CN101735613A - Porous polymer nanoparticle and preparation method thereof - Google Patents
Porous polymer nanoparticle and preparation method thereof Download PDFInfo
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- CN101735613A CN101735613A CN200910216645A CN200910216645A CN101735613A CN 101735613 A CN101735613 A CN 101735613A CN 200910216645 A CN200910216645 A CN 200910216645A CN 200910216645 A CN200910216645 A CN 200910216645A CN 101735613 A CN101735613 A CN 101735613A
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Abstract
The invention discloses a porous polymer nanoparticle and a preparation method thereof. The method is characterized by adding 10-200 parts of polymers, 0-200 parts of additives and 300-1000 parts of solvents by weight into a dissolution kettle with a stirrer and a thermometer, stirring to dissolve the mixture at 30-100 DEG C and obtaining polymer solution through defoaming and aging; and placing the polymer solution into an electrostatic field under 5-25kV to prepare the porous nanoparticle through electrostatic spraying. Smooth split of the nanoparticle is realized by a frozen breaking method, thus achieving the aims of minute observation, research and control of the inside structure of the nanoparticle. Electron microscope scanning test result shows that the diameter of the nanoparticle is distributed from hundreds of nanometers to thousands of nanometers, and the nanoparticle matrices are all of porous structure. The porous nanoparticles in the shapes of balls, red blood cells and round lanterns can be prepared by changing the technological conditions. The nanoparticle has the advantages of small diameter, large specific surface area and controllable surface and inside structure and is used in such fields as drug release, catalyst carriers, chemical sensors, biomolecule analysis, gas chromatography, ion exchange and polymerization carriers.
Description
Technical field:
The present invention relates to a kind of porous polymer nanoparticle and preparation method thereof, belong to the preparation field of porous nano micro-sphere material.
Background technology:
Polymer microsphere be meant diameter at nano level to micron order, be shaped as the macromolecular material or the polymer composite of sphere or other geometrical shapies.Its pattern can be diversified, comprises solid, hollow, porous, dumbbell shape, onion type etc.Because its special size and pattern, polymeric microball material possesses the not available specific function of other materials, has been widely used in fields such as nanotechnology, biological chemistry, electronic information, drug release.
The method for preparing polymer microsphere is a lot, can roughly be divided into two kinds: a kind of is to be the method for preparing microsphere of raw material with the monomer, as emulsion polymerization, emulsifier-free emulsion polymerization method, dispersion copolymerization method etc.; Another kind is to be the method for preparing microsphere of raw material with the polymer, as emulsion-solidification method, single coacervation, complex coacervation etc.And along with the R and D to nanofiber, electrostatic spinning technique is risen, and begins to be applied to polymeric microball material and prepare up.At present, existing investigator adopts Electrostatic Spray Technology to prepare polymer microsphere, and microsphere surface pore-forming mechanism and surface topography carried out studying (document 1.Y qWu, Robert L.Clark.Controllable porous polymer particles generated by electrospraying.Journal of Colloid and Interface Science, 2007,310:529-535. document 2.B Cory, W P Daniel, KKevin.Controlling surface nano-structure using flow-Iimited field-injection electrostaticspraying (FFESS) of poly (d, l-lactide-co-glycolide) .Biomaterials, 2004,25:5649-5658.), compare with traditional method for preparing microsphere, electrostatic spraying prepares polymer microballoon and has the following advantages: equipment is simple, and is low to the preparation environmental requirement; Thereby microballoon itself has static charge and can well disperse and can not reunite.
Want microballoon in real the playing a role of its Application Areas, must realize the controlled of micro-sphere structure, the present invention then provides the method for control micro-sphere structure, adopt the porous nano microballoon of this method preparation, its diameter is nanometer or micron order, add the vesicular structure of itself, its specific surface area is increased greatly, thereby have higher surfactivity, have a wide range of applications at aspects such as efficient chemistry and biological adsorption and separation material, catalytic carrier, efficient transmitter, tissue engineering bracket, cell and drug molecule carrier, ion-exchange, matrix material enhancings.In addition, the present invention also provides the method and the means of the prepared Nano microsphere of a kind of fragmentation, is beneficial to realize observation, the control to this Nano microsphere structure and study.
Summary of the invention:
The objective of the invention is provides a kind of porous nano microballoon and preparation method thereof at the deficiencies in the prior art.Be characterized in polymkeric substance is configured to solution, make Nano microsphere, and cut microballoon, change processing condition and can obtain the structure microballoon different with pattern with the freezing crushing method by electrostatic spraying.Have advantages such as easy to prepare, easy operation.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
Porous polymer nanoparticle is composed of the following components:
10～200 parts in polymkeric substance
0～200 part of additive
300～1000 parts of solvents
Polymkeric substance is at least a in polyaryl thioether sulfone, poly arylidene thio-ester sulfonamide, poly arylidene thio-ester sulfonamide acid amides, polyethersulfone, polysulfones, polybenzimidazole, chitosan, poly-d-lactic acid and thymus nucleic acid and the multipolymer thereof.
Additive is any in sodium-chlor, calcium chloride, polyvinyl alcohol, polyoxyethylene glycol or the polyacrylamide.
Solvent is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, N, at least a in dinethylformamide and the N,N-dimethylacetamide.
The preparation method of porous polymer nanoparticle may further comprise the steps:
1. the preparation of polymers soln
With 10～200 parts in polymkeric substance; 0～200 part of additive; 300～1000 parts of solvents; Adding has in the dissolution kettle of agitator, thermometer, in 30～100 ℃ of stirring and dissolving of temperature.Vacuum tightness 0.05～0.4MPa deaeration 1～2 hour, polymers soln was made in slaking 12 hours;
2. the preparation of porous polymer nanoparticle
Above-mentioned solution is ejected into non-solvent through electrostatic spraying to be received in the bath, stir, finish the curing of microballoon by the immersion precipitation phase inversion process, obtained porous polymer nanoparticle, wherein receive 10～50 ℃ of bath temperatures, ambient moisture is 50～95%, and spray voltage is 5～25kv, and spray distance is 1～10cm; To the inside of microballoon and the control of surface tissue, be to realize by the kind that the kind of additive and content, solvent types, reception are bathed, the regulation and control that receive temperature, electrostatic spraying voltage and the receiving range of bathing;
3. the aftertreatment of microballoon
Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain the porous polymer nanoparticle finished product at 90～95 ℃ of following extracting 2～6h of temperature with deionized water;
4. the microballoon section produces
Above-mentioned microballoon is dispersed in the deionized water, is prepared into suspension liquid under the effect of ultrasonic concussion, wherein, hyperacoustic power is 500W, and frequency is 40KHz; Use liquid nitrogen that this suspension liquid quick freezing is become black ice then, black ice adopts size reduction machinery to be broken into powder fast, and thawing can obtain pattern after air-dry and structure all keeps microballoon section preferably naturally.
Non-solvent accept to be bathed and to be water, ethanol, the aqueous solution of N-Methyl pyrrolidone, N, at least a in the aqueous solution of the aqueous solution of dinethylformamide, the aqueous solution of N,N-dimethylacetamide and dimethyl sulfoxide (DMSO).
Porous polymer nanoparticle is used for drug release, support of the catalyst, chemical sensor, biomolecule analysis, gas chromatographic analysis, ion-exchange and polyreaction carrier field.
Performance test
Adopt the electronic scanning Electronic Speculum to characterize above-mentioned microballoon and microballoon section, characterization result shows that microballoon has 3 kinds of patterns: spheroidal, red corpuscle shape, red light cage type; Microballoon inside is vesicular structure, and structure and pattern are different; Electronic scanning Electronic Speculum characterization result shows that microsphere surface and internal structure thereof have realized effective control, see for details shown in Fig. 1～5.
The present invention has following advantage:
1. present device is simple, and is easy to operate, little to environmental factor dependence, and itself has static charge microballoon, can well disperse and can not reunite.
2. adopt simple and economical method to cut microballoon, realized scrutiny and control, the new research polyalcohol stephanoporate microballoons internal structure and the method for pattern are provided simultaneously the microballoon internal structure.
3. control the surface tissue and the internal structure of microballoon, for subsequent applications is laid a good foundation.
4. solvent used in the present invention and non-solvent is nontoxic or low toxicity has reduced the injury to human body.
5. You Yi good solubility-resistence energy: other porous microsphere the solvent environment that can't exist: as acetate, hexane, trieline, toluene, vinylacetic acid etc., and the special engineered porous polymer nanoparticle among the present invention still can use.
6. high thermal resistance: the special engineered porous polymer nanoparticle among the present invention can use under hot environment.
7. biological activity: the bio-medical porous polymer nanoparticle among the present invention has a wide range of applications in fields such as biotechnology, medical slowly-releasings.
8. bigger specific surface area and activity: the porous polymer nanoparticle diameter among the present invention is a nano level, adds that through the vesicular structure of microballoon matrix, its surface-area is higher than general porous microsphere far away, has bigger surfactivity.
Description of drawings
Fig. 1 is for being shaped as the spherical porous microsphere shape appearance figure of standard round
Fig. 2 is for being shaped as red corpuscle shape porous microsphere shape appearance figure
Fig. 3 is for being shaped as round bird-caging porous microsphere shape appearance figure
Fig. 4,5 is microballoon cross-section morphology figure
Embodiment
Below by embodiment the present invention is specifically described; be necessary that being pointed out that at this that present embodiment only is useful on further specifies the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1: the preparation of PPSS porous nano microballoon:
PPSS 10g, N-Methyl pyrrolidone 300g adding is had in the dissolution kettle of agitator, thermometer, and in 100 ℃ of stirring and dissolving of temperature, vacuum tightness 0.3MPa deaeration 1 hour, EFI solution was made in slaking 12 hours.In the aqueous solution that electrostatic spraying is ejected into N-Methyl pyrrolidone receive to be bathed, stir, finish the curing of microballoon by the immersion precipitation phase inversion process, obtained PPSS porous nano microballoon.Wherein receive 10 ℃ of bath temperatures, ambient moisture is 50%, and spray voltage is 10kv, and spray distance is 10cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain PPSS porous nano finished microballoon products at 90 ℃ of extracting 4h of temperature with deionized water.
Embodiment 2: the preparation of polyphenylene sulfide sulfonamide porous nano microballoon:
Polyphenylene sulfide sulfonamide 50g, sodium-chlor 5g and N-Methyl pyrrolidone 500g add and have in the dissolution kettle of agitator, thermometer, stir swelling for 30 ℃ in temperature, and until dissolving, vacuum tightness 0.1MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.In the aqueous solution that electrostatic spraying is ejected into dimethyl sulfoxide (DMSO) receive to be bathed, stir, finish the curing of microballoon by the immersion precipitation phase inversion process, obtained polyphenylene sulfide sulfonamide porous nano microballoon.Wherein receive 50 ℃ of bath temperatures, ambient moisture is 76%, and spray voltage is 15kv, and spray distance is 1cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polyphenylene sulfide sulfonamide porous nano finished microballoon products at 95 ℃ of extracting 6h of temperature with deionized water.
Embodiment 3: the preparation of polyphenylene sulfide sulfonamide acid amides porous nano microballoon:
Polyphenylene sulfide sulfonamide acid amides 100g, calcium chloride 15g and N,N-dimethylacetamide 900g adding are had in the dissolution kettle of agitator, thermometer, and in 50 ℃ of stirring and dissolving of temperature, vacuum tightness 0.1MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.In the mixing solutions that electrostatic spraying is ejected into the second alcohol and water receive to be bathed, stir, finish the curing of microballoon by the immersion precipitation phase inversion process, obtained polyphenylene sulfide sulfonamide acid amides porous nano microballoon.Wherein receive 40 ℃ of bath temperatures, ambient moisture is 95%, and spray voltage is 25kv, and spray distance is 4cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polyphenylene sulfide sulfonamide acid amides porous nano finished microballoon products at 90 ℃ of following extracting 4h of temperature with deionized water.
Embodiment 4: the preparation of polyethersulfone porous nano microballoon:
Polyethersulfone 200g, dimethyl sulfoxide (DMSO) 700g and N-N dimethyl formamide 200g adding are had in the dissolution kettle of agitator, thermometer, and in 90 ℃ of stirring and dissolving of temperature, vacuum tightness 0.4MPa deaeration 1 hour, EFI solution was made in slaking 12 hours.Be ejected into during ethanol receive to bathe through electrostatic spraying, stir, finish the curing of microballoon, obtained polyethersulfone porous nano microballoon by the immersion precipitation phase inversion process.Wherein receive 30 ℃ of bath temperatures, ambient moisture is 82%, and spray voltage is 5kv, and spray distance is 6cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain polyethersulfone porous nano finished microballoon products, see accompanying drawing 1 at 90 ℃ of extracting 4h of temperature with deionized water.
Embodiment 5: the preparation of polysulfones porous nano microballoon:
With polysulfones (PSF) 100g, polyacrylamide 30g and N, dinethylformamide 900g adds and has in the dissolution kettle of agitator, thermometer, and in 70 ℃ of stirring and dissolving of temperature, vacuum tightness 0.4MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.Be sprayed onto N through electrostatic spraying, the aqueous solution of dinethylformamide stirs in receiving and bathing, and finishes the curing of microballoon by the immersion precipitation phase inversion process, has obtained polysulfones porous nano microballoon.Wherein receive 40 ℃ of bath temperatures, ambient moisture is 90%, and spray voltage is 20kv, and spray distance is 7cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polysulfones porous nano finished microballoon products at 90 ℃ of extracting 6h of temperature with deionized water.
Embodiment 6: the preparation of red corpuscle shape porous nano microballoon:
Polyethersulfone 200g, Macrogol 200 g and dimethyl sulfoxide (DMSO) 1000g adding are had in the dissolution kettle of agitator, thermometer, and in 60 ℃ of stirring and dissolving of temperature, vacuum tightness 0.3MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.Be ejected into during water-bath receive to bathe through electrostatic spraying, stir, finish the curing of microballoon, obtained red corpuscle shape porous nano microballoon by the immersion precipitation phase inversion process.Wherein receive 30 ℃ of bath temperatures, ambient moisture is 69%, and spray voltage is 10kv, and spray distance is 5cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain red corpuscle shape porous nano finished microballoon products, see accompanying drawing 2 at 95 ℃ of extracting 6h of temperature with deionized water.
Embodiment 7: the preparation of circle bird-caging porous nano microballoon:
Polyethersulfone 100g, polyvinyl alcohol 25g and dimethyl sulfoxide (DMSO) 1000g adding are had in the dissolution kettle of agitator, thermometer, and in 80 ℃ of stirring and dissolving of temperature, vacuum tightness 0.05MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.Be ejected into during water-bath receive to bathe through electrostatic spraying, stir, finish the curing of microballoon, obtained round bird-caging porous nano microballoon by the immersion precipitation phase inversion process.Wherein receive 30 ℃ of bath temperatures, ambient moisture is 83%, and spray voltage is 10kv, and spray distance is 6cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain circle bird-caging porous nano finished microballoon products, see accompanying drawing 3 at 91 ℃ of extracting 6h of temperature with deionized water.
Embodiment 8: the preparation of chitosan/polyethersulfone porous nano microballoon:
With chitosan 100g, polyethersulfone 80g and N, dinethylformamide 1000g adds and has in the dissolution kettle of agitator, thermometer, and in 80 ℃ of stirring and dissolving of temperature, vacuum tightness 0.1MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.Be ejected into during water-bath receive to bathe through electrostatic spraying, stir, finish the curing of microballoon, obtained chitosan/polyethersulfone porous nano microballoon by the immersion precipitation phase inversion process.Wherein receive 40 ℃ of bath temperatures, ambient moisture is 86%, and spray voltage is 15kv, and spray distance is 6cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain chitosan/polyethersulfone porous nano finished microballoon products at 92 ℃ of extracting 4h of temperature with deionized water.
Embodiment 9: the preparation of poly-d-lactic acid/polyoxy Yeast Nucleic Acid porous nano microballoon:
Poly-d-lactic acid 50g, polyoxy Yeast Nucleic Acid 10g and dimethyl sulfoxide (DMSO) 500g adding are had in the dissolution kettle of agitator, thermometer, and in 40 ℃ of stirring and dissolving of temperature, vacuum tightness 0.2MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.Be ejected into during ethanol receive to bathe through electrostatic spraying, stir, finish the curing of microballoon, obtained poly-d-lactic acid/polyoxy Yeast Nucleic Acid porous nano microballoon by the immersion precipitation phase inversion process.Wherein receive 30 ℃ of bath temperatures, ambient moisture is 93%, and spray voltage is 10kv, and spray distance is 6cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain poly-d-lactic acid/polyoxy Yeast Nucleic Acid porous nano finished microballoon products at 90 ℃ of extracting 2h of temperature with deionized water.
Embodiment 10: the preparation of polybenzimidazole porous nano microballoon:
Polybenzimidazole 100g, N,N-dimethylacetamide 1000g adding is had in the dissolution kettle of agitator, thermometer, and in 80 ℃ of stirring and dissolving of temperature, vacuum tightness 0.3MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.In the aqueous solution that electrostatic spraying is ejected into N,N-dimethylacetamide receive to be bathed, stir, finish the curing of microballoon by the immersion precipitation phase inversion process, obtained polybenzimidazole porous nano microballoon.Wherein receive 50 ℃ of bath temperatures, ambient moisture is 73%, and spray voltage is 15kv, and spray distance is 6cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain polybenzimidazole porous nano finished microballoon products at 90 ℃ of extracting 6h of temperature with deionized water.
Embodiment 11: the preparation of poly-d-lactic acid porous nano microballoon:
Poly-d-lactic acid 100g, polyvinyl alcohol 25g and dimethyl sulfoxide (DMSO) 1000g adding are had in the dissolution kettle of agitator, thermometer, and in 60 ℃ of stirring and dissolving of temperature, vacuum tightness 0.4MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.Be ejected into during water-bath receive to bathe through electrostatic spraying, stir, finish the curing of microballoon, obtained poly-d-lactic acid porous nano microballoon by the immersion precipitation phase inversion process.Wherein receive 40 ℃ of bath temperatures, ambient moisture is 87%, and spray voltage is 10kv, and spray distance is 5cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain poly-d-lactic acid porous nano finished microballoon products at 90 ℃ of extracting 4h of temperature with deionized water.
Embodiment 12: the preparation of PPSS amide copolymer porous nano microballoon:
PPSS amide copolymer 80g, N-Methyl pyrrolidone 800g adding is had in the dissolution kettle of agitator, thermometer, and in 70 ℃ of stirring and dissolving of temperature, vacuum tightness 0.4MPa deaeration 2 hours, EFI solution was made in slaking 12 hours.Be ejected into during water-bath receive to bathe through electrostatic spraying, stir, finish the curing of microballoon, obtained PPSS amide copolymer porous nano microballoon by the immersion precipitation phase inversion process.Wherein receive 30 ℃ of bath temperatures, ambient moisture is 67%, and spray voltage is 15kv, and spray distance is 7cm.Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain PPSS amide copolymer porous nano finished microballoon products at 95 ℃ of extracting 4h of temperature with deionized water.
Claims (6)
1. a porous polymer nanoparticle is characterized in that this porous nano microballoon is composed of the following components, is by weight:
10～200 parts in polymkeric substance
0～200 part of additive
300～1000 parts of solvents
Wherein, polymkeric substance is at least a in polyaryl thioether sulfone, poly arylidene thio-ester sulfonamide, poly arylidene thio-ester sulfonamide acid amides, polyethersulfone, polysulfones, polybenzimidazole, chitosan, poly-d-lactic acid and thymus nucleic acid and the multipolymer thereof.
2. according to the described porous polymer nanoparticle of claim 1, it is characterized in that additive is any in sodium-chlor, calcium chloride, polyvinyl alcohol, polyoxyethylene glycol or the polyacrylamide.
3. according to the described porous polymer nanoparticle of claim 1, it is characterized in that solvent is dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, N, at least a in dinethylformamide and the N,N-dimethylacetamide.
4. according to the preparation method of the described porous polymer nanoparticle of one of claim 1～3, it is characterized in that this method may further comprise the steps:
(1) preparation of polymers soln
With 10～200 parts in polymkeric substance; 0～200 part of additive; 300～1000 parts of solvents; Adding has in the dissolution kettle of agitator, thermometer, in 30～100 ℃ of stirring and dissolving of temperature.Vacuum tightness 0.05～0.4MPa deaeration 1～2 hour, polymers soln was made in slaking 12 hours;
(2) preparation of porous nano microballoon
Above-mentioned solution is ejected into non-solvent through electrostatic spraying to be received in the bath, stir, finish the curing of microballoon by the immersion precipitation phase inversion process, obtained porous polymer nanoparticle, wherein receive 10～50 ℃ of bath temperatures, ambient moisture is 50～95%, and spray voltage is 5～25kv, and spray distance is 1～10cm; To the inside of microballoon and the control of surface tissue, be to realize by the kind that the kind of additive and content, solvent types, reception are bathed, the regulation and control that receive temperature, electrostatic spraying voltage and the receiving range of bathing;
(3) aftertreatment of microballoon
Above-mentioned microballoon is placed the Soxhlet extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain the porous polymer nanoparticle finished product at 90～95 ℃ of following extracting 2～6h of temperature with deionized water;
(4) the microballoon section produces
Above-mentioned microballoon is dispersed in the deionized water, is prepared into suspension liquid under the effect of ultrasonic concussion, wherein, hyperacoustic power is 500W, and frequency is 40KHz; Use liquid nitrogen that this suspension liquid quick freezing is become black ice then, black ice adopts size reduction machinery to be broken into powder fast, and thawing can obtain pattern after air-dry and structure all keeps microballoon section preferably naturally.
5. according to the preparation method of the described porous polymer nanoparticle of claim 4, it is characterized in that it is water, ethanol, the aqueous solution of N-Methyl pyrrolidone, N that non-solvent is accepted to bathe, at least a in the aqueous solution of the aqueous solution of dinethylformamide, the aqueous solution of N,N-dimethylacetamide and dimethyl sulfoxide (DMSO).
6. be used for drug release, support of the catalyst, chemical sensor, biomolecule analysis, gas chromatographic analysis, ion-exchange and polyreaction carrier field according to the described porous polymer nanoparticle of claim 1.
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