CN102382226A - Preparation method of poly-N-vinylpyrrodidone-divinylbenzene microsphere - Google Patents
Preparation method of poly-N-vinylpyrrodidone-divinylbenzene microsphere Download PDFInfo
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Abstract
The invention provides a preparation method of a poly-N-vinylpyrrodidone-divinylbenzene microsphere, which takes a polystyrene monodisperse microsphere that is prepared through dispersion polymerization as a seed, a crosslinking divinylbenzene microsphere is prepared through a swelling polymerization method, finally, N-vinyl pyrrolidone is directly used for swelling polymerization, so the poly-N-vinylpyrrodidone-divinylbenzene microsphere is produced. The poly-N-vinylpyrrodidone-divinylbenzene microsphere which is produced through the method has uniform grain diameter, and has better absorption effect on polar and nonpolar materials.
Description
Technical field
The present invention relates to the polymer chemistry field, relate to N-vinyl pyrrolidone and divinylbenzene swell cross polymerizing microballoons repolymerization specifically.
Background technology
Polymer microballoon has been widely used in fields such as solid phase organic synthesis, chromatographic column filler, medical science and biological chemistries, and polymer microballoon synthetic is one of new focus of filed of functional research.The solid phase extraction filler that contains vinyl pyrrolidone-divinylbenzene is because while possess hydrophilic property and hydrophobic group; All kinds of polarity, non-polar compound are had than the equilibrated adsorption; Its adsorptive power and sample capacity can be widely used in extraction, enrichment and the purification of all cpds far above the C18 bonded silica gel.Main compound method for this kind solid phase extraction filler has: the one, and the macroporous copolymer that two kinds of monomer suspension polymerizations by a certain percentage of lipotropy divinylbenzene and wetting ability N-vinyl pyrrolidone become; The 2nd, be that monomer suspension polymerization by a certain percentage becomes Archon by vinylbenzene and divinylbenzene, chloromethylation carries out functionalized with pyrrolidone to it more then; The 3rd, the 5um mono-dispersion microballoon is the swelling copolymerization in N-vinyl pyrrolidone and divinylbenzene.
The present invention is on the basis of existing swollen-state polymerization crosslinked microsphere; Adopt N-vinyl pyrrolidone and crosslinked divinylbenzene microspheres repolymerization; Prepare a kind of particle diameter evenly, polarity and apolar substance all had a poly N-vinyl pyrrolidone-divinylbenzene microspheres of better adsorption effect; Make the form and the performance of product be easy to control, increase the homogeneity and the productive rate of product size distribution simultaneously.
Summary of the invention
The present invention improves also and has developed forefathers' polymerization method, has set up one and has prepared polystyrene seed from dispersion polymerization and prepare crosslinked divinylbenzene microspheres to " swollen-state polymerization method ", uses the direct swollen-state polymerization of N-vinyl pyrrolidone at last.Provide a kind of particle diameter even, polarity and apolar substance have all been had the polymer microsphere of adsorption effect preferably.
The preparation method of poly N-ethylene pyrrolidone-divinylbenzene microspheres of the present invention, concrete steps are:
The preparation of A seed: stablizer is dissolved in the alcohol, leads to nitrogen deoxygenation, stirring, heating, add the vinyl monomer that is dissolved with initiator again, reaction is more than 14 hours, and product is through filtration, lotion, drying.
The swollen-state polymerization of the crosslinked divinylbenzene microspheres of B:
B1 is suspended in single seed microballoon that disperses of A preparation in the aqueous solution that contains stablizer, stirs.
B2 joins vinyl monomer, initiator, pore-creating agent thorough mixing in the aqueous solution that is dissolved with stablizer and tensio-active agent, stirs certain hour fast, processes emulsion.
The emulsion that B3 makes B2 slowly is added drop-wise in the said solution of B1, and the dropping time is 2-12 hour.Begin swelling afterwards, swelling time is 2-10 hour, is heated to polymerization temperature, carries out polyreaction, and the reaction times is 2-6 hour.One step swollen-state polymerization is accomplished, and can proceed the secondary swollen-state polymerization to this reaction according to needed specific surface and aperture, particle diameter.
Crosslinked divinylbenzene microspheres of C and pyrrolidone monomer repolymerization
C1 reduces the B3 polymerization temperature.With pyrrolidone monomer, initiator thorough mixing, join in the aqueous solution that is dissolved with stablizer and tensio-active agent, stir certain hour fast, process emulsion.Continuation is added to emulsion droplets in the B3 reaction system, and the dropping time is 2-6 hour.Begin swelling after dripping off, swelling time is 2-10 hour, is heated to polymerization temperature, carries out polyreaction, and the reaction times is 10-15 hour, or to reacting completely.
C2 adopts ordinary method at last, filtration, lotion, refilter, dry, put forward step such as pore-creating agent, reclaim copolymerization microsphere, measure its particle diameter and size distribution, specific surface area etc.
Described vinyl monomer is polymerization single polymerization monomers such as vinylbenzene, divinylbenzene.
Described initiator is Lucidol, t-butyl per(oxy)benzoate, Diisopropyl azodicarboxylate etc.
Described pore-creating agent is good solvent or poor solvent pore-creating agents such as toluene, normal heptane, whiteruss.
Described stablizer is steric hindrance stablizers such as water-soluble cellulose ether, PVP K120 or hydroxypropylcellulose.
Described tensio-active agent is negatively charged ion, positively charged ion and non-ionics, for example SDS, Triton X-405.
Described pyrrolidone monomer is the N-V-Pyrol RC.
The particle diameter of the seed microballoon for preparing in the said steps A is 3-8um.
The weight percent of seed microballoon, stablizer, water is among the said step B1: 20-60: 0.2-1.5: 150-600.
The weight percent of vinyl monomer, initiator, pore-creating agent is among the said step B2: 20-80: 0.3-1.6: 10-100, the weight percent of vinyl monomer, stablizer, tensio-active agent, water is: 20-80: 0.05-0.5: 0.5-5: 50-500.
The weight percent of pyrrolidone monomer, initiator, stablizer, tensio-active agent, water is among the said step C1: 20-100: 0.3-1.6: 0.01-0.5: 0.2-5: 50-500.
Quick churning time is 4-20 hour among said step B2 and the C1, and the emulsion of processing is not stratified, and the dropping time is 2-12 hour among B3 and the C1, and swelling time is 2-10 hour, and the reaction times is 10-15 hour.
Poly N-vinyl pyrrolidone-the divinylbenzene microspheres of the present invention's preparation, specific surface area 100-700m
2/ g, particle diameter 20-80um.Through using dispersion polymerization to prepare PS small-particle seed; Prepare crosslinked divinylbenzene microspheres to " swelling copolymerization method "; Use N-vinyl pyrrolidone swollen-state polymerization at last, make the form of product and performance be easy to control, increase the homogeneity and the productive rate of product size distribution simultaneously.
Description of drawings
PS mono-dispersion microballoon electron scanning micrograph in Fig. 1 example 1
The electron scanning micrograph of Fig. 2 example 2 poly N-vinyl pyrrolidones-divinylbenzene microspheres
The electron scanning micrograph of Fig. 3 example 3 poly N-vinyl pyrrolidones-divinylbenzene microspheres
Embodiment
Embodiment 1:
Add Vinylpyrrolidone polymer 10.8g, absolute ethyl alcohol 600ml in the 1000ml four-hole boiling flask; Being stirred to Vinylpyrrolidone polymer dissolves fully; Under nitrogen protection, be warming up to 70 ℃, add the 150g styrene solution that is dissolved with the 3.8g Diisopropyl azodicarboxylate then, reacted 24 hours.Filter, the absolute ethyl alcohol lotion is dried to constant weight, and is subsequent use.
Gained polystyrene microsphere monodispersity is good, and particle diameter is 5.0um, and its electron scanning micrograph is as shown in Figure 1.
Embodiment 2:
In the 1000ml four-hole boiling flask, mono-dispersion microballoon 40g adding prepared in the example 1 is contained in the 250ml water of 0.3g Vltra tears, stir and be heated to 40 ℃, stirred 3 hours at 40 ℃.
With divinylbenzene 80g, toluene 60g and after Diisopropyl azodicarboxylate 1.0g mixes; Add and mix back emulsification (emulsion 1) in the 200ml water that contains 0.1g Vltra tears and 1g Triton X-405; Under 40 ℃, slowly be added drop-wise in the said solution; Dripped 5 hours altogether, and continued swelling afterwards again 8 hours, and then add 1% Vltra tears aqueous solution 100g.Be heated to 88 ℃, carried out polyreaction 3 hours.
Cooling prepares emulsion 2 simultaneously, after N-vinyl pyrrolidone 60g and Diisopropyl azodicarboxylate 0.8g mixing; Add and mix back emulsification in the 100ml water that contains 0.05g Vltra tears and 0.5g Triton X-405; Under 40 ℃, slowly be added drop-wise in the above-mentioned reaction system, dripped 4 hours altogether, continued swelling afterwards again 8 hours; Be warmed up to 88 ℃, carried out polyreaction 12 hours.
Last ordinary method filtration, lotion, refilter, dry, put forward step such as pore-creating agent, reclaim polymerizing microballoons.The particle diameter of gained polymerizing microballoons concentrates between the 20-25um, narrowly distributing, and specific surface area is 346m
2/ g, its electron scanning micrograph is as shown in Figure 2.
Embodiment 3
In the 1000ml four-hole boiling flask, mono-dispersion microballoon 40g adding prepared in the example 1 is contained in the 200ml water of 0.3g Vltra tears, stir and be heated to 40 ℃, stirred 3 hours at 40 ℃.
With divinylbenzene 80g, toluene 60g and after Diisopropyl azodicarboxylate 1.0g mixes; Add and mix back emulsification (emulsion 1) in the 200ml water that contains 0.1g Vltra tears and 1g Triton X-405; Under 40 ℃, slowly be added drop-wise in the said solution; Dripped 5 hours altogether, and continued swelling afterwards again 8 hours, and then add 1% Vltra tears aqueous solution 100g.Be heated to 88 ℃, carried out polyreaction 3 hours.
Cooling; Prepare emulsion 2 simultaneously,, add and mix back emulsification in the 200ml water that contains 0.1g Vltra tears and 1g Triton X-405 with divinylbenzene 40g, toluene 40g, liquid wax 20g and after Diisopropyl azodicarboxylate 0.8g mixes; Under 40 ℃, slowly be added drop-wise in the said solution; Dripped 5 hours altogether, and continued swelling afterwards again 8 hours, and then add 1% Vltra tears aqueous solution 100g.Be heated to 88 ℃, carried out polyreaction 3 hours.
Cooling prepares emulsion 3 simultaneously, after N-vinyl pyrrolidone 80g and Diisopropyl azodicarboxylate 1.0g mixing; Add and mix back emulsification in the 100ml water that contains 0.05g Vltra tears and 0.5g Triton X-405; Under 40 ℃, slowly be added drop-wise in the above-mentioned reaction system, dripped 4 hours altogether, continued swelling afterwards again 8 hours; Be warmed up to 88 ℃, carried out polyreaction 12 hours.
Last ordinary method filtration, lotion, refilter, dry, put forward step such as pore-creating agent, reclaim copolymerization microsphere.The particle diameter of gained copolymerization microsphere concentrates between the 40-45um, narrowly distributing, and specific surface area is 650m
2/ g, its electron scanning micrograph is as shown in Figure 3.
Claims (10)
1. the preparation method of a poly N-ethylene pyrrolidone-divinylbenzene microspheres is characterized in that:
The preparation of A seed: stablizer is dissolved in the alcohol, leads to nitrogen deoxygenation, stirring, heating, add the vinyl monomer that is dissolved with initiator again, reaction is more than 14 hours, and product is through filtration, lotion, drying.
The swollen-state polymerization of the crosslinked divinylbenzene microspheres of B:
B1 is suspended in single seed microballoon that disperses of A preparation in the aqueous solution that contains stablizer, stirs.
B2 joins vinyl monomer, initiator, pore-creating agent thorough mixing in the aqueous solution that is dissolved with stablizer and tensio-active agent, stirs certain hour fast, processes emulsion.
The emulsion that B3 makes B2 slowly is added drop-wise in the said solution of B1, and the dropping time is 2-12 hour.Begin swelling afterwards, swelling time is 2-10 hour, is heated to polymerization temperature, carries out polyreaction, and the reaction times is 2-6 hour.One step swollen-state polymerization is accomplished, and can proceed the secondary swollen-state polymerization to this reaction according to needed specific surface and aperture, particle diameter.
Crosslinked divinylbenzene microspheres of C and pyrrolidone monomer repolymerization
C1 reduces the B3 polymerization temperature.With pyrrolidone monomer, initiator thorough mixing, join in the aqueous solution that is dissolved with stablizer and tensio-active agent, stir certain hour fast, process emulsion.Continuation is added to emulsion droplets in the B3 reaction system, and the dropping time is 2-6 hour.Begin swelling after dripping off, swelling time is 2-10 hour, is heated to polymerization temperature, carries out polyreaction, and the reaction times is 10-15 hour, or to reacting completely.
C2 adopts ordinary method at last, filtration, lotion, refilter, dry, put forward step such as pore-creating agent, reclaim copolymerization microsphere, measure its particle diameter and size distribution, specific surface area etc.
2. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1; It is characterized in that described vinyl monomer is polymerization single polymerization monomers such as vinylbenzene, divinylbenzene; Initiator is Lucidol, t-butyl per(oxy)benzoate, Diisopropyl azodicarboxylate etc., and pore-creating agent is good solvent or poor solvent pore-creating agents such as toluene, normal heptane, whiteruss.
3. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1; It is characterized in that described stablizer is steric hindrance stablizers such as water-soluble cellulose ether, PVP K120 or hydroxypropylcellulose; Tensio-active agent is negatively charged ion, positively charged ion and non-ionics, for example SDS, Triton X-405.
4. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1 is characterized in that described pyrrolidone monomer is the N-V-Pyrol RC.
5. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1, the particle diameter of the seed microballoon that it is characterized in that preparing in the said steps A is 3-8um.
6. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1 is characterized in that the weight percent of seed microballoon, stablizer, water among the said step B1 is: 20-60: 0.2-1.5: 150-600.
7. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1; The weight percent that it is characterized in that vinyl monomer, initiator, pore-creating agent among the said step B2 is: 20-80: 0.3-1.6: 10-100, the weight percent of described vinyl monomer, stablizer, tensio-active agent, water is: 20-80: 0.05-0.5: 0.5-5: 50-500.
8. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1 is characterized in that the weight percent of pyrrolidone monomer, initiator, stablizer, tensio-active agent, water among the said step C1 is: 20-100: 0.3-1.6: 0.01-0.5: 0.2-5: 50-500.
9. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1; It is characterized in that quick churning time is 4-20 hour among said step B2 and the C1; The emulsion of processing is not stratified; The dropping time is 2-12 hour among B3 and the C1, and swelling time is 2-10 hour, and the reaction times is 10-15 hour.
10. the preparation method of a kind of poly N-ethylene pyrrolidone-divinylbenzene microspheres as claimed in claim 1, the specific surface area that it is characterized in that microballoon is at 100-700m
2/ g, particle diameter 20-80um.
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| CN105037603A (en) * | 2015-09-08 | 2015-11-11 | 天津博纳艾杰尔科技有限公司 | Monodisperse copolymer microsphere and preparation method thereof |
| CN105037630A (en) * | 2015-09-21 | 2015-11-11 | 南京大学 | Hydrophilic polymer microsphere and simple preparing method thereof |
| CN106589210A (en) * | 2016-12-20 | 2017-04-26 | 常州嘉众新材料科技有限公司 | Preparation and application of non-ionic macroporous resin microspheres |
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| CN109627370A (en) * | 2018-12-13 | 2019-04-16 | 中国科学院长春应用化学研究所 | The preparation method of a kind of nitrogen-containing functional group polyalcohol stephanoporate microballoons |
| CN113372474A (en) * | 2021-06-29 | 2021-09-10 | 西安蓝晓科技新材料股份有限公司 | Blood perfusion resin and preparation method and application thereof |
| CN113372474B (en) * | 2021-06-29 | 2023-10-20 | 西安蓝晓科技新材料股份有限公司 | Blood perfusion resin and preparation method and application thereof |
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