CN102382226B - 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 polymer chemistry field, relate to specifically NVP and divinylbenzene swell cross polymerizing microballoons repolymerization.
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.Contain the solid phase extraction filler of vinyl pyrrolidone-divinylbenzene owing to thering is wetting ability and hydrophobic group simultaneously, all kinds of polarity, non-polar compound are had to the adsorption compared with balance, its adsorptive power and sample capacity, far above C18 bonded silica gel, can be widely used in extraction, enrichment and the purification of various compounds.Main synthetic method for this kind of 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 NVP become; The 2nd, by vinylbenzene and divinylbenzene, be that monomer suspension polymerization by a certain percentage becomes Archon, chloromethylation then, then to it, carry out functionalized with pyrrolidone; The 3rd, 5um mono-dispersion microballoon is swelling copolymerization in NVP and divinylbenzene.
The present invention is on the basis of existing swollen-state polymerization crosslinked microsphere, adopt NVP and crosslinked divinylbenzene microspheres repolymerization, prepare a kind of particle diameter evenly, polarity and apolar substance are all there is to the poly N-vinyl pyrrolidone-divinylbenzene microspheres of better adsorption effect, make form and the performance of product be easy to control, increase homogeneity and the productive rate of product size distribution simultaneously.
Summary of the invention
The present invention improves and has developed forefathers' polymerization process, has set up one and has prepared polystyrene seed to the crosslinked divinylbenzene microspheres of " swollen-state polymerization method " preparation, finally with the direct swollen-state polymerization of NVP from dispersion polymerization.Provide a kind of particle diameter even, polarity and apolar substance have all been there is to the polymer microsphere of good adsorption effect.
The preparation method of PVP-divinylbenzene microspheres of the present invention, concrete steps are:
The preparation of A seed: stablizer is dissolved in alcohol, logical nitrogen deoxygenation, stirring, heating, adds the vinyl monomer that is dissolved with initiator again, reaction is more than 14 hours, product after filtration, lotion, dry.
The swollen-state polymerization of the crosslinked divinylbenzene microspheres of B:
Single seed-dispersed microballoon that B1 prepares A is suspended in the aqueous solution that contains stablizer, stirs.
B2 fully mixes vinyl monomer, initiator, pore-creating agent, joins in the aqueous solution that is dissolved with stablizer and tensio-active agent, and rapid stirring certain hour, makes emulsion.
The emulsion that B3 makes B2 is slowly added drop-wise to described in B1 in solution, and time for adding is 2-12 hour.Start afterwards swelling, 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 completes, and can to this reaction, proceed secondary swollen-state polymerization according to needed specific surface and aperture, particle diameter.
The crosslinked divinylbenzene microspheres of C and pyrrolidone monomer repolymerization
C1 reduces B3 polymerization temperature.Pyrrolidone monomer, initiator are fully mixed, join in the aqueous solution that is dissolved with stablizer and tensio-active agent, rapid stirring certain hour, makes emulsion.Continuation is added to emulsion droplets in B3 reaction system, and time for adding is 2-6 hour.Drip off rear beginning swelling, 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 finally adopts ordinary method, filtration, lotion, refilters, is dried, puies forward the steps such as pore-creating agent, reclaims copolymerization microsphere, measures its particle diameter and size distribution, specific surface area etc.
Described vinyl monomer is the polymerization single polymerization monomers such as vinylbenzene, divinylbenzene.
Described initiator is benzoyl peroxide, t-butyl per(oxy)benzoate, Diisopropyl azodicarboxylate etc.
Described pore-creating agent is good solvent or the poor solvent pore-creating agents such as toluene, normal heptane, whiteruss.
Described stablizer is the steric stabilizers such as water-soluble cellulose ether, Polyvinylpyrolidone (PVP) or hydroxypropylcellulose.
Described tensio-active agent is negatively charged ion, positively charged ion and nonionic surface active agent, for example SDS, Triton X-405.
Described pyrrolidone monomer is N-V-Pyrol RC.
The particle diameter of the seed microballoon of preparing in described steps A is 3-8um.
In described step B1, the weight percent of seed microballoon, stablizer, water is: 20-60: 0.2-1.5: 150-600.
In described step B2, the weight percent of vinyl monomer, initiator, pore-creating agent is: 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.
In described step C1, the weight percent of pyrrolidone monomer, initiator, stablizer, tensio-active agent, water is: 20-100: 0.3-1.6: 0.01-0.5: 0.2-5: 50-500.
In described step B2 and C1, the rapid stirring time is 4-20 hour, and the emulsion of making is not stratified, and in B3 and C1, time for adding is 2-12 hour, and swelling time is 2-10 hour, and the reaction times is 10-15 hour.
Poly N-vinyl pyrrolidone-divinylbenzene microspheres prepared by the present invention, specific surface area 100-700m
2/ g, particle diameter 20-80um.By using dispersion polymerization, prepare polystyrene small-particle seed, to the crosslinked divinylbenzene microspheres of " swelling copolymerization method " preparation, finally use NVP swollen-state polymerization, make the form of product and performance be easy to control, increase homogeneity and the productive rate of product size distribution simultaneously.
Accompanying drawing explanation
Polystyrene 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:
In 1000ml four-hole boiling flask, add polyvinylpyrrolidone 10.8g, dehydrated alcohol 600ml; being stirred to polyvinylpyrrolidone dissolves completely; under nitrogen protection, be warming up to 70 ℃, then add the 150g styrene solution that is dissolved with 3.8g Diisopropyl azodicarboxylate, react 24 hours.Filter, dehydrated alcohol lotion, is dried to constant weight, standby.
Gained polystyrene microsphere monodispersity is good, and particle diameter is 5.0um, and its electron scanning micrograph as shown in Figure 1.
Embodiment 2:
In 1000ml four-hole boiling flask, mono-dispersion microballoon 40g prepared in example 1 is added in the 250ml water that contains 0.3g Vltra tears, stir and be heated to 40 ℃, at 40 ℃, stir 3 hours.
After divinylbenzene 80g, toluene 60g are mixed with Diisopropyl azodicarboxylate 1.0g, add emulsification (emulsion 1) after mixing in the 200ml water that contains 0.1g Vltra tears and 1g Triton X-405, at 40 ℃, be slowly added drop-wise in described solution, drip 5 hours altogether, continue again afterwards swelling 8 hours, and then add 1% Vltra tears aqueous solution 100g.Be heated to 88 ℃, carry out polyreaction 3 hours.
Cooling, prepare emulsion 2 simultaneously, by after NVP 60g and Diisopropyl azodicarboxylate 0.8g mixing, add emulsification after mixing in the 100ml water that contains 0.05g Vltra tears and 0.5g Triton X-405, at 40 ℃, be slowly added drop-wise in above-mentioned reaction system, drip 4 hours altogether, continue again afterwards swelling 8 hours, be warmed up to 88 ℃, carry out polyreaction 12 hours.
Last ordinary method filtration, lotion, refilter, be dried, put forward the steps such as pore-creating agent, reclaim polymerizing microballoons.The particle diameter of gained polymerizing microballoons concentrates between 20-25um, narrowly distributing, and specific surface area is 346m
2/ g, its electron scanning micrograph as shown in Figure 2.
Embodiment 3
In 1000ml four-hole boiling flask, mono-dispersion microballoon 40g prepared in example 1 is added in the 200ml water that contains 0.3g Vltra tears, stir and be heated to 40 ℃, at 40 ℃, stir 3 hours.
After divinylbenzene 80g, toluene 60g are mixed with Diisopropyl azodicarboxylate 1.0g, add emulsification (emulsion 1) after mixing in the 200ml water that contains 0.1g Vltra tears and 1g Triton X-405, at 40 ℃, be slowly added drop-wise in described solution, drip 5 hours altogether, continue again afterwards swelling 8 hours, and then add 1% Vltra tears aqueous solution 100g.Be heated to 88 ℃, carry out polyreaction 3 hours.
Cooling, prepare emulsion 2 simultaneously, after divinylbenzene 40g, toluene 40g, liquid wax 20g are mixed with Diisopropyl azodicarboxylate 0.8g, add emulsification after mixing in the 200ml water that contains 0.1g Vltra tears and 1g Triton X-405, at 40 ℃, be slowly added drop-wise in described solution, drip 5 hours altogether, continue again afterwards swelling 8 hours, and then add 1% Vltra tears aqueous solution 100g.Be heated to 88 ℃, carry out polyreaction 3 hours.
Cooling, prepare emulsion 3 simultaneously, by after NVP 80g and Diisopropyl azodicarboxylate 1.0g mixing, add emulsification after mixing in the 100ml water that contains 0.05g Vltra tears and 0.5g Triton X-405, at 40 ℃, be slowly added drop-wise in above-mentioned reaction system, drip 4 hours altogether, continue again afterwards swelling 8 hours, be warmed up to 88 ℃, carry out polyreaction 12 hours.
Last ordinary method filtration, lotion, refilter, be dried, put forward the steps such as pore-creating agent, reclaim copolymerization microsphere.The particle diameter of gained copolymerization microsphere concentrates between 40-45um, narrowly distributing, and specific surface area is 650m
2/ g, its electron scanning micrograph as shown in Figure 3.
Claims (8)
1. a preparation method for PVP-divinylbenzene microspheres, is characterized in that:
The preparation of A seed: stablizer is dissolved in alcohol, logical nitrogen deoxygenation, stirring, heating, adds the vinyl monomer that is dissolved with initiator again, reaction is more than 14 hours, product after filtration, lotion, dry;
The swollen-state polymerization of the crosslinked divinylbenzene microspheres of B:
Single seed-dispersed microballoon that B1 prepares A is suspended in the aqueous solution that contains stablizer, stirs;
B2 fully mixes vinyl monomer, initiator, pore-creating agent, joins in the aqueous solution that is dissolved with stablizer and tensio-active agent, and rapid stirring certain hour, makes emulsion;
The emulsion that B3 makes B2 is slowly added drop-wise to described in B1 in solution, time for adding is 2-12 hour, start afterwards swelling, swelling time is 2-10 hour, be heated to polymerization temperature, carry out polyreaction, the reaction times is 2-6 hour, one step swollen-state polymerization completes, and can to this reaction, proceed secondary swollen-state polymerization according to needed specific surface and aperture, particle diameter;
The crosslinked divinylbenzene microspheres of C and pyrrolidone monomer repolymerization:
C1 reduces B3 polymerization temperature, and pyrrolidone monomer, initiator are fully mixed, and joins in the aqueous solution that is dissolved with stablizer and tensio-active agent, rapid stirring certain hour, make emulsion, continue emulsion droplets to be added in B3 reaction system, time for adding is 2-6 hour, drip off rear beginning swelling, swelling time is 2-10 hour, is heated to polymerization temperature, carries out polyreaction, reaction times is 10-15 hour, or to reacting completely;
C2 finally adopts ordinary method, filtration, lotion, refilters, is dried, puies forward the steps such as pore-creating agent, reclaims copolymerization microsphere, measures its particle diameter and size distribution, specific surface area etc.;
Wherein, described vinyl monomer is vinylbenzene or divinylbenzene;
Wherein, described stablizer is water-soluble cellulose ether, Polyvinylpyrolidone (PVP) or hydroxypropylcellulose;
Wherein, the raw material seed microballoon in B1, the weight percent of stablizer are: 20-60: 0.2-1.5;
Wherein, in B2, the weight percent of vinyl monomer, initiator, pore-creating agent is: 20-80: 0.3-1.6: 10-100, and the weight percent of described vinyl monomer, stablizer, tensio-active agent is: 20-80: 0.05-0.5: 0.5-5;
Wherein, in C1, the weight percent of pyrrolidone monomer, initiator, stablizer, tensio-active agent is: 20-100: 0.3-1.6: 0.01-0.5: 0.2-5.
2. the preparation method of a kind of PVP-divinylbenzene microspheres as claimed in claim 1, it is characterized in that described initiator is benzoyl peroxide, t-butyl per(oxy)benzoate or Diisopropyl azodicarboxylate, pore-creating agent is toluene, normal heptane or whiteruss.
3. the preparation method of a kind of PVP-divinylbenzene microspheres as claimed in claim 1, is characterized in that described tensio-active agent is negatively charged ion, positively charged ion or nonionic surface active agent.
4. the preparation method of a kind of PVP-divinylbenzene microspheres as claimed in claim 1, is characterized in that described tensio-active agent is SDS or Triton X-405.
5. the preparation method of a kind of PVP-divinylbenzene microspheres as claimed in claim 1, is characterized in that described pyrrolidone monomer is N-V-Pyrol RC.
6. the preparation method of a kind of PVP-divinylbenzene microspheres as claimed in claim 1, is characterized in that the particle diameter of the seed microballoon prepared in described steps A is 3-8um.
7. the preparation method of a kind of PVP-divinylbenzene microspheres as claimed in claim 1, it is characterized in that in described step B2 and C1 that the rapid stirring time is 4-20 hour, the emulsion of making is not stratified, in B3 and C1, time for adding is 2-12 hour, swelling time is 2-10 hour, and the reaction times is 10-15 hour.
8. the preparation method of a kind of PVP-divinylbenzene microspheres as claimed in claim 1, is characterized in that the specific surface area of microballoon is at 100-700m
2/ g, particle diameter 20-80um.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182802A (en) * | 1977-12-27 | 1980-01-08 | Samuel Loshaek | Hydrophilic polymers and contact lenses of high water content |
| US5391667A (en) * | 1993-03-04 | 1995-02-21 | Isis Pharmaceuticals | Copolymers of N-vinyl-lactams suitable for oligomer solid phase synthesis |
| EP0714415A1 (en) * | 1993-08-17 | 1996-06-05 | Basf Aktiengesellschaft | Aqueous copolymer dispersions |
| US5955544A (en) * | 1996-06-21 | 1999-09-21 | Bayer Aktiengesellschaft | Graft polymers of unsaturated monomers onto modified polyureas, processes for their preparation and their use |
| EP1159995A2 (en) * | 2000-06-02 | 2001-12-05 | Showa Denko Kabushiki Kaisha | Packing material for solid phase extraction and solid phase extraction method |
| EP2170992A1 (en) * | 2007-06-25 | 2010-04-07 | Bescon.co., Ltd. | Silicone-hydrogel compound for soft contact lens and soft contact lens produced using the compound |
| CN101747473A (en) * | 2008-12-12 | 2010-06-23 | 南开大学 | Surface-functionalized molecularly imprinted polymer microsphere and preparation method thereof |
| CN101757880A (en) * | 2010-02-02 | 2010-06-30 | 天津市富集科技有限公司 | Preparation method of mono-dispersion microballoon resin |
| CN101928365A (en) * | 2010-09-27 | 2010-12-29 | 天津市富集科技有限公司 | Method for preparing amphiphilic monodisperse microspherical resin |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4745134A (en) * | 1984-06-27 | 1988-05-17 | Rohm And Haas Co. | Inert separator beads for regeneration of mixed bed-ion exchange resins |
-
2011
- 2011-08-12 CN CN201110230789.6A patent/CN102382226B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182802A (en) * | 1977-12-27 | 1980-01-08 | Samuel Loshaek | Hydrophilic polymers and contact lenses of high water content |
| US5391667A (en) * | 1993-03-04 | 1995-02-21 | Isis Pharmaceuticals | Copolymers of N-vinyl-lactams suitable for oligomer solid phase synthesis |
| EP0714415A1 (en) * | 1993-08-17 | 1996-06-05 | Basf Aktiengesellschaft | Aqueous copolymer dispersions |
| US5955544A (en) * | 1996-06-21 | 1999-09-21 | Bayer Aktiengesellschaft | Graft polymers of unsaturated monomers onto modified polyureas, processes for their preparation and their use |
| EP1159995A2 (en) * | 2000-06-02 | 2001-12-05 | Showa Denko Kabushiki Kaisha | Packing material for solid phase extraction and solid phase extraction method |
| EP2170992A1 (en) * | 2007-06-25 | 2010-04-07 | Bescon.co., Ltd. | Silicone-hydrogel compound for soft contact lens and soft contact lens produced using the compound |
| CN101747473A (en) * | 2008-12-12 | 2010-06-23 | 南开大学 | Surface-functionalized molecularly imprinted polymer microsphere and preparation method thereof |
| CN101757880A (en) * | 2010-02-02 | 2010-06-30 | 天津市富集科技有限公司 | Preparation method of mono-dispersion microballoon resin |
| CN101928365A (en) * | 2010-09-27 | 2010-12-29 | 天津市富集科技有限公司 | Method for preparing amphiphilic monodisperse microspherical resin |
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