CN1370856A - Regenerated protein fiber and its production process - Google Patents
Regenerated protein fiber and its production process Download PDFInfo
- Publication number
- CN1370856A CN1370856A CN 02109230 CN02109230A CN1370856A CN 1370856 A CN1370856 A CN 1370856A CN 02109230 CN02109230 CN 02109230 CN 02109230 A CN02109230 A CN 02109230A CN 1370856 A CN1370856 A CN 1370856A
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- hair
- keratin
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- per liter
- protein
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Abstract
The regenerated protein fiber is produced with hair keratin as raw material. The production process includes purification and bleaching of hair, dissolving with 5-8 mol/L urea solution in the the presence of mercaptoacetic acid or mercaptoethanol as disulfide bond blocking agent, hollow fiber or translucent membrane dialysis to eliminate low molecular reagent and prepare spinnable solution with keratin content of 10-30 wt%, and wet spinning and drafting for 4-8 times to make protein fiber. The prorudct of the present invention is one kind of green environment protecting product easy to degrade naturally.
Description
The present invention relates to a kind of method of making azlon with hair-keratin.
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 " Star 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 providing respectively in the application number 95111366.6,96116532.4,94114071.7 with pupa albumen, milk protein, fibroin and soybean protein and synthetic high polymer raw material propylene nitrile, acrylamide, polyacrylonitrile, the blend of polyvinyl alcohol, the manufacture method of copolymerized fiber.
The common feature of above-mentioned protein fibre is: protein content is 20-40%, and high molecular synthetic material content is 60-80%.From fibre structure, high molecular synthetic material is a continuous phase, constitute the skeleton of fiber, and protein is decentralized photo, is used for improving performances such as the hygroscopicity of synthetic fiber and dyeability, belongs to the protein composite fibre.
Also useful pure natural protein reproduces the example of protein fibre in this area, with publication " fiber-spinnable solutions of silk-fibroin " (application number 93102069.7), is to utilize silk to reproduce protein fibre as raw material as China.Because silk itself is good natural protein fibre, it is residual, waste material seldom, raw material sources can be subjected to great restriction.
The invention provides a kind of is raw material with the hair-keratin, reproduces the method for protein fibre.Can utilize animal wool (as: pig hair, horsehair, ox hair, wool etc.), poultry feather and people to send out and be raw material.Raw material is worth low, and the source is wide.The fiber of making is made up of 100% protein, does not contain the synthetic high polymer composition.
The macromolecular material that is used for synthetic fiber must have the characteristics of fiber-forming polymer, and promptly molecular structure is linear macromolecule, and side-chain radical is less or less, is beneficial to macromolecule and forms orderly crystal region.And hair itself is exactly natural fibrous raw material, and its keratin molecule possesses the condition that is regenerated as protein fibre.
The method of the manufacturing regeneration keratin fiber that the present invention relates to comprises: (1), hair impurity and purification; (2), bleaching hair; (3), keratolysis is purified; (4), make regenerated protein long filament or staple fibre with wet spinning.
It is necessary at first the raw material hair being purified.With hand picking or mechanical grading, remove sandstone, metal and bigger smoits in the hair earlier; Cut into the 3-5 millimeter; Use detergent 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 handling is added in the reaction vessel, the urea liquid that added 5-8mol/L by weight 1: 10 to 1: 20, add anion surfactant, organic compounds containing sulfur again, under secluding air, 20-100 ℃ condition, constantly stir or supersonic oscillations, reacted 1 to 4 hour, disulfide bond, salt type bond in the keratin molecule are opened, and make the hair-keratin dissolving.Anion surfactant can be selected dodecyl sodium sulfate, neopelex for use, and its consumption is 1-5g/L; Organic compounds containing sulfur can be selected mercaptoethanol, mercaptan, TGA for use, and its consumption is 5-10g/L.With four layers of stainless (steel) wire of 50,200,200,50 purposes keratin solution is filtered, filtrate is that 10000 doughnut or pellicle carry out dialysis with molecular weight cut off, remove the low-molecular-weight reagent of solubility, make the water white keratin protein aqueous solution.
With keratin solution, send into reactor, at 60-80 ℃ of following decompression dehydration, the weight percent concentration of adjusting protein solution is 10-30%, filters and sends into the deaeration still, and is static and keep 60-80 ℃ of temperature, deaeration 4-10 hour, make the spinning solution of spinnability.
Filtration in the said process when small scale experiments, can be used candle filter or dish-shaped filter; Use plate and frame type filter-press during industrial production.Its filtering material uses three layers of polyvinyl single-side pile and one deck Kanakin.
Spinning solution after the deaeration can utilize known spinning process in synthetic fiber field and equipment to carry out spinning, drawing-off, dryness finalization and make keratin long filament or staple fibre.For example: these methods comprise wet spinning, dry-jet wet-spinning and dry-spinning.But the most handy is wet spinning, and it is better simply in these methods.The employed coagulating agent of wet spinning can be selected Na for use
2SO
4, NaCl, (NH
4)
2SO
4, ZnSO
4, H
2SO
4And absolute ethyl alcohol and methyl alcohol.In a kind of wet-spinning method, use by NaSO
4, ZnSO
4, H
2SO
4The aqueous solution in the coagulating bath fluid that constitutes.Wherein each component content is NaSO
4The 400-430 grams per liter; ZnSO
43-10 grams per liter, H
2SO
4(adjustment acidity) 0.2-0.5 grams per liter.Coagulation bath temperature is 40-46 ℃.As-spun fibre stretching 4-8 doubly makes azlon through bleaching, washing, drying again.When the animal wool of selecting white for use is done raw material, can bleach raw material, produce the azelon of white; When using brown or during hair such as black, can not floating look to handle, contain natural colouring matter in the fiber of generation, and directly produce the environmental type colored fibre that contains natural colouring matter of yellowish-brown or grey black.
Characteristics of the present invention are: cheap, the wide material sources of cost of material; The fiber that generates is made of 100% protein, has good moisture absorption, gas permeability and dyeability; Comfortable and easy to wear smooth, skin-friendly is good, and is non-stimulated to skin; Easily natural degradation helps environmental protection, and the method for use is simple, and production cost is low; Can produce the environmental protection fiber type that contains natural colouring matter; Select for use different synthetic fiber production equipments can produce the staple fibre and the long filament of different size, staple fibre is similar to cashmere, and long filament is similar to silk, can blending also can purely spin production underwear fabric and coat lining; When the preparation spinning solution, if grafting germ killing drugs (as 5-nitrofuran acrolein) can be produced the functional fiber with deodorization and sterilization performance.
Present invention will be further described for following example, but can not think to limit scope of invention.In these examples, deal and percentage are by weight, unless other explanation is arranged.
Example one
1, hair purifies
Raw material is selected white wool for use, and sandstone, metal and the bigger smoits in the hair are removed in hand picking; Cut into the 3-5 millimeter; , under 50-55 ℃ of condition, press hair and mix at 1: 20, agitator treating 30-60 minute (consumption of detergent and wash time are decided according to the degree of the contained greasy dirt of hair) with the soda ash solution of 5-10% with the soda ash solution weight ratio; Filter out hair, the washing back dries the hair that must purify.
2, bleaching is handled
Bleaching schedule is as follows:
H
2O
2(30％) 9g/L
Stabilizing agent MJ-H 5g/L
Ammoniacal liquor is transferred PH=10
Bath raio 1: 20
Select heating using microwave power from room temperature, be controlled at 2-3 ℃/min, be warming up to 75 ℃, keep 20min, wash then, dry.
3, preparation spinning solution
Hair after handling is added in the reactor, added the urea liquid of 6mol/L by weight 1: 10, add dodecyl sodium sulfate 5g/L, mercaptoethanol 8g/L again, under secluding air, 50-55 ℃ condition, constantly stir, reacted 4 hours, and made the hair-keratin dissolving.Filter with four layers of stainless (steel) wire of 50,200,200,50 purposes, filtrate was carried out dialysis 20 hours with pellicle, removed the low-molecular-weight reagent of solubility, made the water white keratin aqueous solution.
Keratin solution is added reactor, at 60-80 ℃ of following decompression dehydration, the weight percent concentration of adjusting protein solution is 15-16%, re-using three layers of polyvinyl single-side pile and one deck Kanakin filters and sends into the deaeration still, static and keep 80 ℃ of temperature, the spinning solution of spinnability is made in deaeration 10 hours.
4, spinning
Spinning solution after the deaeration can utilize known wet-spinning method in synthetic fiber field and equipment to carry out spinning.Employed coagulation bath composition is Na
2SO
4416g/L, ZnSO
45g/, H
2SO
40.5g/L.Coagulation bath temperature is 43-45 ℃.As-spun fibre is total to stretch 6 times, carries out at twice, and 3 times of first cold stretch add 2 times of hot-stretchs with 70-80 ℃ hot blast again.Make and reproduce protein fibre through washing, drying again.
Example two
1, hair purifies
Raw material has been selected mixture of colours hair for use, and sandstone, metal and the bigger smoits in the hair are removed in hand picking; Cut into the 3-5 millimeter; , under 50-55 ℃ of condition, press hair and mixed than 1: 20 with " scouring of wool is quiet " solution, agitator treating 30-60 minute (consumption of detergent and wash time are decided according to the degree of the contained greasy dirt of hair) with solution weight; Filter out hair, the washing back dries the hair that must purify.
2, bleaching is handled
Bleaching schedule is as follows:
A, pre-treatment
FeSO
4 5-10g/L
Tartar emetic 2g/L
NaCl 20g/L
Bath raio 1: 20
Handled 20-30 minute at 60 ℃, use cold water flush, dehydration again.
B, oxidation bleaching
H
2O
2(30％) 20-40g/L
Sodium pyrophosphate 3-5g/L
Bath raio 1: 20
Handled 20-30 minute at 60 ℃, use cold water flush, dehydration again.
C, reducing bleach
Float a mao powder 10g/L
Handled 20-30 minute at 50 ℃, again with cleaning, dewatering.
3, preparation spinning solution
Hair after handling is added in the reactor, added the urea liquid of 6mol/L by weight 1: 10, add dodecyl sodium sulfate 5g/L, TGA 10g/L again, under secluding air, 50-55 ℃ condition, constantly stir, reacted 4 hours, and made the hair-keratin dissolving.Filter with four layers of stainless (steel) wire of 50,200,200,50 purposes, filtrate was carried out dialysis 20 hours with pellicle, removed the low-molecular-weight reagent of solubility, made the water white keratin aqueous solution.
Keratin solution is added reactor, at 60-80 ℃ of following decompression dehydration, the weight percent concentration of adjusting protein solution is 15-16%, re-using three layers of polyvinyl single-side pile and one deck Kanakin filters and sends into the deaeration still, static and keep 80 ℃ of temperature, the spinning solution of spinnability is made in deaeration 10 hours.
4, spinning
Spinning solution after the deaeration can utilize known wet-spinning method in synthetic fiber field and equipment to carry out spinning.Employed coagulation bath composition is NaCl 360-400g/L, ZnCl
215g/L, HCl 0.2-0.5g/L.Coagulation bath temperature is 43-45 ℃.As-spun fibre drawn, washing, drying are made and are reproduced protein fibre.
Example three
The method for preparing spinning solution is with example one or example two, and spinning coagulation bath uses methyl alcohol, at room temperature carries out spinning, and drawn, washing, drying are made and reproduced protein fibre again.Aqueous methanol after the spinning recycles after dewatering with distillation or CaO.
Example four
The method for preparing spinning solution is with example one or example two, and the employed coagulation bath composition of wet spinning is (NH
4))
2SO
4425g/, H
2SO
40.3g/L.Bathing temperature is 40-48 ℃.As-spun fibre drawn, washing, drying are made and are reproduced protein fibre.
Example five
Utilize the method for example one or example two to prepare spinning solution, the germ killing drugs (as 5-nitrofuran acrolein) that in the spinning solution of making, add keratin dry weight 0.5-2%, make it with keratin molecule in amino or hydroxyl generation acetalation, germ killing drugs are grafted on the keratin molecule, make through deaeration, spinning, stretching, washing, drying again have sterilization, the protein fibre of deodorization functions.Because chemical reaction has taken place in germ killing drugs and protein, makes the medicine retention phase long, lasting medicine.
Claims (9)
1, azlon is characterized in that: its composition is 100% keratin protein.
2, according to claim 1, it is characterized in that: keratin protein is to send out protein into the raw material separation and Extraction with animal wool, poultry feather and people.
3, the manufacture method of azlon is characterized in that: hair is made spinnability solution through purification, bleaching, dissolving, dialysis, deaeration; With wet spinning and stretch 4-8 doubly, make azlon.
4, method according to claim 3 is characterized in that: the urea liquid that dissolve hair is used 5-8mol/L, dissolve in the presence of disulfide bond blocking agent mercaptoethanol and polymerization inhibitor dodecyl sodium sulfate.
5, according to the described method of claim 3, it is characterized in that: in the spinnability solution of making, the keratin weight percent content is 10-30%.
6, according to the described method of claim 3, it is characterized in that: the used coagulating bath of wet spinning consist of Na
2SO
4400-420 grams per liter, ZnSO
41-5 grams per liter, H
2SO
40.2-0.5 grams per liter is bathed warm 40-48 ℃.
7, according to the described method of claim 3, it is characterized in that: the disulfide bond blocking agent replaces mercaptoethanol with TGA.
8, according to the described method of claim 3, it is characterized in that: the coagulating bath of wet spinning, can use to consist of NaCl 360-400 grams per liter, ZnCl
2The fluid of 1-5g/L, HCl 0.2-0.5 grams per liter replaces.
9, according to the described method of claim 3, it is characterized in that: the coagulating bath fluid of wet spinning can use methyl alcohol to replace.
Priority Applications (1)
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|---|---|---|---|
| CN 02109230 CN1370856A (en) | 2002-02-28 | 2002-02-28 | Regenerated protein fiber and its production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02109230 CN1370856A (en) | 2002-02-28 | 2002-02-28 | Regenerated protein fiber and its production process |
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|---|---|
| CN1370856A true CN1370856A (en) | 2002-09-25 |
Family
ID=4740564
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|---|---|---|---|
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315916C (en) * | 2004-05-27 | 2007-05-16 | 四川省宜宾五粮液集团有限公司 | Preparation and use of raw liquid of ceratin of animal hairs |
| CN100462487C (en) * | 2005-02-05 | 2009-02-18 | 李官奇 | Protein fiber spinning dope and its preparing method |
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN102585277A (en) * | 2012-02-16 | 2012-07-18 | 武汉纺织大学 | Process for preparing keratin porous membrane by refrigerating |
| CN102605453A (en) * | 2012-03-05 | 2012-07-25 | 东华大学 | Method for preparing fiber material by using feather keratin |
| CN102839441A (en) * | 2012-09-25 | 2012-12-26 | 天津工业大学 | High-elasticity keratin regenerated fiber and preparation method thereof |
| CN103102694A (en) * | 2013-03-07 | 2013-05-15 | 河南鼎大生物科技有限公司 | Method for preparation and wet spinning of regenerative keratin and silk-fibroin blended solution |
| CN103114351A (en) * | 2013-03-07 | 2013-05-22 | 河南鼎大生物科技有限公司 | Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution |
| CN103553847A (en) * | 2013-10-24 | 2014-02-05 | 山东全杰皮革研究所有限公司 | Method for preparing slow release fertilizer wrapping film by use of tanning waste cowhair |
| CN104911741A (en) * | 2015-06-26 | 2015-09-16 | 安徽皖翎羽绒制品有限公司 | Down feather composite fiber with good dyeing degree |
| CN104947236A (en) * | 2015-06-26 | 2015-09-30 | 安徽皖翎羽绒制品有限公司 | Composite down feather fiber having good ultraviolet resistance |
| CN104947238A (en) * | 2015-06-26 | 2015-09-30 | 安徽皖翎羽绒制品有限公司 | Down feather composite fiber having good fluffy and antibacterial effects |
| CN108998856A (en) * | 2018-08-22 | 2018-12-14 | 安徽工程大学 | A kind of core-skin bilayer feather protein fiber and preparation method thereof |
| CN109778343A (en) * | 2019-01-14 | 2019-05-21 | 合肥必更赢科技有限公司 | The preparation method and application of azelon and its fabric are blended in a kind of air-permeable anti-bacterial |
| CN111893580A (en) * | 2020-06-17 | 2020-11-06 | 中山大学 | Keratin spinning solution and prepared keratin regenerated fiber |
| CN111910282A (en) * | 2020-07-30 | 2020-11-10 | 南通大学 | Waste feather regenerated pure keratin fiber and preparation method thereof |
| CN115151235A (en) * | 2020-01-21 | 2022-10-04 | 纽泰克温图斯公司 | Continuous production of keratin fibers |
-
2002
- 2002-02-28 CN CN 02109230 patent/CN1370856A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1315916C (en) * | 2004-05-27 | 2007-05-16 | 四川省宜宾五粮液集团有限公司 | Preparation and use of raw liquid of ceratin of animal hairs |
| CN100462487C (en) * | 2005-02-05 | 2009-02-18 | 李官奇 | Protein fiber spinning dope and its preparing method |
| CN102220650A (en) * | 2011-04-29 | 2011-10-19 | 西南科技大学 | Soy protein fibers and preparation method thereof |
| CN102585277A (en) * | 2012-02-16 | 2012-07-18 | 武汉纺织大学 | Process for preparing keratin porous membrane by refrigerating |
| CN102585277B (en) * | 2012-02-16 | 2013-04-24 | 武汉纺织大学 | Process for preparing keratin porous membrane by refrigerating |
| CN102605453A (en) * | 2012-03-05 | 2012-07-25 | 东华大学 | Method for preparing fiber material by using feather keratin |
| CN102839441A (en) * | 2012-09-25 | 2012-12-26 | 天津工业大学 | High-elasticity keratin regenerated fiber and preparation method thereof |
| CN102839441B (en) * | 2012-09-25 | 2014-10-22 | 天津工业大学 | High-elasticity keratin regenerated fiber and preparation method thereof |
| CN103114351B (en) * | 2013-03-07 | 2014-05-14 | 河南鼎大生物科技有限公司 | Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution |
| CN103114351A (en) * | 2013-03-07 | 2013-05-22 | 河南鼎大生物科技有限公司 | Preparation method and dry-wet spinning method of regenerated protein chitosan blended solution |
| CN103102694A (en) * | 2013-03-07 | 2013-05-15 | 河南鼎大生物科技有限公司 | Method for preparation and wet spinning of regenerative keratin and silk-fibroin blended solution |
| CN103553847A (en) * | 2013-10-24 | 2014-02-05 | 山东全杰皮革研究所有限公司 | Method for preparing slow release fertilizer wrapping film by use of tanning waste cowhair |
| CN104911741A (en) * | 2015-06-26 | 2015-09-16 | 安徽皖翎羽绒制品有限公司 | Down feather composite fiber with good dyeing degree |
| CN104947236A (en) * | 2015-06-26 | 2015-09-30 | 安徽皖翎羽绒制品有限公司 | Composite down feather fiber having good ultraviolet resistance |
| CN104947238A (en) * | 2015-06-26 | 2015-09-30 | 安徽皖翎羽绒制品有限公司 | Down feather composite fiber having good fluffy and antibacterial effects |
| CN108998856A (en) * | 2018-08-22 | 2018-12-14 | 安徽工程大学 | A kind of core-skin bilayer feather protein fiber and preparation method thereof |
| CN108998856B (en) * | 2018-08-22 | 2020-12-08 | 东隆家纺股份有限公司 | Skin-core double-layer feather protein fiber and preparation method thereof |
| CN109778343A (en) * | 2019-01-14 | 2019-05-21 | 合肥必更赢科技有限公司 | The preparation method and application of azelon and its fabric are blended in a kind of air-permeable anti-bacterial |
| CN115151235A (en) * | 2020-01-21 | 2022-10-04 | 纽泰克温图斯公司 | Continuous production of keratin fibers |
| CN111893580A (en) * | 2020-06-17 | 2020-11-06 | 中山大学 | Keratin spinning solution and prepared keratin regenerated fiber |
| CN111910282A (en) * | 2020-07-30 | 2020-11-10 | 南通大学 | Waste feather regenerated pure keratin fiber and preparation method thereof |
| CN111910282B (en) * | 2020-07-30 | 2022-03-25 | 南通大学 | Waste feather regenerated pure keratin fiber and preparation method thereof |
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