CN104371066A - PH and temperature double-sensitive intelligent nanogel and preparation method thereof - Google Patents
PH and temperature double-sensitive intelligent nanogel and preparation method thereof Download PDFInfo
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Abstract
The invention provides a pH and temperature double-sensitive intelligent nanogel and a preparation method thereof. The method comprises the following steps: adding ltaconic acid into sodium hydroxide solution to obtain partially neutralized ltaconic acid water solution; adding acrylamide, N-isopropyl acrylamide and a crosslinking agent into the partially neutralized ltaconic acid water solution, and stirring to obtain a transparent single mixture solution; adding the transparent single mixture solution into a mixed solvent containing oil-soluble solvent and Span80/Tween 80 composite surfactant, stirring, heating to 40-60DEG C, and adding an oxidant and a reducing agent, to obtain intelligent transparent or semitransparent nanogel reversed-phase microemulsion; demulsifying and precipitating the intelligent transparent or semitransparent nanogel reversed-phase microemulsion with ethanol, washing, drying and grinding to the pH and temperature double-sensitive intelligent nanogel. The invention further provides the pH and temperature double-sensitive intelligent nanogel prepared by adopting the preparation method. The pH and temperature double-sensitive intelligent nanogel has good pH and temperature double sensitivity.
Description
Technical field
The present invention relates to a kind of intelligent nano-gel and preparation method thereof, particularly a kind of pH and temperature dual susceptibility intelligent nano-gel and preparation method thereof, belong to nano material and preparing technical field.
Background technology
Intelligent nano-gel (Intelligent nanogel) is that particle diameter is at 1-1000nm, the hydrogel particle of external stimulus generation phase in version can be responded, the stimulating responsive nanogel that is therefore otherwise known as (Stimulus responsive nanogel).External stimulus generally includes the change of small envrionment temperature, dispersion medium pH and ionic strength, Yi Jiguang, magnetic field, specific chemical substance or biological substance etc.In the process that phase in version occurs, all can there is corresponding change in the physical and chemical performance such as permeability, hydrophilicity hydrophobicity of the volume of intelligent nano hydrogel, water content, refractive index, colloidal stability, soft durometer, inner gel network.In addition, intelligent nano hydrogel also has following features:
1, can be dispersed in water medium, form stable colloidal dispersion;
2, inside has crosslinking structure, and stability is higher than the stability of other polymer nano-particle (as polymer micelle etc.);
3, specific surface area is large, and the functional group on surface coupling can have the component of specific function;
4, water content is high, is similar to biological tissue, has good biocompatibility;
5, the same with other nanoparticle, easily cross biological barrier;
6, because intelligent aqueous gel capable stimulates the speed of generation response and its size to be inversely proportional to external world, thus intelligent nano hydrogel stimulates the speed of generation response quickly to external world.
Nearly ten years along with the development of nanosecond science and technology, biomedicine and intelligent material, intelligent nano-gel drug conveying and controllable release, medical diagnosis, biosensor, biomaterial, support of the catalyst, adsorb be separated, the field such as water treatment and oil-gas field development shows tempting application prospect, is therefore subject to both domestic and external showing great attention to.
Can start to receive publicity to dual even triple intelligent gel producing response that stimulates in recent years, wherein, the maximum of research are pH/ temperature dual stimulating responsive hydrogels, this is because temperature and pH are two kinds of envrionment conditionss very important in biological and chemical system.
The polymeric constituent with different stimulated responsiveness is incorporated in the polymer network of hydrogel by methods such as random copolymerization method, grafting copolymerization process and nucleocapsid structure methods by the preparation method that current pH/ temperature dual susceptibility intelligent gel adopts, polymerization implementation method mostly is emulsifier-free emulsion polymerization, letex polymerization, solution polymerization, precipitation polymerization and photopolymerization, research emphasis concentrates on pH and temperature response performance, rheological property and the intelligent gel structure etc. of intelligent gel, is applied to drug conveying and controllable release, medical diagnosis, biosensor, support of the catalyst etc.
Wherein, Serrano-Medina adopts emulsifier-free emulsion polymerization to prepare pH and temperature dual susceptibility, has the micro-/ nano gel of nucleocapsid structure, by being incorporated in Thermo-sensitive poly N-isopropyl acrylamide (PNIPAm) by pH sensitive groups-2-methacryloxy phenylformic acid, form the gel of pH and temperature dual susceptibility.
Polyacrylic acid-grafting-poly N-isopropyl acrylamide hydrogel that Durand adopts two-step approach to prepare shows interesting thermic thickening behavior.
Zhao Changwen adopts the L-glutamic acid of degradable, pH susceptibility and poly-(NIPA-HEMA) of Thermo-sensitive, prepared degradable doubling sensitivity hydrogel by photopolymerization, its pH and temperature sensitivity better.
Ju Hee Kyung and Zhang Gaoqi adopts solution polymerization to prepare the doubling sensitivity be made up of crosslinked poly N-isopropyl acrylamide (PNIPAm) and linear sodium alginate (SA), the hydrogel with half interpenetrating network structure respectively, and this gel demonstrates good physical strength and good pH/ temperature-responsive.
Zhang Jing adopts photopolymerization to prepare the intelligent gel with inierpeneirating network structure formed by polyacrylic acid and NIPA, and the rate of permeation of this gel-film by the adjustment of pH and temperature, noticeable change can occur.
Looking into Liu Sheng etc. adopts precipitation polymerization to prepare the pH/ temperature dual stimulating responsive hollow Nano hydrogel with interpenetrating polymer networks (IPN) structure, find to hollow Nano hydrogel drug loading, and the speed changing environmental pH energy Drug controlled release to be passed through by adjusting ambient temperature.
Prepare compared with nanogel method with above-mentioned, microemulsion is thermodynamically stable transparent or semitransparent colloidal dispersion system, and its dispersion size is nano level, and particle diameter is little, the nanogel of narrow diameter distribution therefore to adopt micro-emulsion polymerization to prepare.
Wherein, Bouillt etc. adopt acrylamide and vinylformic acid to be monomer, synthesized by conversed phase micro emulsion copolymerization method there is pH stimulating responsive, nano-hydrogel that two classes have different chemical structures: a class is the polyacrylic acid-acrylamide copolymer nano-hydrogel formed by two kinds of monomers and linking agent copolymerization, and another kind of is be polymerized by two kinds of monomers the nano-hydrogel with interpenetrating polymer networks (IPN) structure that two kinds of homopolymer obtaining are formed by hydrogen bond action respectively.
Deen etc. make N-acryl-N methyl piperazine and methyl methacrylate copolymer obtain the nano-hydrogel with pH stimulating responsive in Reverse Microemulsion System; find that nano-hydrogel occurs swelling in acidic aqueous solution, and produce contraction in basic solution.
Hou Wei etc. adopt conversed phase micro emulsion copolymerization to prepare poly-2-hydroxy ethyl methacrylate-Sipacril 2739OF hydrogel, have studied its rheological property, find that the Young's modulus impact on gel of hydrogel composition, hydrogel concentration, pH value is larger.
Fernandez etc. adopt conversed phase micro emulsion copolymerization to prepare the poly N-isopropyl acrylamide with temperature sensitivity (PNIPAm), find its swelling rate and go swelling rate all very fast, Young's modulus and Young's modulus are all higher than the hydrogel adopting usual way to prepare.
But the nanogel adopting conversed phase micro emulsion copolymerization to prepare both at home and abroad is at present pH susceptibility or temperature sensitivity nanogel, conversed phase micro emulsion copolymerization legal system is adopted still not have relevant report for pH/ temperature dual stimulating responsive intelligent nano-gel.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide the preparation method of a kind of pH and temperature dual susceptibility intelligent nano-gel, NIPA is adopted to be temperature sensitive monomer in this preparation method, methylene-succinic acid is pH sensitive monomer, acrylamide is Hydrophilic nonionic monomer, adopt conversed phase micro emulsion copolymerization legal system for pH and temperature dual susceptibility intelligent nano-gel, the pH responsiveness of intelligent nano-gel is improved by methylene-succinic acid molecule 2 carboxyls, the characteristic that the speed utilizing intelligent gel to stimulate generation to respond to external world and its size are inversely proportional to, the particle diameter of intelligent nano-gel is regulated and controled by regulation and control conversed phase micro emulsion copolymerization reaction parameter, thus regulation and control intelligent nano hydrogel stimulates the speed producing response to external world.The method specifically comprises the following steps:
Step one: methylene-succinic acid slowly being joined concentration in ice bath is in the sodium hydroxide solution of 10wt%, stirs 0.5-2h, obtains the methylene-succinic acid aqueous solution of part neutralization;
Wherein, the mol ratio of described methylene-succinic acid and sodium hydroxide is 1:0.8-1.4;
Step 2: acrylamide, NIPA and linking agent are joined in the methylene-succinic acid aqueous solution of part neutralization, stir 20-40min, obtain transparent monomers mixing solutions;
Wherein, the mass ratio of described methylene-succinic acid and described acrylamide is 4:6-6:4, the mass ratio of described methylene-succinic acid and described NIPA is 3:7-7:3, and the consumption of described linking agent is the 0.1-0.6% of the total mass of methylene-succinic acid, acrylamide and NIPA;
Step 3: transparent monomers mixing solutions is joined in the mixed solvent containing oil-dissolving solvent and Span80/Tween80 complexed surfactant, stir 20-40min, form transparent reverse micro emulsion, then 40-60 DEG C is warming up to gradually, add Oxidizing and Reducing Agents, reaction 3-5 hour, obtains transparent or semitransparent intelligent nano-gel reverse micro emulsion;
Wherein, the mass ratio of Span80 and Tween80 is 3-6:2-4, and the consumption of oxygenant is the 0.4-1.8% of the total mass of methylene-succinic acid, acrylamide and NIPA, and the mol ratio of Oxidizing and Reducing Agents is 1-2:1;
Step 4: by described intelligent nano-gel reverse micro emulsion ethanol breakdown of emulsion precipitation, washing with acetone precipitation 3-5 time, 60 DEG C of freeze-day with constant temperature 10h, obtain white intelligent nano-gel powder by after product drying, porphyrize, this white intelligent nano-gel powder is pH and temperature dual susceptibility intelligent nano-gel.
In the preparation method of pH provided by the invention and temperature dual susceptibility intelligent nano-gel, preferably, the oil-dissolving solvent of employing is selected from hexanaphthene, whiteruss, white oil and sherwood oil.
In the preparation method of pH provided by the invention and temperature dual susceptibility intelligent nano-gel, preferably, when adding 10mL-20mL sodium hydroxide solution in step one, in step 3, transparent monomers mixing solutions is joined in the mixed solvent of the Span80/Tween80 complexed surfactant of oil-dissolving solvent containing 100g and 8-16g.
In the preparation method of pH provided by the invention and temperature dual susceptibility intelligent nano-gel, preferably, the linking agent adopted is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, diethylene glycol double methacrylate, tirethylene glycol double methacrylate and polyethyleneglycol diacrylate.
In the preparation method of pH provided by the invention and temperature dual susceptibility intelligent nano-gel, preferably, the oxygenant of employing is selected from ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
In the preparation method of pH provided by the invention and temperature dual susceptibility intelligent nano-gel, preferably, the reductive agent of employing is selected from sodium bisulfite, S-WAT, Sulfothiorine and formaldehyde and closes Sodium Thiosulfate.
In the preparation method of pH provided by the invention and temperature dual susceptibility intelligent nano-gel, preferably, the median size of intelligent nano-gel reverse micro emulsion is 40-80nm.
Present invention also offers a kind of pH and temperature dual susceptibility intelligent nano-gel, it is that the preparation method of above-mentioned pH and temperature dual susceptibility intelligent nano-gel prepares.
In pH of the present invention and temperature dual susceptibility intelligent nano-gel, preferably, the gel-strength of this pH and temperature dual susceptibility intelligent nano-gel is 5-15Pas.
In pH of the present invention and temperature dual susceptibility intelligent nano-gel, preferably, the equilibrium water absorption of this pH and temperature dual susceptibility intelligent nano-gel is 80-500g/g, and being that the balance salt absorbing rate of the NaCl solution of 5wt% is 25-35g/g to concentration, is the CaCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 10-20g/g, is the MgCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 15-25g/g.
In order to the performance of pH of the present invention and temperature dual susceptibility intelligent nano-gel is better described, carried out water-intake rate mensuration according to following testing method to gel of the present invention, salt absorbing rate measures, gel-strength mensuration, pH responsiveness measure, temperature-responsive measures and particle size determination, concrete measuring method is as follows:
Water-intake rate measures:
The drying of precise a certain amount of (0.5g), the intelligent nano-gel of the present invention of porphyrize, put into beaker (500mL), add distilled water (500mL), fully absorb water at ambient temperature, until intelligent nano-gel water suction of the present invention is saturated, with the water that Bag filter does not adsorb, to substantially anhydrous drippage.Measure the weight of the rear intelligent nano-gel of fully water suction, calculate water-intake rate according to formula (1).
Water-intake rate=(m
2-m
1)/m
1× 100% (1)
Wherein, m
1for the quality of the front intelligent nano-gel that absorbs water, unit is g, m
2for the quality of intelligent nano-gel after absorbing water, unit is g.
Salt absorbing rate measures:
Accurately take the drying of a certain amount of (0.5g), the intelligent nano-gel of the present invention of porphyrize, put into beaker (100mL), then add NaCl, MgCl that concentration is 5% respectively
2and CaCl
2solution (100mL), fully inhales salt solution at ambient temperature, until intelligent nano-gel of the present invention inhales salt water saturation, the salt solution do not adsorbed with Bag filter, to basic salt-free water drippage.After mensuration abundant suction salt solution, the weight of intelligent nano-gel, calculates salt absorbing rate according to formula (2).
Salt absorbing rate=(m
2-m
1)/m
1× 100% (2)
Wherein, m
1for the quality of intelligent nano-gel before suction salt solution, unit is g, m
2for the quality of intelligent nano-gel after suction salt solution, unit is g
The mensuration of gel-strength:
Accurately take a certain amount of drying of (0.2g), the intelligent nano-gel of porphyrize, put into beaker (200mL), then distilled water (200mL) is added, fully absorb water at ambient temperature, reach after water suction balance until gelinite, the water falling not adsorb with Bag filter, to anhydrous drippage, then adopt the apparent viscosity of rotary viscosity design determining water absorbent gel body, be the gel-strength of intelligent nano-gel water absorbent gel body of the present invention.
PH responsiveness measures:
Accurately take a certain amount of drying of (0.2g), the intelligent nano-gel of porphyrize, put into beaker (200mL), then distilled water (200mL) is added, fully absorb water under condition of different pH, until intelligent nano-gel water suction is saturated, with the water that Bag filter does not adsorb, to substantially anhydrous drippage.Measure the rear intelligent nano-gel weight of fully water suction, according to the water-intake rate of intelligent nano-gel under formula (1) calculating condition of different pH.
Temperature-responsive measures:
Accurately take a certain amount of drying of (0.2g), the intelligent nano-gel of porphyrize, put into beaker (200mL), then add distilled water (200mL), fully absorb water under condition of different temperatures, until intelligent nano-gel water suction is saturated.With the water that Bag filter does not adsorb, to substantially anhydrous drippage.Measure the rear intelligent nano-gel weight of fully water suction, according to the water-intake rate of intelligent nano-gel under formula (1) calculating condition of different temperatures.
The mensuration of particle diameter:
FEI Co. Tecnai G2 F20S-TWIN Flied emission transmission electron microscope of the U.S. (TEM) is adopted to observe intelligent nano-gel granular size and microscopic pattern, by reverse micro emulsion sample with after hexanaphthene dilution certain multiple, dye with phospho-wolframic acid, then dip-coating is on copper mesh, be placed in after drying in sample table, be loaded into electron microscopic sample room, imaging is also taken pictures, by Photoshop computed in software intelligent nano-gel grain diameter size.
PH provided by the invention and temperature dual susceptibility intelligent nano-gel and preparation method thereof, have following beneficial effect:
The present invention adopts conversed phase micro emulsion copolymerization to prepare intelligent nano-gel, microemulsion is thermodynamically stable transparent or semitransparent colloidal dispersion system, its dispersion size is nano level, adopt conversed phase micro emulsion copolymerization can prepare transparent or semitransparent, that median size is 40-80nm pH and temperature dual susceptibility intelligent nano-gel, and micro-emulsion polymerization reaction process is stable, speed of reaction is fast.
Because conversed phase micro emulsion copolymerization reaction carries out in nano grade discontinuous phase drop, be not similar to the nucleation process of precipitation polymerization method or letex polymerization, therefore the cross-linking set distribution of the nanogel of preparation method's synthesis of the present invention is relatively more even, is conducive to forming more perfect three-dimensional net structure.
Employing NIPA is temperature sensitive monomer, methylene-succinic acid is pH sensitive monomer, acrylamide is Hydrophilic nonionic monomer, the pH responsiveness of intelligent nano-gel is improved by methylene-succinic acid molecule 2 carboxyls, the characteristic that the speed utilizing intelligent gel to stimulate generation to respond to external world and its size are inversely proportional to, regulated and controled the particle diameter of intelligent nano-gel by regulation and control conversed phase micro emulsion copolymerization reaction parameter, thus regulation and control intelligent nano hydrogel stimulates the speed producing response to external world.
The hydrophilic/hydrophobic ratio that improve whole intelligent gel network is added in gel ionic provided by the invention and non-ionic hydrophilic component, the hydrogen bond number formed with water molecules increases, need comparatively multi-energy could destroy these hydrogen bonds, improve the transformation temperature of intelligent gel, expand the transition temperature range of intelligent gel.
Intelligent nano-gel provided by the invention has good water suction and inhales salt performance and higher gel-strength, be 4-10 in pH value and all show stronger pH and temperature-responsive at 30-50 DEG C, be expected to be applied to drug conveying and controllable release, medical diagnosis, biosensor, biomaterial, support of the catalyst, heavy metal ion with dye adsorption be separated, in water treatment and the field such as the oil field displacement of reservoir oil and profile control.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, existing following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Present embodiments provide a kind of pH and temperature dual susceptibility intelligent nano-gel and preparation method thereof, this preparation method comprises the following steps:
The mass concentration methylene-succinic acid of 4.0625g slowly being joined 10mL in ice bath is in the sodium hydroxide solution of 10%, fully stirs, and reaction 0.5h, obtains the methylene-succinic acid aqueous solution of part neutralization;
By the N of the acrylamide of 6.0938g, the NIPA of 1.7411g and 0.0595g, N '-methylene-bisacrylamide joins in the methylene-succinic acid aqueous solution of part neutralization, and uniform stirring 20min, obtains transparent monomers mixing solutions;
Above-mentioned transparent monomers mixing solutions is joined be equipped with the hexanaphthene of 100g, Span80 and 3.2g of 4.8g Tween80 there-necked flask in, uniform stirring 20min, form transparent reverse micro emulsion, then 40 DEG C are warming up to gradually, the sodium bisulfite of the ammonium persulphate and 0.0434g that add 0.0952g causes conversed phase micro emulsion copolymerization reaction, react 5 hours, obtain transparent or semitransparent, that median size is 50nm intelligent nano-gel reverse micro emulsion;
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, washing with acetone precipitates 3 times, puts into baking oven 60 DEG C of freeze-day with constant temperature 10h, porphyrize, obtain white intelligent nano-gel powder, this powder is described pH and temperature dual susceptibility intelligent nano-gel.
Absorb water to the pH of the present embodiment and temperature dual susceptibility intelligent nano-gel, inhale the performance test of salt etc., result shows, the equilibrium water absorption of the gel of the present embodiment is 120g/g, is that the balance salt absorbing rate of the NaCl solution of 5wt% is 30g/g, CaCl to concentration 5wt% to concentration
2the balance salt absorbing rate of solution is 14g/g, is the MgCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 18g/g; And the gel-strength of the gel of the present embodiment is 13Pas, is 4-10 and 30-50 DEG C in pH value and shows stronger pH and temperature-responsive.
Embodiment 2
Present embodiments provide a kind of pH and temperature dual susceptibility intelligent nano-gel and preparation method thereof, this preparation method comprises the following steps:
The mass concentration methylene-succinic acid of 4.6429g slowly being joined 20mL in ice bath is in the sodium hydroxide solution of 10%, fully stirs, and reaction 2h, obtains the methylene-succinic acid aqueous solution of part neutralization;
The acrylamide of 4.6429g, the NIPA of 10.8334g and 0.1207g ethylene glycol diacrylate are joined in the methylene-succinic acid aqueous solution of part neutralization, uniform stirring 40min, obtains transparent monomers mixing solutions;
Above-mentioned transparent monomers mixing solutions is joined be equipped with the whiteruss of 100g, Span80 and 5.3333g of 10.6667g Tween80 there-necked flask in, uniform stirring 40min, form transparent reverse micro emulsion, then 60 DEG C are warming up to gradually, the formaldehyde of the Potassium Persulphate and 0.0230g that add 0.0805g closes Sodium Thiosulfate and causes conversed phase micro emulsion copolymerization reaction, react 4 hours, obtain transparent or semitransparent, that median size is 60nm intelligent nano-gel reverse micro emulsion;
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, washing with acetone precipitates 5 times, puts into baking oven 60 DEG C of freeze-day with constant temperature 10h, porphyrize, obtain white intelligent nano-gel powder, this powder is described pH and temperature dual susceptibility intelligent nano-gel.
Absorb water to the pH of the present embodiment and temperature dual susceptibility intelligent nano-gel, inhale the performance test of salt etc., result shows, the equilibrium water absorption of the gel of the present embodiment is 80g/g, is that the balance salt absorbing rate of the NaCl solution of 5wt% is 25g/g, CaCl to concentration 5wt% to concentration
2the balance salt absorbing rate of solution is 10g/g, is the MgCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 15g/g; And the gel-strength of the gel of the present embodiment is 15Pas, is 4-10 and 30-50 DEG C in pH value and shows stronger pH and temperature-responsive.
Embodiment 3
Present embodiments provide a kind of pH and temperature dual susceptibility intelligent nano-gel and preparation method thereof, this preparation method comprises the following steps:
In ice bath, the methylene-succinic acid of 2.7083g is slowly joined 10mL mass concentration is in the sodium hydroxide solution of 10%, fully stirs, and reaction 1.5h, obtains the methylene-succinic acid aqueous solution of part neutralization;
Joined by the polyethyleneglycol diacrylate of the acrylamide of 1.8055g, the NIPA of 1.1607g and 0.0057g in the methylene-succinic acid aqueous solution of part neutralization, uniform stirring 30min, obtains transparent monomers mixing solutions;
Above-mentioned transparent monomers mixing solutions is joined be equipped with the white oil of 100g, Span80 and 6.4g of 9.6g Tween80 there-necked flask in, uniform stirring 30min, form transparent reverse micro emulsion, then 50 DEG C are warming up to gradually, the S-WAT of the ammonium persulphate and 0.0342g that add 0.0681g causes conversed phase micro emulsion copolymerization reaction, react 4 hours, obtain transparent or semitransparent, that median size is 40nm intelligent nano-gel reverse micro emulsion;
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, washing with acetone precipitates 5 times, puts into baking oven 60 DEG C of freeze-day with constant temperature 10h, porphyrize, obtain white intelligent nano-gel powder, this powder is described pH and temperature dual susceptibility intelligent nano-gel.
Absorb water to the pH of the present embodiment and temperature dual susceptibility intelligent nano-gel, inhale the performance test of salt etc., result shows, the equilibrium water absorption of the gel of the present embodiment is 500g/g, is that the balance salt absorbing rate of the NaCl solution of 5wt% is 35g/g, CaCl to concentration 5wt% to concentration
2the balance salt absorbing rate of solution is 20g/g, is the MgCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 25g/g; And the gel-strength of the gel of the present embodiment is 5Pas, is 4-10 and 30-50 DEG C in pH value and shows stronger pH and temperature-responsive.
Embodiment 4
Present embodiments provide a kind of pH and temperature dual susceptibility intelligent nano-gel and preparation method thereof, this preparation method comprises the following steps:
In ice bath, the methylene-succinic acid of 6.5g is slowly joined 20mL mass concentration is in the sodium hydroxide solution of 10%, fully stirs, and reaction 2h, obtains the methylene-succinic acid aqueous solution of part neutralization;
Joined by the diethylene glycol double methacrylate of the acrylamide of 6.5g, the NIPA of 4.3333g and 0.0347g in the methylene-succinic acid aqueous solution of part neutralization, uniform stirring 40min, obtains transparent monomers mixing solutions;
Above-mentioned transparent monomers mixing solutions is joined be equipped with the sherwood oil of 100g, Span80 and 6g of 6g Tween80 there-necked flask in, uniform stirring 40min, form transparent reverse micro emulsion, then 55 DEG C are warming up to gradually, the Sulfothiorine of the Sodium Persulfate and 0.1726g that add 0.3120g causes conversed phase micro emulsion copolymerization reaction, react 4 hours, obtain transparent or semitransparent, that median size is 80nm intelligent nano-gel reverse micro emulsion;
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, washing with acetone precipitates 4 times, puts into baking oven 60 DEG C of freeze-day with constant temperature 10h, porphyrize, obtain white intelligent nano-gel powder, this powder is described pH and temperature dual susceptibility intelligent nano-gel.
The pH of the present embodiment and temperature dual susceptibility intelligent nano-gel are absorbed water, inhale the performance tests such as salt, result shows, the equilibrium water absorption of the gel of the present embodiment is 320g/g, is that the balance salt absorbing rate of the NaCl solution of 5wt% is 32g/g, CaCl to concentration 5wt% to concentration
2the balance salt absorbing rate of solution is 17g/g, is the MgCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 22g/g; And the gel-strength of the gel of the present embodiment is 8Pas, is 4-10 and 30-50 DEG C in pH value and shows stronger pH and temperature-responsive.
Embodiment 5
Present embodiments provide a kind of pH and temperature dual susceptibility intelligent nano-gel and preparation method thereof, this preparation method comprises the following steps:
In ice bath, the methylene-succinic acid of 3.75g is slowly joined 15mL mass concentration is in the sodium hydroxide solution of 10%, fully stirs, and reaction 1.5h, obtains the methylene-succinic acid aqueous solution of part neutralization;
Joined by the tirethylene glycol double methacrylate of the acrylamide of 3.75g, the NIPA of 5.625g and 0.0525g in the methylene-succinic acid aqueous solution of part neutralization, uniform stirring 30min, obtains transparent monomers mixing solutions;
Above-mentioned transparent monomers mixing solutions is joined be equipped with the hexanaphthene of 100g, Span80 and 6.4286g of 8.5714g Tween80 there-necked flask in, uniform stirring 30min, form transparent reverse micro emulsion, then 45 DEG C are warming up to gradually, the S-WAT of the Potassium Persulphate and 0.0613g that add 0.1969g causes conversed phase micro emulsion copolymerization reaction, react 5 hours, obtain transparent or semitransparent, that median size is 45nm intelligent nano-gel reverse micro emulsion;
The intelligent nano-gel reverse micro emulsion of synthesis is precipitated with ethanol breakdown of emulsion, washing with acetone precipitates 4 times, puts into baking oven 60 DEG C of freeze-day with constant temperature 10h, porphyrize, obtain white intelligent nano-gel powder, this powder is described pH and temperature dual susceptibility intelligent nano-gel.
The pH of the present embodiment and temperature dual susceptibility intelligent nano-gel are absorbed water, inhale the performance tests such as salt, result shows, the equilibrium water absorption of the gel of the present embodiment is 110g/g, is that the balance salt absorbing rate of the NaCl solution of 5wt% is 28g/g, CaCl to concentration 5wt% to concentration
2the balance salt absorbing rate of solution is 13g/g, is the MgCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 17g/g; And the gel-strength of the gel of the present embodiment is 11Pas, is 4-10 and 30-50 DEG C in pH value and shows stronger pH and temperature-responsive.
Above-described embodiment illustrates, the pH that the preparation method of pH of the present invention and temperature dual susceptibility intelligent nano-gel obtains and temperature dual susceptibility intelligent nano-gel have good water suction, inhale salt performance, higher gel-strength and stronger pH and temperature-responsive.
Claims (10)
1. a preparation method for pH and temperature dual susceptibility intelligent nano-gel, the method comprises the following steps:
Step one: methylene-succinic acid slowly being joined concentration in ice bath is in the sodium hydroxide solution of 10wt%, stirs 0.5-2h, obtains the methylene-succinic acid aqueous solution of part neutralization;
Wherein, the mol ratio of described methylene-succinic acid and sodium hydroxide is 1:0.8-1.4;
Step 2: acrylamide, NIPA and linking agent are joined in the methylene-succinic acid aqueous solution of part neutralization, stir 20-40min, obtain transparent monomers mixing solutions;
Wherein, the mass ratio of described methylene-succinic acid and described acrylamide is 4:6-6:4, the mass ratio of described methylene-succinic acid and described NIPA is 3:7-7:3, and the consumption of described linking agent is the 0.1-0.6% of the total mass of methylene-succinic acid, acrylamide and NIPA;
Step 3: transparent monomers mixing solutions is joined in the mixed solvent containing oil-dissolving solvent and Span80/Tween80 complexed surfactant, stir 20-40min, form transparent reverse micro emulsion, then 40-60 DEG C is warming up to gradually, add Oxidizing and Reducing Agents, reaction 3-5 hour, obtains transparent or semitransparent intelligent nano-gel reverse micro emulsion;
Wherein, the mass ratio of Span80 and Tween80 is 3-6:2-4, and the consumption of oxygenant is the 0.4-1.8% of the total mass of methylene-succinic acid, acrylamide and NIPA, and the mol ratio of Oxidizing and Reducing Agents is 1-2:1;
Step 4: by described intelligent nano-gel reverse micro emulsion ethanol breakdown of emulsion precipitation, washing with acetone precipitation 3-5 time, 60 DEG C of freeze-day with constant temperature 10h, obtain described pH and temperature dual susceptibility intelligent nano-gel.
2. the preparation method of pH according to claim 1 and temperature dual susceptibility intelligent nano-gel, wherein, described oil-dissolving solvent is selected from hexanaphthene, whiteruss, white oil and sherwood oil.
3. the preparation method of pH according to claim 1 and temperature dual susceptibility intelligent nano-gel, wherein, when adding 10mL-20mL sodium hydroxide solution in step one, in step 3, transparent monomers mixing solutions is joined in the mixed solvent of the Span80/Tween80 complexed surfactant of oil-dissolving solvent containing 100g and 8-16g.
4. the preparation method of pH according to claim 1 and temperature dual susceptibility intelligent nano-gel, wherein, described linking agent is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, diethylene glycol double methacrylate, tirethylene glycol double methacrylate and polyethyleneglycol diacrylate.
5. the preparation method of pH according to claim 1 and temperature dual susceptibility intelligent nano-gel, wherein, described oxygenant is selected from ammonium persulphate, Potassium Persulphate and Sodium Persulfate.
6. the preparation method of pH according to claim 1 and temperature dual susceptibility intelligent nano-gel, wherein, described reductive agent is selected from sodium bisulfite, S-WAT, Sulfothiorine and formaldehyde and closes Sodium Thiosulfate.
7. the preparation method of pH according to claim 1 and temperature dual susceptibility intelligent nano-gel, wherein, the median size of described intelligent nano-gel reverse micro emulsion is 40-80nm.
8. pH and a temperature dual susceptibility intelligent nano-gel, it is prepared by the preparation method of the pH described in any one of claim 1-7 and temperature dual susceptibility intelligent nano-gel.
9. pH according to claim 8 and temperature dual susceptibility intelligent nano-gel, wherein, the gel-strength of this pH and temperature dual susceptibility intelligent nano-gel is 5-15Pas.
10. pH according to claim 8 and temperature dual susceptibility intelligent nano-gel, wherein, the equilibrium water absorption of this pH and temperature dual susceptibility intelligent nano-gel is 80-500g/g, and being that the balance salt absorbing rate of the NaCl solution of 5wt% is 25-35g/g to concentration, is the CaCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 10-20g/g, is the MgCl of 5wt% to concentration
2the balance salt absorbing rate of solution is 15-25g/g.
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| CN114058032A (en) * | 2021-12-09 | 2022-02-18 | 广东华美众源生物科技有限公司 | Dual-response nano composite hydrogel and preparation method and application thereof |
| CN114058032B (en) * | 2021-12-09 | 2023-06-02 | 广东华美众源生物科技有限公司 | Dual-response nano composite hydrogel and preparation method and application thereof |
| CN115558133A (en) * | 2022-10-20 | 2023-01-03 | 南京工业大学 | Temperature response type particle gel and preparation method thereof |
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