CN1736609A - Keratin cation exchange material and preparation process thereof - Google Patents
Keratin cation exchange material and preparation process thereof Download PDFInfo
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- CN1736609A CN1736609A CNA2005100138690A CN200510013869A CN1736609A CN 1736609 A CN1736609 A CN 1736609A CN A2005100138690 A CNA2005100138690 A CN A2005100138690A CN 200510013869 A CN200510013869 A CN 200510013869A CN 1736609 A CN1736609 A CN 1736609A
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Abstract
The invention discloses a keratin cation exchange material and the method for preparation, belonging to the art of ion exchange material. The main chain of said material contains a poly- peptide chain made by alpha- amino acids which are linked by amido bonds, the intermolecular or intramolecular disulfide bonds crosslink reticular, and the molecular side-chain contains sulfonic group; while the equivalent molecular weight EW is among 500- 1000g/ eq, the conductivity amounts to 0.001- 0.02S/ cm and the cation exchange capacity to 1.4- 1.9mmol/ g, and the material can be made into particle- body, fibre- body and film. The technique contains: roguing and defatting hair, oxygenizing partly, grilling to prepare powder, reducing, curing, and oxygenizing and cross- linking. The merit of the invention is characterized in that: the prepared keratin cation exchange material has high conductivity and ion exchange capacity, and it does not pollute the environment since the keratin has degradability. And the invention has a broad application value.
Description
Technical field
The present invention relates to a kind of keratin cation exchange material and preparation method thereof, belong to the ion exchange material technology.
Background technology
Keratin extensively is present in the fur and hair of humans and animals, as wool, hair and feather; Also be present in horn, hoof, first-class.The evolution effect makes the structural proteins in this protective histoorgan that premium properties such as intensity height, heatproof, anti-solvent, acid and alkali-resistance, anti-enzymolysis be arranged.The big molecule of keratin is to be made of by many peptides main chain that amido link is connected 19 kinds of a-amino acids, can be described as a kind of natural polyamide from chemical constitution.Be cross-linked to form spatial network by cystine linkage, hydrogen bond and salt type bond again between its main chain.Keratin especially is rich in cystine, accounts for about 40% as cystine in each seed amino acid of wool keratin.Cystine linkage in the cystine makes keratin highly cross-linked, has formed the peculiar property that is different from other albumen.
Available keratin is mainly sent out from wool, poultry feather, people and domestic animal hoof tips etc.They not only originate very abundant, and content is high, thereby make things convenient for deep processing and modification utilization.The wool yield of annual transaction is just had an appointment 3,000,000 tons in the world, also have a large amount of wools to go out of use because of not spinning to be worth, and keratin accounts for 99% of gross mass in the wool.Keratin can also by biodegradation, can high-performance bio regeneration, be the natural macromolecular material resource that development potentiality is arranged therefore.In addition common and braid wool, old wool, poultry feather, the people sends out and domestic animal hoof tips etc. much goes out of use now, causes environmental pollution and ecological disruption.These keratin raw materials are carried out deep processing and modification utilization, may when obtaining economic benefit, obtain environment and ecological benefits.
Although keratin is widely used for a long time, be limited to mostly with its natural form, as various wool fabrics and horn-ware etc.And keratic deep processing and modification being utilized less, correlative study is also limited.Utilize keratic common mode to have two kinds by chemical modification now.A kind of is by physics or chemical method its part to be degraded, to be used as the forage protein that can be digested and assimilated.Another kind is that it is used as the raw material of producing cystine, is about to isolate cystine after the keratin complete hydrolysis.Though this technical easy row of mode that utilizes, value promotion is not high.
Summary of the invention
The object of the present invention is to provide sub-exchange material of a kind of keratin sun and preparation method thereof, this keratin cation exchange material has higher conductance and ion exchange capacity, its electrical conductivity reaches 0.001-0.02s/cm, and cation exchange capacity reaches 1.4-1.9mmol/g.
The present invention is realized by following technical proposals, a kind of keratin cation exchange material, the molecular backbone of this material is many peptides chain that a-amino acid is connected with each other by amido link, and by between molecule and the molecule or intramolecular disulfide bond crosslinking reticulate, it is characterized in that, molecular side chain contains sulfonate radical, equivalent weight EW is 500-1000g/eq, its electrical conductivity reaches 0.001-0.02S/cm, cation exchange capacity reaches 1.4-1.9mmol/g, and to can be made into particle diameter be 200 μ m-3mm granules, the silk footpath is that corpus fibrosum and the thickness of 20 μ m-2mm is the film of 50 μ m-2mm.
The preparation method of above-mentioned keratin cation exchange material, its feature comprises following process:
Impurity elimination degreasing: hair is cleaned with cleaning agent, again with water rinse and dry.Dried hair is with 1: more than the mixed solution dipping 2h of 1.5: 1 ethanol of 1-and ether, further slough the contained lipid of hair extexine.
Partial oxidation: the hair after the degreasing is dipped in the Peracetic acid or hydrogen peroxide that concentration is 1-32%, at 0-100 ℃, reacts and carries out partial oxidation in 0.5-24 hour and make the solid keratin.
Grinding flour: with the solid keratin with washed with de-ionized water to pH=6-8, in baking oven in 40-60 ℃ of dry 0.5-4 days.Dried hair is ground to form the powder that particle diameter is 200 μ m-3mm.
Reduction reaction: with mercaptoethanol, TGA or ammonium mercaptoacetate is reducing agent, the solid keratin was carried out partial reduction 1-9 hour with reactor, make the keratin disulfide bonds partial reduction, use unnecessary reducing agent of deionized water flush away and little molecular reaction product then, obtain being suitable for the keratin powder of extrusion modling; Or be that mercaptoethanol, TGA or the TGA ammonium salt solution of 0.1-5mol/l is reducing agent with concentration, add the urea of concentration 8mol/l and the dodecyl sodium sulfonate of 0.12mol/l simultaneously and receive (SDS) as denaturant, add 1%-10% (wt) solid keratin, at 20 ℃ of-70 ℃ of solubilizing reaction 8-20h, gained solution is removed unnecessary reducing agent and little molecular reaction product with dialysis or ultrafiltration, obtain keratin solution, be suitable for carrying out processing and forming with solution-cast film forming, wet spinning or suspension balling-up etc.
Processing and forming: can prepare keratin membrane or particle with the keratin powder by extrusion modling, also can prepare keratin membrane by casting, prepare keratin filament, also can prepare the keratin particle by the suspension balling-up by wet spinning with keratin solution.
Oxidation cross-linked: as keratin membrane, silk or the particle of moulding to be exposed in the oxygen or air ambient that concentration is 20-50%, to make the keratin sulfydryl form disulfide bond crosslinking again.
The invention has the advantages that resulting keratin material has higher electrical conductivity and ion exchange capacity, raw material sources are convenient, prepares cheaply, thereby make the keratin material of discarding become high value-added product.Because keratin has degradability, can not produce and pollute simultaneously, be worth so the present invention has extensive use to environment.
The specific embodiment
Embodiment one
Get 10 people of gram after the degreasings and send out, cut to 1mm-20mm with scissors, put into the 250ml conical flask, adding 90ml concentration was the peracetic acid soln of 16wt%, 60 ℃ of lower part oxidations 0.5 hour.After the filtration of cellular glass funnel, to pH=7, drying is 24 hours in vacuum drying oven, 50 ℃ of baking temperatures with the Hair grooming washed with de-ionized water.With mortar dried keratin is pulverized, in the reactor of apparatus,Soxhlet's, gained powder partial reduction 5 hours is taken out then with mercaptoethanol, again with washed with de-ionized water to there not being mercaptoethanol.To the extruding of the keratin powder after cleaning, remove and dry behind the part water to the moisture content 20wt% of powder.Get 1 gram powder and place mould, mould is put between two pressing plates of hydraulic press, is warming up to 130 ℃ and, hydraulic press is forced into 176MPa continue presses 10min under this pressure after 0.5 hour in insulation under this temperature with two pressing plates of hydraulic press.Mould is taken out back typing under 0.2MPa be cooled to room temperature and retreat mould from hydraulic press, realized oxidation cross-linked process.So promptly obtain the hot pressing keratin membrane.Get embodiment one prepared keratin membrane and survey electrical conductivity and ion exchange capacity, find that its electrical conductivity reaches 0.01S/cm, ion exchange capacity is 1.54mmol/g
Embodiment two
Get the wool of 10 grams after the degreasings, cut to 1mm-20mm with scissors, put into the 250ml conical flask, adding 90ml concentration was the peracetic acid soln of 16wt%, 60 ℃ of lower part oxidations 2 hours.After the filtration of cellular glass funnel, to pH=7, drying is 24 hours in vacuum drying oven, 50 ℃ of baking temperatures with the Hair grooming washed with de-ionized water.With mortar dried keratin is pulverized, in the reactor of apparatus,Soxhlet's, the partial reduction of gained powder was taken out in 5 hours then with mercaptoethanol steam, again with washed with de-ionized water to there not being mercaptoethanol.To the extruding of the keratin powder after cleaning, remove and dry behind the part water to the moisture content 20wt% of powder.Get 0.5 gram powder and place mould, mould is put between two pressing plates of hydraulic press, is warming up to 110 ℃ and, hydraulic press is forced into 225MPa continue presses 10min under this pressure after 0.5 hour in insulation under this temperature with two pressing plates of hydraulic press.Mould is taken out back typing under 0.2MPa from hydraulic press be cooled to room temperature and retreat mould.Get embodiment two prepared keratin membrane and survey electrical conductivity and ion exchange capacity, find that its electrical conductivity reaches 0.015S/cm, ion exchange capacity reaches 1.67mmol/g.
Embodiment three
Get wool after the 10 gram degreasings, cut to 1mm-20mm with scissors, place the 250ml conical flask, adding 100ml concentration was the peracetic acid soln of 3wt%, 60 ℃ of lower part oxidations 1 hour.After filtering with the cellular glass funnel, with wool with washed with de-ionized water to pH=7, in vacuum drying oven dry 24 hours, 40 ℃ of baking temperatures.With mortar dried keratin is pulverized, get the 2g keratin powder, 3ml mercaptoethanol, 15 gram urea and 6 gram dodecyl sodium sulfates (SDS) mix in conical flask, in shaking bath, in 50 ℃ of lower parts reduction 15 hours, this moment, keratin all dissolved, and was 14000 dialysis bag dialysis 72 hours with molecular cut off, changed water one time every 12 hours, to remove small-molecule substance.Get the solution 10ml after the dialysis, add the 1ml mass concentration and be 50% glutaraldehyde solution, behind the sonic oscillation, it is 25cm that mixed liquor is poured on area
2The polytetrafluoroethylene (PTFE) membrane cisterna in dry naturally, carry out oxidation cross-linked process, take promptly getting keratin membrane off.Get the keratin membrane that embodiment three makes and survey its electrical conductivity and ion exchange capacity, find that its electrical conductivity is 0.001S/cm, ion exchange capacity is 1.32mmol/g.And this film has advantages such as intensity height, percentage elongation is big, swellbility is little.
Claims (2)
1. keratin cation exchange material, the molecular backbone of this material is many peptides chain that a-amino acid is connected with each other by amido link, and by between molecule and the molecule or intramolecular disulfide bond crosslinking reticulate, it is characterized in that, molecular side chain contains sulfonate radical, equivalent weight EW is 500-1000, its electrical conductivity reaches 0.001-0.02S/cm, cation exchange capacity reaches 1.4-1.9mmol/g, and to can be made into particle diameter be that 200 μ m-3mm granules, silk footpath are that corpus fibrosum and the thickness of 20 μ m-2mm is the film of 50 μ m-2mm.
2. the preparation method of a keratin cation exchange material, its feature comprises following process:
1) partial oxidation: the hair after the degreasing is dipped in Peracetic acid, performic acid or the hydrogen peroxide that concentration is 1-32%, at 0-100 ℃, reacts and carries out partial oxidation in 0.5-24 hour and make solid keratin, grind into powder;
2) reduction reaction: with sulfhydryl compound such as mercaptoethanol, TGA or ammonium mercaptoacetate is reducing agent, with reactor reduction 1-9 hour, makes keratin disulfide bonds carry out partial reduction in powder angle albumen, obtains being suitable for the keratin powder of extrusion modling; Or be that sulfhydryl compound such as mercaptoethanol, TGA or the TGA ammonium salt solution of 0.1-5mol/l is reducing agent with concentration, adding the urea of concentration 8mol/l and the dodecyl of 0.12mol/l simultaneously receives as denaturant, the solid keratin that adds quality 1%-10% again, at 20 ℃ of-70 ℃ of solubilizing reaction 8-20h, gained solution is removed unnecessary reducing agent and little molecular reaction product with dialysis or ultrafiltration, obtain keratin solution, be suitable for solution-cast film forming, wet spinning or suspension balling-up etc.;
3) processing and forming: can prepare keratin membrane or particle with the keratin powder by extrusion modling, also can prepare keratin membrane by casting, prepare keratin filament, also can prepare the keratin particle by the suspension balling-up by wet spinning with keratin solution;
4) oxidation cross-linked: as keratin membrane, silk or the particle of moulding to be exposed in the oxygen or air ambient that concentration is 20-50%, to make the keratin sulfydryl form disulfide bond crosslinking again.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2005100138690A CN1736609A (en) | 2005-06-23 | 2005-06-23 | Keratin cation exchange material and preparation process thereof |
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| CNA2005100138690A CN1736609A (en) | 2005-06-23 | 2005-06-23 | Keratin cation exchange material and preparation process thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839441A (en) * | 2012-09-25 | 2012-12-26 | 天津工业大学 | High-elasticity keratin regenerated fiber and preparation method thereof |
| CN110044670A (en) * | 2019-03-27 | 2019-07-23 | 广州市圣鑫生物科技有限公司 | Drugs extracts kit, extracting method and detection method in hair |
-
2005
- 2005-06-23 CN CNA2005100138690A patent/CN1736609A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839441A (en) * | 2012-09-25 | 2012-12-26 | 天津工业大学 | High-elasticity keratin regenerated fiber and preparation method thereof |
| CN102839441B (en) * | 2012-09-25 | 2014-10-22 | 天津工业大学 | High-elasticity keratin regenerated fiber and preparation method thereof |
| CN110044670A (en) * | 2019-03-27 | 2019-07-23 | 广州市圣鑫生物科技有限公司 | Drugs extracts kit, extracting method and detection method in hair |
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