阅读说明：本技术 一种介孔硅树脂阻燃剂、制备方法及其阻燃复合材料 (Mesoporous silicon resin flame retardant, preparation method and flame-retardant composite material thereof ) 是由 戴李宗 王秀 杨杰 陈婷 彭超华 洪静 申应军 鹿振武 陈国荣 曾碧榕 罗伟昂 于 2019-09-02 设计创作，主要内容包括：本发明公开了一种介孔硅树脂阻燃剂、制备方法及其阻燃复合材料,该阻燃剂通过带有环氧基团的氧化石墨烯和氨基改性的介孔二氧化硅反应,再负载羟基锡酸锌而制备得到。利用石墨烯的屏蔽阻隔、介孔二氧化硅对可燃气体的吸附以及羟基锡酸锌的催化成炭的协同阻燃作用,可以提高高分子材料的抑烟阻燃性能。其制备方法简单可行,在高分子抑烟阻燃领域具有广阔的应用前景。(The invention discloses a mesoporous silicon resin flame retardant, a preparation method and a flame-retardant composite material thereof. The smoke suppression and flame retardation performances of the high polymer material can be improved by utilizing the shielding and blocking of graphene, the adsorption of the mesoporous silica to combustible gas and the synergistic flame retardation effect of the zinc hydroxystannate for catalytic carbonization. The preparation method is simple and feasible, and has wide application prospect in the field of high polymer smoke suppression and flame retardance.)

1. A mesoporous silicon resin flame retardant is characterized in that the structural formula is as follows:

wherein ZHS is zinc hydroxystannate, and MCM-41 and SBA-15 are mesoporous silica.

2. A preparation method of a mesoporous silicon resin flame retardant is characterized by comprising the following steps: preparing amino-modified mesoporous silica by using tetraethyl silicate, a template agent, a catalyst, water and ethanol, then reacting with graphene oxide with epoxy groups to obtain reduced graphene oxide grafted with the mesoporous silica, and then loading zinc hydroxystannate to prepare a mesoporous silicon flame retardant; the template agent is one of cetyl trimethyl ammonium bromide and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, and the catalyst is one of ammonia water and hydrochloric acid.

3. The preparation method of the mesoporous silicon resin flame retardant according to claim 1, characterized by comprising the following steps:

(1) mixing tetraethyl silicate, a template agent, a catalyst, water and ethanol, stirring at room temperature for 1-12 h, then reacting at 100-120 ℃ for 18-48 h, filtering to obtain white precipitate, drying at 50-100 ℃, and calcining at 550 ℃ for 6h to obtain mesoporous silica, wherein the mesoporous silica comprises MCM-41 or SBA-15;

(2) mixing the mesoporous silica prepared in the step (1) with aminopropyltriethoxysilane, water and ethanol, stirring for 18-36 h at 70-100 ℃, adding graphene oxide, stirring for 4-10 h at room temperature, centrifugally washing with ethanol, vacuum drying at 50-100 ℃, and thermally reducing for 3-8 h at 600 ℃ in a nitrogen atmosphere to obtain reduced graphene oxide grafted with mesoporous silica;

(3) mixing the reduced graphene oxide grafted with the mesoporous silicon dioxide prepared in the step (2), zinc sulfate, sodium stannate and water, stirring for 3-6 hours at 50-100 ℃, centrifugally washing with ethanol, and vacuum drying at 50-100 ℃ to obtain the mesoporous silicon flame retardant.

4. The preparation method of the mesoporous silicon resin flame retardant according to claim 3, characterized in that: the mole ratio of tetraethyl silicate, the template agent, the catalyst, water and ethanol in the step (1) is 1: 0.1-0.5: 5-15: 130-150: 0 to 60.

5. The preparation method of the mesoporous silicon resin flame retardant according to claim 3, characterized in that: the mass ratio of mesoporous silicon dioxide, aminopropyltriethoxysilane, water, ethanol and graphene oxide in the step (2) is 1: 0.5-1.5: 0.05-0.1: 100-200: 0.1 to 1.

6. The preparation method of the mesoporous silicon resin flame retardant according to claim 3, characterized in that: the mass ratio of the mesoporous silica grafted reduced graphene oxide, zinc sulfate, sodium stannate and water in the step (3) is 1: 0.5-1.5: 0.5-1.5: 80-120 parts.

7. A flame retardant composite characterized by: the mesoporous silicon resin flame retardant comprises the mesoporous silicon resin flame retardant of claim 1, and further comprises a high polymer material and a curing agent, wherein the mesoporous silicon resin flame retardant accounts for 0.1-20 wt% of the high polymer material.

8. A flame retardant composite according to claim 7 wherein: the high polymer material is one of E51 bisphenol A epoxy resin, nylon resin or ABS; the curing agent is 4, 4-diaminodiphenylmethane; the mass ratio of the high polymer material to the curing agent is 3-5: 1.

9. a flame retardant composite according to claim 7 wherein: taking an epoxy resin prepolymer, adding the mesoporous silicon flame retardant and a solvent at the temperature of 60-140 ℃, stirring until the mixture is transparent, pumping until no bubbles are generated, adding the curing agent, completely dissolving, and sequentially curing at the temperature of 110-130 ℃ for 3-5 h, at the temperature of 130-150 ℃ for 1-3 h, and at the temperature of 170-190 ℃ for 1-3 h to obtain the epoxy resin flame-retardant composite material.

10. A flame retardant composite according to claim 7 wherein: drying nylon resin or ABS and mesoporous silicon flame retardant in a vacuum oven at 60-120 ℃, and placing the dried nylon resin or ABS and mesoporous silicon flame retardant in a double-screw extruder for melt blending, wherein the temperatures of three sections of the extruder are respectively set to 210-230 ℃, 220-230 ℃ and 220-230 ℃; and cooling the blend, granulating, drying and carrying out injection molding to obtain the thermoplastic flame-retardant composite material.

Technical Field

The invention belongs to the field of high-molecular flame retardance, and particularly relates to a mesoporous silicon resin flame retardant, a preparation method and a flame-retardant composite material thereof.

Background

The polymer material has good mechanical, physical and chemical properties and corrosion resistance, so the polymer material is widely applied to the fields of automobiles, aerospace, electronic components and the like. However, the polymer material is easy to burn, and toxic and harmful gas is generated in the burning process, so that a huge fire hazard exists, which greatly limits the practical application of the polymer material, and therefore, the improvement of the smoke suppression and flame retardation performance of the polymer material is extremely important. The flame retardants widely used at present include phosphorus flame retardants, nitrogen flame retardants, silicon flame retardants, inorganic flame retardants, and the like. The inorganic flame retardant has small harmfulness and good smoke suppression effect, and can improve the flame retardant property of the composite material and the mechanical property of the material. At present, most flame retardants can generate a large amount of smoke in the combustion process, and the smoke suppression effect is poor, so that the preparation of a novel flame retardant with the smoke suppression function is still the research focus which needs to be explored at present.

Disclosure of Invention

The invention aims to overcome the defects of the prior art, provides a mesoporous silicon resin flame retardant, a preparation method and a flame-retardant composite material thereof, and solves the problems in the background art.

One of the technical schemes adopted by the invention for solving the technical problems is as follows: a mesoporous silicon resin flame retardant is provided, the structural formula of which is shown in figure 5, wherein mesoporous silica comprises MCM-41 or SBA-15.

The second technical scheme adopted by the invention for solving the technical problems is as follows: the preparation method of the mesoporous silicon flame retardant is provided, and the synthetic route is shown in fig. 6.

The method comprises the following specific steps:

(1) adding tetraethyl silicate, a template agent, a catalyst, water and ethanol into a reaction vessel, stirring at room temperature for 1-12 h, then reacting in a tetrafluoroethylene reaction kettle at 100-120 ℃ for 18-48 h, filtering to obtain white precipitate, drying at 50-100 ℃, and calcining at 550 ℃ for 6h to obtain mesoporous silica (MCM-41 or SBA-15).

In a preferred embodiment of the present invention, the template agent is one of cetyl trimethyl ammonium bromide and polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.

In a preferred embodiment of the present invention, the catalyst is one of ammonia and hydrochloric acid.

In a preferred embodiment of the present invention, the mole ratio of the tetraethyl silicate, the template agent, the catalyst, water and ethanol is 1: 0.1-0.5: 5-15: 130-150: 0 to 60.

(2) Adding mesoporous silica, aminopropyltriethoxysilane, water and ethanol into a reaction container, stirring for 18-36 h at 70-100 ℃, then adding graphene oxide, stirring for 4-10 h at room temperature, centrifugally washing with ethanol, vacuum drying at 50-100 ℃, and thermally reducing for 3-8 h at 600 ℃ in a nitrogen atmosphere to obtain reduced graphene oxide grafted with mesoporous silica (MCM-41 or SBA-15).

In a preferred embodiment of the present invention, the mass ratio of the mesoporous silica to the aminopropyltriethoxysilane, to the water to the ethanol to the graphene oxide is 1: 0.5-1.5: 0.05-0.1: 100-200: 0.1 to 1.

(3) Adding reduced graphene oxide grafted with mesoporous silicon dioxide, zinc sulfate, sodium stannate and water into a reaction vessel, stirring for 3-6 h at 50-100 ℃, centrifugally washing with ethanol, and vacuum drying at 50-100 ℃ to obtain the mesoporous silicon flame retardant.

In a preferred embodiment of the present invention, the mass ratio of the mesoporous silica grafted reduced graphene oxide, zinc sulfate, sodium stannate and water is 1: 0.5-1.5: 0.5-1.5: 80-120 parts.

The third technical scheme adopted by the invention for solving the technical problems is as follows: the flame-retardant composite material comprises a high polymer material, the mesoporous silicon flame retardant and a curing agent, wherein the mesoporous silicon flame retardant is blended with the high polymer material to prepare the corresponding flame-retardant composite material, and the mesoporous silicon flame retardant accounts for 0.1-20 wt% of the high polymer material.

The high polymer material is one of E51 bisphenol A type epoxy resin (EP), nylon resin (PA) and ABS.

The curing agent is 4, 4-diaminodiphenylmethane (DDM), and the mass ratio of the high polymer material to the curing agent is 3-5: 1.

in a preferred embodiment of the present invention, a method for preparing an epoxy resin flame-retardant composite material comprises: taking an epoxy resin prepolymer, adding the mesoporous silicon flame retardant and a solvent at the temperature of 60-140 ℃, stirring until the mixture is transparent, pumping until no bubbles are generated, adding the curing agent, completely dissolving, and sequentially curing at the temperature of 110-130 ℃ for 3-5 h, at the temperature of 130-150 ℃ for 1-3 h, and at the temperature of 170-190 ℃ for 1-3 h to obtain the epoxy resin flame-retardant composite material. The solvent is one of acetone, chloroform and dichloromethane.

In a preferred embodiment of the present invention, a thermoplastic flame-retardant composite material is prepared by a method comprising: and (3) drying the thermoplastic high polymer material and the mesoporous silicon flame retardant in a vacuum oven at the temperature of 60-120 ℃, and putting the dried materials and the mesoporous silicon flame retardant into a double-screw extruder according to a certain proportion for melt blending. The temperature of 3 sections of the extruder is set to be 210-230 ℃, 220-230 ℃ and 220-230 ℃ respectively. And cooling the blend, cutting into granules, drying the granules in a drying box, and performing injection molding by using an injection molding machine to obtain a standard sample to obtain the thermoplastic flame-retardant composite material. The thermoplastic high polymer material is one of PA and ABS.

The invention has the beneficial effects that:

(1) the mesoporous silicon flame retardant with the smoke suppression function contains a mesoporous structure, and can effectively delay the diffusion of combustible gas generated in the combustion process of a high polymer material, so that the smoke suppression effect of the high polymer material is improved. Two mesoporous silicon flame retardants can be obtained by changing a template agent and a catalyst, wherein the mesoporous apertures of the two flame retardants are different, and the smoke suppression performance of the SBA-15 series flame retardants with larger apertures is better, so that the influence of the apertures on the smoke suppression effect of a high polymer material is proved;

(2) the thermally reduced graphene in the mesoporous silicon flame retardant has a shielding and blocking effect, has a synergistic flame retardant effect with mesoporous silicon dioxide in practical application, and the corresponding flame retardant sample strip has the advantages of high thermal stability, good smoke suppression effect and good flame retardant property;

(3) the zinc hydroxystannate loaded on the surface of the mesoporous silicon flame retardant has the function of catalyzing and carbonizing, and can catalyze and degrade combustible gas generated in the combustion process of the high polymer material into carbon, so that the smoke suppression and flame retardation performance of the high polymer material is further improved.

Drawings

FIG. 1 TEM spectrum of the mesoporous silica obtained in example 1, wherein (A-C) is MCM-41 and (D-F) is SBA-15.

FIG. 2 is an XRD spectrum of the mesoporous silicon flame retardant obtained in example 1.

FIG. 3 is a graph showing a combustion process of a vertical burning test of the flame retardant epoxy resin obtained in example 1.

FIG. 4 Heat Release and Smoke Release profiles of the flame retardant epoxy resin obtained in example 3, wherein (A) is the heat Release profile of the EP composite and (B) is the Smoke Release profile of the EP composite.

FIG. 5 is a structural formula of the mesoporous silicon flame retardant of the invention.

FIG. 6 is a synthetic route of the mesoporous silicon flame retardant of the present invention.

The smooth spheres in fig. 5 and 6 represent silica, and the spheres with particles on the surface are mesoporous silica supported by zinc hydroxystannate.

Detailed Description