CN102757571B - Preparation method of core-shell temperature-sensitive inorganic/organic hybrid network structure composite microgel - Google Patents
Preparation method of core-shell temperature-sensitive inorganic/organic hybrid network structure composite microgel Download PDFInfo
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- CN102757571B CN102757571B CN2012102300919A CN201210230091A CN102757571B CN 102757571 B CN102757571 B CN 102757571B CN 2012102300919 A CN2012102300919 A CN 2012102300919A CN 201210230091 A CN201210230091 A CN 201210230091A CN 102757571 B CN102757571 B CN 102757571B
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Abstract
The invention relates to a preparation method of a core-shell temperature-sensitive inorganic/organic hybrid network structure composite microgel, which comprises the following steps: preparing a styrene-N-isopropylacrylamide microsphere dispersion liquid, and preparing the core-shell temperature-sensitive inorganic/organic hybrid network structure composite microgel. The core-shell temperature-sensitive inorganic/organic hybrid network structure composite microgel can be regulated by changing the relative content of organic and inorganic components and the total amount of the shell component; and the core-shell temperature-sensitive inorganic/organic hybrid network structure composite microgel has wide application prospects in the field of preparation of colloid crystals, porous materials and hollow materials, and can be widely used in many important fields, such as chemical adsorption, medicine slow release, microreactors, catalyst supporters, chemical sensors and the like.
Description
Technical field
The invention belongs to the material technology field, be specifically related to colloid chemistry, for example: the preparation of other classes colloid material not to be covered or its solution; The preparation of microcapsule or microballoon.
Background technology
Core-Shell Particles Shi You center particle is that core, different components are the formed class matrix material of shell, have the characteristics such as Modulatory character and tailorability at aspects such as composition, structure, surface propertieies due to it, the preparation and application research of this class material has become the hot subject that numerous ambit scientists are paid close attention to.Poly-N-isopropyl acrylamide microgel is one of temperature-sensitive hydrogel commonly used, and its temperature sensitive performance has important applied research at key areas such as drug delivery, bio-sensing, chemical separation and catalysis and is worth.In actual procedure, owing to containing pure organic constituent in poly-N-isopropyl acrylamide microgel, make it in application facet, be subject to a lot of restrictions.And organic and inorganic matrix material has the dual nature of organic constituent and inorganic component concurrently simultaneously, both can have inorganic materials physical strength preferably, can keep again three-dimensional net structure and the temperature sensitive behavior of polymer microgel material.Nano-composite gel with poly N-isopropyl acrylamide/clay of network structure has good physical strength, the content of its tension stress intensity and clay used is proportional, and its elongation at break is along with the slight minimizing of the increase of clay amount, and, with the increase of linking agent clay content, the swelling ratio that goes of plural gel reduces.With N, the poly N-isopropyl acrylamide gel material that the N'-methylene-bisacrylamide forms as linking agent, content of crosslinking agent has remarkably influenced to the swelling ratio that goes of gel, and along with the increase of content of crosslinking agent, the swelling ratio that goes of gelatinous material increases thereupon.In addition, (Macromolecules 2006,39,1898-1905 for Kazutoshi Haraguchi etc.; Macromolecules 2010,43,9848 – 9853) studied the synthetic nano-composite gel that contains organic (polymkeric substance)/inorganic (clay) hybridization network structure, this microgel has fabulous physical strength and swelling property.
Abovely using the composite gel material of clay as the linking agent synthesized, can significantly increase the physical strength of hydrogel material, generally, in order to make hydrogel there is swelling ratio preferably, the dosage of crosslinking agent of using is less, therefore, degree of crosslinking is wayward, thereby its application facet at material is restricted.
In practical study, because silicon-dioxide has good chemical stability, is easy to practical function, good mechanical stability and biocompatibility, so, the polymer that investigators usually will be contained the inorganic network structure of siloxane bond and contain the temperature sensitive performance is undertaken compound by certain mode, the matrix material that has the inorganic-organic hybridization network structure with acquisition.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned preparation method's shortcoming, provide a kind of simple to operate, be easy to functionalization, there is the chemically crosslinked structure, the preparation method of thermally sensitive core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
Solving the problems of the technologies described above adopted technical scheme is comprised of following step:
1, prepare vinylbenzene-NIPA microballoon dispersion liquid
Under nitrogen protection; by filling in the NIPA aqueous solution there-necked flask that concentration is 0.0196mol/L, add vinylbenzene to mix; 400 rev/mins of dispersed with stirring; heating in water bath; be warming up to 70 ℃, the persulfate aqueous solution that is 0.059mol/L by 10mL concentration joins in there-necked flask, and Potassium Persulphate and NIPA, cinnamic mol ratio are 1:3.1:29.3; 70 ℃ are reacted 8 hours, are prepared into vinylbenzene-NIPA microballoon dispersion liquid.
2, prepare core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel
Under nitrogen protection, by NIPA, 3-(methacryloxypropyl) propyl trimethoxy silicane, N, the N'-methylene-bisacrylamide, sodium laurylsulfonate is dissolved in redistilled water, be prepared into mixed solution, sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is 1:4.4:5.8～11.6:96.3～108.3, mixed solution is joined in vinylbenzene-NIPA microballoon dispersion liquid, 400 rev/mins of dispersed with stirring, heating in water bath, be warming up to 70 ℃, the persulfate aqueous solution that is 0.015mol/L by concentration joins in mixed solution, the mass ratio of persulfate aqueous solution and mixed solution is 1:4.5, in the time of 60～70 ℃, reaction is 4～6 hours, second distillation water washing 3～5 times for reaction product, centrifugation, product is placed in to dialysis tubing dialyses two weeks with redistilled water, changed one time redistilled water every 12 hours, use liquid nitrogen freezing,-55 ℃ of lyophilizes 24 hours, be prepared into core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
Prepare core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel step 2 of the present invention, under nitrogen protection, sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the optimum mole ratio of NIPA is that 1:4.4:5.8:108.3 is dissolved in redistilled water, be prepared into mixed solution, mixed solution is joined in vinylbenzene-NIPA microballoon dispersion liquid, 400 rev/mins of dispersed with stirring, heating in water bath, while being warming up to 70 ℃, the persulfate aqueous solution of 0.015mol/L is joined in mixed solution, the optimum quality ratio of persulfate aqueous solution and mixed solution is 1:4.5, in the time of 60～70 ℃, reaction is 4～6 hours, second distillation water washing 3～5 times for reaction product, centrifugation, product is placed in to dialysis tubing dialyses two weeks with redistilled water, changed one time redistilled water every 12 hours, use the liquid nitrogen quick freezing,-55 ℃ of lower lyophilizes 24 hours, be prepared into core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
The core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel that adopts the present invention to prepare, relative content that can be by changing organic and inorganic component and the total amount of shell component are regulated, this class material will have good application prospect preparing aspect colloidal crystal, porous material and hollow material, also will have widespread use at numerous key areas such as chemisorption, medicament slow release, microreactor, catalyst loading and chemical sensors.
The accompanying drawing explanation
Fig. 1 is sodium laurylsulfonate and N, the electron scanning micrograph that the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel for preparing of 1:4.4:11.6:96.3.
Fig. 2 is sodium laurylsulfonate and N, the transmission electron microscope photo that the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel for preparing of 1:4.4:11.6:96.3.
Fig. 3 is sodium laurylsulfonate and N, the electron scanning micrograph that the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel for preparing of 1:4.4:9.9:99.9.
Fig. 4 is sodium laurylsulfonate and N, the transmission electron microscope photo that the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel for preparing of 1:4.4:9.9:99.9.
Fig. 5 is sodium laurylsulfonate and N, the electron scanning micrograph that the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel for preparing of 1:4.4:5.8:108.3.
Fig. 6 is sodium laurylsulfonate and N, the transmission electron microscope photo that the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel for preparing of 1:4.4:5.8:108.3.
Fig. 7 is the infrared spectrogram of different ratios of raw materials core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
Fig. 8 is the particle diameter variation with temperature graph of a relation of the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel of embodiment 1 preparation.
Fig. 9 is that the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel of embodiment 1 preparation is to temperature sensitivity reversibility curve.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but the invention is not restricted to these embodiment.
Preparation method's step of the present embodiment core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is as follows:
1, prepare vinylbenzene-NIPA microballoon dispersion liquid
Under nitrogen protection; by filling in the there-necked flask of the NIPA aqueous solution that 90.2g concentration is 0.0196mol/L, add 1.8g vinylbenzene to mix; NIPA and cinnamic mol ratio are 1:9.6; 400 rev/mins of dispersed with stirring; heating in water bath to 70 ℃; add the persulfate aqueous solution that 10.16g concentration is 0.059mo l/L; Potassium Persulphate and NIPA, cinnamic mol ratio are 1:3.1:29.3; 70 ℃ are reacted 8 hours, are prepared into vinylbenzene-NIPA microballoon dispersion liquid.
2, prepare core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel
Under nitrogen protection, by the 0.90g NIPA, (0.10g3-methacryloxypropyl) propyl trimethoxy silicane, 0.05g N, the N'-methylene-bisacrylamide, 0.02g sodium laurylsulfonate is dissolved in redistilled water, be prepared into mixed solution, sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is that 1:4.4:5.8:108.3 is prepared into mixed solution, mixed solution is joined in vinylbenzene-NIPA microballoon dispersion liquid, 400 rev/mins of dispersed with stirring, heating in water bath, while being warming up to 70 ℃, the persulfate aqueous solution that is 0.015mol/L by 2.04g concentration joins in mixed solution, the mass ratio of persulfate aqueous solution and mixed solution is 1:4.5, in the time of 60～70 ℃, reaction is 4～6 hours, second distillation water washing 3～5 times for reaction product, centrifugation, product is placed in to dialysis tubing dialyses two weeks with redistilled water, changed one time redistilled water every 12 hours, use liquid nitrogen freezing,-55 ℃ of lyophilizes 24 hours, be prepared into core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
Embodiment 2
Preparation method's step of embodiment core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is as follows:
Prepare vinylbenzene-NIPA microballoon dispersion liquid step 1 identical with embodiment 1.
In preparing core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel step 2, under nitrogen protection, by the 0.83g NIPA, (0.17g3-methacryloxypropyl) propyl trimethoxy silicane, 0.05g N, the N'-methylene-bisacrylamide, 0.02g sodium laurylsulfonate is dissolved in redistilled water, be prepared into mixed solution, sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is that 1:4.4:9.9:99.9 is prepared into mixed solution, mixed solution is joined in vinylbenzene-NIPA microballoon dispersion liquid, 400 rev/mins of dispersed with stirring, heating in water bath, while being warming up to 70 ℃, the persulfate aqueous solution that is 0.015mol/L by 2.04g concentration joins in mixed solution, the mass ratio of persulfate aqueous solution and mixed solution is 1:4.5, in the time of 60～70 ℃, reaction is 4～6 hours, second distillation water washing 3～5 times for reaction product, centrifugation, product is placed in to dialysis tubing dialyses two weeks with redistilled water, changed one time redistilled water every 12 hours, use liquid nitrogen freezing,-55 ℃ of lyophilizes 24 hours, be prepared into core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
Embodiment 3
Preparation method's step of the present embodiment core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is as follows:
Prepare vinylbenzene-NIPA microballoon dispersion liquid step 1 identical with embodiment 1.
In preparing core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel step 2, under nitrogen protection, by the 0.80g NIPA, (0.20g3-methacryloxypropyl) propyl trimethoxy silicane, 0.05g N, the N'-methylene-bisacrylamide, 0.02g sodium laurylsulfonate is dissolved in redistilled water, be prepared into mixed solution, sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is that 1:4.4:11.6:96.3 is prepared into mixed solution, mixed solution is joined in vinylbenzene-NIPA microballoon dispersion liquid, 400 rev/mins of dispersed with stirring, heating in water bath, while being warming up to 70 ℃, the persulfate aqueous solution that is 0.015mol/L by 2.04g concentration joins in mixed solution, the mass ratio of persulfate aqueous solution and mixed solution is 1:4.5, in the time of 60～70 ℃, reaction is 4～6 hours, second distillation water washing 3～5 times for reaction product, centrifugation, product is placed in to dialysis tubing dialyses two weeks with redistilled water, changed one time redistilled water every 12 hours, use liquid nitrogen freezing,-55 ℃ of lyophilizes 24 hours, be prepared into core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
In order to determine optimum material proportion of the present invention and optimum process condition, the contriver has carried out a large amount of laboratory study tests, and it is as follows that situation is tested in various experiments:
1, the impact of different ratios of raw materials on the surface topography of prepared core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel
In the step 2 for preparing core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel, get the 0.02g sodium laurylsulfonate, 0.05gN, the N'-methylene-bisacrylamide, (0.20g3-methacryloxypropyl) propyl trimethoxy silicane, 0.80g NIPA, sodium laurylsulfonate and N, N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is 1::4.4:11.6:96.3 as experiment 1, gets the 0.02g sodium laurylsulfonate, 0.05gN, the N'-methylene-bisacrylamide, (0.17g3-methacryloxypropyl) propyl trimethoxy silicane, 0.83gN-N-isopropylacrylamide, sodium laurylsulfonate and N, N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is 1:4.4:9.9:99.9, as experiment 2, gets the 0.02g sodium laurylsulfonate, 0.05gN, the N'-methylene-bisacrylamide, (0.10g3-methacryloxypropyl) propyl trimethoxy silicane, 0.90g NIPA, sodium laurylsulfonate and N, N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is 1:4.4:5.8:108.3, as experiment 3.Other steps are identical with embodiment 1.
Test prepared core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel by three groups and observe with scanning electronic microscope and transmission electron microscope respectively, experimental result is shown in Fig. 1～6.From Fig. 1,2, the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel of experimental group 1 preparation presents spherical morphology, surperficial smoother, but its particle diameter homogeneous not bery, and microgel presents hud typed structure, and median size is 235nm.From Fig. 3 and Fig. 4, the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel of experimental group 2 preparations presents spherical morphology, than the composite microgel of experimental group 1, and its uniform particle diameter, microgel presents hud typed structure, and median size is 242nm.From Fig. 5 and Fig. 6, the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel of experimental group 3 preparations presents regular spherical morphology, and particle diameter is single, presents nucleocapsid structure, and median size is 276nm.This shows, sodium laurylsulfonate and N, the uniform particle diameter of the core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel that the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is 1:4.4:5.8～11.6:96.3～108.3 preparations, monodispersity is better, surperficial smoother.Sodium laurylsulfonate and N are selected in selecting and purchasing of the present invention, the mol ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is 1:4.4:5.8～11.6:96.3～108.3, wherein sodium laurylsulfonate and N, the optimum mole ratio of N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, NIPA is 1:4.4:5.8:108.3.
Test prepared core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel by above-mentioned three groups and carried out composition analysis with Fourier transformation infrared spectrometer, experimental result is shown in Fig. 7, in Fig. 7, curve a is sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel prepared by 1::4.4:11.6:96.3, curve b is sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel prepared by 1:4.4:9.9:99.9, curve c is sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel prepared by 1:4.4:5.8:108.3, as seen from Figure 7, core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is 1647, 1454cm
-1the absorption peak at place can be attributed to respectively the acid amides (I) of NIPA and the characteristic peak of acid amides (II), at 1101cm
-1obvious silicon-oxygen key charateristic avsorption band has appearred in place.The infrared analysis result shows, testing prepared product is core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel material.
2, the sensitivity experiments of core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel to temperature
Utilize the method for dynamic light scattering to core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel prepared in embodiment 1, the susceptibility of temperature to be tested, specific as follows:
The core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel that embodiment 1 is prepared is scattered in redistilled water, be made into the dispersion liquid that concentration is 0.0032g/L, ultrasonic dispersion is after 30 minutes, with laser particle analyzer (BI-90Plus, U.S. BIC instrument company produces) variation that occurs along with the change of temperature of the particle diameter of measuring composite microgel, the temperature measuring scope is 18～42 ℃, and temperature interval is 2 ℃.Experimental result is shown in Fig. 8, as seen from Figure 8, core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is along with the rising of temperature, 30 ℃ of left and right, obvious volume change has occurred, the maximum swelling of its volume has 60nm, with 32 ℃ of the critical phase transition temperatures of NIPA, compare, variation has occurred in the critical phase transition temperature of core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel, critical temperature is moved to low temperature, and core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel has good temperature sensitivity.
The micro-solidifying changing conditions of hydration kinetics particle diameter when 20～40 ℃ of circulation change of core-shell type Thermo-sensitive inorganic-organic hybridization network structure composite after adopting laser particle analyzer to above-mentioned ultrasonic dispersion treatment detected, result is referring to Fig. 9, as seen from Figure 9, in the time of 20 ℃, core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is in solvent swelling state, and median size is about 385nm; In the time of 40 ℃, the diameter of core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel obviously diminishes, this core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is in contraction schedule, its median size is 318nm, the repeatedly swelling of core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel between two temperatures and contraction change of size, show that this core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel has better temperature sensitive performance.
Claims (2)
1. the preparation method of a core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel is comprised of following step:
(1) prepare vinylbenzene-NIPA microballoon dispersion liquid
Under nitrogen protection, by filling in the there-necked flask of the NIPA aqueous solution that concentration is 0.0196mol/L, add vinylbenzene to mix, 400 rev/mins of dispersed with stirring, heating in water bath, be warming up to 70 ℃, the persulfate aqueous solution that is 0.059mol/L by 10mL concentration joins in there-necked flask, and Potassium Persulphate and NIPA, cinnamic mol ratio are 1:3.1:29.3,70 ℃ are reacted 8 hours, are prepared into vinylbenzene-NIPA microballoon dispersion liquid;
(2) prepare core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel
Under nitrogen protection, by NIPA, 3-(methacryloxypropyl) propyl trimethoxy silicane, N, the N'-methylene-bisacrylamide, sodium laurylsulfonate is dissolved in redistilled water, be prepared into mixed solution, sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is 1:4.4:5.8～11.6:96.3～108.3, mixed solution is joined in vinylbenzene-NIPA microballoon dispersion liquid, 400 rev/mins of dispersed with stirring, heating in water bath, be warming up to 70 ℃, the persulfate aqueous solution that is 0.015mol/L by concentration joins in mixed solution, the mass ratio of persulfate aqueous solution and mixed solution is 1:4.5, in the time of 60～70 ℃, reaction is 4～6 hours, second distillation water washing 3～5 times for reaction product, centrifugation, product is placed in to dialysis tubing dialyses two weeks with redistilled water, changed one time redistilled water every 12 hours, use liquid nitrogen freezing,-55 ℃ of lyophilizes 24 hours, be prepared into core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
2. the preparation method of core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel according to claim 1, it is characterized in that: in preparing core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel step (2), under nitrogen protection, sodium laurylsulfonate and N, the N'-methylene-bisacrylamide, 3-(methacryloxypropyl) propyl trimethoxy silicane, the mol ratio of NIPA is that 1:4.4:5.8:108.3 is dissolved in redistilled water, be prepared into mixed solution, mixed solution is joined in vinylbenzene-NIPA microballoon dispersion liquid, 400 rev/mins of dispersed with stirring, heating in water bath, while being warming up to 70 ℃, the persulfate aqueous solution of 0.015mol/L is joined in mixed solution, the mass ratio of persulfate aqueous solution and mixed solution is 1:4.5, in the time of 60～70 ℃, reaction is 4～6 hours, second distillation water washing 3～5 times for reaction product, centrifugation, product is placed in to dialysis tubing dialyses two weeks with redistilled water, changed one time redistilled water every 12 hours, use the liquid nitrogen quick freezing,-55 ℃ of lower lyophilizes 24 hours, be prepared into core-shell type Thermo-sensitive inorganic-organic hybrid network structure composite microgel.
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