CN100462487C - Protein fiber spinning dope and its preparing method - Google Patents
Protein fiber spinning dope and its preparing method Download PDFInfo
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- CN100462487C CN100462487C CNB2005100173637A CN200510017363A CN100462487C CN 100462487 C CN100462487 C CN 100462487C CN B2005100173637 A CNB2005100173637 A CN B2005100173637A CN 200510017363 A CN200510017363 A CN 200510017363A CN 100462487 C CN100462487 C CN 100462487C
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Abstract
This invention discloses a protein fiber filature raw solution composed of protein, PVA and aroma group S compound, in which, the protein is 1-90, PVA is 99-10, the sum is 100 and the aroma group S compound is 0.01-25. This invention also discloses a method for manufacturing the filature raw solution. Since the amido, carboxyl, sulfo group, aldehyde group carried on the aroma ring in the compound can combine with the amido or carboxyl side chains, the protein has high stability and the protein is not easy to be analyzed even if the thermal extension temperature reaches to 200deg.C.
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, contain the clothing that the fiber production of protein goes out and have skin-friendly and gas permeability preferably, feel comfortable especially when therefore people wear, this in addition fiber has wide raw material sources, and can increase added value for agricultural byproducts, so the output of protein fibre will improve a lot.In order further to improve the class of this product, need constantly improve its performance.
Summary of the invention
The purpose of this invention is to provide the fiber spinning dope that contains protein that a kind of flexibility and dyeability are better and have high-temperature stability, the manufacture method of this stoste is provided simultaneously.
The objective of the invention is to realize: a kind of protein fiber spinning dope by following scheme, it is made by protein, polyvinyl alcohol and aromatic series sulfur-containing compound, wherein protein is 1～90 weight portion, polyvinyl alcohol is 99～10 weight portions, sum of the two is 100 weight portions, and the aromatic series sulfur-containing compound is 0.01～25 weight portion.
Described protein is at least a in phytoprotein and the animal protein.
Described aromatic series sulfur-containing compound is carboxylic compound, contain the compound of amino compound, halogen-containing compound, hydroxyl and contain at least a in the compound of aldehyde radical.
This protein fiber spinning dope can be in order to the below manufactured: at first take by weighing raw material by proportional quantity, make and contain the mixed liquor that all take by weighing raw material, and allow their graft copolymerization under 15～105 ℃ condition, become the spinning solution that contains protein.
Making the step that contains all mixed liquors that take by weighing raw material is, the protein that takes by weighing is made solution, adds aromatic series sulfur-containing compound or its solution in this solution earlier, adds polyvinyl alcohol or its solution again, and stirs.
Making the step that contains all mixed liquors that take by weighing raw material is, the polyvinyl alcohol that takes by weighing is made solution, adds aromatic series sulfur-containing compound or its solution and protein or its solution in this solution, and stirs.
Making the step that contains all mixed liquors that take by weighing raw material is, the aromatic series sulfur-containing compound that takes by weighing is made solution, adds protein or its solution in this solution earlier, adds polyvinyl alcohol or its solution again, and stirs.
Making the step that contains all mixed liquors that take by weighing raw material is, the protein that takes by weighing, polyvinyl alcohol and aromatic series sulfur-containing compound are mixed mutually, adds jointly and makes solution in the solvent.
Making the step that contains all mixed liquors that take by weighing raw material is, protein is made solution, adds polyvinyl alcohol or its solution in this solution earlier, adds the aromatic series sulfur-containing compound again.
The solvent of described solubilising protein is an acid flux material, and its pH value is 1～6.5.
The solvent of described solubilising protein is a basic solvent, and its pH value is 7.5～14.
Because this spinning solution is to be made by protein, polyvinyl alcohol and aromatic series sulfur-containing compound, in the aromatic series sulfur-containing compound on the aromatic rings with amino, hydroxyl, carboxyl, aldehyde radical, sulfonic group etc. all can combine with the amino or the carboxylic side-chain of protein, make protein have high-temperature stability, even if hot drawing temperature reaches about 200 ℃ in fiber one-tenth silk process, protein also is difficult for decomposing, therefore make protein fibre have more performance, and have good dyeability.This spinning solution also has hygroscopicity preferably, and spun silk flexibility is increased, and antistatic behaviour increases.
The specific embodiment
Embodiment 1, respectively take by weighing pure phytoprotein 1 weight portion, polyvinyl alcohol 99 weight portions, 4,4 '-dihydroxydiphenylsulisomer 0.01 weight portion.It is in 1 the acid flux material that phytoprotein is added the pH value, make concentration and be 7.5% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 8% solution, then take by weighing 4,4 '-dihydroxydiphenylsulisomer joins in the phytoprotein solution, stir, again poly-vinyl alcohol solution join protein and 4,4 '-mixed liquor of dihydroxydiphenylsulisomer in, their concentration is transferred to 7%, and make their graft copolymerization under 15～105 ℃ temperature conditions, promptly make spinning solution.
Embodiment 2, take by weighing pure animal protein 90 weight portions, polyvinyl alcohol 10 weight portions, orthanilic acid 25 weight portions respectively.It is that to make concentration in 14 the basic solvent be 35% solution that protein is added the pH value, again polyvinyl alcohol is joined in the protein solution after washing, add the orthanilic acid that takes by weighing again, stir, their concentration is transferred to 38%, and make their graft copolymerization under 75 ℃ temperature conditions, promptly make spinning solution.
Embodiment 3, take by weighing pure animal protein 20 weight portions, phytoprotein 25 weight portions, polyvinyl alcohol 55 weight portions, a benzenedisulfonic acid 4.5 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 18% solution, two kinds of protein are mixed the back, and to add the pH values be that to make concentration in 6.5 the acid flux material be 28% solution, again a benzenedisulfonic acid is joined in the poly-vinyl alcohol solution and stir, then protein solution is added in the mixed liquor of a polyvinyl alcohol and a benzenedisulfonic acid, their concentration is transferred to 20%, and make their graft copolymerization under 50 ℃ temperature conditions, promptly make spinning solution.
Embodiment 4, respectively take by weighing pure animal protein 45 amounts part, polyvinyl alcohol 55 weight portions, 4,4 '-dichloro diphenyl sulfone 1 weight portion.It is in 2 the acid flux material that protein is added the pH value, make concentration and be 15% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 9% solution, then take by weighing 4,4 '-dichloro diphenyl sulfone joins in the protein solution, stir, again poly-vinyl alcohol solution join protein and 4,4 '-mixed liquor of dichloro diphenyl sulfone in, their concentration is transferred to 7%, and make their graft copolymerization under 50 ℃ temperature, promptly make spinning solution.
Embodiment 5, take by weighing pure animal protein 2 weight portions, phytoprotein 25 weight portions, 73 parts of polyvinyl alcohol, thio phenyl sodium sulfonate 22 weight portions respectively.Two kinds of protein are mixed the back, and to add the pH values be that to make concentration in 7.5 the basic solvent be 15% solution, again polyvinyl alcohol is joined in the protein solution after washing, add the thio phenyl sodium sulfonate that takes by weighing again, stir, keep 25 ℃ of temperature, and their concentration is transferred to 38%, promptly make spinning solution.
Embodiment 6, take by weighing pure phytoprotein 50 weight portions, polyvinyl alcohol 50 weight portions, p-chlorobenzenesulfonic acid 10 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 20% solution, it is that to make concentration in 4.5 the acid flux material be 7% solution that protein is added the pH value, again p-chlorobenzenesulfonic acid is joined in the poly-vinyl alcohol solution and stir, then protein solution is added in the mixed liquor of polyvinyl alcohol and p-chlorobenzenesulfonic acid, their concentration is transferred to 10%, and make their graft copolymerization under 15 ℃ temperature conditions, promptly make spinning solution.
Embodiment 7, take by weighing pure animal protein 30 weight portions, phytoprotein 6 weight portions, polyvinyl alcohol 64 weight portions, metanilic acid 11 weight portions respectively.Two kinds of protein are mixed the back, and to add the pH values be in 13 the basic solvent, make concentration and be 10% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 22% solution, then the metanilic acid that takes by weighing is joined in the protein solution, stir, again poly-vinyl alcohol solution is joined in the mixed liquor of protein and metanilic acid, their concentration is transferred to 15%, and make their graft copolymerization under 80 ℃ temperature, promptly make spinning solution.
Embodiment 8, take by weighing pure phytoprotein 55 weight portions, polyvinyl alcohol 45 weight portions, sulfanilic acid 15 weight portions respectively.It is that to make concentration in 10 the basic solvent be 16% solution that protein is added pH value, polyvinyl alcohol is joined in the protein solution after washing, the sulfanilic acid that takes by weighing of adding again again, stir, keep 90 ℃ of temperature, and their concentration is transferred to 25%, promptly make spinning solution.
Embodiment 9, take by weighing pure animal protein 60 weight portions, polyvinyl alcohol 40 weight portions, 2,4-diamino benzene sulfonic acid 5 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 30% solution, it is that to make concentration in 5 the acid flux material be 36% solution that protein is added the pH value, again 2, the 4-diamino benzene sulfonic acid joins in the poly-vinyl alcohol solution and stirs, then protein solution is added polyvinyl alcohol and 2, in the mixed liquor of 4-diamino benzene sulfonic acid, their concentration is transferred to 30%, and make their graft copolymerization under 105 ℃ temperature conditions, promptly make spinning solution.
Embodiment 10, take by weighing pure phytoprotein 70 weight portions, polyvinyl alcohol 30 weight portions, aniline-2,4-disulfonic acid 7 weight portions respectively.It is in 3 the acid flux material that phytoprotein is added the pH value, make concentration and be 25% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 18% solution, and then the aniline that takes by weighing-2, the 4-disulfonic acid joins in the protein solution, stir, again poly-vinyl alcohol solution is joined protein and aniline-2, in the mixed liquor of 4-disulfonic acid, their concentration is transferred to 17%, and make their graft copolymerization under 40 ℃ temperature, promptly make spinning solution.
Embodiment 11, take by weighing pure animal protein 80 weight portions, polyvinyl alcohol 20 weight portions, 4-chloroaniline-2-sulfonic acid 2 weight portions respectively.It is that to make concentration in 11 the basic solvent be 15% solution that protein is added the pH value, again polyvinyl alcohol is joined in the protein solution after washing, add the 4-chloroaniline-2-sulfonic acid that takes by weighing again, stir, keep 70 ℃ of temperature, and their concentration is transferred to 14%, promptly make spinning solution.
Embodiment 12, take by weighing pure animal protein 6 weight portions, phytoprotein 6 weight portions, polyvinyl alcohol 88 weight portions, 2,5-dichloroaniline-4-sulfonic acid 0.2 weight portion.Polyvinyl alcohol is added entry, and to make concentration be 12% solution, again 2,5-dichloroaniline-4-sulfonic acid joins in the poly-vinyl alcohol solution and stirs, then two kinds of protein are added polyvinyl alcohol and 2, in the mixed liquor of 5-dichloroaniline-4-sulfonic acid, their concentration is transferred to 9%, and makes their graft copolymerization under 55 ℃ temperature conditions, promptly make spinning solution.
Embodiment 13, respectively take by weighing animal protein 10 weight portions, polyvinyl alcohol 90 weight portions, 4,4 '-diamino-diphenylamine-2-sulfonic acid 2 weight portions, 2-amino-phenol-4-sulfonic acid 1 weight portion.It is in 8.5 the basic solvent that protein is added the pH value, make concentration and be 35% solution, simultaneously polyvinyl alcohol being added acid solution, to make concentration be 17% solution, then take by weighing 4,4 '-diamino-diphenylamine-2-sulfonic acid and 2-amino-phenol-4-sulfonic acid joins in the protein solution, stirs, again poly-vinyl alcohol solution is joined in this mixed liquor, their concentration is transferred to 19%, and makes their graft copolymerization under 65 ℃ temperature, promptly make spinning solution.
Embodiment 14, respectively take by weighing pure animal protein 31 weight portions, phytoprotein 27 weight portions, polyvinyl alcohol 42 weight portions, 4,4 '-dichloro diphenyl sulfone 3 weight portions, 2-amino-4-chlorophenol-6-sulfonic acid 5 weight portions.Two kinds of protein are mixed the back, and to add the pH values be that to make concentration in 4 the acid flux material be 10% solution, again polyvinyl alcohol is joined in the protein solution after washing, add again take by weighing 4,4 '-dichloro diphenyl sulfone and 2-amino-4-chlorophenol-6-sulfonic acid, stir, keep 78 ℃ of temperature, and their concentration is transferred to 16.5%, promptly make spinning solution.
Embodiment 15, take by weighing pure phytoprotein 5 weight portions, polyvinyl alcohol 95 weight portions, benzaldehyde-2,4-disulfonic acid 0.1 weight portion.Polyvinyl alcohol is added distilled water, and to make concentration be 24% solution, it is that to make concentration in 5.5 the acid flux material be 16% solution that protein is added the pH value, again benzaldehyde-2, the 4-disulfonic acid joins in the poly-vinyl alcohol solution and stirs, then protein solution is added polyvinyl alcohol and benzaldehyde-2, in the mixed liquor of 4-disulfonic acid, their concentration is transferred to 22%, and make their graft copolymerization under 95 ℃ temperature conditions, promptly make spinning solution.
Embodiment 16, take by weighing pure animal protein 33 weight portions, phytoprotein 33 weight portions, polyvinyl alcohol 34 weight portions, phenylhydrazine-4-sulfonic acid 1.2 weight portions respectively.Polyvinyl alcohol is added alkaline solution, and to make concentration be 15% solution, simultaneously two kinds of protein being mixed the back, to add the pH values be in 12 the basic solvent, make concentration and be 33% solution, then protein solution is joined in the poly-vinyl alcohol solution, make their graft copolymerization, again the phenylhydrazine that takes by weighing-4-sulfonic acid is joined in the mixed liquor of protein and polyvinyl alcohol, stir, their concentration is transferred to 21%, and makes their graft copolymerization under 55 ℃ temperature, promptly make spinning solution.
Embodiment 17, take by weighing pure phytoprotein 20 weight portions, polyvinyl alcohol 80 weight portions, metanilic acid 2 weight portions respectively.It is that to make concentration in 5 the acid flux material be 18% solution that protein is added pH value, polyvinyl alcohol is joined in the protein solution after washing, the metanilic acid that takes by weighing of adding again again, stir, keep 30 ℃ of temperature, and their concentration is transferred to 35%, promptly make spinning solution.
Embodiment 18, take by weighing pure animal protein 30 weight portions, polyvinyl alcohol 70 weight portions, 4,4 '-dihydroxydiphenylsulisomer 0.5 weight portion.Polyvinyl alcohol is added entry, and to make concentration be 38% solution, it is that to make concentration in 10 the basic solvent be 17% solution that protein is added the pH value, again 4,4 '-dihydroxydiphenylsulisomer joins in the poly-vinyl alcohol solution and stirs, then protein solution add polyvinyl alcohol and 4,4 '-mixed liquor of dihydroxydiphenylsulisomer in, their concentration is transferred to 28%, and make their graft copolymerization under 98 ℃ temperature conditions, promptly make spinning solution.
Embodiment 19, take by weighing pure phytoprotein 40 weight portions, polyvinyl alcohol 60 weight portions, 2,5-dichloro phenyl hydrazine-4-sulfonic acid 1.5 weight portions respectively.It is in 1.5 the acid flux material that phytoprotein is added the pH value, make concentration and be 27.5% solution, simultaneously polyvinyl alcohol being added acid solution, to make concentration be 14% solution, then take by weighing 2,5-dichloro phenyl hydrazine-4-sulfonic acid joins in the protein solution, stir, again poly-vinyl alcohol solution is joined protein and 2, in the mixed liquor of 5-dichloro phenyl hydrazine-4-sulfonic acid, their concentration is transferred to 18%, and make their graft copolymerization under 75 ℃ temperature, promptly make spinning solution.
Embodiment 20, take by weighing pure animal protein 15 weight portions, polyvinyl alcohol 85 weight portions, orthanilic acid 0.05 weight portion respectively.Contain amino and sulfonic group in the orthanilic acid simultaneously.It is that to make concentration in 9.5 the basic solvent be 6% solution that protein is added pH value, polyvinyl alcohol is joined in the protein solution after washing, the orthanilic acid that takes by weighing of adding again again, stir, keep 40 ℃ of temperature, and their concentration is transferred to 13%, promptly make spinning solution.
Embodiment 21, take by weighing pure animal protein 70 weight portions, phytoprotein 5 weight portions, polyvinyl alcohol 25 weight portions, a benzenedisulfonic acid 9 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 34% solution, two kinds of protein are mixed the back, and to add the pH values be that to make concentration in 2.5 the acid flux material be 16% solution, again a benzenedisulfonic acid is joined in the poly-vinyl alcohol solution and stir, then protein solution is added in the mixed liquor of a polyvinyl alcohol and a benzenedisulfonic acid, their concentration is transferred to 14.5%, and make their graft copolymerization under 20 ℃ temperature conditions, promptly make spinning solution.
Embodiment 22, respectively take by weighing pure animal protein 25 amounts part, polyvinyl alcohol 75 weight portions, 4,4 '-dichloro diphenyl sulfone 0.8 weight portion.It is in 6 the acid flux material that protein is added the pH value, make concentration and be 38% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 10% solution, then take by weighing 4,4 '-dichloro diphenyl sulfone joins in the protein solution, stir, again poly-vinyl alcohol solution join protein and 4,4 '-mixed liquor of dichloro diphenyl sulfone in, their concentration is transferred to 13%, and make their graft copolymerization under 40 ℃ temperature, promptly make spinning solution.
Embodiment 23, respectively take by weighing pure animal protein 30 weight portions, phytoprotein 53 weight portions, 17 parts of polyvinyl alcohol, N-normal-butyl-N-phenyl taurine 8 weight portions, 4,4 '-dihydroxydiphenylsulisomer 4 weight portions, 4,4 '-dichloro diphenyl sulfone 2 weight portions.Two kinds of protein are mixed the back, and to add the pH values be that to make concentration in 10.5 the basic solvent be 25% solution; again polyvinyl alcohol being added water, to make concentration be 38% solution; then poly-vinyl alcohol solution is joined in the protein solution; add again the N-normal-butyl-N-phenyl taurine, 4,4 take by weighing '-dihydroxydiphenylsulisomer and 4,4 '-dichloro diphenyl sulfone; stir; keep 100 ℃ of temperature, and their concentration is transferred to 27%, promptly make spinning solution.
Embodiment 24, take by weighing pure phytoprotein 3 weight portions, polyvinyl alcohol 97 weight portions, naphthalidine-3,6,8-trisulfonic acid 2.5 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 18% solution, it is that to make concentration in 4.5 the acid flux material be 5% solution that protein is added the pH value, again naphthalidine-3,6, the 8-trisulfonic acid joins in the poly-vinyl alcohol solution and stirs, and then protein solution is added in this mixed liquor, and their concentration is transferred to 16%, and make their graft copolymerization under 38 ℃ temperature conditions, promptly make spinning solution.
Embodiment 25, take by weighing pure animal protein 6 weight portions, phytoprotein 30 weight portions, polyvinyl alcohol 64 weight portions, 1-amino-8-naphthol-3,6-disulfonic acid 2.5 weight portions respectively.Two kinds of protein are mixed the back, and to add the pH values be in 13 the basic solvent, make concentration and be 10% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 21% solution, then the 1-amino-8-naphthol-3 that takes by weighing, the 6-disulfonic acid joins in the protein solution, stir, again poly-vinyl alcohol solution is joined protein and 1-amino-8-naphthol-3, in the mixed liquor of 6-disulfonic acid, their concentration is transferred to 15%, and make their graft copolymerization under 80 ℃ temperature, promptly make spinning solution.
Embodiment 26, take by weighing pure phytoprotein 22 weight portions, polyvinyl alcohol 78 weight portions, anthraquinone-1,8-disulfonic acid 1.5 weight portions respectively.It is that to make concentration in 10 the basic solvent be 10% solution that polyvinyl alcohol is added pH value, protein is joined in the poly-vinyl alcohol solution, the anthraquinone-1 that takes by weighing of adding again again, the 8-disulfonic acid stirs, and keeps 90 ℃ of temperature, and their concentration is transferred to 15%, promptly make spinning solution.
Embodiment 27, take by weighing pure animal protein 65 weight portions, polyvinyl alcohol 35 weight portions, 1,5-dihydroxy anthraquinone-2,6-disulfonic acid 20 weight portions, to carboxyl benzsulfamide 5 weight portions.1,5-dihydroxy anthraquinone-2 contains hydroxyl and sulfonic group simultaneously in the 6-disulfonic acid, be the compound that contains carboxyl to the carboxyl benzsulfamide.Polyvinyl alcohol is added entry, and to make concentration be 20% solution, it is that to make concentration in 4.5 the acid flux material be 13% solution that protein is added the pH value, again 1,5-dihydroxy anthraquinone-2, the 6-disulfonic acid, the carboxyl benzsulfamide joined in the poly-vinyl alcohol solution stir, then protein solution is added in this mixed liquor, their concentration is transferred to 12%, and make their graft copolymerization under 85 ℃ temperature conditions, promptly make spinning solution.
Embodiment 28, take by weighing pure phytoprotein 55 weight portions, polyvinyl alcohol 45 weight portions, sulfanilic acid 15 weight portions, 1,4-diamino-anthraquinone-2,3-disulfonic acid 8 weight portions respectively.It is that to make concentration in 6 the acid flux material be 16% solution that protein is added the pH value, again polyvinyl alcohol is joined in the protein solution after washing, add the sulfanilic acid and 1 that takes by weighing again, 4-diamino-anthraquinone-2, the 3-disulfonic acid stirs, and keeps 90 ℃ of temperature, and their concentration is transferred to 15%, promptly make spinning solution.
Embodiment 29, take by weighing pure animal protein 60 weight portions, polyvinyl alcohol 40 weight portions, 2,4-diamino benzene sulfonic acid 5 weight portions, to chlorine m-nitro sulfonamide 5 weight portions, p-methyl benzenesulfonic acid formicester 10 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 30% solution, it is that to make concentration in 5 the acid flux material be 36% solution that protein is added the pH value, again 2, the 4-diamino benzene sulfonic acid, chlorine m-nitro sulfonamide and p-methyl benzenesulfonic acid formicester joined in the poly-vinyl alcohol solution stir, then protein solution is added in this mixed liquor, their concentration is transferred to 18%, and makes their graft copolymerization under 105 ℃ temperature conditions, promptly make spinning solution.
Embodiment 30, take by weighing pure phytoprotein 70 weight portions, polyvinyl alcohol 30 weight portions, p-methyl benzenesulfonic acid formicester 7 weight portions respectively.It is in 3 the acid flux material that phytoprotein is added the pH value, make concentration and be 25% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 18% solution, then the p-methyl benzenesulfonic acid formicester that takes by weighing is joined in the protein solution, stir, again poly-vinyl alcohol solution is joined in the mixed liquor of protein and p-methyl benzenesulfonic acid formicester, their concentration is transferred to 17%, and make their graft copolymerization under 40 ℃ temperature, promptly make spinning solution.
Embodiment 31, take by weighing pure animal protein 65 weight portions, phytoprotein 15 weight portions, polyvinyl alcohol 20 weight portions, 3,5-two chloro-4-aminobenzene sulfonamides 8 weight portions respectively.Two kinds of protein are mixed the back, and to add the pH values be that to make concentration in 11 the basic solvent be 15% solution, again polyvinyl alcohol is joined in the protein solution after washing, add again take by weighing 3,5-two chloro-4-aminobenzene sulfonamides, stir, keep 70 ℃ of temperature, and their concentration is transferred to 14%, promptly make spinning solution.
Embodiment 32, take by weighing phytoprotein 16 weight portions, polyvinyl alcohol 84 weight portions, 2,5-dichloroaniline-4-sulfonic acid 2 weight portions, phenylhydrazine-4-sulfonic acid 3 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 12% solution, it is that to make concentration in 3.5 the acid flux material be 12% solution that protein is added the pH value, again 2,5-dichloroaniline-4-sulfonic acid and phenylhydrazine-4-sulfonic acid joins in the poly-vinyl alcohol solution and stirs, then protein solution is added in this mixed liquor, their concentration is transferred to 9%, and makes their graft copolymerization under 65 ℃ temperature conditions, promptly make spinning solution.
Embodiment 33, respectively take by weighing pure animal protein 20 weight portions, phytoprotein 16 weight portions, polyvinyl alcohol 64 weight portions, to chlorine m-nitro sulfonamide 11 weight portions.Two kinds of protein are mixed the back, and to add the pH values be in 13 the basic solvent, make concentration and be 10% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 22% solution, protein solution is mixed with poly-vinyl alcohol solution, then in mixed liquor, add take by weighing to chlorine m-nitro sulfonamide, stir, their concentration is transferred to 15%, and make their graft copolymerization under 70 ℃ temperature, promptly make spinning solution.
Embodiment 34, take by weighing pure phytoprotein 22 weight portions, polyvinyl alcohol 78 weight portions, 3,5-two bromo-Sodium p-aminobenzene sulfonats 12 weight portions respectively.It is that to make concentration in 10 the basic solvent be 10% solution that protein is added the pH value, again polyvinyl alcohol is joined in the protein solution after washing, add again take by weighing 3,5-two bromo-Sodium p-aminobenzene sulfonats, stir, keep 90 ℃ of temperature, and their concentration is transferred to 15%, promptly make spinning solution.
Embodiment 35, take by weighing pure phytoprotein 15 weight portions, polyvinyl alcohol 85 weight portions, 1-amino-8-naphthol-3,6-disulfonic acid 1.5 weight portions respectively.1-amino-8-naphthol-3, the 6-disulfonic acid adds organic solvent, and to make concentration be 1% solution, protein is added this solution, again polyvinyl alcohol is joined after washing and contain 1-amino-8-naphthol-3, in the mixed liquor of 6-disulfonic acid and protein, stir, keep 90 ℃ of temperature, and their concentration is transferred to 15%, promptly make spinning solution.
Embodiment 36, take by weighing pure animal protein 65 weight portions, polyvinyl alcohol 35 weight portions, anthraquinone-1,8-disulfonic acid 20 weight portions, 2,5-dichloro phenyl hydrazine-4-sulfonic acid 5 weight portions.Polyvinyl alcohol is added entry, and to make concentration be 20% solution, it is that to make concentration in 4.5 the acid flux material be 13% solution that protein is added the pH value, again anthraquinone-1,8-disulfonic acid, 2,5-dichloro phenyl hydrazine-4-sulfonic acid joins in the poly-vinyl alcohol solution and stirs, and then protein solution is added in this mixed liquor, and their concentration is transferred to 12%, and make their graft copolymerization under 85 ℃ temperature conditions, promptly make spinning solution.
Embodiment 37, take by weighing pure phytoprotein 65 weight portions, polyvinyl alcohol 35 weight portions, phenylhydrazine-4-sulfonic acid 15 weight portions, p-methyl benzenesulfonic acid formicester 8 weight portions respectively.Making solution after phenylhydrazine-4-sulfonic acid and the mixing of p-methyl benzenesulfonic acid formicester, it is that to make concentration in 6 the acid flux material be 16% solution that protein is added the pH value, protein solution joined in the solution that contains phenylhydrazine-4-sulfonic acid and p-methyl benzenesulfonic acid formicester stir, again polyvinyl alcohol is joined in this mixed liquor after washing, stir, and their concentration is transferred to 15%, and keep 90 ℃ of temperature, promptly make spinning solution.
Embodiment 38, take by weighing pure animal protein 40 weight portions, polyvinyl alcohol 60 weight portions, to carboxyl benzsulfamide 5 weight portions, 4,4 '-dihydroxydiphenylsulisomer 5 weight portions a, benzenedisulfonic acid 10 weight portions.To the carboxyl benzsulfamide, 4,4 '-after mixing, dihydroxydiphenylsulisomer and benzenedisulfonic acid make solution, polyvinyl alcohol is added entry, and to make concentration be 30% solution, it is that to make concentration in 5 the acid flux material be 36% solution that protein is added the pH value, again containing to the carboxyl benzsulfamide, 4,4 '-solution of dihydroxydiphenylsulisomer and a benzenedisulfonic acid joins in the poly-vinyl alcohol solution and stirs, then protein solution is added in this mixed liquor, their concentration is transferred to 18%, and make their graft copolymerization under 105 ℃ temperature conditions, promptly make spinning solution.
Embodiment 39, take by weighing pure animal protein 50 weight portions, phytoprotein 30 weight portions, polyvinyl alcohol 20 weight portions, 4-chloroaniline-2-sulfonic acid 8 weight portions respectively.Adding entry after two kinds of protein and the polyvinyl alcohol mixing, add the 4-chloroaniline-2-sulfonic acid that takes by weighing again, they are stirred, make solution, and their concentration is transferred to 14%, keep 70 ℃ of temperature, promptly make spinning solution.
The polyvinyl alcohol that adopts in the various embodiments described above also can replace the mixture of cellulose or polyacrylic acid or acrylonitrile and polyacrylonitrile, makes the protein fiber spinning dope with said function.
The aromatic series sulfur-containing compound that adds in the various embodiments described above both can have been selected the particulate of solid shape for use, also can select solution for use.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 (11)
1. protein fiber spinning dope, it is characterized in that: it is made by protein, polyvinyl alcohol and aromatic series sulfur-containing compound, wherein protein is 1～90 weight portion, polyvinyl alcohol is 99～10 weight portions, sum of the two is 100 weight portions, and the aromatic series sulfur-containing compound is 0.01～25 weight portion.
2. protein fiber spinning dope according to claim 1 is characterized in that: described protein is at least a in phytoprotein and the animal protein.
3. protein fiber spinning dope according to claim 1 is characterized in that: described aromatic series sulfur-containing compound is carboxylic compound, contain the compound of amino compound, halogen-containing compound, hydroxyl and contain at least a in the compound of aldehyde radical.
4. make the method for protein fiber spinning dope as claimed in claim 1, it is characterized in that: at first take by weighing raw material by proportional quantity, make again and contain the mixed liquor that all take by weighing raw material, and allow their graft copolymerization under 15～105 ℃ condition, become the spinning solution that contains protein.
5. method according to claim 4, it is characterized in that: making the step that contains all mixed liquors that take by weighing raw material is, the protein that takes by weighing is made solution, adds aromatic series sulfur-containing compound or its solution in this solution earlier, add polyvinyl alcohol or its solution again, and stir.
6. method according to claim 4, it is characterized in that: making the step that contains all mixed liquors that take by weighing raw material is, the polyvinyl alcohol that takes by weighing is made solution, in this solution, add aromatic series sulfur-containing compound or its solution and protein or its solution, and stir.
7. method according to claim 4, it is characterized in that: making the step that contains all mixed liquors that take by weighing raw material is, the aromatic series sulfur-containing compound that takes by weighing is made solution, adds protein or its solution in this solution earlier, add polyvinyl alcohol or its solution again, and stir.
8. method according to claim 4 is characterized in that: making the step that contains all mixed liquors that take by weighing raw material is, the protein that takes by weighing, polyvinyl alcohol and aromatic series sulfur-containing compound are mixed mutually, adds jointly and makes solution in the solvent.
9. method according to claim 4 is characterized in that: making the step that contains all mixed liquors that take by weighing raw material is, protein is made solution, adds polyvinyl alcohol or its solution in this solution earlier, adds the aromatic series sulfur-containing compound again.
10. as claim 5 or 9 described methods, it is characterized in that: the solvent of described solubilising protein is an acid flux material, and its pH value is 1～6.5.
11. as claim 5 or 9 described methods, it is characterized in that: the solvent of described solubilising protein is a basic solvent, its pH value is 7.5～14.
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| CN100424242C (en) * | 2006-04-28 | 2008-10-08 | 韩晓根 | Zein fiber and its preparing process |
| CN111020734B (en) * | 2019-11-19 | 2022-04-29 | 石家庄学院 | Preparation method of long-acting antibacterial polyester fiber |
| CN115821410A (en) * | 2022-11-24 | 2023-03-21 | 百事基材料（青岛）股份有限公司 | Milk viscose macrobio-fiber and preparation method thereof |
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| US5134031A (en) * | 1990-04-25 | 1992-07-28 | Descente Ltd. | Highly moisture-absorptive fiber |
| CN1207421A (en) * | 1998-07-16 | 1999-02-10 | 深圳市新纶设计工程有限公司 | Method for spinning bio-absorption stanch fibre |
| CN1364948A (en) * | 2001-05-14 | 2002-08-21 | 胡宗善 | Protein synthetic fibre spinning solution and its producing method |
| CN1370856A (en) * | 2002-02-28 | 2002-09-25 | 陈福库 | Regenerated protein fiber and its production process |
| CN1403643A (en) * | 2001-08-30 | 2003-03-19 | 陈福库 | Composite kerating fiber and its production process |
| CN1415646A (en) * | 2002-12-10 | 2003-05-07 | 宋惠远 | Spinning dope of synthetic fiber of phytoprotein and its producing method |
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Patent Citations (6)
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| US5134031A (en) * | 1990-04-25 | 1992-07-28 | Descente Ltd. | Highly moisture-absorptive fiber |
| CN1207421A (en) * | 1998-07-16 | 1999-02-10 | 深圳市新纶设计工程有限公司 | Method for spinning bio-absorption stanch fibre |
| CN1364948A (en) * | 2001-05-14 | 2002-08-21 | 胡宗善 | Protein synthetic fibre spinning solution and its producing method |
| CN1403643A (en) * | 2001-08-30 | 2003-03-19 | 陈福库 | Composite kerating fiber and its production process |
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| CN1415646A (en) * | 2002-12-10 | 2003-05-07 | 宋惠远 | Spinning dope of synthetic fiber of phytoprotein and its producing method |
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