CN1261626C - A kind of plant protein-cellulose composite fiber and its preparation method - Google Patents

Abstract

A plant protein-cellulose composite fiber, characterized in that it is composed of plant protein and cellulose or cellulose derivatives, plant protein accounts for 10-50%, and cellulose or cellulose derivatives accounts for 50-90%, all by weight percentage. Its preparation method is that the plant protein solution containing 10-40% by weight and the cellulose or its derivative solution containing 8-30% by weight are prepared according to the weight ratio of protein to cellulose: 10-50:50-90 Silk slurry, spun by wet or dry-wet process, coming out of the spinneret hole, coagulated in the spinning bath, drawn into silk, stretched, alkali washed, water washed, oiled, crimped, shaped, oiled and dried get. The composite fiber of the present invention not only retains the original advantages of cellulose fiber such as hygroscopicity, air permeability, antistatic property and good dyeability, but also increases the warmth retention property, human body affinity, natural antibacterial property, silk Like luster and comfortable feel and so on.

Description

A kind of plant protein-cellulose composite fiber and its preparation method

technical field

The invention relates to a plant protein-cellulose composite fiber and a preparation method thereof.

Background technique

Cellulose fiber is the earliest chemical fiber to become textile fiber. Because it uses various cellulose-rich plants that can be continuously regenerated in nature as raw materials, these plants include wood, cotton linters, bagasse, etc., through a series of physical processes. Chemical processing, regenerated fiber made by regenerating cellulose. Cellulose fiber has the advantages of hygroscopicity, air permeability, antistatic property and good dyeability, as well as good warmth retention property, human affinity, natural antibacterial property, silky luster and comfortable hand feeling, etc., so it is widely used in clothing, etc. fields have a wide range of uses. In addition, due to the continuous reduction of the global oil recoverable volume, the further development of synthetic fibers using petroleum as raw materials is limited, so the development of cellulose fibers has attracted increasing attention. However, in the traditional viscose process for producing cellulose fibers, CS ₂ and alkali are used to form a cellulose xanthate solution, i.e. viscose, which has problems such as long process flow, harmful gas and environmental pollution caused by the use of CS ₂ in production.

my country is a large agricultural country with abundant oil crop resources and huge oil processing capacity. The cake produced by processing oil contains a lot of protein, such as soybean meal with 50% protein content, peanut meal with 41.7%, rapeseed meal with 41.7% protein content Meal is 36%, cottonseed meal is 42%, sunflower seed is 39%, ramie cake is 57.8%. Most of these cakes are used as feed and farmyard manure. Recently, research on protein extraction and deep processing is also being carried out for food additive applications. There are also people who have begun to use these proteins for the modification of chemical fibers, such as the modification of proteins for vinylon: application numbers are 99116636.1 and 02109966.9 Chinese patents; plant protein modified acrylic fiber: as application number is 03115288.0 Chinese patent; plant protein Modified viscose fiber: such as the Chinese patent application number 02138823.7, which uses some vinylon raw materials. However, both vinylon and acrylic fibers are synthetic fibers, and their raw materials are coal, oil, natural gas, and calcium carbide. Due to their development being restricted to varying degrees, and their biodegradability is poor, there are serious environmental pollution problems in the production of viscose fibers.

Contents of the invention

The technical problem to be solved by the present invention is to provide a plant protein-cellulose composite fiber.

The technical problem to be solved by the present invention is to provide a preparation method of vegetable protein-cellulose composite fiber.

The invention is a kind of protein-cellulose compound fiber which is obtained by molecular compounding of protein and cellulose extracted from oil cake, spinning and post-processing. This kind of fiber not only retains the original hygroscopicity, air permeability, antistatic and good dyeability of cellulose fiber, but also increases the warmth retention, human affinity, natural antibacterial property and silky luster of the fiber. And comfortable hand feeling, and at the same time, the oil cake is fully utilized, and the slag after protein extraction can also be used as feed and farmyard manure. In addition, the original viscose fiber equipment can be used to produce plant protein-cellulose composite fiber. This fiber has the characteristics of low production cost and high added value, and the raw material is renewable, the product is degradable, and the production pollution is small. , Meet the international requirements for ecological textiles. Technology of the present invention is as shown in Figure 1.

The feature of the invention is to use the property of dissolving protein in some inorganic salt solutions and organic solvents to prepare slurry suitable for cellulose composite spinning. The vegetable protein-cellulose composite fiber is spun by wet or dry-wet spinning process.

The raw material of the vegetable protein used in the present invention is the protein extracted from the dregs of soybeans, cashew nuts, peanuts, rapeseeds, sesame, sunflower seeds, cottonseeds and castor beans. The vegetable protein can be a single species or a mixture of the above-mentioned extracted proteins.

The protein-dissolving solvent used in the present invention is an aqueous solution of inorganic salts, dimethylformamide or dimethyl sulfoxide, alkali or acid.

The protein concentration used in the present invention is 10-40%.

The cellulose raw material used in the present invention is made of renewable plant by-products or waste materials such as cotton linters, unshaped wood, bagasse, straw, bamboo, etc., which contain more than 90% of cellulose, and is dissolved in A solution is made in a solvent; or the cellulose pulp is processed into a derivative - cellulose carbamate, and then dissolved in a solvent to make a solution. The concentration is 8-30% of cellulose or its derivatives.

The cellulose derivative cellulose carbamate used in the present invention is synthesized by adding sodium hydroxide to basification and oxidative degradation of cellulose, and then adding urea for heating reaction.

The solvent for dissolving cellulose used in the present invention is an aqueous solution of inorganic salts, dimethylformamide or dimethyl sulfoxide, N-methylmorpholine-N-oxide-hydrate (NMMO H2O), alkali or acid ; The inorganic salt solution used is an aqueous solution containing 20-60% by weight of zinc chloride, sodium thiocyanate or potassium thiocyanate.

The protein-cellulose spinning slurry of the present invention is a mixture of protein solution and cellulose or its derivative solution in a certain proportion. The ratio of protein: cellulose is 10-50: 50-90.

The spinning of the present invention is that the mixed slurry comes out from the spinneret holes and is solidified and drawn into filaments in the spinning bath. The concentration of the coagulation bath is 1-30% sodium sulfate, sulfuric acid, zinc chloride, zinc sulfate aqueous solution or water, and the temperature is 5-70°C. The drafting ratio is 1 to 7 times.

The coagulation bath of the present invention may be one-stage or multi-stage.

The stretching after solidification of the present invention is carried out at high temperature, and the stretching conditions are that the temperature is 80-140° C., and the stretching ratio is 5-20 times.

The crimping in the present invention is thermal crimping, and the crimping temperature is 70 to 110°C.

The setting of the present invention is carried out at a temperature of 80-160°C.

Finished product drying of the present invention is to carry out under the temperature of 80～180 ℃.

Description of drawings

Fig. 1 is a process flow diagram of a plant protein-cellulose composite fiber of the present invention.

Detailed ways

The present invention will be further elaborated below with four specific examples, but the examples are only for illustration and do not limit the scope of the invention. The following examples will help to understand the present invention, but do not limit the content of the present invention.

Example 1:

Soybean cake is mixed with 10 times the amount of water, soaked at 30°C for 8 hours, and the insoluble polysaccharide residues are separated, and these residues are mixed with water at a ratio of 1:12, and soaked for 1 hour to separate and remove the residues. The two parts of the solution were combined and the pH value of the solution was adjusted to 4.4 with hydrochloric acid and allowed to stand for 2 hours for acid precipitation. The soluble polysaccharides were separated by centrifugation, and dried by centrifugation until the water content of the protein was 15%.

Dissolving the above-mentioned protein in a sodium hydroxide solution with a concentration of 9% makes the protein concentration 25%, and then mixes it with the cotton cellulose slurry at a ratio of 1:4 between protein and cellulose, and mixes it into a spinning slurry. Let stand to defoam.

The spinning slurry enters the coagulation bath from the spinneret hole through the metering pump. The coagulation bath is 10% sulfuric acid aqueous solution, 3% sodium sulfate aqueous solution, and the bath temperature is 50° C. The draw ratio is 1.6 times. After steam stretching, the stretching temperature is 100°C, and the stretching ratio is 10 times, then washed with water, oiled, and dried at a temperature of 120°C. The dried fiber is crimped at 85°C, then heat-set at 130°C, oiled again, and dried at 120°C to obtain the finished protein-cellulose composite fiber.

Example 2:

The sunflower seed meal is mixed with 8 times the amount of sodium hydroxide solution with a pH value of 8.8, soaked at room temperature for 2 hours, and the insoluble polysaccharide residues are separated. : 9 ratio, soak for 1 hour to separate the residue. The two parts of the solution were combined and the pH value of the solution was adjusted to 4.6 with hydrochloric acid and allowed to stand for 2 hours for acid precipitation. The soluble polysaccharides were separated by centrifugation, and dried by centrifugation until the water content of the protein was 20%.

The above-mentioned protein and wood cellulose were dissolved in NMMO·H2O, so that the protein concentration was 20%, and the ratio of protein to cellulose was 1:5 to compound, mixed into spinning slurry, and left to stand for defoaming.

The spinning slurry enters the first coagulation bath through the metering pump from the spinneret hole through the air layer. The coagulation bath is an aqueous solution with a bath temperature of 12°C. Then pass through the second coagulation bath, the coagulation bath is an aqueous solution, the bath temperature is 30°C, and then pre-stretched through the third coagulation bath, the coagulation bath is an aqueous solution, the bath temperature is 45°C, and the stretching ratio is 1.2 times. After steam stretching, the stretching temperature is 120°C, and the stretching ratio is 11 times, then washed with water, oiled, and dried at a temperature of 140°C. The dried fiber is crimped at 90°C, then heat-set at 120°C, oiled again, and dried at 110°C to obtain the finished protein-cellulose composite fiber.

Example 3:

Soybean cake is mixed with 10 times the amount of water, soaked at 30°C for 8 hours, and the insoluble polysaccharide residues are separated, and these residues are mixed with water at a ratio of 1:12, and soaked for 1 hour to separate and remove the residues. The two parts of the solution were combined and the pH value of the solution was adjusted to 4.4 with hydrochloric acid and allowed to stand for 2 hours for acid precipitation. The soluble polysaccharide is separated by centrifugation, and the water content of the protein is 15%, and the above-mentioned protein is dissolved in a 9% sodium hydroxide solution to make the protein concentration 25%.

Add 9% sodium hydroxide solution to the cotton pulp for alkalization and oxidative degradation, then add urea at a ratio of 1:3 between cellulose and urea, and heat at 140°C to synthesize cellulose carbamate. Then it is compounded with protein slurry at a ratio of 5:1 between cellulose and protein, mixed into spinning slurry, and left standing for defoaming.

The spinning slurry enters the coagulation bath from the spinneret hole through the metering pump. The coagulation bath is 10% sulfuric acid aqueous solution, and the bath temperature is 50° C. The draw ratio is 1.6 times, and the silk cake is made. Then alkali washing, water washing, oiling, heat setting at 130°C, oiling again, drying at 120°C, winding to obtain protein-cellulose composite fiber filament finished product.

The vegetable protein-cellulose composite fiber that the present invention makes, its remarkable progressive effect is embodied in that its short fiber fineness is 1～7dtex; Dry strength is 1.5～2.7CN/dtex; Wet strength is 0.7～1.7CN/dtex; The length is 10-30%; the uniformity of dyeing (gray card level) ≥ 3.

Claims (6)

1, a kind of preparation method of plant protein-cellulose composite fiber, it is characterized in that containing 10～40% by weight plant protein solution and containing 8～30% by weight cellulose or cellulose carbamate solution, press protein and The cellulose is formulated into a spinning slurry with a weight ratio of 10-50:50-90, and is spun through a wet or dry-wet process. It comes out of the spinneret hole, is solidified in the spinning bath and drawn into a filament, stretched, Alkali washing, water washing, oiling, curling, styling, oiling and drying; the solvents for the above solutions are aqueous solutions of inorganic salts, dimethylformamide or dimethyl sulfoxide, N-methylmorpholine-N-oxide - Hydrate (NMMO·H2O), alkali or acid, the inorganic salt solution is an aqueous solution containing 20-60% by weight of zinc chloride, sodium thiocyanate or potassium thiocyanate. 2. The method for preparing vegetable protein-cellulose composite fibers according to claim 1, characterized in that the vegetable protein solution is extracted from protein-containing plant dregs by solvent method, and the extraction solvent is Water, dilute alkali solution, dilute acid solution and inorganic salt solution; then dissolve the protein to make a protein solution with a concentration of 10-40%, and the solvent is an aqueous solution of inorganic salt, dimethylformamide or dimethyl sulfoxide, N- Methylmorpholine-N-oxide-hydrate (NMMO·H2O), alkali or acid; the described inorganic salt solution is zinc chloride, sodium thiocyanate or potassium thiocyanate containing 20-60% by weight of aqueous solution. 3. The method for preparing vegetable protein-cellulose composite fibers according to claim 1, characterized in that said cellulose solution is prepared by firstly mixing pulp containing more than 90% cellulose or cellulose amino Formate is dissolved in a solvent to make a cellulose solution containing 8 to 30% by weight; the above-mentioned solvent is an aqueous solution of inorganic salt, dimethylformamide or dimethyl sulfoxide, N-methylmorpholine-N- Oxide-hydrate (NMMO·H2O), alkali or acid; the inorganic salt solution is an aqueous solution containing 20-60% by weight of zinc chloride, sodium thiocyanate or potassium thiocyanate. 4. The method for preparing vegetable protein-cellulose composite fibers according to claim 1, characterized in that the mixed slurry comes out of the spinneret holes and is coagulated and drawn into filaments in the spinning bath, and the concentration of the coagulation bath is 1-30% sodium sulfate, sulfuric acid, zinc chloride, zinc sulfate aqueous solution or water, the temperature is 5-70°C. 5. The method for preparing vegetable protein-cellulose composite fibers according to claim 1, characterized in that the drafting temperature is 80-140°C and the drafting ratio is 1-7 times. 6. The method for preparing vegetable protein-cellulose composite fibers according to claim 1, characterized in that the stretching temperature is 80-140°C, the stretching ratio is 5-20 times, and the crimping temperature is 70-110°C. °C, the setting temperature is 80-160 °C; the drying temperature is 80-180 °C.