CN1468986A - Animal protein and acrylonitrile grafting copolymerizing fiber and its production process - Google Patents
Animal protein and acrylonitrile grafting copolymerizing fiber and its production process Download PDFInfo
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- CN1468986A CN1468986A CNA031484220A CN03148422A CN1468986A CN 1468986 A CN1468986 A CN 1468986A CN A031484220 A CNA031484220 A CN A031484220A CN 03148422 A CN03148422 A CN 03148422A CN 1468986 A CN1468986 A CN 1468986A
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Abstract
The animal protein and acrylonitrile grafting and copolymerizing fiber contains animal hair protein 10-90 weight portions and acrylonitrile 55-90 weight portions. The production process includes washing animal hair, oxidation or reduction of animal hair, drying, dissolving animal hair with water solution of zinc chloride, filtering, grafting and copolymerizing through adding acrylonitrile and initiator, curing, defoaming, spinning, solidifying, desalting, drafting, water washing, drying, crimping, cutting and packing and other steps. The said production process is simple, has no protein extracting and re-dissolving steps and the fiber has outstanding hydroscopcity and excellent hand feeling.
Description
1. technical field
The invention belongs to the weaving technical field of novel materials of high-grade clothing (inside and outside clothing) usefulness, be specifically related to a kind of animal (wool, pig hair) protein and acrylonitrile graft copolymer fibre and manufacture method thereof.
2. background technology
Animal protein fibre belongs to the casein fibrid from the classification of fiber family, and countries in the world are studied it always as problem, and China once carried out preliminary exploration to azlon respectively in the 1950's, the seventies, but did not succeed.The nineties, Sichuan Province once developed the silkworm chrysalis regenerated protein, though fiber has been realized small lot batch manufacture, low percentages of protein, and weave and print and dye processing in have a lot of problems, had a strong impact on such Products Development and technology popularization.Donghua University, Kingsoft, Shanghai Petro-Chemical Corporation once carried out research to the spinning of casein/acrylonitrile graft copolymer, but also stay in theoretic discussion, do not see its product: Fudan University and Donghua University once carried out research to the spinning of regenerated silk solution, also failed to realize suitability for industrialized production.Abroad promptly azlon is studied since 19th century, 20 beginnings of the century.Italian scientist in 1936, Britain ICI company, nineteen thirty-nine con product refinind company in 1938 once inquired into respectively from cow's milk, peanut protein, corn, soybean meal and extracted protein, carried out spinning again.Early 1940s, American and Britain have developed cruel series fiber, American and Britain in 1945 have studied soybean protein fibre again; General Motors Overseas Corporation extracted and had made soybean protein fibre from dregs of beans in 1938, but mostly because the fibre property keyway is relatively poor, can't weaves and process and interruption research.Japanese Japan in 1969 spins company and has successfully developed the milk protein fiber, is subjected to the welcome of textile industry with its good quality.But, in the document of having delivered at present, when relating to animal wool (wool, pig hair) protein and acrylonitrile and propylene derived graft copolymers and fibre manufacturing technique technology, the extraction that all relates to animal protein reaches course of dissolution again, technological process is long and complicated, and production equipment is huge.
3. summary of the invention
The present invention will provide a kind of animal (wool, pig hair) protein and acrylonitrile graft copolymer fibre, for a kind of novel high-tech textile material that is applicable to senior underwear, coat, decorative fabric etc. is provided in the textile garment field.And give this fiber outstanding (clothes with) performance and function, for China and even the world provide a kind of novel, high-grade textile material.And the animal protein that solves extracts and reaches dissolution process long flow path, complexity again, the technical problem that production equipment is huge.
The present invention is achieved through the following technical solutions, a kind of animal wool protein and acrylonitrile graft copolymer fibre, and its component and content are as follows: (weight ratio)
10～90 parts in animal wool protein
55～90 parts of described animal wool protein of acrylonitrile are wool protein, pig hair protein.Acrylonitrile can be an acryloyl derivative.The manufacture method of a kind of animal wool protein and acrylonitrile graft copolymer fibre, it can be prepared by the step of following order:
A, put into that the solution that contains oxidant or reductant carries out oxidation or reduction is handled after animal wool cleaned, dries, wash centrifuge dripping again, the animal wool oxidant is a Peracetic acid, and reductant is a sodium hydrosulfite; The oxidant consumption is that solution weight 0.5～8% reductant consumption is that levelling pH value 0～7 above-mentioned bath raio is 5～12: 100 after 30～70 ℃ of washings of solution weight 0.5～8% oxidization time 20～40 ℃ of reduction temperatures of 6～48 hour 1～28 hour recovery time oxidizing temperature
B, directly be dissolved in the solder(ing)acid, add zinc powder again, reduce the destruction of high-temperature solvent to protein, the concentration of solder(ing)acid is 30～75%; Dissolution time 2～70 hours, solution temperature are 40～130 ℃;
Clear liquid is taken out in c, filtration back, add acrylonitrile and redox system initator, carry out graft copolymerization, polymeric reaction temperature is 5～70 ℃, reaction time is 0.5～2 hour, oxidant: reductant=1: 1～15, and consumption is calculated as 0.3～5% of acrylonitrile amount with oxidant, described oxidant is ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, and described reductant is sodium sulfite, sodium hydrogensulfite, potassium sulfite;
After d, the polymerization again through maturation, deaeration, spinning, solidify, desalination, drawing-off, washing, drying, curl, cut off, packing; Wherein the maturation time is 6～72 hours, and the deaeration time is 2～48 hours, and maturation and deaeration temperature are 30～70 ℃, coagulating bath concentration is 5～50% solder(ing)acid, and coagulation bath temperature is 0～40 ℃, and pH value≤3 are bathed in desalination, the desalination bath temperature is 10～70 ℃, adopt hot bath and steam drafting, temperature is 80～120 ℃, and the total draft multiple is 312 times, fiber number 0.8～6d tex of gained fiber, powerful 2.5～3.5CN/d tex, elongation 15～30%, fiber official regain 3～8%.
The present invention compared with prior art has following beneficial effect: production technology of the present invention is simple, and is workable.On manufacture method, save extraction protein and protein course of dissolution again, adopted special polymerization formula, improved the percent grafting of protein, increased the hygroscopicity and the dyeability of fiber.The raw materials used wide material sources of the present invention; can make discarded animal wool obtain development and use; widened the open of animal wool protein and utilized, the fiber of producing has the same feel of felt, the gloss that real silk is the same, noble quality; but protein fibre moisture absorption, smooth, ventilative; make beautiful in colourly, polyacrylonitrile fibre can strengthen intensity, and this product can be used as the substitute of felt; reduce too much goat quantity, help ecological protection.
4. the specific embodiment:
Embodiment 1
The 10Kg wool is dipped in 2.0% the dithionous acid sodium water solution, molten ratio 1: 10, temperature is at 50 ℃ of reductase 12s hour, washing back centrifuge dripping, be dissolved in 60% the solder(ing)acid, hair content is 30%, and dissolving is 10 hours in the time of 100 ℃, filters and takes out clear liquid, add the 25Kg acrylonitrile, mix to stir and add ammonium persulfate 200g, sodium hydrogensulfite 300g, polymerization 1 hour, polymer molecular weight 8～90,000, make fiber number 0.8～6d tex of fiber after the maturation deaeration through wet spinning, powerful 2.5～3.5CN/d tex, elongation 15～30%, fiber official regain 3～8%.
Example executes 2
10Kg pig hair is dipped in 2.5% the dithionous acid sodium water solution, molten ratio 1: 9,55 ℃ of reductase 12s hour, washing back centrifuge dripping, be dissolved in 60% the solder(ing)acid, hair content is 30%, and dissolving is 10 hours in the time of 100 ℃, filters and takes out clear liquid, add the 25Kg acrylonitrile, mix to stir and add ammonium persulfate 200g, sodium hydrogensulfite 300g, polymerization 1 hour, polymer molecular weight 7～80,000, make fiber number 0.8～6d tex of fiber after the maturation deaeration through wet spinning, powerful 2.5～3.5CN/d tex, elongation 15～30%, fiber official regain 3～8%.
Claims (4)
1, a kind of animal protein and acrylonitrile graft copolymer fibre is characterized in that: its component and content are as follows: (weight ratio)
10～90 parts in animal wool protein
55～90 parts of acrylonitrile.
2, animal protein according to claim 1 and acrylonitrile graft copolymer fibre is characterized in that: described animal wool protein is wool protein, pig hair protein.
3, animal protein according to claim 1 and acrylonitrile graft copolymer fibre is characterized in that: acrylonitrile can be an acryloyl derivative.
4, the manufacture method of a kind of animal protein and acrylonitrile graft copolymer fibre is characterized in that: it can be prepared by the step of following order:
A, put into that the solution that contains oxidant or reductant carries out oxidation or reduction is handled after animal wool cleaned, dries, wash centrifuge dripping again, the animal wool oxidant is a Peracetic acid, and reductant is a sodium hydrosulfite; The oxidant consumption is that solution weight 0.5～8% reductant consumption is that accent pH value 0～7 above-mentioned bath raio is 5～12: 100 after 30～70 ℃ of washings of 20～40 ℃ of former temperature of solution weight 0.5～8% oxidization time 6～48 hour 1～28 hour recovery time oxidizing temperature
B, directly be dissolved in the solder(ing)acid, add zinc powder again, reduce the destruction of high-temperature solvent to protein, the concentration of solder(ing)acid is 30～75%; Dissolution time 2～70 hours, solution temperature are 40～130 ℃;
Clear liquid is taken out in c, filtration back, add acrylonitrile and redox system initator, carry out graft copolymerization, polymeric reaction temperature is 5～70 ℃, reaction time is 0.5～2 hour, oxidant: reductant=1: 1～15, and consumption is calculated as 0.3～5% of acrylonitrile amount with oxidant, described oxidant is ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, and described reductant is sodium sulfite, sodium hydrogensulfite, potassium sulfite;
After d, the polymerization again through maturation, deaeration, spinning, solidify, desalination, drawing-off, washing, drying, curl, cut off, packing; Wherein the maturation time is 6～72 hours, and the deaeration time is 2～48 hours, and maturation and deaeration temperature are 30～70 ℃, coagulating bath concentration is 5～50% solder(ing)acid, and coagulation bath temperature is 0～40 ℃, and pH value≤3 are bathed in desalination, the desalination bath temperature is 10～70 ℃, adopt hot bath and steam drafting, temperature is 80～120 ℃, and the total draft multiple is 3～12 times, fiber number 0.8～6d tex of gained fiber, powerful 2.5～3.5CN/d tex, elongation 15～30%, fiber official regain 3～8%.
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| CN 03148422 CN1257318C (en) | 2003-07-01 | 2003-07-01 | Animal protein and acrylonitrile grafting copolymerizing fiber and its production process |
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| CN 03148422 CN1257318C (en) | 2003-07-01 | 2003-07-01 | Animal protein and acrylonitrile grafting copolymerizing fiber and its production process |
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| CN1468986A true CN1468986A (en) | 2004-01-21 |
| CN1257318C CN1257318C (en) | 2006-05-24 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008071062A1 (en) * | 2006-12-12 | 2008-06-19 | Hiking Group Co., Ltd | A modified polyacrylonitrile fiber and its preparation process and use |
| CN1837424B (en) * | 2005-03-22 | 2010-10-27 | 李官奇 | Method for manufacturing functional fiber with protein and acrylonitrile |
| CN103789857A (en) * | 2014-01-13 | 2014-05-14 | 江苏金太阳纺织科技有限公司 | Preparation method of collagen regenerated cellulose fiber |
| CN105350319A (en) * | 2015-10-26 | 2016-02-24 | 北京石油化工学院 | Method for grafting and modifying cashmere |
| CN108893096A (en) * | 2018-06-12 | 2018-11-27 | 陕西纤润调温材料研究开发有限公司 | A kind of hairless protein microcapsules of storing energy through phase change slurry and the preparation method and application thereof |
| CN109371690A (en) * | 2018-10-26 | 2019-02-22 | 含山县领创新材料科技有限公司 | A kind of Wool composite fabric and preparation method thereof that drapability is good |
| CN113481644A (en) * | 2021-06-03 | 2021-10-08 | 王剑 | Moisture-absorbing and heat-insulating gold-stamping fabric and preparation method thereof |
-
2003
- 2003-07-01 CN CN 03148422 patent/CN1257318C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1837424B (en) * | 2005-03-22 | 2010-10-27 | 李官奇 | Method for manufacturing functional fiber with protein and acrylonitrile |
| WO2008071062A1 (en) * | 2006-12-12 | 2008-06-19 | Hiking Group Co., Ltd | A modified polyacrylonitrile fiber and its preparation process and use |
| JP2010512468A (en) * | 2006-12-12 | 2010-04-22 | ヒキン グループ カンパニー リミテッド | Modified polyacrylonitrile fiber, production method and use thereof |
| CN103789857A (en) * | 2014-01-13 | 2014-05-14 | 江苏金太阳纺织科技有限公司 | Preparation method of collagen regenerated cellulose fiber |
| CN103789857B (en) * | 2014-01-13 | 2016-03-23 | 江苏金太阳纺织科技有限公司 | A kind of preparation method of collagen regenerated celulose fibre |
| CN105350319A (en) * | 2015-10-26 | 2016-02-24 | 北京石油化工学院 | Method for grafting and modifying cashmere |
| CN108893096A (en) * | 2018-06-12 | 2018-11-27 | 陕西纤润调温材料研究开发有限公司 | A kind of hairless protein microcapsules of storing energy through phase change slurry and the preparation method and application thereof |
| CN109371690A (en) * | 2018-10-26 | 2019-02-22 | 含山县领创新材料科技有限公司 | A kind of Wool composite fabric and preparation method thereof that drapability is good |
| CN113481644A (en) * | 2021-06-03 | 2021-10-08 | 王剑 | Moisture-absorbing and heat-insulating gold-stamping fabric and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1257318C (en) | 2006-05-24 |
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Assignee: HOSA Industrial (Fujian) Co., Ltd. Assignor: Zhang Jianhua Contract record no.: 2010350000164 Denomination of invention: Animal protein and acrylonitrile grafting copolymerizing fiber and its production process Granted publication date: 20060524 License type: Exclusive License Open date: 20040121 Record date: 20100713 |
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