Production process of polyester high-efficiency flame retardant and application of polyester high-efficiency flame retardant in thermal insulation material

Abstract

The invention belongs to the technical field of flame retardance, and particularly discloses a production process of a polyester efficient flame retardant and application of the polyester efficient flame retardant to a thermal insulation material. Comprising the following steps: (1) dispersing montmorillonite in deionized water, adding PEG-400, octadecyl trimethyl ammonium chloride and aluminum metaphosphate, stirring at the temperature of 50-60 DEG C, and drying to obtain pretreated montmorillonite; (2) uniformly mixing composite glass fibers, magnesium hydroxide and silicon dioxide, dispersing the mixture into an ethanol solution, adding the pretreated montmorillonite in the step (1), and performing ultrasonic treatment, filtration and drying to obtain a mixture; and (3) spraying an epoxy resin solution on the surface of the mixture obtained in the step (2), and grinding to obtain the high-efficiency polyester flame retardant. According to the flame-retardant polyester material disclosed by the invention, various components are synergistically matched, a compact carbon layer is formed during combustion, heat is prevented from being transferred to a polyester matrix, a flame-retardant effect is achieved, and the inorganic components, the epoxy resin coating and the like can change the mechanical properties of the polyester material.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of flame retardants, and in particular to a production process of a polyester efficient flame retardant and application thereof to thermal insulation materials. BACKGROUND

[0002] A flame retardant is a kind of chemical additive that can prevent or delay combustion of a material and inhibit flame propagation, and is widely applied in the fields of rubber, plastic, textile and paint, and the action principle thereof includes covering and isolating, absorbing heat and reducing temperature, inhibiting free radicals and diluting oxygen.

[0003] Polyester is a kind of high molecular compound generated by polycondensation of polybasic acid and polyhydric alcohol, and has wide application, such as electronic and electrical shell, automotive interior part and building insulation material, and has good mechanical property and processing property, and is required to have good flame retardancy.

[0004] In the prior art, the raw material of the polyester material usually includes polyester resin, flame retardant, toughening agent, thermal stabilizer and plasticizer, and the traditional flame retardant such as aluminum hydroxide and magnesium hydroxide is decomposed at high temperature, which may reduce the high temperature performance of the material, and further affect the high temperature resistance of the polyester material.

[0005] The aluminum hydroxide and the magnesium hydroxide are decomposed and absorb heat and release water vapor at high temperature, and this process helps to retard the flame, but the water vapor generated forms pores in the material, reduces the compactness of the material, and further weakens the mechanical properties such as tensile strength and modulus of the material. SUMMARY

[0006] In order to improve the problem that the traditional flame retardant in the polyester material affects the mechanical property of the polyester, the application provides a production process of a polyester efficient flame retardant and application thereof to thermal insulation materials.

[0007] The application provides a production process of a polyester efficient flame retardant, and adopts the following technical scheme: The production process of the polyester efficient flame retardant comprises the following steps: (1) dispersing montmorillonite in deionized water, adding PEG-400, octadecyl trimethyl ammonium chloride and aluminum metaphosphate, stirring at a temperature of 50-60 DEG C for 1-2 h, drying to obtain pretreated montmorillonite; (2) uniformly mixing composite glass fiber, magnesium hydroxide and silicon dioxide, dispersing into an ethanol solution, adding the pretreated montmorillonite of step (1), ultrasonicating, filtering and drying to obtain a mixture; (3) spraying an epoxy resin solution on the surface of the mixture of step (2), spraying 5-8 times, drying for 10-15 min each time, grinding to obtain the polyester efficient flame retardant.

[0008] By adopting the above technical scheme, the montmorillonite has a layered structure and a large specific surface area, the PEG-400 is adsorbed on the surface of the montmorillonite particles, the repulsive force between the particles is increased, the montmorillonite particles are prevented from agglomerating in water, and it is ensured that the montmorillonite can be uniformly dispersed in the solution. The octadecyl trimethyl ammonium chloride is intercalated into the interlayer space of the montmorillonite, the interlayer distance of the montmorillonite is expanded, and the specific surface area of the montmorillonite is further increased, and the subsequent interfacial bonding force with the organic polymer such as polyester is enhanced. The aluminum metaphosphate interacts with the montmorillonite, the aluminum metaphosphate is adsorbed on the surface of the montmorillonite, and the montmorillonite and the aluminum metaphosphate are compounded to form a synergistic flame-retardant effect, and the thermal stability and chemical resistance of the montmorillonite are enhanced.

[0009] The composite glass fiber provides a physical reinforcing effect, improves the mechanical properties of the polyester, and at the same time, the high melting point of the glass fiber can form a skeleton during combustion to inhibit molten dripping and assist in flame retardation. Magnesium hydroxide has good flame retardant properties, and when heated, it can absorb heat and release water vapor, playing a role in flame retardation and cooling. Silicon dioxide improves the hardness, wear resistance and thermal stability of the material, and hinders heat conduction by increasing the density of the polyester. An inorganic composite system is formed among the pretreated montmorillonite, composite glass fiber, magnesium hydroxide and silicon dioxide, the surface of the composite glass fiber has a certain microporous structure and active groups, the silicon dioxide is filled in the small gaps of the glass fiber, and the magnesium hydroxide forms a layer of covering on the surface of the composite glass fiber, increasing the density of the composite material. After the addition of the pretreated montmorillonite, the montmorillonite is deposited on the surface of the composite glass fiber, magnesium hydroxide and silicon dioxide, forms a network structure with the composite glass fiber, further coats the magnesium hydroxide and silicon dioxide, and ultrasonic treatment makes the combination between these materials more compact, improving the overall performance of the material, including flame retardant performance, thermal stability and mechanical properties.

[0010] The mixture is sprayed with an epoxy resin solution, the epoxy resin has good adhesion, chemical resistance and processability, the epoxy resin uniformly covers the surface of the mixture, forming a dense coating on the surface of the mixture, so that the montmorillonite, composite glass fiber, magnesium hydroxide and silicon dioxide are closely bonded, and at the same time, the epoxy resin is chemically bonded with the polyester matrix, so that the flame retardant is uniformly dispersed in the polyester, avoiding agglomeration. The epoxy resin has a certain flame retardant property, and at high temperature, it can form an expanded carbon layer with montmorillonite, aluminum metaphosphate, etc., enhancing the barrier effect.

[0011] Subsequently applied in polyester, various components cooperate synergistically to form a dense carbon layer during combustion, block heat transfer to the polyester matrix, delay heat conduction, and form a certain physical barrier inside the polyester material, playing a role in heat insulation. Moreover, inorganic components and epoxy resin coatings can change the mechanical properties of the polyester material, fiber interweaving and inorganic particles increase the density of the material, playing a certain role in enhancing the mechanical properties.

[0012] Preferably, the preparation method of the composite glass fiber comprises the following steps: (1) heating the glass fiber at a temperature of 200-210℃ for 10-15 min, then dispersing in an ethanol solution, adding a silane coupling agent KH-9120, and drying to obtain an aminated glass fiber; (2) dispersing the graphite mixture in deionized water, adding the aminated glass fiber of step (1), phosphoric acid, stirring at a temperature of 70-75℃ for 1-2 h, adding starch and sodium dodecyl sulfonate, continuing to stir for 2-3 h, drying, and grinding to obtain the composite glass fiber.

[0013] By using the above technical solution, the water and organic impurities on the surface of the glass fiber are removed by heating, the surface roughness of the glass fiber is improved, and the adhesion with the silane coupling agent in the subsequent process is enhanced. The silane coupling agent contains amino and siloxy groups, the siloxy group can condense with the hydroxyl group on the surface of the glass fiber to form a chemical bond, the amino group is grafted to the fiber surface to realize amination modification. The amino group is a polar group, which can enhance the interfacial compatibility of the glass fiber with polar polymers (such as polyester), and at the same time provides active sites for subsequent reactions (such as reaction with phosphoric acid).

[0014] The graphite mixture is a high-temperature-resistant and heat-conductive material, which is used as a filler in a flame-retardant system to play a flame-retardant role by reflecting heat or forming a carbon layer. The phosphoric acid reacts chemically with the amino group on the surface of the aminated glass fiber to form a network structure of chemical bonding, and the glass fiber and the graphite mixture are connected by chemical bonding, and the graphite mixture is attached to the fiber surface or embedded in the fiber network, thereby improving the interaction between the graphite mixture and other materials.

[0015] The starch and sodium dodecyl sulfonate are added subsequently, the starch can fill the voids in the network structure formed by the graphite mixture and the glass fiber, and at the same time, the molecular chains of the starch can intertwine with the materials to enhance the adhesion, mechanical strength and stability of the composite system. The sodium dodecyl sulfonate reduces the surface tension of the aqueous solution, so that the various materials in the reaction system can be more uniformly dispersed and mixed, preventing material agglomeration. The prepared composite glass fiber has good adhesion, mechanical properties, flame retardancy and thermal insulation, and the corresponding properties of the flame retardant are improved in the subsequent process, so that the flame retardant can be applied to polyester to improve the comprehensive performance of the polyester.

[0016] Preferably, the mass ratio of the glass fiber, the graphite mixture and the starch is 1:0.5-0.6:0.2-0.3.

[0017] By adopting the technical scheme, the mass ratio of the glass fiber, the graphite mixture and the starch mixture is limited in a certain range, so that the prepared composite glass fiber has excellent flame retardance, mechanical property, heat insulation and adhesion. The glass fiber is a fibrous material with high strength and high modulus, and can form a "skeleton" after uniform dispersion. The surface has a porous structure, the graphite mixture can be attached to the surface of the fiber to form a fiber-graphite heat conduction network. The starch has certain adhesion, so that the glass fiber and the graphite mixture are tightly bonded. The hydroxyl group of the starch forms a hydrogen bond with the amino group of the glass fiber and the oxygen-containing group of the graphite, thereby enhancing the binding force between the components. The obtained composite glass fiber has excellent comprehensive performance. The glass fiber, the graphite mixture and the starch cooperate with each other to delay combustion, have flame retardance, block heat conduction and have heat insulation. The corresponding performance of the polyester is improved.

[0018] Preferably, the preparation method of the graphite mixture comprises the following steps: mixing nano-graphite with a particle size of 10-80 nm, diatom ooze and hydrotalcite, wet ball milling at a ball milling speed of 360-370 r / min, and drying to obtain a mixture. The dried mixture is dispersed in deionized water, antimony trioxide, sodium alginate and tetrabutyl titanate are added, and ultrasonic treatment is performed for 2-4 h, and then drying is performed to obtain the graphite mixture.

[0019] By adopting the technical scheme, the nano-graphite, diatom ooze and hydrotalcite are mixed and wet ball milled, so that the three materials are fully mixed at a microscale. During the ball milling process, the structure of the nano-graphite and the diatom ooze is destroyed, and the nano-graphite and the hydrotalcite particles are loaded in the porous structure of the diatom ooze to form a new composite structure, thereby improving the thermal stability and adsorption performance of the material and enhancing the heat insulation performance.

[0020] Antimony trioxide and graphite and other materials synergistically promote the carbon formation on the surface of the material during combustion, thereby improving the flame retardance. Sodium alginate has good film forming property and adhesion, and forms a protective film on the surface of the mixture particles, thereby enhancing the binding property between the nano-graphite, diatom ooze and hydrotalcite and improving the stability of the composite structure. After tetrabutyl titanate is hydrolyzed, nano-TiO2 particles are generated, which can be deposited on the surface of the graphite and diatom ooze to form chemical bonding, thereby improving the compatibility between the mixture and organic materials (such as polyester) and enhancing the interfacial bonding strength. Various components synergistically cooperate to reduce heat radiation conduction and assist heat insulation.

[0021] The obtained graphite mixture is applied to the composite glass fiber, further cooperates with the glass fiber and the starch, improves the heat insulation of the system material, and various components synergistically cooperate to improve the corresponding performance of the composite glass fiber and improve the heat insulation and mechanical property of the polyester.

[0022] Preferably, the preparation method of the epoxy resin solution comprises the following steps: (1) Disperse the epoxy resin in an ethanol solution, stir at 30-35℃ for 2-3h, add melamine and defoaming agent to obtain a mixed solution; (2) Add the nano-zeolite composite powder to the mixed solution of step (1), stir at a rotation speed of 700-800r / min for 1-2h, add phenolic resin and polyvinylpyrrolidone, continue to stir at a temperature of 80-85℃ for 30-35min to obtain an epoxy resin solution.

[0023] By using the above technical solution, melamine improves the flame retardant performance of the epoxy resin, and at the same time, the amino group of melamine can also partially crosslink with the epoxy group of the epoxy resin to form a crosslinked structure with flame retardant performance, thereby increasing the thermal stability of the resin system. The defoaming agent is used to eliminate the foam generated during stirring to prevent the foam from affecting the uniformity and stability of the solution and to ensure the quality of the mixed solution.

[0024] The nano-zeolite composite powder has a high specific surface area and good adsorption performance. The nano-zeolite particles are uniformly dispersed in the epoxy resin matrix by using shear force to avoid agglomeration. The porous structure of the nano-zeolite can adsorb small molecules (such as volatile organic compounds generated during combustion) and catalyze the carbonization reaction of the epoxy resin. At the same time, the high specific surface area of the nano-zeolite forms a strong interfacial bond with the epoxy resin, and the nano-zeolite composite powder chemically bonds with the epoxy resin and melamine to form a stable network structure, thereby improving the mechanical properties and thermal stability of the material.

[0025] The phenolic resin has excellent thermal stability and flame retardancy. After being combined with the epoxy resin, the hydroxyl group of the phenolic resin chemically reacts with the epoxy group of the epoxy resin at high temperature to form an interpenetrating network structure, thereby improving the heat resistance, flame retardancy and rigidity of the material. The phenolic resin can also synergistically act with melamine to enhance the carbonation and flame retardant effect of the material.

[0026] The epoxy resin solution is obtained by spraying it on the surface of the mixture, so that the components in the flame retardant adhere to each other to improve the comprehensive performance of the flame retardant. The microporous structure of the nano-zeolite limits the heat transfer path, reduces the average free path of gas molecules, reduces convective heat transfer, induces acoustic resonance, converts acoustic energy into heat energy consumption, and cooperates with multiple components to improve the flame retardancy and mechanical properties of the system, thereby improving the comprehensive performance of the polyester in the subsequent process.

[0027] Preferably, the mass ratio of the epoxy resin, nano-zeolite composite powder and phenolic resin is 1:0.3-0.4:0.08-0.09.

[0028] By adopting the technical scheme, the mass ratio of the epoxy resin, the nano-zeolite composite powder and the phenolic resin is limited in a certain range, the obtained epoxy resin has good viscosity, mechanical properties and heat insulation performance, various components cooperate with each other, and the corresponding performance of the flame retardant is improved. The epoxy groups in the epoxy resin and the phenolic resin and the like occur cross-linking reaction to form a three-dimensional network, and the thermal stability is enhanced. The nano-zeolite composite powder can be embedded in the three-dimensional network structure, the epoxy groups are combined with the hydroxyl groups on the surface of the nano-zeolite, the interface bonding force is enhanced, and the mechanical strength, the chemical corrosion resistance and the toughness of the system are improved.

[0029] The cured epoxy resin has a relatively high glass transition temperature and can withstand a certain high-temperature environment. The nano-zeolite composite powder has high thermal stability and good heat resistance and can maintain structural stability at high temperatures to provide thermal stability support for the entire composite material. The phenolic resin has a high thermal decomposition temperature and can maintain good structural integrity at high temperatures. The phenolic resin cooperates with the epoxy resin to further improve the thermal stability of the composite material. The porous structure of the nano-zeolite composite powder can effectively hinder the conduction of heat and the propagation of sound, thereby playing a heat insulation role. The high-molecular network structure formed by the cured epoxy resin and the phenolic resin can also block heat and sound to some extent, and cooperates with the porous structure of the nano-zeolite composite powder to further improve the heat insulation performance of the material.

[0030] Preferably, the preparation method of the nano-zeolite composite powder comprises the following steps: calcining zeolite and borax at 540-560℃ for 4-5h, dispersing in a sodium hydroxide solution, soaking for 1-2h, washing with deionized water until neutral, and drying to obtain pretreated zeolite; dispersing the pretreated zeolite in deionized water, adding sodium laurate and limestone, stirring for 2-3h, and drying to obtain a mixture; spraying an acetic acid solution of chitosan onto the mixture, and drying to obtain the nano-zeolite composite powder.

[0031] By adopting the technical scheme, high-temperature calcination removes organic impurities, crystal water and the like in the zeolite and the borax, can activate the pore structure inside the zeolite, increase the specific surface area and improve the adsorption performance. The borax is converted into anhydrous borate salt with higher chemical stability, and the addition of the borax can form a new composite structure with the zeolite to enhance the thermal stability and the chemical stability of the zeolite. The sodium hydroxide solution reacts with the active groups on the surface of the zeolite to further activate the surface of the zeolite and increase the negative charge on the surface.

[0032] The sodium lauryl alcoholate can be adsorbed on the surface of zeolite and borax, further modify the surface properties of the pretreated zeolite, make it have better hydrophilic-hydrophobic balance and dispersibility, and improve the compatibility with the organic matrix (such as epoxy resin, phenolic resin). The limestone not only adjusts the pH of the system, promotes the combination of sodium lauryl alcoholate with zeolite and borax; but also fills the pores of zeolite or adheres to the surface, increases the hardness and thermal stability of the mixture.

[0033] Spray the mixture with an acetic acid solution of chitosan, which has good biocompatibility, film-forming property and adsorption performance. The amino group of chitosan can form coordinate bonds or electrostatic adsorption with the hydroxyl group on the surface of zeolite and the Ca 2+ Form a dense coating layer, so that the limestone is closely combined with the zeolite and borax, forming a whole composite structure. The subsequent addition of epoxy resin improves the mechanical properties, viscosity and flame retardancy, and cooperates with various components to play a heat insulation role. Chitosan itself has flame retardancy, and forms a nitrogen-silicon-calcium synergistic flame retardant system with zeolite and calcium carbonate, improving the thermal stability of the material and reducing the flammability of the material.

[0034] Preferably, the montmorillonite is 20-25 parts, the composite glass fiber is 15-18 parts, the magnesium hydroxide is 9-12 parts, the silicon dioxide is 2-5 parts, and the epoxy resin solution is 7-8 parts.

[0035] By adopting the above technical scheme, the amount of each raw material is further limited, and the obtained polyester efficient flame retardant has excellent flame retardant performance, mechanical properties and heat insulation performance, and the corresponding performance of the polyester is improved subsequently. The porous structure of montmorillonite and silicon dioxide can hinder the conduction of heat, and play a role in heat insulation. The addition of composite glass fiber can reduce the thermal expansion of the material and improve the heat insulation effect.

[0036] Magnesium hydroxide as a flame retardant decomposes to produce water vapor at high temperature, dilutes combustible gas, and inhibits combustion. The layered structure of montmorillonite can adsorb the flame retardant components, improve the flame retardant effect, and epoxy resin can form a dense carbon layer to prevent the transfer of oxygen and heat. The high strength and high modulus of the composite glass fiber can significantly improve the tensile strength and bending strength of the material. The addition of montmorillonite and silicon dioxide can enhance the hardness and wear resistance of the material, and improve the comprehensive mechanical properties of the material.

[0037] Preferably, the particle size of the montmorillonite is 20-30 nm.

[0038] By adopting the above technical scheme, the particle size of the montmorillonite is further limited. The nano-montmorillonite has a large specific surface area, which can effectively adsorb composite glass fiber, magnesium hydroxide, silicon dioxide and other components, form a multi-layer structure, and improve the mechanical properties, thermal stability and flame retardancy.

[0039] In a second aspect, the application provides an application of the flame retardant prepared by the production process of the polyester high-efficiency flame retardant on the heat insulation polyester material.

[0040] In summary, the application has the following beneficial effects: 1. In the application, the pretreated montmorillonite is deposited on the surface of the composite glass fiber, magnesium hydroxide and silicon dioxide, forms a network structure with the composite glass fiber, further coats the magnesium hydroxide and silicon dioxide, and the ultrasonic treatment makes the combination between these materials more compact, improves the overall performance of the material, including the flame retardant performance, thermal stability and mechanical properties.

[0041] 2. In the application, the epoxy resin uniformly covers the surface of the mixture, forms a dense coating on the surface of the mixture, makes the montmorillonite, composite glass fiber, magnesium hydroxide and silicon dioxide adhere closely, and improves the flame retardant performance and mechanical properties of the system.

[0042] 3. In the application, the various components cooperate to form a dense carbon layer during combustion, block the heat transfer to the polyester matrix, play a heat insulation role, and the inorganic components and epoxy resin coating can change the mechanical properties of the polyester material. DETAILED DESCRIPTION

[0043] The application will be further described in detail below in combination with examples.

[0044] The raw materials used in the examples and comparative examples can be obtained by market purchase.

[0045] Preparation example of composite glass fiber Preparation example 1-1 The preparation method of the composite glass fiber comprises the following steps: (1) 25 kg of glass fiber is heated at a temperature of 205℃ for 13 min, then dispersed in 50 L of ethanol solution, 1 kg of silane coupling agent KH-9120 is added, vacuum dried to obtain aminated glass fiber; (2) The graphite mixture is dispersed in 90 L of deionized water, the aminated glass fiber of step (1), 2 kg of phosphoric acid are added, stirred at a temperature of 72℃ for 1.5 h, starch, 0.5 kg of sodium dodecyl sulfonate are added, continue to stir for 2.5 h, dry, grind to obtain the composite glass fiber.

[0046] The mass ratio of glass fiber, graphite mixture and starch is 1:0.5:0.3.

[0047] The preparation method of the graphite mixture comprises the following steps: 20 kg of nano-graphite with a particle size of 10-80 nm, 6 kg of diatom ooze, 2 kg of hydrotalcite are mixed, wet ball milling at a ball milling speed of 365 r / min, and drying to obtain the mixture; The dry mixture was dispersed in 50 L of deionized water, 2 kg of antimony trioxide, 3 kg of sodium alginate, and 1 kg of tetrabutyl titanate were added, ultrasonic treatment was performed for 3 h, and drying was performed to obtain a graphite mixture.

[0048] Preparation Example 1-2 The difference from Preparation Example 1-1 is that in step (2), the graphite mixture is not added.

[0049] Preparation Example 1-3 The difference from Preparation Example 1-1 is that in step (2), the starch is not added.

[0050] Preparation Example 1-4 The difference from Preparation Example 1-1 is that the mass ratio of the glass fiber, the graphite mixture, and the starch is 1:0.6:0.2.

[0051] Preparation Example 1-5 The difference from Preparation Example 1-1 is that the mass ratio of the glass fiber, the graphite mixture, and the starch is 1:0.1:0.8.

[0052] Preparation Example 1-6 The difference from Preparation Example 1-1 is that in the preparation method of the graphite mixture, diatom ooze is not added.

[0053] Preparation Example 1-7 The difference from Preparation Example 1-1 is that in the preparation method of the graphite mixture, sodium alginate is not added.

[0054] Preparation Example of the epoxy resin solution Preparation Example 2-1 The preparation method of the epoxy resin solution comprises the following steps: (1) 5 kg of epoxy resin was dispersed in 40 L of an ethanol solution, stirring was performed at 32°C for 2.5 h, 0.3 kg of melamine and 0.05 kg of a defoaming agent were added to obtain a mixed solution; the defoaming agent is a silicone defoaming agent, which is purchased from Jin Yu Chemical Industry Co., Ltd. in Jinan; the epoxy resin is purchased from Jining Tangyi Chemical Co., Ltd., and the model is Balin Petrochemical E51.

[0055] (2) Nano-zeolite composite powder was added to the mixed solution of step (1), stirring was performed at a rotation speed of 750 r / min for 1.5 h, phenolic resin and 0.3 kg of polyvinylpyrrolidone were added, and stirring was continued at a temperature of 82°C for 33 min to obtain an epoxy resin solution; the phenolic resin is a thermoplastic phenolic resin, which is purchased from a phenolic resin company, and the model is BF01.

[0056] The mass ratio of the epoxy resin, the nano-zeolite composite powder, and the phenolic resin is 1:0.3:0.09.

[0057] The preparation method of the nano-zeolite composite powder comprises the following steps: calcining 3 kg of zeolite and 1 kg of borax at 550 DEG C for 4.5 h, dispersing in 20 L of 8% sodium hydroxide solution, soaking for 1.5 h, washing with deionized water until neutral, and drying to obtain pretreated zeolite; The pretreated zeolite is dispersed in 30 L of deionized water, 0.5 kg of sodium laurate alcoholate and 1.5 kg of limestone are added, stirring for 2.5 h, and drying to obtain a mixture; Spraying 0.6 kg of chitosan acetic acid solution on the mixture, and drying to obtain the nano-zeolite composite powder.

[0058] The chitosan acetic acid solution is prepared by dispersing 3 kg of chitosan in 100 L of 3% acetic acid solution.

[0059] Preparation Example 2-2 The difference from Preparation Example 2-1 is that the nano-zeolite composite powder is not added.

[0060] Preparation Example 2-3 The difference from Preparation Example 2-1 is that the phenolic resin is not added.

[0061] Preparation Example 2-4 The difference from Preparation Example 2-1 is that the mass ratio of the epoxy resin, the nano-zeolite composite powder and the phenolic resin is 1:0.4:0.08.

[0062] Preparation Example 2-5 The difference from Preparation Example 2-1 is that the mass ratio of the epoxy resin, the nano-zeolite composite powder and the phenolic resin is 1:0.08:0.6.

[0063] Preparation Example 2-6 The difference from Preparation Example 2-1 is that the nano-zeolite composite powder is not added in the preparation method of the nano-zeolite composite powder.

[0064] Preparation Example 2-7 The difference from Preparation Example 2-1 is that the chitosan acetic acid solution is not added in the preparation method of the nano-zeolite composite powder. Example

[0065] Example 1 The production process of a polyester efficient flame retardant comprises the following steps: (1) dispersing montmorillonite in 60 L of deionized water, adding 1.5 kg of PEG-400, 1 kg of octadecyl trimethyl ammonium chloride and 3 kg of aluminum metaphosphate, stirring at a temperature of 50 DEG C for 2 h, and drying to obtain pretreated montmorillonite; (2) Mix the composite glass fiber, magnesium hydroxide and silicon dioxide uniformly, disperse into 72 L ethanol solution (volume ratio of ethanol to deionized water is 1:3), add the pretreated montmorillonite in step (1), ultrasonic for 2 h, filter, dry, and obtain a mixture; (3) Spray the mixture in step (2) with the epoxy resin solution, spray 8 times, dry for 10 min each time, grind, and obtain the polyester efficient flame retardant.

[0066] The montmorillonite is 25 kg, the composite glass fiber is 15 kg, the magnesium hydroxide is 12 kg, the silicon dioxide is 2 kg, and the epoxy resin solution is 7 kg.

[0067] The composite glass fiber is prepared by 1-1, and the epoxy resin solution is prepared by 2-1.

[0068] Example 2 A production process of a polyester efficient flame retardant comprises the following steps: (1) Disperse the montmorillonite in 53 L deionized water, add 1.5 kg PEG-400, 3.5 kg octadecyl trimethyl ammonium chloride and 2.5 kg aluminum metaphosphate, stir at 60°C for 1 h, dry, and obtain pretreated montmorillonite; (2) Mix the composite glass fiber, magnesium hydroxide and silicon dioxide uniformly, disperse into 70 L ethanol solution, add the pretreated montmorillonite in step (1), ultrasonic for 1 h, filter, dry, and obtain a mixture; (3) Spray the mixture in step (2) with the epoxy resin solution, spray 5 times, dry for 15 min each time, grind, and obtain the polyester efficient flame retardant.

[0069] The montmorillonite is 20 kg, the composite glass fiber is 18 kg, the magnesium hydroxide is 9 kg, the silicon dioxide is 5 kg, and the epoxy resin solution is 8 kg.

[0070] Example 3 A production process of a polyester efficient flame retardant, which is different from example 1, is that the composite glass fiber is prepared by 1-2.

[0071] Example 4 A production process of a polyester efficient flame retardant, which is different from example 1, is that the composite glass fiber is prepared by 1-3.

[0072] Example 5 A production process of a polyester efficient flame retardant, which is different from example 1, is that the composite glass fiber is prepared by 1-4.

[0073] Example 6 A production process of a polyester efficient flame retardant, which is different from example 1, is that the composite glass fiber is prepared by 1-5.

[0074] Example 7 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the composite glass fiber is prepared by 1-6.

[0075] Example 8 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the composite glass fiber is prepared by 1-7.

[0076] Example 9 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the epoxy resin solution is prepared by 2-2.

[0077] Example 10 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the epoxy resin solution is prepared by 2-3.

[0078] Example 11 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the epoxy resin solution is prepared by 2-4.

[0079] Example 12 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the epoxy resin solution is prepared by 2-5.

[0080] Example 13 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the epoxy resin solution is prepared by 2-6.

[0081] Example 14 A production process of a polyester efficient flame retardant, which is different from Example 1 in that the epoxy resin solution is prepared by 2-7.

[0082] Comparative Example Comparative Example 1 A production process of a polyester efficient flame retardant, which is different from Example 1 in that no composite glass fiber is added.

[0083] Comparative Example 2 A production process of a polyester efficient flame retardant, which is different from Example 1 in that no epoxy resin solution is added.

[0084] Performance detection test The polyester efficient flame retardants prepared by Examples 1-14 and Comparative Examples 1-2 are subjected to performance test; The flame retardant polyester was prepared by melt blending 18 kg of the flame retardant prepared in the above examples and comparative examples, 60 kg of terephthalic acid and 3 kg of 1,4-butanediol at a temperature of 180 ℃, and then the flame retardant polyester was dried and pressed into a plate, cut into a sample of 120 mm x 10 mm x 5 mm, the limiting oxygen index was tested on an HC-2 type oxygen index instrument according to ASTM D2863-77 standard, the tensile strength was tested according to ASTM D638, the bending strength was tested according to ASTM D790, and the impact strength was tested according to ASTM D256. The test results are shown in Table 1.

[0085] Table 1 Test data of examples and comparative examples As can be seen from Table 1, the flame retardancy and mechanical properties of the polyester material are good in Examples 1-2, wherein the limiting oxygen index of Example 1 is 42.3%, the tensile strength is 65.8 Mpa, the bending strength is 78.3 Mpa, and the impact strength is 59 KJ / m 2 . It is illustrated that the flame retardant prepared in the application has excellent flame retardancy, mechanical properties, and when applied to polyester, the various components cooperate to form a certain physical barrier inside the polyester material, which has a strong barrier effect, and the montmorillonite, composite glass fiber, magnesium hydroxide and silicon dioxide are tightly bonded, thereby increasing the mechanical properties of the polyester material.

[0086] The polyester material of Example 1 was tested for thermal insulation performance according to GB / T10294-2008, and the thermal conductivity was 0.035 W / m·K at -20 ℃, 0.038 W / m·K at 0 ℃, and 0.042 W / m·K at 40 ℃. It is illustrated that the polyester material prepared in the application has excellent thermal insulation performance.

[0087] In the preparation method of the composite glass fiber of Examples 3-4, no graphite mixture and starch was added, and in Examples 5-6, the mass ratio of glass fiber, graphite mixture and starch was changed. As can be seen from Table 1, the test results of the limiting oxygen index, tensile strength, bending strength and impact strength of Examples 3-4 are obviously worse than those of Examples 1-2 and Example 5, and the corresponding test results of Example 6 are better than those of Examples 3-4, but worse than those of Examples 1-2 and Example 5. It is illustrated that the starch makes the glass fiber and the graphite mixture tightly bonded, the hydroxyl group of the starch forms a hydrogen bond with the amino group of the glass fiber and the oxygen-containing group of the graphite, thereby enhancing the bonding force between the components, and the composite glass fiber obtained has excellent comprehensive performance, and the subsequent flame retardancy, mechanical properties and thermal stability of the polyester are improved.

[0088] The preparation method of the graphite mixture of examples 7-8 respectively does not add diatom ooze and sodium alginate, and it can be seen from table 1 that the test effects of limiting oxygen index, tensile strength, bending strength and impact strength of examples 7-8 are obviously poorer than examples 1-2, but better than example 3. It is shown that the nano-graphite particles are loaded in the porous structure of diatom ooze to form a new composite structure, sodium alginate has good film forming property and adhesion, and a protective film is formed on the surface of the mixture particles, which enhances the binding between nano-graphite and diatom ooze, and subsequently improves the mechanical properties of polyester.

[0089] The preparation method of the epoxy resin solution of examples 9-10 respectively does not add nano-zeolite composite powder and phenolic resin, and the mass ratio of epoxy resin, nano-zeolite composite powder and phenolic resin is changed in examples 11-12. It can be seen from table 1 that the test effects of limiting oxygen index, tensile strength, bending strength and impact strength of examples 9-10 are obviously poorer than examples 1-2 and example 11, and the corresponding test effects of example 12 are better than examples 9-10, but poorer than examples 1-2 and example 11. It is shown that the high specific surface area of nano-zeolite forms strong interfacial bonding with epoxy resin, nano-zeolite composite powder chemically combines with epoxy resin and melamine to form a stable network structure, which improves the mechanical properties and thermal stability of the material, and the chemical reaction between the hydroxyl group of phenolic resin and the epoxy group of epoxy resin occurs at high temperature to form an interpenetrating network structure, which improves the heat resistance, flame retardance and mechanical properties of the material.

[0090] The preparation method of nano-zeolite composite powder of examples 13-14 respectively does not add limestone and chitosan acetic acid solution, and it can be seen from table 1 that the test effects of limiting oxygen index, tensile strength, bending strength and impact strength of examples 13-14 are obviously poorer than examples 1-2, but better than example 9. It is shown that chitosan has good biocompatibility, film forming property and adsorption performance, and the amino group of chitosan forms coordination bond or electrostatic adsorption with the hydroxyl group on the surface of zeolite and the Ca 2+ The coordination bond or electrostatic adsorption forms a dense coating layer, so that the limestone is combined closely with the zeolite and borax to form a whole composite structure, which subsequently increases the mechanical properties, viscosity and flame retardance of the epoxy resin.

[0091] Comparative Example 1 and Comparative Example 2 do not add composite glass fiber and epoxy resin solution respectively, it can be seen from Table 1 that the test effects of limiting oxygen index, tensile strength, bending strength and impact strength of Comparative Example 1-2 are obviously poorer than those of Example 1-2, which indicates that the composite glass fiber provides physical enhancement and improves the mechanical properties of the polyester, the epoxy resin solution is sprayed on the surface of the mixture, the epoxy resin uniformly covers the surface of the mixture, a dense coating is formed on the surface of the mixture, the montmorillonite, composite glass fiber, magnesium hydroxide and silicon dioxide are closely bonded, the stability of the system is improved, and the subsequent application in the polyester material improves the comprehensive performance of the polyester material.

[0092] The specific embodiments are only an explanation of the present application, which is not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A process for the production of a polyester high efficiency flame retardant, characterized in that, The steps include: (1) Dispersing montmorillonite in deionized water, adding PEG-400, octadecyltrimethylammonium chloride, and aluminum metaphosphate, stirring at a temperature of 50-60°C for 1-2 hours, and drying to obtain pretreated montmorillonite; (2) uniformly mixing the composite glass fiber, magnesium hydroxide, and silicon dioxide, dispersing the mixture into an ethanol solution, adding the pretreated montmorillonite from step (1), sonicating, filtering, and drying to obtain a mixture; (3) Spraying the epoxy resin solution onto the surface of the mixture in step (2) for 5-8 times, drying for 10-15 minutes each time, and grinding to obtain a polyester high-efficiency flame retardant.

2. The production process of a polyester high-efficiency flame retardant according to claim 1, characterized in that: The preparation method of the composite glass fiber comprises the following steps: (1) The glass fiber is heated at a temperature of 200-210°C for 10-15 minutes, then dispersed in an ethanol solution, a silane coupling agent KH-9120 is added, and dried to obtain an amino-treated glass fiber; (2) Dispersing the graphite mixture in deionized water, adding the amino glass fiber and phosphoric acid of step (1), stirring at a temperature of 70-75°C for 1-2 hours, adding starch and sodium dodecyl sulfate, continuing to stir for 2-3 hours, drying, and grinding to obtain composite glass fiber.

3. The process for producing a polyester high efficiency flame retardant according to claim 2, characterized in that, The mass ratio of the glass fiber, the graphite mixture and the starch is 1:0.5-0.6:0.2-0.

3.

4. The process for producing a polyester high efficiency flame retardant according to claim 2, characterized in that, The preparation method of the graphite mixture comprises the following steps: mixing nanographite with a particle size of 10-80 nm, diatom mud, and hydrotalcite, wet ball milling at a ball milling rate of 360-370 r / min, and drying to obtain a mixture; The dried mixture was dispersed in deionized water, antimony trioxide, sodium alginate and tetrabutyl titanate were added, ultrasonically treated for 2-4 hours, and dried to obtain a graphite mixture.

5. The process for producing a polyester high efficiency flame retardant according to claim 1, characterized in that, The preparation method of the epoxy resin solution comprises the following steps: (1) Disperse the epoxy resin in an ethanol solution, stir at 30-35°C for 2-3 hours, add melamine and a defoaming agent to obtain a mixed solution; (2) Add the nano-zeolite composite powder to the mixed solution of step (1), stir at a speed of 700-800 r / min for 1-2 hours, add phenolic resin and polyvinyl pyrrolidone, and continue stirring at a temperature of 80-85°C for 30-35 minutes to obtain an epoxy resin solution.

6. The process for producing a polyester high efficiency flame retardant according to claim 5, characterized in that, The mass ratio of the epoxy resin, the nano-zeolite composite powder and the phenolic resin is 1:0.3-0.4:0.08-0.

09.

7. The process for producing a polyester high efficiency flame retardant according to claim 5, characterized in that, The preparation method of the nano-zeolite composite powder comprises the following steps: calcining zeolite and borax at 540-560° C. for 4-5 hours, dispersing the zeolite and borax in a sodium hydroxide solution, soaking the solution for 1-2 hours, washing the solution with deionized water until the solution is neutral, and drying the solution to obtain pretreated zeolite; Dispersing the pretreated zeolite in deionized water, adding sodium laurate and limestone, stirring for 2-3 hours, and drying to obtain a mixture; The mixture is sprayed with an acetic acid solution of chitosan and dried to obtain nano-zeolite composite powder.

8. The process for producing a polyester high efficiency flame retardant according to claim 1, characterized in that, 20-25 parts of montmorillonite, 15-18 parts of composite glass fiber, 9-12 parts of magnesium hydroxide, 2-5 parts of silicon dioxide, and 7-8 parts of epoxy resin solution.

9. The process for producing a polyester high efficiency flame retardant according to claim 1, characterized in that, The particle size of the montmorillonite is 20-30 nm.

10. Use of a flame retardant prepared according to the process of any one of claims 1 to 9 in a thermally insulated polyester material.

Images