CN1181117C

CN1181117C - Plant animal protein and acrylonitrile graft copolymerized fiber spinning dope and its production method

Info

Publication number: CN1181117C
Application number: CNB021358737A
Authority: CN
Inventors: 宋惠远; 胡宗善
Original assignee: Individual
Current assignee: Individual
Priority date: 2002-12-14
Filing date: 2002-12-14
Publication date: 2004-12-22
Anticipated expiration: 2022-12-14
Also published as: CN1422880A

Abstract

The invention relates to fiber-filature original liquid produced by graft copolymerization of propagation protein and acrylonitrile and a production method thereof, the fiber-filature original liquid can effectively solve product problems of high product cost and poor quality. The original liquid is prepared from 10 to 20 portions of propagation protein and 60 to 80 portions of acrylonitrile polymerizing monomers; the present invention has the method that the propagation protein is dissolved in the aqueous solution of sodium hydroxide according to the concentration of 8 to 10%, the solution is stirred, is gradually warmed up, and is added with side chain modifiers, when the temperature is raised to 90 to 98 DEG C, the aqueous solution of zinc chloride and the solution are mixed together, and a pH value is 1.9(+/-)0.15; a redox agent is added, acrylonitrile polymer graft copolymerization is carried out under nitrogen protection at the temperature of 20 to 75 DEG C for 40 to 180 minutes, and demonimerization is carried out through steam; the present invention has the advantages of low cost, simple method and good product performance; the popularization and the application of the present invention develop the new pathway of the fiber-filature original liquid production, and the social benefit and the economic benefit are great.

Description

Plant animal protein and acrylonitrile graft copolymer fibre spinning raw liquor and production method thereof

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 product 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 the scope of application 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 not only to have reduced product cost, guaranteed product performance, but also solved the relatively poor defective of elasticity color and luster, widened raw material sources greatly.

The present invention realizes like this; spinning solution is by by weight animal protein 10-20 part; plant protein 10-20 part; vinyl cyanide first body or vinyl cyanide first body and methyl methacrylate or butyl methacrylate or hydroxyethyl methylacrylate second monomer 60-80 part; first monomer and second monomer ratio are 90.6: 9.4; its production method be with animal protein and plant protein by weight each 10-20 part be dissolved in the aqueous sodium hydroxide solution that pH value is 8-10 with the weight concentration of 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; hold altogether together with solder(ing)acid again; make the protein after the dissolving; the weight 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; both getting weight concentration is the spinning solution of 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, and its production method is simple, the fiber that has spinning solution to be spun into, its performance is compared with natural protein fibre, not only has skin-friendly, water absorbability and the ventilation property of natural protein fibre, and it is soft, gloss is soft, and dyeability is excellent, and colour fastness is strong, 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 defective 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 weight 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 wt concentration 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 20-75 ℃; steam demonomerization through vacuum, can obtain weight 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.Once 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.).

Above-mentioned animal and plant protein only need be selected wherein a kind of getting final product during use, in case of necessity, also can two or more mixing use, and there is no special meaning.

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 weight concentration of zinc chloride is 55-75% in protein of the present invention and the liquor zinci chloridi, and proteinic weight 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 concrete example the present invention is further described:

Example 1; get animal protein 10kg (kilogram; as follows); plant protein 10kg is dissolved in the aqueous sodium hydroxide solution by 8% weight 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;, being 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%, and the weight concentration of zinc chloride just is being 55%) adds 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; add 80kg acrylonitrile polymerization monomer; keep pH value constant, temperature is 20 ℃, reacts 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 10kg is dissolved in the aqueous sodium hydroxide solution by 9% weight 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 weight concentration be 2.4% in the blended liquid again; Two will to make the weight concentration of zinc chloride be 60%, and transferring pH value is 1.9 ± 0.15, adds peroxyformic acid 110 grams; Potassium hydrogen sulfite 330 grams keep pH value constant, then under protection of nitrogen gas; stir on one side; on one side add 70kg vinyl cyanide 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 is dissolved in the aqueous sodium hydroxide solution by 10% weight concentration together, stir on one side, on one side be warming up to 50 ℃, treat that protein fully dissolves after, when being warming up to 70 ℃, the peracetic acid that adds protein wt 2.5%, insulation reaction 50 minutes is warming up to 98 ℃, and 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, stirs to add 60kg, vinyl cyanide first monomer and butyl methacrylate second monomer under protection of nitrogen gas; keeping pH value is 1.9 ± 0.15; 50 ℃ of temperature were reacted 90 minutes, got spinning property spinning solution preferably behind the demonomerization.

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% weight concentration together; stirring is warming up to 47 ℃; after treating that protein fully dissolves; be warming up to 75 ℃; add the peroxyformic acid of protein wt 3%, insulation reaction 45 minutes is warming up to 93 ℃; insulated and stirred 45 minutes; mix with solder(ing)acid again, make that protein wt concentration is 3.5% in the mixed solution, the weight concentration 75% of zinc chloride; and then add 220 the gram peracetic acid; 1100 gram sodium bisulfites, transferring pH value is 1.9 ± 0.15 also maintenances, under the safeguard protection of nitrogen; stir and 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, and temperature remains on 75 ℃, reacts 40 minutes; after steaming demonomerization, promptly get qualified spinning solution.

Claims

1, a kind of plant animal protein and acrylonitrile graft copolymer fibre spinning raw liquor, it is characterized in that it being that animal protein 10-20 part, plant protein 10-20 part and acrylonitrile polymerization monomer 60-80 part by is by weight made, first monomer and second monomer ratio are 90.6: 9.4.

2, plant animal protein according to claim 1 and acrylonitrile graft copolymer fibre spinning raw liquor is characterized in that said animal protein is animal milk casein matter or ceratin of animal hairs matter or animal skin class collagenic protein or insect 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 or peanut meal or the Semen Brassicae campestris dregs of rice or cotton seed mill or the oily certain herbaceous plants with big flowers benevolence dregs of rice or sesame seed meal or leached tea oil slag or flaxseed meal or castor seed meal or Endosperm Cocois or rice bran.

4; realize the production method of the described spinning solution of claim 1; it is characterized in that it being that by weight animal protein and each 10-20 part of plant protein weight 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; after insulated and stirred 30-50 minute; with the solder(ing)acid blend together; protein wt concentration 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.

5, the production method of spinning solution according to claim 4 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 peracetic acid, and reductive agent is sodium bisulfite, Potassium hydrogen sulfite or xitix.

6, the production method of spinning solution according to claim 4, it is characterized in that said animal, each 10Kg of plant protein, weight concentration with 8% is dissolved in the aqueous sodium hydroxide solution, be warming up to 40 ℃ and treat that protein all is warming up to 60 ℃ after the dissolving, add 300 gram hydrogen peroxide, insulated and stirred 30 minutes, be warming up to 90 ℃, insulated and stirred 30 minutes, with weight concentration be 66.7% solder(ing)acid 1179Kg blend together, adding 60 gram hydrogen peroxide, 180 gram sodium bisulfites, transferring pH value is 1.9 ± 0.15, after stirring evenly, vacuumizes and charges into nitrogen, add 80Kg acrylonitrile polymerization monomer, keep pH value constant, temperature is 20 ℃, reacts 180 minutes, take out negative pressure and steam demonomerization, weight concentration is 6.5% spinning solution.