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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- protein
- acrylonitrile
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- animal
- fiber
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- 239000000835 fiber Substances 0.000 title claims abstract description 38
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 235000021120 animal protein Nutrition 0.000 title claims abstract description 10
- 235000018102 proteins Nutrition 0.000 claims abstract description 26
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 26
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 26
- 241001465754 Metazoa Species 0.000 claims abstract description 19
- 210000004209 hair Anatomy 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000012856 packing Methods 0.000 claims abstract description 3
- 210000002268 wool Anatomy 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 229920000578 graft copolymer Polymers 0.000 claims description 11
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910000679 solder Inorganic materials 0.000 claims description 8
- 238000010612 desalination reaction Methods 0.000 claims description 6
- 230000035800 maturation Effects 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical group CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 230000001112 coagulating effect Effects 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 230000006378 damage Effects 0.000 claims description 2
- 230000010198 maturation time Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract 2
- 238000002788 crimping Methods 0.000 abstract 1
- 238000005520 cutting process Methods 0.000 abstract 1
- 238000011033 desalting Methods 0.000 abstract 1
- 239000003999 initiator Substances 0.000 abstract 1
- 235000005074 zinc chloride Nutrition 0.000 abstract 1
- 239000011592 zinc chloride Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 229920000793 Azlon Polymers 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 108010073771 Soybean Proteins Proteins 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019710 soybean protein Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 241000255789 Bombyx mori Species 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- 102000014171 Milk Proteins Human genes 0.000 description 1
- 108010011756 Milk Proteins Proteins 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 235000019764 Soybean Meal Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000020247 cow milk Nutrition 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000021239 milk protein Nutrition 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004455 soybean meal Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03148422 CN1257318C (en) | 2003-07-01 | 2003-07-01 | Animal protein and acrylonitrile grafting copolymerizing fiber and its production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1468986A true CN1468986A (en) | 2004-01-21 |
| CN1257318C CN1257318C (en) | 2006-05-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03148422 Expired - Fee Related CN1257318C (en) | 2003-07-01 | 2003-07-01 | Animal protein and acrylonitrile grafting copolymerizing fiber and its production process |
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| Country | Link |
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| CN (1) | CN1257318C (en) |
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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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060524 Termination date: 20120701 |