JP4664609B2 - スルホン酸基を有する有機高分子材料及びその製造方法 - Google Patents
スルホン酸基を有する有機高分子材料及びその製造方法 Download PDFInfo
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- JP4664609B2 JP4664609B2 JP2004065108A JP2004065108A JP4664609B2 JP 4664609 B2 JP4664609 B2 JP 4664609B2 JP 2004065108 A JP2004065108 A JP 2004065108A JP 2004065108 A JP2004065108 A JP 2004065108A JP 4664609 B2 JP4664609 B2 JP 4664609B2
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- Prior art keywords
- sulfonic acid
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- organic polymer
- graft
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- 125000000542 sulfonic acid group Chemical group 0.000 title claims description 94
- 229920000620 organic polymer Polymers 0.000 title claims description 49
- 239000002861 polymer material Substances 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 238000000034 method Methods 0.000 claims description 56
- 239000004745 nonwoven fabric Substances 0.000 claims description 35
- 239000000178 monomer Substances 0.000 claims description 31
- 238000010559 graft polymerization reaction Methods 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000012528 membrane Substances 0.000 claims description 23
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 150000003863 ammonium salts Chemical class 0.000 claims description 14
- 230000005855 radiation Effects 0.000 claims description 13
- -1 fluoropolyolefin Polymers 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 229910003002 lithium salt Chemical class 0.000 claims description 11
- 125000000524 functional group Chemical group 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 4
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 4
- 125000002130 sulfonic acid ester group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000463 material Substances 0.000 description 82
- 239000002585 base Substances 0.000 description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 14
- 238000006277 sulfonation reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920000578 graft copolymer Polymers 0.000 description 6
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 150000003459 sulfonic acid esters Chemical class 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- LEDCJBCTEYLBJO-UHFFFAOYSA-N ethyl 2-phenylethenesulfonate Chemical compound CCOS(=O)(=O)C=CC1=CC=CC=C1 LEDCJBCTEYLBJO-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- ZKIAYSOOCAKOJR-UHFFFAOYSA-M lithium;2-phenylethenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 ZKIAYSOOCAKOJR-UHFFFAOYSA-M 0.000 description 2
- YSKIQSYEHUCIFO-UHFFFAOYSA-M lithium;4-ethenylbenzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 YSKIQSYEHUCIFO-UHFFFAOYSA-M 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- QFGALIZFMJDZQJ-UHFFFAOYSA-N styrene;toluene Chemical compound CC1=CC=CC=C1.C=CC1=CC=CC=C1 QFGALIZFMJDZQJ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZPYNCJGACCHGSV-UHFFFAOYSA-N CC1=CC=CC=C1.C(=CC1=CC=CC=C1)S(=O)(=O)OCC Chemical compound CC1=CC=CC=C1.C(=CC1=CC=CC=C1)S(=O)(=O)OCC ZPYNCJGACCHGSV-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004775 Tyvek Substances 0.000 description 1
- 229920000690 Tyvek Polymers 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PQDIYGGPCZTLIJ-UHFFFAOYSA-N n,n-dibutylbutan-1-amine;2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1.CCCCN(CCCC)CCCC PQDIYGGPCZTLIJ-UHFFFAOYSA-N 0.000 description 1
- GQDRZFZESRZTIK-UHFFFAOYSA-N n,n-dibutylbutan-1-amine;4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1.CCCCN(CCCC)CCCC GQDRZFZESRZTIK-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/28—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Graft Or Block Polymers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
ポリエチレン繊維よりなる不織布(DuPont社製、商品名タイベック、平均繊維径0.5〜10μm、平均孔径5μm、目付63g/m2、厚さ0.17mm)6.58gに、ドライアイス冷却下でγ線を160kGy照射した。この照射済み不織布基材に、p−スチレンスルホン酸リチウム塩のエタノール溶液(重量比1/19)を含浸させ、60℃で3時間グラフト重合反応を行なった。反応後、不織布を取出し、エタノール、純水で順次洗浄してふき取った後、温風乾燥機中50℃で3時間乾燥することによって、グラフト率7.0%でスチレンスルホン酸リチウム塩型のグラフト不織布7.04gを得た。
実施例1で用いたものと同じ不織布基材6.15gに対して、実施例1と同様の条件でγ線を照射した。この照射済み基材に、スチレンスルホン酸エチル−トルエン混合液(重量比=1/19)を含浸させ、60℃で3時間グラフト重合反応を行った。反応後、不織布を取り出し、ジクロロメタン(100mL)で3回洗浄してふき取った後、50℃で3時間乾燥させることによって、グラフト率8.6%でスチレンスルホン酸エチルグラフト不織布6.68gを得た。
実施例1で用いたものと同じ不織布基材6.46gに対して、実施例1と同様の条件でγ線を照射した。この照射済みの不織布基材に、スチレン−トルエン混合液(重量比1/19)を含浸させ、60℃で3時間グラフト重合反応を行なった。反応後、不織布を取出し、ジクロロメタン(100mL)で3回洗浄してふき取った後、温風乾燥機中50℃で1時間乾燥することにより、グラフト率2.9%でスチレングラフト不織布6.65gを得た。
超高分子量ポリエチレン(分子量100万)よりなる多孔質膜(厚さ100μm、目付25g/m2)1.52gに対して、実施例1と同様の条件でγ線を照射した。照射済みの多孔質膜基材に、p−スチレンスルホン酸リチウム塩のエタノール溶液(重量比5/95)を含浸させ、60℃で6時間グラフト重合反応を行なった。反応後、多孔質膜を取出し、エタノール、純水で順次洗浄してふき取った後、温風乾燥機中50℃で3時間乾燥することによって、グラフト率5.7%でスチレンスルホン酸リチウム塩型のグラフト多孔質膜1.61gを得た。
実施例3で用いたものと同じ多孔質膜1.51gに対して、実施例3と同様の条件でγ線を照射した。照射済みの多孔質膜基材に、スチレン−トルエン混合液(体積比1/20)を含浸させ、60℃で3時間グラフト重合反応を行なった。反応後、多孔質膜を取出し、ジクロロメタン(500mL)で2回洗浄してふき取った後、温風乾燥機中50℃で3時間乾燥することにより、グラフト率4.5%でスチレングラフト多孔質膜1.58gを得た。
ポリエチレン繊維よりなる不織布(繊維径20〜30μm、目付50〜60g/m2、日本バイリーン社製、商品コードOX8901T6)9.92gに、ドライアイス冷却下でγ線を160kGy照射した。この照射済み不織布基材に、p−スチレンスルホン酸トリブチルアンモニウム塩のトルエン溶液(重量比20/80)を含浸させ、60℃で6時間グラフト重合反応を行なった。反応後、不織布を取出し、エタノール(500mL)で3回洗浄してふき取った後、温風乾燥機中50℃で3時間乾燥することによって、グラフト率12.5%でスチレンスルホン酸トリブチルアンモニウム塩型のグラフト不織布11.16gを得た。
上記で得られたスルホン酸基含有不織布材料1、スルホン酸基含有不織布材料2及びスルホン酸含有不織布材料Aを、それぞれ5cm×5cmの大きさに18枚切り出した。切り出した試験片と表1に示すいずれかの有機溶媒250mLとを、容量500mLの密栓付三角フラスコに入れて密栓し、25℃で48時間振盪した。有機溶媒を容量1リットルのナス型フラスコに移し、液量が2〜3mLになるまでロータリーエバポレーターで濃縮した。濃縮液を、予め重量を測定したアルミニウム製の蒸発皿に移した。また、使用したナス型フラスコをイソプロパノール(10mL)で3回洗浄し、洗浄液を蒸発皿に加えた。蒸発皿を真空乾燥機に入れ、50℃で約3時間真空乾燥した。乾燥後の蒸発皿の重量を測定することにより、有機溶媒への抽出物量を求めた。結果を表1に示す。
上記で得られたスルホン酸基含有不織布材料1及びスルホン酸基含有不織布材料Aを、それぞれ4mm×25mmの短冊状に切り出した。アクリル板の樋(長さ28mm、幅1.5mm、深さ1.5mm)に純水(80μL)を入れ、短冊状の試験片を、長辺を縦にして、下端が水中に配置されるようにして立てかけ、純水が到達した高さの経時変化を測定した。
上記で得られたスルホン酸基含有多孔質膜材料3及びスルホン酸基含有多孔質膜材料Bを、それぞれ1cm×5cmに切り出し、密栓付試験管中でアセトン(10mL)中に浸漬し、室温で20日間放置した。浸漬後のアセトンの吸光度を吸光光度計により測定した。結果を表2に示す。
Claims (7)
- ベンゼン環を有し、ベンゼン環上のビニル基と、アンモニウム塩又はリチウム塩の形態のスルホン酸基とを有するスチレン系モノマーを、ポリオレフィン、フッ素系ポリオレフィンおよびポリエチレンテレフタレートよりなる群より選択される有機高分子基材に放射線グラフト重合することを特徴とする、スルホン酸基を有する有機高分子材料の製造方法。
- 前記アンモニウム塩又はリチウム塩の形態のスルホン酸基は、前記ビニル基に対してパラ位に結合していることを特徴とする請求項1に記載の製造方法。
- 前記アンモニウム塩の窒素原子の置換基は、炭素数が1〜10のアルキル基であることを特徴とする請求項1又は2に記載の製造方法。
- ベンゼン環を有し、ベンゼン環上のビニル基とスルホン酸エステル基とを有するスチレン系モノマーを、ポリオレフィン、フッ素系ポリオレフィンおよびポリエチレンテレフタレートよりなる群より選択される有機高分子基材に放射線グラフト重合し、次いで当該スルホン酸エステル基を加水分解してスルホン酸基に変換することを特徴とする、スルホン酸基を有する有機高分子材料の製造方法。
- 前記スルホン酸エステル基は、前記ビニル基に対してパラ位に結合していることを特徴とする請求項4に記載の製造方法。
- 前記有機高分子基材は、織布、不織布又は多孔質膜の形態である請求項1〜5のいずれかに記載の製造方法。
- ポリオレフィン、フッ素系ポリオレフィンおよびポリエチレンテレフタレートよりなる群より選択される有機高分子基材の主鎖上に、機能性官能基としてベンゼン環上のスルホン酸基のみを有する重合体側鎖を有しており、前記スルホン酸基が、重合体側鎖中のベンゼン環上のパラ位にのみ結合していることを特徴とする有機高分子材料。
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PCT/JP2004/007462 WO2004106622A1 (en) | 2003-05-27 | 2004-05-25 | Organic polymer materials having sulfonic acid groups and method for their preparation |
KR1020057022463A KR20060012647A (ko) | 2003-05-27 | 2004-05-25 | 술폰산기를 갖는 유기 중합체 재료 및 이의 제조 방법 |
US10/557,468 US20070093568A1 (en) | 2003-05-27 | 2004-05-25 | Organic polymer materials having sulfonic acid groups and method for their preparation |
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JP4854284B2 (ja) * | 2005-12-02 | 2012-01-18 | 日東電工株式会社 | 高分子電解質膜の製造方法 |
JP4923598B2 (ja) * | 2006-02-02 | 2012-04-25 | トヨタ自動車株式会社 | 高親水化担体、触媒担持担体、燃料電池用電極、その製造方法、及びこれを備えた固体高分子型燃料電池 |
JP4699950B2 (ja) * | 2006-02-13 | 2011-06-15 | 三井化学株式会社 | 極性重合体がコーティングされたポリオレフィン系成形体の製造方法 |
EP1842592A1 (de) * | 2006-04-04 | 2007-10-10 | Metrohm Ag | Ionenaustauschmaterial, Ionenaustauschsäule und Herstellungsverfahren |
WO2008021533A2 (en) * | 2006-08-18 | 2008-02-21 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Polymerizable sulfonate ionic liquids and liquid polymers therefrom and methods of making same |
JP5004178B2 (ja) * | 2007-09-11 | 2012-08-22 | 独立行政法人日本原子力研究開発機構 | 機械的強度に優れる高プロトン伝導性高分子電解質膜及びその製造方法 |
JP5760326B2 (ja) * | 2010-03-31 | 2015-08-05 | 東ソー株式会社 | 分子量分布の狭いポリスチレンスルホン酸類又はその塩の製造方法 |
JP2013189595A (ja) | 2012-03-15 | 2013-09-26 | Nitto Denko Corp | グラフト鎖を有する高分子電解質膜およびその製造方法 |
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- 2004-05-25 WO PCT/JP2004/007462 patent/WO2004106622A1/en active Application Filing
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EP1627104A4 (en) | 2009-07-01 |
KR20060012647A (ko) | 2006-02-08 |
US20070093568A1 (en) | 2007-04-26 |
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