CN105694319A - Medical polyvinyl alcohol gel and preparing method thereof - Google Patents

Medical polyvinyl alcohol gel and preparing method thereof Download PDF

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Publication number
CN105694319A
CN105694319A CN201610026855.0A CN201610026855A CN105694319A CN 105694319 A CN105694319 A CN 105694319A CN 201610026855 A CN201610026855 A CN 201610026855A CN 105694319 A CN105694319 A CN 105694319A
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polyvinyl alcohol
gel
cross
boric acid
gel according
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袁暾
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions 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
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42Use of materials characterised by their function or physical properties
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02Organic and inorganic ingredients
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/38Boron-containing compounds
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/05Alcohols; Metal alcoholates
    • C08K5/053Polyhydroxylic alcohols
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    • A61LMETHODS 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
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/412Tissue-regenerating or healing or proliferative agents
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    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • C08J2329/00Characterised 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
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Abstract

The invention relates to medical polyvinyl alcohol gel for filling, repairing, application and radiation protection. A preparing method is characterized by including the steps that a cross-linking system is jointly constructed through boric acid in a certain proportion and boraxin a certain proportion, the boric acid and the boraxin are fully dissolved, polyvinyl alcohol is added, the mixture is mixed to be even to be subjected to heating and heat preservation, and the gel is constructed in one or more physical modes. On the basis, 0.9% of sodium chloride is used for reducing the toxicity of the cross-linking system, and blended or copolymerized atactic polyvinyl alcohol, intermittent polyvinyl alcohol and block polyvinyl alcohol are used; monomer alcohol, alkane and aldehyde are added; glycerol is added; the mode that rare earth elements and natural polymers are added is used for adjusting the performance of a gel system and allowing the gel system to meet the requirements of prospective applications of different medical apparatus and instruments. By means of the medical polyvinyl alcohol and the preparing method, the better cross-linking effect, the lower and more controllable toxicity of a cross-linking agent, the better cold accumulation performance and the better radiation protection performance can be provided, biocompatibility is excellent, and the boric acid-boraxin cross-linkage polyvinyl alcohol gel system is can be easily improved in the following process.

Description

A kind of medical polyethylene alcogel and preparation method thereof
Technical field
The present invention relates to a kind of medical apparatus and instruments, be specifically related to a kind of for filling, repair, apply ointment or plaster and the medical polyethylene alcogel of radioprotective, this gel can application in implanting class, wound repair, cold compress and radioprotective apparatus。
Background technology
Many natural and synthesis macromolecular material, all can form gel under appropriate conditions。Some gel rubber materials can have good physics and chemistry and biology performance and be used to medical application。Wherein, because of the cost that it is relatively low, relatively simple one-tenth gel process, being relatively easy to the gelling properties controlled, polyvinyl alcohol gel obtains to be paid attention to widely, all reports to some extent based on the implantation use of polyvinyl alcohol gel, used in tissue engineering and cold compress apparatus。But, the existing polyvinyl alcohol gel effectiveness when using as medical apparatus and instruments, safety and quality controllability still suffer from clearly disadvantageous。
Polyvinyl alcohol gel builds usually by mode physically or chemically。Physics mode includes dehydration and irradiation etc. after multigelation, freeze thawing, and chemical mode then includes the use of multiple acid, aldehyde and salt。It is said that in general, the gel cross-linkage degree built for physically is relatively low, its intensity and stability are also poor。Can being effectively improved with the collaborative of physics mode with chemistry, many reports have been directed to cross-linking agent when using boric acid or borate to build as polyvinyl alcohol gel。Polyvinyl alcohol molecule exists on hydroxyl oxygen atom the lone pair electrons not shared, and the compound with two or more boron atom can have unoccupied orbital, can effectively by polyvinyl alcohol crosslinked formation gelinite。But, when used alone, the salt such as boric acid has acidity, sodium borate have alkalescence, and the pH value condition of this meta-acid or meta-alkali is unfavorable to histiocytic growth。Further, under too low or too high pH value condition, hydroxyl stretches fully, although be conducive to crosslinking, but often because too fast excessively strong partial cross-linking, the crosslinking hampering overall gel on the contrary is uniform。This because cross crosslinking and the partial cross-linking agent that causes fixing be actually also possible to bring to the cleaning process reducing cross-linking agent residual unfavorable。Although it is true that be all included as Cidex-7 at Pharmacopoeia of People's Republic of China mesoboric acid and Borax (sodium borate), it is generally understood that both materials are respectively provided with certain toxicity when excess intake。Therefore, the gel built by this way, when use low concentration cross-linking agent, cross-linking efficiency is limited, and when using higher concentration cross-linking agent and being used for the application needing direct contact tissue cell, residual and cleaning have become again problem。
Polyvinyl alcohol gel can apply to multiple different medical apparatus and instruments, but the character of gel is proposed many requirements that is mutually related by these special applications。Such as, the gel with suitable mechanical property can be used for bone repair of cartilage, but when adopting chemical crosslinking to pursue higher mechanical property, the reaction between residual cross-linker and body can affect safety。When applying at wound surface as dressing, the boron compound discharged gradually can be effectively antibacterial, but be likely to the reparation suppressing tissue simultaneously。During for artificial intraocular lenses, it is desirable to gelinite has good transparency and water-retaining property, but need to avoid improper adhesion and the propagation of cell。When using as radioprotective gel, although gelinite has been able to have certain ability stopping ray, but this ability is still inadequate。During as cold compress gel, cold-storage ability needs the needs according to tissue to be adjusted, and, hardened condition time freezing is also unfavorable for being pasted on to be needed cold compress position and ensures the device design of patient comfort。In a word, existing polyvinyl alcohol gel has various deficiency as medical apparatus and instruments when using, it is necessary to propose superior technique scheme from each side such as gelinite composition, construction method and post processings。
Summary of the invention
It is an object of the invention to: provide and there is better cross-linking effect compared to prior art, lower or more controlled cross-linking agent toxicity, can providing better dynamic performance of ice storage and shielding property, biocompatibility is excellent and is prone to carry out the boric acid-Borax cross-linking polyvinyl alcohol gel rubber system of follow-up improvement。
It is an object of the invention to be achieved through the following technical solutions:
For solving the deficiencies in the prior art, the system jointly building crosslinked polyethylene alcogel with a certain proportion of boric acid and Borax of the invention。The constituent of this system comprises the polyvinyl alcohol that mass concentration (w/v) is 1.0-28%, the boric acid of 0.029-12.6%, the Borax of 0.01-1.0%, and, the ratio of boric acid therein and the amount of substance of Borax is 18:1 to 78:1。Owing to the proper proportion of boric acid Yu Borax can form buffering to system, gel rubber system can be controlled into when continuing to be held in weakly acidic pH, it is possible not only to more uniform one-tenth gel, avoid regional area crosslinking excessively, although and under near-neutral sulfite deinking, become gelation rate to be likely to decline, but whole gel strength can be obviously improved, and the uniformity of system also can provide better cold-storage ability。Near-neutral sulfite deinking is for being uniformly distributed as the boric acid of cross-linking agent-Borax system, and the uniform controlled release of cross-linking agent in degradation process, relatively preferably the histiocyte compatibility etc. are all significant。In this case equally distributed boron element can provide good performance in radioprotective。And, gel rubber system is built with near-neutral sulfite deinking, for many possible subsequent treatment and improvement, the interpolation of such as natural polymer, the introducing of other polymer molecules, the use of softener, fixing and free cross-linker molecule the cleaning of the rare earth element addition and cross-linking system itself that strengthen radioprotective has been provided which favourable condition。
The preparation method building above-mentioned gel rubber system includes: S1) it is sufficiently mixed dissolving boric acid and Borax;S2) in the buffer system built, add polyvinyl alcohol, be warming up to 121 DEG C after mixing and be incubated at least 30 minutes;S3) gel is built by physics mode after cooling。Because boric acid and Borax all as the cross-linking agent of polyvinyl alcohol, only can carry out when weakly acidic pH being sufficiently mixed after both dissolvings build buffer system can to ensure to cross-link with polyvinyl alcohol mixing more all the time。Additionally, the present invention is mainly used for medical apparatus and instruments thus it requires aseptic condition, be warming up to after mixing 121 DEG C and be incubated at least 30 minutes both can effective sterilizing, can help again mix each composition and ensure the exposure of polyvinyl alcohol hydroxyl, promote crosslinking and solve the problem that the cross-linking efficiency brought due to weakly acidic pH system declines to a certain extent。Finally, ensure after cooling that the intensity that the system of mixing also is able to as follow-up collaborative physics becomes gel formats to further enhance gel provides basis。
Although having been able to form gel through above-mentioned building mode, but may be used for collaborative boric acid-Borax chemical crosslinking system including the physics mode of dehydration after multigelation, freeze thawing and one or several steps in irradiation, thus what promote gel further includes the performances such as cold-storage ability, intensity, toughness。Other methods improving gelinite character can include using random, interruption, block and the polyvinyl alcohol with the blended of other high molecular polymers or copolymerization, and other described macromolecules can include but not limited to Polyethylene Glycol, polyacrylic acid and polylactic acid etc.。Due to these different master chain structures polymer molecule in different forms and the interaction of polyvinyl alcohol molecule can effectively adjust in gelinite the interaction between polymer segment and hydrone, therefore, it is possible to embody difference on gelinite physics and chemistry and biological property, thus in concrete medical apparatus and instruments its advantage of application saliency。It addition, when using as cold-storage medical apparatus and instruments, an important parameter request is phase transition temperature。And the neutral system in the present invention ensure that the good compatibility with multiple Molecular regulator, therefore system can add the monomeric polyol less than 1%, alkane and aldehyde to regulate phase transition temperature and cold-storage ability as required。Finally, when using in cold compress apparatus, gelinite firm under low temperature can bring discomfort to user, and adds the glycerol less than 20%, it is possible to well improving the low-temperature flexibility of gelinite, being subject to thus improving use sense。
Using as implantation class and wound repair medical apparatus and instruments is also the potential use that the present invention is possible。Due in these application gelinite can direct contact tissue and cell, the toxicity control of its cross-linking agent and release are the problems that are prioritized of needs。The present invention uses weakly acidic pH buffer system uniformly to become gel, ensure that boric acid-borax crosslinkers used by uniform distribution and is fixed in gel, therefore when gelinite degraded is controlled, the release of cross-linking agent is controlled equally, it is to avoid local cause owing to too much too fast cross-linking agent disengages to histiocytic overt toxicity。Prepare with the sodium chloride solution of 0.9% when preparing gel, and carry out cleaning the control also contributing to cross-linking agent toxicity fully with the sodium chloride solution of 0.9% after becoming gel。This solution ensure that system crystalloid osmotic pressure is close to physiological level, and the cleaning that 0.9% sodium chloride solution carries out effectively removal system can include free cross-linker at interior free molecule, further enhances the biocompatibility of gelinite。Equally, because of the biological effect of its uniqueness, natural polymer, it is widely used in new type medical equipment including protein and polysaccharide, particularly in implanting and applying ointment or plaster in class apparatus。And the weakly acidic pH system character of the present invention, ensure that these natural polymers can be compatible to the gelinite system in the present invention, and ensure the normal performance of its function, and due to these natural high molecular biological effects, some progressively disengage unfavorable factor that cross-linking agent causes will by effective antagonism, and gelinite more can be endowed some more favourable biological effects。Such as, when the release containing borate crosslinker is controlled, and coordinate some natural polymer period of the day from 11 p.m. to 1 a.m and can play such as infection on the contrary, the short effect repaired。
As the another potential use that radioprotective apparatus is gel rubber system of the present invention。As the physical barrier rich in fixing hydrone, namely gel-like medical apparatus and instruments itself has certain capability of resistance to radiation。And the boron atom water in connection in the boric acid-Borax cross-linking system used in the present invention can effectively absorb thermal neutron slowing down fast neutron, thus strengthening capability of resistance to radiation。Gamma-rays, X ray and neutron ray can all be had good protection effect by good radiation shielding requirements simultaneously, the system used in the present invention is mainly for the shielding protection of neutron ray, and in this system, add specific rare earth element, can effectively strengthen the shielding protection to gamma-rays, X ray, to promote gel entirety capability of resistance to radiation。And the weakly acidic pH environment in the present invention, the interpolation for these rare earth elements provides advantage。
The invention provides the boric acid-Borax cross-linking polyvinyl alcohol gel rubber system built with lasting near-neutral sulfite deinking, this system can with the gelling performance regulative mode of multiple beneficial and substances compatible, the release of its cross-linking agent is controlled with toxicity, therefore, it is possible to provide adjustable and be more suitable for the character of clinical demand, it is possible to better meet the application in local cold compress, implantation class medical apparatus and instruments, wound repair apparatus and radioprotective apparatus。Further, because its technological means can quantify and simple, cost is controlled and can provide quality controllability more preferably, it is possible to have wide market prospect。
With the multiple gel that preparation method provided by the invention builds, tentatively carry out meeting GB/T16886(ISO10993) evaluation of series standard, it was demonstrated that its biocompatibility is good。When as cold compress medical apparatus and instruments, gel can provide good cold-storage ability and use susceptibility。When using as radiation proof material, using the teaching of the invention it is possible to provide significantly radioresistance ability。Wounds in mice is applied ointment or plaster and is subcutaneously implanted experiment and also do not observe obvious toxic reaction。
Feature and the difference with the prior art of the present invention are as follows:
As mentioned above, the maximum feature of the present invention is the boric acid using certain amount of substance ratio and the Borax cross-linking agent as polyvinyl alcohol gel, utilize boric acid-Borax buffering that control system pH makes into gel to continue to carry out when gentle weakly acidic pH, thus improving the performance of gelinite, reduce possible toxicity, and promote and other compatibilitys contributing to adjusting the substance system of performance。
Chinese patent application: 200410038808.5, a kind of gel comprising polyvinyl alcohol, borax crosslinkers and other addO-on therapy and its synthetic method disclosed in " polyvinyl alcohol plural gel and synthetic method thereof "。Chinese patent application: 201210329897.3, a kind of polyvinyl alcohol gel using boric acid solution as firming agent and preparation method thereof disclosed in " a kind of polyvinyl alcohol composite hydrogel and preparation method thereof "。Chinese patent application: 201410067443.2, a kind of method relating to preparing gel with calcium chloride-boric acid solution crosslinking disclosed in " a kind of functionalized polyvinyl alcohol hydrogel and preparation method thereof "。Chinese patent application: 201510004442.8, a kind of Borax cross-linking polyvinyl alcohol using glycerol as the gel process for preparing of soft agent disclosed in " a kind of flexible polyethylene alcohol hydrogel cold storing bag preparation method "。But these patent applications be all not related to boric acid and Borax ratio according to a certain ratio build buffering to use, and without system pH being carried out the consideration of Sustainable Control。At present, there is not yet and combine buffering cross-linking system structure polyvinyl alcohol gel the report in the application of biomaterial medical instruments field with certain amount of substance ratio structure boric acid-Borax。
Accompanying drawing explanation
Fig. 1 is the schematic diagram of feature of the present invention and main technical schemes。
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail。
Embodiment 1:
Weigh 0.29g boric acid and 0.1g Borax, fully dissolve with 0.9% sodium chloride solution of 100mL, add the polyvinyl alcohol of 6g and the Polyethylene Glycol of 1g wherein, be warming up to 121 DEG C after again fully mixing and be incubated 60 minutes。Build gel by the multigelation of 20-20 DEG C to 37-20 DEG C circulation after cooling, with physiological saline solution, the gelinite built is cleaned fully, then the stable gel body of acquisition is used for burn wound and applies ointment or plaster reparation。
Embodiment 2:
Weigh 12.6g boric acid and 1.0g Borax, fully dissolve with the distilled water of 100mL, add polyvinyl alcohol and the 0.5g cerous sulfate of 12g wherein, be warming up to 121 DEG C after again fully mixing and be incubated 30 minutes。By building gel after multigelation dehydration after cooling, then the stable gel body of acquisition is used for the application of radioprotective medical apparatus and instruments。
Embodiment 3:
Weigh 5g boric acid and 0.5g Borax, fully dissolve with the distilled water of 100mL, add the polyvinyl alcohol of 10g, 1.0mL ethanol and 10mL glycerol wherein, be warming up to 121 DEG C after again fully mixing and be incubated 30 minutes。Build gel by multigelation and radiation treatment after cooling, then the stable gel body of acquisition is used for local cold compress medical apparatus and instruments。
Embodiment 4:
Weigh 0.029g boric acid and 0.01g Borax, fully dissolve with 0.9% sodium chloride solution of 100mL, add the polyvinyl alcohol of 10g wherein, it is warming up to 121 DEG C after again fully mixing and is incubated 60 minutes, in system, add 1g soluble collagen and 0.5g carboxymethyl chitosan in aseptic condition after being cooled to 40 DEG C, in the way of multigelation, build gel again, then the stable gel body of acquisition being used for implants class medical apparatus and instruments and uses。
Embodiment described above, simply the present invention more preferably detailed description of the invention is several, and the usual variations and alternatives that those skilled in the art carries out within the scope of technical solution of the present invention all should be included in protection scope of the present invention。

Claims (10)

1. a medical polyethylene alcogel, it is characterized in that constituent comprises the polyvinyl alcohol that mass concentration (w/v) is 1.0-28%, the boric acid of 0.029-12.6%, the Borax of 0.01-1.0%, further, boric acid therein is 18:1 to 78:1 with the ratio of the amount of substance of Borax。
2. polyvinyl alcohol gel according to claim 1, it is characterised in that preparation method includes: S1) it is sufficiently mixed dissolving boric acid and Borax;S2) in the buffer system built, add polyvinyl alcohol, be warming up to 121 DEG C after mixing and be incubated at least 30 minutes;S3) gel is built by physics mode after cooling。
3. polyvinyl alcohol gel according to claim 1, it is characterised in that build the physics mode of gel and include dehydration after multigelation, freeze thawing and one or several steps in irradiation。
4. polyvinyl alcohol gel according to claim 1, it is characterized in that polyvinyl alcohol used include random, be interrupted, block and with the blended of other high molecular polymers or copolymerization, other described macromolecules include but not limited to Polyethylene Glycol, polyacrylic acid and polylactic acid。
5. polyvinyl alcohol gel according to claim 1, it is characterised in that add the monomeric polyol less than 1%, alkane and aldehyde, to regulate gelinite crosslinking and dynamic performance of ice storage。
6. polyvinyl alcohol gel according to claim 1, it is characterised in that add the glycerol less than 20%, to regulate the low-temperature flexibility of gelinite。
7. polyvinyl alcohol gel according to claim 1, it is characterised in that the sodium chloride solution with 0.9% is prepared, and clean fully with the sodium chloride solution of 0.9% after becoming gel。
8. polyvinyl alcohol gel according to claim 1, it is characterised in that add natural polymer, including protein and polysaccharide to regulate the biology performance of gelinite。
9. polyvinyl alcohol gel according to claim 1, it is characterised in that add rare earth element, to strengthen the capability of resistance to radiation of gel。
10. polyvinyl alcohol gel according to claim 1, and the application in local cold compress, implantation class medical apparatus and instruments, wound repair apparatus and radioprotective apparatus。
CN201610026855.0A 2016-01-18 2016-01-18 Medical polyvinyl alcohol gel and preparing method thereof Pending CN105694319A (en)

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CN107637893A (en) * 2017-09-26 2018-01-30 中国安全生产科学研究院 A kind of cooling clothes of combination gas cooling and phase-change material
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CN112646209A (en) * 2019-10-11 2021-04-13 天津大学 Double-network physical crosslinking ionic gel electrolyte system based on polyvinyl alcohol-poloxamer and preparation method thereof
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