CN1370859A - Composite protein polyacrylonitrile fiber and its production process - Google Patents
Composite protein polyacrylonitrile fiber and its production process Download PDFInfo
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- CN1370859A CN1370859A CN 02109229 CN02109229A CN1370859A CN 1370859 A CN1370859 A CN 1370859A CN 02109229 CN02109229 CN 02109229 CN 02109229 A CN02109229 A CN 02109229A CN 1370859 A CN1370859 A CN 1370859A
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Abstract
The present invention belongs to one kind of composite protein-polyacrylonitrile fiber and its production process. The said composite fiber has protein distributed homogeneously in polyacrylonitrile and has a protein content of 10-40 % and a polyacrylonitrile content of 60-90 %. It is produced through solution mixing and wet spinning process including the steps of extracting protein from soybean or hair, mixing and dissolution and wet spinning. The protein has wide material source, and the wet spinning process may be completed through conventional Nitrilon producing path.
Description
The present invention relates to a kind of is the method that raw material is made composite protein polyacrylonitrile fiber with soybean protein, keratin and acrylonitrile, polyacrylonitrile
Utilizing native protein to make azlon, is that the problem that solves is sought in the chemical fibre field always.But present successful examples seldom, and be mostly the composite fibre of protein and synthesized polymer material.For example successful examples is the milk protein silk that being called of company's exploitation " ッ ノ Application " (glad you) fiber spins in Japanese Japan, is the composite fibre by the acrylonitrile compolymer of the milk casein of about 40wt% and 60wt%.In China's publication, as the manufacture method with pupa albumen, milk protein, fibroin and synthetic high polymer raw material propylene nitrile, polyacrylonitrile blended, copolymerized fiber is provided respectively in the application number 95111366.6,96116532.4,94114071.7.
The objective of the invention is to seek a kind of preparation method who utilizes abundant, cheap protein raw material in source and polyacrylonitrile to make composite fibre.
The protein that uses among the present invention is to extract with soybean meal that is mainly used in production of fodder or the low animal hair of value, and its raw material sources are extensive, cheap, compare and can reduce production costs more than 10% with milk protein, fibroin.
Composite protein polyacrylonitrile fiber of the present invention extracts protein, protein and method polyacrylonitrile blended, wet spinning with soybean meal or hair and makes.The protein component of low ratio is evenly distributed at high proportion in the component polyacrylonitrile in this fiber, and wherein the content of protein component is 10-40% (wt%), and the content of polyacrylonitrile is 60-90% (wt%).
Soy proteinaceous extraction: utilize the known method of soybean protein isolate industry, from soybean meal, extract with the acid-base precipitation method.
The extraction of hair protein matter: with animal hair, poultry feather is raw material.At first the raw material hair is carried out hand picking, remove sandstone, metal and bigger smoits in the hair; Cut into the 3-5 millimeter; Use washing agent (soda ash, Mao Nengjing) solution again under 40-60 ℃ of condition, press hair and mixed agitator treating 30-60 minute with solution weight than 1: 15 to 1: 20; Filter out hair, the washing back dries the hair that must purify.Can use the known removal of impurities of wool industry, charring process to handle in the industrial production.Hair after the purification can utilize the known redox bleaching principle of wool industry to bleach processing.Hair after the bleaching adds in the NaOH solution of 4-8% (wt%); bath raio is 1: 15-20; solution temperature is 20-80 ℃; stirring and dissolving was dissolved fully to hair more than 1 hour, filtered, and the filtrate temperature adds watery hydrochloric acid after reducing to room temperature; adjust solution PH=4.5-5.0 (keratic isoelectric point); the keratin precipitation was separated out in static 12-24 hour under the room temperature, discarded supernatant liquor, centrifugation makes keratin protein.
Press protein 10-40 part, the ratio (weight ratio) of polyacrylonitrile 60-90 part adds in the NaSCN aqueous solution of 60-80% (wt%), stir, be heated to 40-80 ℃, dissolved 1-3 hour, filter, deaeration 4-8 hour, make the spinning solution that contains protein and polyacrylonitrile 10-30% (wt%).
Perhaps press protein 10-40 part, the ratio (weight ratio) of polyacrylonitrile 60-90 part, the ZnCl of adding 60-80% (wt%)
2In the aqueous solution, stir, be heated to 40-80 ℃, dissolved 1-3 hour, filter, deaeration 4-8 hour, make the spinning solution that contains protein and polyacrylonitrile 10-30% (wt%).
The spinning solution that said method obtains can carry out wet spinning by the acrylic spinning method.
Protein polyacrylonitrile blend composite fiber of the present invention, its raw soybeans dregs of rice, hair originate extensively, are worth low, and the wet spinning production technology does not need to change the acrylic fiber production process process route of Acrylic Fibers Plant routine, technology is simple, processing cost is low, is easy to suitability for industrialized production, remarkable in economical benefits.
The composite protein polyacrylonitrile fiber that the present invention makes, its physics, mechanical performance meet the requirement that routine is taken fiber, and moisture pick-up properties is compared with acrylic fibers greatly and is improved, rate of moisture absorption is accelerated, permeability improves, and the antistatic property of fiber strengthens, and dyeability is also improved greatly.
Following embodiment will further set forth the present invention, and ratio or percentage used among the embodiment all refer to the total amount ratio.
Embodiment one:
Soybean meal and 50 ℃ of demineralized waters add 15%NaOH solution and transfer PH=11-12 by 1: 10 mixed, stirring, and stirring and leaching 30-60 minute, soluble protein etc. is dissolved out, isolate protein solution with centrifuge.In protein solution, slowly add watery hydrochloric acid, stir simultaneously, transfer PH=4.5-4.7, the soybean protein precipitation is separated out, through centrifugation, wash the soy protein isolate of purity more than 90%.
Take by weighing above-mentioned soybean protein 1kg (dry weight), polyacrylonitrile 4kg, add in 28.3 kilogram 70% the NaSCN aqueous solution, stir, be heated to 70 ℃, dissolved 2 hours, and filtered deaeration, make the spinning solution that contains protein and polyacrylonitrile 15 ± 0.5%, make the soybean protein polyacrylonitrile composite fiber with wet spinning.
Embodiment two:
Sandstone, metal and bigger smoits are removed in the hair hand picking; Cut into the 3-5 millimeter; Use Mao Nengjing solution again under 40 ℃ of conditions, press hair and mixed than 1: 15, agitator treating 60 minutes with solution weight; Filter out hair, the washing back dries the hair that must purify.
Hair H after the purification
2O
2And Na
2S
2O
4, bleach processing by the redox method for bleaching that wool industry is known.
Hair after the bleaching adds in 5% the NaOH solution; bath raio is 1: 15; be heated to 70 ℃; stirring and dissolving 1 hour to hair dissolves fully, filters, and the filtrate temperature adds watery hydrochloric acid after reducing to room temperature; adjust solution PH=4.5-5.0; the keratin precipitation was separated out in static 12 hours under the room temperature, discarded supernatant liquor, centrifugation makes keratin protein.
Take by weighing keratin protein 1.5kg (dry weight), polyacrylonitrile 3.5kg adds 28.3 kilogram 75% ZnCl
2In the aqueous solution, stir, be heated to 80 ℃, dissolved 2 hours, filter, the spinning solution that contains protein and polyacrylonitrile 15 ± 0.5% is made in deaeration 8 hours, makes the keratin protein polyacrylonitrile composite fiber with wet spinning.
Claims (6)
1, a kind of composite protein polyacrylonitrile fiber, it is characterized in that it is formed by protein and the blend of polyacrylonitrile raw material, protein is evenly distributed in the polyacrylonitrile in the fiber, and content of protein components is 10-40% (wt%), and the polyacrylonitrile constituent content is 60-90% (wt%).
2, according to claim 1, it is characterized in that protein is is the soybean protein isolate that raw material extracts with the soybean meal.
3, according to claim 1, it is characterized in that protein is is the keratin of raw material extraction with animal hair or poultry feather.
4, a kind of manufacture method of composite protein polyacrylonitrile fiber is characterized in that: with soybean meal or hair is that raw material extracts protein; Protein and polyacrylonitrile blended dissolving; Wet spinning is made fiber.
5, according to claim 4, it is characterized in that using NaSCN aqueous solution solubilising protein and the polyacrylonitrile of 60-80% (wt%).
6, according to claim 4, it is characterized in that the solvent of solubilising protein and polyacrylonitrile, can use the ZnCl of 60-80% (wt%)
2The aqueous solution replaces.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109229 CN1370859A (en) | 2002-02-28 | 2002-02-28 | Composite protein polyacrylonitrile fiber and its production process |
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| CN 02109229 CN1370859A (en) | 2002-02-28 | 2002-02-28 | Composite protein polyacrylonitrile fiber and its production process |
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| CN1370859A true CN1370859A (en) | 2002-09-25 |
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| CN 02109229 Pending CN1370859A (en) | 2002-02-28 | 2002-02-28 | Composite protein polyacrylonitrile fiber and its production process |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294305C (en) * | 2005-03-04 | 2007-01-10 | 东华大学 | Acrylic fiber-crosslinking plant protein composite fiber and method for manufacturing the same |
| CN1298902C (en) * | 2005-03-14 | 2007-02-07 | 东华大学 | Plant protein/polyurethane/polyacrylonitrile blended composite fiber and preparing process |
| WO2008071062A1 (en) * | 2006-12-12 | 2008-06-19 | Hiking Group Co., Ltd | A modified polyacrylonitrile fiber and its preparation process and use |
| CN102357347A (en) * | 2011-10-27 | 2012-02-22 | 天津工业大学 | Preparation method of modified polyacrylonitrile film |
| CN102732981A (en) * | 2012-06-21 | 2012-10-17 | 精源(南通)化纤制品有限公司 | Polyacrylonitrile artificial hair and preparation method thereof |
| CN103397400A (en) * | 2013-08-15 | 2013-11-20 | 苏州龙杰特种纤维股份有限公司 | Preparation method of polyacrylonitrile fibres by using protein as modifier |
| CN108221179A (en) * | 2017-12-29 | 2018-06-29 | 孙祎 | A kind of preparation method of moisture absorption heating Anti-bacteria yarn |
| CN109576816A (en) * | 2018-12-24 | 2019-04-05 | 郑宇� | A kind for the treatment of process recycling milk protein fiber |
| CN110453306A (en) * | 2019-05-28 | 2019-11-15 | 河南瑞贝卡发制品股份有限公司 | Apery hair functional protein fiber and its wet spinning process |
| CN114318867A (en) * | 2020-10-10 | 2022-04-12 | 上海水星家用纺织品股份有限公司 | Preparation method of modified grafted moisture-absorbing and heating silk |
| CN114351454A (en) * | 2022-01-25 | 2022-04-15 | 天津工业大学 | Wool-like flame-retardant polyacrylonitrile composite fiber and preparation method thereof |
-
2002
- 2002-02-28 CN CN 02109229 patent/CN1370859A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294305C (en) * | 2005-03-04 | 2007-01-10 | 东华大学 | Acrylic fiber-crosslinking plant protein composite fiber and method for manufacturing the same |
| CN1298902C (en) * | 2005-03-14 | 2007-02-07 | 东华大学 | Plant protein/polyurethane/polyacrylonitrile blended composite fiber and preparing process |
| WO2008071062A1 (en) * | 2006-12-12 | 2008-06-19 | Hiking Group Co., Ltd | A modified polyacrylonitrile fiber and its preparation process and use |
| CN102357347A (en) * | 2011-10-27 | 2012-02-22 | 天津工业大学 | Preparation method of modified polyacrylonitrile film |
| CN102357347B (en) * | 2011-10-27 | 2013-10-09 | 天津工业大学 | Preparation method of modified polyacrylonitrile film |
| CN102732981A (en) * | 2012-06-21 | 2012-10-17 | 精源(南通)化纤制品有限公司 | Polyacrylonitrile artificial hair and preparation method thereof |
| CN103397400A (en) * | 2013-08-15 | 2013-11-20 | 苏州龙杰特种纤维股份有限公司 | Preparation method of polyacrylonitrile fibres by using protein as modifier |
| CN108221179A (en) * | 2017-12-29 | 2018-06-29 | 孙祎 | A kind of preparation method of moisture absorption heating Anti-bacteria yarn |
| CN109576816A (en) * | 2018-12-24 | 2019-04-05 | 郑宇� | A kind for the treatment of process recycling milk protein fiber |
| CN110453306A (en) * | 2019-05-28 | 2019-11-15 | 河南瑞贝卡发制品股份有限公司 | Apery hair functional protein fiber and its wet spinning process |
| WO2020238543A1 (en) * | 2019-05-28 | 2020-12-03 | 河南瑞贝卡发制品股份有限公司 | Functional protein fiber imitating human hair and wet spinning method therefor |
| CN114318867A (en) * | 2020-10-10 | 2022-04-12 | 上海水星家用纺织品股份有限公司 | Preparation method of modified grafted moisture-absorbing and heating silk |
| CN114351454A (en) * | 2022-01-25 | 2022-04-15 | 天津工业大学 | Wool-like flame-retardant polyacrylonitrile composite fiber and preparation method thereof |
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