CN102827330A - Preparation method of gel nano particles in thermosensitivie nuclear shell structure and application of product thereof - Google Patents
Preparation method of gel nano particles in thermosensitivie nuclear shell structure and application of product thereof Download PDFInfo
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- CN102827330A CN102827330A CN2012103331045A CN201210333104A CN102827330A CN 102827330 A CN102827330 A CN 102827330A CN 2012103331045 A CN2012103331045 A CN 2012103331045A CN 201210333104 A CN201210333104 A CN 201210333104A CN 102827330 A CN102827330 A CN 102827330A
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Abstract
The invention discloses a preparation method of gel nano particles in a thermosensitivie nuclear shell structure and an application of a product thereof. Thermosensitive microgel is prepared by the preparation method by using polybutadiene nanometer emulsion particles as nucleus, grafting poly(N-isopropyl acrylamide) on the surface of the nucleus by a free radical polymerization method under the effect of a cross-linking agent. The microgel can be used as a nano reactor. Nano silver particles with controllable particle size and distribution are prepared through an in-situ reduction reaction. The microgel carrying the nano silver particles can be used as a high-performance catalyst, a bacteriacide and the like.
Description
Technical field
The present invention relates to a kind of preparation method and application of new type structure of hud nanogel; Specifically; Be to prepare cross-linking type in the radical polymerization of polyhutadiene emulsion particle surface by utilizing to gather (N-NSC 11448) micro-gel particles; And with it as reactor drum and carrier system in-situ preparing and silver-loaded nanometer, the composite Nano microgel that obtains can be used as effective catalyst and sterilant.
Background technology
In recent years, noble metal nano particles has obtained very big concern, mainly is because these particles have high-specific surface area and high catalytic activity.If but want to give full play to the catalytic performance of these metal nanoparticles, just must prevent the reunion of particle, keep its good dispersiveness.Therefore find appropriate preparation method and load system, most important to the application of metal nanoparticle.
The polymer microgel material is compared with other materials, has a lot of advantages.Such as good stability is easy to synthesize, and particle size is had reasonable control, forms the behavior (as when pH value, ionic strength or the temperature variation, character such as the volume of particle change) of stimuli responsive easily.This type material plays very big pushing effect to the development of nanosecond science and technology.It also can be used as support of the catalyst in addition, makes catalyzer can keep high catalytic activity, and is easy to separate and utilization again.
In addition; The idea of green chemical industry requires the industry of present catalyzer also to want viridescent notion; Be low temperature, be prone to remove, metal is difficult for being entrained in the product, this just needs carrier system not only long-time stability will be arranged, and is easy to control and prevent the reunion of metal nanoparticle.In recent years; The microgel system carrying metal particles of temperature sensitive property has caused widely in catalysis field to be paid attention to; Because this system can still have temperature-responsive behind metallics in the load; Promptly stretching, extension can be carried out reaction when low temperature, but after temperature was higher than phase transition temperature, system was shunk catalytic rate is obviously descended.So this system can utilize temperature to regulate and control catalyzed reaction as switch.
Most temperature-sensitive macromolecular hydrogel utilizes the emulsion polymerization preparation by gathering (N-NSC 11448), and its lowest critical solution temperature is (LCST) 32 ℃.When temperature was lower than LCST, because water molecules and the intermolecular hydrogen bond that formed of side chain, high molecular form revealed good solubility.When temperature was higher than LCST, because the associated water of hydrophobic grouping is squeezed out from the microgel system gradually, volume shrank thereupon.
Summary of the invention
The objective of the invention is to develop a kind of low cost, be easy to synthetic and raw material sources temperature-sensitive hydrogel widely, and be carrier with the microgel that this kind has a nucleocapsid structure, the silver-loaded nanoparticle is as the intelligent catalysis agent of temperature sensitive property.Concrete technical scheme is following:
A kind of temperature sensitive property nucleocapsid structure gel nanometer particle process method may further comprise the steps:
(1) adopt the polybutadiene latex particle to be nuclear, with the deionized water purifying of dialysing, constant up to outside electrical conductivity of water, wherein the kind of dialysis membrane can be selected according to the size of said polybutadiene latex particle;
(2) with in the nuclear of the polyhutadiene behind the purifying in the step (1) and the water adding reactor drum, stir, vacuumize then inflated with nitrogen 3～5 times with 250～400 rev/mins rotating speeds; Under nitrogen protection, be warming up to 60～80 ℃; Add water-soluble thermal initiator, then add N-NSC 11448 monomer and N, N '-methylene-bisacrylamide linking agent; React after 1～2.5 hour, obtain temperature sensitive property nucleocapsid structure gel nanoparticle and be dispersed in the emulsion in the water;
Said water-soluble thermal initiator is hydrogen peroxide or Potassium Persulphate, and the mass ratio of its consumption and polyhutadiene nuclear is 0.1～0.2:1;
The mass ratio of said N-NSC 11448 monomer and polyhutadiene nuclear is 0.5～1:1, said N, and N '-methylene-bisacrylamide linking agent and the monomeric mol ratio of N-NSC 11448 are 0.01～0.1:1.
Wherein, the add-on of water is that 1～2 wt% is as the criterion and calculates with the solid content of the micro-gel particles that obtains in the step (2).
The particle diameter of said temperature sensitive property nucleocapsid structure gel nanoparticle in the aqueous solution is 200～800 nanometers, has good monodispersity, and particle diameter significantly reduces after being elevated to 32 degrees centigrade with temperature.
The application of the said temperature sensitive property nucleocapsid structure gel nanoparticle that above-mentioned preparation method obtains; Promptly; Said temperature sensitive property nucleocapsid structure gel nanoparticle is as a kind of nano-reactor; Through the in-situ reducing prepared in reaction size and the controlled nano silver particles that distributes, and behind loading nano silvery, be used as effective catalyst and/or sterilant.
The present invention measures the size and the size distribution of polyhutadiene emulsion particle and final micro-gel particles through dynamic light scattering, also detected the temperature-sensing property of the micro-gel particles that step (2) obtains.
The present invention is nuclear with the polyhutadiene; With the N-NSC 11448 is monomer and with N; N '-methylene-bisacrylamide is the microgel nano particle of linking agent preparation; Can be used for silver ions in the adsorbent solution, and in the microgel shell, utilize the sodium borohydride in-situ reducing to be Nano silver grain silver ions, then Nano silver grain loaded in the microgel shell as nano-reactor.The composite microgel particle of this silver-loaded nanoparticle has good stability, temperature sensitive property, and can be through temperature controlled catalytic activity.
Description of drawings
Fig. 1 is the temperature sensitive property synoptic diagram of micro-gel particles;
Fig. 2 is embodiment 1 and 2 product record microgel under the different dosage of crosslinking agent situation with dynamic light scattering a temperature response curve;
Fig. 3 is the synoptic diagram of the product microgel silver-loaded nanoparticle of embodiment 3;
Fig. 4 is the transmission electron microscope picture of the product microgel silver-loaded nanoparticle of embodiment 3; Wherein (1) is the photo of the silver-loaded particle first time; (2) be the photo of the 5th silver-loaded particle;
Fig. 5 is reduced to the catalytic activity that the chemical reaction of PARA AMINOPHENOL demonstrates for p-NP behind the product microgel silver-loaded nanoparticle of embodiment 4 under the Peng Qinghuana effect.X-coordinate is the microgel concentration of silver-loaded nanoparticle, and ordinate zou is a reaction rate constant.
Embodiment
Below, will combine embodiment further to illustrate content of the present invention, but these embodiment do not limit protection scope of the present invention.
35 milliliters polyhutadiene nuclear (solid content is 11.5%) and 165 ml waters are joined in the there-necked flask; Utilize mechanical stirring (300 rev/mins) that it is fully dissolved, vacuumize then inflated with nitrogen 3 times, under nitrogen protection, be warming up to 70 ℃; Stable back adds water-soluble thermal initiator Potassium Persulphate 0.5 gram; React after 30 minutes, add water-soluble N-NSC 11448 monomer 2.0 grams and N, N '-methylene-bisacrylamide linking agent 0.07 gram.React after 1.5 hours, obtain microgel emulsion, the particle diameter that uses dynamic light scattering under 25 ℃, to record wherein temperature sensitive property nucleocapsid structure gel nanoparticle is 712 nanometers.
35 milliliters polyhutadiene nuclear (is 11.5% admittedly contain) and 165 ml waters are joined in the there-necked flask; Utilize mechanical stirring (350 rev/mins) that it is fully dissolved, vacuumize then inflated with nitrogen 3 times, under nitrogen protection, be warming up to 80 ℃; Stable back adds water-soluble thermal initiator Potassium Persulphate 0.3 gram; React after 20 minutes, add water-soluble N-NSC 11448 monomer 1.25 grams and N, N '-methylene-bisacrylamide linking agent 0.08 gram.React after 2 hours, obtain microgel emulsion, the particle diameter that uses dynamic light scattering under 25 ℃, to record wherein temperature sensitive property nucleocapsid structure gel nanoparticle is 650 nanometers.
Embodiment 3
The solid content of getting embodiment 1 or embodiment 2 is 120 milliliters of there-necked flasks that place 500 milliliters of 2% nano microgel emulsion; And add 240 ml deionized water; 0.0672 gram Silver Nitrate solid is dissolved in adds there-necked flask in 40 ml deionized water then; Vacuumize and inflated with nitrogen 3 times, keep nitrogen atmosphere.At room temperature; After fully stirring 3 hours with 300 rev/mins of mechanical stirring; This emulsion was placed ice bath 1 hour, and the sodium borohydride solution that will be dissolved in 0.1656 gram of 10 ml deionized water is afterwards poured into rapidly in the tap funnel, splashes in the there-necked flask solution with 2 seconds/speed.Keep ice bath to continue stirring reaction after 1.5 hours, stopped reaction, and the reaction product dialysis tubing of packing into dialysed a week, obtain the temperature-sensitive nano gel particles of silver-loaded nanoparticle.
Embodiment 4
The solution of an Ag particle of 300 milliliters of loads of dialysing poured in 500 milliliters the there-necked flask, and add the 0.0504 gram silver nitrate solution that is dissolved in 30 ml deionized water.Take out inflated with nitrogen 3 times and put the nitrogen bag, keep nitrogen atmosphere.Under the condition of room temperature; After 3 hours this emulsion was placed ice bath 1 hour with 300 rev/mins of abundant stirrings of mechanical stirring; The sodium borohydride solution that will be dissolved in 0.1242 gram of 10 ml deionized water is afterwards poured into rapidly in the tap funnel, and 2 seconds/speed splashes in the there-necked flask solution.Keep ice bath to continue stirring reaction after 1.5 hours, stopped reaction, and the reaction product dialysis tubing of packing into dialysed a week, obtain the temperature-sensitive nano gel particles of silver-loaded nanoparticle.The gel particle of this silver-loaded particle can adopt the method for repeated load to prepare the Nano silver grain of big particle diameter.Composite nanoparticle demonstrates good catalytic activity for p-NP is reduced to PARA AMINOPHENOL under the Peng Qinghuana effect chemical reaction behind the loading nano silvery, sees accompanying drawing 5.
Claims (4)
1. a temperature sensitive property nucleocapsid structure gel nanometer particle process method is characterized in that, may further comprise the steps:
(1) adopt the polybutadiene latex particle to be nuclear, with the deionized water purifying of dialysing, constant up to outside electrical conductivity of water;
(2) with in the nuclear of the polyhutadiene behind the purifying in the step (1) and the water adding reactor drum, stir, vacuumize then inflated with nitrogen 3～5 times with 250～400 rev/mins rotating speeds; Under nitrogen protection, be warming up to 60～80 ℃; Add water-soluble thermal initiator, then add N-NSC 11448 monomer and N, N '-methylene-bisacrylamide linking agent; React after 1～2.5 hour, obtain temperature sensitive property nucleocapsid structure gel nanoparticle and be dispersed in the emulsion in the water;
Said water-soluble thermal initiator is hydrogen peroxide or Potassium Persulphate, and the mass ratio of its consumption and polyhutadiene nuclear is 0.1～0.2:1;
The mass ratio of said N-NSC 11448 monomer and polyhutadiene nuclear is 0.5～1:1, said N, and N '-methylene-bisacrylamide linking agent and the monomeric mol ratio of N-NSC 11448 are 0.01～0.1:1.
2. preparation method according to claim 1 is characterized in that, wherein, the add-on of water is that 1～2 wt% is as the criterion and calculates with the solid content of the micro-gel particles that obtains in the step (2).
3. preparation method according to claim 1 is characterized in that, the particle diameter of said temperature sensitive property nucleocapsid structure gel nanoparticle in the aqueous solution is 200～800 nanometers.
4. the application of the said temperature sensitive property nucleocapsid structure gel nanoparticle that obtains of the described preparation method of claim 1; It is characterized in that; Said temperature sensitive property nucleocapsid structure gel nanoparticle is as a kind of nano-reactor; Through the in-situ reducing prepared in reaction size and the controlled nano silver particles that distributes, and behind loading nano silvery, be used as effective catalyst and/or sterilant.
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| CN103464203A (en) * | 2013-08-26 | 2013-12-25 | 陕西师范大学 | Preparation method of thermosensitive microgel asymmetric supported nano silver catalyst |
| CN103752237A (en) * | 2014-01-10 | 2014-04-30 | 陕西师范大学 | Preparation method of pH sensitive microgel loaded nanogold |
| CN104031278A (en) * | 2014-05-31 | 2014-09-10 | 黑龙江省科学院技术物理研究所 | Preparation method of thermosensitive nanochannel PB functional film |
| CN104759617A (en) * | 2015-04-02 | 2015-07-08 | 东华大学 | Light/temperature double responsiveness hybrid microgel of silver-loaded nanoparticles and preparation method thereof |
| CN105536869A (en) * | 2016-01-12 | 2016-05-04 | 安徽师范大学 | Nano-silver-supported hybrid microgel catalyst and preparation method and application thereof |
| CN105548153A (en) * | 2015-12-01 | 2016-05-04 | 安徽师范大学 | Gold nanoparticle-containing glucose visual detection sensor and its preparation method and use |
| CN106752543A (en) * | 2017-01-18 | 2017-05-31 | 福州大学 | A kind of temperature-sensitive nano silver controlled release intelligence antibiotic paint and preparation method thereof |
| CN106861755A (en) * | 2017-02-24 | 2017-06-20 | 南开大学 | A kind of Pd catalyst of stimulating responsive material load and its preparation method and application is studied |
| CN107540852A (en) * | 2017-07-27 | 2018-01-05 | 西北工业大学 | A kind of method that ultrasonic field prepares the particle and hollow-particle of core shell structure |
| CN114560763A (en) * | 2022-03-07 | 2022-05-31 | 山东汉峰新材料科技有限公司 | Production process of deuterated acetic acid |
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| CN103464203B (en) * | 2013-08-26 | 2015-06-17 | 陕西师范大学 | Preparation method of thermosensitive microgel asymmetric supported nano silver catalyst |
| CN103464203A (en) * | 2013-08-26 | 2013-12-25 | 陕西师范大学 | Preparation method of thermosensitive microgel asymmetric supported nano silver catalyst |
| CN103752237B (en) * | 2014-01-10 | 2015-12-30 | 陕西师范大学 | The preparation method of the responsive microgel supported nano-gold of a kind of pH |
| CN103752237A (en) * | 2014-01-10 | 2014-04-30 | 陕西师范大学 | Preparation method of pH sensitive microgel loaded nanogold |
| CN104031278A (en) * | 2014-05-31 | 2014-09-10 | 黑龙江省科学院技术物理研究所 | Preparation method of thermosensitive nanochannel PB functional film |
| CN104759617B (en) * | 2015-04-02 | 2017-01-11 | 东华大学 | Preparation method of light/temperature double responsiveness hybrid microgel of silver-loaded nanoparticles |
| CN104759617A (en) * | 2015-04-02 | 2015-07-08 | 东华大学 | Light/temperature double responsiveness hybrid microgel of silver-loaded nanoparticles and preparation method thereof |
| CN105548153A (en) * | 2015-12-01 | 2016-05-04 | 安徽师范大学 | Gold nanoparticle-containing glucose visual detection sensor and its preparation method and use |
| CN105548153B (en) * | 2015-12-01 | 2018-10-30 | 安徽师范大学 | Gold nanoparticle Visual retrieval glucose sensor and its preparation method and application |
| CN105536869A (en) * | 2016-01-12 | 2016-05-04 | 安徽师范大学 | Nano-silver-supported hybrid microgel catalyst and preparation method and application thereof |
| CN106752543A (en) * | 2017-01-18 | 2017-05-31 | 福州大学 | A kind of temperature-sensitive nano silver controlled release intelligence antibiotic paint and preparation method thereof |
| CN106752543B (en) * | 2017-01-18 | 2018-11-27 | 福州大学 | A kind of temperature-sensitive nano silver controlled release intelligence antibiotic paint and preparation method thereof |
| CN106861755A (en) * | 2017-02-24 | 2017-06-20 | 南开大学 | A kind of Pd catalyst of stimulating responsive material load and its preparation method and application is studied |
| CN106861755B (en) * | 2017-02-24 | 2019-11-29 | 南开大学 | A kind of Pd catalyst of stimulating responsive material load and its preparation method and application research |
| CN107540852A (en) * | 2017-07-27 | 2018-01-05 | 西北工业大学 | A kind of method that ultrasonic field prepares the particle and hollow-particle of core shell structure |
| CN107540852B (en) * | 2017-07-27 | 2020-07-14 | 西北工业大学 | Method for preparing particles with core-shell structure and hollow particles by ultrasonic field |
| CN114560763A (en) * | 2022-03-07 | 2022-05-31 | 山东汉峰新材料科技有限公司 | Production process of deuterated acetic acid |
| CN114560763B (en) * | 2022-03-07 | 2024-02-20 | 山东汉峰新材料科技有限公司 | Production process of deuterated acetic acid |
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Application publication date: 20121219 |