CN102127298B - Polymer hollow nano microspheres and preparation method thereof - Google Patents
Polymer hollow nano microspheres and preparation method thereof Download PDFInfo
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Abstract
The invention discloses polymer hollow nano microspheres and a preparation method thereof. The preparation method is characterized by comprising the following steps: adding 10-200 parts by weight of polymer A, 0-200 parts by weight of additive and 100-1000 parts by weight of solvent A into a dissolving kettle provided with a stirrer and a thermometer, dissolving by stirring at 30-100 DEG C, debubbling, and aging to obtain a polymer shell solution; adding 0-400 parts by weight of polymer B and 100-1000 parts by weight of solvent B into a dissolving kettle provided with a stirrer and a thermometer, dissolving by stirring at 30-100 DEG C, debubbling and aging to obtain a core solution; putting the polymer shell solution and the core solution in a high-voltage electrostatic field, and carrying out electrostatic spraying by a coaxial electrostatic sprayer to obtain polymer microspheres, wherein the inner diameter of the needle head of the core is 0.4-0.6mm, the solution flow rate is 1-5ml/h, the inner diameter of the needle head of the shell is 0.9-1.2mm, the solution flow rate is 5-10ml/h, the spraying voltage is adjusted to 5-25kV, the spraying distance is 1-10cm, and the temperature of the receiving bath is 10-50 DEG C; and removing core substances of the microspheres to obtain the polymer hollow nano microspheres.
Description
Technical field:
The present invention relates to a kind of polymkeric substance hollow Nano microsphere and preparation method thereof, belong to the preparation field of polymeric hollow Nano microsphere material.
Background technology:
The polymeric hollow microballoon be one type have unique texture and function, diameter at nano level to micron order; Be shaped as the macromolecular material or the polymer composite of sphere or other solids; Its inner hollow part component can be that gas, liquid, medicine, catalyzer and other have the compound of specific function, and outer shell for macromolecular material formation.The polymeric hollow micro-sphere material since its have that size is little, structure hollow, deformation behavior is good and inside can the various desired material of load etc. performance, be with a wide range of applications in fields such as biology, catalysis, electronics, optics, magnetics and coating.
The preparation method of polymeric hollow microballoon is a lot, mainly can be divided into 3 kinds: self-assembly method, template and emulsion polymerization.These two kinds of methods of self-assembly method and template require tighter to system, thereby their practical application receives very big restriction, and the thermostability of emulsion polymerization and chemicalstability are still waiting improvement.And along with the R and D to nanofiber, electrostatic spinning technique is able to rise, and successfully prepares the polymeric hollow nanofiber, but also electrostatic spinning technique is not applied on the preparation field of polymeric hollow microballoon at present.Compare with traditional hollow microsphere preparation method, electrostatic spraying prepares polymer hollow particles 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.
And the invention provides a kind of method that adopts the coaxial electrostatic spraying technology to prepare polymer hollow particles.Adopt the hollow Nano microsphere of this method preparation; Itself diameter is nano level or micron order; It directly is raw material with the polymkeric substance; Can be easily at the material of the various needs of microballoon internal load, thereby can be widely used in fields such as slow releasing carrier of medication, support of the catalyst, papermaking, leather, makeup.
Summary of the invention:
The objective of the invention is to the deficiency of prior art and a kind of hollow Nano microsphere and preparation method thereof is provided.Be characterized in disposing polymkeric substance shell, sandwich layer solution, adopt coaxial quiet spray apparatus, electrostatic spraying makes microballoon, and means such as utilization dissolving are removed core layer polymer, obtain polymer hollow particles.It is convenient to have preparation, operation easily, inside can directly load desired material etc. advantage.
The object of the invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The starting raw material of polymkeric substance hollow Nano microsphere is composed of the following components:
1. shell solution:
10～200 parts of polymer A
0～200 part of additive
100～1000 parts of solvent orange 2 As
Wherein, polymkeric substance is at least a in polyaryl thioether sulfone, poly arylidene thio-ester sulfonamide, poly arylidene thio-ester keto-amide, poly arylidene thio-ester sulfonamide acid amides, polyethersulfone, polysulfones, polybenzimidazole, chitosan and the sodium-alginate;
2. sandwich layer solution:
0～400 part of polymer B
100～1000 parts of solvent B
Wherein, polymkeric substance is any in Z 150PH, POLYACTIC ACID, polyoxyethylene glycol, chitosan or the sodium-alginate.
Additive is any in sodium-chlor, calcium chloride, Z 150PH, polyoxyethylene glycol or the SEPIGEL 305.
Solvent orange 2 A is DMSO 99.8MIN., N-Methyl pyrrolidone, N, at least a in dinethylformamide, water and the DMAC N,N; Solvent B is DMSO 99.8MIN., acetate, N-Methyl pyrrolidone, N, at least a in dinethylformamide, DMAC N,N, acetone and the water.
The preparation method of polymkeric substance hollow Nano microsphere may further comprise the steps:
1. the preparation of polymkeric substance shell solution
With 10～200 parts of polymer A; 0～200 part of additive; 100～1000 parts of solvent orange 2 As; Adding has in the dissolution equipment of whisking appliance, TM, in 30～100 ℃ of stirring and dissolving of temperature.Vacuum tightness-0.095～-0.08MPa deaeration 1～2h, slaking 12h processes polymkeric substance shell solution;
2. the preparation of core polymer layer solution
With polymer B 0～400 weight part; Solvent B 100～1000 weight parts; Add and to have in the dissolution kettle of whisking appliance, TM, in 30～100 ℃ of stirring and dissolving of temperature, vacuum tightness-0.095～-0.08MPa deaeration 1～2h, slaking 12h obtains sandwich layer solution;
3. the preparation of polymkeric substance hollow Nano microsphere
Above-mentioned shell solution, sandwich layer solution are placed coaxial quiet spray apparatus, and its center core layer syringe needle internal diameter is 0.4～0.6mm, and solution flow rate is 1～5ml/h; Shell syringe needle internal diameter is 0.9～1.2mm, and solution flow rate is 5～10ml/h, and the adjustment spray voltage is 5～25kv; Spray distance is 1～10cm, receives 10～50 ℃ of bath temperatures, and electrostatic spraying is spurted into non-solvent and received in the bath; Stir; Through the curing of immersion precipitation phase inversion process or ionic gel method completion microballoon, adopt the dissolved method to remove core layer polymer or solvent, obtained polymkeric substance hollow Nano microsphere;
4. the aftertreatment of microballoon
Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polymkeric substance hollow Nano microsphere finished product at 90～95 ℃ of following extracting 2～6h of temperature with deionized water.
Non-solvent in receive bathing is water, contain the aqueous solution, the alcoholic acid aqueous solution, the aqueous solution of N-Methyl pyrrolidone, the N of calcium chloride; At least a in the aqueous solution of the aqueous solution of dinethylformamide, the aqueous solution of DMAC N,N and DMSO 99.8MIN..
Polymkeric substance hollow Nano microsphere is used for coating, biomarker, medicine, catalysis, the processing of paper coating, leather or cosmetic field.
Performance test
Adopt electronic scanning Electronic Speculum (SEM) to characterize above-mentioned microballoon and microballoon section, the result shows that the hollow Nano microsphere has good shapes, and inside is hollow structure.See for details shown in Fig. 2～3.
The present invention has following advantage
1. present device is simple, and is easy to operate, mild condition, and cost is low, and is good in economic efficiency, little to environmental factor dependence, and itself has static charge microballoon, can well disperse and can not reunite.
2. can be in the preparation polymer hollow particles, in the inner directly various desired material of load of microballoon, ten minutes is easy.
3. solvent used in the present invention and non-solvent is nontoxic or low toxicity has reduced the injury to human body.
4. excellent good solubility-resistence can: for many other hollow microspheres the solvent environment that can't exist: like acetate, hexane, trieline, toluene, vinylacetic acid etc., the said polymkeric substance hollow of claim 1 Nano microsphere still can use.
5. high thermal resistance: the said polymkeric substance hollow of claim 1 Nano microsphere can use under hot environment.
6. bigger specific surface area and activity: the polymkeric substance hollow Nano microsphere diameter among the present invention is a nano level, and inner hollow has bigger surfactivity.
Description of drawings
Fig. 1 is the coaxial quiet spray apparatus synoptic diagram of preparation polymer hollow particles
1 is equipped with the syringe of sandwich layer solution, 2 sandwich layer solution, and 3 are equipped with the syringe of shell solution, 4 shell solution, 5 sealing-rings, 6 HV generators, 7 coaxial quiet nozzle needle heads.
Fig. 2 is the SEM figure of polymer hollow particles
Fig. 3 is the section SEM figure of polymer hollow particles
Embodiment
Through embodiment the present invention is specifically described below; 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 the restriction to protection domain of the present 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 polyethersulfone hollow Nano microsphere:
Polyethersulfone 60g, DMSO 99.8MIN. 300g added have in the dissolution equipment of whisking appliance, TM, in 60 ℃ of stirring and dissolving of temperature, vacuum tightness-0.08MPa deaeration 1 hour, EFI shell solution was processed in slaking 12 hours.Z 150PH 20g, DMSO 99.8MIN. 200g added have in the dissolution equipment of whisking appliance, TM, in 90 ℃ of stirring and dissolving of temperature, vacuum tightness-0.08MPa deaeration 1 hour, EFI sandwich layer solution was processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.6mm, and solution flow rate is 5ml/h, and shell syringe needle internal diameter is 1.2mm; Solution flow rate is 8ml/h, and the adjustment spray voltage is 15kv, and spray distance is 10cm; Receive 30 ℃ of bath temperatures, during electrostatic spraying injection water inlet bath receives and bathes, stirring; Through the curing of immersion precipitation phase inversion process completion microballoon, adopt the water-soluble Z 150PH of taking off sandwich layer, obtained polyethersulfone hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain polyethersulfone hollow Nano microsphere finished product at 90 ℃ of extracting 4h of temperature with deionized water.
Embodiment 2: the preparation of polyphenylene sulfide sulfonamide hollow Nano microsphere:
Polyphenylene sulfide sulfonamide 100g, sodium-chlor 15g, N-Methyl pyrrolidone 1000g are added and have in the dissolution equipment of whisking appliance, TM; In 30 ℃ of stirring and dissolving of temperature; Vacuum tightness-0.095MPa deaeration 2 hours, EFI shell solution was processed in slaking 12 hours.With PEG 400 g, N-N N 600g, N; N-N,N-DIMETHYLACETAMIDE 400g adds and to have in the dissolution equipment of whisking appliance, TM, in 30 ℃ of stirring and dissolving of temperature, vacuum tightness-0.095MPa deaeration 2 hours; EFI sandwich layer solution is processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.4mm, and solution flow rate is 3ml/h, and shell syringe needle internal diameter is 0.9mm; Solution flow rate is 5ml/h, and the adjustment spray voltage is 15kv, and spray distance is 1cm; 50 ℃ of reception bath temperatures, electrostatic spraying spray into, and the aqueous solution of DMSO 99.8MIN. receives in the bath stirring; Through the curing of immersion precipitation phase inversion process completion microballoon, adopt the water-soluble polyoxyethylene glycol of taking off sandwich layer, obtained polyphenylene sulfide sulfonamide hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polyphenylene sulfide sulfonamide hollow Nano microsphere finished product at 95 ℃ of extracting 6h of temperature with deionized water.
Embodiment 3: the preparation of polyphenylene sulfide sulfonamide acid amides hollow Nano microsphere:
With polyphenylene sulfide sulfonamide acid amides 200g, calcium chloride 15g, N; N-N,N-DIMETHYLACETAMIDE 900g adds and to have in the dissolution equipment of whisking appliance, TM, in 100 ℃ of stirring and dissolving of temperature, vacuum tightness-0.085MPa deaeration 2 hours; EFI shell solution is processed in slaking 12 hours.Chitosan 20g, acetate 300g added have in the dissolution equipment of whisking appliance, TM, stir swelling for 30 ℃ in temperature, until dissolving, vacuum tightness-0.085MPa deaeration 2 hours, EFI sandwich layer solution was processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.4mm, and solution flow rate is 2ml/h, and shell syringe needle internal diameter is 1.1mm; Solution flow rate is 9ml/h, and the adjustment spray voltage is 25kv, and spray distance is 4cm; 10 ℃ of reception bath temperatures, electrostatic spraying spray into, and the aqueous solution of N-Methyl pyrrolidone receives in the bath stirring; Through the curing of immersion precipitation phase inversion process completion microballoon, adopt the water-soluble chitosan of taking off sandwich layer, obtained polyphenylene sulfide sulfonamide acid amides hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polyphenylene sulfide sulfonamide acid amides hollow Nano microsphere finished product at 90 ℃ of extracting 5h of temperature with deionized water.
Embodiment 4: the preparation of polyethersulfone hollow Nano microsphere:
Polyethersulfone 200g, DMSO 99.8MIN. 700g, N-N N 200g added have in the dissolution equipment of whisking appliance, TM, in 90 ℃ of stirring and dissolving of temperature, vacuum tightness-0.085MPa deaeration 1 hour, EFI shell solution was processed in slaking 12 hours.Z 150PH 100g, DMSO 99.8MIN. 600g, N-Methyl pyrrolidone 100g are added and have in the dissolution equipment of whisking appliance, TM; In 100 ℃ of stirring and dissolving of temperature; Vacuum tightness-0.085MPa deaeration 1 hour, EFI sandwich layer solution was processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.6mm, and solution flow rate is 4ml/h, and shell syringe needle internal diameter is 1.2mm; Solution flow rate is 10ml/h, and the adjustment spray voltage is 5kv, and spray distance is 6cm, receives 30 ℃ of bath temperatures; Into N is sprayed in electrostatic spraying, and the aqueous solution of dinethylformamide stirs in receiving and bathing; Through the curing of immersion precipitation phase inversion process completion microballoon, adopt the water-soluble Z 150PH of taking off sandwich layer, obtained polyethersulfone hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain polyethersulfone hollow Nano microsphere finished product at 92 ℃ of extracting 6h of temperature with deionized water.
Embodiment 5: the preparation of polysulfones hollow Nano microsphere:
With polysulfones (PSF) 100g, SEPIGEL 305 30g, N; Dinethylformamide 900g adds and to have in the dissolution equipment of whisking appliance, TM, in 70 ℃ of stirring and dissolving of temperature, vacuum tightness-0.088MPa deaeration 2 hours; EFI shell solution is processed in slaking 12 hours.POLYACTIC ACID 80g, acetone 800g added have in the dissolution equipment of whisking appliance, TM, in 40 ℃ of stirring and dissolving of temperature, vacuum tightness-0.088MPa deaeration 1 hour, EFI sandwich layer solution was processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.55mm, and solution flow rate is 3ml/h, and shell syringe needle internal diameter is 1.2mm; Solution flow rate is 6ml/h, and the adjustment spray voltage is 20kv, and spray distance is 7cm; Receive 40 ℃ of bath temperatures, during electrostatic spraying injection water inlet bath receives and bathes, stirring; Through the curing of immersion precipitation phase inversion process completion microballoon, adopt water and acetone solution to fall the POLYACTIC ACID of sandwich layer, obtained polysulfones hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polysulfones hollow Nano microsphere finished product at 90 ℃ of extracting 4h of temperature with deionized water.
Embodiment 6: the preparation of PPSS hollow Nano microsphere:
PPSS 200g, Macrogol 200 g, DMSO 99.8MIN. 1000g added have in the dissolution equipment of whisking appliance, TM, in 60 ℃ of stirring and dissolving of temperature, vacuum tightness-0.09MPa deaeration 2 hours, EFI shell solution was processed in slaking 12 hours.Directly adopt N, dinethylformamide is an EFI sandwich layer solution.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.45mm, and solution flow rate is 3ml/h, and shell syringe needle internal diameter is 1.1mm; Solution flow rate is 5ml/h, and the adjustment spray voltage is 10kv, and spray distance is 5cm, receives 30 ℃ of bath temperatures; Electrostatic spraying is sprayed in the into alcoholic acid aqueous solution reception bath, stirs, and accomplishes the curing of microballoon through the immersion precipitation phase inversion process; Adopt the water-soluble N that takes off sandwich layer, dinethylformamide has obtained PPSS hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain PPSS hollow Nano microsphere finished product at 93 ℃ of extracting 2h of temperature with deionized water.
Embodiment 7: the preparation of polyphenylene sulfide keto-amide hollow Nano microsphere:
Polyphenylene sulfide keto-amide 10g, Z 150PH 2g, DMSO 99.8MIN. 100g added have in the dissolution equipment of whisking appliance, TM, in 80 ℃ of stirring and dissolving of temperature, vacuum tightness-0.089MPa deaeration 2 hours, EFI shell solution was processed in slaking 12 hours.Sodium-alginate 10g, water 100g added have in the dissolution equipment of whisking appliance, TM, in 40 ℃ of stirring and dissolving of temperature, vacuum tightness-0.089MPa deaeration 1 hour, EFI sandwich layer solution was processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.6mm, and solution flow rate is 1ml/h; Shell syringe needle internal diameter is 1.2mm, and solution flow rate is 5ml/h, and the adjustment spray voltage is 10kv; Spray distance is 6cm, receives 30 ℃ of bath temperatures, and into DMSO 99.8MIN. and N are sprayed in electrostatic spraying; During the aqueous solution of dinethylformamide receives and bathes, and stir, accomplish the curing of microballoon through the immersion precipitation phase inversion process; Adopt the water-soluble sodium-alginate of taking off sandwich layer, obtain polyphenylene sulfide keto-amide hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polyphenylene sulfide keto-amide hollow Nano microsphere finished product at 90 ℃ of extracting 4h of temperature with deionized water.
Embodiment 8: the preparation of chitosan/polyethersulfone hollow Nano microsphere:
With chitosan 100g, polyethersulfone 80g and N, dinethylformamide 1000g adds and to have in the dissolution kettle of whisking appliance, TM, and in 80 ℃ of stirring and dissolving of temperature, vacuum tightness-0.086MPa deaeration 2 hours, EFI shell solution was processed in slaking 12 hours.Z 150PH 30g, DMSO 99.8MIN. 400g added have in the dissolution equipment of whisking appliance, TM, in 90 ℃ of stirring and dissolving of temperature, vacuum tightness-0.086MPa deaeration 2 hours, EFI sandwich layer solution was processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.4mm, and solution flow rate is 3ml/h, and shell syringe needle internal diameter is 1.1mm; Solution flow rate is 10ml/h, and the adjustment spray voltage is 15kv, and spray distance is 6cm; Receive 40 ℃ of bath temperatures, during electrostatic spraying injection water inlet bath receives and bathes, stirring; Through the curing of immersion precipitation phase inversion process completion microballoon, adopt the water-soluble Z 150PH of taking off sandwich layer, obtained chitosan/polyethersulfone hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain chitosan/polyethersulfone hollow Nano microsphere finished product at 94 ℃ of extracting 4h of temperature with deionized water.
Embodiment 9: the preparation of sodium-alginate hollow Nano microsphere:
Sodium-alginate 50g, water 500g added have in the dissolution kettle of whisking appliance, TM, in 40 ℃ of stirring and dissolving of temperature, vacuum tightness-0.09MPa deaeration 2 hours, EFI shell solution was processed in slaking 12 hours.Directly adopting DMAC N,N is EFI sandwich layer solution.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.4mm, and solution flow rate is 2ml/h, and shell syringe needle internal diameter is 0.9mm; Solution flow rate is 8ml/h, and the adjustment spray voltage is 15kv, and spray distance is 6cm, receives 30 ℃ of bath temperatures; Electrostatic spraying is sprayed the water-bath that into contains calcium chloride and is received in the bath, stirs, and accomplishes the curing of microballoon through the ionic gel method; Adopt the water-soluble DMAC N,N of taking off sandwich layer, obtained sodium-alginate hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain sodium-alginate hollow Nano microsphere finished product at 90 ℃ of extracting 4h of temperature with deionized water.
Embodiment 10: the preparation of polybenzimidazole hollow Nano microsphere:
Polybenzimidazole 100g, DMAC N,N 1000g are added and have in the dissolution kettle of whisking appliance, TM, and in 80 ℃ of stirring and dissolving of temperature, vacuum tightness-0.086 deaeration 2 hours, EFI shell solution was processed in slaking 12 hours.Z 150PH 50g, DMSO 99.8MIN. 100g added have in the dissolution equipment of whisking appliance, TM, in 40 ℃ of stirring and dissolving of temperature, vacuum tightness-0.086MPa deaeration 1 hour, EFI sandwich layer solution was processed in slaking 12 hours.Adopt coaxial quiet spray apparatus, its center core layer syringe needle internal diameter is 0.5mm, and solution flow rate is 1ml/h, and shell syringe needle internal diameter is 1.2mm; Solution flow rate is 7ml/h, and the adjustment spray voltage is 15kv, and spray distance is 6cm, receives 50 ℃ of bath temperatures; The aqueous solution that electrostatic spraying is ejected into DMAC N,N receives in the bath, stirs; Through the curing of immersion precipitation phase inversion process completion microballoon, adopt the water-soluble Z 150PH of taking off sandwich layer, obtained polybenzimidazole hollow Nano microsphere.Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove the solvent in the microballoon, obtain polybenzimidazole hollow Nano microsphere finished product at 90 ℃ of extracting 6h of temperature with deionized water.
Claims (6)
1. a polymkeric substance hollow Nano microsphere is characterized in that the starting raw material of this hollow Nano microsphere is composed of the following components, counts by weight:
(1) shell solution:
10～200 parts of polymer A
0～200 part of additive
100～1000 parts of solvent orange 2 As
Wherein, polymer A is at least a in polyaryl thioether sulfone, poly arylidene thio-ester sulfonamide, poly arylidene thio-ester keto-amide, poly arylidene thio-ester sulfonamide acid amides, polyethersulfone, polybenzimidazole, chitosan and the sodium-alginate;
(2) sandwich layer solution:
0～400 part of polymer B
100～1000 parts of solvent B
Wherein, polymer B is any in Z 150PH, POLYACTIC ACID, chitosan or the sodium-alginate.
2. according to the said polymkeric substance hollow of claim 1 Nano microsphere, it is characterized in that additive is any in sodium-chlor, calcium chloride, Z 150PH or the SEPIGEL 305.
3. according to the said polymkeric substance hollow of claim 1 Nano microsphere, it is characterized in that: solvent orange 2 A is DMSO 99.8MIN., N-Methyl pyrrolidone, N, at least a in dinethylformamide, water and the DMAC N,N; Solvent B is DMSO 99.8MIN., acetate, N-Methyl pyrrolidone, N, at least a in dinethylformamide, DMAC N,N, acetone and the water.
4. according to the preparation method of the said polymkeric substance hollow of one of claim 1～3 Nano microsphere, it is characterized in that this method may further comprise the steps:
(1) preparation of polymkeric substance shell solution
With 10～200 parts of polymer A; 0～200 part of additive; 100～1000 parts of solvent orange 2 As; Adding has in the dissolution equipment of whisking appliance, TM, and in 30～100 ℃ of stirring and dissolving of temperature, at vacuum tightness 0.095～0.08MPa deaeration 1～2h, slaking 12h processes polymkeric substance shell solution;
(2) preparation of core polymer layer solution
With 0～400 part of polymer B; 100～1000 parts of solvent B; Adding has in the dissolution kettle of whisking appliance, TM, and in 30～100 ℃ of stirring and dissolving of temperature, at vacuum tightness 0.095～0.08MPa deaeration 1～2h, slaking 12h processes core polymer layer solution;
(3) preparation of hollow Nano microsphere
Above-mentioned shell solution, sandwich layer solution are placed coaxial quiet spray apparatus, and its center core layer syringe needle internal diameter is 0.4～0.6mm, and solution flow rate is 1～5ml/h; Shell syringe needle internal diameter is 0.9～1.2mm, and solution flow rate is 5～10ml/h, and the adjustment spray voltage is 5～25kv; Spray distance is 1～10cm, receives 10～50 ℃ of bath temperatures, and electrostatic spraying is sprayed in the into non-solvent reception bath; Stir; Through the curing of immersion precipitation phase inversion process or ionic gel method completion microballoon, adopt the dissolved method to remove core layer polymer or solvent, obtained polymkeric substance hollow Nano microsphere;
(4) aftertreatment of microballoon
Above-mentioned microballoon is placed the Suo Shi extraction plant, carry out extracting, to remove solvent and the additive in the microballoon, obtain polymkeric substance hollow Nano microsphere finished product at 90～95 ℃ of following extracting 2～6h of temperature with deionized water.
5. according to the preparation method of the said polymkeric substance hollow of claim 4 Nano microsphere; Non-solvent in it is characterized in that accepting to bathe is water, contain the aqueous solution of calcium chloride, the alcoholic acid aqueous solution, 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 DMAC N,N and DMSO 99.8MIN..
6. according to the said polymkeric substance hollow of claim 1 Nano microsphere, it is characterized in that this polymkeric substance hollow Nano microsphere is used for coating, biomarker, medicine, catalysis, the processing of paper coating, leather or cosmetic field.
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| CN111419874B (en) * | 2020-04-17 | 2021-08-13 | 南京鼓楼医院 | Preparation method and application of MSCs (mesenchymal stem cells) -source exosome-loaded oral microspheres |
| CN113527756A (en) * | 2021-07-21 | 2021-10-22 | 江苏大学 | Hollow-out polymer particle and preparation method thereof |
| CN117276611B (en) * | 2023-11-22 | 2024-02-23 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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| CN1542053A (en) * | 2003-11-05 | 2004-11-03 | 四川大学 | Polysulfone porous microsphere and membrane and preparation method and use thereof |
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