CN109021256A - A kind of hybrid cross-linked and pre-stretching obtains the preparation method of low swelling high intensity hydrogel - Google Patents
A kind of hybrid cross-linked and pre-stretching obtains the preparation method of low swelling high intensity hydrogel Download PDFInfo
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Abstract
The present invention provides the preparation methods that a kind of hybrid cross-linked and pre-stretching obtains low swelling high intensity hydrogel.First sodium metasilicate is dissolved in water together with acrylamide and sodium alginate, causes acrylamide polymerization, through calcium ion crosslinking in hydrogel in-situ preparation calcium silicates nanoparticle.Organic-inorganic hybrid structure is formed by calcium ion crosslinking between calcium silicates and alginic acid strand, these hybrid structures improve the stability of alginate network, enhance " effect of tangling " between alginate network and polyacrylamide network, it shares bearer network and deforms shifted stress, the intensity for improving hybridized hydrogel, reduces its swelling under physiological environment.It is reacted using the hydrogen ion of glucono-δ-lactone hydrolysis release with calcium silicates, generates the calcium silicates of surface containing mesopore silica gel.Make nanoparticle and polymer orientation in hydrogel by pre-stretching processing, further increases the intensity of hybridized hydrogel.
Description
Technical field
The present invention relates to the preparation methods that a kind of hybrid cross-linked and pre-stretching obtains low swelling high intensity hydrogel, belong to function
It can material and technical field of biological material.
Background technique
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.Hydrogel is a kind of high molecular material similar to vital tissues, there is good bio-compatible
Property, the metabolic process of life entity is not influenced, and metabolite can be discharged by hydrogel, thus can be used as tissue filling
Agent.In addition polyalcohol hydrogel can be made into the carrier that microcapsules are used as drug, and drug is sent to the somewhere of organism organ
It slowly discharges again.But common hydrogel intensity is low, limits its further practical application.High intensity hydrogel in recent years
Research achieve impressive progress.Gong Jianping etc. proposes the thought of " double-layer network " hydrogel, in the rigidity for forming high-crosslinking-degree
On the basis of the gel of first layer network, the internal synthesizing cross-linked lower flexible second layer network [Advanced of degree
Materials.2014,26:436-442].But double chemical network cross-linked hydrogels need two-stage polymerization, preparation process ratio
It is more complex.The report lock of Nature periodical in 2012 will just et al. has been prepared for high-elasticity high-ductility polyacrylamide/sea with one-step method
Calcium alginate (PAM/CaAlg) double-network hydrogel [Nature, 2012,489 (7414): 133-136].This hydrogel has good
Biocompatibility, excellent lubricity and wearability, can reach substitution cartilaginous tissue requirement [Biomaterials, 2013,
34 (33): 8042-8048].Bakarich etc. is prepared for fibre-reinforced PAM/CaAlg hydrogel artificial using 3D printing technique
Articular cartilage substitute [ACS Applied Materials&Interfaces, 2014,6 (18): 15998-16006].But
Under physiological environment, the cross-linking ion in above-mentioned double-network hydrogel is released, and declines the mechanical property of gel rapidly.
Building has high intensity, high tenacity and the hydrogel of low swelling under physiological environment, and there are still very big challenges at present.
Professor Liu Wenguang etc. is prepared for the supramolecular hydrogel that intensity is 4 times of human body cartilage, this water-setting with hydrogen bond self-identifying mechanism
Glue can be kept in the acid-base solution of different pH value preferable mechanical property [Advanced Materials, 2015,27
(23): 3566-35-7].Silica is introduced into PAM/CaAlg hydrogel by Liu Mingzhu etc., improves the dual network gel
Fracture strength and Young's modulus [Chemical Engineering Journal, 2014,240 (6): 331-337].Kim et al.
Using Van der Waals force existing between mesopore molecular sieve and polymer and hydrogen bond action, obtain when can be longer in physiological solution
Between keep mechanical property PAM/CaAlg hybridized hydrogel [Advanced Functional Materials, 2017, DOI:
10.1002/adfm.201703826].Wu De at et al. short chain chitosans (CS) are integrated into poly- third by hydrogen bond action first
In acrylamide network, CS crystallite and entanglement network are formed it into, obtains the double-network hydrogel with high-mechanical property
[Advanced Materials, 2016,28 (33), 7178-7184].Nature periodical report Tiller in 2017 etc. passes through enzyme
Initiation forms evenly dispersed nano-calcium phosphate in double-network hydrogel, and the elasticity modulus of hydrogel is made to have reached 440MPa
[Nature, 2017,543 (7645): 407-410], but its toughness is poor.
The present invention provides the preparation methods that a kind of hybrid cross-linked and pre-stretching obtains low swelling high intensity hydrogel.First
Sodium metasilicate is dissolved in water together with acrylamide and sodium alginate, causes acrylamide polymerization, through calcium ion crosslinking in hydrogel
Middle in-situ preparation calcium silicates nanoparticle.Organic and inorganic is formed by calcium ion crosslinking between calcium silicates and alginic acid strand
Hybrid structure, these hybrid structures improve the stability of alginate network, enhance alginate network and poly- third
" effect of tangling " between acrylamide network shares bearer network and deforms shifted stress, improve the intensity of hybridized hydrogel,
Reduce its swelling under physiological environment.It is reacted, is generated with calcium silicates using the hydrogen ion of glucono-δ-lactone hydrolysis release
The calcium silicates of surface containing mesopore silica gel.Make nanoparticle and polymer orientation in hydrogel by pre-stretching processing, further
Improve the intensity of hybridized hydrogel.The preparation method is simple and quick, does not introduce any toxic reagent, and material has good life
Object compatibility can be used as articular cartilage substitute.
Summary of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is polyacrylamide/calcium alginate dual network
Hydrogel is difficult to have the problem of high-intensitive, 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
The technical solution for having the problem of high-intensitive, high tenacity and low swelling under border is to design one kind to obtain by hybrid cross-linked and pre-stretching
The low swelling high intensity hydrogel obtained.
It is special the present invention provides the preparation method that a kind of hybrid cross-linked and pre-stretching obtains low swelling high intensity hydrogel
Sign be the following steps are included:
A) 0.01-2g sodium metasilicate, 5-15g acrylamide, 0.5-2g sodium alginate, acrylamide mass percent are weighed
The chemical cross-linking agent of 0.03%-0.30% is dissolved in together in 50-100ml deionized water, and stirring and dissolving is uniform, after standing defoaming
Casting solution is obtained, is placed in spare in sterile chamber；
B) the solubility calcium saline solution that mass percent is 0.5%-50% is prepared；
C) to step a) prepare casting solution in be added acrylamide mass percent 0.1%-5% ammonium persulfate, third
The sodium hydrogensulfite of acrylamide mass percent 0.1%-5% and the tetramethyl second of acrylamide mass percent 0.01%-2%
Diamines is poured this solution on the glass plate of dry cleansing immediately, is spread to knifing stick in homogeneous thickness after being dispersed with stirring uniformly
Liquid film, in N2Lower ultraviolet irradiation 1-30min is protected to cause acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinking 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 nanoparticle 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) the glucono-δ-lactone aqueous solution that mass percent concentration is 0.1%-10% is prepared, step d) is obtained
The gel mould containing calcium silicates be dipped into 0.1-24h in glucono-δ-lactone aqueous solution, glucono-δ-lactone hydrolysis is released
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 and exist
High-intensitive hybridized hydrogel is kept under physiological environment；With calcium alginate and polyacrylamide hydrogen bond phase interaction occurs for mesoporous silica gel
With improving mechanics of the polyacrylamide/calcium alginate hydrogel under physiological environment along with the enhancement effect of nanoparticle
Stability and anti-swelling；
F) in order to further increase the intensity of hydrogel, the hybridized hydrogel prestretching that step e) is obtained is extended into raw footage
0.2-2 times, hybridized hydrogel is then reapposed over the crosslinking of solubility calcium saline solution, the hydridization water-setting in prestretching process
Nanoparticle and polymer chain in glue are orientated along drawing force, and the energy to failure of hybridized hydrogel is improved to original when stretching again
1.1-1.8 times of energy to failure.
Chemical cross-linking agent of the present invention is ethylene glycol dimethacrylate, divinylbenzene, N, N '-di-2-ethylhexylphosphine oxide
Any one in acrylamide and diisocyanate or two or more mixtures, the solubility calcium saline solution are nitric acid
Calcium, calcium chloride, calcium dihydrogen phosphate, any one or two or more mixtures in calcium sulfate aqueous solution.
Preparation method of the present invention is simple, does not use any organic solvent, therefore obtained Biocompatibility is good, can be with
As artificial skin, articular cartilage substitute, artificial tendon etc..
Specific embodiment
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 acrylamide, 0.5g sodium alginate, acrylamide mass percent 0.03%
Ethylene glycol dimethacrylate is dissolved in together in 50ml deionized water, and stirring and dissolving is uniform, obtains casting film after standing defoaming
Liquid is placed in spare in sterile chamber；
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 sodium hydrogensulfite of amine mass percent 0.1% and the tetramethylethylenediamine of acrylamide mass percent 0.01%, stirring point
After dissipating uniformly, is poured this solution on the glass plate of dry cleansing immediately, liquid film in homogeneous thickness is spread to knifing stick, in N2It protects
It protects lower ultraviolet irradiation 1min and causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinking 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 nanoparticle 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) the glucono-δ-lactone aqueous solution that mass percent concentration is 0.1% is prepared, step d) is obtained siliceous
The gel mould of sour calcium is dipped into 0.1h 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
It is lower to keep high-intensitive hybridized hydrogel；Mesoporous silica gel and calcium alginate and polyacrylamide generation interaction of hydrogen bond, then plus
The enhancement effect of upper nanoparticle improves mechanical stability of the polyacrylamide/calcium alginate hydrogel under physiological environment
And anti-swelling；
F) in order to further increase the intensity of hydrogel, the hybridized hydrogel prestretching that step e) is obtained is extended into raw footage
0.2 times, hybridized hydrogel is then reapposed over calcium nitrate aqueous solution crosslinking, in prestretching process in hybridized hydrogel
Nanoparticle and polymer chain are orientated along drawing force, and the energy to failure of hybridized hydrogel is improved to original energy to failure when stretching again
1.1 times.
Embodiment 2.
A) 2g sodium metasilicate, 15g acrylamide, 2g sodium alginate, the diethyl of acrylamide mass percent 0.30% are weighed
Alkenyl benzene is dissolved in together in 100ml deionized water, and stirring and dissolving is uniform, is obtained casting solution after standing defoaming, is placed in sterile appearance
It is spare in device；
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 sodium hydrogensulfite of mass percent 5% and the tetramethylethylenediamine of acrylamide mass percent 2% are 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 crosslinking 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 nanoparticle 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) the glucono-δ-lactone aqueous solution that mass percent concentration is 10% is prepared, step d) is obtained siliceous
The gel mould of sour calcium is dipped into glucono-δ-lactone aqueous solution for 24 hours, and glucono-δ-lactone hydrolysis releases hydrogen ion,
Hydrogen ion is reacted with calcium silicates, is formed mesoporous silica gel structure in calcium silicates nanoparticle surface, is obtained one kind under physiological environment
Keep high-intensitive hybridized hydrogel；Interaction of hydrogen bond occurs for mesoporous silica gel and calcium alginate and polyacrylamide, adds
The enhancement effect of nanoparticle, improve mechanical stability of the polyacrylamide/calcium alginate hydrogel under physiological environment and
Anti-swelling；
F) in order to further increase the intensity of hydrogel, the hybridized hydrogel prestretching that step e) is obtained is extended into raw footage
2 times, hybridized hydrogel is then reapposed over calcium chloride water crosslinking, the receiving in hybridized hydrogel in prestretching process
Rice corpuscles and polymer chain are orientated along drawing force, and the energy to failure of hybridized hydrogel is improved to original energy to failure when stretching again
1.8 again.
Embodiment 3.
A) 1g sodium metasilicate is weighed, 1g acrylamide, 1g sodium alginate, the N of acrylamide mass percent 0.1%, N '-are sub-
Bisacrylamide is dissolved in together in 60ml deionized water, and stirring and dissolving is uniform, obtains casting solution after standing defoaming, is placed
It is spare in sterile chamber；
B) calcium dihydrogen phosphate aqueous solution that mass percent is 2% is prepared；
C) ammonium persulfate of acrylamide mass percent 1%, acrylamide are added in the casting solution prepared to step a)
The sodium hydrogensulfite of mass percent 1% and the tetramethylethylenediamine of acrylamide mass percent 1% are 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 crosslinking 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 nanoparticle 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) the glucono-δ-lactone aqueous solution that mass percent concentration is 5% is prepared, contains silicic acid for what step d) was obtained
The gel mould of calcium is dipped into 1h in glucono-δ-lactone aqueous solution, and glucono-δ-lactone hydrolysis releases hydrogen ion, hydrogen
Ion is reacted with calcium silicates, is formed mesoporous silica gel structure in calcium silicates nanoparticle surface, is obtained one kind and protect under physiological environment
Hold high-intensitive hybridized hydrogel；Interaction of hydrogen bond occurs for mesoporous silica gel and calcium alginate and polyacrylamide, along with receiving
The enhancement effect of rice corpuscles improves mechanical stability of the polyacrylamide/calcium alginate hydrogel under physiological environment and resists
Swellability；
F) in order to further increase the intensity of hydrogel, the hybridized hydrogel prestretching that step e) is obtained is extended into raw footage
0.5 times, hybridized hydrogel is then reapposed over calcium dihydrogen phosphate aqueous solution crosslinking, the hybridized hydrogel in prestretching process
In nanoparticle and polymer chain be orientated along drawing force, the energy to failure of hybridized hydrogel is improved to original disconnected when stretching again
Split 1.4 times of energy.
Embodiment 4.
A) 1.5g sodium metasilicate is weighed, 2g acrylamide, 1.2g sodium alginate, the two of acrylamide mass percent 0.2%
Isocyanates is dissolved in together in 80ml deionized water, and stirring and dissolving is uniform, is obtained casting solution after standing defoaming, is placed in sterile
Containers for future use；
B) the calcium sulfate aqueous solution that mass percent is 1% is prepared；
C) ammonium persulfate of acrylamide mass percent 2%, acrylamide are added in the casting solution prepared to step a)
The sodium hydrogensulfite of mass percent 2% and the tetramethylethylenediamine of acrylamide mass percent 2% are 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 5min causes acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinking 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 nanoparticle 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) the glucono-δ-lactone aqueous solution that mass percent concentration is 2% is prepared, contains silicic acid for what step d) was obtained
The gel mould of calcium is dipped into 2h in glucono-δ-lactone aqueous solution, and glucono-δ-lactone hydrolysis releases hydrogen ion, hydrogen
Ion is reacted with calcium silicates, is formed mesoporous silica gel structure in calcium silicates nanoparticle surface, is obtained one kind and protect under physiological environment
Hold high-intensitive hybridized hydrogel；Interaction of hydrogen bond occurs for mesoporous silica gel and calcium alginate and polyacrylamide, along with receiving
The enhancement effect of rice corpuscles improves mechanical stability of the polyacrylamide/calcium alginate hydrogel under physiological environment and resists
Swellability；
F) in order to further increase the intensity of hydrogel, the hybridized hydrogel prestretching that step e) is obtained is extended into raw footage
1 times, hybridized hydrogel is then reapposed over the crosslinking of calcium sulfate aqueous solution, the receiving in hybridized hydrogel in prestretching process
Rice corpuscles and polymer chain are orientated along drawing force, and the energy to failure of hybridized hydrogel is improved to original energy to failure when stretching again
1.5 again.
Claims (3)
1. a kind of hybrid cross-linked and pre-stretching obtains the preparation method of low swelling high intensity hydrogel, it is characterized in that including following step
It is rapid:
A) 0.01-2g sodium metasilicate, 5-15g acrylamide, 0.5-2g sodium alginate, acrylamide mass percent are weighed
The chemical cross-linking agent of 0.03%-0.30% is dissolved in together in 50-100ml deionized water, and stirring and dissolving is uniform, after standing defoaming
Casting solution is obtained, is placed in spare in sterile chamber；
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 sodium hydrogensulfite of amine mass percent 0.1%-5% and the tetramethyl second two of acrylamide mass percent 0.01%-2%
Amine pours this solution on the glass plate of dry cleansing immediately after being dispersed with stirring uniformly, spreads to liquid in homogeneous thickness with knifing stick
Film, in N2Lower ultraviolet irradiation 1-30min is protected to cause acrylamide polymerization, the gel mould being chemically crosslinked；
D) gel mould of the obtained chemical crosslinking 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 nanoparticle 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, enhances
" effect of tangling " between alginate network and polyacrylamide network shares bearer network and deforms shifted stress, mention
The intensity of high hybridized hydrogel reduces swelling of the hydrogel under physiological environment；
E) the glucono-δ-lactone aqueous solution that mass percent concentration is 0.1%-10% is prepared, is contained what step d) was obtained
The gel mould of calcium silicates is dipped into 0.1-24h 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
High-intensitive hybridized hydrogel is kept under environment；Interaction of hydrogen bond occurs for mesoporous silica gel and calcium alginate and polyacrylamide,
Along with the enhancement effect of nanoparticle, it is steady to improve mechanics of the polyacrylamide/calcium alginate hydrogel under physiological environment
Qualitative and anti-swelling；
F) in order to further increase the intensity of hydrogel, the hybridized hydrogel prestretching that step e) is obtained is extended to the 0.2- of raw footage
2 times, hybridized hydrogel is then reapposed over the crosslinking of solubility calcium saline solution, in prestretching process in hybridized hydrogel
Nanoparticle and polymer chain be orientated along drawing force, the energy to failure of hybridized hydrogel is improved to original fracture when stretching again
1.1-1.8 times of energy.
2. a kind of hybrid cross-linked and pre-stretching obtains the preparation method of low swelling high intensity hydrogel as described in claim 1,
It is characterized in that the chemical cross-linking agent is ethylene glycol dimethacrylate, divinylbenzene, N, N '-methylene-bisacrylamide
With any one or the two or more mixtures in diisocyanate.
3. a kind of hybrid cross-linked and pre-stretching obtains the preparation method of low swelling high intensity hydrogel as described in claim 1,
It is characterized in that the solubility calcium saline solution is any one in calcium nitrate, calcium chloride, calcium dihydrogen phosphate, calcium sulfate aqueous solution
Kind or two or more mixtures.
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