CN102226029B - Preparation method of temperature responsive nanohydrogel carrying silver nanoparticles - Google Patents
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Abstract
The invention relates to a preparation method of temperature responsive nanohydrogel carrying silver nanoparticles. The preparation method comprises the following steps that: (1) a temperature responsive monomer and a chemical cross-linking agent are mixed to form aqueous solution of the reactants; (2) aqueous solution of an initiator is added into the aqueous solution of the reactants at room temperature in the nitrogen atmosphere to obtain dispersion liquid of nanohydrogel; and (3) a silver salt and a reducing agent are added into the dispersion liquid of the nanohydrogel and the mixture undergo a reaction, when the reaction is finished, the reaction products are purified to form temperature responsive nanohydrogel. The preparation method has the advantages of easy process, easy acquirement of raw materials, short reaction time, mild reaction conditions, no poisonous and harmful by-product and environmentally friendly characteristics. Nanohydrogel prepared by the preparation method has a good dispersion stability in an aqueous medium, a responsiveness to temperature stimulation, and a volume phase transition temperature of about 33 DEG C.
Description
Technical field
The invention belongs to the preparation field of nano-hydrogel, particularly a kind of preparation method of silver-carrying nano particle temperature stimulating responsive nano-hydrogel.
Background technology
Nano silver grain has special advantageous property, for example catalytic performance is good, conduct electricity very well, sterilizing ability is strong, optical excitation efficient height and chemical property are good etc., this is so that Nano silver grain is widely used in the industries such as chemical industry, biomedicine, medicine, superconduction, electronics, daily necessities.The performance of Nano silver grain depends primarily on its shape, size, composition, crystallinity and structure, and this is so that its synthesis preparation method seems extremely important.Because the high-ratio surface of Nano silver grain is active, in the situation of not adding tensio-active agent, there are the problems such as easily reunion in Nano silver grain in application process.And be a kind of preferably terms of settlement with polymkeric substance as carrier, with the spacial framework of the polymer support microreactor as Nano silver grain, the Nano silver grain original position can be generated and be evenly dispersed in the polymer support.If Nano silver grain is used for catalyzer, the Nano silver grain that is in the carrier just can be recycled easily, and still keeps higher catalytic activity.Such as with polymer microsphere as the carrier of Nano silver grain, just can be easily method by centrifugation Nano silver grain is separated with reaction mixture, reach the purpose of recycling.
Thermal stimulus responsive nano hydrogel is a kind of can being dispersed in the water medium, and diameter in 10～1000nm scope, can the response environment temperature variation stimulate and the intelligent aqueous gel capable microballoon of generation volumetric expansion or contraction usually.Thermal stimulus responsive nano hydrogel changes and when volume occuring change mutually at response temperature, often be accompanied by the variation of the multiple physicochemical property such as hydrophilic and hydrophobic, specific refractory power, voidage, surface charge density and colloidal stability, dispersion system rheological property, therefore have broad application prospects in fields such as colloidal crystal, sensor, biological substance separating-purifying, drug controllable release.NIPA (PNIPAM) nano-hydrogel is the Typical Representative in the thermal stimulus responsive nano hydrogel, and the temperature that its generation volume changes mutually near body temperature, therefore is subject to special concern in recent years about 33 ℃.
As the carrier of Nano silver grain report was arranged with thermal stimulus responsive polymer microballoon, such as people such as Lu and Chen at document Angew.Chem.Int.Ed.2006,45,813-816 and Adv.Mater.1998,10, mention among the No.14:1122-1126 with polystyrene be nuclear, NIPA be the nucleocapsid complex microsphere of shell as the Nano silver grain carrier, this carrier can be controlled according to temperature variation the catalytic activity of Nano silver grain; The technique of synthetic nucleocapsid complex microsphere is too complicated, the problems such as amount few (about 10%) of silver-carrying nano particle but this method exists.Other research report also has, such as the military favorable to the people grade of Fudan University at document Journal of Polymer Science:Part A:Polymer Chemistry, 2009,47, at first adopt so-called " oneself removes (self-removing) " technique to prepare hollow NIPA microgel among the 4919-4926, then the method by in-situ reducing forms Nano silver grain in the shell of hollow microgel; Although can forming, this kind method has the hollow microgel of Thermosensitive silver-carrying nano particle, but the preparation method is comparatively complicated, and in reaction process, can produce some other impurity, for the purifying of back has increased difficulty, and Nano silver grain mainly is gathered in the shell of microgel in the microgel, disperses even not.On the whole, former method is complicated process of preparation, and by product is more, and the amount of silver-carrying nano particle is lower, is unfavorable for as uses such as catalyzer and sterilant.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of silver-carrying nano particle temperature stimulating responsive nano-hydrogel, this preparation method's technique is simple, raw material is easy to get, reaction conditions is gentle, do not produce harmful poisonous by product, nano-hydrogel of the present invention can be applicable to the fields such as controlled catalyzed reaction, controlled sterilization.
The preparation method of a kind of silver-carrying nano particle temperature stimulating responsive nano-hydrogel of the present invention comprises:
(1) is to join in deionized water at 40～90: 5～50 in molar ratio with thermal stimulus responsiveness monomer and chemical cross-linking agent, stirs the reactant aqueous solution that is made into homogeneous transparent after 5～60 minutes; The gross weight of wherein thermal stimulus responsiveness monomer and chemical cross-linking agent is 1: 10～50 with the ratio of the weight of deionized water;
(2) at room temperature, be that 0.05～0.5wt% initiator solution joins in the above-mentioned reactant aqueous solution with concentration, then pass into nitrogen, be warming up to gradually 50～90 ℃ of back balances 10～120 minutes under stirring, obtain milky nano-hydrogel dispersion liquid; Wherein initiator amount be thermal stimulus responsiveness monomer and chemical cross-linking agent gross weight 0.1～5%;
(3) get the above-mentioned nano-hydrogel dispersion liquid that makes, add silver salt, logical nitrogen also stirred 10～120 minutes, get even milky white solution, and then adding reductive agent, solution becomes rapidly brown, at room temperature continue reaction 1～5 hour, obtain translucent orange-yellow silver-carrying nano particle nano-hydrogel dispersion liquid, final purification, remove unreacted monomer, linking agent, silver ions, namely get silver-carrying nano particle temperature stimulating responsive nano-hydrogel, wherein the weight ratio of the consumption of silver salt and nano-hydrogel dispersion liquid is 0.01～0.1: 1.
Thermal stimulus responsiveness monomer described in the step (1) is a kind of in the derivative compound of acrylamide; Chemical cross-linking agent is to contain a kind of in the water-soluble cpds of two carbon-carbon double bond groups.
Thermal stimulus responsiveness monomer described in the step (1) is a kind of in NIPA, N-isopropyl methyl acrylamide, N-n-propyl acrylamide, the N tert butyl acrylamide; Chemical cross-linking agent is a kind of in methylene-bisacrylamide, the methacrylate TEG ester.
Initiator described in the step (2) is water-soluble thermal initiator, a kind of in Potassium Persulphate, ammonium persulphate, soluble ferrite, the Tetramethyl Ethylene Diamine.
The speed that stirs described in step (1), (2) and (3) is 100～500 rev/mins.
Silver salt described in the step (3) is soluble silver salt, is preferably Silver Nitrate.
Reductive agent described in the step (3) is hydrazine hydrate or sodium borohydride, and the mol ratio of reductive agent and silver salt is 1～5: 1.
Purifying process described in the step (3) is a: with the silver-carrying nano particle nano-hydrogel aqueous dispersions centrifugation of gained, then ultra-sonic dispersion is in deionized water, repeated centrifugation separation and ultra-sonic dispersion 2～5 times, wherein centrifugal speed is 4000～15000 rev/mins.
Or b: with dialysis tubing 1～3 week of dialysis.
Nano-hydrogel particle size analysis scope is 300～800nm in the silver-carrying nano particle temperature stimulating responsive nano-hydrogel of the middle gained of step (3), and the particle diameter of Nano silver grain is 5～20nm, and the mass content of Nano silver grain is 10～25%.
The silver-carrying nano particle temperature stimulating responsive nano-hydrogel of gained can keep in Dark Place at normal temperatures in the step (3).
Thermal stimulus responsive nano hydrogel inside has the chemically crosslinked structure, has satisfactory stability in water medium, and therefore the carrier as the Ag nanoparticle has obvious actual use value.Adopt thermal stimulus responsive nano hydrogel as the carrier of Ag nano-particle catalyst, it is active to control the Ag nano particle catalysis according to the variation of temperature of reaction, and the assurance thermopositive reaction can steadily be carried out.Use in addition nano-hydrogel as the carrier of Ag nanoparticle, be conducive to separate with reaction product after reaction finishes.
The present invention at first adopts the synthetic NIPA nano-hydrogel with thermal stimulus responsiveness of emulsifier-free emulsion polymerization method, then directly form the Ag nanoparticle at this nano-hydrogel internal in-situ, obtained the Ag nanoparticle content up to 25% thermal stimulus responsiveness composite Nano hydrogel.
The present invention adopts the emulsifier-free emulsion polymerization method, first thermal stimulus responsiveness monomer, linking agent and water solvent are made into reactant aqueous solution in the certainweight ratio, logical nitrogen deoxygenation and heat temperature raising add the initiator solution of having prepared after reaching certain temperature, lower the temperature behind the reaction certain hour.At room temperature add silver salt in the products therefrom after the polymerization, stir and add reductive agent behind the certain hour and carry out reduction reaction, at last products therefrom is carried out purifying and namely make silver-carrying nano particle temperature stimulating responsive nano-hydrogel.
Beneficial effect:
(1) preparation technology of the present invention is simple, and raw material is easy to get, and the reaction times is short, and reaction conditions is gentle, does not produce harmful poisonous by product, the technique environmental protection.
(2) the present invention can recently control by changing monomer component the scope of required particle size analysis, recently controls the size of Nano silver grain particle diameter by the component that changes silver salt and reductive agent.
(3) median size under the silver-carrying nano particle nano-hydrogel room temperature of the present invention is about 500nm, the median size of Nano silver grain is less than 10nm, the Ag nanoparticle content is up to 25% in the silver-carrying nano particle temperature stimulating responsive nano-hydrogel, dispersion stabilization in water medium is good, have the thermal stimulus responsiveness, the volume phase transition temperature is about 33 ℃; Be mainly used in the fields such as controlled catalyzed reaction, controlled sterilization.
Description of drawings
Fig. 1 is the high-resolution-ration transmission electric-lens photo of silver-carrying nano particle temperature stimulating responsive nano-hydrogel.
Fig. 2 is the temperature variant relation curve of median size of silver-carrying nano particle temperature stimulating responsive nano-hydrogel.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) be simultaneously to add in deionized water at 40: 5 in molar ratio with thermal stimulus responsiveness monomer NIPA and chemical cross-linking agent methylene-bisacrylamide, stirring velocity is 100 rev/mins, stirs the reactant aqueous solution that is made into homogeneous transparent after 60 minutes; Wherein the gross weight of NIPA and methylene-bisacrylamide is 1: 10 with the ratio of the weight of deionized water;
(2) at room temperature, be that the 0.05wt% initiator potassium persulfate aqueous solution joins in the above-mentioned reactant aqueous solution with concentration, then pass into nitrogen, be warming up to gradually 50 ℃ of back balances 120 minutes under 500 rev/mins of stirrings, obtain milky thermal stimulus responsive nano hydrogel dispersion liquid; Wherein initiator amount be thermal stimulus responsiveness monomer and chemical cross-linking agent gross weight 0.1%;
(3) get the above-mentioned thermal stimulus responsive nano hydrogel dispersion liquid that makes, add Silver Nitrate, logical nitrogen and 100 rev/mins stirred 120 minutes, get even milky white solution, and then adding reductive agent hydrazine hydrate, solution becomes rapidly brown, at room temperature continue reaction 1 hour, obtain translucent orange-yellow silver-carrying nano particle nano-hydrogel dispersion liquid, final purification is removed unreacted monomer, linking agent, silver ions namely gets silver-carrying nano particle temperature stimulating responsive nano-hydrogel, wherein the weight ratio of the consumption of Silver Nitrate and thermal stimulus responsive nano hydrogel dispersion liquid is 0.01: 1, and the mol ratio of hydrazine hydrate and Silver Nitrate is 1: 1; Purifying process is the silver-carrying nano particle nano-hydrogel aqueous dispersions centrifugation with gained, and then ultra-sonic dispersion is in deionized water, and repeated centrifugation is separated and ultra-sonic dispersion 2 times, and wherein centrifugal speed is 15000 rev/mins.
Fig. 1 is the high-resolution-ration transmission electric-lens photo of this silver-carrying nano particle temperature stimulating responsive nano-hydrogel, its nano-hydrogel median size is 270nm, the median size of Nano silver grain is 10nm, the weight percentage of Nano silver grain is 15% in the nano-hydrogel that TGA records, and the maximum absorption wavelength λ max that uv-vis spectra records is 390nm.
Embodiment 2
(1) be simultaneously to add in deionized water at 90: 5 in molar ratio with thermal stimulus responsiveness monomer N tert butyl acrylamide and chemical cross-linking agent methacrylate TEG ester, stirring velocity is 200 rev/mins, stirs the reactant aqueous solution that is made into homogeneous transparent after 60 minutes; Wherein the gross weight of N tert butyl acrylamide and methacrylate TEG ester is 1: 20 with the ratio of the weight of deionized water;
(2) at room temperature, be that 0.05wt% initiator ferrous chloride aqueous solution joins in the above-mentioned reactant aqueous solution with concentration, then pass into nitrogen, be warming up to gradually 70 ℃ of back balances 80 minutes under 300 rev/mins of stirrings, obtain milky thermal stimulus responsive nano hydrogel dispersion liquid; Wherein initiator amount be thermal stimulus responsiveness monomer and chemical cross-linking agent gross weight 0.5%;
(3) get the above-mentioned thermal stimulus responsive nano hydrogel dispersion liquid that makes, add Silver Nitrate, logical nitrogen and 200 rev/mins stirred 60 minutes, get even milky white solution, and then adding borane reducing agent sodium hydride, solution becomes rapidly brown, at room temperature continue reaction 2 hours, obtain translucent orange-yellow silver-carrying nano particle nano-hydrogel dispersion liquid, final purification, remove unreacted monomer, linking agent, silver ions, namely get silver-carrying nano particle temperature stimulating responsive nano-hydrogel, wherein the weight ratio of the consumption of Silver Nitrate and thermal stimulus responsive nano hydrogel dispersion liquid is 0.1: 1, and the mol ratio of sodium borohydride and Silver Nitrate is 1: 3; Purifying process is the silver-carrying nano particle nano-hydrogel aqueous dispersions centrifugation with gained, and then ultra-sonic dispersion is in deionized water, and repeated centrifugation is separated and ultra-sonic dispersion 5 times, and wherein centrifugal speed is 4000 rev/mins.
This silver-carrying nano particle temperature stimulating responsive nano-hydrogel can keep in Dark Place at normal temperatures, its nano-hydrogel particle size analysis scope is 500nm, the particle diameter of Nano silver grain is 20nm, the weight percentage of Nano silver grain is 14% in the nano-hydrogel that TGA records, and the maximum absorption wavelength λ max that uv-vis spectra records is 400nm.
Embodiment 3
(1) be simultaneously to add in deionized water at 50: 50 in molar ratio with thermal stimulus responsiveness monomer N-isopropyl methyl acrylamide and chemical cross-linking agent methylene-bisacrylamide, stirring velocity is 500 rev/mins, stirs the reactant aqueous solution that is made into homogeneous transparent after 20 minutes; Wherein the gross weight of N-isopropyl methyl acrylamide and methylene-bisacrylamide is 1: 50 with the ratio of the weight of deionized water;
(2) at room temperature, be that the 0.2wt% initiator Tetramethyl Ethylene Diamine aqueous solution joins in the above-mentioned reactant aqueous solution with concentration, then pass into nitrogen, be warming up to gradually 90 ℃ of back balances 20 minutes under 100 rev/mins of stirrings, obtain milky thermal stimulus responsive nano hydrogel dispersion liquid; Wherein initiator amount be thermal stimulus responsiveness monomer and chemical cross-linking agent gross weight 4%;
(3) get the above-mentioned thermal stimulus responsive nano hydrogel dispersion liquid that makes, add Silver Nitrate, logical nitrogen and 400 rev/mins stirred 20 minutes, get even milky white solution, and then adding borane reducing agent sodium hydride, solution becomes rapidly brown, at room temperature continue reaction 3 hours, obtain translucent orange-yellow silver-carrying nano particle nano-hydrogel dispersion liquid, final purification, remove unreacted monomer, linking agent, silver ions, namely get silver-carrying nano particle temperature stimulating responsive nano-hydrogel, wherein the weight ratio of the consumption of Silver Nitrate and thermal stimulus responsive nano hydrogel dispersion liquid is 0.05: 1, and the mol ratio of sodium borohydride and Silver Nitrate is 1: 5; Purifying process is for to dialyse for 2 weeks with dialysis tubing.
This silver-carrying nano particle temperature stimulating responsive nano-hydrogel can keep in Dark Place at normal temperatures, its nano-hydrogel particle size analysis scope is 500nm, the particle diameter of Nano silver grain is 5nm, the weight percentage of Nano silver grain is 16% in the nano-hydrogel that TGA records, and the maximum absorption wavelength λ max that uv-vis spectra records is 405nm.
Claims (7)
1. the preparation method of a silver-carrying nano particle temperature stimulating responsive nano-hydrogel comprises:
(1) is to join in deionized water at 40～90: 5～50 in molar ratio with thermal stimulus responsiveness monomer and chemical cross-linking agent, stirs the reactant aqueous solution that is made into homogeneous transparent after 5～60 minutes; The gross weight of wherein thermal stimulus responsiveness monomer and chemical cross-linking agent is 1:10 ~ 50 with the ratio of the weight of deionized water;
(2) at room temperature, be that 0.05～0.5wt% initiator solution joins in the above-mentioned reactant aqueous solution with concentration, then pass into nitrogen, be warming up to gradually 50～90 ℃ of back balances 10～120 minutes under stirring, obtain the nano-hydrogel dispersion liquid; Wherein initiator amount be thermal stimulus responsiveness monomer and chemical cross-linking agent gross weight 0.1～5%;
(3) get the above-mentioned nano-hydrogel dispersion liquid that makes, add silver salt, logical nitrogen also stirred 10～120 minutes, get even milky white solution, and then add reductive agent, at room temperature continue reaction 1～5 hour, obtain silver-carrying nano particle nano-hydrogel dispersion liquid, final purification namely gets silver-carrying nano particle temperature stimulating responsive nano-hydrogel, and wherein the weight ratio of the consumption of silver salt and nano-hydrogel dispersion liquid is 0.01～0.1: 1;
Thermal stimulus responsiveness monomer described in the step (1) is a kind of in NIPA, N-isopropyl methyl acrylamide, N-n-propyl acrylamide, the N tert butyl acrylamide; Chemical cross-linking agent is a kind of in methylene-bisacrylamide, the methacrylate TEG ester.
2. the preparation method of a kind of silver-carrying nano particle temperature stimulating responsive nano-hydrogel according to claim 1, it is characterized in that: the initiator described in the step (2) is water-soluble thermal initiator, a kind of in Potassium Persulphate, ammonium persulphate, soluble ferrite, the Tetramethyl Ethylene Diamine.
3. the preparation method of a kind of silver-carrying nano particle temperature stimulating responsive nano-hydrogel according to claim 1 is characterized in that: the speed that stirs described in step (1), (2) and (3) is 100～500 rev/mins.
4. the preparation method of a kind of silver-carrying nano particle temperature stimulating responsive nano-hydrogel according to claim 1, it is characterized in that: the silver salt described in the step (3) is Silver Nitrate.
5. the preparation method of a kind of silver-carrying nano particle temperature stimulating responsive nano-hydrogel according to claim 1, it is characterized in that: the reductive agent described in the step (3) is hydrazine hydrate or sodium borohydride, the mol ratio of reductive agent and silver salt is 1～5:1.
6. the preparation method of a kind of silver-carrying nano particle temperature stimulating responsive nano-hydrogel according to claim 1, it is characterized in that: the purifying process described in the step (3) is:
A: with the silver-carrying nano particle nano-hydrogel aqueous dispersions centrifugation of gained, then ultra-sonic dispersion is in deionized water, and repeated centrifugation is separated and ultra-sonic dispersion 2～5 times, and wherein centrifugal speed is 4000～15000 rev/mins;
Or b: with dialysis tubing 1～3 week of dialysis.
7. the preparation method of a kind of silver-carrying nano particle temperature stimulating responsive nano-hydrogel according to claim 1, it is characterized in that: nano-hydrogel particle size analysis scope is 100～900nm in the silver-carrying nano particle temperature stimulating responsive nano-hydrogel of the middle gained of step (3), the particle diameter of Nano silver grain is 3～20nm, and the mass content of Nano silver grain is 10～25%.
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