CN108659440A - A kind of secondary swell cross obtains the preparation method of high intensity hydrogel - Google Patents
A kind of secondary swell cross obtains the preparation method of high intensity hydrogel Download PDFInfo
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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Abstract
The present invention provides the preparation methods that a kind of secondary swell cross obtains high intensity hydrogel.The sodium metasilicate of low concentration is dissolved in water together with acrylamide and sodium alginate first, cause acrylamide polymerization, through calcium ion crosslinking in hydrogel the larger calcium silicates nano-particle of situ Particles, then the hybridized hydrogel is dipped into sodium silicate aqueous solution again, moderately swelling makes sodium metasilicate be diffused into hydrogel to hydrogel, again by the hydrogel calcium ion crosslinking after swelling, the more calcium silicates nano-particles of in-situ preparation in hydrogel.It is reacted with calcium silicates using the hydrogen ion of glucono-delta-lactone hydrolysis release, generates the calcium silicates of surface containing mesopore silica gel.With calcium alginate and polyacrylamide hydrogen bond action, the intensity to improve hydrogel and the stability under physiological environment occur for mesoporous silica gel.The preparation method is simple and quick, and material has good biocompatibility, can be used as articular cartilage substitute.
Description
Technical field
The present invention relates to the preparation methods that a kind of secondary swell cross obtains high intensity hydrogel, belong to functional material neck
Domain.
Background technology
The multicomponent system that macromolecule hydrogel is made of polymer three-dimensional network and water, be widely used in industry,
Agricultural, biology and Material Field.But common hydrogel intensity is low, limits its further practical application.Gong Jianping etc. is carried
The thought for going out " double-layer network " hydrogel, it is internal to close on the basis of forming the gel of the first layer network of rigidity of high-crosslinking-degree
At lower flexible second layer network of the degree of cross linking.But double chemical network cross-linked hydrogels need two-stage polymerization, preparation process
It is more complicated【Advanced Materials.2014,26：436-442】.Lock will just et al. be prepared for high resiliency height with one-step method
Toughness polyacrylamide/calcium alginate (PAM/CaAlg) double-network hydrogel【Nature, 2012,489 (7414)：133-
136】, this hydrogel has good biocompatibility, excellent lubricity and wearability, can reach and substitutes cartilaginous tissue and want
It asks.Bakarich etc. is prepared for fibre-reinforced PAM/CaAlg hydrogel artificials articular cartilage substitute using 3D printing technique
【ACS Applied Materials＆Interfaces, 2014,6 (18)：15998-16006】.But under physiological environment, on
The cross-linking ion stated in double-network hydrogel is released, and the mechanical property of gel is made to decline rapidly.Liu Mingzhu etc. is by dioxy
SiClx is introduced into PAM/CaAlg hydrogels, improves the fracture strength and Young's modulus of the dual network gel【Chemical
Engineering Journal, 2014,240 (6)：331-337】.Kim et al. is deposited using between mesopore molecular sieve and polymer
Van der Waals force and hydrogen bond action, obtained can in physiological solution the long period keep mechanical property PAM/CaAlg it is miscellaneous
Change hydrogel.Wu De at et al. short chain chitosans (CS) are integrated by hydrogen bond action in polyacrylamide network first, make
It forms CS crystallites and entanglement network, obtains the double-network hydrogel with high-mechanical property【Advanced Materials,
2016,28 (33), 7178-7184】.But swelling problem of the hydrogel under physiological environment does not solve.Tiller etc. passes through
Enzyme initiation forms evenly dispersed nano-calcium phosphate in double-network hydrogel, and the elasticity modulus of hydrogel is made to reach
440MPa【Nature, 2017,543 (7645)：407-410】, but its toughness is poor, it is difficult to it is applied to cartilage and substitutes.
The present invention provides the preparation methods that a kind of secondary swell cross obtains high intensity hydrogel.First by low concentration
Sodium metasilicate be dissolved in water together with acrylamide and sodium alginate, cause acrylamide polymerization, through calcium ion crosslinking in hydrogel
The larger calcium silicates nano-particle of middle situ Particles, is then dipped into sodium silicate aqueous solution again by the hybridized hydrogel
In, moderately swelling makes sodium metasilicate be diffused into hydrogel to hydrogel, again by the hydrogel calcium ion crosslinking after swelling, in water
The more calcium silicates nano-particles of in-situ preparation in gel.Utilize the hydrogen ion and silicic acid of glucono-δ-lactone hydrolysis release
Calcium reacts, and generates the calcium silicates of surface containing mesopore silica gel.With calcium alginate and polyacrylamide hydrogen bond action occurs for mesoporous silica gel,
Intensity to improve hydrogel and the stability under physiological environment.
Invention content
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is polyacrylamide/calcium alginate dual network
The problem of hydrogel is difficult to keep high intensity, high tenacity and low swelling under physiological environment because of calcium ion loss.
The present invention solves the polyacrylamide/calcium alginate double-network hydrogel because calcium ion loss is difficult in physiologic ring
It is to obtain high intensity water-setting by secondary swell cross that technical solution the problem of high intensity, high tenacity and low swelling is kept under border
Glue.
The present invention provides the preparation methods that a kind of secondary swell cross obtains high intensity hydrogel, it is characterized in that include with
Lower step：
A) 0.01-2g sodium metasilicate, 5-15g acrylamides, 0.5-2g sodium alginates, acrylamide mass percent are weighed
The chemical cross-linking agent of 0.03%-0.30% is dissolved in together in 50-100ml deionized waters, and stirring and dissolving is uniform, after standing defoaming
Obtain casting solution；
B) the solubility calcium saline solution that mass percent is 0.5%-50% is prepared；
C) it is added the ammonium persulfate of acrylamide mass percent 0.1%-5% in the casting solution prepared to step a), third
The tetramethyl second of the sodium hydrogensulfite and acrylamide mass percent 0.01%-2% of acrylamide mass percent 0.1%-5%
Diamines is poured this solution on the glass plate of dry cleansing, is spread to knifing stick in homogeneous thickness after being dispersed with stirring uniformly immediately
Liquid film, in N2The lower ultraviolet irradiation 1-30min of protection causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinkings of step c) and glass plate are dipped into the solubility that step b) is obtained together
In calcium saline solution, 0.1-24h is impregnated, peels gel mould from glass plate in soaking process, soluble calcium salt and sea
The calcium alginate hydrogel of mosanom reacting forming ion cross-linked network structure, while soluble calcium salt is reacted with sodium metasilicate poly-
In-situ preparation calcium silicates nano-particle in acrylamide/calcium alginate hydrogel, passes through between calcium silicates and alginic acid strand
Calcium ion crosslinking forms organic-inorganic hybrid structure, these hybrid structures improve the stability of alginate network, increases
Strong " tangling effect " between alginate network and polyacrylamide network shares bearer network and deforms answering of being shifted
Power improves the intensity of hybridized hydrogel, reduces swelling of the hydrogel under physiological environment；
E) gel mould containing calcium silicates that step d) is obtained is cleaned into removal surface calcium ion with deionized water, is dipped into matter
0.1-24h in the sodium silicate aqueous solution that percent concentration is 0.001%-5% is measured, sodium metasilicate is made to be diffused into the hydrogel of swelling
In, then, the hydrogel of swelling is immersed in solubility calcium saline solution 0.1-24h again and carries out secondary calcium ion crosslinking；
F) the glucono-δ-lactone aqueous solution that mass percent concentration is 0.1%-10% is prepared, step e) is obtained
The gel mould of secondary calcium ion crosslinking be dipped into 0.1-24h in glucono-δ-lactone aqueous solution, glucono-δ-lactone
Hydrolysis releases hydrogen ion, and hydrogen ion is reacted with calcium silicates, forms mesoporous silica gel structure in calcium silicates nanoparticle surface, obtains
A kind of hybridized hydrogel keeping high intensity under physiological environment；With calcium alginate and polyacrylamide hydrogen bond occurs for mesoporous silica gel
Interaction adds the enhancement effect of nano-particle, improves polyacrylamide/calcium alginate hydrogel under physiological environment
Mechanical stability and anti-swelling.
Chemical cross-linking agent of the present invention is ethylene glycol dimethacrylate, divinylbenzene, N, N '-di-2-ethylhexylphosphine oxides
Any one in acrylamide and diisocyanate or two or more mixtures, the solubility calcium saline solution are nitric acid
Any one in calcium, calcium chloride, calcium dihydrogen phosphate, calcium sulfate aqueous solution or two or more mixtures.
Preparation method of the present invention is simple, does not use any organic solvent, therefore obtained Biocompatibility is good, can be with
For artificial skin, articular cartilage substitute and artificial tendon.
Specific implementation mode
Specific embodiments of the present invention are described below, but the present invention should not be limited by the examples.
Embodiment 1.
A) 0.01g sodium metasilicate is weighed, 5g acrylamides, 0.5g sodium alginates, acrylamide mass percent 0.03%
Ethylene glycol dimethacrylate is dissolved in together in 50ml deionized waters, and stirring and dissolving is uniform, and casting film is obtained after standing defoaming
Liquid；
B) calcium nitrate aqueous solution that mass percent is 0.5% is prepared；
C) ammonium persulfate of acrylamide mass percent 0.1%, acryloyl are added in the casting solution prepared to step a)
The tetramethylethylenediamine of the sodium hydrogensulfite and acrylamide mass percent 0.01% of amine mass percent 0.1%, stirring point
After dissipating uniformly, pours this solution into immediately on the glass plate of dry cleansing, liquid film in homogeneous thickness is spread to knifing stick, in N2It protects
The lower ultraviolet irradiation 1min of shield causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinkings of step c) and glass plate are dipped into the calcium nitrate that step b) is obtained together
In aqueous solution, 0.1h is impregnated, is peeled gel mould from glass plate in soaking process, calcium nitrate reacts shape with sodium alginate
At the calcium alginate hydrogel of ionomer network structure, while calcium nitrate is reacted with sodium metasilicate in polyacrylamide/alginic acid
In-situ preparation calcium silicates nano-particle in calcium hydrogel, is formed between calcium silicates and alginic acid strand by calcium ion crosslinking
Machine-inorganic hybrid structure, these hybrid structures improve the stability of alginate network, enhance alginate network
" effect of tangling " between polyacrylamide network shares bearer network and deforms shifted stress, improve hybridized hydrogel
Intensity, reduce swelling of the hydrogel under physiological environment；
E) gel mould containing calcium silicates that step d) is obtained is cleaned into removal surface calcium ion with deionized water, is dipped into matter
0.1h in the sodium silicate aqueous solution that percent concentration is 0.001% is measured, sodium metasilicate is made to be diffused into the hydrogel of swelling, then,
The hydrogel of swelling is immersed in calcium nitrate aqueous solution 0.1h again and carries out secondary calcium ion crosslinking；
F) the glucono-δ-lactone aqueous solution that mass percent concentration is 0.1% is prepared, step e) is obtained secondary
The gel mould of calcium ion crosslinking is dipped into 0.1h in glucono-δ-lactone aqueous solution, and glucono-δ-lactone hydrolysis releases
Hydrogen ion, hydrogen ion are reacted with calcium silicates, are formed mesoporous silica gel structure in calcium silicates nanoparticle surface, are obtained one kind in physiology
The hybridized hydrogel of high intensity is kept under environment；With calcium alginate and polyacrylamide interaction of hydrogen bond occurs for mesoporous silica gel,
Along with the enhancement effect of nano-particle, it is steady to improve mechanics of the polyacrylamide/calcium alginate hydrogel under physiological environment
Qualitative and anti-swelling.
Embodiment 2.
A) 2g sodium metasilicate is weighed, 15g acrylamides, 2g sodium alginates, the two of acrylamide mass percent 0.30% are different
Cyanate is dissolved in together in 100ml deionized waters, and stirring and dissolving is uniform, and casting solution is obtained after standing defoaming；
B) calcium chloride water that mass percent is 50% is prepared；
C) ammonium persulfate of acrylamide mass percent 5%, acrylamide are added in the casting solution prepared to step a)
The tetramethylethylenediamine of the sodium hydrogensulfite and acrylamide mass percent 2% of mass percent 5% is dispersed with stirring uniformly
Afterwards, it pours this solution into immediately on the glass plate of dry cleansing, liquid film in homogeneous thickness is spread to knifing stick, in N2The lower purple of protection
External exposure 30min causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinkings of step c) and glass plate are dipped into the calcium chloride that step b) is obtained together
In aqueous solution, impregnates for 24 hours, peel gel mould from glass plate in soaking process, calcium chloride reacts shape with sodium alginate
At the calcium alginate hydrogel of ionomer network structure, while calcium chloride is reacted with sodium metasilicate in polyacrylamide/alginic acid
In-situ preparation calcium silicates nano-particle in calcium hydrogel, is formed between calcium silicates and alginic acid strand by calcium ion crosslinking
Machine-inorganic hybrid structure, these hybrid structures improve the stability of alginate network, enhance alginate network
" effect of tangling " between polyacrylamide network shares bearer network and deforms shifted stress, improve hybridized hydrogel
Intensity, reduce swelling of the hydrogel under physiological environment；
E) gel mould containing calcium silicates that step d) is obtained is cleaned into removal surface calcium ion with deionized water, is dipped into matter
It measures in the sodium silicate aqueous solution that percent concentration is 5% for 24 hours, so that sodium metasilicate is diffused into the hydrogel of swelling, then, will be swollen
Hydrogel be immersed in calcium chloride water again and carry out secondary calcium ion crosslinking for 24 hours；
F) the glucono-δ-lactone aqueous solution that mass percent concentration is 10% is prepared, step e) is obtained secondary
The gel mould of calcium ion crosslinking is dipped into glucono-δ-lactone aqueous solution for 24 hours, and glucono-δ-lactone hydrolysis releases
Hydrogen ion, hydrogen ion are reacted with calcium silicates, are formed mesoporous silica gel structure in calcium silicates nanoparticle surface, are obtained one kind in physiology
The hybridized hydrogel of high intensity is kept under environment；With calcium alginate and polyacrylamide interaction of hydrogen bond occurs for mesoporous silica gel,
Along with the enhancement effect of nano-particle, it is steady to improve mechanics of the polyacrylamide/calcium alginate hydrogel under physiological environment
Qualitative and anti-swelling.
Embodiment 3.
A) 1g sodium metasilicate, 1g acrylamides, 1g sodium alginates, the N of acrylamide mass percent 0.10%, N '-are weighed
Methylene-bisacrylamide is dissolved in together in 60ml deionized waters, and stirring and dissolving is uniform, and casting solution is obtained after standing defoaming；
B) calcium dihydrogen phosphate aqueous solution that mass percent is 5% is prepared；
C) ammonium persulfate of acrylamide mass percent 1%, acrylamide are added in the casting solution prepared to step a)
The tetramethylethylenediamine of the sodium hydrogensulfite and acrylamide mass percent 1% of mass percent 1% is dispersed with stirring uniformly
Afterwards, it pours this solution into immediately on the glass plate of dry cleansing, liquid film in homogeneous thickness is spread to knifing stick, in N2The lower purple of protection
External exposure 10min causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinkings of step c) and glass plate are dipped into the di(2-ethylhexyl)phosphate that step b) is obtained together
In hydrogen calcium aqueous solution, 1h is impregnated, is peeled gel mould from glass plate in soaking process, calcium dihydrogen phosphate and sodium alginate
The calcium alginate hydrogel of reacting forming ion cross-linked network structure, while calcium dihydrogen phosphate is reacted with sodium metasilicate in polyacrylamide
In-situ preparation calcium silicates nano-particle in amine/calcium alginate hydrogel, passes through calcium ion between calcium silicates and alginic acid strand
It is cross-linked to form hybrid inorganic-organic structure, these hybrid structures improve the stability of alginate network, enhance sea
" effect of tangling " between alginates network and polyacrylamide network shares bearer network and deforms shifted stress, improve
The intensity of hybridized hydrogel reduces swelling of the hydrogel under physiological environment；
E) gel mould containing calcium silicates that step d) is obtained is cleaned into removal surface calcium ion with deionized water, is dipped into matter
1h in the sodium silicate aqueous solution that percent concentration is 1% is measured, so that sodium metasilicate is diffused into the hydrogel of swelling, then, will be swollen
Hydrogel be immersed in calcium dihydrogen phosphate aqueous solution 1h again and carry out secondary calcium ion crosslinking；
F) the glucono-δ-lactone aqueous solution that mass percent concentration is 1%, the secondary calcium that step e) is obtained are prepared
The gel mould of ionomer is dipped into 1h in glucono-δ-lactone aqueous solution, glucono-δ-lactone hydrolysis release hydrogen from
Son, hydrogen ion are reacted with calcium silicates, are formed mesoporous silica gel structure in calcium silicates nanoparticle surface, are obtained one kind in physiological environment
The lower hybridized hydrogel for keeping high intensity；With calcium alginate and polyacrylamide interaction of hydrogen bond occurs for mesoporous silica gel, then adds
The enhancement effect of upper nano-particle improves mechanical stability of the polyacrylamide/calcium alginate hydrogel under physiological environment
And anti-swelling.
Embodiment 4.
A) 1.5g sodium metasilicate is weighed, 10g acrylamides, 1.5g sodium alginates, acrylamide mass percent 0.10%
Divinylbenzene is dissolved in together in 80ml deionized waters, and stirring and dissolving is uniform, and casting solution is obtained after standing defoaming；
B) the calcium sulfate aqueous solution that mass percent is 1% is prepared；
C) ammonium persulfate of acrylamide mass percent 1%, acrylamide are added in the casting solution prepared to step a)
The tetramethylethylenediamine of the sodium hydrogensulfite and acrylamide mass percent 1% of mass percent 1% is dispersed with stirring uniformly
Afterwards, it pours this solution into immediately on the glass plate of dry cleansing, liquid film in homogeneous thickness is spread to knifing stick, in N2The lower purple of protection
External exposure 3min causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinkings of step c) and glass plate are dipped into the calcium sulfate that step b) is obtained together
In aqueous solution, 2h is impregnated, is peeled gel mould from glass plate in soaking process, calcium sulfate reacts to be formed with sodium alginate
The calcium alginate hydrogel of ionomer network structure, while calcium sulfate is reacted with sodium metasilicate in polyacrylamide/calcium alginate
In-situ preparation calcium silicates nano-particle in hydrogel, is formed between calcium silicates and alginic acid strand by calcium ion crosslinking
Machine-inorganic hybrid structure, these hybrid structures improve the stability of alginate network, enhance alginate network
" effect of tangling " between polyacrylamide network shares bearer network and deforms shifted stress, improve hybridized hydrogel
Intensity, reduce swelling of the hydrogel under physiological environment；
E) gel mould containing calcium silicates that step d) is obtained is cleaned into removal surface calcium ion with deionized water, is dipped into matter
2h in the sodium silicate aqueous solution that percent concentration is 2% is measured, so that sodium metasilicate is diffused into the hydrogel of swelling, then, will be swollen
Hydrogel be immersed in calcium sulfate aqueous solution 2h again and carry out secondary calcium ion crosslinking；
F) the glucono-δ-lactone aqueous solution that mass percent concentration is 2%, the secondary calcium that step e) is obtained are prepared
The gel mould of ionomer is dipped into 2h in glucono-δ-lactone aqueous solution, glucono-δ-lactone hydrolysis release hydrogen from
Son, hydrogen ion are reacted with calcium silicates, are formed mesoporous silica gel structure in calcium silicates nanoparticle surface, are obtained one kind in physiological environment
The lower hybridized hydrogel for keeping high intensity；With calcium alginate and polyacrylamide interaction of hydrogen bond occurs for mesoporous silica gel, then adds
The enhancement effect of upper nano-particle improves mechanical stability of the polyacrylamide/calcium alginate hydrogel under physiological environment
And anti-swelling.
Claims (3)
1. a kind of secondary swell cross obtains the preparation method of high intensity hydrogel, it is characterized in that including the following steps：
A) 0.01-2g sodium metasilicate, 5-15g acrylamides, 0.5-2g sodium alginates, acrylamide mass percent are weighed
The chemical cross-linking agent of 0.03%-0.30% is dissolved in together in 50-100ml deionized waters, and stirring and dissolving is uniform, after standing defoaming
Obtain casting solution；
B) the solubility calcium saline solution that mass percent is 0.5%-50% is prepared；
C) ammonium persulfate of acrylamide mass percent 0.1%-5%, acryloyl are added in the casting solution prepared to step a)
The tetramethyl second two of the sodium hydrogensulfite and acrylamide mass percent 0.01%-2% of amine mass percent 0.1%-5%
Amine pours this solution on the glass plate of dry cleansing after being dispersed with stirring uniformly, liquid in homogeneous thickness is spread to knifing stick immediately
Film, in N2The lower ultraviolet irradiation 1-30min of protection causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinkings of step c) and glass plate are dipped into the soluble calcium salt that step b) is obtained together
In aqueous solution, 0.1-24h is impregnated, is peeled gel mould from glass plate in soaking process, soluble calcium salt and alginic acid
The calcium alginate hydrogel of sodium reacting forming ion cross-linked network structure, while soluble calcium salt is reacted with sodium metasilicate in polypropylene
In-situ preparation calcium silicates nano-particle in amide/calcium alginate hydrogel, between calcium silicates and alginic acid strand by calcium from
Son is cross-linked to form hybrid inorganic-organic structure, these hybrid structures improve the stability of alginate network, enhance
" effect of tangling " between alginate network and polyacrylamide network shares bearer network and deforms shifted stress, carry
The intensity of high hybridized hydrogel reduces swelling of the hydrogel under physiological environment；
E) gel mould containing calcium silicates that step d) is obtained with deionized water is cleaned to the calcium ion for removing surface, be dipped into quality
0.1-24h in the sodium silicate aqueous solution that percent concentration is 0.001%-5%, makes sodium metasilicate be diffused into the hydrogel of swelling,
Then, the hydrogel of swelling is immersed in solubility calcium saline solution 0.1-24h again and carries out secondary calcium ion crosslinking；
F) the glucono-δ-lactone aqueous solution that mass percent concentration is 0.1%-10%, two that step e) is obtained are prepared
The gel mould of secondary calcium ion crosslinking is dipped into 0.1-24h in glucono-δ-lactone aqueous solution, glucono-δ-lactone hydrolysis
Hydrogen ion is released, hydrogen ion is reacted with calcium silicates, is formed mesoporous silica gel structure in calcium silicates nanoparticle surface, is obtained one kind
The hybridized hydrogel of high intensity is kept under physiological environment；Mesoporous silica gel and calcium alginate and polyacrylamide generation hydrogen bond are mutual
Effect adds the enhancement effect of nano-particle, improves power of the polyacrylamide/calcium alginate hydrogel under physiological environment
Learn stability and anti-swelling.
2. a kind of secondary swell cross obtains the preparation method of high intensity hydrogel as described in claim 1, it is characterized in that described
Chemical cross-linking agent be ethylene glycol dimethacrylate, divinylbenzene, N, N '-methylene-bisacrylamides and diisocyanate
Any one in ester or two or more mixtures.
3. a kind of secondary swell cross obtains the preparation method of high intensity hydrogel as described in claim 1, it is characterized in that described
Solubility calcium saline solution be calcium nitrate, calcium chloride, calcium dihydrogen phosphate, any one or two kinds in calcium sulfate aqueous solution with
Upper mixture.
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| CN116807520A (en) * | 2023-06-28 | 2023-09-29 | 南方医科大学 | Method for minimally invasive extraction of tissue fluid without damage and pain |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109289947A (en) * | 2018-09-29 | 2019-02-01 | 浙江大学 | Gel base micro-fluidic chip and its manufacturing method based on secondary cross-linking |
| CN110655661A (en) * | 2019-09-30 | 2020-01-07 | 常州大学 | Preparation method of polyacrylic acid-polyacrylamide double-network hydrogel |
| CN111286814A (en) * | 2020-03-18 | 2020-06-16 | 东华大学 | Method for preparing nano composite fiber by utilizing groove type hydraulic gelation |
| CN111286814B (en) * | 2020-03-18 | 2021-07-20 | 东华大学 | Method for preparing nano composite fiber by utilizing groove type hydraulic gelation |
| CN113527723A (en) * | 2021-08-13 | 2021-10-22 | 东北石油大学 | Discontinuous phase profile control and flooding agent and preparation method and application thereof |
| CN113527723B (en) * | 2021-08-13 | 2022-10-04 | 东北石油大学 | Discontinuous phase profile control and flooding agent and preparation method and application thereof |
| CN115432995A (en) * | 2022-06-28 | 2022-12-06 | 广州市北二环交通科技有限公司 | Perforated brick prepared by utilizing engineering waste slurry |
| CN115432995B (en) * | 2022-06-28 | 2023-09-12 | 广州市北二环交通科技有限公司 | Porous brick prepared from engineering waste slurry |
| CN115554462A (en) * | 2022-10-31 | 2023-01-03 | 西安交通大学 | Anti-swelling injectable hydrogel adhesive and preparation method thereof |
| CN115554462B (en) * | 2022-10-31 | 2023-09-22 | 西安交通大学 | Anti-swelling injectable hydrogel adhesive and preparation method thereof |
| CN116807520A (en) * | 2023-06-28 | 2023-09-29 | 南方医科大学 | Method for minimally invasive extraction of tissue fluid without damage and pain |
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