CN108409988A - A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel - Google Patents
A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel Download PDFInfo
- Publication number
- CN108409988A CN108409988A CN201810356499.8A CN201810356499A CN108409988A CN 108409988 A CN108409988 A CN 108409988A CN 201810356499 A CN201810356499 A CN 201810356499A CN 108409988 A CN108409988 A CN 108409988A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- hydrogel
- macroporous
- polyethylene glycol
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/044—Elimination of an inorganic solid phase
- C08J2201/0444—Salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/046—Elimination of a polymeric phase
- C08J2201/0464—Elimination of a polymeric phase using water or inorganic fluids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention discloses a kind of preparation methods of novel spongy macroporous polyvinyl alcohol hydrogel, specially：After polyethylene glycol is dissolved in poly-vinyl alcohol solution, so that mixed solution is separated by reducing temperature, nanometer hydroxyapatite is then added into the mixed solution being separated to stablize phase-separated system.Make water-setting gum forming by circulating frozen/melting method, wash out polyethylene glycol and nanometer hydroxyapatite, obtains the polyvinyl alcohol hydrogel with macroporous structure.With not adding hydroxyapatite compared with the polyvinyl alcohol hydrogel that is only prepared by circulating frozen/melting method, the hydrogel prepared by the present invention has the appearance of similar sponge and the porous structure of elasticity, three-dimensional perforation, high porosity（Aperture is 30 ~ 100 μm）, good mechanical performance and biocompatibility.Spongy macroporous polyvinyl alcohol hydrogel in the present invention has prodigious application potential in biomedical materials field.
Description
Technical field
The present invention relates to a kind of preparation methods of novel spongy macroporous polyvinyl alcohol hydrogel, belong to biochemical industry neck
Domain.
Background technology
Hydrogel is the hydrophilic polymer with three-dimensional net structure by chemically or physically generating.It can be inhaled
It receives a large amount of water-swellable and keeps certain shape.Typical hydrogel is in usually g., jelly-like, soft and high resilience.It is good
Water suction, water conservation and slow release characteristic make it in organizational project, and the fields such as wound dressing and medicine sustained and controlled release all present good answer
Use foreground.
Natural macromolecular material and chemical synthesis high molecular material two major classes, preparation side can be divided by preparing the material of hydrogel
Method is usually to be physical crosslinking and chemical crosslinking, is made point by the interaction of ionic bond, hydrogen bond and hydrophobic bond wherein physical crosslinking refers to
The network structure of sub mutually entanglement and formation.Physical crosslinking is very universal in nature, is especially maintaining large biological molecule（Such as
Protein, enzyme and nucleic acid etc.）Three-D space structure, participate in many biologically processes and play very important work
With.Physical crosslinking is often dynamic, reversible, has remarkable effect in terms of the intensity and toughness to safeguarding hydrogel.Chemistry
Crosslinking refer to use the technologies such as chemical cross-linking agent or photopolymerization, radiation polymerization, cause copolymerization or polycondensation reaction generate covalent bond from
And the covalent cross-linking network formed.Compared with physical crosslinking mode, be chemically crosslinked formation hydrogel mechanical strength is good but toughness
Difference, and other substances can be introduced, therefore its biocompatibility is not so good as hydrogel prepared by Physical cross linking methods.
Polyvinyl alcohol is a kind of high molecular weight hydrophilic polymer, wide due to its good water-soluble and biocompatibility
General research is used for biomedical sector.Poly-vinyl alcohol solution in low temperature and at room temperature freeze-thaw repeatedly is formed by based on hydrogen bond
The physical crosslinking to be acted on has excellent mechanical performance.But hydrogel prepared by this method does not have macroporous structure, limit usually
Its application range is made.
Invention content
It is an object of the present invention to provide a kind of with macroporous structure, the novel spongy that porosity is high, biocompatibility is excellent
Macroporous polyvinyl alcohol hydrogel and preparation method thereof.
The present invention realizes that process is as follows：
A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel：Polyethylene glycol is added to poly-vinyl alcohol solution, stirring is extremely
Polyethylene glycol fully dissolves, and in being stored at room temperature, when mixed solution is become cloudy by clarifying, nanometer hydroxyapatite is added, stirs,
So that nanometer hydroxyapatite is evenly dispersed in mixed solution, the solution mixed is transferred to room temperature in mold, leads to
It crosses circulating frozen/fusion method and is prepared into hydrogel, be washed with deionized and remove polyethylene glycol and nanometer hydroxyapatite to obtain
Obtain the polyvinyl alcohol hydrogel with macroporous structure.
The preparation method of above-mentioned macroporous polyvinyl alcohol hydrogel, includes the following steps：
（1）85-98 DEG C of deionized water is dissolved polyvinyl alcohol in, the polyvinyl alcohol for obtaining a concentration of 8-12% of mass volume ratio is molten
Liquid；
（2）The polyglycol solution of a concentration of 3-10% of mass volume ratio is added into step（1）Poly-vinyl alcohol solution in, normal
Temperature places 0.5-1 h；
（3）When polyvinyl alcohol and polyethylene glycol clarification mixed solution become cloudy, by nanometer hydroxyapatite with mass volume ratio
The content of concentration 6-10% is dissolved in step（3）Polyvinyl alcohol and polyethylene glycol mixed solution in；
（4）By step（3）Mixed solution is in room temperature 1-1.5 h；Plastic is prepared by circulating frozen/fusion method, wherein cold
It is -18 DEG C to -20 DEG C to freeze temperature, and melting temperature is room temperature, cycle-index 3-7 times；
（5）The hydrogel prepared is removed into polyethylene glycol and nanometer hydroxyapatite in deionized water, is obtained spongy big
Hole polyvinyl alcohol hydrogel.
Above-mentioned steps（1）In, the molecular weight of polyvinyl alcohol is 80,000-120,000Da, and alcoholysis degree is more than 99%.
Above-mentioned steps（1）In, it dissolves polyvinyl alcohol in 95 DEG C of deionized waters.
Above-mentioned steps（2）In, the molecular weight of polyethylene glycol is 1000-4000 Da.
Above-mentioned steps（3）In, the grain size of nanometer hydroxyapatite is 10-30 nm.
The present invention has the following advantages：After ethylene glycol is dissolved in poly-vinyl alcohol solution by the present invention, made by reducing temperature
Mixed solution is separated, and nanometer hydroxyapatite is then added into the mixed solution being separated with stable phase point
In vitro system.Make water-setting gum forming by circulating frozen/melting method, wash out polyethylene glycol and nanometer hydroxyapatite, obtains
Polyvinyl alcohol hydrogel with macroporous structure.It is only prepared by circulating frozen/melting method with hydroxyapatite is not added
Polyvinyl alcohol hydrogel compare, the hydrogel prepared by the present invention has appearance and elasticity, the three-dimensional perforation of similar sponge
Porous structure, high porosity（Aperture is 30 ~ 100 μm）, good mechanical performance and biocompatibility.It is spongy in the present invention
Macroporous polyvinyl alcohol hydrogel has good application potential in biomedical materials fields such as burn and scald dressing, hemostasis.
Description of the drawings
Fig. 1 is the wet sample outside drawing of 1 polyvinyl alcohol hydrogel of example；
Fig. 2 is the sample drawing after the wet sample freeze-drying of 1 polyvinyl alcohol hydrogel of example；
Fig. 3 is the scanning electron microscope (SEM) photograph of 1 polyvinyl alcohol hydrogel sample of example；
Fig. 4 is the swelling ratio of 1 polyvinyl alcohol hydrogel sample of example in deionized water；
Fig. 5 is water retention of the 1 polyvinyl alcohol hydrogel sample of example at 25 DEG C；
Fig. 6 is the CCK-8 cytotoxicity test results of 1 polyvinyl alcohol hydrogel sample of example.
Specific implementation mode
The present invention will be described in detail With reference to embodiment.
It is according to the present invention using polyvinyl alcohol, polyethylene glycol and nanometer hydroxyapatite as raw material, prepare novel sponge
The preparation method of shape macroporous polyvinyl alcohol water-setting, is obtained by circulating frozen melting process, wherein polyvinyl alcohol and polyethylene glycol
Mixed solution causes to be separated by cooling, and the addition of nanometer hydroxyapatite stabilizes the phase separation of mixed solution, this phase
Separation is the reason of forming super porous hydrogel.Solution forms the hydrogel with three-dimensional structure by circulating frozen/melting process,
Nanometer hydroxyapatite is washed away using deionized water, polyethylene glycol finally obtains the hydrogel with macropore, high porosity.Specifically
Preparation method is realized by following steps：
Step 1：Dissolve polyvinyl alcohol in 95 DEG C of deionized waters obtain a concentration of 8-12% of mass volume ratio polyvinyl alcohol it is molten
Liquid；
Step 2：Polyethylene glycol is dissolved in the poly-vinyl alcohol solution of step 1 with the content of mass volume ratio concentration 3-10%；
Step 3：By the polyvinyl alcohol of step 2 and polyethylene glycol mixed solution in room temperature 0.5-1 h；
Step 4：The polyvinyl alcohol and polyethylene glycol clarification mixed solution for waiting for step 3 become cloudy nanometer hydroxyapatite with matter
The content of amount volume by volume concentration 6-10% is dissolved in the polyvinyl alcohol and polyethylene glycol mixed solution of step 3；
Step 5：By the solution mixed in step 4 in room temperature 1-1.5 h；Pass through circulating frozen/melting legal system later
Standby plastic, wherein cryogenic temperature are -18 DEG C to -20 DEG C, melting temperature room temperature, cycle-index 3-7 times.The mixed gel prepared
Polyethylene glycol and nanometer hydroxyapatite are removed in deionized water, obtain the novel spongy macroporous polyvinyl alcohol water-setting
Glue.
In step 1, polyvinyl alcohol molecule amount is 80,000-120,000Da, and alcoholysis degree is more than 99%.
In step 2, the molecular weight of polyethylene glycol is 1000-4000 Da.
In step 4, the grain size of nanometer hydroxyapatite is 20 nm.
In step 5, plastic is prepared by circulating frozen/fusion method, wherein cryogenic temperature is -18 DEG C to -20 DEG C, melting
Temperature is room temperature, cycle-index 3-7 times.
Embodiment 1
Step 1：It weighs the polyvinyl alcohol that molecular weight is 89000Da to be dissolved in 20 ml deionized waters, it is dense to obtain mass volume ratio
Degree is 10% poly-vinyl alcohol solution, and being placed in stirring in 95 DEG C of water-baths makes it fully dissolve；
Step 2：The polyethylene glycol that molecular weight is 1500 Da is added into above-mentioned solution makes it be sufficiently mixed uniformly, is formed uniform
Solution makes polyethylene glycol mass volume ratio a concentration of 8%；
Step 3：By above-mentioned polyvinyl alcohol and polyethylene glycol mixed solution in 1 h of room temperature；
Step 4：It waits for that above-mentioned mixed solution becomes cloudy to be dissolved in nanometer hydroxyapatite with the content of mass volume ratio concentration 10%
In the muddiness mixed solution；
Step 5：By the solution of above-mentioned mixing in 1 h of room temperature；Plastic is prepared by circulating frozen/fusion method later, wherein
- 20 DEG C of cryogenic temperature, melting temperature are room temperature, cycle-index 5 times.The mixed gel prepared removes poly- second in deionized water
Glycol and nanometer hydroxyapatite obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Embodiment 2
Step 1：It weighs the polyvinyl alcohol that molecular weight is 98000 Da to be dissolved in 20ml deionized waters, it is 10 to obtain mass fraction
The poly-vinyl alcohol solution of %, being placed in stirring in 95 DEG C of water-baths makes it fully dissolve；
Step 2：The polyethylene glycol that molecular weight is 1500 Da is added into above-mentioned solution makes it be sufficiently mixed uniformly, is formed uniform
Solution makes polyethylene glycol mass volume ratio a concentration of 8%；
Step 3：By above-mentioned polyvinyl alcohol and polyethylene glycol mixed solution in 1 h of room temperature；
Step 4：It waits for that above-mentioned mixed solution becomes cloudy and nanometer hydroxyapatite is dissolved in this with the content of mass volume ratio concentration 6%
In muddy mixed solution；
Step 5：By the solution of above-mentioned mixing in 1 h of room temperature；Plastic is prepared by circulating frozen/fusion method later, wherein
- 20 DEG C of cryogenic temperature, melting temperature are room temperature, cycle-index 5 times.The mixed gel prepared removes poly- second in deionized water
Glycol and nanometer hydroxyapatite obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Embodiment 3
Step 1：It weighs the polyvinyl alcohol that molecular weight is 98000 Da to be dissolved in 20ml deionized waters, it is 8% to obtain mass fraction
Poly-vinyl alcohol solution, being placed in 95 DEG C of water-baths stirring makes it fully dissolve；
Step 2：Molecular weight is added into above-mentioned solution makes it be sufficiently mixed uniformly for 3000 Da polyethylene glycol, is formed uniform molten
Liquid makes polyethylene glycol mass volume ratio a concentration of 4%；
Step 3：By above-mentioned polyvinyl alcohol and polyethylene glycol mixed solution in room temperature 1h；
Step 4：It waits for that above-mentioned mixed solution becomes cloudy to be dissolved in nanometer hydroxyapatite with the content of mass volume ratio concentration 10%
In the muddiness mixed solution；
Step 5：By the solution of above-mentioned mixing in room temperature 1h；Plastic is prepared by circulating frozen/fusion method later, wherein
- 20 DEG C of cryogenic temperature, melting temperature are room temperature, cycle-index 5 times.The mixed gel prepared removes poly- second in deionized water
Glycol and nanometer hydroxyapatite obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Embodiment 4
Step 1：It weighs the polyvinyl alcohol that molecular weight is 89000 Da to be dissolved in 20ml deionized waters, it is 8% to obtain mass fraction
Poly-vinyl alcohol solution, being placed in 95 DEG C of water-baths stirring makes it fully dissolve；
Step 2：Molecular weight is added into above-mentioned solution makes it be sufficiently mixed uniformly for 4000 Da polyethylene glycol, is formed uniform molten
Liquid makes polyethylene glycol mass volume ratio a concentration of 3%；
Step 3：By above-mentioned polyvinyl alcohol and polyethylene glycol mixed solution in 1 h of room temperature；
Step 4：It waits for that above-mentioned mixed solution becomes cloudy to be dissolved in nanometer hydroxyapatite with the content of mass volume ratio concentration 10%
In the muddiness mixed solution；
Step 5：By the solution of above-mentioned mixing in 1 h of room temperature；Plastic is prepared by circulating frozen/fusion method later, wherein
- 20 DEG C of cryogenic temperature, melting temperature are room temperature, cycle-index 5 times.The mixed gel prepared removes poly- second in deionized water
Glycol and nanometer hydroxyapatite obtain the novel spongy macroporous polyvinyl alcohol hydrogel.
Embodiment 5
Step 1：It is that 89000 Da polyvinyl alcohol are dissolved in 20 ml deionized waters to weigh molecular weight, and it is 10% to obtain mass fraction
Poly-vinyl alcohol solution, being placed in 95 DEG C of water-baths stirring makes it fully dissolve；
Step 2：Molecular weight is added into above-mentioned solution makes it be sufficiently mixed uniformly for 1500 Da polyethylene glycol, is formed uniform molten
Liquid makes polyethylene glycol mass volume ratio a concentration of 8%.
Step 3：Above-mentioned uniform solution prepares plastic, wherein -20 DEG C of cryogenic temperature, melting by circulating frozen/fusion method
Temperature is room temperature, cycle-index 5 times.The mixed gel prepared removes polyethylene glycol in deionized water, obtains polyvinyl alcohol
Hydrogel.
In above-described embodiment, embodiment 5 is comparative example, to what is prepared in embodiments of the invention described above 1 and example 5
The various performance parameters of spongy macroporous polyvinyl alcohol hydrogel are measured, including microstructure, swelling behavior, water-retaining property
Energy, cytotoxicity, as a result referring to attached drawing 3-6.
1, the wet sample of hydrogel in the present invention is as shown in Figure 1, Hydrogels are similar to spongiform translucent gels.
2, the freeze-dried pattern of hydrogel sample in the present invention is as shown in Fig. 2, material is white and surface is flat
It is whole.
3, hydrogel microstructure detects.
Prepared sample is cut into about 2 μm of thin slice, be dried using vacuum freezedrying and is sprayed on its surface
Gold.The Study on Microstructure of hydrogel is carried out under an electron microscope.
As shown in figure 3, as seen from the figure, subject hydrogel in embodiment 1 compared with Example 5, microcosmic result
In cellular, even aperture distribution and pore size is between 30-100 μm.
4, swelling behavior performance detection.
The swelling ratio of hydrogel is measured in 37 DEG C of deionized water.Weigh the hydrogel sample after freeze-drying, matter
Amount is denoted as M0.It immerses in deionized water and is taken out in setting time point, after wiping surface moisture with filter paper, weigh and be denoted as M1。
(M1-M0) be hydrogel water suction after quality, M0For the dry weight of hydrogel, ratio is swelling ratio.
As shown in figure 4, subject hydrogel in embodiment 1 compared with Example 5, can reach swelling after 30min
Balance, swelling ratio is about 1500%；And the hydrogel in example 5 can be only achieved swelling equilibrium after 120min, swelling ratio is only
About 500%.
5, hydrogel water retention property detects.
It is up to the wet hydrogel M of swelling equilibrium0It is placed in each beaker, is then placed under 37 DEG C of environment and measures weight
It changes with time.At scheduled time point, hydrogel is taken out and the M that weighs.M and M0Ratio be water retention.
At 37 DEG C as shown in Figure 5, the water retention of two kinds of hydrogels changes with time, by 48h water retentions still greater than
50%, and embodiment 1 and embodiment 5 and comparison example difference are little.
6, hydrogel cytotoxicity detects.
According to GB/T16886.5-2003（《The 5th part of BiologicalEvaluationofMedicalDevice：Vitro cytotoxicity tries
It tests》）Specified in test method tested.
Fig. 6 the result shows that：Using the cytotoxicity of L929 cell CCK-8 method experimental material leaching liquors.After culture five days, carefully
Born of the same parents' survival rate be more than 90%, this experimental results showed that：According to national standard, material toxic grade is 1 grade, and belonging to can trust and make
Bio-medical material.
Present disclosure is not limited to cited by embodiment, and those of ordinary skill in the art are by reading description of the invention
And to any equivalent transformation that technical solution of the present invention is taken, it is that claim of the invention is covered.
Claims (6)
1. a kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel, it is characterised in that：It is added to poly-vinyl alcohol solution poly-
Ethylene glycol, stirring are fully dissolved to polyethylene glycol, and in being stored at room temperature, when mixed solution is become cloudy by clarifying, nanometer hydroxyl is added
Base apatite, is sufficiently stirred, and nanometer hydroxyapatite is made to be evenly dispersed in mixed solution, and the solution mixed is transferred to
Room temperature in mold is prepared into hydrogel by circulating frozen/fusion method, is washed with deionized and removes polyethylene glycol and receive
Rice hydroxyapatite is to obtain the polyvinyl alcohol hydrogel with macroporous structure.
2. the preparation method of macroporous polyvinyl alcohol hydrogel described in claim 1, it is characterised in that include the following steps：
（1）85-98 DEG C of deionized water is dissolved polyvinyl alcohol in, the polyvinyl alcohol for obtaining a concentration of 8-12% of mass volume ratio is molten
Liquid；
（2）The polyglycol solution of a concentration of 3-10% of mass volume ratio is added into step（1）Poly-vinyl alcohol solution in, normal
Temperature places 0.5-1 h；
（3）When polyvinyl alcohol and polyethylene glycol clarification mixed solution become cloudy, by nanometer hydroxyapatite with mass volume ratio
The content of concentration 6-10% is dissolved in step（3）Polyvinyl alcohol and polyethylene glycol mixed solution in；
（4）By step（3）Mixed solution is in room temperature 1-1.5 h；Plastic is prepared by circulating frozen/fusion method, wherein cold
It is -18 DEG C to -20 DEG C to freeze temperature, and melting temperature is room temperature, cycle-index 3-7 times；
（5）The hydrogel prepared is removed into polyethylene glycol and nanometer hydroxyapatite in deionized water, is obtained spongy big
Hole polyvinyl alcohol hydrogel.
3. the preparation method of macroporous polyvinyl alcohol hydrogel according to claim 1 or 2, it is characterised in that：Polyvinyl alcohol
Molecular weight be 80,000-120,000Da, alcoholysis degree be more than 99%.
4. the preparation method of macroporous polyvinyl alcohol hydrogel according to claim 1 or 2, it is characterised in that：Polyethylene glycol
Molecular weight be 1000-4000 Da.
5. the preparation method of macroporous polyvinyl alcohol hydrogel according to claim 2, it is characterised in that：Step（1）In, it will
Polyvinyl alcohol is dissolved in 95 DEG C of deionized waters.
6. the preparation method of macroporous polyvinyl alcohol hydrogel according to claim 2, it is characterised in that：Step（3）In, it receives
The grain size of rice hydroxyapatite is 10-30 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810356499.8A CN108409988B (en) | 2018-04-20 | 2018-04-20 | Preparation method of spongy macroporous polyvinyl alcohol hydrogel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810356499.8A CN108409988B (en) | 2018-04-20 | 2018-04-20 | Preparation method of spongy macroporous polyvinyl alcohol hydrogel |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108409988A true CN108409988A (en) | 2018-08-17 |
| CN108409988B CN108409988B (en) | 2020-10-30 |
Family
ID=63136039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810356499.8A Active CN108409988B (en) | 2018-04-20 | 2018-04-20 | Preparation method of spongy macroporous polyvinyl alcohol hydrogel |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108409988B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110698719A (en) * | 2019-10-30 | 2020-01-17 | 陕西巨子生物技术有限公司 | Preparation of polyvinyl alcohol-based hydrogel |
| CN111494701A (en) * | 2019-01-31 | 2020-08-07 | 西北大学 | Polyvinyl alcohol hydrogels with asymmetric pore size |
| CN112094418A (en) * | 2020-09-27 | 2020-12-18 | 河南省科学院同位素研究所有限责任公司 | Hydrogel composite material with photo-thermal conversion shape memory effect and preparation method thereof |
| CN113773462A (en) * | 2021-08-19 | 2021-12-10 | 华东理工大学 | Invisible orthodontic polyurethane film, preparation method and application |
| CN113813436A (en) * | 2021-08-18 | 2021-12-21 | 西北大学 | Preparation method of visual antibacterial anti-inflammatory dressing for treating bacterial infection type wound |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1527860A (en) * | 2001-05-11 | 2004-09-08 | ������ϵ�о���˾ | Methods for the preparation of cellular hydrogels |
| CN1651506A (en) * | 2003-10-31 | 2005-08-10 | 四川大学 | Preparation method of nano-hydroxy apatitel poly vinyl alcohol composite hydrogel |
| WO2012118662A2 (en) * | 2011-02-28 | 2012-09-07 | The General Hospital Corporation | Highly porous polyvinyl alcohol hydrogels for cartilage resurfacing |
| CN107126583A (en) * | 2017-05-03 | 2017-09-05 | 中国矿业大学 | The preparation technology of multilayer heterogeneous bionic joint cartilage material |
-
2018
- 2018-04-20 CN CN201810356499.8A patent/CN108409988B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1527860A (en) * | 2001-05-11 | 2004-09-08 | ������ϵ�о���˾ | Methods for the preparation of cellular hydrogels |
| CN1651506A (en) * | 2003-10-31 | 2005-08-10 | 四川大学 | Preparation method of nano-hydroxy apatitel poly vinyl alcohol composite hydrogel |
| WO2012118662A2 (en) * | 2011-02-28 | 2012-09-07 | The General Hospital Corporation | Highly porous polyvinyl alcohol hydrogels for cartilage resurfacing |
| CN107126583A (en) * | 2017-05-03 | 2017-09-05 | 中国矿业大学 | The preparation technology of multilayer heterogeneous bionic joint cartilage material |
Non-Patent Citations (2)
| Title |
|---|
| ZHAOYANG XU等: ""Morphological and swelling behavior of cellulose nanofiber (CNF)/poly(vinyl alcohol) (PVA) hydrogels: poly(ethylene glycol) (PEG) as porogen"", 《RSC ADV.》 * |
| 许凤兰等: ""多孔纳米羟基磷灰石/聚乙烯醇复合水凝胶的表征"", 《化学研究与应用》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111494701A (en) * | 2019-01-31 | 2020-08-07 | 西北大学 | Polyvinyl alcohol hydrogels with asymmetric pore size |
| CN111494701B (en) * | 2019-01-31 | 2021-07-02 | 西北大学 | Polyvinyl alcohol hydrogels with asymmetric pore size |
| CN110698719A (en) * | 2019-10-30 | 2020-01-17 | 陕西巨子生物技术有限公司 | Preparation of polyvinyl alcohol-based hydrogel |
| CN112094418A (en) * | 2020-09-27 | 2020-12-18 | 河南省科学院同位素研究所有限责任公司 | Hydrogel composite material with photo-thermal conversion shape memory effect and preparation method thereof |
| CN112094418B (en) * | 2020-09-27 | 2023-04-25 | 河南省科学院同位素研究所有限责任公司 | Hydrogel composite material with photothermal conversion shape memory effect and preparation method thereof |
| CN113813436A (en) * | 2021-08-18 | 2021-12-21 | 西北大学 | Preparation method of visual antibacterial anti-inflammatory dressing for treating bacterial infection type wound |
| CN113813436B (en) * | 2021-08-18 | 2022-08-05 | 西北大学 | Preparation method of visual antibacterial anti-inflammatory dressing for treating bacterial infection type wound |
| CN113773462A (en) * | 2021-08-19 | 2021-12-10 | 华东理工大学 | Invisible orthodontic polyurethane film, preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108409988B (en) | 2020-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108409988A (en) | A kind of preparation method of spongy macroporous polyvinyl alcohol hydrogel | |
| Chen et al. | Synthesis and properties of poly (vinyl alcohol) hydrogels with high strength and toughness | |
| Xu et al. | Morphological and swelling behavior of cellulose nanofiber (CNF)/poly (vinyl alcohol)(PVA) hydrogels: poly (ethylene glycol)(PEG) as porogen | |
| Balaji et al. | Preparation and comparative characterization of keratin–chitosan and keratin–gelatin composite scaffolds for tissue engineering applications | |
| Liu et al. | Preparation of macroporous poly (2-hydroxyethyl methacrylate) hydrogels by enhanced phase separation | |
| Chen et al. | Immobilization of chitosan gel with cross-linking reagent on PNIPAAm gel/PP nonwoven composites surface | |
| Dinu et al. | Ice-templated hydrogels based on chitosan with tailored porous morphology | |
| US8668863B2 (en) | Dendritic macroporous hydrogels prepared by crystal templating | |
| Yu et al. | Evaluation of a polyvinyl alcohol‐alginate based hydrogel for precise 3D bioprinting | |
| EP1595899B1 (en) | Polymer gel containing biocompatible material, dry gel, and process for producing polymer gel | |
| Cascone et al. | Evaluation of poly (vinyl alcohol) hydrogels as a component of hybrid artificial tissues | |
| Zhao et al. | Effects of cellulose nanocrystal polymorphs and initial state of hydrogels on swelling and drug release behavior of alginate-based hydrogels | |
| CN104845382A (en) | Silk protein/cellulose derivative blending hydrogel and preparation method thereof | |
| Gümüşderelioğlu et al. | Superporous polyacrylate/chitosan IPN hydrogels for protein delivery | |
| CN110698719A (en) | Preparation of polyvinyl alcohol-based hydrogel | |
| Khoonkari et al. | Bioinspired processing: Complex coacervates as versatile inks for 3D bioprinting | |
| WO2023143540A1 (en) | Unidirectional nanopore dehydration-based functional polymer film/hydrogel film, and method and apparatus for preparing same | |
| CN100431623C (en) | Method for preparing 3D porous bracket of chitosan - copolymer of poly lactic acid | |
| Wang et al. | Fabrication of methacrylated casein/alginate microspheres crosslinked by UV light coupled with Ca2+ chelation for pH-sensitive drug delivery | |
| JP2507885B2 (en) | Silk fibroin hydrogel | |
| JPH11169703A (en) | Thermally reversible hydrogel forming composition | |
| Elblbesy et al. | Effect of gelatin concentration on the characterizations and hemocompatibility of polyvinyl alcohol–gelatin hydrogel | |
| US6979700B2 (en) | Non-degradable porous materials with high surface areas | |
| DE60122500T2 (en) | PROCESS FOR PRODUCING PROTEIN-CONTAINING HYDROGELS | |
| Choi et al. | 3D bioprinting of cell-laden thermosensitive methylcellulose/nanosilicate composite hydrogels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |