメチル）エーテル、１，２−ジアクリルアミドエチレングリコール、１，３−ジアクリロイルエチレンウレア、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、Ｎ，Ｎ’−ジアリルタータルジアミド、Ｎ，Ｎ’−ビスアクリリルシスタミンなどの二官能性化合物や、トリアリルシアヌレート、トリアリルイソシアヌレートなどの三官能性化合物が例示される。 In the zwitterion-containing polymer gel of the present invention, it is most effective to use only a water-swellable clay mineral separated in layers in water as a crosslinking agent. However, it is also possible to use a small amount of a commonly used organic crosslinking agent (eg, bisacrylamide) together with a water-swellable clay mineral in order to control mechanical properties or suppress excessive swelling. Examples of such organic crosslinking agents include N, N′-methylenebisacrylamide, N, N′-propylenebisacrylamide, di (acrylamidomethyl) ether, 1,2-diacrylamide ethylene glycol, 1,3-di Bifunctional compounds such as acryloylethyleneurea, ethylene glycol diacrylate, ethylene glycol dimethacrylate, N, N′-diallyl tartardiamide, N, N′-bisacrylylcystamine, triallyl cyanurate, triallyl isocyania Examples are trifunctional compounds such as nurate.
本発明における双性イオン含有高分子ゲルの製造方法としては、双性イオンを有するモノマー（A）と水膨潤性粘土鉱物（B）を含む均一水溶液、または（A）と（メタ）アクリルアミド基または（メタ）アクリロイルオキシ基を有する水溶性ラジカル重合性モノマー（C）の混合物と水膨潤性粘土鉱物（B）からなる均一水溶液に、重合開始剤、更に必要に応じて触媒を溶解または均一に分散させた後、（A）または（A）と（C）を水中で層状剥離した（B）の存在下で重合させる高分子ヒドロゲルの製造方法が用いられる。その結果、（A）の重合体または（A）と（C）との共重合体と層状剥離した粘土鉱物（C）が複合して三次元網目を形成して、双性イオンを含有する高分子ゲルが得られる。ここで（A）の重合反応または（A）と（C）の共重合反応は、例えば、開始剤としての過酸化物の存在下、加熱または紫外線照射などの方法を用いたラジカル重合により行わせることができる。ラジカル重合開始剤および触媒としては、慣用のラジカル重合開始剤および触媒のうちから適宜選択して用いることができる。好ましくは水に分散性を有し、系全体に均一に含まれるものが用いられる。特に好ましくは層状に剥離した水膨潤性粘土鉱物（Ｂ）と強い相互作用を有するラジカル重合開始剤である。 As a method for producing a zwitterion-containing polymer gel in the present invention, a homogeneous aqueous solution containing a monomer (A) having a zwitterion and a water-swellable clay mineral (B), or (A) and a (meth) acrylamide group or Dissolve or uniformly disperse the polymerization initiator and, if necessary, the catalyst in a homogeneous aqueous solution consisting of a mixture of the water-soluble radically polymerizable monomer (C) having a (meth) acryloyloxy group and the water-swellable clay mineral (B). Then, a method for producing a polymer hydrogel is used in which (A) or (A) and (C) are polymerized in the presence of (B) delaminated in water. As a result, the polymer of (A) or the copolymer of (A) and (C) and the layered exfoliated clay mineral (C) are combined to form a three-dimensional network, resulting in a high concentration of zwitterions. A molecular gel is obtained. Here, the polymerization reaction of (A) or the copolymerization reaction of (A) and (C) is performed, for example, by radical polymerization using a method such as heating or ultraviolet irradiation in the presence of a peroxide as an initiator. be able to. The radical polymerization initiator and the catalyst can be appropriately selected from conventional radical polymerization initiators and catalysts. Preferably, those having dispersibility in water and uniformly contained in the entire system are used. Particularly preferred is a radical polymerization initiator having a strong interaction with the water-swellable clay mineral (B) exfoliated in layers.
具体的には、重合開始剤として水溶性の過酸化物、例えばペルオキソ二硫酸カリウムやペルオキソ二硫酸アンモニウム、水溶性のアゾ化合物などが好ましく使用できる。例えば、和光純薬工業株式会社製のＶＡ−０４４、Ｖ−５０、Ｖ−５０１などを用いることができる。その他、ポリエチレンオキシド鎖を有する水溶性のラジカル開始剤なども用いられる。また、紫外線照射により重合を行う場合は、親水性または疎水性の光重合開始剤が用いられる。光重合開始剤の具体例としては、ｐ−ｔｅｒｔ−ブチルトリクロロアセトフェノンなどのアセトフェノン類、４，４’−ビスジメチルアミノベンゾフェノンなどのベンゾフェノン類、２−メチルチオキサントンなどのケトン類、ベンゾインメチルエーテルなどのベンゾインエーテル類、ヒドロキシシクロヘキシルフェニルケトンなどのα−ヒドロキシケトン類、メチルベンゾイルホルメートなどのフェニルグリオキシレート類、メタロセン類などが挙げられる。 Specifically, water-soluble peroxides such as potassium peroxodisulfate, ammonium peroxodisulfate, and water-soluble azo compounds can be preferably used as the polymerization initiator. For example, VA-044, V-50, V-501, etc. manufactured by Wako Pure Chemical Industries, Ltd. can be used. In addition, a water-soluble radical initiator having a polyethylene oxide chain is also used. Moreover, when superposing | polymerizing by ultraviolet irradiation, a hydrophilic or hydrophobic photoinitiator is used. Specific examples of the photopolymerization initiator include acetophenones such as p-tert-butyltrichloroacetophenone, benzophenones such as 4,4′-bisdimethylaminobenzophenone, ketones such as 2-methylthioxanthone, and benzoin methyl ether. Examples include benzoin ethers, α-hydroxy ketones such as hydroxycyclohexyl phenyl ketone, phenyl glyoxylates such as methyl benzoyl formate, and metallocenes.
また触媒としては、３級アミン化合物であるＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミンやβ−ジメチルアミノプロピオニトリルなどが好ましく用いられる。重合温度は、用いる水溶性有機モノマー、重合触媒および開始剤の種類などに合わせて０℃〜１００℃の範囲に設定する。重合時間も触媒、開始剤、重合温度、重合溶液量（厚み）などの重合条件によって異なり、一概に規定できないが、一般に数十秒〜十数時間の間で行う。 As the catalyst, tertiary amine compounds such as N, N, N ′, N′-tetramethylethylenediamine and β-dimethylaminopropionitrile are preferably used. The polymerization temperature is set in the range of 0 ° C. to 100 ° C. according to the type of water-soluble organic monomer, polymerization catalyst and initiator used. The polymerization time also varies depending on the polymerization conditions such as the catalyst, initiator, polymerization temperature, polymerization solution amount (thickness) and cannot be generally defined, but it is generally carried out in the range of several tens of seconds to several tens of hours.
本発明における双性イオン含有高分子ゲルは、特に、塩を含む水溶液中で該水溶液を多量に吸収し、膨潤する特徴を有する。また、双性イオンを有するモノマーとしてスルフォベタインを用いた場合は、上限臨界共溶温度で相転移を示す温度応答性を有することができる。また、（A）と（C）との共重合体を用いた場合は、これらの特性と合わせて、更に優れた力学物性に持つようにすることが可能である。 The zwitterion-containing polymer gel in the present invention has a feature that it absorbs a large amount of the aqueous solution in an aqueous solution containing a salt and swells. Further, when sulfobetaine is used as a monomer having zwitterions, it can have temperature responsiveness showing a phase transition at the upper critical solution temperature. Further, when a copolymer of (A) and (C) is used, it is possible to have excellent mechanical properties in combination with these characteristics.
通常用いられている高分子ゲルである非イオン性高分子やイオン性高分子の化学架橋ゲルは、比較例１〜３に示すように、塩を含む水溶液中では膨潤度が低下し、塩濃度が高いほど低い膨潤度を示す。また、非イオン性高分子と粘土鉱物からなる高分子ゲルの場合も、比較例４、５に示すように、塩水溶液中で膨潤度が低下し、塩濃度が高いほど低い膨潤度を示す。一方、架橋密度に関しては、有機架橋剤を用いて合成した化学架橋ゲルの場合も、粘土鉱物を架橋剤に用いて調製した高分子ゲルの場合も、一般に、架橋剤濃度を高くして架橋密度を大きくしたものほど水および塩水溶液の吸収性（膨潤度）が低下する。更に、双性イオン高分子を用いた化学架橋ゲルでも同様に架橋密度の増加により膨潤度は低下する（比較例６、７）。 Chemically cross-linked gels of nonionic polymers and ionic polymers that are commonly used polymer gels, as shown in Comparative Examples 1 to 3, have a reduced degree of swelling in an aqueous solution containing a salt, and a salt concentration The higher the value, the lower the degree of swelling. Also, in the case of a polymer gel composed of a nonionic polymer and a clay mineral, as shown in Comparative Examples 4 and 5, the degree of swelling decreases in the aqueous salt solution, and the degree of swelling decreases as the salt concentration increases. On the other hand, with regard to the crosslink density, in general, the crosslink density is increased by increasing the concentration of the crosslinker both in the case of a chemically crosslinked gel synthesized using an organic crosslinker and in the case of a polymer gel prepared using a clay mineral as a crosslinker. The larger the value is, the lower the absorbability (swelling degree) of water and aqueous salt solution is. Furthermore, the degree of swelling also decreases with an increase in the crosslinking density in a chemically crosslinked gel using a zwitterionic polymer (Comparative Examples 6 and 7).
これに対して、本発明における双性イオン含有高分子ゲルの場合は、実施例に示すように、塩水溶液中の方が水中より高い膨潤度（吸収性）を示した。また、この塩水溶液中の塩濃度が増加するほど高い膨潤度（吸収性）を示した。更に、高分子ゲル中の粘土鉱物の含有量が増すとともに、塩水溶液中での膨潤度（吸収性）が更に高まる特徴を示した。 これに対して、本発明における双性イオン含有高分子ゲルの場合は、実施例で示すように、塩水溶液中の方が水中より高い膨潤度（吸収性）を示した。また、この塩水溶液中の塩濃度が増加するほど高い膨潤度（吸収性）を示した。更に、高分子ゲル中の粘土鉱物の含有量が増すとともに、塩水溶液中での膨潤度（吸収性）が更に高まる特徴を示した。 On the other hand, in the case of the zwitterion-containing polymer gel in the present invention, as shown in the examples, the salt solution showed a higher degree of swelling (absorbability) than the water. Moreover, the higher the salt concentration in the aqueous salt solution, the higher the degree of swelling (absorbability). Furthermore, the content of clay mineral in the polymer gel increased, and the swelling degree (absorbability) in the aqueous salt solution was further increased. On the other hand, in the case of the zwitterion-containing polymer gel in the present invention, as shown in the examples, the salt aqueous solution showed a higher degree of swelling (absorbability) than the water. Moreover, the higher the salt concentration in the aqueous salt solution, the higher the degree of swelling (absorbability). Furthermore, the content of clay mineral in the polymer gel increased, and the swelling degree (absorbability) in the aqueous salt solution was further increased.
次いで本発明を実施例により、より具体的に説明するが、もとより本発明は、以下に示す実施例にのみ限定されるものではない。
（参考例１）１，３−プロパンスルフォネート（３．６６４ｇ、０．０３ｍｏｌ）とアセトニトリル（５ｇ）の混合物を、３−（ジメチルアミノ）プロピルアクリルアミド（４．６８７ｇ、０．０３ｍｏｌ）とアセトニトリル（１０ｇ）の混合物と混ぜ、２５℃、２４時間保持し、次いで４℃で４８時間保持した。得られた沈殿物を濾過し、アセトニトリルとアセトンで洗った後、真空乾燥して白色の化１のモノマーを得た。収率９８％、
（参考例２）参考例１において、１，３−プロパンスルフォネートの代わりに１，４−ブタンスルフォネート（４．０８５ｇ、０．０３ｍｏｌ）を用いることを除くと参考例１と同様にして、双性イオンを有するモノマー（化２）を得た。収率７４％。
（参考例３）参考例１において、３−（ジメチルアミノ）プロピルアクリルアミドの代わりに、２−（ジメチルアミノ）エチルアクリレート（４．２９５ｇ、０．０３ｍｏｌ）を用いることを除くと参考例１と同様にして、双性イオンを有するモノマー（化３）を得た。収率９０％。
EXAMPLES Next, although an Example demonstrates this invention more concretely, this invention is not limited only to the Example shown below from the first.
Reference Example 1 A mixture of 1,3-propane sulfonate (3.664 g, 0.03 mol) and acetonitrile (5 g) was mixed with 3- (dimethylamino) propylacrylamide (4.687 g, 0.03 mol) and acetonitrile. (10 g) of the mixture and held at 25 ° C. for 24 hours and then at 4 ° C. for 48 hours. The resulting precipitate was filtered, washed with acetonitrile and acetone, and then vacuum dried to obtain a white chemical monomer 1. Yield 98%,
Reference Example 2 The same as Reference Example 1 except that, in Reference Example 1, 1,4-butanesulfonate (4.085 g, 0.03 mol) was used instead of 1,3-propanesulfonate. Thus, a monomer having a zwitterion (Chemical Formula 2) was obtained. Yield 74%.
(Reference Example 3) Same as Reference Example 1 except that 2- (dimethylamino) ethyl acrylate (4.295 g, 0.03 mol) was used instead of 3- (dimethylamino) propylacrylamide in Reference Example 1. Thus, a monomer having a zwitterion (Chemical Formula 3) was obtained. Yield 90%.
（実施例１）
水膨潤性粘土鉱物には、［Ｍｇ５．３４Ｌｉ０．６６Ｓｉ８Ｏ２０（ＯＨ）４］Ｎａ＋ ０．６６の組成を有する水膨潤性合成ヘクトライト（商標ラポナイトＸＬＧ、Ｒｏｃｋｗｏｏｄ Ｌｔｄ社製）を、双性イオンを有するモノマーには、参考例１で合成したN,N-ジメチル（アクリルアミドプロピル）アンモニウムプロパンサルフェイト（化１）を用いた。重合開始剤は、ペルオキソ二硫酸カリウム（ＫＰＳ：関東化学株式会社製）を、触媒は、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（ＴＥＭＥＤ：和光純薬工業株式会社製）を使用した。
Example 1
The water-swellable clay mineral includes a water-swellable synthetic hectorite having a composition of [Mg 5.34 Li 0.66 Si 8 O 20 (OH) 4 ] Na + 0.66 (trademark Laponite XLG, manufactured by Rockwood Ltd) ) Was used as the monomer having zwitterions, and N, N-dimethyl (acrylamidopropyl) ammonium propane sulfate (Chemical Formula 1) synthesized in Reference Example 1 was used. The polymerization initiator used was potassium peroxodisulfate (KPS: manufactured by Kanto Chemical Co., Inc.), and the catalyst used was N, N, N ′, N′-tetramethylethylenediamine (TEMED: manufactured by Wako Pure Chemical Industries, Ltd.). .
２０℃の恒温室において、平底ガラス容器に、純水（２０ｍｌ）、ラポナイトＸＬＧ（０．４６ｇ）、双性イオンを有するモノマー（化１）（２０ｍｍｏｌ）、ＫＰＳ（７．４×１０−２ｍｍｏｌ）、ＴＥＭＥＤ（１．０７×１０−１ｍｍｏｌ）からなる均一透明な水溶液を調製した。この溶液の一部を底の閉じた内径５．５ｍｍ、長さ１５０ｍｍの容器３本に酸素にふれないようにして移した後、２０℃の恒温水槽中で２０時間静置して重合を行った。また、残りの溶液は、縦、横が１ｃｍ、長さ５ｃｍの容器に移した後、同様に２０℃の恒温水槽中で２０時間静置して重合を行った。なお、これらの溶液調製から重合までの操作は、全て酸素を遮断した窒素雰囲気下で行った。重合開始から２０時間後に、容器内に高分子と粘土鉱物からなる無色透明で均一な棒状、及び立方体状の高分子ゲルが生成していた。高分子ゲルを室温および１００℃で乾燥して得た高分子ゲル乾燥物の超泊切片の透過型電子顕微鏡観察を行ったところ、１〜３層に層状剥離した粘土鉱物層が均一に高分子マトリックス中に分散しているのが観測された。また、高分子ゲル乾燥物の小角Ｘ線回折測定（２〜１０°）からも、粘土鉱物層の積層層間距離に相当する反射は観測されず、粘土鉱物層が層状剥離していることが支持された。また、得られた高分子ゲルは、温度により透明性が変化し、１６．３℃（上限臨界共溶温度）以下では不透明およびそれ以上では透明であった。 In a constant temperature room at 20 ° C., in a flat bottom glass container, pure water (20 ml), Laponite XLG (0.46 g), monomer having zwitterion (Chemical formula 1) (20 mmol), KPS (7.4 × 10 −2 mmol) ), A homogeneous transparent aqueous solution consisting of TEMED (1.07 × 10 −1 mmol) was prepared. A part of this solution was transferred to three containers with a closed inner diameter of 5.5 mm and a length of 150 mm so as not to come into contact with oxygen, and then left in a constant temperature water bath at 20 ° C. for 20 hours for polymerization. It was. The remaining solution was transferred to a container having a length and width of 1 cm and a length of 5 cm, and then left to stand in a constant temperature water bath at 20 ° C. for 20 hours for polymerization. The operations from preparation of the solution to polymerization were all performed in a nitrogen atmosphere in which oxygen was blocked. Twenty hours after the start of polymerization, a colorless transparent uniform rod-like and cubic polymer gel composed of a polymer and clay mineral was formed in the container. When the transmission electron microscope observation of the super night section of the dried polymer gel obtained by drying the polymer gel at room temperature and 100 ° C. was conducted, the clay mineral layer exfoliated into 1 to 3 layers was uniformly polymerized. Dispersion in the matrix was observed. In addition, from the small-angle X-ray diffraction measurement (2 to 10 °) of the dried polymer gel, no reflection corresponding to the interlayer distance of the clay mineral layer is observed, and the clay mineral layer is delaminated. It was done. Further, the obtained polymer gel changed in transparency with temperature, and was opaque at 16.3 ° C. (upper critical solution temperature) or lower and transparent at higher temperature.
棒状の高分子ゲルの引っ張り試験を、引っ張り試験装置（株式会社島津製作所製、卓上型万能試験機ＡＧＳ−Ｈ）を用い、評点間距離＝３０ｍｍ、引っ張り速度＝１００ｍｍ／分にて行った。この高分子ゲルは、大きな延伸性（破断伸び＝２１００％）および強度（２１ｋＰａ）を有するゴム的な力学物性を示した。また、水中（２０℃）で膨潤試験（膨潤度＝膨潤時の水の質量／乾燥ゲルの質量）を行った結果、特異的な膨潤−収縮挙動を示し、最大膨潤は４５、３００時間後の膨潤度は４．５であった。以上の力学物性および膨潤性および分析結果から、双性イオンを有するモノマーの重合体と粘土鉱物が三次元網目を形成した高分子ゲルであると結論された。また、塩（ＮａＣｌ）濃度０．９％の水溶液（生理食塩水）中では、時間と共に膨潤度が増加する通常の膨潤挙動を示し、３００時間後の膨潤度は６８であった。即ち、高分子ゲルは水中より塩水溶液中でより大きな吸収性を示した。 The tensile test of the rod-shaped polymer gel was performed using a tensile test apparatus (manufactured by Shimadzu Corporation, tabletop universal testing machine AGS-H) at a distance between ratings = 30 mm and a tensile speed = 100 mm / min. This polymer gel exhibited rubber-like mechanical properties having large stretchability (breaking elongation = 2100%) and strength (21 kPa). Moreover, as a result of conducting a swelling test in water (20 ° C.) (swelling degree = mass of water during swelling / mass of dry gel), it shows a specific swelling-shrinkage behavior, and the maximum swelling is 45, 300 hours later. The degree of swelling was 4.5. From the above mechanical properties, swelling properties and analytical results, it was concluded that the polymer polymer of the monomer having zwitterions and the clay mineral was a polymer gel in which a three-dimensional network was formed. Further, in an aqueous solution (physiological saline) having a salt (NaCl) concentration of 0.9%, a normal swelling behavior in which the degree of swelling increases with time was exhibited, and the degree of swelling after 300 hours was 68. That is, the polymer gel exhibited greater absorbability in the salt solution than in water.
（実施例２、３）
参考例２および参考例３で得た双性イオンを有するモノマー（化２：実施例２）および（化３：実施例３）を使用する以外は、実施例１と同様にして、高分子ゲルを調製した。実施例２では、均一だが白色不透明の高分子ゲルが、実施例３では均一透明な高分子ゲルが得られた。得られた高分子ゲルは上限臨界共溶温度を持つ（８５℃（実施例２）、１９℃（実施例３）温度応答性を示した。
(Examples 2 and 3)
Polymer gel in the same manner as in Example 1 except that the monomer having the zwitterion obtained in Reference Example 2 and Reference Example 3 (Chem. 2: Example 2) and (Chem. 3: Example 3) is used. Was prepared. In Example 2, a uniform but white opaque polymer gel was obtained, and in Example 3, a uniform transparent polymer gel was obtained. The obtained polymer gel showed temperature responsiveness (85 ° C. (Example 2), 19 ° C. (Example 3)) having an upper critical solution temperature.
高分子ゲルの引っ張り試験および膨潤試験を実施例１と同様にして行った結果、破断伸びは２０５０％（実施例２）、９４０％（実施例３）、強度は７１ｋＰａ（実施例２）、５ｋＰａ（実施例３）であった。 As a result of conducting a tensile test and a swelling test of the polymer gel in the same manner as in Example 1, the elongation at break was 2050% (Example 2), 940% (Example 3), and the strength was 71 kPa (Example 2), 5 kPa. (Example 3).
（実施例４）
双性イオンモノマー（化１）と共に、水溶性ラジカル重合性モノマーとしてアクリルアミド基を有するＮ，Ｎ−ジメチルアクリルアミドを、モル比で（化１：Ｎ，Ｎ−ジメチルアクリルアミド＝９０：１０）の割合で用いること以外は、実施例１と同様にして合成を行った結果、無色透明の均一な高分子ゲルが得られた。得られた高分子ゲルは温度応答性を有し、上限臨界共溶温度が９．５℃であった。高分子ゲルの引っ張り試験および膨潤試験を実施例１と同様にして行った結果、破断伸びは２４００％、強度は５８ｋＰａと、実施例１の場合より大きく向上した。水中では膨潤−収縮挙動を示し、最大膨潤は５４、３００時間後の膨潤は８．３であった。また、塩水溶液（ＮａＣｌ濃度０．９ｗｔ％）では通常の膨潤挙動を示し、３００時間後の膨潤度は７８であった。
Example 4
Along with the zwitterionic monomer (Chemical Formula 1), N, N-dimethylacrylamide having an acrylamide group as a water-soluble radical polymerizable monomer is used in a molar ratio (Chemical 1: N, N-dimethylacrylamide = 90: 10). As a result of synthesizing in the same manner as in Example 1 except that it was used, a colorless and transparent uniform polymer gel was obtained. The obtained polymer gel had temperature response and the upper critical solution temperature was 9.5 ° C. The tensile test and the swelling test of the polymer gel were conducted in the same manner as in Example 1. As a result, the elongation at break was 2400% and the strength was 58 kPa, which was greatly improved as compared with Example 1. Swelling-shrinkage behavior was exhibited in water, maximum swelling was 54, and swelling after 300 hours was 8.3. Further, the aqueous salt solution (NaCl concentration: 0.9 wt%) showed a normal swelling behavior, and the swelling degree after 300 hours was 78.
（実施例５、６）
実施例４で得られた高分子ゲルをＮａＣｌ濃度の異なる塩水溶液（０．３５ｗｔ％（実施例５）、３．５ｗｔ％（実施例６））に浸漬して膨潤試験を２０℃で行った結果、いずれも通常の膨潤挙動を示し、３００時間後の膨潤度は、各々、４８（実施例５）および１１０（実施例６）であった。実施例４〜６の結果から、塩水溶液の塩濃度が高くなるほど、膨潤度（即ち、高分子ゲルの吸収性）は増加することが明らかとなった。
(Examples 5 and 6)
The polymer gel obtained in Example 4 was immersed in salt aqueous solutions having different NaCl concentrations (0.35 wt% (Example 5), 3.5 wt% (Example 6)), and the swelling test was performed at 20 ° C. As a result, all showed normal swelling behavior, and the swelling degree after 300 hours was 48 (Example 5) and 110 (Example 6), respectively. From the results of Examples 4 to 6, it was revealed that the degree of swelling (that is, the absorbability of the polymer gel) increases as the salt concentration of the aqueous salt solution increases.
（実施例７〜９）
粘土鉱物（ラポナイトＸＬＧ）の量を、０．７６ｇ（実施例７）、１．０７ｇ（実施例８）、２．２９ｇ（実施例９）とする以外は、実施例４と同様にして共重合高分子と粘土鉱物からなる高分子ゲルを調製した。得られた高分子ゲルは、実施例７と８は温度応答性を示し、上限臨界共溶温度は６℃（実施例７）および３．７℃（実施例８）であった。また、実施例９の高分子ゲルは温度応答性を示さず、温度によらず常に透明であった。得られた高分子ゲルの引っ張り試験および膨潤試験を実施例１と同様にして行った結果、破断伸びは２４００％（実施例７）、２３５０％（実施例８）、１６９０％（実施例８）であり、強度は、１４１ｋＰａ（実施例７）、２４２ｋＰａ（実施例８）、２２５ｋＰａ（実施例９）であった。水中ではいずれも膨潤−収縮挙動を示し、最大膨潤は７５（実施例７）、１０２（実施例８）、１５０（実施例９）で、３００時間後の膨潤は３１（実施例７）、５２（実施例８）、１２０（実施例９）であった。粘土鉱物の量が増すにつれて、力学物性における弾性率の増加から架橋密度が増加していることがわかるが、それにも関わらず、膨潤度も増加しているのが観測された。
(Examples 7 to 9)
Copolymerization in the same manner as in Example 4 except that the amount of clay mineral (Laponite XLG) was 0.76 g (Example 7), 1.07 g (Example 8), and 2.29 g (Example 9). A polymer gel composed of a polymer and a clay mineral was prepared. In the obtained polymer gel, Examples 7 and 8 showed temperature responsiveness, and the upper critical solution temperature was 6 ° C. (Example 7) and 3.7 ° C. (Example 8). Further, the polymer gel of Example 9 did not show temperature responsiveness and was always transparent regardless of temperature. As a result of conducting a tensile test and a swelling test of the obtained polymer gel in the same manner as in Example 1, the elongation at break was 2400% (Example 7), 2350% (Example 8), and 1690% (Example 8). The strength was 141 kPa (Example 7), 242 kPa (Example 8), and 225 kPa (Example 9). In water, all showed swelling-shrinkage behavior, maximum swelling was 75 (Example 7), 102 (Example 8), 150 (Example 9), and swelling after 300 hours was 31 (Example 7), 52 (Example 8) and 120 (Example 9). As the amount of clay mineral increases, it can be seen that the crosslink density is increased due to the increase in the elastic modulus in the mechanical properties, but it is observed that the degree of swelling is nevertheless increased.
（実施例１０）
双性イオンモノマー（化１）と共に、水溶性ラジカル重合性モノマーとしてアクリルアミド基を有するＮ，Ｎ−ジメチルアクリルアミドを、モル比で（化１：Ｎ，Ｎ−ジメチルアクリルアミド＝７０：３０）の割合で用いること以外は、実施例４と同様にして合成を行った結果、無色透明の均一な高分子ゲルが得られた。得られた高分子ゲルは温度応答性を示さず、温度によらず常に透明であった。高分子ゲルの引っ張り試験および膨潤試験を実施例４と同様にして行った結果、破断伸びは２４１０％、強度は７８ｋＰａと、実施例４の場合より更に大きく向上した。水中では膨潤−収縮挙動を示し、最大膨潤は６２、３００時間後の膨潤は５５であった。また、塩水溶液（ＮａＣｌ濃度０．９ｗｔ％）では通常の膨潤挙動を示し、３００ｈ後の膨潤度は３８０であった。
(Example 10)
Along with the zwitterionic monomer (Chemical Formula 1), N, N-dimethylacrylamide having an acrylamide group as a water-soluble radical polymerizable monomer is used in a molar ratio (Chemical Formula 1: N, N-dimethylacrylamide = 70: 30). As a result of synthesizing in the same manner as in Example 4 except that it was used, a colorless and transparent uniform polymer gel was obtained. The obtained polymer gel did not show temperature responsiveness and was always transparent regardless of temperature. As a result of conducting a tensile test and a swelling test of the polymer gel in the same manner as in Example 4, the elongation at break was 2410%, and the strength was 78 kPa, which was further improved as compared with Example 4. Swelling-shrinkage behavior was exhibited in water, the maximum swelling was 62, and the swelling after 300 hours was 55. Further, the aqueous salt solution (NaCl concentration: 0.9 wt%) showed a normal swelling behavior, and the swelling degree after 300 hours was 380.
（比較例１〜３）
有機モノマーとして、比較例１と２ではＮ，Ｎ−ジメチルアクリルアミドを２０ｍｍｏｌ、比較例３ではアクリル酸ナトリウムを１０ｍｍｏｌとＮ，Ｎ−ジメチルアクリルアミドを１０ｍｍｏｌ用いること、および架橋剤として、水膨潤性粘土鉱物の代わりに有機架橋剤（Ｎ，Ｎ’−メチレンビスアクリルアミド（和光純薬工業株式会社製））をモノマーに対して１モル％（比較例１と３）または３モル％（比較例２）を用いること以外は、実施例１と同様にして、化学架橋による高分子ゲルを得た。いずれの高分子ゲルも力学的に脆弱で、弱い力で破断し（引っ張り伸びは５０％以下）、引っ張り試験を行うことはできなかった。また、水中および塩（ＮａＣｌ）濃度０．９％の塩水溶液での膨潤度（２０℃、３００時間）は、１８および１２（比較例１）、１６および１０（比較例２）、２３０および２９（比較例３）であり、膨潤度は架橋剤濃度が高いほど低く、また塩水溶液中が水中より低かった。
(Comparative Examples 1-3)
As an organic monomer, 20 mmol of N, N-dimethylacrylamide was used in Comparative Examples 1 and 2, 10 mmol of sodium acrylate and 10 mmol of N, N-dimethylacrylamide were used in Comparative Example 3, and a water-swellable clay mineral as a crosslinking agent Instead of 1 mol% (Comparative Examples 1 and 3) or 3 mol% (Comparative Example 2) of the organic crosslinking agent (N, N′-methylenebisacrylamide (manufactured by Wako Pure Chemical Industries, Ltd.)) with respect to the monomer. A polymer gel by chemical crosslinking was obtained in the same manner as in Example 1 except that it was used. All the polymer gels were mechanically fragile and ruptured with a weak force (tensile elongation was 50% or less), and the tensile test could not be performed. The swelling degree (20 ° C., 300 hours) in water and a salt aqueous solution having a salt (NaCl) concentration of 0.9% was 18 and 12 (Comparative Example 1), 16 and 10 (Comparative Example 2), 230 and 29. (Comparative Example 3) The degree of swelling was lower as the concentration of the crosslinking agent was higher, and the aqueous salt solution was lower than in water.
（比較例４，５）
有機モノマーとして、Ｎ，Ｎ−ジメチルアクリルアミドを２０ｍｍｏｌ用いること以外は、比較例４は実施例４と、比較例５は実施例８と同様にして、高分子ゲルを得た。いずれの高分子ゲルも優れた力学物性を示し、破断伸びは１３００％（比較例４）、１２００％（比較例５）、強度は８９ｋＰａ（比較例４）、１７０ｋＰａ（比較例５）であった。また、水中および塩（ＮａＣｌ）濃度０．９％の塩水溶液での膨潤度（２０℃、３００時間）は、８０および５１（比較例４）、６６および２０（比較例５）であり、膨潤度は架橋剤（粘土鉱物）濃度が高いほど低く、また塩水溶液中が水中より低かった。
(Comparative Examples 4 and 5)
A polymer gel was obtained in the same manner as in Example 4 in Comparative Example 4 and in Example 8 in Comparative Example 5 except that 20 mmol of N, N-dimethylacrylamide was used as the organic monomer. All the polymer gels showed excellent mechanical properties, and the elongation at break was 1300% (Comparative Example 4), 1200% (Comparative Example 5), and the strength was 89 kPa (Comparative Example 4) and 170 kPa (Comparative Example 5). . The swelling degree (20 ° C., 300 hours) in water and a salt aqueous solution having a salt (NaCl) concentration of 0.9% is 80 and 51 (Comparative Example 4), 66 and 20 (Comparative Example 5), and the swelling The degree was lower as the concentration of the crosslinking agent (clay mineral) was higher, and the salt solution was lower than in water.
（比較例６，７）
有機モノマーとして、Ｎ，Ｎ−ジメチルアクリルアミドの代わりに、双性イオンを有するモノマー（化１）を２０ｍｍｏｌ用いること以外は、比較例６は比較例１と、比較例７は比較例２と同様にして高分子ゲルを得た。いずれの高分子ゲルも力学的に脆弱で、弱い力で破断し（引っ張り伸びは４０％以下）、引っ張り試験を行うことはできなかった。また、水および塩（ＮａＣｌ）濃度０．９％の塩水溶液での膨潤度（２０℃、３００時間）は、２．１および５．９（比較例６）、１．２及び４．４（比較例７）であり、架橋剤濃度が高いほど低かった。また、塩水溶液中での膨潤度（吸収量）は絶対値として低かった。
(Comparative Examples 6 and 7)
Comparative Example 6 is the same as Comparative Example 1 and Comparative Example 7 is the same as Comparative Example 2, except that 20 mmol of a monomer having a zwitter ion (Chemical Formula 1) is used instead of N, N-dimethylacrylamide as the organic monomer. Thus, a polymer gel was obtained. All of the polymer gels were mechanically fragile and ruptured with a weak force (tensile elongation was 40% or less), and a tensile test could not be performed. The swelling degree (20 ° C., 300 hours) in a salt solution with water and a salt (NaCl) concentration of 0.9% was 2.1 and 5.9 (Comparative Example 6), 1.2 and 4.4 ( Comparative Example 7), which was lower as the concentration of the crosslinking agent was higher. Further, the degree of swelling (absorption amount) in the salt aqueous solution was low as an absolute value.
本発明の高分子ヒドロゲルは、大気と接触しながら使用される用途、基材に接着させたり、基材間に挟み込んだりして大気中で使用される用途、地中に埋めて使用される用途などで用いられる材料として利用が可能である。 The polymer hydrogel of the present invention is used in contact with the atmosphere, used in the atmosphere by being bonded to a substrate or sandwiched between substrates, and used in the ground. It can be used as a material used in
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013108862A JP6107417B2 (en) | 2013-05-23 | 2013-05-23 | Zwitterion-containing polymer gel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013108862A JP6107417B2 (en) | 2013-05-23 | 2013-05-23 | Zwitterion-containing polymer gel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014227478A JP2014227478A (en) | 2014-12-08 |
| JP6107417B2 true JP6107417B2 (en) | 2017-04-05 |
Family
ID=52127652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013108862A Active JP6107417B2 (en) | 2013-05-23 | 2013-05-23 | Zwitterion-containing polymer gel |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6107417B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200697B (en) * | 2016-03-17 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of preparation method of sulphonic acid betaine type zwitterionic monomer |
| CN113861320A (en) * | 2021-09-26 | 2021-12-31 | 哈尔滨工业大学（深圳） | Anti-freezing hydrogel, preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07242713A (en) * | 1994-03-08 | 1995-09-19 | Toyobo Co Ltd | Zwitterionic polymer which can absorb aqueous electrolyte solution |
| JP3407758B2 (en) * | 1993-09-08 | 2003-05-19 | 東洋紡績株式会社 | Aqueous electrolyte solution absorbing zwitterionic polymer |
| JPH0827225A (en) * | 1994-07-12 | 1996-01-30 | Toyobo Co Ltd | Amphoteric ionic polymer capable of absorbing aqueous electrolytic solution |
| JP4759165B2 (en) * | 2000-05-29 | 2011-08-31 | 一般財団法人川村理化学研究所 | Organic / inorganic composite hydrogel and method for producing the same |
| JP5456344B2 (en) * | 2009-03-17 | 2014-03-26 | 一般財団法人川村理化学研究所 | Organic-inorganic composite hydrogel and method for producing the same |
-
2013
- 2013-05-23 JP JP2013108862A patent/JP6107417B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2014227478A (en) | 2014-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Synthesis and properties of thermo-and pH-sensitive poly (diallyldimethylammonium chloride)/poly (N, N-diethylacrylamide) semi-IPN hydrogel | |
| Zhao et al. | Mechanically strong and thermosensitive macromolecular microsphere composite poly (N-isopropylacrylamide) hydrogels | |
| JP5132278B2 (en) | Method for producing organic-inorganic composite hydrogel | |
| Yiamsawas et al. | Synthesis and swelling properties of poly [acrylamide-co-(crotonic acid)] superabsorbents | |
| MX2011006547A (en) | Method for blocking subterranean formations. | |
| JP5132300B2 (en) | Method for producing cationic organic / inorganic composite hydrogel | |
| JP2009270048A (en) | Method for producing organic-inorganic composite hydrogel having carboxylate structure group or carboxy anion structure group | |
| Boyaci et al. | Poly (N, N-dimethylaminoethyl methacrylate-co-2-acrylamido-2-methyl-propanosulfonic acid)/Laponite nanocomposite hydrogels and cryogels with improved mechanical strength and rapid dynamic properties | |
| JP2006028446A (en) | Organoinorganic composite polymer gel and preparation process of the same | |
| JP3914501B2 (en) | Polymer gel composite and method for producing the same | |
| JP2004027195A (en) | Stimulation-responsive porous polymer gel | |
| JP2011153174A (en) | Organic-inorganic composite hydrogel, dried body thereof and method for producing them | |
| JP6107417B2 (en) | Zwitterion-containing polymer gel | |
| WO2020026715A1 (en) | Hydrogel | |
| JP5285839B2 (en) | Method for producing polymer composite gel | |
| KR101642497B1 (en) | The manufacturing method of super absorbent acrylate resin coated with poly(styrene-etyleneglycol acrylate) copolymer | |
| JP5456344B2 (en) | Organic-inorganic composite hydrogel and method for producing the same | |
| JP4474974B2 (en) | Method for producing polymer hydrogel | |
| JP5202903B2 (en) | Method for producing organic-inorganic composite hydrogel having carboxylic acid group or sulfonic acid group | |
| JP5654208B2 (en) | Organic inorganic composite gel | |
| JP4914157B2 (en) | Amino group-containing organic-inorganic composite hydrogel and method for producing the same | |
| JP5028082B2 (en) | Locally swollen polymer gel | |
| JP5704382B2 (en) | Gel, gel dried body, and production method thereof | |
| JP4730725B2 (en) | Method for producing polymer hydrogel | |
| JP2009256629A (en) | Organic-inorganic composite hydrogel and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160209 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20161128 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20161206 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170126 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170207 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170220 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6107417 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |