CN103992500A - Preparation method for Cr (III) ion composite imprinted polymer adsorbent - Google Patents
Preparation method for Cr (III) ion composite imprinted polymer adsorbent Download PDFInfo
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- CN103992500A CN103992500A CN201410191076.7A CN201410191076A CN103992500A CN 103992500 A CN103992500 A CN 103992500A CN 201410191076 A CN201410191076 A CN 201410191076A CN 103992500 A CN103992500 A CN 103992500A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 49
- 239000003463 adsorbent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002131 composite material Substances 0.000 title abstract description 4
- 150000002500 ions Chemical class 0.000 claims abstract description 48
- 102000008186 Collagen Human genes 0.000 claims abstract description 31
- 108010035532 Collagen Proteins 0.000 claims abstract description 31
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000011651 chromium Substances 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 4
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical group [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 4
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 229920001436 collagen Polymers 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 239000002798 polar solvent Substances 0.000 abstract 1
- 229910052804 chromium Inorganic materials 0.000 description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 230000003252 repetitive effect Effects 0.000 description 7
- 238000005201 scrubbing Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010985 leather Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IUMRWGYGZHKZKF-UHFFFAOYSA-N 2-aminoprop-2-enamide Chemical compound NC(=C)C(N)=O IUMRWGYGZHKZKF-UHFFFAOYSA-N 0.000 description 2
- -1 amino, carboxyl Chemical group 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 108010031480 Artificial Receptors Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method for a Cr (III) ion composite imprinted polymer adsorbent. The adsorbent takes Cr (III) ions as template ions, and adopts collagen and acrylic acid as difunctional monomers. In a polar solvent, N, N-methylene bisacrylamide and a micromolecular crosslinking agent undergo crosslinking, azodiisobutyronitrile is used as an initiator to initiate preparation of the Cr (III) ion composite imprinted polymer adsorbent. The adsorbent prepared by the invention has excellent selective absorption on Cr (III) ions, fast adsorption and elution rate, high elution efficiency, and can be recycled.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to the preparation method of the compound imprinted polymer adsorbent of a kind of Cr (III) ion.
Background technology
In leather industry, in existing tanning agent, containing chrome tanning agent, account for 70%～80%, so far, due to chrome-tanned every premium properties, not yet have any tanning agent can replace chrome tanning agent completely.On the other hand, for the chrome tanning agent of tanning production, approximately there is 1/3rd chromium residues in chroming waste liquor, not only wasted resource but also environment is caused to serious pollution.Due to chromic toxicity, the use of chromic salts causes very big harm to environment, people and animals.Along with the reinforcement of mankind's environmental consciousness, the pollution problem that solves leather industry is very urgent, especially pollution of chromium.
Molecular imprinting is a kind of process a certain specific molecular (template molecule or microsphere) to the new polymers of selectivity recognition capability of preparing, and conventionally can be described as manufacturing the artificial lock technology of identification " molecule key ".Molecular imprinting is a kind of advanced person's technology in the process of synthetic polymeric material, different materials is had to artificial receptor, as bonding point, in a lot of science and technology field, molecular imprinting is applied to molecular recognition process, as Solid-Phase Extraction, chromatographic separation, membrane sepn, inductor block, drug release and catalytic process etc.
An important development direction as molecular imprinting, the molecular imprinting relevant with metal ion, it is ion blotting technology, take yin, yang ion as template ion, select the function monomer that has interaction force (being generally the reactive forces such as static, coordination, chelating) with ion, select suitable linking agent and polymerization process in the aqueous solution, to carry out polymerization, remove template ion and just obtained the ion imprinted polymer with special groups arrangement, fixed cavitation size and shape afterwards.
The engram technology development relevant with metal ion belongs to the forward position content in molecular imprinting, and much research is so far also in the preliminary stage.In metal ion molecular imprinting, there are two class contents to obtain more concern: the metal ion engram technology that the metal ion of take is template; Utilize the coordination of metal ion and biomolecules to promote, realize the molecular imprinting of biomacromolecule.
Summary of the invention
The object of the present invention is to provide that a kind of loading capacity is high, selectivity good, adsorption and desorption speed is fast, and elution efficiency is high, compound imprinted polymer adsorbent of the Cr that regenerative power is strong (III) ion and preparation method thereof.
In order to achieve the above object, the technical solution used in the present invention comprises the following steps:
1) collagen protein and function monomer are dissolved in Cr (III) salts solution, then add N, N-methylene-bisacrylamide and initiator, and at 55 ℃～60 ℃ polyreaction 2-24h, in the reaction system obtaining, add linking agent again, at 0 ℃～50 ℃ reaction 0.5-3.5h, obtain reaction solution; Wherein, Cr (III) salts solution is mixed by solubility Cr (III) salt and polar organic solvent, Cr (III) ion in Cr (III) salts solution, amino, function monomer, the N in collagen protein, the mol ratio of N-methylene radical diene acid amides and linking agent is 1:(2～8): (2～10): (10～40): (0.5～2);
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance, by polymkeric substance desorb, dry, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the method for desorb is: by polymkeric substance, by volume ratio, be the hydrochloric acid cleaning of (1:7)～acetic acid (1:10) and the mixed solution of methyl alcohol and 0.1mol/L～2.0mol/L, finally with distilled water, be washed till filtrate and be neutral.
Described step 1) function monomer in is α-methacrylic acid or acrylamide.
Described step 1) the solubility Cr in (III) salt is chromium acetate, chromium sulphate or chromium nitrate.
Described step 1) polar organic solvent in is dimethyl sulfoxide (DMSO), water, acetone, methyl alcohol or DMF.
Described step 1) in, the mass concentration of Cr (III) salts solution is 10%～30%.
Described step 1) initiator in is dibenzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate or persulphate.
Described initiator accounts for 1.0%～3.0% of collagen protein and function monomer total mass.
Described linking agent is glutaraldehyde, epoxy chloropropane or oxalic dialdehyde.
When the linking agent described step 1) is epoxy chloropropane, adds after linking agent and regulate reaction system to alkalescence.
Described step 1) in, polyreaction is carried out under nitrogen protection; Step 2) the first vacuum-drying of polymkeric substance in, grind, sieve, then get 100～160 purpose polymers and carry out desorb.
Compared with prior art, beneficial effect of the present invention is:
The collagen protein that the present invention adopts is a kind of typical polyamphoteric electrolyte, amino, carboxyl, hydroxyl isoreactivity functional group are contained in its surface, can form complex compound with Cr (III), yet the contained active group quantity in collagen protein surface is limited, Selective adsorption is also poor.Therefore, the present invention utilizes ion blotting method to synthesize the compound imprinted polymer adsorbent of Cr (III) ion, adopt the precordainment that can significantly increase in this way sorbent material, identity and practicality, the adsorptive capacity of raising to chromium in chrome waste liquid, the clearance of chromium from waste chromium reaches as high as 86.3%.So, the compound imprinted polymer adsorbent of the Cr that the present invention makes (III) ion is high to Cr in chromate waste water (III) ionic adsorption selectivity, Cr (III) is had to identity absorption, adsorption rate is large, be easy to suitability for industrialized production, overcome the sorbent material consumption that prior art exists large, adsorb halfway problem.
In addition, the compound imprinted polymer adsorbent of the Cr that the present invention makes (III) ion changes and has stronger adaptability chromate waste water, stable performance, recyclability is good, be easy to reclaim, therefore, production and the use procedure of the compound imprinted polymer adsorbent of Cr of the present invention (III) ion can not cause secondary pollution to environment, and the absorption property of the compound imprinted polymer adsorbent of prepared Cr (III) ion significantly improves.Meanwhile, the solid waste that collagen protein of the present invention can produce from leather production process extracts as starting material, and therefore, raw material sources of the present invention are extensive, and nontoxic, with low cost.
Embodiment
Embodiment 1:
1) chromium nitrate is dissolved in to 28% Cr (III) salts solution of making in dimethyl sulfoxide (DMSO) that mass concentration is, then add collagen protein and α-methacrylic acid, under room temperature, stirring 2h makes evenly, add again N,N methylene bis acrylamide and Diisopropyl azodicarboxylate and pass into nitrogen 30min, sealing, in the water bath with thermostatic control of 60 ℃, react 24h, then in the reaction system obtaining, add glutaraldehyde, under sealed environment and nitrogen protection, in 30 ℃ of reaction 3h, obtain reaction solution; Wherein, amino, α-methacrylic acid, N in the Cr adding (III) salts solution in Cr (III) ion, collagen protein, the mol ratio of N-methylene radical diene acid amides, glutaraldehyde is 1:2:4:20:0.5; The quality of the Diisopropyl azodicarboxylate adding accounts for 1.0% of collagen protein and α-methacrylic acid total mass;
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance; Polymkeric substance, in 60 ℃ of vacuum-dryings, is then milled, sieves, get 100～160 purpose polymers and carry out desorb, then in vacuum drying oven in 60 ℃ of oven dry, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the concrete grammar of desorb is: the hydrochloric acid repetitive scrubbing of the acetic acid that is 1:9 by volume ratio successively by 100～160 purpose polymers and the mixed solution of methyl alcohol, 1.0mol/L, is finally washed till filtrate with distilled water and is neutral.
Embodiment 2:
1) chromium nitrate is dissolved in in methyl alcohol, to make mass concentration be 28% Cr (III) salts solution, then add collagen protein and α-methacrylic acid, under room temperature, stirring 2h makes evenly, add again N,N methylene bis acrylamide and Diisopropyl azodicarboxylate and pass into nitrogen 30min, sealing, in the water bath with thermostatic control of 60 ℃, react 24h, then in the reaction system obtaining, add glutaraldehyde, 30 ℃ of reaction 3.5h, obtain reaction solution; Wherein, amino, α-methacrylic acid, N in the Cr adding (III) salts solution in Cr (III) ion, collagen protein, the mol ratio of N-methylene radical diene acid amides, glutaraldehyde is 1:4:8:10:0.8; The quality of the Diisopropyl azodicarboxylate adding accounts for 3% of collagen protein and α-methacrylic acid total mass;
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance; By polymkeric substance vacuum-drying at 60 ℃, then mill, sieve, get 100～160 purpose polymers and carry out desorb, then in vacuum drying oven in 60 ℃ of oven dry, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the concrete grammar of desorb is: the hydrochloric acid repetitive scrubbing of the acetic acid that is 1:9 by volume ratio by 100～160 purpose polymers and the mixed solution of methyl alcohol, 0.5mol/L, is finally washed till filtrate with distilled water and is neutral.
Embodiment 3:
1) chromium sulphate is dissolved in to 30% Cr (III) salts solution of making in dimethyl sulfoxide (DMSO) that mass concentration is, then the collagen protein adding and α-methacrylic acid, under room temperature, stir 2h and make evenly, then add N,N methylene bis acrylamide and Diisopropyl azodicarboxylate and pass into nitrogen 30min, sealing, in the water bath with thermostatic control of 60 ℃, react 24h, then in the reaction system obtaining, add epoxy chloropropane, and to regulate pH value be 10, at 50 ℃, react 3.5h, obtain reaction solution; Wherein, amino, α-methacrylic acid, N in the Cr adding (III) salts solution in Cr (III) ion, collagen protein, the mol ratio of N-methylene radical diene acid amides, epoxy chloropropane is 1:4:10:20:0.8; The quality of the Diisopropyl azodicarboxylate adding accounts for 2.5% of collagen protein and α-methacrylic acid total mass;
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance; By polymkeric substance vacuum-drying at 60 ℃, then mill, sieve, get 100～160 purpose polymers and carry out desorb, then in vacuum drying oven in 60 ℃ of oven dry, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the concrete grammar of desorb is: the hydrochloric acid repetitive scrubbing of the mixed solution 1.0mol/L of the acetic acid that is 1:10 by volume ratio successively by 100～160 purpose polymers and methyl alcohol, is finally washed till filtrate with distilled water and is neutral.
Embodiment 4:
1) chromium acetate is dissolved in to 15% Cr (III) salts solution of making in methyl alcohol that mass concentration is, then add collagen protein and acrylamide, under room temperature, stirring 2h makes evenly, add again N,N methylene bis acrylamide and Diisopropyl azodicarboxylate and pass into nitrogen 30min, sealing, in the water bath with thermostatic control of 60 ℃, react 24h, then in the reaction system obtaining, add glutaraldehyde, under sealed environment and nitrogen protection, in 50 ℃ of reaction 3.5h, obtain reaction solution; Wherein, amino, acrylamide, N in the Cr adding (III) salts solution in Cr (III) ion, collagen protein, the mol ratio of N-methylene radical diene acid amides, glutaraldehyde is 1:2:10:20:1.0; The quality of the Diisopropyl azodicarboxylate adding accounts for 2% of collagen protein and acrylamide total mass;
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance; By polymkeric substance vacuum-drying at 60 ℃, then mill, sieve, get 100～160 purpose polymers and carry out desorb, then in 60 ℃ of vacuum drying ovens, dry in vacuum drying oven, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the concrete grammar of desorb is: the hydrochloric acid repetitive scrubbing of the mixed solution 1.0mol/L of the acetic acid that is 1:10 by volume ratio successively by 100～160 purpose polymers and methyl alcohol, is finally washed till filtrate with distilled water and is neutral.
Embodiment 5:
1) by chromium acetate 10% Cr (III) salts solution of making that mass concentration is soluble in water, then add collagen protein and acrylamide, under room temperature, stirring 2h makes evenly, add again N,N methylene bis acrylamide and dibenzoyl peroxide and pass into nitrogen 30min, sealing, in the water bath with thermostatic control of 55 ℃, react 2h, then in the reaction system obtaining, add oxalic dialdehyde, under sealed environment and nitrogen protection, in 0 ℃ of reaction 2.0h, obtain reaction solution; Wherein, amino, acrylamide, N in the Cr adding (III) salts solution in Cr (III) ion, collagen protein, N-methylene radical diene acid amides, oxalic dialdehyde mol ratio be 1:8:2:40:2.0; The quality of the dibenzoyl peroxide adding accounts for 1.0% of collagen protein and acrylamide total mass;
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance; By polymkeric substance vacuum-drying at 60 ℃, then mill, sieve, get 100～160 purpose polymers and carry out desorb, then in 60 ℃ of vacuum drying ovens, dry in vacuum drying oven, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the concrete grammar of desorb is: the hydrochloric acid repetitive scrubbing of the mixed solution 2.0mol/L of the acetic acid that is 1:7 by volume ratio successively by 100～160 purpose polymers and methyl alcohol, is finally washed till filtrate with distilled water and is neutral.
Embodiment 6:
1) chromium sulphate is dissolved in to N, 20% Cr (III) salts solution of making mass concentration in dinethylformamide and being, the collagen protein then adding and α-methacrylic acid, stir 2h and make evenly under room temperature, add again N, N-methylene-bisacrylamide and dilauroyl peroxide also pass into nitrogen 30min, and sealing is reacted 16h in the water bath with thermostatic control of 57 ℃, then in the reaction system obtaining, add epoxy chloropropane, and to regulate pH value be 10, at 20 ℃, react 0.5h, obtain reaction solution; Wherein, amino, α-methacrylic acid, N in the Cr adding (III) salts solution in Cr (III) ion, collagen protein, the mol ratio of N-methylene radical diene acid amides, epoxy chloropropane is 1:4:10:30:0.8; The quality of the dilauroyl peroxide adding accounts for 1.0% of collagen protein and α-methacrylic acid total mass;
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance; By polymkeric substance vacuum-drying at 60 ℃, then mill, sieve, get 100～160 purpose polymers and carry out desorb, then in vacuum drying oven in 60 ℃ of oven dry, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the concrete grammar of desorb is: the hydrochloric acid repetitive scrubbing of the mixed solution 1.0mol/L of the acetic acid that is 1:8 by volume ratio successively by 100～160 purpose polymers and methyl alcohol, is finally washed till filtrate with distilled water and is neutral.
Embodiment 7:
1) chromium nitrate is dissolved in in acetone, to make mass concentration be 15% Cr (III) salts solution, then add collagen protein and α-methacrylic acid, under room temperature, stirring 2h makes evenly, add again N,N methylene bis acrylamide and persulphate and pass into nitrogen 30min, sealing, in the water bath with thermostatic control of 60 ℃, react 7h, then in the reaction system obtaining, add glutaraldehyde, 30 ℃ of reaction 3.5h, obtain reaction solution; Wherein, amino, α-methacrylic acid, N in the Cr adding (III) salts solution in Cr (III) ion, collagen protein, the mol ratio of N-methylene radical diene acid amides, glutaraldehyde is 1:4:8:10:0.8; The quality of the persulphate adding accounts for 3% of collagen protein and α-methacrylic acid total mass;
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance; By polymkeric substance vacuum-drying at 60 ℃, then mill, sieve, get 100～160 purpose polymers and carry out desorb, then in vacuum drying oven in 60 ℃ of oven dry, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the concrete grammar of desorb is: the hydrochloric acid repetitive scrubbing of the acetic acid that is 1:9 by volume ratio by 100～160 purpose polymers and the mixed solution of methyl alcohol, 0.5mol/L, is finally washed till filtrate with distilled water and is neutral.
Persulphate in embodiment 7 can be ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
Claims (10)
1. a preparation method for the compound imprinted polymer adsorbent of Cr (III) ion, is characterized in that, comprises the following steps:
1) collagen protein and function monomer are dissolved in Cr (III) salts solution, then add N, N-methylene-bisacrylamide and initiator, and at 55 ℃～60 ℃ polyreaction 2-24h, in the reaction system obtaining, add linking agent again, at 0 ℃～50 ℃ reaction 0.5-3.5h, obtain reaction solution; Wherein, Cr (III) salts solution is mixed by solubility Cr (III) salt and polar organic solvent, Cr (III) ion in Cr (III) salts solution, amino, function monomer, the N in collagen protein, the mol ratio of N-methylene radical diene acid amides and linking agent is 1:(2～8): (2～10): (10～40): (0.5～2);
2) by the standing rear solid-liquid separation of reaction solution, obtain polymkeric substance, by polymkeric substance desorb, dry, obtain the compound imprinted polymer adsorbent of Cr (III) ion; Wherein, the method for desorb is: by polymkeric substance, by volume ratio, be the hydrochloric acid cleaning of (1:7)～acetic acid (1:10) and the mixed solution of methyl alcohol and 0.1mol/L～2.0mol/L, finally with distilled water, be washed till filtrate and be neutral.
2. the preparation method of the compound imprinted polymer adsorbent of Cr according to claim 1 (III) ion, is characterized in that: the function monomer described step 1) is α-methacrylic acid or acrylamide.
3. the preparation method of the compound imprinted polymer adsorbent of Cr according to claim 1 (III) ion, is characterized in that: the solubility Cr described step 1) (III) salt is chromium acetate, chromium sulphate or chromium nitrate.
4. the preparation method of the compound imprinted polymer adsorbent of Cr according to claim 1 (III) ion, is characterized in that: the polar organic solvent described step 1) is dimethyl sulfoxide (DMSO), water, acetone, methyl alcohol or DMF.
5. according to the preparation method of the compound imprinted polymer adsorbent of Cr (III) ion described in claim 1,3 or 4, it is characterized in that: described step 1), the mass concentration of Cr (III) salts solution is 10%～30%.
6. the preparation method of the compound imprinted polymer adsorbent of Cr according to claim 1 (III) ion, is characterized in that: the initiator described step 1) is dibenzoyl peroxide, dilauroyl peroxide, Diisopropyl azodicarboxylate or persulphate.
7. according to claim 61 or the preparation method of the compound imprinted polymer adsorbent of Cr (III) ion, it is characterized in that: described initiator accounts for 1.0%～3.0% of collagen protein and function monomer total mass.
8. the preparation method of the compound imprinted polymer adsorbent of Cr according to claim 1 (III) ion, is characterized in that: described linking agent is glutaraldehyde, epoxy chloropropane or oxalic dialdehyde.
9. the preparation method of the compound imprinted polymer adsorbent of Cr according to claim 1 (III) ion, is characterized in that: when the linking agent described step 1) is epoxy chloropropane, regulate reaction system to alkalescence after adding linking agent.
10. the preparation method of the compound imprinted polymer adsorbent of Cr according to claim 1 (III) ion, is characterized in that: described step 1), polyreaction is carried out under nitrogen protection; Step 2) the first vacuum-drying of polymkeric substance in, grind, sieve, then get 100～160 purpose polymers and carry out desorb.
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| CN110339729A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and application of trivalent chromic ion trace composite membrane |
| CN112898455A (en) * | 2021-01-25 | 2021-06-04 | 徐州工程学院 | Chromium (VI) molecular imprinting material and preparation method and application thereof |
| CN115069223A (en) * | 2022-06-30 | 2022-09-20 | 陕西科技大学 | Chitosan ion imprinted gel for adsorbing Cd (II), and preparation method and application thereof |
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| CN105148851A (en) * | 2015-09-28 | 2015-12-16 | 太原理工大学 | Preparation method and application of carbamido functionalized cadmium ion surface print adsorbent |
| CN105148851B (en) * | 2015-09-28 | 2018-10-19 | 太原理工大学 | A kind of Preparation method and use of urea groups functionalization cadmium ion surface imprint adsorbent |
| CN105949389A (en) * | 2016-05-12 | 2016-09-21 | 广东省稀有金属研究所 | Preparation method of germanium ion imprinted polymer |
| CN110339729A (en) * | 2019-07-02 | 2019-10-18 | 昆明理工大学 | A kind of preparation method and application of trivalent chromic ion trace composite membrane |
| CN112898455A (en) * | 2021-01-25 | 2021-06-04 | 徐州工程学院 | Chromium (VI) molecular imprinting material and preparation method and application thereof |
| CN115069223A (en) * | 2022-06-30 | 2022-09-20 | 陕西科技大学 | Chitosan ion imprinted gel for adsorbing Cd (II), and preparation method and application thereof |
| CN115069223B (en) * | 2022-06-30 | 2023-10-27 | 陕西科技大学 | Chitosan ion imprinting gel for adsorbing Cd (II) as well as preparation method and application thereof |
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