CN1226310C - Magnetic composite microsphere of molecular blot polymer and its preparing process by combination of reverse-phase emulsion polymerization with suspension polymerization - Google Patents

Abstract

The present invention relates to a magnetic compound microsphere of a molecularly imprinted polymer and a compound preparation method thereof for inverse emulsion polymerization and suspension polymerization. According to the principle of molecular imprinting technology, different substances are used as mould plate molecules (imprinted molecules), and different monomers are used as functional monomers and the parent materials of polymers. Different metals (or oxides of the metals) are used as magnetic components. The magnetic compound microsphere of the molecularly imprinted polymer prepared by adopting the compound preparation method of inverse emulsion polymerization and suspension polymerization has special identifying properties to imprinted molecules and has the characteristic of a dynamic state. The product can be used for a plurality of separation fields such as the separation of analogue compounds, the separation of chiral compounds, the separation of byproducts, the separation and the concentration of trace amount compounds, etc. Compared with traditional separation technology, the separation technology of the present invention is accurate and the separation process of the present invention is greatly simplified.

Description

Molecularly imprinted polymer magnetic composite microspheres and composite preparation method of inverse emulsion polymerization and suspension polymerization

Technical field

The invention belongs to the fields of material science and engineering and bioseparation engineering, and particularly relates to a molecularly imprinted polymer magnetic composite microsphere and a composite preparation method thereof by inverse emulsion polymerization and suspension polymerization.

Background technique

Molecular imprinting technology has been widely and deeply researched in many fields, such as separation of similar compounds, antibody binding simulation, enzyme simulation, bioimitation sensors, etc. Molecularly imprinted polymers (MIPs) prepared by this technology have become the new century One of the most promising new materials.

MIPs were prepared by bulk polymerization in the early days (Wulff G. Molecular recognition in polymers prepared by imprinting with template, polymeric reagents and catalysts, Am Chem Soc Sym Ser, 1986, 308(2): 186-200). Although the polymerization process of this method is very simple, the post-treatment process is very cumbersome and must be completed through grinding, sieving, and elution of template molecules (also known as imprinted molecules), which is not only time-consuming, but also obtains irregular particles. The yield is only about 20%. Spherical molecularly imprinted polymers (SMIPs) can be directly prepared by suspension polymerization (Berglund J, Nicholls I A, Lindbladh C. Recognition in molecularly imprinte polymer-adrenoreceptor mimics, Bioorg Med chemLett, 1996, 6(18): 2237-2242), And it can be used directly only after the elution of template molecules. Because SMIPs have many characteristics such as regular shape, large specific surface, strong adsorption capacity, and particle size can be adjusted according to needs, and have physical properties such as mechanical resistance, high temperature and high pressure resistance, and good chemical properties such as acid and alkali resistance, and resistance to various organic solvents. Stability and storage stability, therefore, very suitable as a separation material.

Molecularly imprinted polymer microspheres currently used in the field of bioseparation engineering cannot be easily and conveniently separated by a magnetic field because they do not contain magnetic components, and can only be separated statically (D Wistuba, V Schurig. Enantiomer separation of chiral pharmaceuticals by capillary electrochromatography, Journal of Chromatography A, 2000, 875: 255-276); if dynamic separation is carried out, SMIPs need to be separated through processes such as centrifugation, and the operation process is cumbersome and complicated. When magnetically responsive materials such as iron, cobalt, nickel or their oxides are embedded inside the polymer microspheres, the composite microspheres have simple and rapid magnetic separation characteristics under the action of an external magnetic field (C Bor Fuh, S Y Chen. Magnetic split-flow thin fractionation: new technique for separation of magnetically susceptible particles, Journal of Chromatography A, 1998, 813: 313-324). When magnetically responsive materials are embedded in SMIPs to prepare molecularly imprinted polymer magnetic composite microspheres (MS-SMIPs), the MS-SMIPs can complete the "active" adsorption and recognition of template molecules under the action of an external magnetic field. It is easy to separate it under the environment to achieve the purpose of active identification and convenient separation.

Contents of the invention

The present invention aims to combine molecular imprinting technology with magnetic sensitivity through the composite preparation method of inverse emulsion polymerization and suspension polymerization, endow molecularly imprinted polymer microspheres with a certain magnetic responsiveness, and make the prepared molecularly imprinted polymer magnetic composite After the microsphere completes the "active" adsorption and specific recognition of the template molecule, it is easy to separate it under the action of an external magnetic field, so as to achieve the purpose of active recognition and convenient separation.

The present invention needs to solve the compatibility problem between the metal (or its oxide) powder and the polymer, and realize the embedding of the inorganic substance by the polymer, thereby endowing the polymer microsphere with a certain magnetic responsiveness, and at the same time completing the template molecular The imprinting process enables the magnetic composite microspheres to have a specific recognition performance for the template molecules and achieve the purpose of specific separation.

According to the principle of molecular imprinting technology, the present invention uses different substances as template molecules (imprinted molecules), different monomers as functional monomers and polymer matrix materials, and different metals (or their oxides) as magnetic groups. The polymer stabilizer is a dispersant, and the composite preparation method of inverse emulsion polymerization and suspension polymerization is used to prepare molecularly imprinted polymer magnetic composite microspheres with specific recognition properties for template molecules.

The prepared molecularly imprinted polymer microspheres are compounded with magnetic responsive materials.

Implementation method of the present invention is as follows:

1) Inverse emulsion polymerization

(1) Dissolve acrylamide and N,N'-methylenebisacrylamide in water, add the ground magnetic powder after dissolving, stir to disperse;

(2) dissolving persulfate and sodium bisulfite in water;

(3) Add the non-polar solvent into the reactor, add the emulsifier, stir evenly, add the mixed solution of (1) and (2) in the above steps, and continue to stir; pass _N2 to deoxygenate, stir, and stir at room temperature for 5 ~ 50°C, react for 0.5~5h; after standing still, remove the upper solvent to obtain inverse emulsion A;

2) Suspension polymerization

(1) Add the initiator to the monomer, add inverse emulsion A after dissolving, and then disperse with ultrasonic waves for 1-30 minutes to obtain inverse emulsion B;

(2) Add water in the reactor, then add polymer stabilizer, stir to make it dissolve;

(3) Dissolve the template molecules in water, add functional monomers, stir for 5 to 60 minutes, then add to the reactor, and continue to stir; then add inverse emulsion B; heat up, and replace oxygen with nitrogen, after the reaction, filter out In the aqueous phase, molecularly imprinted polymer magnetic composite microspheres are obtained;

3) Elution of template molecules

The prepared molecularly imprinted polymer magnetic composite microspheres are first washed with acetone, and then soaked in ethanol for 5-60 minutes; after filtering, they are washed repeatedly with water, and after filtering off the water, use 20-100ml of methanol and acetic acid in a volume ratio of 9:1-4 Soak in the solution and vibrate for 2-48 hours; filter off the methanol and acetic acid solution, rinse repeatedly with distilled water until neutral, and then dry it in a vacuum oven at 40-90°C to constant weight.

in:

In reverse emulsion polymerization:

The monomer is acrylamide, N, N'-methylenebisacrylamide;

The magnetic powder is Fe, Co, Ni or their oxides, or their alloys;

Persulfate is potassium persulfate, ammonium persulfate;

Non-polar solvents are toluene, benzene, gasoline or kerosene, etc.;

The emulsifiers are Span and Tween.

In suspension polymerization:

The initiators are azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide and dicumyl peroxide;

The monomers are styrene, divinylbenzene, methyl methacrylate, acrylonitrile, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, etc.;

Polymer stabilizers are hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid and dextrin;

Template molecules are amino acids and their derivatives, chiral compounds, drugs, pesticides, dyes and other water-soluble organic compounds;

The functional monomers are methacrylic acid, acrylic acid, acrylamide, N,N'-methylenebisacrylamide.

The molecularly imprinted polymer magnetic composite microspheres of the present invention combine the dual functions of the precise specific recognition characteristics of molecularly imprinted polymers and the convenient external magnetic field separation characteristics of the magnetic composite microspheres, and will be used in many separation fields, such as the separation of similar compounds, The separation of chiral compounds, separation of by-products, separation and enrichment of trace compounds has broad application prospects, and greatly simplifies the previous cumbersome separation process (such as high-speed centrifugation, etc.). However, the existing molecularly imprinted polymer microspheres used in the field of bioseparation engineering cannot be easily and conveniently separated by a magnetic field because they do not contain magnetic components; the existing magnetic composite microspheres do not have specific recognition functions because they are not molecularly imprinted. , an exact separation cannot be achieved.

Description of drawings

Figure 1: Molecularly imprinted polymer magnetic composite microspheres prepared in Example 1 (average particle size about 220 μm, Fe ₃ O ₄ content 1.56%)

Figure 2: Molecularly imprinted polymer magnetic composite microspheres prepared in Example 2 (average particle size about 200 μm, Fe ₃ O ₄ content 2.15%)

Detailed ways

Example 1.

1. Inverse emulsion polymerization

(1) Dissolve 9g of acrylamide (AM) and 1g of N,N'-methylenebisacrylamide (Bis) in 20ml of water, add 0.6g of ground Fe ₃ O ₄ powder after dissolving, stir to disperse;

(2) Dissolve 0.1g of potassium persulfate (K ₂ S ₂ O ₈ ) and 0.05g of sodium bisulfite (NaHSO ₃ ) in 10ml of water;

(3) Add 100ml of toluene into a 250ml three-neck flask, add 1.0g of Span80 (Span80), stir well, add the mixture of (1) and (2), and continue stirring. Pass N ₂ to deoxygenate, stir at 300r/m, and react at room temperature for 2h. After standing for a certain period of time, the upper solvent was removed to obtain inverse emulsion A.

2. Suspension polymerization

(1) Add 0.1g AIBN to 10ml trimethylolpropane triacrylate (TRIM), dissolve and add 10ml inverse emulsion A, and then disperse with ultrasonic waves for 5min to obtain inverse emulsion B.

(2) Add 130ml of water into a 250ml three-necked flask equipped with a stirrer, a reflux condenser, and a vent tube, then add 0.15g of hydroxyethyl cellulose (HEC), and stir to dissolve it.

(3) Add 0.25mmol tyrosine (Tyr) into water, add 1mmol (mmol, ie 0.001mol) methacrylic acid (MAA) and 1mmol acrylamide (AM) after dissolving, stir for 30min, then add to the three-necked flask, continue Stir. Inverse Emulsion B was then added. Raise the temperature, and pass nitrogen gas for 5 minutes to replace and remove oxygen; control the temperature to 70°C, and react for 12 hours. After the reaction, the water phase was filtered out with a 180-mesh screen to obtain molecularly imprinted polymer magnetic composite microspheres.

3. Elution of template molecules

The prepared molecularly imprinted polymer magnetic composite microspheres were first washed with acetone, and then soaked in ethanol for 10 minutes; after filtering, they were washed repeatedly with water, and after the water was filtered off, they were soaked in 50ml of methanol/acetic acid (9/1, volume ratio) solution and shaken for 24 hours . After the methanol/acetic acid solution was filtered off, it was washed repeatedly with distilled water until neutral, and then dried in a vacuum oven at 80°C to constant weight.

The obtained molecularly imprinted polymer magnetic composite microspheres are composed of Fe ₃ O ₄ magnetic material in tyrosine molecularly imprinted polymer microspheres, the content of Fe ₃ O ₄ is 2.15%, and phenylalanine is used as the The comparative molecule had a separation factor of 3.89 for tyrosine.

Example 2.

1. Inverse emulsion polymerization

(1) Dissolve 9g of acrylamide (AM) and 1g of N,N'-methylenebisacrylamide (Bis) in 20ml of water, add 0.8g of ground Fe ₃ O ₄ powder after dissolving, stir to disperse;

(2) Dissolve 0.1g of ammonium persulfate ((NH ₄ ) ₂ S ₂ O ₈ ) and 0.05g of sodium bisulfite (NaHSO ₃ ) in 10ml of water;

(3) Add 100ml of toluene into a 250ml three-neck flask, add 1.2g of Span85 (Span85), stir well, add the mixture of (1) and (2), and continue stirring. Pass N ₂ to deoxygenate, stir at 300r/m, and react at room temperature for 2h. After standing for a certain period of time, the upper solvent was removed to obtain inverse emulsion A.

2. Suspension polymerization

(1) Add 0.1g of benzoyl peroxide (BPO) into a mixture of 10ml of styrene (St) and 2ml of divinylbenzene (DVB), dissolve it and add 10ml of inverse emulsion A, then disperse it with ultrasonic waves for 5min to obtain Inverse emulsion B.

(2) Add 130ml of water into a 250ml three-neck flask equipped with a stirrer, reflux condenser, and vent tube, then add 1.0g of polyvinyl alcohol (PVA1799), stir and heat to dissolve.

(3) Add 0.25 mmol of phenylalanine (Phe) into water to dissolve, then add 2 mmol of methacrylic acid (MAA), stir for 30 min, then add to a three-necked flask, and continue stirring. Inverse Emulsion B was then added. Raise the temperature, and pass nitrogen gas for 5 minutes to replace and remove oxygen; control the temperature to 70°C, and react for 24 hours. After the reaction, the water phase was filtered out with a 180-mesh screen to obtain molecularly imprinted polymer magnetic composite microspheres.

3. Elution of template molecules

The prepared molecularly imprinted polymer magnetic composite microspheres were first washed with acetone, and then soaked in ethanol for 10 minutes; after filtering, they were washed repeatedly with water, and after the water was filtered off, they were soaked in 50ml of methanol/acetic acid (9/1, volume ratio) solution and shaken for 24 hours . After the methanol/acetic acid solution was filtered off, it was washed repeatedly with distilled water until neutral, and then dried in a vacuum oven at 80°C to constant weight.

The prepared molecularly imprinted polymer magnetic composite microsphere is characterized in that Fe ₃ O ₄ magnetic material is compounded in the phenylalanine molecularly imprinted polymer microsphere, the content of Fe ₃ O ₄ is 1.56%, and tyramine Acid was a comparative molecule with a separation factor of 2.35 for phenylalanine.

Example 3.

1. Inverse emulsion polymerization

(1) Dissolve 9g of acrylamide (AM) and 1g of N,N'-methylenebisacrylamide (Bis) in 20ml of water, add 0.6g of ground Fe ₂ 0 ₃ powder after dissolving, stir to disperse;

(2) Dissolve 0.1g of potassium persulfate (K ₂ S ₂ O ₈ ) and 0.05g of sodium bisulfite (NaHSO ₃ ) in 10ml of water;

(3) Add 100ml of benzene into a 250ml three-neck flask, add 1.0g of Span60 (Span60) and 0.5g of Tween80 (Tween80), stir well, add the mixture of (1) and (2), and continue stirring. Pass N ₂ to deoxygenate, stir at 300r/m, and react at room temperature for 2h. After standing for a certain period of time, the upper solvent was removed to obtain inverse emulsion A.

2. Suspension polymerization

(1) Add 0.1g of AIBN to 10ml of pentaerythritol triacrylate (PETRA), dissolve and add 10ml of inverse emulsion A, and then disperse with ultrasonic waves for 5min to obtain inverse emulsion B.

(2) Add 130ml of water into a 250ml three-necked flask equipped with a stirrer, a reflux condenser, and a vent tube, then add 0.15g of hydroxypropyl cellulose (HPC), and stir to dissolve it.

(3) Add 0.25mmol of tryptophan (Trp) into water, dissolve and add 1mmol of methacrylic acid (MAA) and 1mmol of acrylamide (AM), stir for 30min, then add to a three-necked flask, and continue stirring. Inverse Emulsion B was then added. Raise the temperature, and pass nitrogen gas for 5 minutes to replace and remove oxygen; control the temperature to 70°C, and react for 12 hours. After the reaction is finished, the water phase is filtered out with a NuO mesh screen to obtain molecularly imprinted polymer magnetic composite microspheres.

3. Elution of template molecules

The prepared molecularly imprinted polymer magnetic composite microspheres were first washed with acetone, and then soaked in ethanol for 10 minutes; after filtering, they were washed repeatedly with water, and after the water was filtered off, they were soaked in 50ml of methanol/acetic acid (9/1, volume ratio) solution and shaken for 24 hours . After the methanol/acetic acid solution was filtered off, it was washed repeatedly with distilled water until neutral, and then dried in a vacuum oven at 80°C to constant weight.

The prepared molecularly imprinted polymer magnetic composite microspheres are composed of Fe ₂ O ₃ magnetic materials in tryptophan molecularly imprinted polymer microspheres, the content of Fe ₃ O ₄ is 1.98%, and tyrosine and benzene Alanine was a comparative molecule with a separation factor of 2.87 for tryptophan.

Claims (10)

1. a magnetic composite microsphere of molecular blot polymer is characterized in that being compounded with the magnetic responsiveness material in molecular blotting polymer microsphere.

2. a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 1 is characterized in that being compounded with Fe in the tyrosine molecular blotting polymer microsphere ₃O ₄Magneticsubstance, Fe ₃O ₄Content be 2.15%, with the phenylalanine be the contrast molecule, its separation factor to tyrosine is 3.89.

3. a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 1 is characterized in that being compounded with Fe in the phenylalanine molecular blotting polymer microsphere ₃O ₄Magneticsubstance, Fe ₃O ₄Content be 1.56%, with tyrosine be the contrast molecule, its separation factor to phenylalanine is 2.35.

4. a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 1 is characterized in that being compounded with Fe in the tryptophane molecular blotting polymer microsphere ₂O ₃Magneticsubstance, Fe ₃O ₄Content be 1.98%, with tyrosine and phenylalanine serve as the contrast molecule, its separation factor to tryptophane is 2.87.

5. the composite preparation process of the inverse emulsion polymerization of a kind of magnetic composite microsphere of molecular blot polymer of claim 1 and suspension polymerization may further comprise the steps:

1) inverse emulsion polymerization

(1) with acrylamide, N, N '-methylene-bisacrylamide is soluble in water, and the dissolving back adds the magnetic powder through grinding, and stirs and makes its dispersion;

(2) receive persulphate, bisulfite soluble in water;

(3) non-polar solvent is added in the reactor, add emulsifying agent, the back that stirs adds the mixed solution of (1) and (2) of above-mentioned steps, continues to stir; Logical N ₂Deoxygenation is stirred, 5～50 ℃ of room temperatures, and reaction 0.5～5h; After leaving standstill, divide and go the upper strata solvent to get reversed-phase emulsion A;

2) suspension polymerization

(1) initiator is added in the monomer, the dissolving back adds reversed-phase emulsion A, uses ultrasonic dispersing 1～30min then, gets reversed-phase emulsion B;

(2) water is added in the reactor, add macromolecule stabilizer then, stir and make its dissolving;

(3) template molecule is added adding function monomer in dissolving back in the entry, add in the reactor behind stirring 5～60min, continue to stir; Add reversed-phase emulsion B then; Heat up, and logical nitrogen replacement deoxygenation, after reaction finished, the filtering aqueous portion obtained magnetic composite microsphere of molecular blot polymer;

3) wash-out of template molecule

The magnetic composite microsphere of molecular blot polymer of preparation is used washing with acetone earlier, use alcohol immersion 5～60min then; Filter back water repetitive scrubbing, behind the elimination water with the volume ratio of 20～100ml for 9: 1～4 methyl alcohol and the acetic acid solution 2～48h that soaks, vibrates; Wash repeatedly to neutrality with distilled water behind elimination methyl alcohol, the acetic acid solution, be dried to constant weight in 40～90 ℃ with vacuum drying oven then.

6. the composite preparation process of the inverse emulsion polymerization of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 5 and suspension polymerization is characterized in that in the described reverse emulsion polymerization:

Monomer is acrylamide, N, N '-methylene-bisacrylamide;

Magnetic powder is Fe, Co, Ni or its oxide compound, or its alloy;

Persulphate is Potassium Persulphate, ammonium persulphate;

Non-polar solvent is toluene, benzene, gasoline or kerosene;

Emulsifying agent is this dish, tween.

7. the composite preparation process of the inverse emulsion polymerization of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 5 and suspension polymerization is characterized in that in the described suspension polymerization:

Initiator is Diisopropyl azodicarboxylate, benzoyl peroxide, hydrogen phosphide cumene and dicumyl peroxide;

Monomer is vinylbenzene, divinylbenzene, methyl methacrylate, vinyl cyanide, Ethylene glycol dimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane three CALCIUM ACRYLATE etc.;

Macromolecule stabilizer is Natvosol, hydroxypropylcellulose, polyvinyl alcohol, polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylic acid and dextrin;

Template molecule is water-soluble organic compounds such as amino acid and derivative thereof, chipal compounds, medicine, sterilant, dyestuff;

Function monomer is methacrylic acid, vinylformic acid, acrylamide, N, N '-methylene-bisacrylamide.

8. the composite preparation process of the inverse emulsion polymerization of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 5 and suspension polymerization is characterized in that described step is:

1) inverse emulsion polymerization

(1) with 9g acrylamide, 1gN, N '-methylene-bisacrylamide is dissolved in the 20ml water, and the dissolving back adds the 0.6g Fe through grinding ₃O ₄Powder stirs and makes its dispersion;

(2) 0.1g Potassium Persulphate, 0.05g bisulfite are received be dissolved in the 10ml water;

(3) 100ml toluene is added in the there-necked flask of 250ml, add the 1.0g span 80, the back that stirs adds the mixed solution of (1) and (2), continues to stir; Logical N ₂Control 300r/m is stirred in deoxygenation, room temperature, reaction 2h; After leaving standstill certain hour, divide and go the upper strata solvent to get reversed-phase emulsion A;

2) suspension polymerization

(1) the 0.1g Diisopropyl azodicarboxylate is added in the 10ml trimethylolpropane triacrylate, the reversed-phase emulsion A that the dissolving back adds 10ml uses ultrasonic dispersing 5min then, gets reversed-phase emulsion B;

(2) 130ml water is added in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe, add the 0.15g Natvosol then, stir and make its dissolving;

(3) 0.25mmol tyrosine is added in the entry, the dissolving back adds 1mmol methacrylic acid and 1mmol acrylamide, adds in the there-necked flask behind the stirring 30min, continues to stir; Add reversed-phase emulsion B then; Heat up, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of controlled temperature, reaction 12h; Reaction with 180 eye mesh screen filtering aqueous portions, obtains magnetic composite microsphere of molecular blot polymer after finishing;

3) wash-out of template molecule

The magnetic composite microsphere of molecular blot polymer of preparation is used washing with acetone earlier, use alcohol immersion 10min then; Filtering back water repetitive scrubbing, is 9: 1 methyl alcohol and the acetic acid solution 24h that soaks, vibrates with the 50ml volume ratio behind the elimination water; Wash repeatedly to neutrality with distilled water behind elimination methyl alcohol and the acetic acid solution, be dried to constant weight in 80 ℃ with vacuum drying oven then.

9. the composite preparation process of the inverse emulsion polymerization of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 8 and suspension polymerization is characterized in that described 1), 2) step is:

1) inverse emulsion polymerization

(1) with 9g acrylamide, 1gN, N '-methylene-bisacrylamide is dissolved in the 20ml water, and the dissolving back adds the 0.8g Fe through grinding ₃O ₄Powder stirs and makes its dispersion;

(2) 0.1g Ammonium Persulfate 98.5,0.05g bisulfite are received be dissolved in the 10ml water;

(3) 100ml toluene is added in the there-necked flask of 250ml, add 1.2g Si dish 85, the back that stirs adds the mixed solution of (1) and (2), continues to stir; Logical N ₂Control 300r/m is stirred in deoxygenation, room temperature, reaction 2h; After leaving standstill certain hour, divide and go the upper strata solvent to get reversed-phase emulsion A;

2) suspension polymerization

(1) the 0.1g benzoyl peroxide is added in the mixture of 10ml vinylbenzene and 2ml divinylbenzene, the reversed-phase emulsion A that the dissolving back adds 10ml uses ultrasonic dispersing 5min then, gets reversed-phase emulsion B;

(2) 130ml water is added in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe, add the 1.0g polyvinyl alcohol then, stirring and heating make its dissolving;

(3) the 0.25mmol phenylalanine is added dissolving back adding 2mmol methacrylic acid in the entry, add in the there-necked flask behind the stirring 30min, continue to stir; Add reversed-phase emulsion B then; Heat up, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of controlled temperature, reaction 24h; Reaction with 180 eye mesh screen filtering aqueous portions, obtains magnetic composite microsphere of molecular blot polymer after finishing.

10. the composite preparation process of the inverse emulsion polymerization of a kind of magnetic composite microsphere of molecular blot polymer as claimed in claim 8 and suspension polymerization is characterized in that described 1), 2) step is:

1) inverse emulsion polymerization

(1) with 9g acrylamide, 1gN, N '-methylene-bisacrylamide is dissolved in the 20ml water, and the dissolving back adds the 0.6g Fe through grinding ₂O ₃Powder stirs and makes its dispersion;

(2) 0.1g Potassium Persulphate, 0.05g bisulfite are received, be dissolved in the 10ml water;

(3) 100ml benzene is added in the there-necked flask of 250ml, add 1.0g Si dish 60 and 0.5g tween 80; The mixed solution that adds (1) and (2) after stirring continues to stir; Logical N ₂Control 300r/m is stirred in deoxygenation, room temperature, reaction 2h; After leaving standstill certain hour, divide and go the upper strata solvent to get reversed-phase emulsion A;

2) suspension polymerization

(1) the 0.1g Diisopropyl azodicarboxylate is added 10ml tetramethylolmethane three CALCIUM ACRYLATE; In, the reversed-phase emulsion A that the dissolving back adds 10ml uses ultrasonic dispersing 5min then, gets reversed-phase emulsion B;

(2) 130ml water is added in the there-necked flask of the 250ml that has agitator, reflux exchanger, ventpipe, add the 0.15g hydroxypropylcellulose then; , stir and make its dissolving;

(3) with the 0.25mmol tryptophane; Add in the entry, the dissolving back adds the 1mmol methacrylic acid; Add reversed-phase emulsion B then; Heat up, and logical nitrogen 5min displacement deoxygenation; 70 ℃ of controlled temperature, reaction 12h; Reaction with 180 eye mesh screen filtering aqueous portions, obtains magnetic composite microsphere of molecular blot polymer after finishing.

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