CN104910635B - The chemical crosslinking new method of keratin molecule in ion liquid solvent - Google Patents
The chemical crosslinking new method of keratin molecule in ion liquid solvent Download PDFInfo
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- CN104910635B CN104910635B CN201510296536.7A CN201510296536A CN104910635B CN 104910635 B CN104910635 B CN 104910635B CN 201510296536 A CN201510296536 A CN 201510296536A CN 104910635 B CN104910635 B CN 104910635B
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Abstract
The present invention provides a kind of crosslinked new methods of ion liquid solvent system keratin molecule.A series of keratin molecule dissolved using chemical cross-linking agents to ion liquid solvent system is crosslinked, and is as follows：The animal wool of crushing is cleaned, 1 17% (wt%) is added in ionic liquid according to a certain percentage after ungrease treatment, 20 90min of mechanical agitation at 90 130 DEG C, obtain ionic liquid keratin solution, certain proportion crosslinking agent 1 10% (wt%) is added in keratin solution, and pH value is adjusted 58, mechanical agitation 12 for 24 hours, obtains the keratin solution of different crosslinking degrees at 50 100 DEG C.Crosslinking agent includes glutaraldehyde, paraformaldehyde, oneself different dicyanate, carbodiimides, nitrine diphenylphosphine, Geniposide, ethylene glycol diglycidylether etc..This method is easy to operate, and reagent is cheap and easy to get, improves the keratin degree of cross linking and performance using chemical crosslink technique, improves the mechanical performance of keratin spinning.
Description
Technical field
The invention belongs to biomass resource regeneration fields, are related to ion liquid solvent system passing through of keratin molecule
Learn the technology that crosslinking prepares keratin spinning solution.
Background technology
Keratin is a kind of fibrous proteins, is the basic protein for forming animal wool, epidermis, feather etc., by 20 kinds
Above a-amino acid composition, the α spirals of keratin and β-pleated sheet space are formed by cross-bonds such as disulfide bond, salt type bond, hydrogen bonds
Configuration.China generates discarded and ten tens of thousands of tons of tubbiness wool every year, contains abundant keratin, keratin in these waste resources
With its stabilization and the structure of toughness, become a kind of natural macromolecular material haveing excellent performance, the keratin of macromolecule can be into
Silk, film forming are applied to the fields such as weaving, high-performance biomedical material.Therefore, it is examined from the angle of utilization of resources and environmental protection
Consider, rationally fully using discarded keratin resource, improve its using added value have great scientific meaning.And keratin
Effective dissolving be protein resource recycling basis and premise.Traditional keratolysis method uses a large amount of strong
Acid, highly basic, reducing agent, metal salt etc., course of dissolution angle protein macromolecular chain are destroyed substantially, and keratin molecule amount is low can not be independent
Into silk, and the discharges such as acid-alkali salt pollute the environment, and do not meet the requirement of Modern Green development of chemical industry.Therefore, selection green,
Efficient solvent dissolving wool keratin, control its appropriateness degradation obtain macromolecule regeneration keratin be its it is high-valued should
Key and technological difficulties.
Ionic liquid is a kind of novel, programmable green solvent, is by organic cation and organic/inorganic anion structure
Into, in room temperature or be bordering on the low temperature molten salt being in a liquid state at room temperature, there is a system compared with traditional volatile organic solvent
The good characteristic of row, as polarity it is strong, it is non-volatile, do not aoxidize, good dissolubility, most stable reagents, structure can be set
Meter etc. has been used as a kind of good solvent to be applied to natural high polymer, such as cellulose, chitin, chitosan, fibroin albumen etc.
Solubility property is studied.The preparation method of existing a kind of ionic liquid keratin solution, it is seen that patent " CN 1660901A, a kind of angle
The preparation method of protein solution ", used in the invention ionic liquid synthesis it is simple, cheap, viscosity is low, but without reference to ionic liquid
The effect of body system keratin crosslinking agent；A kind of technology of existing regenerating ceratin fibres, it is seen that patent " CN 1293266A ",
Keratin is dissolved by solvent of inorganic base, using epoxychloropropane, formaldehyde as crosslinking agent, but is not belonging to ion liquid solvent body
It is the crosslinking of keratin molecule.
For more than present Research, coupled ion liquid dissolving keratin characteristic of the present invention and crosslinking agent improve keratin point
The advantage of the sub- degree of cross linking changes ion liquid solvent system keratin attribute using chemical crosslink technique from molecular structure, improves
The degree of cross linking of keratin molecule is regenerated, increases keratin molecule amount, improves the mechanical performance of keratin spinning.And crosslinking agent used
It is cheap and easy to get, it is simple for process, thus the present invention has more practicable application prospect.
Invention content:
The shortcomings that the invention aims to overcome ion liquid system keratin spinning solution intensity relatively low, is handed over by adding
Join agent, using Chemical Crosslinking Methods, improve reproduction angle molecular weight of albumen, improve keratin spinning properties.
The animal wool raw material is mainly selected from wool, pig hair, the rabbit hair, feather of on-woven utility value etc., first clear through water
It washes, then with ethyl alcohol or acetone soak degreasing 1-12 hours, is dried at 60-90 DEG C, fine powder is ground by pulverizer,
It being added in 90-130 DEG C of ionic liquid, mechanical agitation 20-90min adds in crosslinking agent in keratin solution after cooling, and
PH value 5-8 is adjusted, the mechanical agitation 12-24h at 50-100 DEG C obtains the keratin solution of different crosslinking degrees.
The ionic liquid is dialkylimidazolium phosphoric acid ester, quaternary ammonium phosphoric acid ester, dialkylimidazolium acetate type, dialkyl group
Imidazoles chlorine class, alkyl pyridine acetate type plasma liquid, including：1,3- diethyl imidazolium diethyl phosphate, 1- ethyl -3- methyl
Imidazoles dimethyl phosphate, 1- butyl -3- methylimidazole dimethyl phosphates, 1- butyl -3- ethyl imidazol(e) diethyl phosphates, 1- fourths
Base -3- methylimidazole dibutylphosphoric acid esters, 1- ethyl-3-methylimidazole diethyl phosphates, 1,3- methylimidazole dimethyl phosphate,
1- butyl -3- ethyl imidazol(e) dibutylphosphoric acid esters, triethyl methyl dimethyl phosphate, 1- butyl -3- methylimidazole acetate, methyl
Triethylamine dimethyl phosphate, 1- ethyl-3-methylimidazole acetate, pyridine acetic acid salt, 1- pi-allyl -3- methylimidazole acetic acid
Salt, 1- octyl group -3- methylimidazole acetate, 1- butyl -3- methylimidazole chlorine, 1- ethyl-3-methylimidazole chlorine etc..
The adjusting PH reagents include：Urea, dicyanodiamine, triethanolamine, diethanol amine, triethylamine, diethylamine.
The crosslinking agent includes：Glutaraldehyde, paraformaldehyde, oneself different dicyanate, carbodiimides, nitrine diphenylphosphine,
Geniposide, ethylene glycol diglycidylether.
Specific embodiment:
The present invention is illustrated with following embodiment, but the present invention is not limited to the following embodiments, is not departing from the front and rear ancestor
In the range of purport, change is included in the technical scope of the present invention.
Embodiment 1
The goats hair raw material 2.20g after cleaning, degreasing is weighed, is added in 27.50g triethyl methyl dimethyl phosphates,
The mechanical agitation 30min under 120 DEG C of oil baths, obtains keratin solution, and 0.11g glutaraldehydes are added in after cooling, and PH is adjusted with urea
For value to 5.5, mechanical agitation for 24 hours, obtains highly cross-linked keratin solution at 60 DEG C, regenerates to obtain reproduction angle egg by water-bath
In vain, the opposite crystallization index CI of XRD tests display regeneration keratin is increased to 80%, DSC test results by 62% and shows that it is molten
Melt temperature Tm and be increased to 202 DEG C by 162 DEG C, show that keratin molecule is crosslinked successfully.
Embodiment 2
The hair raw material 2.60g of the pig after cleaning, degreasing is weighed, is added to 30.25g 1- ethyl-3-methylimidazole phosphoric acid diformazans
In ester, the mechanical agitation 60min under 115 DEG C of oil baths obtains keratin solution, and 0.14g paraformaldehydes are added in after cooling, use dicyan
Diamines adjusts pH value to 6.0, and the mechanical agitation 12h at 80 DEG C obtains highly cross-linked keratin solution, regenerated by ethanol bath
Obtain regeneration keratin.The opposite crystallization index CI of XRD test display regeneration keratin is increased to 67%, DSC by 61.9% and surveys
Test result shows that its melting temperature Tm is increased to 192 DEG C by 172 DEG C, shows that keratin molecule is crosslinked successfully.
Embodiment 3
The sheep's wool raw material 3.20g after cleaning, degreasing is weighed, is added to 40.25g 1- butyl -3- methylimidazole di(2-ethylhexyl)phosphates
In methyl esters, the mechanical agitation 60min under 105 DEG C of oil baths obtains keratin solution, oneself different dicyanates of 0.18g are added in after cooling,
PH value is adjusted to 6.5 with triethanolamine, and the mechanical agitation 12h at 80 DEG C obtains highly cross-linked keratin solution, passes through water-bath
Regeneration obtains regeneration keratin.The opposite crystallization index CI of XRD test display regeneration keratin is increased to 74%, DSC by 59%
Test result shows that its melting temperature Tm is increased to 195 DEG C by 172 DEG C, shows that keratin molecule is crosslinked successfully.
Embodiment 4
The rabbit hair raw material 2.60g after cleaning, degreasing is weighed, is added to 30.50g 1- butyl -3- ethyl imidazol(e) p diethylaminobenzoic acids
Ester, the mechanical agitation 60min under 110 DEG C of oil baths, obtains keratin solution, and 0.15g carbodiimides is added in after cooling, uses diethyl
Hydramine adjusts pH value to 7.5, and the mechanical agitation 16h at 70 DEG C obtains highly cross-linked keratin solution, regenerated by water-bath
To regeneration keratin.The opposite crystallization index CI of XRD test display regeneration keratin is increased to 68%, DSC test knots by 62%
Fruit shows that its melting temperature Tm is increased to 223 DEG C by 175 DEG C, shows that keratin molecule is crosslinked successfully.
Embodiment 5
The yak hair raw material 3.00g after cleaning, degreasing is weighed, is added to 31.5g 1- butyl -3- methylimidazole di(2-ethylhexyl)phosphates
In butyl ester, the mechanical agitation 40min under 125 DEG C of oil baths obtains keratin solution, and 0.21g nitrine diphenylphosphines are added in after cooling,
PH value is adjusted to 7.5 with urea, and the mechanical agitation 12h at 90 DEG C obtains highly cross-linked keratin solution, by ethanol bath again
It is raw to obtain regeneration keratin.The opposite crystallization index CI of XRD test display regeneration keratin is increased to 72%, DSC by 62% and surveys
Test result shows that its melting temperature Tm is increased to 183 DEG C by 162 DEG C, shows that keratin molecule is crosslinked successfully.
Embodiment 6
The process hides waste wool raw material 3.30g after cleaning, degreasing is weighed, is added to 36.5g 1- ethyl-3-methylimidazole acetic acid
Salt, the mechanical agitation 20min under 100 DEG C of oil baths, obtains keratin solution, 0.25g Geniposides is added in after cooling, with triethylamine tune
PH value is saved to 6.5, the mechanical agitation 12h at 60 DEG C obtains highly cross-linked keratin solution, regenerates to obtain again by ethanol bath
The male character types in Chinese operas, usu. referring tov the bearded character albumen.The opposite crystallization index CI of XRD test display regeneration keratin is increased to 67%, DSC test results by 61% and shows
Show that its melting temperature Tm is increased to 212 DEG C by 165 DEG C, show that keratin molecule is crosslinked successfully.
Embodiment 7
The hair raw material 3.50g of the pig after cleaning, degreasing is weighed, is added in 38.5g 1- butyl -3- methylimidazole villaumites,
Mechanical agitation 90min under 130 DEG C of oil baths, obtains keratin solution, and 0.26g ethylene glycol diglycidylethers are added in after cooling, are added
Enter diethylamine and adjust pH value to 7.5, mechanical agitation for 24 hours, obtains highly cross-linked keratin solution, by water-bath again at 60 DEG C
It is raw to obtain regeneration keratin.The opposite crystallization index CI of XRD test display regeneration keratin is increased to 67%, DSC by 59% and surveys
Test result shows that its melting temperature Tm is increased to 194 DEG C by 172 DEG C, shows that keratin molecule is crosslinked successfully.
Claims (4)
1. a kind of method of ion liquid solvent system keratin protein molecule cross-link, technological process are：Weigh cleaning, ungrease treatment
The animal wool raw material 1-17% (wt%) crossed is added in ionic liquid, and mechanical agitation 20-90min, obtains at 90-130 DEG C
Keratin solution adds in crosslinking agent 1-10% (wt%) in keratin solution, and adjusts pH value 5-8 after cooling, in 50-100
Mechanical agitation 12-24h at DEG C, obtains the keratin solution of different crosslinking degrees, and the ionic liquid is 1- butyl -3- methyl miaows
Azoles dibutylphosphoric acid ester.
2. according to the method described in claim 1, the animal wool raw material is selected from the goats hair of on-woven utility value, sheep
Hair, camel hair, pig hair, the rabbit hair, yak hair, process hides waste wool, useless fowl feather, through washing, degreasing, drying, disintegrating process, source passes through
It is commercially available or prepared by laboratory.
3. according to the method described in claim 1, it is characterized in that the adjusting pH agents useful for same is urea, dicyanodiamine, three
Ethanol amine, diethanol amine, triethylamine, one kind in diethylamine.
4. according to the method described in claim 1, it is characterized in that the crosslinking agent includes penta 2 for a series of chemical cross-linking agents
In aldehyde, paraformaldehyde, oneself different dicyanate, carbodiimides, nitrine diphenylphosphine, Geniposide, ethylene glycol diglycidylether
One kind.
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| US10058502B2 (en) | 2015-12-31 | 2018-08-28 | L'oreal | Nail polish compositions |
| 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 |
| 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 |
| 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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| 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 |
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| 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 |
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