CN102154731A - Animal blood protein fiber and preparation method thereof - Google Patents
Animal blood protein fiber and preparation method thereof Download PDFInfo
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- CN102154731A CN102154731A CN 201110034015 CN201110034015A CN102154731A CN 102154731 A CN102154731 A CN 102154731A CN 201110034015 CN201110034015 CN 201110034015 CN 201110034015 A CN201110034015 A CN 201110034015A CN 102154731 A CN102154731 A CN 102154731A
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Abstract
The invention provides an animal blood protein fiber and a preparation method thereof. The fiber comprises the following components in percentage by weight: 20-60 percent of animal blood proteins and the balance of polyvinyl alcohol. The preparation method comprises the following steps of: slowly adding an acetone hydrochloride solution into blood, stirring and performing suction filtration to obtain precipitated proteins; cleaning 3-4 times with the acetone hydrochloride solution to obtain greyish-white precipitated proteins; dissolving the greyish-white precipitated proteins in a solution prepared from urea and beta-mercaptoethanol or water, mixing with a polyvinyl alcohol aqueous solution in the weight part ratio of 1:(0.7-4), continuously stirring in one direction at low speed at the temperature of 95-100 DEG C and standing at the temperature of 80-95 DEG C until air bubbles are completely eliminated to obtain a spinning solution; and preparing the spinning solution into the animal blood protein fiber by adopting a wet spinning process. Crosslinking treatment is performed on protein tows in the spinning technical process, so that the intensity of the protein fiber is enhanced, and the pilling degree of a fabric is lowered. An experiment indicates that the blood protein fiber has high flexibility and high comfort.
Description
Technical field
The present invention relates to textile material, specifically is a kind of animal blood azelon and manufacture method thereof.
Background technology
Artificial synthetic azelon comprises soybean fiber, milk protein fiber, collagen fabric, ground nut fiber etc.These azelons are to make with soybean, milk, collagen or peanut etc., and raw material sources are limited, and cost is higher, limits its development.The utilization of animal blood is not at present developed fully, and is most of just as animal feed.The present invention becomes the blood protein fiber with animal blood, makes value promotion, can obtain reasonable economic benefit and social benefit.
Summary of the invention
The purpose of this invention is to provide a kind of animal blood azelon and manufacture method thereof.
A kind of animal blood azelon provided by the invention, this fibre composition comprises animal blood albumen and polyvinyl alcohol, wherein animal blood albumen accounts for 20～60% by weight percentage.Described animal blood is the anticoagulated whole blood of fresh animals such as ox, horse, pig, sheep, chicken or duck.
The preparation method of a kind of animal blood azelon provided by the invention comprises the steps:
(1) in 10～15 ℃ cold house, the hydrochloric acid acetone soln that will be equivalent to blood volume 1.5-2 mass concentration 2% doubly slowly adds in the blood and stirred 30 minutes, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3～4 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein;
(2) pale precipitation protein is joined in the solution of 9～9.8 parts of 2～8mol ureas and 1～0.2 part of preparation of 0.02～0.5mol beta-mercaptoethanol, make its dissolving at 40～100 ℃, regulate pH to 8.5～10 with 1molNaOH, the final concentration that makes pale precipitation protein is 14～20%; Be interrupted and stir, 40～50 ℃ of insulation 4～6h obtain protein solution (being labeled as 1.);
The solution of 9～9.8 parts of described 2～8mol ureas and 1～0.2 part of preparation of 0.02～0.5mol beta-mercaptoethanol can replace (being labeled as 2.) for water;
(3) weighing polyvinyl alcohol adds water, is interrupted to stir in boiling water bath to make its dissolving, and making final concentration is 14～20%;
(4) poly-vinyl alcohol solution that obtains of protein solution that step (2) is obtained and step (3) by weight 1: 0.7-4 mixes, the unidirectional stirring of continuous low speed 0.5-1.5h under 95～100 ℃, leave standstill to bubble at 80～95 ℃ and to eliminate fully, perhaps leave standstill under the heat-retaining condition to bleed bubble is eliminated fast, obtain spinning solution with vavuum pump at 80～95 ℃;
(5) adopt wet spinning technology to prepare the blood protein fiber:
Spinning solution after filtration, spray silk, enter coagulating bath, after solidifying, obtain nascent blood protein fiber;
The blood protein fiber of will coming into being stretches in air, and damp and hot stretching in hot salt bath is carried out xeothermic stretching again and obtained the protein tow, and total draw ratio can reach 3～8 times of raw footage;
Handle through acetalation, wash, oil, dry, curl, become the blood protein fiber.
The protein tow that obtains after the xeothermic stretching in step (5) can be again through crosslinkedization processing: the protein tow that will obtain with the solution-treated of urea and beta-mercaptoethanol preparation with hot water wash after, be soaked in the glutaraldehyde water solution that concentration is 2.5～15g/L, transfer pH to 5-6 with acetic acid, 60～70 ℃ of reactions, be interrupted in the course of reaction and stir and measure once every 15～20min, when crosslinkedization degree reaches the index that can finish for reaction more than 25%, wash after the reaction end.If need not use hot water wash, directly be soaked in the glutaraldehyde water solution to handle and get final product with the protein tow that water treatment obtains.The calculating of crosslinkedization degree:
The assay method colorimetric method.
Advantage compared with prior art of the present invention and effect:
The present invention is that raw material is made the blood protein fiber with the animal blood, raw material sources are abundant, do not fight for grain ration with the people, and can make nitrogenous fertilizer behind its fabric waste fermentation, in animal husbandry development, also support this new material the reach of science of blood protein fiber, thereby made up the economic model of the sustainable cycle development of low-carbon (LC).Through crosslinkedization processing, make azelon intensity increase on the protein tow, reduce the fabric pining degree.Better through test blood protein fiber suppleness, comfortableness, as real silk.
Description of drawings
Fig. 1 makes the process chart of blood protein fiber with solubilising proteins such as ureas
Fig. 2 water solubilising protein is made the process chart of blood protein fiber
The specific embodiment
Embodiment 1.
Collect fresh anti-freezing pig blood 2000mL, in 10～15 ℃ cold house, slowly add in the blood and stirred 30 minutes with 4000mL 2% hydrochloric acid acetone soln, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein 220g (the retortable recovery of acetone, the precipitation residue is thick ferroheme, makes with extra care the back conduct and mends purposes such as chalybeate).Get 150g pale precipitation protein, the solution with 0.5 part of 9.5 parts of the 5mol ureas that prepared and 0.1mol beta-mercaptoethanol makes its dissolving at 60～70 ℃, and regulating pH to 9 with 1molNaOH, to make final concentration be 15%, is interrupted and stirs, 45 ℃ of insulation 6h; Weighing polyvinyl alcohol adds water again, and to make final concentration be 15% to stirring and dissolving in boiling water bath, insulation and be interrupted and stir 6h in boiling water bath; Above-mentioned molten pale precipitation protein and polyvinyl alcohol are mixed by 1 to 1, and promptly 100mL protein solution and 100mL poly-vinyl alcohol solution mix, and the unidirectional stirring of continuous low speed 1h makes its abundant mixing under 95～100 ℃.At this moment, many minute bubbles in solution, occur, leave standstill insulation 12h at 90～95 ℃ then and carry out the deaeration processing, eliminate, obtain spinning solution to bubble.
Spinning solution enters coagulating bath by spinneret orifice with the speed of 15cm/s after filtration, and coagulating bath is the aqueous sodium persulfate solution of 410g/L, and 43～45 ℃ of temperature obtain nascent blood protein fiber after solidifying.
The blood protein fiber of will coming into being stretches damp and hot then stretching, 90～100 ℃ of temperature for the first time in air, medium is a saturated aqueous sodium sulfate under this temperature, carries out xeothermic stretching again, 210～230 ℃ of temperature, total stretching can reach 5 times of raw footage, reusable heat water clean the protein tow.
Crosslinkedization processing: the protein tow after the hot water wash is soaked in glutaraldehyde 10g/L, transfers pH to 5,, be interrupted in the course of reaction and stir and measure once,, react and finish, wash when crosslinkedization degree reaches 30% every 15min 65 ℃ of reactions with acetic acid.Acetalation is handled again, and the protein tow is soaked in content of formaldehyde 30～35g/L, and sulfuric acid content 260g/L in the sodium sulphate content 240g/L solution, is interrupted in the course of reaction and stirs 70 ℃ of temperature, time 50min.Wash then, oil, dry, curl, become the blood protein fiber.
Embodiment 2.
Collect fresh anti-freezing pig blood 2000mL, in 10～15 ℃ cold house, slowly add in the blood and stirred 30 minutes with 4000mL 2% hydrochloric acid acetone soln, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein 220g (the retortable recovery of acetone, the precipitation residue is thick ferroheme, makes with extra care the back conduct and mends purposes such as chalybeate).Get 150g pale precipitation protein, the solution with 0.5 part of 9.5 parts of the 3mol ureas that prepared and 0.04mol beta-mercaptoethanol makes its dissolving at 60～70 ℃, and regulating pH to 9 with 1molNa0H, to make final concentration be 15%, is interrupted and stirs, 45 ℃ of insulation 6h; Weighing polyvinyl alcohol adds water again, and to make final concentration be 15% to stirring and dissolving in boiling water bath, insulation and be interrupted and stir 6h in boiling water bath; Above-mentioned molten pale precipitation protein and polyvinyl alcohol are mixed by 1 to 4, and promptly 40mL protein solution and 160mL poly-vinyl alcohol solution mix, and the unidirectional stirring of continuous low speed 1h makes its abundant mixing under 95～100 ℃.At this moment, many minute bubbles in solution, occur, leave standstill insulation 12h at 90～95 ℃ then and carry out the deaeration processing, eliminate, obtain spinning solution to bubble.
Stoste enters coagulating bath by spinneret orifice with the speed of 15cm/s after filtration, freezes solidly on contains sodium sulfate 410g/L, and 43～45 ℃ of temperature obtain nascent blood protein fiber after solidifying.
The blood protein fiber of will coming into being stretches damp and hot then stretching, 90～100 ℃ of temperature for the first time in air, medium is a saturated aqueous sodium sulfate under this temperature, carries out xeothermic stretching again, 210～230 ℃ of temperature, total draw ratio can reach 8 times of raw footage, reusable heat water clean the protein tow.
Crosslinkedization processing: the protein tow after the hot water wash is soaked in glutaraldehyde 3g/L, transfers pH to 5,, be interrupted in the course of reaction and stir and measure once,, react and finish, wash when crosslinkedization degree reaches 30% every 15min 65 ℃ of reactions with acetic acid.Acetalation is handled again, and the protein tow is soaked in content of formaldehyde 30～35g/L, and sulfuric acid content 260g/L in the sodium sulphate content 240g/L solution, is interrupted in the course of reaction and stirs 70 ℃ of temperature, time 50min.Wash then, oil, dry, curl, become the blood protein fiber.
Embodiment 3.
Collect fresh anti-freezing pig blood 2000mL, in 10～15 ℃ cold house, slowly add in the blood and stirred 30 minutes with 4000mL 2% hydrochloric acid acetone soln, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein 220g.Get 150g pale precipitation protein, water makes it 40～100 ℃ of dissolvings, regulates pH to 9 with 1molNaOH again, and making final concentration is 15%, is interrupted and stirs, 45 ℃ of insulation 6h; Weighing polyvinyl alcohol adds water again, agitating solution in boiling water bath, and making final concentration is 15%, insulation and interruption stir 6h in boiling water bath; Above-mentioned molten blood protein and polyvinyl alcohol are mixed by 1 to 2.3 relation, and promptly 60mL protein solution and 140mL poly-vinyl alcohol solution mix, and the unidirectional stirring of continuous low speed 1h under 95～100 ℃ makes its abundant mixing.At this moment, many minute bubbles in solution, occur, leave standstill insulation 12h at 90～95 ℃ then and carry out the deaeration processing, eliminate, obtain spinning solution to bubble.
Stoste enters coagulating bath by spinneret orifice with the speed of 15cm/s after filtration, freezes solidly on contains sodium sulfate 410g/L, and 43～45 ℃ of temperature obtain nascent blood protein fiber after solidifying.
This tow is stretched in air for the first time, damp and hot then stretching, 90～100 ℃ of temperature, medium is a saturated aqueous sodium sulfate under this temperature, carries out xeothermic stretching again, 210～230 ℃ of temperature, total draw ratio can reach 7 times of raw footage, and reusable heat water cleans.
Crosslinkedization processing: the tow after the hot water wash is soaked in the glutaraldehyde 5g/L solution, transfers pH to 5,, be interrupted in the course of reaction and stir and measure once,, react and finish, wash when crosslinkedization degree reaches 30% every 15min 65 ℃ of reactions with acetic acid.Acetalation is handled again, and the protein tow is soaked in content of formaldehyde 30～35g/L, and sulfuric acid content 260g/L in the sodium sulphate content 240g/L solution, is interrupted in the course of reaction and stirs 70 ℃ of temperature, time 50min.Wash then, oil, dry, curl, become the blood protein fiber.
Embodiment 4.
Collect fresh anti-freezing pig blood 2000mL, in 10～15 ℃ cold house, slowly add in the blood and stirred 30 minutes with 4000mL 2% hydrochloric acid acetone soln, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein 220g.Get 150g pale precipitation protein, water makes it 40～100 ℃ of dissolvings, regulates pH to 9 with 1molNaOH again, and making final concentration is 15%, is interrupted and stirs, 45 ℃ of insulation 6h; Weighing polyvinyl alcohol adds water again, agitating solution in boiling water bath, and making final concentration is 15%, insulation and interruption stir 6h in boiling water bath; Above-mentioned molten blood protein and polyvinyl alcohol are mixed by 1 to 1.5 relation, and promptly 80mL protein solution and 120mL poly-vinyl alcohol solution mix, and the unidirectional stirring of continuous low speed 1h under 95～100 ℃ makes its abundant mixing.At this moment, many minute bubbles in solution, occur, leave standstill insulation 12h at 90～95 ℃ then and carry out the deaeration processing, eliminate, obtain spinning solution to bubble.
Stoste enters coagulating bath by spinneret orifice with the speed of 15cm/s after filtration, freezes solidly on contains sodium sulfate 410g/L, and 43～45 ℃ of temperature obtain nascent blood protein fiber after solidifying.
This tow is stretched in air for the first time, damp and hot then stretching, 90～100 ℃ of temperature, medium is a saturated aqueous sodium sulfate under this temperature, carries out xeothermic stretching again, 210～230 ℃ of temperature, total draw ratio can reach 6 times of raw footage, and reusable heat water cleans.
Crosslinkedization processing: tow is soaked in the glutaraldehyde 5g/L solution, transfers pH to 5,, be interrupted in the course of reaction and stir and measure once,, react and finish, wash when crosslinkedization degree reaches 30% every 15min 65 ℃ of reactions with acetic acid.Acetalation is handled again, and the protein tow is soaked in content of formaldehyde 30～35g/L, and sulfuric acid content 260g/L in the sodium sulphate content 240g/L solution, is interrupted in the course of reaction and stirs 70 ℃ of temperature, time 50min.Wash then, oil, dry, curl, become the blood protein fiber.
Embodiment 5.
Collect fresh anti-freezing pig blood 2000mL, in 10～15 ℃ cold house, slowly add in the blood and stirred 30 minutes with 4000mL 2% hydrochloric acid acetone soln, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein 220g.Get 150g pale precipitation protein, the solution with 0.5 part of 9.5 parts of the 5mol ureas that prepared and 0.1mol beta-mercaptoethanol makes its dissolving at 60～70 ℃, and regulating pH to 9 with lmolNaOH, to make final concentration be 15%, is interrupted and stirs, 45 ℃ of insulation 6h; Weighing polyvinyl alcohol adds water again, and to make final concentration be 15% to stirring and dissolving in boiling water bath, insulation and be interrupted and stir 6h in boiling water bath; Above-mentioned molten pale precipitation protein and polyvinyl alcohol are mixed by 1 to 0.7, and promptly 120mL protein solution and 80mL poly-vinyl alcohol solution mix, and the unidirectional stirring of continuous low speed 1h makes its abundant mixing under 95～100 ℃.At this moment, many minute bubbles in solution, occur, leave standstill insulation 12h at 90～95 ℃ then and carry out the deaeration processing, eliminate, obtain spinning solution to bubble.
Spinning solution enters coagulating bath by spinneret orifice with the speed of 15cm/s after filtration, and coagulating bath is the aqueous sodium persulfate solution of 410g/L, and 43～45 ℃ of temperature obtain nascent blood protein fiber after solidifying.
The blood protein fiber of will coming into being stretches damp and hot then stretching, 90～100 ℃ of temperature for the first time in air, medium is a saturated aqueous sodium sulfate under this temperature, carries out xeothermic stretching again, 210～230 ℃ of temperature, total stretching can reach 3.5 times of raw footage, reusable heat water clean the protein tow.
Crosslinkedization processing: the protein tow after the hot water wash is soaked in glutaraldehyde 12g/L, transfers pH to 5,, be interrupted in the course of reaction and stir and measure once,, react and finish, wash when crosslinkedization degree reaches 40% every 15min 65 ℃ of reactions with acetic acid.Acetalation is handled again, and the protein tow is soaked in content of formaldehyde 30～35g/L, and sulfuric acid content 260g/L in the sodium sulphate content 240g/L solution, is interrupted in the course of reaction and stirs 70 ℃ of temperature, time 50min.Wash then, oil, dry, curl, become the blood protein fiber.
Embodiment 6.
Collect fresh anti-freezing pig blood 2000mL, in 10～15 ℃ cold house, slowly add in the blood and stirred 30 minutes with 4000mL 2% hydrochloric acid acetone soln, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein 220g.Get 150g pale precipitation protein, water makes it 40～100 ℃ of dissolvings, regulates pH to 9 with 1molNaOH again, and making final concentration is 15%, is interrupted and stirs, 45 ℃ of insulation 6h; Weighing polyvinyl alcohol adds water again, agitating solution in boiling water bath, and making final concentration is 15%, insulation and interruption stir 6h in boiling water bath; Above-mentioned molten blood protein and polyvinyl alcohol are mixed by 1 to 1.5 relation, and promptly 80mL protein solution and 120mL poly-vinyl alcohol solution mix, and the unidirectional stirring of continuous low speed 1h under 95～100 ℃ makes its abundant mixing.At this moment, many minute bubbles in solution, occur, leave standstill insulation 12h at 90～95 ℃ then and carry out the deaeration processing, eliminate, obtain spinning solution to bubble.
Stoste enters coagulating bath by spinneret orifice with the speed of 15cm/s after filtration, freezes solidly on contains sodium sulfate 410g/L, and 43～45 ℃ of temperature obtain nascent blood protein fiber after solidifying.
This tow is stretched in air for the first time, damp and hot then stretching, 90～100 ℃ of temperature, medium is a saturated aqueous sodium sulfate under this temperature, carries out xeothermic stretching again, 210～230 ℃ of temperature, total draw ratio can reach 6 times of raw footage, and reusable heat water cleans.
Acetalation is handled again, and the protein tow is soaked in content of formaldehyde 30～35g/L, and sulfuric acid content 260g/L in the sodium sulphate content 240g/L solution, is interrupted in the course of reaction and stirs 70 ℃ of temperature, time 50min.Wash then, oil, dry, curl, become the blood protein fiber.
Claims (5)
1. an animal blood azelon is characterized in that, this fibre composition comprises animal blood albumen and polyvinyl alcohol, and wherein animal blood albumen accounts for 20～60% by weight percentage.
2. the preparation method of a kind of animal blood azelon as claimed in claim 1 is characterized in that, comprises the steps:
(1) in 10～15 ℃ cold house, the hydrochloric acid acetone soln that will be equivalent to blood volume 1.5-2 mass concentration 2% doubly slowly adds in the blood and stirred 30 minutes, suction filtration, precipitating proteins; Precipitating proteins is cleaned 3～4 times with 2% hydrochloric acid acetone soln continuation, obtain pale precipitation protein;
(2) pale precipitation protein is joined in the solution of 9～9.8 parts of 2～8mol ureas and 1～0.2 part of preparation of 0.02～0.5mol beta-mercaptoethanol, make its dissolving at 40～100 ℃, regulate pH to 8.5～10 with 1molNaOH, the final concentration that makes pale precipitation protein is 14～20%; Be interrupted and stir, 40～50 ℃ of insulation 4～6h obtain protein solution;
(3) weighing polyvinyl alcohol adds water, is interrupted to stir in boiling water bath to make its dissolving, and making final concentration is 14～20%;
(4) poly-vinyl alcohol solution that obtains of protein solution that step (2) is obtained and step (3) by weight 1: 0.7-4 mixes, the unidirectional stirring of continuous low speed 0.5-1.5h under 95～100 ℃, leave standstill to bubble at 80～95 ℃ and to eliminate fully, perhaps leave standstill under the heat-retaining condition to bleed bubble is eliminated fast, obtain spinning solution with vavuum pump at 80～95 ℃;
(5) adopt wet spinning technology to prepare the blood protein fiber:
Spinning solution after filtration, spray silk, enter coagulating bath, after solidifying, obtain nascent blood protein fiber;
The blood protein fiber of will coming into being stretches in air, and damp and hot stretching in hot salt bath is carried out xeothermic stretching again and obtained the protein tow;
Handle through acetalation, wash, oil, dry, curl, become the blood protein fiber.
3. the preparation method of a kind of animal blood azelon as claimed in claim 2 is characterized in that, the solution of 9～9.8 parts of described 2～8mol ureas and 1～0.2 part of preparation of 0.02～0.5mol beta-mercaptoethanol can replace by water.
4. the preparation method of a kind of animal blood azelon as claimed in claim 2, it is characterized in that, obtain the protein tow after the xeothermic stretching in the described step (5) after before the acetalation processing, earlier through crosslinkedization processing: the protein tow that will obtain with the solution-treated of urea and beta-mercaptoethanol preparation with hot water wash after, be soaked in the glutaraldehyde water solution that concentration is 2.5～15g/L, transfer pH to 5-6 with acetic acid, 60～70 ℃ of reactions, be interrupted to stir in the course of reaction and measure once, wash when above when crosslinkedization degree reaches 25% every 15～20min.
5. the preparation method of a kind of animal blood azelon as claimed in claim 3, it is characterized in that, obtain the protein tow after the xeothermic stretching in the described step (5) after before the acetalation processing, earlier through crosslinkedization processing: the protein tow is soaked in the glutaraldehyde water solution that concentration is 2.5～15g/L, transfer pH to 5-6 with acetic acid, 60～70 ℃ of reactions, be interrupted to stir in the course of reaction and measure once every 15～20min, when reaching 25%, washes when above crosslinkedization degree.
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| CN 201110034015 CN102154731A (en) | 2011-01-26 | 2011-01-26 | Animal blood protein fiber and preparation method thereof |
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| CN 201110034015 CN102154731A (en) | 2011-01-26 | 2011-01-26 | Animal blood protein fiber and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286325A (en) * | 1999-09-01 | 2001-03-07 | 李官奇 | Synthetic plant protein filaments |
| CN1309199A (en) * | 2001-03-02 | 2001-08-22 | 陈富库 | Milk protein and polyvinyl alcohol copolymerized fibre and its preparing process |
| WO2006002572A1 (en) * | 2004-06-30 | 2006-01-12 | Guanqi Li | Synthetic fiber containing animal hair protein and its preparation |
| CN1814871A (en) * | 2005-02-05 | 2006-08-09 | 李官奇 | Fiber spinning dope containing protein and its preparing method |
-
2011
- 2011-01-26 CN CN 201110034015 patent/CN102154731A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1286325A (en) * | 1999-09-01 | 2001-03-07 | 李官奇 | Synthetic plant protein filaments |
| CN1309199A (en) * | 2001-03-02 | 2001-08-22 | 陈富库 | Milk protein and polyvinyl alcohol copolymerized fibre and its preparing process |
| WO2006002572A1 (en) * | 2004-06-30 | 2006-01-12 | Guanqi Li | Synthetic fiber containing animal hair protein and its preparation |
| CN1814871A (en) * | 2005-02-05 | 2006-08-09 | 李官奇 | Fiber spinning dope containing protein and its preparing method |
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Application publication date: 20110817 |