CN102229711B - Preparation and application of silicane functionalized high-water-solubility silicon dioxide nano particles - Google Patents
Preparation and application of silicane functionalized high-water-solubility silicon dioxide nano particles Download PDFInfo
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Abstract
The invention belongs to the field of nano materials and discloses a preparation method of silicane functionalized high-water-solubility silicon dioxide nano particles and an application thereof. The preparation method comprises the following steps of: (1) hydrolyzing a silicane coupling agent with a hydrochloric acid solution with pH of 1-5, adding an acidic nano SiO2 solution and the hydrolyzedsilicane coupling agent into a round bottomed flask, stirring for 1-4 hours in a water bath at the temperature of 40-80 DEG C, extracting reaction liquid with an organic solvent and dispersing the reaction liquid into deionized water, dialyzing for one week with the deionized water to obtain a high-water-solubility functionalized nano SiO2 solution; and (2) preparing the functionalized nano SiO2 solution obtained by the step (1) into a solution with the mass fraction of 5-25%, mixing with vinyl monomers and a catalyst to form a uniform aqueous solution, adding an initiator, and carrying out free radical polymerization at room temperature to obtain the high-strength SiO2-based nano compound hydrogel.
Description
Technical field
The present invention relates to field of nanometer material technology, be specifically related to a kind of preparation and application thereof of high water soluble Nano particles of silicon dioxide of silane-functionalized.
Background technology
Nano material is the focus of 21 century scientific research field, because it has small-size effect, surface and interface effect, quantum size effect and macro quanta tunnel effect etc. has caused nanoparticle to have unusual physical and chemical performance.
Nano silicon (SiO
2) have superior stability, reinforcement, thickening property and thixotropy, have simultaneously that material source is easy to get, cheap, the advantage such as processing power consumption is low, environmental pollution is little, so in polymer-filled, modification, be widely used.Because nanometer SiO
2Particle is very little, and specific surface area is large, and (OH), be easy to reunite, simple blend is difficult to evenly spread in the polymeric matrix, has affected nanometer SiO to have hydrophilic radical
2The performance of performance, and nanometer SiO
2Surface functional group is single, has limited nanometer SiO
2In the application of other field, so need to be to nanometer SiO
2Carry out functional modification.
To nanometer SiO
2The method of functional modification has had a lot of reports.The most frequently used method is chemical graft process, with the modified material of functional group by with nanometer SiO
2The hydroxyl effect of particle surface is linked to nanometer SiO with modified monomer
2Particle surface.This functional method can access interface binding power strong, with the nanometer SiO of various functional groups
2Particle, the nanometer SiO of the functionalization that obtains
2Have been widely used.Silane coupling agent is the silane that a class has organo-functional group, and the reactive group that has simultaneously energy and the chemically combined reactive group of inanimate matter material and be combined with organic materials chemistry in its molecule is widely used in nanometer SiO
2Functional modification.The Ou Yangzhao of Wuhan University Of Technology brightness etc. use silane coupling A-151 (vinyltriethoxysilane) to nanometer SiO
2Surface-functionalized modification, the reunion behavior is greatly improved, the nanometer SiO of functionalization
2With isoprene-isobutylene rubber good consistency is arranged, fill isoprene-isobutylene rubber and can significantly improve its tensile strength.The not big grade of Beijing University of Chemical Technology prepares nanometer SiO in sol-gel method
2Process in, use silane coupling agent KH-560 (γ-glycidyl ether oxygen propyl trimethoxy silicane) to nanometer SiO
2Carry out modification, the nano silicon of formation-silane coupling agent hybrid material has good application performance in epoxy resin varnish, shows not only to strengthen but also toughness reinforcing characteristic, demonstrates nano effect.The Li Lijun of South China Science ﹠ Engineering University waits and uses silane coupling A 2151(vinyltriethoxysilane) to nanometer SiO
2Carry out modification, have a large amount of organic membrane to exist through the aluminium surface of pigments of silane coupler modified coated with silica, thereby its hydrophobicity strengthens, improved the consistency of itself and organic resin etc.
Existing silane coupling agent functional modification technology obtains nanometer SiO
2Particle is powder mostly, and perhaps redispersion uses after the solution drying, causes the nanometer SiO of functionalization
2Particle is reunited again, has affected the dispersiveness in water.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the high water soluble Nano particles of silicon dioxide of silane-functionalized, overcome silane-modified nanometer SiO
2The difficult problem of poorly water-soluble, and successfully with the nanometer SiO of functionalization
2Particle prepares Nanometer composite hydrogel as a polyfunctional crosslinking agent.
In order to address the above problem, the invention discloses a kind of preparation method of high water soluble Nano particles of silicon dioxide of silane-functionalized, comprising:
With the hydrochloric acid soln of silane coupling agent and 6 times of pH=1 to the silane coupling agent quality-5, and dehydrated alcohol joins in the reaction vessels the ultrasonic silane coupling agent complete hydrolysis that makes;
Silane coupling agent, nanometer SiO with hydrolysis
2Solution and deionized water, reaction is 1-4 hour in liquid bath, and temperature is controlled at 40-80 ℃;
Add organic solvent extraction, the lower floor's solid redispersion that obtains after centrifugal is in deionized water;
The functionalized nano SiO of highly water-soluble will be obtained after the aqueous solution dialysis that disperse to obtain
2Solution.
In the preferred example, silane coupling agent is 0.1-5g; Dehydrated alcohol is 2-10ml; Nanometer SiO
2Solution is 30% the nanometer SiO of 5-35g
2Solution;
Wherein, the organic solvent of described extraction usefulness is a kind of or mixture in tetrahydrofuran (THF), ether, acetone, methyl alcohol, the ethanol, and the organic solvent quality of extraction usefulness is 6:1-10:1 with the mass ratio that is extracted liquid.
Preferably, silane coupling agent of the present invention can be selected vinyltriethoxysilane, vinyltrimethoxy silane, a kind of in methyl allyl acyloxypropyl trimethoxysilane or vinyl ('beta '-methoxy oxyethyl group) silane.
According to another embodiment of grace invention, also disclose and a kind ofly adopted aforementioned high water soluble Nano particles of silicon dioxide to prepare the method for high strength silicon dioxide base Nanometer composite hydrogel, comprising:
To functionalized nano SiO
2Solution led to nitrogen 1-6 hour under the magnetic agitation condition;
Adding monomer under logical inert gas conditions stirred 5-30 minute;
Ice-water bath 5-50 minute;
After adding the stirring of initiator and catalyzer, move into to seal in the container and left standstill 12-48 hour, obtain high-intensity silicon dioxide base Nanometer composite hydrogel.
Preferably, described monomer is acrylamide, NIPA, a kind of in N,N-DMAA and the N hydroxymethyl acrylamide.
Preferably, described catalyzer is N, N, N ', N '-Tetramethyl Ethylene Diamine, a kind of in trolamine and the Sulfothiorine.
Preferably, described initiator is Potassium Persulphate, a kind of in ammonium persulphate and the Diisopropyl azodicarboxylate.
Preferably, described rare gas element is nitrogen, a kind of in helium and the argon gas.
Compared with prior art, the present invention has the following advantages:
The functionalized nano SiO that makes among the present invention
2Particle diameter remains between the 10-20nm, substantially between particle does not reunite, in deionized water, have well water-soluble, can widespread use in aqueous phase solution.With functionalized nano SiO
2Particle is much better than unmodified nanometer SiO as the Nanometer composite hydrogel performance that the polyfunctionality linking agent obtains
2The hydrogel of particle preparation, the hydrogel that obtains uses accurate universal testing machine and equilibrium swelling experiments to test respectively its mechanical property and swelling property, and the result shows that the former compressive strength is 8 times of the latter, tensile strength is 10 times of the latter, and swelling equilibrium speed is 4 times of the latter.
Description of drawings
Fig. 1 is preparation method's the steps flow chart synoptic diagram of the high water soluble Nano particles of silicon dioxide of a kind of silane-functionalized of the present invention;
Fig. 2 is the preparation method's of a kind of high strength silicon dioxide base of the present invention Nanometer composite hydrogel steps flow chart synoptic diagram;
Fig. 3 is the prepared functionalized nano SiO of example 3
2The transmission electron microscope of particle (TEM) photo;
Fig. 4 is the functionalized nano SiO of 4 method preparations of example
2Hydrogel and functionalized nano SiO not
2Hydrogel compressive strain-stress curve comparison diagram;
Fig. 5 is the prepared functionalized nano SiO of example 5
2Hydrogel and functionalized nano SiO not
2Before the hydrogel compression and be compressed to 95% photo in kind after recovering, wherein (a) (b) is the nanometer SiO of functionalization
2Solution prepares the comparison diagram before and after the hydrogel compression, (c), (d) is the nanometer SiO of functionalization not
2Solution prepares the comparison diagram before and after the hydrogel compression.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
With reference to Fig. 1, show the preparation method of the high water soluble Nano particles of silicon dioxide of a kind of silane-functionalized of the present invention, specifically can may further comprise the steps:
Obtain the functionalized nano SiO of highly water-soluble after step 104, the aqueous solution dialysis that will disperse to obtain
2Solution.
Step 105, silane coupling agent are vinyltriethoxysilane, vinyltrimethoxy silane, a kind of in methyl allyl acyloxypropyl trimethoxysilane or vinyl ('beta '-methoxy oxyethyl group) silane.
The present invention adopt silane coupling agent under the water condition to nanometer SiO
2Particle carries out functionalization, with an organic solvent to the nanometer SiO of functionalization
2Redispersion has been avoided nanometer SiO after the extraction in water
2Particle is reunited again, the nanometer SiO that obtains
2High water soluble is arranged, and good stability.Nanometer SiO with functionalization
2As the Nanometer composite hydrogel of linking agent preparation, intensity is high, and is restorative good after the compression, and swelling property is little in liquid, and these character make it at artificial-muscle, drug release, and there is good application prospect in the fields such as biological promoters.
With reference to Fig. 2, the present invention can also be based on aforesaid nanometer SiO
2Particle prepares high strength silicon dioxide base Nanometer composite hydrogel, and its concrete grammar can comprise:
After step 204, adding initiator and catalyzer stir, move into to seal in the container and left standstill 12-48 hour, obtain high-intensity silicon dioxide base Nanometer composite hydrogel.
Wherein said catalyzer can be selected N, N, N ', N '-Tetramethyl Ethylene Diamine, a kind of in trolamine and the Sulfothiorine.Described initiator is Potassium Persulphate, a kind of in ammonium persulphate and the Diisopropyl azodicarboxylate.
The below provides specific exampless more of the present invention, so that further the present invention will be described.
Inventory in these examples is substantially all take the laboratory rank as example, and certainly, when actual production, the inventory span of each reactant can be with the amplification of ratio, and the present invention describes in detail no longer one by one to this.
Example 1
0.5g vinyltriethoxysilane, 2ml dehydrated alcohol, the hydrochloric acid soln of 3g pH=2 join in the 50ml reaction flask, ultrasonic 30 minutes, make the silane complete hydrolysis, and be 30% nanometer SiO with silane and the 10g concentration of hydrolysis
2Solution, the 17g deionized water joins in the round-bottomed flask, 80 ℃ of stirred in water bath 1 hour, stirs and reaction solution is transferred in the beaker after finishing, add and use the 180g tetrahydrofuran (THF), vigorous stirring is used the solution centrifuge tube of packing into, centrifugal 10min under the 7000r/min condition, in the lower floor's solid redispersion and deionized water that obtains, the aqueous solution dialysis tubing of packing into was dialysed for 1 week, changed water in per 24 hours, obtain water miscible functionalized nano SiO
2Solution, being concentrated into concentration with Rotary Evaporators is 10%
Nanometer SiO with the functionalization of 9.5g
2Solution joins in the 30ml bottle, logical nitrogen is 1 hour under the magnetic agitation condition, add the 0.71g acrylamide, stirred 15 minutes under the condition of nitrogen gas, ice-water bath 10 minutes, adding 0.5ml concentration is 2% ammonium persulphate, changes in the 3ml cuvette after 8 μ l trolamines stir, sealing standing and reacting 12 hours obtains the silicon dioxide base Nanometer composite hydrogel.
When this gel was 95% at compressive set, stress was 6.2MPa, remove pressure after, the hydrogel immediate recovery to the compression before shape.
Example 2
The 1g vinyltriethoxysilane, 4ml dehydrated alcohol, the hydrochloric acid soln of 6g pH=4 join in the 50ml reaction flask, and ultrasonic 30 minutes, make the silane complete hydrolysis, be 30% nanometer SiO with silane and the 20g concentration of hydrolysis
2Solution, the 14g deionized water joined in the round-bottomed flask, 60 ℃ of stirred in water bath 2 hours, after stirring end reaction solution is transferred in the beaker, add and use 200g methyl alcohol, alcohol mixeding liquid (mass ratio 1:1), vigorous stirring, with the solution centrifuge tube of packing into, centrifugal 10min under the 7000r/min condition in the lower floor's solid redispersion and deionized water that obtains, dialyses the aqueous solution dialysis tubing of packing into 1 week, change water in per 24 hours, and obtained water miscible functionalized nano SiO
2Solution, being concentrated into concentration with Rotary Evaporators is 15%
Nanometer SiO with the functionalization of 9.5g
2Solution joins in the 30ml bottle, logical nitrogen is 3 hours under the magnetic agitation condition, add the 0.71g acrylamide, stirred 20 minutes under the condition of nitrogen gas, ice-water bath 20 minutes, adding 0.5ml concentration is 2% ammonium persulphate, changes in the 3ml cuvette after 8 μ l trolamines stir, sealing standing and reacting 16 hours obtains the silicon dioxide base Nanometer composite hydrogel.
When this gel was 95% at compressive set, stress was 7.1MPa, remove pressure after, the hydrogel immediate recovery to the compression before shape.
Example 3
0.8g vinyltrimethoxy silane, 6ml dehydrated alcohol, the hydrochloric acid soln of 4.8g pH=5 join in the 50ml reaction flask, ultrasonic 30 minutes, make the silane complete hydrolysis, and be 30% nanometer SiO with silane and the 15g concentration of hydrolysis
2Solution, the 20g deionized water joined in the round-bottomed flask, 60 ℃ of stirred in water bath 2 hours, after stirring end reaction solution is transferred in the beaker, add and use 240g methyl alcohol, alcohol mixeding liquid (mass ratio 1:1), vigorous stirring, with the solution centrifuge tube of packing into, centrifugal 5min under the 10000r/min condition in the lower floor's solid redispersion and deionized water that obtains, dialyses the aqueous solution dialysis tubing of packing into 1 week, change water in per 24 hours, and obtained water miscible functionalized nano SiO
2Solution, being concentrated into concentration with Rotary Evaporators is 20%
Nanometer SiO with the functionalization of 9.5g
2Solution joins in the 30ml bottle, and logical nitrogen is 2 hours under the magnetic agitation condition, adds 0.99g N, the N-DMAA stirred 30 minutes ice-water bath 30 minutes under the condition of nitrogen gas, adding 0.5ml concentration is 2% Potassium Persulphate, 8 μ l N, N, N ', N '-Tetramethyl Ethylene Diamine, change over to after stirring in the 3ml cuvette, sealing standing and reacting 24 hours obtains the silicon dioxide base Nanometer composite hydrogel.
When this gel was 95% at compressive set, stress was 7.5MPa, remove pressure after, the hydrogel immediate recovery to the compression before shape.
Referring to Fig. 3, be the prepared functionalized nano SiO of example 3
2The transmission electron microscope of particle (TEM) photo.The nanometer SiO of the functionalization that prior art obtains
2Particle is easily reunited in preparation and use procedure, and in the bad dispersibility of aqueous phase, as can be seen from Figure 3 the nanometer SiO of the functionalization for preparing of the present invention
2Particle is monodisperse status, without agglomeration, thereby higher dispersiveness is arranged in water.
Example 4
1.2g methyl allyl acyloxypropyl trimethoxysilane, 6ml dehydrated alcohol, the hydrochloric acid soln of 7.2g pH=3 join in the 50ml reaction flask, ultrasonic 30 minutes, make the silane complete hydrolysis, and be 30% nanometer SiO with silane and the 25g concentration of hydrolysis
2Solution, the 7g deionized water joined in the round-bottomed flask, 60 ℃ of stirred in water bath 2 hours, after stirring end reaction solution is transferred in the beaker, add and use 320g ether, acetone mixed solution (mass ratio 1:1), vigorous stirring, with the solution centrifuge tube of packing into, centrifugal 5min under the 10000r/min condition in the lower floor's solid redispersion and deionized water that obtains, dialyses the aqueous solution dialysis tubing of packing into 1 week, change water in per 24 hours, and obtained water miscible functionalized nano SiO
2Solution, being concentrated into concentration with Rotary Evaporators is 20%
Nanometer SiO with the functionalization of 9.5g
2Solution joins in the 30ml bottle, and logical nitrogen is 3 hours under the magnetic agitation condition, adds the 1.13g NIPA, stirred 30 minutes under the condition of nitrogen gas, ice-water bath 10 minutes, adding 0.5ml concentration are 2% Potassium Persulphate, 8 μ l N, N, N ', N '-Tetramethyl Ethylene Diamine changes over to after stirring in the 3ml cuvette, sealing standing and reacting 30 hours obtains the silicon dioxide base Nanometer composite hydrogel.
When this gel was 95% at compressive set, stress was 7.8MPa, remove pressure after, the hydrogel immediate recovery to the compression before shape.
Referring to Fig. 4, be the functionalized nano SiO of 4 method preparations of example
2Hydrogel and functionalized nano SiO not
2Hydrogel compressive strain-stress curve comparison diagram.Can find out the functionalized nano SiO of the present invention's preparation
2Strain-the stress performance of hydrogel is better than existing not functionalized nano SiO far away
2Hydrogel.
Example 5
1.5g methyl allyl acyloxypropyl trimethoxysilane, 8ml dehydrated alcohol, the hydrochloric acid soln of 9g pH=3 join in the 50ml reaction flask, ultrasonic 30 minutes, make the silane complete hydrolysis, and be 30% nanometer SiO with silane and the 30g concentration of hydrolysis
2Solution, the 11g deionized water joined in the round-bottomed flask, 50 ℃ of stirred in water bath 4 hours, after stirring end reaction solution is transferred in the beaker, add 500 ether, acetone mixed solution (mass ratio 3:2), vigorous stirring, with the solution centrifuge tube of packing into, centrifugal 8min under the 8000r/min condition in the lower floor's solid redispersion and deionized water that obtains, dialyses the aqueous solution dialysis tubing of packing into 1 week, change water in per 24 hours, and obtained water miscible functionalized nano SiO
2Solution, being concentrated into concentration with Rotary Evaporators is 25%
Nanometer SiO with the functionalization of 9.5g
2Solution joins in the 30ml bottle, logical nitrogen is 4 hours under the magnetic agitation condition, add the 1.13gN-N-isopropylacrylamide, stirred 40 minutes under the condition of nitrogen gas, ice-water bath 10 minutes, adding 0.5ml concentration is 2% Potassium Persulphate, 8 μ l Diisopropyl azodicarboxylates, change over to after stirring in the 3ml cuvette, sealing standing and reacting 36 hours obtains the silicon dioxide base Nanometer composite hydrogel.
When this gel was 95% at compressive set, stress was 8.2MPa.After removing pressure, the hydrogel immediate recovery is to the front shape of compression.
Referring to Fig. 5, be the prepared functionalized nano SiO of example 5
2Hydrogel and functionalized nano SiO not
2Before the hydrogel compression and be compressed to 95% photo in kind after recovering, wherein (a) (b) is the nanometer SiO of functionalization
2Solution prepares the comparison diagram before and after the hydrogel compression, (c), (d) is the nanometer SiO of functionalization not
2Solution prepares the comparison diagram before and after the hydrogel compression.Can find out obviously that change not quite before and after the hydrogel compression of the present invention, compressive strength is far longer than the nanometer SiO of existing not functionalization
2Solution.
Example 6
2g vinyl ('beta '-methoxy oxyethyl group) silane, 10ml dehydrated alcohol, the hydrochloric acid soln of 10g pH=5 join in the 50ml reaction flask, and ultrasonic 30 minutes, make the silane complete hydrolysis, be 30% nanometer SiO with silane and the 30g concentration of hydrolysis
2Solution, the 10g deionized water joined in the round-bottomed flask, 50 ℃ of stirred in water bath 4 hours, after stirring end reaction solution is transferred in the beaker, add 500 ether, acetone mixed solution (mass ratio 2:3), vigorous stirring, with the solution centrifuge tube of packing into, centrifugal 5min under the 10000r/min condition in the lower floor's solid redispersion and deionized water that obtains, dialyses the aqueous solution dialysis tubing of packing into 1 week, change water in per 24 hours, and obtained water miscible functionalized nano SiO
2Solution, being concentrated into concentration with Rotary Evaporators is 20%
Nanometer SiO with the functionalization of 9.5g
2Solution joins in the 30ml bottle, logical nitrogen is 5 hours under the magnetic agitation condition, add the 1.01g N hydroxymethyl acrylamide, stirred 30 minutes under the condition of nitrogen gas, ice-water bath 50 minutes, adding 0.5ml concentration is 2% Sulfothiorine, 8 μ l Diisopropyl azodicarboxylates, change over to after stirring in the 3ml cuvette, sealing standing and reacting 48 hours obtains the silicon dioxide base Nanometer composite hydrogel.
When this gel was 95% at compressive set, stress was 7.6MPa, remove pressure after, the hydrogel immediate recovery to the compression before shape.
More than to the preparation method of the high water soluble Nano particles of silicon dioxide of the preparation method of the high water soluble Nano particles of silicon dioxide of a kind of silane-functionalized provided by the present invention and silane-functionalized, be described in detail, used specific case herein principle of the present invention and embodiment are set forth, the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; Simultaneously, for one of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, in sum, this description should not be construed as limitation of the present invention.
Claims (8)
1. the preparation method of the high water soluble Nano particles of silicon dioxide of a silane-functionalized is characterized in that, comprising:
With the hydrochloric acid soln of silane coupling agent and 6 times of pH=1 to the silane coupling agent quality-5, and dehydrated alcohol joins in the reaction vessels the ultrasonic silane coupling agent complete hydrolysis that makes;
Silane coupling agent, nanometer SiO with hydrolysis
2Solution and deionized water, reaction is 1-4 hour in liquid bath, and temperature is controlled at 40-80 ℃;
Add organic solvent extraction, the lower floor's solid redispersion that obtains after centrifugal is in deionized water;
The functionalized nano SiO of highly water-soluble will be obtained after the aqueous solution dialysis that disperse to obtain
2Solution;
Wherein, the organic solvent of described extraction usefulness is a kind of or mixture in tetrahydrofuran (THF), ether, acetone, methyl alcohol, the ethanol, and the organic solvent quality of extraction usefulness is 6:1-10:1 with the mass ratio that is extracted liquid.
2. the method for claim 1 is characterized in that,
Silane coupling agent is 0.1-5g;
Dehydrated alcohol is 2-10ml;
Nanometer SiO
2Solution is 30% the nanometer SiO of 5-35g
2Solution.
3. the method for claim 1 is characterized in that,
Silane coupling agent is vinyltriethoxysilane, vinyltrimethoxy silane, a kind of in methyl allyl acyloxypropyl trimethoxysilane or vinyl ('beta '-methoxy oxyethyl group) silane.
4. one kind prepares the method for high strength silicon dioxide base Nanometer composite hydrogel based on claim 1 high water soluble Nano particles of silicon dioxide, it is characterized in that, comprising:
To functionalized nano SiO
2Solution led to nitrogen 1-6 hour under the magnetic agitation condition;
Adding monomer under logical inert gas conditions stirred 5-30 minute;
Ice-water bath 5-50 minute;
After adding the stirring of initiator and catalyzer, move into to seal in the container and left standstill 12-48 hour, obtain high-intensity silicon dioxide base Nanometer composite hydrogel.
5. method as claimed in claim 4 is characterized in that,
Described monomer is acrylamide, NIPA, a kind of in N,N-DMAA and the N hydroxymethyl acrylamide.
6. method as claimed in claim 4 is characterized in that,
Described catalyzer is N, N, N ', N '-Tetramethyl Ethylene Diamine, a kind of in trolamine and the Sulfothiorine.
7. method as claimed in claim 4 is characterized in that,
Described initiator is Potassium Persulphate, a kind of in ammonium persulphate and the Diisopropyl azodicarboxylate.
8. method as claimed in claim 4 is characterized in that
Described rare gas element is nitrogen, a kind of in helium and the argon gas.
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CN104710584B (en) * | 2015-03-16 | 2018-08-03 | 清华大学 | macromolecule hydrogel and preparation method thereof |
ES2753723T3 (en) * | 2016-03-24 | 2020-04-14 | Sika Tech Ag | A composition of single or multiple components to produce a hydrogel |
CN108409901A (en) * | 2018-03-08 | 2018-08-17 | 东南大学 | A kind of Nanometer composite hydrogel and preparation method thereof |
CN109758618A (en) * | 2018-12-14 | 2019-05-17 | 重庆科技学院 | A kind of anti-bacterial hydrogel and preparation method thereof of nano-silver ionic controllability release |
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