CN102605672A - High-porosity chitosan/macromolecule blending thin film felt and preparation method thereof - Google Patents

High-porosity chitosan/macromolecule blending thin film felt and preparation method thereof Download PDF

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Publication number
CN102605672A
CN102605672A CN2012101094172A CN201210109417A CN102605672A CN 102605672 A CN102605672 A CN 102605672A CN 2012101094172 A CN2012101094172 A CN 2012101094172A CN 201210109417 A CN201210109417 A CN 201210109417A CN 102605672 A CN102605672 A CN 102605672A
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shitosan
wadding
cotton
quilt
fine
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CN102605672B (en
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杨庆
郯志清
沈新元
吉亚丽
吴文华
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Donghua University
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Donghua University
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Abstract

The invention relates to a high-porosity chitosan/macromolecule blending thin film felt and a preparation method thereof. The blending thin film felt is a film structure formed by stacking various flocculent fibers in a mixed manner. The preparation method comprises the following steps of: (1) putting chitosan into an acetic acid water solution so as to prepare chitosan pulp; (2) dissolving sodium hydroxide, urea and zinc acetate in water to be used as chitosan coagulating liquid; (3) spraying the chitosan pulp to the coagulating liquid at a high-speed stirring condition, so as to the coagulating liquid to coagulate to be chitosan flocculent fibers, and diffusing the chitosan flocculent fibers in deionized water after filtering and water washing so as to form chitosan flocculent fiber suspension supernatant; (4) carrying out the steps (1)-(3) to prepare corresponding macromolecule flocculent fiber suspension supernatant by using a certain macromolecule raw material; (5) mixing the chitosan flocculent fiber suspension supernatant with the macromolecule flocculent fiber suspension supernatant at a proper ratio, and then picking obtained blending thin film felt out by using a filter screen; and (6) deeply freezing and sublimating the thin film felt after water on the surface of the thin film felt is drained, so as to obtain the high-porosity chitosan/macromolecule blending thin film felt. The material has good solution adsorbability and is suitable for being used as wound dressing.

Description

A kind of high porosity shitosan/polymer blended film felt and preparation method thereof
Technical field
The present invention relates to a kind of high porosity shitosan/polymer blended film felt and preparation method thereof.
Background technology
Shitosan is the product of chitin N-deacetylation, and its chemical name is β-(1 → 4)-2-amino-2-deoxy-D-glucose.Pure chitosan is translucent, the tasteless odorless avirulence of a kind of white, has a little nacreous powdery solid; Chemical reactions such as hydrolysis, alkylation, acylated, carboxy methylation, sulfonation, nitrated, halogenation, oxidation, reduction, condensation and complexing can take place under given conditions; Can generate chitosan derivatives, enlarge the Application of Chitosan scope with different performance.
Shitosan has physiologically active preferably, can suppress bacterial activity, activates airframe systems, absorption and drainage heavy metal, keep immune effect and dissolubility etc.Shitosan also has other special purpose, like the special-purpose shitosan of cosmetics, the special-purpose shitosan of flocculant, agriculture feed and the special-purpose shitosan of bait, the special-purpose shitosan of tobacco smoked sheet etc.Shitosan also has extensive use aspect food, like antiseptic, fruit and vegetable fresh-keeping agent, anti-oxidant, food supplement, clarification of water agent, enzyme immobilization agent etc.The application of shitosan aspect medical science mainly contains: styptic, Wound filling, bactericidal agent, Wound-healing agent, medicinal slow release agent, tooth filler, artificial blood vessel, wound ulcer dressing, operation suture thread etc.
One of modal form was fiber and fabric nonwoven cloth during shitosan was used.The spinning of chitin fiber has multiple mode, the most generally wet spinning.People such as Hu Qiaoling are spinning solution with basic solvent dissolving shitosan; The shitosan macromolecular chain is existed with the height solvent swelling state; Macromolecular chain is arranged tightr, has overcome shitosan unsure state in acid solution, guarantees that shitosan not hydrolysis of macromolecular chain and glycosidic bond do not rupture; Make the mechanical property of chitin fiber be improved [Hu Qiaoling etc., a kind of preparation method of chitin fiber (201110099174.4)].Zhou Jia village etc. prepares medical chitosan fibre with wet spinning process; Place glacial acetic acid aqueous solution temp-controlling and time-controlling under stirring condition slowly to dissolve chitosan powder; Shitosan content>99.9% in the chitin fiber of processing [Zhou Jia village etc., medical chitosan fibre and preparation method thereof (200810015053.5)].People such as Yu Shitao adopt ionic liquid aqueous solution as solvent; Slowly add the shitosan powder; After stirring, filtration, deaeration, obtain concentration and be 3~7.5% homogeneous phase transparent spinning solution; Adopt the conventional wet spinning process to obtain chitin fiber [Yu Shitao etc., a kind of preparation method of chitin fiber (200910138811.7)] subsequently.
In recent years, method of electrostatic spinning is used to spin the Chitosan Ultrafine fiber.People such as Xu Xiongli are solvent with formic acid; Gelatin solution and shitosan slurries are mixed the back according to a certain percentage add silver nitrate; Gelatin/chitosan/liquor argenti nitratis ophthalmicus to gained carries out electrostatic spinning; Prepared composite nanometer fiber felt containing nano silver gelatin/chitosan can be used as medical dressing [Xu Xiongli etc. are used for medical dressing composite nanometer fiber felt containing nano silver gelatin/chitosan and preparation (200710171324.1)].People such as Huang Xiaojun are dissolved in shitosan and polyvinyl alcohol in the mixed solvent of glacial acetic acid and water and form clear solution; Process the chitosan nano fiber composite membrane through method of electrostatic spinning; And with its carrier as enzyme immobilization; [Huang Xiaojun etc., a kind of preparation method of chitosan nano fiber composite film immobilized enzyme (200610154566.5)].Human method of electrostatic spinning such as Wu Dayong prepare chitosan nano fiber membrane; With obtaining the chitosan nano fiber membrane sorbing material after the immersion in alkaline solution of this tunica fibrosa, cleaning and the dried; This material is Adsorption of Cu (II), Hg (II), Cd (II) and Pb heavy metal ion [Wu Dayong etc., chitosan nano fiber membrane sorbing material and preparation method thereof (201110146164.1)] such as (II) efficiently.
The wet spinning process of chitin fiber is to use the most extensively, also is the most traditional spinning process that whole spinning technique route is too tediously long, and production cost is very high; Though method of electrostatic spinning can obtain superfine fibre, output is extremely low.Of the present inventionly copy the paper legal system to be equipped with the method technological process of shitosan and shitosan/polymer blended film felt thereof simple; Equipment investment is few, owing to adopted freeze drying to copying paper film felt, the resulting paper film felt of copying is the high porosity structure; Water absorbing properties is extremely strong, is suitable for surface of a wound auxiliary material.
Summary of the invention
Technical problem to be solved by this invention provides a kind of high porosity shitosan/polymer blended film felt and preparation method thereof, and this blend film felt has good solution absorbs property, biocidal property and strength and elongation, can be used for the treatment of human body surface wound; And the preparation method is simple, is suitable for suitability for industrialized production.
A kind of high porosity shitosan of the present invention/polymer blended film felt, described high porosity shitosan/polymer blended film felt are the fine and fine high voidage membrane structure that forms of piling up of macromolecule wadding of shitosan wadding; Its mass ratio is that the shitosan wadding is fine: macromolecule wadding fibre=99.9: 0.1~50: 50; Described wadding fibre is meant cotton-shaped short fiber, and described cotton-shaped short fiber is meant little and loose short fiber coagula; The voidage of described high porosity shitosan/polymer blended film felt is 30~80 (V/V) %.
As optimized technical scheme:
Aforesaid a kind of high porosity shitosan/polymer blended film felt, described macromolecule are one or more mixing in polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA and the cellulose.
Aforesaid a kind of high porosity shitosan/polymer blended film felt, described cotton-shaped short fiber spray solidification forming with the coagulating bath of slurries under high-speed stirred and obtain; Described high voidage membrane structure adopts freeze-drying to process.
The present invention also provides the preparation method of a kind of high porosity shitosan/polymer blended film felt, may further comprise the steps:
(1) shitosan slurry preparation: it is that the shitosan slurries are processed in dissolving in 2~8 (V/V) % acetic acid that the shitosan powder is invested in concentration, and the shitosan content in the said shitosan slurries is 0.5~5.0 (W/W) %;
(2) the shitosan solidification liquid prepares: NaOH, urea and zinc acetate are invested in to stir in the deionized water process the shitosan solidification liquid; In the said shitosan solidification liquid, naoh concentration is 4~12 (W/W) %, and urea concentration is 0.5~1.0 (W/W) %, and zinc acetate concentration is 0.1~0.5 (W/W) %;
(3) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: under high-speed stirred,, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton to shitosan solidification liquid jetski glycan slurries; The described shitosan fine suspension of wadding a quilt with cotton is made up of cotton-shaped shitosan short fiber and suspension, and described cotton-shaped shitosan short fiber is suspended in the suspension; Described cotton-shaped shitosan short fiber is meant little and loose shitosan short fiber coagula; The shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, obtaining cotton-shaped shitosan short fiber is that the shitosan wadding is fine; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1~5 (W/W) %;
(4) macromolecule raw material of an amount of ratio is invested in processes Polymer Solution in the corresponding solvent; Allocate the solidification liquid of corresponding Polymer Solution;
(5) under high-speed stirred, spray Polymer Solution, make it be frozen into the macromolecule fine suspension of wadding a quilt with cotton to solidification liquid;
(6) the fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, obtaining cotton-shaped polymeric staple fiber is that the macromolecule wadding is fine;
(7) again the macromolecule fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the macromolecule fine suspension clear liquid of wadding a quilt with cotton, its concentration is 0.1~5 (W/W) %;
(8) wad a quilt with cotton fine suspension clear liquid and macromolecule of shitosan wadded a quilt with cotton fine suspension clear liquid with 1~9: 9~1 weight ratio mixing and stirring, with filter screen the wadding of the mixing in suspension fibre is taken up, obtain one deck by mixing the fine blend film felt that forms of wadding;
(9) carry out cryogenic refrigeration behind the dried surface moisture of film felt filter to be taken up, it is freezing then it to be distilled, and obtains high porosity shitosan/polymer blended film felt.
The preparation method of aforesaid a kind of high porosity shitosan/polymer blended film felt, described macromolecule raw material is polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA or cellulose; Described coordinative solvent and the mass concentration of processing Polymer Solution are: for polycaprolactone, solvent is an oxolane, and concentration is 3~30% (W/W) %; For polyethylene glycol, molecular weight is 2000~20000, and solvent is 75 ± 5 ℃ of hot water, and concentration is 3~30% (W/W) %; For polytetramethylene carbonate diol, solvent is a dimethyl formamide, and concentration is 3~30 (W/W) %; For PLA, solvent is a carrene, and concentration is 3~30 (W/W) %; For cellulose, solvent is 4-methyl morpholine-N-oxide, and concentration is 1~10 (W/W) %.
The preparation method of aforesaid a kind of high porosity shitosan/polymer blended film felt, described solidification liquid is allocated as: for polycaprolactone/tetrahydrofuran solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polyethylene glycol/75 ± 5 ℃ aqueous solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polytetramethylene carbonate diol/dimethyl formamide solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For PLA/dichloromethane solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For cellulose/4-methyl morpholine-N-oxide solution, solidification liquid is 25 ± 2 ℃ of deionized waters.
The preparation method of aforesaid a kind of high porosity shitosan/polymer blended film felt, it is 100~1000rpm that described high-speed stirred refers to the speed of agitator interval; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine, open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.2~0.3l/min with vaporific form.
The preparation method of aforesaid a kind of high porosity shitosan/polymer blended film felt; Described filter operation is: the Buchner funnel that will lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into; Suspension is drawn into beaker under suction function, the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Through repeatedly filtration with disperse the coagulating agent in can the original solution of flush away, fine suspension clear liquid obtains wadding a quilt with cotton.
The preparation method of aforesaid a kind of high porosity shitosan/polymer blended film felt, described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 200~400 orders; Described cryogenic refrigeration is meant and sample is refrigerated to-40~-50 ℃ that the moisture content that contains has become ice cube; Described distillation is freezing to be carried out in vacuum freeze drier, and the distillation refrigerating process is: freeze-drying time is 48 ± 2 hours, freeze-drying pressure 80 ± 5Pa, 60 ± 2 ℃ of temperature of heating plate.
The present invention provides the preparation method of a kind of high porosity shitosan/polymer blended film felt again; The fine suspension clear liquid blend of wadding a quilt with cotton of the macromolecule of two or more that will make by above-mentioned steps (4)~(7), (7) then set by step~(8) operation obtains the polymer blended film felt of high porosity shitosan/multicomponent.
Traditional chitosan short fiber film felt production process route is very long, will experience usually: the shitosan dissolving, and----stoste--is measured-refilter and--is sprayed silk and--solidify-slubbing stretching-drawing and setting--washing-coiling long fiber-cut-out-staple fibre--shredding-lapping-chitosan short fiber film felt in filtration.Long process route causes cost to improve, and invest greatly, and the chitin fiber market price that makes basic material come from discarded shrimp shell, crab shell remains high.The preparation of polymeric staple fiber dimension film felt and nonwoven fabric will be experienced tediously long technical process equally, and technological process is usually: macromolecule raw material-wet spinning (or melt spinning)--long fiber-cut-out-staple fibre--shredding-lapping-polymeric staple fiber dimension film felt.Though spinning, static also can be used for preparing tunica fibrosa, also one step forming just from stoste to the tunica fibrosa, and also fibre fineness reaches micron order, and its output is minimum, is difficult to substitute the market demand of conventional staple fibre film felt (nonwoven fabric).
The present invention has adopted a kind of new forming polymer method--spray-up method, has obtained the cotton-shaped shape short fiber that floats on a liquid, after copying the film felt that the paper method produced high moisture percentage, adopts the freezing and sublimation mode to remove moisture and keeps the space in the structure simultaneously.The advantage of this new material is to have very high porosity and good solution absorbs property, is well suited for as wound dressing.Its preparation method is simple in addition, and process route shortens greatly, and its typical process flow is: the fine shaping-wadding fibre of slurry preparation-wadding cleans-copies paper shaping-freeze drying-wadding fibrous film felt.
Beneficial effect:
(1) shitosan of the present invention/polymer blended film felt is the high-voidage membrane structure that forms with wadding fibrous accumulation, has strength and elongation preferably, and maximum characteristics are that voidage is high, and absorbency is good, is well suited for as wound dressing.Its preparation method is simple, and cost is low, and is environmentally friendly, and economic benefit is high.
(2) one of key of the present invention: shitosan and high molecular slurries are to get into coagulating bath and solidified forming under the high-speed stirred through spray regime.
(3) two of key of the present invention: employing is copied the paper method and is prepared the blend film felt, prepares tunica fibrosa with conventional wet spinning process and compares, and its technological process is shortened greatly.
(4) three of key of the present invention: nascent blend film felt is carried out freeze drying, and the final products of gained have high porosity and pick up.
The specific embodiment
Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The two component blend film felt preparation methods of a kind of high porosity shitosan and polycaprolactone may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 2 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 0.5 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 4 (W/W) %, and urea concentration is 0.5 (W/W) %, and zinc acetate concentration is 0.1 (W/W) %; , the rotating speed of 100rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(2) the polycaprolactone fine suspension clear liquid preparation of wadding a quilt with cotton: polycaprolactone is invested in processes the polycaprolactone solution that concentration is 3% (W/W) % in the oxolane; Solidification liquid is 23 ℃ of deionized waters; Stir down to polycaprolactone solidification liquid injection polycaprolactone slurries at the rotating speed of 100rpm, make it be frozen into the polycaprolactone fine suspension of wadding a quilt with cotton; This polycaprolactone fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polycaprolactone wadding; Again the polycaprolactone fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polycaprolactone fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polycaprolactone of shitosan wadded a quilt with cotton fine suspension clear liquid with 2: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/polycaprolactone with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polycaprolactone.
Embodiment 2
The two component blend film felt preparation methods of a kind of high porosity shitosan and polycaprolactone may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 8 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 5.0 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 12 (W/W) %, and urea concentration is 1.0 (W/W) %, and zinc acetate concentration is 0.5 (W/W) %; , the rotating speed of 1000rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(2) the polycaprolactone fine suspension clear liquid preparation of wadding a quilt with cotton: polycaprolactone is invested in processes the polycaprolactone solution that concentration is 30% (W/W) % in the oxolane; Solidification liquid is 27 ℃ of deionized waters; Stir down to polycaprolactone solidification liquid injection polycaprolactone slurries at the rotating speed of 1000rpm, make it be frozen into the polycaprolactone fine suspension of wadding a quilt with cotton; This polycaprolactone fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polycaprolactone wadding; Again the polycaprolactone fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polycaprolactone fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polycaprolactone of shitosan wadded a quilt with cotton fine suspension clear liquid with 3: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/polycaprolactone with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polycaprolactone.
Embodiment 3
The two component blend film felt preparation methods of a kind of high porosity shitosan and polycaprolactone may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 5 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the polycaprolactone fine suspension clear liquid preparation of wadding a quilt with cotton: polycaprolactone is invested in processes the polycaprolactone solution that concentration is 15% (W/W) % in the oxolane; Solidification liquid is 25 ℃ of deionized waters; Stir down to polycaprolactone solidification liquid injection polycaprolactone slurries at the rotating speed of 500rpm, make it be frozen into the polycaprolactone fine suspension of wadding a quilt with cotton; This polycaprolactone fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polycaprolactone wadding; Again the polycaprolactone fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polycaprolactone fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polycaprolactone of shitosan wadded a quilt with cotton fine suspension clear liquid with 2.5: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/polycaprolactone with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polycaprolactone.
Embodiment 4
The two component blend film felt preparation methods of a kind of high porosity shitosan and polyethylene glycol may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 2 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 0.5 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 4 (W/W) %, and urea concentration is 0.5 (W/W) %, and zinc acetate concentration is 0.1 (W/W) %; , the rotating speed of 100rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(2) the polyethylene glycol fine suspension clear liquid preparation of wadding a quilt with cotton: with molecular weight is that 10000 polyethylene glycol is invested in and processes the polyglycol solution that concentration is 3% (W/W) % in 70 ℃ of hot water; Solidification liquid is 23 ℃ of deionized waters; Stir down to polyethylene glycol solidification liquid injection polyethylene glycol slurries at the rotating speed of 100rpm, make it be frozen into the polyethylene glycol fine suspension of wadding a quilt with cotton; This polyethylene glycol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polyethylene glycol wadding; Again the polyethylene glycol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polyethylene glycol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polyethylene glycol of shitosan wadded a quilt with cotton fine suspension clear liquid with 2: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/polyethylene glycol with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polyethylene glycol.
Embodiment 5
The two component blend film felt preparation methods of a kind of high porosity shitosan and polyethylene glycol may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 8 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 5.0 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 12 (W/W) %, and urea concentration is 1.0 (W/W) %, and zinc acetate concentration is 0.5 (W/W) %; , the rotating speed of 1000rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(2) the polyethylene glycol fine suspension clear liquid preparation of wadding a quilt with cotton: with molecular weight is that 10000 polyethylene glycol is invested in and processes the polyglycol solution that concentration is 30% (W/W) % in 80 ℃ of hot water; Solidification liquid is 27 ℃ of deionized waters; Stir down to polyethylene glycol solidification liquid injection polyethylene glycol slurries at the rotating speed of 1000rpm, make it be frozen into the polyethylene glycol fine suspension of wadding a quilt with cotton; This polyethylene glycol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polyethylene glycol wadding; Again the polyethylene glycol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polyethylene glycol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polyethylene glycol of shitosan wadded a quilt with cotton fine suspension clear liquid with 3: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/polyethylene glycol with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polyethylene glycol.
Embodiment 6
The two component blend film felt preparation methods of a kind of high porosity shitosan and polyethylene glycol may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 5 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the polyethylene glycol fine suspension clear liquid preparation of wadding a quilt with cotton: with molecular weight is that 10000 polyethylene glycol is invested in and processes the polyglycol solution that concentration is 15% (W/W) % in 75 ℃ of hot water; Solidification liquid is 25 ℃ of deionized waters; Stir down to polyethylene glycol solidification liquid injection polyethylene glycol slurries at the rotating speed of 500rpm, make it be frozen into the polyethylene glycol fine suspension of wadding a quilt with cotton; This polyethylene glycol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polyethylene glycol wadding; Again the polyethylene glycol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polyethylene glycol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polyethylene glycol of shitosan wadded a quilt with cotton fine suspension clear liquid with 2.5: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/polyethylene glycol with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polyethylene glycol.
Embodiment 7
The two component blend film felt preparation methods of a kind of high porosity shitosan and polytetramethylene carbonate diol may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 2 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 0.5 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 4 (W/W) %, and urea concentration is 0.5 (W/W) %, and zinc acetate concentration is 0.1 (W/W) %; , the rotating speed of 100rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(2) the polytetramethylene carbonate diol fine suspension clear liquid preparation of wadding a quilt with cotton: polytetramethylene carbonate diol is invested in processes the polytetramethylene carbonate diol solution that concentration is 3% (W/W) % in the dimethyl formamide; Solidification liquid is 23 ℃ of deionized waters; Stir down to polytetramethylene carbonate diol solidification liquid injection polytetramethylene carbonate diol slurries at the rotating speed of 100rpm, make it be frozen into the polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton; This polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polytetramethylene carbonate diol wadding; Again the polytetramethylene carbonate diol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polytetramethylene carbonate diol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polytetramethylene carbonate diol of shitosan wadded a quilt with cotton fine suspension clear liquid with 2: 1 weight ratio mixing and stirring; With filter screen the wadding of the mixing in suspension fibre is taken up, obtained one deck and mix the fine blend film felt that forms of wadding by shitosan/polytetramethylene carbonate diol.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polytetramethylene carbonate diol.
Embodiment 8
The two component blend film felt preparation methods of a kind of high porosity shitosan and polytetramethylene carbonate diol may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 8 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 5.0 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 12 (W/W) %, and urea concentration is 1.0 (W/W) %, and zinc acetate concentration is 0.5 (W/W) %; , the rotating speed of 1000rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(2) the polytetramethylene carbonate diol fine suspension clear liquid preparation of wadding a quilt with cotton: polytetramethylene carbonate diol is invested in processes the polytetramethylene carbonate diol solution that concentration is 30% (W/W) % in the dimethyl formamide; Solidification liquid is 27 ℃ of deionized waters; Stir down to polytetramethylene carbonate diol solidification liquid injection polytetramethylene carbonate diol slurries at the rotating speed of 1000rpm, make it be frozen into the polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton; This polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polytetramethylene carbonate diol wadding; Again the polytetramethylene carbonate diol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polytetramethylene carbonate diol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polytetramethylene carbonate diol of shitosan wadded a quilt with cotton fine suspension clear liquid with 3: 1 weight ratio mixing and stirring; With filter screen the wadding of the mixing in suspension fibre is taken up, obtained one deck and mix the fine blend film felt that forms of wadding by shitosan/polytetramethylene carbonate diol.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polytetramethylene carbonate diol.
Embodiment 9
The two component blend film felt preparation methods of a kind of high porosity shitosan and polytetramethylene carbonate diol may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 5 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the polytetramethylene carbonate diol fine suspension clear liquid preparation of wadding a quilt with cotton: polytetramethylene carbonate diol is invested in processes the polytetramethylene carbonate diol solution that concentration is 15% (W/W) % in the dimethyl formamide; Solidification liquid is 25 ℃ of deionized waters; Stir down to polytetramethylene carbonate diol solidification liquid injection polytetramethylene carbonate diol slurries at the rotating speed of 500rpm, make it be frozen into the polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton; This polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polytetramethylene carbonate diol wadding; Again the polytetramethylene carbonate diol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polytetramethylene carbonate diol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and polytetramethylene carbonate diol of shitosan wadded a quilt with cotton fine suspension clear liquid with 2.5: 1 weight ratio mixing and stirring; With filter screen the wadding of the mixing in suspension fibre is taken up, obtained one deck and mix the fine blend film felt that forms of wadding by shitosan/polytetramethylene carbonate diol.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/polytetramethylene carbonate diol.
Embodiment 10
The two component blend film felt preparation methods of a kind of high porosity shitosan and PLA may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 2 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 0.5 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 4 (W/W) %, and urea concentration is 0.5 (W/W) %, and zinc acetate concentration is 0.1 (W/W) %; , the rotating speed of 100rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(2) the PLA fine suspension clear liquid preparation of wadding a quilt with cotton: PLA is invested in processes the PLA solution that concentration is 3% (W/W) % in the carrene; Solidification liquid is 23 ℃ of deionized waters; Stir down to PLA solidification liquid injection PLA slurries at the rotating speed of 100rpm, make it be frozen into the PLA fine suspension of wadding a quilt with cotton; This PLA fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the PLA wadding; Again the PLA fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the PLA fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and PLA of shitosan wadded a quilt with cotton fine suspension clear liquid with 2: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/PLA with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/PLA.
Embodiment 11
The two component blend film felt preparation methods of a kind of high porosity shitosan and PLA may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 8 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 5.0 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 12 (W/W) %, and urea concentration is 1.0 (W/W) %, and zinc acetate concentration is 0.5 (W/W) %; , the rotating speed of 1000rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(2) the PLA fine suspension clear liquid preparation of wadding a quilt with cotton: PLA is invested in processes the PLA solution that concentration is 30% (W/W) % in the carrene; Solidification liquid is 27 ℃ of deionized waters; Stir down to PLA solidification liquid injection PLA slurries at the rotating speed of 1000rpm, make it be frozen into the PLA fine suspension of wadding a quilt with cotton; This PLA fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the PLA wadding; Again the PLA fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the PLA fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and PLA of shitosan wadded a quilt with cotton fine suspension clear liquid with 3: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/PLA with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/PLA.
Embodiment 12
The two component blend film felt preparation methods of a kind of high porosity shitosan and PLA may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 5 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the PLA fine suspension clear liquid preparation of wadding a quilt with cotton: PLA is invested in processes the PLA solution that concentration is 15% (W/W) % in the carrene; Solidification liquid is 25 ℃ of deionized waters; Stir down to PLA solidification liquid injection PLA slurries at the rotating speed of 500rpm, make it be frozen into the PLA fine suspension of wadding a quilt with cotton; This PLA fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the PLA wadding; Again the PLA fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the PLA fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) wad a quilt with cotton fine suspension clear liquid and PLA of shitosan wadded a quilt with cotton fine suspension clear liquid with 2.5: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/PLA with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/PLA.
Embodiment 13
The two component blend film felt preparation methods of a kind of high porosity shitosan and cellulose may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 2 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 0.5 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 4 (W/W) %, and urea concentration is 0.5 (W/W) %, and zinc acetate concentration is 0.1 (W/W) %; , the rotating speed of 100rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(2) the fine suspension clear liquid of cellulose wadding prepares: cellulose is invested in processes the cellulose solution that concentration is 3% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 23 ℃ of deionized waters; , the rotating speed of 100rpm, makes the fine suspension of the plain wadding of its solidificating fiber under stirring to the plain slurries of cellulose gel solid-liquid jet fiber; The fine suspension of this cellulose wadding is filtered, clean with deionized water, it is fine to obtain cellulose wadding; The cellulose wadding fibre is dispersed in again and forms the fine suspension clear liquid of cellulose wadding in the deionized water, its fine concentration of wadding a quilt with cotton is 0.1 (W/W) %.
(3) shitosan is wadded a quilt with cotton the fine suspension clear liquid of fine suspension clear liquid and cellulose wadding with 2: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/cellulose with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/cellulose.
Embodiment 14
The two component blend film felt preparation methods of a kind of high porosity shitosan and cellulose may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 8 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 5.0 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 12 (W/W) %, and urea concentration is 1.0 (W/W) %, and zinc acetate concentration is 0.5 (W/W) %; , the rotating speed of 1000rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(2) the fine suspension clear liquid of cellulose wadding prepares: cellulose is invested in processes the cellulose solution that concentration is 30% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 27 ℃ of deionized waters; , the rotating speed of 1000rpm, makes the fine suspension of the plain wadding of its solidificating fiber under stirring to the plain slurries of cellulose gel solid-liquid jet fiber; The fine suspension of this cellulose wadding is filtered, clean with deionized water, it is fine to obtain cellulose wadding; The cellulose wadding fibre is dispersed in again and forms the fine suspension clear liquid of cellulose wadding in the deionized water, its fine concentration of wadding a quilt with cotton is 0.2 (W/W) %.
(3) shitosan is wadded a quilt with cotton the fine suspension clear liquid of fine suspension clear liquid and cellulose wadding with 3: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/cellulose with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/cellulose.
Embodiment 15
The two component blend film felt preparation methods of a kind of high porosity shitosan and cellulose may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 5 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the fine suspension clear liquid of cellulose wadding prepares: cellulose is invested in processes the cellulose solution that concentration is 15% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 25 ℃ of deionized waters; , the rotating speed of 500rpm, makes the fine suspension of the plain wadding of its solidificating fiber under stirring to the plain slurries of cellulose gel solid-liquid jet fiber; The fine suspension of this cellulose wadding is filtered, clean with deionized water, it is fine to obtain cellulose wadding; The cellulose wadding fibre is dispersed in again and forms the fine suspension clear liquid of cellulose wadding in the deionized water, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) shitosan is wadded a quilt with cotton the fine suspension clear liquid of fine suspension clear liquid and cellulose wadding with 2.5: 1 weight ratio mixing and stirring, the wadding of the mixing in suspension fibre is taken up, obtain one deck and mix the fine blend film felt that forms of wadding by shitosan/cellulose with filter screen.
(4) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains the two component blend film felts of high porosity shitosan/cellulose.
Embodiment 16
A kind of high porosity shitosan, polycaprolactone and polyethylene glycol three-component blend film felt preparation method may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 4 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3.0 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the polycaprolactone fine suspension clear liquid preparation of wadding a quilt with cotton: polycaprolactone is invested in processes the polycaprolactone solution that concentration is 15% (W/W) % in the oxolane; Solidification liquid is 25 ℃ of deionized waters; Stir down to polycaprolactone solidification liquid injection polycaprolactone slurries at the rotating speed of 500rpm, make it be frozen into the polycaprolactone fine suspension of wadding a quilt with cotton; This polycaprolactone fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polycaprolactone wadding; Again the polycaprolactone fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polycaprolactone fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) the polyethylene glycol fine suspension clear liquid preparation of wadding a quilt with cotton: with molecular weight is that 20000 polyethylene glycol is invested in and processes the polyglycol solution that concentration is 15% (W/W) % in 80 ℃ of hot water; Solidification liquid is 25 ℃ of deionized waters; Stir down to polyethylene glycol solidification liquid injection polyethylene glycol slurries at the rotating speed of 500rpm, make it be frozen into the polyethylene glycol fine suspension of wadding a quilt with cotton; This polyethylene glycol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polyethylene glycol wadding; Again the polyethylene glycol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polyethylene glycol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(4) shitosan wad a quilt with cotton fine suspension clear liquid and the polyethylene glycol of fine suspension clear liquid, polycaprolactone of wadding a quilt with cotton wadded a quilt with cotton fine suspension clear liquid with 3: 2: 1 weight ratio mixing and stirring; With filter screen the wadding of the mixing in suspension fibre is taken up, obtained one deck and mix the fine blend film felt that forms of wadding by shitosan/polycaprolactone/polyethyleneglycol.
(5) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains high porosity shitosan/polycaprolactone/polyethyleneglycol three component blend film felts.
Embodiment 17
A kind of high porosity shitosan, polytetramethylene carbonate diol and PLA three-component blend film felt preparation method may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 5 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the polytetramethylene carbonate diol fine suspension clear liquid preparation of wadding a quilt with cotton: polytetramethylene carbonate diol is invested in processes the polytetramethylene carbonate diol solution that concentration is 15% (W/W) % in the dimethyl formamide; Solidification liquid is 25 ℃ of deionized waters; Stir down to polytetramethylene carbonate diol solidification liquid injection polytetramethylene carbonate diol slurries at the rotating speed of 500rpm, make it be frozen into the polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton; This polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polytetramethylene carbonate diol wadding; Again the polytetramethylene carbonate diol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polytetramethylene carbonate diol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) the PLA fine suspension clear liquid preparation of wadding a quilt with cotton: PLA is invested in processes the PLA solution that concentration is 15% (W/W) % in the carrene; Solidification liquid is 25 ℃ of deionized waters; Stir down to PLA solidification liquid injection PLA slurries at the rotating speed of 500rpm, make it be frozen into the PLA fine suspension of wadding a quilt with cotton; This PLA fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the PLA wadding; Again the PLA fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the PLA fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(4) shitosan wad a quilt with cotton fine suspension clear liquid and the PLA of fine suspension clear liquid, polytetramethylene carbonate diol of wadding a quilt with cotton wadded a quilt with cotton fine suspension clear liquid with 3: 2: 1 weight ratio mixing and stirring; With filter screen the wadding of the mixing in suspension fibre is taken up, obtained one deck and mix the fine blend film felt that forms of wadding by shitosan/polytetramethylene carbonate diol/PLA.
(5) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains high porosity shitosan/polytetramethylene carbonate diol/PLA three component blend film felts.
Embodiment 18
A kind of high porosity shitosan, polycaprolactone, polytetramethylene carbonate diol and cellulose four component blend film felt preparation methods may further comprise the steps:
(1) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: it is that the shitosan slurries are processed in dissolving in 5 (V/V) % acetic acid that the shitosan powder is invested in concentration, and shitosan content is 3 (W/W) %; NaOH, urea and zinc acetate be invested in to stir in the deionized water process the shitosan solidification liquid; Naoh concentration is 8 (W/W) %, and urea concentration is 0.7 (W/W) %, and zinc acetate concentration is 0.3 (W/W) %; , the rotating speed of 500rpm, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton under stirring to shitosan solidification liquid jetski glycan slurries; This shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the shitosan wadding; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(2) the polycaprolactone fine suspension clear liquid preparation of wadding a quilt with cotton: polycaprolactone is invested in processes the polycaprolactone solution that concentration is 15% (W/W) % in the oxolane; Solidification liquid is 25 ℃ of deionized waters; Stir down to polycaprolactone solidification liquid injection polycaprolactone slurries at the rotating speed of 500rpm, make it be frozen into the polycaprolactone fine suspension of wadding a quilt with cotton; This polycaprolactone fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polycaprolactone wadding; Again the polycaprolactone fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polycaprolactone fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(3) the polytetramethylene carbonate diol fine suspension clear liquid preparation of wadding a quilt with cotton: polytetramethylene carbonate diol is invested in processes the polytetramethylene carbonate diol solution that concentration is 15% (W/W) % in the dimethyl formamide; Solidification liquid is 25 ℃ of deionized waters; Stir down to polytetramethylene carbonate diol solidification liquid injection polytetramethylene carbonate diol slurries at the rotating speed of 500rpm, make it be frozen into the polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton; This polytetramethylene carbonate diol fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, it is fine to obtain the polytetramethylene carbonate diol wadding; Again the polytetramethylene carbonate diol fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the polytetramethylene carbonate diol fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(4) the fine suspension clear liquid of cellulose wadding prepares: cellulose is invested in processes the cellulose solution that concentration is 5% (W/W) % in 4-methyl morpholine-N-oxide; Solidification liquid is 25 ℃ of deionized waters; , the rotating speed of 500rpm, makes the fine suspension of the plain wadding of its solidificating fiber under stirring to the plain slurries of cellulose gel solid-liquid jet fiber; The fine suspension of this cellulose wadding is filtered, clean with deionized water, it is fine to obtain cellulose wadding; The cellulose wadding fibre is dispersed in again and forms the fine suspension clear liquid of cellulose wadding in the deionized water, its fine concentration of wadding a quilt with cotton is 0.15 (W/W) %.
(5) shitosan the wad a quilt with cotton fine suspension clear liquid, polytetramethylene carbonate diol of fine suspension clear liquid, polycaprolactone of wadding a quilt with cotton wadded a quilt with cotton fine suspension clear liquid and the fine suspension clear liquid of cellulose wadding with 3: 2: 2: 1 weight ratio mixing and stirring; With filter screen the wadding of the mixing in suspension fibre is taken up, obtained one deck and mix the fine four component blend film felts that form of wadding by shitosan/polycaprolactone/polytetramethylene carbonate diol/cellulose.
(6) carry out cryogenic refrigeration behind the dried surface moisture of blend film felt filter to be taken up, it is freezing then it to be distilled, and obtains high porosity shitosan/polycaprolactone/polytetramethylene carbonate diol/cellulose four component blend film felts.

Claims (10)

1. high porosity shitosan/polymer blended film felt is characterized in that: described high porosity shitosan/polymer blended film felt is the fine high voidage membrane structure that fine accumulation forms with the macromolecule wadding of shitosan wadding; Its mass ratio is that the shitosan wadding is fine: macromolecule wadding fibre=99.9: 0.1~50: 50; Described wadding fibre is meant cotton-shaped short fiber, and described cotton-shaped short fiber is meant little and loose short fiber coagula; The voidage of described high porosity shitosan/polymer blended film felt is 30~80 (V/V) %.
2. a kind of high porosity shitosan according to claim 1/polymer blended film felt is characterized in that, described macromolecule is one or more mixing in polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA and the cellulose.
3. a kind of high porosity shitosan according to claim 1/polymer blended film felt is characterized in that, described cotton-shaped short fiber sprays solidification forming with the coagulating bath of slurries under high-speed stirred and obtains; Described high voidage membrane structure adopts freeze-drying to process.
4. the preparation method of a kind of high porosity shitosan as claimed in claim 1/polymer blended film felt is characterized in that may further comprise the steps:
(1) shitosan slurry preparation: it is that the shitosan slurries are processed in dissolving in 2~8 (V/V) % acetic acid that the shitosan powder is invested in concentration, and the shitosan content in the said shitosan slurries is 0.5~5.0 (W/W) %;
(2) the shitosan solidification liquid prepares: NaOH, urea and zinc acetate are invested in to stir in the deionized water process the shitosan solidification liquid; In the said shitosan solidification liquid, naoh concentration is 4~12 (W/W) %, and urea concentration is 0.5~1.0 (W/W) %, and zinc acetate concentration is 0.1~0.5 (W/W) %;
(3) the shitosan fine suspension clear liquid preparation of wadding a quilt with cotton: under high-speed stirred,, make it be frozen into the shitosan fine suspension of wadding a quilt with cotton to shitosan solidification liquid jetski glycan slurries; The described shitosan fine suspension of wadding a quilt with cotton is made up of cotton-shaped shitosan short fiber and suspension, and described cotton-shaped shitosan short fiber is suspended in the suspension; Described cotton-shaped shitosan short fiber is meant little and loose shitosan short fiber coagula; The shitosan fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, obtaining cotton-shaped shitosan short fiber is that the shitosan wadding is fine; Again the shitosan fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the shitosan fine suspension clear liquid of wadding a quilt with cotton, its fine concentration of wadding a quilt with cotton is 0.1~5 (W/W) %;
(4) macromolecule raw material of an amount of ratio is invested in processes Polymer Solution in the corresponding solvent; Allocate the solidification liquid of corresponding Polymer Solution;
(5) under high-speed stirred, spray Polymer Solution, make it be frozen into the macromolecule fine suspension of wadding a quilt with cotton to solidification liquid;
(6) the fine suspension of wadding a quilt with cotton is filtered, clean with deionized water, obtaining cotton-shaped polymeric staple fiber is that the macromolecule wadding is fine;
(7) again the macromolecule fibre of wadding a quilt with cotton is dispersed in the deionized water and forms the macromolecule fine suspension clear liquid of wadding a quilt with cotton, its concentration is 0.1~5 (W/W) %;
(8) wad a quilt with cotton fine suspension clear liquid and macromolecule of shitosan wadded a quilt with cotton fine suspension clear liquid with 1~9: 9~1 weight ratio mixing and stirring, with filter screen the wadding of the mixing in suspension fibre is taken up, obtain one deck by mixing the fine blend film felt that forms of wadding;
(9) carry out cryogenic refrigeration behind the dried surface moisture of film felt filter to be taken up, it is freezing then it to be distilled, and obtains high porosity shitosan/polymer blended film felt.
5. the preparation method of a kind of high porosity shitosan according to claim 4/polymer blended film felt is characterized in that described macromolecule raw material is polycaprolactone, polyethylene glycol, polytetramethylene carbonate diol, PLA or cellulose; Described coordinative solvent and the mass concentration of processing Polymer Solution are: for polycaprolactone, solvent is an oxolane, and concentration is 3~30% (W/W) %; For polyethylene glycol, molecular weight is 2000~20000, and solvent is 75 ± 5 ℃ of hot water, and concentration is 3~30% (W/W) %; For polytetramethylene carbonate diol, solvent is a dimethyl formamide, and concentration is 3~30 (W/W) %; For PLA, solvent is a carrene, and concentration is 3~30 (W/W) %; For cellulose, solvent is 4-methyl morpholine-N-oxide, and concentration is 1~10 (W/W) %.
6. the preparation method of a kind of high porosity shitosan according to claim 4/polymer blended film felt is characterized in that described solidification liquid is allocated as: for polycaprolactone/tetrahydrofuran solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polyethylene glycol/75 ± 5 ℃ aqueous solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For polytetramethylene carbonate diol/dimethyl formamide solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For PLA/dichloromethane solution, solidification liquid is 25 ± 2 ℃ of deionized waters; For cellulose/4-methyl morpholine-N-oxide solution, solidification liquid is 25 ± 2 ℃ of deionized waters.
7. the preparation method of a kind of high porosity shitosan according to claim 4/polymer blended film felt is characterized in that it is 100~1000rpm that described high-speed stirred refers to the speed of agitator interval; Described injection refers to: Polymer Solution is packed in the charging basket of Electronic spraying machine, open electric air pump Polymer Solution is sprayed into solidification liquid with the speed of 0.2~0.3l/min with vaporific form.
8. the preparation method of a kind of high porosity shitosan according to claim 4/polymer blended film felt; It is characterized in that; Described filter operation is: the Buchner funnel that will lay filter paper earlier is inserted in Bu Shi flask top opening and with sealing joint; To spray the fine suspension of wadding of solidification forming then and pour Buchner funnel into, suspension is drawn into beaker under suction function, and the fine solid of wadding a quilt with cotton is stayed in the Buchner funnel; Described dispersion is with putting into beaker through the fine solid of the wadding that filters, adding deionized water and make the wadding fibre be dispersed in the water again; Through repeatedly filtration with disperse the coagulating agent in can the original solution of flush away, fine suspension clear liquid obtains wadding a quilt with cotton.
9. the preparation method of a kind of high porosity shitosan according to claim 4/polymer blended film felt is characterized in that, described filter screen is a kind of diddle-net that paper is used of copying, and the filter screen material is a stainless steel, and mesh size is 200~400 orders; Described cryogenic refrigeration is meant and sample is refrigerated to-40~-50 ℃ that the moisture content that contains has become ice cube; Described distillation is freezing to be carried out in vacuum freeze drier, and the distillation refrigerating process is: freeze-drying time is 48 ± 2 hours, freeze-drying pressure 80 ± 5Pa, 60 ± 2 ℃ of temperature of heating plate.
10. the preparation method of a kind of high porosity shitosan as claimed in claim 4/polymer blended film felt; It is characterized in that: will be set by step the fine suspension clear liquid blend of wadding a quilt with cotton of two or more the macromolecule that makes of (4)~(7), (7) then set by step~(8) operation obtains the polymer blended film felt of high porosity shitosan/multicomponent.
CN201210109417.2A 2012-04-13 2012-04-13 High-porosity chitosan/macromolecule blending thin film felt and preparation method thereof Expired - Fee Related CN102605672B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544097A (en) * 2003-11-27 2004-11-10 四川大学 Biologic material for medical use and its preparing process and usage
CN101405038A (en) * 2006-03-20 2009-04-08 株式会社Jms Porous bioabsorbable material and method of producing the same
CN101538371A (en) * 2009-04-13 2009-09-23 重庆文理学院 Preparation method of high-strength degradable polysaccharide blend film
CN102206387A (en) * 2011-03-30 2011-10-05 东华大学 High molecule and inorganic nano-particle hybrid film and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1544097A (en) * 2003-11-27 2004-11-10 四川大学 Biologic material for medical use and its preparing process and usage
CN101405038A (en) * 2006-03-20 2009-04-08 株式会社Jms Porous bioabsorbable material and method of producing the same
CN101538371A (en) * 2009-04-13 2009-09-23 重庆文理学院 Preparation method of high-strength degradable polysaccharide blend film
CN102206387A (en) * 2011-03-30 2011-10-05 东华大学 High molecule and inorganic nano-particle hybrid film and preparation method thereof

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