CN1422880A - Plant animal protein and acrylonitrile graft copolymerized fiber spinning dope and its production method - Google Patents
Plant animal protein and acrylonitrile graft copolymerized fiber spinning dope and its production method Download PDFInfo
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- CN1422880A CN1422880A CN 02135873 CN02135873A CN1422880A CN 1422880 A CN1422880 A CN 1422880A CN 02135873 CN02135873 CN 02135873 CN 02135873 A CN02135873 A CN 02135873A CN 1422880 A CN1422880 A CN 1422880A
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Abstract
The invention refers to the fiber-filature original liquid produced by the graft copolymerization of propagation protein and propylene nitrile and the method, animal protein 10-20 shares, plant protein 10-20 shares, the propylene nitrile 60-80 shares. The method; dissolve the propagation protein into the NaOH water solution at 8-10% concentration, stir, gradually raise temperature and add side-chain dressing agent, raise the temperature to 90-98 C degree and mix with zinc chloride water solution, pH 1.9+/-0.15, and redox agent, then make the graft copolymerization reaction with propylene nitrile polymer under the nitrogen protection at 20-75 C degree for 40-180 minutes, and then vacuum-evaporate to obtain the monomer of the invention.
Description
One, technical field
The present invention relates to a kind of spinning solution and production method thereof of novel textile material, especially a kind of animal protein and plant protein blended plant animal protein and acrylonitrile graft copolymer fibre spinning raw liquor and production method thereof.
Two, background technology
The protein fibre of known synthetic, mainly contain casein protein and acrylonitrile graft copolymer fibre, soy-protein and polyvinyl alcohol copolymerized fibre, animal wool protein and polyvinyl alcohol copolymerized fibre, animals and plants mixing protein and polyvinyl alcohol copolymerized fibre; More than various products compare, relatively the quality of casein protein and acrylonitrile graft copolymer fibre is better, but costs an arm and a leg, and output is subjected to the restriction of resource-constrained, no matter this is all can not satisfy the demands from price or on resource.And the protein of all the other several synthetic and polyvinyl alcohol copolymerized fibre, for casein protein and acrylonitrile graft copolymer fibre, though have cheap, the advantage of aboundresources, but quality product is relatively poor relatively, especially the elasticity lustre index is relatively poor, and shortcomings such as the easy fold of fabric are so use range is restricted.
Three, summary of the invention
The present invention's purpose provides a kind of new plant animal protein and acrylonitrile graft copolymer fibre spinning raw liquor and production method thereof.Compare with its currently available products and both to have reduced product cost, guaranteed product performance, solved the relatively poor scarce limit of elasticity color and luster again, widened raw material sources greatly.
The present invention realizes like this; spinning solution is by animal protein 10-20 part; plant protein 10-20 part; vinyl cyanide first monomer or vinyl cyanide first monomer and methymethacrylate or methacrylic acid fourth fat or hydroxyethyl methacrylate second fat second monomer 60-80 part are made; first monomer and second monomer ratio are 90.6: 9.4; its production method is that animal protein and each 10-20 part of plant protein concentration with 8-10% is dissolved in the aqueous sodium hydroxide solution that pH value is 8-10; during dissolving; be warming up to 40-50 ℃ while stirring; after protein fully dissolves; when being warming up to 60-75 ℃; the side chain modifier that adds the 1.5-3% of protein wt is modified; stirred 30-50 minute; be warming up to 90-98 ℃; after insulated and stirred 30-50 minute; be dissolved in altogether with solder(ing)acid again; make the protein after the dissolving; the concentration of solder(ing)acid is controlled at 1.4-3.7% and 55-75% respectively; transferring pH value is 1.9 ± 0.15; after mixing; the oxygenant of the 0.06-0.22% of adding protein and polymerization single polymerization monomer material gross weight and the reductive agent of 0.18-1.1%; then under nitrogen protection; add 60-80 part acrylonitrile polymerization material while stirring; transferring pH value is 1.9 ± 0.15; temperature is to react between 20-75 ℃ after 40-180 minute; steam demonomerization through vacuum; promptly get the spinning solution that concentration is 6.5-9%; select existing acrylic fibre wet spinning technique and equipment then for use, just can spin becomes animals and plants egg-pair white matter and acrylonitrile graft copolymer fibre (long filament or staple fibre all can).
Abundant raw materials of the present invention, cost is low, its production method is simple, and by the fiber that its spinning solution is spun into, its performance is compared with natural protein fibre, the skin-friendly, water absorbability and the ventilation property that not only have natural protein fibre, and soft, gloss is soft, and dyeability is excellent, colour fastness is strong, and intensity surpasses the intensity of natural fiber.Compare with the dairy protein fiber of synthetic, it is low to have a cost, resourceful advantage.Compare with polyvinyl alcohol synthetic fiber with plant protein, it is excellent to have dyeability, and colour fastness is strong, particularly changes the scarce limit of the color and luster and the easy fold of precursor.
Four, embodiment
Below in conjunction with specific embodiment the specific embodiment of the present invention is elaborated.
Get animal protein 10-20 part by weight, plant protein 10-20 part, the two is dissolved in the aqueous sodium hydroxide solution that pH value is 8-10 with the concentration of 8-10% together, during dissolving, stir on one side, be warming up to 40-50 ℃ on one side, after treating that protein fully dissolves, when being warming up to 60-75 ℃, add the modifier of protein wt 1.5-3%, the stirring that does not stop, reacted 30-50 minute, and be warming up to 90-98 ℃, after insulated and stirred 30-50 minute, be dissolved in altogether with solder(ing)acid again, make protein concn after the dissolving at 1.4-3.7%, zinc oxide concentration is at 55-75 ℃, and transferring pH value is 1.9 ± 0.15, after stirring, add protein and the oxygenant of polymerization single polymerization monomer material gross weight 0.06-0.22% and the reductive agent of 0.18-1.1%.Then; under protection of nitrogen gas; stir on one side; add 60-80 part vinyl cyanide first monomer or vinyl cyanide and methyl methacrylate or butyl methacrylate or hydroxyethyl methylacrylate second monomer on one side; and to make first monomer and the second monomeric ratio be 90.6: 9.4; after PH1.9 ± 0.15, temperature are to react 40-180 minute between the 20-75%; steam demonomerization through vacuum, can obtain concentration is the animals and plants mixing protein of 6.5-9% and the spinning solution of vinyl cyanide first monomer or vinyl cyanide first monomer and the second monomer-grafted copolymerization.Below it is to be noted:
Animal protein of the present invention is animal milk casein matter, animal wool keratin like protein matter, animal skin class collagenic protein, (wherein hairs comprises wool, pig hair, yak hair, the rabbit hair, camel hair and chicken, duck, goose, ostrich feather on one's body to insects protein; The skin class comprises ox-hide, pigskin, sheepskin; Insects comprises tenebrio molitor, silkworm chrysalis, chrysalis, grub, fly maggot etc.).
Plant protein of the present invention is the protein that extracts in soybean meal, peanut meal, the Semen Brassicae campestris dregs of rice, cotton seed mill, the oily certain herbaceous plants with big flowers benevolence dregs of rice, sesame seed meal, leached tea oil slag, flaxseed meal, castor seed meal, Endosperm Cocois, the rice bran etc.
Protein side chain modifier of the present invention is hydrogen peroxide or peroxyformic acid or peracetic acid, and modifier accounts for the 1.5-3% of protein wt.
The chlorination zinc concentration is 55-75% (weight) in protein of the present invention and the liquor zinci chloridi, and proteinic concentration is 1.4-3.7%, and pH value is 1.9 ± 0.15.
In the redox system of the present invention, oxygenant is hydrogen peroxide or peroxyformic acid or peracetic acid, and reductive agent is sodium bisulfite or Potassium hydrogen sulfite or xitix, and add-on is respectively the 0.06-0.22% and the 0.18-1.1% of total polymer weight.
Animal protein of the present invention accounts for 10-20 part, plant protein accounts for 10-20 part, acrylonitrile polymerization monomeric substance 60-80 part, acrylonitrile polymerization monomeric substance are vinyl cyanide first monomer or vinyl cyanide first monomer and methyl methacrylate or butyl methacrylate or hydroxyethyl methylacrylate second monomer; First monomer and the second monomeric ratio are 90.6: 9.4.
Below in conjunction with specific examples the present invention is further described:
Example 1; get animal protein 10kg (kilogram; as follows); plant protein 10kg; be dissolved in the aqueous sodium hydroxide solution by 8% concentration together, stir on one side, be warming up to 40 ℃ on one side; after treating that protein all dissolves; when being warming up to 60 ℃, adding protein wt 1.5% is the hydrogen peroxide of 300 grams, insulated and stirred reaction 30 minutes; be warming up to 90 ℃; insulated and stirred is 30 minutes again, again with concentration be 66.7% solder(ing)acid 1179kg blend together, (this moment, proteinic concentration just was 1.4%; the chlorination zinc concentration just is being 55%); add 60 gram hydrogen peroxide again, 180 gram sodium bisulfites, transferring pH value is 1.9 ± 0.15; and after stirring; vacuum pumping is full of nitrogen protection, adds 80kg acrylonitrile polymerization monomer, keeps pH value constant; temperature is 20 ℃; react after 180 minutes, take out again and be that negative pressure steams demonomerization, promptly get concentration and be 6.5% spinning solution.
Example 2, get animal protein 15kg, plant protein 15kg is dissolved in the aqueous sodium hydroxide solution by 9% concentration together, stir on one side, on one side be warming up to 45 ℃, treat that protein fully dissolves after, when being warming up to 65 ℃, the peroxyformic acid that adds protein wt 2%, insulation reaction 40 minutes is warming up to 94 ℃, and insulated and stirred is 40 minutes again, mix mutually with solder(ing)acid, one will to make proteinic concentration be 2.4% in the blended liquid again; Two will to make the chlorination zinc concentration be 60%, and transferring pH value is 1.9 ± 0.15, adds peroxyformic acid 110 grams; bisulfite first 330 grams keep pH value constant, then under protection of nitrogen gas; stir on one side; on one side add 70kg acrylonitrile first monomer and methyl methacrylate second monomer, and to control first monomer be 90.6: 9.4 than second monomer, the maintenance pH value is constant; temperature is 35 ℃; reacted 130 minutes, and behind the demonomerization, just got spinning solution.
Example 3; get animal protein 20kg; plant protein 20kg; be dissolved in the aqueous sodium hydroxide solution by 10% concentration together, stir on one side, be warming up to 50 ℃ on one side; after treating that protein fully dissolves; when being warming up to 70 ℃, add the peracetic acid of protein wt 2.5%, insulation reaction 50 minutes; be warming up to 98 ℃; insulated and stirred is 50 minutes again, again with the solder(ing)acid blend together, and make that Protein content is 3.7% in the mixed solution; the content of zinc chloride is 65% (weight); add 170 gram peracetic acid again, 200 gram xitix, transferring pH value is 1.9 ± 0.15; under protection of nitrogen gas, stir and add 60kg; vinyl cyanide first monomer and methylacrylic acid butyl ester second monomer are 1.9 ± 0.15 keeping pH value, and temperature is 50 ℃; reacted 90 minutes, take off after single spinning property spinning solution preferably.
Example 4: get respectively; each 10kg of plant protein and 20kg; or 20kg and 10kg; be dissolved in the aqueous sodium hydroxide solution by 8.5% concentration together; stirring heats up weighs 47 ℃; after treating that protein fully dissolves, be warming up to 75 ℃, add the peroxyformic acid of protein wt 3%; insulation reaction 45 minutes; be warming up to 93 ℃, insulated and stirred 45 minutes mixes with solder(ing)acid again; make that protein concn is 3.5% in the mixed solution; chlorination zinc concentration 75%, and then add 220 gram peracetic acid, 1100 gram sodium bisulfites; transferring pH value is 1.9 ± 0.15 also maintenances; under the safeguard protection of nitrogen, stir to add 70kg vinyl cyanide first monomer and hydroxyethyl methylacrylate second polymerization single polymerization monomer, and to make first monomer be 90.6: 9.4 than second monomer; temperature remains on 75 ℃; reacted 40 minutes, and after unit is taken off in steaming, promptly got qualified spinning solution.
Claims (7)
1, a kind of plant animal protein and acrylonitrile graft copolymer fibre spinning raw liquor, it is characterized in that it being to be made by animal protein 10-20 part, plant protein 10-20 part and acrylonitrile polymerization monomer 60-80 part, first monomer and second monomer ratio are 90.6: 9.4.
2, plant animal protein according to claim 1 and vinyl cyanide connect skill copolymer fibre spinning solution, it is characterized in that said animal protein is animal milk casein matter, ceratin of animal hairs matter, animal skin class collagenic protein, insects protein.
3, plant animal protein according to claim 1 and acrylonitrile graft copolymer fibre spinning raw liquor is characterized in that the protein of said plant protein for extracting from soybean meal, peanut meal, the coleseed dregs of rice, cotton seed mill, the oily certain herbaceous plants with big flowers benevolence dregs of rice, sesame seed meal, leached tea oil slag, flaxseed meal, the comb fiber crops seed dregs of rice, Endosperm Cocois, rice bran.
4, plant animal protein according to claim 1 and acrylonitrile graft copolymer fibre spinning raw liquor is characterized in that said acrylonitrile polymerization monomer is vinyl cyanide first monomer or vinyl cyanide first monomer and methymethacrylate or methacrylic acid fourth fat or hydroxyethyl methacrylate second fat second monomer.
5; realize the production method of the described spinning solution of claim 1; it is characterized in that it being that animal protein and each 10-20 part of plant protein concentration with 8-10% is dissolved in the aqueous sodium hydroxide solution that pH value is 8-10; warming while stirring is to 40-50 ℃; be warming up to 60-75 ℃ after the protein dissolving; the side chain modifier that adds the 1.5-3% of protein wt is modified; stir and be warming up to 90-98 ℃ in 30-50 minute; again after insulated and stirred 30-50 minute; with the solder(ing)acid blend together; protein concn is 1.4-3.7%; solder(ing)acid concentration is 55-75%; pH value is 1.9 ± 0.15; the oxygenant of the 0.06-0.22% of adding protein and polymerization single polymerization monomer material gross weight and the reductive agent of 0.18-1.1%; under nitrogen protection, add 60-80 part acrylonitrile polymerization material while stirring, transferring pH value is 1.9 ± 0.15; temperature is 20-75 ℃ reacted after 40-180 minute, and vacuum is steamed demonomerization.
6, the production method of spinning solution according to claim 5 is characterized in that said side chain modifier is hydrogen peroxide or peroxyformic acid or peracetic acid; Said oxygenant is hydrogen peroxide or peroxyformic acid or crosses ethanol that reductive agent is sodium bisulfite, potassium or xitix.
7, the production method of spinning solution according to claim 5, it is characterized in that said animal, each 10kg of plant protein, concentration with 8% is dissolved in the aqueous sodium hydroxide solution, be warming up to 40 ℃, be warming up to 60 ℃ after protein is all molten, add 300 gram hydrogen peroxide, insulated and stirred 30 minutes is warming up to 90 ℃, insulated and stirred is 30 minutes again, with concentration be 66.7% solder(ing)acid 1179kg blend together, add 60 gram hydrogen peroxide again, 180 gram sodium bisulfites, transferring pH value is 1.9 ± 0.15, after mixing thoroughly, vacuumize and charge into nitrogen, add 80kg acrylonitrile polymerization monomer, keep pH value constant, temperature is 20 ℃, reacted 180 minutes, and took out negative pressure and steam demonomerization, concentration is 6.5% spinning solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021358737A CN1181117C (en) | 2002-12-14 | 2002-12-14 | Plant animal protein and acrylonitrile graft copolymerized fiber spinning dope and its production method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB021358737A CN1181117C (en) | 2002-12-14 | 2002-12-14 | Plant animal protein and acrylonitrile graft copolymerized fiber spinning dope and its production method |
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| CN1422880A true CN1422880A (en) | 2003-06-11 |
| CN1181117C CN1181117C (en) | 2004-12-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677191A (en) * | 2011-10-31 | 2012-09-19 | 中原工学院 | Preparation method of hair protein fiber spinning solution |
| CN113668142A (en) * | 2021-09-29 | 2021-11-19 | 河南迪怡疗护科技开发有限公司 | Medical and sanitary antibacterial non-woven fabric and production method thereof |
| CN114232337A (en) * | 2021-12-27 | 2022-03-25 | 罗莱生活科技股份有限公司 | Double-protein acrylic fiber and preparation method thereof |
-
2002
- 2002-12-14 CN CNB021358737A patent/CN1181117C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102677191A (en) * | 2011-10-31 | 2012-09-19 | 中原工学院 | Preparation method of hair protein fiber spinning solution |
| CN102677191B (en) * | 2011-10-31 | 2014-07-02 | 中原工学院 | Preparation method of hair protein fiber spinning solution |
| CN113668142A (en) * | 2021-09-29 | 2021-11-19 | 河南迪怡疗护科技开发有限公司 | Medical and sanitary antibacterial non-woven fabric and production method thereof |
| CN113668142B (en) * | 2021-09-29 | 2022-11-04 | 广州市醒目医药科技有限公司 | Medical and sanitary antibacterial non-woven fabric and production method thereof |
| CN114232337A (en) * | 2021-12-27 | 2022-03-25 | 罗莱生活科技股份有限公司 | Double-protein acrylic fiber and preparation method thereof |
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| Publication number | Publication date |
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| CN1181117C (en) | 2004-12-22 |
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