阅读说明：本技术 一种防静电阻燃防油的洗涤棉麻混纺织物及其制备方法 (Anti-static flame-retardant oil-proof washing cotton-hemp blended fabric and preparation method thereof ) 是由 唐雪金 于 2019-08-26 设计创作，主要内容包括：本发明涉及纺织面料技术领域,尤其涉及一种防静电阻燃防油的洗涤棉麻混纺织物及其制备方法和应用。一种防静电阻燃防油的洗涤棉麻混纺织物的制备方法,步骤至少包括：(1)制备初级混纺面料：混纺面料由麻纤维、棉纤维、蛋白纤维通过成条、纺纱、织布而制得；(2)浸渍蛋白酶浸渍液,得第一浸渍面料；(3)浸渍纳米粒子浸渍液,得第二浸渍面料；(4)阻燃整理液处理,干燥即得。该面料不仅手感柔软、舒适,还同时兼具优异的防静电、阻燃、防油的性能,是一种集多功能于一体棉麻混纺织物,可广泛应用于服装、家纺领域。(The invention relates to the technical field of textile fabrics, in particular to an anti-static, flame-retardant and oil-proof washing cotton-hemp blended fabric and a preparation method and application thereof. A preparation method of an antistatic flame-retardant oil-proof washing cotton-hemp blended fabric at least comprises the following steps: (1) preparing a primary blended fabric: the blended fabric is prepared from fibrilia, cotton fiber and protein fiber by slivering, spinning and weaving; (2) dipping protease dipping liquid to obtain a first dipped fabric; (3) dipping the nano particle dipping solution to obtain a second dipped fabric; (4) and (4) treating the flame-retardant finishing liquid, and drying to obtain the flame-retardant finishing liquid. The fabric is soft and comfortable in hand feeling, has excellent antistatic, flame retardant and oil resistant performances, is a cotton-hemp blended fabric integrating multiple functions, and can be widely applied to the fields of clothing and home textiles.)

1. The preparation method of the antistatic flame-retardant oil-proof washing cotton-hemp blended fabric is characterized by at least comprising the following steps:

(1) preparing a primary blended fabric: the blended fabric is prepared from fibrilia, cotton fiber and protein fiber by slivering, spinning and weaving;

(2) dipping protease dipping solution: spreading the primary blended fabric, slowly adding a protease impregnation liquid, heating to 25-50 ℃, standing and soaking for 10-20min, taking out, repeatedly washing with clear water, placing in a 70-90 ℃ water tank for soaking for 0.2-1h, taking out, and drying at 60-100 ℃ for 2-5h to obtain a first impregnated fabric; the mass concentration of the protease solution is 0.1-0.3 wt%;

(3) dipping nano particle dipping solution: adding the first impregnated fabric into the nanoparticle impregnation liquid, heating to 50-70 ℃, standing and soaking for 10-20min, taking out, repeatedly washing with clear water, placing in a 70-90 ℃ water tank, soaking for 10-45min, taking out, and drying at 60-100 ℃ for 2-5h to obtain a second impregnated fabric;

(4) and (3) treating the flame-retardant finishing liquid: according to the bath ratio of 1: (20-40) weighing the flame-retardant finishing liquid, immersing the second dipped fabric into a container containing the finishing liquid, treating for 20-40min at 60-90 ℃, then carrying out two-dipping and two-rolling to keep the rolling residue rate at 90% -100%, taking out, and drying for 5-10h at 80-120 ℃ to obtain the flame-retardant finishing liquid.

2. The method of claim 1, wherein the protein fiber is a graphene oxide-modified protein fiber.

3. The method according to claim 1, wherein the weight ratio of the cotton fiber, the hemp fiber and the protein fiber is 1: (0.5-1): (0.1-0.5).

4. The method as claimed in claim 1, wherein the warp density of the primary blended fabric is 450-600 pieces/10 cm; the weft density is 400-500 pieces/10 cm; the fiber thickness is 40-70D.

5. The method according to claim 1, wherein the nanoparticle impregnating solution contains nanoparticles and an inorganic base.

6. The preparation method according to claim 5, wherein the nanoparticles are selected from one or more of nano-silica, nano-titanium dioxide, nano-zinc oxide, nano-alumina and mica powder.

7. The method of claim 5, wherein the nanoparticles have a particle size of 10 to 50 nm.

8. The method of claim 5, wherein the nanoparticles are aminosiloxane derivative-modified nanoparticles; the aminosilicone derivative contains at least 2 ether bonds.

9. An antistatic flame-retardant oil-resistant washed cotton-linen blended fabric prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the antistatic flame-retardant oil-proof washing cotton-linen blended fabric as claimed in claim 9, which is characterized by being applied to the fields of clothing and home textiles.

Technical Field

The invention relates to the technical field of textile fabrics, in particular to an anti-static, flame-retardant and oil-proof washing cotton-hemp blended fabric and a preparation method and application thereof.

Background

The cotton-flax blended fabric has the comfort of cotton and the softness of flax, has bright color and luster and smooth and full hand feeling, and is deeply loved by wide consumers. However, the fibrilia in the cotton-linen blended fabric has strong affinity to oil stains, is easy to adsorb the oil stains, and is easy to generate static electricity to adsorb dust in the wearing process.

Static electricity can adsorb dust, is not beautiful, affects wearing comfort and is not easy to clean. In some special cases, static electricity can generate sparks, which can cause fire and even explosion accidents. The textile can be quickly burnt once encountering fire, and the textile is often burnt to cause fire due to negligence in daily life or industrial production.

In order to enhance the safety protection of personnel, higher requirements are put forward on the functions of the cotton-linen blended fabric. Aiming at the problems, the antistatic, flame retardant and oil-proof performances of the textile are widely researched at present. However, the common cotton-hemp blended fabric in the market generally has only single functions of static electricity prevention, flame retardance and oil resistance, and can only meet a part of requirements. Aiming at the special working fields, such as labor protection clothes of petroleum, electric power and coal mining industry, the development of the cotton-hemp blended fabric which can not only prevent static electricity, but also has the functions of flame retardance and oil resistance is urgently needed.

Therefore, aiming at the problems, the invention provides the antistatic flame-retardant oil-proof washing cotton-hemp blended fabric and the preparation method thereof, and the prepared cotton-hemp blended fabric has excellent antistatic, flame-retardant and oil-proof performances.

Disclosure of Invention

In order to solve the technical problems, the invention provides a preparation method of an antistatic flame-retardant oil-proof washing cotton-hemp blended fabric, which at least comprises the following steps:

(1) preparing a primary blended fabric: the blended fabric is prepared from fibrilia, cotton fiber and protein fiber by slivering, spinning and weaving;

(2) dipping protease dipping solution: spreading the primary blended fabric, slowly adding a protease impregnation liquid, heating to 25-50 ℃, standing and soaking for 10-20min, taking out, repeatedly washing with clear water, placing in a 70-90 ℃ water tank for soaking for 0.2-1h, taking out, and drying at 60-100 ℃ for 2-5h to obtain a first impregnated fabric; the mass concentration of the protease solution is 0.1-0.3 wt%;

(3) dipping nano particle dipping solution: adding the first impregnated fabric into the nanoparticle impregnation liquid, heating to 50-70 ℃, standing and soaking for 10-20min, taking out, repeatedly washing with clear water, placing in a 70-90 ℃ water tank, soaking for 10-45min, taking out, and drying at 60-100 ℃ for 2-5h to obtain a second impregnated fabric;

(4) and (3) treating the flame-retardant finishing liquid: according to the bath ratio of 1: (20-40) weighing the flame-retardant finishing liquid, immersing the second dipped fabric into a container containing the finishing liquid, treating for 20-40min at 60-90 ℃, then carrying out two-dipping and two-rolling to keep the rolling residue rate at 90% -100%, taking out, and drying for 5-10h at 80-120 ℃ to obtain the flame-retardant finishing liquid.

As a preferable technical scheme of the present invention, the protein fiber is a graphene oxide modified protein fiber.

As a preferable technical scheme of the invention, the weight ratio of the cotton fiber, the fibrilia and the protein fiber is 1: (0.5-1): (0.1-0.5).

As a preferable technical scheme of the invention, the warp-wise density of the primary blended fabric is 450-600 pieces/10 cm; the weft density is 400-500 pieces/10 cm; the fiber thickness is 40-70D.

In a preferred embodiment of the present invention, the nanoparticle impregnating solution contains nanoparticles and an inorganic base.

As a preferable technical scheme of the invention, the nano particles are selected from one or more of nano silicon dioxide, nano titanium dioxide, nano zinc oxide, nano aluminum oxide and mica powder.

As a preferable technical scheme of the invention, the particle size of the nano particles is 10-50 nm.

As a preferable technical scheme, the nano particles are modified by aminosiloxane derivatives; the aminosilicone derivative contains at least 2 ether bonds.

The second aspect of the invention provides the antistatic flame-retardant oil-proof washing cotton-linen blended fabric prepared by the preparation method.

The third aspect of the invention provides an application of the antistatic flame-retardant oil-proof washing cotton-hemp blended fabric, which can be applied to the fields of clothing and home textiles.

The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.

Has the advantages that: the invention provides an antistatic flame-retardant oil-proof washing cotton-hemp blended fabric and a preparation method and application thereof. The cotton-linen blended fabric is prepared by four steps of preparing a primary blended fabric of fibrilia, cotton fiber and graphene oxide modified protein fiber, impregnating protease impregnating solution, impregnating nano particle impregnating solution and treating flame-retardant finishing solution. The fabric has excellent antistatic, flame-retardant and oil-proof performances, and can be widely applied to the fields of clothes and home textiles.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.

In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.

"Polymer" means a polymeric compound prepared by polymerizing monomers of the same or different types. The generic term "polymer" embraces the terms "homopolymer", "copolymer", "terpolymer" and "interpolymer".

"interpolymer" means a polymer prepared by polymerizing at least two different monomers. The generic term "interpolymer" includes the term "copolymer" (which is generally used to refer to polymers prepared from two different monomers) and the term "terpolymer" (which is generally used to refer to polymers prepared from three different monomers). It also includes polymers made by polymerizing four or more monomers. "blend" means a polymer formed by two or more polymers being mixed together by physical or chemical means.

The invention provides a preparation method of an antistatic flame-retardant oil-proof washing cotton-hemp blended fabric, which at least comprises the following steps:

(1) preparing a primary blended fabric: the blended fabric is prepared from fibrilia, cotton fiber and protein fiber by slivering, spinning and weaving;

(2) dipping protease dipping solution: spreading the primary blended fabric, slowly adding a protease impregnation liquid, heating to 25-50 ℃, standing and soaking for 10-20min, taking out, repeatedly washing with clear water, placing in a 70-90 ℃ water tank for soaking for 0.2-1h, taking out, and drying at 60-100 ℃ for 2-5h to obtain a first impregnated fabric; the mass concentration of the protease solution is 0.1-0.3 wt%;

(3) dipping nano particle dipping solution: adding the first impregnated fabric into the nanoparticle impregnation liquid, heating to 50-70 ℃, standing and soaking for 10-20min, taking out, repeatedly washing with clear water, placing in a 70-90 ℃ water tank, soaking for 10-45min, taking out, and drying at 60-100 ℃ for 2-5h to obtain a second impregnated fabric;

(4) and (3) treating the flame-retardant finishing liquid: according to the bath ratio of 1: (20-40) weighing the flame-retardant finishing liquid, immersing the second dipped fabric into a container containing the finishing liquid, treating for 20-40min at 60-90 ℃, then carrying out two-dipping and two-rolling to keep the rolling residue rate at 90% -100%, taking out, and drying for 5-10h at 80-120 ℃ to obtain the flame-retardant finishing liquid.

In a preferred embodiment, the preparation method of the antistatic flame-retardant oil-proof washing cotton-hemp blended fabric at least comprises the following steps:

(1) preparing a primary blended fabric: the blended fabric is prepared from fibrilia, cotton fiber and protein fiber by slivering, spinning and weaving;

(2) dipping protease dipping solution: spreading the primary blended fabric, slowly adding a protease impregnation liquid, heating to 40 ℃, standing and soaking for 15min, taking out, repeatedly washing with clear water, placing in a 90 ℃ water tank for soaking for 0.5h, taking out, and drying at 100 ℃ for 5h to obtain a first impregnated fabric; the mass concentration of the protease solution is 0.15 wt%;

(3) dipping nano particle dipping solution: adding the first impregnated fabric into the nanoparticle impregnation liquid, heating to 60 ℃, standing and soaking for 15min, taking out, repeatedly washing with clear water, placing in a 90 ℃ water tank, soaking for 30min, taking out, and drying at 100 ℃ for 5h to obtain a second impregnated fabric;

(4) and (3) treating the flame-retardant finishing liquid: according to the bath ratio of 1: 30, weighing the flame-retardant finishing liquid, immersing the second dipped fabric into a container containing the finishing liquid, treating for 30min at 80 ℃, then carrying out two-time dipping and two-time rolling to keep the rolling residual rate at 90-100%, taking out, and drying for 10h at 100 ℃ to obtain the flame-retardant finishing liquid.

In the invention, the protein fiber is modified by graphene oxide.

Preferably, the protein fiber is modified porous graphene oxide modified protein fiber.

Preferably, the modified porous graphene oxide is an aminosiloxane derivative-modified porous graphene oxide.

Graphene oxide

In the invention, the preparation method of the porous graphene oxide comprises the following steps:

(1) preparing polystyrene nano-spheres:

introducing nitrogen to remove air in the three-mouth bottle at room temperature, adding deionized water and styrene monomer, continuously introducing nitrogen to remove air in the solution, and magnetically stirring for 20-40 min; gradually raising the temperature to 30-90 ℃, dissolving an initiator potassium persulfate in deionized water, then adding the solution into a three-necked bottle at one time, continuing to react for 10-24h, and centrifugally drying to obtain polystyrene spheres;

(2) preparing graphene oxide with a three-dimensional porous structure:

preparing graphene oxide into a solution with the concentration of 2-5g/L, ultrasonically mixing polystyrene spheres and the graphene oxide for 2-3h to form colloidal particles, adjusting the pH value of the solution to 6-8 to uniformly disperse the polystyrene nano spheres in the graphene oxide, performing suction filtration and drying, calcining at high temperature in a nitrogen environment to thermally decompose the polystyrene spheres and thermally reduce the graphene oxide to obtain the graphene oxide with a three-dimensional porous structure.

Preferably, the volume ratio of the deionized water to the styrene monomer in the step (1) is 10: (0.5-3), wherein the mass of the initiator is 0.2-1% of that of the styrene monomer.

Preferably, the mass ratio of the polystyrene to the graphene oxide in the step (2) is (2-5): 1; the temperature for calcining the polystyrene spheres by heat at high temperature is 300-550 ℃, and the calcining time is 1-2 h; the temperature of the high-temperature thermal reduction graphite oxide is 700-.

Preferably, the graphene oxide is not particularly limited, and may be obtained by purchase or preparation.

Preferably, the preparation method of the graphene oxide comprises the following steps: under the condition of ice-water bath, 30g of graphite powder and 15g of NaNO are mixed₃And 900mL of concentrated H₂SO₄(H₂SO₄98 percent of the mass fraction) is put into a three-neck flask and stirred for 0.5 h; then 90g KMnO was slowly added₄Keeping the ice-water bath condition to continue stirring and reacting for 2 hours, and at the moment, changing the reactant from black to dark green; transferring the three-neck flask into a 35 ℃ constant temperature water bath, stirring for 3h, then dropwise adding 2000mL of distilled water, controlling the temperature not to exceed 98 ℃, and then continuing to react for 30min at 70 ℃ until the solution is yellow brown; then 100mL of 30% H₂O₂Adding the reactant and stirring for 30min, wherein the solution turns bright yellow; and (3) centrifugally washing by using 0.01mol/L HCl to remove metal ions in the solution, centrifugally washing by using absolute ethyl alcohol and deionized water respectively until the pH value of the filtrate is neutral, carrying out ultrasonic treatment, and carrying out freeze drying to obtain the product.

In a preferred embodiment, the preparation method of the porous graphene oxide comprises the following steps:

(1) adding 90mL of deionized water and 9mL of styrene monomer into a three-necked bottle, continuously introducing nitrogen to remove air in the solution, and magnetically stirring for 30 min; gradually raising the temperature to 70 ℃, and adding 10mL of 0.03g/mL potassium persulfate; continuously reacting for 24 hours, and centrifugally drying to obtain polystyrene spheres;

(2) ultrasonically stripping the prepared graphite oxide at room temperature to obtain a graphene oxide solution with the concentration of 5g/L, adding polystyrene spheres and the graphene oxide into the solution according to the mass ratio of 3:1, mixing and ultrasonically treating for 2h to form colloidal particles, adjusting the pH value to 8, uniformly dispersing the polystyrene nanospheres in the graphene oxide, filtering and drying, calcining at high temperature in a nitrogen environment to thermally decompose the polystyrene nanospheres, and thermally reducing the graphene oxide to obtain the porous graphene oxide.

In the invention, the modified porous graphene oxide is porous graphene oxide modified by aminosiloxane derivatives.

Preferably, the weight ratio of the aminosiloxane derivative to the porous graphene oxide is 1: (2-5).

Most preferably, the weight ratio of the aminosiloxane derivative to the porous graphene oxide is 1: 4.

preferably, the aminosiloxane derivative is one or more of N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine, 1, 3-bis (4-aminobutyl) tetramethyldisiloxane, 2-amino-1- (butyldimethylsiloxy) butane, 3-aminopropylbis (trimethylsiloxy) methylsilane, in combination.

Most preferably, the aminosiloxane derivative is N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine.

The N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine, CAS number: 49869-07-0.

In a preferred embodiment, the preparation method of the modified porous graphene oxide comprises the following steps: adding 5g of graphene oxide into 1.5L of absolute ethyl alcohol, performing ultrasonic dispersion for 10min, adding an aminosiloxane derivative with a certain mass ratio, continuing to perform ultrasonic dispersion for 1h, adding the dispersion into a three-neck flask, and performing magnetic stirring reaction for 24h at 80 ℃; cooling the product to room temperature, centrifugally washing the product with absolute ethyl alcohol for 6 times, and then washing the product with distilled water for 1 time to remove residual aminosiloxane derivatives; and completely drying the product at 60 ℃ to obtain the aminosiloxane derivative modified porous graphene oxide.

In a more preferred embodiment, the preparation method of the modified porous graphene oxide comprises the following steps: adding 5g of graphene oxide into 1.5L of absolute ethyl alcohol, performing ultrasonic dispersion for 10min, adding 20g of N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine, continuing to perform ultrasonic dispersion for 1h, adding the dispersion into a three-neck flask, and performing magnetic stirring reaction at 80 ℃ for 24 h; after the product was cooled to room temperature, it was washed 6 times by centrifugation with anhydrous ethanol and 1 time with distilled water to remove the residual N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine; and completely drying the product at the temperature of 60 ℃ to obtain the N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine modified porous graphene oxide.

Modified protein fiber

In the invention, the addition amount of the modified porous graphene oxide is 2-6% of the total mass of the modified protein fiber.

Preferably, the addition amount of the modified porous graphene oxide is 5% of the total mass of the modified protein fiber.

Preferably, the blending spinning process of the modified porous graphene oxide modified protein fiber comprises the following steps:

(1) melting: taking a certain amount of protein fiber and modified porous graphene oxide as raw materials according to a mass ratio, and melting the raw materials into spinning solution by a screw;

(2) metering and spinning: the spinning stock solution is sprayed out of a 12-hole spinneret plate for spinning and forming after the flow of the spinning stock solution is regulated by a metering pump, so that a modified protein fiber bundle is prepared; a slow cooling heating device is arranged below the spinneret plate; the temperature of the slow cooling heating device is 8-12 ℃ higher than the plate surface temperature of the spinneret plate;

(3) cooling and oiling: performing circular air blowing cooling on the modified protein fiber bundle by hot air equipment, and then performing double-oil-nozzle oiling treatment by adopting a polyester oiling agent, wherein the oiling rate is 0.85-0.95;

(4) pre-networking: pre-networking the oiled modified protein fiber bundle by a pre-networking device;

(5) stretching and shaping: adopting three pairs of rollers to stretch and shape the pre-networked modified protein fiber bundle, wherein the stretching multiple is 1.75-1.85;

(6) a main network: carrying out main networking on the stretched and shaped modified protein fiber bundle by a main networking device;

(7) winding: and (3) fully automatically winding the modified protein fiber bundle passing through the main network at the winding speed of 2450-2500m/min to obtain a modified protein fiber finished product.

Preferably, in the step (1), the temperature at the time of melting is 272 ℃ to 275 ℃.

Preferably, in the step (2), the temperature of the plate surface of the spinneret plate is controlled to be between 293 ℃ and 295 ℃.

Preferably, in the step (2), the diameter of the spinneret plate is 0.13 mm.

Preferably, in the step (3), the air temperature of the hot air device for air-cooling the modified protein fiber bundle is 20 ℃ +/-1 ℃.

Preferably, in the step (5), the temperatures of the three pairs of rollers during the stretching and setting are respectively: 90-100 ℃, 120-130 ℃ and 210-220 ℃.

More preferably, in the step (5), the temperatures of the three pairs of rolls during the stretching and setting are respectively: 95 ℃, 125 ℃ and 215 ℃.

In a preferred embodiment, the modified porous graphene oxide modified protein fiber blend spinning process comprises the following steps:

(1) melting: weighing 95 parts of protein fiber and 5 parts of modified graphene oxide as raw materials in parts by mass, and melting the raw materials by a screw to form a spinning solution; the temperature at the time of the melting was 275 ℃;

(2) metering and spinning: the spinning stock solution is sprayed out of a 12-hole spinneret plate for spinning and forming after the flow of the spinning stock solution is regulated by a metering pump, so that a modified protein fiber bundle is prepared; a slow cooling heating device is arranged below the spinneret plate; the temperature of the slow cooling heating device is 10 ℃ higher than the plate surface temperature of the spinneret plate; the plate surface temperature of the spinneret plate is 295 ℃; the aperture of the spinneret plate is 0.13 mm;

(3) cooling and oiling: performing circular air blowing cooling on the modified protein fiber bundle by hot air equipment, and then performing double-oil-nozzle oiling treatment by adopting a polyester oiling agent, wherein the oiling rate is 0.9; the air temperature of the hot air equipment is 20 ℃ when the modified protein fiber bundle is cooled by blowing air;

(4) pre-networking: pre-networking the oiled modified protein fiber bundle by a pre-networking device;

(5) stretching and shaping: stretching and shaping the pre-networked modified protein fiber bundle by three pairs of rollers, wherein the stretching ratio is 1.85; the temperatures of the three pairs of rollers during stretching and setting are respectively as follows: 95 ℃, 125 ℃ and 215 ℃;

(6) a main network: carrying out main networking on the stretched and shaped modified protein fiber bundle by a main networking device;

(7) winding: and (3) fully automatically winding the modified protein fiber bundle passing through the main network at a winding speed of 2450m/min to obtain a modified protein fiber finished product.

The natural protein fiber is adopted, so that the natural protein fiber has soft hand feeling, soft luster, excellent moisture absorption, moisture conduction and heat preservation performance, good skin affinity, obvious antibacterial function and especially excellent characteristics of very soft and good moisture absorption effect. The invention can well improve the softness and skin-friendly property of the cotton and linen fibers by selecting the protein fibers to be blended with the cotton fibers and the linen fibers. However, the protein fiber and the cotton and hemp fiber are easy to break the cotton net in the blending process, which causes the poor quality of the textile. The inventor selects the aminosiloxane modified graphene oxide to modify the terylene, so that the antistatic effect can be effectively improved, and the quality and the softness of the fiber can be remarkably improved. The inventors consider that possible reasons are: the graphene oxide can conduct and disperse charges, so that the accumulation of the charges is avoided, and the antistatic effect is improved; the aminosiloxane modifies the graphene oxide, particularly the selected N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine has a special claw-shaped structural characteristic, each claw contains a plurality of oxygen atoms, the structural monomer is attached to the surface of the polyester fiber, and the protein fiber has more polar groups, so that the cohesive force of the polyester fiber on the protein fiber can be improved in the blending process, the quality uniformity of the blended fiber is improved, and the quality of a product is improved.

Primary blended fabric

In the invention, the weight ratio of the cotton fiber, the fibrilia and the protein fiber is 1: (0.5-1): (0.1-0.5).

Preferably, the weight ratio of the cotton fibers, the hemp fibers and the protein fibers is 1: 0.8: 0.25.

the primary blended fabric is prepared from fibrilia, cotton fiber and protein fiber through the processes of slivering, spinning, weaving and the like.

Preferably, the protein fiber can be selected from milk fiber or/and soybean protein fiber.

In the invention, the composition of the warp and the weft in the primary blended fabric is the same, and the warp and the weft are blended by fibrilia, cotton fiber and protein fiber.

In the invention, the warp density of the primary blended fabric is 450-600 pieces/10 cm; the weft density is 400-500 pieces/10 cm; the fiber thickness is 40-70D.

Preferably, the warp density of the primary blended fabric is 550 threads/10 cm; the weft density is 450 pieces/10 cm; the fiber thickness was 60D.

Protease impregnation liquid

In the invention, the prepared blended fabric is impregnated by the impregnating solution, and the impregnating method comprises the following steps: and (3) paving the primary blended fabric, slowly adding 0.15 wt% of protease impregnation liquid, heating to 40 ℃, standing and soaking for 15min, taking out, repeatedly washing with clear water, placing in a 90 ℃ water tank for soaking for 0.5h, taking out, and drying at 100 ℃ for 5h to obtain the first impregnated fabric.

According to the invention, cotton fibers, fibrilia and protein fibers are blended, and the blended fabric is soaked in the special soaking solution by the inventor, so that the comfortable softness of the fabric can be further improved, and the air permeability of the fabric can be effectively improved. The inventors believe that this may be due to the specific impregnation of the fabric with the enzyme solution of the present invention. The protease is utilized to carry out degradation action to certain degree on protein fibers in the fabric to generate more three-dimensional void structures on the surfaces of the fibers, so that the air permeability of the fabric can be improved. Meanwhile, the surface of the fabric is also provided with a plurality of microporous structures, namely micropores generated on the surface of the fiber, so that the internal structure of the fiber can generate looseness to a certain extent, and the fabric is softer and more comfortable.

Nanoparticle impregnating solution

In the invention, the prepared blended fabric is impregnated by the impregnating solution, and the impregnating method comprises the following steps: adding the first impregnated fabric into the nanoparticle impregnation liquid, heating to 60 ℃, standing and soaking for 15min, taking out, repeatedly washing with clear water, placing in a 90 ℃ water tank, soaking for 30min, taking out, and drying at 100 ℃ for 5h to obtain a second impregnated fabric.

In the present invention, the nanoparticle impregnating solution contains nanoparticles and an inorganic base.

In the invention, the nano particles are selected from one or more of nano silicon dioxide, nano titanium dioxide, nano zinc oxide, nano aluminum oxide and mica powder.

Preferably, the nano particles are selected from one or more of nano silicon dioxide, nano titanium dioxide and nano zinc oxide.

Most preferably, the nanoparticles are selected from nanosilica.

In the present invention, the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, soda ash (anhydrous sodium carbonate), sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium phosphate, and sodium sulfate.

Preferably, the inorganic base is sodium hydroxide.

In the invention, the preparation method of the nanoparticle impregnating solution comprises the following steps: adding the nano particles into the alkaline solution, fully stirring and uniformly mixing to obtain the nano particle impregnation liquid.

Preferably, the alkaline solution is an aqueous sodium hydroxide solution.

More preferably, the concentration of the aqueous sodium hydroxide solution is 0.1 to 0.5 g/mL.

Most preferably, the concentration of the aqueous sodium hydroxide solution is 0.3 g/mL.

Preferably, the concentration of nanoparticles in the nanoparticle-impregnating solution is 0.1 to 0.3 g/mL.

Most preferably, the concentration of nanoparticles in the nanoparticle impregnating solution is 0.25 g/mL.

Preferably, the particle size of the nanoparticles is 10-50 nm.

Most preferably, the nanoparticles have a particle size of 20nm and are available from Shanghai Ulowei nanotechnology, Inc.

In the invention, the nano particles are modified by aminosiloxane derivatives.

Preferably, the aminosilicone derivative contains at least 2 ether linkages.

More preferably, the aminosiloxane derivative is one or a combination of N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine, 1, 3-bis (4-aminobutyl) tetramethyldisiloxane, 2-amino-1- (butyldimethylsiloxy) butane, 3-aminopropylbis (trimethylsiloxy) methylsilane.

Most preferably, the aminosiloxane derivative is N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine.

In the invention, the preparation method of the modified silica nanoparticle comprises the following steps:

(1) adding deionized water into ethanol, and uniformly oscillating by ultrasonic to obtain a solution 1;

(2) under ultrasonic oscillation, adding tetraethoxysilane (TEOS for short) into the solution 1, wherein the molar ratio of tetraethoxysilane to ethanol is 1: (50-100), wherein the molar ratio of the ethyl orthosilicate to the deionized water is 1: (4-8), uniformly oscillating by ultrasonic to obtain a solution 2;

(3) adjusting the pH value of the solution 2 to 3-5 by hydrochloric acid, dropwise adding N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine into the solution 2 at the speed of 0.5-1.0g/min to obtain a reaction system, wherein the using amount of the N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine is 5% -20% of the mass of ethyl orthosilicate, and stirring and reacting the obtained reaction system at the reaction temperature of 40-60 ℃ for 4-6h to obtain a solution 3;

(4) adjusting the pH value of the solution 3 to 7-10 by ammonia water, and reacting for 1-4h under the condition of heat preservation to obtain modified nano-silica sol;

(5) drying, crushing, screening, centrifugally washing with absolute ethyl alcohol, washing with water, vacuum drying and grinding the modified nano-silica sol to obtain the in-situ modified nano-silica.

Preferably, in the step (3), the concentration of the hydrochloric acid solution is 0.1 mol/L; the N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine was added dropwise to the solution using a constant pressure funnel.

Preferably, in the step (4), the concentration of the ammonia water is 0.05 mol/L.

Preferably, in the step (5), the vacuum drying is performed under the specific condition of 40-80 ℃ for 10-24 h.

In a preferred embodiment, the modified silica nanoparticles are prepared by the following steps:

(1) adding deionized water into ethanol, and uniformly oscillating by ultrasonic to obtain a solution 1;

(2) under ultrasonic oscillation, adding tetraethoxysilane (TEOS for short) into the solution 1, wherein the molar ratio of tetraethoxysilane to ethanol is 1: 80, the molar ratio of the ethyl orthosilicate to the deionized water is 1: 6, uniformly oscillating by ultrasonic to obtain a solution 2;

(3) adjusting the pH value of the solution 2 to be 4 by using hydrochloric acid with the concentration of 0.1mol/L, dropwise adding N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine into the solution 2 through a constant pressure funnel at the speed of 0.8g/min to obtain a reaction system, wherein the using amount of the N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine is 15% of the mass of tetraethoxysilane, and stirring and reacting the obtained reaction system at the reaction temperature of 50 ℃ for 6 hours to obtain a solution 3;

(4) keeping the pH value of the solution 3 at 8 by using ammonia water with the concentration of 0.05mol/L, and reacting for 4 hours under the condition of heat preservation to obtain modified nano-silica sol;

(5) drying, crushing and screening the modified nano-silica sol, centrifugally washing with absolute ethyl alcohol, washing with water, drying in vacuum at 80 ℃ for 24 hours, and grinding to obtain the in-situ modified nano-silica.

According to the invention, the oil resistance of the cotton and linen fabric is improved by introducing the nano silicon dioxide particles, but the inventor finds that although the oil resistance of the cotton and linen fibers can be improved to a certain extent by the introduced nano silicon dioxide particles, the oil resistance of the cotton and linen fabric is reduced with the increase of the washing times of the cotton and linen fabric. After the N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine is used for modifying the nano silicon dioxide, the washing resistance of the cotton and linen fabric can be effectively improved, and the fabric is ensured to have excellent oil-proof performance after being washed for many times. The inventors believe that this may be due to the N- [3- [ tris (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine itself having abundant ether linkages and amino groups which may further increase the oil repellency of textiles. In addition, the modified nano silicon dioxide can be dispersed in a three-dimensional microporous structure generated after the textile fabric is treated by protease in the dipping process, and the N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine has special claw-shaped structural characteristics, and each claw is respectively provided with a plurality of oxygen atoms, so that the whole oil resistance can be further improved; because a plurality of claws can firmly lock the modified nano silicon dioxide in gaps of the cotton and linen fabric, the water washing resistance of the fabric is effectively improved.

Flame-retardant finishing liquid

In the invention, the second impregnated fabric prepared by the method is subjected to flame-retardant finishing liquid treatment, and the treatment method comprises the following steps: according to the bath ratio of 1: 30, weighing the flame-retardant finishing liquid, immersing the second dipped fabric into a container containing the finishing liquid, treating for 30min at 80 ℃, then carrying out two-time dipping and two-time rolling to keep the rolling residual rate at 90-100%, taking out, and drying for 8h at 120 ℃ to obtain the flame-retardant finishing liquid.

According to the invention, the flame-retardant finishing liquid comprises a poly-type phosphorus-nitrogen intumescent flame retardant and trimethyl silicic acid caged thioPEPA ester; the polymeric phosphorus-nitrogen intumescent flame retardant is poly (trimethylolpropane thiophosphoryl urea).

Poly (trimethylolpropane thiophosphoryl urea)

The poly (trimethylolpropane thiophosphoryl urea) is called PDTPT for short.

The preparation method of the poly-ditrimethylolpropane thiophosphoryl urea comprises the following steps:

(1) synthesis of intermediate ditrimethylolpropane diphosphoryl chloride (DTDC)

Adding Ditrimethylolpropane (DTMP) and dichloroethane as solvent in a certain proportion into a four-mouth flask, slowly heating to 40 deg.C under electric stirring, adding POCl after DTMP is completely dissolved₃Absorbing HCl gas generated by the reaction with alkali liquor, keeping the temperature for reaction for 6 hours, cooling to room temperature after the reaction is finished, and removing dichloroethane and unreacted POCl by reduced pressure distillation₃And adding a certain amount of absolute ethyl alcohol into the obtained white solid crude product, placing the obtained product in a freezer (-20 ℃) for 2 hours, filtering the obtained white solid, and drying the obtained white solid at 70 ℃ in vacuum to constant weight to obtain white powdery solid DTDC.

(2) Synthesis of poly (trimethylolpropane thiophosphoryl urea)

Adding a certain amount of DTDC and acetonitrile serving as a solvent into a flask, heating, adding thiourea in a certain proportion after the DTDC is completely dissolved, heating to 80 ℃, carrying out heat preservation reaction for 6 hours, cooling to room temperature after the reaction is finished, filtering to remove a white byproduct, distilling the solution under reduced pressure to evaporate the acetonitrile serving as the solvent, and drying the obtained yellow sticky substance at 120 ℃ for 12 hours to obtain yellow crystal PDTPT.

Preferably, in the step (1), the mass ratio of the dichloroethane solvent to the DTMP solvent is 2.0: 1.

preferably, in step (1), the DTMP and POCl are₃In a molar ratio of 1: 2.2.

preferably, in the step (2), the mass ratio of the solvent acetonitrile to DTDC is 2.0: 1.

preferably, in the step (2), the molar ratio of the thiourea to the DTDC is 1.2: 1.

trimethylsilicic acid caged thioPEPA ester

The trimethyl silicic acid caged thioPEPA ester is short for TMSSPE

The preparation method of the trimethyl silicic acid caged thioPEPA ester comprises the following steps:

(1) preparation of 4-hydroxymethyl-1-thio-1-phospha-2, 6, 7-trioxabicyclo [2,2,2] -octane (SPEPA)

10mol of pentaerythritol and 10mol of trichlorothion were charged into a 1000mL four-necked flask equipped with a thermometer and a reflux condenser. The reaction mixture was heated with stirring in an oil bath at an external bath temperature of 145-160 deg.C and was maintained at this temperature until no hydrogen chloride gas was evolved (as detected by pH paper), which took about 8 h. Then raising reaction temperature to about 170 deg.C, heating for 1h, cooling to obtain block solid, extracting with 20L boiling water for four times, and removing sticky substance deposited on the bottom of the bottle by decantation. In the cooled aqueous solution, a large amount of white solid was precipitated and filtered. Heating the mother liquor to evaporate most of water to obtain a plurality of white solids, drying the white solids obtained twice, and recrystallizing with dimethylbenzene to obtain white flaky crystals.

(2) Preparation of caged thiopepa trimethylsilanoate

In a 1000mL four-mouth reaction bottle provided with a stirrer, a thermometer, a condenser tube and a hydrogen chloride (HCl) absorption device, nitrogen is used for completely removing air in the bottle, 196.0-276.5g (1.0-1.4mol) SPEPA and 800mL dioxane are added at room temperature, stirring is carried out to completely dissolve SPEA, 108.6g (1.0mol) Trimethylchlorosilane (TMCS) is slowly dripped, the system temperature is not higher than 20 ℃ in the dripping process, after dripping is finished, reaction is carried out at 30-50 ℃ for 9 hours under heat preservation, after HCl gas is discharged, the pH value of the system is adjusted to 5-6 by melamine, suction filtration is carried out, and organic solvent is removed from filtrate by a reduced pressure distillation method; washing the obtained solid powder with ethanol, filtering, and vacuum drying.

Preferably, in the step (1), the molar ratio of the pentaerythritol to the trichloro-sulfur is 1: 1.

preferably, in step (2), the molar ratio of SPEPA to TMCS is 1.2: 1.

in the invention, the mass ratio of the poly (trimethylolpropane thiophosphoryl urea) to the trimethyl silicic acid caged thioPEPA ester is 1: (0.6-2.5).

Preferably, the mass ratio of the poly (trimethylolpropane thiophosphoryl urea) to the trimethyl silicic acid caged thioPEPA ester is 1: 1.8.

in the invention, the mass concentration of the flame retardant in the finishing liquid is 50-200 g/L.

Preferably, the mass concentration of the flame retardant in the finishing liquid is 100 g/L.

In a preferred embodiment, the finishing liquid is prepared by the following method: 50g of PDTPT and 60g of TMSSPE are weighed in a container according to the mass ratio respectively, 1.1L of ethanol is added to dissolve the PDTPT and the TMSSPE to prepare finishing liquid, and the finishing liquid is placed in a water bath kettle at the temperature of 80 ℃ for heat preservation.

In a preferred embodiment, the process of treating the modified polyester base fabric by the finishing liquid comprises the following steps: according to the bath ratio of 1: 30, weighing finishing liquid, immersing the modified polyester base fabric into a container containing the finishing liquid, treating for 30min at 80 ℃, then carrying out two-time soaking and two-time rolling to keep the rolling residual rate at 90-100%, taking out, and drying for 10h at 100 ℃ to obtain the polyester fabric.

The inventors found that when the content of the modified graphene oxide in the soy protein fiber is too high, the thermal stability is reduced due to the fact that the thermal conductivity of the graphene oxide is excellent, and the heat transfer rate of the graphene oxide is increased. The inventor finds that the PDTPT and the TMSSPE are selected for compounding in the invention, so that the thermal stability of the thermal fabric can be improved, and the fabric has good fireproof and flame-retardant properties. Especially when the fabric is subjected to local high temperature, the fabric has excellent thermal stability and flame-retardant self-extinguishing property, and the human body can not hurt the skin because the fabric is heated. The inventors consider that possible reasons are: the-N-H in the PDTPT and the oxygen in the TMSSPE form a hydrogen bond to play a role of a coupling agent, so that the small molecular TMSSPE is uniformly distributed around the polymer PDTPT to form the uniformly dispersed blending finishing liquid. The PDTPT finally forms a porous foam carbon layer, so that internal fibers are effectively protected, and the overall thermal stability of the fabric is improved. Meanwhile, when the fabric is in a high-temperature environment for a long time, and heat is transferred to the inner layer through the outer expanded carbon layer, the amide bond of the N- [3- [ tri (2-methoxyethoxy) silyl ] propyl ] ethane-1, 2-diamine of the modified graphene oxide is broken under the high-temperature condition, and a C-Si-O-C protective layer is formed on the inner layer of the expanded carbon layer, so that the inward transfer of heat is further blocked, and the thermal stability and the flame retardant property of the fabric are improved.

The second aspect of the invention provides the antistatic flame-retardant oil-proof washing cotton-linen blended fabric prepared by the preparation method.

The third aspect of the invention provides an application of the antistatic flame-retardant oil-proof washing cotton-hemp blended fabric, which can be applied to the fields of clothing and home textiles.

The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.

In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.