CN1314732C - Process for preparing wool keratin protein and its products - Google Patents
Process for preparing wool keratin protein and its products Download PDFInfo
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- CN1314732C CN1314732C CNB2004100529223A CN200410052922A CN1314732C CN 1314732 C CN1314732 C CN 1314732C CN B2004100529223 A CNB2004100529223 A CN B2004100529223A CN 200410052922 A CN200410052922 A CN 200410052922A CN 1314732 C CN1314732 C CN 1314732C
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Abstract
The present invention relates to a method for preparing a pure wool keratin solution, a keratin film, keratin powder, a block-shaped keratin substance and plasticized wool keratin thereof. The keratin solution is a neutral dissolving solution prepared from a disulfide bond containing tearing agent, a high polarity neutral auxiliary agent and wool through filtration, dialysis and concentration and is a colorless, tasteless and transparent keratin solution. The wool keratin film, the keratin powder and the block-shaped keratin substance are prepared by purifying, solidifying and forming the wool keratin solution or pulverizing or processing a solidified substance thereof by powdering. The plasticized wool keratin is prepared by mixing the wool keratin solution and a plasticizing agent. The present invention can also be used for the dissolving solutions of pashm, yak hairs, yak wool, camel hairs, camel wool, other hair fibers of animals, etc.
Description
Technical field
The present invention relates to the preparation method of a kind of wool keratin and goods thereof.Comprise the wool dissolving, produce wool keratin solution, and the technology of film, powder and the block etc. of preparation wool angle protein solution.
Background technology
China's wool resource is abundant, but can not satisfy user demand, be near mouth; The quality of wool resource is not high, and fiber is thick, short, and weak joint is many, and easily work in-process is discarded, produces waste and environmental pollution; The Keratin sulfate raw material is again the important source material of light textile, foodstuffs industry, need utilize these resources, though and the regeneration techniques of relevant wool keratin early has research, the report of related application is seldom.Exploitation and regeneration wool fiber are to the effective utilization and the crucial meaning of having protected national resource.
The regeneration protein fibre has the regeneration animal protein fiber, as extract the fiber of protein spinning from wool, silk, milk; The aftergrowth protein fibre is arranged, as from soybean, peanut, corn etc., extracting the fiber of protein spinning.This patent introduction be the technology of preparing of regenerated wool keratin solution and goods thereof.Though existing patent (method that comprises Japan [Japanese patent application No.: JP4-9291138 and JP-537842281] and this country's [number of patent application: 02155362.9 and 02155407.2]) and article report, auxiliary agent, solution principle, reparation technology and the method used with the present invention exist different.
At present domestic have about patent: " a kind of keratin solution and solid technology of preparing " (number of patent application: 02155362.9).It is characterized in that: from the keratin protein raw material, extract Keratin sulfate with acidic solution; Its chemism is crosslinked with method of reducing cut-out keratin protein molecule interchain S-S, select reagent such as inorganic salt with strong expanded effect, urea, thiocarbamide on this basis for use, make the abundant swelling of keratin protein material until dissolving, obtain keratin solution and solid; Its technical process is: raw material pulverizing → clean → dissolving → keratin solution → crosslinked → cohesion → washing → keratin protein solid.Wool is under acid, comparatively high temps (>60 ℃) and long period (>1 hour) act on, and keratin just has very big damage and macromolecular degraded, causes that the keratin row yielding is low, industrialization cost height.In addition, the metal ion in the acidic liquid, particularly calcium ion easily make protein generation sex change, produce insolubles.
" technology of regenerating ceratin fibres " (number of patent application: 99116699.X).This invention is to extract albumen from the Keratin sulfate raw material, invents the manufacture method into the protein renaturation fiber.Its main technique flow process is: raw material → degreasing impurity elimination → dissolving → proteinic is crosslinked → and sealing free amine group → albumen spinning solution → spinning → protein renaturation fiber.It is characterized in that with various albumen such as various animal wools (comprising toe feathering under the woollen mill, pig hair, chicken and duck hair, ox hair etc.), useless silk, waste leathers as the thiozell raw material.This patent employing basic solution and epoxy chloropropane, formaldehyde are made linking agent.Alkalescence is to wool peptide chain macromolecules degradation and thoroughly destroy Gelucystine, so the keratin molecular weight that extracts is little, concentration is low, and processing parameter is wayward, and row yielding is low, and formaldehyde has environmental issue.
The present invention adopts the auxiliary agent of strong polarity neutral solution, from wool and other keratin fibers, produce keratin, used chemical reagent belongs to organic chemicals, chemism is to break disulfide linkage and hydrogen bond action between the keratin macromole with method of reducing, and keep the integrity of angle protein macromolecular main chain, the destruction of reducing diagonal angle protein macromolecular chain as far as possible.Agents useful for same all has stabilization to amino acid.Lysate with its preparation keeps neutral state (pH=6.5~7.5) always in whole wool and other keratin fibrolysises and goods preparation process.And in whole experiment, do not contain heavy metal element, can in reaction, not cause the rotten of keratin.The wool angle protein lysate of being produced, the dissolution rate height is 87% (being generally less than 60%); Row yielding height (>80%); Viscosity is big, and (viscosity number is 328 seconds, measures with Ubbelohde viscometer, and capillary diameter is 5~6mm); The keratin film toughness of making big (breaking tenacity is 0.35Mpa).
Summary of the invention
The object of the invention provides a kind of keratin film, powder and block and plasticising wool keratin thereof at interior wool keratin and article process thereof, relates to the reparation technology flow process of this keratin film, powder, block simultaneously.Method of the present invention can obtain keratin plasma membrane, powder and the block of the colorless and odorless of water absorbability, good permeability.
The technical scheme that achieves the above object is:
This solid component is a keratin matter.Described component keratin is produced from wool solution.
1, preparation technology's flow process of wool angle protein solution is:
Wool, dissolving, filtration, dialysis, concentrated.
This programme manufacturing process flow is:
1. wool carries out degreasing with 1: 1 mixture of ethanol and ether;
2. the wool after the degreasing is immersed in the auxiliary agent and dissolve.Solvent temperature is 50~80 ℃, and dissolution time is 4~10 hours, and pH value remains between 6.5~7.5.The neutral strong polar solvent that described auxiliary agent is made up of solvent, key point reductive agent, tensio-active agent, linking agent and water, the weight percent of each component is respectively: solvent 5%~25%, reductive agent 10%~20%, tensio-active agent 0.5%~5%, linking agent 0~8%, and all the other are water;
3. the keratin solution after will dissolving successively filters, and pore size filter obtains not having the solution of residue from 0.2~0.06mm;
4. with the filtering solution deionized water, nature or pressure dialysis, dialysis time are 0.5~24 hour;
5. above-mentioned dialyzate being concentrated into viscosity is that (measure with Ubbelohde viscometer, capillary diameter is 5~6mm) more than 120 seconds; Obtain colorless and odorless, purified pure wool keratin solution;
6. for the viscosity of raising angle protein solution and the brute force of decorating film, can add linking agent as required again.
The weight ratio of softening agent and keratin solution is 0.02-2%: 1.
Described softening agent can be that 1 in glycerol, ethylene glycol or the N.F,USP MANNITOL or 2 kind are at interior polyvalent alcohol.
Described solvent is aqueous solution of urea, thiourea solution, the Guanidinium hydrochloride aqueous solution, and dimethyl sulfoxide (DMSO), dimethyl formamide or N,N-DIMETHYLACETAMIDE, or be selected from wherein 2 kinds;
Described reductive agent is a dithiothreitol (DTT), 2 mercapto ethanol, and mercaptoethylamine, gsh, Thiovanic acid or thiohydracrylic acid, or be selected from wherein 2~3 kinds;
Described tensio-active agent is an aniorfic surfactant, comprises that the carbon number of lipid acid, sodium alkyl sulfate, sodium alkyl benzene sulfonate or the described alkyl of alkyl sodium sulfonate of oleic acid, lauric acid, linolenic acid, stearic acid is 10~20;
Described linking agent is water miscible polynary epoxy compounds or polycarboxylic acid, can select for use wherein 0~2 kind composite; Described polynary epoxy compounds is that diepoxy propyl group-4,5 dihydroxy ethylene urea, polyoxyethylated n are 1~5 diepoxy propyl group Soxylat A 25-7, three epoxypropyl glyceryl ethers; Polycarboxylic acid is citric acid, furoate clothing, oxalic acid, propanedioic acid, butene dioic acid.
2, preparation technology's flow process of pure wool angle protein film, powder, block and plasticising wool keratin film, powder, block:
1. the method with the above prepares pure wool angle protein solution, or plasticising wool angle protein solution is through casting or blade coating film forming in homemade film forming device, produce pure wool angle protein or plasticising wool angle protein film, temperature is 30~80 ℃, 0.5~4 hour time, directly enter in the solidification liquid through casting method and to solidify, and with after the pure water rinsing, at room temperature drying and forming-film;
2. the cured article that wool keratin solution is made is collected with grinding mode and is obtained, or the ultra-high speed stirring in solidification liquid of wool keratin liquid, or spraying drying makes powder;
3. spissated wool keratin liquid is poured in the container with solid form, distillation or drying, temperature is 30~80 ℃, 0.5~6 hour time, evaporate fully up to moisture, after the cooling, form wool angle protein block;
Method of the present invention also is applicable to cashmere, yak hair, yakwool, camel hair, camel's hair and other animal hair fibrids etc.
By solution and solid that technical solution of the present invention is produced, its performance has close with wool fiber.Therefore have the characteristics of water absorbability, good permeability.These utilization again and " lanital ", " artificial cashmere ", " artificial ox suedes " etc. for discarded animal protein fibre have very practical meaning.Because this product is produced from wool fiber, belongs to protein one class, has good affinity with human body skin, can be used for " artificial skin ", " artificial organ " etc.; Coating or manufacture medical textile can be applicable to the protective membrane of wound face; Also can be used for the human body soft tissue packing material, also can be used for histiocytic cultivation carrier.These all have profound significance for medical science, biological aspect.
Description of drawings
Fig. 1 is a schema of producing wool keratin solution of the present invention.
Embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
One, preparation technology's flow process of pure wool angle protein film, powder, block:
Embodiment 1
The strong polarity neutral solution that wool 10~20 gram and following substances are formed was 60 ℃ of following dissolution times of temperature 5 hours: urea soln (concentration 20%~35%) 150~400 grams, 2 mercapto ethanol 10~20 grams, sodium lauryl sulphate (SDS) 5~20 grams and water 100~400 restrain.
Make colourless, tasteless, transparent pure wool keratin solution.The wool dissolution rate is 87.3%, and viscosity is that (measure with Ubbelohde viscometer, capillary diameter was 5~6mm) in 332 seconds.
With the method for postponing pure wool keratin solution is poured in the film forming device, on the flat board or in the container, allowed its seasoning, form the pure film of keratin, powder or block.Temperature is room temperature (27 ℃), and the time is 10-24 hour.
Embodiment 2
The strong polarity neutral solution that waste wool tankage 10~20 gram and following substances are formed was 50 ℃ of following dissolution times of temperature 6 hours: dimethyl formamide solution (concentration 15%~35%) 200~400 grams, Thiovanic acid 10~20 grams, sodium lauryl sulphate (SDS) 5~20 grams, three epoxypropyl glyceryl ethers 0.2%~3% and water 100~400 restrain.
Make colourless, tasteless, transparent pure wool keratin solution.The wool dissolution rate is 84.6%, and viscosity is that (use Ubbelohde viscometer, diameter was 5~6mm) in 353 seconds.Made keratin film toughness is to contain being higher than of linking agent not contain 20%~25% of linking agent.
With the method for postponing pure wool keratin solution is poured in the film forming device, on the flat board or in the container, is put in the baking oven, drying becomes the pure film of keratin, powder or block.Temperature is 50-80 ℃, and the time is 0.5-1 hour.
Two, preparation technology's flow process of plasticising wool keratin film, powder, block:
Embodiment 3
The strong polarity neutral solution that scoured wool 10~20 gram and following substances are formed was 50 ℃ of following dissolution times of temperature 6 hours: urea soln (concentration 20%~35%) 200~400 grams, 2 mercapto ethanol 10~20 grams, Sodium dodecylbenzene sulfonate 5~20 grams and water 100~400 restrain.
Make colourless, tasteless, transparent pure wool keratin solution, the wool dissolution rate is 87.1%.
Add the glycerol of weight percent amount 0.05~2% in the protein solution of pure wool angle, the room temperature that stirs 0.5~10 minute, obtains the plasticising wool keratin solution.Method with casting is poured keratin solution in the film forming device into, on flat board or in the container, is put in room temperature or the baking oven, formation keratin plasticising film, powder or block.Temperature is 30~80 ℃, 0.5~4 hour time.
Embodiment 4
The strong polarity neutral solution that yak hair 10~20 gram and following substances are formed was 50 ℃ of following dissolution times of temperature 8 hours: urea soln (concentration 20%~35%) 200~400 grams, 2 mercapto ethanol 10~20 grams, Sodium dodecylbenzene sulfonate 5~20 grams and water 100~400 restrain.
Make colourless, tasteless, transparent pure keratin solution, the ox hair dissolution rate is 81.4%.
Add the glycerol of weight percent amount 0.05~2% in the protein solution of pure angle, the room temperature that stirs 0.5~10 minute, obtains the plasticising keratin solution.Method with casting is poured keratin solution in the film forming device into, on flat board or in the container, is put in room temperature or the baking oven, formation keratin plasticising film, powder or block.Temperature is 30~80 ℃, 0.5~4 hour time.
Embodiment 5
With the keratin solution among the embodiment 1~4, spraying drying makes powder, and particle diameter is 0.6~20 μ m.
Claims (7)
1, a kind of preparation method of wool keratin solution, its feature adopts following step:
1) wool carries out degreasing with 1: 1 mixture of ethanol and ether;
2) with the neutral auxiliary agent dissolving of the strong polarity of dissolving woolen scoured wool, 50~80 ℃ of temperature, pH value are 6.5~7.5, dissolving after-filtration impurity elimination in 4~10 hours, get neutral angle PrPC lysate, with deionized water to this lysate nature or pressure dialysis, dialysis time is normal temperature 0.5~24 hour, concentrates at last and makes the pure keratin solution of colorless and odorless;
Wool in the described lysate is 1 with the weight ratio of strong polarity neutral solution: (10~30);
The strong polarity neutral solution that the neutral auxiliary agent of described strong polarity is formed by following weight percent configuration by solvent, key point reductive agent, tensio-active agent, linking agent and water: solvent 5%~25%, key point reductive agent 10%~20%, tensio-active agent 0.5%~5%, linking agent are greater than 0 to being equal to or less than 8%, and all the other are water;
Described solvent is aqueous solution of urea, thiourea solution, the Guanidinium hydrochloride aqueous solution, dimethyl sulfoxide (DMSO), dimethyl formamide or N,N-DIMETHYLACETAMIDE, or is selected from wherein 2 kinds;
Described key point reductive agent is dithiothreitol (DTT), 2 mercapto ethanol, mercaptoethylamine, gsh, Thiovanic acid or thiohydracrylic acid, or is selected from wherein 2~3 kinds;
Described tensio-active agent is an aniorfic surfactant, is selected from oleic acid, lauric acid, linolenic acid, stearic acid, sodium alkyl sulfate, sodium alkyl benzene sulfonate or alkyl sodium sulfonate, and the carbon number of described alkyl is 10~20;
Described linking agent is water miscible polynary epoxy compounds or polycarboxylic acid, is selected from wherein one or both; Described polynary epoxy compounds is that diepoxy propyl group-4,5 dihydroxy ethylene urea, polyoxyethylated n are 1~5 diepoxy propyl group Soxylat A 25-7 or three epoxypropyl glyceryl ethers; Described polycarboxylic acid is citric acid, furoate clothing, oxalic acid, propanedioic acid or butene dioic acid.
2, a kind of preparation method of wool keratin solution goods, it is characterized in that: add softening agent at the temperature 50-80 ℃ of pure keratin solution that the described method of claim 1 is obtained, with wool keratin solution purification, concentrated, solidifying formation, or to its cured article pulverizing or powderization; Described softening agent is a polyalcohols, and the weight ratio that is mixed of softening agent and wool keratin solution is 0.05~2%: 1.
3, a kind of preparation method of wool keratin solution goods is characterized in that: at temperature 50-80 ℃ of wool keratin solution purification, concentrated, the solidifying formation that the described method of claim 1 is obtained, or to its cured article pulverizing or powderization.
4, as the preparation method of claim 2 or 3 described a kind of wool keratin solution goods, it is characterized in that: described solidifying formation is with the wool keratin solution film forming, be about to keratin solution through casting or blade coating film forming in film forming device, heating cure makes the wool keratin film, temperature is 30-80 ℃, 0.5~4 hour time; Or directly enter in the solidification liquid through casting method and to solidify, and with after the pure water rinsing, drying and forming-film at room temperature;
Described powderization is that the wool keratin cured article is pulverized, or described wool keratin solution ultra-high speed in solidification liquid stirs or spraying drying makes powder;
The described piece that is cast into is that spissated wool keratin liquid is poured in the container with solid form, distillation or drying, and temperature is 30~80 ℃, 0.5~4 hour time, to evaporate fully up to moisture, cooling forms the wool keratin block.
5, the preparation method of a kind of wool keratin solution goods as claimed in claim 2, it is characterized in that described softening agent be selected from ethylene glycol, propylene glycol or glycol ether 1 or 2 kind.
6, a kind of wool keratin solution preparation method as claimed in claim 1 is characterized in that being, described filtration is that the wool lysate is successively filtered by the filter opening footpath screen cloth from 0.2 to 0.06mm, obtains not having the solution of residue and insolubles.
7, the preparation method of a kind of cashmere, yak hair, yakwool, camel hair or camel's hair keratin solution is characterized in that, with the described wool in cashmere, yak hair, yakwool, camel hair or the camel's hair replacement claim 1.
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CN1306106C (en) * | 2005-03-29 | 2007-03-21 | 东华大学 | Method for fabricating wool keratin clad acrylon, polypropylene, capron and textiles |
CN100362075C (en) * | 2005-05-18 | 2008-01-16 | 东华大学 | Animal protein external coated phase change energy storage microcapsule, preparing method and its use |
CN101280000B (en) * | 2008-05-28 | 2012-05-16 | 陕西师范大学 | Method for processing livestock hair keratin with ultrasonic |
CN101508782B (en) * | 2009-03-09 | 2013-01-16 | 东华大学 | Method for separating and extracting fibrillar structure body in natural keratin fiber with organic acid solvent |
CN102585277B (en) * | 2012-02-16 | 2013-04-24 | 武汉纺织大学 | Process for preparing keratin porous membrane by refrigerating |
CN104927777B (en) * | 2015-06-02 | 2018-04-24 | 清华大学深圳研究生院 | Microcapsules of storing energy through phase change preparation method and application |
CN107558204A (en) * | 2017-09-04 | 2018-01-09 | 西南大学 | Magnetic wool fabric is prepared with the dithiothreitol (DTT) aqueous solution |
CN108568279B (en) * | 2018-03-21 | 2021-02-09 | 安徽工程大学 | Feather down protein nano-microsphere and preparation method thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2946491B2 (en) * | 1990-11-16 | 1999-09-06 | 武田薬品工業株式会社 | Method for producing micellar aqueous solution of keratin |
JP3283302B2 (en) * | 1992-09-22 | 2002-05-20 | 株式会社成和化成 | Method for producing reduced keratin |
CN1435432A (en) * | 2002-12-11 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Keratin solution and solid preparing process |
-
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2946491B2 (en) * | 1990-11-16 | 1999-09-06 | 武田薬品工業株式会社 | Method for producing micellar aqueous solution of keratin |
JP3283302B2 (en) * | 1992-09-22 | 2002-05-20 | 株式会社成和化成 | Method for producing reduced keratin |
CN1435432A (en) * | 2002-12-11 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Keratin solution and solid preparing process |
Non-Patent Citations (4)
Title |
---|
人发角蛋白溶液成膜的结构与性能 胡继文等,高分子材料科学与工程,第18卷第02期 2002 * |
人发角蛋白溶液成膜的结构与性能 胡继文等,高分子材料科学与工程,第18卷第02期 2002;羊毛角朊蛋白的再生利用技术 陈莉萍等,毛纺科技,第2003年第4期 2003;羊毛角朊蛋白的再生利用技术 陈莉萍等,毛纺科技,第4期 2003 * |
羊毛角朊蛋白的再生利用技术 陈莉萍等,毛纺科技,第2003年第4期 2003 * |
羊毛角朊蛋白的再生利用技术 陈莉萍等,毛纺科技,第4期 2003 * |
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