阅读说明：本技术 一种不同包覆厚度的聚磷腈聚合物改性埃洛石纳米管复合材料的制备方法及其应用 (Preparation method and application of polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses ) 是由 戴李宗 洪静 杨杰 武彤 吴海洋 陈婷 王秀 鹿振武 陈国荣 刁雪峰 于 2019-08-30 设计创作，主要内容包括：本发明公开了一种不同包覆厚度的聚磷腈聚合物改性埃洛石纳米管复合材料的制备方法及其应用,包括如下步骤：(1)将适量的埃洛石纳米管置于乙腈中进行超声分散,再依次加入双端胺物质和三乙胺进行搅拌；(2)向步骤(1)所得的物料中缓慢滴入不同浓度的六氯环三磷腈的乙腈溶液,在40-80℃下搅拌进行缩合聚合反应6-24h；(3)将步骤(2)所得的物料用无水乙醇洗涤,在40-80℃的条件下进行真空干燥至恒重得淡黄色固体,即得。(The invention discloses a preparation method and application of polyphosphazene polymer modified halloysite nanotube composite materials with different coating thicknesses, which comprises the following steps: (1) placing a proper amount of halloysite nanotubes in acetonitrile for ultrasonic dispersion, and then sequentially adding a double-end amine substance and triethylamine for stirring; (2) slowly dripping acetonitrile solutions of hexachlorocyclotriphosphazene with different concentrations into the material obtained in the step (1), and stirring at 40-80 ℃ to perform condensation polymerization reaction for 6-24 h; (3) and (3) washing the material obtained in the step (2) by using absolute ethyl alcohol, and drying the material in vacuum at the temperature of 40-80 ℃ until the weight is constant to obtain a light yellow solid, thus obtaining the light yellow solid.)

1. A preparation method of polyphosphazene polymer modified halloysite nanotube composite materials with different coating thicknesses is characterized by comprising the following steps: the method comprises the following steps:

(1) placing a proper amount of halloysite nanotubes in acetonitrile for ultrasonic dispersion, and then sequentially adding a double-end amine substance and triethylamine for stirring; the above-mentioned amine-terminated substance is 4, 4 '-diaminodiphenyl sulfone or 4,' -diaminodiphenyl methane;

(2) slowly dripping acetonitrile solutions of hexachlorocyclotriphosphazene with different concentrations into the material obtained in the step (1), and stirring at 40-80 ℃ to perform condensation polymerization reaction for 6-24 h;

(3) and (3) washing the material obtained in the step (2) with absolute ethyl alcohol, and drying the material in vacuum at the temperature of 40-80 ℃ until the weight of the material is constant to obtain a light yellow solid, namely the polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses.

2. The method of claim 1The preparation method is characterized by comprising the following steps: the molecular formula of the halloysite nanotube is Al₂Si₂O₅(OH)₄·2H₂O, diameter of 30-70nanometers, length of 1-3 microns.

3. The method of claim 1, wherein: the ratio of the halloysite nanotube to the acetonitrile is 0.1-0.2 g: 50-100 mL.

4. The method of claim 1, wherein: the ratio of the halloysite nanotube to the amine terminated substance is 0.1-0.2 g: 0.03-0.06 mol.

5. The method of claim 1, wherein: the ratio of the halloysite nanotube to triethylamine is 0.1-0.2 g: 2-6 mL.

6. The method of claim 1, wherein: the ratio of the halloysite nanotube to the acetonitrile to the amine terminated substance to the triethylamine is 0.1-0.2 g: 50-100 mL: 0.03-0.06 mol: 2-6 mL.

7. Use of polyphosphazene polymer modified halloysite nanotube composite material prepared by the preparation method of any one of claims 1 to 6 in the preparation of flame retardant polymer material.

8. The use of claim 7, wherein: the polymer in the flame-retardant polymer material is E51 type bisphenol A epoxy resin or polylactic acid.

9. Use of polyphosphazene polymer modified halloysite nanotube composite material prepared by the preparation method of any one of claims 1 to 6 for improving the mechanical properties of flame retardant polymer materials.

10. The use of claim 9, wherein: the polymer in the flame-retardant polymer material is E51 type bisphenol A epoxy resin or polylactic acid.

Technical Field

The invention belongs to the technical field of flame retardant materials, and particularly relates to a preparation method and application of a polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses.

Background

In a new era of rapid development of materials, polymer materials have the advantages of excellent physical and chemical stability, corrosion resistance, easy processing and forming and the like, and are widely applied to the fields of marine diving, electronics and electrics, coating adhesives, buildings and the like. However, the polymer material has disadvantages of poor fire resistance, flammability, etc. in practical use, and has problems of improvement of flame retardancy accompanied by a decrease in mechanical properties, etc.

The phosphazene polymer is green and environment-friendly, and has good flame retardant performance due to phosphorus and nitrogen on the main chain and good compatibility with a matrix due to organic components obtained by various substitution reactions on side chains. Therefore, the polyphosphazenes with different structures are selected and designed to endow the organic polymer matrix with good water resistance, high and low temperature resistance, good mechanical property and optical transparency, flame retardance and other excellent properties. The halloysite nanotube with porous property can also be used as a flame retardant, is applied to high polymer materials such as polyurethane, nylon 6, epoxy resin and the like, plays roles in resisting dripping, inhibiting smoke and promoting carbon formation, and can effectively improve the mechanical and other synergistic properties of the polymer material while preparing a high-performance polymer nanocomposite.

In order to improve the flame-retardant properties of polymer materials without affecting their mechanical properties. Therefore, it is necessary to design a functional flame retardant which can improve the mechanical properties of the polymer material and simultaneously has a good flame retardant effect.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of a polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses.

The invention also aims to provide application of the polyphosphazene polymer modified halloysite nanotube composite material

The technical scheme of the invention is as follows:

a preparation method of polyphosphazene polymer modified halloysite nanotube composite materials with different coating thicknesses is characterized by comprising the following steps: the method comprises the following steps:

(1) placing a proper amount of halloysite nanotubes in acetonitrile for ultrasonic dispersion, and then sequentially adding a double-end amine substance and triethylamine for stirring; the above-mentioned amine-terminated substance is 4, 4 '-diaminodiphenyl sulfone or 4,' -diaminodiphenyl methane;

(2) slowly dripping acetonitrile solutions of hexachlorocyclotriphosphazene with different concentrations into the material obtained in the step (1), and stirring at 40-80 ℃ to perform condensation polymerization reaction for 6-24 h;

(3) and (3) washing the material obtained in the step (2) with absolute ethyl alcohol, and drying the material in vacuum at the temperature of 40-80 ℃ until the weight of the material is constant to obtain a light yellow solid, namely the polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses.

In a preferred embodiment of the invention, saidThe molecular formula of the halloysite nanotube is Al₂Si₂O₅(OH)₄·2H₂O, diameter of 30-70nanometers, length of 1-3 microns.

In a preferred embodiment of the invention, the ratio of halloysite nanotubes to acetonitrile is 0.1-0.2 g: 50-100 mL.

In a preferred embodiment of the invention, the ratio of halloysite nanotubes to amine-terminated species is 0.1-0.2 g: 0.03-0.06 mol.

In a preferred embodiment of the invention, the ratio of halloysite nanotubes to triethylamine is 0.1-0.2 g: 2-6 mL.

In a preferred embodiment of the invention, the ratio of halloysite nanotubes, acetonitrile, amine-terminated species and triethylamine is 0.1-0.2 g: 50-100 mL: 0.03-0.06 mol: 2-6 mL.

The polyphosphazene polymer modified halloysite nanotube composite material prepared by the preparation method is applied to preparation of flame-retardant polymer materials.

In a preferred embodiment of the present invention, the polymer in the flame retardant polymer material is bisphenol a epoxy resin type E51 or polylactic acid.

The polyphosphazene polymer modified halloysite nanotube composite material prepared by the preparation method is applied to improving the mechanical property of a flame-retardant polymer material.

In a preferred embodiment of the present invention, the polymer in the flame retardant polymer material is bisphenol a epoxy resin type E51 or polylactic acid.

The invention has the beneficial effects that:

1. the polyphosphazene polymer modified halloysite nanotube composite material with different coating thicknesses has the advantages of low price and easy obtainment of raw materials and simple synthesis and preparation.

2. The polyphosphazene polymer serving as the shell layer can fully play a role in capturing free radicals, inhibiting combustion and promoting carbon formation and diluting gas during combustion. Meanwhile, the porous clay halloysite nanotube containing crystal water can not only dilute combustible gas during combustion, but also lock part of small-molecular organic volatile gas due to the porous characteristic of the porous clay halloysite nanotube to reduce smoke, and the halloysite nanotube can reduce mass and energy transfer by forming physical barriers when being compounded with polymers, so that the flame-retardant synergistic effect is achieved.

3. The polyphosphazene-containing polymer modified silver-doped halloysite nanotube with the core-shell structure can effectively improve the thermodynamic property of the polymer, and can improve the flame retardant property of a polymer material by reducing the transfer of substance energy and promoting catalytic carbonization, so that the polyphosphazene-containing polymer modified silver-doped halloysite nanotube has good application prospects in the aspects of flame retardance, reinforcement and the like of high polymer materials.

Drawings

The invention is further illustrated by the following figures and examples.

FIG. 1 is a TEM image of polyphosphazene polymer modified halloysite nanotube composites with different coating thicknesses obtained in examples 1-3 of the present invention.

FIG. 2 shows infrared spectra (FT-IR) of polyphosphazene polymer modified halloysite nanotube composites with different coating thicknesses obtained in example 1 of the present invention.

FIG. 3 is a graph comparing the micro calorimetry heat release rate of polyphosphazene polymer modified halloysite nanotube/epoxy composites of different coating thicknesses obtained in examples 1-3 and unmodified halloysite nanotube/epoxy obtained in comparative example 1.

FIG. 4 is a graph showing a comparison of the thermodynamic properties of polyphosphazene polymer modified halloysite nanotube/epoxy composites of different coating thicknesses obtained in examples 1-3 and unmodified halloysite nanotube/epoxy composite obtained in comparative example 1.

Detailed Description

The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.