WO2009107902A1 - Brush polyether-based polymers, preparation methods thereof and chemical sensors comprising the polymers - Google Patents
Brush polyether-based polymers, preparation methods thereof and chemical sensors comprising the polymers Download PDFInfo
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- WO2009107902A1 WO2009107902A1 PCT/KR2008/003378 KR2008003378W WO2009107902A1 WO 2009107902 A1 WO2009107902 A1 WO 2009107902A1 KR 2008003378 W KR2008003378 W KR 2008003378W WO 2009107902 A1 WO2009107902 A1 WO 2009107902A1
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- alkyl group
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- 229920000642 polymer Polymers 0.000 title claims abstract description 55
- 239000000126 substance Substances 0.000 title claims abstract description 23
- 229920000570 polyether Polymers 0.000 title claims description 20
- 239000004721 Polyphenylene oxide Substances 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 44
- 150000002500 ions Chemical class 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000012528 membrane Substances 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 229910052740 iodine Inorganic materials 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 9
- -1 cyclic ether compound Chemical class 0.000 claims description 8
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229960004132 diethyl ether Drugs 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- WLTZCRCZDLLXQP-UHFFFAOYSA-N 4-(2,2,2-trifluoroacetyl)benzoic acid Chemical compound OC(=O)C1=CC=C(C(=O)C(F)(F)F)C=C1 WLTZCRCZDLLXQP-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 21
- 239000004014 plasticizer Substances 0.000 abstract description 9
- 238000001727 in vivo Methods 0.000 abstract description 5
- 230000003287 optical effect Effects 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000002555 ionophore Substances 0.000 description 11
- 230000000236 ionophoric effect Effects 0.000 description 11
- 230000009257 reactivity Effects 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000011088 calibration curve Methods 0.000 description 6
- 150000001768 cations Chemical group 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229940093499 ethyl acetate Drugs 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 239000002491 polymer binding agent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920002755 poly(epichlorohydrin) Polymers 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XFGANBYCJWQYBI-UHFFFAOYSA-N 11-bromoundecan-1-ol Chemical compound OCCCCCCCCCCCBr XFGANBYCJWQYBI-UHFFFAOYSA-N 0.000 description 1
- ZCVUGIYVLJLWCS-UHFFFAOYSA-N 11-hydroxyundecyl thiophene-2-carboxylate Chemical compound OCCCCCCCCCCCOC(=O)C=1SC=CC1 ZCVUGIYVLJLWCS-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- 0 C*(C)O*C(*)(*C1=CC=CIC1)C(C)(C)C(C)(C)O*CIC Chemical compound C*(C)O*C(*)(*C1=CC=CIC1)C(C)(C)C(C)(C)O*CIC 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 101000653548 Homo sapiens Trichoplein keratin filament-binding protein Proteins 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 102100030645 Trichoplein keratin filament-binding protein Human genes 0.000 description 1
- BZKPWHYZMXOIDC-UHFFFAOYSA-N acetazolamide Chemical compound CC(=O)NC1=NN=C(S(N)(=O)=O)S1 BZKPWHYZMXOIDC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000009534 blood test Methods 0.000 description 1
- WBLIXGSTEMXDSM-UHFFFAOYSA-N chloromethane Chemical compound Cl[CH2] WBLIXGSTEMXDSM-UHFFFAOYSA-N 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000002634 lipophilic molecules Chemical class 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- YCCHNFGPIFYNTF-UHFFFAOYSA-N tertiary cymene hydroperoxide Natural products CC1=CC=C(C(C)(C)OO)C=C1 YCCHNFGPIFYNTF-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/24—Epihalohydrins
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/3311—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group
- C08G65/3312—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing a hydroxy group acyclic
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
- C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/3332—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group
- C08G65/33324—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group acyclic
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
Definitions
- the present invention relates to a functional brush polymer compound, and, more particularly, to a brash polymer compound for a chemical sensor, a method of preparing the same, and a chemical sensor including the same.
- the ion selective electrode membrane is composed of about 33% of a polymer binder, about 66% of a plasticizer, and small amounts of an ionophore and a lipophilic additive.
- a typical example of the polymer binder used in the ion selective electrode membrane includes poly(vinyl chloride) (PVC), and in addition thereto, synthetic polymers including polyurethane, polyacrylate, silicone rubber, epoxy aery late, polystyrene and so on are known (Bakker, E.; Buhlmann, P.; Pretch, E. Chem. Rev.
- the ion selective electrode membrane composed essentially of the polymer binder is disadvantageous because an active component used in the ion selective electrode, namely, an ionophore, a lipophilic additive and a plasticizer may leach out, undesirably deteriorating electrode performance.
- an active component used in the ion selective electrode namely, an ionophore, a lipophilic additive and a plasticizer may leach out, undesirably deteriorating electrode performance.
- the demand for a polymer compound which prevents leaching out of the lipophilic additive and the active component is easily processed and has a chemical sensor function having high ion selectivity continues.
- the present invention provides a brash polymer for use in a chemical sensor.
- the present invention provides a polymer compound, which prevents leaching out of a lipophilic additive and an active component, obviates a processing plasticizer, and has a chemical sensor function having high ion selectivity.
- the present invention provides a method of preparing the polymer compound, which prevents leaching out of a lipophilic additive and an active component, obviates a processing plasticizer, and has a chemical sensor function having high ion selectivity.
- the present invention provides a novel chemical sensor which prevents leaching out of a lipophilic additive and an active component and contains no plasticizer.
- the present invention provides use of the brush polymer for detecting ions.
- An aspect of the present invention provides a functional brush polymer composed of a brush polymer represented by Formula I below. [13] Formula I
- the functional brush polymer is not theoretically limited but the functional brush polymer compound includes brushes having a polyether backbone and, as terminal groups, a trifluoroacetophenyl group and a lipophilic functional group, and thus prevents leaching out of the active component and the lipophilic functional group. Also, even when the brush polymer contains no plasticizer, it may be processed into various forms thanks to good melt processability and solubility. Also, the brush polymer is usefully applied to a chemical sensor device including an ion selective electrode, an optical sensor and a gas sensor to detect and analyze a compound in an environment and in vivo.
- the brush polymer compound may have a weight average molecular weight ranging from 5,000 to 5,000,000, and preferably from 5,000 to 500,000.
- a which is a content (mol%) of the brush polymer compound monomer, ranges from 10 to 100, and preferably from 50 to 100.
- a representative example of the brush polymer compound having a chemical sensor function as represented by Formula I is poly[oxy(4-(2,2,2-trifluoroacetyl)benzoate)undecylthiomethyl]ethylene-ran-oxy((didoc ylmethylundecylsuccinate ammonium chloride)undecylthiomethyl)ethylene] (hereinafter, referred to as poly(TFBa-ran-DAb)) represented by Formula II below.
- a and b each are a content (mol%) of a polyether monomer, 0 ⁇ a ⁇
- a is in the range of from 10 to 100 and more preferably from 50 to 100.
- Another aspect of the present invention provides a method of preparing the functional brush polymer represented by Formula I, including reacting a polymer compound represented by Formula IX below with a compound represented by Formula
- R 6 is a C 1 ⁇ 20 alkyl group, and X is a halogen.
- Formula IX may be prepared by reacting a polymer compound represented by Formula VII below, a compound represented by Formula IV below, and a compound represented by Formula D below. [31] Formula VII
- R 3 , R 4 and R 5 are independently H or a C 1 ⁇ 20 alkyl group, and D is -
- Q is trifluoroacetyl
- T is H, -R*0H, -R*CHO, -R*COOH, -R*C00R,
- R* is H or a C 1 ⁇ 50 alkyl group
- L is -COOH, -OH, -NH 2 or -OCOCH 2 CH 2 OCOH.
- the polyether polymer compound represented by Formula VII may be prepared by reacting a polymer compound rep- resented by Formula VI below with compounds represented by Formulas XI and XII below thus introducing a functional group to an alkyl side-chain.
- R 1 is a C ⁇ 20 alkyl group
- A is H or -CH 2 X
- X is F, Cl, Br or I
- d is a repeating unit.
- Formula VI may be prepared through cation ring-opening polymerization of a cyclic ether compound represented by Formula V below in the presence of a cation initiator.
- A is H or -CH 2 X, in which X is F, Cl, Br or I.
- the lipophilic compound precursor represented by Formula IV may be prepared by reacting a compound represented by Formula III below with a compound represented by Formula IH-I below.
- R 4 and R 5 are a Ci_ 2 o alkyl group.
- D is -COOH, -OH, -NH 2 or a halogen
- X and R 3 are a C ⁇ 20 alkyl group.
- the method of preparing the brush polymer compound having a chemical sensor function as represented by Formula I includes 1) reacting the compound of Formula III with the compound of Formula III- 1 , thus preparing a precursor of a lipophilic functional group represented by Formula IV, 2) subjecting the cyclic ether compound of Formula V to cation ring- opening polymerization in the presence of a cation initiator, thus preparing a polyether compound of Formula VI, 3) reacting the polyether compound of Formula VI with the compounds of Formulas XI and XII in the presence of an organic solvent, thus preparing the compound of Formula VII having a functional group introduced to an alkyl side-chain, 4) reacting the compound of Formula VII with the compound of Formula IV and the compound of Formula D in the presence of an organic solvent, thus preparing the compound of Formula IX, and 5) reacting the compound of Formula IX with the compound of Formula X in the presence of an organic solvent.
- the precursor of the lipophilic functional group is prepared through alkylation.
- the polyether compound of Formula VI which is a backbone of Formula I is prepared.
- the cyclic ether compound of Formula V is subjected to cation ring-opening polymerization in the presence of the cation initiator, such as triphenyl- carbenium hexafluorophosphate, triphenylcarbenium hexachloroantimoniate or alkyl aluminum, with or without use of a solvent such as dichloromethane, chloroform or di- ethylether.
- the cation initiator such as triphenyl- carbenium hexafluorophosphate, triphenylcarbenium hexachloroantimoniate or alkyl aluminum
- the polyether polymer compound of Formula VI is reacted with the compounds of Formulas XI and XII in the presence of an organic solvent, thus preparing the compound of Formula VII having brushes introduced thereto.
- the solvent is selected from the group consisting of dimethylacetamide, dimethylformamide, diethylether, dichloromethane, tetrahydrofuran and mixtures thereof. This reaction may be performed at a temperature ranging from -100 0 C to 100 0 C under pressure of 1-5 atm.
- the compound of Formula VI is reacted with the compounds of Formulas IV and D in the presence of the organic solvent, thus preparing the brush polyether polymer containing a precursor of a lipophilic functional group and 4-trifluoroacetophenyl group (an ionophore).
- the ratio of compound of Formula IV and compound of Formula D is adjusted, thus introducing functional groups in a desired content to the side-chain of the brush polyether.
- the organic solvent is selected from the group consisting of dichloromethane, dimethylacetamide, dimethylformamide and mixtures thereof.
- the compound of Formula IX is reacted with R 6 X in the presence of the organic solvent and thus alkylated, thereby introducing the lipophilic functional group.
- the organic solvent is selected from the group consisting of dichloromethane, chloroform, methanol and mixtures thereof.
- a further aspect of the present invention provides use of the functional brush polymer represented by Formula I for sensing an ion.
- the ion-sensing function may be realized using an ion selective sensor, and more specifically, the ion selective sensor may be provided in the form of a sensor membrane applied on a sensing part.
- sensibility to the ion may be controlled through adjustment of the content of the brush having an ionophore as a terminal group and the content of the brush having a lipophilic functional group as a terminal group.
- a method of preparing a coated wire ion selective electrode using the brush polymer compound having a chemical sensor function as represented by Formula I may be performed through a process known in the art.
- Still a further aspect of the present invention provides a molded product having any shape or a thin film produced by processing the polymer of Formula I, for example, a nano thin film member produced from a sheet.
- the product prevents leaching out of a plasticizer, an active component and a lipophilic functional group and is thus is environmentally friendly. Hence, the product is easily used to detect a compound in vivo and to detect and analyze chemical material in blood tests, drinking water and an environment.
- the brush polymer compound having a chemical sensor function with a trifluoroacetophenyl group and a lipophilic functional group leaches out neither an active component nor a lipophilic functional group, and can be processed into various forms thanks to good melt processability and solubility even in the absence of a plasticizer.
- the brush polymer compound can be usefully applied to a chemical sensor device, such as an ion selective electrode, an optical sensor, or a gas sensor, to detect and analyze a compound in the environment and in vivo.
- FIG. 1 is a cross-sectional view showing a solid electrode coated with an ion selective membrane of the present invention, in which reference number 1 indicates a plastic electrode body, reference number 2 indicates a copper wire, reference number 3 indicates a silver layer, reference number 4 indicates a silver/silver chloride layer, and reference number 5 indicates an ion selective membrane;
- FIG. 2 is a graph showing sensitivity of the ion selective electrode membrane according to the present invention to a carbonate ion, in which a, b, c, d, e, f, g and h respectively graph sensitivity of poly(TFB90-ran-DA10), poly(TFB80-ran-DA20), poly(TFB70-ran-DA30), poly(TFB60-ran-DA40), poly(TFB50-ran-DA50), poly(TFB40-ran-DA60), poly(TFB30-ran-DA70), and poly(TFB20-ran-DA80) membranes to the carbonate ion; [75] FIG.
- FIG. 3 is a calibration curve of the ion selective membrane according to the present invention with respect to a carbonate ion;
- FIG. 4 is a calibration curve of the carbonate ion selective membrane with respect to an interference ion, for example, a chloride ion; and
- FIG. 5 is a calibration curve of the carbonate ion selective membrane with respect to an interference ion, for example, a salicylate ion.
- Example 3 was dissolved in 2 ml of dimethylacetamide, thus preparing a solution which was then mixed with a solution of 1,382 mg(5.4 mmol) of 11-hydroxyundecylthioleate dissolved in 10 ml of DMAc. This mixture was stirred at room temperature for 2 hours, extracted with chloroform, washed with water to remove the solvent, and then precipitated in hexane. This precipitate was dried at 4O 0 C for 8 hours in a vacuum, thus obtaining a desired compound (1.34 g, yield 95%).
- the sensitivity curve of the carbonate ion selective membrane was determined in a manner such that the solid ion selective electrode coated with the ion selective membrane of Example 2, an outer reference electrode, a double junction Ag/ AgCl electrode (Model 90-02-00, Orion) were connected to a 16-channel analog- to-digital converter, two electrodes were immersed in a buffer solution (0.1 M Tris-HCl (pH 8.6)), and the concentration of NaHCO 3 was changed as high as 10 times at temporal intervals of 100 seconds. From FIG.
- reactivity to the carbonate ion could be seen to vary depending on the difference between the content of the brush having an ionophore as a terminal group and the content of the brush having a lipophilic functional group as a terminal group. If the content of the brush having the lipophilic functional group as a terminal group was much smaller than the content of the brush having the ionophore as a terminal group, reactivity to the carbonate ion was low (a, b). When the content of the brush having the lipophilic functional group as a terminal group was increased, reactivity to the carbonate ion was gradually increased and then was made constant within a certain range (c, d, e).
- FIG. 4 is a calibration curve obtained by adding a NaCl solution to the reference solution to evaluate reactivity to a chlorine ion having the lowest interference with respect to the carbonate ionophore.
- the polymer compound can be usefully applied to a chemical sensor device such as an ion selective electrode, an optical sensor and a gas sensor to detect and analyze a compound in an environment and in vivo.
Abstract
This invention relates to a functional brush polymer compound, a method of preparing the same, and a chemical sensor including the same. When the functional brush polymer compound is used as a chemical sensor, an active compound and a lipophilic functional group thereof do not leach out. The brush polymer compound is easily processed into various forms thanks to good melt processability and solubility even in the presence of a plasticizer, and is usefully applied to a chemical sensor device such as an ion selective electrode, an optical sensor and a gas sensor to detect and analyze a compound in the environment and in vivo.
Description
Description
BRUSH POLYETHER-BASED POLYMERS, PREPARATION
METHODS THEREOF AND CHEMICAL SENSORS
COMPRISING THE POLYMERS
Technical Field
[1] The present invention relates to a functional brush polymer compound, and, more particularly, to a brash polymer compound for a chemical sensor, a method of preparing the same, and a chemical sensor including the same.
Background Art [2] Thorough research into ion selective electrodes has continued to date, and also, various ion selective electrode membranes containing an ion carrier have been proposed. [3] The ion selective electrode membrane is composed of about 33% of a polymer binder, about 66% of a plasticizer, and small amounts of an ionophore and a lipophilic additive. [4] A typical example of the polymer binder used in the ion selective electrode membrane includes poly(vinyl chloride) (PVC), and in addition thereto, synthetic polymers including polyurethane, polyacrylate, silicone rubber, epoxy aery late, polystyrene and so on are known (Bakker, E.; Buhlmann, P.; Pretch, E. Chem. Rev.
1997, 97, 3083-3132). [5] However, the ion selective electrode membrane composed essentially of the polymer binder is disadvantageous because an active component used in the ion selective electrode, namely, an ionophore, a lipophilic additive and a plasticizer may leach out, undesirably deteriorating electrode performance. [6] Thus, the demand for a polymer compound which prevents leaching out of the lipophilic additive and the active component, is easily processed and has a chemical sensor function having high ion selectivity continues.
Disclosure of Invention
Technical Problem
[7] Accordingly, the present invention provides a brash polymer for use in a chemical sensor.
[8] In addition, the present invention provides a polymer compound, which prevents leaching out of a lipophilic additive and an active component, obviates a processing plasticizer, and has a chemical sensor function having high ion selectivity.
[9] In addition, the present invention provides a method of preparing the polymer
compound, which prevents leaching out of a lipophilic additive and an active component, obviates a processing plasticizer, and has a chemical sensor function having high ion selectivity. [10] In addition, the present invention provides a novel chemical sensor which prevents leaching out of a lipophilic additive and an active component and contains no plasticizer. [11] In addition, the present invention provides use of the brush polymer for detecting ions.
Technical Solution [12] An aspect of the present invention provides a functional brush polymer composed of a brush polymer represented by Formula I below. [13] Formula I
[15] In Formula I, R1, R2, R3, R4, R5 and R6 are independently H or a C1^20 alkyl group, a and b each are a content (mol%) of a polyether monomer, 0 < a < 100, 0 < b < 100, a + b = 100, Y is H, a CL20 alkyl group, -ZPh(Q5T) or -WR3N+[R4R5R6]X", Q is trifluo- roacetyl, T is H, -R*OH, -R*CHO, -R*COOH, -R*COOR, -R*NHCOR or - R*CONHR, in which R* is H or a C1-S0 alkyl group, X is F, Cl, Br or I, and Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2SROCO-, -CH2SRCOO-, -CH2 SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2SRCO-, -CH2SO2ROCO-, -CH 2SO2RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO2ROCO(CH2)2OCO-, -CH2SO2 RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, -OCORNHCO-, -OCOROCO(CH2)2 OCO-, -OCORCO-, -COOROCO-, -COORCOO-, -COORO-, -COORNHCO-, - COOROCO(CH2)2OCO-, -COORCO-, -OROCO-, -ORCOO-, -ORO-, -ORNHCO-, - OROCO(CH2)2OCO-, -ORCO-, -NHR0C0-, -NHRCOO-, -NHRO-, -NHRNHCO-, - NHROCO(CH2)2OCO-, -NHRCO-, -CH2ROCO-, -CH2RCOO-, -CH2RO-, -CH2 RNHCO-, -CH2ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4RCOO-, -OC6 H4RO-, -OC6H4RNHCO-, -OC6H4ROCO(CH2)2OCO-, -OC6H4RCO-, -OC6H4 COOROCO-, -OC6H4COORCOO-, -OC6H4COORO-, -OC6H4COORNHCO-, -OC6H4 COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4CONHROCO-, -OC6H4 CONHRCOO-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, -OC6H4
CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group.
[16] In the present invention, the functional brush polymer is not theoretically limited but the functional brush polymer compound includes brushes having a polyether backbone and, as terminal groups, a trifluoroacetophenyl group and a lipophilic functional group, and thus prevents leaching out of the active component and the lipophilic functional group. Also, even when the brush polymer contains no plasticizer, it may be processed into various forms thanks to good melt processability and solubility. Also, the brush polymer is usefully applied to a chemical sensor device including an ion selective electrode, an optical sensor and a gas sensor to detect and analyze a compound in an environment and in vivo.
[17] In the present invention, the brush polymer compound may have a weight average molecular weight ranging from 5,000 to 5,000,000, and preferably from 5,000 to 500,000.
[18] In the present invention, in the brush polymer compound of Formula I, a, which is a content (mol%) of the brush polymer compound monomer, ranges from 10 to 100, and preferably from 50 to 100.
[19] A representative example of the brush polymer compound having a chemical sensor function as represented by Formula I is poly[oxy(4-(2,2,2-trifluoroacetyl)benzoate)undecylthiomethyl]ethylene-ran-oxy((didoc ylmethylundecylsuccinate ammonium chloride)undecylthiomethyl)ethylene] (hereinafter, referred to as poly(TFBa-ran-DAb)) represented by Formula II below.
[20] Formula II
[22] In Formula II, a and b each are a content (mol%) of a polyether monomer, 0 < a <
100, 0 < b < 100, a + b = 100, and preferably a is in the range of from 10 to 100 and more preferably from 50 to 100.
[23] Another aspect of the present invention provides a method of preparing the functional brush polymer represented by Formula I, including reacting a polymer
compound represented by Formula IX below with a compound represented by Formula
X below.
[24] Formula IX
[26] In Formula IX, R1, R2, R3, R4 and R5 are independently H or a C1^o alkyl group, a and b each are a content (mol%) of a polyether monomer, 0 < a < 100, 0 < b < 100, a + b = 100, Y is H, a C1^20 alkyl group, -ZPh(Q,T) or -WR3N+[R4R5R6]X", Q is trifluoroacetyl, T is H, -R*OH, -R*CHO, -R*COOH, -R*COOR, -R*NHCOR or -R*CONHR, in which R* is H or a C1^50 alkyl group, X is F, Cl, Br or I, and Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2SROCO-, -CH2SRCOO-, -CH2SRO-, -CH2 SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2SRCO-, -CH2SO2ROCO-, -CH2SO2 RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO2ROCO(CH2)2OCO-, -CH2SO2 RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, -OCORNHCO-, -OCOROCO(CH2)2 OCO-, -OCORCO-, -COOROCO-, -COORCOO-, -COORO-, -COORNHCO-, - COOROCO(CH2)2OCO-, -COORCO-, -OROCO-, -ORCOO-, -ORO-, -ORNHCO-, - OROCO(CH2)2OCO-, -ORCO-, -NHROCO-, -NHRCOO-, -NHRO-, -NHRNHCO-, - NHROCO(CH2)2OCO-, -NHRCO-, -CH2ROCO-, -CH2RCOO-, -CH2RO-, -CH2 RNHCO-, -CH2ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4RCOO-, -OC6 H4RO-, -OC6H4RNHCO-, -OC6H4ROCO(CH2)2OCO-, -OC6H4RCO-, -OC6H4 COOROCO-, -OC6H4COORCOO-, -OC6H4COORO-, -OC6H4COORNHCO-, -OC6H4 COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4CONHROCO-, -OC6H4 CONHRCOO-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, -OC6H4 CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group.
[27] Formula X
[28] R6X
[29] In Formula X, R6 is a C1^20 alkyl group, and X is a halogen.
[30] In an embodiment of the present invention, the polymer compound represented by
Formula IX may be prepared by reacting a polymer compound represented by Formula VII below, a compound represented by Formula IV below, and a compound represented by Formula D below.
[31] Formula VII
[33] In Formula VII, Ri and R2 are independently H or a C1^20 alkyl group, a and b each are a content (mol%) of a polyether monomer, 0 < a < 100, 0 < b < 100, a + b = 100, and Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2SROCO-, -CH2 SRCOO- , -CH2SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2SRCO-, -CH2SO2 ROCO-, -CH2SO2RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO2ROCO(CH2)2 OCO-, -CH2SO2RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, -OCORNHCO-, - OCOROCO(CH2)2OCO-, -OCORCO-, -COOROCO-, -COORCOO-, -COORO-, - COORNHCO-, -COOROCO(CH2)2OCO-, -COORCO-, -OROCO-, -ORCOO-, -ORO-, -ORNHCO-, -OROCO(CH2)2OCO-, -ORCO-, -NHROCO-, -NHRCOO-, -NHRO-, - NHRNHCO-, -NHROCO(CH2)2OCO-, -NHRCO-, -CH2ROCO-, -CH2RCOO-, -CH2 RO-, -CH2RNHCO-, -CH2ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4 RCOO-, -OC6H4RO-, -OC6H4RNHCO-, -OC6H4ROCO(CH2)2OCO-, -OC6H4RCO-, - OC6H4COOROCO-, -OC6H4COORCOO-, -OC6H4COORO-, -OC6H4COORNHCO-, - OC6H4COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4CONHROCO-, -OC6H4 CONHRCOO-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, -OC6H4 CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group.
[34] Formula IV
[35] D
[36] In Formula IV, R3, R4 and R5 are independently H or a C1^20 alkyl group, and D is -
COOH, -OH, -NH2 or a halogen. [37] Formula D
[39] In Formula D, Q is trifluoroacetyl, T is H, -R*0H, -R*CHO, -R*COOH, -R*C00R,
-R*NHC0R or -R*C0NHR, in which R* is H or a C1^50 alkyl group, and L is -COOH, -OH, -NH2 or -OCOCH2CH2OCOH.
[40] In the embodiment of the present invention, the polyether polymer compound represented by Formula VII may be prepared by reacting a polymer compound rep-
resented by Formula VI below with compounds represented by Formulas XI and XII below thus introducing a functional group to an alkyl side-chain. [41] Formula VI
[43] In Formula VI, R1 is a C^20 alkyl group, A is H or -CH2X, X is F, Cl, Br or I, and d is a repeating unit.
[44] Formula XI
[45] H-Z-H
[46] Formula XII
[47] H-W-H
[48] In Formulas XI and XII, Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2 SROCO-, -CH2SRCOO-, -CH2SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2 SRCO-, -CH2SO2ROCO-, -CH2SO2RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO 2ROCO(CH2)2OCO-, -CH2SO2RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, - OCORNHCO-, -OCOROCO(CH2)2OCO-, -OCORCO-, -COOROCO-, -COORCOO-, -COORO-, -COORNHCO-, -COOROCO(CH2)2OCO-, -COORCO-, -OROCO-, - ORCOO-, -ORO-, -ORNHCO-, -OROCO(CH2)2OCO-, -ORCO-, -NHROCO-, - NHRCOO-, -NHRO-, -NHRNHCO-, -NHROCO(CH2)2OCO-, -NHRCO-, -CH2 ROCO-, -CH2RCOO-, -CH2RO-, -CH2RNHCO-, -CH2ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4RCOO-, -OC6H4RO-, -OC6H4RNHCO-, -OC6H4ROCO(CH2)2 OCO-, -OC6H4RCO-, -OC6H4COOROCO-, -OC6H4COORCOO-, -OC6H4COORO-, - OC6H4COORNHCO-, -OC6H4COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4 CONHROCO-, -OC6H4CONHRCOO-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, - OC6H4CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group.
[49] In the embodiment of the present invention, the polyether polymer represented by
Formula VI may be prepared through cation ring-opening polymerization of a cyclic ether compound represented by Formula V below in the presence of a cation initiator.
[50] Formula V
[51] o
CH2X
[52] In Formula V, A is H or -CH2X, in which X is F, Cl, Br or I.
[53] In the embodiment of the present invention, the lipophilic compound precursor represented by Formula IV may be prepared by reacting a compound represented by
Formula III below with a compound represented by Formula IH-I below. [54] Formula III
[55]
H
[56] In Formula III, R4 and R5 are a Ci_2o alkyl group.
[57] Formula III- 1
[58] DR3X
[59] In Formula III- 1 , D is -COOH, -OH, -NH2 or a halogen, and X and R3 are a C^20 alkyl group.
[60] In a preferred embodiment of the present invention, the method of preparing the brush polymer compound having a chemical sensor function as represented by Formula I includes 1) reacting the compound of Formula III with the compound of Formula III- 1 , thus preparing a precursor of a lipophilic functional group represented by Formula IV, 2) subjecting the cyclic ether compound of Formula V to cation ring- opening polymerization in the presence of a cation initiator, thus preparing a polyether compound of Formula VI, 3) reacting the polyether compound of Formula VI with the compounds of Formulas XI and XII in the presence of an organic solvent, thus preparing the compound of Formula VII having a functional group introduced to an alkyl side-chain, 4) reacting the compound of Formula VII with the compound of Formula IV and the compound of Formula D in the presence of an organic solvent, thus preparing the compound of Formula IX, and 5) reacting the compound of Formula IX with the compound of Formula X in the presence of an organic solvent.
[61] In 1), the precursor of the lipophilic functional group is prepared through alkylation.
In 2), the polyether compound of Formula VI which is a backbone of Formula I is prepared. To this end, the cyclic ether compound of Formula V is subjected to cation ring-opening polymerization in the presence of the cation initiator, such as triphenyl- carbenium hexafluorophosphate, triphenylcarbenium hexachloroantimoniate or alkyl aluminum, with or without use of a solvent such as dichloromethane, chloroform or di- ethylether.
[62] In 3), the polyether polymer compound of Formula VI is reacted with the compounds of Formulas XI and XII in the presence of an organic solvent, thus preparing the compound of Formula VII having brushes introduced thereto. The solvent is selected from the group consisting of dimethylacetamide, dimethylformamide, diethylether, dichloromethane, tetrahydrofuran and mixtures thereof. This reaction may be performed at a temperature ranging from -1000C to 1000C under pressure of 1-5 atm.
[63] In 4), the compound of Formula VI is reacted with the compounds of Formulas IV and D in the presence of the organic solvent, thus preparing the brush polyether
polymer containing a precursor of a lipophilic functional group and 4-trifluoroacetophenyl group (an ionophore). As such, the ratio of compound of Formula IV and compound of Formula D is adjusted, thus introducing functional groups in a desired content to the side-chain of the brush polyether. The organic solvent is selected from the group consisting of dichloromethane, dimethylacetamide, dimethylformamide and mixtures thereof.
[64] In 5), the compound of Formula IX is reacted with R6X in the presence of the organic solvent and thus alkylated, thereby introducing the lipophilic functional group. The organic solvent is selected from the group consisting of dichloromethane, chloroform, methanol and mixtures thereof.
[65] A further aspect of the present invention provides use of the functional brush polymer represented by Formula I for sensing an ion.
[66] Formula I
[68] In Formula I, R1, R2, R3, R4, R5 and R6 are independently H or a C1^20 alkyl group, a and b each are a content (mol%) of a polyether monomer, 0 < a < 100, 0 < b < 100, a + b = 100, Y is H, a CL20 alkyl group, -ZPh(Q5T) or -WR3N+[R4R5R6]X , Q is trifluo- roacetyl, T is H, -R*OH, -R*CHO, -R*COOH, -R*COOR, -R*NHCOR or - R*CONHR, in which R* is H or a C1^50 alkyl group, X is F, Cl, Br or I, and Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2SROCO-, -CH2SRCOO-, -CH2 SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2SRCO-, -CH2SO2ROCO-, -CH 2SO2RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO2ROCO(CH2)2OCO-, -CH2SO2 RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, -OCORNHCO-, -OCOROCO(CH2)2 OCO-, -OCORCO-, -COOROCO-, -COORCOO-, -COORO-, -COORNHCO-, - COOROCO(CH2)2OCO-, -COORCO-, -OROCO-, -ORCOO-, -ORO-, -ORNHCO-, - OROCO(CH2)2OCO-, -ORCO-, -NHR0C0-, -NHRCOO-, -NHRO-, -NHRNHCO-, - NHROCO(CH2)2OCO-, -NHRCO-, -CH2ROCO-, -CH2RCOO-, -CH2RO-, -CH2 RNHCO-, -CH2ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4RCOO-, -OC6 H4RO-, -OC6H4RNHCO-, -OC6H4ROCO(CH2)2OCO-, -OC6H4RCO-, -OC6H4 COOROCO-, -OC6H4COORCOO-, -OC6H4COORO-, -OC6H4COORNHCO-, -OC6H4 COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4CONHROCO-, -OC6H4
CONHRCOO-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, -OC6H4 CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group.
[69] In an embodiment of the present invention, the ion-sensing function may be realized using an ion selective sensor, and more specifically, the ion selective sensor may be provided in the form of a sensor membrane applied on a sensing part. In the embodiment of the present invention, sensibility to the ion may be controlled through adjustment of the content of the brush having an ionophore as a terminal group and the content of the brush having a lipophilic functional group as a terminal group.
[70] A method of preparing a coated wire ion selective electrode using the brush polymer compound having a chemical sensor function as represented by Formula I may be performed through a process known in the art.
[71] Still a further aspect of the present invention provides a molded product having any shape or a thin film produced by processing the polymer of Formula I, for example, a nano thin film member produced from a sheet. The product prevents leaching out of a plasticizer, an active component and a lipophilic functional group and is thus is environmentally friendly. Hence, the product is easily used to detect a compound in vivo and to detect and analyze chemical material in blood tests, drinking water and an environment.
Advantageous Effects
[72] According to the present invention, the brush polymer compound having a chemical sensor function with a trifluoroacetophenyl group and a lipophilic functional group leaches out neither an active component nor a lipophilic functional group, and can be processed into various forms thanks to good melt processability and solubility even in the absence of a plasticizer. Also, the brush polymer compound can be usefully applied to a chemical sensor device, such as an ion selective electrode, an optical sensor, or a gas sensor, to detect and analyze a compound in the environment and in vivo. Brief Description of Drawings
[73] FIG. 1 is a cross-sectional view showing a solid electrode coated with an ion selective membrane of the present invention, in which reference number 1 indicates a plastic electrode body, reference number 2 indicates a copper wire, reference number 3 indicates a silver layer, reference number 4 indicates a silver/silver chloride layer, and reference number 5 indicates an ion selective membrane;
[74] FIG. 2 is a graph showing sensitivity of the ion selective electrode membrane according to the present invention to a carbonate ion, in which a, b, c, d, e, f, g and h respectively graph sensitivity of poly(TFB90-ran-DA10), poly(TFB80-ran-DA20), poly(TFB70-ran-DA30), poly(TFB60-ran-DA40), poly(TFB50-ran-DA50),
poly(TFB40-ran-DA60), poly(TFB30-ran-DA70), and poly(TFB20-ran-DA80) membranes to the carbonate ion; [75] FIG. 3 is a calibration curve of the ion selective membrane according to the present invention with respect to a carbonate ion; [76] FIG. 4 is a calibration curve of the carbonate ion selective membrane with respect to an interference ion, for example, a chloride ion; and [77] FIG. 5 is a calibration curve of the carbonate ion selective membrane with respect to an interference ion, for example, a salicylate ion.
Best Mode for Carrying out the Invention [78] A better understanding of the present invention may be obtained through the following synthesis examples and examples which are set forth to illustrate, but are not to be construed as limiting the present invention. [79] <Synthesis Example 1>
[80]
H o
H Br(CH2)^ 1OH (CH2). ,
H3C(H;C),,-' N "(CH?)11CHj *» H3C(H2Q1 ,-'N "{CH2)1, CH3
[81] Into a 250 ml three-neck round bottom flask with a nitrogen inlet, 2.5 g (7.1 mmol) of didodecylamine, 2.14 g (8.52 mmol) of 11-bromo-l-undecanol and 3.53 g (25.56 mmol) of potassium carbonate (K2CO3) were rapidly placed. Thereafter, 150 ml of an ethylacetate solvent was added thereto, and reaction was then performed at 9O0C for 24 hours under a stream of nitrogen. The resultant reaction product was extracted with water and ethylacetate, thus obtaining an organic layer. Thereafter, the organic layer was dried over magnesium sulfate, vacuum filtered, and then vacuum distilled and thus concentrated. The concentrated product was subjected to column chromatography (chloroform, ethylacetate) two times and thus separated and purified. (1.66 g, yield 43%).
[82] <Synthesis Example 2>
[83] oj)2
H5C(H2C)1 ,^
%C H2), ,CH1 - HjC[H2C)i rN "-(CH2).1CH0
[84] 1.66 g (3.19 mmol) of the precursor obtained in Synthesis Example 1 was dissolved in 60 ml of dichloromethane, added with 1.6 g (15.59 mmol) of succinic anhydride, stirred at room temperature for 12 hours, and then extracted with water and
dichloromethane. The resultant organic layer was dried over magnesium sulfate, vacuum filtered, vacuum distilled and thus concentrated, and dried in a vacuum, thus obtaining a compound (1.69 g, yield 80%).
[85] <Synthesis Example 3>
[86]
O TCHP , \
^\ *- 4- O CH2 CH Y
CH*CI CH2Cl ' d
[87] Into a 100 ml round bottom flask, 40 ml (512 mmol) of epichlorohydrin was placed and cooled to 50C in a nitrogen atmosphere. Then, the epichlorohydrin was added with a solution of 2.56 mmol initiator in dichloromethane, and then stirred at room temperature for 4 days. The resultant reaction product was dissolved in a small amount of dichloromethane, re-precipitated in methanol and thus purified, and then dried at 4O0C for 8 hours in a vacuum, thus obtaining polyepichlorohydrin.
[88] <Synthesis Example 4>
[90] 500 mg (5.4 mmol) of the polyepichlorohydrin compound obtained in Synthesis
Example 3 was dissolved in 2 ml of dimethylacetamide, thus preparing a solution which was then mixed with a solution of 1,382 mg(5.4 mmol) of 11-hydroxyundecylthioleate dissolved in 10 ml of DMAc. This mixture was stirred at room temperature for 2 hours, extracted with chloroform, washed with water to remove the solvent, and then precipitated in hexane. This precipitate was dried at 4O0C for 8 hours in a vacuum, thus obtaining a desired compound (1.34 g, yield 95%).
[91] <Synthesis Example 5>
[92]
I
, N
3
[93] 400 mg (1.54 mmol) of the compound obtained in Synthesis Example 4, 81 mg (0.37 mmol) of 4-trifluorobenzoic acid, 0.924 g (1.48 mmol) of the precursor obtained in
Synthesis Example 1, 882 mg of N-(3-dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride and 282 mg of N,N-dimethylaminopyridine were dissolved in 40 ml of methylene chloride, and then stirred at room temperature for 24 hours. The solution thus obtained was vacuum distilled and thus concentrated, and then subjected to column chromatography (dichloromethane:methanol = 7:3) and thus separated and purified. (1010 mg, yield 90%). IH NMR (300 MHz, CDCl3) δ 8.23-8.14 (m, 0.4H), δ 4.41-4.36 (t, 0.3H), δ 4.09-4.03 (t, v4H), δ 3.73-3.64 (m, 5H), δ 2.70-2.51 (m, 15H), δ 1.61-1.25 (m, 81H), δ 0.9-0.85 (t, 6H).
[94] <Synthesis Example 6> — V
p, CMi
[96] 1010 mg (1.27 mmol) of the compound obtained in Synthesis Example 5 was dissolved in 70 ml of a mixture (chloroform: methanol = 50:20) of chloroform and methanol. To this solution, 1 ml of iodomethane was slowly added in droplets, after which the solution was stirred at room temperature for 12 hours. Thereafter, the resultant reaction product was ion exchanged with a Cl-exchange resin, vacuum distilled and thus concentrated and then vacuum dried, thus obtaining a final compound. (Poly(TFB20-ran-DA80)) (1010 mg, yield 90%). IH NMR (300 MHz, CDCl3) δ 8.23-8.14 (m, 0.4H), δ 4.41-4.36 (t, 0.3H), δ 4.09-4.03 (t, 4H), δ 3.73-3.33 (m, 8H), δ 2.97-2.91 (m, 3.7H), δ 2.70-2.51 (m, 7H), δ 1.61-1.59 (m, 81H), δ 0.9-0.85 (m, 6H); IR (membrane, cm-1) = 2930, 1725, 1463, 1276, 1187, 732. Mode for the Invention
[97] <Example 1>: Manufacture of Ion Selective Sensor
[98] An ion selective sensor having a structure as shown in FIG. 1 was manufactured through the following procedures.
[99] The surface of a silver electrode in a plastic body was treated with a 0.1 M FeCl3 solution thus forming an Ag/ AgCl layer, thereby making an Ag/ AgCl electrode. A solution of 5 wt% of the compound obtained in Synthesis Example 6 in THF was dropped on the Ag/ AgCl electrode and dried in a vacuum for one day, thereby manufacturing a solid ion selective electrode coated with a carbonate ion selective membrane.
[100] <Example 2>: Sensitivity of Ion Selective Electrode Membrane to Carbonate Ion [101] Using the solid ion selective electrode of Example 1, sensitivity to a carbonate ion was measured.
[102] The sensitivity curve of the carbonate ion selective membrane was determined in a manner such that the solid ion selective electrode coated with the ion selective membrane of Example 2, an outer reference electrode, a double junction Ag/ AgCl electrode (Model 90-02-00, Orion) were connected to a 16-channel analog- to-digital converter, two electrodes were immersed in a buffer solution (0.1 M Tris-HCl (pH 8.6)), and the concentration of NaHCO3 was changed as high as 10 times at temporal intervals of 100 seconds. From FIG. 2, reactivity to the carbonate ion could be seen to vary depending on the difference between the content of the brush having an ionophore as a terminal group and the content of the brush having a lipophilic functional group as a terminal group. If the content of the brush having the lipophilic functional group as a terminal group was much smaller than the content of the brush having the ionophore as a terminal group, reactivity to the carbonate ion was low (a, b). When the content of the brush having the lipophilic functional group as a terminal group was increased, reactivity to the carbonate ion was gradually increased and then was made constant within a certain range (c, d, e). However, as the content of the brush having the lipophilic functional group as a terminal group was larger than the content of the brush having the ionophore as a terminal group, reactivity to the carbonate ion was reduced (f, g, h). From FIG. 3, c, d and e having good reactivity to the carbonate ion could be seen to have values close to the Nernst slope.
[103] <Example 3> Selectivity of Ion Selective Electrode Membrane
[104] To evaluate reactivity to an interference ion in the presence of an appropriate amount of the carbonate ion, a NaHCO3 solution was added to a buffer solution (0.1 M Tris- HCl (pH 8.6)) so that the concentration of NaHCO3 solution in the buffer solution was set to 1 mM. Using the solution thus obtained as a reference electrode, the interference ion was added over time. FIG. 4 is a calibration curve obtained by adding a NaCl solution to the reference solution to evaluate reactivity to a chlorine ion having the lowest interference with respect to the carbonate ionophore. FIG. 5 is a calibration curve obtained by adding a NaC7H5O3 solution to the reference solution to evaluate reactivity to a salicylate ion having the highest interference with respect to the carbonate ionophore. Unlike the calibration curve for the carbonate ion of FIG. 3, as the content of the brush having the lipophilic functional group as the terminal group was increased, reactivity to the interference ion became large. In a conventional experiment using a PVC -based ion selective electrode, results varied depending on the amount of material used for the ion selective membrane. Likewise, in the present experiment, in the case of the polymer in which both the ionophore and the lipophilic functional group were
attached to the terminal groups of the polymer in the form of brushes, selectivity for the carbonate ion and reactivity to the interference ion could be seen to vary through adjustment of the brush content. As results, when the ratio of ionophore and lipophilic functional group was 70:30 and 60:40, namely, poly(TFB70-ran-DA30) and poly(TFB60-ran-DA40), the greatest results were exhibited. Also, the solid ion selective electrode having the above membrane as the ion selective membrane exhibited results similar or superior to those of the PVC -based electrode. Industrial Applicability According to the present invention, the polymer compound can be usefully applied to a chemical sensor device such as an ion selective electrode, an optical sensor and a gas sensor to detect and analyze a compound in an environment and in vivo.
Claims
[ 1 ] A brush polymer compound represented by Formula I below:
Formula I
Y is H, a CK20 alkyl group, -ZPh(Q5T) or -WR3N+[R4R5R6]X", Q is trifluoroacetyl,
T is H, -R*OH, -R*CHO, -R*COOH, -R*COOR, -R*NHCOR or -R*CONHR, in which R* is H or a C1^50 alkyl group, X is F, Cl, Br or I, and
Z and W are an aliphatic or aromatic derivative selected from the group consisting Of -CH2SROCO-, -CH2SRCOO-, -CH2SRO-, -CH2SRNHCO-, -CH2 SROCO(CH2)2OCO-, -CH2SRCO-, -CH2SO2ROCO-, -CH2SO2RCOO-, -CH2SO2 RO-, -CH2SO2RNHCO-, -CH2SO2ROCO(CH2)2OCO-, -CH2SO2RCO-, - OCOROCO-, -OCORCOO-, -OCORO-, -OCORNHCO-, -OCOROCO(CH2)2 OCO-, -OCORCO-, -COOROCO-, -COORCOO-, -COORO-, -COORNHCO-, - COOROCO(CH2)2OCO-, -COORCO-, -OROCO-, -ORCOO-, -ORO-, - ORNHCO-, -OROCO(CH2)2OCO-, -ORCO-, -NHROCO-, -NHRCOO-, - NHRO-, -NHRNHCO-, -NHROCO(CH2)2OCO-, -NHRCO-, -CH2ROCO-, -CH2 RCOO-, -CH2RO-, -CH2RNHCO-, -CH2ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4 ROCO-, -OC6H4RCOO-, -OC6H4RO-, -OC6H4RNHCO-, -OC6H4ROCO(CH2)2 OCO-, -OC6H4RCO-, -OC6H4COOROCO-, -OC6H4COORCOO-, -OC6H4 COORO-, -OC6H4COORNHCO-, -OC6H4COOROCO(CH2)2OCO-, -OC6H4 COORCO-, -OC6H4CONHROCO-, -OC6H4CONHRCOO-, -OC6H4CONHRO-, - OC6H4CONHRNHCO-, -OC^CONHROCOCCH^OCO-, and -OC6H4 CONHRCO-, in which R is H or a C1^20 alkyl group.
[2] The brush polymer compound according to claim 1, wherein the brush polymer compound has a weight average molecular weight ranging from 5,000 to 5,000,000.
[3] The brush polymer compound according to claim 1, wherein the brush polymer
compound has a weight average molecular weight ranging from 5,000 to
500,000.
[4] The brush polymer compound according to claim 1, wherein the brush polymer compound is poly[oxy(4-(2,2,2-trifluoroacetyl)benzoate)undecylthiomethyl]ethylene-ran-oxy(
(didocylmethylundecylsuccinate ammonium chloride)undecylthiomethyl)ethylene].
[5] A method of preparing a brush polymer, comprising reacting a polymer compound represented by Formula IX below with a compound represented by
Formula X below;
Formula IX
100, a + b = 100,
Y is H, a Ci-20 alkyl group, -ZPh(Q5T) or -WR3N+[R4R5R6]X",
Q is trifluoroacetyl,
T is H, -R*OH, -R*CHO, -R*COOH, -R*COOR, -R*NHCOR or -R*CONHR, in which R* is H or a C1^50 alkyl group,
X is F, Cl, Br or I, and
Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2SROCO-, -CH2
SRCOO-, -CH2SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2SRCO-, -
CH2SO2ROCO-, -CH2SO2RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO2
ROCO(CH2)2OCO-, -CH2SO2RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, -
OCORNHCO-, -OCOROCO(CH2)2OCO-, -OCORCO-, -COOROCO-, -
COORCOO-, -COORO-, -COORNHCO-, -COOROCO(CH2)2OCO-, -
COORCO-, -OROCO-, -ORCOO-, -ORO-, -ORNHCO-, -OROCO(CH2)2OCO-,
-ORCO-, -NHROCO-, -NHRCOO-, -NHRO-, -NHRNHCO-, -NHROCO(CH2)2
OCO-, -NHRCO-, -CH2ROCO-, -CH2RCOO-, -CH2RO-, -CH2RNHCO-, -CH2
ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4RCOO-, -OC6H4RO-, -
OC6H4RNHCO-, -OC6H4ROCO(CH2)2OCO-, -OC6H4RCO-, -OC6H4 COOROCO-
, -OC6H4COORCOO-, -OC6H4COORO-, -OC6H4COORNHCO-, -OC6H4 COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4CONHROCO-, -OC6H4 CONHRCOO-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, -OC6H4 CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group; and Formula X
R6X wherein R6 is a C^20 alkyl group, and X is a halogen.
[6] The method according to claim 5, wherein the polymer compound represented by
Formula IX is prepared by reacting a polymer compound represented by Formula VII below, a compound represented by Formula IV below, and a compound represented by Formula D below: Formula VII
wherein R1 and R2 are independently H or a Ci_2o alkyl group, a and b each are a content (mol%) of a polyether monomer, O < a < 100, O < b < 100, a + b = 100, and
Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2SROCO-, -CH2 SRCOO-, -CH2SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2SRCO-, - CH2SO2ROCO-, -CH2SO2RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO2 ROCO(CH2)2OCO-, -CH2SO2RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, - OCORNHCO-, -OCOROCO(CH2)2OCO-, -OCORCO-, -COOROCO-, - COORCOO-, -COORO-, -COORNHCO-, -COOROCO(CH2)2OCO-, - COORCO-, -OROCO-, -ORCOO-, -ORO-, -ORNHCO-, -OROCO(CH2)2OCO-, -ORCO-, -NHROCO-, -NHRCOO-, -NHRO-, -NHRNHCO-, -NHROCO(CH2)2 OCO-, -NHRCO-, -CH2ROCO-, -CH2RCOO-, -CH2RO-, -CH2RNHCO-, -CH2 ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4RCOO-, -OC6H4RO-, - OC6H4RNHCO-, -OC6H4ROCO(CH2)2OCO-, -OC6H4RCO-, -OC6H4 COOROCO- , -OC6H4COORCOO-, -OC6H4COORO-, -OC6H4COORNHCO-, -OC6H4 COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4CONHROCO-, -OC6H4 CONHRCOO-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, -OC6H4 CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group; Formula IV
wherein R3, R4 and R5 are independently H or a C^20 alkyl group, and D is - COOH, -OH, -NH2 or a halogen; and Formula D
T is H, -R*0H, -R*CH0, -R*COOH, -R*COOR, -R*NHCOR or -R*CONHR, in which R* is H or a Ci_5o alkyl group, and L is -COOH, -OH, -NH2 or -OCOCH2CH2OCOH.
[7] The method according to claim 6, wherein the polymer compound represented by
Formula VII is prepared by reacting a polyether polymer compound represented by Formula VI below with compounds represented by Formulas XI and XII below: Formula VI
wherein R1 is a C1^20 alkyl group, A is H or -CH2X, X is F, Cl, Br or I, and d is a repeating unit; and Formula XI H-Z-H Formula XII H-W-H wherein Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2 SROCO-, -CH2SRCOO-, -CH2SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2 OCO- , -CH2SRCO-, -CH2SO2ROCO-, -CH2SO2RCOO-, -CH2SO2RO-, -CH2SO2 RNHCO-, -CH2SO2ROCO(CH2)2OCO-, -CH2SO2RCO-, -OCOROCO-, - OCORCOO-, -OCORO-, -OCORNHCO-, -OCOROCO(CH2)2OCO-, - OCORCO-, -COOROCO-, -COORCOO-, -COORO-, -COORNHCO-, - COOROCO(CH2)2OCO-, -COORCO-, -OROCO-, -ORCOO-, -ORO-, - ORNHCO-, -OROCO(CH2)2OCO-, -ORCO-, -NHROCO-, -NHRCOO-, - NHRO-, -NHRNHCO-, -NHROCO(CH2)2OCO-, -NHRCO-, -CH2ROCO-, -CH2
RCOO-, -CH2RO-, -CH2RNHCO-, -CH2ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4 ROCO-, -OC6H4RCOO-, -OC6H4RO-, -OC6H4RNHCO-, -OC6H4ROCO(CH2)2 OCO-, -OC6H4RCO-, -OC6H4COOROCO-, -OC6H4COORCOO-, -OC6H4 C00R0-, -OC6H4COORNHCO-, -OC6H4COOROCO(CH2)2OCO-, -OC6H4 C00RC0-, -OC6H4CONHROCO-, -OC6H4CONHRCOO-, -OC6H4CONHRO-, - OC6H4CONHRNHCO-, -OQHtCONHROCOCCH^OCO-, and -OC6H4 CONHRCO-, in which R is H or a C1^20 alkyl group.
[8] The method according to claim 6, wherein the compound represented by
Formula IV is prepared by reacting a compound represented by Formula III below with a compound represented by Formula III- 1 below: Formula III
H
wherein R4 and R5 are a Ci_20 alkyl group; and
Formula III- 1
DR3X wherein D is -COOH, -OH, -NH2 or a halogen,
R3 is a Ci_2o alkyl group, and
X is F, Cl, Br or I.
[9] The method according to claim 8, wherein the reacting is performed in presence of potassium carbonate.
[10] The method according to claim 6, wherein the polymer compound represented by
Formula VII is prepared through ring-opening polymerization of a cyclic ether compound represented by Formula V below:
Formula V o
CH1K wherein A is H or -CH2X, in which X is F, Cl, Br or I.
[11] The method according to claim 10, wherein the ring-opening polymerization is performed in presence of triphenylcarbenium hexafluorophosphate, triphenyl- carbenium hexachloroantimoniate or alkyl aluminum with or without use of a solvent including dichloromethane, chloroform or diethylether.
[12] The method according to claim 7, wherein the reacting is performed using dimethylacetamide, dimethylformamide, diethylether, dichloromethane, tetrahy- drofuran or a mixture thereof.
[13] The method according to claim 6, wherein the reacting is performed in presence
of N-CS-dimethylaminopropy^-N-ethylcarbodiimide hydrochloride and
N,N-dimethylaminopyridine.
[14] The method according to claim 5, wherein the reacting for alkylation is performed in presence of iodomethane.
[15] A chemical sensor device, comprising a sensor membrane including a brush polymer compound represented by Formula I and having a chemical sensor function.
[16] The chemical sensor device according to claim 15, wherein the sensor membrane is an ion selective membrane.
[17] A functional brush polymer precursor compound represented by Formula IX below:
Formula IX
100, a + b = 100,
Y is H, a C1^20 alkyl group, -ZPh(Q5T) or -WR3N+[R4R5R6]X ,
Q is trifluoroacetyl,
T is H, -R*OH, -R*CHO, -R*COOH, -R*COOR, -R*NHCOR or -R*CONHR, in which R* is H or a C1^50 alkyl group,
X is F, Cl, Br or I, and
Z and W, which are identical to or different from each other, are an aliphatic or aromatic derivative selected from the group consisting of -CH2SROCO-, -CH2
SRCOO-, -CH2SRO-, -CH2SRNHCO-, -CH2SROCO(CH2)2OCO-, -CH2SRCO-, -
CH2SO2ROCO-, -CH2SO2RCOO-, -CH2SO2RO-, -CH2SO2RNHCO-, -CH2SO2
ROCO(CH2)2OCO-, -CH2SO2RCO-, -OCOROCO-, -OCORCOO-, -OCORO-, -
OCORNHCO-, -OCOROCO(CH2)2OCO-, -OCORCO-, -COOROCO-, -
COORCOO-, -COORO-, -COORNHCO-, -COOROCO(CH2)2OCO-, -
COORCO-, -OROCO-, -ORCOO-, -ORO-, -ORNHCO-, -OROCO(CH2)2OCO-,
-ORCO-, -NHROCO-, -NHRCOO-, -NHRO-, -NHRNHCO-, -NHROCO(CH2)2
OCO-, -NHRCO-, -CH2ROCO-, -CH2RCOO-, -CH2RO-, -CH2RNHCO-, -CH2
ROCO(CH2)2OCO-, -CH2RCO-, -OC6H4ROCO-, -OC6H4RCOO-, -OC6H4RO-, -
OC6H4RNHCO-, -OC6H4ROCO(CH2)2OCO-, -OC6H4RCO-, -OC6H4 COOROCO- , -OC6H4COORCOO-, -OC6H4COORO-, -OC6H4COORNHCO-, -OC6H4 COOROCO(CH2)2OCO-, -OC6H4COORCO-, -OC6H4CONHROCO-, -OC6H4 C0NHRC00-, -OC6H4CONHRO-, -OC6H4CONHRNHCO-, -OC6H4 CONHROCO(CH2)2OCO-, and -OC6H4CONHRCO-, in which R is H or a C1^20 alkyl group.
[18] A coating agent comprising a brush polymer represented by Formula I.
[19] Use of the brush polymer compound of claim 1 for sensing an ion.
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| KR10-2008-0017952 | 2008-02-27 | ||
| KR1020080017952A KR100934125B1 (en) | 2008-02-27 | 2008-02-27 | Brush polymer compound, preparation method thereof and chemical sensor device using same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025990A1 (en) * | 1996-12-09 | 1998-06-18 | Daiso Co., Ltd. | Copolyether and solid polymer electrolyte |
| JP2002308985A (en) * | 2001-04-09 | 2002-10-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Polyether-based polymer compound, ion conductive polymer composition obtained by using the same and electrochemical device |
| WO2004113443A1 (en) * | 2003-06-19 | 2004-12-29 | Daiso Co., Ltd. | Crosslinked polymer electrolyte and use thereof |
| JP2005011663A (en) * | 2003-06-19 | 2005-01-13 | Daiso Co Ltd | Cross-linked polymer electrolyte and its use |
| KR100798596B1 (en) * | 2006-12-21 | 2008-01-28 | 포항공과대학교 산학협력단 | Brush polyether-based polymer having chemical sensing capability, preparation thereof and chemical sensor comprising the polymer |
-
2008
- 2008-02-27 KR KR1020080017952A patent/KR100934125B1/en not_active IP Right Cessation
- 2008-06-16 WO PCT/KR2008/003378 patent/WO2009107902A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998025990A1 (en) * | 1996-12-09 | 1998-06-18 | Daiso Co., Ltd. | Copolyether and solid polymer electrolyte |
| JP2002308985A (en) * | 2001-04-09 | 2002-10-23 | Dai Ichi Kogyo Seiyaku Co Ltd | Polyether-based polymer compound, ion conductive polymer composition obtained by using the same and electrochemical device |
| WO2004113443A1 (en) * | 2003-06-19 | 2004-12-29 | Daiso Co., Ltd. | Crosslinked polymer electrolyte and use thereof |
| JP2005011663A (en) * | 2003-06-19 | 2005-01-13 | Daiso Co Ltd | Cross-linked polymer electrolyte and its use |
| KR100798596B1 (en) * | 2006-12-21 | 2008-01-28 | 포항공과대학교 산학협력단 | Brush polyether-based polymer having chemical sensing capability, preparation thereof and chemical sensor comprising the polymer |
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