CN109652977B - Flame-retardant ultraviolet-resistant aramid fiber - Google Patents

Flame-retardant ultraviolet-resistant aramid fiber Download PDF

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CN109652977B
CN109652977B CN201811497406.XA CN201811497406A CN109652977B CN 109652977 B CN109652977 B CN 109652977B CN 201811497406 A CN201811497406 A CN 201811497406A CN 109652977 B CN109652977 B CN 109652977B
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aramid fiber
flame
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drying
ultraviolet
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CN109652977A (en
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梁国正
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Suzhou University
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    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
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Abstract

The patent relates to a flame-retardant ultraviolet-resistant aramid fiber, and a preparation method thereof comprises the following steps: adding the nano particles into a hydrogen peroxide solution, magnetically stirring for 0.5-1 h, adding a sulfuric acid solution, and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing and drying the filter cake to obtain modified particles, modifying the modified particles with curcumin and dopamine to obtain organic modified particles, and finally reacting the organic modified particles with silicon methoxylated aramid fibers to obtain the surface modified aramid fibers. The high-performance ultraviolet-absorbing aramid fiber has high ultraviolet absorptivity and extremely low catalytic activity, avoids damage of photocatalysis to a fiber structure in a radiation process, and particularly improves the flame retardant property of the aramid fiber.

Description

Flame-retardant ultraviolet-resistant aramid fiber
Technical Field
The invention relates to a surface modification technology of aramid fiber, in particular to flame-retardant ultraviolet-resistant aramid fiber.
Background
In recent years, in order to improve the surface activity and ultraviolet resistance of aramid fibers, ultraviolet shielding agents are introduced to the surfaces of the aramid fibers. The ultraviolet screening agent is divided into an organic ultraviolet screening agent and an inorganic ultraviolet screening agent. However, organic uv screeners suffer from poor heat and oxidation resistance. The problems are well controlled in the inorganic ultraviolet shielding agent, but the problem of high catalytic activity exists, and the organic fiber is subjected to photocatalytic degradation; in addition, the binding force between the inorganic material and the organic fiber is limited, and the inorganic material can fall off in the using process, so that the service reliability is influenced.
In addition, in some special occasions, such as tools worn by fire fighters, steelmaking workers, electric welders, chemical plant workers, oil refinery workers, oil field drilling workers and the like and combat uniforms of troops fighters all need the flame retardant function, and simultaneously, the flame retardant function and the requirement of the flame retardant on the presence or absence of molten drops are needed so as to avoid secondary scalding; in many civil occasions, such as decoration of hotels, halls and stages, the decoration of seat covers, curtains, bed appliances and the like of transportation means such as airplanes, trains, automobiles and the like, and children clothes and the like also have the flame retardant function.
The inventor aims to develop a novel aramid fiber with surface activity and ultraviolet resistance, which has a good ultraviolet resistance effect, but does not relate to flame retardant property.
Disclosure of Invention
The invention aims to research and develop a novel inorganic ultraviolet modifier on the premise of keeping the original mechanical property and ultraviolet resistance of the fiber, and form a coating with stronger bonding force on the surface of aramid fiber by a novel preparation method, thereby endowing the modified aramid fiber with ultraviolet resistance and flame retardance.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the preparation method of the flame-retardant ultraviolet-resistant aramid fiber comprises the following steps:
(1) dissolving cerium salt and inorganic base in water, stirring for 20-45 min, then adding hydrogen peroxide to obtain a suspension, adjusting the pH of the suspension to 10-14, reacting for 10-20 h at 20-50 ℃, washing with water, filtering, drying, and calcining for 1-3 h at 500-800 ℃ to obtain nano cerium oxide; dispersing the nano cerium oxide, the boron source and the nitrogen-containing compound in a mixed solution consisting of ethanol and water, ultrasonically stirring for 0.5-1.5 h, then carrying out rotary steaming and drying, then dispersing in a cobalt nitrate aqueous solution, ultrasonically stirring for 0.5-1 h, and carrying out rotary steaming and drying to obtain a solid; calcining the solid for 13-15 h at 850-950 ℃ in the atmosphere of nitrogen source gas, and then crushing to obtain nano particles;
(2) adding the nano particles into a hydrogen peroxide solution, magnetically stirring for 0.5-1 h, adding a sulfuric acid solution, and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing the filter cake with water, and drying to obtain modified particles;
(3) adding the modified particles and dopamine hydrochloride into a buffer solution with the pH value of 8.3-8.8, and stirring at room temperature for 2-3 hours; then adding a curcumin ethanol solution, and continuously stirring for 1-2 h; then filtering, washing and drying to obtain organic modified particles;
(4) immersing silicon methoxylated aramid fiber in an aqueous solution containing trimethylsilanol, and oscillating for 0.5-1 h; then immersing the particles into an aqueous solution containing organic matter modified particles, and carrying out oscillation reaction for 2-3 h at the temperature of 70-80 ℃; and after the reaction is finished, washing and drying to obtain the flame-retardant ultraviolet-resistant aramid fiber.
A preparation method of flame-retardant ultraviolet-resistant aramid fibers comprises the following steps:
(1) dissolving cerium salt and inorganic base in water, stirring for 20-45 min, then adding hydrogen peroxide to obtain a suspension, adjusting the pH of the suspension to 10-14, reacting for 10-20 h at 20-50 ℃, washing with water, filtering, drying, and calcining for 1-3 h at 500-800 ℃ to obtain nano cerium oxide; dispersing the nano cerium oxide, the boron source and the nitrogen-containing compound in a mixed solution consisting of ethanol and water, ultrasonically stirring for 0.5-1.5 h, then carrying out rotary steaming and drying, then dispersing in a cobalt nitrate aqueous solution, ultrasonically stirring for 0.5-1 h, and carrying out rotary steaming and drying to obtain a solid; calcining the solid for 13-15 h at 850-950 ℃ in the atmosphere of nitrogen source gas, and then crushing to obtain nano particles;
(2) adding the nano particles into a hydrogen peroxide solution, magnetically stirring for 0.5-1 h, adding a sulfuric acid solution, and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing the filter cake with water, and drying to obtain modified particles;
(3) adding the modified particles and dopamine hydrochloride into a buffer solution with the pH value of 8.3-8.8, and stirring at room temperature for 2-3 hours; then adding a curcumin ethanol solution, and continuously stirring for 1-2 h; then filtering, washing and drying to obtain organic modified particles;
(4) immersing silicon methoxylated aramid fiber in an aqueous solution containing trimethylsilanol, and oscillating for 0.5-1 h; then immersing the particles into an aqueous solution containing organic matter modified particles, and carrying out oscillation reaction for 2-3 h at the temperature of 70-80 ℃; and after the reaction is finished, washing and drying to obtain the flame-retardant ultraviolet-resistant aramid fiber.
In the invention, the silicon methoxylated aramid fiber is the prior art and is described in the invention application 2018104223562; the aramid fiber is para-aramid fiber or meta-aramid fiber.
In the invention, the inorganic alkali is sodium hydroxide or potassium hydroxide; the cerium salt is one or any combination of cerium nitrate and cerium chloride; the boron source is one of boric acid and metaboric acid; the nitrogen-containing compound is one of urea, trichlorocyanamide and ammonium bromide.
In the invention, the mass ratio of the nano cerium oxide to the boron source to the nitrogen-containing compound to the cobalt nitrate is 100 to (30-50) to (60-120) to (10-13). According to the invention, after the nano cerium oxide, the boron source and the nitrogen-containing compound are mixed and adsorbed and react, cobalt nitrate is added, the disadvantages of wrapping boron nitride are reduced, cobalt is adsorbed on the surface of the nano cerium oxide, and according to element analysis, the cobalt ions contained in the nano particles can be found; the presence of cobalt is believed to enhance the reactivity of the nanoparticles, particularly the reactivity with the aramid interface, which is beneficial for the attachment of the nanoparticles to the aramid surface and thus for the flame retardancy, and in addition, cobalt may enhance the performance of the bond at the interface between the nanoparticles and the aramid, which is beneficial for the improvement of the flame retardancy at the interface.
In the invention, the mass ratio of the cerium salt to the inorganic base is 100 to (20-50); the nitrogen source gas is one of nitrogen and ammonia; the buffer solution is one of Tris-HCl and disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution. The mass ratio of the nano particles to the hydrogen peroxide solution to the sulfuric acid solution is 100 to (60-70) to (5-7); the mass concentrations of the hydrogen peroxide solution and the sulfuric acid solution are respectively 30% and 98%. The step is disclosed for the first time, micro grooves can be formed on the surfaces of the nano particles, and the micro grooves are caused by oxidation etching and can also increase the surface active groups of the nano particles, such as hydroxyl; this is advantageous for improving the reactivity and interfacial action of the nanoparticles.
In the invention, the mass ratio of the modified particles to the dopamine hydrochloride to the curcumin is 100 to (30-50) to (8-12). The effect of the combination of a small amount of curcumin on the reaction of dopamine hydrochloride on the surface of the modified particles is small, and the curcumin can react on the surface of the particles, so that the improvement of the interfacial effect of the particles and the aramid fibers is facilitated.
In the invention, the mass ratio of the silicon methoxylated aramid fiber to the organic matter modified particle to the trimethylsilanol is 1 to (2-9) to (0.3-0.35). The addition of trimethylsilanol can be compatible with silicon methoxyl on the surface of aramid fiber on one hand, and can react with curcumin and dopamine to a certain extent on the other hand, and more importantly, can be cooperated with boron nitride to improve the flame retardant property; as can be seen from the examples, the addition of trimethylsilanol is advantageous for flame retardancy.
In the present invention, the silicon methoxylated aramid fiber may be prepared by, by mass,
(1) sequentially immersing aramid fibers in acetone, petroleum ether and deionized water, respectively staying for 2-4 h, then washing and drying to obtain the aramid fibers with clean surfaces;
(2) soaking 1 part of aramid fiber with clean surface into an alcohol solution of alkali metal hydroxide with the mass concentration of 5.0-15.0 wt%, and carrying out oscillation reaction for 4-8 h at the temperature of 50-80 ℃; after the reaction is finished, washing and drying to obtain the aramid fiber with amino and carboxyl on the surface;
(3) and (3) under an inert gas atmosphere, soaking 1 part of the aramid fiber with amino and carboxyl on the surface obtained in the step (2) into 150-350 parts of organic solvent containing 100-200 parts of gamma-glycidyl ether oxypropyl trimethoxy silane, and reacting at 50-100 ℃ for 10-18 h to obtain the silicon methoxylated aramid fiber.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, on the basis that the polydopamine is modified to ensure that the inorganic nanoparticles are connected with the aramid fiber surface by chemical bonds, the nanoparticles are treated by hydrogen peroxide and sulfuric acid solution to obtain modified particles with improved surface structures and activities, so that the reactivity of the nanoparticles is further improved.
2. The inorganic nano modifier provided by the invention keeps the capability of polydopamine modified turbostratic boron nitride coated cerium oxide of high ultraviolet absorptivity, high heat resistance and very low photocatalytic activity, and the adhesive force of the nano particles is improved by adding cobalt, so that the inorganic nano modifier is beneficial to flame retardance.
3. According to the invention, the flame retardant effect is obviously improved on the surface of aramid fiber with good flame retardancy by virtue of the nanometer particles, the interface action of the nanometer particles and the aramid fiber and the synergistic action of silanol, and the influence on the ultraviolet resistance is very small.
Detailed Description
Reference 2018104223562:
(1) 1g of aramid fiber (Kevlar-49, diameter 12 μm, density 1.45 g/m)3Manufactured by dupont, usa) were sequentially immersed in acetone at 70 ℃, petroleum ether at 75 ℃ and deionized water at 115 ℃ for 3 hours, respectively; then taking out the fiber, and drying in a vacuum oven at 80 ℃ to obtain clean aramid fiber, which is marked as KF;
(2) dissolving 10.5g of sodium hydroxide in 120mL of ethanol to prepare an ethanol solution A of the sodium hydroxide; immersing the clean aramid fiber KF obtained in the step (1) in the solution A, carrying out oscillation reaction for 5h at 65 ℃, and washing and drying after the reaction is finished to obtain the aramid fiber with amino and carboxyl on the surface;
(3) adding 0.25g of aramid fiber with amino and carboxyl on the surface and 30mL of gamma-glycidoxypropyltrimethoxysilane into 70mL of ethanol, and reacting at 70 ℃ for 12h in a nitrogen atmosphere; and after the reaction is finished, taking out the fiber to obtain the aramid fiber with silicon methoxyl on the surface.
Example 1
1. Preparation of modified aramid fiber
(1) Dissolving 12.32g of cerium chloride and 6g of sodium hydroxide in an aqueous solution, and stirring for 35min to obtain a suspension A; adding hydrogen peroxide, adjusting the pH value of the suspension A to 12 by using sodium hydroxide, reacting for 12 hours at 40 ℃, filtering, washing and drying; calcining the mixture for 2 hours at 700 ℃ in a muffle furnace to obtain the nano cerium oxide CeO2(ii) a 3g of nano cerium oxide and 1.2g of boric acidAnd 2.1g of urea are put into a mixed solution of 400mL of ethanol and 200mL of water, and are subjected to ultrasonic dispersion for 1 hour; performing rotary evaporation and drying to obtain a dried substance, then dispersing the dried substance in 100 mL of cobalt nitrate aqueous solution (3.6 mg/mL), performing ultrasonic stirring for 50 minutes, and performing rotary evaporation and drying to obtain a solid substance; calcining the solid for 15 hours at 950 ℃ in a nitrogen atmosphere; after the reaction is finished, washing, drying and crushing to obtain nano particles with the particle size of less than 100nm, wherein the nano particles contain cobalt element through elemental analysis;
(2) adding 5g of nano particles into 3g of hydrogen peroxide solution (30 wt%), magnetically stirring for 0.5-1 h, adding 0.3 wt% of sulfuric acid solution (98 wt%), and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing the filter cake with water, and drying to obtain modified particles; scanning electron microscope shows that the modified particle has a rougher surface than the nano particle, and when the modified particle is added into water in the same way, the modified particle generates slightly more bubbles than the nano particle;
(3) preparing a Tris-HCl buffer solution with the concentration of 10mM, and adjusting the pH value of the buffer solution to 8.5 by using sodium hydroxide to obtain a buffer solution B; adding the modified particles and dopamine hydrochloride into the buffer solution B according to the mass ratio of the modified particles to the dopamine hydrochloride of 5:2.2, stirring for 2 hours at room temperature, then adding a curcumin ethanol solution, and continuing stirring for 2 hours; after the reaction is finished, filtering, washing and drying to obtain organic modified particles, wherein the mass ratio of the modified particles to the curcumin is 10: 0.8;
(4) immersing 0.2g of silicon methoxylated aramid fiber in an aqueous solution containing 0.06g of trimethylsilanol, and oscillating for 0.5 h; after the reaction is finished, taking out the fiber, dispersing the fiber and 1g of organic matter modified particles in an aqueous solution, and oscillating for 2.5 hours at the temperature of 80 ℃; and (3) taking out the fiber after the reaction is finished, washing and drying to obtain the flame-retardant ultraviolet-resistant aramid fiber which is called as modified aramid fiber.
2. Ultraviolet irradiation of clean and modified fibers
Exposing clean aramid fiber and flame-retardant ultraviolet-resistant aramid fiber to QUV/spray type ultraviolet light accelerated aging tester (U.S. Q-Lab company) for 168h of UV irradiation (the irradiation illumination is 1.55W/m)2At a test temperature of 60 ℃) to give a radiation of 168hClean aramid fiber and modified aramid fiber, the performance test results are as follows:
the modified aramid fiber of example 1 had a work of rupture 1.32 times that of the clean fiber and a tensile strength 1.28 times that of the clean fiber, indicating that the surface modification contributes to the improvement of the work of rupture and the tensile strength of the fiber.
After 168 hours of ultraviolet radiation, the breaking work and the tensile strength of the clean fiber are reduced by 47.43 percent and 27.64 percent, while the breaking work of the example 1 is reduced by 15.12 percent and the tensile strength is reduced by 9.9 percent.
After 30 times of conventional soaping, after 168 hours of ultraviolet radiation, the work of rupture of the modified aramid fiber prepared in example 1 is reduced by 22.02%, the tensile strength is reduced by 12.29%, the work of rupture of the modified aramid fiber prepared in example 1 is reduced by 28.32%, and the tensile strength is reduced by 17.99%.
The flame-retardant fiber and the performance characterization method thereof are adopted for research, the oxygen index of the modified aramid fiber in example 1 is 36, smoldering and molten drop phenomena are avoided, the oxygen index of the modified aramid fiber prepared in example 2018104223562 is 31, and the oxygen index of the clean aramid fiber is 27; after 30 regular soaping, the modified aramid fiber of example 1 has an oxygen index of 32, and the modified aramid fiber prepared in example 1 of 2018104223562 has an oxygen index of 28.
Comparative example
By adopting the method of example 1, wherein the nanoparticles are used for replacing the modified particles in the step (3), the prepared modified aramid fiber has an oxygen index of 30 after being subjected to conventional soaping for 30 times, the UV irradiation breaking work of 168 hours is reduced by 26.88%, and the tensile strength is reduced by 15.79%.
By adopting the method of example 1, wherein cobalt nitrate is not added in the step (1), after the prepared modified aramid fiber is subjected to conventional soaping for 30 times, the oxygen index is 31, the UV irradiation breaking work of 168 hours is reduced by 24.58%, and the tensile strength is reduced by 14.02%.
The method of example 1 is adopted, wherein no curcumin is added in the step (3), and after the prepared modified aramid fiber is subjected to conventional soaping for 30 times, the oxygen index is 30, the UV irradiation work of rupture for 168 hours is reduced by 27.36%, and the tensile strength is reduced by 16.89%.
The method of example 1 was used, wherein trimethylsilanol was not added in step (4), and the prepared modified aramid fiber had an oxygen index of 34, which was 31 after 30 regular soapings.
2018104223562 the method of example 1 is adopted, wherein the modified aramid fiber prepared by adding the existing phosphate ester flame retardant in the step (7) has an oxygen index of 32, and the oxygen index is 28 after 30 times of conventional soaping; if additive flame retardants (such as phosphorus-nitrogen based) are used, the effect is even worse.
The modified aramid fiber is used as a composite material, the combustion mechanism is complex, the process influence factors are many, the interface action of the modified particles and the aramid fiber and the synergistic action of the property of the modified particles and the combined elements seem to be an effective method for improving the flame retardant property, and further research is needed for the thermal property and the electrical property; on the basis of the earlier stage work of a subject group, the invention not only solves the problems of low surface activity, poor ultraviolet resistance and the like of aramid fiber, but also mainly improves the flame retardant property of the aramid fiber, so that the aramid fiber can be used as a typical representative of high-performance organic fiber and plays an important role in the fields of aerospace, safety protection, electronic information, sports goods, tire frameworks and the like.

Claims (5)

1. The flame-retardant ultraviolet-resistant aramid fiber is characterized in that the preparation method of the flame-retardant ultraviolet-resistant aramid fiber comprises the following steps:
(1) dissolving cerium salt and inorganic base in water, stirring for 20-45 min, then adding hydrogen peroxide to obtain a suspension, adjusting the pH of the suspension to 10-14, reacting for 10-20 h at 20-50 ℃, washing with water, filtering, drying, and calcining for 1-3 h at 500-800 ℃ to obtain nano cerium oxide; dispersing the nano cerium oxide, the boron source and the nitrogen-containing compound in a mixed solution consisting of ethanol and water, ultrasonically stirring for 0.5-1.5 h, then, rotationally steaming, drying, then, dispersing in a cobalt nitrate aqueous solution, ultrasonically stirring for 0.5-1 h, and rotationally steaming and drying to obtain a solid; calcining the solid for 13-15 h at 850-950 ℃ in the atmosphere of nitrogen source gas, and then crushing to obtain nano particles; the mass ratio of the nano cerium oxide to the boron source to the nitrogen-containing compound to the cobalt nitrate is 100 to (30-50) to (60-120) to (10-13); the mass ratio of the cerium salt to the inorganic base is 100: 20-50;
(2) adding the nano particles into a hydrogen peroxide solution, magnetically stirring for 0.5-1 h, adding a sulfuric acid solution, and continuously magnetically stirring for 0.5 h; then filtering to obtain a filter cake, washing the filter cake with water, and drying to obtain modified particles; the mass ratio of the nano particles to the hydrogen peroxide solution to the sulfuric acid solution is 100 to (60-70) to (5-7);
(3) adding the modified particles and dopamine hydrochloride into a buffer solution with the pH value of 8.3-8.8, and stirring at room temperature for 2-3 hours; then adding a curcumin ethanol solution, and continuously stirring for 1-2 h; then filtering, washing and drying to obtain organic modified particles; the mass ratio of the modified particles to the dopamine hydrochloride to the curcumin is 100 to (30-50) to (8-12);
(4) immersing silicon methoxylated aramid fiber in an aqueous solution containing trimethylsilanol, and oscillating for 0.5-1 h; then immersing the particles into an aqueous solution containing organic matter modified particles, and carrying out oscillation reaction for 2-3 h at the temperature of 70-80 ℃; after the reaction is finished, washing and drying to obtain the flame-retardant ultraviolet-resistant aramid fiber; the mass ratio of the silicon methoxylated aramid fiber to the organic matter modified particles to the trimethylsilanol is 1: 2-9: 0.3-0.35.
2. The flame-retardant ultraviolet-resistant aramid fiber according to claim 1, characterized in that: the aramid fiber is para-aramid fiber or meta-aramid fiber.
3. The flame-retardant ultraviolet-resistant aramid fiber according to claim 1, characterized in that: the inorganic alkali is sodium hydroxide or potassium hydroxide; the cerium salt is one or any combination of cerium nitrate and cerium chloride; the boron source is one of boric acid and metaboric acid; the nitrogen-containing compound is one of urea, trichlorocyanamide and ammonium bromide.
4. The flame-retardant ultraviolet-resistant aramid fiber according to claim 1, characterized in that: the buffer solution is one of Tris-HCl and disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution.
5. The flame-retardant ultraviolet-resistant aramid fiber according to claim 1, characterized in that: the nitrogen source gas is one of nitrogen and ammonia.
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