CN114134587A - Preparation method of high-performance regenerated pure keratin fiber - Google Patents
Preparation method of high-performance regenerated pure keratin fiber Download PDFInfo
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- 102000011782 Keratins Human genes 0.000 title claims abstract description 65
- 108010076876 Keratins Proteins 0.000 title claims abstract description 65
- 239000000835 fiber Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000009987 spinning Methods 0.000 claims abstract description 40
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims abstract description 34
- 210000002268 wool Anatomy 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 238000002166 wet spinning Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- VHJLVAABSRFDPM-UHFFFAOYSA-N 1,4-dithiothreitol Chemical compound SCC(O)C(O)CS VHJLVAABSRFDPM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010008 shearing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 60
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 21
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920001661 Chitosan Polymers 0.000 claims description 6
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- 239000006228 supernatant Substances 0.000 claims description 6
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- 238000000944 Soxhlet extraction Methods 0.000 claims description 5
- 229940008309 acetone / ethanol Drugs 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 5
- 238000005345 coagulation Methods 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 210000004209 hair Anatomy 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 210000003746 feather Anatomy 0.000 claims description 4
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 238000000578 dry spinning Methods 0.000 claims description 2
- 244000144977 poultry Species 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
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- 210000004027 cell Anatomy 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101710200191 Feather keratin Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 231100000956 nontoxicity Toxicity 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000003381 deacetylation reaction Methods 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- VHJLVAABSRFDPM-QWWZWVQMSA-N dithiothreitol Chemical compound SC[C@@H](O)[C@H](O)CS VHJLVAABSRFDPM-QWWZWVQMSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 210000001724 microfibril Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 210000000282 nail Anatomy 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 wearable technology Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of high-performance regenerated pure keratin fibers, which relates to the technical field of keratin regenerated fibers and comprises the following steps of washing, drying and shearing waste wool; carrying out ultrasonic treatment on waste wool in a lithium bromide solution, adding 1, 4-dithio-DL-threitol into the treated solution for high-temperature dissolution, and filtering after dissolution to obtain a keratin extracting solution; adding tackifier into the extracting solution to obtain high-viscosity spinning solution; the spinning solution is subjected to dry-jet wet spinning to obtain the high-strength pure keratin fiber, which has the effects of extracting fine structures such as base fibrils of keratin in a targeted manner, regenerating the pure keratin fiber with excellent physical and mechanical properties by utilizing the self-assembly characteristic of the pure keratin fiber, and improving the molecular weight of the keratin.
Description
Technical Field
The invention relates to the technical field of keratin regenerated fibers, in particular to a preparation method of high-performance regenerated pure keratin fibers.
Background
Keratin is rich in nature and is a main component of feathers, hair, wool, horns and nails, the textile industry also always hopes to regenerate the waste keratin into fibers so as to be applied to textiles, particularly has high expectation on the aspect of recycling and utilizing wool keratin, and in recent years, the keratin has good biocompatibility and degradability, so the keratin has wide attention in the fields of medical materials, wearable technology, air and water filtration and the like, and the aim of preparing the keratin solution is to improve the dissolution rate of wool as much as possible and prepare the keratin solution with high stability, molecular weight, high purity and no toxicity.
At present, the research on keratin dissolution and regeneration mainly focuses on the extraction of keratin macromolecular structures, and the mainstream extraction process is a reduction method, wherein a strong reducing agent has certain damage to the keratin macromolecular structures of keratin to cause the reduction of molecular weight, and the difficulty is brought to the subsequent fiber regeneration, so that high-performance fiber materials are difficult to obtain.
Disclosure of Invention
The invention aims to provide a preparation method of high-performance regenerated pure keratin fibers, which has the advantages that the fine structures such as base fibrils of keratin are extracted in a targeted mode, the pure keratin fibers with excellent physical and mechanical properties are regenerated by utilizing the self-assembly characteristic of the fine structures, the keratin molecular weight is improved, and the problems that a strong reducing agent in a reduction method damages the keratin macromolecular structure of the keratin to a certain extent, the molecular weight is reduced, the subsequent fiber regeneration is difficult, and high-performance fiber materials are difficult to obtain are solved.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of high-performance regenerated pure keratin fibers comprises the following steps:
step S1: preparing raw materials, namely cleaning, drying and shearing waste wool;
step S2: ultrasonic treatment, namely adding the wool in the step S1 into a lithium bromide solution for ultrasonic treatment;
step S3: dissolving, namely adding 1, 4-dithio-DL-threitol into the solution obtained in the step S2, sealing, heating to 90-95 ℃ under the protection of nitrogen, oscillating for dissolving, and filtering to obtain a wool keratin solution;
step S4: tackifying, adding a tackifier and an antibacterial material under the stirring state, centrifuging and removing supernatant to obtain viscous antibacterial spinning solution;
step S5: spinning and water bath drafting, standing the spinning solution, vacuumizing and defoaming, spinning by a dry spinning method by using spinning equipment, and obtaining pure keratin filament fibers after drafting.
Alternatively, the waste wool in step S1 may be, but not limited to, feather, pig hair, and human hair of poultry.
Optionally, the cleaning process in step S1 is to use a soxhlet extraction apparatus, clean the solvent system with acetone/ethanol for 48 hours, then rinse the solvent system with distilled water, and dry the solvent system in an oven at 100 ℃ for 12 hours.
Optionally, the bath ratio in step S2 is 1: 10-1: 20; the concentration of lithium bromide in the solution is 7-9mol/l, the ultrasonic power is 900w, the ultrasonic time is 2-4h, the ultrasonic is carried out for 3-5S when 30mins of operation is carried out each time, and the intermittence is 2-4S.
Optionally, in step S3, the bath ratio is 1: 10-1:20(w/v), the concentration of DTT is 0.05-0.1mol/l, the dissolving temperature is 90-95 ℃, the dissolving time is 5-12h, and the keratin extracting solution is obtained by filtering with a 400-mesh stainless steel wire net.
Optionally, in the step S4, one of the following tackifiers is used, and the tackifier includes, but is not limited to, high-concentration formic acid, hydrochloric acid solution and acetic acid solution; the addition amount of 88% formic acid is 1-2%; the addition amount of 38% hydrochloric acid is 1-2%; 30 percent of acetic acid is added, the addition amount is 1 to 2 percent, and the viscosity of the spinning solution is 50 to 100Pa.s after the viscosity is increased.
Optionally, the antibacterial material in step S4 is chitosan with high acetyl degree.
Optionally, the dry-jet wet spinning process parameters in step S5 are as follows: the spinning nozzle is a needle nozzle, and the distance between the nozzle and the liquid level of the coagulation bath is 3-5 cm; the extrusion capacity of the injection pump is 0.3-0.5 ml/h; the coagulating bath adopts a mixed solution of water and 2-5% of glutaraldehyde, or a solution of 10-30% ammonium sulfate, or a solution of 10-40% sodium chloride; the temperature of the coagulating bath is 25-30 ℃; the drawing speed is 2-15 m/min; washing and drying at 80-100 ℃ for 60-120S.
Compared with the prior art, the invention has the following beneficial effects:
the invention extracts the fine structure of the base fibril of the keratin and the like in a targeted way, utilizes the self-assembly characteristic of the fine structure, regenerates the pure keratin fiber with excellent physical and mechanical properties, can be directly applied to the textile field, medical materials and the like, is a pure keratin component, has easy biodegradability, can be biodegraded by 100 percent, has good biocompatibility simultaneously, and realizes the recovery and regeneration of the waste keratin and the cyclic utilization of resources.
The antibacterial material is added, the antibacterial material is chitosan with high acetyl degree, the reaction activity of amino groups in the molecular structure of the chitosan is stronger than that of acetyl amino groups in chitin molecules, and the chitosan has multiple physiological functions of biodegradability, biocompatibility, nontoxicity, bacteriostasis, cancer resistance, lipid reduction, immunity enhancement and the like, so that the antibacterial performance of the fiber is improved.
And thirdly, the combined action of the high-concentration LiBr solution and the ultrasonic wave is adopted, so that the fiber is contracted and expanded, the distance between macromolecules is greatly increased, and chemical bonds such as hydrogen bonds, salt bonds and the like between the macromolecules are removed. Different from common urea, the LiBr can also play the roles of swelling and removing hydrogen bonds, and the LiBr can enter a crystallization area to reduce the crystallinity, so that the extraction efficiency can be greatly improved.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a comparison of fiber performance tests according to the present invention;
fig. 3 is an SEM image of pure keratin fibers of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Anhydrous lithium bromide LiBr of not less than 99.5% in chemical purity, national drug group chemical reagent limited; 1, 4-dithio-DL-threitol, DTT, biochemical reagent, more than or equal to 98.0 percent, national medicine group chemical reagent company Limited; anhydrous sodium dihydrogen phosphate NaH2PO4, analytically pure, not less than 99.7%, national drug group chemical reagent Co., Ltd; formic acid aqueous solution, analytically pure, more than or equal to 88 percent, national drug group chemical reagent limited; hydrochloric acid, chemical purity, 36-38%, national drug group chemical reagents limited; chitosan, Shandong Onkang Biotech Co., Ltd., molecular weight 50KDa, degree of deacetylation 92%; wool, 60S, is derived from wool waste from the white spinning and combing process of Jiangsu Dan wool textile GmbH. An ultrasonic cell disruptor, model KC-900W, Suzhou Kangchuan electronics Co.
In a first embodiment, referring to fig. 1 to 3, the present invention provides a method for preparing a high-performance regenerated pure keratin fiber, comprising the steps of:
step S1: the waste wool is cleaned by an acetone/ethanol mixed solvent system for 48 hours, then is washed by distilled water, is dried in an oven at 100 ℃ for 12 hours, and is cut into short fibers with the length of 3-5 mm.
Step S2: weighing 10g of wool short fibers, dissolving the wool short fibers in 100ml of LiBr aqueous solution, placing the mixed solution in an ultrasonic cell disruption instrument, placing an amplitude transformer below the liquid level by 1cm, outputting power by 60 percent, carrying out ultrasonic treatment for 2 hours, operating for 30min each time, operating in a pulse mode, working for 3S, and pausing for 2S.
Step S3: under the protection of N2, 1g of DTT was added, and the mixture was dissolved for 5 hours while stirring and heating to 90 ℃. And directly carrying out hot filtration on the dissolved solution by using a sand core funnel to obtain the wool-based raw fiber dissolving solution. To the dissolved solution was added 2ml of a 98% formic acid solution, and the supernatant was removed by centrifugation to obtain a viscous spinning solution.
Step S4: adding spinning solution into an injector, standing for 3h, removing bubbles, and carrying out dry-jet wet spinning, wherein a spinning nozzle is a needle nozzle, the distance from the liquid level of a coagulation bath is 3cm, the spinning temperature is 25 ℃, the ambient relative humidity is 75%, and the extrusion capacity of an injection pump is 5 ml/h.
Step S5: the concentration of the acetic acid solution in the drawing water bath is 0.8M, the concentration of glutaraldehyde is 2.0%, the drawing speed is 9.9M/min, the drying temperature is 80 ℃, and the drying time is 60S.
The product performance test results are shown in fig. 2.
In a second embodiment, referring to fig. 1 to 3, the present invention provides a method for preparing a high-performance regenerated pure keratin fiber, comprising the steps of:
step S1: the waste wool is cleaned by an acetone/ethanol mixed solvent system for 48 hours, then is washed by distilled water, is dried in an oven at 100 ℃ for 12 hours, and is cut into short fibers with the length of 3-5 mm.
Step S2: weighing 10g of wool short fibers, dissolving the wool short fibers in 100ml of LiBr aqueous solution, placing the mixed solution in an ultrasonic cell disruption instrument, placing an amplitude transformer below the liquid level by 1cm, outputting power by 60 percent, carrying out ultrasonic treatment for 2 hours, operating for 30min each time, operating in a pulse mode, working for 3S, and pausing for 2S.
Step S3: under the protection of N2, 1g of DTT was added, and the mixture was dissolved for 5 hours while stirring and heating to 90 ℃. And directly carrying out hot filtration on the dissolved solution by using a sand core funnel to obtain the wool-based raw fiber dissolving solution. 5ml of 38% hydrochloric acid was added to the dissolved solution, and the supernatant was removed by centrifugation to obtain a viscous spinning solution.
Step S4: adding spinning solution into an injector, standing for 3h, removing bubbles, and carrying out dry-jet wet spinning, wherein a spinning nozzle is a needle nozzle, the distance from the spinning nozzle to the liquid level of a coagulation bath is 4cm, the spinning temperature is 25 ℃, the ambient relative humidity is 35%, and the extrusion capacity of an injection pump is 5 ml/h.
Step S5: the concentration of the acetic acid solution in the draw water bath was 0.8M and the concentration of glutaraldehyde was 2.0%. The drawing speed is 6.5m/min, the drying temperature is 100 ℃, and the drying time is 60S.
The product performance test results are shown in fig. 2.
In a third embodiment, referring to fig. 1 to 3, the present invention provides a method for preparing a high-performance regenerated pure keratin fiber, comprising the steps of:
step S1: the waste wool is cleaned by an acetone/ethanol mixed solvent system for 48 hours, then is washed by distilled water, is dried in an oven at 100 ℃ for 12 hours, and is cut into short fibers with the length of 3-5 mm.
Step S2: weighing 10g of wool short fibers, dissolving the wool short fibers in 100ml of LiBr aqueous solution, placing the mixed solution in an ultrasonic cell disruption instrument, placing an amplitude transformer below the liquid level by 1cm, outputting power by 60 percent, carrying out ultrasonic treatment for 2 hours, operating for 30min each time, operating in a pulse mode, working for 3S, and pausing for 2S.
Step S3: under the protection of N2, 1g of DTT was added, and the mixture was dissolved for 5 hours while stirring and heating to 90 ℃. And directly carrying out hot filtration on the dissolved solution by using a sand core funnel to obtain the wool-based raw fiber dissolving solution. Adding 0.5g acetic acid solution into the dissolved solution, rapidly stirring, centrifuging to remove supernatant, and obtaining viscous spinning solution.
Step S4: adding spinning solution into an injector, standing for 3h, removing bubbles, and carrying out dry-jet wet spinning, wherein a spinning nozzle is a needle nozzle, the distance from the liquid level of a coagulation bath is 3cm, the spinning temperature is 25 ℃, the environmental relative humidity is 35%, and the extrusion capacity of an injection pump is 5 ml/h.
Step S5: the concentration of the acetic acid solution in the drawing water bath is 0.8M, the concentration of the glutaraldehyde is 2.0 percent, the drawing speed is 5.5M/min, the drying temperature is 100 ℃, and the drying time is 100S.
The product performance test results are shown in fig. 2.
Comparative example 1
Comparative example one is from a research paper published in Watermanagement 2020, pp.115-65-73, and the keratin spinning dope is prepared as follows: the natural feathers were completely immersed in 8M urea, pH 8, with 4 mmole DTT in the urea solution. Stirring at 70 deg.C for 12 hr at a dissolving bath ratio of 1:17, centrifuging the dispersion to remove insoluble residue, adding hydrochloric acid into regenerated feather keratin solution to adjust pH to 4.6 to separate keratin from the supernatant, washing with deionized water, oven drying, and grinding into keratin powder.
Dissolving 3g of feather keratin powder and 0.3g of SDS in Na2CO3/NaHCO3 buffer solution to obtain a spinning solution, aging the spinning solution at 25 ℃ for 24h, stirring the spinning solution at 90 ℃ for 60min before spinning, extruding filaments into a coagulating bath of 10% ethanol and 10% acetic acid by a spinning device, drying the filaments at 25 ℃, and finally heating at 150 ℃ for 120min to obtain the regenerated keratin fiber.
Comparative example No. two
Comparative example two the patent CN111893580A provides a keratin spinning dope and a keratin regenerated fibre obtained by wet spinning.
The preparation method of the keratin spinning solution comprises the following steps: under the protection of nitrogen, 20g of waste wool, 10g of sodium dodecyl sulfate, 5g of dithiothreitol and 65g of distilled water are added into a three-neck flask with a condensation reflux device and stirring magnetons, and stirred and refluxed at a high speed for 24 hours at 80 ℃. And after the wool is fully dissolved, stopping heating to naturally cool the wool to room temperature and keeping fully stirring to obtain the light gray wool keratin spinning solution.
The preparation method of the keratin regenerated fiber comprises the following steps: centrifuging the obtained spinning solution at 1000rpm for 10min for degassing bubble treatment, and wet spinning with saturated ammonium chloride solution as coagulating bath to obtain nascent fiber. And then soaking the nascent fiber in a 5% glutaraldehyde water solution at room temperature for post-crosslinking for 1-2 min, taking out the crosslinked regenerated fiber, washing the regenerated fiber with distilled water, and naturally drying the regenerated fiber in the air to obtain the regenerated fiber with the wool keratin content of 100%.
The method adopts the combined action of high-concentration LiBr solution and ultrasonic wave to shrink and expand the fiber, greatly increases the distance between macromolecules and removes chemical bonds such as hydrogen bonds, salt bonds and the like between the macromolecules. LiBr is different from common urea, urea also can play the effect of swelling and demolition hydrogen bond, and LiBr can get into the crystallization zone, reduce the degree of crystallinity, thereby can improve the efficiency of extracting greatly, after LiBr ultrasonic wave joint treatment, remaining strong covalent bond disulfide bond between the macromolecule, need adopt DTT to reduce, DTT compares with other reducing agents as the reducing agent, it has the restriction of accessibility, can't unpack the disulfide bond of embedding in the macromolecule promptly, like the disulfide bond of the base fibril of keratin, but can unpack the disulfide bond between base fibril and microfibril. In this way, the targeted extraction of the elementary fibrils, which are essentially dimers or tetramers of keratin macromolecules, is possible, so that the molecular weight can be greatly increased, and it can be seen from FIG. 2 that the fibers obtained in example one, example two and example three, and in comparative example one and comparative example two, have better mechanical properties.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of high-performance regenerated pure keratin fibers is characterized by comprising the following steps:
step S1: preparing raw materials, namely cleaning, drying and shearing waste wool;
step S2: ultrasonic treatment, namely adding the wool in the step S1 into a lithium bromide solution for ultrasonic treatment;
step S3: dissolving, namely adding 1, 4-dithio-DL-threitol into the solution obtained in the step S2, sealing, heating to 90-95 ℃ under the protection of nitrogen, oscillating for dissolving, and filtering to obtain a wool keratin solution;
step S4: tackifying, namely adding a tackifier and an antibacterial material into the keratin solution under the stirring state, and centrifuging to remove supernatant to obtain viscous antibacterial spinning solution;
step S5: spinning and water bath drafting, standing the spinning solution, vacuumizing and defoaming, spinning by a dry spinning method by using spinning equipment, and obtaining pure keratin filament fibers after drafting.
2. The method for preparing high-performance regenerated pure keratin fibers according to claim 1, comprising: the waste wool in step S1 can be, but not limited to, feather, pig hair, and human hair of poultry.
3. The method for preparing high-performance regenerated pure keratin fibers according to claim 1, comprising: the cleaning process in the step S1 is to adopt a Soxhlet extraction device, clean the Soxhlet extraction device for 48 hours by using an acetone/ethanol mixed solvent system, then wash the Soxhlet extraction device by using distilled water, and dry the Soxhlet extraction device for 12 hours in an oven at 100 ℃.
4. The method for preparing high-performance regenerated pure keratin fibers according to claim 1, comprising: the bath ratio in step S2 is 1: 10-1: 20; the concentration of lithium bromide in the solution is 7-9mol/l, the ultrasonic power is 900w, the ultrasonic time is 2-4h, the ultrasonic is carried out for 3-5S when 30mins of operation is carried out each time, and the intermittence is 2-4S.
5. The method for preparing high-performance regenerated pure keratin fibers according to claim 1, comprising: in the step S3, bath ratio 1: 10-1:20(w/v), the concentration of DTT is 0.05-0.1mol/l, the dissolving temperature is 90-95 ℃, the dissolving time is 5-12h, and the keratin extracting solution is obtained by filtering with a 400-mesh stainless steel wire net.
6. The method for preparing high-performance regenerated pure keratin fibers according to claim 1, comprising: in the step S4, one of the following tackifiers is used, and the tackifier includes, but is not limited to, high-concentration formic acid, hydrochloric acid solution and acetic acid solution; the addition amount of 88% formic acid is 1-2%; the addition amount of 38% hydrochloric acid is 1-2%; 30 percent of acetic acid is added, the addition amount is 1 to 2 percent, and the viscosity of the spinning solution is 50 to 100Pa.s after the viscosity is increased.
7. The method for preparing high-performance regenerated pure keratin fibers according to claim 1, comprising: the step S4 antibacterial material is chitosan with high acetyl degree.
8. The method for preparing high-performance regenerated pure keratin fiber according to claim 1, wherein the dry-jet wet spinning process parameters in step S5 are as follows: the spinning nozzle is a needle nozzle, and the distance between the nozzle and the liquid level of the coagulation bath is 3-5 cm; the extrusion capacity of the injection pump is 0.3-0.5 ml/h; the coagulating bath adopts a mixed solution of water and 2-5% of glutaraldehyde, or a solution of 10-30% ammonium sulfate, or a solution of 10-40% sodium chloride; the temperature of the coagulating bath is 25-30 ℃; the drawing speed is 2-15 m/min; washing and drying at 80-100 ℃ for 60-120S.
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