KR20120065848A - Improved preparation of metal ion imprinted microporous polymer particles - Google Patents
Improved preparation of metal ion imprinted microporous polymer particles Download PDFInfo
- Publication number
- KR20120065848A KR20120065848A KR1020100127165A KR20100127165A KR20120065848A KR 20120065848 A KR20120065848 A KR 20120065848A KR 1020100127165 A KR1020100127165 A KR 1020100127165A KR 20100127165 A KR20100127165 A KR 20100127165A KR 20120065848 A KR20120065848 A KR 20120065848A
- Authority
- KR
- South Korea
- Prior art keywords
- monomer
- polymer particles
- solvent
- ratio
- microporous polymer
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 119
- 239000002245 particle Substances 0.000 title claims abstract description 97
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title description 9
- 239000000178 monomer Substances 0.000 claims abstract description 149
- 239000002904 solvent Substances 0.000 claims abstract description 74
- 239000003381 stabilizer Substances 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 150000002500 ions Chemical class 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 19
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001431 copper ion Inorganic materials 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- -1 C 6 hydrocarbons Chemical class 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 7
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229940071826 hydroxyethyl cellulose Drugs 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- OIEWLITYBUYJOH-UHFFFAOYSA-N 2,3-bis(ethenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C=C)=C1C=C OIEWLITYBUYJOH-UHFFFAOYSA-N 0.000 claims description 2
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 claims description 2
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 claims description 2
- AOIDYWIUVADOPM-UHFFFAOYSA-N 2-hydroxyethyl 2,3-dimethylbut-2-enoate Chemical compound CC(C)=C(C)C(=O)OCCO AOIDYWIUVADOPM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 19
- 238000000926 separation method Methods 0.000 description 15
- 239000012798 spherical particle Substances 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 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 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QYPPRTNMGCREIM-UHFFFAOYSA-N methylarsonic acid Chemical compound C[As](O)(O)=O QYPPRTNMGCREIM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/18—Suspension polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/128—Polymer particles coated by inorganic and non-macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
- C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/08—Homopolymers or copolymers of acrylic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
Abstract
Description
The present invention relates to a method for reducing solvent / monomer raw material ratios that effectively maintains adsorptivity, selectivity, particle structure and size, but in terms of economics, determines the productivity of metal ion- imprinted polymer (MIP) manufacturing processes.
Environmental pollution is a serious problem around the world. One of the main causes of such environmental pollution is heavy metal ions contained in industrial wastewater. Heavy metal ions released into the natural environment tend to accumulate in living organisms, which can adversely affect the ecosystem. Filtration, chemical precipitation, neutralization, ion chelation, and adsorption are used to remove these toxic ions. Among these methods, adsorption is generally preferred in consideration of efficiency, ease of operation, selectivity, and price.
Molecular imprinting is one of the emerging technologies in the field of selective adsorption. The ability of the selective adsorption to recognize target molecules / ions is due to the addition of corresponding template molecules / ions and the resulting extraction, imparting high selective separation properties for the target material. Such molecular imprinting techniques are used in a variety of fields, including drug delivery, separation and screening of biological mixtures, membranes for biological molecules and proteins in aqueous media, and detection and observation of uranium.
However, the basic idea of applying such molecular imprinting polymer technology to the selective separation of heavy metal ions has been presented very recently. Currently, research is being conducted in several advanced countries, such as the United States, Japan, and Sweden. Recently, the scope of research has been further expanded. The Mosbach group of the University of Lund, Sweden, reported the selective separation effect of several types of similar structural compounds by molecular imprinting. Murray Group of the University of Maryland, U.S., synthesized ion-imprinted polymers to produce Pb (II), Cd (II), Li (II), Na (II), Mg (II), Ca (II), Cu (II), Zn ( II), selective separation characteristics for metal ions such as Hg (II) was reported. Fish Group of Lawrence Berkely Laboratories in the United States confirmed the selective separation of Zn (II) ions using triazacyclononane ligands. Recently, Japan has been conducting research on separation characteristics using metal ion imprinting at Kyushu University.
As a heavy metal ion separator having a function similar to the present technology, chelated ion exchange resins are manufactured in the United States, Japan, China, and exported to overseas countries. In the US, DOW is applying a chelate type ionic resin known under the trade name DOWEX to separate nickel during the cobalt purification process. Invitrongen of the United States is also applied to the nickel separation process under the trade name Probond, which has a separation property for Ni ions. Amberlate, a chelating ion exchange resin from Rohm and Haas of the United States, is being applied to the process of separating metal ions. Chelated ion exchange resins are manufactured and sold under the trade name DIAION at Mitsubishi Chemical in Japan. As described above, the chelate type ion exchange resin manufactured and sold in the United States or Japan is currently applied in various forms in the process, but the selectivity is not so excellent and is limited to the separation of some metal ions. In this regard, the present inventors can easily adjust the number of adsorption sites compared to the general ion exchange resin, the adsorption power is very good, can be given arbitrarily according to the intended use, the regeneration effect is excellent and economically excellent, It has been developed as a patent application No. 10-2009-008954 by developing a method for producing a porous stamping polymer particles that can separate specific heavy metal ions.
In the production of polymer particles through suspension polymerization, the raw material ratio of solvent / monomer (hereinafter also referred to as 'S / M ratio') is a very important factor that determines the productivity of the manufacturing process from the viewpoint of economics. For industrial production, the reduction of the solvent / monomer raw material ratio is a problem that must be achieved. To date, there have been no studies on the method for reducing the raw material ratio of solvent / monomer for determining the productivity in the molecular imprinting technology, particularly in the production of metal ion imprinted polymer particles capable of selectively separating heavy metal ions. .
The present inventors have developed a method for producing spherical metal ion-engraved polymer particles which are economically superior and can effectively separate specific heavy metal ions by reducing the solvent / monomer raw material ratio for industrial production (mass production). Reached.
SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a porous polymer of metal ion engraving having excellent process economics by reducing a solvent / monomer ratio.
It is still another object of the present invention to provide a method for effectively preparing a spherical metal ion imprinted porous polymer by revealing a correlation between the concentration of a stabilizer aqueous solution and a solvent / monomer ratio for a specific metal.
In order to achieve the above object, the present invention,
Suspension polymerization reaction of a stabilizer aqueous solution and a porous solvent with a metal salt-acid monomer complex solution to obtain a polymer containing metal ions, and then removing metal ions from the polymer In the method of preparing porous polymer particles, the metal salt-acid monomer complex solution is prepared by mixing a metal salt solution, an acidic monomer, a basic monomer, a crosslinking agent, and an initiator, and by increasing the concentration of the stabilizer, a solvent system (water and a porous solvent solvent). It provides a method for producing a metal ion-engraved microporous polymer particles, characterized in that the ratio of the total amount) / monomer system (the total amount of the monomer and the crosslinking agent).
According to the present invention, the stabilizer is selected in the range of 1 to 15% by weight based on the total weight of the monomers such that the ratio of the solvent system (total amount of water and porous agent solvent) / monomer system (total amount of the monomer and crosslinking agent) is 2 to 15. Can be.
In addition, the present invention is a copper ion imprint comprising the step of suspending polymerization reaction of a stabilizer aqueous solution and a porous solvent with a copper salt-acid monomer complex solution to obtain a polymer containing copper ions, and then removing copper ions from the polymer In the method for producing microporous polymer particles, the copper salt-acid monomer complex solution is prepared by mixing a copper salt solution, an acidic monomer, a basic monomer, a crosslinking agent and an initiator, and a polymerization temperature of the suspension reaction is 70 ° C., and a stabilizer. Provided is a method for producing a copper ion-engraved microporous polymer particle, wherein the concentration and the ratio of solvent system / monomer are selected from the table below.
In addition, the present invention by suspension polymerization reaction of the stabilizer aqueous solution and the porous solvent with a lead salt-acid monomer complex solution to obtain a polymer containing lead ions, the lead ion imprinting comprising the step of removing lead ions from the polymer In the method for producing microporous polymer particles, the copper salt-acid monomer complex solution is prepared by mixing a lead salt solution, an acid monomer, a basic monomer, a crosslinking agent and an initiator, and a polymerization temperature of the suspension reaction is 70 ° C., and a stabilizer concentration. It provides a method for producing a lead ion-engraved microporous polymer particles with a solvent-based / monomer ratio is selected from the table below.
In addition, the present invention by suspension polymerization of the stabilizer aqueous solution and the porous solvent with a nickel salt-acid monomer complex solution to obtain a polymer containing nickel ions, and then removing the nickel ions from the polymer In the method for producing microporous polymer particles, the nickel salt-acid monomer complex solution is prepared by mixing a nickel salt solution, an acid monomer, a basic monomer, a crosslinking agent and an initiator, and a polymerization temperature of the suspension reaction is 70 ° C., and a stabilizer. It provides a method for producing nickel ion-engraved microporous polymer particles wherein the concentration and the ratio of solvent system / monomer are selected from the table below.
In addition, the present invention by suspension polymerization reaction of the stabilizer aqueous solution and the porous solvent with a zinc salt-acid monomer complex solution to obtain a polymer containing zinc ions, zinc ion engraving comprising the step of removing zinc ions from the polymer In the method for producing microporous polymer particles, the zinc salt-acid monomer complex solution is prepared by mixing a zinc salt solution, an acid monomer, a basic monomer, a crosslinking agent and an initiator, and a polymerization temperature of the suspension reaction is 70 ° C., and a stabilizer. It provides a method for producing zinc ion-engraved microporous polymer particles, wherein the concentration and the ratio of solvent system / monomer are selected from the table below.
According to the manufacturing method of the present invention, the solvent-based / monomer system that determines the industrial production by revealing the correlation between the stabilizer concentration and the solvent / monomer system ratio during the production of metal ion- imprinted microporous polymer particles through suspension polymerization (S / M) can reduce the ratio. Thus, well-processed spherical particles can be mass produced in a more economical way.
In addition, according to the manufacturing method of the present invention, while reducing the ratio of the solvent-based / monomer system can increase the process economics, the adsorption and selectivity of the metal ion-engraved microporous polymer particles are very excellent, the regeneration effect is also remarkable.
1 is a copper ion imprinted in Example 1-1 with an S / M ratio of 7.1 and a concentration of a stabilizer aqueous solution of (a) 1% by weight, (b) 2.5% by weight, and (c) 3.5% by weight. Scanning electron microscope photograph of microporous polymer particles.
Figure 2 is a copper ion stamped in Example 1-1 with an S / M ratio of 4.7 and the concentration of the stabilizer aqueous solution (a) 1 wt%, (b) 1.5 wt%, (c) 2.5 wt% Scanning electron microscope photograph of microporous polymer particles.
3 is a copper ion imprinted in Example 1-1 with an S / M ratio of 3.5 and a concentration of stabilizer aqueous solution of (a) 1 wt%, (b) 3 wt%, (c) 5 wt% Scanning electron microscope photograph of microporous polymer particles.
4 is a copper ion stamped in Example 1-1 with an S / M ratio of 2.7 and a concentration of stabilizer aqueous solution of (a) 2.5% by weight, (b) 5% by weight, and (c) 7% by weight. Scanning electron microscope photograph of microporous polymer particles.
5 is a graph showing the optimum concentration of the stabilizer aqueous solution for the production of spherical porous stamping polymer at different S / M ratio.
6 is a scanning electron microscope photograph of the shape of the porous stamping polymer particles prepared in Example 2-2.
FIG. 7 shows the results of measuring specific surface areas of copper ion-engraved microporous polymer particles prepared at different S / M ratios in Example 1-1.
Figure 8 is a graph showing the results of measuring the adsorption capacity according to the concentration of the copper ion-engraved microporous polymer particles prepared in different S / M ratio in Example 1-1.
FIG. 9 is a graph showing the relationship between pH and adsorption capacity of copper ion-engraved microporous polymer particles prepared at different S / M ratios in Example 1-1.
FIG. 10 shows the adsorption capacity of copper ion imprinted microporous polymer particles prepared at different S / M ratios in Example 1-1 as a function of time.
FIG. 11 is a graph showing the results of measuring adsorption capacities for copper ion-engraved microporous polymer particles prepared at different S / M ratios in Example 1-1.
12 is a scanning electron micrograph of the lead ion-engraved microporous polymer particles prepared in Example 2-1. (a) S / M ratio 14.2, (b) S / M ratio 7.1, (c) S / M ratio 4.7, and (d) S / M ratio 4.5.
13 is a scanning electron micrograph of the lead ion-engraved microporous polymer particles prepared in Example 2-2.
FIG. 14 is a scanning electron microscope photograph of the nickel ion-engraved microporous polymer particle prepared in Example 3. FIG.
15 is a scanning electron micrograph of the zinc ion-engraved microporous polymer particles prepared in Example 4. FIG.
EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
Preparation of Metal Ion Imprinted Microporous Polymer Particles
Method for producing a metal ion-engraved microporous polymer particles according to the present invention is obtained by obtaining a polymer containing metal ions by suspension polymerization reaction of a stabilizer aqueous solution and a porous solvent with a metal salt-acid monomer complex solution Removing metal ions from one polymer, wherein the metal salt-acid monomer complex solution is prepared by mixing a metal salt solution, an acidic monomer, a basic monomer, a crosslinking agent and an initiator.
The metal salt solution may be prepared by mixing a metal salt and a solvent. The metal salt may be a salt of a metal selected from the group consisting of Cu, Pb, Cd, Li, Na, Mg, Ca, Zn, Hg, and Fe as a metal salt including a metal ion to be selectively separated, and preferably CuSO 4 can be used.
As a solvent for preparing a metal salt solution by mixing with a metal salt, a solvent selected from the group consisting of water, C 1 to C 6 alcohols and C 1 to C 6 hydrocarbons may be used.
The acidic monomer may be an acrylate monomer, a styrene monomer or a silane monomer containing a carboxyl group. Preferably, acrylic acid, methacrylic acid, ethacrylic acid, vinyl benzoic acid, divinylbenzoic acid, ethylene glycol dimethyl methacrylate, or the like may be used. Can be used.
The basic monomer may be a vinylpyridine-based monomer, and is preferably selected from the group consisting of 4-vinylpyridine and 2-vinylpyridine. In the present invention, the basic monomer plays a role of assisting the binding of the metal ion and the acidic monomer. Specifically, in the formation of a complex in which an acidic monomer containing a carboxyl group and a metal ion are combined, a separate salt forming a metal salt-acidic monomer complex is formed in the general aqueous solution because the carboxyl group of the acidic monomer containing a carboxyl group is not easily ionized. Although a process is required, when the basic monomer is added as in the present invention, the basic monomer can be easily ionized by drawing positive charge (H + ) from the carboxyl group of the acidic monomer to form a metal salt-acidic monomer complex. As described above, in the present invention, by using the basic monomer when forming the metal salt-acid monomer complex, the synthesis process of the metal ion-containing monomer and the polymerization process thereof may be performed at a time without performing a separate process. As a result, the reaction time can be greatly shortened in the preparation of the porous-marked polymer particles, and it is very economically useful because it can be obtained in high yield.
According to the invention, the ratio of the basic monomers to the acidic monomers is preferably from 0.01 to 100. When the ratio of the basic monomer to the acid monomer is less than 0.01, the formation of a complex with the metal ion will be difficult because the lack of the basic monomer which can help the ionization of the acid monomer is almost no ionization of the acid monomer. On the contrary, when the ratio of the basic monomer to the acidic monomer is greater than 100, the adsorption capacity and selectivity may be reduced. This is because the amount of acidic monomers that can form complexes with metal ions is reduced.
As the crosslinking agent according to the present invention, an acrylate monomer, a styrene monomer or a silane-based monomer may be used, and ethylene glycol dimethacrylate may be preferably used.
As the initiator according to the present invention, a redox-based initiator or a peroxide-based initiator may be used, and preferably, azodiisobutyronitrile may be used.
Stabilizers according to the present invention may be used hydroxy ethyl cellulose, modified hydroxy ethyl cellulose, poly (vinyl alcohol), poly (ethylene oxide), polyvinyl methyl ether, polymethacrylic acid and the like.
The porous solvent according to the present invention refers to a solvent that induces pore formation during polymer polymerization, and may be one selected from the group consisting of toluene, benzene, xylene, C 1 to C 6 alcohols and C 1 to C 6 hydrocarbons. May be, but is not limited thereto. By manufacturing a porous structure having a large surface area using a porous solvent, it is possible not only to maintain the selectivity to a specific metal but also to exhibit a high adsorption force and a high separation rate, thereby exhibiting a very excellent effect in the separation process.
Effect of Stabilizer Concentration on Solvent / Meter Ratio (S / M) Ratio
According to the method for producing a metal ion-engraved microporous polymer particle according to the present invention, it is possible to increase the concentration of the stabilizer to reduce the ratio of the solvent system / monomer system. The ratio of solvent system / monomer is determined by the amount of solvent and the amount of monomer. The solvent according to the invention comprises water and a porous solvent and the monomer according to the invention comprises an acidic monomer, a basic monomer and a crosslinking agent. That is, the ratio of solvent system / monomer is the ratio of “total amount of water and porous agent solvent” belonging to the solvent system and “total amount of acidic monomers, basic monomers and crosslinking agents belonging to the monomer system”. This solvent / monomeric ratio is very closely related to the supply of raw materials in the manufacturing process and thus determines the productivity of the process in terms of economics.
In one embodiment of the present invention, the concentration of the stabilizer may be increased to reduce the solvent / monomer ratio. The concentration of the stabilizer and the ratio of the solvent system / monomer may be inversely related, and the stabilizer may be selected in the range of 1 to 15% by weight based on the total weight of the monomers such that the ratio of the solvent system / monomer is 2 to 15. Stabilizers play a very important role in the formation and aggregation of particles. If the amount of the stabilizer is less than 1% by weight, the amount of particles is not spherical but aggregates with other particles. In addition, when the amount of the stabilizer is excessively high, in excess of 15% by weight, a problem may occur such that the size of the particles is rather reduced or solidified before having a uniform spherical particle shape. If the solvent / monomer ratio is in the range of 2 to 15, the efficiency (adsorption capacity, etc.) of the metal ion- imprinted microporous polymer particles is good, but the ratio of the solvent / monomer system determines the economics of the process in terms of raw material supply. For example, a person skilled in the art may reduce the process concentration within 2-15 by adjusting the stabilizer concentration in consideration of efficiency and economical efficiency.
In addition, the ratio of the solvent system / monomer system of the present invention differs in the optimum numerical range depending on the metal ion used. More specifically, in the case of copper ions, the ratio of solvent system / monomer is preferably in the range of 2.7 to 7.1, and in the case of lead ions, the ratio of solvent system / monomer is in the range of 4.5 to 14.2, In this case, the range of 2.5 to 6.3 is preferable, and for nickel ions, the range of 2.1 to 6.4 is preferable.
In particular, in the method for producing copper ion-engraved microporous polymer particles according to the present invention, in order to prepare spherical particles of uniform size, the ratio of the stabilizer concentration and the solvent system / monomer system is preferably selected from the following table.
In addition, in the method for producing lead ion-engraved microporous polymer particles according to the present invention, in order to prepare spherical particles having a uniform size, the ratio of the stabilizer concentration and the solvent system / monomer system is preferably selected from the following table.
In addition, in the method for producing nickel ion-engraved microporous polymer particles according to the present invention, in order to prepare spherical particles having a uniform size, the ratio of the stabilizer concentration and the solvent-based / monomer system is preferably selected from the following table.
In addition, in the method for producing zinc ion-engraved microporous polymer particles according to the present invention, in order to prepare spherical particles having a uniform size, the ratio of the stabilizer concentration and the solvent-based / monomer system is preferably selected.
In the production method of the metal ion-engraved microporous polymer particles of the present invention, the reaction temperature of the suspension polymerization can be arbitrarily selected by those skilled in the art, but in general, the suspension polymerization reaction according to the present invention is 60? 90 It is preferable to carry out at ° C, and particularly preferably carried out at 70 ° C.
Hereinafter, the present invention will be described in detail with reference to examples, but these examples are only presented to more clearly understand the present invention, and are not intended to limit the scope of the present invention. It will be determined within the scope of the technical spirit of the claims.
Example 1 Preparation of Copper (II) Imprinted Microporous Polymer Particles
Example 1-1: Effect of Stabilizer Concentration on S / M Ratio
The CuSO 4? 5H 2 O 0.625 g was dissolved in deionized water to prepare an aqueous solution of Cu 2+ ions. In the aqueous solution of Cu 2+ ions, methacrylic acid (MAA, Sigma-Aldrich) as an acidic monomer, 4-vinylpyridine (4-VP, Sigma-Aldrich) as a basic monomer, ethylene glycol dimethacrylate (EGDMA, Sigma) as a crosslinking agent Azodiisobutyronitrile (AIBN, Sigma-Aldrich) in turn as an initiator and stirred sufficiently for 2 hours to form a complex of Cu 2+ and methacrylic acid. Hydroxy cellulose (HEC) was added to water and stirred until it completely dissolved at about 70 ℃ to prepare a stabilizer aqueous solution. The composition of Cu 2+ , MAA, 4-VP, EGDMA was 1: 2: 2: 8 in molar ratio and the amount of AIBN was 2% by weight of the total monomer amount in deionized water.
The suspension polymerization was carried out in a 500 mL three-necked flask equipped with a stirrer operating at a speed of 200 rpm for 2 hours at room temperature. 10 mL of toluene and the aqueous solution of stabilizer prepared above were added to the reactor. The polymerization reaction was carried out at a stirring speed of 250 rpm, stirred for 15 minutes at room temperature and then maintained in a nitrogen atmosphere for 6 hours at 70 ℃. After completion of the polymerization reaction, the finished particles were continuously washed with demineralized water and acetone was used to remove monomers that did not react with impurities. The washed particles were dried under vacuum for 24 hours. The metal ions adsorbed to the polymer particles were stirred in an aqueous solution of 1 mol of nitric acid for 1 hour and filtered. This process was repeated 20 times until the metal ions were completely removed, followed by washing in water and drying in vacuo.
The experimental conditions of Example 1 are shown in Table 5.
stabilizator
(weight%)
(ml)
(ml)
(ml)
(ml)
(ml)
7.1
4.7
3.5
2.7
1 to 4 are scanning electron micrographs taken of copper ion-engraved microporous polymer particles prepared under the above conditions, and FIG. 5 is a stabilizer aqueous solution for preparing spherical porous stamping polymer at a ratio of S / M. Is a graph showing the optimal concentration. 5, it can be seen that as the concentration of the stabilizer increases, the ratio of the solvent system (total amount of water and porous agent solvent) / monomer system (total amount of the monomer and crosslinking agent) decreases.
Example 1-2: Effect of Temperature on S / M Ratio
Further experiments were carried out in the same manner as in Example 1-1, except that the polymerization reaction was carried out at 70 ° C, 80 ° C and 85 ° C with a ratio of S / M of 2.7 and a stabilizer of 3.5% by weight. FIG. 6 shows copper ion-imprinted microporous polymer particles prepared at (a) 70 ° C., (b) 80 ° C., and (c) 85 ° C. when the S / M ratio is 2.7 and the stabilizer (HEC) is 3.5 wt%. Scanning electron microscope photograph taken. From the photograph, it can be confirmed that the production rate of the spherical particles at the reaction temperature of 70 ° C. did not reach the production rate when the temperature increased to 80 ° C.
Experimental Example 1: Specific Surface Area Experiment
The copper ion- imprinted microporous polymer particles prepared in Example 1 are shown in Table 6 using BET surface area and total pore volume. As shown in Table 6, it can be seen that as the S / M ratio decreases, the specific surface area decreases, and the total pore volume decreases. This result is because, as the S / M ratio increases, the concentration of toluene which imparts porosity to the particles increases. The specific surface area of the range shown in Table 6 below is a numerical range sufficient to adsorb copper ions.
Experimental Example 2: Adsorption and Selectivity Experiment
Adsorption of metal ions in an aqueous solution containing metal ions was measured through batch experiments, and the adsorption capacity was measured according to the initial concentration of metal ions and the pH concentration of the medium. 0.1 g of copper ion-engraved microporous polymer particles prepared in Example 1-1 were placed in a 10 mL test tube and sealed in a 5 mL solution containing 2.5 to 70 ppm of Cu 2+ . The pH was adjusted to the desired value between 2.0 and 7.0 using 100 mM sodium hydroxide and 100 mM hydrochloric acid aqueous solution. The mixture was stirred at room temperature for 4 hours using a magnetic rod. The particles were filtered through a polyethylene membrane filter (Sumplep LCR 25-LG, Nippon Millipore, Japan). After filtering the metal ions absorbed in the particles, the concentration of the remaining aqueous solution was measured using a Hitachi 180-70 polarized Zeeman atomic absorption spectrophotometer (AAS). The absorption capacity (mmol / g) efficiency of metal ions is calculated from the following equation:
Q = (C o -C e ) V / W (1)
Where Q is the metal ion absorption capacity of the polymer (mg? G −1 ); C o and C e are the initial ionic concentration in the aqueous solution and the concentration after adsorption (mg? L −1 ), respectively, and V is the volume of the aqueous solution. (mL); W is the amount of polymer (g))
In addition, experiments using Cu 2+ , Ni 2+ and Zn 2+ were performed in parallel to observe the tendency of selective adsorption of the imprinted particles. Adsorption experiments were carried out using 0.1 g of copper ion-engraved microporous polymer particles prepared in Example 1 in 5 mL of three kinds of ionic mixtures. After the adsorption equilibrium was reached, the metal ions remaining in the solvent were measured using AAS.
* Results and Analysis
(1) Correlation between S / M Ratio and Adsorption Capacity
The adsorption tendency of the copper ion- imprinted microporous polymer particles prepared in Example 1-1 was tested at pH 6.2. As shown in FIG. 8, the amount of adsorbed metal ions per unit mass of copper ion-engraved microporous polymer particles prepared at different S / M increased as the concentration of initial metal ions increased, and more than 350 mmol / g. The increase of the metal ions adsorbed by the catalysts no longer appeared. The maximum adsorption capacities of the copper ion imprinted microporous polymer particles prepared at different S / Ms are almost similar. These results demonstrate that there is no correlation between the S / M ratio and the maximum adsorption capacity.
(2) Correlation between adsorption capacity and S / M ratio according to pH
Adsorption capacities were measured for solutions from
(3) adsorption dynamics
Pore volume is an important variable controlling the adsorption kinetics of metal ion imprinted microporous polymer particles. FIG. 10 shows the adsorption capacity of the copper ion imprinted microporous polymer particles prepared in Example 1-1 prepared at different S / M ratios as a function of time. It can be seen from FIG. 10 that as the S / M ratio is reduced to decrease the void volume, the adsorption time to reach equilibrium was longer.
(4) selective separation tendency
In order to examine the selective separation tendency of the copper ion-engraved microporous polymer particles prepared in Example 1-1 prepared at different S / M ratios, Cu 2+ , Ni 2+ to the imprinted polymer in aqueous solution at pH 6.2 , Zn 2+ adsorption tendency was investigated. As shown in FIG. 11, the copper ion concentration was saturated at about 100 μmol / g, and no correlation between the specific S / M ratio and the selective separation tendency was observed.
Example 2: Preparation of Lead (II) Imprinted Microporous Polymer Particles
Example 2-1: Effect of Stabilizer Concentration on S / M Ratio
0.828 g of Pb (NO 3 ) 2 is used, the molar ratio of MAA, 4-VP and EGDMA is 1: 1: 4, Pb 2+ is 2.5 mmol, and the S / M ratio is 14.2, 7.1, 4.7, 4.5 Except for one, it was carried out in the same manner as in Example 1-1.
The optimal stabilizer concentrations at different S / M ratios according to this example are shown in Table 7.
(weight%)
(ml)
(ml)
(ml)
(ml)
In the preparation of lead ion-engraved microporous polymer particles from the above experimental results, the optimum stabilizer concentrations were different at different S / M ratios, and each of (1) 2% by weight at 14.2 S / M ratio; (2) 2.5 wt% at S / M ratio 7.1, (3) 2.5 wt% at S / M ratio 4.7; (4) It can be confirmed that the S / M 4.5 in 5% by weight. It can be deduced that increasing the stabilizer concentration can reduce the S / M ratio from the experimental results. An electron scanning microscope photograph of the lead ion-engraved microporous polymer particles prepared in this example is shown in FIG. 12.
Example 2-2: Influence of temperature on S / M ratio
The polymerization was further carried out in the same manner as in Example 2-1, except that the polymerization reaction was performed at 70 ° C. and 80 ° C., respectively, when the S / M ratio was 3.5, 15 ml of toluene was used, and the HEC concentration was 10% by weight. FIG. 13 is a scanning electron microscope photograph of the lead ion-engraved microporous polymer particles prepared at (a) 70 ° C. and (b) 80 ° C. FIG. From the above picture, when the temperature was increased from 70 ° C. to 80 ° C. at the same S / M ratio, the particle size was reduced, but it can be seen that the amount of the microporous polymer particles produced was greater. It can also be seen that at higher temperatures, more spherical particles are produced, which increases the reaction kinetics as the temperature increases in the free radical polymerization reaction, leading to chain growth and termination before the particles aggregate at increased temperatures. This is because it produces spherical particles.
Example 3: Preparation of Nickel (II) Imprinted Microporous Polymer Particles
? Using NiSO 4 6H 2 O 0.657 g, and the metal ion, MAA, 4-VP and the molar ratio of EGDMA: except that the and 8, S / M ratio of 6.4, 4.3, 3.2, 2.1: 1: 2 And the same as in Example 1-1.
The optimal stabilizer concentrations at different S / M ratios according to this example are shown in Table 8.
stabilizator
(weight%)
(ml)
(ml)
(ml)
(ml)
Example 4 Preparation of Zinc (II) Imprinted Microporous Polymer Particles
287.56 g / mol-2.5 mmol-10 -3 = 0.719 g of Zn 2+ (ZnSO 4 -7H 2 O) was used, and the molar ratio of metal ions, MAA, 4-VP and EGDMA was 1: 1: 2: 8 , And was carried out in the same manner as in Example 1-1 except that the S / M ratio was set to 6.3, 4.2, 3.2, and 2.5.
The optimal stabilizer concentrations at different S / M ratios according to this example are shown in Table 9.
(weight%)
(ml)
(ml)
(ml)
(ml)
Claims (21)
The metal salt-acid monomer complex solution is prepared by mixing a metal salt solution, an acidic monomer, a basic monomer, a crosslinking agent and an initiator,
And increasing the concentration of the stabilizer to reduce the ratio of solvent system (total amount of water and porous agent solvent) / single system (total amount of monomers and crosslinking agent).
The stabilizer is selected in the range of 1 to 15% by weight based on the total weight of the monomers such that the ratio of the solvent system (total amount of water and porous agent solvent) / monomer system (total amount of monomer and crosslinking agent) is 2 to 15. Method of producing a metal ion-engraved microporous polymer particles.
The suspension polymerization reaction is a method of producing a metal ion-engraved microporous polymer particles, characterized in that carried out in the range of 60 ~ 90 ℃.
The reaction temperature of the suspension polymerization is a method for producing a metal ion-engraved microporous polymer particles, characterized in that 70 ℃.
The metal salt solution is a metal salt; And water, a C 1 to C 6 alcohol, and a solvent selected from the group consisting of C 1 to C 6 hydrocarbons.
The metal salt is a method of producing a metal ion-engraved microporous polymer particles, characterized in that the salt of the metal selected from the group consisting of Cu, Pb, Cd, Ni, Li, Na, Mg, Ca, Zn, Hg and Fe.
The acidic monomer is a method of producing a metal ion-engraved microporous polymer particles, characterized in that the carboxyl group-containing acrylate monomer, styrene monomer or silane monomer.
Wherein said acidic monomer is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, vinyl benzoic acid, divinylbenzoic acid and ethylene glycol dimethyl methacrylate.
The basic monomer is a method for producing a metal ion-engraved microporous polymer particles, characterized in that the vinylpyridine monomer.
The vinylpyridine monomer is a method for producing metal ion-engraved microporous polymer particles, characterized in that selected from the group consisting of 4-vinylpyridine and 2-vinylpyridine.
Method for producing a metal ion-engraved microporous polymer particles, characterized in that the ratio of the basic monomer to the acid monomer is 0.01 to 100.
The crosslinking agent is a method for producing a metal ion-engraved microporous polymer particles, characterized in that the acrylate monomer, styrene monomer or silane monomer.
The crosslinking agent is a method for producing a metal ion-engraved microporous polymer particles, characterized in that the ethylene glycol dimethacrylate.
Wherein the initiator is a redox-based initiator or a peroxide-based initiator.
The initiator is azodiisobutyronitrile (azodiisobutyronitrile) characterized in that the manufacturing method of the metal ion-engraved microporous polymer particles.
The stabilizer is selected from the group consisting of hydroxy ethyl cellulose, modified hydroxy ethyl cellulose, poly (vinyl alcohol), poly (ethylene oxide), polyvinyl methyl ether and polymethacrylic acid Method for producing microporous polymer particles.
The porous agent solvent is toluene, benzene, xylene, C 1 to C 6 alcohol and C 1 to C 6 hydrocarbons, characterized in that the method for producing a metal ion-engraved microporous polymer particles.
The copper salt-acid monomer complex solution is prepared by mixing a copper salt solution, an acidic monomer, a basic monomer, a crosslinking agent and an initiator,
The polymerization temperature of the suspension reaction is 70 ℃,
A ratio of the stabilizer concentration and the solvent-based / monomer system is selected from the table below.
The copper salt-acid monomer complex solution is prepared by mixing a lead salt solution, an acidic monomer, a basic monomer, a crosslinking agent and an initiator,
The polymerization temperature of the suspension reaction is 70 ℃,
The ratio of the stabilizer concentration and the solvent-based / monomer system is selected from the table below.
The nickel salt-acid monomer complex solution is prepared by mixing a nickel salt solution, an acid monomer, a basic monomer, a crosslinking agent and an initiator,
The polymerization temperature of the suspension reaction is 70 ℃,
The ratio of the stabilizer concentration and the solvent-based / monomer system is selected from the table below.
The zinc salt-acid monomer complex solution is prepared by mixing a zinc salt solution, an acid monomer, a basic monomer, a crosslinking agent and an initiator,
The polymerization temperature of the suspension reaction is 70 ℃,
The ratio of the stabilizer concentration and the solvent-based / monomer system is selected from the table below.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20100127165A KR101206826B1 (en) | 2010-12-13 | 2010-12-13 | Improved preparation of metal ion imprinted microporous polymer particles |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20100127165A KR101206826B1 (en) | 2010-12-13 | 2010-12-13 | Improved preparation of metal ion imprinted microporous polymer particles |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20120065848A true KR20120065848A (en) | 2012-06-21 |
KR101206826B1 KR101206826B1 (en) | 2012-11-30 |
Family
ID=46685435
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR20100127165A KR101206826B1 (en) | 2010-12-13 | 2010-12-13 | Improved preparation of metal ion imprinted microporous polymer particles |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR101206826B1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103254354A (en) * | 2013-05-24 | 2013-08-21 | 福州大学 | Cadmium ion imprinted adsorbent, and preparation method and application thereof |
CN103450394A (en) * | 2013-06-24 | 2013-12-18 | 西北大学 | Preparation method of copper ion imprinted polymer adsorbent |
WO2014188158A1 (en) * | 2013-05-23 | 2014-11-27 | The University Of Lincoln | Metals recovery method and polymer for use in metals re-covery and process for making such a polymer |
WO2019045551A3 (en) * | 2017-09-04 | 2019-04-18 | 서강대학교산학협력단 | Method for manufacturing 3-dimensional mesoporous graphene structure |
CN110407976A (en) * | 2018-04-27 | 2019-11-05 | 中国科学院过程工程研究所 | A kind of iron ion imprinted polymer and its preparation method and application |
US10610858B2 (en) | 2016-08-18 | 2020-04-07 | Sri International | Metal ion extraction from brines |
KR102200819B1 (en) * | 2019-07-30 | 2021-01-08 | 서울여자대학교 산학협력단 | Zinc ion imprinted polymer and the method for preparing thereof |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104128168A (en) * | 2014-02-19 | 2014-11-05 | 安徽科技学院 | Preparation method for chromium ion-imprinted silica gel |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU5859796A (en) | 1995-05-26 | 1996-12-11 | Igen, Inc. | Molecularly imprinted beaded polymers and stabilized suspens ion polymerization of the same in perfluorocarbon liquids |
KR100723919B1 (en) | 2006-02-16 | 2007-08-10 | 성균관대학교산학협력단 | Selective separation of heavy metal ion using the metal ion imprinted polymer(miip) |
KR100841421B1 (en) | 2007-06-20 | 2008-06-26 | 경북대학교 산학협력단 | Method for preparing microspherical molecular imprinted polymer |
-
2010
- 2010-12-13 KR KR20100127165A patent/KR101206826B1/en not_active IP Right Cessation
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014188158A1 (en) * | 2013-05-23 | 2014-11-27 | The University Of Lincoln | Metals recovery method and polymer for use in metals re-covery and process for making such a polymer |
CN103254354A (en) * | 2013-05-24 | 2013-08-21 | 福州大学 | Cadmium ion imprinted adsorbent, and preparation method and application thereof |
CN103254354B (en) * | 2013-05-24 | 2016-03-09 | 福州大学 | A kind of cadmium ion trace sorbent material and its preparation method and application |
CN103450394A (en) * | 2013-06-24 | 2013-12-18 | 西北大学 | Preparation method of copper ion imprinted polymer adsorbent |
US10610858B2 (en) | 2016-08-18 | 2020-04-07 | Sri International | Metal ion extraction from brines |
EP3500362A4 (en) * | 2016-08-18 | 2020-07-22 | SRI International | Metal ion extraction from brines |
US11014085B2 (en) | 2016-08-18 | 2021-05-25 | Exsorbtion Inc. | Concentrating lithium carbonate after regeneration of lithium sorbent |
WO2019045551A3 (en) * | 2017-09-04 | 2019-04-18 | 서강대학교산학협력단 | Method for manufacturing 3-dimensional mesoporous graphene structure |
CN110407976A (en) * | 2018-04-27 | 2019-11-05 | 中国科学院过程工程研究所 | A kind of iron ion imprinted polymer and its preparation method and application |
CN110407976B (en) * | 2018-04-27 | 2020-08-21 | 中国科学院过程工程研究所 | Iron ion imprinted polymer and preparation method and application thereof |
KR102200819B1 (en) * | 2019-07-30 | 2021-01-08 | 서울여자대학교 산학협력단 | Zinc ion imprinted polymer and the method for preparing thereof |
WO2021020630A1 (en) * | 2019-07-30 | 2021-02-04 | 서울여자대학교 산학협력단 | Zinc ion-imprinted polymer and preparation method therefor |
Also Published As
Publication number | Publication date |
---|---|
KR101206826B1 (en) | 2012-11-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101206826B1 (en) | Improved preparation of metal ion imprinted microporous polymer particles | |
Liu et al. | Rapid and efficient removal of heavy metal and cationic dye by carboxylate-rich magnetic chitosan flocculants: role of ionic groups | |
Wang et al. | Green multi-functional monomer based ion imprinted polymers for selective removal of copper ions from aqueous solution | |
Luo et al. | Recovery of lithium from wastewater using development of Li ion-imprinted polymers | |
KR100861452B1 (en) | Method for preparing surface-imprinted polyacrylate microsphere in the form of core-shell for the selective separation of heavy metal ion | |
CN107999037B (en) | Magnetic polymer adsorption material, preparation method and application | |
Li et al. | Removal of aqueous Hg (II) and Cr (VI) using phytic acid doped polyaniline/cellulose acetate composite membrane | |
CN107442082B (en) | A kind of magnetism polyacrylamide/alginic acid zirconium gel ball and its preparation method and application | |
Jiang et al. | Effect of solvent/monomer feed ratio on the structure and adsorption properties of Cu2+-imprinted microporous polymer particles | |
Cui et al. | Preparation and application of Aliquat 336 functionalized chitosan adsorbent for the removal of Pb (II) | |
He et al. | Design and fabrication of highly ordered ion imprinted SBA-15 and MCM-41 mesoporous organosilicas for efficient removal of Ni2+ from different properties of wastewaters | |
Song et al. | A bioinspired strategy towards super-adsorbent hydrogel spheres via self-sacrificing micro-reactors for robust wastewater remediation | |
JP2007217670A (en) | Selective separation of heavy metal ion using the metal ion imprinted polymer | |
CN109715288B (en) | Extraction of metal ions from brine | |
Wang et al. | Adsorption of copper ions by ion-imprinted simultaneous interpenetrating network hydrogel: thermodynamics, morphology and mechanism | |
Jing et al. | Free-standing large-mesoporous silica films decorated with lanthanum as new adsorbents for efficient removal of phosphate | |
Li et al. | Synthesis and application of a surface-grafted In (III) ion-imprinted polymer for selective separation and pre-concentration of indium (III) ion from aqueous solution | |
CN112897627A (en) | Method for removing heavy metal wastewater | |
Sun et al. | A novel modified carboxymethyl cellulose hydrogel adsorbent for efficient removal of poisonous metals from wastewater: Performance and mechanism | |
CN113908815B (en) | High-molecular modified adsorbent and preparation method and application thereof | |
CN111974366A (en) | Preparation and application of amphoteric carboxymethyl chitosan-based microspheres based on magnetic separation technology | |
CN108295812B (en) | Graphene oxide composite membrane for selectively removing metal ions in water, and preparation method and application thereof | |
KR101016231B1 (en) | Method for preparing porous imprinted polymer particles for the selective separation of heavy metal ions | |
Zheng et al. | Kapok fiber structure-oriented polyallylthiourea: Efficient adsorptive reduction for Au (III) for catalytic application | |
Li et al. | Experimental and DFT studies on highly selective separation of indium ions using silica gel/graphene oxide based ion-imprinted composites as a sorbent |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20151118 Year of fee payment: 4 |
|
LAPS | Lapse due to unpaid annual fee |