CN104725547A - Method for preparing melamine molecularly imprinted polymer by virtue of distillation, precipitation and polymerization - Google Patents
Method for preparing melamine molecularly imprinted polymer by virtue of distillation, precipitation and polymerization Download PDFInfo
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- CN104725547A CN104725547A CN201510060046.7A CN201510060046A CN104725547A CN 104725547 A CN104725547 A CN 104725547A CN 201510060046 A CN201510060046 A CN 201510060046A CN 104725547 A CN104725547 A CN 104725547A
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Abstract
The invention discloses a method for preparing a melamine molecularly imprinted polymer by virtue of distillation, precipitation and polymerization. The method comprises the following steps: (1) dissolving melamine, a polymerization reaction monomer and divinylbenzene in acetonitrile, and standing; (2) adding an initiating agent into the solution of the step (1), removing oxygen, and heating to distill acetonitrile; and (3) after the distillation in the step (2), filtering the reaction solution, performing refluxing extraction on filter residues by using a methanol-acetic acid mixed solution, and drying to obtain the melamine molecularly imprinted polymer. By adopting the method disclosed by the invention, the problems that the molecularly imprinted polymer obtained by the conventional method is non-uniform in particle size, difficult in size control and low in binding capacity; the method disclosed by the invention is simple to operate and does not need a complex after-treatment process, and the obtained molecularly imprinted polymer microspheres have good monodispersity and binding capacity of 32-44mg/g, and can be used for separating and detecting melamine in a sample.
Description
Technical field
The invention belongs to molecularly imprinted polymer field, be specifically related to a kind of method of distilling precipitation polymerization and preparing melamine molecular engram polymer.
Background technology
Trimeric cyanamide (Melamine, MEL), is commonly called as " extract of protein ", is a kind of important nitrogen heterocyclic Organic Chemicals, nitrogen content about 66%, far away higher than the average nitrogen content of protein.Due to the defect of Various Methods for Determing Different Proteins, trimeric cyanamide is often doped in food or feed by illegal businessman, to improve the protein content index in food or feed detection.Experimentation on animals proves that long-term trimeric cyanamide of taking in can cause urinary system calculus, even can bring out bladder cancer.2008, it was exactly that milk powder pollutes by trimeric cyanamide that well-known baby milk powder poisoning is traced it to its cause.The Ministry of Health and relevant department combine issue bulletin, formulate the temporary control and education value of trimeric cyanamide in breast with milk-product: in milk power for infant and young children, the Limited Doses of trimeric cyanamide is 1 mg/kg.But after 2 years, trimeric cyanamide event breaks out again, brings serious negative impact to the production and sales of China's Dairy Industry.Therefore, set up the detection method that in the food samples such as a kind of milk preparation, trace melamine is residual, for ensureing that human consumer is healthy and safeguard that the stable of economic society is of great practical significance.
The detection method of current trimeric cyanamide mainly contains high performance liquid chromatography, high performance liquid phase-mass spectroscopy, gas phase-mass spectrography.But no matter adopt which kind of method, all first should carry out pre-treatment to actual sample.Solid-Phase Extraction is conventional Sample Pretreatment Technique, but the solid-phase extraction column of routine is owing to lacking the specificity adsorption selection ability to target components to be measured, is difficult to effectively get rid of complex sample matrix to the interference of component to be measured.
Molecular imprinting energy synthetic has molecularly imprinted polymer (the Molecularly imprinted polymers of predetermined selectivity to target molecule, MIPs), the corresponding identification relation that the MIPs obtained has with target molecule " lock-key ", so have highly selective.Secondly, MIPs also has the advantage of high strength (i.e. high temperature resistant, organic solvent-resistant, acid and alkali-resistance etc.).Therefore, this technology development in recent years is rapid, has been widely used in medical separation, food and environment measuring, antibody or has been subject to n-body simulation n catalysis, sensor numerous areas, having demonstrated good application prospect.Melamine molecular engram polymer can carry out effective purifying and enrichment to the trimeric cyanamide in powdered milk sample, realizes trimeric cyanamide and detects fast and accurately.
Report that the preparation method about melamine molecular engram polymer mainly contains precipitation polymerization and suspension polymerization etc. both at home and abroad at present.Yang Weihai, guard the precipitation polymerization method that thunder etc. adopts rigidly and prepared the molecularly imprinted polymer of trimeric cyanamide.Monomer used for reaction, linking agent, initiator are dissolved in suitable solvent by precipitation polymerization usually, and the polymkeric substance produced in reaction precipitates with microballoon form because being insoluble to solvent.The normally used quantity of solvent of this method is comparatively large, and the concentration of function monomer is lower, and the selection of solvent is comparatively harsh.Wang Xindi adopts suspension polymerization to prepare trimeric cyanamide imprinted material, and uses it for the pre-treatment of milk powder.Reactant is normally dissolved in organic solvent by suspension polymerization, then transfers in the aqueous phase containing dispersion stabilizer, stirs and initiation reaction.But there is the shortcomings such as the stablizers such as tensio-active agent are difficult to remove, and obtained component of polymer is complicated.And the binding capacity of the melamine molecular engram polymer adopting these methods above-mentioned to obtain and trimeric cyanamide is the highest also less than 20 mg/g.
Summary of the invention
The object of the invention is the problems referred to above overcoming prior art existence, a kind of method being prepared melamine molecular engram polymer by distillation precipitation polymerization is provided.
It is as follows that the present invention realizes the technical scheme that above-mentioned purpose adopts:
Distill the method that precipitation polymerization prepares melamine molecular engram polymer, comprise the steps:
(1) trimeric cyanamide, polymerization reaction monomer and Vinylstyrene are dissolved in acetonitrile, leave standstill;
(2) in the solution of step (1), add initiator, deoxygenation, heating distills out acetonitrile;
(3), after step (2) distillation terminates, reacting liquid filtering, filter residue methanol-acetic acid mixed-liquor return extracts, wash-out removing melamine molecule, dry, obtains melamine molecular engram polymer.
Further, the mol ratio of described trimeric cyanamide and polymerization reaction monomer is preferably 1: (2 ~ 16).Preferred mol ratio is 1: (2 ~ 5).
Further, in the solution of step (1), the total volume concentration of polymerization reaction monomer and Vinylstyrene is 5 ~ 7%, and the mol ratio of polymerization reaction monomer and Vinylstyrene is 1: (4 ~ 7).
Further, described polymerization reaction monomer is methacrylic acid or methyl methacrylate.
Described the leaving standstill of step (1) preferably leaves standstill 10 ~ 20 h under the condition of lucifuge.
Further, described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
Further, described initiator is preferably 1 ~ 5% of polymerization reaction monomer and Vinylstyrene total mass.
Further, step (2) distillation speed controls to be steamed by the acetonitrile of half in 1.5 ~ 2 hours.
Further, in the described methanol-acetic acid mixed solution of step (3), the volume ratio of methyl alcohol and acetic acid is preferably (10 ~ 8): 1.
The melamine molecular engram polymer prepared according to aforesaid method is applied to the separation and detection of trimeric cyanamide.
The inventive method operation is comparatively simple, preparation condition is easy to control, and without the need to the last handling process of complexity, and gained molecularly imprinted polymer is that monodispersity is good, the microballoon of uniform particle diameter, the particle diameter of microballoon is at about 0.5 ~ 5 μm, and binding capacity can reach 32 ~ 44 mg/g.
Accompanying drawing explanation
Fig. 1 is the electron microscopic picture of embodiment 1 polymkeric substance.
Fig. 2 is the infrared spectrogram of polymkeric substance.
Fig. 3 is the electron microscopic picture of embodiment 2 polymkeric substance.
Fig. 4 be polymkeric substance and trimeric cyanamide in conjunction with isothermal curve.
Fig. 5 is the high-efficient liquid phase chromatogram adding trimeric cyanamide (1 μ g/g) in powdered milk sample.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further details.
The synthesis I of embodiment 1 MEL imprinted polymer
Get trimeric cyanamide (MEL) 0.22 g, methacrylic acid 0.60 mL, Vinylstyrene 5.0 mL is dissolved in 80 mL acetonitriles, ultrasonic 2 min make it to mix, lucifuge leaves standstill 12 h and is placed in there-necked flask, then Diisopropyl azodicarboxylate 0.13 g is added, stir with the speed of 120 r/min after passing into argon gas deoxygenation 5 min and start heating in water bath in room temperature, acetonitrile boiling point is heated in about 30 min, now start to collect distillate, by control temperature, when steaming 40 mL acetonitrile in 1.5 ~ 2 h, terminate reaction.Be polymerized the emulsion that obtains, after ultrasonic, suction filtration, filter residue methanol wash 3 times, with methanol-acetic acid (9: 1,
v/v) in cable type extractor according, extract 24 h as eluent, afterwards with washed with methanol several, baking oven 50 DEG C of dryings, namely obtain melamine molecular engram polymer (Molecularly imprinted polymers, MIPs).Except not adding template molecule MEL, the preparation method of non-imprinted polymer (Non-imprinted polymers, NIPs) is the same.
Resulting polymers is (A1 is MIPs, A2 is NIPs) as shown in Figure 1, all can obtain that particle diameter is more homogeneous, the good microballoon of monodispersity as seen.
Infrared spectrogram before and after wash-out is (a MIPs that to be MEL, b be before wash-out, c is the MIPs after wash-out) as shown in Figure 2, before wash-out, still has the characteristic peak of MEL in polymkeric substance, and after wash-out, in polymkeric substance, the characteristic peak of MEL disappears, and illustrates that MEL removes.
The synthesis II of embodiment 2 MEL imprinted polymer
Methacrylic acid consumption is 0.43 mL, Vinylstyrene consumption is 3.57 mL, and other condition is with embodiment 1, and resulting polymers is (B1 is MIPs, B2 is NIPs) as shown in Figure 3.
The synthesis III of embodiment 3 MEL imprinted polymer
Get trimeric cyanamide (MEL) 0.22 g, methyl methacrylate 0.80 mL, Vinylstyrene 5.0 mL is dissolved in 80 mL acetonitriles, ultrasonic 2 min make it to mix, lucifuge leaves standstill 12 h and is placed in there-necked flask, then benzoyl peroxide 0.19 g is added, stir with the speed of 120 r/min after passing into argon gas deoxygenation 5 min and start heating in water bath in room temperature, acetonitrile boiling point is heated in about 30 min, now start to collect distillate, by control temperature, when steaming 40 mL acetonitrile in 1.5 ~ 2 h, terminate reaction.Other conditions are with embodiment 1.The maximum binding capacity of this MEL imprinted polymer is that 32.75 mg/g(testing method are with embodiment 4).
The binding capacity test of embodiment 4 MEL imprinted polymer
Take 9 parts of MIPs or NIPs(50 mg that embodiment 1 is obtained) in 10 mL centrifuge tubes, except portion adds 5 mL methyl alcohol as blank, another 8 parts add MEL methanol solution 5 mL that concentration is followed successively by 1.00,2.00,4.00,7.00,10.00,13.00,16.00,20.00 mg/mL respectively.Sealed by centrifuge tube, put into vibrator 25 DEG C of constant temperature oscillation 24 h, take out centrifugal, Aspirate supernatant high performance liquid chromatograph measures MEL content, calculates MEL binding capacity on polymer, draws static state in conjunction with thermoisopleth, as shown in Figure 4.
As can be seen from Fig. 4, MIPs, NIPs are in conjunction with thermoisopleth trend, along with the increase of MEL concentration, the adsorptive capacity of MIPs and NIPs is all in increase, but, the adsorptive capacity of MIPs is obviously greater than NIPs, the maximum binding capacity that MIPs and NIPs maximal absorptive capacity is respectively MIPs and NIPs is respectively 44.04 mg/g and 17.05 mg/g, this is because MIPs has three-dimensional hole with the space structure of template molecule and functional group binding sites's complementation, there is specific binding in these cavity energies and MEL, after these holes are all occupied, namely absorption arrives balance.And NIPs can only rely on non-specific adsorption, therefore MIPs has higher loading capacity to MEL, mainly the result of trace effect.
The selective binding test of embodiment 5 MEL imprinted polymer
Take in 3 part of 50 mg MIPs to 10 mL centrifuge tube, respectively add MEL methanol solution 5 mL of 3.00 mg/mL; Take 3 part of 50 mg MIPs simultaneously in centrifuge tube, respectively add tricyanic acid (CYA) methanol solution of 3.00 mg/mL.Two groups of sample liquids are placed in vibrator, sample after 25 DEG C of constant temperature oscillation 3h, centrifugal, measure the content of each material in supernatant liquor.NIPs is undertaken by same operation.The results are shown in Table 1.
table 1mIPs and NIPs bonding properties compares
。
The selective recognition performance of MIPs to molecule uses static allocation coefficient usually
k p, separation factor
α,relative separation factors
βcharacterize.Static allocation coefficient
k pbe defined as:
K P=
C i / C j (1)
In formula,
c i,
c jrepresent the concentration of substrate in polymkeric substance and solution respectively.
k pembody the size of MIPs to substrate binding ability, larger description taken in conjunction ability is stronger.
Separation factor
αbe defined as:
α=
K P ’ /
K P ’’ (2)
k p ' with
k p ' ' represent the static allocation coefficient of template molecule and competition molecule respectively.
αshow that more greatly the selection specificity of MIPs to template molecule is better.If
α<1 or near 1, then show that MIPs does not have selectivity to substrate; If
α>1 then shows, MIPs has certain selectivity to substrate.
Relative separation factors
βbe defined as follows:
β=
α m/
α n(3)
Wherein
α mwith
α nrepresent that MIPs and NIPs is to the separation factor of substrate respectively.
βembody the difference of MIPs and NIPs in molecular recognition and selectivity, namely embody the quality of imprinting effect.
βshow that more greatly imprinting effect is better.
As seen in Table 1, MIPs and NIPs
k p (MEL)obviously be greater than
k p (CYA), illustrate that the binding ability of MIP to MEL is stronger.
α mEL=2.8891>1,
α cYA=0.9497, close to 1, show that MIP has certain selectivity to template molecule MEL, and not there is selectivity to CYA.
The Solid-Phase Extraction experiment of embodiment 6 MEL imprinted polymer
Step 1: the preparation of molecular imprinted solid phase extraction cartridge
Take each 0.2 g of MIPs and NIPs that embodiment 1 is obtained, be respectively charged into (column capacity 5 mL, diameter 8 mm) in poly-third ethene pillar, repeatedly rinse with methyl alcohol, obtain solid phase extraction column, infiltrate with acetonitrile, for subsequent use.
Step 2: the preparation of sample solution
Take four parts, 2 g commercially available dried milk powder, be placed in 10 mL centrifuge tubes respectively, three parts add the MEL standard substance of high, medium and low concentration wherein, the 4th part add solvent acetonitrile-water (75: 25,
v/v) as blank.Add subsequently 10 mL acetonitrile-waters (75: 25,
v/v), after supersound extraction 20 min, with centrifugal 10 min of 10000 r/min, get supernatant liquor for subsequent use.
Step 3: Solid-Phase Extraction
Getting above-mentioned gained supernatant liquor 5 mL joins in solid phase extraction column with the speed of 1 mL/min, with 2.0 mL acetonitrile-methanol (3: 1,
v/v) be leacheate, 3.0 mL methyl alcohol-ammoniacal liquor (9: 1,
v/v) for elutriant extracts, finally elutriant nitrogen is dried up, be settled to 100 μ L by moving phase, detect with high performance liquid chromatography.
Solid-Phase Extraction result
As shown in Fig. 5 (for before extraction, b is NIPs column extracting to a, and c is MIPs column extracting), powdered milk sample without Solid-Phase Extraction is difficult to the detection realizing MEL, after Solid-Phase Extraction (MIPs and NIPs post), the concentration of analyte MEL all increases, and can carry out quantitatively.But after MIPs column solid phase extraction, the concentration of MEL is comparatively larger through NIPs post, and illustrate that MIPs post enrichment degree is higher, this comes from the MIPs affinity higher to MEL.To the average recovery measurement result of MEL in powdered milk sample in table 2, the average recovery of MEL is 92.3 ~ 100.1%, RSD≤6.4%, detects and is limited to 0.01 μ g/g.
table 2the average recovery (n=3) of MEL in powdered milk sample
。
Claims (10)
1. distill the method that precipitation polymerization prepares melamine molecular engram polymer, comprise the steps:
(1) trimeric cyanamide, polymerization reaction monomer and Vinylstyrene are dissolved in acetonitrile, leave standstill;
(2) in the solution of step (1), add initiator, deoxygenation, heating distills out acetonitrile;
(3) after step (2) distillation terminates, reacting liquid filtering, after filter residue extracts with methanol-acetic acid mixed-liquor return, dry, obtain melamine molecular engram polymer.
2. distill the method that precipitation polymerization prepares melamine molecular engram polymer according to claim 1, it is characterized in that, the mol ratio of described trimeric cyanamide and polymerization reaction monomer is 1: (2 ~ 16).
3. distill the method that precipitation polymerization prepares melamine molecular engram polymer according to claim 1, it is characterized in that, in the solution of step (1), the total volume concentration of polymerization reaction monomer and Vinylstyrene is 5 ~ 7%, and the mol ratio of polymerization reaction monomer and Vinylstyrene is 1: (4 ~ 7).
4. distill the method that precipitation polymerization prepares melamine molecular engram polymer according to claim 1, it is characterized in that, described polymerization reaction monomer is methacrylic acid or methyl methacrylate.
5. distill the method that precipitation polymerization prepares melamine molecular engram polymer according to claim 1, it is characterized in that, described initiator is Diisopropyl azodicarboxylate or benzoyl peroxide.
6. according to claim 1 or 5, distill the method that precipitation polymerization prepares melamine molecular engram polymer, it is characterized in that, described initiator amount is 1 ~ 5% of polymerization reaction monomer and Vinylstyrene total mass.
7. distill the method that precipitation polymerization prepares melamine molecular engram polymer according to claim 1, it is characterized in that, step (2) distillation speed controls to be steamed by the acetonitrile of half in 1.5 ~ 2 hours.
8. distill the method that precipitation polymerization prepares melamine molecular engram polymer according to claim 1, it is characterized in that, in the described methanol-acetic acid mixed solution of step (3), the volume ratio of methyl alcohol and acetic acid is (10 ~ 8): 1.
9. prepare melamine molecular engram polymer according to the arbitrary described method of claim 1-8.
10. melamine molecular engram polymer described in claim 9 is applied to the separation and detection of trimeric cyanamide.
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| CN109839466A (en) * | 2019-01-24 | 2019-06-04 | 唐玉乐 | A method of testing melamine content in milk powder is detected based on three-dimensional magnetic molecularly imprinted polymer |
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