CN110685035B - Special enhanced elastic composite protein fiber for close-fitting textiles and preparation method - Google Patents

Special enhanced elastic composite protein fiber for close-fitting textiles and preparation method Download PDF

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CN110685035B
CN110685035B CN201911011003.4A CN201911011003A CN110685035B CN 110685035 B CN110685035 B CN 110685035B CN 201911011003 A CN201911011003 A CN 201911011003A CN 110685035 B CN110685035 B CN 110685035B
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protein fiber
spinning
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elastic composite
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CN110685035A (en
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关会堂
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Zhejiang juyitang Clothing Co.,Ltd.
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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • 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
    • D01D5/06—Wet spinning methods
    • 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
    • D01D5/12—Stretch-spinning methods
    • 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
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)
  • Multicomponent Fibers (AREA)

Abstract

The invention provides a reinforced elastic composite protein fiber special for close-fitting textiles and a preparation method thereof, wherein the composite protein fiber is prepared by preparing nano colloidal particles from polyurethane liquid and nano materials, then adding the nano colloidal particles into a mixed solution of soybean protein liquid, cellulose liquid and polyvinyl alcohol liquid, then carrying out wet spinning, and then sequentially carrying out coagulation bath, primary stretching, drying and solidification, secondary hot stretching, cooling, reeling and shaping. The nano colloidal particles uniformly dispersed in the composite protein fiber provided by the invention are beneficial to the enhancement, toughening and elasticity improvement of the composite protein fiber, and the skin-friendly property of the protein fiber is not influenced, so that the obtained composite protein fiber has excellent strength and elasticity, and the textile has good skin-friendly property, is soft and smooth, and is particularly suitable for next-to-skin textiles such as underwear and the like.

Description

Special enhanced elastic composite protein fiber for close-fitting textiles and preparation method
Technical Field
The invention relates to the technical field of composite fibers, in particular to a reinforced elastic composite protein fiber special for close-fitting textiles and a preparation method thereof.
Background
With the rapid development of functional textiles, new types of fibers are emerging. Among them, natural environment-friendly textiles using natural fibers as raw materials are most popular with customers. In particular, in the field of textile products for next to the skin, natural fibers are attracting much attention from consumers because of their advantages such as no damage to the skin, comfortable hand feeling, moisture absorption, and air permeability, and among them, soybean protein fibers are attracting much attention for their good properties.
The soybean protein fiber belongs to regenerated plant protein fiber, and is prepared with squeezed soybean dregs as material, and through extracting globulin from the soybean dregs and adding functional assistant to spin with nitrile group, hydroxyl group and other polymer. The soybean protein fiber has the advantages of soft and smooth hand feeling, bright luster, moisture absorption, good moisture permeability and the like. The intentional skin-friendly property is particularly suitable for knitted underwear products, and has good market application and development prospects.
The soybean protein fiber has a soft feeling similar to cashmere and silky smoothness. However, soybean fibers have low strength, poor elasticity and large shrinkage deformation. Pure soybean fiber is difficult to be directly used for spinning, the currently commonly known soybean fiber is basically obtained by mixing and spinning soybean protein liquid and polymer liquid, and other fibers are required to be added for twisting when the soybean fiber is used. For example, the soybean protein liquid can be prepared into fibers suitable for textile processing by adding functional additives and blending the functional additives based on polymers such as composite nitrile groups, hydroxyl groups and the like to prepare a spinning solution; for example, the soybean protein fiber is prepared by compounding and spinning polyamide and soybean fiber.
The soybean protein fiber is often shown in the way that the spinnability is influenced by the poor cohesion between the fibers, the soybean protein fiber is low in strength and elasticity, and when the conventional soybean protein fiber is used for textiles, the conventional soybean protein fiber needs to be combined with more polyurethane fibers, polyamide fibers and the like in a twisting mode in order to improve the strength and the elasticity, so that the pilling problem is caused, and the skin-friendly property, the moisture absorption property, the air permeability and other properties of the protein fiber are influenced.
Chinese patent application No. 201711261763.1 discloses a multifunctional protein fiber, which is prepared by using soybean protein, polyvinyl alcohol (PVA) and carboxymethyl chitosan as main raw materials, adding natural additives with the functions of antibiosis, mould prevention, mosquito prevention, insect prevention and cooling to prepare spinning stock solution with multiple functions, preparing the spinning stock solution into a semi-finished fiber by a wet spinning process, and improving the mechanical property of the protein fiber by a post-finishing process to finally obtain the multifunctional protein fiber with excellent mechanical property. Chinese patent application No. 201811210037.1 discloses a preparation method of protein composite fiber, which adopts polyhydroxy compound to modify nano titanium dioxide, so that the nano titanium dioxide is surrounded by hydroxyl, and the dispersibility of the nano titanium dioxide in the protein fiber is improved; simultaneously, the problem that the nano titanium dioxide is difficult to be compatible with the organic protein fiber is solved; the cross-linking agent prepared by the invention has excellent bonding performance, contains more active groups, and can connect the modified nano titanium dioxide to the protein fiber in a hydrogen bond mode, thereby improving the tensile strength and the friction resistance of the protein fiber; the invention simplifies the production process of the protein fiber, reduces the use of aldehyde harmful substances, improves the spinnability of the protein fiber, and has low energy consumption and no pollution.
In order to fully show the skin-friendly performance of the soybean protein fiber, ensure good strength and elasticity and be suitable for application in close-fitting textiles such as underwear and the like, a novel composite soybean protein fiber is needed to be provided, and the strength and the elasticity of the soybean protein fiber are further effectively improved.
Disclosure of Invention
Aiming at the defects that the existing soybean protein fibers have poor cohesion between fibers to influence spinnability and have low strength and elasticity, the invention provides the special enhanced elastic composite protein fiber for the close-fitting textiles and the preparation method thereof, thereby improving the strength and the elasticity of the soybean protein fibers and promoting the development and the application of the soybean protein fibers in the close-fitting textiles.
In order to solve the problems, the invention adopts the following technical scheme:
a preparation method of a special enhanced elastic composite protein fiber for next-to-skin textiles comprises the following specific steps:
(1) adding polyurethane liquid into the nano material, and then controlling the airflow flow to be 2-2.5m3H, stirring for 15-30min by high-speed airflow impact so that the polyurethane liquid fully coats the nano material, and then carrying out high-pressure spray drying to obtain nano colloidal particles;
(2) uniformly mixing the soybean protein liquid with the cellulose liquid and the polyvinyl alcohol liquid, then adding the nano colloidal particles for uniform dispersion to obtain a spinning solution, then carrying out wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, and carrying out primary stretching, wherein the stretching ratio is controlled to be 4-6, so as to obtain a primary stretched composite fiber;
(3) further drying and solidifying the composite fiber of the primary drawn yarn for 30-50min at the temperature of 90-110 ℃, then heating to 145-155 ℃, carrying out secondary hot drawing, controlling the drawing multiple at 7-10, cooling, coiling and shaping to obtain the special enhanced elastic composite protein fiber for the close-fitting textile.
Preferably, the solvent of the polyurethane liquid is N, N-dimethylacetamide, and the mass concentration of the solvent is 10-15%. According to the invention, the polyurethane solution is coated on the surface of the nano material, and elastic nano colloidal particles are obtained by spray drying and dispersed in the soybean protein fiber, so that the elasticity and toughness of the composite fiber are improved.
Preferably, the nano material is one or the combination of more than two of silicon oxide, titanium oxide, aluminum oxide and zinc oxide with the particle size of 5-100 nm. The invention selects the nano material as the filler of the composite fiber, has the obvious advantages of excellent dispersibility after the treatment by the polyurethane liquid, and can endow the protein fiber with excellent strength and toughness by uniformly dispersing in the spinning in a nano size. On the other hand, the nano material is coated by polyurethane to form nano colloidal particles for dispersion, and the nano colloidal particles show excellent elasticity, so that certain elasticity can be endowed to the soybean protein fiber.
Preferably, the mass concentration of the soybean protein liquid is 8-12%. The soybean protein liquid can be selected from commercially available soybean protein liquid, soybean protein liquid prepared by taking soybean meal as a raw material and utilizing a biological technology, and industrial common soybean protein spinning liquid.
Preferably, the cellulose solution has a mass concentration of 5-8% and the solvent is NMMO having a mass concentration of 85%. NMMO is an aliphatic cyclic tertiary amine oxide, is formed by reacting diethylene glycol and ammonia to generate morpholine, and is a good solvent for cellulose through methylation and oxidation. Further, the strength and skin-friendly property of the composite protein fiber can be further improved by dispersing the cellulose liquid in the protein liquid.
Preferably, the mass concentration of the polyvinyl alcohol solution is 10-15%.
Preferably, the high-pressure spray drying in the step (1) adopts a conventional high-pressure spray dryer, the pressure is 0.2-0.5MPa, and the temperature of the supplied hot air is 60-75 ℃. According to the invention, the wet composite formed by mixing polyurethane liquid and the nano material is spray-dried by high-pressure hot air, so that polyurethane is coated on the nano material to form nano colloidal particles.
Preferably, in the preparation of the nano colloidal particle in the step (1), the mass ratio of the nano material to the polyurethane liquid is 100: 25-30.
Preferably, the spinneret plate adopted in the wet spinning in the step (2) has 6-8 holes, the diameter of the spinneret hole is 100-200 μm, the spinning speed is 20-30m/min, and the spinning temperature is 70-90 ℃.
Preferably, the coagulating bath in the step (2) adopts 5 wt% of acetic acid solution, and the temperature of the coagulating bath is 30-60 ℃.
Preferably, in the spinning solution in the step (2), the mass ratio of the soybean protein solution, the cellulose solution and the polyvinyl alcohol solution is 100: 30-50: 15-20 percent, wherein the addition amount of the nano colloidal particles is 0.5-1 percent of the total mass of the soybean protein liquid and the cellulose liquid.
The composite protein fiber is prepared by taking polyurethane liquid and a nano material as raw materials to prepare nano colloidal particles, then adding the nano colloidal particles into a mixed solution of soybean protein liquid, cellulose liquid and polyvinyl alcohol liquid, then carrying out wet spinning, and then sequentially carrying out coagulation bath, primary stretching, drying and coagulation, secondary hot stretching, cooling and reeling and shaping.
The composite fiber is prepared by selecting a wet spinning process, the spinning stability can be ensured by effectively controlling the temperature and the speed of the wet spinning, the fineness of the precursor fiber with high performance is smaller, the fineness of the precursor fiber can be greatly reduced by primary stretching by adopting a method of twice stretching, and the nascent fiber is a highly swollen colloid and is not suitable for being directly subjected to high-power stretching, so that the stretching ratio is controlled to be 4-6, and a good section form can be formed. Furthermore, the composite fiber drawn for the first time is heated and then is subjected to second hot drawing, so that the nano-sized fiber with better strength, better toughness and more uniformity can be obtained under high drawing multiple.
The existing soybean protein fiber usually shows that the spinnability is influenced by the poor cohesion between the fibers, and the soybean protein fiber has low strength and low elasticity, so that the application of the soybean protein fiber is limited. In view of the above, the invention provides a reinforced elastic composite protein fiber special for close-fitting textiles and a preparation method thereof, polyurethane liquid is added into a nano material, high-speed airflow impact stirring is carried out, the nano material is fully coated by the polyurethane liquid, and then high-pressure spray drying is carried out, so as to obtain nano colloidal particles; uniformly mixing the soybean protein liquid with the cellulose liquid and the polyvinyl alcohol liquid, then adding the nano colloidal particles, carrying out wet spinning by a spinneret plate, spraying the mixture into a coagulating bath, coagulating the mixture into wet filaments, and then carrying out primary stretching; and further drying and solidifying the primary drawn yarn, raising the temperature, carrying out secondary hot drawing, cooling, coiling and shaping to obtain the enhanced elastic composite protein fiber special for the close-fitting textile. The nano colloidal particles uniformly dispersed in the composite protein fiber provided by the invention are beneficial to the enhancement, toughening and elasticity improvement of the composite protein fiber, and the skin-friendly property of the protein fiber is not influenced, so that the obtained composite protein fiber has excellent strength and elasticity, and the textile has good skin-friendly property, is soft and smooth, and is particularly suitable for next-to-skin textiles such as underwear and the like.
Compared with the prior art, the invention provides the special enhanced elastic composite protein fiber for the close-fitting textile and the preparation method thereof, and the outstanding characteristics and excellent effects are as follows:
1. the invention prefabricates the nano colloidal particles with elasticity and reinforcing function, and the nano colloidal particles are added during the spinning of the protein fiber, so that the nano colloidal particles are uniformly dispersed in the protein fiber, and the nano size of the nano colloidal particles is beneficial to reinforcing and toughening of the fiber; meanwhile, the polyurethane is coated with the nano particles, so that the polyurethane has good elasticity and can improve the elasticity of the protein fiber.
2. The invention is different from the method of directly spinning the polyurethane liquid and the protein liquid, and adopts the polyurethane dispersed in the protein fiber in the form of elastic nanometer particles, thereby ensuring the elasticity of the fiber and avoiding the influence on the skin-friendly property of the protein fiber caused by directly utilizing the spinning of the polyurethane liquid and the protein liquid. Furthermore, the cellulose liquid is dispersed in the protein liquid, so that the strength and the skin friendliness of the composite protein fiber are promoted.
3. The composite protein fiber obtained by the invention has excellent strength and elasticity, and the textile has good skin-friendly property, is soft and smooth, and is particularly suitable for next-to-skin textiles such as underwear and the like.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Taking N, N-dimethylacetamide as a solventAdding 12.5% polyurethane solution into 50nm silicon oxide at air flow rate of 2.2m3Impact stirring is carried out for 25min by high-speed airflow per hour, so that the polyurethane liquid fully coats the nano material, and then high-pressure spray drying is carried out, so as to obtain nano colloidal particles; the high-pressure spray drying adopts a conventional high-pressure spray dryer, the pressure is 0.4MPa, and the temperature of hot air supply is 68 ℃; in the preparation of the nano colloidal particle, the mass ratio of the nano material to the polyurethane liquid is 100: 28;
(2) uniformly mixing 10% of soybean protein liquid, 6.5% of cellulose liquid and 12.5% of polyvinyl alcohol liquid, wherein the solvent of the cellulose liquid is 85% of NMMO, adding nano colloidal particles, uniformly dispersing to obtain spinning solution, carrying out wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, carrying out primary stretching, and controlling the stretching multiple to be 5 to obtain primary stretched composite fibers; the spinning plate adopted by the method for spinning has 6 holes, the diameter of the spinning hole is 150 mu m, the spinning speed is 25m/min, and the spinning temperature is 80 ℃; 5 wt% of acetic acid solution is adopted in the coagulating bath, and the temperature of the coagulating bath is 45 ℃; in the spinning solution, the mass ratio of the soybean protein liquid to the cellulose liquid to the polyvinyl alcohol liquid is 100: 40: 18, the adding amount of the nano colloidal particles is 0.5 percent of the total mass of the soybean protein liquid and the cellulose liquid;
(3) and (3) further drying and solidifying the composite fiber of the primary drawn yarn for 40min at the temperature of 100 ℃, then heating to 150 ℃, carrying out secondary hot drawing with the drawing multiple controlled at 8.5, cooling, reeling and shaping to obtain the special enhanced elastic composite protein fiber for the next-to-skin textile.
The test method comprises the following steps:
the composite protein fiber prepared in this example was subjected to tensile property testing, using a YG001A type single fiber electronic strength tester, with a holding distance of 10mm, a tensile speed of 10mm/min, a number of tests of 30 times, a temperature of 20 ℃, a relative humidity of 65%, and dry breaking strength and elastic recovery of 100% elongation of the composite fiber, and the results are shown in Table 1.
Example 2
(1) Adding polyurethane solution with 10% mass concentration and N, N-dimethylacetamide as solvent into titanium oxide with average particle diameter of 10nm, and then controlling air flow rate to be 2m3H, stirring for 30min by high-speed airflow impact to fully coat the polyurethane liquid with the nano material, and then carrying out high-pressure spray drying to obtain nano colloidal particles; the high-pressure spray drying adopts a conventional high-pressure spray dryer, the pressure is 0.2MPa, and the temperature of supplied hot air is 60 ℃; in the preparation of the nano colloidal particle, the mass ratio of the nano material to the polyurethane liquid is 100: 25;
(2) uniformly mixing 8% of soybean protein liquid, 5% of cellulose liquid and 10% of polyvinyl alcohol liquid, wherein the solvent of the cellulose liquid is NMMO with the mass concentration of 85%, adding nano colloidal particles, uniformly dispersing to obtain spinning solution, performing wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, performing primary stretching, and controlling the stretching ratio to be 4 to obtain primary stretched composite fibers; the spinning plate adopted by the method is 8 holes, the diameter of the spinning hole is 100 mu m, the spinning speed is 20m/min, and the spinning temperature is 70 ℃; the coagulating bath adopts 5 wt% of acetic acid solution, and the temperature of the coagulating bath is 30 ℃; in the spinning solution, the mass ratio of the soybean protein liquid to the cellulose liquid to the polyvinyl alcohol liquid is 100: 30: 15, the adding amount of the nano colloidal particles is 0.6 percent of the total mass of the soybean protein liquid and the cellulose liquid;
(3) and (3) further drying and solidifying the composite fiber of the primary drawn yarn for 50min at the temperature of 90 ℃, then heating to 145 ℃, carrying out secondary hot drawing, controlling the drawing multiple to be 7, cooling, reeling and shaping to obtain the special enhanced elastic composite protein fiber for the next-to-skin textile.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 3
(1) Adding 15% polyurethane solution with N, N-dimethylacetamide as solvent into 100nm alumina, and controlling air flow at 2.5m3H high-speed airflow impact stirring for 15min to fully coat the polyurethane liquid with the nano material, then high-pressure spray drying,obtaining nano colloidal particles; the high-pressure spray drying adopts a conventional high-pressure spray dryer, the pressure is 0.5MPa, and the temperature of supplied hot air is 75 ℃; in the preparation of the nano colloidal particle, the mass ratio of the nano material to the polyurethane liquid is 100: 30, of a nitrogen-containing gas;
(2) uniformly mixing a soybean protein liquid with the mass concentration of 12%, a cellulose liquid with the mass concentration of 8% and a polyvinyl alcohol liquid with the mass concentration of 15%, wherein the solvent of the cellulose liquid is NMMO with the mass concentration of 85%, then adding nano colloidal particles to uniformly disperse to obtain a spinning solution, then carrying out wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, carrying out primary stretching, and controlling the stretching multiple to be 5 to obtain primary stretched composite fibers; the spinning plate adopted by the method for spinning has 6 holes, the diameter of the spinning hole is 200 mu m, the spinning speed is 30m/min, and the spinning temperature is 90 ℃; 5 wt% of acetic acid solution is adopted in the coagulating bath, and the temperature of the coagulating bath is 60 ℃; in the spinning solution, the mass ratio of the soybean protein liquid to the cellulose liquid to the polyvinyl alcohol liquid is 100: 50: 20, the adding amount of the nano colloidal particles is 0.7 percent of the total mass of the soybean protein liquid and the cellulose liquid;
(3) and (3) further drying and solidifying the composite fiber of the primary drawn yarn for 30min at 110 ℃, then heating to 155 ℃, carrying out secondary hot drawing with the drawing multiple controlled at 10, cooling, reeling and shaping to obtain the special enhanced elastic composite protein fiber for the next-to-skin textile.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 4
(1) Adding 11% polyurethane solution with N, N-dimethylacetamide as solvent into 30nm zinc oxide, and controlling gas flow at 2.1m3H, stirring for 26min by high-speed airflow impact to fully coat the polyurethane liquid with the nano material, and then carrying out high-pressure spray drying to obtain nano colloidal particles; the high-pressure spray drying adopts a conventional high-pressure spray dryer, the pressure is 0.3MPa, and the temperature of supplied hot air is 65 ℃; in the preparation of the nano colloidal particle, the mass ratio of the nano material to the polyurethane liquid is 100: 26;
(2) uniformly mixing 9% of soybean protein liquid, 6% of cellulose liquid and 11% of polyvinyl alcohol liquid, wherein the solvent of the cellulose liquid is NMMO with the mass concentration of 85%, adding nano colloidal particles, uniformly dispersing to obtain spinning solution, performing wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, performing primary stretching, and controlling the stretching ratio to be 4.5 to obtain primary stretched composite fibers; the spinning plate adopted by the method for spinning has 8 holes, the diameter of the spinning hole is 120 mu m, the spinning speed is 23m/min, and the spinning temperature is 75 ℃; the coagulating bath adopts 5 wt% of acetic acid solution, and the temperature of the coagulating bath is 40 ℃; in the spinning solution, the mass ratio of the soybean protein liquid to the cellulose liquid to the polyvinyl alcohol liquid is 100: 35: 17, the adding amount of the nano colloidal particles is 0.8 percent of the total mass of the soybean protein liquid and the cellulose liquid;
(3) and (3) further drying and solidifying the composite fiber of the primary drawn yarn for 45min at the temperature of 95 ℃, then heating to 148 ℃, carrying out secondary hot drawing with the drawing multiple controlled at 8, and then cooling, reeling and shaping to obtain the special enhanced elastic composite protein fiber for the next-to-skin textiles.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 5
(1) Adding polyurethane solution with mass concentration of 14% and using N, N-dimethylacetamide as solvent into silica with average particle diameter of 80nm, and then using air flow rate of 2.4m3Impact stirring is carried out for 25min by high-speed airflow per hour, so that the polyurethane liquid fully coats the nano material, and then high-pressure spray drying is carried out, so as to obtain nano colloidal particles; the high-pressure spray drying adopts a conventional high-pressure spray dryer, the pressure is 0.4MPa, and the temperature of supplied hot air is 72 ℃; in the preparation of the nano colloidal particle, the mass ratio of the nano material to the polyurethane liquid is 100: 29;
(2) uniformly mixing a soybean protein liquid with the mass concentration of 11%, a cellulose liquid with the mass concentration of 7% and a polyvinyl alcohol liquid with the mass concentration of 14%, wherein the solvent of the cellulose liquid is NMMO with the mass concentration of 85%, then adding nano colloidal particles to uniformly disperse to obtain a spinning solution, then carrying out wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, carrying out primary stretching, and controlling the stretching multiple to be 5.5 to obtain primary stretched composite fibers; the spinning plate adopted by the method for spinning has 6 holes, the diameter of the spinning hole is 180 mu m, the spinning speed is 28m/min, and the spinning temperature is 85 ℃; the coagulating bath adopts 5 wt% of acetic acid solution, and the temperature of the coagulating bath is 50 ℃; in the spinning solution, the mass ratio of the soybean protein liquid to the cellulose liquid to the polyvinyl alcohol liquid is 100: 45: 18, the adding amount of the nano colloidal particles is 0.9 percent of the total mass of the soybean protein liquid and the cellulose liquid;
(3) and (3) further drying and solidifying the composite fiber of the primary drawn yarn for 45min at 105 ℃, then heating to 152 ℃, carrying out secondary hot drawing with the drawing ratio controlled at 9, cooling, reeling and shaping to obtain the special enhanced elastic composite protein fiber for the next-to-skin textile.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Example 6
(1) Adding 13% polyurethane solution with N, N-dimethylacetamide as solvent into titanium oxide with average particle diameter of 60nm, and controlling gas flow rate to be 2.3m3H, stirring for 23min by high-speed airflow impact to fully coat the polyurethane liquid with the nano material, and then carrying out high-pressure spray drying to obtain nano colloidal particles; the high-pressure spray drying adopts a conventional high-pressure spray dryer, the pressure is 0.4MPa, and the temperature of supplied hot air is 67 ℃; in the preparation of the nano colloidal particle, the mass ratio of the nano material to the polyurethane liquid is 100: 27;
(2) uniformly mixing a soybean protein liquid with the mass concentration of 11%, a cellulose liquid with the mass concentration of 7% and a polyvinyl alcohol liquid with the mass concentration of 12%, wherein the solvent of the cellulose liquid is NMMO with the mass concentration of 85%, then adding nano colloidal particles to uniformly disperse to obtain a spinning solution, then carrying out wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, carrying out primary stretching, and controlling the stretching ratio to be 6 to obtain primary stretched composite fibers; the spinneret plate adopted by the method for spinning has 8 holes, the diameter of the spinneret hole is 160 mu m, the spinning speed is 26m/min, and the spinning temperature is 82 ℃; the coagulating bath adopts 5 wt% of acetic acid solution, and the temperature of the coagulating bath is 50 ℃; in the spinning solution, the mass ratio of the soybean protein liquid to the cellulose liquid to the polyvinyl alcohol liquid is 100: 43: 17, the adding amount of the nano colloidal particles is 1 percent of the total mass of the soybean protein liquid and the cellulose liquid;
(3) and (3) further drying and solidifying the composite fiber of the primary drawn yarn for 40min at 100 ℃, then heating to 155 ℃, carrying out secondary hot drawing with the drawing multiple controlled at 8.5, cooling, reeling and shaping to obtain the special enhanced elastic composite protein fiber for the next-to-skin textile.
The test was carried out by the method of example 1, and the test results are shown in Table 1.
Comparative example 1
Comparative example 1 in comparison with example 1, the elastic nano colloidal particles were not added, other conditions were the same as those of example 1, and the obtained composite protein fiber was tested by the method of example 1, and the test results are shown in table 1.
Comparative example 2
Comparative example 1 in comparison with example 1, 50nm of silica was directly added without applying the elastification treatment using the urethane coating, and other conditions were identical to those of example 1, and the prepared composite protein fiber was tested by the method of example 1, and the test results are shown in table 1.
Table 1:
Figure BDA0002244199070000101
through test comparison, the nano colloidal particles with elasticity are added, so that the nano size of the nano colloidal particles is favorable for reinforcing and toughening the fibers; with the increase of the addition of the nano colloidal particles, the strength is increased, and meanwhile, the polyurethane is coated with the nano colloidal particles of the nano particles, so that the polyurethane has good elasticity and can endow the fiber with good elasticity. In contrast, the comparative example 1, in which the elastic nanoparticles are not added, reduces the strength of the composite protein fiber, has poor elasticity, and breaks when 100% stretching is performed; comparative example 2, with only the addition of the nanomaterial, had some reinforcement but no significant elastic reinforcement, and the fibers broke when stretched to 95%.

Claims (9)

1. A preparation method of a reinforced elastic composite protein fiber special for close-fitting textiles is characterized by comprising the following specific steps:
(1) adding polyurethane liquid into the nano material, and then controlling the airflow flow to be 2-2.5m3H, stirring for 15-30min by high-speed airflow impact so that the polyurethane liquid fully coats the nano material, and then carrying out high-pressure spray drying to obtain nano colloidal particles; in the preparation of the nano colloidal particle, the mass ratio of the nano material to the polyurethane liquid is 100: 25-30;
(2) uniformly mixing the soybean protein liquid with the cellulose liquid and the polyvinyl alcohol liquid, then adding the nano colloidal particles for uniform dispersion to obtain a spinning solution, then carrying out wet spinning on the spinning solution through a spinneret plate, spraying the spinning solution into a coagulating bath, coagulating into wet filaments, and carrying out primary stretching, wherein the stretching ratio is controlled to be 4-6, so as to obtain a primary stretched composite fiber;
(3) further drying and solidifying the composite fiber of the primary drawn yarn for 30-50min at the temperature of 90-110 ℃, then heating to 145-155 ℃, carrying out secondary hot drawing, controlling the drawing multiple at 7-10, cooling, coiling and shaping to obtain the special enhanced elastic composite protein fiber for the close-fitting textile.
2. The preparation method of the reinforced elastic composite protein fiber specially used for the personal textile as claimed in claim 1, wherein the solvent of the polyurethane solution is N, N-dimethylacetamide, and the mass concentration is 10-15%.
3. The method for preparing the enhanced elastic composite protein fiber specially used for the close-fitting textiles according to claim 1, wherein the nano material is one or a combination of more than two of silicon oxide, titanium oxide, aluminum oxide and zinc oxide with the particle size of 5-100 nm.
4. The preparation method of the enhanced elastic composite protein fiber specially used for the body-fitting textiles according to claim 1, wherein the mass concentration of the soybean protein liquid is 8-12%; the mass concentration of the cellulose solution is 5-8%, and the solvent is NMMO with the mass concentration of 85%; the mass concentration of the polyvinyl alcohol solution is 10-15%.
5. The method for preparing the enhanced elastic composite protein fiber specially used for the skin-tight textiles according to claim 1, wherein the high pressure spray drying in the step (1) adopts a conventional high pressure spray dryer, the pressure is 0.2-0.5MPa, and the temperature of the supplied hot air is 60-75 ℃.
6. The method for preparing the enhanced elastic composite protein fiber specially used for the next to skin textiles as claimed in claim 1, wherein the number of the holes of the spinneret plate used in the wet spinning in the step (2) is 6-8, the diameter of the spinneret hole is 100-200 μm, the spinning speed is 20-30m/min, and the spinning temperature is 70-90 ℃.
7. The method for preparing the enhanced elastic composite protein fiber specially used for the next-to-skin textiles according to claim 1, wherein 5 wt% of acetic acid solution is adopted in the coagulating bath in the step (2), and the temperature of the coagulating bath is 30-60 ℃.
8. The preparation method of the enhanced elastic composite protein fiber specially used for the body-fitting textile according to claim 1, wherein in the spinning solution in the step (2), the mass ratio of the soybean protein solution, the cellulose solution and the polyvinyl alcohol solution is 100: 30-50: 15-20 percent, wherein the addition amount of the nano colloidal particles is 0.5-1 percent of the total mass of the soybean protein liquid and the cellulose liquid.
9. An enhanced elastic composite protein fiber specially used for close-fitting textiles, which is characterized by being prepared by the method of any one of claims 1 to 8.
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