CN114232337A - Double-protein acrylic fiber and preparation method thereof - Google Patents
Double-protein acrylic fiber and preparation method thereof Download PDFInfo
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- CN114232337A CN114232337A CN202111609071.8A CN202111609071A CN114232337A CN 114232337 A CN114232337 A CN 114232337A CN 202111609071 A CN202111609071 A CN 202111609071A CN 114232337 A CN114232337 A CN 114232337A
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H1/00—Macromolecular products derived from proteins
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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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/328—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
- D06M2101/28—Acrylonitrile; Methacrylonitrile
Abstract
The invention relates to a double-protein acrylic fiber and a preparation method thereof. The preparation method comprises the following steps: adding vegetable protein and glucose into water, carrying out glycosylation reaction, and freeze-drying to obtain saccharified vegetable protein; adding animal protein and glucose into water, carrying out glycosylation reaction, and freeze-drying to obtain glycosylated animal protein; adding the saccharified plant protein and the saccharified animal protein into water to obtain a protein solution; soaking the acrylic fiber in a sodium hydroxide aqueous solution, washing and drying, then placing the acrylic fiber in a thionyl chloride atmosphere for an acylchlorination reaction, then placing the acrylic fiber in a protein solution for a grafting reaction, washing and drying for the second time. By the above treatment, glucose is introduced into the protein, and then glycated protein is introduced into the fiber; when the protein is heated and unfolded, the steric effect of glucose prevents the aggregation of unfolded protein molecules, and improves the thermal stability of the double-protein fiber; the prepared fiber has good elasticity and excellent thermal stability.
Description
Technical Field
The invention relates to the technical field of household textiles, in particular to a double-protein acrylic fiber and a preparation method thereof.
Background
Natural protein fibers such as wool, silk and the like are important textile raw materials and have the characteristics of high elasticity, high strength, high toughness, light weight, softness and the like. However, the yield of natural protein fiber is limited and cannot meet the market demand. For this reason, regenerated protein fibers have been developed. The regenerated protein fiber is fiber prepared from protein extracted from pupa Bombycis, milk, semen glycines, semen Arachidis Hypogaeae, etc. The regenerated protein fiber has the excellent characteristics of natural protein fiber and the physical and chemical performance of synthetic fiber.
The regenerated protein fibers can be classified into the following two main categories according to the source of the protein: regenerated plant protein fiber and regenerated animal protein fiber. Common animal protein fibers include casein/polyacrylonitrile fibers, animal hair protein/polyvinyl alcohol fibers, and the like. The casein/polyacrylonitrile fiber has high strength, excellent hydroscopic property, good friction performance and excellent dyeing property. However, casein/polyacrylonitrile fibers are costly and have low yields.
In order to reduce the cost of casein/polyacrylonitrile fibers and improve the yield of the casein/polyacrylonitrile fibers, patent document CN1422880A attempts to add widely sourced plant proteins into acrylonitrile graft copolymerization spinning solution, specifically: dissolving 10-20 parts of animal protein and plant protein in 8-10% concentration sodium hydroxide water solution with pH of 8-10, stirring while heating to 40-50 deg.C, heating to 60-75 deg.C, adding 1.5-3% side chain modifier, stirring for 30-50 min, heating to 90-98 deg.C, stirring for 30-50 min, mixing with zinc chloride water solution, controlling the concentration of the dissolved protein and zinc chloride water solution at 1.4-3.7% and 55-75%, regulating pH to 1.9 + -0.15, stirring, mixing uniformly, adding 0.06-0.22% oxidant and 0.18-1.1% reducer based on the total weight of protein and polymer monomer, and stirring under nitrogen protection, adding 60-80 parts of acrylonitrile polymer while stirring, adjusting the pH value to 1.9 +/-0.15, reacting at the temperature of 20-75 ℃ for 40-180 minutes, and removing monomers by vacuum evaporation to obtain spinning stock solution with the concentration of 6.5-9%. The fiber prepared from the spinning solution has the skin-friendly property, the hygroscopicity and the air permeability of natural protein fiber, and is soft in hand feeling, soft in luster, good in dyeing property and strong in color fastness.
However, the double-protein acrylic fiber prepared from the spinning solution has poor thermal stability, and the processed fabric has the problems of easy protein thermal denaturation and the like in the after-finishing process, so that the moisture absorption and other properties of the fabric are affected.
Disclosure of Invention
In view of the above, the invention aims to provide a double-protein acrylic fiber and a preparation method thereof, which are used for solving the problems that in the prior art, the double-protein acrylic fiber is poor in thermal stability, and the processed fabric is easy to generate the problems of protein thermal denaturation and the like in the post-finishing process, so that the performance of the fabric in the aspects of moisture absorption and the like is affected.
In a first aspect, the invention aims to provide a preparation method of double-protein acrylic fiber, which comprises the following steps:
A. and (3) glycosylation: adding vegetable protein and glucose into water, carrying out glycosylation reaction, and then freeze-drying to obtain saccharified vegetable protein; adding animal protein and glucose into water, carrying out glycosylation reaction, and then freeze-drying to obtain glycosylated animal protein;
B. grafting: adding the saccharified plant protein and the saccharified animal protein into water to obtain a protein solution; and (2) soaking the acrylic fiber in a sodium hydroxide aqueous solution, washing and drying, then placing the acrylic fiber in a thionyl chloride atmosphere for an acylchlorination reaction, then placing the acrylic fiber in a protein solution for a grafting reaction, and then washing and drying for the second time to obtain the double-protein acrylic fiber.
Optionally, in step a, the vegetable protein is one or more of soy protein, zein and peanut protein.
Optionally, in step a, the animal protein is milk casein or animal collagen or a mixture of milk casein and animal collagen.
Optionally, in step a, the mass ratio of the plant protein to the glucose is 1: 1-1.5, preferably 1: 1-1.2.
Optionally, in step a, the mass ratio of the plant protein to water is 2-6: 100, preferably 2 to 4: 100.
optionally, in step a, the mass ratio of the animal protein to glucose is 1: 1-1.5, preferably 1: 1-1.2.
Optionally, in step a, the mass ratio of the animal protein to water is 2-6: 100, preferably 2 to 4: 100.
optionally, in step a, the glycosylation reaction has a pH of 8 to 10, preferably 9 to 10; the temperature of the glycosylation reaction is 75-85 ℃, preferably 80-85 ℃; the time of the glycosylation reaction is 35-45min, preferably 30-40 min.
Optionally, in the step A, the temperature of the freeze drying is-45 ℃ to-55 ℃, and is preferably-45 ℃ to-50 ℃; the pressure of freeze drying is 500-600Pa, preferably 550-600 Pa.
Optionally, the pH of the glycosylation reaction system is adjusted to 8-10 using sodium hydroxide solution or phosphate buffer solution.
Alternatively, the concentration of the sodium hydroxide solution is 0.005-0.1mol/L, preferably 0.01-0.1 mol/L.
Optionally, the concentration of the dihydrated dihydrogen phosphate in the phosphate buffer solution is 11.5-12g/L, preferably 11.5-11.8 g/L; the concentration of the monobasic phosphate monohydrate is 9 to 10g/L, preferably 9.2 to 10 g/L.
Optionally, in step a, the glycosylation reaction is performed under sonication conditions.
Optionally, the power of the ultrasound is 250-.
Optionally, in step B, the mass ratio of the glycated plant protein to the glycated animal protein is 1-3: 1-3, preferably 1-3: 1.
optionally, in step B, the concentration of the glycated vegetable protein in the protein solution is 1wt% to 3wt%, preferably 1wt% to 2 wt%.
Optionally, in step B, the fineness of the acrylic fiber is 1 to 10dtex, preferably 1 to 5 dtex.
Optionally, in step B, the concentration of sodium hydroxide in the aqueous sodium hydroxide solution is 10wt% to 15wt%, preferably 12wt% to 15 wt%.
Optionally, in the step B, the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 10-15: 1, preferably 10 to 12: 1.
optionally, in the step B, the drying temperature is 70-80 ℃, preferably 75-80 ℃; the drying time is 15-25min, preferably 20-25 min.
Optionally, in the step B, the soaking temperature is 70-80 ℃, preferably 75-80 ℃; the soaking time is 10-15min, preferably 12-15 min.
Optionally, in the step B, the temperature of the acyl chlorination reaction is 100-115 ℃, preferably 105-115 ℃; the time of the acyl chlorination reaction is 20-40min, preferably 30-40 min.
Optionally, in step B, the temperature of the grafting reaction is 75-85 ℃, preferably 80-85 ℃; the time of the grafting reaction is 30-40min, preferably 35-40 min.
Optionally, in the step B, the mass ratio of the protein solution to the acrylic fiber is 5-10: 1, preferably 8 to 10: 1.
optionally, in the step B, the temperature of the secondary drying is 60-70 ℃, and the time of the secondary drying is 15-20 min.
Optionally, in step B, triethylamine is further added to the protein solution.
Optionally, the concentration of triethylamine in the protein solution is 0.8wt% to 1.5 wt%.
In a second aspect, the present invention also provides the double protein acrylic fiber prepared by the above preparation method.
The invention has the beneficial effects that:
(1) glucose is introduced into protein through glycosylation reaction, and when the protein is heated and unfolded, steric effect of the glucose prevents unfolded protein molecules from aggregating, namely, the steric effect prevents the change (namely denaturation) of the spatial structure of the protein, so that the thermal stability of the protein is improved, and further, the thermal stability of the double-protein acrylic fiber is improved.
(2) According to the invention, sodium hydroxide can hydrolyze acrylic fiber to generate carboxyl, the carboxyl can react with thionyl chloride to generate acyl chloride groups, and the acyl chloride groups can perform a grafting reaction with amino in protein, so that the saccharified plant protein and the saccharified animal protein are introduced into the acrylic fiber.
(3) In the invention, the protein structure is loosened by the ultrasonic action, and the glycosylation reaction process is accelerated.
(4) In the invention, the phosphate buffer solution can influence the stability of glucose and accelerate the progress of glycosylation reaction.
(5) In the invention, triethylamine can react with hydrogen chloride which is a product of the grafting reaction, thereby promoting the grafting reaction.
(6) The double-protein acrylic fiber prepared by the invention has good elasticity and excellent thermal stability.
Detailed Description
The invention is further illustrated by the following specific examples, but it should be noted that the embodiments of the invention are
The specific material ratios, process conditions and results described in the specification are merely illustrative of the present invention and are not intended to limit the present invention thereto
All changes and modifications that come within the spirit of the invention are desired to be protected
Within the scope of protection. It is to be noted that "wt%" as indicated in the description herein means "mass fraction" unless otherwise specified.
The invention provides a preparation method of double-protein acrylic fiber, which comprises the following steps:
and (3) glycosylation: mixing plant protein and glucose according to a mass ratio of 1: 1-1.5, adding the mixture into water, wherein the vegetable protein is one or more of soybean protein, corn protein and peanut protein, and the mass ratio of the vegetable protein to the water is (2-6): 100, respectively; then, adjusting the pH value of the system to 8-10 by adopting 0.005-0.1mol/L sodium hydroxide solution or 9-10g/L dibasic hydrogen phosphate solution, carrying out glycosylation reaction at the temperature of 75-85 ℃ for 35-45min, and then carrying out freeze drying at the temperature of-45 ℃ to-55 ℃ and under the pressure of 500Pa to obtain the glycosylated plant protein; animal protein and glucose are mixed according to the mass ratio of 1: 1-1.5, adding into water, wherein the animal protein is milk casein or animal collagen or a mixture of the milk casein and the animal collagen, and the mass ratio of the animal protein to the water is 2-6: 100, respectively; then, adjusting the pH value of the system to 8-10 by adopting 0.005-0.1mol/L sodium hydroxide solution or 9-10g/L dibasic hydrogen phosphate solution, carrying out glycosylation reaction at the temperature of 75-85 ℃ for 35-45min, and then carrying out freeze drying at the temperature of-45 ℃ to-55 ℃ and under the pressure of 500Pa to obtain the glycosylated animal protein;
B. grafting: mixing the saccharified plant protein and the saccharified animal protein according to the mass ratio of 1-3: 1-3, adding into water to prepare a protein solution with the concentration of 1-3 wt% of the saccharified vegetable protein; soaking 1-4dtex acrylic fiber in 10-15 wt% sodium hydroxide aqueous solution at 70-80 ℃ for 10-15min, wherein the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 10-15: 1; then washing with water for 2-3 times, drying at 70-80 ℃ for 15-25min, then placing the acrylic fiber in thionyl chloride atmosphere for acylchlorination reaction at 100-115 ℃ for 20-40min, then placing the acrylic fiber in protein solution for grafting reaction at 75-85 ℃ for 30-40min, wherein the mass ratio of the protein solution to the acrylic fiber is 5-10: 1; then washing with water for 2-3 times, and then drying for 15-20min at 60-70 ℃ for the second time to obtain the double-protein acrylic fiber.
In another embodiment of the present invention, the glycosylation reaction is performed under the ultrasonic conditions of 250-350W.
In another embodiment of the present invention, triethylamine is further added to the protein solution, and the concentration of triethylamine is 0.8wt% to 1.5 wt%.
The present invention will be described in detail below with reference to specific exemplary embodiments. It should also be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations of the invention described above will occur to those skilled in the art. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
A preparation method of double-protein acrylic fiber comprises the following steps:
A. and (3) glycosylation: mixing soybean protein and glucose according to a mass ratio of 1: 1.5, adding the soybean protein into deionized water, wherein the mass ratio of the soybean protein to the deionized water is 6: 100, and then adjusting the pH of the system to 9 by using 0.01mol/L sodium hydroxide solution; then carrying out glycosylation reaction at 80 ℃ for 40min, and then carrying out freeze drying at-45 ℃ and under the pressure of 600Pa to obtain the glycosylated vegetable protein;
mixing milk casein and glucose according to a mass ratio of 1: 1.5, adding the milk casein and deionized water in a mass ratio of 6: 100, respectively; then adjusting the pH value of the system to 9 by using 0.01mol/L sodium hydroxide solution; then carrying out glycosylation reaction at 80 ℃ for 40min, and then carrying out freeze drying at-45 ℃ and under the pressure of 600Pa to obtain glycosylated animal protein;
B. grafting: and (2) mixing the saccharified plant protein and the saccharified animal protein according to the mass ratio of 3: 1 adding into deionized water to prepare a protein solution with the concentration of saccharified vegetable protein being 3 wt%;
soaking 1dtex acrylic fiber in a sodium hydroxide aqueous solution with the temperature of 75 ℃ and the concentration of 15wt% for 15min, wherein the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 15: 1; then washing with water for 3 times, drying at the temperature of 75 ℃ for 25min, then placing the acrylic fiber in a thionyl chloride atmosphere and carrying out an acyl chlorination reaction at the temperature of 115 ℃ for 25min, then placing the acrylic fiber in a protein solution and carrying out a grafting reaction at the temperature of 115 ℃ for 30min, wherein the mass ratio of the protein solution to the acrylic fiber is 10: 1; then washing with water for 3 times, and then drying for 15min at 70 ℃ for the second time to obtain the double-protein acrylic fiber.
Example 2
A preparation method of double-protein acrylic fiber comprises the following steps:
A. and (3) glycosylation: mixing zein and glucose according to a mass ratio of 1: 1.2 adding the corn protein into deionized water, wherein the mass ratio of the corn protein to the water is 5: 100, and then adjusting the pH of the system to 8.5 by using 0.01mol/L sodium hydroxide solution; then carrying out glycosylation reaction at 85 ℃ for 30min, and then carrying out freeze drying at-55 ℃ and 550Pa to obtain glycosylated vegetable protein;
animal collagen and glucose are mixed according to the mass ratio of 1: 1.2 adding the collagen into deionized water, wherein the mass ratio of the animal collagen to the water is 5: 100, respectively; then adjusting the pH value of the system to 8.5 by using 0.01mol/L sodium hydroxide solution; then carrying out glycosylation reaction at 85 ℃ for 30min, and then carrying out freeze drying at-55 ℃ and 550Pa to obtain glycosylated animal protein;
B. grafting: and (2) mixing the saccharified plant protein and the saccharified animal protein according to the mass ratio of 2: 1 adding into deionized water to prepare a protein solution with the concentration of 2wt% of saccharified vegetable protein;
soaking 2dtex acrylic fiber in a sodium hydroxide aqueous solution with the temperature of 80 ℃ and the concentration of 12wt% for 13min, wherein the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 12: 1; then washing with water for 2 times, drying at the temperature of 80 ℃ for 20min, then placing the acrylic fiber in a thionyl chloride atmosphere and carrying out an acyl chlorination reaction at the temperature of 110 ℃ for 38min, then placing the acrylic fiber in a protein solution and carrying out a grafting reaction at the temperature of 80 ℃ for 35min, wherein the mass ratio of the protein solution to the acrylic fiber is 10: 1; then washing with water for 2 times, and then drying for 20min at 65 ℃ for the second time to obtain the double-protein acrylic fiber.
Example 3
A preparation method of double-protein acrylic fiber comprises the following steps:
A. and (3) glycosylation: mixing peanut protein and glucose according to a mass ratio of 1: 1, adding the peanut protein into deionized water, wherein the mass ratio of the peanut protein to the deionized water is 2: 100, and then adjusting the pH of the system to 9.5 by using 0.01mol/L sodium hydroxide solution; then carrying out glycosylation reaction at 75 ℃ for 35min, and then carrying out freeze drying at-50 ℃ and under the pressure of 500Pa to obtain glycosylated vegetable protein;
animal collagen and glucose are mixed according to the mass ratio of 1: 1, adding the animal collagen and the water into deionized water, wherein the mass ratio of the animal collagen to the water is 2: 100, respectively; then adjusting the pH value of the system to 9.5 by using 0.01mol/L sodium hydroxide solution; then carrying out glycosylation reaction at 75 ℃ for 35min, and then carrying out freeze drying at-50 ℃ and under the pressure of 500Pa to obtain glycosylated animal protein;
B. grafting: and (2) mixing the saccharified plant protein and the saccharified animal protein according to the mass ratio of 1: 1 adding into deionized water to prepare a protein solution with the concentration of saccharified vegetable protein being 3 wt%;
soaking 4dtex acrylic fiber in a sodium hydroxide aqueous solution with the temperature of 78 ℃ and the concentration of 12wt% for 10min, wherein the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 10: 1; then washing with water for 3 times, drying at 70 ℃ for 25min, then placing the acrylic fiber in a thionyl chloride atmosphere and performing an acyl chlorination reaction at 105 ℃ for 40min, then placing the acrylic fiber in a protein solution and performing a grafting reaction at 75 ℃ for 38min, wherein the mass ratio of the protein solution to the acrylic fiber is 7: 1; then washing with water for 3 times, and then drying for 17min at 65 ℃ for the second time to obtain the double-protein acrylic fiber.
Example 4
A bi-protein acrylic fiber was prepared in the same manner as in example 1, except that the following conditions were applied:
A. and (3) glycosylation: mixing soybean protein and glucose according to a mass ratio of 1: 1.5, adding the soybean protein into deionized water, wherein the mass ratio of the soybean protein to the deionized water is 6: 100, and then adjusting the pH of the system to 9 by using 0.01mol/L sodium hydroxide solution; then, carrying out glycosylation reaction for 40min under 350W ultrasound and 80 ℃, and then carrying out freeze drying under the conditions that the temperature is minus 45 ℃ and the pressure is 600Pa to obtain the saccharified vegetable protein;
mixing milk casein and glucose according to a mass ratio of 1: 1.5, adding the milk casein and deionized water in a mass ratio of 6: 100, respectively; then adjusting the pH value of the system to 9 by using 0.01mol/L sodium hydroxide solution; then, carrying out glycosylation reaction for 40min under 350W ultrasound and 80 ℃, and then carrying out freeze drying under the conditions that the temperature is minus 45 ℃ and the pressure is 600Pa to obtain the glycosylated animal protein.
Example 5
A bi-protein acrylic fiber was prepared in the same manner as in example 1, except that the following conditions were applied:
A. and (3) glycosylation: mixing soybean protein and glucose according to a mass ratio of 1: 1.5, adding the soybean protein into deionized water, wherein the mass ratio of the soybean protein to the deionized water is 6: 100, and then adjusting the pH of the system to 9 by using 0.01mol/L sodium hydroxide solution; then, carrying out glycosylation reaction for 40min under the conditions of 250W ultrasound and 80 ℃, and then carrying out freeze drying under the conditions of-45 ℃ and 600Pa to obtain the saccharified vegetable protein;
mixing milk casein and glucose according to a mass ratio of 1: 1.5, adding the milk casein and deionized water in a mass ratio of 6: 100, respectively; then adjusting the pH value of the system to 9 by using 0.01mol/L sodium hydroxide solution; then, glycosylation reaction is carried out for 40min under the conditions of 250W ultrasound and 80 ℃, and then, the glycosylated animal protein is obtained by freeze drying under the conditions of-45 ℃ and 600 Pa.
Example 6
A bi-protein acrylic fiber was prepared in the same manner as in example 4, except that the following conditions were applied:
A. and (3) glycosylation: mixing soybean protein and glucose according to a mass ratio of 1: 1.5, adding the soybean protein into deionized water, wherein the mass ratio of the soybean protein to the deionized water is 6: 100, then adding phosphate buffer solution with the concentration of dibasic hydrogen phosphate dihydrate of 12g/L and the concentration of monobasic hydrogen phosphate monohydrate of 10g/L, and adjusting the pH value of the system to 9; then, carrying out glycosylation reaction for 40min under 350W ultrasound and 80 ℃, and then carrying out freeze drying under the conditions that the temperature is minus 45 ℃ and the pressure is 600Pa to obtain the saccharified vegetable protein;
mixing milk casein and glucose according to a mass ratio of 1: 1.5, adding the milk casein and deionized water in a mass ratio of 6: 100, respectively; then adding phosphate buffer solution with the concentration of dibasic hydrogen phosphate dihydrate being 12g/L and the concentration of monobasic hydrogen phosphate monohydrate being 10g/L, and adjusting the pH value of the system to 9; then, carrying out glycosylation reaction for 40min under 350W ultrasound and 80 ℃, and then carrying out freeze drying under the conditions that the temperature is minus 45 ℃ and the pressure is 600Pa to obtain the glycosylated animal protein.
Example 7
A bi-protein acrylic fiber was prepared in the same manner as in example 4, except that the following conditions were applied:
A. and (3) glycosylation: mixing soybean protein and glucose according to a mass ratio of 1: 1.5, adding the soybean protein into deionized water, wherein the mass ratio of the soybean protein to the deionized water is 6: 100, adding a phosphate buffer solution with the concentration of the dibasic hydrogen phosphate dihydrate being 11.5g/L and the concentration of the monobasic hydrogen phosphate monohydrate being 9g/L, and adjusting the pH value of the system to 9; then, carrying out glycosylation reaction for 40min under 350W ultrasound and 80 ℃, and then carrying out freeze drying under the conditions that the temperature is minus 45 ℃ and the pressure is 600Pa to obtain the saccharified vegetable protein;
mixing milk casein and glucose according to a mass ratio of 1: 1.5, adding the milk casein and deionized water in a mass ratio of 6: 100, respectively; then adding phosphate buffer solution with the concentration of dihydrate dihydrogen phosphate being 11.5g/L and the concentration of monohydrate dihydrogen phosphate being 9g/L, and adjusting the pH value of the system to 9; then, carrying out glycosylation reaction for 40min under 350W ultrasound and 80 ℃, and then carrying out freeze drying under the conditions that the temperature is minus 45 ℃ and the pressure is 600Pa to obtain the glycosylated animal protein.
Example 8
A bi-protein acrylic fiber was prepared in the same manner as in example 1, except that the following conditions were applied:
B. grafting: and (2) mixing the saccharified plant protein and the saccharified animal protein according to the mass ratio of 3: 1, adding the mixture into deionized water, stirring, then adding triethylamine, and stirring to prepare a protein solution with the concentration of saccharified vegetable protein being 3wt% and the concentration of triethylamine being 1.5 wt%;
soaking 1dtex acrylic fiber in a sodium hydroxide aqueous solution with the temperature of 75 ℃ and the concentration of 15wt% for 15min, wherein the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 15: 1; then washing with water for 3 times, drying at the temperature of 75 ℃ for 25min, then placing the acrylic fiber in a thionyl chloride atmosphere, carrying out an acyl chlorination reaction at the temperature of 115 ℃ for 25min, placing the acrylic fiber in a protein solution, carrying out a grafting reaction at the temperature of 115 ℃ for 30min, wherein the mass ratio of the protein solution to the acrylic fiber is 10: 1; then washing with water for 3 times, and then drying for 15min at 70 ℃ for the second time to obtain the double-protein acrylic fiber.
Example 9
A bi-protein acrylic fiber was prepared in the same manner as in example 1, except that the following conditions were applied:
B. grafting: and (2) mixing the saccharified plant protein and the saccharified animal protein according to the mass ratio of 3: 1, adding the mixture into deionized water, stirring, then adding triethylamine, and stirring to prepare a protein solution with the concentration of saccharified vegetable protein being 3wt% and the concentration of triethylamine being 0.8 wt%;
soaking 1dtex acrylic fiber in a sodium hydroxide aqueous solution with the temperature of 75 ℃ and the concentration of 15wt% for 15min, wherein the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 15: 1; then washing with water for 3 times, drying at the temperature of 75 ℃ for 25min, then placing the acrylic fiber in a thionyl chloride atmosphere to perform an acyl chlorination reaction at the temperature of 115 ℃ for 25min, placing the acrylic fiber in a protein solution to perform a grafting reaction at the temperature of 115 ℃ for 30min, wherein the mass ratio of the protein solution to the acrylic fiber is 10: 1; then washing with water for 3 times, and then drying for 15min at 70 ℃ for the second time to obtain the double-protein acrylic fiber.
Comparative example 1
A preparation method of double-protein acrylic fiber comprises the following steps:
mixing soybean protein and milk casein according to a mass ratio of 3: 1 adding the soybean protein into deionized water to prepare a protein solution with the concentration of 3wt percent of the soybean protein;
soaking 1dtex acrylic fiber in a 15wt% sodium hydroxide aqueous solution at the temperature of 75 ℃ for 15min, wherein the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 15: 1; then washing with water for 3 times, drying at the temperature of 75 ℃ for 25min, then placing the acrylic fiber in a protein solution in the atmosphere of thionyl chloride, and carrying out grafting reaction at the temperature of 115 ℃ for 30min, wherein the mass ratio of the protein solution to the acrylic fiber is 10: 1; then washing with water for 3 times, and then drying for 15min at 70 ℃ for the second time to obtain the double-protein acrylic fiber.
Performance detection
The double-protein acrylic fibers obtained in examples 1 to 9 and comparative example 1 were made into a cloth, and then dipped in 45g/L of MS-F018-2 water repellent finishing liquid (solvent is water), the mass ratio of the finishing liquid to the cloth being 20: 1; then carrying out mangling with the mangling rate of 75 percent, treating at the temperature of 90 ℃ for 30s, and then treating at the temperature of 110 ℃ for 3 min; subsequently, 50g of the sample was taken, and the moisture regain of the sample at 20 ℃ and 65% relative humidity was measured by an in-box weighing method (oven temperature 108 ℃ C., drying time 1 h) in GB/T06503 chemical fiber moisture regain, and the results are shown in Table 1.
Table 1 results of performance testing
| Source | Moisture regain/% |
| Example 1 | 7.3 |
| Example 2 | 6.9 |
| Example 3 | 6.7 |
| Example 4 | 8.4 |
| Example 5 | 8.1 |
| Example 6 | 10.2 |
| Example 7 | 9.8 |
| Example 8 | 8.7 |
| Example 9 | 8.0 |
| Comparative example 1 | 2.7 |
As can be seen from Table 1, the moisture regain of the fabrics made of the fibers of examples 1 to 9 was significantly improved as compared with that of comparative example 1, and the above results indicate that the protein in the fabrics made of the acrylic fibers of examples 1 to 9 was not denatured during the post-finishing process at 110 ℃ and that they had good moisture absorption, i.e., the acrylic fibers of examples 1 to 9 had good heat resistance.
Compared with the comparative example 1, the moisture regain of the fabric made of the fiber of the example 1 is improved by about 1.7 times.
Compared with example 1, the moisture regain of the fabrics made of the fibers of example 4 and example 5 is improved by about 15.1% and 11.0%, respectively.
Compared with example 1, the moisture regain of the fabrics made of the fibers of example 8 and example 9 is improved by about 19.2% and about 9.6%, respectively.
Compared with example 4, the moisture regain of the fabrics made of the fibers of example 6 and example 7 is improved by about 21.4% and about 16.7%, respectively.
In conclusion, the heat resistance of the fabric processed by the double-protein acrylic fiber is effectively improved.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The preparation method of the double-protein acrylic fiber is characterized by comprising the following steps of:
A. and (3) glycosylation: adding vegetable protein and glucose into water, carrying out glycosylation reaction, and then freeze-drying to obtain saccharified vegetable protein; adding animal protein and glucose into water, carrying out glycosylation reaction, and then freeze-drying to obtain glycosylated animal protein;
B. grafting: adding the saccharified plant protein and the saccharified animal protein into water to obtain a protein solution; and (2) soaking the acrylic fiber in a sodium hydroxide aqueous solution, washing and drying, then placing the acrylic fiber in a thionyl chloride atmosphere for an acylchlorination reaction, then placing the acrylic fiber in a protein solution for a grafting reaction, and then washing and drying for the second time to obtain the double-protein acrylic fiber.
2. The method according to claim 1, wherein in the step a, the vegetable protein is one or more of soybean protein, corn protein and peanut protein;
and/or, in the step A, the animal protein is milk casein or animal collagen or a mixture of the milk casein and the animal collagen;
and/or in the step A, the mass ratio of the plant protein to the glucose is 1: 1-1.5;
and/or in the step A, the mass ratio of the vegetable protein to the water is 2-6: 100, respectively;
and/or in the step A, the mass ratio of the animal protein to the glucose is 1: 1-1.5;
and/or in the step A, the mass ratio of the animal protein to the water is 2-6: 100, respectively;
and/or in the step A, the pH value of the glycosylation reaction is 8-10, the temperature of the glycosylation reaction is 75-85 ℃, and the time of the glycosylation reaction is 35-45 min;
and/or in the step A, the temperature of the freeze drying is-45 ℃ to-55 ℃, and the pressure of the freeze drying is 500-600 Pa.
3. The method according to claim 2, wherein the pH of the glycosylation reaction system is adjusted to 8 to 10 using a sodium hydroxide solution or a phosphate buffer solution.
4. The production method according to claim 3, wherein the concentration of the sodium hydroxide solution is 0.005 to 0.1 mol/L;
or in the phosphate buffer solution, the concentration of the dihydrogenphosphate dihydrate is 11.5-12g/L, and the concentration of the dihydrogenphosphate monohydrate is 9-10 g/L.
5. The method according to claim 1, wherein the glycosylation reaction is performed under ultrasonic conditions in step A.
6. The method as claimed in claim 5, wherein the power of the ultrasound is 250-350W.
7. The process according to claim 1, wherein in the step B, the mass ratio of the glycated plant protein to the glycated animal protein is from 1 to 3: 1-3;
and/or in the step B, the concentration of the saccharified vegetable protein in the protein solution is 1wt% -3 wt%;
and/or in the step B, the fineness of the acrylic fiber is 1-4 dtex;
and/or in the step B, the concentration of sodium hydroxide in the sodium hydroxide aqueous solution is 10-15 wt%;
and/or in the step B, the mass ratio of the sodium hydroxide aqueous solution to the acrylic fiber is 10-15: 1;
and/or in the step B, the soaking temperature is 70-80 ℃, and the soaking time is 10-15 min;
and/or in the step B, the drying temperature is 70-80 ℃, and the drying time is 15-25 min;
and/or in the step B, the temperature of the acyl chlorination reaction is 100-115 ℃, and the time of the acyl chlorination reaction is 20-40 min;
and/or in the step B, the temperature of the grafting reaction is 75-85 ℃, and the time of the grafting reaction is 30-40 min;
and/or in the step B, the mass ratio of the protein solution to the acrylic fiber is 5-10: 1;
and/or in the step B, the temperature of the secondary drying is 60-70 ℃, and the time of the secondary drying is 15-20 min.
8. The method according to claim 1, wherein triethylamine is further added to the protein solution in the step B.
9. The method according to claim 8, wherein the concentration of triethylamine in the protein solution is 0.8wt% to 1.5 wt%.
10. The double protein acrylic fiber produced by the production method according to any one of claims 1 to 9.
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