CN104910635A - New method for chemical crosslinking for keratin molecules in ionic liquid solvent - Google Patents
New method for chemical crosslinking for keratin molecules in ionic liquid solvent Download PDFInfo
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- CN104910635A CN104910635A CN201510296536.7A CN201510296536A CN104910635A CN 104910635 A CN104910635 A CN 104910635A CN 201510296536 A CN201510296536 A CN 201510296536A CN 104910635 A CN104910635 A CN 104910635A
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Abstract
The invention provides a new method for chemical crosslinking for keratin molecules in an ionic liquid solvent. According to the new method, the keratin molecules dissolved in the ionic liquid solvent system are crosslinked by virtue of a series of chemical crosslinking agents. The new method comprises the following steps: cleaning and degreasing the crushed animal hair and then adding the crushed animal hair in an ionic liquid in a certain ratio of 1-17%(wt%), mechanically stirring for 20-90min at 90-130 DEG C to obtain an ionic liquid keratin solution, adding the crosslinking agents in the keratin solution in a certain ratio of 1-10%(wt%), adjusting the pH value to 5-8, and mechanically stirring for 12-24h at 50-100 DEG C to obtain a keratin solution with different crosslinking degrees. The crosslinking agents comprise glutaraldehyde, paraformaldehyde, hexyl diisocyanate, carbodiimide, phosphoric acid diphenyl ester azide, genipin, ethylene glycol diglycidyl ether and the like. The method is simple to operate, the reagents are cheap and easily available, and the crosslinking degree and properties of keratin, and the mechanical properties of keratin spinning are improved by virtue of the chemical crosslinking method.
Description
Technical field
The invention belongs to biomass resource regeneration field, relate to ion liquid solvent system keratin molecule prepares Keratin sulfate spinning solution technology by chemically crosslinked.
Background technology
Keratin sulfate is a kind of fibrous protein, is the basic protein forming animal wool, epidermis, feather etc., is made up of, forms keratic α spiral and β-pleated sheet structure sterie configuration by cross-link bonds such as disulfide linkage, salt type bond, hydrogen bonds the a-amino acid of more than 20 kinds.China produces discarded and tubbiness wool tens0000 tons every year, containing abundant Keratin sulfate in these waste resources, Keratin sulfate stablizes the structure with toughness with it, become a kind of natural macromolecular material of excellent performance, the Keratin sulfate of macromolecule can become silk, film forming is applied to the field such as weaving, high-performance biomedical material.Therefore, consider from the angle of utilization of resources and environmental protection, rationally utilize discarded keratin resource fully, improve it and utilize added value to have great scientific meaning.And keratic effective dissolving is basis and the prerequisite of protein resource recycling.Traditional keratolysis method uses a large amount of strong acid, highly basic, reductive agent, metal-salt etc., dissolution process angle protein macromolecular chain is substantially destroyed, keratin molecule amount is low cannot become silk separately, and the discharge such as acid-alkali salt is to environment, does not meet the requirement of Modern Green development of chemical industry.Therefore, select green, efficient dissolution with solvents wool keratin, control key and technological difficulties that the reproduction angle albumen of the degraded acquisition macromolecule of its appropriateness is its high-valued application.
Ionic liquid is a kind of novel, programmable green solvent, be made up of organic cation and organic/inorganic negatively charged ion, at room temperature or the low temperature molten salt that is in a liquid state under being bordering on room temperature, compared with traditional volatile organic solvent, there is a series of good characteristic, as strong in polarity, non-volatile, be not oxidized, good solubility, can design most stable reagent, structure, be applied to natural high polymer as a kind of good solvent, the solubility property as Mierocrystalline cellulose, chitin, chitosan, silk fibroin etc. is studied.The preparation method of existing a kind of ionic liquid keratin solution, visible patent " CN 1660901A; a kind of preparation method of keratin solution ", this invention ionic liquid synthesis used is simple, cheap, viscosity is low, but does not relate to the effect of ion liquid system Keratin sulfate linking agent; The technology of existing a kind of regenerating ceratin fibres, visible patent " CN 1293266A " take mineral alkali as dissolution with solvents Keratin sulfate, adopts epoxy chloropropane, formaldehyde as linking agent, but does not belong to the crosslinked of ion liquid solvent system keratin molecule.
For above present Research, coupled ion liquid dissolves Keratin sulfate characteristic of the present invention and linking agent improve the advantage of keratin molecule degree of crosslinking, chemical crosslink technique is utilized to change ion liquid solvent system Keratin sulfate attribute from molecular structure, improve the degree of crosslinking of reproduction angle protein molecular, increase keratin molecule amount, improve the mechanical property of Keratin sulfate spinning.And linking agent used is cheap and easy to get, technique is simple, and thus the present invention has more practicable application prospect.
Summary of the invention:
The present invention seeks to overcome the lower shortcoming of ion liquid system Keratin sulfate spinning solution intensity, by adding linking agent, utilizing Chemical Crosslinking Methods, improve reproduction angle molecular weight of albumen, improve Keratin sulfate spinning properties.
Described animal wool raw material, mainly be selected from the wool of adhesive-bonded utility value, pig hair, the rabbit hair, feather etc., first through water cleaning, then with ethanol or acetone soak degreasing 1-12 hour, dry at 60-90 DEG C, be ground into fine powder by pulverizer, joined in the ionic liquid of 90-130 DEG C, mechanical stirring 20-90min, in keratin solution, linking agent is added after cooling, and regulate pH value 5-8, mechanical stirring 12-24h at 50-100 DEG C, obtain the keratin solution of different crosslinking degree.
Described ionic liquid is dialkylimidazolium phosphoric acid ester, quaternary ammonium phosphoric acid ester, dialkylimidazolium acetate type, dialkylimidazolium chlorine class, alkyl pyridine acetate type plasma liquid, comprise: 1, 3-diethyl imidazolium diethyl phosphoric acid, 1-ethyl-3-methylimidazole dimethyl phosphate, 1-butyl-3-Methylimidazole dimethyl phosphate, 1-butyl-3-ethyl imidazol(e) diethyl phosphoric acid, 1-butyl-3-Methylimidazole dibutyl phosphate, 1-ethyl-3-methylimidazole diethyl phosphoric acid, 1, 3-methylimidazole dimethyl phosphate, 1-butyl-3-ethyl imidazol(e) dibutyl phosphate, triethyl methyl dimethyl phosphate, 1-butyl-3-Methylimidazole acetate, methyl triethylamine dimethyl phosphate, 1-ethyl-3-methylimidazole acetate, PAA salt, 1-allyl group-3-Methylimidazole acetate, 1-octyl group-3-Methylimidazole acetate, 1-butyl-3-Methylimidazole chlorine, 1-ethyl-3-methylimidazole chlorine etc.
Described adjustment PH reagent comprises: urea, Dicyanodiamide, trolamine, diethanolamine, triethylamine, diethylamine.
Described linking agent comprises: glutaraldehyde, paraformaldehyde, own different dicyanate, carbodiimide, nitrine diphenylphosphine, genipin, ethylene glycol diglycidylether.
Embodiment:
The present invention's following examples illustrate, but the present invention is not limited to following embodiment, and in the scope not departing from the described aim in front and back, change is included in technical scope of the present invention.
Embodiment 1
Take cleaning, goathair raw material 2.20g after degreasing, join in 27.50g triethyl methyl dimethyl phosphate, mechanical stirring 30min under 120 DEG C of oil baths, obtain keratin solution, 0.11g glutaraldehyde is added after cooling, pH value to 5.5 is regulated with urea, mechanical stirring 24h at 60 DEG C, obtain highly cross-linked keratin solution, reproduction angle albumen is obtained by water-bath regeneration, the keratic relative crystalline indice CI of XRD test display regeneration is elevated to 80% by 62%, DSC test result shows its melt temperature Tm and is increased to 202 DEG C by 162 DEG C, show that keratin molecule is cross-linked successfully.
Embodiment 2
Take the pig hair raw material 2.60g after cleaning, degreasing, join in 30.25g 1-ethyl-3-methylimidazole dimethyl phosphate, mechanical stirring 60min under 115 DEG C of oil baths, obtain keratin solution, add 0.14g paraformaldehyde after cooling, regulate pH value to 6.0 by Dicyanodiamide, mechanical stirring 12h at 80 DEG C, obtain highly cross-linked keratin solution, obtain reproduction angle albumen by ethanol bath regeneration.The keratic relative crystalline indice CI of XRD test display regeneration is elevated to 67%, DSC test result by 61.9% and shows its melt temperature Tm and be increased to 192 DEG C by 172 DEG C, shows that keratin molecule is cross-linked successfully.
Embodiment 3
Take the sheep's wool raw material 3.20g after cleaning, degreasing, join in 40.25g 1-butyl-3-Methylimidazole dimethyl phosphate, mechanical stirring 60min under 105 DEG C of oil baths, obtain keratin solution, add the own different dicyanate of 0.18g after cooling, regulate pH value to 6.5 with trolamine, mechanical stirring 12h at 80 DEG C, obtain highly cross-linked keratin solution, obtain reproduction angle albumen by water-bath regeneration.The keratic relative crystalline indice CI of XRD test display regeneration is elevated to 74%, DSC test result by 59% and shows its melt temperature Tm and be increased to 195 DEG C by 172 DEG C, shows that keratin molecule is cross-linked successfully.
Embodiment 4
Take the rabbit hair raw material 2.60g after cleaning, degreasing, join 30.50g 1-butyl-3-ethyl imidazol(e) diethyl phosphoric acid, mechanical stirring 60min under 110 DEG C of oil baths, obtain keratin solution, add 0.15g carbodiimide after cooling, regulate pH value to 7.5 with diethanolamine, mechanical stirring 16h at 70 DEG C, obtain highly cross-linked keratin solution, obtain reproduction angle albumen by water-bath regeneration.The keratic relative crystalline indice CI of XRD test display regeneration is elevated to 68%, DSC test result by 62% and shows its melt temperature Tm and be increased to 223 DEG C by 175 DEG C, shows that keratin molecule is cross-linked successfully.
Embodiment 5
Take the yak hair raw material 3.00g after cleaning, degreasing, join in 31.5g 1-butyl-3-Methylimidazole dibutyl phosphate, mechanical stirring 40min under 125 DEG C of oil baths, obtain keratin solution, add 0.21g nitrine diphenylphosphine after cooling, regulate pH value to 7.5 with urea, mechanical stirring 12h at 90 DEG C, obtain highly cross-linked keratin solution, obtain reproduction angle albumen by ethanol bath regeneration.The keratic relative crystalline indice CI of XRD test display regeneration is elevated to 72%, DSC test result by 62% and shows its melt temperature Tm and be increased to 183 DEG C by 162 DEG C, shows that keratin molecule is cross-linked successfully.
Embodiment 6
Take the process hides waste wool raw material 3.30g after cleaning, degreasing, join 36.5g 1-ethyl-3-methylimidazole acetate, mechanical stirring 20min under 100 DEG C of oil baths, obtain keratin solution, add 0.25g genipin after cooling, regulate pH value to 6.5 with triethylamine, mechanical stirring 12h at 60 DEG C, obtain highly cross-linked keratin solution, obtain reproduction angle albumen by ethanol bath regeneration.The keratic relative crystalline indice CI of XRD test display regeneration is elevated to 67%, DSC test result by 61% and shows its melt temperature Tm and be increased to 212 DEG C by 165 DEG C, shows that keratin molecule is cross-linked successfully.
Embodiment 7
Take the pig hair raw material 3.50g after cleaning, degreasing, join in 38.5g 1-butyl-3-Methylimidazole villaumite, mechanical stirring 90min under 130 DEG C of oil baths, obtain keratin solution, add 0.26g ethylene glycol diglycidylether after cooling, add diethylamine and regulate pH value to 7.5, mechanical stirring 24h at 60 DEG C, obtain highly cross-linked keratin solution, obtain reproduction angle albumen by water-bath regeneration.The keratic relative crystalline indice CI of XRD test display regeneration is elevated to 67%, DSC test result by 59% and shows its melt temperature Tm and be increased to 194 DEG C by 172 DEG C, shows that keratin molecule is cross-linked successfully.
Claims (5)
1. the novel method that an ion liquid solvent system keratin protein is molecule crosslinked, technical process is: take cleaning, the animal wool raw material 1-17% (wt%) of skimming treatment joins in ionic liquid, mechanical stirring 20-90min at 90-130 DEG C, obtain keratin solution, in keratin solution, linking agent 1-10% (wt%) is added after cooling, and regulate pH value 5-8, mechanical stirring 12-24h at 50-100 DEG C, obtain the keratin solution of different crosslinking degree.
2. method according to claim 1, described ionic liquid is dialkylimidazolium phosphoric acid ester, quaternary ammonium phosphoric acid ester, dialkylimidazolium acetate, alkyl pyridine acetate, dialkylimidazolium villaumite etc., originate by commercially available or by experiment room prepare.
3. method according to claim 1, described animal wool raw material is selected from the goathair of adhesive-bonded utility value, sheep's wool, camel hair, pig hair, the rabbit hair, yak hair, process hides waste wool, useless fowl feather and the wool without spinning utility value, through washing, degreasing, drying, disintegrating process, originate by commercially available or room preparation by experiment.
4. method according to claim 1, is characterized in that described adjustment PH agents useful for same is urea, Dicyanodiamide, trolamine, diethanolamine, triethylamine, the one in diethylamine.
5. method according to claim 1, is characterized in that described linking agent is the one that a series of chemical cross-linking agent comprises in glutaraldehyde, paraformaldehyde, own different dicyanate, carbodiimide, nitrine diphenylphosphine, genipin, ethylene glycol diglycidylether.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10058502B2 (en) | 2015-12-31 | 2018-08-28 | L'oreal | Nail polish compositions |
| CN109881279A (en) * | 2018-03-26 | 2019-06-14 | 新乡化纤股份有限公司 | A kind of ionic liquid method regeneration animal ceratin fiber and preparation method thereof |
| CN114108360A (en) * | 2021-11-24 | 2022-03-01 | 安徽工程大学 | Waste feather-based heat-preservation sound-absorption material and preparation method thereof |
| CN116180483A (en) * | 2022-12-30 | 2023-05-30 | 苏州隆瑞绝热材料有限公司 | Superfine glass fiber heat insulation blanket formula and process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1660901A (en) * | 2004-12-24 | 2005-08-31 | 中国科学院长春应用化学研究所 | Method for preparing solution of keratin |
| CN103102694A (en) * | 2013-03-07 | 2013-05-15 | 河南鼎大生物科技有限公司 | Method for preparation and wet spinning of regenerative keratin and silk-fibroin blended solution |
| CN103710775A (en) * | 2013-12-18 | 2014-04-09 | 中国科学院过程工程研究所 | Preparation method of ionic liquid keratin spinning solutions |
-
2015
- 2015-06-02 CN CN201510296536.7A patent/CN104910635B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1660901A (en) * | 2004-12-24 | 2005-08-31 | 中国科学院长春应用化学研究所 | Method for preparing solution of keratin |
| CN103102694A (en) * | 2013-03-07 | 2013-05-15 | 河南鼎大生物科技有限公司 | Method for preparation and wet spinning of regenerative keratin and silk-fibroin blended solution |
| CN103710775A (en) * | 2013-12-18 | 2014-04-09 | 中国科学院过程工程研究所 | Preparation method of ionic liquid keratin spinning solutions |
Non-Patent Citations (2)
| Title |
|---|
| 于小娟 等: "羊毛角蛋白的还原法溶解及其交联", 《毛纺科技》 * |
| 邓湘文: "羽毛角蛋白膜的制备及其交联改性研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10058502B2 (en) | 2015-12-31 | 2018-08-28 | L'oreal | Nail polish compositions |
| CN109881279A (en) * | 2018-03-26 | 2019-06-14 | 新乡化纤股份有限公司 | A kind of ionic liquid method regeneration animal ceratin fiber and preparation method thereof |
| CN109881279B (en) * | 2018-03-26 | 2021-08-03 | 新乡化纤股份有限公司 | Ion liquid method for regenerating animal keratin fiber and preparation method thereof |
| CN114108360A (en) * | 2021-11-24 | 2022-03-01 | 安徽工程大学 | Waste feather-based heat-preservation sound-absorption material and preparation method thereof |
| CN114108360B (en) * | 2021-11-24 | 2022-08-05 | 安徽工程大学 | Waste feather-based heat-preservation sound-absorption material and preparation method thereof |
| CN116180483A (en) * | 2022-12-30 | 2023-05-30 | 苏州隆瑞绝热材料有限公司 | Superfine glass fiber heat insulation blanket formula and process |
| CN116180483B (en) * | 2022-12-30 | 2024-05-31 | 苏州隆瑞绝热材料有限公司 | Superfine glass fiber heat insulation blanket formula and process |
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