CN1261626C - Vegetable protein cellulose composite fibre and preparing method thereof - Google Patents
Vegetable protein cellulose composite fibre and preparing method thereof Download PDFInfo
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- CN1261626C CN1261626C CN 200410024650 CN200410024650A CN1261626C CN 1261626 C CN1261626 C CN 1261626C CN 200410024650 CN200410024650 CN 200410024650 CN 200410024650 A CN200410024650 A CN 200410024650A CN 1261626 C CN1261626 C CN 1261626C
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Abstract
The present invention relates to a vegetable protein-cellulose composite fiber, which is characterized in that the present invention is composed of vegetable proteins and celluloses or cellulose derivatives, and the present invention comprises the components of the following weight percentage: 10 to 50% of the vegetable proteins and 50 to 90% of the celluloses or the cellulose derivatives. The preparing method comprises the following steps: preparing vegetable protein solutions containing weight of 10 to 40% and cellulose or derivatives solutions containing weight of 8 to 30% into spinning slurry according to the weight proportion of 10 to 50 shares of the proteins and 50 to 90 shares of the celluloses, carrying out spinning by a wet process or a drying wet process, ejecting the matters from a nozzle hole, solidifying and drawing the matters into threads, and then obtaining fibers after carrying out stretching, alkali washing, water washing, first oil spraying, curling, forming, second oil spraying and drying. The composite fiber of the present invention not only reserves original advantages of good hydroscopic property, good ventilation property, good antistatic property, favorable chromaticity, etc. in cellulose fibers, but also increases characteristics of heat insulating property of fibers, compatibility for human bodies, natural bacteriostatic property, luster like natural silk, comfortable handle, etc.
Description
Technical field
The present invention relates to one kind of plant protein-cellulose composite fiber and preparation method thereof.
Background technology
Cellulose fibre is the chemical fibre that becomes textile fabric the earliest, because it is a raw material with the plant of the various rich cellulose that occurring in nature can constantly be regenerated, these plants comprise timber, cotton linter, bagasse etc., by the series of physical chemical process, with cellulose regenerated and regenerated fiber that make.Cellulose fibre has hygroscopicity, gas permeability, antistatic behaviour and good dyeability, has advantage such as gloss and comfort feel as good warmth retention property, human body compatibility, natural biocidal property, the real silk again, therefore in fields such as clothes purposes is widely arranged.In addition, because global oil allowable exploitation constantly reduces, having limited is the further developing of synthetic fiber of raw material with the oil, thereby the exploitation of cellulose fibre is subject to people's attention day by day.But in the adhering process of traditional produce cellulose fibers, use CS
2Forming cellulose xanthate solution with alkali is viscose glue, exists in technological process length, the production and uses CS
2Problems such as pernicious gas and three-waste pollution environment.
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 chemical fibre, is used for the modification of polyvinyl as protein: application number is 99116636.1 and 02109966.9 Chinese patent; Vegetable protein modified acrylic fibers: be 03115288.0 Chinese patent as application number; The vegetable protein modified viscose fiber: as application number is 02138823.7 Chinese patent, has wherein used part polyvinyl raw material.Yet polyvinyl and acrylic fibers are synthetic fiber, and its raw material is coal, oil, natural gas and calcium carbide etc., because its development is subjected to restriction in various degree, and biodegradability is relatively poor, has the serious environmental pollution problem in the viscose production.
Summary of the invention
Technical problem to be solved by this invention is to provide one kind of plant protein-cellulose composite fiber.
Technical problem to be solved by this invention is to provide the preparation method of one kind of plant protein-cellulose composite fiber.
The present invention is that to utilize the protein extract from oil meal and cellulose to carry out molecule compound, a kind of protein-cellulose composite fiber that makes through spinning and after-processing technology.This fiber had both kept the original hygroscopicity of cellulose fibre, gas permeability, antistatic behaviour and good advantages such as dyeability, gloss and comfort feel as the warmth retention property, human body compatibility, natural biocidal property, real silk of fiber have been increased again, simultaneously again oil meal has been carried out sufficient utilization, the also capable of using as feed and farm manure use of the slag charge behind the extraction protein.Can utilize original viscose equipment in addition, just can carry out the production of phytoprotein-cellulose composite fiber, this fiber has low and the characteristics that added value is high of production cost, and raw material is renewable, the product degradable, produce pollute little, meet in the world requirement to ecological textile.Technology of the present invention as shown in Figure 1.
Feature of 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 cellulose composite spinning.Get phytoprotein-cellulose composite fiber by wet method or dry-wet spinning technology spinning.
The raw material of the phytoprotein 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 phytoprotein 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 dimethyl sulfoxide (DMSO), alkali or the acid of inorganic salts.
The used protein concentration of the present invention is 10～40%.
The used cellulosic material of the present invention is by recyclability plant by-products such as cotton linter, non-sawn timber, bagasse, straw, bamboo or waste material etc., makes the pulp of cellulose more than 90%, it is dissolved in makes solution in the solvent; Or cellulose pulp is processed into derivative--cellulose carbamate is dissolved in it and makes solution in the solvent.Concentration is to contain 8～30% cellulose or derivatives thereof.
The plain carbamate of used cellulose derivative fibres among the present invention is with alkalization of cellulose hydrogenation sodium oxide molybdena and oxidative degradation, adds urea then and adds that thermal response is synthetic to be made.
The solvent of the dissolving cellulos that the present invention is used is the aqueous solution, dimethyl formamide or dimethyl sulfoxide (DMSO), N-methylmorpholine-N-oxide-hydrate (NMMOH2O), alkali or the acid of inorganic salts; Used inorganic salt solution is the aqueous solution of the zinc chloride, sodium sulfocyanate or the potassium rhodanide that contain 20～60% percentage by weights.
Protein of the present invention-cellulose spinning slurries are a certain proportion of protein solution and cellulose or derivatives thereof solution mixture.Described ratio is a protein: cellulose is 10～50: 50～90.
Spinning of the present invention is that 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 sulphate, sulfuric acid, zinc chloride, zinc sulfate, 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 drawing-off 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.
Description of drawings
Fig. 1 is the process chart of one kind of plant protein of the present invention-cellulose composite fiber.
The specific embodiment
The invention will be further elaborated with four specific embodiments below, but embodiment only is used for explanation, does not limit scope of invention.To help to understand the present invention by following examples, but not limit content of the present invention.
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 9% the sodium hydroxide solution be 25% that above-mentioned protein is dissolved in concentration, is that 1: 4 ratio is composite with the gossypin slurries with protein and cellulose ratios subsequently, is mixed into spinning slurry, standing and defoaming.
Spinning slurry enters coagulating bath through measuring pump by spinneret orifice, and coagulating bath is 10% aqueous sulfuric acid, 3% aqueous sodium persulfate 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 120 ℃ of temperature.Dry fiber curls at 85 ℃, and the back oils once more 130 ℃ of temperature HEAT SETTING, obtains protein-cellulose 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%.
Above-mentioned protein and lignose are dissolved among the NMMOH2O, and making its protein concentration is 20%, and protein and cellulose ratios are that 1: 5 ratio is composite, are mixed into spinning slurry, standing and defoaming.
Spinning slurry enters first coagulating bath by spinneret orifice through air layer through measuring pump, and coagulating bath is the aqueous solution, and bathing temperature is 12 ℃.Through second coagulating bath, coagulating bath is the aqueous solution again, and bathing temperature is 30 ℃, carries out predraft through the 3rd coagulating bath again, and coagulating bath is the aqueous solution, 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 140 ℃ of temperature.Dry fiber curls at 90 ℃, and the back oils once more 120 ℃ of temperature HEAT SETTING, obtains protein-cellulose composite fiber finished product 110 ℃ of dryings.
Embodiment 3:
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, centrifugal get rid of thousand to the protein moisture content be 15%, it is that making its protein concentration is 25% in 9% the sodium hydroxide solution that above-mentioned protein is dissolved in concentration.
The sodium hydroxide solution of cotton pulp dregs of rice adding 9% alkalizes and oxidative degradation, is 1: 3 ratio adding urea then in cellulose and urea ratio, adds thermal response and synthesize cellulose carbamate under 140 ℃.Be that 5: 1 ratio is composite with protein slurry with cellulose and protein ratio subsequently, be mixed into spinning slurry, standing and defoaming.
Spinning slurry enters coagulating bath through measuring pump by spinneret orifice, and coagulating bath is 10% aqueous sulfuric acid, and bathing temperature is that 50 ℃ of stretching ratios are 1.6 times, makes spinning cake.Alkali cleaning subsequently, washing oils, and 130 ℃ of temperature HEAT SETTING, oils once more, obtains protein-cellulose composite fiber long filament finished product at 120 ℃ of dry back winders.
Phytoprotein-cellulose composite fiber that the present invention makes, it is 1～7dtex that its obvious improvement effect is embodied in its staple fibre fiber number; Dry strength is 1.5～2.7CN/dtex; Wet strength is 0.7～1.7CN/dtex; Elongation is 10～30%; Dye uniformity (ash card level) 〉=3.
Claims (6)
1, the preparation method of one kind of plant protein-cellulose composite fiber is characterized in that containing the phytoprotein solution of 10～40% weight and contains the cellulose or the cellulose carbamate solution of 8～30% weight, is that 10～50: 50～90 weight ratio is mixed with spinning slurry by protein and cellulose, by wet method or dried wet processing spinning, come out from spinneret orifice, in spinning bath, solidify drawing-off and become silk, stretch, alkali cleaning, washing oils, and curls, typing oils and drying; The solvent of above-mentioned solution is the aqueous solution, dimethyl formamide or dimethyl sulfoxide (DMSO), N-methylmorpholine-N-oxide-hydrate (NMMOH2O), alkali or the acid of inorganic salts, and described inorganic salt solution is the aqueous solution of the zinc chloride, sodium sulfocyanate or the potassium rhodanide that contain 20～60% percentage by weights.
2, the preparation method of phytoprotein-cellulose composite fiber according to claim 1, 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 and inorganic salt solution; Again concentration being made in the protein dissolving is 10～40% protein solutions, and solvent is the aqueous solution, dimethyl formamide or dimethyl sulfoxide (DMSO), N-methylmorpholine-N-oxide-hydrate (NMMOH2O), alkali or the acid of inorganic salts; Described inorganic salt solution is the aqueous solution of the zinc chloride, sodium sulfocyanate or the potassium rhodanide that contain 20～60% percentage by weights.
3, the preparation method of phytoprotein-cellulose composite fiber according to claim 1, it is characterized in that described cellulose solution, is to adopt that to produce be earlier pulp or the cellulose carbamate of cellulose more than 90% to be dissolved in and to make the cellulose solution that contains 8～30% percentage by weights in the solvent; Above-mentioned solvent is the aqueous solution, dimethyl formamide or dimethyl sulfoxide (DMSO), N-methylmorpholine-N-oxide-hydrate (NMMOH2O), alkali or the acid of inorganic salts; Described inorganic salt solution is the aqueous solution of the zinc chloride, sodium sulfocyanate or the potassium rhodanide that contain 20～60% percentage by weights.
4, the preparation method of phytoprotein-cellulose composite fiber according to claim 1, it is characterized in that described mixed slurry comes out to solidify drawing-off from spinneret orifice and becomes silk spinning bath, the concentration of coagulating bath is the aqueous solution or the water of 1～30% sodium sulphate, sulfuric acid, zinc chloride, zinc sulfate, and temperature is 5～70 ℃.
5, the preparation method of phytoprotein-cellulose composite fiber according to claim 1 is characterized in that described drawing-off, and drawing temperature is 80～140 ℃, and drafting multiple is 1～7 times.
6, the preparation method of phytoprotein-cellulose composite fiber according to claim 1 is characterized in that described draft temperature is 80～140 ℃, and stretching ratio is 5～20 times, and curling temperature is 70～110 ℃, and setting temperature is 80～160 ℃; Baking temperature is 80～180 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410024650 CN1261626C (en) | 2004-05-26 | 2004-05-26 | Vegetable protein cellulose composite fibre and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410024650 CN1261626C (en) | 2004-05-26 | 2004-05-26 | Vegetable protein cellulose composite fibre and preparing method thereof |
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| CN1584151A CN1584151A (en) | 2005-02-23 |
| CN1261626C true CN1261626C (en) | 2006-06-28 |
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| CN 200410024650 Expired - Fee Related CN1261626C (en) | 2004-05-26 | 2004-05-26 | Vegetable protein cellulose composite fibre and preparing method thereof |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101358001B (en) * | 2007-08-02 | 2011-05-04 | 绵阳宝新容科科技有限公司 | Biodegradable natural plant cellulose material |
| CN102677221B (en) * | 2012-06-04 | 2014-03-26 | 武汉纺织大学 | Method for preparing cellulose protein fibers |
| CN103668546A (en) * | 2012-09-21 | 2014-03-26 | 江苏蓝品纤维科技发展有限公司 | Yonic fiber and functional fiber prepared therefrom |
| CN104562281B (en) * | 2015-01-22 | 2016-08-24 | 罗莱家纺股份有限公司 | A kind of preparation method of nanometer fibroin bamboo pulp fiber |
| CN107142543B (en) * | 2017-07-06 | 2020-01-07 | 汕头市欣和棉麻纺织有限公司 | Animal colloidal protein composite apocynum venetum cellulose fiber and preparation method thereof |
| CN107227505A (en) * | 2017-07-13 | 2017-10-03 | 芜湖慧宇商贸有限公司 | A kind of preparation method of soybean fiber towel |
| CN110886025B (en) * | 2019-12-17 | 2022-07-05 | 上海里奥纤维企业发展有限公司 | Solvent method high wet modulus protein fiber and preparation method thereof |
| CN112323164B (en) * | 2020-12-01 | 2023-02-17 | 许昌学院 | Protein modified regenerated cellulose fiber and production process thereof |
| CN113005601A (en) * | 2021-02-28 | 2021-06-22 | 佛山奥轩科技有限公司 | Amino acid protein textile fabric with skin care and moisture retention functions |
| CN114086270A (en) * | 2021-12-13 | 2022-02-25 | 上海水星家用纺织品股份有限公司 | Preparation method of composite plant protein fiber |
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