CN100556924C - The preparation method of temperature and pH value valve sensitive nano microgel - Google Patents
The preparation method of temperature and pH value valve sensitive nano microgel Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method with temperature and the dual nanometer grade sensitivity microgel of pH value.This preparation method is under the condition of no any emulsifying agent, adopt specific dropping technology and emulsifier-free emulsion polymerization method, monomer, linking agent and the water solvent that will have temperature and pH value susceptibility be the anabolic reaction thing aqueous solution in proportion, regularly dropwise be added dropwise in the initiator solution it, by purified homogeneous transparent or the nano level microgel of the dual sensitivity of translucent high stability made of random copolymerization, its particle diameter is 40～300nm, easily preservation, easy to use.This preparation method adopts the dropping technology, waits and regulates its particle size range by change monomer functional classification, monomer component ratio, drop rate, can be widely used in fields such as pharmaceutical carrier, coating.It is applied widely for this preparation method, technology is simple, be produced on a large scale.
Description
Technical field
The present invention relates to the preparation method of a kind of microgel in the polymeric material field, be meant a kind of preparation method especially with temperature and pH value valve sensitive nano microgel.The microgel of gained is mainly used in fields such as pharmaceutical carrier, chemical separation and biosensor.
Background technology
Gel by liquid and macromolecule network form can the oneself keep stable, be formed by connecting, have that the class of three-dimensional net structure is solid, the material of class liquid with Van der Waals force, hydrogen bond action power and chemical bonding force.Can be divided into hydrogel and organogel according to contained liquid in the macromolecule network.Hydrogel is a kind of can swell in water significantly and keep large quantity of moisture but be not dissolved in the hydrophilic polymer of water between liquid and solid, a kind of hydrophilic network of water-soluble or hydrophilic high mol can be regarded as, the several times of the weight of polymer own and even hundreds of times water can be held.Along with the develop rapidly of field science and technology such as information, life, environment, the intelligent aqueous gel capable of a collection of excellent performance is come out one after another.These progress in Intelligent Hydrogel comprise temperature-sensitive hydrogel, pH sensitive aqueous gel and sensitivity of light hydrogel etc., and the most extensive with the research of temperature and pH sensitive aqueous gel.
Wherein, temperature-sensitive hydrogel is that hydrophilic-hydrophobic balance by cross-linked network is subjected to temperature variation and changes to cause.Particularly, the swelling process of hydrogel is the process that water molecules hydrophilic radical on gel internal divergence and gel side chain forms hydrogen bond, and temperature raises, and hydrogen bond is destroyed, and a large amount of combination water spin off from macromolecular scaffold, and the hydrogel volume descends.Otherwise temperature reduces, and hydrogen bond action power strengthens, and water and polymer are in conjunction with tight, and the hydrogel volume increases; The pH sensitive aqueous gel is to be subjected to the pH value change to take place protonated or to be dissociated into ion and to cause by the group that has in the hydrogel macromolecular network (as carboxyl), the group of macromolecular network can be changed by environment pH value and captures or discharge proton, make its network structure and electric density cause the osmotic pressure of gel network to change, finally cause the variation of hydrogel volume with the pH value variation of medium.
But in some field,, it is found that these intelligent hydrogels because volume causes the drug release poor effect more greatly as aspect the hydrogel medicine sustained release.People such as Tanaka in 1978 find that swelling behavior or contraction reach the required time of balance and be directly proportional with the linear dimension of hydrogel, and promptly the hydrogel size is more little, and it is just short more to reach the needed time of balance.Thereby if the size of hydrogel is contracted to nano level, then will improve its sensitive property greatly, so people again with microgel as one of focus of research.
Microgel is the polymer particles of a kind of 5nm-5 μ m or the gel of microballoon, its character and gel-like seemingly, can be in water or organic solvent abundant swelling and not dissolving, and present solubility on the macroscopic view.Compare with the bulk hydrogel, microgel has characteristics such as size is little, specific surface area is big, response speed is fast, encapsulation rate is high, good stability, injectable, thereby has a good application prospect at aspects such as medicine, biological substance, chemical separation, coating and dyestuff, oil productions.
Since people's reported first such as Canadian Pelton in 1986 intelligence microgel, the Study of Sensitivity of intelligent microgel never stopped, and had formed many patents and reported in literature, now was summarized as follows:
(1) non intelligent type microgel: with Chinese patent No.1125086C and No.1132849C is representative, two patents all adopt improved positive microemulsion polymerization method, add ionic emulsifying agent and assistant for emulsifying agent (as Sodium dodecylbenzene sulfonate and amylalcohol etc.), prepare the methacrylic microgel through redispersion in centrifugation, drying, the organic solvent, though prepared particle is less than 100nm, but, can not directly apply to medicament slow release because the emulsifying agent and the oil-based solvent that adopt are toxic substance.In addition, this complex process, its product does not have intelligent characteristics such as temperature or pH value.
(2) temperature sensitivity microgel:
A) be representative with Chinese patent No.1212342C, No.1275999C, U.S. Patent No. 2004156906.It is main body that three patents all adopt polyvalent alcohol, with Ammonium Persulfate 98.5 and Tetramethyl Ethylene Diamine is initiator, with Span (sapn) and Tween (tween) is emulsifying agent, by suspending or the inverse suspension polymerization technology, obtain temperature sensitive property or have the microgel of degradability in the presence of organic solvents such as toluene, products therefrom after filtration, acetone precipitation, washing obtain the colloidal particle of 5nm～5mm after anti-phase.Though prepared particle has temperature sensitive property, colloid size is bigger.These three patents have all adopted and have had toxic emulsifying agent and organic solvent in addition, and the gained microgel still need just can be applied in the drug release after anti-phase through washing.
B) people such as Tang Xiaozhen is at document Polymer International, 2005,54:83 and Materials Letters, 2004,58, open report on 3400, adopt emulsifier-free emulsion polymerization method (not adding any emulsifying agent), make poly-(isopropyl methyl acrylate-co-isopropylacrylic acid ester) and poly-(vinyl methacrylic ester-co-isopropylacrylic acid ester) microgel of temperature sensitive property respectively at aqueous phase, but owing to there is not sufficiently high electric charge to come the small-particle of stable high concentrations, even make the gained colloid diameter under hydrophobic monomer high-content and high temperature (T＞30 ℃) still more than 200nm because this particle is still greater than 100nm, its effect is not good.
(3) pH sensibility microgel:
Chen Ming waits the people at Southern Yangtze University's journal (natural science edition) clearly, 2004,3, open report on 83 adds linking agent methylene-bisacrylamide and vinylformic acid in ethanol, 60 ℃ were reacted 24 hours down, prepared methacrylic acid list end-blocking polyoxyethylene glycol grafted polyacrylic acid microgel with pH sensitive property by the dispersion copolymerization method, the particle size analysis that records under the different pH after the polymerization is 300～1200nm, and skewness one, does not have using value.
Above patent or document all relate to microgel of single sensitive property and preparation method thereof, products therefrom or have temperature sensitive property, or has pH susceptibility, but in this complex environment of human body fluid, microgel can be subjected to multiple stimulation effects such as temperature and pH simultaneously, as when human body fever body temperature surpasses 37 ℃, the slowly-releasing of medicine also is subjected to the stimulation of temperature variation except the pH that is subjected to stomach (pH=2.4) intestines (pH=7.4) stimulates.Therefore, prepare microgel and become one of focus of present research with temperature and the dual susceptibility of pH value.
(4) the dual susceptibility intelligence of temperature and pH value microgel:
With international monopoly WO03063909 is representative; With people such as Canadian Pelton at document Macromolecules, 2004,37,2544, people such as the Lyon of the U.S. are at document Macromolecules, 2000,33,8301, people such as the Vincent of Britain are at document Colloidand Polymer Science, 2000, openly be reported to representative on the 278:74.Though the microgel that above-mentioned patent and document are reported has temperature and the dual susceptibility of pH, but prepared colloid diameter under transformation temperature much larger than 200nm, and the hydrophilic acid of adopting the pH sensitivity (as vinylformic acid, vinylacetic acid etc.) in the structure monomer more, because the existence of these acid, make the enhancing of this microgel and water molecules hydrogen bond effect, its particle diameter increases with the increase of acid content, even makes micelle increase to micron order.If make particle diameter reach nano level, then need use emulsifying agent, in aftertreatment, must remove emulsifying agent again, finally increased total cost and time; If do not add emulsifying agent, then particle size analysis is big, uses limited in fields such as medicament slow release and chemical separation.
Summary of the invention
The objective of the invention is under no any emulsifying agent situation, to provide the preparation method of a kind of temperature and the dual valve sensitive nano microgel of pH value, to solve the problems referred to above that prior art exists.With the prepared microgel of preparation method of the present invention, should have the characteristic except that what have a common microgel, it also has temperature and the dual sensitive property of pH value simultaneously, its microgel transparency height, micelle is little, specific surface area is big, stability is high, adsorptivity is strong, can be widely used in the temperature in fields such as pharmaceutical carrier, chemical separation, optoelectronic switch, rubber, coating, artificial muscle and biosensor and the preparation method of pH value valve sensitive nano microgel.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of a kind of temperature and pH value valve sensitive nano microgel, under the condition of no any emulsifying agent, adopt specific dropping technology and emulsifier-free emulsion polymerization method, earlier temperature sensitivity monomer M, pH value sensitive monomer N, linking agent O and water solvent are made into reactant aqueous solution in proportion, again it dropwise is added dropwise in the initiator solution of having prepared at regular time and quantity, makes temperature and pH value valve sensitive nano microgel after purified by the product of gained after the random copolymerization; Preparation method of the present invention controls the scope of required particle size analysis by changing monomer component ratio or drop rate; Preparation method of the present invention is by changing monomeric functional classification and component thereof, preparing the microgel of the satisfied different application field needs that do not have intelligence, unicity or multiple susceptibility; The method for preparing microgel of the present invention specifically may further comprise the steps:
1) adopting the compound of the amide group that contains easy and water molecules formation hydrogen bond is the temperature sensitivity monomer M; Contain in pH solution legibility from or the compound of protonated carboxylic group be pH sensitive monomer N; And the compound that contains acryloyl group is chemical cross-linking agent O, with above-mentioned three's consumption is 50～90: 40～5: 10～5 in molar ratio, and put in the water solvent simultaneously, be made into the reactant aqueous solution of homogeneous transparent after the stirring, water solvent weight is M, N and O three's gross weight 15～50 times, its processing condition: stirring velocity is 100～400 rev/mins, and the time is 15～40 minutes;
2) initiator is added in the above-mentioned solvent, initiator amount is 3～10% of three total monomer weights, at room temperature be made into weight percent concentration and be 0.2～0.5% initiator solution, earlier with weak acid furnishing pH=3 ± 0.5, feed nitrogen again, stirring velocity is 100～400 rev/mins, is warming up to 60～80 ℃ gradually, and starting time is stand-by after 15～40 minutes;
3) do not using under any emulsifying agent and the logical condition of nitrogen gas, adopt specific dropping technology, the transparent reactant aqueous solution that is about to step 1 preparation dropwise drips at regular time and quantity in the initiator solution of step 2 preparation, after the emulsifier-free emulsion polymerization method, make milky temperature and pH value valve sensitive nano microgel dispersion liquid, its processing condition: rate of addition is 10～80 seconds/, dropping temperature is 60～80 ℃, and the dropping time is 1～3 hour;
4) dropwise after, continue reaction 1～3 hour by above-mentioned processing condition and finish until reaction, then at room temperature, non-shock chilling 6～12 hours, products therefrom are transparent or semitransparent microgel dispersion; Owing to decrease of temperature, be lower than the transformation temperature of polymkeric substance, gained microgel dispersion color is changed into transparent or semitransparent by oyster white.
5) above-mentioned transparent or semitransparent microgel dispersion is removed unreacted monomer, linking agent or small molecules by purifying process and obtain particle diameter uniform temperature and pH value valve sensitive nano microgel dispersion liquid, the gained microgel dispersion is to deposit under 4 ℃ not have any precipitation generation half a year in temperature, and its particle size analysis scope is 40～300nm.
Described purifying process is specially microgel dispersion by repeating 3～6 times high speed centrifugation, the technology of ultra-sonic dispersion, or by in the dialysis tubing technology in 1～3 week of dialysis any one.
The gained microgel dispersion can be obtained solid-state microgel micelle behind high speed centrifugation, after lyophilize, can obtain pressed powder again, but the following prolonged preservation of low temperature can obtain microgel dispersion with this pressed powder after with the deionized water dissolving ultra-sonic dispersion again.
The gained microgel dispersion is that 25 ℃～50 ℃ and pH value are to test its particle diameter at 40～300nm by dynamic light scattering under 3.0～11.0 the condition in temperature.
The preparation method's of described microgel temperature sensitive monomer M is any one in acrylamide, N-isopropylacrylamide, tertiary butyl acrylamide, vinyl acrylamide or the vinyl pyrrolidone.
Because contain amide group in the monomer whose structure, when being lower than the phase transition temperature of microgel, amide group on the macromolecular scaffold and bound water molecule easily form hydrogen bond, microgel molecular chain full extension, the ydrodynamics diameter reduces with temperature and increases; When being higher than the phase transition temperature of microgel, this temperature is higher than the bond energy of hydrogen bond, and hydrogen bond is destroyed, and a large amount of combination water spin off from macromolecular scaffold, and molecular chain shrinks, and the ydrodynamics diameter raises with temperature and descends; But when temperature during far above the phase transition temperature of microgel because the molecular chain that takes place to curl has been retracted to the limit, this moment particle diameter with the temperature increase almost remain unchanged (± 3nm).
The preparation method's of described microgel pH value sensitive monomer N is any one in vinylformic acid, 4-pentenoic acid, methacrylic acid, diethylaminoethyl methacrylate, tert-butyl acrylate or the vinylacetic acid.
Owing to contain groups such as carboxyl among the monomer N, in pH＞7 o'clock, with the rising of pH value, (COOH) ion turns to strongly hydrophilic (COO to carboxyl
-), electric density increases, and the osmotic pressure of gel network increases thereupon, the polymer molecule chain-unfolding, particle diameter increases; In pH＜7 o'clock, the carboxyl proton turns to-COOH, and electric density descends, and the osmotic pressure of gel network decreases, and polymer molecular chain curls, and particle diameter descends.
The preparation method's of described microgel linking agent monomer O be in methylene-bisacrylamide or the two methacryloxypropyl phenyl-propane any one, methylene-bisacrylamide most preferably wherein.
It is solvent that the preparation method's of described microgel microgel adopts water, be specially in ultrapure water or the deionized water behind 0.22 micron filter membrane filtration any one, its consumption is temperature sensitive monomer M, pH value sensitive monomer N and three total monomer weights of linking agent O 15～50 times.
The preparation method's of described microgel initiator is to be selected from redox initiation system or the thermal initiation system two class initiator systems any one, wherein, the initiator of redox system is specially in Potassium Persulphate, Ammonium Persulfate 98.5, hydrogen peroxide, sodium pyrosulfate, ferrous salt or the Tetramethyl Ethylene Diamine any one, wherein Ammonium Persulfate 98.5 most preferably; The initiator of thermal initiation system is specially in Diisopropyl azodicarboxylate or the benzoyl peroxide any one.
The product of gained makes temperature and pH value valve sensitive nano microgel after purified after the preparation method's of described microgel the copolymerization, and the structural formula of this microgel is:
In the formula
The chemically crosslinked of expression arbitrary form, M-O-N represents the segment of polymkeric substance, Z represents the polymerization degree, is specially 10～500.
Described specific dropping technology is a kind ofly dropwise to be dripped at regular time and quantity in initiator solution by reactant aqueous solution, be a kind of dropping method of utilizing initiator to be in hungry attitude, this method is different from traditional discontinuous method---the aqueous solution of initiator is directly joined in the reactant aqueous solution.
Compare with other traditional microgel and preparation method thereof, the present invention has following advantage:
1, include two kinds of functional response monomers in the microgel structure monomer of the present invention, thereby the prepared microgel of the present invention has temperature and the dual sensitive property of pH value simultaneously to temperature and pH sensitivity.
2, owing to adopt a kind of utilization to be in the dropping method and the emulsifier-free emulsion polymerization technology of hungry attitude among the preparation method of the present invention, therefore, though the present invention does not use any emulsifying agent, but still the particle diameter of made microgel micelle is reached to nano level, then make and economize the operation that removes emulsifying agent in the overall process, saved total cost and time.
3, microgel dispersion stability of the present invention is high, deposits under 4 ℃ and does not have any precipitation generation half a year.
4, preparation method of the present invention controls the size of required microgel particle size analysis by changing monomer component ratio or drop rate.Made microgel can be widely used in fields such as pharmaceutical carrier, chemical separation, optoelectronic switch, rubber, coating and biosensor.
5, it is applied widely for preparation method of the present invention, adopt the specific dropping technology and the emulsifier-free emulsion polymerization method of present method, can be according to the demand of different field to its microgel, by changing the functional classification and the component thereof of monomer whose, can be used for preparation to the microgel of the different functionalities that do not have intelligence, unicity or multiple susceptibility.
6, preparation method's technology of the present invention simple, be produced on a large scale.
Embodiment
Embodiment 1
1.5g N-isopropylacrylamide, 0.05g vinylformic acid, 0.1g methylene-bisacrylamide put into simultaneously be dissolved in the 50g deionized water, be made into the reactant aqueous solution of homogeneous transparent after the stirring, its processing condition: stirring velocity is 300 rev/mins, and the time is 30 minutes.
The Ammonium Persulfate 98.5 initiator of 0.1g is added in the 50g deionized water, at room temperature be made into weight percent concentration and be 0.2% initiator solution, earlier with acetic acid furnishing pH=3 ± 0.5, feed nitrogen again, stirring velocity is 200 rev/mins, is warming up to 75 ℃ gradually, and balance is stand-by after 30 minutes.
Under logical condition of nitrogen gas, the 51.65g reactant aqueous solution of preparation is dripped in aforementioned initiator solution, reaction beginning after 10 minutes system by transparent become light blue, make milky nano level microgel dispersion at last, its processing condition: rate of addition is 20 seconds/, dropping temperature is 75 ℃, and the dropping time is 1 hour.
After dropwising, continue to react 3 hours until the reaction end by above-mentioned processing condition, then at room temperature, non-shock chilling 12 hours, products therefrom are nattier blue microgel dispersion.
Above-mentioned gained microgel dispersion is passed through to repeat 3 times high speed centrifugation, the purifying process of ultrasonic redispersion, remove unreacted monomer, linking agent or small molecules, obtain the uniform microgel dispersion of particle diameter, this microgel dispersion is deposited in 4 ℃ refrigerator did not have any variation in 180 days.
In temperature is that 25 ℃～50 ℃ and pH value are under 3.0～11.0 the condition, adopt dynamic laser light scattering measurement instrument to test its size, gained microgel dispersion particle diameter descends with the temperature increase in the 150-250nm scope after testing, increases with the pH value.
Embodiment 2
1.4g N-isopropylacrylamide, 0.4g vinylformic acid, 0.1g methylene-bisacrylamide put into simultaneously be dissolved in the 50g deionized water, be made into the reactant aqueous solution of homogeneous transparent after the stirring, its processing condition: stirring velocity is 300 rev/mins, and the time is 30 minutes.
The Potassium Persulphate initiator of 0.1g is added in the 50g deionized water, at room temperature be made into weight percent concentration and be 0.2% initiator solution, with acetic acid furnishing pH=3 ± 0.5, feed N more earlier
2, stirring velocity is 200 rev/mins, is warming up to 70 ℃ gradually, balance is stand-by after 30 minutes.
Under logical condition of nitrogen gas, the 51.9g reactant aqueous solution of preparation is dripped in aforementioned initiator solution, reaction beginning after 10 minutes system by transparent become light blue, make milky nano level microgel dispersion at last, its processing condition: rate of addition is 60 seconds/, dropping temperature is 70 ℃, and the dropping time is 3 hours.
After dropwising, continue to react 1 hour until the reaction end by above-mentioned processing condition, then at room temperature, non-shock chilling 10 hours, products therefrom are the microgel dispersion of transparence.Pour the microgel dispersion of above-mentioned gained microgel dispersion after in the dialysis tubing (Spectra/Por7 dialysis membrane with polymerization, MWCO 10000, VWR), dialysis tubing is put into beaker 2 weeks of dialysis that fill ultrapure water, removes unreacted monomer, linking agent or small molecules.
In temperature is that 25 ℃～50 ℃ and pH value are under 3.0～11.0 the condition, adopt dynamic laser light scattering measurement instrument to test its size, gained microgel dispersion particle diameter descends with the temperature increase in the 40-100nm scope after testing, increases with the pH value.
Embodiment 3
1.4g vinyl acrylamide, 0.2g vinylformic acid, 0.1g methylene-bisacrylamide put into simultaneously be dissolved in the 50g deionized water, be made into the reactant aqueous solution of homogeneous transparent after the stirring, its processing condition: stirring velocity is 300 rev/mins, and the time is 40 minutes.
The Ammonium Persulfate 98.5 initiator of 0.1g is added in the 50g deionized water, at room temperature be made into weight percent concentration and be 0.2% initiator solution, with acetic acid furnishing pH=3 ± 0.5, feed N more earlier
2, stirring velocity is 200 rev/mins, is warming up to 75 ℃ gradually, balance is stand-by after 30 minutes.
Under logical condition of nitrogen gas, the 51.7g reactant aqueous solution of preparation is dripped in aforementioned initiator solution, reaction beginning after 10 minutes system by transparent become light blue, make milky nano level microgel dispersion at last, its processing condition: rate of addition is 40 seconds/, dropping temperature is 75 ℃, and the dropping time is 2 hours.
After dropwising, continue to react 2 hours until the reaction end by above-mentioned processing condition, then at room temperature, non-shock chilling 12 hours, products therefrom are transparent microgel dispersion.
The microgel dispersion of above-mentioned gained microgel dispersion after with polymerization poured in the dialysis tubing, and dialysis tubing is put into beaker 3 weeks of dialysis that fill ultrapure water, obtains the uniform microgel of particle diameter.
In temperature is that 25 ℃～50 ℃ and pH value are under 3.0～11.0 the condition, adopt dynamic laser light scattering measurement instrument to test its size, gained microgel dispersion particle diameter descends with the temperature increase in the 40-110nm scope after testing, increases with the pH value.
Claims (8)
1, the preparation method of a kind of temperature and pH value valve sensitive nano microgel, it is characterized in that: under the condition of no any emulsifying agent, adopt specific dropping technology and emulsifier-free emulsion polymerization method, earlier with the temperature sensitivity monomer M, pH value sensitive monomer N, linking agent O and water solvent are made into reactant aqueous solution in proportion, dropwise be added dropwise to it in initiator solution of having prepared at regular time and quantity again, make temperature and pH value valve sensitive nano microgel by the product of gained after the random copolymerization after purified, this preparation method is by changing the monomer functional classification, monomer component ratio or drop rate are controlled the scope of required particle size analysis, specifically may further comprise the steps:
1) adopting the compound of the amide group that contains easy and water molecules formation hydrogen bond is the temperature sensitivity monomer M; Contain in pH solution legibility from or the compound of protonated carboxylic group be pH sensitive monomer N; And the compound that contains acryloyl group is chemical cross-linking agent O, with above-mentioned three's consumption is 50～90: 40～5: 10～5 in molar ratio, and put in the water solvent simultaneously, be made into the reactant aqueous solution of homogeneous transparent after the stirring, water solvent weight is M, N and O three's gross weight 15～50 times, its processing condition: stirring velocity is 100～400 rev/mins, and the time is 15～40 minutes;
2) initiator is added in the above-mentioned solvent, initiator amount is 3～10% of three total monomer weights, at room temperature be made into weight percent concentration and be 0.2～0.5% initiator solution, earlier with weak acid furnishing pH=3 ± 0.5, feed nitrogen again, stirring velocity is 100～400 rev/mins, is warming up to 60～80 ℃ gradually, and starting time is stand-by after 15～40 minutes;
3) do not using under any emulsifying agent and the logical condition of nitrogen gas, adopt specific dropping technology, the transparent reactant aqueous solution that is about to step 1 preparation dropwise drips at regular time and quantity in the initiator solution of step 2 preparation, after the emulsifier-free emulsion polymerization method, make milky temperature and pH value valve sensitive nano microgel dispersion liquid, its processing condition: rate of addition is 10～80 seconds/, dropping temperature is 60～80 ℃, and the dropping time is 1～3 hour;
4) dropwise after, continue reaction 1～3 hour by above-mentioned processing condition and finish until reaction, then at room temperature, non-shock chilling 6～12 hours, products therefrom are transparent or semitransparent microgel dispersion;
5) above-mentioned transparent or semitransparent microgel dispersion is removed unreacted monomer, linking agent or small molecules by purifying process and obtain particle diameter uniform temperature and pH value valve sensitive nano microgel dispersion liquid, its microgel dispersion is to deposit under 4 ℃ not have any precipitation generation half a year in temperature, and its particle size analysis scope is 40～300nm.
2, the preparation method of microgel according to claim 1 is characterized in that described temperature sensitive monomer M is any one in acrylamide, N-isopropylacrylamide, tertiary butyl acrylamide, vinyl acrylamide or the vinyl pyrrolidone.
3, the preparation method of microgel according to claim 1 is characterized in that described pH value sensitive monomer N is any one in vinylformic acid, 4-pentenoic acid, methacrylic acid, diethylaminoethyl methacrylate, tert-butyl acrylate or the vinylacetic acid.
4, the preparation method of microgel according to claim 1, it is characterized in that described linking agent monomer O be in methylene-bisacrylamide or the two methacryloxypropyl phenyl-propane any one.
5, the preparation method of microgel according to claim 1, it is characterized in that it is solvent that described microgel adopts water, be specially in ultrapure water or the deionized water behind 0.22 micron filter membrane filtration any one, its consumption is temperature sensitive monomer M, pH value sensitive monomer N and three total monomer weights of linking agent O 15～50 times.
6, the preparation method of microgel according to claim 1, it is characterized in that described initiator is to be selected from redox initiation system or the thermal initiation system two class initiator systems any one, wherein, the initiator of redox system is specially in Potassium Persulphate, Ammonium Persulfate 98.5, hydrogen peroxide, sodium pyrosulfate, ferrous salt or the Tetramethyl Ethylene Diamine any one; The initiator of thermal initiation system is specially in Diisopropyl azodicarboxylate or the benzoyl peroxide any one.
7, the preparation method of microgel according to claim 1, it is characterized in that described purifying process is by repeating 3～6 times high speed centrifugation, the technology of ultra-sonic dispersion, or by in the dialysis tubing technology in 1～3 week of dialysis any one with microgel dispersion.
8, the preparation method of microgel according to claim 1 is characterized in that described specific dropping technology is a kind ofly dropwise to be dripped in initiator solution promptly a kind of dropping method of utilizing initiator to be in hungry attitude at regular time and quantity by reactant aqueous solution.
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