WO2018047700A1 - イオン交換膜 - Google Patents
イオン交換膜 Download PDFInfo
- Publication number
- WO2018047700A1 WO2018047700A1 PCT/JP2017/031245 JP2017031245W WO2018047700A1 WO 2018047700 A1 WO2018047700 A1 WO 2018047700A1 JP 2017031245 W JP2017031245 W JP 2017031245W WO 2018047700 A1 WO2018047700 A1 WO 2018047700A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ion exchange
- ion
- monomer
- exchange membrane
- polyethylene
- Prior art date
Links
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 76
- 239000000178 monomer Substances 0.000 claims abstract description 107
- -1 polyethylene Polymers 0.000 claims abstract description 92
- 239000000203 mixture Substances 0.000 claims abstract description 87
- 239000004698 Polyethylene Substances 0.000 claims abstract description 84
- 229920000573 polyethylene Polymers 0.000 claims abstract description 84
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 81
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 81
- 229920000098 polyolefin Polymers 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 42
- 238000005342 ion exchange Methods 0.000 claims abstract description 38
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims description 75
- 239000012528 membrane Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 22
- 230000035699 permeability Effects 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 238000005341 cation exchange Methods 0.000 description 27
- 238000002844 melting Methods 0.000 description 19
- 230000008018 melting Effects 0.000 description 19
- 239000002759 woven fabric Substances 0.000 description 19
- 150000002500 ions Chemical class 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 239000010419 fine particle Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 125000000524 functional group Chemical group 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003011 anion exchange membrane Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000002562 thickening agent Substances 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012798 spherical particle Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- JCLFHZLOKITRCE-UHFFFAOYSA-N 4-pentoxyphenol Chemical compound CCCCCOC1=CC=C(O)C=C1 JCLFHZLOKITRCE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-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
- FCMUPMSEVHVOSE-UHFFFAOYSA-N 2,3-bis(ethenyl)pyridine Chemical compound C=CC1=CC=CN=C1C=C FCMUPMSEVHVOSE-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
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
- ZWAPMFBHEQZLGK-UHFFFAOYSA-N 5-(dimethylamino)-2-methylidenepentanamide Chemical compound CN(C)CCCC(=C)C(N)=O ZWAPMFBHEQZLGK-UHFFFAOYSA-N 0.000 description 1
- HXQXSNNOGXXMLU-UHFFFAOYSA-N 6-bromohex-1-enylbenzene Chemical compound BrCCCCC=CC1=CC=CC=C1 HXQXSNNOGXXMLU-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- QZEJHHGVNNHHSU-UHFFFAOYSA-N hexyl benzenecarboperoxoate Chemical compound CCCCCCOOC(=O)C1=CC=CC=C1 QZEJHHGVNNHHSU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- PFBLRDXPNUJYJM-UHFFFAOYSA-N tert-butyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(C)(C)C PFBLRDXPNUJYJM-UHFFFAOYSA-N 0.000 description 1
- JZFHXRUVMKEOFG-UHFFFAOYSA-N tert-butyl dodecaneperoxoate Chemical compound CCCCCCCCCCCC(=O)OOC(C)(C)C JZFHXRUVMKEOFG-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/461—Apparatus therefor comprising only a single cell, only one anion or cation exchange membrane or one pair of anion and cation membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
- B01D71/261—Polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
- B01D71/262—Polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
-
- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/16—Halogens
- C08F212/18—Chlorine
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- 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
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
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- 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
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- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/08—Copolymers of styrene
- C08J2325/12—Copolymers of styrene with unsaturated nitriles
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/16—Homopolymers or copolymers of alkyl-substituted styrenes
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- 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
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- 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
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/06—Polyethene
Definitions
- the present invention relates to an ion exchange membrane, and more specifically, a polymerizable composition for an ion exchange resin precursor used for production of an ion exchange membrane, a method for producing an ion exchange membrane using the composition, and the method
- the present invention relates to an ion exchange membrane obtained by the method.
- the ion exchange membrane has a structure in which an ion exchange resin is held on a specific base material.
- a membrane is formed with an ion exchange resin alone, it is not suitable for practical use because of its low strength and a large change in shape due to swelling that occurs when it is immersed in a liquid. For this reason, a material that has a predetermined strength, does not change its shape due to swelling, and does not impair the ion-exchange ability peculiar to the ion-exchange resin is used as an ion-exchange membrane.
- the ion exchange membrane based on polyolefin has extremely high heat resistance and chemical resistance compared to those based on polyvinyl chloride, but the adhesion between the polyolefin base and ion exchange resin is very high. It is scarce. Along with this, when the swelling and drying (shrinkage) are repeated, the ion exchange resin and the base material are likely to be peeled off. As a result, the function as a diaphragm is deteriorated, the water permeability is increased, and the current efficiency is increased. There is a problem that will decrease. Furthermore, the low adhesion between the polyolefin base material and the ion exchange resin naturally leads to low durability.
- Patent Document 1 an ion exchange membrane as a base material a woven fabric made of multifilaments having a weight average molecular weight of 10 5 or more polyethylene (so-called ultra-high molecular weight polyethylene) has been proposed.
- ultra-high molecular weight polyethylene not only the strength and the like are improved by the multifilament of ultra high molecular weight polyethylene, but the contact area between the ion exchange resin and the base material is increased, so the adhesion between the two is enhanced. That's it.
- ultra high molecular weight polyethylene is a special polymer that is difficult to form normally, so it is very expensive, and its multifilament woven fabric is very difficult to obtain. Therefore, there is a demand for a technique that improves the adhesion even with an easily available and inexpensive monofilament woven fabric.
- Patent Document 2 discloses that an ion exchanger formed by applying a monomer paste for an ion exchange resin precursor containing polyethylene fine particles having a particle size of 10 ⁇ m or less to a polyethylene cloth-like substrate and performing polymerization.
- a method for producing an ion exchange membrane in which an ion exchange group is introduced into a resin precursor has been proposed. According to this method, since the polyethylene fine particles function as a thickener, the monomer paste is imparted with an appropriate viscosity and spinnability, and can be uniformly adhered to the polyethylene cloth-like substrate.
- a sea-island structure composed of polyethylene distributed in a sea shape and ion-exchange resin distributed in an island shape is formed, and polyethylene continuously connected in the sea shape is polyethylene. Since it is heat-sealed with a cloth-like base material, even if the base material is a woven fabric formed from monofilaments, the adhesion with the ion exchange resin is improved. However, this method requires heat treatment at a high temperature in order to melt the polyethylene cloth-like substrate, and there is a problem that the mechanical strength of the resulting ion exchange membrane is lowered.
- Patent Document 3 instead of the polyethylene fine particles used in the method of Patent Document 2, ethylene / ⁇ -unsaturated carboxylic acid-modified polyethylene fine particles (acid-modified polyethylene fine particles) such as acrylic acid-modified polyethylene are used.
- a method for producing an ion exchange membrane by using the same has been proposed. Such a method is an improvement of the method of Patent Document 2, and forms a sea-island structure of acid-modified polyethylene distributed in a sea state and ion-exchange resin distributed in an island shape.
- the acid-modified polyethylene fine particles and the monomer for the ion exchange resin (or precursor) have high affinity, and graft polymerization occurs at the interface between the acid-modified polyethylene fine particles and the ion exchange resin. And high adhesion between the island-like ion exchange resins.
- the adhesion between the sea-like acid-modified polyethylene and the island-like ion exchange resin is ensured by this method, the adhesion between the polyethylene substrate and the ion exchange resin is not improved.
- a sufficient contact area is not ensured between the ion exchange resin and the substrate, so that improvement in adhesion remains as a problem.
- JP-A-6-322156 Japanese Patent Publication No. 6-37568 Japanese Patent No. 3461991
- an object of the present invention is to provide an ion exchange membrane in which excellent adhesion is ensured between a polyolefin-based substrate and an ion exchange resin, a composition used for the production of the ion exchange membrane, and the ion exchange membrane. It is in providing the manufacturing method of.
- a fat represented by acrylonitrile is included in a monomer for producing an ion exchange resin precursor (a resin having a functional group capable of introducing an ion exchange group). It has been found that an ion exchange membrane exhibiting excellent adhesion between a polyolefin base material and an ion exchange resin can be obtained by the presence of a group nitrogen-containing monomer, and the present invention has been completed.
- the present invention comprises a monomer component and 50 to 120 parts by mass of polyethylene particles per 100 parts by mass of the monomer component, the monomer component comprising an aromatic monomer for introducing an ion exchange group, a nitrogen-containing aliphatic monomer, There is provided a polymerizable composition for forming an ion exchange resin precursor, wherein the nitrogen-containing aliphatic monomer is present in the monomer component in an amount of 10 to 35% by mass.
- the nitrogen-containing aliphatic monomer is acrylonitrile
- the polyethylene particles are unmodified polyethylene particles, Is preferred.
- the polymerizable composition is applied to a polyolefin-based filament base material, and then the composition is polymerized to form an ion exchange resin precursor, and then the ion exchange is performed on the precursor.
- a method for producing an ion exchange membrane characterized by introducing a group.
- the polyolefin filament substrate is a polyolefin monofilament substrate
- the polyolefin filament substrate is a polyethylene filament substrate, Is desirable.
- the ion exchange membrane obtained by the said manufacturing method is further provided. That is, such an ion exchange membrane has a structure in which a void portion of a polyolefin filament base material is filled with an ion exchanger and is obtained by the above production method. And having a water permeability of 50 ml / (m 2 ⁇ hour) or less,
- the ion exchanger includes, as a resin component, an aromatic ion-exchange resin and polyethylene.
- the aromatic ion-exchange resin contains a structural unit derived from a nitrogen-containing aliphatic monomer.
- unmodified polyethylene means that it is not acid-modified polyethylene, that is, polyethylene that does not have a structural unit derived from a comonomer having an acidic group such as acrylic acid or maleic anhydride. .
- the voids of the polyolefin-based filament base material are filled with an ion exchanger.
- an ion exchange membrane is conventionally known in that it has a sea-island structure in which an ion-exchange resin is distributed in an island shape in polyethylene that is distributed in a sea shape formed from polyethylene particles.
- an important feature is that a structural unit derived from a nitrogen-containing aliphatic monomer is introduced into the ion exchange resin.
- the ion exchange resin exhibits excellent adhesion to polyethylene and polyolefin-based filament base materials distributed in a sea state, and has a water permeability of 0.1 MPa. It is suppressed to a low range of 50 ml / (m 2 ⁇ hour) or less as measured by The mechanism of the development of such excellent adhesiveness is unknown in detail, but the reason why the adhesiveness increases is that the flexibility of the ion exchange resin is due to the fact that the ion exchange resin has a structural unit derived from a nitrogen-containing aliphatic monomer.
- the low water permeability means that the amount of gaps generated when a certain pressure is applied during the manufacturing process of the exchange membrane and the water permeability measurement is small. Therefore, it is shown that the ion exchange resin is firmly bonded to the polyolefin filament base material or the sea-like polyethylene. For this reason, in the ion exchange membrane of the present invention, the base material and the ion exchanger filled in the voids of the base material are firmly bonded, resulting in excellent durability, low electrical resistance, High current efficiency when used for dialysis.
- the excellent adhesiveness as described above is realized not only when the substrate is formed of not only multifilaments but also monofilaments that are easily available and inexpensive, and this is the maximum of the present invention. Is the advantage.
- the ion exchange membrane of the present invention uses a polymerizable composition for an ion exchange resin precursor having a specific composition, and this polymerizable composition is applied to a polyolefin-based filament base material and polymerized in this state to perform ion exchange. It is produced by forming a resin precursor and finally introducing ion exchange groups into the precursor.
- composition for forming ion-exchange resin precursor The polymerizable composition for forming an ion exchange resin precursor used for forming the ion exchange membrane of the present invention forms an ion exchange resin precursor by polymerization.
- This ion exchange resin precursor is a polymer which does not have an ion exchange group itself but has a functional group into which an ion exchange group can be introduced. Accordingly, an ion exchange resin is formed by reacting such a precursor with a compound having an ion exchange group.
- this polymerizable composition for forming an ion exchange resin precursor (hereinafter sometimes simply referred to as a polymerizable composition) includes a monomer component and a polymerization initiator for forming an ion exchange resin precursor by polymerization. And polyethylene particles for imparting the viscosity and spinnability necessary to uniformly attach the polymerizable composition to the polyolefin filament substrate.
- the monomer component includes an ion exchange group-introducing aromatic monomer for forming a basic skeleton of an ion exchange resin precursor (or ion exchange resin), a crosslinkable monomer, and an ion exchange resin precursor.
- an ion exchange group-introducing aromatic monomer for forming a basic skeleton of an ion exchange resin precursor (or ion exchange resin), a crosslinkable monomer, and an ion exchange resin precursor.
- a nitrogen-containing aliphatic monomer that is introduced into the basic skeleton of the body (or ion exchange resin) and forms a structural unit that greatly contributes to improvement in adhesion is used.
- Aromatic monomers for introducing ion exchange groups are a monofunctional compound having one radical polymerizable group, and further has a functional group for introducing an ion exchange group.
- Monomers having such groups are also used in the production of conventionally known ion exchange membranes, but in the present invention, aromatic monomers, that is, those having an aromatic group in the molecule. Must. This is because an aliphatic monomer having no aromatic group becomes excessively flexible, and an ion exchange resin having a certain strength and shape stability cannot be formed.
- Such an aromatic monomer has a radical polymerizable unsaturated group and an aromatic group, and is used when forming a cation exchange resin (that is, a functional group for introducing a cation exchange group).
- a cation exchange resin that is, a functional group for introducing a cation exchange group.
- Monomer having a group) or one used when forming an anion exchange resin that is, a monomer having a functional group for introducing an anion exchange group.
- conventionally known monomers can be used.
- examples of the monomer having a functional group for introducing a cation exchange group include styrene, vinyl toluene, vinyl xylene, ⁇ -methyl styrene, vinyl naphthalene, ⁇ -halogenated styrenes and the like.
- examples of the monomer having a functional group for introducing an anion exchange group include styrene, bromobutyl styrene, vinyl toluene, chloromethyl styrene, vinyl pyridine, vinyl imidazole, ⁇ -methyl styrene, vinyl naphthalene, and the like.
- the above aromatic monomers can be used alone or in combination of two or more.
- the aromatic monomer is contained in all the monomer components in an amount of at least 25% by mass because the resistance of the obtained ion exchange membrane can be particularly lowered.
- the aromatic monomer is less than 60% by mass in the total monomer components, so that the moisture content of the ion exchanger can be lowered, and the peeling from the polyolefin filament substrate is particularly difficult when the swelling / shrinking is repeated. Since it can suppress, it is preferable.
- the aromatic monomer is particularly preferably contained in an amount of 30 to 55% by mass in all monomer components.
- the aromatic monomer has an ion exchange group, for example, an acid group such as a sulfonic acid group or a carboxylic acid group or a quaternary ammonium base.
- an ion exchange group for example, an acid group such as a sulfonic acid group or a carboxylic acid group or a quaternary ammonium base.
- a method of directly producing an ion exchange resin by polymerization is also employed.
- a monomer for the ion-exchange resin can be introduced by using a monomer having a functional group capable of introducing an ion-exchange group. It is necessary to adopt a method of introducing an ion exchange group.
- the use of polyethylene particles is essential, and when a monomer having an ion exchange group is used, a uniform polymerizable composition cannot be obtained because of poor compatibility with polyethylene particles. .
- the crosslinkable monomer is a monomer that is suitably used for densifying the ion exchange resin and enhancing swelling suppression, membrane strength, and the like.
- the above-mentioned aromatic monomer is a monofunctional compound having one radical polymerizable group, whereas this crosslinkable monomer is a polyfunctional compound having two or more radical polymerizable groups. .
- Such a crosslinkable monomer is not particularly limited, and examples thereof include divinyl compounds such as divinylbenzene, divinylsulfone, butadiene, chloroprene, divinylbiphenyl, divinylnaphthalene, diallylamine, and divinylpyridine; or trivinylbenzenes, etc. These may be used alone or in combination of two or more.
- Such a crosslinkable monomer is generally used in an amount of 1 to 20% by mass, particularly 2 to 10% by mass in the total monomer components.
- a nitrogen-containing aliphatic monomer is used together with the aromatic monomer described above.
- This nitrogen-containing aliphatic monomer has one radical polymerizable group and a nitrogen-containing group.
- a nitrogen-containing aliphatic monomer it is derived from the monomer in the basic skeleton of the ion exchange resin.
- the adhesion to the ion exchanger (mixture of ion exchange resin and polyethylene) penetrating into the voids of the base material is high, and the water permeability is predetermined. It is possible to obtain an ion exchange membrane suppressed to a low range.
- the ion exchange resin can be used in the filament base material and the polyethylene phase even when the swelling and shrinking are repeated. It is presumed that a major factor is that it becomes easier to follow the gap and it is difficult to form a gap between the two.
- the nitrogen-containing aliphatic monomer does not have an aromatic group, and must be a monofunctional radically polymerizable compound having one ethylenically unsaturated bond. Don't be. If it has an aromatic group, it will not be possible to give flexibility, and if it is polyfunctional like a crosslinkable monomer, the resulting ion exchange resin will be dense and low in flexibility. In either case, the adhesion cannot be improved.
- the nitrogen-containing aliphatic monomer used in the present invention includes a polar nitrogen-containing group such as a nitrile group or an amide group bonded to an aliphatic group having one radical polymerizable unsaturated bond.
- a polar nitrogen-containing group such as a nitrile group or an amide group bonded to an aliphatic group having one radical polymerizable unsaturated bond.
- a heterocyclic nitrogen-containing group-containing monomer an amino group-containing monomer such as allylamine; and a single type or a combination of two or more types.
- a nitrile group-containing monomer is preferable, and acrylonitrile is most preferable in that the effect of improving the adhesiveness is maximized and the copolymerizability with an aromatic monomer is high.
- the nitrogen-containing aliphatic monomer is used in a proportion of 10 to 35% by mass, particularly 10 to 25% by mass, based on the total monomer components. If the amount of the nitrogen-containing aliphatic monomer is small, the desired improvement in adhesion cannot be realized, and if this amount is excessively large, physical properties such as resistance and mechanical strength of the resulting ion-exchange membrane are obtained. It is because it will be damaged.
- a polymerization initiator As the polymerization initiator, conventionally known polymerization initiators are used without particular limitation. Specifically, octanoyl peroxide, lauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-butyl peroxyisobutyrate, tert-butyl peroxylaurate, tert- Organic peroxides such as hexyl peroxybenzoate and di-tert-butylperoxycyclohexane are used.
- Such a polymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of all monomer components.
- Polyethylene particles The polymerizable composition used in the present invention is blended with polyethylene particles. That is, the blending of the polyethylene fine particles imparts an appropriate viscosity and spinnability to the polymerizable composition, and can be uniformly attached to the polyolefin filament substrate. Such polyethylene fine particles form a continuous phase distributed in a sea state when the polymerizable composition is polymerized, and a sea-island structure is formed in which the ion-exchange resin is distributed in an island shape in the sea-like continuous phase. .
- the ion exchange group is not introduced into the polyethylene phase even in the ion exchange group introduction step described later, the water content of the ion exchanger (mixture of ion exchange resin and polyethylene) that has penetrated into the voids of the polyolefin filament base material. The rate is kept low. As a result, it is difficult for the ion exchanger to be peeled off from the polyolefin filament substrate even by swelling or drying (shrinking).
- Such polyethylene fine particles are the same as those used in the technique described in Patent Document 2 (Japanese Patent Publication No. 6-37568), and those usually composed of fine particles having a particle size of 20 ⁇ m or less are suitable. . That is, the polymerizable composition used in the present invention is paste-like and needs to have an appropriate viscosity and spinnability. However, when the polyethylene fine particles are too large, the viscosity of the polymerizable composition decreases, and the polyolefin There is a possibility that it is difficult to uniformly adhere to the system filament substrate.
- the size of the aforementioned sea-island structure formed after polymerizing the polymerizable composition may become too large, and the adhesion between the ion exchange resin and polyethylene may be reduced. Furthermore, from the viewpoint of ensuring a viscosity that is uniformly distributed in the polymerizable composition and exhibits good coating properties, those composed of spherical particles are preferable to amorphous particles obtained by mechanical grinding. It is.
- the polyethylene forming the fine particles is not particularly limited, but a polyethylene having a lower melting point than the polyolefin forming the filament base material described later is preferable.
- a low density polyethylene having a melting point of 120 ° C. or lower. For example, the density is 0.910 g / cm 3 or more and less than 0.930 g / cm 3 ).
- the polymerization step of the polymerizable composition described later at least a part of the polyethylene fine particles is thermally melted to form a sea-like continuous phase in contact with the filament base material.
- the polyethylene particles described above are used in an amount of 50 to 120 parts by mass, particularly 55 to 100 parts by mass, per 100 parts by mass of the monomer component described above. If the amount used is large, the ion exchange capacity of the ion exchange membrane is impaired. If the amount used is small, the ion exchanger in the membrane (polymer component including an ion exchange resin and polyethylene) and a polyolefin base material are used. The ion exchange membrane having the desired physical properties cannot be obtained.
- the polymerizable composition for forming an ion exchange resin precursor used in the present invention is generated by thermal decomposition of a plasticizer or a monomer component such as dioctyl phthalate (DOP) or tributyl acetylcitrate in order to adjust the coating property.
- DOP dioctyl phthalate
- Epoxy compounds such as ethylene glycol diglycidyl ether to supplement hydrochloric acid, and various other known additives, the ion exchange characteristics of the membrane finally formed, the functions of the nitrogen-containing aliphatic monomer and polyethylene particles described above, etc. You may mix
- conventionally known thickeners other than the polyethylene particles may be added as necessary for the purpose of adjusting the viscosity for uniformly attaching the polymerizable composition to the polyolefin filament substrate.
- thickeners include polyvinyl chloride, nitrile butadiene rubber, styrene butadiene rubber and hydrogenated products thereof, and these are 0 to 30 parts by mass with respect to 100 parts by mass of all monomer components in the polymerizable composition. It is preferable to add in the range of parts.
- Polyvinyl chloride is most preferred in that a sufficient viscosity can be imparted with a small amount of addition.
- the above-mentioned polymerizable composition for forming an ion exchange resin precursor containing various components is easily prepared by uniformly mixing various components.
- the ion exchange membrane of the present invention is polymerized in such a state that the above-described polymerizable composition for forming an ion exchange resin precursor is applied to a polyolefin-based filament base material, and the polymerizable composition is filled in voids of the filament base material. Thereafter, it is produced by introducing ion exchange groups into an ion exchange resin precursor formed by polymerization.
- the polyolefin-based filament base material used functions as a reinforcing member of the ion exchange membrane, and is intended to ensure a form as a membrane and to give practical membrane strength.
- the filament base material referred to in the present invention refers to a material in which fibrous structural units are gathered and formed into a cloth shape.
- the form of the filament base material is not particularly limited, and may be a woven fabric, a non-woven fabric, a net, or the like. It is preferable in terms of strength and the like. In these woven fabrics, the intersection of single yarns may be heat-sealed.
- such a filament base material may be formed of monofilaments or may be a multifilament obtained by twisting a plurality of monofilaments (single yarns), but in the present invention, it is formed of monofilaments. Some are preferred. That is, since the multifilament is formed by twisting a plurality of monofilaments, the contact area with the polymerizable composition is increased, and as a result, a high anchoring effect is obtained, which is advantageous in obtaining high adhesive strength. However, it is expensive. However, in the present invention, a monofilament base material is preferably used in order to obtain high adhesive strength even when an inexpensive monofilament is used by using the nitrogen-containing aliphatic monomer described above. Is an advantage.
- Such a filament base material is preferably 10 to 300 mesh from the viewpoint of ensuring the strength of the obtained ion exchange membrane while keeping membrane resistance low.
- the filament diameter of the warp and weft forming the woven fabric is in the range of 10 to 250 denier (20 to 200 ⁇ m) in order to suppress the increase in resistance due to the increase in film thickness while maintaining the strength of the ion exchange membrane. Is preferred.
- the thickness of the filament base material is generally 50 to 500 ⁇ m and the opening area is 20 to 60%.
- the polyolefin forming the filament base material is not particularly limited, and for example, polyethylene; polypropylene; poly 1-butene; poly 4-methyl-1-pentene; or ethylene, propylene, 1-butene, 4-methyl- A random or block copolymer of ⁇ -olefins such as 1-pentene;
- polyethylene is optimal in that it has a high affinity for the monomer component in the polymerizable composition and ensures high adhesion between the substrate and the ion exchanger.
- the filament base material used has a melting point higher than the melting point of the polyethylene particles in order to form a sea-like polyethylene continuous phase derived from the above-mentioned polyethylene particles without being thermally deformed during the polymerization described below.
- it has a melting point of 120 ° C. or higher.
- high density polyethylene having a density of 0.930 g / cm 3 or more is preferably used.
- such a polyethylene may have an ultrahigh molecular weight as proposed in Patent Document 1, but such an ultrahigh molecular weight polyethylene is disadvantageous in terms of cost, so that the molecular weight in the normal range. It may be a polyethylene having a weight average molecular weight of less than 1 ⁇ 10 5 (for example).
- Filling the gap of the filament base material with the polymerizable composition is performed, for example, by immersing the filament base material in a tank filled with the above-described polymerizable composition.
- the polymerizable composition can be filled by application or the like.
- the polyolefin filament base material in which the polymerizable composition is filled in the voids is supplied and heated in a polymerization apparatus such as a heating oven, whereby polymerization of the polymerizable composition is performed. Is called.
- this polymerization step a method is generally adopted in which a polyolefin filament substrate filled with a polymerizable composition is sandwiched between films of polyester or the like and the temperature is raised from room temperature under pressure.
- the pressurization is generally performed at a pressure of about 0.1 to 1.0 MPa by pressurization with an inert gas such as nitrogen or a roll.
- an inert gas such as nitrogen or a roll.
- the polymerization conditions depend on the type of polymerization initiator, the type of monomer, etc., but in the present invention, in particular, the melting point of the polyethylene particles is lower than the melting point of the polyolefin filament substrate used. Higher temperature, for example, in the range of about 80 to 120 ° C. Thereby, while preventing the deformation of the polyolefin-based filament base material, simultaneously with the formation of the polymer (ion exchange resin precursor), it is possible to form a polyethylene continuous phase in which the polyethylene particles are melt-flowed and distributed in a sea state. .
- the polymerization time varies depending on the polymerization temperature and the like, but is generally about 3 to 20 hours.
- the ion exchange resin precursor formed by the polymerization operation as described above is surrounded by the polyethylene continuous phase distributed in the sea state in the voids of the filament base material, and is distributed in an island shape. It exists in the state which contacted the surface of the filament base material.
- the polymer obtained above that is, the ion exchange resin precursor has a functional group for introducing an ion exchange group, but does not have an ion exchange group.
- ion exchange groups are introduced after the polymerization step.
- the introduction of the ion exchange group is carried out by a method known per se.
- a treatment such as sulfonation, chlorosulfonation, phosphoniumation, hydrolysis, and the like.
- an exchange membrane it is carried out by a process such as amination or alkylation.
- the ion exchange membrane thus obtained is fixed by filling the voids of the filament base material with an ion exchanger made of island-like ion exchange resin and sea-like polyethylene continuous phase. Has a structured.
- the continuous phase of sea-like polyethylene is firmly adhered to the surface of the filament base material.
- the structural unit derived from the nitrogen-containing aliphatic monomer described above is introduced into the ion exchange resin that is in contact with the surface of the filament base material, the continuous phase of the ion exchange resin and sea-like polyethylene and In order to exhibit high adhesiveness with the filament base material, the ion exchanger is firmly fixed to the filament base material.
- the ion exchange membrane of the present invention has a low water permeability and is in the range of 50 ml / (m 2 ⁇ hour) or less, particularly 25 ml / (m 2 ⁇ hour) or less as measured with 0.1 MPa pressurized water.
- This water permeability is measured by the method described in the examples described later. The smaller this value, the higher the adhesion between the ion exchanger and the filament base material, and the swelling / drying (shrinkage). It shows that there are few gaps generated in the film even when repeated.
- the filament base material is made of polyethylene having a normal molecular weight and is easily made of monofilament, it has a low water permeability as described above. From the viewpoint of the above, it is extremely useful industrially.
- an appropriate ion exchange capacity for example, about 0.1 to 2.5 meq / g-dry mass is set by introducing the above-described ion exchange group. Since high adhesiveness (low water permeability) is realized with the base material, it has excellent durability and current efficiency is usually 60 to 85%, particularly 65 to 80%. Further, generally, the thickness of the ion exchange membrane is 60 to 550 ⁇ m, and the mullen burst strength is 0.2 to 2.0 MPa. Further, even such a high-strength ion exchange membrane has a low membrane resistance of about 5 to 25 ⁇ ⁇ cm 2 in a 0.5 M NaCl aqueous solution. Of course, since the base material is polyolefin, it is excellent in heat resistance, mechanical strength, and chemical resistance.
- Such an ion exchange membrane of the present invention is appropriately cut into an appropriate size and used or sold.
- the invention is illustrated by the following experimental example.
- various characteristics about a filament base material and an ion exchange membrane were measured with the following method.
- a counter ion is substituted from a chloride ion to a nitrate ion with a 1 mol / L-NaNO 3 aqueous solution, and the liberated chloride ion is converted into a potentiometric titrator (COMMITITE-900) using an aqueous silver nitrate solution. Quantified by Hiranuma Sangyo Co., Ltd. (Amol). Next, the same ion exchange membrane was immersed in a 1 mol / L-NaCl aqueous solution for 4 hours or more and sufficiently washed with ion exchange water.
- Ion Exchange Membrane Thickness After immersing the ion exchange membrane in a 0.5 mol / L-NaCl solution for 4 hours or more, wipe the moisture on the membrane surface with tissue paper, and use a micrometer MED-25PJ (Mitutoyo Co., Ltd.) It measured using.
- Viscosity of Polymerizable Composition The viscosity of the polymerizable composition was measured at 25 ° C. using a single cylindrical rotational viscometer Viscotester VT-06 (manufactured by Lion Co., Ltd.).
- the sodium hydroxide concentration of the collected liquid and the initial liquid was quantified with a potentiometric titrator (KEM Auto Titorator) using an aqueous sulfuric acid solution, and the current efficiency was calculated using the following formula.
- KEM Auto Titorator Potentiometric titrator
- an anion exchange membrane a two-chamber cell having the following configuration was used.
- Anode (Pt plate) 1.0 mol / L-sulfuric acid aqueous solution
- Cathode (Pt plate) After energizing for 1 hour at a liquid temperature of 25 ° C.
- Example 1 A mixture having the following formulation was prepared. Styrene (St) 39.7 parts by weight Divinylbenzene (DVB) 5.2 parts by weight Chloromethylstyrene (CMS) 40.6 parts by weight Acrylonitrile (AN) 14.5 parts by weight Tributyl acetylcitrate (ATBC) 13.0 parts by weight Part tert-Butylperoxy-2-ethylhexanoate (PBO) (Perbutyl O manufactured by NOF Corporation) 7.3 parts by mass Unmodified spherical low-density polyethylene particles PE1 (Flow Beads LE- manufactured by Sumitomo Seika Co., Ltd.) 87.0 parts by mass (1080, particle size 6 ⁇ m, melting point 105 ° C.) was added and stirred for 5 hours to obtain a uniform polymerizable composition. The viscosity of this composition was 2.2 (dPa ⁇ sec).
- High density polyethylene monofilament woven fabric (PE120) was prepared.
- Weft 76 mesh-wire diameter 122 ⁇ m (71 denier)
- Thickness 260 ⁇ m Opening area: 38%
- Melting point 130 ° C
- the polymerizable composition obtained above was applied and coated on both sides using a polyester film as a release material, followed by polymerization at 95 ° C. for 5 hours.
- the obtained membranous polymer was sulfonated with chlorosulfonic acid at 40 ° C. for 2 hours to obtain a cation exchange membrane.
- the characteristics of the obtained cation exchange membrane were as follows. Film thickness: 285 ⁇ m Ion exchange capacity: 1.4 meq / g-dry mass Moisture content: 30% Membrane resistance: 12.2 ⁇ ⁇ cm 2 Water permeability: 0 ml / (m 2 ⁇ hour) Current efficiency: 72% Next, the cation exchange membrane was subjected to a repeated test at 80 ° C., and the water permeability and current efficiency were measured. As a result, the water permeability was 0 ml / (m 2 ⁇ hour) and the current efficiency was 68%, which was hardly decreased. .
- Example 2 to Example 6> A polymerizable composition was prepared in the same manner as in Example 1 using the composition shown in Table 1. The viscosity of the resulting polymerizable composition is shown in Table 1.
- 40E and PHC are the following abbreviations.
- PHC 1,1-di-tert-butylperoxycyclohexane (Perhexa C manufactured by NOF Corporation)
- the cation exchange membrane of this invention was obtained like Example 1 except having changed the superposition
- Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test.
- Example 7 The following unmodified spherical low density polyethylene particles (PE2) were prepared. Unmodified spherical low density polyethylene particles (PE2); Sumitomo Seika's Flow Beads LE-2080 Particle size: 11 ⁇ m Melting point: 105 ° C A polymerizable composition having the composition shown in Table 1 was prepared using the above-described unmodified spherical low-density polyethylene particles (PE2). The viscosity of the obtained polymerizable composition was 4.2 (dPa ⁇ sec).
- polypropylene woven fabric (PP) was prepared as a polyolefin monofilament substrate.
- Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test.
- Example 8> The following ethylene-acrylic acid copolymer spherical particles (PE3) were prepared. Spherical particles of ethylene-acrylic acid copolymer (PE3); Sumitomo Seika's Flow Beads EA-209 Particle size: 10 ⁇ m Melting point: 101 ° C 10% acrylic acid unit content A polymerizable composition having the composition shown in Table 1 was prepared using spherical particles (PE3) of the ethylene-acrylic acid copolymer. The polymerizable composition had a viscosity of 20.0 (dPa ⁇ sec). Subsequently, it carried out similarly to Example 1, and obtained the cation exchange membrane of this invention. Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test.
- Example 9 Polyvinyl chloride (PVC) was blended as a thickener to prepare the polymerizable composition shown in Table 1. This polymerizable composition had a viscosity of 1.5 (dPa ⁇ sec). Next, a cation exchange membrane of the present invention was obtained in the same manner as in Example 2. Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test.
- PVC polyvinyl chloride
- Example 10 A mixture having the following formulation was prepared. Chloromethylstyrene (CMS) 54.0 parts by weight Divinylbenzene (DVB) 4.0 parts by weight Styrene (St) 30.0 parts by weight Acrylonitrile (AN) 12.0 parts by weight Ethylene glycol diglycidyl ether (40E) (Epolite 40E manufactured by Kyoeisha Chemical Co., Ltd.) 2.0 parts by mass 1,1-di-tert-butylperoxycyclohexane (PBO) (Perhexa C manufactured by NOF Corporation) 7.3 parts by mass
- unmodified spherical low density 87.0 parts by mass of polyethylene particles (PE1) was added and stirred for 5 hours to obtain a uniform polymerizable composition. The viscosity of this composition was 2.0 (dPa ⁇ sec).
- High density polyethylene monofilament woven fabric PE200
- NBC industrial nip strong net warp 156 mesh-wire diameter 86 ⁇ m (50 denier)
- Weft 100 mesh-wire diameter 86 ⁇ m (50 denier)
- Thickness 185 ⁇ m Opening area: 32%
- Melting point 130 ° C
- the composition obtained above was applied onto the high density polyethylene monofilament woven fabric (PE200) and coated on both sides using a polyester film as a release material, and then polymerized at 100 ° C. for 5 hours.
- the obtained film-like polymer was immersed in a mixture of 15 parts by weight of a 30% trimethylamine aqueous solution, 52.5 parts by weight of water, and 22.5 parts by weight of acetone at 30 ° C. for 16 hours, and was subjected to quaternary ammonium type shade.
- An ion exchange membrane was obtained.
- Table 2 shows the membrane characteristics of the obtained anion exchange membrane and the results of the 80 ° C. repeat test.
- Example 11 The polymerizable composition of Example 1 was applied on a high-density polyethylene monofilament woven fabric (PE200), coated on both sides with a polyester film as a release material, and then polymerized at 95 ° C. for 5 hours. The obtained membranous polymer was sulfonated with chlorosulfonic acid at 40 ° C. for 2 hours to obtain a cation exchange membrane. Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test.
- PE200 high-density polyethylene monofilament woven fabric
- Example 12 Using the polymerizable composition of Example 1, a cation exchange membrane of the present invention was obtained in the same manner as Example 7. Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test.
- Example 1 A polymerizable composition shown in Table 1 was prepared without adding a nitrogen-containing aliphatic monomer, and a cation exchange membrane was obtained in the same manner as in Example 1.
- Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test. Compared with Example 1, the water permeability and current efficiency were deteriorated, and the deterioration became remarkable after the 80 ° C. repeated test.
- Example 9 a polymerizable composition was prepared without adding a nitrogen-containing aliphatic monomer, and a cation exchange membrane was obtained in the same manner as in Example 9.
- Table 2 shows the membrane characteristics of the obtained cation exchange membrane and the results of the 80 ° C. repeat test.
- Example 7 a polymerizable composition was prepared without adding a nitrogen-containing aliphatic monomer, and an anion exchange membrane was obtained in the same manner as in Example 10.
- Table 2 shows the membrane characteristics of the obtained anion exchange membrane and the results of the 80 ° C. repeat test.
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Abstract
Description
しかしながら、超高分子量ポリエチレンは、通常の成形が困難な特殊なポリマーであるため、極めて高価であり、しかもそのマルチフィラメント織布は極めて入手が困難である。
従って、入手が容易で安価なモノフィラメント織布でも接着性が向上するような手法が求められている。
しかしながら、この方法ではポリエチレン製の布状基材を溶融させるために高温での熱処理が必要となり、得られるイオン交換膜の機械的強度が低下する課題がある。さらには、一旦高い接着性が得られても、例えばイオン交換樹脂が膨潤・収縮を繰り返すと、基材とイオン交換樹脂との間に隙間が形成されて透水度が増大し、結果として電流効率が低く、さらなる接着性の向上が求められている。
かかる方法は、特許文献2の方法を改善したものであり、海状に分布した酸変性ポリエチレンと島状に分布したイオン交換樹脂との海島構造を形成するというものである。この方法では、酸変性ポリエチレン微粒子とイオン交換樹脂(或いは前駆体)用モノマーとの親和性が高く、酸変性ポリエチレン微粒子とイオン交換樹脂との界面でグラフト重合が生じるため、海状の酸変性ポリエチレンと島状のイオン交換樹脂との間に高い接着性が確保されるというものである。
しかしながら、この方法では海状の酸変性ポリエチレンと島状のイオン交換樹脂との間の接着性は確保されても、ポリエチレン製基材とイオン交換樹脂との間の接着性は改善されていない。特に、基材が安価なモノフィラメントからなる織布の場合には、イオン交換樹脂と基材との間に十分な接触面積が確保されていないため、依然として接着性向上が課題として残されている。
(1)前記含窒素脂肪族モノマーが、アクリロニトリルであること、
(2)前記ポリエチレン粒子が、未変性ポリエチレン粒子であること、
が好適である。
かかる製造方法においては、
(1)前記ポリオレフィン系フィラメント基材が、ポリオレフィン系モノフィラメント基材であること、
(2)前記ポリオレフィン系フィラメント基材が、ポリエチレン系フィラメント基材であること、
が望ましい。
即ち、かかるイオン交換膜は、ポリオレフィン系フィラメント基材の空隙部分にイオン交換体が充填されている構造を有しており、上記製造方法により得られていることから、0.1MPaの加圧水で測定して50ml/(m2・hour)以下の透水度を有しており、さらに、
前記イオン交換体は、樹脂成分として、含芳香族系イオン交換樹脂とポリエチレンとを含み、
前記含芳香族系イオン交換樹脂は、含窒素脂肪族モノマーに由来する構成単位を含んでいる。
即ち、このような構成単位の導入により、このイオン交換樹脂は、海状に分布しているポリエチレン及びポリオレフィン系フィラメント基材に対して優れた接着性を示し、その透水度が0.1MPaの加圧水で測定して50ml/(m2・hour)以下と低い範囲に抑制されているのである。
かかる優れた接着性の発現機構は詳細には不明であるが、接着性が増す理由としては、イオン交換樹脂が含窒素脂肪族モノマーに由来する構成単位を有すことでイオン交換樹脂の柔軟性が増し、その結果イオン交換膜の製造プロセスで不可避なイオン交換樹脂の膨潤、収縮によっても、ポリオレフィンフィラメント基材等からの剥離が抑制されるからであると考えられる。さらには、イオン交換樹脂と基材を構成するポリオレフィンとの主鎖構造が類似することによって、ポリオレフィンフィラメント基材等に対する親和性そのものが増すからであると推定される。
本発明のイオン交換膜の形成に用いるイオン交換樹脂前駆体形成用重合性組成物は、重合することによって、イオン交換樹脂前駆体を形成するものである。このイオン交換樹脂前駆体は、それ自体、イオン交換基は有していないが、イオン交換基導入可能な官能基を有している重合体である。従って、かかる前駆体にイオン交換基を有する化合物を反応させることによってイオン交換樹脂が形成されることとなる。
本発明において、上記のモノマー成分としては、イオン交換樹脂前駆体(或いはイオン交換樹脂)の基本骨格を形成するためのイオン交換基導入用芳香族系モノマーと、架橋性モノマーと、イオン交換樹脂前駆体(或いはイオン交換樹脂)の基本骨格中に導入され、接着性向上に大きく寄与する構成単位を形成する含窒素脂肪族モノマーとが使用される。
イオン交換基導入用芳香族系モノマーは、1つのラジカル重合性基を有する単官能性の化合物であり、さらに、イオン交換基導入用の官能基を有している。このような基を有するモノマーは、従来公知のイオン交換膜の製造にも使用されているが、本発明においては、芳香族系のもの、すなわち、分子中に芳香族基を有しているものでなければならない。芳香族基を有していない脂肪族系のモノマーでは、過度に柔軟となってしまい、一定の強度や形態安定性を有するイオン交換樹脂を形成することができないからである。
また、陰イオン交換基導入用官能基を有するモノマーとしては、スチレン、ブロモブチルスチレン、ビニルトルエン、クロロメチルスチレン、ビニルピリジン、ビニルイミダゾール、α-メチルスチレン、ビニルナフタレン等が挙げられる。
また、架橋性モノマーは、イオン交換樹脂を緻密化し、膨潤抑止性や膜強度等を高めるために、好適に使用されるモノマーである。前述した芳香族系モノマーが1つのラジカル重合性基を有する単官能性の化合物であるのに対して、この架橋性モノマーは、2個以上のラジカル重合性基を有する多官能性の化合物である。このような架橋性モノマーは、特に制限されるものでは無いが、例えば、ジビニルベンゼン、ジビニルスルホン、ブタジエン、クロロプレン、ジビニルビフェニル、ジビニルナフタレン、ジアリルアミン、ジビニルピリジン等のジビニル化合物;あるいはトリビニルベンゼン類等のトリビニル化合物;を挙げることができ、単独または2種以上を組み合わせて使用される。
本発明においては、上述した芳香族系モノマーと共に、含窒素脂肪族モノマーが使用される。この含窒素脂肪族モノマーは、1つのラジカル重合性基と含窒素基とを有するものであり、このような含窒素脂肪族モノマーを用いて、イオン交換樹脂の基本骨格中に、該モノマーに由来する構成単位を導入することにより、後述するポリエチレン粒子の使用と相俟って、イオン交換樹脂のポリオレフィン系フィラメント基材に対する接着性が大きく向上する。しかも、ポリエチレン粒子に対する接着性も向上し、結果として、該基材の空隙に浸透しているイオン交換体(イオン交換樹脂とポリエチレンとの混合体)との接着性が高く、透水度が所定の範囲に低く抑制されたイオン交換膜を得ることが可能となるものである。
即ち、含窒素脂肪族モノマーにより導入される構成単位が存在すると、含窒素基の極性によって、さらには、イオン交換樹脂と基材を構成するポリオレフィンとの主鎖構造が類似することによって、ポリオレフィン系フィラメント基材とポリエチレン粒子に由来するポリエチレン相との界面での密着性が向上する。また、前記脂肪族モノマー由来の構成単位の存在によりイオン交換樹脂に適度な柔軟性がもたらされ、この結果、膨潤・収縮が繰り返されたときにもイオン交換樹脂が該フィラメント基材やポリエチレン相に追随し易くなり、両者の間に隙間が形成されにくくなることが大きな要因であると推定している。
本発明においては、上記のような各種モノマーと共に、必要に応じて、得られるイオン交換樹脂の強度等の物性調整を目的として、これらモノマーと共重合可能なコモノマーを、前述した各種モノマーの量割合が損なわれない範囲の適宜の量で使用することができる。このようなコモノマーは、当然、前述した含窒素脂肪族モノマーの機能を損なうものであってはならず、例えば、スチレン、メチルスチレン、クロロメチルスチレン、α-メチルスチレン、アクロレイン、メチルビニルケトン、ビニルビフェニル等である。
重合開始剤としては、従来公知のものが特に制限されること無く使用される。具体的には、オクタノイルパーオキシド、ラウロイルパーオキシド、tert-ブチルパーオキシ-2-エチルヘキサノエート、ベンゾイルパ-オキシド、tert-ブチルパーオキシイソブチレート、tert-ブチルパーオキシラウレート、tert-ヘキシルパーオキシベンゾエート、ジ-tert-ブチルパーオキシシクロヘキサン等の有機過酸化物が用いられる。
このような重合開始剤は、全モノマー成分100重量部に対して、0.1~20重量部が好ましく、更に好ましくは0.5~10重量部である。
本発明で用いる重合性組成物には、ポリエチレン粒子が配合される。即ち、このポリエチレン微粒子の配合によって重合性組成物に適度な粘度や曳糸性が付与され、ポリオレフィン系フィラメント基材へ均一に付着させることが可能になる。かかるポリエチレン微粒子は、重合性組成物を重合したときに、海状に分布した連続相を形成するものであり、該海状連続相にイオン交換樹脂が島状に分布した海島構造が形成される。かつ、該ポリエチレン相には、後述するイオン交換基導入工程によってもイオン交換基が導入されないため、ポリオレフィン系フィラメント基材の空隙に浸透したイオン交換体(イオン交換樹脂とポリエチレンの混合体)の含水率が低く抑えられる。その結果、膨潤や乾燥(収縮)によっても該イオン交換体がポリオレフィン系フィラメント基材から剥離しがたくなるというものである。
さらに、重合性組成物中に均一に分布し、良好な塗布性を示す粘度を確保するという観点から、機械的粉砕により得られた不定形の粒子よりも、球形状の粒子からなるものが好適である。
本発明で用いるイオン交換樹脂前駆体形成用重合性組成物には、その塗布性を調整するためにジオクチルフタレート(DOP)やアセチルクエン酸トリブチルなどの可塑剤や、モノマー成分の熱分解により発生する塩酸を補足するためのエチレングリコールジグリシジルエーテルなどのエポキシ化合物、その他公知の各種添加剤が、最終的に形成される膜のイオン交換特性、前述した含窒素脂肪族モノマーやポリエチレン粒子の機能等を損なわない範囲の量で配合されていてもよい。
特に、前記重合性組成物をポリオレフィン系フィラメント基材により均一に付着させるための粘度調整の目的で、必要に応じて前記ポリエチレン粒子以外の従来公知の増粘剤を添加しても良い。かかる増粘剤としては、ポリ塩化ビニル、ニトリルブタジエンゴム、スチレンブタジエンゴム及びその水添物を挙げることができ、これらは重合性組成物中の全モノマー成分100質量部に対して0~30質量部の範囲で添加されるのが好適である。これらの増粘剤の添加によって、ポリエチレン微粒子を極端に増やすことなく重合性組成物に適度な粘度を付与できる。少量の添加で十分な粘度を付与できる点でポリ塩化ビニルが最も好ましい。
本発明のイオン交換膜は、上述したイオン交換樹脂前駆体形成用重合性組成物を、ポリオレフィン系フィラメント基材に塗布し、該重合性組成物を該フィラメント基材の空隙に充填した状態で重合させ、この後、重合により形成されたイオン交換樹脂前駆体にイオン交換基を導入することにより製造される。
かかるフィラメント基材は、得られるイオン交換膜の強度を十分なものとし、一方で、膜抵抗を低く抑える観点から、10~300メッシュであることが好ましい。また、織布を形成する縦糸や横糸のフィラメント径は、イオン交換膜の強度を維持しつつ、膜厚増大による抵抗増を抑制するため、10~250デニール(20~200μm)の範囲にあることが好ましい。同様に、イオン交換膜の強度と膜抵抗をバランスさせるために、一般に、該フィラメント基材の膜厚は50~500μmであり、オープニングエリアは20~60%である。
このような観点から、フィラメント基材を形成するポリオレフィンとしては、密度が0.930g/cm3以上の高密度ポリエチレンが好適に使用される。
さらに、かかるポリエチレンは、特許文献1で提案されているような超高分子量のものであってもよいが、このような超高分子量ポリエチレンは、コスト的に不利となるので、通常の範囲の分子量(例えば重量平均分子量が1×105未満)を有するポリエチレンであってよい。
また、重合条件は、重合開始剤の種類、単量体の種類等によって左右されるものであるが、本発明では、特に、用いるポリオレフィン系フィラメント基材の融点よりも低温で且つポリエチレン粒子の融点よりも高温、例えば80~120℃程度の範囲である。これにより、ポリオレフィン系フィラメント基材の変形を防止しながら、重合体(イオン交換樹脂前駆体)の形成と同時に、ポリエチレン粒子を溶融流動させて海状に分布したポリエチレン連続相を形成することができる。
尚、重合時間は、重合温度等によっても異なるが、一般には、3~20時間程度である。
このようにして得られるイオン交換膜は、フィラメント基材の空隙に、島状に分布しているイオン交換樹脂と海状に分布しているポリエチレン連続相とからなるイオン交換体が充填されて固定された構造を有している。
尚、フィラメント基材やイオン交換膜についての各種特性は、次の方法により測定した。
セイコー電子工業(株)製DSC-220Cを使用し測定した。基材は直径5mmの円形に打ち抜き、数枚重ね合わせて3mgとし、ポリエチレン粒子はそのまま3mg量り取り測定サンプルとして用いた。これを直径5mmのアルミ製オープンサンプルパンに敷き詰め、クランピングカバーを乗せサンプルシーラーでアルミパン内に固定した。窒素雰囲気下、昇温速度10℃/minで30℃から180℃までを測定し、融解吸熱曲線の極大となる温度を基材の融点とした。融解曲線のピークが複数存在する場合はピーク面積が最も大きいピークの温度を基材の融点とした。
基材を構成する糸の線径(μm)とメッシュ数から、下記式に従って計算した。
オープニングエリア(%)
=(オープニング)2/(オープニング+線径)2 (1)
式(1)中、
オープニング(μm)=25400/メッシュ数-線径(μm)
メッシュ数=1インチ当たりの糸の本数
円筒状のセルにイオン交換膜を挟み、上部に50mlの水を入れ、更にその上から0.1MPaで圧力をかけた際に、イオン交換膜を1時間に透過してくる水量Wpwを測定し、下記式に従って透水度を算出した。この際、膜の有効面積は12.6cm2である。
透水度(ml/(m2×hour))
=Wpw/(S×t) (2)
式(2)中、
S:膜の有効面積(m2)
t:試験時間(hour)
イオン交換膜を1mol/L-HCl水溶液に10時間以上浸漬する。
その後、陽イオン交換膜の場合には、1mol/L-NaCl水溶液でイオン交換基の対イオンを水素イオンからナトリウムイオンに置換させ、遊離した水素イオンを水酸化ナトリウム水溶液を用いて電位差滴定装置(COMTITE-900、平沼産業株式会社製)で定量した(Amol)。
一方、陰イオン交換膜の場合には、1mol/L-NaNO3水溶液で対イオンを塩化物イオンから硝酸イオンに置換させ、遊離した塩化物イオンを硝酸銀水溶液を用いて電位差滴定装置(COMTITE-900、平沼産業株式会社製)で定量した(Amol)。
次に、同じイオン交換膜を1mol/L-NaCl水溶液に4時間以上浸漬し、イオン交換水で十分水洗した。その後ティッシュペーパーで表面の水分を拭き取り、湿潤時の膜の質量(Wg)を測定した。さらに、60℃で5時間減圧乾燥して乾燥時の重さ(Dg)を測定した。上記測定値に基づいて、イオン交換膜のイオン交換容量および含水率を次式により求めた。
イオン交換容量[meq/g-乾燥質量]=A×1000/D
含水率[%]=100×(W-D)/D
イオン交換膜を0.5mol/L-NaCl溶液に4時間以上浸漬した後、ティッシュペーパーで膜の表面の水分を拭き取り、マイクロメ-タ MED-25PJ(株式会社ミツトヨ社製)を用いて測定した。
白金黒電極を有する2室セル中にイオン交換膜を挟み、イオン交換膜の両側に0.5mol/L-NaCl水溶液を満たし、交流ブリッジ(周波数1000サイクル/秒)により25℃における電極間の抵抗を測定し、該電極間抵抗とイオン交換膜を設置しない場合の電極間抵抗との差により膜抵抗(Ω・cm2)を求めた。なお、上記測定に使用するイオン交換膜は、予め0.5mol/L-NaCl水溶液中で平衡にしたものを用いた。
単一円筒形回転粘度計ビスコテスタ VT-06(リオン株式会社製)を用いて、重合性組成物の粘度を25℃で測定した。
陽イオン交換膜の場合は、以下の構成を有する2室セルを使用した。
陽極(Pt板)(0.5mol/L-NaOH水溶液)/陽イオン交換膜/(3.0mol/L-NaOH水溶液)陰極(Pt板)
液温25℃で電流密度10A/dm2で1時間通電した後、陽極側の溶液を回収した。回収した液と初期液の水酸化ナトリウム濃度を、硫酸水溶液を用いて電位差滴定装置 (KEM製Auto Titrator)により定量し、下記式を用いて電流効率を算出した。
陰イオン交換膜の場合は、以下の構成を有する2室セルを使用した。
陽極(Pt板)(1.0mol/L-硫酸水溶液)/陰イオン交換膜/(0.25mol/L-硫酸水溶液)陰極(Pt板)
液温25℃で電流密度10A/dm2で1時間通電した後、陰極側の溶液を回収した。回収した液と初期液の硫酸濃度を、水酸化ナトリウム水溶液を用いて電位滴定装置 (KEM製Auto Titrator)により定量し、下記式を用いて電流効率を算出した。
電流効率(%)=(CB-CS)/(I×t/F)×100
上記式中、
CB:初期液の濃度
CS:通電後に回収した液濃度
I:電流値(A)
t:通電時間(sec)
F:はファラデー定数(96500C/mol)
イオン交換膜を80℃の純水に1時間浸漬後、25℃の純水に1時間以上浸漬する処理を10回繰り返した後、透水性及び電流効率を測定した。
下記処方の混合物を調製した。
スチレン(St) 39.7質量部
ジビニルベンゼン(DVB) 5.2質量部
クロロメチルスチレン(CMS) 40.6質量部
アクリロニトリル(AN) 14.5質量部
アセチルクエン酸トリブチル(ATBC) 13.0質量部
tert-ブチルパーオキシ-2-エチルヘキサノエート
(PBO)(日本油脂製パーブチルO) 7.3質量部
この混合物に、未変性球状の低密度ポリエチレン粒子PE1(住友精化製フロービーズLE-1080、粒径6μm、融点105℃)87.0質量部を加え、5時間攪拌して均一な重合性組成物を得た。本組成物の粘度は2.2(dPa・sec)であった。
高密度ポリエチレンモノフィラメント織布(PE120);
NBC工業製ニップ強力網
縦糸:96メッシュ-線径106μm(62デニール)
横糸:76メッシュ-線径122μm(71デニール)
厚さ:260μm
オープニングエリア:38%
融点:130℃
上記の高密度ポリエチレンモノフィラメント織布(PE120)の上に、上記で得られた重合性組成物を塗布し、ポリエステルフィルムを剥離材として両面被覆した後、95℃で5時間重合を行った。
膜厚:285μm
イオン交換容量:1.4meq/g-乾燥質量
含水率:30%
膜抵抗:12.2Ω・cm2
透水度:0ml/(m2・hour)
電流効率:72%
次いで、この陽イオン交換膜を80℃の繰返し試験に供し、透水度と電流効率を測定したところ、透水度0ml/(m2・hour)、電流効率68%であり、ほとんど低下していなかった。
表1に示す組成を用いて実施例1と同様にして重合性組成物を調製した。得られた重合性組成物の粘度を表1に示す。
尚、表1中、40E及びPHCは、以下の略語である。
40E:エチレングリコールジグリシジルエーテル
(共栄社化学製エポライト40E)
PHC:1,1-ジ-tert-ブチルパーオキシシクロヘキサン
(日本油脂製パーヘキサC)
次いで、重合温度を100℃に変えた以外は実施例1と同様にして、本発明の陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
下記の未変性球状の低密度ポリエチレン粒子(PE2)を用意した。
未変性球状の低密度ポリエチレン粒子(PE2);
住友精化製フロービーズLE-2080
粒径:11μm
融点:105℃
上記の未変性球状の低密度ポリエチレン粒子(PE2)を用いて表1に示す組成の重合性組成物を調製した。
得られた重合性組成物の粘度は4.2(dPa・sec)であった。
ポリプロピレン織布(PP);
メッシュ数:100
線径:68μm(30デニール)
厚さ:128μm
オープニングエリア:53%
融点:168℃
上記のポリプロピレン織布(PP)を用いた以外は実施例1と同様にして、本発明の陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
下記のエチレン-アクリル酸共重合体の球状粒子(PE3)を用意した。
エチレン-アクリル酸共重合体の球状粒子(PE3);
住友精化製フロービーズEA-209
粒径:10μm
融点:101℃
アクリル酸単位の含有量10%
上記のエチレン-アクリル酸共重合体の球状粒子(PE3)を用いて表1に示す組成の重合性組成物を調製した。この重合性組成物の粘度は20.0(dPa・sec)であった。
次いで、実施例1と同様にして、本発明の陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
ポリ塩化ビニル(PVC)を増粘剤として配合し、表1の重合性組成物を調製した。この重合性組成物の粘度は1.5(dPa・sec)であった。
次いで、実施例2と同様にして、本発明の陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
下記処方の混合物を調製した。
クロロメチルスチレン(CMS) 54.0質量部
ジビニルベンゼン(DVB) 4.0質量部
スチレン(St) 30.0質量部
アクリロニトリル(AN) 12.0質量部
エチレングリコールジグリシジルエーテル(40E)
(共栄社化学製エポライト40E) 2.0質量部
1,1-ジ-tert-ブチルパーオキシシクロヘキサン
(PBO)(日本油脂製パーヘキサC) 7.3質量部
上記の混合物に、未変性球状の低密度ポリエチレン粒子(PE1)87.0質量部を加え、5時間攪拌して均一な重合性組成物を得た。この組成物の粘度は2.0(dPa・sec)であった。
高密度ポリエチレンモノフィラメント織布(PE200);
NBC工業製ニップ強力網
縦糸:156メッシュ-線径86μm(50デニール)
横糸:100メッシュ-線径86μm(50デニール)
厚さ:185μm
オープニングエリア:32%
融点:130℃
上記で得られた組成物を、上記の高密度ポリエチレンモノフィラメント織布(PE200)の上に塗布し、ポリエステルフィルムを剥離材として両面被覆した後、100℃で5時間重合を行った。得られた膜状高分子体を、30%トリメチルアミン水溶液15質量部、水52.5質量部、アセトン22.5質量部の混合物中に30℃で16時間浸漬して、4級アンモニウム型の陰イオン交換膜を得た。
得られた陰イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
実施例1の重合性組成物を、高密度ポリエチレンモノフィラメント織布(PE200)の上に塗布し、ポリエステルフィルムを剥離材として両面被覆した後、95℃で5時間重合を行った。得られた膜状高分子体を40℃で2時間クロロスルホン酸によりスルホン化して陽イオン交換膜を得た。
得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
実施例1の重合性組成物を用い、実施例7と同様にして本発明の陽イオン交換膜を得た。
得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
含窒素脂肪族モノマーを添加することなく、表1に示す重合性組成物を調整し、実施例1と同様にして陽イオン交換膜を得た。
得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。実施例1に比べて、透水度と電流効率が悪化しており、80℃繰返し試験後には悪化が顕著となった。
含窒素脂肪族モノマーやポリエチレン粒子の配合量を実施例1から大きく増減させて、表1に示す組成の重合性組成物を調製した。得られた重合性組成物の粘度を表1に示す。
得られた重合性組成物を用いて、実施例2と同様にして陽イオン交換膜を作製したが、比較例5では重合性組成物の粘度が高く均一な膜状物を得ることができなかった。
比較例2~5で得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
実施例9において、含窒素脂肪族モノマーを添加することなく重合性組成物を調整し、実施例9と同様にして陽イオン交換膜を得た。得られた陽イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
実施例10において、含窒素脂肪族モノマーを添加することなく重合性組成物を調整し、実施例10と同様にして陰イオン交換膜を得た。得られた陰イオン交換膜の膜特性と、80℃繰返し試験の結果を表2に示す。
Claims (7)
- モノマー成分と、該モノマー成分100質量部あたり50~120質量部のポリエチレン粒子とを含み、前記モノマー成分は、イオン交換基導入用芳香族系モノマーと含窒素脂肪族モノマーとを含んでおり、該含窒素脂肪族モノマーが、前記モノマー成分中に10~35質量%の量で存在していることを特徴とする、イオン交換樹脂前駆体形成用重合性組成物。
- 前記含窒素脂肪族モノマーが、アクリロニトリルである、請求項1記載の重合性組成物。
- 前記ポリエチレン粒子が、未変性ポリエチレン粒子である、請求項2記載の重合性組成物。
- 請求項1に記載の重合性組成物を、ポリオレフィン系フィラメント基材に塗布し、次いで、該重合性組成物を重合して、イオン交換樹脂前駆体を形成した後、該前駆体にイオン交換基を導入することを特徴とする、イオン交換膜の製造方法。
- 前記ポリオレフィン系フィラメント基材が、ポリオレフィン系モノフィラメント基材である、請求項4記載のイオン交換膜の製造方法。
- 前記ポリオレフィン系フィラメント基材が、ポリエチレン系フィラメント基材である、請求項4に記載のイオン交換膜の製造方法。
- ポリオレフィン系フィラメント基材の空隙部分にイオン交換体が充填されているイオン交換膜において、
該イオン交換膜は、0.1MPaの加圧水で測定して50ml/(m2・hour)以下の透水度を有していると共に、
前記イオン交換体は、樹脂成分として、含芳香族系イオン交換樹脂とポリエチレンとを含み、
前記含芳香族系イオン交換樹脂は、含窒素脂肪族モノマーに由来する構成単位を含んでいる、ことを特徴とするイオン交換膜。
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CN201780051067.XA CN109641978B (zh) | 2016-09-06 | 2017-08-30 | 离子交换膜 |
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WO2023038133A1 (ja) * | 2021-09-13 | 2023-03-16 | Agcエンジニアリング株式会社 | イオン交換膜及び触媒層付きイオン交換膜の製造方法 |
JP7448716B1 (ja) | 2023-07-12 | 2024-03-12 | 株式会社合同資源 | ヨウ化水素酸製造用電気透析膜、バイポーラ膜電気透析装置、およびヨウ化水素酸の製造方法 |
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WO2020226441A1 (ko) | 2019-05-07 | 2020-11-12 | 주식회사 엘지화학 | 배터리 컨트롤러, 무선 배터리 제어 시스템, 배터리 팩 및 배터리 밸런싱 방법 |
CN110860211B (zh) * | 2019-11-29 | 2021-10-19 | 绿邦膜分离技术(江苏)有限公司 | 一种均相pvc基阴离子交换膜制备方法 |
EP4119601A4 (en) * | 2020-03-27 | 2023-08-30 | Astom Corporation | ANION EXCHANGE MEMBRANE AND METHOD FOR THE PRODUCTION |
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