CN1297699C - Collagen-polyvinyl alcohol composite fiber modified by metallic ion, and preparation method - Google Patents
Collagen-polyvinyl alcohol composite fiber modified by metallic ion, and preparation method Download PDFInfo
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- CN1297699C CN1297699C CNB2005100209022A CN200510020902A CN1297699C CN 1297699 C CN1297699 C CN 1297699C CN B2005100209022 A CNB2005100209022 A CN B2005100209022A CN 200510020902 A CN200510020902 A CN 200510020902A CN 1297699 C CN1297699 C CN 1297699C
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Abstract
The present invention relates to a collagen-polyvinyl alcohol composite fiber modified by metallic ions. On the basis of containing collagen protein and polyvinyl alcohol, the composite fiber also contains metal ions performing the function of producing chelation crosslinking. The present invention also relates to a preparation method of the composite fiber. The method comprises: metal salt is added to a mixed solution of collagen-polyvinyl alcohol for modification through chelation crosslinking, and a spinning stock solution is prepared; after a series of subsequent technologies, a novel collagen-polyvinyl alcohol composite fiber which can be used for textile industry is prepared. The composite fiber prepared by the present invention has the advantages of high intensity, high protein content, even distribution good chromaticity, low production cost and certain mildewproof and antibacterial functions.
Description
One, technical field
The invention belongs to the collagen-polyvinyl alcohol composite fiber technical field, what be specifically related to is a kind of metal ion-modified collagen-polyvinyl alcohol composite fiber and manufacture method thereof of adopting.
Two, background technology
Textile fabric can be divided into natural fabric and synthetic fiber usually, and natural fabric comprises cotton, fiber crops, silk, hair etc., and synthetic fiber comprise terylene, acrylic fibers, polypropylene fibre, polyvinyl etc.
Though synthetic fiber are compared at aspects such as output, intensity with natural fabric huge advantage is arranged, but because of its hygroscopicity, gas permeability poor, the level of comfort of its dress can not show a candle to natural fabric, and the polyvinyl alcohol of acetalization fiber is the shortcoming that also there is the dyeability difference in polyvinyl, cause polyvinyl to be mainly used in industrial products, be subjected to very big restriction aspect the product for civilian use, therefore the modification to polyvinyl just seems very necessary.
In modifying process to polyvinyl, people are according to natural protein fibre, as real silk show as good hygroscopicity, soft glossy, comfortable and easy to wear, distinct advantages such as dyeing is good, begin to seek the performance of transforming polyvinyl with native protein, make it to be used for more the product for civilian use.
Main component collagen in the Animal Skin is exactly a kind of native protein.This native protein and other albumen, different with milk protein as soybean protein, it is the rigidity chain structure that is closely linked with alpha-helix by three polypeptide chains.The big molecular spiral structure of this uniqueness and aggregated structure make it have very strong toughness, heat endurance and mechanical strength just.In addition, collagen also has very strong moisture pick-up properties.But at present the Animal Skin of the overwhelming majority all are used for leather production, and because of the particularity of leather products, it has only the raw material skin of 20%-40% to change product in producing, and remaining then becomes the leather industry discarded object.It is reported that China will produce the leather solid waste of more than 100 ten thousand tons of cheapnesss every year,, not only wasted valuable natural resources, also to a certain extent environment has been caused pollution owing to well do not utilized.Therefore, make full use of the rawhide of animal, the collagen that extracts in the leather industry discarded object especially, preparing collagen-polyvinyl alcohol composite fiber with polyvinyl alcohol blending, spinning after the purified modification becomes one of direction of polyvinyl modification.
Disclose a kind of " collagen composite fibre and preparation method thereof " as CN 1492087A, it is to use from rawhide or the leather industry discarded object of animal to extract the protein that obtains, after adding the grafting of vinyl monomer modifier, mix and stir with polyvinyl alcohol, produce spinning solution with finite concentration and viscosity, again through wet spinning, solidify, after stretching and acetalation handle, can obtain collagen composite fibre as textile material.But the inventor finds under study for action, this method is lower to the grafting rate of collagen, thereby makes in the spinning solution after the blend and have many vinyl monomers and homopolymers thereof, is unfavorable for very much spinning, especially when monomer and and homopolymers amount when too much, even be difficult in and be frozen into fibre in the solidification liquid.The inventor finds that also the stability of the spinning solution that obtains with its disclosed preparation method is not fine in addition, is prone to lamination in spinning process, thereby makes the skewness of collagen in the fiber that spinning comes out, and causes fibre strength also inhomogeneous.
Three, summary of the invention
The objective of the invention is to solve prior art with the problem that can not really obtain practical fiber that vinyl monomer modifier grafting collagen is brought, a kind of collagen-polyvinyl alcohol composite fiber metal ion-modified, novel practical that utilizes is provided.
Another object of the present invention is to obtaining metal ion-modified collagen-polyvinyl alcohol composite fiber, and a kind of preparation method is provided.
Metal ion-modified collagen-polyvinyl alcohol composite fiber provided by the invention is characterized in that wherein also containing metal ion except that containing collagen and polyvinyl alcohol.
Each components contents is by weight percentage in this composite fibre:
Polyvinyl alcohol 63～88%
Collagen 10～35%
Metal ion 0.1～3.0%.
The metal ion that wherein contains is one or both in zinc ion, zirconium ion, aluminium ion, copper ion and the iron ion.
Because the modified metal ion that the present invention adopts all has certain coordination ability, thereby it is crosslinked to form chelating in collagen-polyvinyl alcohol, not only make fibre smoothly, the intensity of fiber is even, and has obtained a kind of fiber of novel practical.
The method of the above-mentioned metal ion-modified collagen-polyvinyl alcohol composite fiber of the preparation that another object of the present invention provides, the step of preparation process of this method is followed successively by: stoste preparation, wet spinning, solidify, hot-stretch typing, acetalation handle, wherein the operation of stoste preparation is as follows:
1. be that 15～20% collagen solutions filter with consoluet weight percent concentration, and be 4～6 with its pH value of acid adjusting, standby;
2. the degree of polymerization that will wash is 1700～2000 spinning level polyvinyl alcohol and water, and heating is stirred to 90～100 ℃ and dissolved 6～9 hours down, and adjusts weight percent concentration to 15～20%;
3. with the collagen solution and poly-vinyl alcohol solution 11～36: 64～89 the ratio by weight of preparation, mixed 1～2 hour down, obtain faint yellow uniform mixed liquor at 65～80 ℃;
4. adding in mixed liquor in collagen and polyvinyl alcohol total weight of solids is benchmark, and percentage by weight is the slaine of 1.0-10%, and 65～80 ℃ of following insulated and stirred 2.5～3 hours;
5. after spinning solution being filtered, under 65～75 ℃ of temperature, standing and defoaming 5～7 hours can obtain the used uniform and stable blending and modifying collagen-polyvinyl alcohol stoste of next step spinning.
Spinning solution after the deaeration, in 70～80 ℃ of insulations down of temperature, and through the compensator pressure regulation, promptly send into spinning machine and become silk through spinneret orifice, tow enters coagulating bath and solidifies and drawing-off, then successively through hot-stretch typing, acetalation, washing, drying, oil, curl, steps such as cut-out, packing promptly get metal ion-modified collagen-polyvinyl alcohol composite fiber finished product.This finished product also can dye as required.
Wherein spinning temperature is controlled to be 70～80 ℃; Coagulation bath composition is NaOH 15～50 grams per liters, and sodium sulphate 350～420 grams per liters, coagulation bath temperature are 40～50 ℃, and drafting multiple is 1.5～3.0 times; 200～230 ℃ of hot-stretch temperature; Draw ratio is 1.5～3.0; Acetalation is bathed consists of formaldehyde 10～30 grams per liters, modified glutaraldehyde 20～40 grams per liters, and sulfuric acid 10～20 grams per liters, sodium sulphate 200～300 grams per liters, the acetalation temperature is 60～70 ℃.
Metal ion-modified collagen-the polyvinyl alcohol composite fiber of Huo Deing at last, the general performance that records its fiber by the conventionally test method of polyvinyl alcohol is:
Filament number 1.2～3.5dtex
Do fracture strength 1.8～3.0cN/dtex
Wet breaking strength 1.2～2.5CN/dtex
Dried elongation at break 20～35%
Wet elongation at break 25～40%
Regain 8～12%
Compared with the prior art the present invention has the following advantages:
1, because the present invention has adopted the metal ion with coordination ability, can that chelating takes place simultaneously be crosslinked with collagen and polyvinyl alcohol, therefore a series of problems of not only having avoided prior art to adopt vinyl monomer grafting modification by copolymerization to occur, and obviously improved the stability of spinning solution and the intensity of composite fibre.
2, contain metal ion owing in the collagen-polyvinyl alcohol composite fiber provided by the invention, thereby this fiber also has certain antimildew and antibacterial performance with certain biocidal property.
3, because collagen-polyvinyl alcohol composite fiber protein content height provided by the invention, reach as high as 35%, thereby this fiber not only has feel exquisiteness, softness, smooth, characteristics that drapability is good, and contacted compatibility with human body, and smooth, elegant sense comfortable and easy to wear is strong.
4, because collagen-polyvinyl alcohol composite fiber protein content height provided by the invention, be evenly distributed, thereby make and be rich in amino acid whose composite fibre and the combination of dyes ability obviously improves, dyeability is good, and the color and luster homogeneous is bright-coloured.
5, because the collagen that the present invention uses can be taken from cheap leather industry discarded object, thereby sufficient raw not only, the fiber production cost is low, and meets the resource that makes full use of that country vigorously advocates, and reduces the recycling economy requirement of environmental pollution.
Four, the specific embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for that the invention will be further described; can not be interpreted as limiting the scope of the invention; some nonessential improvement and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above still belong to protection scope of the present invention.
Embodiment 1
Discarded skin is cut after getting tannery's graywall shaving, behind the Weighing, places rotary drum, washes 2 times with 4 times 35 ℃ warm water is vexed, each 20 minutes, washes 10 minutes with flowing water behind the venting water again; The warm water, the skin that add 1 times 30 ℃ are again cut the ammonium sulfate of weight 2% and 0.5% surfactant fatty alcohol ethylene oxide condensate, rotate 60 minutes, discharge the water in the rotary drum; After being washed till pH that skin cuts and being 7～8 with 38 ℃ warm water is vexed again, with 40 ℃ flow of hot water washings 10 minutes; The hot water and the skin that add 1 times 40 ℃ are cut the 1398 neutral proteinase of weight 0.1%, rotate after 1.5 hours, do with the clear water washing and the control of flowing; The skin of wash clean is cut in the reactor of transferring to the band agitating device, added 2 times of water, be warmed up to 70 ℃ gradually, and be incubated 3 hours and make skin cut abundant dissolving, filter then, getting filtrate and being concentrated to weight percent concentration is 20%, with the salt acid for adjusting pH value to 5.0 of 0.1N, standby.
With the degree of polymerization of washing is 2000, and alcoholysis degree is that 99% polyvinyl alcohol adds in the entry, and heating is stirred to 90 ℃ of dissolvings 9 hours down, polyvinyl alcohol is dissolved fully after, adjusting weight percent concentration is 20%; Take by weighing 11 parts of collagen solutions by weight, 89 parts of poly-vinyl alcohol solutions mix stirring 1.5 hours down in 80 ℃; Under the state that stirs, progressively dripping in collagen and polyvinyl alcohol total weight of solids is benchmark, and percentage by weight is 1.0% liquor alumini chloridi, continues stirring action 2.5 hours, and the ultimate density that makes spinning solution is 18%; Spinning solution is incubated filtration down in 65 ℃, and the normal pressure standing and defoaming is after 5 hours, through the compensator pressure regulation, with stoste send into spinning machine under 80 ℃ of spinning temperatures through spinneret orifice Cheng Sihou, enter temperature and be that 45 ℃ coagulating bath is solidified and 3.0 times of drawing-offs, the coagulating bath component is: sodium sulphate 430 grams per liters, its proportion are 1.3～1.4 grams per milliliters; Under 230 ℃ of temperature, carry out the hot-stretch typing then, stretch 1.5 times, finalized the design two minutes; It is acetal during 60 ℃ acetalation is bathed that tow after the stretching enters temperature again, and acetalation is bathed consists of formaldehyde 30 grams per liters, modified glutaraldehyde 40 grams per liters, sulfuric acid 20 grams per liters, sodium sulphate 230 grams per liters; After the acetalation tow through washing, dry, oil, curl, cut off, pack, promptly get collagen-polyvinyl alcohol composite fiber.
Embodiment 2
The leather of getting behind the blue wet shaving of tannery is cut, behind the Weighing, place rotary drum, wash 2 times with 4 times 35 ℃ warm water is vexed, each 20 minutes, wash after 10 minutes control with flowing water again behind the venting water and do, the clean leather of washing is cut transferred in the reactor, add weight and cut 7 times water and leather for leather and cut heavy 3% calcium hydroxide, be warmed up to 95 ℃ gradually, and be incubated 5 hours and make leather and cut abundant dissolving, filter then, with in the sulfuric acid solution after the dilution with pH value to 7.0 about, refilter and remove calcium sulfate precipitation, and filtrate is concentrated to concentration is 20%, and the sulphur acid for adjusting pH value with 1N is 5.5 again, and is standby.
With the degree of polymerization of washing is 1700, and alcoholysis degree is that 99% polyvinyl alcohol adds in the entry, and heating is stirred to 98 ℃ of down dissolvings 6 hours, polyvinyl alcohol is dissolved fully after, adjusting weight percent concentration is 15%; Take by weighing 20 parts of collagen solutions by weight, 80 parts of poly-vinyl alcohol solutions mix stirring 1.0 hours down in 70 ℃; Under the state that stirs, progressively dripping in collagen and polyvinyl alcohol total weight of solids is benchmark, and percentage by weight is 3.0% solution of zinc sulfate, continues stirring action 3 hours, and the ultimate density that makes spinning solution is 16%; Spinning solution is incubated filtration down in 70 ℃, and the normal pressure standing and defoaming is after 6 hours, through the compensator pressure regulation, stoste is sent into spinning machine 75 ℃ of spinning temperatures, through spinneret orifice Cheng Sihou, enter temperature and be that 50 ℃ coagulating bath is solidified and 2.0 times of drawing-offs, coagulation bath composition is: NaOH 15 grams per liters, sodium sulphate 350 grams per liters; Carry out the hot-stretch typing then under 210 ℃ of temperature, draw ratio is 2.0, finalizes the design two minutes; It is acetal during 65 ℃ acetalation is bathed that tow after the stretching enters temperature again, and acetalation is bathed consists of formaldehyde 20 grams per liters, modified glutaraldehyde 40 grams per liters, sulfuric acid 20 grams per liters, sodium sulphate 200 grams per liters; After the acetalation tow through washing, dry, oil, curl, cut off, pack, promptly get collagen-polyvinyl alcohol composite fiber.
Embodiment 3
Discarded skin is cut after getting tannery's graywall shaving, behind the Weighing, places rotary drum, washes 2 times with 4 times 35 ℃ warm water is vexed, each 20 minutes, washes 10 minutes with flowing water behind the venting water again; The warm water, the skin that add 1 times 30 ℃ are again cut the ammonium sulfate of weight 2% and 0.5% surfactant fatty alcohol oxirane volume compound, rotate 60 minutes, discharge the water in the rotary drum; After being washed till pH that skin cuts and being 7～8 with 38 ℃ warm water is vexed again, with 40 ℃ flow of hot water washings 10 minutes; The hot water and the skin that add 1 times 40 ℃ are cut the 1398 neutral proteinase of weight 0.1%, rotate after 1.5 hours, do with the clear water washing and the control of flowing; The skin of wash clean is cut in the reactor of transferring to the band agitating device, added 2 times of water, be warmed up to 70 ℃ gradually, and be incubated 3 hours and make skin cut abundant dissolving, filter then, getting filtrate and being concentrated to weight percent concentration is 20%, with the salt acid for adjusting pH value to 6.0 of 0.1N, standby.
With the degree of polymerization of washing is 1700, and alcoholysis degree is that 99% polyvinyl alcohol adds in the entry, and heating is stirred to 98 ℃ of down dissolvings 8 hours, polyvinyl alcohol is dissolved fully after, adjusting weight percent concentration is 18%; Take by weighing 25 parts of collagen solutions by weight, 75 parts of poly-vinyl alcohol solutions mix stirring 2 hours down in 75 ℃; Under the state that stirs, progressively dripping in collagen and polyvinyl alcohol total weight of solids is benchmark, and percentage by weight is 8.0% copper-bath, continues stirring action 3 hours, and the ultimate density that makes spinning solution is 16%; Spinning solution is incubated filtration down in 70 ℃, and the normal pressure standing and defoaming is after 7 hours, through the compensator pressure regulation, with stoste send into spinning machine 70 ℃ of spinning temperatures through spinneret orifice Cheng Sihou, enter temperature and be that 40 ℃ coagulating bath is solidified and 1.5 times of drawing-offs, the coagulating bath component is: NaOH 30 grams per liters, sodium sulphate 380 grams per liters; Under 215 ℃ of temperature, carry out the hot-stretch typing then, stretch 2.0 times; It is acetal during 70 ℃ acetalation is bathed that tow after the stretching enters temperature again, and acetalation is bathed consists of formaldehyde 10 grams per liters, modified glutaraldehyde 30g/l, sulfuric acid 10g/l, sodium sulphate 260g/l; After the acetalation tow through washing, dry, oil, curl, cut off, pack, promptly get collagen-polyvinyl alcohol composite fiber.
Embodiment 4
The leather of getting behind the blue wet shaving of tannery is cut, behind the Weighing, place rotary drum, wash 2 times with 4 times 35 ℃ warm water is vexed, each 20 minutes, wash after 10 minutes control with flowing water again behind the venting water and do, the clean leather of washing is cut transferred in the reactor, add weight and cut 7 times water and leather for leather and cut heavy 3% calcium hydroxide, be warmed up to 95 ℃ gradually, and be incubated 5 hours and make leather and cut abundant dissolving, filter then, with in the sulfuric acid solution after the dilution with pH value to 7.0 about, refilter and remove calcium sulfate precipitation, and filtrate is concentrated to concentration is 20%, and the sulphur acid for adjusting pH value with 1N is 6.0 again, and is standby.
With the degree of polymerization of washing is 1700, and alcoholysis degree is that 99% polyvinyl alcohol adds in the entry, and heating is stirred to 95 ℃ of down dissolvings 8 hours, polyvinyl alcohol is dissolved fully after, adjusting weight percent concentration is 18%; Take by weighing 30 parts of collagen solutions by weight, 70 parts of poly-vinyl alcohol solutions mix stirring 2 hours down in 75 ℃; Under the state that stirs, progressively dripping in collagen and polyvinyl alcohol total weight of solids is benchmark, and percentage by weight is 8.0% copper-bath, continues stirring action 2.5 hours, and the ultimate density that makes spinning solution is 17%; Spinning solution is incubated filtration down in 75 ℃, and the normal pressure standing and defoaming is after 6 hours, through the compensator pressure regulation, with stoste send into spinning machine 75 ℃ of spinning temperatures through spinneret orifice Cheng Sihou, enter temperature and be that 50 ℃ coagulating bath is solidified and 1.5 times of drawing-offs, the coagulating bath component is: NaOH 40 grams per liters, sodium sulphate 400 grams per liters; Under 220 ℃ of temperature, carry out the hot-stretch typing then, stretch 3.0 times; It is acetal during 65 ℃ acetalation is bathed that tow after the stretching enters temperature again, and acetalation is bathed consists of formaldehyde 15 grams per liters, modified glutaraldehyde 20g/l, sulfuric acid 15g/l, sodium sulphate 280g/l; After the acetalation tow through washing, dry, oil, curl, cut off, pack, promptly get the compound fibre of collagen-polyvinyl alcohol.
Embodiment 5
The leather of getting behind the blue wet shaving of tannery is cut, behind the Weighing, place rotary drum, wash 2 times with 4 times 35 ℃ warm water is vexed, each 20 minutes, wash after 10 minutes control with flowing water again behind the venting water and do, the clean leather of washing is cut transferred in the reactor, add weight and cut 7 times water and leather for leather and cut heavy 3% calcium hydroxide, be warmed up to 95 ℃ gradually, and be incubated 5 hours and make leather and cut abundant dissolving, filter then, with in the sulfuric acid solution after the dilution with pH value to 7.0 about, refilter and remove calcium sulfate precipitation, and filtrate is concentrated to concentration is 20%, and the sulphur acid for adjusting pH value with 1N is 6.0 again, and is standby.
With the degree of polymerization of washing is 700, and alcoholysis degree is that 99% polyvinyl alcohol adds in the entry, and heating is stirred to 95 ℃ of down dissolvings 8 hours, polyvinyl alcohol is dissolved fully after, adjusting weight percent concentration is 18%; Take by weighing 36 parts of collagen solutions by weight, 64 parts of poly-vinyl alcohol solutions mix stirring 2 hours down in 80 ℃; Under the state that stirs, progressively dripping in collagen and polyvinyl alcohol total weight of solids is benchmark, and percentage by weight is 10.0% ferric chloride solution, continues stirring action 2.5 hours, and the ultimate density that makes spinning solution is 16.5%; Spinning solution is incubated filtration down in 80 ℃, and the normal pressure standing and defoaming is after 6 hours, through the compensator pressure regulation, with stoste send into spinning machine 80 ℃ of spinning temperatures through spinneret orifice Cheng Sihou, enter temperature and be that 45 ℃ coagulating bath is solidified and 1.5 times of drawing-offs, the coagulating bath component is: NaOH 50 grams per liters, sodium sulphate 420 grams per liters; Under 200 ℃ of temperature, carry out the hot-stretch typing then, stretch 1.5 times; It is acetal during 68 ℃ acetalation is bathed that tow after the stretching enters temperature again, and acetalation is bathed consists of formaldehyde 25 grams per liters, modified glutaraldehyde 25 grams per liters, sulfuric acid 20 grams per liters, sodium sulphate 300g/l; After the acetalation tow through washing, dry, oil, curl, cut off, pack, promptly get collagen-polyvinyl alcohol composite fiber.
Embodiment 6
It is to be benchmark in collagen and polyvinyl alcohol total weight of solids that present embodiment removes what progressively drip, and percentage by weight is that other are not stated so omit with embodiment 2 outside the zirconium sulfate mixed solution of 3% zinc sulfate and 3%.
The main performance of above embodiment gained collagen-polyvinyl alcohol composite fiber sees the following form:
Claims (10)
1, a kind of metal ion-modified collagen-polyvinyl alcohol composite fiber, this composite fibre contains collagen and polyvinyl alcohol, it is characterized in that wherein also containing metal ion.
2, metal ion-modified collagen-polyvinyl alcohol composite fiber according to claim 1 is characterized in that each components contents is by weight percentage in this composite fibre:
Polyvinyl alcohol 63～88%
Collagen 10～35%
Metal ion 0.1～3.0%.
3, metal ion-modified collagen-polyvinyl alcohol composite fiber according to claim 1 and 2 is characterized in that metal ion in this composite fibre is one or both in zinc ion, aluminium ion, copper ion, zirconium ion and the iron ion.
4, a kind of method for preparing the described metal ion-modified collagen-polyvinyl alcohol composite fiber of claim 1～3, the step of preparation process of this method is followed successively by: stoste preparation, wet spinning, solidify, hot-stretch typing, acetalation handle, wherein the operation of stoste preparation is as follows:
1. be that 15～20% collagen solutions filter with consoluet weight percent concentration, and be 4～6 with its pH value of acid adjusting, standby;
2. the degree of polymerization that will wash is 1700～2000 spinning level polyvinyl alcohol and water, and heating is stirred to 90～100 ℃ and dissolved 6～9 hours down, and adjusts weight percent concentration to 15～20%;
3. with the collagen solution and poly-vinyl alcohol solution 11～36: 64～89 the ratio by weight of preparation, mixed 1～2 hour down, obtain faint yellow uniform mixed liquor at 65～80 ℃;
4. adding in mixed liquor in collagen and polyvinyl alcohol total weight of solids is benchmark, and percentage by weight is the slaine of 1.0-10%, and 65～80 ℃ of following insulated and stirred 2.5～3 hours;
5. after spinning solution being filtered, under 65～75 ℃ of temperature, standing and defoaming 5～7 hours can obtain the used uniform and stable blending and modifying collagen-polyvinyl alcohol stoste of next step spinning.
5, the method for the metal ion-modified collagen-polyvinyl alcohol composite fiber of preparation according to claim 4 is characterized in that the slaine that adds is a metal salt solution, and adopts the dropping mode to drip in 20～40 minutes.
6, require the method for the metal ion-modified collagen-polyvinyl alcohol composite fiber of 4 or 5 described preparations according to power, it is characterized in that the slaine that adds is selected from one or both in zinc sulfate, aluminium chloride, copper sulphate, zirconium sulfate and the iron chloride.
7, according to the method for the metal ion-modified collagen-polyvinyl alcohol composite fiber of claim 4 or 5 described preparations, it is characterized in that the coagulation bath composition that coagulation step adopts is: NaOH 15～50 grams per liters, sodium sulphate 350～420 grams per liters, coagulation bath temperature are 40～50 ℃.
8, the method for the metal ion-modified collagen-polyvinyl alcohol composite fiber of preparation according to claim 6, it is characterized in that the coagulation bath composition that coagulation step adopts is: NaOH 15～50 grams per liters, sodium sulphate 350～420 grams per liters, coagulation bath temperature are 40～50 ℃.
9, according to the method for the metal ion-modified collagen-polyvinyl alcohol composite fiber of claim 4 or 5 described preparations, what it is characterized in that acetalation that the acetalation step adopts bathes consists of: formaldehyde 10～30 grams per liters, modified glutaraldehyde 20～40 grams per liters, sulfuric acid 10～20 grams per liters, sodium sulphate 200～300 grams per liters, acetalation temperature are 60～70 ℃.
10, the method for the metal ion-modified collagen-polyvinyl alcohol composite fiber of preparation according to claim 8, what it is characterized in that acetalation that the acetalation step adopts bathes consists of: formaldehyde 10～30 grams per liters, modified glutaraldehyde 20～40 grams per liters, sulfuric acid 10～20 grams per liters, sodium sulphate 200～300 grams per liters, acetalation temperature are 60～70 ℃.
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| CN101215733B (en) * | 2008-01-14 | 2010-06-02 | 四川大学 | Collagen-base PEG composite fibre and spinning technique thereof |
| CN102181959A (en) * | 2011-04-07 | 2011-09-14 | 北京服装学院 | Fish collagen composite fibers and preparation method thereof |
| CN103436986B (en) * | 2013-08-01 | 2015-04-08 | 湖州珠力纳米材料科技开发有限公司 | Preparation method of polypeptide soybean protein complex fiber |
| CN107673885A (en) * | 2017-11-16 | 2018-02-09 | 安徽耘泰农业发展有限公司 | A kind of preparation method of green paddy rice-dedicated fertilizer |
| CN108396403A (en) * | 2018-03-07 | 2018-08-14 | 兴业皮革科技股份有限公司 | A method of preparing the compound biodegradable fiber of collagen-based using shavings containing metallic |
| CN111286813B (en) * | 2020-03-03 | 2022-03-11 | 青岛大学 | Preparation method of metal ion induced liquid crystal carrageenan fibers |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364948A (en) * | 2001-05-14 | 2002-08-21 | 胡宗善 | Protein synthetic fibre spinning solution and its producing method |
| CN1458307A (en) * | 2002-05-17 | 2003-11-26 | 曾宪珉 | Skin protein/water soluble polymer blended fiber and its preparing method |
| CN1492087A (en) * | 2002-10-25 | 2004-04-28 | 中国皮革和制鞋工业研究院 | Collagen protein composite fiber and its producing method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1364948A (en) * | 2001-05-14 | 2002-08-21 | 胡宗善 | Protein synthetic fibre spinning solution and its producing method |
| CN1458307A (en) * | 2002-05-17 | 2003-11-26 | 曾宪珉 | Skin protein/water soluble polymer blended fiber and its preparing method |
| CN1492087A (en) * | 2002-10-25 | 2004-04-28 | 中国皮革和制鞋工业研究院 | Collagen protein composite fiber and its producing method |
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