CN101514497B - Method for separating and extracting fibrillar structural body in natural keratin fiber - Google Patents
Method for separating and extracting fibrillar structural body in natural keratin fiber Download PDFInfo
- Publication number
- CN101514497B CN101514497B CN2009100472548A CN200910047254A CN101514497B CN 101514497 B CN101514497 B CN 101514497B CN 2009100472548 A CN2009100472548 A CN 2009100472548A CN 200910047254 A CN200910047254 A CN 200910047254A CN 101514497 B CN101514497 B CN 101514497B
- Authority
- CN
- China
- Prior art keywords
- shape structure
- diameter
- fibril shape
- density gradient
- keratin fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The present invention provides a method for separating and extracting fibrillar structural body in natural keratin fiber, and is characterized by comprising the concrete steps: the natural keratin fiber is sequentially processed by opening and scotching, decontaminating, washing and drying, dipped into oxidizer solution according to the solid-to-liquid ratio of 1-3g/50ml at the room temperature for 0.5-2h, and then is cleaned and dried; the obtained natural keratin fiber is cut into small sections of 3-5mm, dipped into swelling reagent according to the solid-to-liquid ratio of 0.5-2g/50ml and then is stirred for ultrasonic oscillation or ultrasonic fragmentation; the obtained solid-liquid mixture is filtered by 80-120 meshes screen mesh to remove the natural keratin fiber which does not react; the filtrate is filtered by 350-450 meshes screen mesh to obtain the fibrillar structural body with the diameter of 3-5mu and filtrate. The fibrillar structural body prepared by the invention reserves the characteristics of the self internal structure of wool and has the structural characteristic of anisotropism. The keratin fibrillar structural body is simple in preparation technique and adopts recoverable chemical agent, so as to be low in environmental pollution.
Description
Technical field
The present invention relates to the method for fibril shape structure in a kind of separation and Extraction natural keratin fiber, belong to the natural fabric processing technique field.
Background technology
The annual wool that consumes of China's weaving industry reaches more than 60 ten thousand tons, in the weaving process, produce the waste wool that a large amount of coarse wool and short flannel etc. can not spin value, abandoning arbitrarily not only of these discarded objects can cause the great wasting of resources, also can bring serious environmental to pollute.Therefore, the new way of exploitation waste wool regeneration realizes that the sustainable development of keratin resource is a very significant job.
Animal hair itself is keratin material more than 90%, can be used as the important source material and the auxiliary agent of cosmetics, biological medicine, fabric finishing, feed processing and other fields.At present, both at home and abroad all relevant for the patent report of wool and other keratin fiber regeneration aspects.
World patent (WO99/26570) has proposed then to re-construct by the disulfide bond that oxidation, reduction destroy keratin material the method for disulfide bond again and has made keratin membrane material and bulk material.
Japan Patent (JP6100600) extracts the keratin that macromolecule has the crosslinkable sulfydryl with reductant, protein denaturant and surfactant from keratin material, be used to make film, fiber and timbering material.
Chinese patent " nanometer wool emulsion and powder, its preparation method and purposes " (CN1693371) is handled wool with base catalysis, make its hydrolysis, then under stirring condition, slowly drip electrolyte (inorganic acid) in the solution after hydrolysis, adjustment solution Ph value is in isoelectric point or be higher than isoelectric point, obtains emulsion.After adopting the further dispersion emulsion of ultrasonic wave, prepare the keratin powder with spray drying process or freeze-drying.
Chinese patent " a kind of chemical fibre and production method thereof with the modification of natural protein fiber superfine powder " (CN1594682) adopts after the natural protein fiber material drying, be cut into the 3-5mm particle with disintegrating apparatus, adopt super-refinement powder process equipment particle to be processed into the super-refinement powder of average grain diameter＜5 μ m.
Chinese patent " a kind of effective animal protein feed " (CN1063800).Animal feather is cleaned, at 4-5Kg/cm
2Under the pressure, 108-112 ℃ of boiling 6h then dried pulverizing, preparation keratin powder.
Above patented technology is mainly carried out regeneration by two kinds of approach to the keratin natural material: the first adopts the interior and intermolecular disulfide bond effect of the method opening angle protein molecular of oxidation or reduction, makes the natural keratin material dissolves; After filtration, dialysis, concentrate, obtain the big molecular solution of keratin; Then prepare keratin membrane, bulk material, timbering material or keratin powder by suitable casting technique.It two is that method by physics directly is ground into powder with natural protein fibre.More than the shortcoming of two kinds of approach be that the keratin powder that is obtained all is isotropic spherical particle powders, destroyed the intrinsic fibrillar structure unit of natural keratin animal fiber itself.
Summary of the invention
The purpose of this invention is to provide a kind of method that from natural keratin fiber, obtains anisotropy fibril shape structure.
In order to achieve the above object, technical scheme of the present invention provides the method for fibril shape structure in a kind of separation and Extraction natural keratin fiber, it is characterized in that, concrete steps are:
The first step: after natural keratin fiber carried out shredding, removal of impurities, cleaning and dried successively, be immersed in solid-to-liquid ratio 1-3g/50ml and soak 0.5-2 hour afterwash, oven dry in the oxidizing agent solution under the room temperature;
Second step: the first step is dried the segment of fiber that the natural keratin fiber that obtains is cut into the 3-5 millimeters long, be immersed in the swelling reagent stirring, supersonic oscillations or ultrasonic disruption with solid-to-liquid ratio 0.5-2g/50ml;
The 3rd step: with second step broken obtain solidliquid mixture remove by filter not broken natural keratin fiber with the 80-120 eye mesh screen, filtrate is obtained fibrillar structure body and the filtrate that diameter is 3-5 μ m with the filtration of 350-450 eye mesh screen.
Further, also have in described the 3rd step back:
The 4th step: with the 3rd diameter that obtain of step is that the fibril shape structure of 3-5 μ m is scattered in dimethylbenzene with solid-to-liquid ratio 0.2-0.5g/10ml, obtain dispersion liquid in normal heptane or the absolute ethyl alcohol, with dispersion liquid with volume ratio 1-3: 10 to place density range be the density gradient solution top layer of 1.278-1.282, and collecting the natural keratin fiber orthocortex diameter that is arranged in the density gradient solution top layer at 20 ℃ respectively after with the centrifugal 1-3h of rotating speed 3600rpm is that the fibril shape structure of 3-5 μ m and the secondary cortex diameter of the natural keratin fiber that is arranged in the density gradient solution bottom are the fibril shape structure of 3-5 μ m;
The 5th step: the filtrate that the 3rd step was obtained obtains solid particulate matter at 15-25 ℃ with rotating speed 3000-7000rpm centrifugation 0.2-1h, clean the back and be scattered in dimethylbenzene with solid-to-liquid ratio 0.2-0.5g/10ml, obtain dispersion liquid in normal heptane or the absolute ethyl alcohol, with dispersion liquid with volume ratio 1-3: 10 to place density range be the density gradient solution top layer of 1.278-1.282,20 ℃ with the centrifugal 1-3h of rotating speed 4200rpm after, collecting the diameter be positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.
Also have in described the 5th step back:
The 6th step: with the 4th diameter that obtain of step is that orthocortex fibril shape structure and the secondary cortex fibril shape structure of 3-5 μ m is immersed in the swelling reagent stirring, supersonic oscillations or ultrasonic disruption respectively with solid-to-liquid ratio 0.5-2g/50ml;
The 7th step: with the 6th step broken obtain solidliquid mixture remove by filter the not micron order fibrillar structure body of fragmentation with the 350-450 eye mesh screen, filtrate is obtained orthocortex fibril shape structure and the secondary cortex fibril shape structure that diameter is 0.3-1 μ m at 20 ℃ with rotating speed 4200rpm centrifugation 1-3h.
The oxidant of the described first step is preferably the performic acid aqueous solution that mass percent concentration is 0.5-3%, and mass percent concentration is that peroxide acetate aqueous solution or the mass percent concentration of 0.5-3% is the aqueous hydrogen peroxide solution of 0.5-3%.
It is that aqueous formic acid, mass percent concentration more than 80% is that the dichloroacetic acid aqueous solution more than 70% or mass percent concentration are the trifluoroacetic acid aqueous solution more than 70% that the swelling reagent in described second step is preferably pure formic acid, pure dichloroacetic acid, pure trifluoroacetic acid, mass percent concentration.
It is that aqueous formic acid, mass percent concentration more than 80% is that the dichloroacetic acid aqueous solution more than 70% or mass percent concentration are the trifluoroacetic acid aqueous solution more than 70% that the swelling reagent in described the 6th step is preferably pure formic acid, pure dichloroacetic acid, pure trifluoroacetic acid, mass percent concentration.
The stirring in described second step is preferably at 20-90 ℃ and stirs 1-6h with speed 50-600r/min; Supersonic oscillations are preferably in 20-100 ℃ of water bath with thermostatic control with frequency 20-40kHz and power 200-600W vibration 2-5h; Ultrasonic disruption is preferably the probe type ultrasonic fragmentation, at 20-40 ℃ with the broken 1-3h of frequency 20-40kHz and power 200-600W, ice-water bath cooling.
The stirring in described the 6th step is preferably at 20-90 ℃ and stirs 1-6h with speed 50-600r/min; Supersonic oscillations are preferably in 20-100 ℃ of water bath with thermostatic control with frequency 20-40kHz and power 50-200W vibration 2-5h; Ultrasonic disruption is preferably the probe type ultrasonic fragmentation, at 20-40 ℃ with the broken 1-3h of frequency 20-40kHz and power 50-200W, ice-water bath cooling.
Density gradient solution in described the 4th step and the 5th step is preferably by injecting the low-density organic solvent with the high density organic solvent, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor is collected in the centrifuge tube obtains, wherein, the high density organic solvent is preferably carbon tetrachloride, and the low-density organic solvent is preferably dimethylbenzene, normal heptane or absolute ethyl alcohol.
Natural keratin fiber in the described first step is preferably that wool, people are sent out, cashmere, the rabbit hair, camel hair, horsehair or ox hair.
The invention provides a kind of physics and chemical method combines, from wool, extract the compound separation and the extractive technique of keratin fibril shape structure fast, its characteristics are on separation method, adopt the disulfide bond in the comparatively loose amorphous matrix of oxidant preliminary treatment destruction wool internal structure, reduce the chemical bond power between the inner fibril shape of the wool structure; Then, make matrix swelling between the fibril shape structure, and then reduce the modulus of shearing between the structure, under mechanicals efforts, realize the separation between the keratin fibril shape structure by swelling reagent.On extractive technique, adopted screen cloth to sieve the method that combines with density gradient centrifugation step by step, the wool that extracts resulting separation respectively just, fibril structure in the secondary cortex, and in leaching process, product is carried out purifying and removal of impurities.
The prepared keratin fibril shape structure of the present invention has kept the feature of wool internal structure itself, has anisotropic design feature.Preparation technology is simple for keratin fibril shape structure, the recyclable utilization of the chemical reagent that is adopted, and environmental pollution is little.
The present invention not only can solve the problem of environmental pollution that discarded keratin fiber brought that is difficult to natural degradation to a certain extent, the keratin fibril shape structure that is obtained has simultaneously kept the anisotropic architectural characteristic of keratin fiber microstructure itself, is with a wide range of applications in fields such as bio-medical membrane material, timbering material, tencel preparations.
Description of drawings
The keratin powder electromicroscopic photograph of Fig. 1 for obtaining with grinding natural keratin animal fiber method;
The diameter that Fig. 2 obtains for the inventive method is at keratin fibril shape structure first electromicroscopic photograph of 3-5 μ m;
The diameter that Fig. 3 obtains for the inventive method is at keratin fibril shape structure second electromicroscopic photograph of 3-5 μ m;
The diameter that Fig. 4 obtains for the inventive method is at the keratin fibril shape structure electromicroscopic photograph of 0.3-1 μ m.
The specific embodiment
Specify the present invention below by embodiment.
Embodiment 1
After waste wool after 1g shredding, the removal of impurities washed grease and drying with absolute ethyl alcohol, immerse the 50ml mass concentration and be in 0.5% the aqueous hydrogen peroxide solution behind the oxidation 0.5h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 3mm fragment.Wool after the oxidation processes is immersed in the pure aqueous formic acid of 100ml, in 20 ℃ of waters bath with thermostatic control, stir 1h with speed 50r/min.Remove by filter unreacted natural keratin fiber with 80 eye mesh screens, filtrate is filtered with 350 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 15 ℃ with rotating speed 3000rpm centrifugation 1h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 3000rpm centrifugation 1h with distilled water at 15 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the dimethylbenzene with solid-to-liquid ratio 0.2g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in dimethylbenzene and carbon tetrachloride preparation at 1: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and dimethylbenzene is 1.22: 1) in the dimethylbenzene with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor received slowly to combine in the centrifuge tube obtain, 20 ℃ with the centrifugal 1h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.Separation acquisition diameter is that the productive rate of the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 42.6%, and wherein the product that is obtained in the wool orthocortex accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the dimethylbenzene with solid-to-liquid ratio 0.2g/10ml, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 1: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and dimethylbenzene is 1.22: 1) in the dimethylbenzene with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 3h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure are respectively 26.5% and 17.2%.
To be that the fibril shape structure of 3-5 μ m is immersed in the pure formic acid with solid-to-liquid ratio 0.5g/50ml by the diameter that extracts in wool orthocortex and the secondary cortex respectively, in 20 ℃ of waters bath with thermostatic control, stir 1h with speed 50r/min; The mixture that obtains is filtered through 350 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 3h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the orthocortex of acquisition diameter 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex submicron order fibril shape structure and be respectively 37.5% and 23.4%.
Embodiment 2
After discarded people's hair ether after 3g shredding, the removal of impurities washed grease and drying, immerse the 50ml mass concentration and be in 3% the aqueous hydrogen peroxide solution behind the oxidation 2h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 5mm fragment.People after the oxidation processes is sent out immersion 75ml, in the pure dichloroacetic acid aqueous solution, in 90 ℃ of waters bath with thermostatic control, stir 6h with speed 600r/min.Remove by filter unreacted natural keratin fiber with 120 eye mesh screens, filtrate is filtered with 450 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 25 ℃ with rotating speed 7000rpm centrifugation 0.2h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 7000rpm centrifugation 0.2h with distilled water at 25 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the normal heptane with solid-to-liquid ratio 0.5g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in normal heptane and carbon tetrachloride preparation at 3: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and normal heptane is 1.86: 1) in the normal heptane with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 1.5h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.The productive rate that separate to obtain diameter and be the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 37.2%, and wherein people's product of sending out in the orthocortex to be obtained accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the normal heptane with solid-to-liquid ratio 0.5g/10m, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 3: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and normal heptane is 1.86: 1) in the normal heptane with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 1h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure are respectively 38.5% and 25.4%.
To send out the diameter that extracts in orthocortex and the secondary cortex by the people respectively is that the fibril shape structure of 3-5 μ m is immersed in the pure dichloroacetic acid with solid-to-liquid ratio 2g/50ml, stirs 6h with speed 600r/min in 90 ℃ of waters bath with thermostatic control; The mixture that obtains is filtered through 450 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 1h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the submicron order orthocortex of acquisition diameter 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure and be respectively 56.5% and 38.6%.
Embodiment 3
After discarded cashmere after 2g shredding, the removal of impurities washed grease and drying with absolute ethyl alcohol, immerse the 50ml mass concentration and be in 3% the peroxide acetate aqueous solution behind the oxidation 1h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 5mm fragment.Cashmere after the oxidation processes is immersed 75ml, in the pure trifluoroacetic acid aqueous solution, in 20 ℃ of waters bath with thermostatic control with frequency 20kHz and power 200W supersonic oscillations 2h.Remove by filter unreacted natural keratin fiber with 100 eye mesh screens, filtrate is filtered with 400 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 20 ℃ with rotating speed 5000rpm centrifugation 0.5h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 5000rpm centrifugation 0.5h with distilled water at 20 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in absolute ethyl alcohol and carbon tetrachloride preparation at 2: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 1h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.Separation acquisition diameter is that the productive rate of the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 51.6%, and wherein the product that is obtained in the cashmere orthocortex accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10m, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 2: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 3h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure are respectively 28.3% and 15.6%.
To be that the fibril shape structure of 3-5 μ m is immersed in the pure trifluoroacetic acid with solid-to-liquid ratio 1g/50ml by the diameter that extracts in cashmere orthocortex and the secondary cortex respectively, in 20 ℃ of waters bath with thermostatic control with frequency 20kHz and power 50W supersonic oscillations 2h; The mixture that obtains is filtered through 400 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 3h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the submicron order orthocortex of acquisition diameter 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure and be respectively 43.7% and 31.8%.
Embodiment 4
After the discarded rabbit hair after 2g shredding, the removal of impurities washed grease and drying with absolute ethyl alcohol, immerse the 50ml mass concentration and be in 0.5% the peroxide acetate aqueous solution behind the oxidation 1h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 5mm fragment.The rabbit hair after the oxidation processes is immersed 75ml, and mass percent concentration is in 80% the aqueous formic acid solution, in 100 ℃ of waters bath with thermostatic control with frequency 40kHz and power 600W supersonic oscillations 5h.Remove by filter unreacted natural keratin fiber with 100 eye mesh screens, filtrate is filtered with 400 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 22 ℃ with rotating speed 6000rpm centrifugation 0.3h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 6000rpm centrifugation 0.3h with distilled water at 22 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in absolute ethyl alcohol and carbon tetrachloride preparation at 2: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 1h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.Separation acquisition diameter is that the productive rate of the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 22.1%, and wherein the product that is obtained in the rabbit hair orthocortex accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10m, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 2: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 3h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure are respectively 63.7% and 49.6%.
Respectively will by the diameter that extracts in rabbit hair orthocortex and the secondary cortex be the fibril shape structure of 3-5 μ m to be immersed in mass percent concentration with solid-to-liquid ratio 1g/50ml be in 80% the aqueous formic acid, in 100 ℃ of waters bath with thermostatic control with frequency 40kHz and power 150W supersonic oscillations 5h; The mixture that obtains is filtered through 400 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 3h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the submicron order orthocortex of acquisition diameter 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure and be respectively 72.5% and 57.7%.
Embodiment 5
After discarded camel hair after 2g shredding, the removal of impurities washed grease and drying with absolute ethyl alcohol, immerse the 50ml mass concentration and be in 0.5% the performic acid aqueous solution behind the oxidation 1h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 5mm fragment.Camel hair after the oxidation processes is immersed 75ml, and mass percent concentration is in 70% the dichloroacetic acid aqueous solution solution, at 20 ℃ with frequency 20kHz and the broken 1h of power 200W probe type ultrasonic, ice-water bath cooling.Remove by filter unreacted natural keratin fiber with 100 eye mesh screens, filtrate is filtered with 400 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 15 ℃ with rotating speed 4200rpm centrifugation 0.8h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 4200rpm centrifugation 0.8h with distilled water at 15 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in absolute ethyl alcohol and carbon tetrachloride preparation at 2: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 1h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.Separation acquisition diameter is that the productive rate of the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 49.6%, and wherein the product that is obtained in the camel hair orthocortex accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10m, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 2: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 2h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure are respectively 38.5% and 22.9%.
To be that to be immersed in mass percent concentration with solid-to-liquid ratio 1g/50ml be in 70% the dichloroacetic acid aqueous solution for the fibril shape structure of 3-5 μ m by the diameter that extracts in camel hair orthocortex and the secondary cortex respectively, at 20 ℃ with the broken 1h of frequency 20kHz and power 50W probe type ultrasonic, ice-water bath cooling; The mixture that obtains is filtered through 400 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 2h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the submicron order orthocortex of acquisition diameter 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure and be respectively 45.8% and 33.6%.
Embodiment 6
After discarded horsehair after 2g shredding, the removal of impurities washed grease and drying with absolute ethyl alcohol, immerse the 50ml mass concentration and be in 3% the performic acid aqueous solution behind the oxidation 1h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 5mm fragment.Horsehair after the oxidation processes is immersed 75ml, and mass percent concentration is in 70% the aqueous trifluoroacetic acid solution, at 40 ℃ with frequency 40kHz and the broken 3h of power 600W probe type ultrasonic, ice-water bath cooling.Remove by filter unreacted natural keratin fiber with 100 eye mesh screens, filtrate is filtered with 400 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 20 ℃ with rotating speed 7000rpm centrifugation 0.3h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 7000rpm centrifugation 0.3h with distilled water at 20 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in absolute ethyl alcohol and carbon tetrachloride preparation at 2: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 3h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.Separation acquisition diameter is that the productive rate of the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 31.6%, and wherein the product that is obtained in the horsehair orthocortex accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the absolute ethyl alcohol with solid-to-liquid ratio 0.3g/10m, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 2: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and absolute ethyl alcohol is 1.5: 1) in the absolute ethyl alcohol with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 3h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure are respectively 57.8% and 44.1%.
To be that to be immersed in mass percent concentration with solid-to-liquid ratio 1g/50ml be in 70% the trifluoroacetic acid aqueous solution for the fibril shape structure of 3-5 μ m by the diameter that extracts in horsehair orthocortex and the secondary cortex respectively, at 40 ℃ with the broken 3h of frequency 40kHz and power 200W probe type ultrasonic, ice-water bath cooling; The mixture that obtains is filtered through 400 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 3h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the submicron order orthocortex of acquisition diameter 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure and be respectively 68.5% and 50.7%.
Embodiment 7
After discarded yak hair after 2g shredding, the removal of impurities washed grease and drying with absolute ethyl alcohol, immerse the 50ml mass concentration and be in 3% the performic acid aqueous solution behind the oxidation 1h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 5mm fragment.Yak hair after the oxidation processes is immersed 75ml, and mass percent concentration is in 70% the aqueous trifluoroacetic acid solution, at 40 ℃ with frequency 40kHz and the broken 3h of power 400W probe type ultrasonic, ice-water bath cooling.Remove by filter unreacted natural keratin fiber with 100 eye mesh screens, filtrate is filtered with 400 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 25 ℃ with rotating speed 3000rpm centrifugation 1h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 3000rpm centrifugation 1h with distilled water at 25 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the normal heptane with solid-to-liquid ratio 0.3g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in normal heptane and carbon tetrachloride preparation at 2: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and normal heptane is 1.86: 1) in the normal heptane with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 1h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.Separation acquisition diameter is that the productive rate of the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 40.4%, and wherein the product that is obtained in the yak hair orthocortex accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the normal heptane with solid-to-liquid ratio 0.3g/10m, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 2: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and normal heptane is 1.86: 1) in the normal heptane with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 3h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m (length is 20-50 μ m).Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure are respectively 43.7% and 33.8%.
To be that to be immersed in mass percent concentration with solid-to-liquid ratio 1g/50ml be in 70% the trifluoroacetic acid aqueous solution for the fibril shape structure of 3-5 μ m by the diameter that extracts in yak hair orthocortex and the secondary cortex respectively, at 40 ℃ with the broken 2h of frequency 40kHz and power 100W probe type ultrasonic, ice-water bath cooling; The mixture that obtains is filtered through 400 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 3h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the submicron order orthocortex of acquisition diameter 0.3-1 μ m (length is 20-50 μ m) and the productive rate of secondary cortex fibril shape structure and be respectively 57.5% and 42.3%.
Embodiment 8
After discarded ox hair after 2g shredding, the removal of impurities washed grease and drying with absolute ethyl alcohol, immerse the 50ml mass concentration and be in 3% the performic acid aqueous solution behind the oxidation 1h, clean with distilled water, 40 ℃ of low temperature dryings shred into the 5mm fragment.Ox hair after the oxidation processes is immersed 75ml, and mass percent concentration is in 70% the aqueous trifluoroacetic acid solution, at 40 ℃ with frequency 20kHz and the broken 2h of power 500W probe type ultrasonic, ice-water bath cooling.Remove by filter unreacted natural keratin fiber with 100 eye mesh screens, filtrate is filtered with 400 eye mesh screens obtain fibrillar structure body and the filtrate that diameter is 3-5 μ m (length is 80-120 μ m).
To filtrate 20 ℃ with rotating speed 5500rpm centrifugation 0.5h, collect solid particulate matter wherein.Clean resulting product repeatedly and collect with rotating speed 5500rpm centrifugation 0.5h with distilled water at 20 ℃.With the diameter that extracts is that the micron order fibril shape structure of 3-5 μ m is scattered in the dimethylbenzene with solid-to-liquid ratio 0.3g/10ml, be the density gradient solution top layer of 1.278-1.282 with the density that volume ratio is tiled in dimethylbenzene and carbon tetrachloride preparation at 2: 10 then with dispersion liquid, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and dimethylbenzene is 1.22: 1) in the dimethylbenzene with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 1h of rotating speed 3600rpm, collects orthocortex fibril shape structure that is positioned at the density gradient solution top layer and the secondary cortex fibril shape structure that is positioned at the density gradient solution bottom respectively.Separation acquisition diameter is that the productive rate of the micron order fibril shape structure of 3-5 μ m (length is 80-120 μ m) is 38.6%, and wherein the product that is obtained in the ox hair orthocortex accounts for 80wt%, and the product that is obtained in the secondary cortex accounts for 20wt%.
The solid particulate matter that obtains is collected in centrifugal sedimentation in the filtrate to be scattered in the dimethylbenzene with solid-to-liquid ratio 0.3g/10m, then dispersion liquid is tiled in the density gradient solution top layer that density is 1.278-1.282 with volume ratio at 2: 10, wherein, the compound method of described density gradient solution is for slowly to be injected into (volume ratio of carbon tetrachloride and dimethylbenzene is 1.22: 1) in the dimethylbenzene with carbon tetrachloride, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor slowly is collected in the centrifuge tube obtains, 20 ℃ with the centrifugal 3h of rotating speed 4200rpm, and collecting the diameter that is positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m (length is 20-50 μ m).Separating the acquisition diameter is that the submicron order orthocortex of 0.3-1 μ m and the productive rate of secondary cortex fibril shape structure are 43.9% and 31.1%.
To be that to be immersed in mass percent concentration with solid-to-liquid ratio 1g/50ml be in 70% the trifluoroacetic acid aqueous solution for the fibril shape structure of 3-5 μ m by the diameter that extracts in ox hair orthocortex and the secondary cortex respectively, at 40 ℃ with the broken 2h of frequency 40kHz and power 100W probe type ultrasonic, ice-water bath cooling; The mixture that obtains is filtered through 400 eye mesh screens, remove not broken micron order structure, then 20 ℃ with rotating speed 4200rpm centrifugation 3h, collecting diameter respectively is the orthocortex submicron order fibril shape structure of 0.3-1 μ m (length is 20-50 μ m) and the secondary cortex submicron order fibril shape structure that diameter is 0.3-1 μ m (length is 20-50 μ m).Separate the submicron order orthocortex of acquisition diameter 0.3-1 μ m and the productive rate of secondary cortex fibril shape structure and be respectively 65.7% and 48.1%.
Performance comparison:
As shown in Figure 1, be the keratin powder electromicroscopic photograph that obtains with grinding natural keratin animal fiber method, the keratin powder that is obtained by mechanical lapping natural keratin animal fiber is the fine particle shape, has destroyed the anisotropic structure of keratin fiber itself.
As shown in Figures 2 and 3, the diameter that obtains for the inventive method is at keratin fibril shape structure first and second electromicroscopic photographs of 3-5 μ m, as shown in Figure 4, the diameter that obtains for the inventive method is at the keratin fibril shape structure electromicroscopic photograph of 0.3-1 μ m, and draw ratio is 20-50.The diameter that is extracted is the phenomenon that there is bifurcated in the keratin fibril shape structure head end of 3-5 μ m, show that oxidation reaction destroyed the disulfide bond of matrix between the keratin fibrillar structure body, has quickened the speed that keratin fiber is decomposed into its multistage micro-structural step by step.Aspect application performance, fibrillar structure head end bifurcated has increased the specific area of fibril, thereby is of value to the mechanical property that improves the former fiber composite material of keratin.
Compare with the keratin powder that polishing obtains, the keratin fibril shape structure of the described method of this patent preparation not only kept the microstructure of keratin fiber unit own intrinsic form, be elongated anisotropic structures, and have higher specific surface area.Compare with the method for the isotropism keratin powder that fully keratin fiber dissolving extraction keratin solution is then prepared, keratin fibril shape structure has also kept the macromolecular natural form of keratin except having modal advantage.Keratin fibril shape structure can be used as packing material and reinforcing material is used for fields such as synthetic fiber modification, biologic medical and new packaging material.Keratin fibrillar structure structural reform has become in the past that isotropic material causes the weak point that material mechanical performance descends easily, and it introduces the mechanical characteristic that not only can not reduce material, can improve the mechanical property of material on the contrary.
Claims (9)
1. the method for fibril shape structure in the separation and Extraction natural keratin fiber is characterized in that concrete steps are:
The first step: after natural keratin fiber carried out shredding, removal of impurities, cleaning and dried successively, be immersed in solid-to-liquid ratio 1-3g/50ml and soak 0.5-2 hour afterwash, oven dry in the oxidizing agent solution under the room temperature;
Second step: the first step is dried the segment of fiber that the natural keratin fiber that obtains is cut into the 3-5 millimeters long, be immersed in the swelling reagent stirring, supersonic oscillations or ultrasonic disruption with solid-to-liquid ratio 0.5-2g/50ml;
The 3rd step: with second step broken obtain solidliquid mixture remove by filter not broken natural keratin fiber with the 80-120 eye mesh screen, filtrate is obtained fibrillar structure body and the filtrate that diameter is 3-5 μ m with the filtration of 350-450 eye mesh screen;
The 4th step: with the 3rd diameter that obtain of step is that the fibril shape structure of 3-5 μ m is scattered in dimethylbenzene with solid-to-liquid ratio 0.2-0.5g/10ml, obtain dispersion liquid in normal heptane or the absolute ethyl alcohol, with dispersion liquid with volume ratio 1-3: 10 to place density range be the density gradient solution top layer of 1.278-1.282, and collecting the natural keratin fiber orthocortex diameter that is arranged in the density gradient solution top layer at 20 ℃ respectively after with the centrifugal 1-3h of rotating speed 3600rpm is that the fibril shape structure of 3-5 μ m and the secondary cortex diameter of the natural keratin fiber that is arranged in the density gradient solution bottom are the fibril shape structure of 3-5 μ m;
The 5th step: the filtrate that the 3rd step was obtained obtains solid particulate matter at 15-25 ℃ with rotating speed 3000-7000rpm centrifugation 0.2-1h, clean the back and be scattered in dimethylbenzene with solid-to-liquid ratio 0.2-0.5g/10ml, obtain dispersion liquid in normal heptane or the absolute ethyl alcohol, with dispersion liquid with volume ratio 1-3: 10 to place density range be the density gradient solution top layer of 1.278-1.282,20 ℃ with the centrifugal 1-3h of rotating speed 4200rpm after, collecting the diameter be positioned at the density gradient solution top layer respectively is that the orthocortex fibril shape structure of 0.3-1 μ m and the diameter that is positioned at the density gradient solution bottom are the secondary cortex fibril shape structure of 0.3-1 μ m.
2. the method for claim 1 is characterized in that, also has in described the 5th step back:
The 6th step: with the 4th diameter that obtain of step is that orthocortex fibril shape structure and the secondary cortex fibril shape structure of 3-5 μ m is immersed in the swelling reagent stirring, supersonic oscillations or ultrasonic disruption respectively with solid-to-liquid ratio 0.5-2g/50ml;
The 7th step: with the 6th step broken obtain solidliquid mixture remove by filter the not micron order fibrillar structure body of fragmentation with the 350-450 eye mesh screen, filtrate is obtained orthocortex fibril shape structure and the secondary cortex fibril shape structure that diameter is 0.3-1 μ m at 20 ℃ with rotating speed 4200rpm centrifugation 1-3h.
3. the method for claim 1, it is characterized in that, the oxidant of the described first step is that mass percent concentration is the performic acid aqueous solution of 0.5-3%, and mass percent concentration is that peroxide acetate aqueous solution or the mass percent concentration of 0.5-3% is the aqueous hydrogen peroxide solution of 0.5-3%.
4. the method for claim 1, it is characterized in that the swelling reagent in described second step is that pure formic acid, pure dichloroacetic acid, pure trifluoroacetic acid, mass percent concentration are that aqueous formic acid, mass percent concentration more than 80% is that the dichloroacetic acid aqueous solution more than 70% or mass percent concentration are the trifluoroacetic acid aqueous solution more than 70%.
5. method as claimed in claim 2, it is characterized in that the swelling reagent in described the 6th step is that pure formic acid, pure dichloroacetic acid, pure trifluoroacetic acid, mass percent concentration are that aqueous formic acid, mass percent concentration more than 80% is that the dichloroacetic acid aqueous solution more than 70% or mass percent concentration are the trifluoroacetic acid aqueous solution more than 70%.
6. the method for claim 1 is characterized in that, the stirring in described second step is to stir 1-6h at 20-90 ℃ with speed 50-600r/min; Supersonic oscillations are with frequency 20-40kHz and power 200-600W vibration 2-5h in 20-100 ℃ of water bath with thermostatic control; Ultrasonic disruption is the probe type ultrasonic fragmentation, at 20-40 ℃ with the broken 1-3h of frequency 20-40kHz and power 200-600W, ice-water bath cooling.
7. method as claimed in claim 2 is characterized in that, the stirring in described the 6th step is to stir 1-6h at 20-90 ℃ with speed 50-600r/min; Supersonic oscillations are with frequency 20-40kHz and power 50-200W vibration 2-5h in 20-100 ℃ of water bath with thermostatic control; Ultrasonic disruption is the probe type ultrasonic fragmentation, at 20-40 ℃ with the broken 1-3h of frequency 20-40kHz and power 50-200W, ice-water bath cooling.
8. the method for claim 1, it is characterized in that, density gradient solution in described the 4th step and the 5th step is by the high density organic solvent is injected the low-density organic solvent, marginal not is gone into the limit and is stirred, simultaneously, mixed liquor is collected in the centrifuge tube obtains, wherein, the high density organic solvent is a carbon tetrachloride, and the low-density organic solvent is dimethylbenzene, normal heptane or absolute ethyl alcohol.
9. the method for claim 1 is characterized in that, the natural keratin fiber in the described first step is that wool, people send out, cashmere, the rabbit hair, camel hair, horsehair or ox hair.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100472548A CN101514497B (en) | 2009-03-09 | 2009-03-09 | Method for separating and extracting fibrillar structural body in natural keratin fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100472548A CN101514497B (en) | 2009-03-09 | 2009-03-09 | Method for separating and extracting fibrillar structural body in natural keratin fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101514497A CN101514497A (en) | 2009-08-26 |
| CN101514497B true CN101514497B (en) | 2011-08-31 |
Family
ID=41039111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100472548A Expired - Fee Related CN101514497B (en) | 2009-03-09 | 2009-03-09 | Method for separating and extracting fibrillar structural body in natural keratin fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101514497B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839441B (en) * | 2012-09-25 | 2014-10-22 | 天津工业大学 | High-elasticity keratin regenerated fiber and preparation method thereof |
| CN109629045B (en) * | 2018-12-24 | 2021-12-31 | 上海正家牛奶丝科技有限公司 | Milk protein fiber recovery and separation method |
| CN110496694B (en) * | 2019-08-30 | 2021-07-09 | 大连工业大学 | Waste wool fiber powder and preparation method and application thereof |
Citations (2)
| 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 |
| CN1680467A (en) * | 2004-05-27 | 2005-10-12 | 四川省宜宾五粮液集团有限公司 | Preparation and use of raw liquid of ceratin of animal hairs |
-
2009
- 2009-03-09 CN CN2009100472548A patent/CN101514497B/en not_active Expired - Fee Related
Patent Citations (2)
| 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 |
| CN1680467A (en) * | 2004-05-27 | 2005-10-12 | 四川省宜宾五粮液集团有限公司 | Preparation and use of raw liquid of ceratin of animal hairs |
Non-Patent Citations (2)
| Title |
|---|
| 汤燕伟等.羊毛溶液和角蛋白膜的实用制备技术与基本问题.《膜科学与技术》.2007,第27卷(第2期),80-84页. * |
| 范杰等.羊毛微观结构的分离方法及其应用可能性研究.《材料导报》.2007,第21卷(第9期),98-102页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101514497A (en) | 2009-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102220718B (en) | Method for preparing nano celluloses through high-pressure crushing and low-temperature cooling | |
| CN101514497B (en) | Method for separating and extracting fibrillar structural body in natural keratin fiber | |
| CN108659135B (en) | Preparation method of cellulose nanofiber or chitin nanofiber dispersion liquid | |
| CN102093484B (en) | Method for preparing nano crystal cellulose by dissociating ZnCl2 | |
| CN102191680B (en) | Preparation method of shearing thickened fluid based on SiO2 nano-scale microspheres | |
| CN103031618B (en) | Preparation method of graphene oxide hollow fiber and graphene hollow fiber | |
| CN105150328B (en) | A kind of method of parenchyma cell and fiber separation in bamboo wood | |
| CN103572394B (en) | A kind of preparation method cellulose nano-fibrous simply and rapidly | |
| CN102433786A (en) | Method for preparing micro nano-crystalline cellulose with mechanical force chemical method | |
| CN101590388A (en) | A kind of preparation method of nano hydroxyapatite/polylactic acid composite microspheres | |
| CN105536567B (en) | A kind of ascidian nano-cellulose ultrafiltration membrane and its preparation method and application | |
| CN105906909B (en) | A kind of high density polyethylene (HDPE) water-oil separating material and preparation method thereof | |
| CN108976304A (en) | A kind of acorn starch and its preparation method and application | |
| CN108675289A (en) | A kind of preparation method of graphene dispersing solution | |
| CN114656680B (en) | Super-elastic silk fibroin micro-nano hybrid fiber aerogel and preparation method and application thereof | |
| CN108976303B (en) | Method for preparing cellulose nano-microcrystal by solid acid catalysis sanding | |
| KR20160115051A (en) | A method for manufacturing of sponge powder having acicular structure and a sponge powder having acicular structure manufactured therefrom | |
| CN100999827A (en) | Preparation process of hollow superfine fibre through emulsion | |
| CN101508782B (en) | Method for separating and extracting fibrillar structure body in natural keratin fiber with organic acid solvent | |
| CN101375828B (en) | Attapulgite non-foam depilatory paste for animal | |
| CN107587259A (en) | A kind of composite electrospun tunica fibrosa of high efficiency filter performance and preparation method thereof | |
| CN108166098A (en) | A kind of banana nanofiber preparation method | |
| CN1943865A (en) | Internal stress self explosion auxiliary crushing method | |
| CN103643578B (en) | The Fourier Series expansion technique of a kind of N-of utilization methyl morpholine oxide and magnetic graphene prepares the method for nano micro crystal cellulose | |
| CN109180777A (en) | A method of it improving consumption ox hair polypeptide nano particle and rate is made |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110831 Termination date: 20160309 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |