CN106916333A - A kind of polyvinyl alcohol medical sponge and preparation method thereof - Google Patents

A kind of polyvinyl alcohol medical sponge and preparation method thereof Download PDF

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CN106916333A
CN106916333A CN201511003518.1A CN201511003518A CN106916333A CN 106916333 A CN106916333 A CN 106916333A CN 201511003518 A CN201511003518 A CN 201511003518A CN 106916333 A CN106916333 A CN 106916333A
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polyvinyl alcohol
medical sponge
preparation
starch
sponge
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CN106916333B (en
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张鸾
王威
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Wuhan Mindray Technology Co Ltd
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Wuhan Dragonbio Surgical Implant Co Ltd
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26Working-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
    • 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
    • A61L15/26Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • 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
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    • 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
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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
    • 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
    • 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
    • A61L15/42Use of materials characterised by their function or physical properties
    • A61L15/425Porous materials, e.g. foams or sponges
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/04Foams characterised by their properties characterised by the foam pores
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    • C08J2205/05Open cells, i.e. more than 50% of the pores are open
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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
    • C08J2329/14Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols

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Abstract

The invention provides a kind of polyvinyl alcohol medical sponge and preparation method thereof, preparation method includes:By in polyvinyl alcohol and starch addition distilled water, in 50 95 DEG C of 1~24h of stirring and dissolving, mixed solution is obtained;To crosslinking agent, emulsifying agent and foam stabilizer is added in the mixed solution, in being stirred 2~8 hours at 20~60 DEG C, the second mixed solution is obtained;To acidic catalyst is added in the second mixed solution, acetalation 30~180min of cross-linking reaction is carried out in 20~90 DEG C of constant temperature, obtain emulsion liquid;After the completion of reaction, emulsion liquid is poured into mould, 50~95 DEG C are heating and curing, demoulding washing, cuts sterilizing after cooling, obtains final product polyvinyl alcohol medical sponge.The polyvinyl alcohol medical sponge has insertion open-celled structure, and uniform pore diameter, and good biocompatibility, affine excellent performance, product porosity are high, rate of liquid aspiration fast, can be used for surgical medicine field, are particularly suitable as negative-pressure sealed drainage art sponge consumptive material.

Description

A kind of polyvinyl alcohol medical sponge and preparation method thereof
Technical field
The present invention relates to biological medicine Material Field, and in particular to a kind of polyvinyl alcohol medical sponge and its preparation Method.
Background technology
Polyvinyl acetaldehyde high water absorption sponge material (abbreviation PVF sponges) due to possess water absorbing properties it is strong, Tensile strength is high, and biocompatibility is excellent, wear-resisting, creep resistance, alkali resistance, and good hydrophilic property is non-aging The advantages of, it is widely used in surgical medicine field, especially in negative-pressure sealed drainage iatrotechnics, play biography Pass the effect of negative pressure and drainage secretion.
And the sponge used in negative-pressure sealed drainage iatrotechnics has many following special requirements:Must have one Fixed pressure-proof elasticity modulus to avoid the void collapse that causes by negative pressure and plug-hole;There must be certain hole chi The very little open-celled structure connected with height is to deflect from wound exudate;There must be uniform distribution of pores with by negative pressure Uniformly transfer to the whole surface of a wound for being contacted;There must be certain moisture retention to prevent sponge to be hardened the stimulation surface of a wound; The impurity for causing lesion must not contained.
At present, it is exactly to dissolve polyvinyl alcohol that existing PVF sponges production technology is most classical, foamed/crosslinking Technique, is obtained polyvinyl acetaldehyde high water absorption sponge.China Patent Publication No. be CN101508747 and The application of CN101508814, individually disclose " melamine modified polyvinylalcohol formal foam and Its preparation method and application " and " silicon dioxide modified polyvinylalcohol formal foam and preparation method thereof And application ", in both preparation methods, using starch granules as pore-forming core agent, complete to receive in polyvinyl alcohol After heat cure formative stage, then starch is cleared out from polyvinyl alcohol with substantial amounts of water.If polyethylene Starch is internally formed closed pore in polyvinyl alcohol after the completion of alcohol solidification, and this is difficult completely to clean up starch, and And this kind of technique starch value is low, water consumption is big, is unfavorable for the cost that economizes on resources and cut down.In addition, China Patent Publication No. discloses " high water absorption polyvinyl alcohol foaming body and its preparation for the application of CN1557872 Method ", this application uses to be reacted with inorganic acid with foaming agent sodium acid in poly-vinyl alcohol solution releases two The method of carbon oxide gas is come the pore-forming that foams, but the sponge products cell diameter obtained by foaming is big, and very Hardly possible control is uniform, and rapid because of sodium acid carbonate and inorganic acid strong reaction, abrupt release goes out a large amount of gas Body, gas escapes serious, therefore sodium acid carbonate addition is larger, while also consume more inorganic acid urging Agent, this kind of method is difficult to be applied in industrialized production.
The content of the invention
To solve the above problems, the invention provides a kind of polyvinyl alcohol medical sponge and preparation method thereof, institute Sponge uniform pore diameter is easily controllable, porosity communication performance is good, and hardness is moderate, and wet compressive elasticity is big, soft Tough functional, multiplying power that sponge sucks in water is high, good water-retaining property, and has good hydrophily, can be used for surgery Medical domain, is particularly suitable as negative-pressure sealed drainage art sponge consumptive material.
First aspect present invention provides a kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) polyvinyl alcohol and starch are added in distilled water, in 50-95 DEG C, under 100~600r/min rotating speeds 1~24h of stirring and dissolving, obtains the mixed solution of starch and polyvinyl alcohol;
(2) to crosslinking agent, emulsifying agent and foam stabilizer is added in the mixed solution, in 20~60 DEG C, Stirred 2~8 hours under 200~350r/min rotating speeds, obtain the second mixed solution;
(3) to acidic catalyst is added in second mixed solution, in 20~90 DEG C of constant temperature, acetalation is carried out 30~180min of cross-linking reaction, obtain emulsion liquid;
(4) after the completion of cross-linking reaction, the emulsion liquid is poured into mould, in 50~95 DEG C of 2~8h that are heating and curing, Demoulding washing after room temperature is cooled to, after cutting sterilizing, polyvinyl alcohol medical sponge is obtained final product.
The present invention by the way that starch is soluble in water together with polyvinyl alcohol, by heating send out in aqueous by starch Raw gelatinization reaction, gelatinized starch occupies segment space in acidic catalyst agent solution because of expansion, afterwards poly- second Ketene acetal reacts to be formed, and gelatinized starch is changed into fragment, and the starch remained after solidification is removed by washing with water, The polyvinyl alcohol medical sponge for obtaining just has the structure of continuous perforate and uniform pore diameter.The preparation method is kept away The formation of a large amount of closed pores is exempted from, starch is readily cleaned removal, improves the absorbent of sponge.And the present invention Preparation method need not add foaming agent, and occupying segment space by gelatinized starch just can form height communication aperture Uniform perforate, it is to avoid due to the problem that addition foaming agent causes, such as open pore size size, perforate is uniform Distribution is difficult to control to.The medical sponge tensile strength and compression strength are relatively strong, good biocompatibility, affine Excellent performance, product porosity are high, rate of liquid aspiration is fast, and each process procedure of the preparation method it is simple, Efficiently, the medical sponge can be applied to the clinical medicine domains such as treatment burn, wound, and cell growth has Significant facilitation.
Preferably, calculate in parts by weight, the proportioning of each raw material is as follows:
Polyvinyl alcohol:50~100 parts;Starch:5~10 parts;Distilled water:300~1000 parts;Crosslinking agent:30~70 Part;Emulsifying agent:1~10 part;Foam stabilizer:1~10 part;Acidic catalyst:25~50 parts.
Preferably, the polyvinyl alcohol is poly- second that 1700~2600, alcoholysis degree is 80~99.9% selected from the degree of polymerization One or more in enol.
Preferably, the starch is selected from wheaten starch, starch from sweet potato, tapioca, farina and jade One or more of rice starch.
Preferably, the crosslinking agent be selected from propanetriol-diglycidyl-ether, hexamethylenetetramine, formaldehyde, acetaldehyde, Glyoxal, propionic aldehyde, butyraldehyde, butanedial, glutaraldehyde, capraldehyde, lauryl aldehyde (lauric aldehyde), tridecylic aldehyde, meat Cardamom aldehyde (undecalactone), Methylethyl acetaldehyde, methyl octyl acetaldehyde, methyl nonyl acetaldehyde, trimethyl-acetaldehyde, One or more in benzaldehyde, phenylacetaldehyde, benzenpropanal, cinnamic aldehyde, paraformaldehyde and formalin.
Preferably, the emulsifying agent is selected from polysorbas20, tween 21, polysorbate40, polysorbate60, Tween61, tells Temperature 80, sorbimacrogol oleate100, polysorbate85, benzene sulfonic acid sodium salt, sodium alkyl sulfonate, ethoxylated dodecyl alcohol, diglycerol One or more in polypropylene glycol ether and diisopropyl sodium naphthalene sulfonate.
Preferably, the foam stabilizer is selected from glycerine, polyacrylamide, DDAO, list One or more in monoethanolamine and diethanol amine.
Preferably, the acidic catalyst is selected from hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, acetic acid and ethanedioic acid One or more.
Preferably, the polyvinyl alcohol and the starch in mass ratio 5~10:1 mixing, the polyvinyl alcohol and steaming Distilled water in mass ratio 1:6~10 mixing.
Preferably, the emulsifying agent and the foam stabilizer in mass ratio 1:1 mixing, the emulsifying agent is poly- with described Vinyl alcohol in mass ratio 1:10~100 mixing, the crosslinking agent and the polyvinyl alcohol in mass ratio 0.6~0.7:1 mixes Conjunction, the acidic catalyst and the polyvinyl alcohol in mass ratio 0.5~1:1 mixing.
Step (1)-(3) of the present invention can heat in water-bath or oil bath.
Preferably, the washing methods is that sponge material before cutting dries-leaching by drying-immersion- The endless form of water-dry again is tentatively cleaned;Sponge after cutting dries also by-immersion-is dried - the endless form for soak-drying again is cleaned again.
First aspect present invention provide polyvinyl alcohol medical sponge preparation method, process is simple, efficiently, And by the way that starch is soluble in water together with polyvinyl alcohol, heating makes starch that gelatinization reaction, gelatinized starch to occur Segment space is occupied because of expansion, after perforate is formed after gelatinized starch removal, so that the aperture of sponge is equal Even easily controllable, porosity communication performance is good, and the sponge material is nontoxic to human body, in use not Human body can be caused any harm, can be used for surgical medicine field, be particularly suitable as negative-pressure sealed drainage art Use sponge consumptive material.
Second aspect present invention provides one kind polyvinyl alcohol medical sponge, institute as obtained in above-mentioned preparation method Stating polyvinyl alcohol medical sponge inside has insertion open-celled structure, and the aperture of the perforate is 0.5-3mm, hole Rate is 80%-95%.
Preferably, the water absorbent rate of the polyvinyl alcohol medical sponge is 6-12/gg-1, rate of water absorption is 5-10/g·min-1, in 30-60KPa, apparent density is in 0.08-0.15g/cm for hygrometric state modulus of elasticity in comperssion3
The polyvinyl alcohol medical sponge that second aspect present invention is provided, uniform pore diameter is easily controllable, porosity communication Performance is good, and hardness is moderate, and wet compressive elasticity is big, and flexility is good, and multiplying power that sponge sucks in water is high, water conservation Property is good, and has good hydrophily, can be used for surgical medicine field, is particularly suitable as negative-pressure sealed drawing Stream art sponge consumptive material.
Specific embodiment
As described below is the preferred embodiment of the present invention, it is noted that for the common skill of the art For art personnel, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, this A little improvements and modifications are also considered as protection scope of the present invention.
In the following embodiments of the present invention, the water absorbent rate and rate of water absorption of sponge press the survey of GB/T 8810-2005 standards It is fixed, the hygrometric state modulus of elasticity in comperssion of sponge be by after sponge sucks in water by GB-/T14694-93 standard tests, it is apparent Density presses GB-/T 6343-2009 standard tests, and porosity is determined by quality-volumetric method.
Embodiment 1
A kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) by weight, it is 1700, the polyvinyl alcohol of alcoholysis degree 99.9% and 5 parts small by 50 parts of degree of polymerization After wheat starch blending is uniform, it is added in reactor with 300 parts of distilled water, under 50 DEG C of oil baths, rotating speed is 100r/min, stirring and dissolving 24h, obtain starch and polyvinyl alcohol solution;
(2) to 1 part of sodium alkyl sulfonate, 1 part of glycerine, 30 of addition in above-mentioned starch and polyvinyl alcohol solution Part hexamethylenetetramine, at a temperature of 20 DEG C, rotating speed is 200r/min, at the uniform velocity stirs 8h, obtains second and mixes Close solution;
(3) to 25 parts of hydrochloric acid are added in above-mentioned second mixed solution, oil bath steady temperature is 20 DEG C, is contracted The cross-linking reaction 6min of hydroformylation, after the completion of cross-linking reaction, obtains emulsion liquid, now abscess in emulsion liquid Structure is preliminarily formed;
(4) gained emulsion liquid is poured into mould, mould is heating and curing 2h in the environment of temperature 50 C, cold But to the demoulding after room temperature, carried out tentatively by the endless form for dry-soak-dry-soak-drying again Cleaning;The specification specified is cut into by size again after preliminary cleaning, the sponge after cutting is also by drying-leaching The endless form of water-drying-immersion-dry again is cleaned again, last irradiated sterilizing, is obtained final product poly- Vinyl alcohol medical sponge.
Embodiment of the present invention products therefrom is white spongy, uniform foam cell, and aperture is in 0.5-3mm;Light weight has Elasticity, pliability is good, and hardness is moderate, softens after water suction, and water-absorbing-retaining performance is excellent, possesses height The property of liquid absorption sponge.
The polyvinyl alcohol medical sponge performance test results that the present embodiment is prepared show that water absorbent rate is 6.3/g·g-1, rate of water absorption is 6.7/gmin-1, hygrometric state modulus of elasticity in comperssion exists in 49.1KPa, apparent density 0.104g/cm3, porosity is 87%.
Embodiment 2
A kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) by weight, it is 2000, the polyvinyl alcohol of alcoholysis degree 80% and 5 parts of corns by 50 parts of degree of polymerization After starch blending is uniform, it is added in reactor with 400 parts of distilled water, under 95 DEG C of oil baths, rotating speed is 600r/min, stirring and dissolving 1h, obtain starch and polyvinyl alcohol solution;
(2) to 0.5 part of diglycerol polypropylene glycol ether, 0.5 of addition in above-mentioned starch and polyvinyl alcohol solution Part diethanol amine, 30 parts of formaldehyde, at a temperature of 60 DEG C, rotating speed is 350r/min, at the uniform velocity stirs 2h, is obtained Second mixed solution;
(3) to 50 parts of hydrochloric acid are added in above-mentioned second mixed solution, oil bath steady temperature is 60 DEG C, is contracted The cross-linking reaction 0.5min of hydroformylation, after the completion of cross-linking reaction, obtains emulsion liquid, now abscess in emulsion liquid Structure is preliminarily formed;
(4) gained emulsion liquid is poured into mould, mould is heating and curing 8h in the environment of 95 DEG C of temperature, cold But to the demoulding after room temperature, carried out tentatively by the endless form for dry-soak-dry-soak-drying again Cleaning;The specification specified is cut into by size again after preliminary cleaning, the sponge after cutting is also by drying-leaching The endless form of water-drying-immersion-dry again is cleaned again, last irradiated sterilizing, is obtained final product poly- Vinyl alcohol medical sponge.
The present embodiment products therefrom is white spongy, uniform foam cell, and aperture is in 0.5-3mm;Light weight is flexible, Pliability is good, and hardness is moderate, softens after water suction, and water-absorbing-retaining performance is excellent, possesses imbibition sea high Continuous property.
The polyvinyl alcohol medical sponge performance test results that the present embodiment is prepared show that water absorbent rate is 7.4/g·g-1, rate of water absorption is 8.1/gmin-1, hygrometric state modulus of elasticity in comperssion exists in 45.3KPa, apparent density 0.121g/cm3, porosity is 85%.
Embodiment 3
A kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) by weight, by 50 parts of degree of polymerization be 2400, the polyvinyl alcohol of alcoholysis degree 88%, 50 parts gather Right is 1700, and the polyvinyl alcohol of alcoholysis degree 99.9% and 5 portions of wheaten starches and 5 parts of cornstarch blendings are After even, it is added in reactor with 1000 parts of distilled water, under 95 DEG C of oil baths, rotating speed is 100r/min, is stirred Dissolving 24h, obtains starch and polyvinyl alcohol solution;
(2) to added in above-mentioned starch and polyvinyl alcohol solution 10 parts of sodium alkyl sulfonates, 10 parts of glycerine, 70 parts of formaldehyde, at a temperature of 60 DEG C, rotating speed is 350r/min, at the uniform velocity stirs 8h, obtains the second mixed solution;
(3) 50 parts of sulfuric acid are added to above-mentioned second mixed solution, oil bath steady temperature is 60 DEG C, carries out acetal The cross-linking reaction 3min of change, after the completion of cross-linking reaction, obtains emulsion liquid, now abscess knot in emulsion liquid Structure is preliminarily formed;
(4) gained emulsion liquid is poured into mould, mould is heating and curing 2h in the environment of 95 DEG C of temperature, cold But to the demoulding after room temperature, carried out tentatively by the endless form for dry-soak-dry-soak-drying again Cleaning;The specification specified is cut into by size again after preliminary cleaning, the sponge after cutting is also by drying-leaching The endless form of water-drying-immersion-dry again is cleaned again, last irradiated sterilizing, is obtained final product poly- Vinyl alcohol medical sponge.
The present embodiment products therefrom is white spongy, uniform foam cell, and aperture is in 0.5-3mm;Light weight is flexible, Pliability is good, and hardness is moderate, softens after water suction, and water-absorbing-retaining performance is excellent, possesses imbibition sea high Continuous property.
The polyvinyl alcohol medical sponge performance test results that the present embodiment is prepared show that water absorbent rate is 8.7/g·g-1, rate of water absorption is 6.0/gmin-1, hygrometric state modulus of elasticity in comperssion exists in 37.8KPa, apparent density 0.147g/cm3, porosity is 82.3%.
Embodiment 4
A kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) by weight, it is 2600, the polyvinyl alcohol of alcoholysis degree 99.9% and 10 parts by 100 parts of degree of polymerization After tapioca blending is uniform, it is added in reactor with 1000 parts of distilled water, under 95 DEG C of oil baths, rotating speed It is 100r/min, stirring and dissolving 24h, obtains starch and polyvinyl alcohol solution;
(2) to 5 parts of sodium alkyl sulfonates, 5 parts of glycerine, 70 of addition in above-mentioned starch and polyvinyl alcohol solution Part formaldehyde, at a temperature of 20 DEG C, rotating speed is 200r/min, at the uniform velocity stirs 8h, obtains the second mixed solution;
(3) to 50 parts of hydrochloric acid are added in above-mentioned second mixed solution, oil bath steady temperature is 20 DEG C, is contracted The cross-linking reaction 1.5min of hydroformylation, after the completion of cross-linking reaction, obtains emulsion liquid, now abscess in emulsion liquid Structure is preliminarily formed;
(4) gained emulsion liquid is poured into mould, mould is heating and curing 8h in the environment of temperature 50 C, cold But to the demoulding after room temperature, carried out tentatively by the endless form for dry-soak-dry-soak-drying again Cleaning;The specification specified is cut into by size again after preliminary cleaning, the sponge after cutting is also by drying-leaching The endless form of water-drying-immersion-dry again is cleaned again, last irradiated sterilizing, is obtained final product poly- Vinyl alcohol medical sponge.
The present embodiment products therefrom is white spongy, uniform foam cell, and aperture is in 0.5-3mm;Light weight is flexible, Pliability is good, and hardness is moderate, softens after water suction, and water-absorbing-retaining performance is excellent, possesses imbibition sea high Continuous property.
The polyvinyl alcohol medical sponge performance test results that the present embodiment is prepared show that water absorbent rate is 11.4/g·g-1, rate of water absorption is 9.4/gmin-1, hygrometric state modulus of elasticity in comperssion is in 51.6KPa, apparent density In 0.096g/cm3, porosity is 91%.
Embodiment 5
A kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) by weight, it is 2600, the polyvinyl alcohol of alcoholysis degree 99.9%, 50 parts by 50 parts of degree of polymerization The degree of polymerization is 2000, after the polyvinyl alcohol of alcoholysis degree 80% and 10 parts of wheaten starch blendings uniformly, with 1000 parts of steamings Distilled water is added in reactor, and under 95 DEG C of oil baths, rotating speed is 600r/min, stirring and dissolving 24h, is formed sediment Powder and polyvinyl alcohol solution;
(2) to above-mentioned starch and polyvinyl alcohol solution add 5 parts of sodium alkyl sulfonates, 5 parts of benzene sulfonic acid sodium salts, 5 parts of diethanol amine, 5 parts of MEAs, 30 parts of glutaraldehydes, 20 parts of acetaldehyde, 10 parts of Methylethyl acetaldehyde, At a temperature of 20 DEG C, rotating speed is 200r/min, at the uniform velocity stirs 8h, obtains the second mixed solution;
(3) to 50 parts of hydrochloric acid are added in above-mentioned second mixed solution, oil bath steady temperature is 20 DEG C, is contracted The cross-linking reaction 6min of hydroformylation, after the completion of cross-linking reaction, obtains emulsion liquid, now abscess in emulsion liquid Structure is preliminarily formed;
(4) gained emulsion liquid is poured into mould, mould is heating and curing 8h in the environment of temperature 50 C, cold But to the demoulding after room temperature, carried out tentatively by the endless form for dry-soak-dry-soak-drying again Cleaning;The specification specified is cut into by size again after preliminary cleaning, the sponge after cutting is also by drying-leaching The endless form of water-drying-immersion-dry again is cleaned again, last irradiated sterilizing, is obtained final product poly- Vinyl alcohol medical sponge.
The present embodiment products therefrom is white spongy, uniform foam cell, and aperture is in 0.5-3mm;Light weight is flexible, Pliability is good, and hardness is moderate, softens after water suction, and water-absorbing-retaining performance is excellent, possesses imbibition sea high Continuous property.
The polyvinyl alcohol medical sponge performance test results that the present embodiment is prepared show that water absorbent rate is 11.4/g·g-1, rate of water absorption is 7.6/gmin-1, hygrometric state modulus of elasticity in comperssion is in 54.2KPa, apparent density In 0.103g/cm3, porosity is 93%.
Embodiment 6
A kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) by weight, it is 2600, the polyvinyl alcohol of alcoholysis degree 80% and 10 parts small by 50 parts of degree of polymerization After wheat starch blending is uniform, it is added in reactor with 500 parts of distilled water, under 95 DEG C of oil baths, rotating speed is 600r/min, stirring and dissolving 24h, obtain starch and polyvinyl alcohol solution;
(2) to added in above-mentioned starch and polyvinyl alcohol solution 5 parts of diglycerol polypropylene glycol ethers, 5 part two Monoethanolamine, 15 parts of glutaraldehydes, 15 parts of formaldehyde, at a temperature of 20 DEG C, rotating speed is 200r/min, is at the uniform velocity stirred 8h, obtains the second mixed solution;
(3) to 50 parts of sulfuric acid are added in above-mentioned second mixed solution, oil bath steady temperature is 20 DEG C, is contracted The cross-linking reaction 6min of hydroformylation, after the completion of cross-linking reaction, obtains emulsion liquid, now abscess in emulsion liquid Structure is preliminarily formed;
(4) gained emulsion liquid is poured into mould, mould is heating and curing 8h in the environment of 95 DEG C of temperature, cold But to the demoulding after room temperature, carried out tentatively by the endless form for dry-soak-dry-soak-drying again Cleaning;The specification specified is cut into by size again after preliminary cleaning, the sponge after cutting is also by drying-leaching The endless form of water-drying-immersion-dry again is cleaned again, last irradiated sterilizing, is obtained final product poly- Vinyl alcohol medical sponge.
The present embodiment products therefrom is white spongy, uniform foam cell, and aperture is in 0.5-3mm;Light weight is flexible, Pliability is good, and hardness is moderate, softens after water suction, and water-absorbing-retaining performance is excellent, possesses imbibition sea high Continuous property.
The polyvinyl alcohol medical sponge performance test results that the present embodiment is prepared show that water absorbent rate is 10.2/g·g-1, rate of water absorption is 5.9/gmin-1, hygrometric state modulus of elasticity in comperssion is in 49.9KPa, apparent density In 0.095g/cm3, porosity is 87%.
Embodiment 7
A kind of preparation method of polyvinyl alcohol medical sponge, comprises the following steps:
(1) by weight, it is 2600 by 40 parts of degree of polymerization, the polyvinyl alcohol of alcoholysis degree 80%, 30 parts of polymerizations It is 1700 to spend, and the polyvinyl alcohol of alcoholysis degree 99.9%, 30 parts of degree of polymerization are 2000, the polyethylene of alcoholysis degree 80% After alcohol and 10 parts of wheaten starch blendings are uniform, it is added in reactor with 800 parts of distilled water, under 95 DEG C of oil baths, Rotating speed is 600r/min, stirring and dissolving 24h, obtains starch and polyvinyl alcohol solution;
(2) to added in above-mentioned starch and polyvinyl alcohol solution 2 parts of diglycerol polypropylene glycol ethers, 2 part two Monoethanolamine, 60 parts of glutaraldehydes, at a temperature of 20 DEG C, rotating speed is 200r/min, at the uniform velocity stirs 8h, obtains Two mixed solutions;
(3) to 80 parts of sulfuric acid are added in above-mentioned second mixed solution, oil bath steady temperature is 20 DEG C, is contracted The cross-linking reaction 3min of hydroformylation, after the completion of cross-linking reaction, obtains emulsion liquid, now abscess in emulsion liquid Structure is preliminarily formed;
(4) gained emulsion liquid is poured into mould, mould is heating and curing 8h in the environment of 95 DEG C of temperature, cold But to the demoulding after room temperature, carried out tentatively by the endless form for dry-soak-dry-soak-drying again Cleaning;The specification specified is cut into by size again after preliminary cleaning, the sponge after cutting is also by drying-leaching The endless form of water-drying-immersion-dry again is cleaned again, last irradiated sterilizing, is obtained final product poly- Vinyl alcohol medical sponge.
The present embodiment products therefrom is white spongy, uniform foam cell, and aperture is in 0.5-3mm;Light weight is flexible, Pliability is good, and hardness is moderate, softens after water suction, and water-absorbing-retaining performance is excellent, possesses imbibition sea high Continuous property.
The polyvinyl alcohol medical sponge performance test results that the present embodiment is prepared show that water absorbent rate is 9.5/g·g-1, rate of water absorption is 6.0/gmin-1, hygrometric state modulus of elasticity in comperssion exists in 46KPa, apparent density 0.099g/cm3, porosity is 88%.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, But therefore can not be interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for this area Those of ordinary skill for, without departing from the inventive concept of the premise, can also make it is some deformation and Improve, these belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended Claim is defined.

Claims (10)

1. a kind of preparation method of polyvinyl alcohol medical sponge, it is characterised in that comprise the following steps:
(1) polyvinyl alcohol and starch are added in distilled water, in 50-95 DEG C, under 100~600r/min rotating speeds 1~24h of stirring and dissolving, obtains the mixed solution of starch and polyvinyl alcohol;
(2) to crosslinking agent, emulsifying agent and foam stabilizer is added in the mixed solution, in 20~60 DEG C, Stirred 2~8 hours under 200~350r/min rotating speeds, obtain the second mixed solution;
(3) to acidic catalyst is added in second mixed solution, in 20~90 DEG C of constant temperature, acetalation is carried out 30~180min of cross-linking reaction, obtain emulsion liquid;
(4) after the completion of cross-linking reaction, the emulsion liquid is poured into mould, in 50~95 DEG C of 2~8h that are heating and curing, Demoulding washing after room temperature is cooled to, after cutting sterilizing, polyvinyl alcohol medical sponge is obtained final product.
2. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that with weight Amount part calculates, and the proportioning of each raw material is as follows:
Polyvinyl alcohol:50~100 parts;Starch:5~10 parts;Distilled water:300~1000 parts;Crosslinking agent:30~70 Part;Emulsifying agent:1~10 part;Foam stabilizer:1~10 part;Acidic catalyst:25~50 parts.
3. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that described Polyvinyl alcohol is selected from the one kind or many in the polyvinyl alcohol that the degree of polymerization is that 1700~2600, alcoholysis degree is 80~99.9% Kind;The starch is selected from wheaten starch, starch from sweet potato, tapioca, farina and cornstarch One or more.
4. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that described Crosslinking agent be selected from propanetriol-diglycidyl-ether, hexamethylenetetramine, formaldehyde, acetaldehyde, glyoxal, propionic aldehyde, Butyraldehyde, butanedial, glutaraldehyde, capraldehyde, lauryl aldehyde, tridecylic aldehyde, myristic aldehyde, Methylethyl acetaldehyde, Methyl octyl acetaldehyde, methyl nonyl acetaldehyde, trimethyl-acetaldehyde, benzaldehyde, phenylacetaldehyde, benzenpropanal, cinnamic aldehyde, One or more in paraformaldehyde and formalin.
5. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that described Emulsifying agent is selected from polysorbas20, tween 21, polysorbate40, polysorbate60, Tween61, Tween 80, sorbimacrogol oleate100, tells Temperature 85, benzene sulfonic acid sodium salt, sodium alkyl sulfonate, ethoxylated dodecyl alcohol, diglycerol polypropylene glycol ether and two are different One or more in naphthalene sulfonate;The foam stabilizer is selected from glycerine, polyacrylamide, dodecyl One or more in dimethyl amine, MEA and diethanol amine.
6. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that described Acidic catalyst is selected from one or more in hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, acetic acid and ethanedioic acid.
7. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that described Polyvinyl alcohol and the starch in mass ratio 5~10:1 mixing, the polyvinyl alcohol and distilled water are in mass ratio 1:6~10 mixing.
8. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that described Emulsifying agent and the foam stabilizer in mass ratio 1:1 mixing, the emulsifying agent is with the polyvinyl alcohol in mass ratio 1:10~100 mixing.
9. the preparation method of polyvinyl alcohol medical sponge as claimed in claim 1, it is characterised in that described Crosslinking agent and the polyvinyl alcohol in mass ratio 0.6~0.7:1 mixing, the acidic catalyst and the polyvinyl alcohol In mass ratio 0.5~1:1 mixing.
10. a kind of polyvinyl alcohol medical sponge, it is characterised in that it is prepared as described in claim any one of 1-9 Method is obtained;The polyvinyl alcohol medical sponge inside has insertion open-celled structure, and the aperture of the perforate is 0.5-3mm, porosity is 80%-95%.
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CN110898319A (en) * 2019-12-19 2020-03-24 北京英佳麦迪克医用材料有限公司 Cervical auxiliary dilator made of sponge material
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CN112625389A (en) * 2020-12-16 2021-04-09 湖北魔洗高新材料制品有限公司 Production process of mop head production line based on PVA collodion
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CN113045793A (en) * 2021-04-02 2021-06-29 宁波因天之序生物科技有限公司 Medical hemostatic sponge material and preparation method thereof
CN113861515A (en) * 2021-09-16 2021-12-31 无锡学院 Water-soluble starch-based packaging buffer filler and preparation method thereof
CN113930038A (en) * 2021-10-18 2022-01-14 广州润虹医药科技股份有限公司 Soft polyvinyl formal sponge in dry state and preparation method thereof
CN113980340A (en) * 2021-11-26 2022-01-28 广州德棉科技有限公司 Water-absorbing sponge suitable for plant growth and preparation method thereof
CN114874575A (en) * 2021-12-07 2022-08-09 广安职业技术学院 Low-density small-aperture polyvinyl formal foam material
CN116159178A (en) * 2023-04-18 2023-05-26 上海汇禾医疗器械有限公司 Small-particle-size embolism microsphere and preparation method thereof

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CN110835448A (en) * 2019-12-09 2020-02-25 成都博创必成生物技术有限公司 Polyvinyl acetal foam material, preparation method thereof and cervical dilation device
CN110898319A (en) * 2019-12-19 2020-03-24 北京英佳麦迪克医用材料有限公司 Cervical auxiliary dilator made of sponge material
CN110935055A (en) * 2019-12-19 2020-03-31 北京英佳麦迪克医用材料有限公司 Medical hemostatic sponge material and preparation method thereof
CN112625389A (en) * 2020-12-16 2021-04-09 湖北魔洗高新材料制品有限公司 Production process of mop head production line based on PVA collodion
CN112891997A (en) * 2021-01-29 2021-06-04 中国科学院长春应用化学研究所 Emulsion separation material and preparation method thereof
CN112891997B (en) * 2021-01-29 2021-11-09 中国科学院长春应用化学研究所 Emulsion separation material and preparation method thereof
CN113045793A (en) * 2021-04-02 2021-06-29 宁波因天之序生物科技有限公司 Medical hemostatic sponge material and preparation method thereof
CN113861515A (en) * 2021-09-16 2021-12-31 无锡学院 Water-soluble starch-based packaging buffer filler and preparation method thereof
CN113930038A (en) * 2021-10-18 2022-01-14 广州润虹医药科技股份有限公司 Soft polyvinyl formal sponge in dry state and preparation method thereof
CN113930038B (en) * 2021-10-18 2023-09-19 广州倍健医疗用品有限公司 Soft polyvinyl formal sponge in dry state and preparation method thereof
CN113980340A (en) * 2021-11-26 2022-01-28 广州德棉科技有限公司 Water-absorbing sponge suitable for plant growth and preparation method thereof
CN113980340B (en) * 2021-11-26 2023-03-14 广州德棉科技有限公司 Water-absorbing sponge suitable for plant growth and preparation method thereof
CN114874575A (en) * 2021-12-07 2022-08-09 广安职业技术学院 Low-density small-aperture polyvinyl formal foam material
CN114874575B (en) * 2021-12-07 2024-01-26 广安职业技术学院 Low-density small-pore-size polyvinyl formal foam material
CN116159178A (en) * 2023-04-18 2023-05-26 上海汇禾医疗器械有限公司 Small-particle-size embolism microsphere and preparation method thereof
CN116159178B (en) * 2023-04-18 2023-07-04 上海汇禾医疗器械有限公司 Small-particle-size embolism microsphere and preparation method thereof

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Address before: 430065, Tsing Ling Town Industrial Zone, Hongshan District, Hubei, Wuhan Province, No. 18

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