CN105199281B - It is a kind of to possess superelevation mechanical strength and the hydrogel of chemical stability - Google Patents
It is a kind of to possess superelevation mechanical strength and the hydrogel of chemical stability Download PDFInfo
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Abstract
The invention discloses a kind of preparation method for possessing superelevation mechanical strength and the hydrogel of chemical stability, methods described includes:Polyvinyl alcohol water solution is prepared with the distilled water that boils after cooling, by maleic acid, acrylamide, crosslinking agent, initiator, catalyst dissolution in polyvinyl alcohol water solution, by the solution fast transfer prepared into glass mold, 2~6h of insulation reaction in the environment of the mould after sealing is placed in 45~55 DEG C;The hydrogel of in-mold molding is taken out through drying, calcined crystalline processing, is then immersed in 12h in the soluble metal salt solution that concentration is 0.05~0.25M, it is high intensity, the hydrogel of high stability to take out.Hydrogel of the present invention possesses higher intensity and good stability in electrolyte solution (PBS) relative to conventional hydrogels, to meet its application demand in human body repair of cartilage, organizational project etc..
Description
Technical field
The present invention relates to a kind of preparation field of hydrogel, the especially preparation of high intensity, high chemical stability hydrogel.
Technical background
The flexible material very high as a kind of water content, hydrogel achieve very big development in some fields, such as:Group
Weaver's journey, drug delivery etc..Compared with hard polymer material, the very high soft hydrogel of these water content can be in biological field
Outstanding performance is shown, because this hydrogel possesses the three-dimensional structure similar with cytoplasm.But this structure is led to
Often lack a kind of energy dissipation mechanism of stabilization to assign hydrogel stable mechanical strength, so as to limit hydrogel a lot
Aspect is further applied.In order to solve this problem, increasing researcher has attempted various methods and has removed synthesizing new
Hydrogel.In recent years, use ionic crosslinking structure hydrogel mentality of designing to increase substantially hydrogel mechanical property with
And promoting its application study in biomaterial significant, high strength ionic cross-linked hydrogel research constantly acquirement is outstanding to enter
Exhibition.Wherein, lock will just et al. has had a hydrogel of high tensile property using one-step synthesis method, the hydrogel with acrylamide and
Natural macromolecular maleic acid is monomer, ion crosslinking agent of the calcium sulfate as maleic acid, N, N '-methylene bisacrylamide
Acid amides, ammonium persulfate and tetramethylethylenediamine are respectively the crosslinking agent, thermal initiator and catalyst of acrylamide, and a step is prepared into
To maleic acid/PAHG.The hydrogel is stretchable to about 20 times, but corresponding tensile strength is only about
156kPa.And the hydrogel occurs mechanical strength drastically in the phosphate buffer (PBS) of simulated body fluid environment
The unstable situation of performance of decline.Therefore, it is higher and can keep stablizing mechanical strength in PBS solution to prepare a kind of intensity
Hydrogel there is very big practical application meaning and prospect.
Polyvinyl alcohol is a kind of macromolecular compound that can form crystalline temperature under suitable conditions, should by this material
Preparation for hydrogel can both produce the intensity that crystal crosslinking points strengthen hydrogel inside hydrogel structure, moreover it is possible to make water
Gel network shows fabulous stability in PBS solution.In addition, maleic acid, which is one kind, contains two carboxyls and one
The polymer monomer of unsaturated double-bond, the monomer that can contain double bond with other in the case where retaining carboxyl produce copolymerization, altogether
Due to containing a large amount of carboxyls on macromolecular long-chain after poly-, so as to form ionic bond to hydrogel network with metal cation
Network produces ionic crosslinking.
It is of the invention to be copolymerized maleic acid in the aqueous solution of polyvinyl alcohol with acrylamide, then pass sequentially through calcining
Crystallization treatment, the method for metal cation immersion treatment construct a kind of simultaneously containing covalently cross-linked, crystal dots crosslinking, ion
The mixing macromolecular network of key crosslinking, this hydrogel product show the mechanical strength of superelevation, and soaked in PBS
During still there is good chemical stability.
The content of the invention
To prepare a kind of hydrogel for possessing high strength and there is good chemical stability in PBS solution, this
Maleic acid is copolymerized in the aqueous solution of polyvinyl alcohol by invention with acrylamide, then pass sequentially through calcined crystalline processing,
The method of metal cation immersion treatment constructs a kind of simultaneously containing covalently cross-linked, crystal dots crosslinkings, ionic crosslinking
Macromolecular network is mixed, realizes the preparation of above-mentioned superhigh intensity, high chemical stability hydrogel.Prepared high intensity hydrogel
Elongation strain is up to 580%, and tensile strength is up to 8MPa, and energy to failure is up to 25.4MJ/m3.Performance is compared to sodium alginate/poly-
Acrylamide ionomer type hydrogel, which has, significantly to be lifted.
In order to achieve the above object, the technical solution used in the present invention is as follows:
A kind of hydrogel, it is prepared by each component of following weight parts:
3~6 parts of polyvinyl alcohol, 4~6 parts of the polymeric monomer intermixture of acrylamide and maleic acid composition, and both
Mass ratio be 1:2~1:4, crosslinking agent, initiator, catalyst be respectively the 0.03~0.09% of polymerized monomer number, 0.1~
0.2%th, 0.2~0.3%, 0.05~0.25 part of soluble metallic salt.
Described crosslinking agent is selected from N, N '-methylene-bisacrylamide, GDMA, divinyl
Benzene;
Described initiator is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate;
Described catalyst is selected from tetramethylethylenediamine, five methyl diethylentriamine;
Described soluble metallic salt is selected from FeCl3, AlCl3, CaCl2, MgCl2。
The specific preparation process for preparing described hydrogel is as follows:Wherein step 2)~3) in vacuum, lasting stirring condition
Lower progress;
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, take 3~6 parts of polyvinyl alcohol to add cooling
6 hours are stirred in distilled water afterwards, under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) polymeric monomer intermixture is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.03~0.09%, 0.1~0.2%, the 0.2~0.3% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 45~55 DEG C, insulation reaction
2~6h, the hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal saline solution that concentration is 0.05~0.25M 12 hours, takes out water
Gel continues to soak 24 hours in deionized water, produces product.
In the present invention maleic acid and acrylamide be copolymerized and by covalently cross-linked formation macromolecular network with it is molten
Polyvinyl alcohol long-chain in liquid, which interts, to be mixed, the polyvinyl alcohol long-chain inside the hydrogel after being handled by calcined crystalline
The crystalline temperature formed to a certain extent makes polyvinyl alcohol long-chain form polymer network, and so far hydrogel has been internally formed two kinds
The mixture of polymer network, after then hydrogel is soaked by metal cation solution, carboxyl and gold on polymer chain
Category cation forms the intensity that ionic bond further strengthens this hybrid network.This preparation method first by covalent bond,
Three kinds of different crosslinking methods of ionic bond and crystal dots have been applied in same system, and three kinds of crosslinking methods cooperate performance
Chemical stability excellent in high mechanical strength and PBS is gone out.
During ionic crosslinking is built, we have selected maleic acid as the polymerization with reactivity point
Monomer.Maleic acid, which is compared to acrylic acid and possesses the carboxyls of two times of equivalents, can improve more crosslinking points, simultaneously because
Acrylic acid has stronger corrosivity and toxicity, and the potential danger in production process can be reduced using maleic acid replacement acrylic acid
Evil.
Beneficial effects of the present invention:
1st, the present invention uses the method for radical polymerization and calcined crystalline by two kinds of polymer with different qualities successively
It is interspersed to mix, form a kind of high intensity dual network system simultaneously containing the crosslinking of covalently cross-linked and crystal dots.By
Do not influenceed in crystal dots by ion competition, thus the network of this crystal crosslinking shown in solion it is extraordinary steady
It is qualitative.
2nd, the present invention by the ionic bond that carboxyl and metal cation are formed by ionic crosslinking be also introduced into system come,
This significantly improves the mechanical strength of whole dual network.Being different from that covalent bond is broken after significantly deformation simultaneously forever can not be extensive
Hydrogel is caused to lose intensity again, ionic bond has the characteristic that can independently recover after fracture, and this characteristic imparts water-setting
Glue can recover the ability close to the flat mechanical strength of raw water in a short time after significantly deformation.
3rd, the present invention employs polymer monomer of the maleic acid as structure ionic crosslinking first, solves use
It can be network that toxicity that acrylic monomers is brought, corrosive harm, while maleic acid, which have the carboxyl of two times of equivalents,
More crosslinking points are provided so as to increase network strength.
In summary, the superelevation mechanical strength and the hydrogel of chemical stability that prepared by the present invention have preparation method simple
Effectively, mechanical strength is big, good chemical stability.
Brief description of the drawings
Fig. 1 is the load-deformation curve of the high intensity hydrogel sample stretching experiment of the gained of the embodiment of the present invention 1~3.
Fig. 2 is the energy to failure data of the high intensity hydrogel sample of the gained of the embodiment of the present invention 1~3.
Fig. 3 is that the high intensity hydrogel sample of the gained of the embodiment of the present invention 1~3 soaks 24 hours in phosphate buffer
Load-deformation curve afterwards.
Embodiment
To make those skilled in the art more fully understand the present invention, illustrate below by way of specific embodiment in the application
Possesses the preparation method of superelevation mechanical strength and the hydrogel of chemical stability.
Embodiment 1
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, after taking 4 parts of polyvinyl alcohol to add cooling
Distilled water in, 6 hours are stirred under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:3, and the total amount of maleic acid and acrylamide is 6 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.06%, 0.15%, the 0.25% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 50 DEG C, insulation reaction 5h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.15M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel product that the present embodiment obtains is named as 40%PVA/AM/15%MA, and its elongation strain is reachable
520%, tensile strength can reach 17MJ/m up to 5.5MPa, energy to failure3, intensity 84% is kept after soaking PBS24 hours.
Embodiment 2
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, after taking 5 parts of polyvinyl alcohol to add cooling
Distilled water in, 6 hours are stirred under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:2, and the total amount of maleic acid and acrylamide is 5 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.06%, 0.15%, the 0.25% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 50 DEG C, insulation reaction 5h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.15M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel product that the present embodiment obtains is named as 50%PVA/AM/15%MA, and its elongation strain is reachable
500%, tensile strength is up to 8MPa, and energy to failure is up to 23MJ/m3, intensity 93% is kept after soaking PBS24 hours.
Embodiment 3
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, take 4.5 parts of polyvinyl alcohol to add cooling
6 hours are stirred in distilled water afterwards, under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:3, and the total amount of maleic acid and acrylamide is 5.5 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.06%, 0.15%, the 0.25% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 50 DEG C, insulation reaction 5h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.15M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel product that the present embodiment obtains is named as 45%PVA/AM/15%MA, and its elongation strain is reachable
580%, tensile strength is up to 7.4MPa, and energy to failure is up to 26MJ/m3, intensity 89% is kept after soaking PBS24 hours.
Embodiment 4
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, after taking 3 parts of polyvinyl alcohol to add cooling
Distilled water in, 6 hours are stirred under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:4, and the total amount of maleic acid and acrylamide is 7 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.06%, 0.15%, the 0.25% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 50 DEG C, insulation reaction 5h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.15M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel elongation strain that the present embodiment obtains is up to 570%, and tensile strength is up to 7.1MPa, energy to failure
Up to 22MJ/m3, intensity 85% is kept after soaking PBS24 hours.
Embodiment 5
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, after taking 6 parts of polyvinyl alcohol to add cooling
Distilled water in, 6 hours are stirred under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:3, and the total amount of maleic acid and acrylamide is 4 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.06%, 0.15%, the 0.25% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 50 DEG C, insulation reaction 5h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.15M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel elongation strain that the present embodiment obtains is up to 585%, and tensile strength is up to 7.0MPa, energy to failure
Up to 21.5MJ/m3, intensity 84% is kept after soaking PBS24 hours.
Embodiment 6
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, take 4.5 parts of polyvinyl alcohol to add cooling
6 hours are stirred in distilled water afterwards, under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:3, and the total amount of maleic acid and acrylamide is 5.5 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.06%, 0.15%, the 0.25% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 50 DEG C, insulation reaction 5h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.25M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel elongation strain that the present embodiment obtains is up to 600%, and tensile strength is up to 6.9MPa, energy to failure
Up to 20MJ/m3, intensity 80% is kept after soaking PBS24 hours.
Embodiment 7
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, take 4.5 parts of polyvinyl alcohol to add cooling
6 hours are stirred in distilled water afterwards, under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:3, and the total amount of maleic acid and acrylamide is 5.5 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.06%, 0.15%, the 0.25% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 50 DEG C, insulation reaction 5h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.05M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel elongation strain that the present embodiment obtains is up to 610%, and tensile strength is up to 6.5MPa, energy to failure
Up to 18MJ/m3, intensity 80% is kept after soaking PBS24 hours.
Experimental example 8
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, take 4.5 parts of polyvinyl alcohol to add cooling
6 hours are stirred in distilled water afterwards, under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:3, and the total amount of maleic acid and acrylamide is 5.5 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.03%, 0.2%, the 0.3% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 55 DEG C, insulation reaction 2h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.15M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel elongation strain that the present embodiment obtains is up to 620%, and tensile strength is up to 6.56MPa, fracture
Can be up to 19MJ/m3, intensity 81% is kept after soaking PBS24 hours.
Embodiment 9
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, take 4.5 parts of polyvinyl alcohol to add cooling
6 hours are stirred in distilled water afterwards, under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) maleic acid and acrylamide is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation, described maleic
The mass ratio of diacid and acrylamide is 1:3, and the total amount of maleic acid and acrylamide is 5.5 parts;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, urged
Agent accounts for 0.09%, 0.1%, the 0.2% of polymerized monomer number respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 45 DEG C, insulation reaction 6h,
The hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold dries to moisture is not contained, by dry water-setting at ambient temperature
Glue is placed in vacuum drying chamber 80 DEG C and heats 3 hours, and 120 DEG C of heating are taken out after 1 hour, are cooled to room temperature;
6) hydrogel is immersed in the soluble metal salt solution that concentration is 0.15M 12 hours, takes out hydrogel and continue
Soak 24 hours in deionized water, produce product.
The high intensity hydrogel elongation strain that the present embodiment obtains is up to 625%, and tensile strength is up to 6.7MPa, energy to failure
Up to 19.5MJ/m3, intensity 77% is kept after soaking PBS24 hours.
Experimental example
Extension test:Using universal testing machine (LR10K Plus) be respectively to length, width, thickness 50mm,
10mm, 3mm sheet-like hydrous gel sample carry out extension test, gauge length 10mm, rate of extension 20mm/min.Same sample
Three times, test result is averaged for test.Gained sample extension test result is as shown in Figure 2 in embodiment 1,2,3.
Claims (2)
1. a kind of hydrogel, it is characterised in that be prepared by each component of following weight parts:3~6 parts of polyvinyl alcohol, third
Acrylamide and 4~6 parts of the polymeric monomer intermixture of maleic acid composition, and both mass ratioes are 1:2~1:4, crosslinking agent,
Initiator, catalyst are respectively 0.03~0.09%, 0.1~0.2%, the 0.2~0.3% of polymerized monomer number, soluble gold
Belong to 0.05~0.25 part of salt;
The hydrogel is prepared according to following steps:
1) distilled water is boiled into sealing and is cooled to room temperature to remove the oxygen in water, after taking 3~6 parts of polyvinyl alcohol to add cooling
6 hours are stirred in distilled water, under the conditions of 85 DEG C into poly-vinyl alcohol solution;
2) polymeric monomer intermixture is taken to be dissolved in the polyvinyl alcohol water solution of step 1) preparation;
3) crosslinking agent, initiator, catalyst are added in the solution obtained by step 2), described crosslinking agent, initiator, catalyst
0.03~0.09%, 0.1~0.2%, the 0.2~0.3% of polymerized monomer number is accounted for respectively;
4) solution for preparing step 3) is transferred in glass mold, after sealing, is placed at 45~55 DEG C, and insulation reaction 2~
6h, the hydrogel being as molded;
5) hydrogel for taking out shaping in glass mold is dried to moisture is not contained at ambient temperature, and dry hydrogel is put
In vacuum drying chamber 80 DEG C heat 3 hours, 120 DEG C heating 1 hour after take out, be cooled to room temperature;
6) hydrogel is immersed in the soluble metal saline solution that concentration is 0.05~0.25M 12 hours, takes out hydrogel
Continue to soak 24 hours in deionized water, produce product;
Wherein step 2) and 3) vacuum, continue stirring condition under carry out.
2. hydrogel as claimed in claim 1, it is characterised in that described crosslinking agent is selected from N, N '-methylene bisacrylamide acyl
Amine, GDMA, divinylbenzene;
Described initiator is selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate;
Described catalyst is selected from tetramethylethylenediamine, five methyl diethylentriamine;
Described soluble metallic salt is selected from FeCl3, AlCl3, CaCl2, MgCl2。
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