CN116065391A - Modified soybean protein fiber and antibacterial composite fabric as well as preparation and application thereof - Google Patents

Modified soybean protein fiber and antibacterial composite fabric as well as preparation and application thereof Download PDF

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Publication number
CN116065391A
CN116065391A CN202310111778.9A CN202310111778A CN116065391A CN 116065391 A CN116065391 A CN 116065391A CN 202310111778 A CN202310111778 A CN 202310111778A CN 116065391 A CN116065391 A CN 116065391A
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China
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soybean protein
protein fiber
reaction
polyethylene glycol
fiber
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宫怀瑞
朱剑
何留根
徐良平
沈晶茹
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Luolai Lifestyle Technology Co Ltd
Shanghai Luolai Lifestyle Technology Co Ltd
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Luolai Lifestyle Technology Co Ltd
Shanghai Luolai Lifestyle Technology Co Ltd
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Priority to CN202310111778.9A priority Critical patent/CN116065391A/en
Publication of CN116065391A publication Critical patent/CN116065391A/en
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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
    • D06M15/15—Proteins or derivatives thereof
    • 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
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/208—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based
    • D03D15/217—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads cellulose-based natural from plants, e.g. cotton
    • 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
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/233—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads protein-based, e.g. wool or silk
    • 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
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • 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
    • D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
    • D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • 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
    • 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
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • 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
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35—Abrasion, pilling or fibrillation resistance
    • 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
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/01—Natural vegetable fibres
    • D10B2201/02—Cotton
    • 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
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D10B2201/20—Cellulose-derived artificial fibres
    • 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
    • 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
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Botany (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to the technical field of household textiles, and discloses a modified soybean protein fiber, an antibacterial composite fabric and preparation and application thereof. Specifically, polyethylene glycol is subjected to oxidation and acylation reaction to obtain polyethylene glycol reaction liquid X, the polyethylene glycol reaction liquid X is added into zein solution, and the mixture is stirred uniformly to perform grafting reaction to obtain water-soluble zein; placing the pretreated soybean protein fiber into an aqueous solution of water-soluble zein and chitosan biguanide hydrochloride, oscillating, and performing a crosslinking reaction to obtain a mixed solution Y; adding sodium bicarbonate solution into the mixed solution Y, soaking, taking out the soybean protein fiber, washing with water, and airing to obtain the modified soybean protein fiber. The modified soybean protein fiber prepared by the preparation method disclosed by the invention has the advantages of good tensile strength, good hygroscopicity, high antibacterial rate and good antibacterial durability, and the prepared antibacterial composite fabric is anti-pilling and soft in handfeel.

Description

Modified soybean protein fiber and antibacterial composite fabric as well as preparation and application thereof
Technical Field
The invention relates to the technical field of household textiles, in particular to a modified soybean protein fiber and antibacterial composite fabric, and preparation and application thereof.
Background
The soybean protein fiber belongs to regenerated plant protein fiber, is prepared by taking oil-pressed soybean meal as a raw material, extracting globulin from the soybean meal by utilizing a biological engineering technology, adding functional auxiliary agents, grafting, copolymerizing and blending with high polymers such as nitrile groups, hydroxyl groups and the like to prepare protein spinning solution with certain concentration, changing the protein space structure, and carrying out wet spinning. The fiber has the excellent performances of cashmere-like soft hand feeling, silk-like soft luster, cotton warmth retention, good skin-friendly property and the like, and also has obvious antibacterial function, and is known as a healthy and comfortable fiber in the new century.
The cross section of the soybean protein fiber is dumbbell or waist round, the skin-core structure is obvious, and the skin layer is quite thick and has certain deformation resistance. The longitudinal section is irregular in shape of ravines and islands, and fine gaps are beneficial to ventilation, moisture conduction and heat transfer of the fiber. The soybean protein fiber has the characteristics of fine monofilament fineness, light specific gravity, antibacterial property and the like, but the soybean protein fiber has uneven breaking strength, brings difficulty to spinning, has common breaking elongation and has no wool recovery rate; the soybean protein fiber has low high temperature resistance and poor breaking strength and hygroscopicity under the high-humidity and hot conditions; the soybean protein fiber and other fibers are blended and then have small friction force, and the manufactured fabric has low durability and tensile strength.
At present, most of the production methods of the antibacterial soybean protein fiber are to weave fibrils and then carry out subsequent treatment, namely, finishing agents containing antibacterial agents are coated on the surface of a woven fabric in the presence of a certain adhesive, so that the soybean protein fiber with an antibacterial effect is formed. However, in the antibacterial soybean protein fiber formed by such a method, the adhesion of the antibacterial agent to the fiber surface is relatively poor, resulting in unsatisfactory durability of the antibacterial effect. In addition, the prior art also often blends soy protein fibers with other natural fibers having antimicrobial properties to obtain antimicrobial soy protein fibers, such as bamboo charcoal fibers.
Therefore, in order to improve the performance of the soybean protein fiber, it has been attempted to modify the soybean protein fiber in various ways, for example, immersing the soybean protein fiber in a textile finishing liquid made of compounds such as hydrolyzed fibroin, tea polyphenol, tea tree essential oil, antibacterial inhibitor, composite DNA repair agent, ammonium laureth sulfate, etc., and graft reacting the soybean protein fiber with the compounds such as ammonium laureth sulfate in the finishing liquid, thereby obtaining the modified soybean protein fiber.
The soybean protein fiber has less curl, poor cohesion and small friction coefficient, is easy to fuzzing in the sliver drafting process, is easy to kink and break in the processing process of fiber fineness and poor rigidity, and finally is easy to fuzzing and pilling in the use and washing process of the fabric.
The zein molecular structure contains obvious hydrophilic area and hydrophobic area, has unique self-assembly property, film forming property and gel property, is insoluble in water or absolute ethyl alcohol, and is applied to the aspects of drug delivery carrier systems and edible material preparation.
The chitosan biguanide hydrochloride has stronger and spectral antibacterial activity than chitosan, is a chitosan derivative with higher antibacterial activity and wider antibacterial range, solves the problem of bad influence on textiles caused by poor self performance of the existing antibacterial agent, improves the defects of bad antibacterial effect and washing fastness of the general antibacterial agent, and can keep good antibacterial performance under alkaline conditions. In summary, it is needed to provide a preparation method of a composite fabric, which can modify soybean protein fibers to improve the antibacterial property and the hydrophilicity of the soybean protein fibers, improve the tensile strength, the toughness and the moisture absorption performance of the soybean protein fibers, and solve the problem of pilling on the surface of the fabric by blending the soybean protein fibers with other fibers.
Disclosure of Invention
In view of the above, the invention aims to provide a modified soybean protein fiber, an antibacterial composite fabric and preparation and application thereof, which are used for solving the problems that soybean protein fibers are easy to fuzzing and pilling, the tensile strength, toughness and hygroscopicity of the soybean protein fibers are poor, and the antibacterial property of the soybean protein fibers is reduced in a plurality of washing processes in the prior art.
In order to achieve the above and related objects, the present invention provides a method for preparing modified soy protein fiber, comprising the steps of pretreatment and modification of soy protein fiber, specifically comprising the following steps:
(1) Performing oxidation and acylation reaction on polyethylene glycol to obtain polyethylene glycol reaction liquid X; adding polyethylene glycol reaction solution X into zein solution, uniformly stirring, and performing grafting reaction to obtain water-soluble zein;
(2) Placing the pretreated soybean protein fiber into the water solution of the water-soluble zein and chitosan biguanide hydrochloride obtained in the step (1), oscillating, and performing a crosslinking reaction to obtain a mixed solution Y;
(3) Adding sodium bicarbonate solution into the mixed solution Y in the step (2), soaking, taking out the soybean protein fiber, washing with water, and airing to obtain the modified soybean protein fiber.
Further, the solution and the reaction pH of the step (2) and the step (3) are controlled to be 7.5-8.
Further, the aqueous solution of the water-soluble zein and chitosan biguanide hydrochloride also comprises butane tetracarboxylic acid and/or citric acid.
Further, the dipping time in the step (3) is 5-15 min.
Further, the reaction temperature in the step (3) is 90-95 ℃; and/or the concentration of the water-soluble zein in the step (2) is 2-4 g/L, and the concentration of the chitosan biguanide hydrochloride is 2-4 g/L.
Further, in the step (1), polyethylene glycol is subjected to oxidation reaction under the action of an oxidant to obtain polyethylene glycol carboxyl, wherein the oxidant is one or a combination of more of potassium permanganate, succinic anhydride and chromium trioxide.
Further, polyethylene glycol is added into thionyl chloride through carboxyl, stirring and heating, and acylation reaction is carried out, so that polyethylene glycol reaction liquid X is obtained.
Further, the pretreatment of the soybean protein fiber in the step (2) comprises high-pressure temperature change, and the high-pressure temperature change comprises the following steps: controlling the moisture content of the soybean protein fiber to 7-9%, and performing variable temperature treatment for 4-5 times.
Further, the pressure of the temperature changing treatment is 30-40 Mpa, the temperature changing treatment comprises the treatment for 20-30 min at the temperature of 90-95 ℃ and the treatment for 30-35 min at the temperature of 150-155 ℃.
The invention also provides a preparation method of the antibacterial composite fabric, which comprises the following steps: the modified soybean protein fiber and the textile fiber prepared by the preparation method are blended and woven to obtain the antibacterial composite fabric.
Further, the textile fibers include cotton fibers, polyester fibers, and tencel fibers.
Further, the blending ratio of the modified soybean protein fiber to the textile fiber is 20-50: 50-80.
Further, the modified soybean protein fiber and antibacterial composite fabric provided by the invention can be applied to home textile products, such as four pieces of sleeves, quilts and the like.
Further, the modified soy protein fiber provided by the invention can also be used as an antibacterial quilt core.
The beneficial technical effects of the invention are as follows:
the invention makes zein which is insoluble in water and soluble in ethanol and polyethylene glycol undergo the process of grafting reaction, so that the hydrophobic zein can be changed into hydrophilic water-soluble zein by means of chemical modification; in addition, the use of water-soluble zein to avoid the use of ethanol, if used to dissolve zein, would make the solution more acidic, the chitosan biguanide hydrochloride reacts with the acid, reducing the chitosan biguanide hydrochloride bound to the fiber, resulting in a decrease in the bacteriostatic rate of the soy protein fiber. Since the soybean protein fiber is suitable for washing under alkaline conditions, chitosan biguanide hydrochloride having high antibacterial rate under alkaline conditions is used as an antibacterial agent.
In the water-soluble zein/chitosan hydrochloride aqueous solution, the soybean protein fiber and the water-soluble zein undergo a crosslinking reaction, and more hydrophilic parts of the water-soluble zein are combined into the soybean protein fiber, so that the hydrophilia, hygroscopicity and moisture regain of the modified soybean protein fiber are improved, and the modified soybean protein fiber has fuzzing and pilling resistance. The guanidine group of the chitosan biguanide hydrochloride and the soybean protein fiber are subjected to crosslinking reaction under the action of a crosslinking agent such as citric acid, so that the antibacterial effect is improved compared with the method that the chitosan biguanide hydrochloride is adsorbed onto the soybean protein fiber by Van der Waals force. The invention carries out dry heat temperature treatment on the soybean protein fiber under high pressure, and expands and contracts in repeated high and low temperature alternation, thereby improving the tensile strength, toughness and hygroscopicity of the soybean protein fiber and the compactness of the internal structure of the soybean protein fiber.
The modified soybean protein fiber can obtain better antibacterial effect, softness and drapability by improving the proportion of the modified soybean protein fiber in the blended yarn due to the good mechanical property and fuzzing and pilling resistance of the modified soybean protein fiber.
Detailed Description
Unless defined otherwise, all technical and/or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It is appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable combination or in any other described embodiment of the invention as appropriate. Certain features described in the context of various embodiments will not be considered essential features of those embodiments unless the embodiments are not operable without those elements. The present invention will be further described with reference to the following specific examples, but it should be noted that the specific blending ratios, process conditions, results, etc. described in the examples of the present invention are merely illustrative of the present invention, and are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
The invention provides a preparation method of modified soybean protein fiber, which comprises the following steps of pretreatment and modification of soybean protein fiber:
(1) Performing oxidation reaction on polyethylene glycol under the action of an oxidant, wherein the oxidant comprises, but is not limited to, potassium permanganate, manganese dioxide, dibasic acid, succinic anhydride and chromium trioxide to obtain polyethylene glycol carboxyl; and adding polyethylene glycol carboxyl into thionyl chloride, stirring, heating, and performing acylation reaction to obtain polyethylene glycol reaction liquid X.
(2) Pretreatment of soybean protein fibers: the moisture content of the soybean protein fiber is controlled to be 7-9%, the soybean protein fiber is placed into a temperature changing box, is treated for 20-30 min under the conditions of 30-40 Mpa and 90-95 ℃ and is treated for 30-35 min under the conditions of 150-155 ℃ and the temperature changing treatment is repeated for 4-5 times, so that the soybean protein fiber is contracted and expanded, and the compactness of the internal structure of the soybean protein fiber is improved while the tensile strength, the toughness and the hygroscopicity of the soybean protein fiber are improved. Placing the pretreated soybean protein fiber into the water solution of the water-soluble zein and chitosan biguanide hydrochloride obtained in the step (1), oscillating, and performing a crosslinking reaction to obtain a mixed solution Y.
(3) Adding sodium bicarbonate solution as a catalyst into the mixed solution Y in the step (2), reducing the hydrolysis of chitosan biguanide hydrochloride, keeping the solution in an alkaline environment, soaking for 5-15 min, taking out the soybean protein fiber, washing to be neutral, and airing to obtain the modified soybean protein fiber.
The solution and the reaction pH of the step (2) and the step (3) are controlled at 7.5-8, and the water solution of the water-soluble zein and the chitosan biguanide hydrochloride also comprises cross-linking agents such as butane tetracarboxylic acid, citric acid and the like to promote the combination of the chitosan biguanide hydrochloride and the soybean protein fiber so as to improve the antibacterial rate of the soybean protein fiber.
The temperature of the reaction in the step (3) is 90-95 ℃; the concentration of the water-soluble zein is 2-4 g/L, and the concentration of the chitosan biguanide hydrochloride is 2-4 g/L.
The invention also provides a preparation method of the antibacterial composite fabric, which comprises the following steps of blending and weaving the modified soybean protein fiber and the textile fiber prepared by the method to obtain the antibacterial composite fabric; textile fibers include, but are not limited to, cotton fibers, polyester fibers, and tencel fibers; the blending ratio of the modified soybean protein fiber to the textile fiber is 20-50: 50-80.
The modified soybean protein fiber and antibacterial composite fabric provided by the invention can be applied to home textile products, such as four pieces of sleeves, quilts and the like.
The modified soybean protein fiber provided by the invention can also be used as an antibacterial quilt core.
The method for preparing the antibacterial quilt core by using the modified soybean protein fiber comprises the following steps:
putting the prepared modified soybean protein fibers into a carding machine, and obtaining a modified soybean protein fiber quilt cover with uniform thickness through cotton scattering, cotton feeding, roller lapping, screen shaking and cotton feeding;
and opening the quilt cover, firstly grabbing a proper amount of modified soybean protein fibers to fill the two corners of the quilt cover, then filling the combed light tires (combed modified soybean protein fibers) of the carding machine into the quilt cover, then grabbing a proper amount of modified soybean protein fibers to fill the remaining two corners of the quilt cover, and finishing the quilt cover to obtain the antibacterial quilt core.
The present invention will be described in detail with reference to specific exemplary examples. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, as many insubstantial modifications and variations are within the scope of the invention as would be apparent to those skilled in the art in light of the foregoing disclosure. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below.
Example 1
A preparation method of modified soybean protein fiber comprises the following steps:
(1) Performing oxidation reaction on polyethylene glycol and chromium trioxide at room temperature to obtain polyethylene glycol carboxyl; and adding excessive thionyl chloride into polyethylene glycol carboxyl, stirring, heating to 80 ℃ to reflux for 8 hours, and removing thionyl chloride to obtain polyethylene glycol reaction liquid X.
(2) Slowly dripping polyethylene glycol reaction liquid X into zein solution, stirring, heating to 60 ℃, and reacting for 10 hours to obtain water-soluble zein, wherein the mass ratio of the polyethylene glycol reaction liquid X to zein is 6:1.
(3) Controlling the moisture content of the soybean protein fiber to 8%, then placing the soybean protein fiber in a temperature changing box for temperature changing treatment, wherein the pressure is 35Mpa, firstly, treating the soybean protein fiber at a low temperature of 95 ℃ for 25min, then treating the soybean protein fiber at a high temperature of 155 ℃ for 30min, and repeatedly carrying out high-temperature treatment and low-temperature treatment for 4 times to obtain the pretreated soybean protein fiber.
(4) Placing the pretreated soybean protein fiber into an aqueous solution of water-soluble zein and chitosan biguanide hydrochloride, and oscillating for 10min to obtain a mixed solution Y.
(5) Adding sodium bicarbonate into the mixed solution Y, soaking for 10min at 90 ℃, taking out, washing to neutrality, and air drying to obtain the modified soybean protein fiber. The concentration of the water-soluble zein is 2g/L, and the concentration of the chitosan biguanide hydrochloride is 2g/L; the mass ratio of the water-soluble zein to the chitosan biguanide hydrochloride is 30:1.
(6) The aqueous solution of the water-soluble zein and chitosan biguanide hydrochloride also comprises citric acid, and the solutions in the steps (2), (4), (5) and (6) and the reaction pH are controlled at 7.5.
The preparation method of the antibacterial composite fabric comprises the following steps of blending and weaving the modified soybean protein fiber and the textile fiber prepared by the method to obtain the antibacterial composite fabric; the textile fiber adopts cotton fiber; the blending ratio of the modified soybean protein fiber to the cotton fiber is 20:80.
example 2
A modified soy protein fiber and antibacterial composite fabric was prepared in the same manner as in example 1, except for the following conditions:
the concentration of the water-soluble zein is 3g/L, and the concentration of the chitosan biguanide hydrochloride is 3g/L; the mass ratio of the water-soluble zein to the chitosan biguanide hydrochloride is 40:1.
example 3
A modified soy protein fiber and antibacterial composite fabric was prepared in the same manner as in example 1, except for the following conditions:
the concentration of the water-soluble zein is 4g/L, and the concentration of the chitosan biguanide hydrochloride is 4g/L; the mass ratio of the water-soluble zein to the chitosan biguanide hydrochloride is 50:1.
example 4
Modified soybean protein fiber and antibacterial composite fabric were prepared in the same manner as in example 3 except for the following conditions:
the solutions and reaction pH of steps (2), (4), (5), (6) were controlled at 8.0.
Example 5
A modified soy protein fiber and antibacterial composite fabric was prepared in the same manner as in example 4, except for the following conditions:
the aqueous solution of the water-soluble zein and chitosan biguanide hydrochloride does not contain cross-linking agents such as butane tetracarboxylic acid and/or citric acid.
Example 6
A modified soy protein fiber and antibacterial composite fabric was prepared in the same manner as in example 4, except for the following conditions:
the blending ratio of the modified soybean protein fiber to the cotton fiber is 30:70.
example 7
A modified soy protein fiber and antibacterial composite fabric was prepared in the same manner as in example 4, except for the following conditions:
the blending ratio of the modified soybean protein fiber to the cotton fiber is 35:65.
example 8
A modified soy protein fiber and antibacterial composite fabric was prepared in the same manner as in example 4, except for the following conditions:
the blending ratio of the modified soybean protein fiber to the cotton fiber is 50:50.
comparative example 1
Dissolving 4g/L chitosan in glycine hydrochloride aqueous solution with concentration of 0.5% to obtain chitosan modified solution, and soaking soybean protein fiber in the 4g/L chitosan modified solution with bath ratio of 1:30, padding, twice padding, wherein each time of padding is performed for 30min, the padding residual rate is 90%, and drying is performed for 5min at 100 ℃ to obtain the chitosan modified soybean protein fiber.
Comparative example 2
Blending and weaving soybean protein fibers and cotton fibers to obtain a composite fabric; the blending ratio of the soybean protein fiber to the cotton fiber is 30:70.
performance testing
Antibacterial properties: the antibacterial properties of the soybean protein fibers against staphylococcus aureus ATCC6538, escherichia coli ATCC25922 and candida albicans ATCC10231 before and after treatment were measured by the shake flask method according to GB/T20944.3-2008, evaluation of antibacterial properties of textiles, section 3 shaking method.
Breaking strength and elongation at break: YG001 type electronic single fiber strength tester, according to GB/T997-1998 standard test soybean protein fiber, modified soybean protein fiber breaking strength and breaking elongation. Test conditions: the temperature is 20 ℃, the relative humidity is 65%, the clamping distance is 10mm, the stretching speed is 10mm/min, the pre-tension is 0.21cN, and the number of tests is 30.
The soybean protein fibers obtained after modification in examples 1 to 5 and comparative example 1 were subjected to the breaking strength and elongation at break test, and the test results are shown in Table 3.
Moisture regain: the moisture regain of the soy protein fiber and the modified soy protein fiber was measured using a direct assay.
The soybean protein fibers obtained after modification in examples 1 to 5 and comparative example 1 were subjected to the breaking strength and elongation at break test, and the test results are shown in Table 4.
Anti-pilling: with reference to GB/T4802.2-1997 fabric pilling test, the pilling test was performed on the composite fabrics of examples 6 to 8 and comparative example 2 on a Martindale tester by Martindale method. The test results are shown in Table 5.
The modified soybean protein fibers of examples 1 to 5 and comparative example 1 were subjected to antibacterial tests, and the obtained results were recorded as initial antibacterial rates; the modified soy protein fiber was then washed as follows: at 25 ℃, the modified soybean protein fiber is soaked in a sodium stearate solution with the concentration of 20 percent for 5min, then is washed for 5 times by clean water, and is dried, thus completing one-time washing. The modified soy protein fiber was washed 10 times, 20 times, 30 times. The antibacterial test results are shown in tables 1 and 2.
Table 1 antibacterial test results 1 of modified soybean protein fibers in examples and comparative examples
Figure BDA0004077007230000091
Figure BDA0004077007230000101
Table 2 results of antibacterial test of modified soybean protein fiber 2 in each of examples and comparative examples
Figure BDA0004077007230000102
( And (3) injection: the antibacterial rate to staphylococcus aureus and escherichia coli is more than or equal to 70 percent, the antibacterial rate to candida albicans is more than or equal to 60 percent, and the sample has antibacterial effect )
As can be seen from Table 1, the modified soybean protein fiber in example 1 was washed 30 times, and the antibacterial rates thereof were 80% (Staphylococcus aureus) and 78% (Escherichia coli), respectively, which were reduced by 12.09% and 12.36%, respectively, compared with the initial antibacterial rate. After 30 times of washing, the antibacterial rate of the modified soybean protein fiber in comparative example 1 is reduced by 20.45% and 22.73% respectively compared with the initial antibacterial rate.
As shown in Table 2, the modified soybean protein fiber of example 1 was washed 30 times, and the antibacterial rate was 77%, which was reduced by 14.44% as compared with the initial antibacterial rate. And the antibacterial rate of the modified soybean protein fiber in the comparative example 1 is reduced by 23.53% compared with the initial antibacterial rate after 30 times of washing.
Comparison of examples 1 to 5 with comparative example 1 shows that the modified soybean protein fiber prepared by the preparation method of the present invention has excellent antibacterial effect under the weak alkaline environment under the action of the crosslinking agent. The chitosan biguanide hydrochloride without the cross-linking agent is adsorbed on the surface of the soybean protein fiber through Van der Waals force, hydrogen bond and the cation property of biguanide, so that the soybean protein fiber modified by the chitosan biguanide hydrochloride only has poor washing fastness, and after the cross-linking agent is added, the cross-linking agent can react with the soybean protein fiber to generate carboxyl cellulose, and can also react with the chitosan biguanide hydrochloride to a certain extent. In addition, when the mass concentration of the chitosan biguanide hydrochloride is increased from 2g/L to 4g/L, the antibacterial rate is obviously improved. In summary, it can be stated that the modification of the soybean protein fiber by the chitosan biguanide hydrochloride not only can make the soybean protein fiber have good antibacterial property, but also can make the antibacterial rate of the soybean protein fiber against staphylococcus aureus and escherichia coli still be maintained above 70% after 30 times of washing, and the antibacterial rate against candida albicans still be maintained above 60%, namely, the antibacterial property of the soybean protein fiber can be maintained for a long time.
TABLE 3 results of breaking Strength and elongation at break test of modified soybean protein fibers in examples and comparative examples
Figure BDA0004077007230000111
As is clear from Table 3, the modified soybean protein fiber prepared by the preparation method of the present invention has an improved breaking strength of 18.18 to 38.64% and an improved elongation at break of 6.33 to 15.33% compared with the soybean protein fiber which is not modified by water-soluble zein and high-pressure temperature change.
Table 4 results of moisture regain test of modified soy protein fibers in examples and comparative examples
Moisture regain%
Example 1 10.54
Example 2 11.78
Example 3 12.66
Example 4 13.15
Example 5 13.00
Comparative example 1 8.6
As can be seen from Table 4, the modified soybean protein fiber prepared by the preparation method of the present invention has a moisture regain increased by 52.91% as compared with the soybean protein fiber which is not modified by water-soluble zein and high-pressure temperature change, and the soybean protein fiber and the water-soluble zein undergo a crosslinking reaction, and more hydrophilic part of the water-soluble zein is incorporated into the soybean protein fiber, so that the moisture regain of the modified soybean protein fiber is increased.
Table 5 fuzzing and pilling test results for the composite fabrics of examples and comparative examples
Stage number of fuzzing and pilling
Example 6 4
Example 7 3.5
Example 8 3
Comparative example 2 2.5
(note: 5 represents the best or substantially no pilling performance and 1 represents the worst pilling performance
As can be seen from table 5, the blending ratio of the modified soybean protein fiber to the cotton fiber is 30: the antibacterial composite fabric has the best fuzzing and pilling resistance at 70. This is because the more hydrophilic portion of the water-soluble zein is incorporated into the soy protein fiber, so that the hydrophilicity of the modified soy protein fiber is improved, thereby improving the fuzzing and pilling resistance of the soy protein fiber.
In conclusion, the modified soybean protein fiber prepared by the preparation method has good mechanical property and fuzzing and pilling resistance, and the composite fabric can obtain better antibacterial effect, softness and drapability by increasing the proportion of the modified soybean protein fiber in the blended yarn.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (10)

1. A method for preparing modified soybean protein fiber, which comprises pretreatment and modification of soybean protein fiber, and is characterized by comprising the following steps:
(1) Performing oxidation and acylation reaction on polyethylene glycol to obtain polyethylene glycol reaction liquid X; adding the polyethylene glycol reaction solution X into zein solution, uniformly stirring, and performing grafting reaction to obtain water-soluble zein;
(2) Placing the pretreated soybean protein fiber into the water solution of the water-soluble zein and chitosan biguanide hydrochloride obtained in the step (1), oscillating, and performing a crosslinking reaction to obtain a mixed solution Y;
(3) And (3) adding sodium bicarbonate solution into the mixed solution Y in the step (2), soaking, taking out the soybean protein fiber, washing with water, and airing to obtain the modified soybean protein fiber.
2. The preparation method according to claim 1, wherein the solution and the reaction pH of the step (2) and the step (3) are controlled to 7.5-8;
and/or, the aqueous solution of the water-soluble zein and chitosan biguanide hydrochloride in the step (2) further comprises butane tetracarboxylic acid and/or citric acid.
3. The method according to claim 1, wherein the dipping time in the step (3) is 5 to 15min;
and/or, the reaction temperature in the step (3) is 90-95 ℃;
and/or the concentration of the water-soluble zein in the step (2) is 2-4 g/L, and the concentration of the chitosan biguanide hydrochloride is 2-4 g/L.
4. The preparation method of claim 1, wherein the polyethylene glycol in the step (1) is subjected to an oxidation reaction under the action of an oxidant to obtain polyethylene glycol carboxyl, wherein the oxidant is one or a combination of more of potassium permanganate, succinic anhydride and chromium trioxide.
5. The preparation method according to claim 4, wherein the polyethylene glycol is added into thionyl chloride, stirred, heated, and subjected to acylation reaction to obtain the polyethylene glycol reaction solution X.
6. The method of claim 1, wherein the pretreatment of the soy protein fiber in step (2) comprises high-pressure temperature swing, the high-pressure temperature swing comprising the steps of: controlling the moisture content of the soybean protein fiber to 7-9%, and performing variable temperature treatment for 4-5 times.
7. The method according to claim 6, wherein the temperature-changing treatment is performed at a pressure of 30 to 40Mpa, and the temperature-changing treatment comprises a treatment at 90 to 95 ℃ for 20 to 30 minutes and a treatment at 150 to 155 ℃ for 30 to 35 minutes.
8. The preparation method of the antibacterial composite fabric is characterized by comprising the following steps of: blending and weaving the modified soybean protein fiber and the textile fiber according to any one of claims 1 to 7 to obtain the antibacterial composite fabric.
9. The method of claim 8, wherein the textile fibers comprise cotton fibers, polyester fibers, tencel fibers; the blending ratio of the modified soybean protein fiber to the textile fiber is 20-50: 50-80.
10. A modified soy protein fiber produced according to the method of any one of claims 1 to 7 or an antimicrobial composite fabric, an antimicrobial quilt core produced according to the method of any one of claims 8 to 9.
CN202310111778.9A 2023-02-14 2023-02-14 Modified soybean protein fiber and antibacterial composite fabric as well as preparation and application thereof Pending CN116065391A (en)

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GB1342900A (en) * 1969-12-03 1974-01-03 Ciba Geigy Ag Coating textiles
US5208075A (en) * 1990-09-15 1993-05-04 Basf Aktiengesellschaft Sizing agent for staple fiber and filament yarns
CN102120823A (en) * 2011-01-06 2011-07-13 鲁传华 Synthesis of water soluble zein and application thereof in pharmaceutical preparation
CN106978721A (en) * 2017-03-22 2017-07-25 广西科技大学 A kind of preparation method of long-acting antibiotic textile
CN108714239A (en) * 2018-05-30 2018-10-30 广东泰宝医疗器械技术研究院有限公司 A kind of high liquid-absorbing chitosan anti-bacteria glue dressing and preparation method thereof
CN111441182A (en) * 2020-04-26 2020-07-24 广州扬新科技有限公司 Antibacterial soybean protein fiber fabric and dyeing and finishing processing technology thereof
CN114481632A (en) * 2022-02-28 2022-05-13 江苏锐晟纺织科技有限公司 Long-acting biological antibacterial washable rayon crepe and preparation method thereof
CN115012227A (en) * 2022-07-14 2022-09-06 江南大学 Method for preparing hydrophobic textile by utilizing biomacromolecules

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1342900A (en) * 1969-12-03 1974-01-03 Ciba Geigy Ag Coating textiles
US5208075A (en) * 1990-09-15 1993-05-04 Basf Aktiengesellschaft Sizing agent for staple fiber and filament yarns
CN102120823A (en) * 2011-01-06 2011-07-13 鲁传华 Synthesis of water soluble zein and application thereof in pharmaceutical preparation
CN106978721A (en) * 2017-03-22 2017-07-25 广西科技大学 A kind of preparation method of long-acting antibiotic textile
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