WO2006081749A1

WO2006081749A1 - Spinning dope of a protein-containing, wave absorbing, shielding, heatabsorbing fibre and the process thereof

Info

Publication number: WO2006081749A1
Application number: PCT/CN2006/000122
Authority: WO
Inventors: Guanqi Li
Original assignee: Guanqi Li
Priority date: 2005-02-05
Filing date: 2006-01-23
Publication date: 2006-08-10
Also published as: CN100420777C; CN1814868A

Abstract

A spinning dope of a protein-containing, wave absorbing, shielding, heatabsorbing fibre is composed of protein(s), polyvinyl alcohol(s), heterocyclic compound(s), and metal-containing substance(s). The composition of the dope is 1-90 parts by weight of protein(s), 99-10 parts by weight of polyvinyl alcohol(s), 0.001-23 parts by weight of heterocyclic compound(s), and 0.001-23 parts by weight of metal-containing substance(s). Processes for preparing the dope are also disclosed. The fibre made from said dope has preferable properties, such as skin-friendly, moisture conductivity, and wear resistance, besides the properties of wave absorbing, shielding, heatabsorbing. The products can bear long period or multi wash cycles without the functional deterioration.

Description

Protein fiber spinning dope with absorbing, shielding and endothermic functions and preparation method thereof

The present invention relates to a spinning dope for producing a protein-containing fiber, and to a method for producing the same.

Background technique

Some of the protein-containing fibers and the method for producing the same are disclosed in the patents No. 99116636.1, 02109966.9, Application No. 03111737.6, 03111814.3. The fibers produced by the protein-containing fibers have better skin-friendly and breathable properties. Moisture permeable, is a very comfortable fiber, 'but these fibers do not have other functions. · In the document of patent application No. 200410010164.9, I disclose a "protein functional fiber" which has more functions, but because the spinning dope is directly related to atoms or ions of metal and non-metal elements. It is difficult to copolymerize and blend protein and bismuth molecular polymers. Therefore, in some cases, metal or non-metal particles adhere to protein-containing fibers. This fiber has good function in the early stage of use, but if used Or, after too many washings, some of the metal or non-metallic particles on the fibers are lost, thereby reducing the functionality of the fibers.

Summary of the invention

The object of the present invention is to provide a protein fiber spinning dope which has both skin-friendly and moisture-conducting properties, and which has the functions of absorbing, shielding and heat absorbing, and can maintain this function for a long period of time, and provides the spinning dope. Production method. ' '

The object of the present invention is achieved by the following technical solutions: a protein fiber spinning dope having absorbing, shielding and endothermic functions, which is made of protein, polyvinyl alcohol, heterocyclic compound and metal element-containing substance. The protein is 1 to 90 parts by weight, the polyvinyl alcohol is 99 to 10 parts by weight, the sum of the two is 100 parts by weight, the heterocyclic compound is 0.001 to 23 parts by weight, and the metal element-containing substance is 0.001 to 23 parts by weight.

The protein is a vegetable protein or a mixture of a vegetable protein and an animal protein. The metal element-containing substance is a metal element or a metal compound.

The metal element is an alkaline earth metal or a transition metal.

The heterocyclic compound is a three-membered heterocyclic compound, a five-membered heterocyclic compound, a six-membered heterocyclic compound, a fused heterocyclic compound, a heterocyclic carbon, a tandem heterocyclic compound, a benzoheterocyclic compound or a heterocyclic derivative. Creature.

The method for producing a protein fiber spinning dope having absorbing, shielding and endothermic functions is as follows: first, protein, polyvinyl alcohol, heterocyclic compound and metal element-containing substance are weighed according to the ratio, and then the least A raw material is prepared into a solution, and the weighed raw materials or solutions thereof are mixed, and finally a mixed liquid containing all the weighed raw materials is prepared, and they are graft copolymerized at a temperature of 15 to 105 ° C. Into the spinning dope.

The step of preparing the mixed solution is: forming the weighed protein into a solution, and then adding a heterocyclic compound, a metal element-containing substance, and polyvinyl alcohol to the solution to prepare a mixed solution.

The step of preparing the mixed liquid may further be: preparing the two raw materials of the weighed protein and the heterocyclic compound into a solution, first adding the metal element-containing substance to the solution made of the heterocyclic compound, and then The mixture is mixed with a protein solution, and then polyvinyl alcohol is added, and finally a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance is prepared.

The step of preparing the mixed solution may further be: forming the two raw materials of the weighed protein and the polyvinyl alcohol into a solution, mixing the heterocyclic compound and the metal element-containing substance to form a solution, and firstly mixing the protein solution with the polymer solution. The vinyl alcohol solution is mixed, and the above two mixed liquid phases are mixed to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

The step of preparing the mixed liquid may further be: forming the two materials containing the metal element and the polyvinyl alcohol into a solution, adding the protein to the solution prepared by the metal element, and mixing The cyclic compound is added to the polyvinyl alcohol solution, and the above two mixed liquid phases are mixed to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

The step of preparing the mixed liquid may further be: forming the two raw materials of the weighed heterocyclic compound and the metal element-containing material into a solution, adding the polyvinyl alcohol to the solution containing the metal element substance, and adding the protein. To the solution of the heterocyclic compound, the above two mixed liquid phases are mixed to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

The step of preparing the mixed solution may further be: forming the weighed protein, the polyvinyl alcohol, the heterocyclic compound and the metal-containing element into a solution, and then mixing the four solutions to form a protein, a polyvinyl alcohol, A solution of a heterocyclic compound and a metal element-containing substance. ·

The step of preparing the mixed liquid may further be: forming the weighed protein and the polyvinyl alcohol into a solution, mixing the heterocyclic compound and the metal element-containing substance to form a solution; and further containing the heterocyclic compound and the metal element-containing substance The solution is added to a polyvinyl alcohol solution to mix them, and then the protein solution is mixed with the solution to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance. The step of preparing the mixed solution may further be: forming the weighed protein into a solution, mixing the heterocyclic compound and the metal-containing element to form a solution; adding the polyvinyl alcohol to the protein solution to prepare a mixed solution, and then A solution containing a heterocyclic compound and a metal element-containing substance is mixed with a solution containing a protein and a polyvinyl alcohol to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

The concentration of the mixture comprising protein, polyvinyl alcohol, heterocyclic compound and metal-containing substance is 7% to 38%.

The spinning dope contains protein, so that the fiber has better skin-friendly and moisture-conducting properties, and the polyvinyl alcohol has good strength and wear resistance, so it has better resistance to the fiber after protein polymerization. Grinding. When the protein is combined with the metal ion in the metal compound, the fiber has a certain function of absorbing, shielding, and endothermic, and the spinning dope in the present invention also incorporates a heterocyclic compound, which makes the metal ion It can form two polymerizations with heterocyclic compounds and proteins, and the reaction is more complete, and it is more firmly bonded to each other, and the protein becomes a metal-containing protein, which produces extremely high biological activity, so the fiber absorbs and shields the fiber. The heat absorption function is better, and the function is not reduced due to the long use period or the number of washings.

detailed description

Example 1. 1 part by weight of pure plant protein, 99 parts by weight of polyvinyl alcohol, 0.001 part by weight of thiazole, and 0.001 part by weight of calcium carbonate were weighed. The plant protein was added to an acidic solution having a pH of 1 to prepare a solution having a concentration of 7.5%, and the thiazole was dissolved in ethanol to prepare a solution having a concentration of 1%. Add calcium carbonate to the thiazole solution, stir well, mix the mixture with the prepared protein solution, and stir it; then add the washed polyvinyl alcohol to the protein, thiazole and calcium carbonate. In the mixed solution, the mixture was uniformly stirred, and their concentrations were adjusted to 7%, and they were graft copolymerized at a temperature of 15 ° C to prepare a spinning dope.

Example 2 90 parts by weight of vegetable protein, 10 parts by weight of polyvinyl alcohol, 23 parts by weight of pyrrole, 1 part by weight of molybdenum chloride and 10 parts by weight of ferrous sulfate were weighed. The pyrrole is made into a solution having a concentration of 5% with an acidic solvent having a pH of 6.5, and then the protein is added to the pyrrole solution to copolymerize them, and the molybdenum chloride and the ferrous sulfate are made into a solution having a concentration of 20%, and then Polyvinyl alcohol is added to a mixed solution of molybdenum chloride and ferrous sulfate, stirred uniformly, and the solution containing protein and pyrrole is mixed with a solution containing molybdenum chloride, ferrous sulfate and polyvinyl alcohol, and mixed. The concentration of the liquid was adjusted to 10%, stirring was continued, and they were graft copolymerized at a temperature of 30 ° C to obtain a spinning dope.

Example 3, 25 parts by weight of vegetable protein, 2 parts by weight of animal protein, 73 parts by weight of polyvinyl alcohol, 4.5 parts by weight of azine, and 4.5 parts by weight of silver nitrate were weighed. Plant protein and animal After the protein is mixed, it is added to an acidic solution with a pH of 4 to prepare a solution having a concentration of 15%, and then the polyvinyl alcohol is washed with water and added to the protein solution, stirred uniformly, and graft copolymerized, and the pyridazine and The silver nitrate was mixed and then added to a hot acid having a pH of 3 to prepare a mixed solution, and the two were copolymerized. The liquid containing protein and polyvinyl alcohol is mixed with a liquid containing azine and silver nitrate, and their concentrations are adjusted to 38%, and graft copolymerization is carried out at a temperature of 25 ° C to prepare a spinning. Stock solution. The polyvinyl alcohol in this embodiment can also be made into a solution, which is added to the protein solution.

Example 4 20 parts by weight of vegetable protein, 25 parts by weight of animal protein, 55 parts by weight of polyvinyl alcohol, 6 parts by weight of pyrimidine and 6 parts by weight of aluminum oxide were weighed. The plant protein and the animal protein are mixed and added to an alkaline solution having a pH of 14 and the concentration is 25%. The pyrimidine is mixed with the aluminum oxide and then added with water to prepare a solution having a concentration of 25%. Polyvinyl alcohol was added to water to a solution having a concentration of 25%. Then, a mixture containing pyrimidine and aluminum oxide is added to the polyvinyl alcohol solution, stirred uniformly, and then the protein solution is added, and copolymerized at a temperature of 80 ° C to prepare a spinning solution having a concentration of 25%. Silk stock solution.

Example 5 80 parts by weight of plant protein, 20 parts by weight of polyvinyl alcohol, 23 parts by weight of quinoline, and 0.001 parts by weight of triiron tetroxide were weighed according to the ratio. Add the protein to the acidic solution with a pH of 5, prepare a solution with a concentration of 15%, add the quinoline directly to the protein solution, stir evenly, let them copolymerize, then add the fine powder of ferroferric oxide, stir evenly. And keeping their temperature at 90 ° C, continue copolymerization and blending, then add water-washed polyvinyl alcohol to the mixed solution, adjust the concentration to 17%, stir evenly, and keep their temperature at At 90 ° C, they are blended and copolymerized, and finally become a spinning dope.

Example 6. 50 parts by weight of vegetable protein, 50 parts by weight of polyvinyl alcohol, 10 parts by weight of benzofuran, 10 parts by weight of acridine, and 15 parts by weight of palladium nitrate were weighed. The plant protein was added to an acidic solution having a pH of 6.5 to prepare a solution having a concentration of 18%, and the benzofuran and acridine were mixed and dissolved to prepare a solution having a concentration of 10%. Palladium nitrate is added to a solution containing benzofuran and acridine, and stirred uniformly, and the mixture is added to the prepared protein solution and stirred uniformly; then the washed polyvinyl alcohol is added to the protein. In a mixture of benzofuran, acridine and palladium nitrate, the mixture was stirred uniformly, and their concentrations were adjusted to 15%, and they were graft copolymerized at a temperature of 7QO to prepare a spinning dope. '

Example 7 20 parts by weight of vegetable protein, 80 parts by weight of polyvinyl alcohol, 5 parts by weight of melamine, 3 parts by weight of isoquinoline and 6 parts by weight of cobalt carbonate were weighed. After mixing melamine and isoquinoline, it is dissolved to prepare a solution having a concentration of 5%, and then the protein is added to the solution to copolymerize them, and cobalt carbonate is made into a solution having a concentration of 10%, and then polyvinyl alcohol is prepared. Add A to the cobalt carbonate solution, stir Mix well, then mix the solution containing protein, melamine and isoquinoline with the solution containing cobalt carbonate and polyvinyl alcohol, let them stand at 105 ° C, let the concentration reach 15%, that is, make the spinning Silk stock solution. .

Example 8, weighing 55 parts by weight of vegetable protein, 10 parts by weight of animal protein, 35 parts by weight of polyvinyl alcohol, 10 parts by weight of imidazole, 5 parts by weight of pyridine, 3 parts by weight of titanium trichloride, 10 parts by weight of zinc sulfate, and 10 parts by weight of magnesium chloride. The plant protein and the animal protein are mixed and added to an alkaline solution having a pH of 13 to prepare a solution having a concentration of 20%, and the polyvinyl alcohol is washed with water and added to the protein solution, and stirred uniformly to graft them. Copolymerization. Imidazole, pyridine, titanium trichloride, zinc sulfate and magnesium chloride are mixed and dissolved in water to prepare a solution. The liquid containing the protein and polyvinyl alcohol is mixed with a liquid containing imidazole, pyridine, titanium trichloride, zinc sulfate and magnesium chloride, and their concentrations are adjusted to 13% at a temperature of 55 ° C. Graft copolymerization to form a spinning dope.

Example 9. 5 parts by weight of plant protein, 5 parts by weight of animal protein, 90 parts by weight of polyvinyl alcohol, 12 parts by weight of polythiophene, and 8 parts by weight of nickel sulfate were weighed according to the ratio. The plant protein and the animal protein are mixed, added to an alkaline solution having a pH of 7.5, and the concentration is 38%. The polythiophene and the nickel sulfate are mixed to prepare a solution, and the polyvinyl alcohol is added to water to prepare a concentration of 35% solution. Then, the mixture containing polythiophene and nickel sulfate is mixed with the polyvinyl alcohol solution, stirred uniformly, and then the protein solution is added, and they are uniformly mixed, and then copolymerized at a temperature of 65 ° C to prepare a concentration of 30% spinning solution.

Example 10 35 parts by weight of plant protein, 65 parts by weight of polyvinyl alcohol, 0.1 part by weight of triazoleazole boron, and 2.5 parts by weight of copper sulfate were weighed. Add the protein to the acidic solution with a pH of 3, make a solution with a concentration of 30%, add the triazoleazole boron directly to the protein solution, stir evenly, let them copolymerize, then add copper sulfate, stir evenly, and Their temperature was maintained at 60 ° C, then water-washed polyvinyl alcohol was added to the mixed solution, and the concentration was adjusted to 27%, stirred evenly, and their temperature was maintained at 60 ° C. The mixed copolymerization finally becomes a spinning dope.

Example 11 70 parts by weight of vegetable protein, 30 parts by weight of polyvinyl alcohol, 10 parts by weight of 8-hydroxyquinoline, and 5 parts by weight of zirconium tetrachloride were weighed. The plant protein is added to an alkaline solution having a pH of 12, and a solution having a concentration of 18% is prepared, and 8-hydroxyquinoline is dissolved in an acid to prepare a solution. Adding zirconium tetrachloride to the acid solution of 8-hydroxyquinoline, stirring and hooking, adding the mixture to the prepared protein solution, and stirring uniformly; then adding the washed polyvinyl alcohol Into a mixture of protein, 8-hydroxyquinoline and zirconium tetrachloride, stir evenly, adjust their concentration to 18%, and graft copolymerize them at 85 °C to form a spinning Stock solution.

Example 12, weighing 5 parts by weight of vegetable protein, 95 parts by weight of polyvinyl alcohol, and phenyl boron 2 Parts by weight, 2 parts by weight of bismuth, 1 part by weight of chromium chloride and 0.5 parts by weight of cobalt carbonate. The benzene boron and the hydrazine are mixed and dissolved, and a solution having a concentration of 5% is prepared, and then the protein is added to the solution to copolymerize them, and chromium chloride and cobalt carbonate are made into a solution having a concentration of 10%. Then, the polyvinyl alcohol is added to the solution containing the chloride chloride and the cobalt carbonate, stirred uniformly, and the solution containing the protein, benzo boron and hydrazine is mixed with the solution containing chromium chloride, cobalt carbonate and polyvinyl alcohol. And the concentration of the mixture was adjusted to 16%, stirring was continued, and they were graft copolymerized at a temperature of 105 ° C to obtain a spinning dope.

Example 13 10 parts by weight of vegetable protein, 30 parts by weight of animal protein, 60 parts by weight of polyvinyl alcohol, 4.5 parts by weight of phenanthrenequinone and 4 parts by weight of manganese chloride were weighed. The plant protein and the animal protein are mixed and added to an acidic solution having a pH of 6 to prepare a solution having a concentration of 22%, and the polyvinyl alcohol is washed with water and added to the protein solution, and stirred uniformly to graft copolymerize them. Mixing phenanthrene with manganese chloride, and then adding it to a hot acid of pH 5 to make a mixture, and mixing the liquid containing protein and polyvinyl alcohol with the liquid containing nitrogen phenanthrene and manganese chloride. And adjusting their concentration to 15%, graft copolymerization at a temperature of 75 ° C, to make a spinning dope.

Example 14. 3 parts by weight of plant protein, 25 parts by weight of animal protein, 72 parts by weight of polyvinyl alcohol, 16 parts by weight of chlorotriazine and 6 parts by weight of silver powder were weighed according to the ratio. Mixing plant protein and animal protein, adding it to an alkaline solution with a pH of 14 and making it 15%, making chlorotriazine into a solution with a concentration of 25%, putting silver into dilute hydrochloric acid, and collecting The vinyl alcohol was dissolved in water to make a solution having a concentration of 25%. Then, they were mixed, and the concentration was adjusted to 18%, and after stirring, they were graft copolymerized at a temperature of 95 ° C to prepare a spinning dope.

Example 15 13 parts by weight of vegetable protein, 87 parts by weight of polyvinyl alcohol, 23 parts by weight of thiazole, and 1 part by weight of copper fine particles were weighed. Add the protein to the acidic solution with a pH of 3.5 to prepare a solution with a concentration of 10%. Dissolve the thiazole and add it to the protein solution. Stir well, let them copolymerize, then add copper particles, stir evenly, and continue copolymerization. Then, the water-washed polyvinyl alcohol was added to the mixed solution, and the concentration was adjusted to 7%, the mixture was uniformly stirred, and their temperatures were maintained at 80 ° C, and they were blended and copolymerized, and finally became a spinning dope.

Example 16: 35 parts by weight of vegetable protein, 65 parts by weight of polyvinyl alcohol, 10 parts by weight of bipyridine, 3 parts by weight of pyrrole, and 0.5 parts by weight of nickel were weighed. The plant protein was added to an acidic solution having a pH of 4 to prepare a solution having a concentration of 12%, and bipyridine and pyrrole were mixed and dissolved in an organic solvent to prepare a solution having a concentration of 10%. Add the particulate nickel to the solution containing bipyridine and pyrrole, stir well, mix the mixture with the prepared protein solution, and stir evenly; then add the washed polyvinyl alcohol to the protein. In a mixture of bipyridine, pyrrole and nickel, stir evenly, adjust their concentration to 15%, and graft copolymerize them at a temperature of 50 °C. That is, a spinning dope is prepared.

Example 17. 20 parts by weight of vegetable protein, 80 parts by weight of polyvinyl alcohol, 5 parts by weight of aziridine and 2 parts by weight of cobalt carbonate were weighed. Aziridine is made into a solution having a concentration of 5%, and then the protein is added to the solution, and they are mixed and copolymerized, cobalt carbonate is made into a solution having a concentration of 10%, and then polyvinyl alcohol is added to the cobalt carbonate solution. , let them mix and copolymerize, then mix the solution containing protein and aziridine with the solution containing cobalt carbonate and polyvinyl alcohol, adjust the concentration of the mixture to 18%, continue to stir, let them at 98 ° C Graft copolymerization at a temperature to obtain a spinning dope.

• Example 18: 15 parts by weight of vegetable protein, 50 parts by weight of animal protein, 35 parts by weight of polyvinyl alcohol, 10 parts by weight of porphyrin, 5 parts by weight of pyridine, and 10 parts by weight of magnesium oxide were weighed. The plant protein and the animal protein are mixed and added to an alkaline solution having a pH of 11 to prepare a solution having a concentration of 15%, and then the polyvinyl alcohol is washed with water and added to the protein solution, and the mixture is stirred to make them Branch copolymerization. After mixing porphyrin, pyridine and magnesium oxide, a solution is prepared. The liquid containing the protein and polyvinyl alcohol is mixed with a liquid containing porphyrin, pyridine, and magnesium oxide, and their concentrations are adjusted to 13%, and graft copolymerization is carried out at a temperature of 85 ° C. Into the spinning dope. The polyvinyl alcohol to be added to the protein solution in this embodiment may also be a polyvinyl alcohol solution.

Example 19 5 parts by weight of plant protein, 25 parts by weight of animal protein, 70 parts by weight of polyvinyl alcohol, 12 parts by weight of imidazole, and 8 parts by weight of zinc sulfate were weighed according to the ratio. The plant protein and the animal protein are mixed and added to an alkaline solution having a pH of 8 and a concentration of 38%. The imidazole and zinc sulfate are mixed to prepare a solution, and the polyvinyl alcohol is added to water to a concentration of 35. %The solution. Then, a mixture containing imidazole and zinc sulfate is added to the polyvinyl alcohol solution, stirred uniformly, and then the protein solution is added and copolymerized at a temperature of 100 ° C to prepare a spinning solution having a concentration of 20%. Stock solution.

Example 20: 35 parts by weight of vegetable protein, 65 parts by weight of polyvinyl alcohol, 10 parts by weight of benzotriazole, and 2 parts by weight of cerium chloride were weighed. Add the protein to the acidic solution with a pH of 5 to make a solution with a concentration of 20%. Dissolve the benzotriazole and add it to the egg white matter solution. Stir well, then add barium chloride, stir evenly, and then The water-washed polyvinyl alcohol was added to the mixed solution, and the concentration was adjusted to 22%, and the mixture was stirred. During this period, the temperature was maintained at 85 ° C., and they were blended and copolymerized, and finally became a spinning dope. .

In Example 21, 30 parts by weight of vegetable protein, 70 parts by weight of polyvinyl alcohol, 10 parts by weight of cyclopentadiene, and 5 parts by weight of calcium chloride were weighed. The plant protein was added to an alkaline solution having a pH of 12 to prepare a solution having a concentration of 20%. The cyclopentadiene is made into a solution, calcium chloride is added to the solution of cyclopentadiene, and stirred uniformly, and the mixture is mixed with the prepared protein solution and stirred uniformly; then washed with water Polyvinyl alcohol is added to the mixture of protein, cyclopentadiene and calcium chloride In the liquid, the mixture was evenly stirred, and their concentrations were adjusted to 16%, and they were graft copolymerized at a temperature of 45 ° C to prepare a spinning dope.

Example 22: 25 parts by weight of vegetable protein, 75 parts by weight of polyvinyl alcohol, 2 parts by weight of piperidine, 2 parts by weight of pyrazine, 1 part by weight of carbonic acid bonds, and 2 parts by weight of cerium chloride were weighed. The piperidine and pyrazine are mixed and dissolved to prepare a solution having a concentration of 15%, and then the protein is added to the solution to copolymerize them, and nickel carbonate and barium chloride are made into a solution having a concentration of 10%, and then Polyvinyl alcohol is added to a solution containing nickel carbonate and cesium chloride, stirred and hooked, and the solution containing protein, piperidine and pyrazine is mixed with a solution containing nickel carbonate, cesium chloride and polyvinyl alcohol. The concentration of the mixture was adjusted to 16%, stirring was continued, and they were copolymerized at a temperature of 100 ° C to obtain a spinning dope.

In Example 23, 70 parts by weight of vegetable protein, 5 parts by weight of animal protein, 25 parts by weight of polyvinyl alcohol, 20 parts by weight of spheroidal boron (C ₅₉ B), and 5 parts by weight of ferrous chloride were weighed. After mixing the plant protein and the animal protein, an alkaline solution having a pH of 12 was added to prepare a solution having a concentration of 18%, and the spherical carbon boron was made into a solution. Add ferrous chloride to the ball-boron solution and mix well, then mix the mixture with the prepared protein solution and mix well; then add the washed polyvinyl alcohol to the protein, spheroidal boron In a mixture with ferrous chloride, the mixture was uniformly stirred, and their concentrations were adjusted to 15%, and they were graft copolymerized at a temperature of 85 ° C to prepare a spinning dope.

The spherical carbon boron in this embodiment can also be replaced by a five-membered nitrogen heterocyclic structure C _6Q derivative.

Example 24 28 parts by weight of vegetable protein, 72 parts by weight of polyvinyl alcohol, 5 parts by weight of polypyrrole and 20 parts by weight of silver nitrate were weighed. The polypyrrole is dissolved to prepare a solution having a concentration of 10%, and then the protein is added to the polypyrrole solution to prepare a mixture, which is copolymerized, and the silver nitrate is made into a solution having a concentration of 10%, and then the polyethylene is added. The alcohol is added to the silver nitrate solution, stirred uniformly, and the solution containing the protein and the polypyrrole is mixed with the solution containing the silver nitrate and the polyvinyl alcohol, and the concentration of the mixture is adjusted to 13%, and the stirring is continued. They were graft copolymerized at a temperature of 20 ° C to obtain a spinning dope.

In Example 25, 10 parts by weight of vegetable protein, 30 parts by weight of animal protein, 60 parts by weight of polyvinyl alcohol, 10 parts by weight of tetrazine, and 7 parts by weight of zinc chloride were weighed. The plant protein and the animal protein are mixed and added to an acidic solution having a pH of 6 to prepare a solution having a concentration of 22%, and the polyvinyl alcohol is washed with water and added to the protein solution, and stirred uniformly to graft copolymerize them. The tetrazine is mixed with zinc chloride and then added to an acidic solution having a pH of 4 to copolymerize the two. The liquid containing the protein and polyvinyl alcohol is mixed with the liquid containing tetrazine and zinc chloride, and their concentrations are adjusted to 12%, and graft copolymerization is carried out at a temperature of 105 Torr to prepare a spinning dope. . The polyvinyl alcohol added to the protein solution in this embodiment may also be a polyvinyl alcohol solution. In Example 26, 23 parts by weight of vegetable protein, 15 parts by weight of animal protein, 62 parts by weight of polyvinyl alcohol, 6 parts by weight of cerium, and 2 parts by weight of silver chloride were weighed. The plant protein and the animal protein are mixed and added to an alkaline solution having a pH of 12, and the concentration is 19%. The cerium is mixed with silver chloride to prepare a solution having a concentration of 20%. Dissolved in water to make a 15% solution. Then, the mixture containing strontium and silver chloride is mixed with the polyvinyl alcohol solution, and the mixture is mixed with the protein solution, and their concentrations are adjusted to 16% at a temperature of 70 ° C. Under the graft copolymerization, a spinning dope is prepared.

Example 27 33 parts by weight of vegetable protein, 67 parts by weight of polyvinyl alcohol, 13 parts by weight of thiazole, 5 parts by weight of pyrimidine and 8 parts by weight of copper chloride were weighed. The protein is added to an acidic solution having a pH of 3.5 to prepare a solution having a concentration of 15%. The thiazole and pyrimidine are dissolved in an organic solvent to form a solution, and the copper chloride is added to the acid phase solution to prepare a solution. The solution is made up to a concentration of 15%, and then the four solutions are mixed together, stirred and hooked, and the concentration is adjusted to 17%, so that their temperature is maintained at 98 ° C, they are blended and copolymerized, and finally become spun. Stock solution.

Example 28: 55 parts by weight of vegetable protein, 45 parts by weight of polyvinyl alcohol, 20 parts by weight of hydroxy hydroxypyridine, 3 parts by weight of hydrazine, and 5.5 parts by weight of copper sulfate were weighed. The plant protein was added to an acidic solution having a pH of 4 to prepare a solution having a concentration of 22%, and the hydroxypyridine was mixed with hydrazine and dissolved in an organic solvent to prepare a solution having a concentration of 10%. Adding copper sulfate to the solution containing the hydroxy hydroxypyridine and the hydrazine, stirring uniformly, mixing the mixture with the prepared protein solution, and stirring uniformly; then adding the washed polyvinyl alcohol to the solution In a mixture of protein, hydroxypyridine, hydrazine and copper sulfate, the mixture was uniformly stirred, and their concentrations were adjusted to 15%, and they were graft copolymerized at a temperature of 80 ° C to prepare a spinning dope.

Example 29 50 parts by weight of vegetable protein, 50 parts by weight of polyvinyl alcohol, 15 parts by weight of aziridine, 5 parts by weight of ferrous sulfate, and 22 parts by weight of cobalt carbonate were weighed. The aziridine is made into a solution having a concentration of 8%, and then the protein is added to the solution to copolymerize them, and the ferrous sulfate and the cobalt carbonate are mixed to prepare a solution having a concentration of 10%, and then the polyvinyl alcohol is added. In a mixture of ferrous sulfate and cobalt carbonate, stir well, and then mix the solution containing protein and aziridine with a solution containing ferrous sulfate, cobalt carbonate and polyvinyl alcohol, and adjust the concentration of the mixture. To 20%, stirring was continued, and they were graft copolymerized at a temperature of 88 Torr to obtain a spinning dope.

In Example 30, 25 parts by weight of vegetable protein, 45 parts by weight of animal protein, 35 parts by weight of polyvinyl alcohol, 23 parts by weight of polyporphyrin, and 23 parts by weight of magnesium chloride were weighed. The plant protein and the animal protein are mixed and added to an alkaline solution having a pH of 9 to prepare a solution having a concentration of 15%, and the polyvinyl alcohol is washed with water and added to the protein solution, and stirred uniformly to graft them. Copolymerization. Put After the polyporphyrin and magnesium chloride are mixed, a solution is prepared. Further, a liquid containing protein and polyvinyl alcohol was mixed with a liquid containing polyporphyrin and magnesium chloride, and their concentrations were adjusted to 23%, and graft copolymerization was carried out at a temperature of 55 Torr to prepare a spinning dope.

Example 31: 5 parts by weight of plant protein, 25 parts by weight of animal protein, 70 parts by weight of polyvinyl alcohol, 12 parts by weight of imidazole, 5 parts by weight of tetrazine and 18 parts by weight of zinc sulfate were weighed according to the ratio. The plant protein and the animal protein are mixed and added to an alkaline solution having a pH of 10.5, and the concentration is 26%. The imidazole, the tetrazine and the zinc sulfate are mixed to prepare a solution, and the polyvinyl alcohol is added to water. A solution with a concentration of 35%. Then, a mixture containing imidazole, tetrazine and zinc sulfate is added to the polyvinyl alcohol solution, and after stirring, the protein solution is added, and the concentration is adjusted to 18%, and the copolymerization is carried out at a temperature of 75 ° C. Make a spinning dope. .

Example 32: 15 parts by weight of vegetable protein, 85 parts by weight of polyvinyl alcohol, 10 parts by weight of benzotriazole, and 2 parts by weight of cobalt were weighed. Add the protein to the acidic solution with a pH of 4.5 to make a solution with a concentration of 10%, dissolve the benzotriazole, add it to the protein solution, stir evenly, then add the cobalt particles, stir evenly, and then mix the solution. The water-washed polyvinyl alcohol was added thereto, and the concentration was adjusted to 12%, and the mixture was uniformly stirred. During this period, their temperature was maintained at 85 C, they were blended and copolymerized, and finally, a spinning dope was obtained.

In Example 33, 50 parts by weight of vegetable protein, 50 parts by weight of polyvinyl alcohol, 20 parts by weight of spheroidal carbon nitrogen (C ₅₉ N), and 3 parts by weight of cerium chloride were weighed. The vegetable protein is added to an acidic solution having a pH of 4 to prepare a solution having a concentration of 15%, and the polyvinyl alcohol is washed with water, added to the protein solution, and stirred uniformly to cause graft copolymerization. The ball carbon and nitrogen are mixed and made into a solution. The liquid containing the protein and the polyvinyl alcohol is mixed with the liquid containing the spherical carbon nitrogen and the ruthenium chloride, and the concentration thereof is adjusted to 20%, and graft copolymerization is carried out at a temperature of 75 ° C. Spinning stock solution.

The polyvinyl alcohol used in each of the above examples may be replaced by cellulose or polyacrylic acid or a mixture of acrylonitrile and polyacrylonitrile, and a protein fiber crepe stock solution having absorbing, shielding and endothermic functions can also be obtained.

In addition to the use of plant proteins or mixtures of vegetable proteins and animal proteins, animal proteins can also be used alone.

Before the raw materials are weighed, pure protein can be obtained by the method of producing protein disclosed in the aforementioned patent documents or the other methods for preparing proteins which have been disclosed.

The spinning dope prepared in the present invention can be made into a yarn by the spinning method of the patent document disclosed in the above-mentioned publication, and can also be produced by a conventional synthetic fiber spinning method.

Claims

Claim

1. A protein fiber spinning dope having absorbing, shielding and endothermic functions, which is characterized in that it is made of protein, polyvinyl alcohol, a heterocyclic compound and a metal-containing substance, wherein the protein is 1 to 90. The polyvinyl alcohol is 99 to 10 parts by weight, the sum of the two is 100 parts by weight, the heterocyclic compound is 0.001 to 23 parts by weight, and the metal element-containing substance is 0.001 23 parts by weight.

2. The spinning dope according to claim 1, wherein the protein is a plant protein or a mixture of a vegetable protein and an animal protein.

The spinning dope according to claim 1, wherein the metal element-containing substance is a metal element or a metal compound.

The spinning dope according to claim 3, wherein the metal element is an alkaline earth metal or a transition metal.

The spinning dope according to claim 1, wherein the heterocyclic compound is a three-membered heterocyclic compound, a five-membered heterocyclic compound, a six-membered heterocyclic compound, a fused heterocyclic compound, and a heterocyclic carbon. a series heterocyclic compound, a benzoheterocyclic compound or a heterocyclic derivative.

6. A method for producing a protein fiber spinning dope having absorbing, shielding and endothermic functions according to claim 1, 2, 3, 4 or 5, wherein: the protein is first weighed according to the amount of the compound. a vinyl alcohol, a heterocyclic compound and a metal element-containing substance, and then a minimum of one of the raw materials is made into a solution, and the weighed raw material or a solution thereof is mixed, and finally a mixture containing all the weighed raw materials is prepared. And let them graft copolymerize at a temperature of 15 to 105 ° C to prepare a spinning dope.

The method according to claim 6, wherein the weighed protein is made into a solution, and then a mixed solution of a heterocyclic compound, a metal element-containing substance and polyvinyl alcohol is added to the solution. ' ■

The method according to claim 6, wherein the two raw materials of the weighed protein and the heterocyclic compound are respectively made into a solution, and the metal element-containing substance is first added to the heterocyclic compound/manufacture. In the solution, the mixture is mixed with a protein solution, and then polyvinyl alcohol is added, and finally a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance is prepared.

9. The method according to claim 6, wherein the two raw materials of the weighed protein and the polyvinyl alcohol are separately prepared into a solution, and the heterocyclic compound and the metal element-containing substance are mixed to form a solution. The protein solution is first mixed with a polyvinyl alcohol solution, and the above two mixed liquid phases are mixed to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

10. The manufacturing method according to claim 6, wherein: the weighed metal-containing element is used The two materials of the substance and the polyvinyl alcohol are respectively made into a solution, the protein is added to the solution prepared by the metal element, the heterocyclic compound is added to the polyvinyl alcohol solution, and the two kinds of the above are mixed. The liquid phase is mixed to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

The method according to claim 6, wherein the two raw materials of the weighed heterocyclic compound and the metal element-containing material are respectively made into a solution, and the polyvinyl alcohol is added to the solution containing the metal element substance. Inside, the protein is added to a solution of the heterocyclic compound, and the above two mixed liquid phases are mixed to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

The method according to claim 6, wherein the weighed protein, the polyvinyl alcohol, the heterocyclic compound, and the metal-containing element are respectively made into a solution, and the four solutions are mixed to form a solution. A solution of a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance.

The method according to claim 6, wherein the weighed protein and the polyvinyl alcohol are respectively made into a solution, and the heterocyclic compound and the metal element-containing substance are mixed to form a solution; The compound and the solution containing the metal element substance are added to the polyvinyl alcohol solution to mix them, and then the protein solution is mixed with the solution to prepare a substance containing a protein, a polyvinyl alcohol, a heterocyclic compound and a metal element. Solution.

14. The method according to claim 6, wherein: the weighed protein is made into a solution, and the heterocyclic compound and the metal-containing element are mixed to form a solution; and the polyvinyl alcohol is added to the protein solution. A mixed solution is prepared, and a solution containing a heterocyclic compound and a metal element-containing substance is mixed with a solution containing a protein and a polyvinyl alcohol to prepare a solution containing a protein, a polyvinyl alcohol, a heterocyclic compound, and a metal element-containing substance. .

The method according to claim 6, 7, 8, 9, 10, 11, 12, 13 or 14, characterized in that the protein comprises a protein, a polyvinyl alcohol, a heterocyclic compound and a metal element-containing substance. The concentration of the mixture is 7% to 38%.