CN106009044A - Surface modifying method of hollow glass beads and flame-retardant application thereof - Google Patents

Abstract

The invention relates to a surface modifying method of hollow glass beads and a flame-retardant application thereof. The surface modifying method of the hollow glass beads comprises the following steps: (1) performing ultrasonic washing of the hollow glass beads by using a sodium hydroxide solution; (2) repeatedly washing the hollow glass beads obtained in the step (1) with deionized water and absolute ethyl alcohol respectively, and drying; and (3) dissolving the treated hollow glass beads in a mixed solution of ethanol and deionized water, and performing reflux, heating and stirring; in the heating process, dropwise adding a solution for obtaining a coating, and then adding the sodium hydroxide solution while keeping a neutral environment; and stirring for 5h, performing suction filtration and drying. In the invention, the modified hollow glass beads are adopted as a flame retardant to prepare a flame-retardant thermoplastic polyurethane composite; cone calorimeter experiments indicate that the parameters of the composite such as heat release rate, total heat release, smoke generation rate and smoke factor are remarkably reduced while the residual mass of carbon residues is greatly increased.

Description

A surface modification method of hollow glass microspheres and its flame retardant application

technical field

The invention belongs to the technical field of flame-retardant modification of thermoplastic polyurethane elastomers, and in particular relates to a method for surface modification of hollow glass microspheres and the application of the modified hollow glass microspheres in the preparation of flame-retardant thermoplastic polyurethane composite materials.

Background technique

Hollow glass microspheres (hollow glass microspheres) are hollow, thin-walled, hard, and lightweight glass spherical shells. It is a new micron-scale lightweight material developed in the 1950s and 1960s. Its main component is borosilicate, which is a unique and stable hollow particle, containing inert gas, and has many physical and chemical properties unmatched by other light fillers. It has the advantages of non-toxicity, high melting point, low thermal conductivity, high strength, high dispersion, good electrical insulation and good thermal stability. Known as the "space age material" of the 21st century. Hollow glass microspheres have obvious weight reduction and sound insulation effects, so that the product has good crack resistance and reprocessing performance, and is widely used in composite materials such as artificial marble, glass fiber reinforced plastic, artificial agate, as well as aerospace and petroleum industries. , automobile ships, new high-speed trains, heat-insulating coatings and other fields, which have effectively promoted the development of my country's scientific and technological undertakings.

According to "Polymer Combustion and Flame Retardant Technology" (edited by Zhang Jun, Ji Kuijiang, Xia Yanzhi, etc., Chemical Press, April 2005), the polyurethane synthetic material is a polymer with special properties and a wide range of uses. Polyurethane is mainly formed by the reaction of polyisocyanate and polyol, in which the isocyanate part constitutes the hard segment, and the polyol part constitutes the soft segment. After different types of isocyanate react with polyols, various structures of polyurethane can be produced to obtain properties. different polymers. Such as polyurethane foam, polyurethane elastomer. Polyurethane foam has excellent elasticity, softness, elongation and compressive strength; good chemical stability, resistant to many solvents and oils; excellent wear resistance, 20 times larger than natural sponge; excellent processability, heat insulation It is a kind of buffer material with excellent performance, but the price is high, and it is a highly flammable material with an oxygen index of only 16.5%.

According to "Polyurethane Resin and Its Application" (edited by Liu Yijun, Chemical Industry Press), polyurethane elastomer is a high-performance elastomer and a type of elastic polymer containing more carbamate groups in the molecular chain. Material, polyurethane elastomer has excellent comprehensive performance, the modulus is between general rubber and plastic, has excellent strength and elasticity, load capacity, wear resistance, oil resistance, oxidation resistance, chemical resistance, fatigue resistance and resistance Impact and other properties, and the advantages of light weight, low noise, wear resistance, corrosion resistance, and no brittleness. However, its flammability also limits its wider application. Due to its special structure, it is extremely easy to burn. When burning, the flame is violent and accompanied by thick black smoke, the heat release is large, and it has serious dripping phenomenon. , so that its direct application to industry has great limitations, so the research of flame-retardant polyurethane has become a hot spot in the research of polyurethane materials today.

In view of the special structure and good performance of hollow glass microspheres, they have also been used in improving the combustion performance of materials. According to "The Effect of Hollow Microspheres on the Fireproof Performance of Intumescent Coatings" (Li Shaoxiang, Chen Xilei, China Paint), hollow glass microspheres will significantly improve the fireproof performance of fireproof coatings. According to the "Effect of Hollow Glass Microspheres on the Combustion and Mechanical Properties of Polyurethane Foam" (Chen Weihong, Yang Ying, Guo Zidong, Xu Xiaonan, Shi Zhizhan, Chemical Research ISTIC), when hollow glass microspheres are added to polyurethane alone, the oxygen index and horizontal combustion The speed has little effect. After adding APP or IFR, the flame retardant effect of hollow glass microspheres is significantly improved.

Contents of the invention

In order to solve the problem in the prior art that hollow glass microspheres are used alone as a flame retardant, the addition amount is large and the effect is not obvious, the present invention provides a method for surface modification of hollow glass microspheres, the modified hollow glass microspheres Beads are used alone as a flame retardant or synergistic ammonium polyphosphate is added to thermoplastic polyurethane elastomers. The present invention overcomes the shortcomings of existing hollow glass microspheres, such as large amount of hollow glass microspheres, low flame retardant efficiency, and large heat release of thermoplastic polyurethane elastomers. , to improve the flame retardant properties of thermoplastic polyurethane elastomers.

Technical scheme of the present invention is as follows:

A method for surface modification of hollow glass microspheres, comprising the following steps:

(1) ultrasonically washing the hollow glass microspheres with a 10% sodium hydroxide solution for 30 minutes to remove surface impurities and obtain surface hydroxylated hollow glass microspheres;

(2) The hollow glass microspheres obtained in step (1) were washed repeatedly with deionized water and absolute ethanol 4 times respectively, and dried in a vacuum drying oven at a temperature of 80° C. for 8 hours;

(3) Dissolve the treated hollow glass microspheres in a mixed solution of ethanol and deionized water with a volume ratio of 1:1, and add them to a three-necked flask for reflux, heating in a water bath at a constant temperature of 70°C, and mechanical stirring; during the heating process, First add the solution that can get the coating dropwise, then add the sodium hydroxide solution with a concentration of 1%, measure the concentration of the mixed solution in the three-necked flask at the same time, constantly test the pH value of the solution, and maintain a neutral environment; stir for 5 hours, and filter with suction , dried in a vacuum drying oven at a temperature of 80° C. for 8 hours.

Preferably, the hollow glass microspheres have a density of 0.10-0.70 g/cm ³ and a particle size of 0.01-400 μm.

Preferably: the solutions of the coatings available in step (3) are respectively 20% mass fraction of titanium sulfate solution, 8% ferric chloride solution, 6% ammonium phosphomolybdate solution, or 20% Heptadecafluorodecyltriethoxysilane solution.

Preferably, the available coating in step (3) includes at least one of titanium dioxide, ferric oxide, ammonium phosphomolybdate, and heptadecafluorodecyltriethoxysilane.

Among them: titanium dioxide modified hollow glass microspheres are used as a flame retardant. Titanium dioxide has the characteristics of small particle size, large specific surface area, high surface hydroxyl content, good thermal stability, non-toxicity and no secondary pollution. In particular, the addition of nano-titanium dioxide is beneficial to improve the heat resistance of the elastomer.

Among them: Fe2O3 modified hollow glass microspheres are used as a flame retardant, and Fe2O3 can improve the surface morphology of the carbon layer and enhance the formation of the carbon layer. When the polymer burns, this layer can play the role of flame retardant, heat insulation, and oxygen insulation, preventing combustible gas from entering the combustion gas phase, thereby enhancing the flame retardant effect.

Among them: ammonium phosphomolybdate modified hollow glass microspheres are used as flame retardant, ammonium phosphomolybdate contains phosphorus flame retardant elements, and phosphorus will be oxidized into phosphorus oxyacid. This kind of phosphoric acid can cover the surface of the material, and Dehydration and carbonization on the surface of the material, the carbon layer formed can separate the external oxygen, volatile combustibles and heat from the internal polymer, so that the combustion is interrupted. At the same time, the addition of molybdenum element can not only enhance the flame retardant effect, but also make the material have good smoke suppression performance.

Among them: hollow glass microspheres modified by heptadecafluorodecyltriethylsilane are used as flame retardant, and heptadecafluorodecyltriethylsilane contains fluorine, silicon and other flame retardant elements. Fluorine, as a halogen, decomposes when heated to generate halogen radicals, which can extract hydrogen atoms to generate hydrogen halide gas and enter the gaseous phase. In the gas phase, hydrogen halide molecules interfere with the chain combustion reaction of hydroxyl radicals. The action of hydrogen halide and hydroxyl radicals can generate water, thereby improving the flame retardant performance. At the same time, the flame retardant contains silicon, which can promote combustion into charcoal in the solid phase, and can capture active free radicals in the gas phase to inhibit combustion.

Preferably: the modified hollow glass microspheres, the mass ratio of the coating to the hollow glass microspheres is: titanium dioxide: hollow glass microspheres = 15.3: 84.7, ferric oxide: hollow glass microspheres = 1.4 : 98.6, ammonium phosphomolybdate: hollow glass microspheres = 8.3: 91.7, heptadecafluorodecyltriethoxysilane: hollow glass microspheres = 19.3: 80.7.

Preferably: when the available coatings are titanium dioxide, ferric oxide, and ammonium phosphomolybdate, the step (3) also includes a roasting step, specifically placing the dried hollow glass microspheres in a 500°C muffle Roasting in the furnace for 2h. The modified hollow glass microspheres obtained after this step can be used alone as a flame retardant to flame-retardant thermoplastic polyurethane elastomers, and a good flame-retardant effect has been achieved.

The invention also provides the application of the hollow glass microspheres prepared by the above modification method as a flame retardant in a flame retardant thermoplastic polyurethane elastomer.

Based on the application of modified hollow glass microspheres in the preparation of flame-retardant thermoplastic polyurethane elastomers, in order to reduce the amount of flame retardants added during the flame-retardant modification of thermoplastics and prevent the decline in mechanical properties, the present invention uses modified hollow glass microspheres as flame-retardant Flame-retardant thermoplastic polyurethane elastomers, providing two flame-retardant thermoplastic polyurethane composite materials, the mass fraction is: thermoplastic polyurethane elastomer 98%-99.875%, flame retardant 0.125%-2%; or thermoplastic polyurethane elastomer 90%, modified Hollow glass microspheres 0.1%-1%, ammonium polyphosphate 9%-9.9%. While ensuring the flame retardant effect, the total amount of flame retardant additives is reduced, and the thermal stability is good, which overcomes the problems of high energy consumption due to the large amount of flame retardant added and the high melt viscosity during processing. The shortcomings of the droplet resistance need to be improved, so as to reduce the impact of the decrease in the mechanical properties of the material (such as tensile strength and breaking strength) caused by additives.

Preferably: the flame retardant is titanium dioxide modified hollow glass microspheres, titanium dioxide modified hollow microspheres synergistic ammonium polyphosphate, ferric oxide modified hollow glass microspheres, ferric oxide modified Hollow glass microspheres synergistic ammonium polyphosphate, ammonium phosphomolybdate modified hollow glass microspheres, ammonium phosphomolybdate modified hollow glass microspheres synergistic ammonium polyphosphate, heptadecafluorodecyltriethoxysilane Modified hollow glass microspheres synergize at least one group of ammonium polyphosphates.

The present invention further provides a method for preparing the above-mentioned flame-retardant thermoplastic polyurethane elastomer. The modified hollow glass microspheres are mixed with the thermoplastic polyurethane elastomer in an internal mixer, and the temperature is controlled at 175-180°C and the rotation speed is 10-50r /min, melt blending for 10-30min, molding; or mix modified hollow glass microspheres, ammonium polyphosphate and thermoplastic polyurethane elastomer in an internal mixer, control the temperature at 175-180°C, and rotate at 10-50r/min min, melt blending for 10-30min, molding.

The present invention uses modified hollow glass microspheres as a flame retardant to prepare a flame-retardant thermoplastic polyurethane composite material. The cone calorimeter experiment shows that the parameters such as the heat release rate, total heat release, smoke generation rate, and smoke factor of the composite material are significant. Reduced, while the remaining quality of carbon residue is greatly improved.

The beneficial effects of the present invention are:

1) The modification method of the hollow glass microspheres has simple process, easy operation, short modification time, low cost and no toxic substances involved and generated.

2) The mass of the flame retardant is 0.125%-2%, and the addition amount is small, which has little influence on the mechanical properties of the material.

3) The results of the cone calorimeter showed that with the addition of the flame retardant, the heat release rate, total heat release, smoke generation rate, and smoke factor of the flame-retardant thermoplastic polyurethane elastomer composite material were significantly reduced, while the remaining mass of carbon residue It is greatly improved, and the flame retardant effect is better.

detailed description

In order to better illustrate the good performance of the modified hollow glass microsphere flame-retardant thermoplastic polyurethane elastomer, the following examples are used to illustrate:

1. Thermoplastic polyurethane elastomer (TPU)/titanium dioxide modified hollow glass microspheres (TiO ₂ -HGM)/ammonium polyphosphate (APP) comparative example 1-1:

Add 100% thermoplastic polyurethane elastomer into the internal mixer according to the mass percentage, and control the rotational speed at 10-50r/min at room temperature, and internally knead for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizing machine, the temperature is controlled at 175-180° C., the pressure is maintained for 10-20 minutes, and the product is cooled for 1-2 minutes. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate (PHRR) was 1415kW/m ² and the remaining mass was (MASS) 8%, the total heat release (THR) is 97MJ/m ² , the total smoke yield (TSR) is 600g, and the smoke factor (SF) is 850g/s.

Comparative example 1-2:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 0.5% by mass of unmodified hollow glass microspheres and 9.5% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 184kW/m ² , the remaining mass was 35%, and the total heat The release is 70MJ/m ² , the total smoke production is 300g, and the smoke factor is 62g/s.

Example 1-1:

Add 99.875% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer and banbury for 3 minutes, add 0.125% of the mass percentage of titanium dioxide modified hollow glass microspheres, under room temperature conditions, control the rotating speed to be 10-50r/min, compact Refining for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 734kW/m ² , the remaining mass was 9%, and the total heat The release is 105MJ/m ² , the total smoke production is 772g, and the smoke factor is 567g/s.

Embodiment 1-2:

Add 99.75% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer for banburying for 3 minutes, add 0.25% of the mass percentage of titanium dioxide modified hollow glass microspheres, at room temperature, control the rotating speed to be 10-50r/min, close Refining for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 575kW/m ² , the remaining mass was 9%, and the total heat The release is 104MJ/m ² , the total smoke production is 755g, and the smoke factor is 441g/s.

Embodiment 1-3:

Add 99.5% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer and banbury for 3 minutes, add 0.5% titanium dioxide-modified hollow glass microspheres in the mass percentage, and control the rotating speed at 10-50r/min under room temperature conditions. Refining for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 481kW/m ² , the remaining mass was 9%, and the total heat The release is 93MJ/m ² , the total smoke production is 711g, and the smoke factor is 342g/s.

Embodiment 1-4:

Add 99.0% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer and banbury for 3 minutes, add 1.0% of the mass percentage of titanium dioxide-modified hollow glass microspheres, under room temperature conditions, control the rotating speed to be 10-50r/min, compact Refining for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 407kW/m ² , the remaining mass was 10%, and the total heat The release is 101MJ/m ² , the total smoke production is 694g, and the smoke factor is 305g/s.

Embodiment 1-5:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 0.125% by mass of titanium dioxide-modified hollow glass microspheres and 9.875% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 210kW/m ² , the remaining mass was 41%, and the total heat The release is 58MJ/m ² , the total smoke production is 426g, and the smoke factor is 44g/s.

Embodiment 1-6:

90% by mass percentage of thermoplastic polyurethane elastomer was added to the internal mixer for internal mixing for 3 minutes, and 0.25% by mass of titanium dioxide modified hollow glass microspheres and 9.75% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 157kW/m ² , the remaining mass was 48%, and the total heat The release is 54MJ/m ² , the total smoke production is 363g, and the smoke factor is 42g/s.

Embodiment 1-7:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 0.5% by mass of titanium dioxide-modified hollow glass microspheres and 9.5% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 142kW/m ² , the remaining mass was 49%, and the total heat The release is 53MJ/m ² , the total smoke production is 307g, and the smoke factor is 40g/s.

Embodiment 1-8:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 1% by mass of titanium dioxide-modified hollow glass microspheres and 9% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 95kW/m ² , the remaining mass was 54%, and the total heat The release is 27MJ/m ² , the total smoke production is 306g, and the smoke factor is 38g/s.

Table 1 comparative example 1-1 and embodiment 1-1 to 1-8 sample experiment data table

It can be seen from Table 1 that whether the modified hollow glass microspheres are added alone or the modified hollow glass microspheres are synergistic with ammonium polyphosphate in the thermoplastic polyurethane elastomer. With the increase of the addition amount, the heat release rate, total smoke production, smoke factor and smoke generation rate all decrease obviously, but the more the addition amount, the better. It can be seen that the range of change in the later stage is not very large. When the fuel content is 1%, the effect is better. Under the same content, the unmodified hollow glass microsphere synergistic ammonium polyphosphate flame-retardant thermoplastic polyurethane elastomer and the modified hollow glass microsphere synergistic ammonium polyphosphate flame-retardant thermoplastic polyurethane elastomer were compared, and the modified hollow glass microsphere The heat release rate of is significantly reduced, indicating that the modification is meaningful. Judging from the remaining quality of carbon residue, the amount of char is also significantly increased, which is very beneficial to flame retardancy.

2. Thermoplastic polyurethane elastomer (TPU)/ferric oxide modified hollow glass microspheres (Fe ₂ O ₃ -HGM)/ammonium polyphosphate (APP) comparative example 2-1:

Add 100% thermoplastic polyurethane elastomer into the internal mixer according to the mass percentage, and control the rotational speed at 10-50r/min at room temperature, and internally knead for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizing machine, the temperature is controlled at 175-180° C., the pressure is maintained for 10-20 minutes, and the product is cooled for 1-2 minutes. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate (PHRR) was 1526kW/m ² and the remaining mass was (MASS) 8%, the total heat release (THR) is 121MJ/m ² , the total smoke yield (TSR) is 742g, and the smoke factor (SF) is 1133g/s.

Comparative example 2-2:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 0.5% by mass of unmodified hollow glass microspheres and 9.5% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 176kW/m ² , the remaining mass was 38%, and the total heat The release is 79MJ/m ² , the total smoke production is 307g, and the smoke factor is 54g/s.

Example 2-1:

Add 99.875% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer for internal mixing for 3 minutes, add 0.125% by mass percentage of ferric oxide modified hollow glass microspheres, and control the rotational speed at 10-50r/m at room temperature. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 1373kW/m ² , the remaining mass was 9%, and the total heat The release is 117MJ/m ² , the total smoke production is 670g, and the smoke factor is 919g/s.

Example 2-2:

Add 99.75% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer for internal mixing for 3 minutes, add 0.25% of ferric oxide-modified hollow glass microspheres in the mass percentage, and control the rotating speed at 10-50r/m at room temperature. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 995kW/m ² , the remaining mass was 7%, and the total heat The release is 114MJ/m ² , the total smoke production is 771g, and the smoke factor is 768g/s.

Embodiment 2-3:

Add 99.5% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer for banburying for 3 minutes, add 0.5% of ferric oxide modified hollow glass microspheres in the mass percentage, and control the rotating speed at 10-50r/m at room temperature. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 1409kW/m ² , the remaining mass was 9%, and the total heat The release is 114MJ/m ² , the total smoke production is 672g, and the smoke factor is 641g/s.

Embodiment 2-4:

Add 99.0% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer for internal mixing for 3 minutes, add 1.0% of ferric oxide-modified hollow glass microspheres in the mass percentage, and control the rotating speed at 10-50r/m at room temperature. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 892kW/m ² , the remaining mass was 9%, and the total heat The release is 111MJ/m ² , the total smoke production is 789g, and the smoke factor is 520g/s.

Embodiment 2-5:

According to mass percentage, 98.0% of thermoplastic polyurethane elastomer is added into the internal mixer for banburying for 3 minutes, and 2.0% of mass percentage of ferric oxide-modified hollow glass microspheres is added. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 968kW/m ² , the remaining mass was 9%, and the total heat The release is 115MJ/m ² , the total smoke production is 774g, and the smoke factor is 432g/s.

Embodiment 2-6:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 0.125% by mass of ferric oxide-modified hollow glass microspheres and 9.875% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 237kW/m ² , the remaining mass was 33%, and the total heat The release is 59MJ/m ² , the total smoke production is 273g, and the smoke factor is 37g/s. Embodiment 2-7:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 0.25% by mass of ferric oxide-modified hollow glass microspheres and 9.75% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 140kW/m ² , the remaining mass was 41%, and the total heat The release is 57MJ/m ² , the total smoke production is 367g, and the smoke factor is 69g/s.

Embodiment 2-8:

90% by mass percentage of thermoplastic polyurethane elastomer was added to the internal mixer for internal mixing for 3 minutes, and 0.5% by mass percentage of ferric oxide-modified hollow glass microspheres and 9.5% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 151kW/m ² , the remaining mass was 41%, and the total heat The release is 48MJ/m ² , the total smoke production is 288g, and the smoke factor is 44g/s.

Embodiment 2-9:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 1% by mass of ferric oxide-modified hollow glass microspheres and 9% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 139kW/m ² , the remaining mass was 62%, and the total heat The release is 51MJ/m ² , the total smoke production is 293g, and the smoke factor is 41g/s.

Embodiment 2-10:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 2% by mass of ferric oxide-modified hollow glass microspheres and 8% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 147kW/m ² , the remaining mass was 38%, and the total heat The release is 47MJ/m ² , the total smoke production is 323g, and the smoke factor is 48g/s.

Table 2 comparative example 2-1 and embodiment 2-1 to 2-10 sample experiment data table

It can be seen from Table 2 that whether the modified hollow glass microspheres are added alone to the thermoplastic polyurethane elastomer, or the modified hollow glass microspheres are synergistic with ammonium polyphosphate. With the increase of the addition amount, the heat release rate, the total smoke generation, the smoke factor and the smoke generation rate all showed a trend of decreasing obviously, but the more the addition amount, the better, when the modified hollow glass microsphere content was 1% When , the heat release rate is the lowest, the char formation is relatively high, and the flame retardant effect is the best. Under the same content, the unmodified hollow glass microsphere synergistic ammonium polyphosphate flame-retardant thermoplastic polyurethane elastomer and the modified hollow glass microsphere synergistic ammonium polyphosphate flame-retardant thermoplastic polyurethane elastomer were compared, and the modified hollow glass microsphere The heat release rate of is significantly reduced, indicating that the modification is meaningful.

3. Thermoplastic polyurethane elastomer (TPU)/ammonium phosphomolybdate modified hollow glass microspheres (APT-HGM)/ammonium polyphosphate (APP)

Comparative example 3-1:

Add 100% thermoplastic polyurethane elastomer into the internal mixer according to the mass percentage, and control the rotational speed at 10-50r/min at room temperature, and internally knead for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizing machine, the temperature is controlled at 175-180° C., the pressure is maintained for 10-20 minutes, and the product is cooled for 1-2 minutes. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate (PHRR) was 1416kW/m ² and the remaining mass was (MASS) 9%, the total heat release (THR) is 97MJ/m ² , the total smoke yield (TSR) is 600g, and the smoke factor (SF) is 850g/s.

Comparative example 3-2:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 0.5% by mass of unmodified hollow glass microspheres and 9.5% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 372kW/m ² , the remaining mass was 10%, and the total heat The release is 130MJ/m ² , the total smoke production is 753g, and the smoke factor is 320g/s.

Example 3-1:

Add 99.75% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer for banburying for 3 minutes, add 0.25% of the mass percentage of ammonium phosphomolybdate modified hollow glass microspheres, and control the speed at 10-50r/m at room temperature. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 611kW/m ² , the remaining mass was 8%, and the total heat The release is 100MJ/m ² , the total smoke production is 674g, and the smoke factor is 412g/s.

Example 3-2:

Add 99.5% of thermoplastic polyurethane elastomer according to the mass percentage into the internal mixer for internal mixing for 3 minutes, add 0.5% by mass percentage of ammonium phosphomolybdate-modified hollow glass microspheres, and control the speed at 10-50r/min at room temperature. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 506kW/m ² , the remaining mass was 9%, and the total heat The release is 97MJ/m ² , the total smoke production is 716g, and the smoke factor is 362g/s.

Embodiment 3-3:

Add 99.0% of the thermoplastic polyurethane elastomer according to the mass percentage into the banbury mixer for 3 min, add 1.0% of the mass percentage of ammonium phosphomolybdate modified hollow glass microspheres, and at room temperature, control the rotational speed to 10-50r/ min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 375kW/m ² , the remaining mass was 10%, and the total heat The release is 128MJ/m ² , the total smoke production is 785g, and the smoke factor is 394g/s.

Embodiment 3-4:

Add 98.0% of thermoplastic polyurethane elastomer according to the mass percentage into the banbury mixer for 3 minutes, add 2.0% of the mass percentage of ammonium phosphomolybdate modified hollow glass microspheres, and control the speed at 10-50r/m at room temperature. min, banburying 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 426kW/m ² , the remaining mass was 11%, and the total heat The release is 95MJ/m ² , the total smoke production is 657g, and the smoke factor is 246g/s.

Embodiment 3-5:

90% by mass percentage of thermoplastic polyurethane elastomer was added to the internal mixer for internal mixing for 3 minutes, and 0.125% by mass of ammonium phosphomolybdate-modified hollow glass microspheres and 9.875% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 132kW/m ² , the remaining mass was 34%, and the total heat The release is 51MJ/m ² , the total smoke production is 372g, and the smoke factor is 45g/s.

Embodiment 3-6:

90% by mass percentage of thermoplastic polyurethane elastomer was added to the internal mixer for internal mixing for 3 minutes, and 0.25% by mass of ammonium phosphomolybdate-modified hollow glass microspheres and 9.75% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 127kW/m ² , the remaining mass was 36%, and the total heat The release is 47MJ/m ² , the total smoke production is 289g, and the smoke factor is 37g/s.

Embodiment 3-7:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for banburying for 3 minutes, and 0.5% by mass of ammonium phosphomolybdate-modified hollow glass microspheres and 9.5% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 122kW/m ² , the remaining mass was 39%, and the total heat The release is 43MJ/m ² , the total smoke production is 219g, and the smoke factor is 29g/s.

Embodiment 3-8:

90% by mass percentage of thermoplastic polyurethane elastomer was added to an internal mixer for internal mixing for 3 minutes, and 1% by mass of ammonium phosphomolybdate-modified hollow glass microspheres and 9% by mass of ammonium polyphosphate were added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 132kW/m ² , the remaining mass was 30%, and the total heat The release is 64MJ/m ² , the total smoke production is 286g, and the smoke factor is 37g/s.

Table 3 comparative example 3-1 and embodiment 3-1 to 3-8 sample experiment data table

It can be seen from Table 3 that whether the modified hollow glass microspheres are added alone to the thermoplastic polyurethane elastomer, or the modified hollow glass microspheres are synergistic with ammonium polyphosphate. With the increase of the addition amount, the heat release rate, the total smoke generation, the smoke factor and the smoke generation rate all showed a trend of decreasing obviously, but the more the addition amount, the better, when the modified hollow glass microsphere content was 1% When , the heat release rate is the lowest, the char formation is relatively high, and the flame retardant effect is the best. Under the same content, the unmodified hollow glass microsphere synergistic ammonium polyphosphate flame-retardant thermoplastic polyurethane elastomer and the modified hollow glass microsphere synergistic ammonium polyphosphate flame-retardant thermoplastic polyurethane elastomer were compared, and the modified hollow glass microsphere The heat release rate of is significantly reduced, indicating that the modification is meaningful.

4. Thermoplastic polyurethane elastomer (TPU)/heptadecafluorodecyltriethoxysilane modified hollow glass microspheres (FAS-HGM)/ammonium polyphosphate (APP)

Comparative example 4-1:

Add 100% thermoplastic polyurethane elastomer into the internal mixer according to the mass percentage, and control the rotational speed at 10-50r/min at room temperature, and internally knead for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizing machine, the temperature is controlled at 175-180° C., the pressure is maintained for 10-20 minutes, and the product is cooled for 1-2 minutes. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate (PHRR) was 1416kW/m ² and the remaining mass was (MASS) 9%, the total heat release (THR) is 97MJ/m ² , the total smoke yield (TSR) is 600g, and the smoke factor (SF) is 850g/s.

Comparative example 4-2:

99.75% of the thermoplastic polyurethane elastomer was added into the internal mixer according to the mass percentage and mixed for 3 minutes, and 0.25% of the mass percentage of unmodified hollow glass microspheres was added. At room temperature, control the rotational speed at 10-50r/min, and banbury for 10 minutes. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 1142kW/m ² , the remaining mass was 9%, and the total heat The release is 93MJ/m ² , the total smoke production is 551g, and the smoke factor is 630g/s.

Example 4-1:

Add 99.75% of thermoplastic polyurethane elastomer by mass percentage into the internal mixer and banbury for 3min, add 0.25% heptadecafluorodecyltriethoxysilane modified hollow glass microspheres by mass percentage, at room temperature, control The rotating speed is 10-50r/min, and the banburying is 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, the temperature is controlled at 175-180° C., the pressure is kept for 10-20 minutes, and cooled for 1-2 minutes to obtain the product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 684kW/m ² , the remaining mass was 11%, and the total heat The release is 92MJ/m ² , the total smoke production is 588g, and the smoke factor is 419g/s.

Example 4-2:

Add 99.5% of thermoplastic polyurethane elastomer by mass percentage into the banbury mixer for banburying 3min, add 0.5% heptadecafluorodecyltriethoxysilane modified hollow glass microspheres by mass percentage, at room temperature, control The rotating speed is 10-50r/min, and the banburying is 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 595kW/m ² , the remaining mass was 11%, and the total heat The release is 103MJ/m ² , the total smoke production is 614g, and the smoke factor is 418g/s.

Embodiment 4-3:

Add 99.0% of thermoplastic polyurethane elastomer by mass percentage into the internal mixer and banbury for 3min, add 1.0% of heptadecafluorodecyltriethoxysilane modified hollow glass microspheres by mass percentage, at room temperature, control The rotating speed is 10-50r/min, and the banburying is 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 523kW/m ² , the remaining mass was 12%, and the total heat The release is 99MJ/m ² , the total smoke production is 547g, and the smoke factor is 325g/s.

Embodiment 4-4:

Add 98.0% of thermoplastic polyurethane elastomer by mass percentage into the internal mixer and banbury for 3min, add 2.0% of heptadecafluorodecyltriethoxysilane-modified hollow glass microspheres by mass percentage, at room temperature, control The rotating speed is 10-50r/min, and the banburying is 10min. The obtained material is put into a mold of 100×100×3mm ³ , pressed into tablets with a flat vulcanizer, controlled at a temperature of 175-180° C., maintained at a pressure of 10-20 minutes, and cooled for 1-2 minutes to obtain a product. Under the radiation power of 35kW/m ² and 25kW/m ² respectively, the cone calorimeter test and the smoke density test were carried out on the sample. The peak heat release rate was 1142kW/m ² , the remaining mass was 9%, and the total heat The release is 124MJ/m ² , the total smoke production is 643g, and the smoke factor is 380g/s.

Table 4 comparative example 4-1 and embodiment 4-1 to 4-4 sample experimental data

It can be seen from Table 4 that with the addition of modified hollow glass microspheres in thermoplastic polyurethane elastomers, the heat release rate, total smoke generation, smoke factor and smoke generation rate all showed a trend of decreasing significantly, but it did not The more the better, when the content of modified hollow glass microspheres is 1%, the heat release rate is the lowest, the amount of char formation is relatively high, and the flame retardant effect is the best. Under the same content, the unmodified hollow glass microsphere flame retardant thermoplastic polyurethane elastomer is compared with the modified hollow glass microsphere flame retardant thermoplastic polyurethane elastomer. The heat release rate of the modified hollow glass microsphere is significantly reduced, indicating that the modification is meaningful.

Claims (10)

1. the surface modifying method of a hollow glass micropearl, it is characterised in that: comprise the following steps:

(1) with the sodium hydroxide solution that concentration is 10% to hollow glass micropearl supersound washing 30min, surface impurity is removed, Hollow glass micropearl to surface hydroxylation；

(2) hollow glass micropearl obtained in step (1) is used respectively deionized water, dehydrated alcohol cyclic washing 4 times, In vacuum drying oven, under the conditions of temperature is 80 DEG C, it is dried 8h；

(3) hollow glass micropearl after processing is dissolved in the mixed solution of ethanol that volume ratio is 1:1 and deionized water, and Add backflow, constant temperature water bath 70 DEG C heating, mechanical agitation in there-necked flask；In heating process, first dropping can obtain the molten of coating Liquid, then add the sodium hydroxide solution that concentration is 1%, measure the concentration of mixed liquor in there-necked flask simultaneously, continuous test solution PH value, maintains neutral environment；Stirring 5h, sucking filtration, in vacuum drying oven, under the conditions of temperature is 80 DEG C, it is dried 8h.

The surface modifying method of a kind of hollow glass micropearl the most as claimed in claim 1, it is characterised in that: described hollow glass Bead density is 0.10-0.70g/cm³, particle diameter is 0.01-400 μm.

The surface modifying method of a kind of hollow glass micropearl the most as claimed in claim 1, it is characterised in that: step (3) is described The solution of obtained coating be respectively the titanium sulfate solution of mass fraction 20%, the ferric chloride solution of 8%, 6% ammonium phosphomolybdate molten Liquid or the 17 fluorine decyl triethoxysilane solution of 20%.

The surface modifying method of a kind of hollow glass micropearl the most as claimed in claim 1, it is characterised in that: step (3) is described Obtained coating include titanium dioxide, iron sesquioxide, ammonium phosphomolybdate, 17 fluorine decyl triethoxysilanes at least one.

The method of modifying of a kind of hollow glass micropearl the most as claimed in claim 4, it is characterised in that: modified hollow glass Microballon, the mass ratio that can obtain coating and hollow glass micropearl is: titanium dioxide: hollow glass micropearl=15.3:84.7, three oxygen Change two ferrum: hollow glass micropearl=1.4:98.6, ammonium phosphomolybdate: hollow glass micropearl=8.3:91.7,17 fluorine decyl three ethoxies Base silane: hollow glass micropearl=19.3:80.7.

The surface modifying method of a kind of hollow glass micropearl the most as claimed in claim 4, it is characterised in that: can obtain coating is When titanium dioxide, iron sesquioxide, ammonium phosphomolybdate, also include the step of roasting after step (3), specially by dried Hollow glass micropearl is placed in 500 DEG C of Muffle kiln roasting 2h.

7. use claim 1-6 arbitrarily as described in the hollow glass micropearl prepared of method of modifying as fire retardant at flame-proofed thermoplastic Application in polyurethane elastomer.

8. based on the flame retardant thermoplastic polyurethane elastomer of application described in claim 7, it is characterised in that: mass fraction is: heat Plastic polyurethane elastomer 98%-99.875%, fire retardant 0.125%-2%；Or Polyurethane Thermoplastic Elastomer 90%, modified empty Heart glass microballoon 0.1%-1%, APP 9%-9.9%.

9. flame retardant thermoplastic polyurethane elastomer as claimed in claim 8, it is characterised in that: described fire retardant is titanium dioxide The hollow glass that the hollow glass micropearl of titanium modification, titania modified cenosphere synergistic APP, ferric oxide are modified The hollow glass micropearl synergistic APP of microballon, iron sesquioxide modification, the hollow glass micropearl of ammonium phosphomolybdate modification, phosphorus molybdenum The hollow glass micropearl synergistic that the hollow glass micropearl synergistic APP of acid ammonium modification, 17 fluorine decyl triethoxysilanes are modified Least one set in APP.

10. the method for preparation flame retardant thermoplastic polyurethane elastomer as described in claim 8-9 is arbitrary, it is characterised in that:

Modification hollow glass micropearl is mixed in banbury with Polyurethane Thermoplastic Elastomer, control temperature at 175-180 DEG C, Rotating speed is 10-50r/min, melt blending 10-30min, molding；

Or modification hollow glass micropearl, APP are mixed in banbury with Polyurethane Thermoplastic Elastomer, control temperature and exist 175-180 DEG C, rotating speed is 10-50r/min, melt blending 10-30min, molding.