CN110656503B - Water-absorbing composite silk fabric and processing method thereof - Google Patents
Water-absorbing composite silk fabric and processing method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- 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
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- 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
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D13/00—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft
- D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
- D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
- D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
- D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2211/00—Protein-based fibres, e.g. animal fibres
- D10B2211/20—Protein-derived artificial fibres
- D10B2211/22—Fibroin
Abstract
The invention discloses a water-absorbing composite silk fabric and a processing method thereof, and relates to the field of textile weaving. The invention firstly uses modified polyethylene glycol to react with silk protein, then carries out spinning and twisting to prepare modified silk fiber, then spider silk protein liquid is mixed with glucan, carries out spinning and twisting to prepare modified spider silk fiber, and carries out blending on the prepared modified silk fiber and the modified spider silk fiber to prepare water-absorbing composite silk fabric blank, and the water-absorbing composite silk fabric blank is mixed with protease solution to react, then carries out enzyme deactivation at high temperature, and is added with chitosan mixed solution, and after stirring reaction, filtration and freeze drying are carried out to obtain the water-absorbing composite silk fabric. The water-absorbing composite silk fabric prepared by the invention has excellent water absorption and good drapability.
Description
Technical Field
The invention relates to the field of textile weaving, in particular to a water-absorbing composite silk fabric and a processing method thereof.
Background
Silk is woven by taking silk fiber as a raw material, and the silk fiber is protein fiber and is known as fiber queen, which is a treasure in China. The silk fibroin in the silk contains 18 amino acids which have great nutritive value for human bodies, so that the silk fabric has good affinity effect on the skin of the human bodies and has the reputation of 'second skin of the human bodies'. The cross section of the silk fiber is triangular, the silk fiber is longitudinally smooth and flat, and the silk fiber is of a laminated structure, so that the silk fiber has better glossiness than other fibers, fine fineness and better moisture absorption capacity. In addition, the silk also has strong ultraviolet resistance and the scroop effect which other fibers do not have. The characteristics of the silk fiber endow the silk fabric with the characteristics of smooth hand feeling, moisture absorption, air permeability, softness, comfort, soft luster, lightness, thinness, elegance and the like. However, silk fabrics have the defects of easy crease, easy yellowing, easy breakage, easy pollution and the like, which limit the development of the silk fabrics. The mulberry silk and other fibers are compounded, the mulberry silk is taken as a main body to carry out processing technologies such as mutual compounding, coating, blending, interweaving and the like, and the defects of silk broadcloth can be improved after the compounding, so that the silk fabric has the advantages of the silk and other fibers, the performance of the silk fabric is improved, and the functionalization can be realized.
The fibroin fiber is rich in a plurality of hydrophilic groups such as amino (-CONH), amino (-NH 2) and the like, and water molecules are easy to diffuse due to the porosity, so that the fibroin fiber can absorb or emit water in the air and keep certain water. At normal temperature, it can help skin keep certain moisture, and does not dry skin too much; when the sweat-absorbent garment is worn in summer, sweat and heat discharged by a human body can be quickly dissipated, so that people feel cool. Due to the performance, the silk fabrics are more suitable for being in direct contact with human skin, so people all use silk clothes as one of necessary summer clothes. However, silk cannot absorb a large amount of water, so that it is necessary to develop a water-absorbent composite silk fabric having high water absorption capacity.
Disclosure of Invention
The invention aims to provide a water-absorbing composite silk fabric and a processing method thereof, which aim to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the water-absorbing composite silk fabric is characterized by mainly comprising the following raw materials in parts by weight: 20-35 parts of spidroin, 4-8 parts of glucan and 4-10 parts of chitosan.
The water-absorbing composite silk fabric is characterized by also comprising the following raw material components in parts by weight: 20-30 parts of modified silk fiber.
Preferably, the modified silk fiber is prepared by mixing and reacting fibroin and modified polyethylene glycol, spinning and twisting
As optimization, the water-absorbing composite silk fabric comprises the following raw material components in parts by weight: 32 parts of spidroin, 6 parts of glucan, 8 parts of chitosan and 30 parts of modified silk fiber.
As optimization, the processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps:
(1) degumming, dissolving, dialyzing and performing enzymolysis on silk to obtain silk protein powder, mixing silk protein liquid and modified polyethylene glycol for reaction, and performing electrostatic spinning and twisting to obtain modified silk fiber;
(2) mixing the spider silk protein liquid with glucan, and performing electrostatic spinning and twisting to prepare modified spider silk fibers;
(3) blending the modified silk fiber obtained in the step (1) with the modified spider silk fiber obtained in the step (2) to prepare a water-absorbing composite silk fabric blank;
(4) mixing the water-absorbing composite silk fabric blank obtained in the step (3) with a protease solution, heating, adding a chitosan mixed solution, stirring for reaction, filtering, and drying to obtain a water-absorbing composite silk fabric;
(5) and (4) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (4).
As optimization, the processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps:
(1) mixing the waste silkworm cocoons and isopropyl ether according to a mass ratio of 1: 6, mixing, soaking for 3-4 h at room temperature, filtering to obtain pretreated waste silkworm cocoons, and mixing the pretreated waste silkworm cocoons with absolute ethyl alcohol according to a mass ratio of 1: 5, mixing and soaking for 2-3 hours, filtering to obtain filter residue, and mixing the filter residue with deionized water according to a mass ratio of 1: 5, mixing, boiling for 5-6 h, filtering to obtain fibrous silk protein, mixing the fibrous silk protein with a sodium hydrosulfide solution with the mass fraction of 60%, dialyzing in a dialysis bag for 3-4 h, concentrating to obtain silk protein liquid, and mixing the silk protein liquid with protease according to the mass ratio of 100: 3, mixing, reacting for 2-3 hours at room temperature, filtering, washing and drying to obtain fibroin powder; mixing fibroin powder and modified polyethylene glycol according to a mass ratio of 3: 1, mixing, adding dimethyl sulfoxide 8-15 times of the mass of the fibroin powder, stirring and reacting, performing suction filtration to obtain modified fibroin, and mixing the modified fibroin with hexafluoroisopropanol in a mass ratio of 1: 12, mixing to obtain modified silk fiber spinning solution, performing electrostatic spinning on the modified silk fiber spinning solution to obtain modified silk fiber fibrils, and twisting the modified silk fiber fibrils until the linear density is 60D to obtain modified silk fibers;
(2) mixing spider silk and hexafluoroisopropanol according to a mass ratio of 1: 10, mixing, adding glucan with the mass of 0.1-0.2 times of that of the spider silk, stirring and mixing to obtain modified spider silk fiber spinning solution, carrying out electrostatic spinning on the modified spider silk fiber spinning solution to obtain modified spider silk fiber fibrils, and twisting the modified spider silk fiber fibrils to the linear density of 30-80 dtex to obtain modified spider silk fibers;
(3) blending the modified silk fiber obtained in the step (1) and the modified spider silk fiber obtained in the step (2) in a plain weave mode, wherein the modified silk fiber is used as a warp, the density of the warp is 400-600 pieces/cm, the modified spider silk fiber is used as a weft, the density of the warp is 200-400 pieces/cm, and a water-absorbing composite silk fabric blank is prepared;
(4) and (3) mixing the water-absorbing composite silk fabric blank obtained in the step (3) with a protease solution according to a mass ratio of 1: 10, mixing the materials in a reaction kettle, stirring and reacting for 1-2 hours, heating the physical temperature in the reaction kettle to 80-90 ℃, adding chitosan mixed liquor with the mass 2-4 times of that of the water-absorbing composite silk fabric blank into the reaction kettle, stirring and reacting, filtering to obtain a filter cake, and freeze-drying the filter cake to obtain the water-absorbing composite silk fabric;
(5) and (4) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (4).
Preferably, the modified polyethylene glycol in the step (1) is prepared by mixing polyethylene glycol 400 and succinic anhydride according to a mass ratio of 1: 1.2, mixing, adding N, N-dimethylformamide 6-8 times the mass of polyethylene glycol 400, stirring for reaction, extracting with cyclohexane, removing redundant succinic anhydride to obtain polyethylene glycol esterified substance dispersion liquid, and mixing the polyethylene glycol esterified substance dispersion liquid with thionyl chloride according to a mass ratio of 10: 1, stirring, reacting, and distilling under reduced pressure to obtain the modified polyethylene glycol.
And (2) optimally, the electrostatic spinning conditions in the step (1) are that the spinning voltage is 18kV, the total flow of the spinning solution is 0.9mL/h, the distance between a positive spray nozzle and a negative spray nozzle is 17.5cm, and the inner diameter of the spray nozzle is 0.5 mm.
And (3) optimizing, wherein the electrostatic spinning conditions in the step (2) are that the spinning voltage is 6-14 Kv, the distance between a spray head and a spinning plate is 6-14 cm, the total flow of a spinning solution is 1-2 mL/h, and the inner diameter of the spray head is 0.8 mm.
Preferably, the chitosan mixed solution in the step (3) is prepared by mixing chitosan and an acetic acid solution with the mass fraction of 5% according to the mass ratio of 1: 10, adding 2-methylamino pyridine accounting for 0.5-1.0 time of the mass of the chitosan and 1-ethyl- (3-dimethyl aminopropyl) carbonyl diimine hydrochloride accounting for 0.1-0.3 time of the mass of the chitosan, and stirring and mixing to obtain a chitosan mixed solution.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses modified silk fiber and modified spider silk fiber when preparing water-absorbing composite silk fabric, and adds chitosan in the subsequent treatment process; firstly, polyethylene glycol modified silk fiber and modified spider silk fiber containing glucan are blended to prepare the water-absorbing composite silk fabric, the product can have the drapability of silk, secondly, the glucan added into the spider silk fiber can be exposed when the blank of the prepared water-absorbing composite silk fabric is mixed and reacted with protease solution, so that the glucan reacts with the polyethylene glycol on the surface of the silk fiber to form water-absorbing microcapsules, further the water absorption rate of the water-absorbing composite silk fabric is improved, meanwhile, when the blank of the water-absorbing composite silk fabric is treated by using the protease solution, certain pits can be generated on the surface of the blank, further the water absorption rate of the product is improved, finally, the chitosan is added in the subsequent treatment process of the blank of the water-absorbing composite silk fabric, so that the chitosan can react with the spider silk protein and the silk protein decomposed by the protease to form a three-dimensional framework to be wound on the surface of the fiber in the water-absorbing composite silk fabric, thereby fixing the microcapsule formed by the polyethylene glycol and the glucan better and further improving the water absorption of the product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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.
In order to more clearly illustrate the method provided by the invention, the following examples are used for detailed description, and the method for testing each index of the water-absorbing composite silk fabric manufactured in the following examples is as follows:
coefficient of drape: the water-absorbing composite silk fabrics obtained in each example and the comparative product are tested by a fabric draping instrument.
Water absorption: the water-absorbing composite silk fabrics obtained in each example and the comparative products are placed in water, and after being soaked for 30min, the weight gain rate of each square centimeter of the fabrics is measured.
Example 1
The water-absorbing composite silk fabric mainly comprises the following raw materials in parts by weight: 32 parts of spidroin, 6 parts of glucan, 8 parts of chitosan and 30 parts of modified silk fiber.
The processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps of:
(1) mixing the waste silkworm cocoons and isopropyl ether according to a mass ratio of 1: 6, mixing, soaking for 4 hours at room temperature, filtering to obtain pretreated waste silkworm cocoons, and mixing the pretreated waste silkworm cocoons with absolute ethyl alcohol according to a mass ratio of 1: 5, mixing and soaking for 3 hours, filtering to obtain filter residue, and mixing the filter residue with deionized water according to a mass ratio of 1: 5, mixing, heating a mixture of filter residues and deionized water to boiling, keeping the temperature constant for 6 hours, filtering to obtain fibrous fibroin, mixing the fibrous fibroin with a sodium hydrosulfide solution with the mass fraction of 60%, dialyzing in a dialysis bag for 4 hours, concentrating at the temperature of 70 ℃ under the pressure of 500-600 kPa until the water content is 15% to obtain a fibroin liquid, and mixing the fibroin liquid with protease according to the mass ratio of 100: 3, mixing, reacting for 3 hours at room temperature, filtering to obtain pretreated silk protein liquid, washing the pretreated silk protein liquid for 3 times by using deionized water, and drying for 2 hours at the temperature of 70 ℃ to obtain silk protein powder; mixing fibroin powder and modified polyethylene glycol according to a mass ratio of 3: 1, mixing and boiling in a beaker, adding dimethyl sulfoxide 15 times of the weight of the fibroin powder into the beaker, stirring and reacting for 5 hours at the temperature of 50 ℃ and the rotating speed of 380r/min, filtering to obtain modified fibroin, mixing the modified fibroin and hexafluoroisopropanol according to the mass ratio of 1: 12, mixing to obtain modified silk fiber spinning solution, performing electrostatic spinning on the modified silk fiber spinning solution to obtain modified silk fiber fibrils, and twisting the modified silk fiber fibrils until the linear density is 60D to obtain modified silk fibers;
(2) mixing spider silk and hexafluoroisopropanol according to a mass ratio of 1: 10, adding glucan with the mass 0.2 times that of the spider silk into a mixture of the spider silk and hexafluoroisopropanol, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain modified spider silk fiber spinning solution, performing electrostatic spinning on the modified spider silk fiber spinning solution to obtain modified spider silk fiber fibrils, and twisting the modified spider silk fiber fibrils to the linear density of 50dtex to obtain modified spider silk fibers;
(3) blending the modified silk fiber obtained in the step (1) and the modified spider silk fiber obtained in the step (2) in a plain weave mode, wherein the modified silk fiber is used as a warp, the density of the warp is 600 pieces/cm, the modified spider silk fiber is used as a weft, the density of the warp is 400 pieces/cm, and a water-absorbing composite silk fabric blank is prepared;
(4) and (3) mixing the water-absorbing composite silk fabric blank obtained in the step (3) with a trypsin solution with the mass fraction of 5% according to the mass ratio of 1: 10, mixing the materials in a reaction kettle, stirring and reacting for 1h under the conditions that the temperature is 40 ℃ and the rotating speed is 280r/min, heating the physical temperature in the reaction kettle to 90 ℃, adding a chitosan mixed solution with the mass 4 times that of a water-absorbing composite silk fabric blank into the reaction kettle, stirring and reacting for 4h under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min, filtering to obtain a filter cake, and freeze-drying the filter cake to obtain the water-absorbing composite silk fabric;
(5) and (4) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (4).
Preferably, the modified polyethylene glycol in the step (1) is prepared by mixing polyethylene glycol 400 and succinic anhydride according to a mass ratio of 1: 1.2, mixing, adding N, N-dimethylformamide with the mass of polyethylene glycol of 8 times that of 400, stirring for reaction, extracting with cyclohexane, removing redundant succinic anhydride to obtain polyethylene glycol ester dispersion liquid, and mixing the polyethylene glycol ester dispersion liquid with thionyl chloride according to the mass ratio of 10: 1, stirring, reacting, and distilling under reduced pressure to obtain the modified polyethylene glycol.
And (2) optimally, the electrostatic spinning conditions in the step (1) are that the spinning voltage is 18kV, the total flow of the spinning solution is 0.9mL/h, the distance between a positive spray nozzle and a negative spray nozzle is 17.5cm, and the inner diameter of the spray nozzle is 0.5 mm.
And (3) optimizing, wherein the electrostatic spinning conditions in the step (2) are that the spinning voltage is 10Kv, the distance between a spray head and a spinning plate is 12cm, the total flow of a spinning solution is 1.5mL/h, and the inner diameter of the spray head is 0.8 mm.
Preferably, the chitosan mixed solution in the step (3) is prepared by mixing chitosan and an acetic acid solution with the mass fraction of 5% according to the mass ratio of 1: 10, adding 2-methylamino pyridine with the mass of 0.60 time of that of the chitosan and 1-ethyl- (3-dimethyl aminopropyl) carbonyl diimine hydrochloride with the mass of 0.2 time of that of the chitosan, and stirring and mixing to obtain a chitosan mixed solution.
Example 2
The water-absorbing composite silk fabric mainly comprises the following raw materials in parts by weight: 32 parts of spidroin, 6 parts of glucan and 30 parts of modified silk fiber.
The processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps of:
(1) mixing the waste silkworm cocoons and isopropyl ether according to a mass ratio of 1: 6, mixing, soaking for 4 hours at room temperature, filtering to obtain pretreated waste silkworm cocoons, and mixing the pretreated waste silkworm cocoons with absolute ethyl alcohol according to a mass ratio of 1: 5, mixing and soaking for 3 hours, filtering to obtain filter residue, and mixing the filter residue with deionized water according to a mass ratio of 1: 5, mixing, heating a mixture of filter residues and deionized water to boiling, keeping the temperature constant for 6 hours, filtering to obtain fibrous fibroin, mixing the fibrous fibroin with a sodium hydrosulfide solution with the mass fraction of 60%, dialyzing in a dialysis bag for 4 hours, concentrating at the temperature of 70 ℃ under the pressure of 500-600 kPa until the water content is 15% to obtain a fibroin liquid, and mixing the fibroin liquid with protease according to the mass ratio of 100: 3, mixing, reacting for 3 hours at room temperature, filtering to obtain pretreated silk protein liquid, washing the pretreated silk protein liquid for 3 times by using deionized water, and drying for 2 hours at the temperature of 70 ℃ to obtain silk protein powder; mixing fibroin powder and modified polyethylene glycol according to a mass ratio of 3: 1, mixing and boiling in a beaker, adding dimethyl sulfoxide 15 times of the weight of the fibroin powder into the beaker, stirring and reacting for 5 hours at the temperature of 50 ℃ and the rotating speed of 380r/min, filtering to obtain modified fibroin, mixing the modified fibroin and hexafluoroisopropanol according to the mass ratio of 1: 12, mixing to obtain modified silk fiber spinning solution, performing electrostatic spinning on the modified silk fiber spinning solution to obtain modified silk fiber fibrils, and twisting the modified silk fiber fibrils until the linear density is 60D to obtain modified silk fibers;
(2) mixing spider silk and hexafluoroisopropanol according to a mass ratio of 1: 10, adding glucan with the mass 0.2 times that of the spider silk into a mixture of the spider silk and hexafluoroisopropanol, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain modified spider silk fiber spinning solution, performing electrostatic spinning on the modified spider silk fiber spinning solution to obtain modified spider silk fiber fibrils, and twisting the modified spider silk fiber fibrils to the linear density of 50dtex to obtain modified spider silk fibers;
(3) blending the modified silk fiber obtained in the step (1) and the modified spider silk fiber obtained in the step (2) in a plain weave mode, wherein the modified silk fiber is used as a warp, the density of the warp is 600 pieces/cm, the modified spider silk fiber is used as a weft, the density of the warp is 400 pieces/cm, and a water-absorbing composite silk fabric blank is prepared;
(4) and (3) mixing the water-absorbing composite silk fabric blank obtained in the step (3) with a trypsin solution with the mass fraction of 5% according to the mass ratio of 1: 10, mixing the materials in a reaction kettle, stirring and reacting for 1h under the conditions that the temperature is 40 ℃ and the rotating speed is 280r/min, heating the physical temperature in the reaction kettle to 90 ℃, adding a mixed solution with the mass 4 times that of a water-absorbing composite silk fabric blank into the reaction kettle, stirring and reacting for 4h under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min, filtering to obtain a filter cake, and freeze-drying the filter cake to obtain the water-absorbing composite silk fabric;
(5) and (4) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (4).
Preferably, the modified polyethylene glycol in the step (1) is prepared by mixing polyethylene glycol 400 and succinic anhydride according to a mass ratio of 1: 1.2, mixing, adding N, N-dimethylformamide with the mass of polyethylene glycol of 8 times that of 400, stirring for reaction, extracting with cyclohexane, removing redundant succinic anhydride to obtain polyethylene glycol ester dispersion liquid, and mixing the polyethylene glycol ester dispersion liquid with thionyl chloride according to the mass ratio of 10: 1, stirring, reacting, and distilling under reduced pressure to obtain the modified polyethylene glycol.
And (2) optimally, the electrostatic spinning conditions in the step (1) are that the spinning voltage is 18kV, the total flow of the spinning solution is 0.9mL/h, the distance between a positive spray nozzle and a negative spray nozzle is 17.5cm, and the inner diameter of the spray nozzle is 0.5 mm.
And (3) optimizing, wherein the electrostatic spinning conditions in the step (2) are that the spinning voltage is 10Kv, the distance between a spray head and a spinning plate is 12cm, the total flow of a spinning solution is 1.5mL/h, and the inner diameter of the spray head is 0.8 mm.
Preferably, the mixed solution in the step (3) is prepared by mixing water and 2-methylaminopyridine according to the mass ratio of 50:3, adding 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride accounting for 0.02 time of the mass of the water, and stirring and mixing to obtain the mixed solution.
Example 3
The water-absorbing composite silk fabric mainly comprises the following raw materials in parts by weight: 32 parts of spidroin, 6 parts of glucan, 8 parts of chitosan and 30 parts of silk fiber.
The processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps of:
(1) mixing spider silk and hexafluoroisopropanol according to a mass ratio of 1: 10, adding glucan with the mass 0.2 times that of the spider silk into a mixture of the spider silk and hexafluoroisopropanol, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain modified spider silk fiber spinning solution, performing electrostatic spinning on the modified spider silk fiber spinning solution to obtain modified spider silk fiber fibrils, and twisting the modified spider silk fiber fibrils to the linear density of 50dtex to obtain modified spider silk fibers;
(2) blending the silk fiber and the modified spider silk fiber obtained in the step (1) in a plain weave mode, wherein the modified silk fiber is used as a warp, the density of the warp is 600 pieces/cm, the modified spider silk fiber is used as a weft, the density of the warp is 400 pieces/cm, and a water-absorbing composite silk fabric blank is prepared;
(3) mixing the water-absorbing composite silk fabric blank obtained in the step (2) with a trypsin solution with the mass fraction of 5% according to the mass ratio of 1: 10, mixing the materials in a reaction kettle, stirring and reacting for 1h under the conditions that the temperature is 40 ℃ and the rotating speed is 280r/min, heating the physical temperature in the reaction kettle to 90 ℃, adding a chitosan mixed solution with the mass 4 times that of a water-absorbing composite silk fabric blank into the reaction kettle, stirring and reacting for 4h under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min, filtering to obtain a filter cake, and freeze-drying the filter cake to obtain the water-absorbing composite silk fabric;
(4) and (4) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (3).
And (2) optimizing, wherein the electrostatic spinning conditions in the step (1) are that the spinning voltage is 10Kv, the distance between a spray head and a spinning plate is 12cm, the total flow of a spinning solution is 1.5mL/h, and the inner diameter of the spray head is 0.8 mm.
Preferably, the chitosan mixed solution in the step (2) is prepared by mixing chitosan and an acetic acid solution with the mass fraction of 5% according to the mass ratio of 1: 10, adding 2-methylamino pyridine with the mass of 0.60 time of that of the chitosan and 1-ethyl- (3-dimethyl aminopropyl) carbonyl diimine hydrochloride with the mass of 0.2 time of that of the chitosan, and stirring and mixing to obtain a chitosan mixed solution.
Example 4
The water-absorbing composite silk fabric mainly comprises the following raw materials in parts by weight: 32 parts of spidroin, 8 parts of chitosan and 30 parts of modified silk fiber.
The processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps of:
(1) mixing the waste silkworm cocoons and isopropyl ether according to a mass ratio of 1: 6, mixing, soaking for 4 hours at room temperature, filtering to obtain pretreated waste silkworm cocoons, and mixing the pretreated waste silkworm cocoons with absolute ethyl alcohol according to a mass ratio of 1: 5, mixing and soaking for 3 hours, filtering to obtain filter residue, and mixing the filter residue with deionized water according to a mass ratio of 1: 5, mixing, heating a mixture of filter residues and deionized water to boiling, keeping the temperature constant for 6 hours, filtering to obtain fibrous fibroin, mixing the fibrous fibroin with a sodium hydrosulfide solution with the mass fraction of 60%, dialyzing in a dialysis bag for 4 hours, concentrating at the temperature of 70 ℃ under the pressure of 500-600 kPa until the water content is 15% to obtain a fibroin liquid, and mixing the fibroin liquid with protease according to the mass ratio of 100: 3, mixing, reacting for 3 hours at room temperature, filtering to obtain pretreated silk protein liquid, washing the pretreated silk protein liquid for 3 times by using deionized water, and drying for 2 hours at the temperature of 70 ℃ to obtain silk protein powder; mixing fibroin powder and modified polyethylene glycol according to a mass ratio of 3: 1, mixing and boiling in a beaker, adding dimethyl sulfoxide 15 times of the weight of the fibroin powder into the beaker, stirring and reacting for 5 hours at the temperature of 50 ℃ and the rotating speed of 380r/min, filtering to obtain modified fibroin, mixing the modified fibroin and hexafluoroisopropanol according to the mass ratio of 1: 12, mixing to obtain modified silk fiber spinning solution, performing electrostatic spinning on the modified silk fiber spinning solution to obtain modified silk fiber fibrils, and twisting the modified silk fiber fibrils until the linear density is 60D to obtain modified silk fibers;
(2) mixing spider silk and hexafluoroisopropanol according to a mass ratio of 1: 10, mixing, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain modified spider silk fiber spinning solution, carrying out electrostatic spinning on the modified spider silk fiber spinning solution to obtain spider silk fiber fibrils, and twisting the spider silk fiber fibrils to the linear density of 50dtex to obtain spider silk fibers;
(3) blending the modified silk fiber obtained in the step (1) and the modified spider silk fiber obtained in the step (2) in a plain weave mode, wherein the modified silk fiber is used as a warp, the density of the warp is 600 pieces/cm, the modified spider silk fiber is used as a weft, the density of the warp is 400 pieces/cm, and a water-absorbing composite silk fabric blank is prepared;
(4) and (3) mixing the water-absorbing composite silk fabric blank obtained in the step (3) with a trypsin solution with the mass fraction of 5% according to the mass ratio of 1: 10, mixing the materials in a reaction kettle, stirring and reacting for 1h under the conditions that the temperature is 40 ℃ and the rotating speed is 280r/min, heating the physical temperature in the reaction kettle to 90 ℃, adding a chitosan mixed solution with the mass 4 times that of a water-absorbing composite silk fabric blank into the reaction kettle, stirring and reacting for 4h under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min, filtering to obtain a filter cake, and freeze-drying the filter cake to obtain the water-absorbing composite silk fabric;
(5) and (4) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (4).
Preferably, the modified polyethylene glycol in the step (1) is prepared by mixing polyethylene glycol 400 and succinic anhydride according to a mass ratio of 1: 1.2, mixing, adding N, N-dimethylformamide with the mass of polyethylene glycol of 8 times that of 400, stirring for reaction, extracting with cyclohexane, removing redundant succinic anhydride to obtain polyethylene glycol ester dispersion liquid, and mixing the polyethylene glycol ester dispersion liquid with thionyl chloride according to the mass ratio of 10: 1, stirring, reacting, and distilling under reduced pressure to obtain the modified polyethylene glycol.
And (2) optimally, the electrostatic spinning conditions in the step (1) are that the spinning voltage is 18kV, the total flow of the spinning solution is 0.9mL/h, the distance between a positive spray nozzle and a negative spray nozzle is 17.5cm, and the inner diameter of the spray nozzle is 0.5 mm.
And (3) optimizing, wherein the electrostatic spinning conditions in the step (2) are that the spinning voltage is 10Kv, the distance between a spray head and a spinning plate is 12cm, the total flow of a spinning solution is 1.5mL/h, and the inner diameter of the spray head is 0.8 mm.
Preferably, the chitosan mixed solution in the step (3) is prepared by mixing chitosan and an acetic acid solution with the mass fraction of 5% according to the mass ratio of 1: 10, adding 2-methylamino pyridine with the mass of 0.60 time of that of the chitosan and 1-ethyl- (3-dimethyl aminopropyl) carbonyl diimine hydrochloride with the mass of 0.2 time of that of the chitosan, and stirring and mixing to obtain a chitosan mixed solution.
Comparative example
The water-absorbing composite silk fabric mainly comprises the following raw materials in parts by weight: 32 parts of spidroin and 30 parts of silk fiber.
The processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps of:
(1) mixing spider silk and hexafluoroisopropanol according to a mass ratio of 1: 10, mixing, stirring and mixing for 30min at the temperature of 30 ℃ and the rotating speed of 300r/min to obtain modified spider silk fiber spinning solution, carrying out electrostatic spinning on the modified spider silk fiber spinning solution to obtain spider silk fiber fibrils, and twisting the spider silk fiber fibrils to the linear density of 50dtex to obtain spider silk fibers;
(2) blending the silk fiber and the modified spider silk fiber obtained in the step (1) in a plain weave mode, wherein the modified silk fiber is used as a warp, the density of the warp is 600 pieces/cm, the modified spider silk fiber is used as a weft, the density of the warp is 400 pieces/cm, and a water-absorbing composite silk fabric blank is prepared;
(3) mixing the water-absorbing composite silk fabric blank obtained in the step (2) with a trypsin solution with the mass fraction of 5% according to the mass ratio of 1: 10, mixing the materials in a reaction kettle, stirring and reacting for 1h under the conditions that the temperature is 40 ℃ and the rotating speed is 280r/min, heating the physical temperature in the reaction kettle to 90 ℃, adding a mixed solution with the mass 4 times that of a water-absorbing composite silk fabric blank into the reaction kettle, stirring and reacting for 4h under the conditions that the temperature is 60 ℃ and the rotating speed is 300r/min, filtering to obtain a filter cake, and freeze-drying the filter cake to obtain the water-absorbing composite silk fabric;
(4) and (4) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (3).
And (2) optimizing, wherein the electrostatic spinning conditions in the step (1) are that the spinning voltage is 10Kv, the distance between a spray head and a spinning plate is 12cm, the total flow of a spinning solution is 1.5mL/h, and the inner diameter of the spray head is 0.8 mm.
Preferably, the mixed solution in the step (2) is prepared by mixing water and 2-methylaminopyridine according to the mass ratio of 50:3, adding 1-ethyl- (3-dimethylaminopropyl) carbonyldiimine hydrochloride accounting for 0.02 time of the mass of the water, and stirring and mixing to obtain the mixed solution.
Examples of effects
Table 1 below shows the results of the analysis of the drapability and water absorption of the water-absorbent composite silk fabrics using examples 1 to 4 of the present invention and comparative examples.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Drape coefficient (%) | 36.8 | 35.2 | 42.3 | 48.6 | 50.1 |
| Water absorption (%) | 93 | 83 | 76 | 60 | 52 |
From the comparison of the experimental data of example 1 and the comparative example in table 1, it can be found that when the water-absorbing composite silk fabric is prepared, the water absorption rate of the water-absorbing composite silk fabric can be effectively improved on the premise of not influencing the drapability of the fabric by blending the polyethylene glycol modified silk fiber and the glucan modified spider silk fiber; from the comparison of the experimental data of the example 1 and the example 2, it can be found that when chitosan is not added in the preparation of the water-absorbing composite silk fabric, when the water-absorbing composite silk fabric blank is treated, the microspheres formed by polyethylene glycol and glucan cannot be firmly adsorbed in the water-absorbing composite silk fabric, so that the water absorption rate of the product is affected; from the comparison of the experimental data of example 1 and example 3, it can be seen that when the polyethylene glycol modified silk fiber is not used in the preparation of the water-absorbent composite silk fabric, water-absorbent microcapsules cannot be formed at a later stage, thereby greatly reducing the water absorption rate of the product, and similarly, the experimental data of example 1 and example 4 are compared. When the water-absorbing composite silk fabric is prepared, the modified spider silk fibers added with glucan cannot form water-absorbing microcapsules at the later stage, so that the water absorption rate of the product is influenced.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (5)
1. The water-absorbing composite silk fabric is characterized by mainly comprising the following raw materials in parts by weight: 20-35 parts of spidroin, 4-8 parts of glucan, 4-10 parts of chitosan and 20-30 parts of modified silk fiber;
the processing method of the water-absorbing composite silk fabric mainly comprises the following preparation steps:
(1) mixing the waste silkworm cocoons and isopropyl ether according to a mass ratio of 1: 6, mixing, soaking for 3-4 h at room temperature, filtering to obtain pretreated waste silkworm cocoons, and mixing the pretreated waste silkworm cocoons with absolute ethyl alcohol according to a mass ratio of 1: 5, mixing and soaking for 2-3 hours, filtering to obtain filter residue, and mixing the filter residue with deionized water according to a mass ratio of 1: 5, mixing, boiling for 5-6 h, filtering to obtain fibrous silk protein, mixing the fibrous silk protein with a sodium hydrosulfide solution with the mass fraction of 60%, dialyzing in a dialysis bag for 3-4 h, concentrating to obtain silk protein liquid, and mixing the silk protein liquid with protease according to the mass ratio of 100: 3, mixing, reacting for 2-3 hours at room temperature, filtering, washing and drying to obtain fibroin powder; mixing fibroin powder and modified polyethylene glycol according to a mass ratio of 3: 1, mixing, adding dimethyl sulfoxide 8-15 times of the mass of the fibroin powder, stirring and reacting, performing suction filtration to obtain modified fibroin, and mixing the modified fibroin with hexafluoroisopropanol in a mass ratio of 1: 12, mixing to obtain modified silk fiber spinning solution, performing electrostatic spinning on the modified silk fiber spinning solution to obtain modified silk fiber fibrils, and twisting the modified silk fiber fibrils until the linear density is 60D to obtain modified silk fibers;
(2) mixing spider silk and hexafluoroisopropanol according to a mass ratio of 1: 10, mixing, adding glucan with the mass of 0.1-0.2 times of that of the spider silk, stirring and mixing to obtain modified spider silk fiber spinning solution, carrying out electrostatic spinning on the modified spider silk fiber spinning solution to obtain modified spider silk fiber fibrils, and twisting the modified spider silk fiber fibrils to the linear density of 30-80 dtex to obtain modified spider silk fibers;
(3) blending the modified silk fiber obtained in the step (1) and the modified spider silk fiber obtained in the step (2) in a plain weave mode, wherein the modified silk fiber is used as a warp, the density of the warp is 400-600 pieces/cm, the modified spider silk fiber is used as a weft, the density of the warp is 200-400 pieces/cm, and a water-absorbing composite silk fabric blank is prepared;
(4) and (3) mixing the water-absorbing composite silk fabric blank obtained in the step (3) with a protease solution according to a mass ratio of 1: 10, mixing the materials in a reaction kettle, stirring and reacting for 1-2 hours, heating the physical temperature in the reaction kettle to 80-90 ℃, adding chitosan mixed liquor with the mass 2-4 times of that of the water-absorbing composite silk fabric blank into the reaction kettle, stirring and reacting, filtering to obtain a filter cake, and freeze-drying the filter cake to obtain the water-absorbing composite silk fabric;
(5) carrying out index analysis on the water-absorbing composite silk fabric obtained in the step (4);
the modified polyethylene glycol in the step (1) is prepared by mixing polyethylene glycol 400 and succinic anhydride according to a mass ratio of 1: 1.2, mixing, adding N, N-dimethylformamide 6-8 times the mass of polyethylene glycol 400, stirring for reaction, extracting with cyclohexane, removing redundant succinic anhydride to obtain polyethylene glycol esterified substance dispersion liquid, and mixing the polyethylene glycol esterified substance dispersion liquid with thionyl chloride according to a mass ratio of 10: 1, stirring, reacting, and distilling under reduced pressure to obtain the modified polyethylene glycol.
2. The water-absorbing composite silk fabric according to claim 1, which comprises the following raw material components in parts by weight: 32 parts of spidroin, 6 parts of glucan, 8 parts of chitosan and 30 parts of modified silk fiber.
3. The water-absorbing composite silk fabric according to claim 1, wherein the electrospinning conditions in the step (1) are that the spinning voltage is 18kV, the total flow rate of the spinning solution is 0.9mL/h, the distance between the positive nozzle and the negative nozzle is 17.5cm, and the inner diameter of the nozzles is 0.5 mm.
4. The water-absorbing composite silk fabric according to claim 1, wherein the electrostatic spinning conditions in the step (2) are that the spinning voltage is 6-14 Kv, the distance between the nozzle and the filament receiving plate is 6-14 cm, the total flow rate of the spinning solution is 1-2 mL/h, and the inner diameter of the nozzle is 0.8 mm.
5. The water-absorbing composite silk fabric according to claim 1, wherein the chitosan mixed solution in the step (3) is prepared by mixing chitosan with 5% by mass of acetic acid solution in a mass ratio of 1: 10, adding 2-methylamino pyridine accounting for 0.5-1.0 time of the mass of the chitosan and 1-ethyl- (3-dimethyl aminopropyl) carbonyl diimine hydrochloride accounting for 0.1-0.3 time of the mass of the chitosan, and stirring and mixing to obtain a chitosan mixed solution.
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