CN102617769A - Nanometer composite porous gel microsphere and preparation method thereof - Google Patents
Nanometer composite porous gel microsphere and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nanometer composite porous gel microsphere and a preparation method thereof, which are characterized in that the nanometer composite porous gel microsphere is prepared by the steps of using double Pickering emulsion (O/W/O) as a template, using a water-soluble polymerizable monomer and an initiator as aqueous phase, and adding hydrophilic moderate nanometer particles in the aqueous phase to form oil-in-water type emulsion through emulsification; adding hydrophobic nanometer particles in outer oil phase, adding colostrums into a dispersing agent of the outer oil phase to perform emulsification once again to obtain water-in-oil and oil-in-water type double Pickering emulsion. An aqueous monomer of intermediate phase of the obtained double Pickering emulsion is polymerized to obtain the nanometer composite porous gel microsphere. By means of the preparation method, a large amount of independent gel microspheres with holes insides can be simply prepared. Due to the fact that the functionalization of the nanometer particles can further endow special responsiveness of the microsphere, the nanometer composite porous gel microsphere has wide application prospect in drug encapsulation, targeted slow release, cell culture and other fields.
Description
Technical field
The present invention relates to functional high polymer material field, be specifically related to a kind of nano compound stephanoporate gel micro-ball and preparation method thereof.
Background technology
Porous polymer microsphere is widely used in fields such as chromatographic column filler, ion exchange resin, bioseparation and support of the catalyst.The preparation method of porous microsphere is mainly compound emulsion method, seed swelling polymerization and SPG film emulsion process.People such as Nelissen (Polymer, 1999,40 (13): 3685-3689) be utilized in monomer and exist the condition low suspension polymerization of pore-creating agent to prepare the porous polystyrene microsphere mutually.People such as Krajnc (React.Funct.Polym., 2005,65 (1-2): 37-45) on the basis of High Internal Phase Emulsion (the water volume accounts for more than 74% of emulsion volume promptly) polymerization technique, prepare with the W/O/W compound emulsion method and to gather the p-chloromethyl styrene porous microsphere.(Int.J.Pharm., 2002,242 (1-2): 225-228) utilize the W/O/W compound emulsion method, prepared porous polymer microsphere such as Rosa also through adding XA 1007 as pore-creating agent at interior aqueous phase.
In addition, adopt in recent years fluid channel technology (microfluidic technology) preparation multiple emulsion and with its be the template extensive concern for preparing porous microsphere and caused people (2007, Angew.Chem., Int.Ed., 46,8970; 2008, Adv.Mater., 20,3498-3503; 2009, Small, 5,1932-1935).Though these class methods can be controlled the particle diameter and the size distribution of inside and outside emulsion droplet well.But it is the same with above-mentioned additive method, when the preparation porous microsphere, all need add exhibiting high surface promoting agent or pore-creating agent, remove fully than difficulty during the preparation aftertreatment, and process is loaded down with trivial details, and this brings many problems to application.
Do not use the pickering emulsion polymerization technique of tensio-active agent to be widely used in preparing hydridization core/shell structure polymer microballoon, and also do not report based on the multiple emulsion polymerization technique of pickering emulsion.This method can be simple, a large amount of the nano combined porous microsphere of preparation.
Summary of the invention
The object of the invention and content are defective and the deficiency to existing preparation porous microsphere technology, and a kind of preparation method of nano combined porous microsphere is provided.This microballoon inside has independently pore space structure, and can regulate the size and the quantity of hole effectively, thereby makes it have higher medicine stowage capacity and good control-release function; The preparation process need not tensio-active agent and pore-creating agent, product nontoxicity, the application that can obtain at biomedical sector.
The object of the invention and content also are to provide said preparing method's nano compound stephanoporate gel micro-ball.
The preparation method of nano compound stephanoporate gel micro-ball of the present invention specifically may further comprise the steps:
(1) water-soluble monomer, linking agent, water-based initiator are dissolved in the water, then clay particle (Laponite RD) ultra-sonic dispersion are added proper amount of sodium chloride again in this solution, be made into aqueous phase solution.Oil phase is distributed in the above-mentioned aqueous phase solution, forms oil-in-water (O/W) type colostrum through emulsification.
(2) above-mentioned colostrum is added in the oil phase that is dispersed with the hydrophobic silica nanoparticle, processes the double pickering emulsion of water-in-oil bag oil (O/W/O) type through emulsification again.
(3) with the above-mentioned two gravity emulsion intermediate phase aqueous monomers polymerizations that obtain, the washing drying obtains nano combined porous gel microballoon.
In the step (1), water-soluble monomer is acrylic amide (Am), NSC 11448 (NIPAm) or vinylformic acid (AA); Linking agent is N, N-methylene-bis third rare acid amides (BIS); Initiator is azo-bis-isobutyrate hydrochloride (V-50) or Potassium Persulphate (KPS); Oil phase is a benzene,toluene,xylene.
Wherein, monomer is 5%～15% with respect to the mass percent concentration of whole water; Linking agent is 10%～100% with respect to monomeric mass percent; Initiator accounts for 0.5%～2% of monomer mass; The addition of clay particle is 1%～2% of a whole water quality; The addition of sodium-chlor accounts for 0.5%～2% of whole water quality; The volume ratio of colostrum profit phase is 1: 1～10.
In the step (2), the hydrophobic nano particle is 0.25%～1% with respect to the massfraction of outer oil phase; The volume ratio of colostrum and outer oil phase is 1: 2～10.
For better emulsification, stirred down 1～5 minute perhaps ultrasonic 5～10 minutes 5000～10000 rev/mins of rotating speeds with high speed dispersor during emulsification in the step (1) with ultrasonic cleaning machine.In order to obtain two stable gravity emulsions, use hand emulsification in the step (2).
For reaction is better carried out, being reflected under the no agitation condition in the step (3) carried out.
The present invention has following difference and advantage with respect to prior art:
The present invention is to adopt emulsion template method to prepare porous polymer microsphere with the similarity of prior art.
Difference is that existing emulsion template fado adopts tensio-active agent to make emulsifying agent, and after the polymerization, small-molecular emulsifier and pore-creating agent are difficult to eliminate, the aftertreatment trouble, and certain toxicity is arranged.And the present invention adopts nanoparticle as emulsifying agent, and in the emulsion process, nanoparticle is through the irreversible water-oil interface that are adsorbed on of self-assembly, stable emulsion, and emulsion process just need not added tensio-active agent.
What the present invention adopted is double pickering emulsion, through the polymerization intermediate phase, obtains the nano composite polymer microballoon that inside has independent pore space structure, because need not add pore-creating agent.If select the nanoparticle with some responsiveness for use, after the polymerization, nanoparticle is retained on the polymer interface, thereby makes the nano combined porous microsphere that obtains have function corresponding property.This composite gel microsphere with vesicular structure and some responsiveness can have potential to use at medicine loading and sustained release field.
Description of drawings
Fig. 1 is the opticmicroscope picture of the nano compound stephanoporate PAm gel micro-ball of the inventive method preparation; Wherein, polymerizing condition is at ice-water bath medium ultraviolet initiated polymerization;
Fig. 2 is the opticmicroscope picture of the nano compound stephanoporate PNIPAm gel micro-ball of the inventive method preparation; Wherein, the polymerizing condition among Fig. 2 a is at ice-water bath medium ultraviolet initiated polymerization; Polymerizing condition among Fig. 2 b is thermal-initiated polymerization in 70 ℃ of baking ovens.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify, and all should be the substitute mode of equivalence, is included within protection scope of the present invention.
Embodiment 1
200mg monomer A m, 20mg crosslinking agent B IS, 10mg initiator V-50 are dissolved in the 2mL water, and with 20mg clay particle ultra-sonic dispersion in this solution, add 11mg sodium-chlor, be made into aqueous phase solution.1mL toluene and aqueous phase solution mixing are prepared the O/W colostrum through ultrasonic emulsification.The 2mL colostrum joins 8mL and contains 40mgSiO
2In the toluene of particle, hand vibration with colostrum once more emulsification prepare the O/W/O emulsion.Then, the logical Ar gas deoxygenation in 5 minutes of multiple pickering emulsion with the two-step approach preparation obtains places ice-water bath to use light intensity to be 30mW/cm
2Uv-light polymerization.Irradiation 5min, emulsion is 47cm apart from the UV lamp.Reaction finishes to obtain porous polypropylene acid amides (PAm) gel micro-ball (see figure 1).
Embodiment 2
Monomer NIPAm, 20mg crosslinking agent B IS, the 10mg initiator V-50 of 200mg are dissolved in the 2mL water, and with 20mg clay particle ultra-sonic dispersion in this solution, add 11mgNaCl, be made into aqueous phase solution.0.5mL toluene and aqueous phase solution mixing are prepared the O/W colostrum through ultrasonic emulsification.The 2mL colostrum joins 8mL and contains 40mg SiO
2In the toluene of particle, hand vibration with colostrum once more emulsification prepare the O/W/O emulsion.Then, after the logical Ar gas deoxygenation in 5 minutes of multiple pickering emulsion that two-step approach preparation is obtained, place ice-water bath to use the uv-light polymerization of light intensity as 30mW/cm2.Irradiation 5min, emulsion is 47cm apart from the UV lamp.Reaction finishes to obtain multi-cavity PNIPAm gel micro-ball and (sees Fig. 2 a).
Embodiment 3
200mg monomer NIPAm, 20mg crosslinking agent B IS, 10mg initiator KPS are dissolved in the 2mL water, and with 20mg clay particle ultra-sonic dispersion in this solution, add 11mg sodium-chlor, be made into aqueous phase solution.0.5mL YLENE and aqueous phase solution mixing are prepared the O/W colostrum through ultrasonic emulsification.The 2mL colostrum joins 8mL and contains 40mg SiO
2In the toluene of particle, hand vibration with colostrum once more emulsification prepare the O/W/O emulsion.Then, the logical Ar gas deoxygenation in 5 minutes of multiple pickering emulsion with the two-step approach preparation obtains places 70 ℃ baking oven to react 12h.Reaction finishes to obtain multi-cavity PNIPAm gel micro-ball (seeing Fig. 2 b).
Embodiment 4
200mg monomer NIPAm, 20mg crosslinking agent B IS, 10mg initiator V-50 are dissolved in the 2mL water, and with 20mg clay particle ultra-sonic dispersion in this solution, add 11mg sodium-chlor, be made into aqueous phase solution.1mL benzene and aqueous phase solution mixing are prepared the O/W colostrum through ultrasonic emulsification.The 2mL colostrum joins 8mL and contains 40mgSiO
2In the toluene of particle, hand vibration with colostrum once more emulsification prepare the O/W/O emulsion.Then, the logical Ar gas deoxygenation in 5 minutes of multiple pickering emulsion with the two-step approach preparation obtains places ice-water bath to use the uv-light polymerization of light intensity as 30mW/cm2.Irradiation 5min, emulsion is 47cm apart from the UV lamp.Reaction finishes to obtain multi-cavity PNIPAm gel micro-ball.
Embodiment 5
200mg monomer NIPAm, 20mg crosslinking agent B IS, 10mg initiator V-50 are dissolved in the 2mL water, and with 20mg clay particle ultra-sonic dispersion in this solution, add 11mg sodium-chlor, be made into aqueous phase solution.0.2mL toluene and aqueous phase solution mixing are prepared the O/W colostrum through ultrasonic emulsification.The 2mL colostrum joins 8mL and contains 40mgSiO
2In the toluene of particle, hand vibration with colostrum once more emulsification prepare the O/W/O emulsion.Then, the logical Ar gas deoxygenation in 5 minutes of multiple pickering emulsion with the two-step approach preparation obtains places ice-water bath to use the uv-light polymerization of light intensity as 30mW/cm2.Irradiation 5min, emulsion is 47cm apart from the UV lamp.Reaction finishes to obtain multi-cavity PNIPAm gel micro-ball.
Visible by above-mentioned instance and accompanying drawing, the gel micro-ball of the present invention's preparation is a double nano particle compound porous gel microballoon.This microballoon inside has independently pore space structure, and can regulate the size and the quantity of hole effectively.Simultaneously microballoon outside surface and empty surface enrichment inorganic nano-particle have improved the physical strength of how empty gel micro-ball.
Claims (9)
1. the preparation method of a nano combined porous polymer microsphere is characterized in that may further comprise the steps:
(1) water-soluble monomer, linking agent, water-based initiator are dissolved in the water, then with clay particle ultra-sonic dispersion in this solution, add proper amount of sodium chloride again, be made into aqueous phase solution; Oil phase is distributed in the above-mentioned aqueous phase solution, forms oil-in-water (O/W) type colostrum through emulsification;
(2) above-mentioned colostrum is added in the oil phase that is dispersed with the hydrophobic silica nanoparticle, processes the double pickering emulsion of water-in-oil bag oil (O/W/O) type through emulsification again;
(3) with the above-mentioned double pickering emulsion intermediate phase aqueous monomers polymerization that obtains, the washing drying obtains the nano compound stephanoporate gel micro-ball.
2. preparation method according to claim 1 is characterized in that in the step (1), water-soluble monomer is acrylic amide, NSC 11448 or vinylformic acid; Linking agent does
N, N-methylene-bis third rare acid amides; Initiator is azo-bis-isobutyrate hydrochloride or Potassium Persulphate; Oil phase is benzene, toluene or YLENE.
3. preparation method according to claim 1 and 2 is characterized in that, water-soluble monomer is 5% ~ 15% with respect to the mass percent concentration of whole aqueous phase solution in the step (1); Linking agent is 10% ~ 100% with respect to monomeric mass percent; Initiator accounts for 0.5% ~ 2% of monomer mass; The addition of clay particle is 1% ~ 2% of a whole aqueous phase solution quality; The addition of sodium-chlor accounts for 0.5% ~ 2% of whole aqueous phase solution quality; The volume ratio of said colostrum profit phase is 1:1 ~ 10.
4. preparation method according to claim 1 is characterized in that in the step (2) that the hydrophobic nano particle is 0.25% ~ 1% with respect to the massfraction of outer oil phase; The volume ratio of colostrum and outer oil phase is 1:2 ~ 10.
5. preparation method according to claim 1 stirred down 1 ~ 5 minute perhaps with ultrasonic cleaning machine ultrasonic 5 ~ 10 minutes with 5000 ~ 10000 rev/mins of high speed dispersors when it is characterized in that in the step (1) emulsification.
6. preparation method according to claim 1 is characterized in that using in the step (2) hand emulsification.
7. preparation method according to claim 1 is characterized in that being reflected under the no agitation condition in the step (3) carry out.
8. preparation method according to claim 1 is characterized in that in the step (3) the logical Ar gas deoxygenation of double pickering emulsion, places ice-water bath to cause with UV-light or places the baking oven heated polymerizable.
9. the nano combined porous polymer microsphere that makes by each said preparation method of claim 1 ~ 9.
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| CN103554320A (en) * | 2013-10-25 | 2014-02-05 | 东北大学秦皇岛分校 | Method for preparing polyacrylamide |
| CN103613704A (en) * | 2013-10-10 | 2014-03-05 | 华东理工大学 | Photocatalyst nanopacticle-loaded polymer porous bead carrier material preparation method |
| CN103962074A (en) * | 2014-02-28 | 2014-08-06 | 中国科学院化学研究所 | Hollow sub-microsphere as well as preparation method and application thereof |
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| CN114643026A (en) * | 2022-03-18 | 2022-06-21 | 浙江裕华木业股份有限公司 | Essential oil-coated thermo-sensitive polymer microcapsule and double-emulsion preparation method thereof |
| CN114643026B (en) * | 2022-03-18 | 2023-09-26 | 浙江裕华木业股份有限公司 | Temperature-sensitive polymer microcapsule coated with essential oil and double-emulsion preparation method thereof |
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