CN106810704A - Polyvinyl alcohol hydrogel and its preparation method and application - Google Patents
Polyvinyl alcohol hydrogel and its preparation method and application Download PDFInfo
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- CN106810704A CN106810704A CN201710068497.4A CN201710068497A CN106810704A CN 106810704 A CN106810704 A CN 106810704A CN 201710068497 A CN201710068497 A CN 201710068497A CN 106810704 A CN106810704 A CN 106810704A
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- polyvinyl alcohol
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- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 189
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 189
- 239000000017 hydrogel Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 120
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000499 gel Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000004698 Polyethylene Substances 0.000 claims abstract description 4
- -1 polyethylene Polymers 0.000 claims abstract description 4
- 229920000573 polyethylene Polymers 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 11
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 11
- 229920001610 polycaprolactone Polymers 0.000 claims description 11
- 239000004632 polycaprolactone Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000004626 polylactic acid Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000033228 biological regulation Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 210000004204 blood vessel Anatomy 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 239000002473 artificial blood Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 2
- 238000002791 soaking Methods 0.000 claims 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 150000003462 sulfoxides Chemical class 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000012046 mixed solvent Substances 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 144
- 229940068984 polyvinyl alcohol Drugs 0.000 description 143
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005538 encapsulation Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000010257 thawing Methods 0.000 description 5
- 238000005498 polishing Methods 0.000 description 4
- 238000000518 rheometry Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000001900 immune effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004218 vascular function Effects 0.000 description 1
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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
-
- 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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions 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; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
-
- 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
- C08J2427/00—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 a halogen; Derivatives of such polymers
- C08J2427/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
-
- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Dermatology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Vascular Medicine (AREA)
- Materials For Medical Uses (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Prostheses (AREA)
Abstract
本发明涉及一种聚乙烯醇水凝胶及其制备方法和应用，属于及高分子水凝胶领域。本发明提供一种聚乙烯醇水凝胶的制备方法，所述方法为：将聚乙烯醇与有机溶剂在110℃～145℃下加热溶解制得聚乙烯醇溶液，然后将所得聚乙烯醇溶液静置自然冷却至室温即可形成具有凝胶结构的聚乙烯醇，再将具有凝胶结构的聚乙烯醇去除有机溶剂后制得聚乙烯醇水凝胶；其中，所述有机溶剂为二甲基亚砜和N‑N,二甲基甲酰胺的共混溶剂，二甲基亚砜和N‑N,二甲基甲酰胺的体积比为0.25～1；所得聚乙烯醇溶液的质量浓度为10～30％。本发明在制备聚乙烯醇溶液时，采用了恰当配比的溶剂，使得所得聚乙烯溶液通过静置自然冷却的方式即可制得聚乙烯醇水凝胶。
The invention relates to a polyvinyl alcohol hydrogel and a preparation method and application thereof, belonging to the field of polymer hydrogels. The invention provides a preparation method of polyvinyl alcohol hydrogel. The method is as follows: heating and dissolving polyvinyl alcohol and an organic solvent at 110°C to 145°C to obtain a polyvinyl alcohol solution, and then dissolving the obtained polyvinyl alcohol solution The polyvinyl alcohol with a gel structure can be formed after standing and naturally cooled to room temperature, and then the polyvinyl alcohol hydrogel is obtained by removing the organic solvent from the polyvinyl alcohol with a gel structure; wherein, the organic solvent is dimethyl The mixed solvent of sulfoxide and N-N, dimethylformamide, the volume ratio of dimethyl sulfoxide and N-N, dimethylformamide is 0.25～1; The mass concentration of gained polyvinyl alcohol solution is 10-30%. When preparing the polyvinyl alcohol solution, the present invention adopts an appropriate proportion of solvents, so that the obtained polyethylene solution can be left to stand and naturally cooled to prepare the polyvinyl alcohol hydrogel.
Description
Technical field
The present invention relates to a kind of polyvinyl alcohol hydrogel and its preparation method and application, belong to macromolecule hydrogel field.
Background technology
Polyvinyl alcohol hydrogel torpescence in the chemically, non-toxic, good biocompatibility, good mechanical performance is inhaled
Water is high, and easily processed into type, and each is led to be widely used in agricultural, medicine, daily-use chemical industry, environmental protection and desert preventing and treating etc.
Domain.
At present, preparing polyvinyl alcohol hydrogel can make it using the method for physical crosslinking, chemical crosslinking or crosslinking with radiation
Form the gel of water-insoluble.The method being wherein physical crosslinking, i.e., carry out freeze-thaw, repeatedly by by poly-vinyl alcohol solution
The mode of freeze thawing, makes polyvinyl alcohol that physical crosslinking to occur and forms gel.
However, there is following defect in physical crosslinking method：
1st, using physical crosslinking method, it is necessary to thawing；General cooling time is 24h, and thawing time is 2-12h, so
The freeze thawing time once is at least 26h, and whole process thawing generally requires 80h.
2nd, by the way of physical crosslinking, the water insoluble hydrogel of formation be it is reversible, under certain condition easily
Redissolve in water, it is unstable；The hydrogel intensity of physical crosslinking is very poor, it is easy to damaged.
The content of the invention
For drawbacks described above, the technical problems to be solved by the invention are to provide a kind of preparation side of polyvinyl alcohol hydrogel
Method, the method is simple and easy to do, and the used time is few, and production cost is relatively low.
Technical scheme：
The invention solves the problems that first technical problem be to provide a kind of preparation method of polyvinyl alcohol hydrogel, specifically
For：By polyvinyl alcohol and organic solvent, heating for dissolving is obtained poly-vinyl alcohol solution at 110 DEG C~145 DEG C, then gathers gained
Glycohol solution stands by naturally cooling to room temperature and forms the polyvinyl alcohol with gel structure, finally will be with gel structure
Polyvinyl alcohol removal organic solvent after i.e. be obtained polyvinyl alcohol hydrogel；Wherein, the organic solvent is dimethyl sulfoxide (DMSO)
(DMSO) and N-N, the blend solvent of dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and N-N, dimethylformamide
(DMF) volume ratio is 0.25~1；The mass concentration of gained poly-vinyl alcohol solution is 10~30%.
Further, in the organic solvent, dimethyl sulfoxide (DMSO) (DMSO) and N-N, the volume ratio of dimethylformamide (DMF)
For：2:8、3:7、4:6 or 5:5.
Further, first standing 4~6h at room temperature before the polyvinyl alcohol removal organic solvent with gel structure makes gel
Structure is full cross-linked.
Further, micro-bubble therein is removed before poly-vinyl alcohol solution natural cooling, it is preferred to use the side of ultrasonic vibration
Method removes bubble, ultrasonic vibration 10~30 minutes.
Further, in the above method, regulation and control polyvinyl alcohol hydrogel mechanics is additionally added in polyvinyl alcohol and organic solvent
The modifying agent of performance, biocompatibility, degradation property and other performances；The modifying agent is with the mass ratio of polyvinyl alcohol：1~
60：99~40.
Preferably, the modifying agent is selected from：Kynoar (PVDF), PLA (PLA), polymethyl methacrylate
(PMMA), at least one in polyethylene glycol (PEG) or polycaprolactone (PCL).
Further, the polyvinyl alcohol with gel structure removes organic solvent by the way of being soaked in water, during immersion
Between 24~48h.
The invention solves the problems that second technical problem be to provide a kind of polyvinyl alcohol hydrogel, it uses above method system
It is standby to obtain.
The invention solves the problems that the 3rd technical problem be to provide a kind of preparation method of polyvinyl alcohol hydrogel micro-pipe, wrap
Include following steps：
1) poly-vinyl alcohol solution is prepared：Polyvinyl alcohol is obtained poly- second with organic solvent heating for dissolving at 110 DEG C~145 DEG C
Enolate solution, the organic solvent is dimethyl sulfoxide (DMSO) (DMSO) and N-N, the blend solvent of dimethylformamide (DMF), diformazan
Base sulfoxide (DMSO) and N-N, the volume ratio of dimethylformamide (DMF) is 0.25~1；The quality of gained poly-vinyl alcohol solution is dense
Spend is 10~30%；
2) micro-pipe is prepared：By step 1) gained poly-vinyl alcohol solution casting enters in mould, and standing is cooled to room temperature and is formed
Polyvinyl alcohol micro-pipe with gel structure, then removes organic solvent therein using solution extraction；
The mould includes：Mold, core rod；The mold has cylindrical cavity, the cylindrical cavity two ends
Concentric fixing device is provided with, the core rod two ends are connected with concentric fixing device respectively, the core rod is by fixed with one heart
Device is fixed in cylindrical cavity, and coaxial with cylindrical cavity.
Further, step 1) in, to ensure that the uniform bubble-free of micro-pipe, poly-vinyl alcohol solution need to carry out after the completion of preparing
Ultrasonic vibration 10~30 minutes.
Further, step 1) in, regulation and control polyvinyl alcohol hydrogel micro-pipe mechanical property, biology are additionally added in polyvinyl alcohol
The modifying agent of compatibility, degradation property and other performances；The modifying agent is with the mass ratio of polyvinyl alcohol：1~60：99~
40。
Preferably, step 1) in, Kynoar (PVDF), PLA (PLA), poly- methyl-prop are added in polyvinyl alcohol
At least one in e pioic acid methyl ester (PMMA), polyethylene glycol (PEG) or polycaprolactone (PCL).
Further, step 2) in, polyvinyl alcohol micro-pipe stands 4~6h to ensure to coagulate at room temperature before organic solvent is removed
Glue is full cross-linked.
Further, step 2) in, the solution extraction is：Polyvinyl alcohol hydrogel micro-pipe is soaked in deionized water
24~36h, changes deionized water in every 4~6 hours；Extraction process, heating temperature can preferably be accelerated by the way of heating is aided in
Degree is in the range of 60~70 DEG C (preferably 65 DEG C).
The invention solves the problems that the 4th technical problem be to provide a kind of polyvinyl alcohol hydrogel micro-pipe, it uses above-mentioned side
Method is obtained.
The invention solves the problems that the 5th technical problem be to provide above-mentioned polyvinyl alcohol hydrogel micro-pipe in artificial blood vessel
Application, the diameter of the polyvinyl alcohol hydrogel micro-pipe can be adjusted arbitrarily in 1~6mm, and the wall thickness of micro-pipe is controllable.
Beneficial effects of the present invention：
The present invention provides a kind of preparation method of polyvinyl alcohol hydrogel, and the present invention is adopted when poly-vinyl alcohol solution is prepared
With DMSO the and DMF mixed liquors of appropriate proportioning as solvent, gained polyethylene solution is set to need not move through freeze-thaw repeatedly
Cyclic process, only need to can be prepared by polyvinyl alcohol hydrogel, and gained polyvinyl alcohol water by way of standing natural cooling
Gel has excellent mechanical strength.The method that the present invention prepares polyvinyl alcohol hydrogel is short compared with the conventional physical cross-linking method used time,
Gel forming process is only needed 8 hours or so, and technique is simple and easy to do.
Additionally, the present invention can also further prepare polyvinyl alcohol hydrogel micro-pipe, the casting of hydrogel micro-pipe can be realized
Shaping, relative to traditional extrusion molding, can effectively ensure that the controllability of micro-pipe size, improve the accurate of micro-pipe product size
Degree；Gel forming process is simple, reduces production cost；Simultaneously because the convenience of mould processing, can be obtained various small chis
Very little pipe product, and can guarantee that the uniformity of pipe wall thickness.
In addition, polyvinyl alcohol (PVA) is a kind of biocompatible materials, the organism hydrogel made of this kind of material is micro-
Blood vessel matrix does not result in the immunological rejection of body.Its inner diameter size of obtained polyvinyl alcohol hydrogel micro-pipe of the invention
Regulation can be arbitrarily customized in the range of 1~6mm, and wall thickness is controllable, so as to provide matrix material for prepared by later stage capilary
Support, to improve vascular function (as addition different bioavailability group improves blood vessel to the stimulation organized so as to make
Into different gene expression) materials for support is provided.
Brief description of the drawings
Fig. 1 is the tensile strength figure of the gained polyvinyl alcohol hydrogel of embodiment 1~3, and 4-6 represents 4 in figure:6,3-7 represent
3:7,5-5 represents 5:5.
Fig. 2 is the elongation at break figure of the gained polyvinyl alcohol hydrogel of embodiment 1~3, and 4-6 represents 4 in figure:6,3-7 tables
Show 3:7,5-5 represents 5:5.
Fig. 3 is the rheological temperature scanning curve of the gained polyvinyl alcohol hydrogel of embodiment 1~3.
Fig. 4 is to prepare the mould structure schematic diagram used in polyvinyl alcohol hydrogel micro-pipe in the embodiment of the present invention 4~6.
Specific embodiment
The invention solves the problems that first technical problem be to provide a kind of preparation method of polyvinyl alcohol hydrogel, specifically
For：By polyvinyl alcohol and organic solvent, heating for dissolving is obtained poly-vinyl alcohol solution at 110 DEG C~145 DEG C, then gathers gained
Glycohol solution stands by naturally cooling to room temperature and forms the polyvinyl alcohol with gel structure, finally will be with gel structure
Polyvinyl alcohol removal organic solvent after i.e. be obtained polyvinyl alcohol hydrogel；Wherein, the organic solvent is dimethyl sulfoxide (DMSO)
(DMSO) and N-N, the blend solvent of dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) and N-N, dimethylformamide
(DMF) volume ratio is 0.25~1；The mass concentration of gained poly-vinyl alcohol solution is 10~30%.
In the present invention, when polyvinyl alcohol concentration is less than 10%, gel structure poor mechanical property is formed, without practical valency
Value；Solvent dissolution method configuration solution performance difficulty when polyvinyl alcohol concentration is more than 30%.
The mode of heating is that oil bath or baking oven are heated.
The invention solves the problems that second technical problem be to provide a kind of polyvinyl alcohol hydrogel, it uses above method system
It is standby to obtain.
The invention solves the problems that the 3rd technical problem be to provide a kind of preparation method of polyvinyl alcohol hydrogel micro-pipe, wrap
Include following steps：
1) poly-vinyl alcohol solution is prepared：Polyvinyl alcohol is obtained poly- second with organic solvent heating for dissolving at 110 DEG C~145 DEG C
Enolate solution, the organic solvent is dimethyl sulfoxide (DMSO) (DMSO) and N-N, the blend solvent of dimethylformamide (DMF), diformazan
Base sulfoxide (DMSO) and N-N, the volume ratio of dimethylformamide (DMF) is 0.25~1；The quality of gained poly-vinyl alcohol solution is dense
Spend is 10~30%；
2) micro-pipe is prepared：By step 1) gained poly-vinyl alcohol solution casting enters in mould, and standing is cooled to room temperature and is formed
Polyvinyl alcohol micro-pipe with gel structure, then removes organic solvent therein using solution extraction；
The mould includes：Mold 1, core rod 2；The mold 1 has cylindrical cavity, the cylindrical cavity two
End is provided with concentric fixing device 3, and the two ends of the core rod 2 are connected with concentric fixing device 3 respectively, and the core rod 2 is by same
Heart fixing device 3 is fixed in cylindrical cavity, and coaxial with cylindrical cavity.
In the present invention, in order to prepare polyvinyl alcohol micro-pipe of the diameter in 1~5mm, the interior diameter of the mold 1 is 2
Arbitrary dimension in the range of~6mm, wall thickness is 2mm and dimensions above, and material is quartz glass, polishing stainless steel material and other are hard
Material；The overall diameter of the core rod be 1~5mm in the range of arbitrary dimension, material be quartz glass, polishing stainless steel material and
Other hard materials；Core rod is nested among mold and fixed by concentric fixing device 3, it is ensured that core rod 2 is same with mold 1
Heart pipe nested arrangement；For step-like, each section of inside dimension is according to mold 1 and core rod 2 is special sets for the concentric fixing device 3
Meter, material is polishing stainless steel or other hard materials；Concentric fixing device 3 ensure that mold 1 is concentrically nested with core rod 2
Device, it is ensured that the uniformity of micro-pipe wall thickness.
Further, step 2) in polyvinyl alcohol gel micro-pipe using solution extraction remove organic solvent, specific embodiment party
Method is：Soak enters 24~36h in deionized water, changes deionized water within every 4~6 hours, can be by the way of heating is aided in
Accelerate extraction process, heating-up temperature is in the range of 60~70 DEG C (preferably 65 DEG C).
Further, it is the uniform bubble-free of guarantee micro-pipe, needs to carry out ultrasonic vibration after the completion of poly-vinyl alcohol solution preparation
10~30 minutes.
Further, step 1) in, regulation and control polyvinyl alcohol hydrogel micro-pipe mechanical property, biology are additionally added in polyvinyl alcohol
The modifying agent of compatibility, degradation property and other performances；The modifying agent is with the mass ratio of polyvinyl alcohol：1~60：99~
40。
Preferably, step 1) in, Kynoar (PVDF), PLA (PLA), poly- methyl-prop are added in polyvinyl alcohol
At least one in e pioic acid methyl ester (PMMA), polyethylene glycol (PEG) or polycaprolactone (PCL).
Further, step 2) in, it is full cross-linked to ensure gel that polyvinyl alcohol micro-pipe stands 4~6h at room temperature.
The invention solves the problems that the 4th technical problem be to provide a kind of polyvinyl alcohol hydrogel micro-pipe, it uses above-mentioned side
Method is obtained.
The polyvinyl alcohol gel prepared using the inventive method has good plasticity, can set according to actual needs
Various sizes of mould is counted so as to obtain the PVOH hydrogel micro-pipe of different-diameter
The invention solves the problems that the 5th technical problem be to provide above-mentioned polyvinyl alcohol hydrogel micro-pipe in artificial blood vessel
Application, the diameter of the polyvinyl alcohol hydrogel micro-pipe can be adjusted arbitrarily in 1~6mm, and the wall thickness of micro-pipe is controllable.
Using dimethyl sulfoxide (DMSO) (DMSO) and N-N, dimethylformamide (DMF) solution ratio is 2 to the present invention:8,3:7,4:
6,5:5 and other ratios, mass fraction ratio shared by configuration polyvinyl alcohol be 10% and above ratio solution be heated to 110~
145 DEG C, polyethylene dissolving alcohol (PVA)；Then ultrasonic vibration removes micro-bubble in solution, and standing naturally cools to room temperature
Form gel structure.Regulation and control polyvinyl alcohol based hydrogel mechanical property, biology in addition, the present invention can also adulterate in polyvinyl alcohol
Compatibility, degradation property and other altered contents, such as Kynoar (PVDF), PLA (PLA), polymethyl methacrylate
(PMMA), one or more mixtures such as polyethylene glycol (PEG), polycaprolactone (PCL)；So as to PVA-based water-setting is obtained
Glue.
With reference to specific embodiment, the present invention is further described.
The preparation of the polyvinyl alcohol hydrogel of embodiment 1
11 grams of polyvinyl alcohol (PVA) are weighed, 60 degrees Celsius of dryings 24 hours weigh 35.20 grams of DMSO, 45.48 grams of DMF
(DMSO is 4 with DMF volume ratios:6), bottle carries out encapsulation process, be placed into the baking oven that temperature is 130 degree (or oil bath pan
It is interior) it is heated to PVA and is completely dissolved, magnetic stirrer makes PVA be uniformly dissolved prepared PVA solution；PVA solution is stood into nature
Room temperature is cooled to, 6h is stood at room temperature to ensure the full cross-linked of PVA gels.PVA gels are removed using solvent-extracted method
Interior organic solvent：Obtained PVA soaks are entered in deionized water, deionized water is changed within every 6 hours, circulated 4-6 times.System
Standby PVA gel standard tensile battens have carried out extension test, and have carried out rheology testing, to characterize the mechanics of PVA gels
Performance and heat endurance.
The preparation of the polyvinyl alcohol hydrogel of embodiment 2
10.84 grams of polyvinyl alcohol (PVA) are weighed, 60 degrees Celsius of dryings 24 hours weigh 26.4 grams of DMSO, 53.06 grams of DMF
(DMSO is 3 with DMF volume ratios:7), bottle carries out encapsulation process, be placed into the baking oven that temperature is 130 degree (or oil bath pan
It is interior) it is heated to PVA and is completely dissolved, magnetic stirrer makes PVA be uniformly dissolved prepared PVA solution；PVA solution is stood into nature
Room temperature is cooled to, 6h is stood at room temperature to ensure the full cross-linked of PVA gels.PVA gels are removed using solvent-extracted method
Interior organic solvent：Obtained PVA soaks are entered in deionized water, deionized water is changed within every 6 hours, circulated 4-6 times.System
Standby PVA gel standard tensile battens have carried out extension test, and have carried out rheology testing, to characterize the mechanics of PVA gels
Performance and heat endurance.
The preparation of the polyvinyl alcohol hydrogel of embodiment 3
Weigh 11.17 grams of polyvinyl alcohol (PVA), 60 degrees Celsius of dryings 24 hours, weigh 44.00 grams of DMSO, 37.90 grams
(DMSO is 5 with DMF volume ratios to DMF:5), bottle carries out encapsulation process, be placed into the baking oven that temperature is 130 degree (or oil bath
In pot) it is heated to PVA and is completely dissolved, magnetic stirrer makes PVA be uniformly dissolved prepared PVA solution；PVA solution is stood certainly
Room temperature so is cooled to, 6h is stood at room temperature to ensure the full cross-linked of PVA gels.Coagulated using solvent-extracted method removal PVA
Organic solvent in glue, obtained PVA soaks are entered in deionized water, change deionized water within every 6 hours, are circulated 4-6 times.
Preparing PVA gel standard tensile battens has carried out extension test, and has carried out rheology test, to characterize the mechanics of PVA gels
Performance and heat endurance.
Embodiment 1-3 gained PVA gels mechanical property experimental results such as Fig. 1 (tensile strength), Fig. 2 (elongation at break) institute
Show, rheological temperature scanning experimental result is as shown in Figure 3；As shown in Figure 1, wherein when solvent ratios are 4:The gel tool prepared when 6
There is preferable mechanical property, mean intensity is 1.143Mpa, and standard deviation is 0.177Mpa；As shown in Figure 2, each component solvent ratios
Obtained PVA gels elongation at break is more than 500%；Rheology test as shown in Figure 3 shows in 65 DEG C of scope inner gels
The cross-linked structure of stabilization can be kept.
The preparation of the polyvinyl alcohol hydrogel micro-pipe of embodiment 4
11 grams of polyvinyl alcohol (PVA) are weighed, 60 degrees Celsius of dryings 24 hours weigh 35.2 grams of DMSO, 45.48 grams of DMF
(DMSO is 4 with DMF volume ratios:6), bottle carries out encapsulation process, be placed into the baking oven that temperature is 130 degree (or oil bath pan
It is interior) it is heated to PVA and is completely dissolved, magnetic stirrer is uniformly dissolved PVA, and ultrasonic vibration dispels bubble in solution, uses
Be injected into solution in the mould of one end assembling by disposable syringe, and solution assembles the concentric stent of the other end after being filled up completely with
Block；Make mould and pyrosol natural cooling at room temperature, 6h is stood at room temperature to ensure the full cross-linked of PVA gels；Take out PVA
Gel micro-pipe, micro-pipe is soaked into 36 hours in deionized water (wall thickness difference soak time difference) and uses solution extraction side
Method removes organic solvent, changes deionized water in immersion process every 6 hours, and supplementary means can use ultrasonic vibration, heat up etc.
Method accelerates extraction process.
Embodiment 5
11 grams of polyvinyl alcohol (PVA) are weighed, 5.5 grams of Kynoar (PVDF), 60 degrees Celsius of dryings 24 hours are weighed
35.2 grams of DMSO, (DMSO and DMF volume ratios are 4 to 45.48 grams of DMF:6), bottle carries out encapsulation process, is placed into setting temperature
For (or in oil bath pan) is heated to PVA and PVDF is completely dissolved in 130 degree of baking ovens, magnetic stirrer makes PVA and PVDF
It is uniformly dissolved, ultrasonic vibration dispels bubble in solution, solution is injected into the mould that one end is assembled using disposable syringe,
Solution assembles the concentric stuck-module of the other end after being filled up completely with.Make mould and pyrosol natural cooling at room temperature, at room temperature
6h is stood to ensure the full cross-linked of PVA gels.Take out PVA and PVDF mixed matrix gel micro-pipes, by micro-pipe be soaked into from
(wall thickness difference soak time difference) removes organic solvent using solution extracting process 36 hours in sub- water, in immersion process
Deionized water was changed every 6 hours, supplementary means can use the methods such as ultrasonic vibration, intensification to accelerate extraction process.
Embodiment 6
Weigh 11 grams of polyvinyl alcohol (PVA), 5.5 grams of polymethyl methacrylates (PMMA), 60 degrees Celsius of dryings 24 hours,
Weigh 35.2 grams of DMSO, (DMSO and DMF volume ratios are 4 to 45.48 grams of DMF:6), bottle carries out encapsulation process, is placed into setting
Temperature is that (or in oil bath pan) is heated to PVA and PMMA is completely dissolved in 130 degree of baking oven, magnetic stirrer make PVA and
PMMA is uniformly dissolved, and ultrasonic vibration dispels bubble in solution, and solution is injected into the mould that one end is assembled using disposable syringe
In tool, solution assembles the concentric stuck-module of the other end after being filled up completely with.Make mould and pyrosol natural cooling, room at room temperature
Temperature is lower to be stood 6h to ensure the full cross-linked of PVA gels.PVA and PMMA mixed matrix gel micro-pipes are taken out, micro-pipe is soaked into
(wall thickness difference soak time difference) removes organic solvent using solution extracting process 36 hours in deionized water, soaks
Deionized water was changed in journey every 6 hours, supplementary means can use the methods such as ultrasonic vibration, intensification to accelerate extraction process.
PVA is White Flocculus in examples detailed above；PVDF is white powdery solids；PMMA is solid for water white transparency graininess
Body.The gel rubber system used in examples detailed above is pure PVA matrixes and PVDF the and PMMA polyphosphazene polymers of doping regulation and control gelling performance
Compound mixed gel matrix, regulation and control polyvinyl alcohol based hydrogel mechanical property, biocompatibility, degradation property and other be modified to
Point, such as PLA (PLA), polyethylene glycol (PEG), polycaprolactone (PCL) one or more mixture gel-in-matrixes equally fall
Enter the present invention and use gel-in-matrix protection category.
The interior diameter of mold 1 used in examples detailed above is arbitrary dimension in the range of 2~6mm, core rod 2 be overall diameter 1~
Arbitrary dimension in the range of 5mm, concentric fixing device 3 is the concentric arresting fitting therefor for matching therewith.It is similar with present apparatus outward appearance
Other sizes mould it is same in protection category of the present invention.
After for the ease of casting micro-pipe formed product, the demoulding of finished product, the inwall of mold 1 and the outer surface of core rod 2 need to be carried out
Polishing, mold 1 and the selection of the material of core rod 2 can be used stainless steel and other hard materials, will to meet surface smoothness
Ask, preferentially use quartz glass as mold 1 and the material of core rod 2.
Claims (10)
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| CN107513116A (en) * | 2017-09-26 | 2017-12-26 | 四川大学 | A kind of polyvinyl alcohol hydrogel and its production and use |
| CN110240714A (en) * | 2019-06-26 | 2019-09-17 | 武汉工程大学 | A kind of polyvinyl alcohol-based conductive hydrogel and its preparation method and application |
| CN110951093A (en) * | 2019-12-12 | 2020-04-03 | 上海工程技术大学 | A kind of medical gel bionic muscle material and preparation method thereof |
| CN114015079A (en) * | 2021-12-14 | 2022-02-08 | 四川大学 | A kind of polyvinyl alcohol-based piezoelectric active hydrogel and preparation and molding method thereof |
| CN115975320A (en) * | 2023-01-10 | 2023-04-18 | 青岛振昌工贸有限公司 | Plastic packaging bag and preparation process thereof |
| CN117700824A (en) * | 2024-02-06 | 2024-03-15 | 中山大学 | Preparation method of superstructured porous multifunctional hydrogel and its products and applications |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107513116A (en) * | 2017-09-26 | 2017-12-26 | 四川大学 | A kind of polyvinyl alcohol hydrogel and its production and use |
| CN110240714A (en) * | 2019-06-26 | 2019-09-17 | 武汉工程大学 | A kind of polyvinyl alcohol-based conductive hydrogel and its preparation method and application |
| CN110951093A (en) * | 2019-12-12 | 2020-04-03 | 上海工程技术大学 | A kind of medical gel bionic muscle material and preparation method thereof |
| CN110951093B (en) * | 2019-12-12 | 2022-06-28 | 上海工程技术大学 | Medical gel type bionic muscle material and preparation method thereof |
| CN114015079A (en) * | 2021-12-14 | 2022-02-08 | 四川大学 | A kind of polyvinyl alcohol-based piezoelectric active hydrogel and preparation and molding method thereof |
| CN114015079B (en) * | 2021-12-14 | 2022-11-15 | 四川大学 | A polyvinyl alcohol-based piezoelectric active hydrogel and its preparation method |
| CN115975320A (en) * | 2023-01-10 | 2023-04-18 | 青岛振昌工贸有限公司 | Plastic packaging bag and preparation process thereof |
| CN115975320B (en) * | 2023-01-10 | 2024-05-24 | 青岛振昌工贸有限公司 | Plastic packaging bag and preparation process thereof |
| CN117700824A (en) * | 2024-02-06 | 2024-03-15 | 中山大学 | Preparation method of superstructured porous multifunctional hydrogel and its products and applications |
| CN117700824B (en) * | 2024-02-06 | 2024-04-23 | 中山大学 | Preparation method, product and application of super-structure porous multifunctional hydrogel |
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