CN114213683A - Preparation method of high-concentration keratin eutectic system solution - Google Patents

Preparation method of high-concentration keratin eutectic system solution Download PDF

Info

Publication number
CN114213683A
CN114213683A CN202111646480.5A CN202111646480A CN114213683A CN 114213683 A CN114213683 A CN 114213683A CN 202111646480 A CN202111646480 A CN 202111646480A CN 114213683 A CN114213683 A CN 114213683A
Authority
CN
China
Prior art keywords
keratin
eutectic system
hair
solution
eutectic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111646480.5A
Other languages
Chinese (zh)
Other versions
CN114213683B (en
Inventor
袁久刚
代琛璐
徐进
娄江飞
王利涛
范雪荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ZHENGZHOU ZHONGYUAN SPANDEX ENGINEERING TECHNOLOGY CO LTD
Original Assignee
Jiangnan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangnan University filed Critical Jiangnan University
Priority to CN202111646480.5A priority Critical patent/CN114213683B/en
Publication of CN114213683A publication Critical patent/CN114213683A/en
Application granted granted Critical
Publication of CN114213683B publication Critical patent/CN114213683B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/096Nitrogen containing compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/165Ethers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402Amides imides, sulfamic acids
    • D06M13/432Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2389/00Characterised by the use of proteins; Derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/10Animal fibres
    • D06M2101/12Keratin fibres or silk

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)

Abstract

The invention discloses a preparation method of a high-concentration keratin eutectic system solution, and belongs to the technical field of fiber dissolution and regeneration. According to the invention, the reducing agent is permeated into hair fibers in advance through the high-efficiency pretreatment solution, and the hair is dissolved by utilizing the non-reducing eutectic system, so that the keratin eutectic system solution with the concentration of 10-50% can be conveniently prepared. The method has the characteristics of high dissolving efficiency, simple operation, economy and environmental protection, and greatly reduces the preparation difficulty of the high-concentration keratin eutectic system solution.

Description

Preparation method of high-concentration keratin eutectic system solution
Technical Field
The invention relates to a preparation method of a high-concentration keratin eutectic system solution, belonging to the technical field of fiber dissolution and regeneration.
Background
The waste hair contains rich keratin, and if the waste hair can be dissolved and regenerated to obtain a high-concentration (more than or equal to 10 wt%) keratin solution, the application performance of the keratin material can be greatly improved. This is because highly concentrated solutions of keratin have a particular rheological behaviour, which can undergo molecular chain orientation under the action of shear forces, which changes facilitate the preparation of high-strength, high-modulus recycled materials.
The aqueous system reduction method represented by "reduced C" is the most common keratin solubilization method at present. The method mainly adopts high-concentration urea (usually 4-8moL/L), a reducing agent and Sodium Dodecyl Sulfate (SDS) to dissolve keratin. In the system, high-concentration urea is responsible for breaking up hydrogen bonds, a reducing agent is responsible for breaking up disulfide bonds, and SDS is used for stabilizing the system and preventing sulfhydryl groups from being recombined. The reducing agent used in the method is generally a sulfhydryl compound, such as thioglycolate, beta-mercaptoethanol, dithiothreitol and the like, and researchers also adopt reducing agents such as L-cysteine, sodium sulfide, sodium bisulfite and the like, but the extraction effect is not as high as that of the sulfhydryl compound. The biggest problems with this system are: the presence of large amounts of water limits the raveling of hydrogen bonds of keratin by urea, and the aqueous solutions of keratin prepared are not only very low in concentration (usually the keratin concentration obtained by direct dissolution is between 1 and 5 wt%), but also unstable, easily precipitated and require large amounts of SDS to stabilize. Because SDS isolates protein molecules in the system in a micelle form, keratin molecules in a solution cannot approach each other, and then an ordered high-regular folding structure cannot be formed; also, SDS foams easily and needs to be removed by dialysis during subsequent processing, which further reduces protein concentration and stability. Therefore, if the keratin solution produced by using the system is used for spinning or filming, the mechanical property of the obtained regenerated material is not high generally.
In recent years, with the rapid development of the eutectic system (DES), the eutectic system is widely used for dissolving and regenerating protein fibers. The eutectic system is formed by combining a hydrogen bond acceptor and a hydrogen bond donor in a stoichiometric ratio, such as a urea/choline chloride mixture in a molar ratio of 2: 1. Common hydrogen bond donors and acceptors that can compose eutectic systems are as follows: hydrogen bond donor: urea, thiourea, carboxylic acids (phenylacetic acid, malic acid, citric acid, succinic acid, etc.), polyols (ethylene glycol, glycerol, butylene glycol, xylitol, etc.), amino acids, saccharides (glucose, fructose) trifluoroacetamide, etc.; hydrogen bond acceptors: quaternary ammonium salts (such as choline chloride), zwitterions (such as betaine), and the like. However, studies show that most eutectic systems are non-reducing and cannot effectively break off a large number of disulfide bonds in keratin fibers, and high dissolution concentration needs to be achieved through high temperature and long-term action, and the process is mainly to realize dissolution through thermal degradation of peptide chains of protein molecules. For example: according to the research, the urea/choline chloride eutectic system has certain dissolving capacity on wool, but the dissolving mass fraction is only about 3.3%, and the dissolving rate is less than 85%. Hereafter, Yuanjian et al studied the dissolution of wool using choline thioglycolate eutectic system with reducibility to disulfide bonds, with a maximum dissolution mass fraction of 16% at 120 ℃, but requiring about 800 min. In addition, the irritation of a mercaptoacetic choline eutectic system is strong, and the pollution in the preparation process is serious; recently, researchers prepare an environment-friendly lactic acid/L-cysteine eutectic system, and use the system to dissolve wool and the like, and researches show that the time required for achieving 90% dissolution rate is 3.5 hours, but the total dissolution mass fraction is lower and is only 22mg/g of the eutectic system, L-cysteine cannot effectively promote the dissolution of wool keratin, which is also reflected in researches of Zhang et al, and the introduction of L-cysteine not only causes the synthesis difficulty of DES, but also causes poor dissolution performance. Furthermore, the production costs of such reductive eutectic systems, as typified by choline thioglycolate and lactic acid/L-cysteine, far exceed those of conventional eutectic systems, because: reducing agents such as thioglycolic acid, L-cysteine and the like are high in price, and the reducing agents are used as solvent parts of a eutectic system, so that the use amount of the reducing eutectic system is too large, and the application value of extracting keratin by adopting the reducing eutectic system is not high.
In conclusion, in the field of keratin dissolution, although a conventional non-reducing eutectic system represented by urea/choline chloride shows higher dissolving capacity than that of a reduction C method, the problems that disulfide bonds cannot be effectively destroyed and a reducing agent is difficult to add are still faced, and if a novel dissolution regeneration method can be researched, a high-concentration keratin solution is prepared by the conventional eutectic system, and the method has extremely important practical significance for reducing production cost and preparing high-performance regenerated keratin materials.
Disclosure of Invention
[ problem ] to provide a method for producing a semiconductor device
A non-reducing eutectic system represented by urea/choline chloride can dissolve keratin under high-temperature assisted degradation, but cannot effectively destroy disulfide bonds, so that a high-concentration keratin solution cannot be obtained. And conventional inorganic salt reducing agents cannot be added into the system, and the adoption of mercaptoethanol or mercaptoacetic acid reducing agents has intolerable pungent odor, so that the protection is difficult, and the high-concentration keratin solution cannot be quickly prepared, so that the preparation and the application of the regenerated keratin material are hindered.
Therefore, the technical problems to be solved by the invention are as follows: a process for the preparation of a keratin solution having a keratin concentration of up to 10-50 wt% is provided.
[ technical solution ] A
In order to solve the problems, the invention adopts a reducing agent pre-infiltration strategy, the efficient and environment-friendly disulfide bond reducing agent is infiltrated into the hair fiber in advance through novel pretreatment, after the hair fiber is dried and crushed, the pretreated hair powder containing a large amount of reducing agent can be obtained, and when a non-reducing eutectic system is adopted for dissolution in the follow-up process, the problem that the disulfide bond is difficult to disassemble and the problem that the high-concentration keratin solution is difficult to prepare due to the fact that the reducing agent cannot be added can be solved.
The first purpose of the invention is to provide a method for extracting keratin from keratin fibers, which comprises the steps of pretreating the keratin fibers by using pretreatment liquid, and dissolving by using a eutectic system to obtain a solution of the eutectic system of the keratin; the pretreatment solution comprises 10-100g/L of reducing agent, 0-20g/L of penetrating agent, 0-20g/L of polyethylene glycol (PEG) and 10-500g/L of urea; the reducing agent is tris (3-hydroxypropyl) phosphine, mercaptoethanol, L-cysteine, tris (2-carboxyethyl) phosphine or sodium bisulfite.
In one embodiment of the present invention, preferably, the pretreatment solution comprises 20-100g/L of a reducing agent, 2-20g/L of a penetrant, 5-20g/L of polyethylene glycol and 50-500g/L of urea.
In one embodiment of the invention, the polyethylene glycol has a molecular weight of 200-.
In one embodiment of the present invention, the eutectic system refers to a melt formed by combining a hydrogen bond acceptor and a hydrogen bond donor in a stoichiometric ratio. It is formed by melting certain homogeneous solid mixtures when heated to a particular temperature, which is lower than the melting point of these compounds or elements. Common hydrogen bond donors and acceptors that can compose eutectic systems are as follows: hydrogen bond donor: urea, thiourea, carboxylic acids (phenylacetic acid, malic acid, citric acid, succinic acid, etc.), polyols (ethylene glycol, glycerol, butylene glycol, xylitol, etc.), amino acids, saccharides (glucose, fructose) trifluoroacetamide, etc.; hydrogen bond acceptors: quaternary ammonium salts (such as choline chloride), zwitterions (such as betaine), and the like. The non-reducing eutectic system in the present invention refers to a eutectic system having no reduction property for disulfide bonds, and includes: urea/choline chloride eutectic system, choline chloride/ethylene glycol eutectic system, citric acid/choline chloride eutectic system, and the like.
In one embodiment of the present invention, the pretreatment liquid has a pH of 1 to 12.
In one embodiment of the present invention, keratin fibers are pretreated with the pretreatment liquid described above, followed by mechanical pulverization to screen out particles having a diameter of more than 200 μm, to obtain a pretreated powder.
In an embodiment of the present invention, the pretreatment method comprises: the keratin fiber is soaked in a pretreatment solution at a temperature of-20-60 ℃ for 0.1-24 h, rinsed and dried, and finally the water content of the fiber is controlled to be 2-15%. If the moisture content is too high, the eutectic system will not dissolve the hair.
In one embodiment of the present invention, keratin fibers refer to hair fibers containing keratin as a main component, including human hair, wool, rabbit hair, yak hair, mohair, camel hair, pig hair, chicken hair, duck hair, and goose hair.
In one embodiment of the invention, the pretreatment powder and the eutectic system are dissolved according to the mass ratio of 10-200% (w/w), and a high-concentration keratin eutectic system solution is prepared when the eutectic system presents a uniform and transparent amber color.
In one embodiment of the present invention, the dissolving method is: firstly heating the eutectic system to 70-100 ℃, then adding the pretreatment powder into the solvent according to the mass ratio of 10-200% (w/w), stirring and mixing uniformly, then heating the system to 110-.
In one embodiment of the invention, the mass ratio of the pre-treatment powder to the eutectic system is preferably 15% to 150% w/w.
It is a second object of the present invention to provide a keratin eutectic system solution prepared according to the above method.
In one embodiment of the present invention, the keratin eutectic system solution has a keratin concentration of 10 to 50 wt%.
The third purpose of the invention is to provide the application of the keratin eutectic system solution in spinning, film forming, coating and porous material preparation.
Compared with a conventional water system reduction method, a common eutectic system, a eutectic system/mercaptoethanol composite system or a mercaptoacetic choline reductive eutectic system, the method has the following advantages and effects:
(1) the dissolution mass fraction is high: the invention adopts a reducing agent pre-infiltration strategy, and pre-infiltrates a novel efficient disulfide bond reducing agent, namely tris (3-hydroxypropyl) phosphine, into the hair fibers under the action of urea and a penetrating agent through pretreatment, so that the problem that the reducing agent cannot be added into a eutectic system is solved, and the reducing agent can be uniformly contacted with disulfide bonds in the fibers in advance. When the hair powder treated by the method is dissolved at high temperature in the eutectic system, the problem that the disulfide bonds can not be broken down in the conventional non-reducing eutectic system can be solved, and the dissolving efficiency of the hair powder is greatly improved. And large-particle substances are crushed and screened out, and a homogenizer is used for shearing at high speed to destroy the formation of micelles, so that the dissolution mass fraction of the colloidal substances can reach 50 wt%, which is far beyond the common reduction method (<10 wt%), non-reducing eutectic system (<10 wt%), eutectic system/mercaptoethanol composite system (<16 wt%) or reducing eutectic system (<20 wt%) such as mercaptoacetic acid choline.
(2) The dissolution speed is high, and the degradation degree of keratin is light. The invention permeates the high-efficiency reducing agent into the fiber in advance, and can greatly reduce the dissolving time required by the disassembly of the disulfide bond under the high-temperature condition. When the conventional eutectic system is adopted for dissolving, a step of adding a reducing agent is not needed, so that the time for waiting for the penetration and action of the reducing agent is saved, the dissolving rate can be improved, and the thermal degradation of the protein can be reduced.
(3) The operation is simple, and mass production can be realized: after the hair fibers permeated with the reducing agent are mechanically crushed and screened, fine and smooth pretreatment powder can be obtained, which is beneficial to increasing the permeation of a eutectic system to the fibers, improving the dissolution rate, reducing the problems of filter screen blockage and the like in the subsequent production; in addition, a high-speed refiner is adopted to assist dissolution, and the high-speed shearing action of the cutter head of the refiner can effectively solve the entanglement problem of the swollen hair fibers, so that the dissolution is quicker.
(4) Economic and environment-friendly: the pretreatment liquid is simple and reliable to prepare, has no pungent smell, is simple and convenient to operate in the process of pretreating hair, and meets the requirement of green production.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
1. Measurement of dissolution time, dissolution rate and dissolution mass fraction
Taking 1 support, plugging the colorimetric tubes, respectively adding 10gDES, then respectively adding certain mass of hair powder, when the system is dissolved to be in a clear and transparent state, recording the dissolving time, filtering the solution, drying filter residues, and weighing.
The dissolution mass fraction is (mass of hair-mass of residue)/mass of DES 100%;
the dissolution rate is (mass of hair-mass of residue)/mass of hair 100%.
Example 1:
firstly, preparing a pretreatment solution according to the following formula: 20g/L of tris (3-hydroxypropyl) phosphine, 20g/L of penetrant JFC-M20g/L, PEG (Mn is 200), 50g/L of urea, and pH is adjusted to be 4.2. And then, putting the wool fibers into the pretreatment liquid, soaking for 3 hours at 60 ℃, rinsing for 3 times by using tap water at room temperature, centrifugally dewatering, and finally drying to ensure that the water content of the fibers is 5%.
And secondly, mechanically crushing the pretreated wool fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated wool powder.
And finally, heating the urea/choline chloride eutectic system to 100 ℃, adding the pretreated wool powder into the DES according to the mass ratio of 15%, uniformly stirring and mixing, heating the system to 130 ℃, and stirring by adopting a high-speed homogenizer at 10000r/min until the system is completely dissolved.
Tests prove that the time required for completely dissolving the pretreated wool powder is about 45min, the final keratin solution mass fraction is 12.5 wt%, and the dissolution rate is 95.8%.
Compared with the prior art, the untreated wool fibers are dissolved according to the same conditions, most of the fibers are still intact after 12 hours, the dissolution cannot be completed, the keratin mass fraction is only 4.1% after 12 hours, and the dissolution rate is about 28.0%.
Example 2:
firstly, preparing a pretreatment solution according to the following formula: 50g/L of tri (3-hydroxypropyl) phosphine, 10g/L of penetrating agent JFC-M10g/L, PEG (Mn is 400), and 200g/L of urea, wherein the pH value is adjusted to be 2. Then, the chicken feather is placed in the pretreatment liquid, soaked for 24 hours at 20 ℃, rinsed for 3 times by tap water at room temperature, centrifugally dewatered and finally dried, so that the water content of the fiber is 10%.
And secondly, mechanically crushing the pretreated chicken feather by adopting a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated chicken feather powder.
And finally, heating the choline chloride/ethylene glycol eutectic system to 100 ℃, adding the pretreated chicken feather powder into the solvent according to the mass ratio of 30%, uniformly stirring and mixing, heating the system to 130 ℃, and stirring by adopting a high-speed homogenizer at 5000r/min until the dissolution is finished.
Tests show that the dissolution speed of the pretreated chicken feather powder is obviously improved, the time required for complete dissolution is 300min, the keratin solution mass fraction is 23.0%, and the dissolution rate is 98.2%;
in contrast, when the untreated chicken feathers were dissolved under the above conditions, the addition amount thereof failed to complete the complete dissolution, and the keratin mass fraction was measured to be 5.1 wt% and the dissolution rate was 17% after 12 hours.
Example 3:
firstly, preparing a pretreatment solution according to the following formula: 100g/L of tris (3-hydroxypropyl) phosphine, 5g/L of penetrant JFC-M2 g/L, PEG (Mn is 400), and 100g/L of urea, wherein the pH is adjusted to be 12. Then, the pig hair fiber is placed in the pretreatment liquid, soaked for 24 hours at 60 ℃, rinsed for 3 times by tap water at room temperature, centrifugally dewatered and finally dried, so that the water content of the fiber is 7%.
And secondly, mechanically crushing the pretreated pig hair fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain the pretreated pig hair powder.
And finally, dissolving the citric acid/choline chloride eutectic system, heating the eutectic system to 70 ℃, adding the pretreated pig hair powder into the solvent according to the mass ratio of 50%, uniformly stirring and mixing, heating the system to 140 ℃, and stirring the system by using a high-speed homogenizer at 30000r/min until the system is completely dissolved.
Tests show that in a citric acid/choline chloride eutectic system, the dissolution speed of the pretreated pig hair powder is obviously improved, the time required for complete dissolution is 10.5 hours, the mass fraction of the solution is 33.1%, and the dissolution rate is 95.4%;
in contrast, when the untreated pig hair is dissolved according to the above conditions, after 2 hours, stirring is not possible due to swelling and excessive viscosity, and when the dissolution is observed by a microscope, the dissolution is carried out for 24 hours, and a large amount of dissolution is still carried out by the microscope. After 24h, the keratin weight fraction was measured to be 6.2 wt%, and the dissolution rate was about 18.5%.
Example 4:
firstly, preparing a pretreatment solution according to the following formula: 50g/L of tris (3-hydroxypropyl) phosphine, 20g/L of penetrant JFC-M20g/L, PEG (Mn is 200), 500g/L of urea, and pH adjusted to be 4.2. And then, putting the wool fibers into the pretreatment liquid, soaking for 3 hours at 60 ℃, rinsing for 3 times by using tap water at room temperature, centrifugally dewatering, and finally drying to ensure that the moisture content of the fibers is 5%.
And secondly, mechanically crushing the pretreated wool fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated wool powder.
And finally, heating the urea/choline chloride eutectic system to 100 ℃, adding the pretreated wool powder into the DES solvent according to the mass ratio of 105%, uniformly stirring and mixing, heating the system to 140 ℃, and stirring by using a high-speed homogenizer at 30000r/min until the system is completely dissolved.
Tests show that in a urea/choline chloride eutectic system, the complete dissolution time of the wool powder after the pretreatment is 5.5 hours, the final keratin solution mass fraction is 50.2 wt%, and the dissolution rate is 98.0%.
In contrast, when untreated wool was dissolved under the same conditions, the amount of the solution added was not completely dissolved after 12 hours, and at this time, the keratin mass fraction was only 3.5% and the dissolution rate was about 6.8%.
Example 5:
firstly, preparing a pretreatment solution according to the following formula: 100g/L of tris (3-hydroxypropyl) phosphine, 20g/L of penetrant JFC-M20g/L, PEG (Mn is 200), 500g/L of urea, and the pH is adjusted to be 12. And then, putting the wool fibers into the pretreatment liquid, soaking for 3 hours at 60 ℃, rinsing for 3 times by using tap water at room temperature, centrifugally dewatering, and finally drying to ensure that the moisture content of the fibers is 5%.
And secondly, mechanically crushing the pretreated wool fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated wool powder.
And finally, heating the urea/choline chloride eutectic system to 100 ℃, adding the pretreated wool powder into the DES solvent according to the mass ratio of 15%, uniformly stirring and mixing, heating the system to 120 ℃, and stirring by adopting a high-speed homogenizer at 10000r/min until the system is completely dissolved.
Tests show that in a urea/choline chloride eutectic system, the wool powder after the pretreatment is completely dissolved for 30min, the final keratin solution mass fraction is 13.0 wt%, and the dissolution rate is 98.5%.
Compared with the prior art, the untreated wool fibers are dissolved according to the same conditions, most of the fibers are still intact after 12 hours, the dissolution cannot be completed, the keratin mass fraction is only 4.1% after 12 hours, and the dissolution rate is about 28.0%.
Example 6:
firstly, preparing a pretreatment solution according to the following formula: 100g/L of tris (3-hydroxypropyl) phosphine, 20g/L of penetrant JFC-M20g/L, PEG (Mn is 200), 500g/L of urea, and pH value is adjusted to be 4.2. Then, the wool fibers are placed in the pretreatment liquid, soaked for 3 hours at the temperature of minus 20 ℃, rinsed for 3 times by tap water at room temperature and centrifugally dewatered, and finally dried to enable the moisture content of the fibers to be 5%.
And secondly, mechanically crushing the pretreated wool fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated wool powder.
And finally, heating the urea/choline chloride eutectic system to 100 ℃, adding the pretreated wool powder into the DES solvent according to the mass ratio of 15%, uniformly stirring and mixing, heating the system to 120 ℃, and stirring by adopting a high-speed homogenizer at 10000r/min until the system is completely dissolved.
Tests show that in a urea/choline chloride eutectic system, the complete dissolution time of the wool powder after the pretreatment is 60min, the final keratin solution mass fraction is 11.2 wt%, and the dissolution rate is 85.9%.
Compared with the prior art, the untreated wool fibers are dissolved according to the same conditions, most of the fibers are still intact after 12 hours, the dissolution cannot be completed, the keratin mass fraction is only 4.1% after 12 hours, and the dissolution rate is about 28.0%.
Example 7: application of keratin eutectic system solution
Firstly, preparing a pretreatment solution according to the following formula: 100g/L of tris (3-hydroxypropyl) phosphine, 20g/L of penetrant JFC-M20g/L, PEG (Mn is 200), 500g/L of urea, and pH value is adjusted to be 4.2. And then, putting the wool fibers into the pretreatment liquid, soaking for 3 hours at 60 ℃, rinsing for 3 times by using tap water at room temperature, centrifugally dewatering, and finally drying to ensure that the water content of the fibers is 5%.
And secondly, mechanically crushing the pretreated wool fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated wool powder.
And finally, heating the urea/choline chloride eutectic system to 100 ℃, adding the pretreated wool powder into the DES according to the mass ratio of 15%, uniformly stirring and mixing, heating the system to 120 ℃, and stirring at 10000r/min by using a high-speed homogenizer until the system is completely dissolved.
Defoaming and filtering the solution of the keratin eutectic system, controlling the length of an air gap by a metering pump and a spinneret plate by adopting a dry-jet wet spinning process, finally, carrying out solidification forming in urea aqueous solution, stretching, washing with water, drying and forming fibers to obtain the keratin fibers, wherein the strength of the fibers is about 0.5 cN/dT.
Example 8: application of keratin eutectic system solution
Firstly, preparing a pretreatment solution according to the following formula: 100g/L of tris (3-hydroxypropyl) phosphine, 20g/L of penetrant JFC-M20g/L, PEG (Mn is 200), 500g/L of urea, and pH value is adjusted to be 4.2. And then, putting the wool fibers into the pretreatment liquid, soaking for 3 hours at 60 ℃, rinsing for 3 times by using tap water at room temperature, centrifugally dewatering, and finally drying to ensure that the water content of the fibers is 5%.
And secondly, mechanically crushing the pretreated wool fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated wool powder.
And finally, heating the urea/choline chloride eutectic system to 100 ℃, adding the pretreated wool powder into the DES according to the mass ratio of 15%, uniformly stirring and mixing, heating the system to 120 ℃, and stirring at 10000r/min by using a high-speed homogenizer until the system is completely dissolved.
And (2) defoaming and filtering the keratin eutectic system solution, forming a film by adopting a tape casting method, taking water as a coagulating bath, and precipitating urea and choline chloride to obtain a transparent hard keratin film.
Comparative example 1:
wool was treated according to the method of example 1, except that the order of treatment of the reducing system and the eutectic solvent system was changed.
The specific implementation is as follows: firstly, heating a urea/choline chloride eutectic system to 100 ℃, adding wool fibers into the DES according to the mass ratio of 15%, uniformly stirring and mixing, heating the system to 130 ℃, stirring by adopting a high-speed homogenizer at 10000r/min, and treating for 45 min.
And secondly, mechanically crushing the pretreated wool fibers by using a ball mill, and screening out particles with the diameter of more than 200 mu m to obtain pretreated wool powder.
Finally, a dissolving solution is prepared according to the following formula: 20g/L of L-cysteine, 20g/L of penetrant JFC-M20g/L, PEG (Mn is 200), 50g/L of urea, and pH value is adjusted to be 4.2. Then, the pretreated powder was placed in the above-mentioned solution and immersed at 60 ℃ for 3 hours.
The other conditions were the same as in example 1. The results show that the wool dissolution rate is reduced to 21.2% after the treatment sequence is replaced by the L-cysteine instead of the tris (3-hydroxypropyl) phosphine, and the mass fraction of the prepared keratin aqueous solution is only 2.5%, which indicates that the treatment sequence of the reduction system and the eutectic solvent system is particularly critical.
Comparative example 2:
the pretreatment liquid was prepared with reference to the method of example 1, except that: tris (3-hydroxypropyl) phosphine was replaced with L-cysteine, mercaptoethanol, sodium sulfide, tris (2-carboxyethyl) phosphine or sodium bisulfite, and the other conditions were the same as in example 1. The results show that both the dissolution rate and the mass fraction of the prepared solution are reduced. This shows that the reduction system adopted by the invention has better treatment effect and is helpful for promoting the dissolution of keratin.
TABLE 1
Figure BDA0003445383140000081
Figure BDA0003445383140000091
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A method for extracting keratin from keratin fiber is characterized in that the method comprises the steps of pretreating the keratin fiber by using pretreatment liquid, and dissolving by using a eutectic system to obtain a solution of the eutectic system of the keratin; the pretreatment solution comprises 10-100g/L of reducing agent, 0-20g/L of penetrating agent, 0-20g/L of polyethylene glycol and 10-500g/L of urea; the reducing agent is tris (3-hydroxypropyl) phosphine, mercaptoethanol, L-cysteine, tris (2-carboxyethyl) phosphine or sodium bisulfite.
2. The method of claim 1, wherein the pretreatment solution has a pH of 1 to 12.
3. A method according to claim 1 or 2, characterized in that the keratin fibres are pretreated with a pretreatment liquid, and thereafter mechanically crushed to screen out particles having a diameter of more than 200 μm, to obtain a pretreated powder.
4. The method according to any one of claims 1 to 3, wherein the pre-treatment method is: the keratin fiber is soaked in a pretreatment solution at a temperature of-20-60 ℃ for 0.1-24 h, rinsed and dried, and finally the water content of the fiber is controlled to be 2-15%.
5. The method according to any one of claims 1 to 4, wherein the keratin fiber is hair fiber containing keratin as main component, and comprises human hair, wool, rabbit hair, yak hair, mohair, camel hair, pig hair, chicken hair, duck hair, and goose hair.
6. The method as claimed in any one of claims 1 to 5, wherein the dissolving is carried out by dissolving the pretreatment powder with the eutectic system according to the mass ratio of 10% to 200%, and when the eutectic system presents a uniform and transparent amber color, a high-concentration keratin eutectic system solution is prepared.
7. The method according to any one of claims 1 to 6, wherein the dissolution method is: firstly heating the eutectic system to 70-100 ℃, then adding the pretreatment powder into the eutectic system according to the mass ratio of 10% -200%, stirring and mixing uniformly, then heating the system to 110-140 ℃, and stirring until the system is dissolved uniformly.
8. A keratin eutectic system solution prepared according to the method of any one of claims 1 to 7.
9. The keratin eutectic system solution of claim 8, wherein the keratin eutectic system solution has a keratin concentration of 10-50 wt%.
10. Use of the keratin eutectic system solution of claim 9 for spinning, film forming, coating and porous material preparation.
CN202111646480.5A 2021-12-30 2021-12-30 Preparation method of high-concentration keratin eutectic system solution Active CN114213683B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111646480.5A CN114213683B (en) 2021-12-30 2021-12-30 Preparation method of high-concentration keratin eutectic system solution

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111646480.5A CN114213683B (en) 2021-12-30 2021-12-30 Preparation method of high-concentration keratin eutectic system solution

Publications (2)

Publication Number Publication Date
CN114213683A true CN114213683A (en) 2022-03-22
CN114213683B CN114213683B (en) 2023-06-13

Family

ID=80706973

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111646480.5A Active CN114213683B (en) 2021-12-30 2021-12-30 Preparation method of high-concentration keratin eutectic system solution

Country Status (1)

Country Link
CN (1) CN114213683B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1587302A (en) * 2004-07-16 2005-03-02 东华大学 Aids for dissolving wool keratin protein from wool, and its preparing method and use
CN101508847A (en) * 2009-03-09 2009-08-19 东华大学 Method for separating and extracting fibrillar structure body in natural keratin fiber with reducing solvent
JP2010236149A (en) * 2009-03-31 2010-10-21 Aichi Prefecture Production method of reduction salting-out keratin fiber
CN101979428A (en) * 2010-10-09 2011-02-23 天津工业大学 Animal hair solvent and preparation method and use of keratin solution
CN104861663A (en) * 2015-04-28 2015-08-26 东华大学 Method for regenerating wool keratin by L-cysteine
CN108467427A (en) * 2018-03-27 2018-08-31 南通纺织丝绸产业技术研究院 The method for preparing keratin using eutectic solvent dissolving wool
CN112888420A (en) * 2018-08-09 2021-06-01 米尼奥大学 Hair treatment compositions, methods and uses thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1587302A (en) * 2004-07-16 2005-03-02 东华大学 Aids for dissolving wool keratin protein from wool, and its preparing method and use
CN101508847A (en) * 2009-03-09 2009-08-19 东华大学 Method for separating and extracting fibrillar structure body in natural keratin fiber with reducing solvent
JP2010236149A (en) * 2009-03-31 2010-10-21 Aichi Prefecture Production method of reduction salting-out keratin fiber
CN101979428A (en) * 2010-10-09 2011-02-23 天津工业大学 Animal hair solvent and preparation method and use of keratin solution
CN104861663A (en) * 2015-04-28 2015-08-26 东华大学 Method for regenerating wool keratin by L-cysteine
CN108467427A (en) * 2018-03-27 2018-08-31 南通纺织丝绸产业技术研究院 The method for preparing keratin using eutectic solvent dissolving wool
CN112888420A (en) * 2018-08-09 2021-06-01 米尼奥大学 Hair treatment compositions, methods and uses thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘子同等: ""鸡毛在低共熔体系中的溶解再生及其多孔复合材料制备"", 《毛纺科技》 *
袁久刚等: ""羊毛角蛋白在巯基乙酸胆碱中的溶解再生"", 《纺织学报》 *

Also Published As

Publication number Publication date
CN114213683B (en) 2023-06-13

Similar Documents

Publication Publication Date Title
CN101979428B (en) Animal hair solvent and preparation method and use of keratin solution
CN101550614B (en) Method of using non-adhesive method to prepare cellulose base fiber
CN105113034A (en) Regenerated cellulose fiber and preparing method thereof
CN104861663A (en) Method for regenerating wool keratin by L-cysteine
CN110172754A (en) A kind of preparation method of antigen fibrillated fibers element fiber
CN1986920A (en) Alginate/polyvinyl alcohol composite fiber and its preparing process
CN101429682A (en) Method for producing regenerated cellulose fiber by dual-bath coagulation
CN101550610A (en) Preparation method of chitosan fiber
CN111910282B (en) Waste feather regenerated pure keratin fiber and preparation method thereof
CN103147144B (en) Method for dissolving cellulose and method for preparing regenerated fiber
CN103102695B (en) Preparation of regenerative keratin solution and method of wet spinning
CN107142542A (en) A kind of fibroin regenerated celulose fibre and preparation method thereof
CN105133077B (en) A kind of fine count fiber cellulose fiber and preparation method thereof
CN103554247A (en) Method for preparing collagen microfiber by use of ionic liquid mixing solvent
CN1252163C (en) Lithium hydrate and carbamide composition solvent for dissolving cellulous fiber and its use
CN110760943B (en) Preparation and application of fresh flower fiber filament for spinning
CN114213683A (en) Preparation method of high-concentration keratin eutectic system solution
CN103146790A (en) Method for preparing composite fiber by copolymerization of reconstructed feather protein/chitin
CN113981557A (en) Milk tea short fiber and preparation method thereof
JP5604294B2 (en) Protein separation method, protein dissolution method, non-animal fiber fraction collection method, and animal fiber-derived protein
CN108624974B (en) Preparation method of pearl fiber
CN109576803A (en) A kind of production method of chitin fiber
CN102877159B (en) Feather keratin viscose staple fiber and method for producing same
CN1235962C (en) Solvent for solving cellulose and its application
CN109267180B (en) Colored alginate fiber with stable coloring and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20231108

Address after: 450001 jinshuttle Road, Zhengzhou hi tech Zone, Henan Province, No. 25

Patentee after: ZHENGZHOU ZHONGYUAN SPANDEX ENGINEERING TECHNOLOGY Co.,Ltd.

Address before: No. 1800 road 214122 Jiangsu Lihu Binhu District City of Wuxi Province

Patentee before: Jiangnan University