CN1431343A - Composite fiber of plant protein and acrylon and its manufacturing method - Google Patents
Composite fiber of plant protein and acrylon and its manufacturing method Download PDFInfo
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- CN1431343A CN1431343A CN 03115288 CN03115288A CN1431343A CN 1431343 A CN1431343 A CN 1431343A CN 03115288 CN03115288 CN 03115288 CN 03115288 A CN03115288 A CN 03115288A CN 1431343 A CN1431343 A CN 1431343A
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Abstract
A composite plant protein-acrylic fibre is prepared from natural high-molecular plant protein and polyacrylonitrile in Wt. ratio of (10-50):(50-90) through respectively preparing their solutions, proportional mixing, wet spinning, coagulating, drafting, hot stretching, curling, fixating shape, coating oil and drying. Its advantages are good thermal insulating, high dyeability and human affinity, and high antistatic performance.
Description
Technical field
The present invention relates to a kind of vegetable protein-acrylic composite fiber and manufacture method thereof
Background technology
Acrylic fibers are a kind of synthetic fiber, good warmth retention property, excellent dyeability are arranged and do not have moth erosion and mould sex change, can obtain after its dyeing than wool gay colours more, and acrylic fibers are widely used in makes the simulate wool goods, so acrylic fibers are known as artificial wool again.But acrylic fibers also have a lot of shortcomings: the hydrophily difference causes at the easy static electrification of dry weather, and it is that petroleum product compatibility synthetic and human body is poor fully.
In order to improve the performance of acrylic fibers, the researcher has done a large amount of work with the animal protein modified acrylic fibers, as silk graft polypropylene nitrile, milk protein graft polypropylene nitrile fiber, but these all will just carry out very big change to existing equipment, technology at polymerization stage, the production cost height can not obtain a large amount of popularizations.
China is a large agricultural country, abundant oil crops resource and huge oil plant working ability are arranged, the grouts of wherein processing oil plant and being produced contain amounts of protein, as the protein content of soybean meal be 50%, peanut meal is 41.7%, rapeseed dregs is 36%, cottonseed meal is 42%, sunflower seeds is 39%, the ramie cake is 57.8%.These grouts use as feed and farm manure mostly, recently also in the research of carrying out the protein extraction deep processing, use to make food additives.Also the someone begins these protein is used for the modification of polyvinyl, is 99116636.1 Chinese patent as the patent No..
Summary of the invention
The purpose of this invention is to provide a kind of vegetable protein-acrylic composite fiber.
The purpose of this invention is to provide a kind of vegetable protein-acrylic composite fiber manufacture method.
A kind of vegetable protein-acrylic composite fiber of the present invention is made up of vegetable protein and polyacrylonitrile, phytoprotein accounts for 10～50% of gross weight, polyacrylonitrile accounts for 50～90% of gross weight, and in other words, the weight ratio of phytoprotein and polyacrylonitrile is 10～50: 50～90.
The present invention is a performance of utilizing protein to dissolve in some inorganic salt solutions and organic solvent, thereby makes the slurries that are suitable for the acrylic fibers composite spinning.Wet spinning technology spinning by routine gets vegetable protein-acrylic composite fiber.Main technique of the present invention such as Fig. 1 represent.
The raw material of the vegetable protein that the present invention is used is the protein that extracts in the slag dregs of rice of soybean, cashew nut, peanut, rapeseed, sesame, sunflower seeds, cottonseed, castor bean.Described vegetable protein can be the single variety or the mixture of said extracted protein.
The solvent of the solubilising protein that the present invention is used is the aqueous solution, dimethyl formamide or the dimethyl sulfoxide (DMSO) of inorganic salts, and wherein inorganic salts are zinc chloride, sodium sulfocyanate, potassium rhodanide, and the concentration of inorganic salt solution is 20～60%.
The used protein concentration of the present invention is to contain 10～40% weight.
The used acrylic fibers slurries of the present invention be Acrylic Fibers Plant directly synthetic or obtain through concentrating or being dissolved in the solvent by the fibrous polypropylene nitrile, its concentration is to contain 8～30% weight.Solvent is the aqueous solution, dimethyl formamide or the dimethyl sulfoxide (DMSO) of inorganic salts, and wherein inorganic salts are zinc chloride, sodium sulfocyanate, potassium rhodanide, and the concentration of inorganic salt solution is for containing 20～60 weight %.
Albumen of the present invention-acrylic spinning slurries are by a certain proportion of above-mentioned protein solution and composite the forming of polypropylene nitrile solution.Wherein the weight ratio of protein and polymer is 10～50: 50～90.
Spinning of the present invention is that above-mentioned mixed slurry comes out to solidify drawing-off one-tenth silk from spinneret orifice spinning bath.The concentration of coagulating bath is the aqueous solution or the water of 1～30% sodium sulfocyanate, potassium rhodanide or zinc chloride, and temperature is 5～70% ℃.1～7 times of drafting multiple.
Coagulating bath of the present invention can be one or more levels.
Of the present inventionly solidify first break draft and at high temperature carry out, the condition of stretching is that temperature is 80～140 ℃, and stretching ratio is 5～20 times.
Of the present invention curling is the hot rolling song, and curling temperature is 70～110 ℃.
Typing of the present invention is to carry out under 80～160 ℃ temperature.
Finished product drying of the present invention is to carry out under 80～180 ℃ temperature.
The present invention is that to utilize the protein extract from oil meal and acrylic fibers raw material polyacrylonitrile to carry out molecule compound, a kind of albumen-acrylic composite fiber that makes through spinning and after-processing technology.This fiber has not only kept the original advantage of acrylic fiber but also overcome the acrylic fibers static electrification and the shortcoming of human body compatibility difference, again oil meal has been carried out sufficient utilization simultaneously, the also capable of using as feed and farm manure use of the slag charge behind the extraction protein.On technology, also overcome the complex technology of animal protein graft polypropylene nitrile fiber, needn't change original polymerization technique equipment, only need to add some simple devices and just can carry out the production of vegetable protein-acrylic composite fiber, this fiber has low and the characteristics that added value is high of production cost.
Description of drawings
Fig. 1 is a kind of vegetable protein of the present invention-acrylic composite fiber process chart.
Specific implementation method will help to understand the present invention by following examples, but not limit content of the present invention.Ratio described in the embodiment, concentration are all by weight.
Embodiment 1
Soybean cake dregs mixes the water of its 10 times of amounts, soaks 8 hours at 30 ℃, isolates undissolved polysaccharide residue, these residues again with the mixed of water with 1: 12, soak 1 hour branch residue of leaving away.It is 4.4 to leave standstill 2 hours that two parts solution merges with the hydrochloric acid conditioning solution pH value, carries out acid and sinks.Centrifugation dissolubility polysaccharide, centrifuge dripping to protein moisture content is 15%.
It is that to make its protein concentration in 17% the sodium thiocyanate solution be 25% that above-mentioned protein is dissolved in concentration, is that 1: 4 ratio is composite with the acrylic fibers slurries with protein and polymer ratio subsequently, is mixed into spinning slurry, preferably through standing and defoaming.
Spinning slurry enters first coagulating bath through measuring pump by spinneret orifice, and coagulating bath is 10% sulphur nitrile acid sodium aqueous solution, and bathing temperature is 9 ℃.Carry out predraft through second coagulating bath again, coagulating bath is 3% sulphur nitrile acid sodium aqueous solution, and bathing temperature is that 50 ℃ of stretching ratios are 1.6 times.Through steam stretching, draft temperature is 100 ℃ again, and stretching ratio is 10 times, with after washing, oils, and is dry under the condition of 100 ℃ of temperature.Dry fiber curls at 85 ℃, and the back oils once more 130 ℃ of temperature HEAT SETTING, obtains albumen-acrylic composite fiber finished product 120 ℃ of dryings.
Embodiment 2
The pH value of sunflower seed dregs and its 8 times of amounts is that 8.8 sodium hydroxide solution mixes, and soak at room temperature 2 hours is isolated undissolved polysaccharide residue, and these residues are 8.8 sodium hydroxide solution with 1: 9 mixed with pH value again, soaks 1 hour branch residue of leaving away.It is 4.6 to leave standstill 2 hours that two parts solution merges with the hydrochloric acid conditioning solution pH value, carries out acid and sinks.Centrifugation dissolubility polysaccharide, centrifuge dripping to albumen moisture content is 20%.
It is that to make its protein concentration in 18% the liquor zinci chloridi be 20% that above-mentioned protein is dissolved in concentration, the fibrous polypropylene nitrile is dissolved in 16% the liquor zinci chloridi, is protein solution and polyacrylonitrile solution that 1: 5 ratio is composite with protein and polymer ratio, be mixed into spinning slurry, preferably standing and defoaming.
Spinning slurry enters first coagulating bath through measuring pump by spinneret orifice, and coagulating bath is 8% solder(ing)acid, and bathing temperature is 12 ℃.Through second coagulating bath, coagulating bath is 5% solder(ing)acid again, and bathing temperature is 30 ℃, carries out predraft through the 3rd coagulating bath again, and coagulating bath is 1.5% zinc chloride, and bathing temperature is that 45 ℃ of stretching ratios are 1.2 times.Through steam stretching, draft temperature is 120 ℃ again, and stretching ratio is 11 times, with after washing, oils, and is dry under the condition of 90 ℃ of temperature.Dry fiber curls at 90 ℃, and the back oils once more 120 ℃ of temperature HEAT SETTING, obtains albumen-acrylic composite fiber finished product 110 ℃ of dryings.
Embodiment 3
The pH value of peanut dregs and its 9 times of amounts is that 6.8 hydrochloric acid solution mixes, and 50 ℃ were soaked 30 minutes, isolated undissolved polysaccharide residue, these residues again with the mixed of water with 1: 10, soak 30 minutes branches residue of leaving away.It is 4.3 to leave standstill 1.5 hours that two parts solution merges with the sulfuric acid regulation solution pH value, carries out acid and sinks.Centrifugation dissolubility polysaccharide, centrifuge dripping to albumen moisture content is 23%.
Above-mentioned protein is dissolved in to make its protein concentration in the dimethyl formamide be 15%, the fibrous polypropylene nitrile is dissolved in the dimethyl formamide, is protein solution and polyacrylonitrile solution that 1: 4.5 ratio is composite with protein and spinning level polymer ratio, be mixed into spinning slurry, preferably through standing and defoaming.
Spinning slurry enters first coagulating bath through measuring pump by spinneret orifice, and coagulating bath is the 6% dimethyl formamide aqueous solution, and bathing temperature is 12 ℃.Carry out predraft through second coagulating bath again, coagulating bath is the 1% dimethyl formamide aqueous solution, and bathing temperature is that 50 ℃ of stretching ratios are 1.8 times.Through steam stretching, draft temperature is 90 ℃ again, and stretching ratio is 9 times, with after washing, oils, and is dry under the condition of 110 ℃ of temperature.Dry fiber curls at 110 ℃, and the back oils once more 130 ℃ of temperature HEAT SETTING, obtains albumen-acrylic composite fiber finished product 120 ℃ of dryings.
Claims (10)
1, a kind of vegetable protein-acrylic composite fiber, its composition is made up of vegetable protein and polyacrylonitrile, and wherein the weight ratio of phytoprotein and polyacrylonitrile is 10～50: 50～90.
2,, it is characterized in that the protein that extracts in the slag dregs of rice of soybean, cashew nut, peanut, rapeseed, sesame, sunflower seeds, cottonseed or castor bean after described phytoprotein is utilized by extracting oil or their mixture according to claims 1 described vegetable protein-acrylic composite fiber.
3,, it is characterized in that described acrylic fibers are acrylic fibers slurries, polyacrylonitrile or fibre-grade polypropylene nitrile according to claims 1 described vegetable protein-acrylic composite fiber.
4, as the spinning moulding technology of claims 1 described vegetable protein-acrylic fiber, the solution and the concentration that it is characterized in that containing 10～40% weight phytoproteins are the solution that contains the polyacrylonitrile of 8～30% weight, by protein and polymer is that 10～50: 50～90 the weight ratio that contains is mixed with spinning slurry, through wet spinning, comes out to solidify drawing-off from spinneret orifice spinning bath and becomes silk, stretch, washing oils, and curls, typing oils and drying; Above-mentioned solution is inorganic salt solution, dimethyl formamide solution or the dimethyl sulphoxide solution that contains phytoprotein or polyacrylonitrile, and wherein inorganic salt solution is the aqueous solution of the zinc chloride, sodium sulfocyanate or the potassium rhodanide that contain 20～60% weight.
5, as the spinning moulding technology of claims 4 described vegetable protein-acrylic fibers, it is characterized in that described phytoprotein solution, be to adopt solvent method from the proteinaceous plant slag dregs of rice Protein Extraction to be come out, the extraction solvent is water, dilute alkaline soln, dilute acid soln or inorganic salt solution; Again the aqueous solution, dimethyl formamide or the dimethyl sulphoxide solution that concentration is the inorganic salts of 10～40% protein made in the protein dissolving, described inorganic salt solution is described with claim 4.
6, as the spinning moulding technology of claims 4 described vegetable protein-acrylic fibers, the solution that it is characterized in that described polyacrylonitrile is the slurries directly used with former spinning, be dissolved in the polyacrylonitrile slurries that are made in the aqueous solution, dimethyl formamide or the dimethyl sulfoxide solvent of inorganic salts with concentrated spinning slurry or with the fibrous polypropylene nitrile, its concentration is the polymer that contains 8～30% weight, and described inorganic salt solution is described with claim 4.
7, as the spinning moulding technology of claims 4 described vegetable protein-acrylic fibers, it is characterized in that described mixed slurry comes out to solidify drawing-off from spinneret orifice and becomes silk spinning bath, solidify and be divided into 1～4 grade, the concentration of coagulating bath is the aqueous solution or the water of 1～30% sodium sulfocyanate, potassium rhodanide, zinc chloride, and temperature is 5～70 ℃.
8, as the spinning moulding technology of claims 4 described vegetable protein-acrylic fibers, it is characterized in that described drawing-off, under 80～140 ℃ of high temperature, carry out, 1～7 times of drafting multiple.
9, as the spinning moulding technology of claims 4 described vegetable protein-acrylic fibers, it is characterized in that described draft temperature is 80～140 ℃, stretching ratio is 5～20 times; Curling temperature is 70～110 ℃; Setting temperature is 80～160 ℃.
10,, it is characterized in that described baking temperature is 80～180 ℃ as the spinning moulding technology of claims 4 described vegetable protein-acrylic fibers.
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| CN 03115288 CN1431343A (en) | 2003-01-30 | 2003-01-30 | Composite fiber of plant protein and acrylon and its manufacturing method |
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| CN 03115288 CN1431343A (en) | 2003-01-30 | 2003-01-30 | Composite fiber of plant protein and acrylon and its manufacturing method |
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Cited By (9)
| 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 |
| CN1298901C (en) * | 2005-03-14 | 2007-02-07 | 东华大学 | Soya protein/polyurethane/polyacrylonitrile blended composite fiber and its preparing method |
| CN100344808C (en) * | 2006-04-25 | 2007-10-24 | 东华大学 | Method for preparing hydrolytic polyacrylonitrilel soybean protein intelligent gel fiber |
| CN101831806A (en) * | 2010-05-05 | 2010-09-15 | 山东理工大学 | Manufacturing method of protein modified fiber in acrylic fiber surface ingrafted bean juice |
| CN102732987A (en) * | 2012-06-21 | 2012-10-17 | 精源(南通)化纤制品有限公司 | Artificial sub-gloss high temperature resistant polyacrylonitrile hair and its preparation method |
| CN103088456A (en) * | 2011-11-01 | 2013-05-08 | 陈福库 | Protein-polyacrylonitrile composite fiber for hairpiece and manufacturing method of composite fiber |
| CN106498515A (en) * | 2016-10-31 | 2017-03-15 | 朱锦 | High speed acrylic spinning technique |
| CN110359127A (en) * | 2019-08-01 | 2019-10-22 | 丹阳市三江纤维材料有限公司 | A kind of composite fibre and its textile fabric |
-
2003
- 2003-01-30 CN CN 03115288 patent/CN1431343A/en active Pending
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 |
| CN1298901C (en) * | 2005-03-14 | 2007-02-07 | 东华大学 | Soya protein/polyurethane/polyacrylonitrile blended composite fiber and its preparing method |
| CN100344808C (en) * | 2006-04-25 | 2007-10-24 | 东华大学 | Method for preparing hydrolytic polyacrylonitrilel soybean protein intelligent gel fiber |
| CN101831806A (en) * | 2010-05-05 | 2010-09-15 | 山东理工大学 | Manufacturing method of protein modified fiber in acrylic fiber surface ingrafted bean juice |
| CN103088456A (en) * | 2011-11-01 | 2013-05-08 | 陈福库 | Protein-polyacrylonitrile composite fiber for hairpiece and manufacturing method of composite fiber |
| CN103088456B (en) * | 2011-11-01 | 2014-10-15 | 陈福库 | Protein-polyacrylonitrile composite fiber for hairpiece and manufacturing method of composite fiber |
| CN102732987A (en) * | 2012-06-21 | 2012-10-17 | 精源(南通)化纤制品有限公司 | Artificial sub-gloss high temperature resistant polyacrylonitrile hair and its preparation method |
| CN102732987B (en) * | 2012-06-21 | 2015-03-04 | 保利源(南通)实业有限公司 | Artificial sub-gloss high temperature resistant polyacrylonitrile hair and its preparation method |
| CN106498515A (en) * | 2016-10-31 | 2017-03-15 | 朱锦 | High speed acrylic spinning technique |
| CN110359127A (en) * | 2019-08-01 | 2019-10-22 | 丹阳市三江纤维材料有限公司 | A kind of composite fibre and its textile fabric |
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