CN101531742B - Method for preparing nanometer composite aquagel using nanometer microsphere as junction - Google Patents
Method for preparing nanometer composite aquagel using nanometer microsphere as junction Download PDFInfo
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Abstract
The invention relates to a method for preparing nanometer composite aquagel using nanometer microsphere as a junction. The method comprises the following steps that: (1) water, a hydrophobic monomer and a cationic comonomer are added into a three-neck flask which is provided with a stirring device, a reflux device and an N2 inlet, the three-neck flask is heated to 70 DEG C and is dripped with cationic initiator; the temperature is preserved and reaction is kept on for 3 to 5 hours to prepare a cationic nanometer microsphere; and (2) the cationic microsphere emulsion obtained in the step (1), the water, the soluble monomer, the soluble anionic initiator and a catalyst are mixed to prepare a prepolymer solution with microsphere concentration between 3 to 35 percent, and are polymerized at room temperature to prepare the nanometer composite aquagel. The method has simple process and high polymerization rate, obtains the nanometer composite aquagel with excellent mechanical performance; furthermore, raw materials have large selection range, and the aquagel has high application value.
Description
Technical field
The invention belongs to the preparation field of Nanometer composite hydrogel, particularly relate to the preparation method that a kind of Nano microsphere is the Nanometer composite hydrogel of cross-linking set.
Background technology
High-molecular gel is that system has solvophilic by polymer and polymer three-dimensional network system of solvent composition, can be in solvent swelling but do not dissolve, be dispersed in the solvent simultaneously and can keep certain shape.Though solvent can not be with the macromolecule dissolution of tridimensional network, solvophilic group part can be made the polymer swelling by solvent action in the macromolecular compound, and this also is one of reason that forms high-molecular gel.The cross-link bond of high-molecular gel differs, and to establish a capital be chemical covalent linkage, also can be by such as secondary valence bonds such as hydrogen bonds, and perhaps modes such as the mutual IPN of segment, entanglement form crosslinking structure.Hydrogel is the viscoelastic body that the hydrophilic macromolecule of the swell cross of water as solvent forms, and is a kind of special soft wet materials.
Hydrogel is used in the every aspect of national life owing to its special physicochemical property.The traditional water gel is mainly on the high absorbency materials such as daily necessities, industrial goods.Along with the bioid of hydrogel with intelligently cause widening of its Application Areas, be used as materials such as pharmaceutical carrier, drug controllable release, cell culture substrate and hemostatic agent, binding agent as hydrogel material in medical field, the application of hydrogel in fields such as chemical machinery, organizational projects also obtains exploitation in addition.
Yet the gel of traditional chemically crosslinked is because the cross-linking set skewness, caused the stress concentration when stressed, makes its poor mechanical property, seriously limited its application in every respect.And because the single network structure of conventional gel, the polyfunctional development of gel also is greatly limited.Functional gel will make that gel response is rapider, function is more complete, will further expand the application of gel in fields such as chemical machinery, medical science and organizational projects.
In recent years, three kinds of novel high intensity hydrogels are in the news: topological gel, dual network gel and nano-composite gel, and by original position radical polymerization the synthetic nano-composite gel because its synthesis technique is simple, mechanical property improves and significantly is subjected to paying close attention to widely.As patent publication No. CN 101161689A, it is high-performance hydrogel synthetic of cross-linking set that CN 1908035A has related to the commodity clay.
Summary of the invention
Technical problem to be solved by this invention provides the preparation method that a kind of Nano microsphere is the Nanometer composite hydrogel of cross-linking set, this method technology is simple, and percent polymerization height, the Nanometer composite hydrogel that obtains have excellent mechanical property, the material choice scope is big in addition, has very high using value.
A kind of Nano microsphere of the present invention is the preparation method of the Nanometer composite hydrogel of cross-linking set, comprising:
(1) synthetic cation nanometer microballoon as cross-linking set
Water, hydrophobic monomer and cationic comonomer add there-necked flask, and flask is equipped with whipping appts, reflux and N
2Inlet adds cationic initiator after being heated to 70 ℃, and insulation continues reaction 3-5 hour, promptly gets the cation nanometer microballoon, and whole process is at N
2Carry out in the atmosphere; Wherein water accounts for the 60%-95% of system total mass, and monomer accounts for the 5%-38% of system total mass, and comonomer accounts for the 2%-8% of monomer content, and cationic initiator accounts for the 0.5%-1% of monomer content;
(2) be that cross-linking set prepares Nanometer composite hydrogel with the cation nanometer microballoon
With step (1) cation nanometer microballoon emulsion (10-20g), water (0-10g), water-soluble monomer (3-20g), it is 3%-35% pre-polymerization liquid that water soluble anion initiator (0.01-0.05g) and catalyzer (8-32 μ l) mixing obtains microballoon concentration, pre-polymerization liquid is (20-30 ℃) polyase 13 0 hour at room temperature, can obtain Nanometer composite hydrogel.
Described step (1) hydrophobic monomer comprises that vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, methyl methacrylate etc. can be used for the hydrophobic monomer of letex polymerization.
Described step (1) cationic comonomer is unsaturated quaternary ammonium salts such as methylacryoyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride, acrylyl oxy-ethyl-trimethyl salmiac.
Described step (1) cationic initiator is an azo diisobutyl amidine hydrochloride.
Described step (1) cation nanometer microballoon yield＞98%, particle diameter is 50-200nm, and monodispersity is good, and emulsion solid content is between 5%-35%.
Described step (2) water-soluble monomer is that N-isopropylacrylamide and acrylamide are at any interior non-ionic water-soluble monomer.
Described step (2) anionic initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
Described step (2) catalyzer is N, N, N ', a kind of in N '-Tetramethyl Ethylene Diamine, trolamine, the sodium thiosulfate.
The breaking tenacity of described step (2) Nanometer composite hydrogel maximum surpasses 1MPa, and maximum extension at break surpasses 6500%.
Described step (2) is that monomer can synthesize the Nanometer composite hydrogel with temperature sensitivity with the N-isopropylacrylamide.
The present invention utilizes intermolecular electrostatic interaction, realizes that microballoon and molecule interchain are crosslinked, constructs network structure, has prepared Nanometer composite hydrogel, is cross-linking set assemble nanometer composite aquogel with this microballoon then.The preparation of Nanometer composite hydrogel is characterized in that at first making the saponin-free cation emulsion, make positively charged ion microballoon homodisperse in water, particle diameter is between 50-200nm, be mono-dispersion microballoon, then water-soluble nonionic type monomer, water soluble anion initiator or less water are added in the microballoon emulsion, drip catalyzer again and in container, react.
Beneficial effect
(1) the inventive method as cross-linking set, and realizes the polymerization of monomer at microsphere surface by original position radical polymerization with Nano microsphere, has further synthesized nano-composite gel.This nano-composite gel mechanical property excellence, maximum breaking tenacity can surpass 1MPa, and maximum extension at break can reach 6500%, the polymerization efficiency height, method is simple, and the material choice scope is big;
(2) all to be better than with the clay be the performance of the plural gel of cross-linking set for resulting Nanometer composite hydrogel breaking tenacity of the present invention and extension at break.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
With the 40g deionized water, 18g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.9g methylacryoyloxyethyl trimethyl ammonium chloride
2In the there-necked flask of inlet, stir logical N
2, drip the 2ml 5.1% azo diisobutyl amidine hydrochloride aqueous solution after being warming up to 70 ℃, and be incubated three hours.Stop logical N afterwards
2, stopping heating, reaction stops; Get saponin-free cation emulsion 20g, add the 10g acrylamide monomer in the stirring, logical N
230 minutes, add Potassium Persulphate 0.02g and 24 μ lN, N, N ', N '-Tetramethyl Ethylene Diamine continues to stir five minutes, then solution is injected long 400mm, in the Glass tubing of diameter 5.5mm, at room temperature (20-30 ℃) polyase 13 is 0 hour, realizes the assembling of nano-composite gel.
This gel breaking tenacity can reach 0.18MPa, and extension at break reaches 4500%.
Embodiment 2
With the 40g deionized water, 18g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.9g methylacryoyloxyethyl trimethyl ammonium chloride
2In the there-necked flask of inlet, stir logical N
2, drip the 2ml 5.1% azo diisobutyl amidine hydrochloride aqueous solution after being warming up to 70 ℃, be incubated three hours.Stop logical N afterwards
2, stopping heating, reaction stops, and emulsion is taken out; Get cation emulsion 10g, add water 9g, add the 10g acrylamide monomer in the stirring, logical N
230 minutes, add Potassium Persulphate 0.02g and 24 μ l N, N, N ', N '-Tetramethyl Ethylene Diamine continues to stir five minutes, then solution is injected long 400mm, in the Glass tubing of diameter 5.5mm, at room temperature (20-30 ℃) polyase 13 is 0 hour, realizes the assembling of nano-composite gel.This gel breaking tenacity can reach 0.38MPa, and extension at break reaches 5000%.
Embodiment 3
With the 46g deionized water, 12g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.6g methylacryoyloxyethyl trimethyl ammonium chloride
2In the there-necked flask of inlet, stir logical N
2, drip the 2ml 3.5% azo diisobutyl amidine hydrochloride aqueous solution after being warming up to 70 ℃, be incubated three hours.Stop logical N afterwards
2, stopping heating, reaction stops, and emulsion is taken out; Get cation emulsion 20g, add the 15g acrylamide monomer in the stirring, logical N
230 minutes, add Potassium Persulphate 0.03g and 24 μ l N, N, N ', N '-Tetramethyl Ethylene Diamine continues to stir five minutes, then solution is injected long 400mm, in the Glass tubing of diameter 5.5mm, at room temperature (20-30 ℃) polyase 13 is 0 hour, realizes the assembling of nano-composite gel.This gel breaking tenacity can reach more than the 1.0MPa, and extension at break is greater than 2000%.
Embodiment 4
With the 52g deionized water, 6g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.3g methylacryoyloxyethyl trimethyl ammonium chloride
2In the there-necked flask of inlet, stir logical N
2, drip the 2ml 3% azo diisobutyl amidine hydrochloride aqueous solution after being warming up to 70 ℃, be incubated three hours.Stop logical N afterwards
2, stopping heating, reaction stops, and emulsion is taken out; Get cation emulsion 20g, add the 15g acrylamide monomer in the stirring, logical N
230 minutes, add Potassium Persulphate 0.03g and 24 μ lN, N, N ', N '-Tetramethyl Ethylene Diamine continues to stir ten minutes, then solution is injected long 400mm, in the Glass tubing of diameter 5.5mm, at room temperature (20-30 ℃) polyase 13 is 0 hour, realizes the assembling of nano-composite gel.
This gel breaking tenacity can reach more than the 0.5MPa, and extension at break is greater than 6500%.
Embodiment 5
With the 40g deionized water, 18g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.9g methylacryoyloxyethyl trimethyl ammonium chloride
2In the there-necked flask of inlet, stir logical N
2, drip the 2ml 5.1% azo diisobutyl amidine hydrochloride aqueous solution after being warming up to 70 ℃, be incubated three hours.Stop logical N afterwards
2, stopping heating, reaction stops, and emulsion is taken out; Get cation emulsion 5g, add water 12.5g, add the 10g acrylamide monomer in the stirring, logical N
230 minutes, add Potassium Persulphate 0.02g and 24 μ l N, N, N ', N '-Tetramethyl Ethylene Diamine continues to stir five minutes, then solution is injected long 400mm, in the Glass tubing of diameter 5.5mm, at room temperature (20-30 ℃) polyase 13 is 0 hour, realizes the assembling of nano-composite gel.This gel breaking tenacity can reach 0.5MPa, and extension at break is greater than 6000%.
Embodiment 6
With the 40g deionized water, 18g vinylbenzene, whipping appts, reflux and N are equipped with in the adding of 0.9g methylacryoyloxyethyl trimethyl ammonium chloride
2In the there-necked flask of inlet, stir logical N
2, drip the 2ml 5.1% azo diisobutyl amidine hydrochloride aqueous solution after being warming up to 70 ℃, be incubated three hours.Stop logical N afterwards
2, stopping heating, reaction stops, and emulsion is taken out; Get cation emulsion 10g, water 8g adds the 4g acrylamide monomer in the stirring, logical N
230 minutes, add Potassium Persulphate 0.01g and 24 μ l N, N, N ', N '-Tetramethyl Ethylene Diamine continues to stir five minutes, then solution is injected long 400mm, in the Glass tubing of diameter 5.5mm, at room temperature (20-30 ℃) polyase 13 is 0 hour, realizes the assembling of nano-composite gel.
This gel breaking tenacity can reach 0.15MPa, and extension at break is greater than 2000%.
Claims (5)
1. preparation method that Nano microsphere is the Nanometer composite hydrogel of cross-linking set comprises:
(1) water, vinylbenzene and cationic comonomer add there-necked flask, flask is equipped with whipping appts, reflux and N2 inlet, adds cationic initiator after being heated to 70 ℃, and insulation continues reaction 3-5 hour, promptly get the cation nanometer microballoon, whole process is carried out in N2 atmosphere; Wherein water accounts for the 60%-95% of system total mass, the 5%-38% of styrene comprise system total mass, and comonomer accounts for the 2%-8% of styrene content, and cationic initiator accounts for the 0.5%-1% of styrene content; Described cationic comonomer is methylacryoyloxyethyl trimethyl ammonium chloride, dimethyl diallyl ammonium chloride or acrylyl oxy-ethyl-trimethyl salmiac;
(2) with the cation emulsion of step (1) 10g-20g, the water of 0g-10g, the water-soluble monomer of 3g-20g, 0.01g-0.05g the water soluble anion initiator and the catalyst mix of 8 μ l-32 μ l to obtain microballoon concentration be 3%-35% pre-polymerization liquid, pre-polymerization liquid can obtain Nanometer composite hydrogel room temperature 20-30 ℃ polyase 13 0 hour; Described water-soluble monomer is N-isopropylacrylamide or acrylamide; Described catalyzer is N, N, N ', a kind of in N '-Tetramethyl Ethylene Diamine, trolamine, the sodium thiosulfate.
2. a kind of Nano microsphere according to claim 1 is the preparation method of the Nanometer composite hydrogel of cross-linking set, it is characterized in that: described step (1) cationic initiator is an azo diisobutyl amidine hydrochloride.
3. a kind of Nano microsphere according to claim 1 is the preparation method of the Nanometer composite hydrogel of cross-linking set, it is characterized in that: described step (1) cation nanometer microballoon yield＞98%, and particle diameter is 50-200nm, emulsion solid content is between 5%-35%.
4. a kind of Nano microsphere according to claim 1 is the preparation method of the Nanometer composite hydrogel of cross-linking set, it is characterized in that: described step (2) initiator is Potassium Persulphate, ammonium persulphate or Sodium Persulfate.
5. a kind of Nano microsphere according to claim 1 is the preparation method of the Nanometer composite hydrogel of cross-linking set, it is characterized in that: described step (2) Nanometer composite hydrogel breaking tenacity is 0.1MPa-1MPa, and maximum extension at break surpasses 6500%.
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| CN101864045B (en) * | 2010-04-27 | 2012-01-11 | 东华大学 | Preparation method of chemically crosslinked nanocomposite hydrogel |
| CN101880440A (en) * | 2010-06-11 | 2010-11-10 | 新疆大学 | Novel nano-composite double network hydrogel and preparation method thereof |
| CN103159878B (en) * | 2013-04-03 | 2016-04-13 | 湖南科技大学 | A kind of simple method preparing monodisperse cationic polystyrene microballoon sphere |
| CN106188389B (en) * | 2016-07-14 | 2018-01-12 | 长春工业大学 | A kind of preparation method of electronegative macromolecular nanoparticle composite aquogel |
| CN106220873A (en) * | 2016-08-16 | 2016-12-14 | 潘忠宁 | A kind of synthetic method of microgel base composite aquogel |
| CN106496394A (en) * | 2016-11-01 | 2017-03-15 | 长春工业大学 | A kind of cation emulsion particle toughening hydrophobic association hydrogel and preparation method |
| CN110776599B (en) * | 2019-10-31 | 2021-12-24 | 南方医科大学南方医院 | Antibacterial hydrogel |
| CN114560965B (en) * | 2022-02-25 | 2023-12-22 | 苏州仁端生物医药科技有限公司 | Preparation method and application of nanoscale cationic carboxyl latex microspheres |
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