CN103992500B - A kind of Cr (III) ion is combined the preparation method of imprinted polymer adsorbent - Google Patents
A kind of Cr (III) ion is combined the preparation method of imprinted polymer adsorbent Download PDFInfo
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- CN103992500B CN103992500B CN201410191076.7A CN201410191076A CN103992500B CN 103992500 B CN103992500 B CN 103992500B CN 201410191076 A CN201410191076 A CN 201410191076A CN 103992500 B CN103992500 B CN 103992500B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 68
- 239000003463 adsorbent Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 102000008186 Collagen Human genes 0.000 claims abstract description 29
- 108010035532 Collagen Proteins 0.000 claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 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 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 7
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011651 chromium Substances 0.000 claims description 66
- 150000002500 ions Chemical class 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 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 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
- -1 N, N-methylene Chemical group 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 229940055042 chromic sulfate Drugs 0.000 claims description 4
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [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
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 claims description 4
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 4
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 239000003495 polar organic solvent Substances 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- UPBLAVFWWWKVAJ-UHFFFAOYSA-N [Cl].CCC Chemical compound [Cl].CCC UPBLAVFWWWKVAJ-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 108010031480 Artificial Receptors Proteins 0.000 description 1
- 238000007445 Chromatographic isolation Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 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
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of Cr (III) ion and be combined the preparation method of imprinted polymer adsorbent, this adsorbent with Cr (III) ion as template ion, collagen protein and acrylic compounds are bi-functional monomer, in polar solvent, with N, N methylene-bisacrylamide and little molecule cross-linking agents, azodiisobutyronitrile is that initiator causes preparation Cr (III) ion to be combined imprinted polymer adsorbent.Adsorbent prepared by the present invention has the adsorption selectivity of excellence to Cr (III) ion, and soon, elution efficiency is high, renewable recycling for absorption, elution rate.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to the compound print of a kind of Cr (III) ion
The preparation method of mark polymer absorbant.
Background technology
In leather industry, in existing tanning agent, account for 70%～80% containing chrome tanning agent, so far,
Due to chrome-tanned every premium properties, not yet there is any tanning agent can replace chrome tanning agent completely.Separately
On the one hand, in the chrome tanning agent of tanning production, there are about the chromium residues of 1/3rd in chroming waste liquor,
Not only waste resource but also environment is caused serious pollution.Due to chromic toxicity, the use of chromic salts is right
Environment, people and animals cause high risks.Along with the reinforcement of mankind's environmental consciousness, solve the pollution of leather industry
Problem is the most very urgent, especially pollution of chromium.
Molecular imprinting is that one is prepared and had a certain specific molecular (template molecule or microsphere)
The process of the new polymers of Selective recognition ability, can be described generally as manufacturing identification " molecule key "
Artificial lock technology.Molecular engram is the technology of a kind of advanced person during synthetic polymeric material, to not
Same material has artificial receptor, and such as bonding point, in a lot of science and technology field, molecular engram is answered
For molecular recognition process, such as Solid-Phase Extraction, chromatographic isolation, membrance separation, induction apparatus, drug release and
Catalytic process etc..
As an important development direction of molecular imprinting, the molecular engram skill relevant with metal ion
Art, i.e. ionic imprinting technique, with anions and canons as template ion, select and have interaction force with ion
(usually electrostatic, be coordinated, the active force such as chelating) function monomer, select suitable cross-linking agent and poly-
Conjunction method is polymerized in aqueous, remove just obtain after template ion have special groups arrangement,
The ion imprinted polymer of fixed cavitation size and shape.
The engram technology development relevant with metal ion belongs to the forward position content in molecular imprinting, many
Research is so far also in the elementary step.In metal ion molecular imprinting, two class contents are had to obtain relatively
Many concerns: the metal ion engram technology with metal ion as template；Utilize metal ion and biomolecule
Coordination promote, realize the molecular imprinting of biomacromolecule.
Summary of the invention
It is an object of the invention to provide that a kind of adsorption capacity is high, selectivity is good, adsorption and desorption speed is fast,
Elution efficiency is high, and Cr (III) ion that regeneration capacity is strong is combined imprinted polymer adsorbent and preparation side thereof
Method.
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) saline solution, are subsequently adding N, N-methylene
Base bisacrylamide and initiator, and polyreaction 2-24h at 55 DEG C～60 DEG C, then to the reaction obtained
System adds cross-linking agent, reacts 0.5-3.5h at 0 DEG C～50 DEG C, obtain reactant liquor；Wherein, Cr (III)
Saline solution is mixed by solubility Cr (III) salt and polar organic solvent, Cr (III) saline solution
In Cr (III) ion, the amino in collagen protein, function monomer, N, N-di-2-ethylhexylphosphine oxide acrylamide
It is 1:(2～8 with the mol ratio of cross-linking agent): (2～10): (10～40): (0.5～2)；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer, by polymer desorbing, is dried, obtains
Cr (III) ion is combined imprinted polymer adsorbent；Wherein, the method for desorbing is: by polymer body
Long-pending than for (1:7)～the acetic acid of (1:10) and the mixed liquor of methanol and the salt of 0.1mol/L～2.0mol/L
Acid is cleaned, and being finally washed till filtrate with distilled water is neutrality.
Described step 1) in function monomer be α-methacrylic acid or acrylamide.
Described step 1) in solubility Cr (III) salt be chromium acetate, chromic sulfate or chromic nitrate.
Described step 1) in polar organic solvent be dimethyl sulfoxide, water, acetone, methanol or N,
Dinethylformamide.
Described step 1) in the mass concentration of Cr (III) saline solution be 10%～30%.
Described step 1) in initiator be that dibenzoyl peroxide, dilauroyl peroxide, azo two are different
Butyronitrile or persulfate.
Described initiator accounts for collagen protein and the 1.0% of function monomer gross mass～3.0%.
Described cross-linking agent is glutaraldehyde, epoxychloropropane or Biformyl.
Described step 1) in cross-linking agent when being epoxychloropropane, regulate reaction system after adding cross-linking agent
To alkalescence.
Described step 1) in polyreaction carry out under nitrogen protection；Step 2) in polymer first
It is vacuum dried, grinds, sieves, then take 100～160 purpose polymers and carry out desorbing.
Compared with prior art, the beneficial effects of the present invention is:
The collagen protein that the present invention uses is a kind of typical polyampholyte, its surface contain amino,
Carboxyl, hydroxyl isoreactivity functional group, it is possible to form complex with Cr (III), but collagen protein surface
Contained active group quantity is limited, and Selective adsorption is the most poor.Therefore, the present invention utilizes ion
Blotting synthesizes Cr (III) ion and is combined imprinted polymer adsorbent, and adopting in this way can be notable
Increase the precordainment of adsorbent, identity and practicality, improve the adsorbance of chromium in chrome waste liquid, useless
In liquid, the clearance of chromium reaches as high as 86.3%.So, Cr (III) ion that the present invention prepares is combined trace and gathers
Compound adsorbent is high to Cr in chromate waste water (III) ionic adsorption selectivity, and Cr (III) is had identification
Property absorption, the rate of adsorption is big, it is easy to industrialized production, overcome prior art exist adsorbent amount
Greatly, halfway problem is adsorbed.
It addition, the Cr that the present invention prepares (III) ion is combined imprinted polymer adsorbent, chromate waste water is changed
Having stronger adaptability, stable performance, recyclability is good, it is easy to reclaim, therefore, and Cr of the present invention (III)
Ion is combined the production of imprinted polymer adsorbent and use process does not results in secondary pollution to environment, institute
Cr (III) ion prepared is combined the absorption property of imprinted polymer adsorbent and is greatly improved.Meanwhile, this
The solid waste that bright used collagen protein can produce from leather production process carries as raw material
Taking out, therefore, raw material sources of the present invention are extensive, and nontoxic, with low cost.
Detailed description of the invention
Embodiment 1:
1) chromic nitrate is dissolved in dimethyl sulfoxide make mass concentration is 28% Cr (III) saline solution,
It is subsequently adding collagen protein and α-methacrylic acid, stirs 2h under room temperature and make uniformly, to add N, N-
Methylene-bisacrylamide and azodiisobutyronitrile are also passed through nitrogen 30min, seal, in the constant temperature of 60 DEG C
Water-bath is reacted 24h, in the reaction system obtained, then adds glutaraldehyde, protect in sealed environment and nitrogen
Protect down and react 3h in 30 DEG C, obtain reactant liquor；Wherein, Cr (III) in Cr (III) saline solution added
Amino in ion, collagen protein, α-methacrylic acid, N, N-di-2-ethylhexylphosphine oxide acrylamide, glutaraldehyde
Mol ratio is 1:2:4:20:0.5；The quality of the azodiisobutyronitrile added accounts for collagen protein and α-first
The 1.0% of base acrylic acid gross mass；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer；By polymer in 60 DEG C of vacuum drying,
Then mill, sieve, take 100～160 purpose polymers and carry out desorbing, then in 60 DEG C in vacuum drying oven
Dry, i.e. obtain Cr (III) ion and be combined imprinted polymer adsorbent；Wherein, desorbing method particularly includes:
By 100～160 purpose polymers successively with the acetic acid that volume ratio is 1:9 and the mixed liquor of methanol, 1.0mol/L
Hydrochloric acid cyclic washing, being finally washed till filtrate with distilled water is neutrality.
Embodiment 2:
1) chromic nitrate is dissolved in methanol makes Cr (III) saline solution that mass concentration is 28%, then add
Enter collagen protein and α-methacrylic acid, stir 2h under room temperature and make uniformly, add N, N-di-2-ethylhexylphosphine oxide
Acrylamide and azodiisobutyronitrile are also passed through nitrogen 30min, seal, anti-in the water bath with thermostatic control of 60 DEG C
Answer 24h, in the reaction system obtained, then add glutaraldehyde, 30 DEG C of reaction 3.5h, obtain reactant liquor；
Wherein, the amino in Cr (III) ion, collagen protein, α-first in Cr (III) saline solution added
Base acrylic acid, N, N-di-2-ethylhexylphosphine oxide acrylamide, the mol ratio of glutaraldehyde are 1:4:8:10:0.8；Added
The quality of the azodiisobutyronitrile entered accounts for collagen protein and the 3% of α-methacrylic acid gross mass；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer；Polymer is vacuum dried at 60 DEG C,
Then mill, sieve, take 100～160 purpose polymers and carry out desorbing, then in 60 DEG C in vacuum drying oven
Dry, i.e. obtain Cr (III) ion and be combined imprinted polymer adsorbent；Wherein, desorbing method particularly includes:
By acetic acid that 100～160 purpose polymers volume ratios are 1:9 and the mixed liquor of methanol, the salt of 0.5mol/L
Acid cyclic washing, being finally washed till filtrate with distilled water is neutrality.
Embodiment 3:
1) chromic sulfate is dissolved in dimethyl sulfoxide make mass concentration is 30% Cr (III) saline solution,
The collagen protein being subsequently adding and α-methacrylic acid, stir 2h and make uniformly, to add N under room temperature,
N-methylene-bisacrylamide and azodiisobutyronitrile are also passed through nitrogen 30min, seal, in the perseverance of 60 DEG C
Tepidarium is reacted 24h, in the reaction system obtained, then adds epoxychloropropane, and regulate pH value
It is 10, at 50 DEG C, reacts 3.5h, obtain reactant liquor；Wherein, in Cr (III) saline solution added
Amino in Cr (III) ion, collagen protein, α-methacrylic acid, N, N-di-2-ethylhexylphosphine oxide acrylamide,
The mol ratio of epoxychloropropane is 1:4:10:20:0.8；The quality of the azodiisobutyronitrile added accounts for glue
Former albumen and the 2.5% of α-methacrylic acid gross mass；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer；Polymer is vacuum dried at 60 DEG C,
Then mill, sieve, take 100～160 purpose polymers and carry out desorbing, then in 60 DEG C in vacuum drying oven
Dry, i.e. obtain Cr (III) ion and be combined imprinted polymer adsorbent；Wherein, desorbing method particularly includes:
By 100～160 purpose polymers successively with the acetic acid that volume ratio is 1:10 and the mixed liquor 1.0mol/L of methanol
Hydrochloric acid cyclic washing, being finally washed till filtrate with distilled water is neutrality.
Embodiment 4:
1) chromium acetate is dissolved in methanol make mass concentration is 15% Cr (III) saline solution, then
Add collagen protein and acrylamide, stir 2h under room temperature and make uniformly, add N, N-di-2-ethylhexylphosphine oxide third
Acrylamide and azodiisobutyronitrile are also passed through nitrogen 30min, seal, and react in the water bath with thermostatic control of 60 DEG C
24h, then adds glutaraldehyde, in 50 DEG C under sealed environment and nitrogen are protected in the reaction system obtained
Reaction 3.5h, obtains reactant liquor；Cr (III) ion in Cr (III) saline solution wherein, added,
Amino in collagen protein, acrylamide, N, N-di-2-ethylhexylphosphine oxide acrylamide, the mol ratio of glutaraldehyde are 1:
2:10:20:1.0；The quality of the azodiisobutyronitrile added accounts for collagen protein and acrylamide gross mass
2%；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer；Polymer is vacuum dried at 60 DEG C,
Then mill, sieve, take 100～160 purpose polymers and carry out desorbing, then in 60 DEG C in vacuum drying oven
Vacuum drying oven is dried, i.e. obtains Cr (III) ion and be combined imprinted polymer adsorbent；Wherein, desorbing
Method particularly includes: by 100～160 purpose polymers successively with the acetic acid that volume ratio is 1:10 and methanol
The hydrochloric acid cyclic washing of mixed liquor 1.0mol/L, being finally washed till filtrate with distilled water is neutrality.
Embodiment 5:
1) by soluble in water for chromium acetate make mass concentration is 10% Cr (III) saline solution, then add
Enter collagen protein and acrylamide, stir 2h under room temperature and make uniformly, add N, N-methylene bisacrylamide
Amide and dibenzoyl peroxide are also passed through nitrogen 30min, seal, and react in the water bath with thermostatic control of 55 DEG C
2h, then adds Biformyl in the reaction system obtained, anti-in 0 DEG C under sealed environment and nitrogen are protected
Answer 2.0h, obtain reactant liquor；Wherein, Cr (III) ion, glue in Cr (III) saline solution added
Amino in former albumen, acrylamide, N, N-di-2-ethylhexylphosphine oxide acrylamide, the mol ratio of Biformyl are 1:8:
2:40:2.0；The quality of the dibenzoyl peroxide added accounts for collagen protein and acrylamide gross mass
1.0%；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer；Polymer is vacuum dried at 60 DEG C,
Then mill, sieve, take 100～160 purpose polymers and carry out desorbing, then in 60 DEG C in vacuum drying oven
Vacuum drying oven is dried, i.e. obtains Cr (III) ion and be combined imprinted polymer adsorbent；Wherein, desorbing
Method particularly includes: mixed with the acetic acid that volume ratio is 1:7 and methanol successively by 100～160 purpose polymers
Closing the hydrochloric acid cyclic washing of liquid 2.0mol/L, being finally washed till filtrate with distilled water is neutrality.
Embodiment 6:
1) chromic sulfate is dissolved in DMF make mass concentration is 20% Cr (III)
Saline solution, the collagen protein being subsequently adding and α-methacrylic acid, stir 2h and make uniformly, then add under room temperature
Enter N,N methylene bis acrylamide and dilauroyl peroxide and be passed through nitrogen 30min, sealing, in 57 DEG C
Water bath with thermostatic control in react 16h, in the reaction system obtained, then add epoxychloropropane, and regulate
PH value is 10, reacts 0.5h, obtain reactant liquor at 20 DEG C；Wherein, Cr (III) salt added is molten
Amino in Cr (III) ion, collagen protein, α-methacrylic acid, N, N-methylene diene acyl in liquid
Amine, the mol ratio of epoxychloropropane are 1:4:10:30:0.8；The quality of the dilauroyl peroxide added
Account for collagen protein and the 1.0% of α-methacrylic acid gross mass；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer；Polymer is vacuum dried at 60 DEG C,
Then mill, sieve, take 100～160 purpose polymers and carry out desorbing, then in 60 DEG C in vacuum drying oven
Dry, i.e. obtain Cr (III) ion and be combined imprinted polymer adsorbent；Wherein, desorbing method particularly includes:
By 100～160 purpose polymers successively with the acetic acid that volume ratio is 1:8 and the mixed liquor 1.0mol/L of methanol
Hydrochloric acid cyclic washing, being finally washed till filtrate with distilled water is neutrality.
Embodiment 7:
1) chromic nitrate is dissolved in acetone makes Cr (III) saline solution that mass concentration is 15%, then add
Enter collagen protein and α-methacrylic acid, stir 2h under room temperature and make uniformly, add N, N-di-2-ethylhexylphosphine oxide
Acrylamide and persulfate are also passed through nitrogen 30min, seal, and react 7h in the water bath with thermostatic control of 60 DEG C,
Then in the reaction system obtained, add glutaraldehyde, 30 DEG C of reaction 3.5h, obtain reactant liquor；Wherein,
Amino in Cr (III) ion, collagen protein, Alpha-Methyl propylene in Cr (III) saline solution added
Acid, N, N-di-2-ethylhexylphosphine oxide acrylamide, the mol ratio of glutaraldehyde are 1:4:8:10:0.8；The mistake added
The quality of sulfate accounts for collagen protein and the 3% of α-methacrylic acid gross mass；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer；Polymer is vacuum dried at 60 DEG C,
Then mill, sieve, take 100～160 purpose polymers and carry out desorbing, then in 60 DEG C in vacuum drying oven
Dry, i.e. obtain Cr (III) ion and be combined imprinted polymer adsorbent；Wherein, desorbing method particularly includes:
By acetic acid that 100～160 purpose polymers volume ratios are 1:9 and the mixed liquor of methanol, the salt of 0.5mol/L
Acid cyclic washing, being finally washed till filtrate with distilled water is neutrality.
Persulfate in embodiment 7 can be Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate.
Claims (8)
1. Cr (III) ion is combined the preparation method of imprinted polymer adsorbent, it is characterised in that
Comprise the following steps:
1) collagen protein and function monomer are dissolved in Cr (III) saline solution, are subsequently adding N, N-methylene
Base bisacrylamide and initiator, and polyreaction 2-24h at 55 DEG C～60 DEG C, then to the reaction obtained
System adds cross-linking agent, reacts 0.5-3.5h at 0 DEG C～50 DEG C, obtain reactant liquor；Wherein, Cr (III)
Saline solution is mixed by solubility Cr (III) salt and polar organic solvent, Cr (III) saline solution
In Cr (III) ion, the amino in collagen protein, function monomer, N, N-di-2-ethylhexylphosphine oxide acrylamide
It is 1:(2～8 with the mol ratio of cross-linking agent): (2～10): (10～40): (0.5～2)；Described step 1)
In function monomer be α-methacrylic acid or acrylamide；Described cross-linking agent is glutaraldehyde, epoxy chlorine
Propane or Biformyl；
2) solid-liquid separation after being stood by reactant liquor, obtains polymer, by polymer desorbing, is dried, obtains
Cr (III) ion is combined imprinted polymer adsorbent；Wherein, the method for desorbing is: by polymer body
Long-pending than for (1:7)～the acetic acid of (1:10) and the mixed liquor of methanol and the salt of 0.1mol/L～2.0mol/L
Acid is cleaned, and being finally washed till filtrate with distilled water is neutrality.
Cr the most according to claim 1 (III) ion is combined the preparation side of imprinted polymer adsorbent
Method, it is characterised in that: described step 1) in solubility Cr (III) salt be chromium acetate, chromic sulfate
Or chromic nitrate.
Cr the most according to claim 1 (III) ion is combined the preparation side of imprinted polymer adsorbent
Method, it is characterised in that: described step 1) in polar organic solvent be dimethyl sulfoxide, acetone, first
Alcohol or DMF.
4. it is combined imprinted polymer adsorbent according to Cr (III) ion described in claim 1,2 or 3
Preparation method, it is characterised in that: described step 1) in the mass concentration of Cr (III) saline solution be
10%～30%.
Cr the most according to claim 1 (III) ion is combined the preparation side of imprinted polymer adsorbent
Method, it is characterised in that: described step 1) in initiator be dibenzoyl peroxide, peroxidating 12
Acyl, azodiisobutyronitrile or persulfate.
Cr the most according to claim 5 (III) ion is combined the preparation side of imprinted polymer adsorbent
Method, it is characterised in that: described initiator accounts for collagen protein and the 1.0% of function monomer gross mass～3.0%.
Cr the most according to claim 1 (III) ion is combined the preparation side of imprinted polymer adsorbent
Method, it is characterised in that: described step 1) in cross-linking agent when being epoxychloropropane, after adding cross-linking agent
Regulation reaction system is to alkalescence.
Cr the most according to claim 1 (III) ion is combined the preparation side of imprinted polymer adsorbent
Method, it is characterised in that: described step 1) in polyreaction carry out under nitrogen protection；Step 2)
Middle polymer is first vacuum dried, grinds, sieves, and then takes 100～160 purpose polymers and carries out desorbing.
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| CN105949389B (en) * | 2016-05-12 | 2018-01-12 | 广东省稀有金属研究所 | A kind of 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 |
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| 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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| CN102824899A (en) * | 2012-09-07 | 2012-12-19 | 盐城工学院 | Metal ion imprinted hydrogel adsorbing material with interpenetrating polymer network (IPN) structure and preparation method for metal ion imprinted hydrogel adsorbing material |
| CN103642063A (en) * | 2013-11-04 | 2014-03-19 | 江苏大学 | Preparation method of mythyl p-hydroxybenzoate molecular imprinting composite membrane and application thereof |
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| CN103642063A (en) * | 2013-11-04 | 2014-03-19 | 江苏大学 | Preparation method of mythyl p-hydroxybenzoate molecular imprinting composite membrane and application thereof |
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