CN109180864A - Molecularly imprinted polymer material and application for sulfa drugs in purified water - Google Patents
Molecularly imprinted polymer material and application for sulfa drugs in purified water Download PDFInfo
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- CN109180864A CN109180864A CN201810790112.XA CN201810790112A CN109180864A CN 109180864 A CN109180864 A CN 109180864A CN 201810790112 A CN201810790112 A CN 201810790112A CN 109180864 A CN109180864 A CN 109180864A
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- China
- Prior art keywords
- molecularly imprinted
- polymer material
- imprinted polymer
- sulfa drugs
- purified water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 41
- 239000002861 polymer material Substances 0.000 title claims abstract description 39
- 239000003814 drug Substances 0.000 title claims abstract description 38
- 229940079593 drug Drugs 0.000 title claims abstract description 35
- 239000008213 purified water Substances 0.000 title claims abstract description 26
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 229960002135 sulfadimidine Drugs 0.000 claims abstract description 15
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 3
- 239000003403 water pollutant Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000012719 thermal polymerization Methods 0.000 claims description 6
- 230000010148 water-pollination Effects 0.000 claims description 6
- 239000010865 sewage Substances 0.000 claims description 3
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 abstract description 8
- 229940124530 sulfonamide Drugs 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 abstract description 5
- 229960004306 sulfadiazine Drugs 0.000 abstract description 4
- QPPBRPIAZZHUNT-UHFFFAOYSA-N sulfamerazine Chemical compound CC1=CC=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 QPPBRPIAZZHUNT-UHFFFAOYSA-N 0.000 abstract description 4
- GPTONYMQFTZPKC-UHFFFAOYSA-N sulfamethoxydiazine Chemical compound N1=CC(OC)=CN=C1NS(=O)(=O)C1=CC=C(N)C=C1 GPTONYMQFTZPKC-UHFFFAOYSA-N 0.000 abstract description 4
- 229960001544 sulfathiazole Drugs 0.000 abstract description 4
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000845 anti-microbial effect Effects 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 7
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- -1 chemistry Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DGUWRXBLZVOIFX-UHFFFAOYSA-N 1-methoxypiperazine Chemical compound CON1CCNCC1 DGUWRXBLZVOIFX-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 239000003640 drug residue Substances 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000002607 hemopoietic effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of molecularly imprinted polymer materials for sulfa drugs in purified water, and under the action of initiator free radical polymerization is occurred for template molecule, function monomer, crosslinking agent, and the microballoon Molecularly Imprinted Polymer of high-crosslinking-degree is formed with emulsion polymerization.A kind of molecularly imprinted polymer material for sulfa drugs in purified water proposed by the present invention, by being enriched with, being purified to target contaminant, which has very high adsorption capacity and preferable selectivity to 7 kinds of sulfanilamide (SN) antimicrobial DP finish such as water pollutant sulfamethazine, sulphadiazine, kynix, bacteresulf, sulphathiazole, 5-methoxysulfadiazine, sulfamethyldiazine.
Description
Technical field
The invention belongs to environmental purification technical fields, and in particular to it is a kind of for being enriched with, sulfa drugs in purified water
Molecularly imprinted polymer material and application.
Background technique
In recent years, because caused by mass production, abuse agricultural and veterinary chemicals some negative effects it is increasingly prominent, it is raw not only to influence agricultural
It produces, destroys ecological environment, also seriously endanger human health.With the mass production of agricultural and veterinary chemicals, abuse, cause drug largely residual
It stays, causes water pollution serious.Therefore, develop and a kind of simple, fast and efficient purify, dispel agricultural and veterinary chemicals in water body and pollute
The method of object is extremely important.
Sulfa drugs is the artificial synthesized antibacterial of one kind, sterilization class drug, has easy to use, cheap, curative effect
The features such as good, so be widely used in livestock-raising and human clinical medicine, but due to the unreasonable use of the mankind, indiscriminate
With phenomena such as, cause a large amount of agricultural and veterinary chemicals residual to enter water body, serious polluted source.The water source influences human body after human body is taken in
Hemopoietic system, urinary system, digestive system, kidney, be detrimental to health.And ought residual in vivo reach certain level
When, it can also carcinogenic, teratogenesis, mutagenesis.In order to guarantee that the mankind are healthy and safe, it is ensured that drinking water safety, high-efficient purification are dispelled in water
Drug contamination object residual, be focus of attention all the time.
Agricultural and veterinary chemicals bring pollutant component is complicated, administers the problems such as difficult, and existing water purification technology can not filter out in water completely
Agricultural and veterinary chemicals, and fouling membrane is easily caused for a long time, threat is brought to safe drinking water.Molecular imprinting technology is to obtain space knot
On structure and binding site with target molecule exact matching polymer technology of preparing, be collection Polymer Synthesizing, MOLECULE DESIGN with
The new interdisciplinary that numerous branch superiority exhibitions such as identification, bionical bioengineering are got up.Molecularly imprinted polymer is for medicine
The high molecular material of object pollutant target molecule " making to measure ", therefore have the good, physics of selectivity and chemical stability good, anti-
Interference performance is strong, long service life and the advantages that have a wide range of application, and leads in material, chemistry, medicine, biology and environmental project etc.
Domain has a wide range of applications.
Summary of the invention
Technical problems based on background technology, the present invention aiming at the above shortcomings existing in the prior art, provide one
Molecularly imprinted polymer material of the kind for sulfa drugs in purified water, the material is to water pollutant sulfanilamide (SN) antimicrobial DP finish
With very high adsorption capacity and preferable selectivity, the pollutant in water can be made thoroughly to be filtered out, purification is reached to water
Effect ensures domestic water safety.
A kind of molecularly imprinted polymer material for sulfa drugs in purified water proposed by the present invention, by template point
Under the action of initiator free radical polymerization occurs for son, function monomer, crosslinking agent, forms the micro- of high-crosslinking-degree with emulsion polymerization
Sphere molecule polymer, the adding proportion of the template molecule, function monomer, crosslinking agent, initiator are as follows: (0.2-0.4) mol:
(0.6-0.7)mol:(1.1-1.3)mol:(61-68)g。
Preferably, the template molecule is sulfamethazine.
Preferably, the function monomer includes methacrylic acid and hydroxyethyl methacrylate, and molal weight adds ratio
Example is (1-1.1): 1.
Preferably, the crosslinking agent is Triallyl isocyanurate.
Preferably, the initiator is azodiisobutyronitrile.
A kind of preparation method for the molecularly imprinted polymer material of sulfa drugs in purified water, method and step is such as
Under:
S1: being dissolved in sulfamethazine as template molecule in acetonitrile, and function is added after ultrasonic disperse 15-25min
Monomer methacrylic acid shakes 1.5-2.5h on shaking table, forms pre-polymer solution；
S2: and then hydrophily function monomer hydroxyethyl methacrylate is added and continues to shake 1-2h, it adds crosslinking agent and fills
Divide stirring 1-2h, adds initiator stirring 0.5h；
S3: utilizing nitrogen protection, heat under 60-65 DEG C of water bath condition, bring it about thermal polymerization, water-bath 23-25h,
Target molecule polymer material can be obtained.
Further, the rate stirred in the S2 is 400-600rpm.
A kind of molecularly imprinted polymer material for sulfa drugs in purified water proposed by the present invention is applied to sewage
Processing.
Molecularly imprinted polymer material proposed by the present invention can prepare the mistake applied to sewage treatment in accordance with the following steps
Chimney filter:
(1) molecularly imprinted polymer of synthesis is pulverized last sieving, takes 600~800 mesh polymer filter paper packets
It wraps up in, is transferred in Soxhlet extractor and extracts 80h, extractant is methanol: formic acid (v:v, 9:1), up to no template molecule detects.
(2) 2h then is washed with the methanol of the hydrochloric acid of 20ml 1mol/L and 20ml, finally uses the hydroxide of 0.25mol/L
Sodium, water repeated flushing are until neutral.Being subsequently placed in 75 DEG C of baking ovens, drying to constant weight to get sulfamethazine molecular engram is arrived
Polymer beads.
(3) it weighs 300g adsorbent material to be filled in blank pipe, tabletting compression in both ends vacuumizes spare.
Action principle:
Molecular engram passes through the side of covalent bond or non-covalent bond i.e. using target contaminant molecule as template, by function monomer
Formula adds crosslinking agent and carries out polymerization reaction, then extract template molecule to be formed with hole in conjunction with template molecule
The template molecule that can be identified macromolecule, this macromolecule is referred to as molecularly imprinted polymer.
By in a large amount of media reaction prepare the microspheric molecularly imprinted polymer of high-crosslinking-degree, Jie of the reaction system
Matter is much higher than dosage when preparing bulk polymer, and using sulfamethazine as template molecule synthetic molecules trace polymerization
Object.The recognition capability of imprinted polymer is decided by that polymerization reaction front template molecule and function monomer form the stabilization journey of complex
Degree and the action mode between template molecule and function monomer.Since sulphadiazine class drug pyridine ring is electron-withdrawing group
Group ,-NH2With stronger alkalinity, so electrostatic and hydrogen bond can occur simultaneously when forming complex with MAA (pKa 4.6)
Synergistic effect, is shown in Fig. 2.
The preparation of microballoon molecularly imprinted polymer, first, in accordance with polymerization theory, polymerization reaction starts from homogeneous function list
Body, template molecule, crosslinking agent and initiator mixture；Initiator causes function monomer and free radical polymerization shape occurs for crosslinking agent
At the microballoon Molecularly Imprinted Polymer of high-crosslinking-degree, make polymer stabilizing not by the stabilizers such as polyethylene glycol are added with suspension polymerization
Together, the polymer of this method preparation does not need to add stabilizer, can avoid by stabilizer to the non-selective adsorption of template molecule；So
Template molecule to be taken out by elution process afterwards, so that it may realization carries out absorption enrichment to the sulfa drug residue in water,
To achieve the effect that purified water.
Compared with prior art, the device have the advantages that being:
The present invention is compared to the prior art, and molecular engram high molecular polymer has precordainment for target molecule, knows
The features such as other property, practicability, it is widely used in chemobionics sensor, Solid Phase Extraction, mimetic enzyme catalysis, enantiomerism at present
The area researches such as body separation, membrane separation technique.The recognition site that molecularly imprinted polymer generates during molecular engram is usually
The effects of being coordinated by ion, hydrogen bond and metal power selectively combines template molecule.Molecular engram macromolecule polymer material
Binding site is formed in molecular surface, so that the polymer material adsorption capacity is big, absorption, resolution speed are fast, and specificity is high, selects
Selecting property is good, long service life, the features such as recycling can be achieved.
Molecularly imprinted polymer proposed by the present invention is microspheric, the relatively good microspheric molecularly imprinted polymer of monodisperse
Material, not only molecular recognition is high-efficient, is convenient for Functional Design, but also preparation and application are also more convenient.Existing molecule print at present
The shape of mark polymer is bulk, is used after grinding and sieving, but process is tedious, time-consuming for this method subsequent processing, and grinds sieve
Product is easily caused to lose in the process, shape of product is irregular, and dispersibility is poor, and chromatographic efficiency is low.
A kind of molecularly imprinted polymer material for sulfa drugs in purified water proposed by the present invention, by target
Pollutant is enriched with, is purified, the molecularly imprinted polymer material to sulfamethazine, sulphadiazine, kynix,
7 kinds of sulfanilamide (SN) antimicrobial DP finish residuals such as bacteresulf, sulphathiazole, 5-methoxysulfadiazine, sulfamethyldiazine have very
High adsorption capacity and preferable selectivity.Material after activation thoroughly filters out sulfa drugs pollutant in water, right
Water achievees the effect that purification, ensures domestic water safety.Meanwhile the polymer material can be by methanol to it using long-time
It is cleaned, is reused.This kind of molecularly imprinted polymer material has target molecule drug contamination object highly selective, special
A variety of advantages such as anisotropic good, long service life, reusable.
Detailed description of the invention
Fig. 1 is the electron-microscope scanning figure of molecularly imprinted polymer material produced by the present invention；
Fig. 2 is the forming process figure and identification process figure of imprinted polymer.
Specific embodiment
Combined with specific embodiments below the present invention is made further to explain.
Embodiment 1
A kind of molecularly imprinted polymer material for sulfa drugs in purified water, including following each component: azo two
Isobutyronitrile 0.2mol, Triallyl isocyanurate 1.1mol, azodiisobutyronitrile 61g, function monomer 0.6mol, function monomer
Including 0.3mol methacrylic acid and 0.3mol hydroxyethyl methacrylate.
A kind of preparation method for the molecularly imprinted polymer material of sulfa drugs in purified water, method and step is such as
Under:
S1: being dissolved in sulfamethazine as template molecule in 120mL acetonitrile, and function is added after ultrasonic disperse 15min
Energy monomer methacrylic acid, shakes 2.5h on shaking table, forms pre-polymer solution；
S2: and then hydrophily function monomer hydroxyethyl methacrylate is added and continues to shake 2h, it is abundant to add crosslinking agent
2h is stirred, initiator stirring 0.5h, rate 400rpm are added；
S3: nitrogen protection is utilized, is heated under 62 DEG C of water bath condition, brings it about thermal polymerization, water-bath 23h can be obtained
To target molecule polymer material.
Embodiment 2
A kind of molecularly imprinted polymer material for sulfa drugs in purified water, including following each component: azo two
Isobutyronitrile 0.4mol, Triallyl isocyanurate 1.3mol, azodiisobutyronitrile 68g, function monomer 0.7mol, function monomer
Including 0.36mol methacrylic acid and 0.34mol hydroxyethyl methacrylate.
A kind of preparation method for the molecularly imprinted polymer material of sulfa drugs in purified water, method and step is such as
Under:
S1: being dissolved in sulfamethazine as template molecule in 120mL acetonitrile, and function is added after ultrasonic disperse 25min
Energy monomer methacrylic acid, shakes 1.5h on shaking table, forms pre-polymer solution；
S2: and then hydrophily function monomer hydroxyethyl methacrylate is added and continues to shake 2h, it is abundant to add crosslinking agent
2h is stirred, initiator stirring 0.5h, rate 600rpm are added；
S3: nitrogen protection is utilized, is heated under 65 DEG C of water bath condition, brings it about thermal polymerization, water-bath 25h can be obtained
To target molecule polymer material.
Embodiment 3
A kind of molecularly imprinted polymer material for sulfa drugs in purified water, including following each component: azo two
Isobutyronitrile 0.3mol, Triallyl isocyanurate 1.2mol, azodiisobutyronitrile 65g, function monomer 0.65mol, function list
Body includes 0.34mol methacrylic acid and 0.31mol hydroxyethyl methacrylate.
A kind of preparation method for the molecularly imprinted polymer material of sulfa drugs in purified water, method and step is such as
Under:
S1: being dissolved in sulfamethazine as template molecule in 120mL acetonitrile, and function is added after ultrasonic disperse 20min
Energy monomer methacrylic acid, shakes 2h on shaking table, forms pre-polymer solution；
S2: and then hydrophily function monomer hydroxyethyl methacrylate is added and continues to shake 1h, it is abundant to add crosslinking agent
1h is stirred, initiator stirring 0.5h, rate 500rpm are added；
S3: nitrogen protection is utilized, is heated under 60 DEG C of water bath condition, brings it about thermal polymerization, water-bath for 24 hours, can obtain
To target molecule polymer material.
Embodiment 4
A kind of molecularly imprinted polymer material for sulfa drugs in purified water, including following each component: azo two
Isobutyronitrile 0.2mol, Triallyl isocyanurate 1.3mol, azodiisobutyronitrile 66g, function monomer 0.7mol, function monomer
Including 0.35mol methacrylic acid and 0.35mol hydroxyethyl methacrylate.
A kind of preparation method for the molecularly imprinted polymer material of sulfa drugs in purified water, method and step is such as
Under:
S1: being dissolved in sulfamethazine as template molecule in 120mL acetonitrile, and function is added after ultrasonic disperse 20min
Energy monomer methacrylic acid, shakes 1.5h on shaking table, forms pre-polymer solution；
S2: and then hydrophily function monomer hydroxyethyl methacrylate is added and continues to shake 1.5h, it adds crosslinking agent and fills
Divide stirring 1h, adds initiator stirring 0.5h, rate 400rpm；
S3: nitrogen protection is utilized, is heated under 60 DEG C of water bath condition, brings it about thermal polymerization, water-bath 23-25h
Obtain target molecule polymer material.
Properties of product experiment
The molecularly imprinted polymer of synthesis is pulverized last sieving, 600~800 mesh polymer is taken to be wrapped up with filter paper,
It is transferred in Soxhlet extractor and extracts 80h, extractant is methanol: formic acid (v:v, 9:1), up to no template molecule detects.So
2h is washed with the methanol of the hydrochloric acid of 20mL 1mol/L and 20mL afterwards, repeatedly with the sodium hydroxide of 0.25mol/L, distilled water finally
It rinses until neutral.Being subsequently placed in 75 DEG C of baking ovens, drying to constant weight to get sulfamethazine molecularly imprinted polymer is arrived
Grain.It weighs 300g adsorbent material to be filled in blank pipe, tabletting compression in both ends vacuumizes spare.First with 200mL methanol to material
It is activated, elution 5 times is carried out to material repeatedly with distilled water, it can realize the purified treatment of underwater trace pollutant.
7 kinds of pharmaceutical sample solution of 50mg/L are respectively configured, with spare molecular engram packed column successively to pharmaceutical sample
Adsorption treatment is carried out, finally use eluant, eluent methanol: formic acid (v:v, 9:1) is eluted, is concentrated, finally by HPLC to sample point
Analysis detection, experimental result are shown in Table 1.
1 processing result of table
| Drug | Before processing (mg/L) | After processing (mg/L) | Removal rate % |
| Sulfamethazine | 50 | 4.2×10-1 | 99.2 |
| Sulphadiazine | 50 | 3.7 | 92.6 |
| Kynix | 50 | 2.1 | 95.8 |
| Bacteresulf | 50 | 5.3 | 89.4 |
| Sulphathiazole | 50 | 1.1 | 97.8 |
| 5-methoxysulfadiazine | 50 | 6.4×10-1 | 98.7 |
| Sulfamethyldiazine | 50 | 4.8 | 90.4 |
By being enriched with, being purified to target molecule, polymer material is to sulfamethazine, sulphadiazine, sulfanilamide (SN)
Methoxy piperazine, bacteresulf, sulphathiazole, 5-methoxysulfadiazine, sulfamethyldiazine have very high adsorption capacity and compared with
Good selectivity, the material after activation thoroughly filter out sulfa drugs pollutant in water, achieve the effect that purification to water.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of molecularly imprinted polymer material for sulfa drugs in purified water, which is characterized in that by template molecule, function
Under the action of initiator free radical polymerization occurs for energy monomer, crosslinking agent, and the microballoon point of high-crosslinking-degree is formed with emulsion polymerization
Sub- polymer, the adding proportion of the template molecule, function monomer, crosslinking agent, initiator are as follows: (0.2-0.4) mol:(0.6-
0.7)mol:(1.1-1.3)mol:(61-68)g。
2. a kind of molecularly imprinted polymer material for sulfa drugs in purified water according to claim 1, special
Sign is that the template molecule is sulfamethazine.
3. a kind of molecularly imprinted polymer material for sulfa drugs in purified water according to claim 1, special
Sign is that the function monomer includes methacrylic acid and hydroxyethyl methacrylate, and molal weight adding proportion is (1-
1.1): 1.
4. a kind of molecularly imprinted polymer material for sulfa drugs in purified water according to claim 1, special
Sign is that the crosslinking agent is Triallyl isocyanurate.
5. a kind of molecularly imprinted polymer material for sulfa drugs in purified water according to claim 1, special
Sign is that the initiator is azodiisobutyronitrile.
6. a kind of preparation for the molecularly imprinted polymer material of sulfa drugs in purified water according to claim 1
Method, which is characterized in that method and step is as follows:
S1: being dissolved in sulfamethazine as template molecule in acetonitrile, and function monomer is added after ultrasonic disperse 15-25min
Methacrylic acid shakes 1.5-2.5h on shaking table, forms pre-polymer solution；
S2: and then hydrophily function monomer hydroxyethyl methacrylate is added and continues to shake 1-2h, it adds crosslinking agent and sufficiently stirs
1-2h is mixed, initiator stirring 0.5h is added；
S3: nitrogen protection is utilized, is heated under 60-65 DEG C of water bath condition, brings it about thermal polymerization, water-bath 23-25h
Obtain target molecule polymer material.
7. a kind of preparation for the molecularly imprinted polymer material of sulfa drugs in purified water according to claim 6
Method, which is characterized in that the rate stirred in the S2 is 400-600rpm.
8. a kind of molecular engram for purifying water pollutant sulfa drugs according to claim 1-5 is poly-
It closes object material and is applied to sewage treatment.
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| CN109749028A (en) * | 2019-01-21 | 2019-05-14 | 河南永泽环境科技有限公司 | A kind of novel trace pickering emulsion synthetic method of polymers |
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|---|---|---|---|---|
| WO2007096135A1 (en) * | 2006-02-20 | 2007-08-30 | Kist-Europe Forschungsgesellschaft Mbh | Molecularly imprinted polymer, process for production thereof and process for the selective treatment of poorly degradable and/or toxic compounds in liquids |
| CN102344527A (en) * | 2010-07-29 | 2012-02-08 | 上海市农业科学院 | Method for purifying sulfanilamide drug by using molecularly imprinted polymer |
| CN104001486A (en) * | 2014-05-13 | 2014-08-27 | 齐鲁工业大学 | Preparation method of hydrophilic sulfa drug molecularly imprinted solid-phase extraction column |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007096135A1 (en) * | 2006-02-20 | 2007-08-30 | Kist-Europe Forschungsgesellschaft Mbh | Molecularly imprinted polymer, process for production thereof and process for the selective treatment of poorly degradable and/or toxic compounds in liquids |
| CN102344527A (en) * | 2010-07-29 | 2012-02-08 | 上海市农业科学院 | Method for purifying sulfanilamide drug by using molecularly imprinted polymer |
| CN104001486A (en) * | 2014-05-13 | 2014-08-27 | 齐鲁工业大学 | Preparation method of hydrophilic sulfa drug molecularly imprinted solid-phase extraction column |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109749028A (en) * | 2019-01-21 | 2019-05-14 | 河南永泽环境科技有限公司 | A kind of novel trace pickering emulsion synthetic method of polymers |
| CN109749028B (en) * | 2019-01-21 | 2021-04-20 | 河南永泽环境科技有限公司 | Novel synthesis method of imprinted pickering emulsion polymer |
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