CN101109115B - Method of preparing protein modified polyacrylonitrile fibre - Google Patents
Method of preparing protein modified polyacrylonitrile fibre Download PDFInfo
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- CN101109115B CN101109115B CN200710044994A CN200710044994A CN101109115B CN 101109115 B CN101109115 B CN 101109115B CN 200710044994 A CN200710044994 A CN 200710044994A CN 200710044994 A CN200710044994 A CN 200710044994A CN 101109115 B CN101109115 B CN 101109115B
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Abstract
The invention relates to a preparing method for a protein modified polyacrylonitrile fiber, which comprises the following procedures: (1) some protein and polyacrylonitrile are solved in some ion liquid to prepare some equal-phase mixed crude liquid for spinning; (2) the spinning liquid is de-bubbled, filtered, dosed, then extruded by a spinning jet to form a fine spinning flow, which passes a wet air layer and enters into a condensing bath to condense and form; (3) fiber is spun after pre-tensioning, tensioning, water washing, drying and thermal forming, so protein modified polyacrylonitrile fiber is prepared. The method is environmental friendly, easy to recycle, of low production cost and high productivity; the clothing from the product made by the method is highly comfortable and healthy, and is of high fiber property.
Description
Technical field
The invention belongs to the preparation method field of polyacrylonitrile fibre, particularly relate to the preparation method of protein modified polyacrylonitrile fibre.
Background technology
The peptide chain that the Main Ingredients and Appearance of protein is made up of amino acid, it has the necessary amino acid of a lot of human bodies, have excellent biological compatibility and functions of skin protection and health care, the protein fibre that comprises real silk and wool is subjected to consumer's welcome always, yet the output of natural protein fibre is limited, be difficult to satisfy the demand in market, utilize the technology of native protein raw material production azlon so be born.But the azlon that utilizes pure protein to prepare is owing to intensity is crossed the low practical requirement that is difficult to reach.
Polyacrylonitrile fibre has fleecy feel, and bulkiness is good, and the title of " synthetic wool " is arranged, and is a kind of light-duty fiber with good draping property, and elasticity and resilience tool are good, and has excellent anti-sunlight and weather-resistant property.The shortcoming of polyacrylonitrile fibre is hygroscopicity relatively poor (regain is 1%), and static and pilling effect often take place.
The protein modified polyacrylonitrile fibre moisture pick-up properties is compared with acrylic fibers greatly and is improved, and its hydroscopicity improves greatly, and rate of moisture absorption is accelerated, and permeability improves, and the antistatic property of fiber increases, and outward appearance has gloss similar to silk and soft hand feeling.Application number is 02139295.1,011331919.4 and 03148421.2 patent disclosure prepares the method for protein and polyacrylonitrile graft copolymer fibre spinning raw liquor and fiber, but the problem that this method exists is that the percent grafting of acrylonitrile is lower, and the method for employing copolymerization, technology path is complicated, percent grafting is difficult to control, and manufacturing cost increases relatively.The patent that disclosed blending method prepares protein modified polyacrylonitrile fibre has, application number be 94114071.7 and the patent of 02109229.X announced respectively and the preparation method of protein/polyacrylonitrile composite fiber and silk/polyacrylonitrile composite fiber adopted NaSCN or ZnCl
2The aqueous solution be solvent, carry out wet spinning, make with protein-modified polyacrylonitrile fibre; Application number is that the patent of 200510024370.X and 200510024372.9 adopts methyl-sulfoxide and inorganic salts such as NaSCN, KSCN and ZnCl
2The aqueous solution dissolve vegetable protein, polyurethane and polyacrylonitrile respectively as solvent, then with the even blend of the solution of vegetable protein, polyurethane and polyacrylonitrile, the modulation spinning solution adopts wet spinning to prepare fiber.But said method used solvent in the spinning solution preparation process is organic reagent or inorganic salts all, and organic solvent has volatility, the health that environment is caused serious pollution and jeopardizing operating personnel; And inorganic reagent all has severe corrosive, and is very big to the corrosion of equipment.In addition, the recovery of these chemical reagent need be carried out multi-step pressure reduction evaporation and multistage crystallization sedimentation, whole recovery operation not only technological process is loaded down with trivial details, strict to control of process parameters, and can produce a large amount of waste gas and waste water, again environment is caused severe contamination.
The green solvent that latest developments are got up---ionic liquid, directly solubilising protein and polyacrylonitrile provide the new method for preparing protein modified polyacrylonitrile fibre.The report that protein dissolves in ionic liquid has: Phillips etc. have reported to be preparation (the David M.Phillips of dissolution with solvents fibroin and albuminous membranae and fiber with the ionic liquid, Lawrence F.Drummy, Deborah G.Conrady, et al.Dissolution and Regeneration of Bombyx mori Silk FibroinUsing Ionic Liquids[J] .AM.CHEM.SOC.2004,126:14350-14351; David M.Phillips; LawrenceF.Drummy; Rajesh R.Naik; et al.Regenerated silk fiber wet spinning from an ionic liquidsolution[J] .Mater.Chem; 2005; 15:4206-4208); it is solvent that Atanu Biswas etc. has studied with the ionic liquid; starch and zein are dissolved back acyl groupization (Atanu Biswas therein; R.L.Shogren; D.G.Stevenson; J.L.Willett; Pradip K.Bhowmik.Ionic liquids as solvents for biopolymers:Acylation of starch andzein protein[J] .Carbohydrate Polymers, 2006,66:546-550).The disclosed patent CN1660901A of research institute " a kind of preparation method of keratin solution " should be changed in Chinese Academy of Sciences Changchun, and disclosing with the ionic liquid is the method that solvent prepares protein solution.The patent 200510077288.3 of Chinese Academy Of Sciences Process Engineering Research Institute's application, disclosing with the ionic liquid is the method that solvent dissolving animal hair and cellulosic material prepare bioprotein hair fibre.We the patent ZL200410016369.8 of application discloses the preparation method of a kind of acrylonitrile polymer in ionic liquid, further we the application patent 200410066610.8,200410066608.0,200410066609.5 200410066607.6 to disclose with the ionic liquid be the spinning process of the polyacrylonitrile fibre of solvent.Utilize the ionic liquid characteristic of solubilising protein and polyacrylonitrile simultaneously, can improve the comfort health-care function of polyacrylonitrile fibre and obtain the weaving face fabric of high added value.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of protein modified polyacrylonitrile fibre, this method is solvent with the ionic liquid, adopt even mixed method to prepare the homogeneous phase spinning solution of protein modified polyacrylonitrile, be used in jet wet-spinning technique, be coagulating agent with water, the method of spinning protein modified polyacrylonitrile fibre has fully overcome the deficiency that adopts organic solvent or inorganic solution in the conventional art.
The preparation method of protein modified polyacrylonitrile fibre of the present invention comprises the following steps:
(1) protein and polyacrylonitrile are dissolved in the ionic liquid preparation homogeneous phase blend spinning stoste;
(2) extrude the back by spinning head after the deaeration of spinning solution process, filtration, the metering and form dynamic analysis of spinning, by entering the coagulating bath solidification forming behind the humid air layer;
(3) carry out predraft, stretching, washing, dry heat typing back spinning technique, preparation protein modified polyacrylonitrile fibre.
Described protein is animal protein or vegetable protein, protein content 〉=90%;
Described polyacrylonitrile is selected from copolymer or the copolymer of first and second monomer or the homopolymers of acrylonitrile of first, second and third monomer, and viscosity average molecular weigh is 2.0 * 10
4～2.0 * 10
5
The copolymer of described first, second and third monomer is meant that the mass percent of second monomer in the copolymer is that the content of the 3～18%, the 3rd monomer is 0.1～1.0%;
The copolymer of described first and second monomer is meant that the content of second monomer in the copolymer is 0～18wt%;
Described first monomer is an acrylonitrile, second monomer is selected from a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate or the acrylamide, and the 3rd monomer is taken from a kind of in the amino ethyl ester of itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, 2-methyl-5-vinylpyridine or dimethylaminoethyl acrylate methyl;
Described ionic liquid is made up of CATION and anion;
Described CATION comprises a kind of in the following CATION:
Alkyl quaternary ammonium ion ethoxy alkyl quaternary ammonium ion alkyl sulfonium cation alkyl quaternary phosphonium ion
Alkyl pyridinium ion alkyl pyrroles ion alkyl pyrazoles ion alkyl imidazol ion
Wherein, R1, R2, R3, R4, R5 and R6 are that H or carbon number are the alkyl of 1-8, can be identical, also can be different.
Described anion is Cl
-, Br
-, CH
3COO
-, SCN
-, HCOO
-A kind of;
Described homogeneous phase spinning solution consist of polyacrylonitrile, protein and ionic liquid, the mass percent that polyacrylonitrile and protein sum account for solution is 5～20%;
Described homogeneous phase preparation method of spinning dope is selected from one of following manner: the one, the protein and the polyacrylonitrile of drying mixed, and be dissolved in and prepare spinning solution in the ionic liquid; The 2nd, polyacrylonitrile and protein are dissolved in respectively in the ionic liquid, be mixed with spinning solution then; Three mix polyacrylonitrile and protein, swelling in ionic liquid, dehydration, dissolving preparation spinning solution;
Described spinning solution temperature is 50～120 ℃;
Described humid air layer is meant in spinnerets and the coagulating bath that the distance of air layer is 1～10cm between the liquid level, and the temperature of air layer is 5～30 ℃, and relative humidity is 60～95%;
Described coagulating bath is made up of ionic liquid and water, and temperature is 0～30 ℃, and wherein ion liquid mass percent is 0～20%, and the mass percent of water is 80～100%;
Described predraft is bathed and is water, and water temperature is 40～65 ℃.
Described stretch bath is a water, 80～99 ℃ of water temperatures.
Described method for washing is selected from the method that adopts the spray washing, and water temperature is 20～80 ℃ or adopts the method for water at atmospheric pressure steam washing;
Described drying means is to adopt hot-air dry, and baking temperature is 120～165 ℃;
Described spinning speed is 20～200m/min;
Described protein modified polyacrylonitrile fibre is meant that the mass percent of protein is 1～20%, comprises protein modified polyacrylonitrile fibre long filament or short silk, and filament number is 1.5～5.0dtex, intensity 2.0～4.2cN/dtex.
Beneficial effect of the present invention:
(1) solvent of Cai Yonging is an ionic liquid, and nontoxic non-volatility helps environmental protection and operating personnel's health, and is easy to reclaim, and reduces production costs;
(2) adopt with a kind of dissolution with solvents protein and polyacrylonitrile, that has avoided producing in the mixing of multiple solvent and the mixed process is separated, and helps preparing uniform spinning solution;
(3) be used in jet wet-spinning technique, help improving spinning speed, improve product mechanical property and production efficiency;
(4) improve comfortable, the health of dress ornament of product, improved fibre property, increased added value of product, increased economic benefit.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Raw material: fibroin, protein content 90%;
Polyacrylonitrile, viscosity average molecular weigh are 2.0 * 10
4, be a kind of copolymer that comprises first monomer, second monomer and the 3rd monomer, wherein first monomer is that the mass percent of acrylonitrile is that the mass percent of 81.8%, the second monomer methyl acrylate is that the content of 18%, the three monomer itaconic acid is 0.2%;
Ionic liquid, 1-allyl-3-methylimidazole chloride.
With mass percent is that 1% dry fibroin and mass percent are that 99% dry polyacrylonitrile mixes, add in 1-allyl-3-methylimidazole chloride, dissolved 2 hours down at 50 ℃, obtain the spinning solution of stable uniform, 1-allyl in the solution-muriatic mass percent of 3-methylimidazole is 95%, spinning solution filters deaeration down at 50 ℃, extrude through measuring pump and spinnerets, humid air layer through 1cm, temperature is 5 ℃, and humidity is 95%, enters 5 ℃ coagulating bath, coagulating bath is a water, predraft is carried out in the hot bath that enters 40 ℃ through deflector roll, and the hot bath that enters 80 ℃ then stretches, and washes and 120 ℃ hot-air dry through the water at atmospheric pressure steam water, speed with 20m/min is wound into long filament, and obtaining filament number is 5.0dtex, the protein modified polyacrylonitrile fibre of intensity 2.0cN/dtex.
Embodiment 2
Raw material: wool albumen, protein content 92%;
Polyacrylonitrile, viscosity average molecular weigh 2.0 * 10
5, be a kind of copolymer that comprises first monomer and second monomer, wherein first monomer is that the content of acrylonitrile is that the content of 90%, the second monomers methyl methacrylate is 10%;
Ionic liquid, 1-butyl-3-methylimidazole chloride.
Being 20% wool albumen with mass percent mixes with 80% polyacrylonitrile, add in 1-butyl-3-methylimidazole chloride, 30 ℃ of following swellings 2 hours, dehydration, dissolved 1.5 hours down at 120 ℃, obtain the stable uniform spinning solution, 1-butyl in the solution-muriatic mass percent of 3-methylimidazole is 92%, filter deaeration down at 120 ℃, extrude through measuring pump and spinnerets, through the humid air layer of 2cm, temperature is 15 ℃, humidity 80%, enter 0 ℃ coagulating bath, 1-butyl in the coagulating bath-muriatic mass percent of 3-methylimidazole is 5%, and predraft is carried out in the hot bath that enters 45 ℃ through deflector roll, and the hot bath that enters 85 ℃ then stretches, through 20 ℃ spray washings and 130 ℃ hot-air dry, spinning speed is 50m/min, is cut to the short silk of length 56mm, and obtaining filament number is 4.5dtex, the protein modified polyacrylonitrile fibre of intensity 2.4cN/dtex.
Embodiment 3
Raw material: soybean protein, protein content 94%;
Polyacrylonitrile, viscosity average molecular weigh 5.0 * 10
4, be acrylonitrile homopolymer;
Ionic liquid: 1-butyl-2-methylpyrazole bromide.
Be 1% dry soybean protein with mass percent with mass percent be that 1-butyl-2-methylpyrazole bromide of 99% mixes, 70 ℃ down dissolving obtained solution 1. in 2 hours; Be 15% dry polyacrylonitrile with mass percent with mass percent be that 1-butyl-2-methylpyrazole bromide of 85% mixes, 2. dissolving obtained solution in 1 hour under 80 ℃, again with 1. 2. mixed in equal amounts of solution, under 80 ℃, stir and obtained the stable uniform spinning solution in 0.5 hour, filter deaeration down at 80 ℃, extrude through measuring pump and spinnerets, humid air layer through 3cm, temperature is 15 ℃, humidity 75%, enter 20 ℃ coagulating bath, the mass percent of 1-butyl in the coagulating bath-2-methylpyrazole bromide is 8%, and predraft is carried out in the hot bath that enters 50 ℃ through deflector roll, the hot bath that enters 90 ℃ then stretches, wash and 140 ℃ hot-air dry through the water at atmospheric pressure steam water, be wound into long filament with the speed of 80m/min, obtaining filament number is 4.0dtex, the protein modified polyacrylonitrile fibre of intensity 2.8cN/dtex.
Embodiment 4
Raw material: zein, protein content 95%;
Polyacrylonitrile, viscosity average molecular weigh 6.0 * 10
4, be a kind of copolymer that comprises first monomer and second monomer, the content of the first monomer acrylonitrile is that the content of 86%, the second monomer methacrylonitrile is 14%.
Ionic liquid, 3-methyl-N-butyl-pyridinium chloride.
With mass percent be 3% zein and mass percent be that 97% polyacrylonitrile mixes, adding ionic liquid 3-methyl-N-butyl-pyridinium chloride mixes, 30 ℃ of following swellings 2 hours, dehydration, dissolved 1.5 hours down at 100 ℃, obtain the stable uniform spinning solution, 3-methyl in the solution-muriatic mass percent of N-butyl-pyridinium is 90%, under 100 ℃ of degree, filter deaeration, extrude through measuring pump and spinnerets, through the humid air layer of 4cm, temperature is 10 ℃, humidity 85%, enter 30 ℃ coagulating bath, 3-methyl in the coagulating bath-muriatic mass percent of N-butyl-pyridinium is 10%, and predraft is carried out in the hot bath that enters 55 ℃ through deflector roll, and the hot bath that enters 95 ℃ then stretches, through 40 ℃ spray washings and 150 ℃ hot-air dry, spinning speed is 100m/min, is cut to the short silk of length 38mm, and obtaining filament number is 3.5dtex, intensity is the protein modified polyacrylonitrile fibre of 3.0cN/dtex.
Embodiment 5
Raw material: milk casein, protein content 96%;
Polyacrylonitrile, viscosity average molecular weigh 8.0 * 10
4, be a kind of copolymer that comprises first monomer, second monomer and the 3rd monomer, the content of the first monomer acrylonitrile is that the content of 83.6%, the second monomer vinylacetate is that the content of 16%, the three monomer sodium allylsulfonate is 0.4%;
Ionic liquid, benzyl dimethyl myristyl ammonium chloride.
With mass percent is that 5% dry milk casein and mass percent are that 95% dry polyacrylonitrile mixes, add in the benzyl dimethyl myristyl ammonium chloride, dissolved 2 hours down at 110 ℃, obtain the spinning solution of stable uniform, the muriatic mass percent of benzyl dimethyl myristyl ammonium is 88% in the solution, spinning solution filters deaeration down at 110 ℃, extrude through measuring pump and spinnerets, humid air layer through 5cm, temperature is 30 ℃, humidity 60%, enter 25 ℃ coagulating bath, benzyl dimethyl myristyl ammonium chloride quality percentage in the coagulating bath is 12%, predraft is carried out in the hot bath that enters 60 ℃ through deflector roll, and the hot bath that enters 99 ℃ then stretches, and washes and 160 ℃ hot-air dry through the water at atmospheric pressure steam water, speed with 120m/min is wound into long filament, and obtaining filament number is 3.0dtex, the protein modified polyacrylonitrile fibre of intensity 3.2cN/dtex.
Embodiment 6
Raw material: rapeseed protein, protein content 98%;
Polyacrylonitrile, viscosity average molecular weigh 1.0 * 10
5, be acrylonitrile homopolymer;
Ionic liquid, trimethyl butyl phosphorus bromide.
Be 3% dry rapeseed protein with mass percent with mass percent be that 99% trimethyl butyl phosphorus bromide mixes, 100 ℃ down dissolving obtained solution 1. in 1 hour; Be 15% dry polyacrylonitrile with mass percent with mass percent be that 85% trimethyl butyl phosphorus bromide mixes, 2. dissolving obtained solution in 2 hours under 110 ℃, again with 1. 2. mixed in equal amounts of solution, under 100 ℃, stir and obtained the stable uniform spinning solution in 0.5 hour, filter deaeration down at 120 ℃, extrude through measuring pump and spinnerets, humid air layer through 6cm, temperature is 20 ℃, humidity 75%, enter 12 ℃ coagulating bath, trimethyl butyl phosphorus bromide quality percentage in the coagulating bath is 14%, predraft is carried out in the hot bath that enters 65 ℃ through deflector roll, the hot bath that enters 90 ℃ then stretches, and through 60 ℃ spray washings and 165 ℃ hot-air dry, spinning speed is 140m/min, be cut to the short silk of length 65mm, obtaining filament number is 2.5dtex, the protein modified polyacrylonitrile fibre of intensity 3.5cN/dtex.
Embodiment 7
Raw material: peanut protein, protein content 92%;
Polyacrylonitrile, viscosity average molecular weigh 8 * 10
4, be a kind of copolymer that comprises first monomer and second monomer, wherein the content of the first monomer acrylonitrile is that the content of 88%, the second monomer methacrylonitrile is 12%;
Ionic liquid, N-ethylpyridine formates.
Being 10% peanut protein with mass percent mixes with 90% polyacrylonitrile, adding N-ethylpyridine formates mixes, 40 ℃ of following swellings 2 hours, dehydration, dissolved 1 hour down at 100 ℃, obtain the stable uniform spinning solution, the mass percent of N-ethylpyridine formates is 84% in the solution, filter deaeration down at 100 ℃, extrude through measuring pump and spinnerets, humid air layer through 7cm, temperature is 25 ℃, and humidity 70% enters 17 ℃ coagulating bath, N-ethylpyridine formates mass percent in the coagulating bath is 16%, predraft is carried out in the hot bath that enters 65 ℃ through deflector roll, and the hot bath that enters 99 ℃ then stretches, and washes and 125 ℃ hot-air dry through the water at atmospheric pressure steam water, speed with 160m/min is wound into long filament, and obtaining filament number is 2.0dtex, the protein modified polyacrylonitrile fibre of intensity 3.8cN/dtex.
Embodiment 8
Raw material: rabbit hair albumen, protein content 90%;
Polyacrylonitrile, viscosity average molecular weigh 1.2 * 10
5, be a kind of copolymer that comprises first monomer and second monomer, wherein the content of content 90%, the second monomer vinylacetate of the first monomer acrylonitrile is 10%;
Ionic liquid, N, N '-dimethyl pyrrole acetate.
With mass percent is that 15% dry rabbit hair albumen and mass percent are that 85% dry polyacrylonitrile mixes, add N, in N '-dimethyl pyrrole acetate, dissolved 2 hours down at 110 ℃, obtain the spinning solution of stable uniform, N in the solution, the mass percent of N '-dimethyl pyrrole acetate is 82%, spinning solution filters deaeration down at 110 ℃, extrude through measuring pump and spinnerets, through the humid air layer of 10cm, temperature is 25 ℃, humidity 70%, enter 21 ℃ coagulating bath, the N in the coagulating bath, N '-dimethyl pyrrole acetate mass percent is 20%, predraft is carried out in the hot bath that enters 40 ℃ through deflector roll, the hot bath that enters 70 ℃ then stretches, and through 80 ℃ spray washings and 135 ℃ hot-air dry, spinning speed is 200m/min, be cut to the short silk of length 48mm, obtaining filament number is 1.5dtex, the protein modified polyacrylonitrile fibre of intensity 4.2cN/dtex.
Claims (14)
1. the preparation method of protein modified polyacrylonitrile fibre comprises the following steps:
(1) protein and polyacrylonitrile are dissolved in the ionic liquid preparation homogeneous phase blend spinning stoste;
(2) extrude the back by spinning head after the deaeration of spinning solution process, filtration, the metering and form dynamic analysis of spinning, by entering the coagulating bath solidification forming behind the humid air layer, wherein the humid air layer is meant in spinnerets and the coagulating bath that the distance of air layer is 1～10cm between the liquid level, the temperature of air layer is 5～30 ℃, and relative humidity is 60～95%;
(3) carry out predraft, stretching, washing, dry heat typing back spinning technique, preparation protein modified polyacrylonitrile long filament or short fiber.
2. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described protein is animal protein or vegetable protein, protein content 〉=90%.
3. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described polyacrylonitrile is selected from copolymer or the copolymer of first and second monomer or the homopolymers of acrylonitrile of first, second and third monomer, and viscosity average molecular weigh is 2.0 * 10
4～2.0 * 10
5The copolymer of first, second and third monomer is meant that the mass percent of second monomer in the copolymer is that the content of the 3～18%, the 3rd monomer is 0.1～1.0%; The copolymer of first and second monomer is meant that the content of second monomer in the copolymer is 0～18wt%; First monomer is an acrylonitrile, second monomer is selected from a kind of in methyl acrylate, methyl methacrylate, methacrylonitrile, vinylacetate or the acrylamide, and the 3rd monomer is taken from a kind of in the amino ethyl ester of itaconic acid, sodium allylsulfonate, methylpropene sodium sulfonate, metering system benzene sulfonic acid sodium salt, vinylpyridine, 2-methyl-5-vinylpyridine or dimethylaminoethyl acrylate methyl.
4. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described ionic liquid is made up of CATION and anion, and CATION comprises a kind of in the following CATION:
Alkyl quaternary ammonium ion ethoxy alkyl quaternary ammonium ion alkyl sulfonium cation alkyl quaternary phosphonium ion
Alkyl pyridinium ion alkyl pyrroles ion alkyl pyrazoles ion alkyl imidazol ion
Wherein, R1, R2, R3, R4, R5 and R6 are that H or carbon number are the alkyl of 1-8, can be identical, also can be different; Anion is Cl
-, Br
-, CH
3COO
-, SCN
-, HCOO
-A kind of.
5. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described homogeneous phase spinning solution consist of polyacrylonitrile, protein and ionic liquid, the mass percent that polyacrylonitrile and protein sum account for solution is 5～20%.
6. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described homogeneous phase preparation method of spinning dope is selected from one of following manner: the one, the protein and the polyacrylonitrile of drying mixed, and be dissolved in and prepare spinning solution in the ionic liquid; The 2nd, polyacrylonitrile and protein are dissolved in respectively in the ionic liquid, be mixed with spinning solution then; Three mix polyacrylonitrile and protein, swelling in ionic liquid, dehydration, dissolving preparation spinning solution.
7. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described coagulating bath is made up of ionic liquid and water, temperature is 0～30 ℃, and wherein ion liquid mass percent is 0～20%, and the mass percent of water is 80～100%.
8. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: the spinning solution temperature in the described step (2) is 50～120 ℃.
9. the preparation method of protein modified polyacrylonitrile fibre according to claim 1 is characterized in that: described predraft is bathed and is water, and water temperature is 40～65 ℃.
10. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described stretch bath is a water, 80～99 ℃ of water temperatures.
11. the preparation method of protein modified polyacrylonitrile fibre according to claim 1 is characterized in that: described method for washing is selected from the method that adopts the spray washing, and water temperature is 20～80 ℃ or adopts the method for water at atmospheric pressure steam washing.
12. the preparation method of protein modified polyacrylonitrile fibre according to claim 1 is characterized in that: the hot-air that described dry employing is 120～165 ℃ carries out drying.
13. the preparation method of protein modified polyacrylonitrile fibre according to claim 1 is characterized in that: the spinning speed in the described step (3) is 20～200m/min.
14. the preparation method of protein modified polyacrylonitrile fibre according to claim 1, it is characterized in that: described protein modified polyacrylonitrile fibre is meant that the mass percent of protein is 1～20%, comprise protein modified polyacrylonitrile fibre long filament or short silk, filament number is 1.5～5.0dtex, intensity 2.0～4.2cN/dtex.
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| WO2018038885A1 (en) * | 2016-08-26 | 2018-03-01 | Ferro Corporation | Slurry composition and method of selective silica polishing |
| CN110453306A (en) * | 2019-05-28 | 2019-11-15 | 河南瑞贝卡发制品股份有限公司 | Apery hair functional protein fiber and its wet spinning process |
| CN111358061A (en) * | 2020-04-26 | 2020-07-03 | 安徽农业大学 | Moisture-absorbing and heating uterus-warming underpants and preparation method thereof |
| CN115434019B (en) * | 2022-10-21 | 2023-11-10 | 辛集市梅花皮业有限公司 | Spinning system for collagen fibers |
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| WO2005098546A2 (en) * | 2004-03-26 | 2005-10-20 | The University Of Alabama | Polymer dissolution and blend formation in ionic liquids |
| CN1752302A (en) * | 2004-09-23 | 2006-03-29 | 中国石化上海石油化工股份有限公司 | Wet spinning method for polyacryl-nitrile fibre |
| CN1884642A (en) * | 2005-06-21 | 2006-12-27 | 中国科学院过程工程研究所 | Biological protein hair fiber preparation method by dissolving animal hair and cellulose material mixture |
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