CN100420777C - Protein fiber spinning dope capable of absorbing wave, shielding and absorbing heat, and its preparing method - Google Patents
Protein fiber spinning dope capable of absorbing wave, shielding and absorbing heat, and its preparing method Download PDFInfo
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- CN100420777C CN100420777C CNB2005100173603A CN200510017360A CN100420777C CN 100420777 C CN100420777 C CN 100420777C CN B2005100173603 A CNB2005100173603 A CN B2005100173603A CN 200510017360 A CN200510017360 A CN 200510017360A CN 100420777 C CN100420777 C CN 100420777C
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- protein
- polyvinyl alcohol
- heterocyclic compound
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
Abstract
The present invention discloses protein fiber spinning raw liquor capable of absorbing waves, shielding and absorbing heat, which is prepared from 1 to 90 parts by weight of protein, 99 to 10 parts by weight of polyvinyl alcohol, 0.001 to 23 parts by weight of heterocyclic compound and 0.001 to 23 parts by weight of substance containing metallic elements, wherein the sum of the parts by weight of the protein and the polyvinyl alcohol is equal to 100. The present invention also discloses a method for preparing the spinning raw liquor. A fiber made from the spinning raw liquor has the advantages of favorable comfort, moisture conductivity and abrasion resistance, has favorable functions of wave absorption, shielding and heat absorption, and the function abatement caused by use for a long period or wash for many times can not occur.
Description
Technical field
The present invention relates to the spinning solution that a kind of production contains the fiber of protein, relate to the manufacture method of this stoste simultaneously.
Background technology
I once was 99116636.1,02109966.9 in the patent No., application number is to disclose some proteinaceous fiber and manufacture methods thereof in 03111737.6,03111814.3 the document, containing clothing that the fiber production of protein goes out has preferably skin-friendly, gas permeability and leads moist, be the very comfortable fiber of a kind of dress, but these fibers do not possess other functions.I disclose a kind of " protein function fiber " again in the document of number of patent application 200410010164.9, this fiber has more function, but since its spinning solution be with the atom of metal and nonmetalloid or ion directly and protein and high molecular polymer carry out copolymerizing and blending, difficulty is bigger, therefore be in some cases metal or nonmetallic particulate attached to proteinaceous fiber on, this fiber is functional better in the early stage of using, but if use or washing times too much after, metal on some fiber or non-metal particle then can be lost, thereby make the functional reduction of this fiber.
Summary of the invention
The object of the present invention is to provide a kind ofly both to have had skin-friendly and led moistly, have again and inhale ripple, shielding, heat absorption function, and can keep the protein fiber spinning dope of this function for a long time, the manufacture method of this spinning solution is provided simultaneously.
The objective of the invention is to be achieved through the following technical solutions: a kind of protein fiber spinning dope that suction ripple, shielding, heat absorption function are arranged, it is made by the material of protein, polyvinyl alcohol, heterocyclic compound and containing metal element, wherein protein is 1～90 weight portion, polyvinyl alcohol is 99～10 weight portions, sum of the two is 100 weight portions, heterocyclic compound is 0.001～23 weight portion, and the material of containing metal element is 0.001～23 weight portion.
Described protein is the mixture of phytoprotein or phytoprotein and animal protein.
The material of described containing metal element is metal simple-substance or metallic compound.
Described metallic element is alkaline-earth metal or transition metal.
Described heterocyclic compound is three member ring heterocyclic compound, five member ring heterocyclic compound, 6-membered heterocyclic compound, fused heterocyclic compound, assorted ball carbon, series connection heterocyclic compound, Benzoheterocyclic compounds or Hete rocyclic derivatives.
This have the manufacture method of the protein fiber spinning dope of inhaling ripple, shielding, heat absorption function to be: the material that takes by weighing protein, polyvinyl alcohol, heterocyclic compound and containing metal element earlier by proportional quantity respectively, then at least a raw material is wherein made solution, again the raw material that takes by weighing or its solution are mixed mutually, make the mixed liquor that contains the raw material composition that all takes by weighing at last, and allow their graft copolymerization under 15～105 ℃ temperature, make spinning solution.
The step of making mixed liquor is: the protein that takes by weighing is made solution, and the material and the polyvinyl alcohol that add heterocyclic compound, containing metal element then in this solution are made mixed liquor.
The step of making mixed liquor can also be: the protein that takes by weighing and these two kinds of raw materials of heterocyclic compound are made solution respectively, earlier the material of containing metal element is joined in the solution of being made by heterocyclic compound, again this mixed liquor is mixed mutually with protein solution, then add polyvinyl alcohol, make the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element at last.
The step of making mixed liquor can also be: the protein that takes by weighing and these two kinds of raw materials of polyvinyl alcohol are made solution respectively, making solution after the mixing of the material of heterocyclic compound and containing metal element, earlier protein solution is mixed mutually with poly-vinyl alcohol solution, again two kinds of above-mentioned blended liquid phases are mixed and made into the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
The step of making mixed liquor can also be: the material of the containing metal element that takes by weighing and these two kinds of raw materials of polyvinyl alcohol are made solution respectively, protein is joined in the made solution of the material of containing metal element, heterocyclic compound is added in the poly-vinyl alcohol solution, again two kinds of above-mentioned blended liquid phases are mixed and made into the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
The step of making mixed liquor can also be: these two kinds of raw materials of the material of heterocyclic compound that takes by weighing and containing metal element are made solution respectively, polyvinyl alcohol is joined in the solution of containing metal elemental substance, protein is joined in the solution of heterocyclic compound, again two kinds of above-mentioned blended liquid phases are mixed and made into the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
The step of making mixed liquor can also be: the protein that takes by weighing, polyvinyl alcohol, heterocyclic compound and containing metal elemental substance are made solution respectively, again these four kinds of solution are mixed mutually, become the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
The step of making mixed liquor can also be: protein that takes by weighing and polyvinyl alcohol are made solution respectively, making solution after heterocyclic compound and the mixing of containing metal elemental substance; The solution that contains heterocyclic compound and containing metal elemental substance being joined allows them mix mutually again in the poly-vinyl alcohol solution, then again protein solution is mixed mutually with this solution, be made for the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
The step of making mixed liquor can also be: the protein that takes by weighing is made solution, making solution after heterocyclic compound and the mixing of containing metal elemental substance; Polyvinyl alcohol is joined in the protein solution, make mixed liquor, again the solution that contains heterocyclic compound and containing metal elemental substance is mixed mutually with the solution that contains protein and polyvinyl alcohol, be made for the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
The described concentration that comprises the mixed liquor of protein, polyvinyl alcohol, heterocyclic compound and containing metal elemental substance is 7%～38%.
Because of containing protein, institute is so that fiber has preferably skin-friendly and leads moistly in this spinning solution, and polyvinyl alcohol intensity and ABRASION RESISTANCE are good, so the fiber behind it and the polymerization of protein also has ABRASION RESISTANCE preferably.When the metal ion in the protein metallizing thing combines, fiber will have the function of certain suction ripple, shielding, heat absorption, and also added heterocyclic compound in the spinning solution among the present invention, this just make metal ion can and heterocyclic compound and protein between form twice polymerization, react more abundant, be bonded to each other more firmly, and protein is become contain the protein of metal, produced high biologically active, therefore suction ripple, shielding, the heat absorption function of this fiber are better, and can be because of life cycle long or washing times make its hypofunction more.
The specific embodiment
Embodiment 1, take by weighing pure phytoprotein 1 weight portion, polyvinyl alcohol 99 weight portions, thiazole 0.001 weight portion, calcium carbonate 0.001 weight portion respectively.It is in 1 the acid solution that phytoprotein is added pH value, makes concentration and be 7.5% solution, and thiazole is dissolved with ethanol, makes concentration and be 1% solution.Calcium carbonate is joined in the thiazole solution, and stir, more this mixed liquor is mixed mutually with the protein solution of preparation, and stir; Then the polyvinyl alcohol after washing is joined in the mixed liquor of protein, thiazole and calcium carbonate, stir, their concentration is transferred to 7%, and makes their graft copolymerization under 15 ℃ temperature conditions, promptly make spinning solution.
Embodiment 2, take by weighing phytoprotein 90 weight portions, polyvinyl alcohol 10 weight portions, pyrroles's 23 weight portions, molybdenum chloride 1 weight portion and ferrous sulfate 10 weight portions respectively.Is the pyrroles that to make concentration be 5% solution for 6.5 acid flux material with PH, then protein is joined in pyrroles's solution, make their copolymerization, it is 20% solution that molybdenum chloride and ferrous sulfate are made concentration, then polyvinyl alcohol is joined in the mixed solution of molybdenum chloride and ferrous sulfate, stir, the solution that will contain protein and pyrroles again mixes with the solution that contains molybdenum chloride, ferrous sulfate and polyvinyl alcohol, and the concentration of mixed liquor transferred to 10%, continue to stir, allow their graft copolymerization under 30 ℃ temperature, promptly make spinning solution.
Embodiment 3, take by weighing phytoprotein 25 weight portions, animal protein 2 weight portions, polyvinyl alcohol 73 weight portions, pyridazine 4.5 weight portions and silver nitrate 4.5 weight portions respectively.Join pH value after phytoprotein and animal protein mixed and be in 4 the acid solution, make concentration and be 15% solution, again polyvinyl alcohol is joined in the protein solution after washing, stir, make their graft copolymerization, pyridazine is mixed with silver nitrate, then join pH value and be in 3 the hot acid, make mixed liquor, and make the two copolymerization.The liquid that will contain protein and polyvinyl alcohol again is in the same place with the liquid mixing that contains pyridazine and silver nitrate, and their concentration is transferred to 38%, is graft copolymerization under 25 ℃ the condition in temperature, makes spinning solution.Polyvinyl alcohol in the present embodiment also can be made into solution, and this solution is joined in the protein solution.
Embodiment 4, take by weighing phytoprotein 20 weight portions, animal protein 25 weight portions, polyvinyl alcohol 55 weight portions, pyrimidine 6 weight portions and alundum (Al 6 weight portions by proportioning.Join pH value after phytoprotein and animal protein mixed and be in 14 the alkaline solution, and to make its concentration be 25%, to make concentration be 25% solution with adding entry after alundum (Al mixes pyrimidine, and equally polyvinyl alcohol being added entry, to make concentration be 25% solution.Then again the mixed liquor that contains pyrimidine and alundum (Al is joined in the poly-vinyl alcohol solution, after stirring, add protein solution again, and be copolymerization under 80 ℃ the condition in temperature, make concentration and be 25% spinning solution.
Embodiment 5, take by weighing phytoprotein 80 weight portions, polyvinyl alcohol 20 weight portions, quinoline 23 weight portions, tri-iron tetroxide 0.001 weight portion by proportioning.It is in 5 the acid solution that protein is added pH value, makes concentration and be 15% solution, directly adds quinoline in the protein solution, stir, allow their copolymerization, and then add the tri-iron tetroxide fine powder, stir, and make their temperature remain on 90 ℃, continue copolymerizing and blending, then in this mixed solution, add the polyvinyl alcohol after washing, and concentration transferred to 17%, stir, and make their temperature still remain on 90 ℃, allow their blend copolymerization, become spinning solution at last.
Embodiment 6, take by weighing phytoprotein 50 weight portions, polyvinyl alcohol 50 weight portions, benzofuran 10 weight portions, acridine 10 weight portions, palladium nitrate 15 weight portions.It is in 6.5 the acid solution that phytoprotein is added pH value, makes concentration and be 18% solution, and benzofuran and acridine are mixed the back dissolving, makes concentration and be 10% solution.Palladium nitrate is joined in the solution that contains benzofuran and acridine, and stir, more this mixed liquor is joined in the protein solution of preparation, and stir; Then the polyvinyl alcohol after washing is joined in the mixed liquor of protein, benzofuran, acridine and palladium nitrate, stir, their concentration is transferred to 15%, and makes their graft copolymerization under 70 ℃ temperature conditions, promptly make spinning solution.
Embodiment 7, take by weighing phytoprotein 20 weight portions, polyvinyl alcohol 80 weight portions, melamine 5 weight portions, isoquinolin 3 weight portions and cobalt carbonate 6 weight portions respectively.Melamine and isoquinolin are mixed the back dissolving, make concentration and be 5% solution, then protein is joined in this solution, make their copolymerization, it is 10% solution that cobalt carbonate is made concentration, then polyvinyl alcohol is joined in the cobalt carbonate solution, stir, the solution that will contain protein, melamine and isoquinolin again mixes with the solution that contains cobalt carbonate and polyvinyl alcohol, allows them leave standstill under 105 ℃ temperature, make its concentration to 15%, promptly make spinning solution.
Embodiment 8, take by weighing phytoprotein 55 weight portions, animal protein 10 weight portions, polyvinyl alcohol 35 weight portions, imidazoles 10 weight portions, pyridine 5 weight portions, titanium trichloride 3 weight portions, zinc sulfate 10 weight portions and magnesium chloride 10 weight portions respectively.Join pH value after phytoprotein and animal protein mixed and be in 13 the alkaline solution, make concentration and be 20% solution, again polyvinyl alcohol is joined in the protein solution after washing, stir, make their graft copolymerization.Water-soluble imidazoles, pyridine, titanium trichloride, zinc sulfate and magnesium chloride mixing back, make solution.The liquid that will contain protein and polyvinyl alcohol again is in the same place with the liquid mixing that contains imidazoles, pyridine, titanium trichloride, zinc sulfate and magnesium chloride, and their concentration is transferred to 13%, is graft copolymerization under 55 ℃ the condition in temperature, makes spinning solution.
Embodiment 9, take by weighing phytoprotein 5 weight portions, animal protein 5 weight portions, polyvinyl alcohol 90 weight portions, polythiophene 12 weight portions and nickelous sulfate 8 weight portions by proportioning.Join pH value after phytoprotein and animal protein mixed and be in 7.5 the alkaline solution, and to make its concentration be 38%, make solution after polythiophene and nickelous sulfate are mixed, polyvinyl alcohol is added entry, and to make concentration be 35% solution.Then again the mixed liquor that contains polythiophene and nickelous sulfate is mixed mutually with poly-vinyl alcohol solution, after stirring, adds protein solution again, allow them mix after, be copolymerization under 65 ℃ the condition in temperature, make concentration and be 30% spinning solution.
Embodiment 10, take by weighing phytoprotein 35 weight portions, polyvinyl alcohol 65 weight portions, three pyrazoles boron, 0.1 weight portion, copper sulphate 2.5 weight portions by proportioning.It is in 3 the acid solution that protein is added pH value, makes concentration and be 30% solution, directly adds three pyrazoles boron in the protein solution, stir, allow their copolymerization, and then add copper sulphate, stir, and the temperature that makes them remains on 60 ℃, then adds the polyvinyl alcohol after washing in this mixed solution, and concentration is transferred to 27%, stir, and make their temperature still remain on 60 ℃, and allow their blend copolymerization, become spinning solution at last.
Embodiment 11, take by weighing phytoprotein 70 weight portions, polyvinyl alcohol 30 weight portions, oxine 10 weight portions, zirconium chloride 5 weight portions.It is in 12 the alkaline solution that phytoprotein is added pH value, makes concentration and be 18% solution, oxine is dissolved in acid makes solution.Zirconium chloride is joined in the acid solution of oxine, and stir, more this mixed liquor is joined in the protein solution of preparation, and stir; Then the polyvinyl alcohol after washing is joined in the mixed liquor of protein, oxine and zirconium chloride, stir, their concentration is transferred to 18%, and makes their graft copolymerization under 85 ℃ temperature conditions, promptly make spinning solution.
Embodiment 12, take by weighing phytoprotein 5 weight portions, polyvinyl alcohol 95 weight portions, benzene boron 2 weight portions, indoles 2 weight portions, chromium chloride 1 weight portion and cobalt carbonate 0.5 weight portion respectively.Benzene boron and indoles are mixed the back dissolving, make concentration and be 5% solution, then protein is joined in this solution, make their copolymerization, it is 10% solution that chromium chloride and cobalt carbonate are made concentration, then polyvinyl alcohol is joined in the solution that contains chromium chloride and cobalt carbonate, stir, the solution that will contain protein, benzene boron and indoles again mixes with the solution that contains chromium chloride, cobalt carbonate and polyvinyl alcohol, and the concentration of mixed liquor transferred to 16%, continue to stir, allow they under 105 ℃ temperature by the branch copolymerization, promptly make spinning solution.
Embodiment 13, take by weighing luxuriant and rich with fragrance 4.5 weight portions of phytoprotein 10 weight portions, animal protein 30 weight portions, polyvinyl alcohol 60 weight portions, nitrogen and manganese chloride 7 weight portions respectively.Join pH value after phytoprotein and animal protein mixed and be in 6 the acid solution, make concentration and be 22% solution, again polyvinyl alcohol is joined in the protein solution after washing, stir, make their graft copolymerization, the nitrogen phenanthrene is mixed with manganese chloride, then join pH value and be in 5 the hot acid, make mixed liquor, to contain the liquid of protein and polyvinyl alcohol again and contain the nitrogen phenanthrene and be in the same place with the liquid mixing of manganese chloride, and their concentration transferred to 15%, and in temperature graft copolymerization under 75 ℃ the condition, make spinning solution.
Embodiment 14, take by weighing phytoprotein 3 weight portions, animal protein 25 weight portions, polyvinyl alcohol 72 weight portions, chlorotriazine 16 weight portions and silver powder 6 weight portions by proportioning.Join pH value after phytoprotein and animal protein mixed and be in 14 the alkaline solution, and to make its concentration being 15% that it is 25% solution that chlorotriazine is made concentration, and silver is put into watery hydrochloric acid, is the water-soluble concentration of making of polyvinyl alcohol 25% solution.Then again they are mixed mutually, and concentration is transferred to is 18%, stir relief they be graft copolymerization under 95 ℃ the condition in temperature, the spinning solution of making.
Embodiment 15, take by weighing phytoprotein 13 weight portions, polyvinyl alcohol 87 weight portions, thiazole 23 weight portions, copper particulate 1 weight portion by proportioning.It is in 3.5 the acid solution that protein is added pH value, makes concentration and be 10% solution, and thiazole dissolving back is added in the protein solution, stir, allow their copolymerization, and then add the copper particulate, stir, continue copolymerizing and blending, then in this mixed solution, add the polyvinyl alcohol after washing, and concentration is transferred to 7%, stir, and the temperature that makes them remains on 80 ℃, allows their blend copolymerization, becomes spinning solution at last.
Embodiment 16, take by weighing phytoprotein 35 weight portions, polyvinyl alcohol 65 weight portions, bipyridyl 10 weight portions, pyrroles's 3 weight portions, nickel 0.5 weight portion.It is in 4 the acid solution that phytoprotein is added pH value, makes concentration and be 12% solution, bipyridyl and pyrroles is mixed the back use organic solvent dissolution, makes concentration and be 10% solution.Particulate nickel is joined in the solution that contains bipyridyl and pyrroles, and stir, more this mixed liquor is mixed mutually with the protein solution of preparation, and stir; Then the polyvinyl alcohol after washing is joined in the mixed liquor of protein, bipyridyl, pyrroles and nickel, stir, their concentration is transferred to 15%, and makes their graft copolymerization under 50 ℃ temperature conditions, promptly make spinning solution.
Embodiment 17, take by weighing phytoprotein 20 weight portions, polyvinyl alcohol 80 weight portions, aziridine 5 weight portions and cobalt carbonate 2 weight portions respectively.It is 5% solution that aziridine is made concentration, then protein is joined in this solution, make their mix copolymerization, it is 10% solution that cobalt carbonate is made concentration, then polyvinyl alcohol is joined in the cobalt carbonate solution, allow them mix copolymerization, the solution that will contain protein and aziridine again mixes with the solution that contains cobalt carbonate and polyvinyl alcohol, and the concentration of mixed liquor is transferred to 18%, continues to stir, allow their graft copolymerization under 98 ℃ temperature, promptly make spinning solution.
Embodiment 18, take by weighing phytoprotein 15 weight portions, animal protein 50 weight portions, polyvinyl alcohol 35 weight portions, porphyrin 10 weight portions, pyridine 5 weight portions, magnesia 10 weight portions respectively.Join pH value after phytoprotein and animal protein mixed and be in 11 the alkaline solution, make concentration and be 15% solution, again polyvinyl alcohol is joined in the protein solution after washing, stir, make their graft copolymerization.After porphyrin, pyridine and magnesia mixing, make solution.The liquid that will contain protein and polyvinyl alcohol again with contain porphyrin, pyridine and magnesian liquid mixing and be in the same place, and their concentration is transferred to 13%, be graft copolymerization under 85 ℃ the condition in temperature, make spinning solution.In the present embodiment in protein solution added polyvinyl alcohol, also can adopt poly-vinyl alcohol solution.
Embodiment 19, take by weighing phytoprotein 5 weight portions, animal protein 25 weight portions, polyvinyl alcohol 70 weight portions, imidazoles 12 weight portions and zinc sulfate 8 weight portions by proportioning.Join pH value after phytoprotein and animal protein mixed and be in 8 the alkaline solution, and to make its concentration be 38%, make solution after imidazoles and zinc sulfate are mixed, polyvinyl alcohol is added entry, and to make concentration be 35% solution.Then again the mixed liquor that contains imidazoles and zinc sulfate is joined in the poly-vinyl alcohol solution, after stirring, add protein solution again, and be copolymerization under 100 ℃ the condition in temperature, make concentration and be 20% spinning solution.
Embodiment 20, take by weighing phytoprotein 35 weight portions, polyvinyl alcohol 65 weight portions, benzotriazole 10 weight portions, cerium chloride 2 weight portions by proportioning.It is in 5 the acid solution that protein is added pH value, make concentration and be 20% solution, benzotriazole dissolving back is added in the protein solution, stir, and then adding cerium chloride, stir, then in this mixed solution, add the polyvinyl alcohol after washing, and concentration is transferred to 22%, stir, make their temperature remain on 85 ℃ during this period, allow their blend copolymerization, become spinning solution at last.
Embodiment 21, take by weighing phytoprotein 30 weight portions, polyvinyl alcohol 70 weight portions, cyclopentadiene 10 weight portions, calcium chloride 5 weight portions.It is in 12 the alkaline solution that phytoprotein is added pH value, makes concentration and be 20% solution.Cyclopentadiene is made solution, calcium chloride is joined in the solution of cyclopentadiene, and stir, more this mixed liquor is mixed mutually with the protein solution of preparation, and stir; Then the polyvinyl alcohol after washing is joined in the mixed liquor of protein, cyclopentadiene and calcium chloride, stir, their concentration is transferred to 16%, and makes their graft copolymerization under 45 ℃ temperature conditions, promptly make spinning solution.
Embodiment 22, take by weighing phytoprotein 25 weight portions, polyvinyl alcohol 75 weight portions, piperidines 2 weight portions, pyrazine 2 weight portions, nickelous carbonate 1 weight portion and samarium trichloride 2 weight portions respectively.Piperidines and pyrazine are mixed the back dissolving, make concentration and be 15% solution, then protein is joined in this solution, make their copolymerization, it is 10% solution that nickelous carbonate and samarium trichloride are made concentration, then polyvinyl alcohol is joined in the solution that contains nickelous carbonate and samarium trichloride, stir, the solution that will contain protein, piperidines and pyrazine again mixes with the solution that contains nickelous carbonate, samarium trichloride and polyvinyl alcohol, and the concentration of mixed liquor transferred to 16%, continue to stir, allow their graft copolymerization under 100 ℃ temperature, promptly make spinning solution.
Embodiment 23, take by weighing phytoprotein 70 weight portions, animal protein 5 weight portions, polyvinyl alcohol 25 weight portions, ball carbon boron (C
29B) 20 weight portions, frerrous chloride 5 weight portions.After phytoprotein and animal protein mixed, add pH value and be in 12 the alkaline solution, make concentration and be 18% solution, ball carbon boron is made solution.Frerrous chloride is joined in the ball carbon B solution, and stir, more this mixed liquor is mixed mutually with the protein solution of preparation, and stir; Then the polyvinyl alcohol through washing is joined in the mixed liquor of protein, ball carbon boron and frerrous chloride, stir, their concentration is transferred to 15%, and makes their graft copolymerization under 85 ℃ temperature conditions, promptly make spinning solution.
The also available penta azacyclo structure C of ball carbon boron in the present embodiment
60Derivative replaces.
Embodiment 24, take by weighing phytoprotein 28 weight portions, polyvinyl alcohol 72 weight portions, polypyrrole 5 weight portions and silver nitrate 20 weight portions respectively.Polypyrrole is dissolved, make concentration and be 10% solution, then protein is joined in the polypyrrole solution, make mixed liquor, and make their copolymerization, it is 10% solution that silver nitrate is made concentration, then polyvinyl alcohol is joined in the liquor argenti nitratis ophthalmicus, stir, the solution that will contain protein and polypyrrole again mixes with the solution that contains silver nitrate and polyvinyl alcohol, and the concentration of mixed liquor is transferred to 13%, continues to stir, allow their graft copolymerization under 20 ℃ temperature, promptly make spinning solution.
Embodiment 25, take by weighing phytoprotein 10 weight portions, animal protein 30 weight portions, polyvinyl alcohol 60 weight portions, tetrazine 10 weight portions and zinc chloride 7 weight portions respectively.Join pH value after phytoprotein and animal protein mixed and be in 6 the acid solution, make concentration and be 22% solution, again polyvinyl alcohol is joined in the protein solution after washing, stir, make their graft copolymerization, tetrazine is mixed with zinc chloride, then join pH value and be in 4 the acid solution, make the two copolymerization.The liquid that will contain protein and polyvinyl alcohol again is in the same place with the liquid mixing that contains tetrazine and zinc chloride, and their concentration is transferred to 12%, is graft copolymerization under 105 ℃ the condition in temperature, makes spinning solution.In the present embodiment in protein solution added polyvinyl alcohol, also can adopt poly-vinyl alcohol solution.
Embodiment 26, take by weighing phytoprotein 23 weight portions, animal protein 15 weight portions, polyvinyl alcohol 62 weight portions, purine 6 weight portions and silver chlorate 2 weight portions by proportioning.Join pH value after phytoprotein and animal protein mixed and be in 12 the alkaline solution, and to make its concentration being 19%, is purine 20% solution with making concentration after silver chlorate mixes, and is the water-soluble concentration of making of polyvinyl alcohol 15% solution.Then mix mutually with poly-vinyl alcohol solution with the mixed liquor of silver chlorate containing purine, this again mixed liquor mixes mutually with protein solution, and their concentration is transferred to 16% again, is graft copolymerization under 70 ℃ the condition in temperature, makes spinning solution.
Embodiment 27, take by weighing phytoprotein 33 weight portions, polyvinyl alcohol 67 weight portions, thiazole 13 weight portions, pyrimidine 5 weight portions and copper chloride 8 weight portions by proportioning.It is in 3.5 the acid solution that protein is added pH value, make concentration and be 15% solution, thiazole and pyrimidine are made solution with organic solvent dissolution, copper chloride is added sour phase solution make solution, it is 15% solution that polyvinyl alcohol is made concentration, then these four kinds of solution are mixed, stir, and concentration is transferred to 17%, make their temperature remain on 98 ℃, allow their blend copolymerization, become spinning solution at last.
Embodiment 28, take by weighing phytoprotein 55 weight portions, polyvinyl alcohol 45 weight portions, quinoline pyridone 20 weight portions, indoles 3 weight portions, copper sulphate 5.5 weight portions.It is in 4 the acid solution that phytoprotein is added pH value, makes concentration and be 22% solution, quinoline pyridone and indoles is mixed the back use organic solvent dissolution, makes concentration and be 10% solution.Copper sulphate is joined in the solution that contains quinoline pyridone and indoles, and stir, more this mixed liquor is mixed mutually with the protein solution of preparation, and stir; Then the polyvinyl alcohol after washing is joined in the mixed liquor of protein, quinoline pyridone, indoles and copper sulphate, stir, their concentration is transferred to 15%, and makes their graft copolymerization under 80 ℃ temperature conditions, promptly make spinning solution.
Embodiment 29, take by weighing phytoprotein 50 weight portions, polyvinyl alcohol 50 weight portions, aziridine 15 weight portions, ferrous sulfate 5 weight portions and cobalt carbonate 22 weight portions respectively.It is 8% solution that aziridine is made concentration, then protein is joined in this solution, make their copolymerization, make concentration after ferrous sulfate and cobalt carbonate mixed and be 10% solution, then polyvinyl alcohol is joined in the mixed liquor of ferrous sulfate and cobalt carbonate, stir, the solution that will contain protein and aziridine again mixes with the solution that contains ferrous sulfate, cobalt carbonate and polyvinyl alcohol, and the concentration of mixed liquor transferred to 20%, continue to stir, allow their graft copolymerization under 88 ℃ temperature, promptly make spinning solution.
Embodiment 30, take by weighing phytoprotein 25 weight portions, animal protein 45 weight portions, polyvinyl alcohol 35 weight portions, poly-porphyrin 23 weight portions, magnesium chloride 23 weight portions respectively.Join pH value after phytoprotein and animal protein mixed and be in 9 the alkaline solution, make concentration and be 15% solution, again polyvinyl alcohol is joined in the protein solution after washing, stir, make their graft copolymerization.After poly-porphyrin and magnesium chloride mixing, make solution.The liquid that will contain protein and polyvinyl alcohol again is in the same place with the liquid mixing that contains poly-porphyrin and magnesium chloride, and their concentration is transferred to 23%, is graft copolymerization under 55 ℃ the condition in temperature, makes spinning solution.
Embodiment 31, take by weighing phytoprotein 5 weight portions, animal protein 25 weight portions, polyvinyl alcohol 70 weight portions, imidazoles 12 weight portions, tetrazine 5 weight portions and zinc sulfate 18 weight portions by proportioning.Join pH value after phytoprotein and animal protein mixed and be in 10.5 the alkaline solution, and to make its concentration be 26%, make solution after imidazoles, tetrazine and zinc sulfate are mixed, polyvinyl alcohol is added entry, and to make concentration be 35% solution.Then the mixed liquor that contains imidazoles, tetrazine and zinc sulfate is joined in the poly-vinyl alcohol solution again, after stirring, add protein solution again, and to transfer its concentration being 18%, is that 75 ℃ following of condition is poly-in temperature, makes spinning solution.
Embodiment 32, take by weighing phytoprotein 15 weight portions, polyvinyl alcohol 85 weight portions, benzotriazole 10 weight portions, cobalt 2 weight portions by proportioning.It is in 4.5 the acid solution that protein is added pH value, make concentration and be 10% solution, benzotriazole dissolving back is added in the protein solution, stir, and then adding cobalt particulate, stir, then in this mixed solution, add the polyvinyl alcohol after washing, and concentration is transferred to 12%, stir, make their temperature remain on 85 ℃ during this period, allow their blend copolymerization, become spinning solution at last.
Embodiment 33, take by weighing phytoprotein 50 weight portions, polyvinyl alcohol 50 weight portions, ball carbon nitrogen (C respectively
29N) 20 weight portions, neodymium chloride 3 weight portions.It is in 4 the acid solution that phytoprotein is joined pH value, makes concentration and be 15% solution, polyvinyl alcohol is joined in the protein solution after washing again, stirs, and makes their graft copolymerization.After ball carbon nitrogen and neodymium chloride mixing, make solution.The liquid that will contain protein and polyvinyl alcohol again is in the same place with the liquid mixing that contains ball carbon nitrogen and neodymium chloride, and their concentration is transferred to 20%, is graft copolymerization under 75 ℃ the condition in temperature, makes spinning solution.
The polyvinyl alcohol that adopts in the various embodiments described above also replaces the mixture of cellulose or polyacrylic acid or acrylonitrile and polyacrylonitrile, can be made into equally to have the protein fiber spinning dope of inhaling ripple, shielding, heat absorption function.
Protein wherein also can adopt animal protein separately except that the mixture that adopts phytoprotein or phytoprotein and animal protein.
Before taking by weighing raw material, can adopt I in the aforementioned patent document disclosed produce method of protein or now disclosed other produce method of protein, produce pure protein.
Made spinning solution among the present invention can adopt me to make silk by the spinning process in aforementioned disclosed patent documentation, and also available existing synthetic fiber spinning process is made silk.
Claims (15)
1. one kind has the protein fiber spinning dope of inhaling ripple, shielding, heat absorption function, it is characterized in that: it is made by the material of protein, polyvinyl alcohol, heterocyclic compound and containing metal element, wherein protein is 1～90 weight portion, polyvinyl alcohol is 99～10 weight portions, sum of the two is 100 weight portions, heterocyclic compound is 0.001～23 weight portion, and the material of containing metal element is 0.001～23 weight portion.
2. spinning solution according to claim 1 is characterized in that: described protein is the mixture of phytoprotein or phytoprotein and animal protein.
3. spinning solution according to claim 1 is characterized in that: the material of described containing metal element is metal simple-substance or metallic compound.
4. spinning solution according to claim 3 is characterized in that: described metallic element is alkaline-earth metal or transition metal.
5. spinning solution according to claim 1 is characterized in that: described heterocyclic compound is three member ring heterocyclic compound, five member ring heterocyclic compound, 6-membered heterocyclic compound, fused heterocyclic compound, assorted ball carbon, series connection heterocyclic compound, Benzoheterocyclic compounds or Hete rocyclic derivatives.
6. make as claim 1,2,3, the 4 or 5 described methods that the protein fiber spinning dope of inhaling ripple, shielding, heat absorption function is arranged, it is characterized in that: the material that takes by weighing protein, polyvinyl alcohol, heterocyclic compound and containing metal element earlier by proportional quantity respectively, then at least a raw material is wherein made solution, again the raw material that takes by weighing or its solution are mixed mutually, make the mixed liquor that contains the raw material composition that all takes by weighing at last, and allow their graft copolymerization under 15～105 ℃ temperature, make spinning solution.
7. manufacture method according to claim 6 is characterized in that: the protein that takes by weighing is made solution, and the material and the polyvinyl alcohol that add heterocyclic compound, containing metal element then in this solution are made mixed liquor.
8. manufacture method according to claim 6, it is characterized in that: the protein that takes by weighing and these two kinds of raw materials of heterocyclic compound are made solution respectively, earlier the material of containing metal element is joined in the solution of being made by heterocyclic compound, again this mixed liquor is mixed mutually with protein solution, then add polyvinyl alcohol, make the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element at last.
9. manufacture method according to claim 6, it is characterized in that: the protein that takes by weighing and these two kinds of raw materials of polyvinyl alcohol are made solution respectively, making solution after the mixing of the material of heterocyclic compound and containing metal element, earlier protein solution is mixed mutually with poly-vinyl alcohol solution, again two kinds of above-mentioned blended liquid phases are mixed and made into the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
10. manufacture method according to claim 6, it is characterized in that: the material of the containing metal element that takes by weighing and these two kinds of raw materials of polyvinyl alcohol are made solution respectively, protein is joined in the made solution of the material of containing metal element, heterocyclic compound is added in the poly-vinyl alcohol solution, again two kinds of above-mentioned blended liquid phases are mixed and made into the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
11. manufacture method according to claim 6, it is characterized in that: these two kinds of raw materials of the material of heterocyclic compound that takes by weighing and containing metal element are made solution respectively, polyvinyl alcohol is joined in the solution of containing metal elemental substance, protein is joined in the solution of heterocyclic compound, again two kinds of above-mentioned blended liquid phases are mixed and made into the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
12. manufacture method according to claim 6, it is characterized in that: the protein that takes by weighing, polyvinyl alcohol, heterocyclic compound and containing metal elemental substance are made solution respectively, again these four kinds of solution are mixed mutually, become the solution of the material that closes protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
13. manufacture method according to claim 6 is characterized in that: protein that takes by weighing and polyvinyl alcohol are made solution respectively, making solution after heterocyclic compound and the mixing of containing metal elemental substance; The solution that contains heterocyclic compound and containing metal elemental substance being joined allows them mix mutually again in the poly-vinyl alcohol solution, then again protein solution is mixed mutually with this solution, be made for the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
14. manufacture method according to claim 6 is characterized in that: the protein that takes by weighing is made solution, making solution after heterocyclic compound and the mixing of containing metal elemental substance; Polyvinyl alcohol is joined in the protein solution, make mixed liquor, again the solution that contains heterocyclic compound and containing metal elemental substance is mixed mutually with the solution that contains protein and polyvinyl alcohol, be made for the solution of the material that contains protein, polyvinyl alcohol, heterocyclic compound and containing metal element.
15. according to claim 6,7,8,9,10,11,12,13 or 14 described manufacture methods, it is characterized in that: the described concentration that comprises the mixed liquor of protein, polyvinyl alcohol, heterocyclic compound and containing metal elemental substance is 7%～38%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100173603A CN100420777C (en) | 2005-02-05 | 2005-02-05 | Protein fiber spinning dope capable of absorbing wave, shielding and absorbing heat, and its preparing method |
| PCT/CN2006/000122 WO2006081749A1 (en) | 2005-02-05 | 2006-01-23 | Spinning dope of a protein-containing, wave absorbing, shielding, heatabsorbing fibre and the process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100173603A CN100420777C (en) | 2005-02-05 | 2005-02-05 | Protein fiber spinning dope capable of absorbing wave, shielding and absorbing heat, and its preparing method |
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| Publication Number | Publication Date |
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| CN1814868A CN1814868A (en) | 2006-08-09 |
| CN100420777C true CN100420777C (en) | 2008-09-24 |
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| WO (1) | WO2006081749A1 (en) |
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| WO2011113446A1 (en) * | 2010-03-17 | 2011-09-22 | Amsilk Gmbh | Method for production of polypeptide containing fibres |
| CN102758265B (en) * | 2012-05-14 | 2014-11-26 | 毛盈军 | Cooling and chilling fiber, preparation method and textile product |
| CN102747440B (en) * | 2012-05-14 | 2014-10-22 | 毛盈军 | Fibers with characteristics of temperature increasing and heat storage, preparation method and textile thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435516A (en) * | 2002-12-12 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Technique for processing regenerated keratin functional fibre |
| CN1478929A (en) * | 2003-07-01 | 2004-03-03 | 郝小生 | Animal and vegetable protein and acrylonitrile grafting copolymerization fiber and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1574545B1 (en) * | 1996-05-10 | 2009-01-28 | Shishiai-Kabushikigaisha | Energy conversion composition |
| CN1168858C (en) * | 2002-01-04 | 2004-09-29 | 李官奇 | Plant protein synthetic fiber and its manufacturing method |
| CN1676689A (en) * | 2004-03-29 | 2005-10-05 | 李官奇 | Protein functional fiber |
-
2005
- 2005-02-05 CN CNB2005100173603A patent/CN100420777C/en not_active Expired - Fee Related
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- 2006-01-23 WO PCT/CN2006/000122 patent/WO2006081749A1/en not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1435516A (en) * | 2002-12-12 | 2003-08-13 | 内蒙古鄂尔多斯羊绒集团有限责任公司 | Technique for processing regenerated keratin functional fibre |
| CN1478929A (en) * | 2003-07-01 | 2004-03-03 | 郝小生 | Animal and vegetable protein and acrylonitrile grafting copolymerization fiber and its manufacturing method |
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| Publication number | Publication date |
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| WO2006081749A1 (en) | 2006-08-10 |
| CN1814868A (en) | 2006-08-09 |
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