CN101215733B - Collagen-base PEG composite fibre and spinning technique thereof - Google Patents
Collagen-base PEG composite fibre and spinning technique thereof Download PDFInfo
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Abstract
The invention provides a novel collagen protein-based PEG composite fiber and spinning technology, comprises extracting collagen protein, preparing collagen protein-PEG blending spinning original liquid, spinning composite fiber, preparing coagulating liquid and fixing fiber, and carrying out acetalation process of composite fiber and the like, wherein collagen protein is extracted through alkalimethod or enzymatical method from chrome leather scraps, and can be also extracted from raw hide or heel tendon of healthy animals through enzymatical method. PEG is high molecular polymer which has biocompatibility. Spinning fluid which has certain concentration and viscosity is prepared through mixing collagen protein 100 parts and PEG 5-30 parts according to weight by parts, then composite fiber is prepared through wet spinning, and collagen protein-based composite fiber which is used in fabric needs carrying out acetalization and stretching and the like to improve intensity, swellability,water-absorbing quality and the like of composite fiber. The collagen protein-based PEG composite fiber which is disclosed by the invention can be both used in fabric material and in biological medical material.
Description
Technical field
The present invention relates to collagen-base PEG composite fibre and spinning technique thereof.Be specifically related to the extraction of collagen, the preparation of collagen-PEG co-blended spinning liquid, the spinning of composite fibre, the preparation of fiber coagulating bath and fiber fixing, the acetalation processing of composite fibre etc.Its preparation method belongs to technical field of textile industry, and the complex fiber material of formation can be used for textile material and bio-medical materials such as clothes.
Background technology
Every molecule is a line style, and molecular weight can be made fiber by suitable method at the big molecule more than 3000.Collagen is the rich in protein of content in the mammalian body, accounts for the 25%-30% of total protein, is the main component of connective tissues such as tendon, cartilage, skin and blood vessel.Natural collagen is the fibrous protein that a class has Gly-Xaa-Yaa (X, Y are generally Pro or Hyp) repetitive sequence, and has unique triple helix structure, and ordered aggregation becomes the very high fibrillation of mechanical strength each other in organism.From animal tissue, extract collagen (collagen and the hydrolysate thereof) molecular weight obtain several ten thousand to the hundreds of thousands, have the skeleton structure and the active group of natural collagen, therefore can be used to the synthesis of artificial protein fibre.The advantage that collagen is used is its wide material sources, and cost is cheaper, particularly has excellent biological compatibility, biodegradability and reduced immunogenicity, therefore has been applied to the such value segment of bio-medical material; In recent years its application feasibility in fiber and textile industry also causes more concern.
Use the collagen spinning separately, spinnability and mechanical property are all very poor, if use as bio-medical material, have in vivo defectives such as degraded and absorbed is too fast.Therefore, the general collagen material that uses all is to have passed through the modification processing, to improve its intensity and modulus, hot water resistance, acid and alkali-resistance and anti-dried damp and hot performance.So far, collagen-modified spinning mainly contains two kinds of methods: a kind ofly be to use the chemical cross-linking agent modification, as with metal ion, formaldehyde, glutaraldehyde, epoxide etc. as crosslinking agent (CN 1213191C; CN 1481461A; CN 1100165C); Another kind is the blending and modifying with other synthetic material (CN 1206393C) or natural macromolecular material (CN 1584150A).When using the crosslinking agent method to carry out the modification of collagen, must consider the toxicity and the unstability of crosslinking agent itself, and defective such as cross-linking reaction is wayward; There is research to think that cross-linking modified collagen tissue engineering materials such as formaldehyde, glutaraldehyde can suppress the cell growth, produce inflammatory reaction even cause calcification during as biomaterial.And use in the report of macromolecule and the spinning of collagen blending and modifying, as collagen and polyvinyl alcohol (PVA) (CN 1492087A; CN1696362A) blend prepares composite fibre, be to take as the leading factor and collagen only serves as the role of additive therein in fact with polyvinyl alcohol (itself being exactly the good chemical fibre raw material of spinnability), do not give full play to the performance of collagen like this, and can limit its application as main fibre.
The present invention is based on collagen, utilize the hydrogen bond action of polyethylene glycol (PEG) and collagen, the two blend spinning collagen-base PEG composite fibre, both overcome the problem of simple collagen albumen spinnability difference, and because PEG also has good biological property, as hydrophily, histocompatbility, avirulence etc., the fibrous composite that is spinned also can be used as bio-medical materials such as operation suture thread, hemostatic gauze.To so far, yet there are no the bibliographical information or the patent of collagen-PEG composite fibre research both at home and abroad.
In addition, be worth should be mentioned that, can produce a large amount of chromium hide offal discarded object---chrome shavinges that contain in the leather production inevitably, probably account for about 30% of raw material skin, only China just produces more than 100 ten thousand tons of chrome leather slag discarded objects every year.Therefore, make full use of chrome shavinge and extract collagen, and behind the PEG blending and modifying, be spun into fabric composite fibres such as clothes by wet method, have economic benefit and environmental benefit characteristics with unified mutually.Collagen-base PEG composite fibre has good hygroscopicity and tinctorial property, gives natural texture of fabric and advantage comfortable and easy to wear.
Summary of the invention
The object of the present invention is to provide a kind of novel collagen-base polyethylene glycol (PEG) composite fibre and spinning technique thereof, prepared complex fiber material can be used for textile material and bio-medical materials such as clothes.
The present invention is according to the final use of product, and used collagen can be to extract from the rawhide of healthy animal and tendon in the technology, also can extract from chrome shavinge.These two kinds of extracting methods have difference, and therefore chrome shavinge wants separate chromium (III) because contain the chromic salt that the process hides tannery adds when extracting collagen, make residual chromium amount below 3ppm.Collagen to these extractions carries out suitable concentration adjustment then, sneak into the spinning solution that the PEG preparation has finite concentration and viscosity, obtain composite fibre through wet spinning again, further intensity, swellability and the water imbibition etc. of post processing to improve fiber, the collagen-base fibrous material that obtains having certain mechanical strength at last.
To achieve these goals, the present invention realizes by the following technical solutions: a kind of collagen-base PEG composite fibre, it is characterized in that: use by the collagen of 100 parts of dry weight basis and 5～30 parts polyethylene glycol (PEG) blend to prepare spinning solution with certain suitable concn and viscosity, prepare composite fibre through wet spinning again, wherein collagen and PEG are the solution that obtains through water-soluble.For the collagen based composite fibre that fabric is used, also need carry out acetalation, stretching, go up the wet goods post processing, with intensity, swellability and the water imbibition etc. of improving composite fibre.
Collagen be from chrome shavinge through alkaline process or Enzymatic Extraction, the perhaps protein of molecular weight distribution between 30～300kDa that from the rawhide of healthy animal or heel string, obtains through Enzymatic Extraction.
Except as otherwise noted, related umber and concentration is all by weight among the present invention.
The preparation of above-mentioned collagen-base PEG composite fibre, operating procedure is as follows:
The extraction of 1 collagen
1.1 extract the method for collagen in the chrome leather discarded object:
(1) raw material is prepared: take from tannery's chrome tanning wet blue leather sheet and cut and repair leftover pieces.
(2) clean: the chrome leather angle is expected to soak 0.5～1 hour in 35～50 ℃ of warm water, clean then and remove the impurity such as dust on chrome shavinge surface.So repeated washing is 3～4 times, dries standby.
(3) shear: chrome leather pin material is cut into 0.5～1cm
2About fritter, pulverize with pulverizer then, chrome shavinge.
(4) hydrolysis:
Alkali process hydrolysis: take by weighing 100 parts of chrome shavinges addings and be equipped with in the reactor of mixer, thermometer and condenser pipe, add 5～10 parts CaO or MgO, or 3～7 parts NaOH, add 500～900 parts in water again, hydrolysis 4～8hrs under 80～100 ℃ of stirring conditions.With suction filtration method separating filtrate and filter residue, concentrated filtrate gets collagen after the hydrolysis.
Enzymatic hydrolysis: take by weighing 100 parts of chrome shavinges addings and be equipped with in the reactor of mixer, thermometer and condenser pipe, add 500～900 parts in 2～3 parts MgO and water, 1398 enzymes, 2709 enzymes or the pancreatin that add 1～2 part behind stirring 10～15hrs stir hydrolysis 4～8hrs down at 25～30 ℃.With suction filtration method separating filtrate and filter residue, concentrated filtrate gets collagen after the hydrolysis.
1.2 in fresh rawhide (pigskin or ox-hide) or ox heel string, extract the method for collagen:
(1) pretreatment of raw material: to clean fresh healthy ox-hide, ox heel string or pigskin is raw material.Remove the grease and the impurity on raw material surface as far as possible, then raw material is cut into small pieces.After in acetone, soaking 12～24hrs, take out and air dry, with pulverizer raw material is broken into bits afterwards.
(2) enzymolysis: take by weighing 10 parts of raw material bits, add and be equipped with in the reactor of mixer and thermometer, add 600～800 parts of 1mol/L acetums, add 0.05～0.2 part pepsin behind the immersion 1h, under 5～25 ℃, started the mixer enzymolysis 48～72 hours.
(3) centrifugal: as to use the 1mol/L acetum with 3～5 times of enzymolysis liquid dilutions, and constantly stir.Enzymolysis part completely not in the centrifugal removal enzymolysis liquid obtains the thick solution of collagen.
(4) saltout: preparation and isopyknic 2mol/LNaCl of the thick solution of collagen or (NH
4)
2SO
4Solution, with enzymolysis liquid slowly blend under stirring condition, placing afterwards spends the night in 5 ℃ the refrigerator saltouts.
(5) dialysis: the turbid liquid after centrifugal the saltouing, the thing of saltouing of collagen.The thing of will saltouing is dialysed in distilled water, and continuous magnetic agitation, to bag filter, distill electrical conductivity of water near distilled water till.
(6) freeze-drying: the product freeze-drying after will dialysing with freeze drier obtains collagen.
The preparation of 2 collagens-PEG co-blended spinning liquid
(1) preparation of collagen solution: take by weighing 10～40 parts of collagen dry products, join in the reactor that mixer, thermometer are housed, add water to 100 parts again, 50～70 ℃ of heating are also constantly stirred after 0.5～1 hour, obtain concentration and be 10～40% collagen solution.
(2) preparation of PEG solution: take by weighing 10～30 parts of PEG, join in the reactor that mixer, thermometer are housed, add water to 100 parts again, 50～70 ℃ of heating are also constantly stirred after 0.5～1 hour, obtain 10～30% PEG solution.
(3) blend of collagen and PEG solution
Under 50～70 ℃ condition, collagen solution and PEG solution while thread are added in the reactor of band mixer, and constantly slowly stir.The dry weight ratio of collagen and PEG is 100: 5～30, and preferred proportion is 100: 10～25, and more preferably ratio is 100: 15～20.The gained blend solution continues to stir 0.5～2 hour at 50～70 ℃.
(4) deaeration of blended liquid is handled: gained collagen and PEG blend solution, behind 50～70 ℃ of heat filterings, keeping warm mode nature deaeration or ultrasonic deaeration obtain uniform and stable collagen-PEG composite spinning liquid.
The preparation of 3 coagulating baths
Prepare saturated NaSO
4Solution is as the coagulating bath of spinning.Wherein, use recirculated water that temperature is controlled at about 15～30 ℃, and add aluminium chloride and NaOH, making concentration of aluminum chloride is 10～30 grams per liters, and naoh concentration is 0.5～1 grams per liter.
The spinning of 4 composite fibres
Composite spinning liquid is joined in the storage liquid filling that has insulation jacket, use 50～70 ℃ of abundant preheating spinning heads of recirculated water simultaneously, and remain on 50～70 ℃.Slowly pressurize with gas then, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with suitable diameter to spinning solution from spinneret orifice.Regulate the slewing rate of cops, the fiber after fixing is wound on the cops continuously, thereby realize continuous spinning.
The acetalation of 5 composite fibres is handled
In order to improve intensity and the hydrophobicity of fabric, also need to use formaldehyde or glutaraldehyde that fabric is carried out acetalation with composite fibre and handle with composite fibre.Concrete technological parameter is: aldehyde concentration is about 0.5～1%, and the hydroformylation time is 40s～1min, and hydroformylation pH value is 7～8, and the hydroformylation temperature is 30～50 ℃.
The subsequent treatment of 6 composite fibres
Acetalation or without the composite fibre of acetalation through washing, dry, oil, after the step such as cut-out the composite fibre finished product.
Collagen is a kind of fibrous big molecule, and collagen and PEG blend can be improved the spinning property of blended liquid greatly, also helps improving the intensity of fiber; Composite fibre easily is orientated in follow-up spin-drawing process, easily forms the oriented crystalline structure.Compared with the prior art the present invention has the following advantages:
(1) the invention provides a kind of collagen-base PEG composite fibre and spinning technique thereof, the fibrous material that makes is based on collagen, can give full play to the biology performance advantage of collagen sill.
(2) the present invention determines the source and the extracting method of collagen according to the final use difference of product and the height of added value, makes later technical transform more feasible.Employed structure keeps the more intact collagen can be through Enzymatic Extraction from the rawhide of healthy animal or heel string, and the collagen base fibrous material of spinning is mainly used in high added value industrial circles such as biological medicine; Perhaps from chrome shavinge cheap and easy to get through alkaline process or Enzymatic Extraction hydrolytic collagen, the final collagen-base complex fiber material that forms is applicable to that mainly textile industry is as textile material.The latter has found a feasible path for the recycling of chrome leather discarded object.
(3) first that biology performance is good polyethylene glycol (PEG) is incorporated in the collagen spinning solution, has improved the spinnability of collagen, has improved the intensity of collagen fabric; The fibrous material possess hydrophilic property of the two compound spinning, histocompatbility, avirulence etc. not only can be used for textile industry as the DRESS FABRIC material, and are applicable to field of biomedical materials.
(4) because collagen is an ampholytes, when the composite fibre that adopts the present invention to prepare was used for rag trade, making had stronger binding ability between composite fibre and dyestuff, and dyeability is good.
(5) collagen of this technology use is similar to the human body skin collagen structure, and is because collagen accounts for most proportions in the spinning solution, so the fiber that uses the present invention to obtain has natural texture, comfortable and easy to wear salubrious when being used for rag trade.
The specific embodiment
Provide four embodiment of the present invention below, to specify the spinning method for genuine of collagen-base PEG composite fibre.
Embodiment 1
The chrome leather discarded object is cut into 1cm after cleaning up with 40 ℃ warm water
2Fritter, afterwards with pulverizer pulverize chrome shavinge.Take by weighing 100 parts of chrome shavinges addings and be equipped with in the reactor of mixer, thermometer and condenser pipe, add the CaO of chrome leather chip weight 10%, add the water of 8 times of chrome leather chip weights again, hydrolysis is 6 hours under 90 ℃ of stirring conditions.With suction filtration method separating filtrate and filter residue, concentrated filtrate, drying get the collagen powder after the hydrolysis.
Take by weighing 40 parts of collagen powder and add in 60 parts the water, 60 ℃ of water-bath heating also stir constantly that to obtain concentration in 30 minutes be 40% collagen solution.Take by weighing 20 parts of PEG simultaneously and add in 80 parts the water, 60 ℃ of water-bath heating also stir constantly that to obtain concentration in 30 minutes be 20%PEG solution.With two solution in 60 ℃ be 5: 1 slowly blend and constantly stirring of ratio in collagen and PEG, after 30 minutes, mixed solution vacuum heat filtering places afterwards that standing and defoaming 12hrs gets composite spinning liquid in 60 ℃ of baking ovens.
Composite spinning liquid is added in the storage liquid filling that has insulation jacket, keep recirculated water, use 60 ℃ of recirculated water preheating spinning heads 10 minutes simultaneously at 60 ℃.Slowly pressurize with nitrogen then, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of inorganic salts coagulating bath is 20 ℃, and it consists of: saturated sodium sulphate, aluminium chloride 30 grams per liters, NaOH 1 grams per liter.Regulate the slewing rate of cops, fiber is wound on the cops continuously.Using formaldehyde or glutaraldehyde that composite fibre is carried out acetalation then handles.Concrete technological parameter is: aldehyde concentration is about 1%, and the hydroformylation time is about 40s; Hydroformylation pH value is 7～8; The hydroformylation temperature is about 40 ℃.Composite fibre after the acetalation through washing, dry, oil, step such as cut-out promptly gets the composite fibre finished product.
Embodiment 2
The chrome leather discarded object is cut into 1cm after cleaning up with 40 ℃ warm water
2Fritter, afterwards with pulverizer pulverize chrome shavinge.Take by weighing 100 parts of chrome leather slags addings and be equipped with in the reactor of mixer, thermometer and condenser pipe, add the MgO of chrome leather chip weight 3%, add the water of 7 times of chrome leather chip weights again, add 1398 enzymes of chrome leather chip weight 2% behind the stirring 12hrs, 25 ℃ of following hydrolysis 6 hours.Use suction filtration method separating filtrate and filter residue after the hydrolysis, concentrated filtrate, the dry collagen powder that gets.
Take by weighing 30 parts of collagen powder and add in 60 parts of water, it is 30% collagen solution that 70 ℃ of water-bath heating and continuous stirring obtained concentration in 40 minutes.Take by weighing 30 parts PEG and add in 70 parts the water, it is 30% PEG solution that 70 ℃ of water-bath heating and constantly stirring obtained concentration in 40 minutes.With two solution in 70 ℃ be 6: 1 slowly blend and constantly stirring of ratio in collagen and PEG, after 1 hour, mixed solution vacuum heat filtering places 60 ℃ of ultrasonic deaeration 2hrs of ultrasonic water bath to get composite spinning liquid afterwards.
Composite spinning liquid is added in the storage liquid filling that has insulation jacket, keep recirculated water, use 70 ℃ of recirculated water preheating spinning heads after 10 minutes simultaneously at 70 ℃.Slowly pressurize with nitrogen then, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of inorganic salts coagulating bath is 25 ℃, and it consists of: saturated sodium sulphate, aluminium chloride 25 grams per liters, NaOH 0.75 grams per liter.Regulate the slewing rate of cops, fiber is wound on the cops continuously.Using formaldehyde or glutaraldehyde that composite fibre is carried out acetalation then handles.Concrete technological parameter is: aldehyde concentration is about 0.5%, and the hydroformylation time is about 1min; Hydroformylation pH value is 7～8; The hydroformylation temperature is about 50 ℃.Composite fibre after the acetalation through washing, dry, oil, after the step such as cut-out the composite fibre finished product.
Embodiment 3
Remove hair, grease and other impurity on the fresh porcine skin surface of buying in market as far as possible, then raw material is cut into small pieces.After acetone soaked 24hrs, air dry in the fume hood broke into the rawhide bits with pulverizer with raw material afterwards.Take by weighing 10 parts of rawhide bits, packing into has in the reactor of mixer and thermometer, adds the 1mol/L acetum of 80 times of rawhide chip weights, adds the pepsin of rawhide chip weight 2% behind the immersion 1h, starts the mixer enzymolysis 72 hours under 20 ℃.Use the 1mol/L acetum with 3～5 times of enzymolysis liquid dilutions, and constantly stir.The part of enzymolysis not in the centrifugal removal enzymolysis liquid obtains the thick solution of collagen.
(the NH of preparation and the isopyknic 2mol/L of enzymolysis liquid
4)
2SO
4Solution, with enzymolysis liquid slowly blend under stirring condition, placing afterwards spends the night in 5 ℃ the refrigerator saltouts.Turbid liquid after centrifugal the saltouing obtains the thing of saltouing of collagen.The thing of will saltouing is contained in the bag filter, in distilled water, dialyse, and continuous magnetic agitation, to bag filter the conductance of distilled water constant till.Product freeze-drying after utilizing freeze drier to dialyse obtains collagen.
Take by weighing 10 parts of collagen powder and add in 90 parts the water, 60 ℃ of water-bath heating also stir constantly that to obtain concentration in 30 minutes be 10% collagen solution.Take by weighing 10 parts of PEG simultaneously and add in 90 parts the water, 60 ℃ of water-bath heating also stir constantly that to obtain concentration in 30 minutes be 20%PEG solution.With two solution in 60 ℃ be 9: 1 slowly blend and constantly stirring of ratio in collagen and PEG, after 30 minutes, mixed solution vacuum heat filtering places afterwards that standing and defoaming 12hrs gets composite spinning liquid in 60 ℃ of baking ovens.
Composite spinning liquid is added in the storage liquid filling that has insulation jacket, keep recirculated water, use 60 ℃ of recirculated water preheating spinning heads after 10 minutes simultaneously at 60 ℃.Slowly pressurize with nitrogen then, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of coagulating bath is 25 ℃, and it consists of: saturated sodium sulphate, aluminium chloride 20 grams per liters, NaOH 0.75 grams per liter.Regulate the slewing rate of cops, fiber is wound on the cops continuously.Composite fibre again through washing, dry, oil, after the step such as cut-out the composite fibre finished product.
Embodiment 4
Remove fresh heel string surface grease and impurity that market is bought as far as possible, then raw material is cut into small pieces.After acetone soaks 12hrs, air dry in the fume hood, pulverizer breaks into bits with raw material afterwards.Take by weighing 10g raw material bits, add and be equipped with in the reactor of mixer and thermometer, add the 1mol/L acetum of 80 times of raw material chip weights, add the pepsin of raw material chip weight 1% behind the immersion 1h, under 20 ℃, started the mixer enzymolysis 48 hours.Use the 1mol/L acetum that enzymolysis liquid is diluted 3-5 doubly, and constantly stir.The part of enzymolysis not in the centrifugal removal enzymolysis liquid obtains the thick solution of collagen.
The NaCl solution of preparation and the isopyknic 2mol/L of enzymolysis liquid, with enzymolysis liquid slowly blend under stirring condition, placing afterwards spends the night in the refrigerator saltouts.Turbid liquid after centrifugal the saltouing obtains the thing of saltouing of collagen.The thing of will saltouing is contained in the bag filter, in distilled water, dialyse, and continuous magnetic agitation, to bag filter the conductance of distilled water constant till.Product freeze-drying after utilizing freeze drier to dialyse obtains collagen.
Take by weighing 10 parts of collagen powder and add in 90 parts of water, 70 ℃ of water-bath heating and continuous the stirring got collagen solution in 40 minutes.Take by weighing 10 parts PEG and add in 90 parts the water, 70 ℃ of water-baths heating and constantly stirred 40 minutes PEG solution.With two solution in 70 ℃ be 10: 1 slowly blend and constantly stirring of ratio in collagen and PEG, after 1 hour, mixed solution vacuum heat filtering places 60 ℃ of ultrasonic deaeration 2hrs of ultrasonic water bath afterwards.
70 ℃ of recirculated water preheating spinning heads added composite spinning liquid in the storage liquid filling that has insulation jacket to after 10 minutes, kept recirculated water at 70 ℃.Slowly pressurize with nitrogen, become plume to go out to enter coagulating bath with given pace, then the fixing fiber that forms in coagulating bath with certain diameter to spinning solution from spinneret orifice.The temperature of coagulating bath is 25 ℃, and it consists of: saturated sodium sulphate, aluminium chloride 15 grams per liters, NaOH 0.5 grams per liter.Regulate the slewing rate of cops, fiber is wound on the cops continuously.Composite fibre again through washing, dry, oil, after the step such as cut-out the composite fibre finished product.
Claims (10)
1. collagen-base PEG composite fibre, it is characterized in that: use to prepare spinning solution by the collagen of 100 parts of dry weight basis and 5～30 parts PEG blend, prepare composite fibre through wet spinning again, described collagen and PEG are the solution that obtains through water-soluble, and described collagen is the protein of molecular weight distribution between 30～300kDa.
2. collagen-base PEG composite fibre according to claim 1 is characterized in that: the usage ratio of collagen and PEG is for pressing dry weight basis 100: 10～25.
3. as collagen-base PEG composite fibre as described in the claim 2, it is characterized in that: the usage ratio of collagen and PEG is for pressing dry weight basis 100: 15～20.
4. as collagen-base PEG composite fibre as described in claim 1 or 2 or 3, it is characterized in that: collagen be from chrome shavinge through alkaline process or Enzymatic Extraction, perhaps from the rawhide of healthy animal or heel string, obtain through Enzymatic Extraction.
5. as collagen-base PEG composite fibre as described in the claim 4, it is characterized in that collagen takes the step of alkaline process or Enzymatic Extraction as follows respectively from chrome shavinge:
(1) alkaline process: take by weighing the adding of 100 weight portion chrome shavinges and be equipped with in the reactor of mixer, thermometer and condenser pipe, add the CaO of 5～10 weight portions or the NaOH of MgO or 3～7 weight portions, add water 500～900 weight portions again, hydrolysis 4～8hrs under 80～100 ℃ of stirring conditions, with suction filtration method separating filtrate and filter residue, concentrated filtrate gets collagen after the hydrolysis;
(2) enzyme process: take by weighing the adding of 100 weight portion chrome shavinges and be equipped with in the reactor of mixer, thermometer and condenser pipe, the MgO and water 500～900 weight portions that add 2～3 weight portions, 1398 enzymes, 2709 enzymes or the pancreatin that add 1～2 weight portion behind stirring 10～15hrs, stir hydrolysis 4～8hrs down at 25～30 ℃, with suction filtration method separating filtrate and filter residue, concentrated filtrate gets collagen after the hydrolysis.
6. as collagen-base PEG composite fibre as described in the claim 4, it is characterized in that the step through the Enzymatic Extraction collagen is as follows from the rawhide of healthy animal or heel string: animal hides or heel string with health are raw material, be cut into small pieces after removing surperficial grease, acetone degreasing 12～24hrs, take out dry back and be broken into bits with pulverizer, take by weighing 10 weight portion material bits, measure 1mol/L acetum 600～800 weight portions, add and be equipped with in the reactor of mixer and thermometer, the pepsin that adds 0.05～0.2 weight portion behind the immersion 1h, centrifugation after stirring enzymolysis 48～72hrs under 5～25 ℃, saltout, dialysis, freeze-drying makes collagen.
7. preparation method who is used for spinning the collagen-PEG co-blended spinning liquid of the described collagen-base PEG composite fibre of each claim of claim 1 to 6, it is characterized in that described spinning solution is that the collagen solution of 10～40 weight % and concentration are 10～30 weight %PEG solution at 50～70 ℃ in dry weight basis collagen: PEG=100 by concentration: 5～30 ratio blend, after stirring full and uniform mixing in 0.5～2 hour, through 50～70 ℃ of heat filterings, produce in keeping warm mode nature deaeration or ultrasonic deaeration.
8. method for preparing the described collagen-base PEG composite fibre of each claim in the claim 1 to 6, it is characterized in that spinning solution irritates and to extrude through spinning head from storing liquid in 50～70 ℃ under the effect of gas pressure, enter then in the inorganic salts coagulating bath and solidify, regulate the slewing rate of cops, be wound into the fiber after fixing on the cops continuously, thereby the realization continuous spinning makes composite fibre through follow-up acetalation, dried again.
9. as method as described in the claim 8, it is characterized in that: the temperature of described inorganic salts coagulating bath is 15～30 ℃, consists of, saturated sodium sulphate, aluminium chloride 10～30 grams per liters and NaOH 0.5～1 grams per liter.
10. as method as described in the claim 8, it is characterized in that acetalation is used formaldehyde or glutaraldehyde that composite fibre is carried out acetalation and handled, concrete technological parameter is: aldehyde concentration is 0.5～1 weight %, the hydroformylation time is 40s～1min, and hydroformylation pH value is 7～8, and the hydroformylation temperature is 30～50 ℃.
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