A high flame retardant breathable protective fabric and its preparation method (ramie fiber)

The invention relates to a high flame retardant breathable protective fabric and a preparation method thereof, belonging to the technical field of textile fabrics. The highly flame-retardant breathable fabric comprises a base cloth and a flame retardant layer bonded on the surface of the base cloth, and the base cloth is made of modified ramie fiber and polyester fiber. At first, the modified ramie fiber with good air permeability is selected as the main fiber to ensure the air permeability and heat dissipation of the base cloth, and the ramie fiber is modified to improve its elasticity, cohesion and spinnability; Secondly, in order to ensure the air permeability of the base cloth, the outer layer of the base cloth was modified unilaterally, and a flame retardant layer was grafted on the outer layer of the base cloth; Thirdly, the flame retardant layer is modified unilaterally to improve the adhesion between the flame retardant layer and the base cloth; After that, the flame retardant layer contains flame retardant with excellent flame retardancy, and the flame retardant contains fluorine containing branch chain, which endows the flame retardant layer with high flame retardancy, water resistance and chemical resistance.

right-claiming document

1. A high flame retardant breathable protective fabric, which is characterized in that it includes a flame retardant layer bonded to the surface of the base cloth, and the base cloth is made of modified ramie fiber and polyester fiber; The flame retardant layer comprises the following steps: one side of the flame retardant polyester film is pasted and sealed with polyethylene tape, and the unprotected side of the flame retardant polyester film after unilateral protection is put into the oxidant solution, and the unprotected side is oxidized at 95 ℃ for 7h to obtain the flame retardant layer modified by unilateral oxidation.

2. The high flame retardant breathable protective fabric according to claim 1, which is characterized in that the content of modified ramie fiber in the base cloth is 75? 85%, the content of polyester fiber is 15? 25％。

3. The high flame retardant breathable protective fabric according to claim 1, which is characterized in that the modified ramie fiber comprises the following steps:

A1. Put ramie fiber in 18% sodium hydroxide solution, react for 3h at room temperature, wash to neutral, and obtain alkali treated ramie fiber;

A2. Put the alkali treated ramie fiber in mixed solution A to react at 55 ℃ for 5h, wash it in turn with water, wash it with anhydrous ethanol, wash it to neutral, and then dry it to obtain etherified modified ramie fiber. The mixed solution A consists of epichlorohydrin, 5% sodium hydroxide solution and anhydrous ethanol according to 3? 4g：

50g：3? 5mL mixed composition;

A3. The etherified modified ramie fiber is put into mixed solution B to react at 50 ℃ for 5h, washed with water, absolute ethanol, and then washed to neutral to obtain the modified ramie fiber. The mixed solution B consists of amino terminated polysiloxane, sodium bicarbonate and absolute ethanol according to 0.65? 0.85mol：5? 7g：100? 120mL mixed.

4. The high flame retardant breathable protective fabric according to claim 1, which is characterized in that the flame retardant polyester film comprises the following steps:

Mix flame retardant polyester resin particles and organic solvent evenly to obtain flame retardant polyester solution; The flame-retardant polyester solution is electrospun, and the flame-retardant polyester film is obtained after the solution is completely spun.

5. The highly flame-retardant breathable protective fabric according to claim 4, which is characterized in that the flame-retardant polyester resin particle comprises the following steps:

C1. Add hexafluorobutyl methacrylate, phosphate monomer, 1,1,3,3? After mixing tetramethylsilane and anhydrous toluene, stir them evenly, heat them to 96 ℃ under nitrogen protection, then add isopropanol solution of chloroplatinic acid, react for 5h, and obtain flame retardant after post-treatment;

C2. Add polyester particles, flame retardant and compatibilizer into the extruder to extrude and granulate to obtain flame retardant polyester resin particles.

6. The high flame retardant breathable protective fabric according to claim 5, which is characterized in that the phosphate monomer comprises the following steps:

After the cage phosphate, acetonitrile, anhydrous aluminum trichloride and triethylamine are mixed, allyldimethylchlorosilane is added, stirred at 70 ℃ for 1.5h, then heated and refluxed for 12h, the reaction is stopped, and the phosphate monomer is obtained after post-treatment.

7. The high flame retardant breathable protective fabric according to claim 6, which is characterized in that the dosage ratio of caged phosphate, acetonitrile, anhydrous aluminum trichloride, triethylamine and allyldimethylchlorosilane is 0.21? 0.25mol：100? 200mL：3? 5g：0.35? 0.55mol：0.1mol。

8. The preparation method of high flame retardant breathable protective fabric according to claim 1, which is characterized in that it comprises the following steps:

Step, spinning the modified ramie fiber and the polyester fiber into a base cloth;

The second step is to bleach and dye the base cloth, remove wrinkles, and dry it to obtain the treated base cloth;

The third step is to take the flame retardant layer as the surface layer, in which the single-sided oxidation modified surface of the flame retardant layer is used as the bonding surface, and the treated base cloth is used as the bottom layer. The flame retardant layer and the base cloth are bonded together by hot pressing to obtain a high flame retardant breathable protective fabric.

technical field 

The invention belongs to the technical field of textile fabrics, in particular to a high flame retardant breathable protective fabric and a preparation method thereof.

Background technology

Ordinary synthetic fibers and natural fibers are relatively easy to burn. In high temperature industries such as fire fighting and smelting, the powerful radiant heat makes ordinary clothing melt, decompose and burn rapidly, which easily burns the skin of operators and threatens their life safety. Flame retardant clothing can greatly slow down the burning speed due to the addition of flame retardant fiber in the fabric or the coating of flame retardant on the fabric, which will extinguish itself immediately after moving, and the burning part will carbonize rapidly without melting, dripping or piercing, giving people time to leave the burning scene or take off the burning clothes, reducing or avoiding burns and scalds, so as to achieve the purpose of protection. Therefore, flame retardant clothing becomes one of the necessary protective articles for high-temperature workers.

The general fireproof fabric is made of flame retardant materials or flame retardant components added to ordinary fibers, and has a

It has been used in decorative firewall cloth and fire clothing, but its air permeability is poor and its wearing comfort is poor,

Fire fighting and other high-temperature workers are often exposed to flame or high temperature, and they need protective clothing or protective products in addition to

Besides being able to withstand high temperature, the human body's sweat output is doubled due to intense exercise, and the external environment temperature is extremely high

The degree will make firefighters feel extremely stuffy and wet, which will seriously affect the operational efficiency of firefighters.

For example, a waterproof, moisture permeable and fireproof all polyester PU protective fabric disclosed in Chinese patent CN105113257A, including

The surface of the base cloth is coated with a waterproof and flame retardant coating, a second waterproof and flame retardant coating and a third waterproof and flame retardant coating in turn

And the fourth waterproof and flame retardant coating. In the invention, the surface of the fabric is coated with a multi-layer flame retardant coating, and the air permeability must be reduced.

Therefore, the invention provides a protective fabric with good flame retardancy and good air permeability and a preparation method thereof.

summary of the invention

The invention aims at providing a high flame retardant breathable protective fabric and a preparation method thereof.

The invention aims to solve the technical problem that the flame retardancy and air permeability of the existing protective fabric cannot be achieved at the same time.

The purpose of the invention can be realized through the following technical solutions:

The utility model relates to a high flame retardant breathable protective fabric, which comprises a flame retardant layer bonded on the base cloth and the surface of the base cloth.

Further, the base cloth is made of modified ramie fiber and polyester fiber with good air permeability. The obtained base cloth has the characteristics of air permeability, moisture permeability and good shape retention by taking advantage of the characteristics of ramie fiber, such as large gap, good air permeability, high modulus, high strength, high elasticity, and good shape retention; To solve the problems of high rigidity, small elasticity, poor cohesion and spinnability of the ramie fiber caused by the high orientation and crystallinity of the macromolecule of the ramie cellulose, straight surface and no curl, the invention modifies the ramie fiber to obtain the modified ramie fiber.

Furthermore, the content of modified ramie fiber in the base cloth is 75? 85%, the content of polyester fiber is 15? 25%. Ramie fiber is used as the main fiber to ensure the air permeability and heat dissipation of the base cloth. The shape retention of the base cloth is improved by adding polyester fiber.

Further, the modified ramie fiber is made by the following steps:

A1. Put ramie fiber in 18% sodium hydroxide solution, react for 3h at room temperature, wash to neutral, and obtain alkali treated ramie fiber. The mass ratio of ramie fiber to 18% sodium hydroxide solution is 1:30-40;

A2. Put the alkali treated ramie fiber in mixed solution A to react at 55 ℃ for 5h, wash it in turn with water, wash it with absolute ethanol, wash it to neutral, and dry it to obtain etherified modified ramie fiber. The mass ratio of alkali treated ramie fiber and mixed solution A is 1:30? 40； Mixed solution A is composed of epichlorohydrin, 5% sodium hydroxide solution and anhydrous ethanol according to 3-4g: 50g: 3? 5mL mixed composition;

In the above reaction, the hydroxyl group on the surface of the ramie fiber reacts with the chlorine in epichlorohydrin to graft the epoxy group onto the alkali treated ramie fiber surface;

A3. Put the etherified ramie fiber in mixed solution B and react at 50 ℃ for 5h, wash it with water, absolute ethanol, and then wash it to neutral to obtain the modified ramie fiber. The mass ratio of etherified ramie fiber to mixed solution B is 1:30? 40, mixed solution B consists of amino terminated polysiloxane, sodium bicarbonate and absolute ethanol according to 0.65? 0.85mol：5? 7g：100? 120mL mixed.

In the above reaction, the epoxy group on the surface of the etherified ramie fiber and the amino reaction in the amino terminated polysiloxane are used to polymerize and link the siloxane onto the surface of the ramie fiber, and the flexibility of the siloxane polymerization chain and the amino group are used to improve the elasticity, cohesion and spinnability of the ramie fiber.

Further, the amino terminated polysiloxane is prepared by the following steps:

Under the protection of nitrogen gas flow, add D4 (octamethylcyclotetrasiloxane) and catalyst benzyltrimethylamine hydroxide methanol solution (0.5wt%) into a four necked flask, heat to 50 ℃ under magnetic stirring, add end capping agent, and remove residual water and methanol in the system under reduced pressure. When the viscosity of the system remains unchanged, continue to react for 12h, continue to rise to 175 ℃ to destroy the catalytic center activity, and then cool to 150 ℃, Remove the remaining D4 monomer and low boiling small molecule from the reaction under negative pressure to obtain amino terminated polysilane, wherein, the end capping agent is 1,3? Bis (3-aminopropyl)? 1，1，3，3? Dosage ratio of tetramethyldisiloxane, D4, catalyst and capping agent

60g: 0.6g: 6? 9g, the molecular weight of amino terminated polysiloxane is 1000? 1500。

Further, the flame retardant layer is made by the following steps:

B1. Add flame-retardant polyester resin particles and organic solvent into a three necked bottle, and continue to stir at room temperature until completely dissolved to obtain flame-retardant polyester solution; The flame-retardant polyester solution is electrospun, and the flame-retardant polyester film is obtained after the solution is completely spun. The mass ratio of flame-retardant polyester resin particles to organic solvent is 15? 18：82? 85, the organic solvent is acetone and N, N? Dimethylformamide is 70? 85：15? 30 Mixed solvent, in which the spinning voltage is 18kV, the spinning speed is 0.6mL/h, the spinning receiving distance is 18cm, the spinning temperature is 28 ℃, and the spinning humidity is 35%;

B2. Paste and seal one side of the flame retardant polyester film with polyethylene tape, protect the surface of the pasted side film, put the unprotected side of the flame retardant polyester film after unilateral protection into an oxidant solution, and oxidize the unprotected side at 95 ℃ for 7h to obtain a flame retardant layer modified by unilateral oxidation, wherein the oxidant solution is made by mixing potassium permanganate powder and 68% nitric acid with a mass ratio of 1:1.

Furthermore, the flame-retardant polyester resin granules are prepared by the following steps: C1, mixing hexafluorobutyl methacrylate, phosphate monomer, 1,1,1,3,3? After the tetramethylsilane and anhydrous toluene are mixed, they are stirred evenly, and then heated to 96 ℃ under the protection of nitrogen, and then chloroplatinic acid isopropanol solution is added to react for 5h. After the reaction, platinum catalyst is adsorbed on active carbon, filtered, and the solvent is removed by rotary evaporation to obtain a flame retardant, in which hexafluorobutyl methacrylate, phosphate monomer, 1,3,3? The molar ratio of tetramethylsilane is 1:1:1, and the addition amount of chloroplatinic acid isopropanol solution is hexafluorobutyl methacrylate, phosphate monomer and 1,1,3,3? 2? Of the total mass of tetramethylsilane? 4％；

In C1 reaction, the flame retardant is obtained by polymerization of olefin compound and hydrosilane, and the molecular structure formula of the flame retardant is as follows:;

C2. Add polyester particles, flame retardants and compatibilizers into the extruder, extrude and granulate to obtain flame retardant polyester resin particles. The rotational speed of the extruder is 200? 400 rpm, extrusion temperature 160? At 200 ℃, the mass ratio of polyester particles, flame retardant and compatibilizer is 100:15? 30：1.5? 4.5. The compatibilizer is one of maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene, and the polyester particles are PET particles.

In the C2 reaction, the flame retardant obtained from C1 reaction is added to the polyester particles, and then extruded and granulated to obtain flame retardant polyester resin particles. The flame retardant and polyester particles are mixed and extruded and granulated under the effect of the compatibilizer, so that the polyester particles have flame retardant properties. First, the flame retardant is a linear polymer, containing cage like phosphate structure and fluorine containing branches. Under the effect of the compatibilizer and fluorine containing branches, the flame retardant is uniformly dispersed in the polyester system, It also has excellent flame retardancy due to its cage like phosphate structure, fluorine containing branch chains and silicon oxygen bonds on the main chain.

Further, the phosphate monomer is prepared by the following steps:

D1. Pentaerythritol, phosphorus oxychloride and 1,4? Add dioxane into a three port flask with mechanical stirring, thermometer, condensation reflux, drying and hydrogen chloride gas absorption device, raise the temperature to 85 ℃, stir until no hydrogen chloride gas is generated, stop the reaction, cool to room temperature, filter, and use 1,4? For precipitation? The dioxane and ethanol were washed twice respectively, and then vacuum dried to constant weight to obtain cage shaped phosphate, in which pentaerythritol, phosphorus oxychloride, 1,4? The dosage ratio of dioxane is 0.11? 0.13mol：0.1mol：40-60mL；

In the above reaction, the hydroxyl group in pentaerythritol and chlorine in phosphorus trichloride are used to react to obtain cage phosphate, and its molecular structure formula is as follows:;

D2. Add caged phosphate, acetonitrile, anhydrous aluminum trichloride and triethylamine into a three necked flask with mechanical stirring, condensation reflux, temperature control, nitrogen protection and constant pressure drop funnel, add allyldimethylchlorosilane, stir it at 70 ℃ for 1.5h, then rise the temperature and reflux for 12h, stop the reaction, cool it to room temperature, filter it by suction, wash the solid matter with acetonitrile for several times, and then wash it with deionized water for several times, After vacuum drying to constant weight, phosphate monomer is obtained, in which the dosage ratio of caged phosphate, acetonitrile, anhydrous aluminum trichloride, triethylamine and allyldimethylchlorosilane is 0.21? 0.25mol：100? 200mL：3? 5g：0.35?

0.55mol：0.1mol。

In the above reaction, the hydroxyl group of cage phosphate is used to react with the chlorine of allyldimethylchlorosilane to obtain the phosphate monomer, and its molecular structure formula is as follows.

A high flame retardant breathable protective fabric is made by the following steps:

Step, spinning the modified ramie fiber and the polyester fiber into a base cloth;

The second step is to bleach and dye the base cloth, remove wrinkles, and dry it to obtain the treated base cloth;

The third step is to take the flame retardant layer as the surface layer, in which the single-sided oxidation modified surface of the flame retardant layer is used as the bonding surface, and the treated base cloth is used as the bottom layer, and the flame retardant layer and the base cloth are hot pressed