CN100398708C - Fiber spinning dope containing protein and its preparing method - Google Patents
Fiber spinning dope containing protein and its preparing method Download PDFInfo
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- CN100398708C CN100398708C CNB2005100173641A CN200510017364A CN100398708C CN 100398708 C CN100398708 C CN 100398708C CN B2005100173641 A CNB2005100173641 A CN B2005100173641A CN 200510017364 A CN200510017364 A CN 200510017364A CN 100398708 C CN100398708 C CN 100398708C
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Abstract
The present invention discloses fiber spinning raw liquor containing protein, which is prepared from 1 to 90 parts by weight of protein, 99 to 10 parts by weight of polyvinyl alcohol and 0.01 to 25 parts by weight of phenol or ether in an aromatic compound, wherein the sum of the parts of the protein and the polyvinyl alcohol is equal to 100. The present invention also discloses a method for preparing the spinning raw liquor. The hydroxyl group on an aroma ring of the phenol can combine with the side chain of the amino group or the carboxy group of the protein to form a stable structure and the ether in aromatic series is a good organic solvent, so various organic components in spinning fibers can be thoroughly dissolved and stably combined together, and thus, the protein has stability; additionally, the phenol or the ether in the aromatic series is a dyeing intermediate, and thus, the produced fibers have good dyeability.
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.But above-mentioned fiber dyeing is relatively poor.
Summary of the invention
The purpose of this invention is to provide the fiber spinning dope that contains protein that a kind of fiber dyeing is better, stability is high, the manufacture method of this stoste is provided simultaneously.
The objective of the invention is to realize: a kind of fiber spinning dope that contains protein by following scheme, it is made by phenol in protein, polyvinyl alcohol and the aromatic compound or ether, wherein protein is 1～90 weight portion, polyvinyl alcohol is 99～10 weight portions, sum of the two is 100 weight portions, and phenol in the aromatic compound or ether are 0.01～25 weight portion.
Described protein is at least a in phytoprotein and the animal protein.
Phenol in the described aromatic compound is 1,4-bisnaphthol, 2,4,6-trichlorophenol, 2,4,6,-T, 4-chloro resorcinol, 2,4,6-tribromphenol, 4-bromo-2,5-chlorophenesic acid, adjacent bromophenol and at least a in the iodophenol.
Ether in the described aromatic compound be trichlorophenol diphenyl ether, 4,4 '-at least a in dibromodiphenyl ether and the 4-dihydroxy diphenyl ether.
This fiber spinning dope that contains protein can be in order to the below manufactured: 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.
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 phenol or ether or its solution in the aromatic compound 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 phenol or ether or its solution and protein or its solution in the aromatic compound in this solution, and stirs.
Making the step that contains all mixed liquors that take by weighing raw material is, phenol in the aromatic compound that takes by weighing or ether are 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, phenol in the protein that takes by weighing, polyvinyl alcohol and the aromatic compound or ether 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 phenol or ether in the aromatic 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 phenol in protein, polyvinyl alcohol and the aromatic compound or ether, hydroxyl on the aromatic rings of phenol can combine with the amino or the carboxylic side-chain of protein, form rock-steady structure, ether in the aromatic series is a kind of good organic solvent, various organic components are fully dissolved and stable bond is rising, institute is so that protein has stability, phenol in the aromatic series or ether mostly are the dyeing intermediate again, so make the fiber of making have good dyeability.
The specific embodiment
Embodiment 1, take by weighing pure phytoprotein 1 weight portion, polyvinyl alcohol 99 weight portions, 1,4-bisnaphthol 0.01 weight portion respectively.It is in 1 the acid flux material that phytoprotein is added 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 1, the 4-bisnaphthol joins in the phytoprotein solution, stir, again poly-vinyl alcohol solution is joined protein and 1, in the mixed liquor of 4-bisnaphthol, their concentration is transferred to 7%, and make their graft copolymerization under 15 ℃ temperature conditions, promptly make spinning solution.
Embodiment 2, take by weighing pure animal protein 90 weight portions, polyvinyl alcohol 10 weight portions, 2,4,6-trichlorophenol, 2,4,6,-T 25 weight portions respectively.It is that to make concentration in 14 the basic solvent be 35% solution that protein is added pH value, again polyvinyl alcohol is joined in the protein solution after washing, add again weigh up 2,4, the 6-trichlorophenol, 2,4,6,-T stirs, and 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, 4-chloro resorcinol 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 pH values be that to make concentration in 6.5 the acid flux material be 28% solution, again the 4-chloro resorcinol is joined in the poly-vinyl alcohol solution and stir, then protein solution is added in the mixed liquor of polyvinyl alcohol and 4-chloro resorcinol, their concentration is transferred to 20%, and make their graft copolymerization under 50 ℃ temperature conditions, promptly make spinning solution.
Embodiment 4, take by weighing pure animal protein 45 weight portions, polyvinyl alcohol 55 weight portions, 2,4,6-tribromphenol 1 weight portion respectively.It is in 2 the acid flux material that protein is added pH value, makes concentration and be 15% solution, and simultaneously polyvinyl alcohol being added water, to make concentration be 9% solution, then take by weighing 2,4, the 6-tribromphenol joins in the protein solution, stirs, again poly-vinyl alcohol solution is joined protein and 2,4, in the mixed liquor of 6-tribromphenol, 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, polyvinyl alcohol 73 weight portions, 4-bromo-2,5-chlorophenesic acid 22 weight portions respectively.Two kinds of protein are mixed the back, and to add 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 4-bromo-2 that weighs up again, the 5-chlorophenesic acid, 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, trichlorophenol diphenyl ether 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 pH value, again the trichlorophenol diphenyl ether is joined in the poly-vinyl alcohol solution and stir, then protein solution is added in the mixed liquor of polyvinyl alcohol and trichlorophenol diphenyl ether, 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, trichlorophenol diphenyl ether 11 weight portions respectively.It is in 13 the basic solvent that protein is added pH value, make concentration and be 10% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 22% solution, then the trichlorophenol diphenyl ether 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 trichlorophenol diphenyl ether, their concentration is transferred to 15%, and make their graft copolymerization under 80 ℃ temperature, promptly make spinning solution.
Embodiment 8, respectively take by weighing pure phytoprotein 55 weight portions, polyvinyl alcohol 45 weight portions, 4,4 '-dibromodiphenyl ether 15 weight portions.It is that to make concentration in 10 the basic solvent be 16% solution that protein is added pH value, again polyvinyl alcohol is joined in the protein solution after washing, add then weigh up 4,4 '-dibromodiphenyl ether, 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, 4,4 '-dibromodiphenyl ether 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 pH value, again 4,4 '-dibromodiphenyl ether joins in the poly-vinyl alcohol solution and stirs, then protein solution add polyvinyl alcohol and 4,4 '-mixed liquor of dibromodiphenyl ether in, 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, 4-dihydroxy diphenyl ether 7 weight portions respectively.It is in 3 the acid flux material that phytoprotein is added pH value, make concentration and be 25% solution, simultaneously polyvinyl alcohol being added alkaline solution, to make concentration be 18% solution, then the 4-dihydroxy diphenyl ether 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 4-dihydroxy diphenyl ether, 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, adjacent bromophenol 2 weight portions respectively.It is that to make concentration in 11 the basic solvent be 15% solution that protein is added pH value, polyvinyl alcohol is joined in the protein solution after washing again, adds the adjacent bromophenol that weighs up 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, 4-dihydroxy diphenyl ether 0.2 weight portion.Polyvinyl alcohol is added entry, and to make concentration be 12% solution, again the 4-dihydroxy diphenyl ether is joined in the poly-vinyl alcohol solution and stir, then two kinds of protein are added in the mixed liquor of polyvinyl alcohol and 4-dihydroxy diphenyl ether, their concentration is transferred to 9%, and make their graft copolymerization under 55 ℃ temperature conditions, promptly make spinning solution.
Embodiment 13, respectively take by weighing pure animal protein 10 weight portions, polyvinyl alcohol 90 weight portions, to iodophenol 2 weight portions, 2,4,6-trichlorophenol, 2,4,6,-T 1 weight portion.It is in 8.5 the basic solvent that protein is added 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 to iodophenol and 2,4, the 6-trichlorophenol, 2,4,6,-T joins in the protein solution, stir, again poly-vinyl alcohol solution is joined in this mixed liquor, their concentration is transferred to 19%, and make their graft copolymerization under 65 ℃ temperature, promptly make spinning solution.
Embodiment 14, take by weighing pure animal protein 31 weight portions, phytoprotein 27 weight portions, polyvinyl alcohol 42 weight portions, adjacent bromophenol 3 weight portions, trichlorophenol diphenyl ether 5 weight portions respectively.Two kinds of protein are mixed the back, and to add 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 adjacent bromophenol and the trichlorophenol diphenyl ether that takes by weighing again, 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, 1,4-bisnaphthol 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 pH value, again 1, the 4-bisnaphthol joins in the poly-vinyl alcohol solution and stirs, then protein solution is added polyvinyl alcohol and 1, in the mixed liquor of 4-bisnaphthol, 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, 4-chloro resorcinol 1.2 weight portions respectively.Two kinds of protein are mixed the back, and to add pH values be in 12 the basic solvent, make concentration and be 33% solution, simultaneously polyvinyl alcohol being added alkaline solution, to make concentration be 15% solution, then the 4-chloro resorcinol 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 4-chloro resorcinol, their concentration is transferred to 21%, and make 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, 4-bromo-2,5-chlorophenesic 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, again polyvinyl alcohol is joined in the protein solution after washing, add the 4-bromo-2 that weighs up again, the 5-chlorophenesic acid, 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-bromo-2,5-chlorophenesic acid 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 pH value, again 4-bromo-2, the 5-chlorophenesic acid joins in the poly-vinyl alcohol solution and stirs, then protein solution is added polyvinyl alcohol and 4-bromo-2, in the mixed liquor of 5-chlorophenesic acid, 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, trichlorophenol diphenyl ether 1.5 weight portions respectively.It is in 1.5 the acid flux material that phytoprotein is added pH value, make concentration and be 27.5% solution, simultaneously polyvinyl alcohol being added acid solution, to make concentration be 14% solution, then the trichlorophenol diphenyl ether 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 trichlorophenol diphenyl ether, 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, 2,4,6-trichlorophenol, 2,4,6,-T 0.05 weight portion respectively.It is that to make concentration in 9.5 the basic solvent be 6% solution that protein is added pH value, again polyvinyl alcohol is joined in the protein solution after washing, add again weigh up 2,4, the 6-trichlorophenol, 2,4,6,-T stirs, and keeps 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, trichlorophenol diphenyl ether 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 pH values be that to make concentration in 2.5 the acid flux material be 16% solution, again the trichlorophenol diphenyl ether is joined in the poly-vinyl alcohol solution and stir, then protein solution is added in the mixed liquor of polyvinyl alcohol and trichlorophenol diphenyl ether, 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 weight portions, polyvinyl alcohol 75 weight portions, to iodophenol 0.8 weight portion.It is in 6 the acid flux material that protein is added pH value, make concentration and be 38% solution, simultaneously polyvinyl alcohol being added water, to make concentration be 10% solution, then take by weighing iodophenol is joined in the protein solution, stir, again poly-vinyl alcohol solution is joined in protein and the mixed liquor to iodophenol, their concentration is transferred to 13%, and make their graft copolymerization under 40 ℃ temperature, promptly make spinning solution.
Embodiment 23, take by weighing pure animal protein 30 weight portions, phytoprotein 53 weight portions, polyvinyl alcohol 17 weight portions, 2,4 respectively, 6-tribromphenol 8 weight portions, 4-bromo-2,5-chlorophenesic acid 4 weight portions, adjacent bromophenol 2 weight portions.Two kinds of protein are mixed the back, and to add 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 take by weighing 2,4,6-tribromphenol, 4-bromo-2,5-chlorophenesic acid and adjacent bromophenol stir, and 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, 4-dihydroxy diphenyl ether 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 pH value, again the 4-dihydroxy diphenyl ether is joined in the poly-vinyl alcohol solution and stir, then protein solution is added in this mixed liquor, their concentration is transferred to 16%, and make their graft copolymerization under 38 ℃ temperature conditions, promptly make spinning solution.
Embodiment 25, respectively take by weighing pure animal protein 6 weight portions, phytoprotein 30 weight portions, polyvinyl alcohol 64 weight portions,, 2,4,6-trichlorophenol, 2,4,6,-T 2.5 weight portions.Two kinds of protein are mixed the back, and to add pH values be in 13 the basic solvent, makes concentration and be 10% solution, and simultaneously polyvinyl alcohol being added water, to make concentration be 21% solution, then take by weighing, 2,4, the 6-trichlorophenol, 2,4,6,-T joins in the protein solution, stirs, again poly-vinyl alcohol solution join protein with, 2,4, in the mixed liquor of 6-trichlorophenol, 2,4,6,-T, 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, trichlorophenol diphenyl ether 1.5 weight portions respectively.The trichlorophenol diphenyl ether is added organic solvent, and to make concentration be 1% solution, protein is added this solution, again polyvinyl alcohol is joined in the mixed liquor that contains trichlorophenol diphenyl ether and protein after washing, stir, keep 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, 1,4-bisnaphthol 20 weight portions, 4-dihydroxy diphenyl ether 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 pH value, again 1,4-bisnaphthol, 4-dihydroxy diphenyl ether join in the poly-vinyl alcohol solution and stir, then protein solution is added in this mixed liquor, their concentration is transferred to 12%, and makes their graft copolymerization under 85 ℃ temperature conditions, promptly make spinning solution.
Embodiment 28, respectively take by weighing pure phytoprotein 55 weight portions, polyvinyl alcohol 45 weight portions, adjacent bromophenol 15 weight portions, 4,4 '-dibromodiphenyl ether 8 weight portions.Adjacent bromophenol and 4,4 '-after mixing, dibromodiphenyl ether makes solution, it is that to make concentration in 6 the acid flux material be 16% solution that protein is added pH value, protein solution join contain adjacent bromophenol and 4,4 '-stir in the solution of dibromodiphenyl ether, 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 29, take by weighing pure animal protein 60 weight portions, polyvinyl alcohol 40 weight portions, 4-bromo-2,5-chlorophenesic acid 5 weight portions, trichlorophenol diphenyl ether 5 weight portions, 4,4 '-dibromodiphenyl ether 10 weight portions.4-bromo-2, the 5-chlorophenesic acid, trichlorophenol diphenyl ether and 4,4 '-after mixing, dibromodiphenyl ether makes 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 pH value, again containing 4-bromo-2, the 5-chlorophenesic acid, trichlorophenol diphenyl ether and 4,4 '-solution of dibromodiphenyl ether 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 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, 1,4-bisnaphthol 7 weight portions respectively.1, it is 5% solution that the 4-bisnaphthol is made concentration, simultaneously polyvinyl alcohol being added water, to make concentration be 18% solution, then the protein that takes by weighing joined 1, in the 4-bisnaphthol solution, stir, again poly-vinyl alcohol solution is joined protein and 1, in the mixed liquor of 4-bisnaphthol, 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, 4-chloro resorcinol 8 weight portions respectively.Adding entry after two kinds of protein and the polyvinyl alcohol mixing, add the 4-chloro resorcinol that weighs up again, they are stirred, make solution, and their concentration is transferred to 14%, keep 70 ℃ of temperature, promptly make spinning solution.
Embodiment 32, take by weighing phytoprotein 16 weight portions, polyvinyl alcohol 84 weight portions, 4-dihydroxy diphenyl ether 2 weight portions, 2,4,6-tribromphenol 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 pH value, again 4-dihydroxy diphenyl ether and 2,4, the 6-tribromphenol 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 9%, and make their graft copolymerization under 65 ℃ temperature conditions, promptly make spinning solution.
Embodiment 33, take by weighing pure animal protein 20 weight portions, phytoprotein 16 weight portions, polyvinyl alcohol 64 weight portions, 4-dihydroxy diphenyl ether 11 weight portions respectively.Two kinds of protein are mixed the back, and to add 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, the 4-dihydroxy diphenyl ether is added ethanol, and to make concentration be 10% solution, above-mentioned three kinds of solution are mixed and made into mixed liquor mutually, stir, and their concentration is transferred to 15%, 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, 4-bromo-2,5-chlorophenesic acid 5 weight portions respectively.It is that to make concentration in 10 the basic solvent be 10% solution that protein is added pH value, again polyvinyl alcohol is joined in the protein solution after washing, add the 4-bromo-2 that takes by weighing again, the 5-chlorophenesic acid, stir, keep 90 ℃ of temperature, and their concentration is transferred to 15%, 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 compound that adds in the various embodiments described above, except that phenol or ether, the also mixture of phenol and ether, they both can select 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 (12)
1. fiber spinning dope that contains protein, it is characterized in that: it is made by phenol in protein, polyvinyl alcohol and the aromatic compound or ether, wherein protein is 1～90 weight portion, polyvinyl alcohol is 99～10 weight portions, sum of the two is 100 weight portions, and phenol in the aromatic compound or ether are 0.01～25 weight portion.
2. the fiber spinning dope that contains protein according to claim 1 is characterized in that: described protein is at least a in phytoprotein and the animal protein.
3. the fiber spinning dope that contains protein according to claim 1, it is characterized in that: the phenol in the described aromatic compound is 1,4-bisnaphthol, 2,4,6-trichlorophenol, 2,4,6,-T, 4-chloro resorcinol, 2,4,6-tribromphenol, 4-bromo-2,5-chlorophenesic acid, adjacent bromophenol and at least a in the iodophenol.
4. the fiber spinning dope that contains protein according to claim 1 is characterized in that: the ether in the described aromatic compound be trichlorophenol diphenyl ether, 4,4 '-at least a in dibromodiphenyl ether and the 4-dihydroxy diphenyl ether.
5. make as claim 1, the 2 or 3 described methods that contain the fiber spinning dope of protein, 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.
6. manufacture method according to claim 5, 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, in this solution, add phenol or ether or its solution in the aromatic compound earlier, add polyvinyl alcohol or its solution again, and stir.
7. manufacture method according to claim 5, 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 phenol or ether or its solution and protein or its solution in the aromatic compound, and stir.
8. manufacture method according to claim 5, it is characterized in that: making the step that contains all mixed liquors that take by weighing raw material is, phenol in the aromatic compound that takes by weighing or ether are made solution, in this solution, add protein or its solution earlier, add polyvinyl alcohol or its solution again, and stir.
9. manufacture method according to claim 5 is characterized in that: making the step that contains all mixed liquors that take by weighing raw material is, phenol in the protein that takes by weighing, polyvinyl alcohol and the aromatic compound or ether are mixed mutually, adds jointly and makes solution in the solvent.
10. manufacture method according to claim 5 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 phenol or ether in the aromatic compound again.
11. as claim 6 or 10 described methods, it is characterized in that: the solvent of described solubilising protein is an acid flux material, its pH value is 1～6.5.
12. as claim 6 or 10 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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| CNB2005100173641A CN100398708C (en) | 2005-02-05 | 2005-02-05 | Fiber spinning dope containing protein and its preparing method |
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| CNB2005100173641A CN100398708C (en) | 2005-02-05 | 2005-02-05 | Fiber spinning dope containing protein and its preparing method |
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| CN100398708C true CN100398708C (en) | 2008-07-02 |
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| CN102154731A (en) * | 2011-01-26 | 2011-08-17 | 尹兆明 | Animal blood protein fiber and preparation method 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 |
| CN1518612A (en) * | 2001-04-02 | 2004-08-04 | ϣ | Silk-based fibre |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518612A (en) * | 2001-04-02 | 2004-08-04 | ϣ | Silk-based fibre |
| 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 |
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| CN1814871A (en) | 2006-08-09 |
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