A highly flame-retardant polyether TPU material and preparation method thereof

Abstract

The invention relates to the technical field of polymer materials, and in particular to a highly flame-retardant polyether type TPU material and a preparation method thereof. In the preparation of the modified polyether type TPU, the invention adds amino nano-silica, which can make the amino nano-silica uniformly dispersed in a TPU matrix to form physical cross-linking points, thereby enhancing the mechanical strength, modulus and wear resistance of the TPU. The nano-scale dispersion can significantly improve the overall mechanical properties of the material, and the addition of the amino nano-silica can improve the resilience, tear resistance and fatigue resistance of the TPU; the amino nano-silica can shield ultraviolet rays through its surface properties, thereby indirectly improving the ultraviolet aging resistance of the TPU, and enabling the TPU to maintain stable performance in a humid environment; the amino group on the surface of the amino nano-silica has high reactivity and can be coupled with a variety of molecules and groups, laying a foundation for the subsequent functional modification of the TPU through a flame retardant.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a highly flame-retardant polyether TPU material and a preparation method thereof. Background Art

[0002] In recent years, with the increasing attention paid to environmental protection and fire safety around the world, the flame retardant properties of polymer materials have become the focus of industry attention. Polyurethane, or TPU, as a polymer material with excellent performance, is widely used in industry, life, medical and military fields due to its wear resistance, aging resistance, high resilience and other characteristics. However, the flammability of ordinary TPU materials limits its application in scenarios with higher safety requirements. The limiting oxygen index of traditional TPU materials is only 16%-18%. When exposed to fire, it will burn rapidly and produce a large amount of toxic smoke, posing huge safety hazards to users and the environment.

[0003] As an important branch of TPU materials, polyether TPU has shown great application potential in the fields of cables, wiring harnesses, etc. with its excellent hydrolysis resistance and aging resistance. By combining flame retardants with polyether TPU, the highly flame-retardant polyether TPU material developed can not only significantly improve the flame retardant properties of the material, but also maintain its original physical and chemical properties, providing safer and more reliable solutions for the fields of wires and cables, automotive electronics, etc. In summary, the development of a highly flame-retardant polyether TPU material can not only meet the market demand for high-performance flame-retardant materials, but also promote the green and sustainable development of related industries. Summary of the invention

[0004] In view of the above-mentioned shortcomings of the prior art, the present invention provides a highly flame-retardant polyether TPU material and a preparation method thereof, which can effectively solve the problem of poor flame retardancy of the polyether TPU in the prior art.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0006] A highly flame-retardant polyether TPU material, the highly flame-retardant polyether TPU material is composed of the following components: modified polyether TPU, phosphorus-based flame retardant, dopamine flame retardant and silane coupling agent KH-560;

[0007] The modified polyether TPU is prepared with amino nano-silicon dioxide, phosphorus-based flame retardant, polyethylene glycol, toluene diisocyanate and 1,4-butanediol as raw materials;

[0008] The phosphorus-based flame retardant is prepared using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and p-hydroxybenzaldehyde as raw materials;

[0009] The dopamine type flame retardant is prepared by taking nano silicon dioxide and dopamine hydrochloride as raw materials.

[0010] Furthermore, the preparation method of the amino-modified nano-silica is:

[0011] 1 g of nano-silica was dispersed in 300 mL of anhydrous ethanol, and ultrasonically dispersed at a frequency of 26 kHz for 30 min, and then 2 mL of 3-aminopropyltriethoxysilane was added at a drop rate of 2 drops / s. After ultrasonic dispersion at a frequency of 27 kHz for 30 min, the mixture was placed in an oil bath at 60°C and stirred at a speed of 200 r / min for 6 h. The filtrate was removed by vacuum filtration and washed with anhydrous ethanol for 5 times. The mixture was placed in a vacuum oven at 60°C and dried for 24 h, and the result was recorded as amino-nano-silica.

[0012] Furthermore, the preparation method of the phosphorus-based flame retardant is:

[0013] Under nitrogen protection, 5 g of bisphenol fluorene and 1 mL of triethylamine were added to 50 mL of dichloromethane, and stirred at 500 r / min for 10 min in a water bath at 10°C. Then, 1.5 g of phenylphosphoryl dichloride was added and stirred at 200 r / min for 10 h. The obtained white solid was dried in an oven at 50°C for 2 h and then ground through a 200-mesh sieve to obtain a phosphorus-based flame retardant.

[0014] Furthermore, the preparation steps of the modified polyether TPU are:

[0015] Step 1, place 60g of polyethylene glycol at a temperature of 110-120°C and a vacuum degree of 133.3Pa for vacuum dehydration for 2h, cool to 70°C, pour into a flask, add 155g of toluene diisocyanate dropwise at a rate of 1 drop / s under stirring, keep constant temperature in a water bath at 80°C for 2h after the addition is completed, and the obtained result is recorded as the reaction component;

[0016] Step 2: Add 0.2 g of amino-modified nano-silica and 0.1 g of phosphorus-based flame retardant to 30 g of 1,4-butanediol, disperse evenly by ultrasonication, and add to the reaction components heated to 100°C and under vigorous stirring conditions. After the addition, continue stirring for 10 minutes, pour into a mold, and place in an oven at 110°C for aging for 10 hours to obtain a modified polyether TPU.

[0017] Furthermore, the stirring speed in the stirring condition in step 1 is 200 r / min, the operation method for uniform ultrasonic dispersion in step 2 is ultrasonic dispersion at a frequency of 28 kHz for 30 minutes, and the stirring speed in the violent stirring condition in step 2 is 600 r / min.

[0018] Furthermore, the preparation steps of the phosphorus-based flame retardant are:

[0019] Step A, weigh 13 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dissolve it in 100 mL of dichloromethane, stir and dissolve it as the first component, weigh 6 g of p-hydroxybenzaldehyde and dissolve it in 50 mL of dichloromethane, ultrasonically dissolve it as the second component;

[0020] Step B, pour the second component into the first component and mix evenly, and react for 4 hours in a water bath at 80°C. After the reaction is completed, pour into a beaker, seal it, let it stand, stratify and dry in the shade, and the result is a phosphorus-based flame retardant.

[0021] Furthermore, the stirring and dissolving operation method in step A is stirring at a speed of 500 r / min for 30 min, the ultrasonic dissolution operation method in step A is ultrasonic dispersion at a frequency of 28 kHz for 10 min, and the uniform mixing operation method in step B is stirring at a speed of 300 r / min for 5 min.

[0022] Furthermore, the preparation method of the dopamine type flame retardant is:

[0023] To 200g of deionized water, add 0.2g of nano-silicon dioxide, 0.25g of dopamine hydrochloride and 0.4g of tris(hydroxymethyl)aminomethane, mix thoroughly, then add 10% by mass sodium hydroxide solution to adjust the pH value to 9. After ultrasonic dispersion, place it at a constant temperature of 28°C and stir it mechanically for 8h. After centrifugation to remove the filtrate, rinse it with deionized water 3 times, and dry it to obtain a dopamine flame retardant.

[0024] Furthermore, in the preparation method of the dopamine-type flame retardant, the method of fully mixing is stirring at a speed of 300 r / min for 30 minutes, the method of ultrasonic dispersion is ultrasonic dispersion at a frequency of 23 kHz for 5 minutes, the speed of mechanical stirring is 200 r / min, the method of centrifugation is centrifugation at a speed of 6000 r / min for 5 minutes, and the method of drying is drying in an oven at 55°C for 3 hours.

[0025] A method for preparing a highly flame-retardant polyether TPU material, the preparation method comprising the following steps:

[0026] Pour 100 parts by weight of modified polyether TPU into a double-roll mill, and grind for 2-3 minutes at the conditions where the front and rear roller temperatures are 110°C and 100°C respectively. Add 5-8 parts by weight of phosphorus flame retardant, 6-10 parts by weight of dopamine flame retardant and 1-2 parts by weight of silane coupling agent KH-560, and continue to grind for 10 minutes. Make triangle packages 10 times and then discharge the material. Finally, preheat on a flat vulcanizer at 170°C for 5 minutes, then hot press for 3 minutes, and then cold press for 2 minutes to remove from the mold. The resulting material is a highly flame-retardant polyether TPU material.

[0027] The present invention provides a highly flame-retardant polyether TPU material and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. The present invention adds amino nano-silica in the preparation of modified polyether TPU, which can make the amino nano-silica uniformly dispersed in the TPU matrix to form physical cross-linking points, thereby enhancing the mechanical strength, modulus and wear resistance of TPU. The nano-scale dispersion can significantly improve the overall mechanical properties of the material, and the addition of amino nano-silica can improve the resilience, tear resistance and fatigue resistance of TPU; secondly, the amino nano-silica can shield ultraviolet rays through its surface properties, thereby indirectly improving the ultraviolet aging resistance of TPU. The addition of amino nano-silica can also enhance the hydrolysis resistance of TPU, so that it can still maintain stable performance in a humid environment; finally, the amino group on the surface of the amino nano-silica has a high reactivity and can be coupled with a variety of molecules and groups, laying a foundation for the subsequent functional modification of TPU through flame retardants.

[0029] 2. The phosphorus-based flame retardant synthesized from bisphenol fluorene and phenylphosphoryl dichloride as raw materials is added as a chain extender to the preparation of modified polyether TPU, which can make the prepared modified polyether TPU have stable flame retardant properties. Moreover, the phosphorus-based flame retardant as a chain extender can participate in the polymerization reaction of TPU, thereby increasing the length and crosslinking degree of the TPU molecular chain, and can also improve the physical properties of TPU, such as tensile strength, tear strength and wear resistance; secondly, the phosphorus-based flame retardant itself has high heat resistance and can maintain stable chemical properties at high temperatures, thereby playing a role in improving the thermal stability of the modified polyether TPU.

[0030] 3. The present invention adds phosphorus flame retardant, dopamine flame retardant and silane coupling agent KH-560 to the modified polyether TPU, so that the amino groups on the surface of the amino-modified nano-silica in the modified polyether TPU can be coupled and grafted with the phosphorus flame retardant, dopamine flame retardant and silane coupling agent KH-560 respectively, so that the phosphorus flame retardant and dopamine flame retardant can be stably dispersed in the modified polyether TPU molecules, so that the prepared highly flame-retardant polyether TPU material has stable flame retardant properties; silane coupling agent KH-560 is used as An excellent adhesion promoter that can significantly improve the interfacial bonding force between fillers and TPU. Adding silane coupling agent KH-560 to modified polyether TPU can improve the dispersibility and wettability of phosphorus-based flame retardants and dopamine-type flame retardants in TPU, thereby improving the mechanical properties of the material such as tensile strength, flexural strength and interlaminar shear strength. Secondly, the dopamine molecules in the dopamine-type flame retardant can undergo self-polymerization under ultraviolet light to form a stable protective layer, which effectively blocks the destructive effects of ultraviolet rays and improves the weather resistance of the material. DETAILED DESCRIPTION

[0031] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] The present invention will be further described below in conjunction with the embodiments.

[0033] Example 1

[0034] A highly flame-retardant polyether TPU material of this embodiment, the highly flame-retardant polyether TPU material is composed of the following components: modified polyether TPU, phosphorus-based flame retardant, dopamine-based flame retardant and silane coupling agent KH-560;

[0035] The modified polyether TPU is prepared from amino-modified nano-silica, phosphorus-based flame retardant, polyethylene glycol, toluene diisocyanate and 1,4-butanediol;

[0036] Wherein, the preparation method of amino-modified nano-silicon dioxide is:

[0037] 1 g of nano-silica was dispersed in 300 mL of anhydrous ethanol, and ultrasonically dispersed at a frequency of 26 kHz for 30 min, and then 2 mL of 3-aminopropyltriethoxysilane was added at a drop rate of 2 drops / s. After ultrasonic dispersion at a frequency of 27 kHz for 30 min, the mixture was placed in an oil bath at 60°C and stirred at a speed of 200 r / min for 6 h. The filtrate was removed by vacuum filtration and washed with anhydrous ethanol for 5 times. The mixture was placed in a vacuum oven at 60°C and dried for 24 h, and the result was recorded as amino-nano-silica.

[0038] The preparation method of phosphorus-based flame retardant is:

[0039] Under nitrogen protection, 5 g of bisphenol fluorene and 1 mL of triethylamine were added to 50 mL of dichloromethane, and stirred at 500 r / min for 10 min in a water bath at 10°C. Then, 1.5 g of phenylphosphoryl dichloride was added and stirred at 200 r / min for 10 h. The obtained white solid was dried in an oven at 50°C for 2 h and then ground through a 200-mesh sieve to obtain a phosphorus-based flame retardant.

[0040] The preparation steps of modified polyether TPU are:

[0041] Step 1, 60g of polyethylene glycol was placed in a vacuum dehydration condition at a temperature of 110°C and a vacuum degree of 133.3Pa for 2h, and then cooled to 70°C and poured into a flask, and 155g of toluene diisocyanate was added dropwise at a rate of 1 drop / s under stirring at a speed of 200r / min. After the addition was completed, the mixture was kept constant temperature in a water bath at 80°C for 2h, and the obtained mixture was recorded as the reaction component;

[0042] Step 2: Add 0.2 g of amino-modified nano-silica and 0.1 g of phosphorus-based flame retardant to 30 g of 1,4-butanediol, disperse them ultrasonically at a frequency of 28 kHz for 30 min, and then add them to the reaction components heated to 100 ° C and under vigorous stirring conditions at a speed of 600 r / min. After the addition, continue stirring for 10 min, pour it into a mold and place it in an oven at 110 ° C for aging for 10 hours to obtain a modified polyether TPU.

[0043] The phosphorus flame retardant is prepared from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and p-hydroxybenzaldehyde as raw materials, wherein the preparation steps of the phosphorus flame retardant are as follows:

[0044] Step A, weighing 13g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dissolving it in 100mL of dichloromethane, stirring at a speed of 500r / min for 30min, and recording it as the first component; weighing 6g of p-hydroxybenzaldehyde and dissolving it in 50mL of dichloromethane, and ultrasonically dispersing it at a frequency of 28kHz for 10min, and recording it as the second component;

[0045] Step B, pour the second component into the first component, stir at a speed of 300r / min for 5min, and react in a water bath at 80°C for 4h. After the reaction is completed, pour into a beaker, seal it, let it stand, separate into layers and dry in the shade, and the result is a phosphorus-based flame retardant.

[0046] The dopamine type flame retardant is prepared with nano silicon dioxide and dopamine hydrochloride as raw materials, wherein the preparation method of the dopamine type flame retardant is as follows:

[0047] To 200g of deionized water, 0.2g of nano-silicon dioxide, 0.25g of dopamine hydrochloride and 0.4g of tris(hydroxymethyl)aminomethane were added, and the mixture was stirred at 300r / min for 30min, and then a 10% sodium hydroxide solution was added dropwise to adjust the pH value to 9. After ultrasonic dispersion at a frequency of 23kHz for 5min, the mixture was placed at a constant temperature of 28°C and mechanically stirred at a speed of 200r / min for 8h. The mixture was centrifuged at a speed of 6000r / min for 5min to remove the filtrate, and then rinsed with deionized water 3 times. After drying in an oven at 55°C for 3h, the resulting mixture was a dopamine-type flame retardant.

[0048] A method for preparing a highly flame-retardant polyether TPU material, the preparation method comprising the following steps:

[0049] 100 parts by weight of modified polyether TPU were poured into a double-roll mill, and the milling was carried out for 2 minutes at the conditions where the front and rear roller temperatures were 110°C and 100°C respectively. After adding 5 parts by weight of phosphorus flame retardant, 6 parts by weight of dopamine flame retardant and 1 part by weight of silane coupling agent KH-560, the milling was continued for 10 minutes. The material was triangularly packaged 10 times and then discharged. Finally, it was preheated on a flat vulcanizer at 170°C for 5 minutes, followed by hot pressing for 3 minutes and cold pressing for 2 minutes to remove from the mold. The result was a highly flame-retardant polyether TPU material.

[0050] Example 2

[0051] A highly flame-retardant polyether TPU material of this embodiment, the highly flame-retardant polyether TPU material is composed of the following components: modified polyether TPU, phosphorus-based flame retardant, dopamine-based flame retardant and silane coupling agent KH-560;

[0052] The modified polyether TPU is prepared from amino-modified nano-silica, phosphorus-based flame retardant, polyethylene glycol, toluene diisocyanate and 1,4-butanediol;

[0053] Wherein, the preparation method of amino-modified nano-silicon dioxide is:

[0054] 1 g of nano-silica was dispersed in 300 mL of anhydrous ethanol, and ultrasonically dispersed at a frequency of 26 kHz for 30 min, and then 2 mL of 3-aminopropyltriethoxysilane was added at a drop rate of 2 drops / s. After ultrasonic dispersion at a frequency of 27 kHz for 30 min, the mixture was placed in an oil bath at 60°C and stirred at a speed of 200 r / min for 6 h. The filtrate was removed by vacuum filtration and washed with anhydrous ethanol for 5 times. The mixture was placed in a vacuum oven at 60°C and dried for 24 h, and the result was recorded as amino-nano-silica.

[0055] The preparation method of phosphorus-based flame retardant is:

[0056] Under nitrogen protection, 5 g of bisphenol fluorene and 1 mL of triethylamine were added to 50 mL of dichloromethane, and stirred at 500 r / min for 10 min in a water bath at 10°C. Then, 1.5 g of phenylphosphoryl dichloride was added and stirred at 200 r / min for 10 h. The obtained white solid was dried in an oven at 50°C for 2 h and then ground through a 200-mesh sieve to obtain a phosphorus-based flame retardant.

[0057] The preparation steps of modified polyether TPU are:

[0058] Step 1, 60g of polyethylene glycol was placed in a vacuum dehydration condition at a temperature of 120°C and a vacuum degree of 133.3Pa for 2h, and then cooled to 70°C and poured into a flask, and 155g of toluene diisocyanate was added dropwise at a rate of 1 drop / s under stirring at a speed of 200r / min. After the addition was completed, the mixture was kept constant temperature in a water bath at 80°C for 2h, and the obtained mixture was recorded as the reaction component;

[0059] Step 2: Add 0.2 g of amino-modified nano-silica and 0.1 g of phosphorus-based flame retardant to 30 g of 1,4-butanediol, disperse them ultrasonically at a frequency of 28 kHz for 30 min, and then add them to the reaction components heated to 100 ° C and under vigorous stirring conditions at a speed of 600 r / min. After the addition, continue stirring for 10 min, pour it into a mold and place it in an oven at 110 ° C for aging for 10 hours to obtain a modified polyether TPU.

[0060] The phosphorus flame retardant is prepared from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and p-hydroxybenzaldehyde as raw materials, wherein the preparation steps of the phosphorus flame retardant are as follows:

[0061] Step A, weighing 13g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dissolving it in 100mL of dichloromethane, stirring at a speed of 500r / min for 30min, and recording it as the first component; weighing 6g of p-hydroxybenzaldehyde and dissolving it in 50mL of dichloromethane, and ultrasonically dispersing it at a frequency of 28kHz for 10min, and recording it as the second component;

[0062] Step B, pour the second component into the first component, stir at a speed of 300r / min for 5min, and react in a water bath at 80°C for 4h. After the reaction is completed, pour into a beaker, seal it, let it stand, separate into layers and dry in the shade, and the result is a phosphorus-based flame retardant.

[0063] The dopamine type flame retardant is prepared with nano silicon dioxide and dopamine hydrochloride as raw materials, wherein the preparation method of the dopamine type flame retardant is as follows:

[0064] To 200g of deionized water, 0.2g of nano-silicon dioxide, 0.25g of dopamine hydrochloride and 0.4g of tris(hydroxymethyl)aminomethane were added, and the mixture was stirred at 300r / min for 30min, and then a 10% sodium hydroxide solution was added dropwise to adjust the pH value to 9. After ultrasonic dispersion at a frequency of 23kHz for 5min, the mixture was placed at a constant temperature of 28°C and mechanically stirred at a speed of 200r / min for 8h. The mixture was centrifuged at a speed of 6000r / min for 5min to remove the filtrate, and then rinsed with deionized water 3 times. After drying in an oven at 55°C for 3h, the resulting mixture was a dopamine-type flame retardant.

[0065] A method for preparing a highly flame-retardant polyether TPU material, the preparation method comprising the following steps:

[0066] 100 parts by weight of modified polyether TPU were poured into a double-roll mill, and the milling was carried out for 3 minutes under the conditions that the front and rear roller temperatures were 110°C and 100°C respectively. After adding 8 parts by weight of phosphorus flame retardant, 10 parts by weight of dopamine flame retardant and 2 parts by weight of silane coupling agent KH-560, the milling was continued for 10 minutes. The material was triangularly packaged 10 times and then discharged. Finally, it was preheated on a flat vulcanizer at 170°C for 5 minutes, followed by hot pressing for 3 minutes and cold pressing for 2 minutes to remove from the mold. The resulting material is a highly flame-retardant polyether TPU material.

[0067] Example 3

[0068] A highly flame-retardant polyether TPU material of this embodiment, the highly flame-retardant polyether TPU material is composed of the following components: modified polyether TPU, phosphorus-based flame retardant, dopamine-based flame retardant and silane coupling agent KH-560;

[0069] The modified polyether TPU is prepared from amino-modified nano-silica, phosphorus-based flame retardant, polyethylene glycol, toluene diisocyanate and 1,4-butanediol;

[0070] Wherein, the preparation method of amino-modified nano-silicon dioxide is:

[0071] 1 g of nano-silica was dispersed in 300 mL of anhydrous ethanol, and ultrasonically dispersed at a frequency of 26 kHz for 30 min, and then 2 mL of 3-aminopropyltriethoxysilane was added at a drop rate of 2 drops / s. After ultrasonic dispersion at a frequency of 27 kHz for 30 min, the mixture was placed in an oil bath at 60°C and stirred at a speed of 200 r / min for 6 h. The filtrate was removed by vacuum filtration and washed with anhydrous ethanol for 5 times. The mixture was placed in a vacuum oven at 60°C and dried for 24 h, and the result was recorded as amino-nano-silica.

[0072] The preparation method of phosphorus-based flame retardant is:

[0073] Under nitrogen protection, 5 g of bisphenol fluorene and 1 mL of triethylamine were added to 50 mL of dichloromethane, and stirred at 500 r / min for 10 min in a water bath at 10°C. Then, 1.5 g of phenylphosphoryl dichloride was added and stirred at 200 r / min for 10 h. The obtained white solid was dried in an oven at 50°C for 2 h and then ground through a 200-mesh sieve to obtain a phosphorus-based flame retardant.

[0074] The preparation steps of modified polyether TPU are:

[0075] Step 1, 60g of polyethylene glycol was placed in a vacuum dehydration condition at a temperature of 115°C and a vacuum degree of 133.3Pa for 2h, and then cooled to 70°C and poured into a flask, and 155g of toluene diisocyanate was added dropwise at a rate of 1 drop / s under stirring at a speed of 200r / min. After the addition was completed, the mixture was kept constant temperature in a water bath at 80°C for 2h, and the obtained mixture was recorded as the reaction component;

[0076] Step 2: Add 0.2 g of amino-modified nano-silica and 0.1 g of phosphorus-based flame retardant to 30 g of 1,4-butanediol, disperse them ultrasonically at a frequency of 28 kHz for 30 min, and then add them to the reaction components heated to 100 ° C and under vigorous stirring conditions at a speed of 600 r / min. After the addition, continue stirring for 10 min, pour it into a mold and place it in an oven at 110 ° C for aging for 10 hours to obtain a modified polyether TPU.

[0077] The phosphorus flame retardant is prepared from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and p-hydroxybenzaldehyde as raw materials, wherein the preparation steps of the phosphorus flame retardant are as follows:

[0078] Step A, weighing 13g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dissolving it in 100mL of dichloromethane, stirring at a speed of 500r / min for 30min, and recording it as the first component; weighing 6g of p-hydroxybenzaldehyde and dissolving it in 50mL of dichloromethane, and ultrasonically dispersing it at a frequency of 28kHz for 10min, and recording it as the second component;

[0079] Step B, pour the second component into the first component, stir at a speed of 300r / min for 5min, and react in a water bath at 80°C for 4h. After the reaction is completed, pour into a beaker, seal it, let it stand, separate into layers and dry in the shade, and the result is a phosphorus-based flame retardant.

[0080] The dopamine type flame retardant is prepared with nano silicon dioxide and dopamine hydrochloride as raw materials, wherein the preparation method of the dopamine type flame retardant is as follows:

[0081] To 200g of deionized water, 0.2g of nano-silicon dioxide, 0.25g of dopamine hydrochloride and 0.4g of tris(hydroxymethyl)aminomethane were added, and the mixture was stirred at 300r / min for 30min, and then a 10% sodium hydroxide solution was added dropwise to adjust the pH value to 9. After ultrasonic dispersion at a frequency of 23kHz for 5min, the mixture was placed at a constant temperature of 28°C and mechanically stirred at a speed of 200r / min for 8h. The mixture was centrifuged at a speed of 6000r / min for 5min to remove the filtrate, and then rinsed with deionized water 3 times. After drying in an oven at 55°C for 3h, the resulting mixture was a dopamine-type flame retardant.

[0082] A method for preparing a highly flame-retardant polyether TPU material, the preparation method comprising the following steps:

[0083] 100 parts by weight of modified polyether TPU were poured into a double-roll mill, and the milling was carried out for 3 minutes under the conditions that the front and rear roller temperatures were 110°C and 100°C respectively. After adding 6 parts by weight of phosphorus flame retardant, 8 parts by weight of dopamine flame retardant and 2 parts by weight of silane coupling agent KH-560, the milling was continued for 10 minutes. The material was triangularly packaged 10 times and then discharged. Finally, it was preheated on a flat vulcanizer at 170°C for 5 minutes, followed by hot pressing for 3 minutes and cold pressing for 2 minutes to remove from the mold. The result was a highly flame-retardant polyether TPU material.

[0084] Comparative Example 1

[0085] The highly flame-retardant polyether TPU material and the preparation method thereof provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in this comparative example 1, the modified polyether TPU in Example 1 is replaced with a polyether TPU.

[0086] Comparative Example 2

[0087] The highly flame-retardant polyether TPU material and the preparation method thereof provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in this comparative example 2, the phosphorus-based flame retardant in Example 1 is replaced with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0088] Comparative Example 3

[0089] The highly flame-retardant polyether TPU material and the preparation method thereof provided in this comparative example are substantially the same as those in Example 1, with the main difference being that in this comparative example 3, the dopamine flame retardant in Example 1 is replaced with nano-silicon dioxide.

[0090] Performance Testing

[0091] The highly flame-retardant polyether TPU materials prepared in Examples 1-3 and Comparative Examples 1-3 are marked as Example 1, Example 2, Example 3, Comparative Example 1, Comparative Example 2 and Comparative Example 3, respectively. Then, the performance of Examples 1-3 and Comparative Examples 1-3 is tested. The specific testing methods and test items are as follows:

[0092] 1. The tensile strength and elongation at break of Examples 1-3 and Comparative Examples 1-3 were tested according to the standard of GB / T528-1998, and the obtained data are recorded in the following table;

[0093] 2. The limiting oxygen index of Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard of GB / T2406-2009, and the obtained data were recorded in the following table;

[0094] 3. According to the standard of ANSI / UL-94-1985, vertical combustion test was carried out on Examples 1-3 and Comparative Examples 1-3. The size of the sample was 127 mm × 12 mm × 3 mm. The obtained data are recorded in the following table;

[0095]

[0096] It can be seen from the data in the above table that the mechanical properties of the high flame retardant polyether TPU materials in Examples 1-3 are significantly better than those in Comparative Example 1, indicating that the addition of amino-containing nano-silica and phosphorus-based flame retardants to the high flame retardant polyether TPU materials can improve the mechanical properties of TPU, and the limiting oxygen index of the high flame retardant polyether TPU materials in Examples 1-3 is significantly higher than that of Comparative Examples 1-3, indicating that the addition of phosphorus-based flame retardants and dopamine-type flame retardants can improve the flame retardant properties of TPU. In summary, the high flame retardant polyether TPU material prepared by the present invention has excellent market application prospects.

[0097] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the existence of other identical elements in the process, method, article or device including the elements.

[0098] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A highly flame retardant polyether TPU material, characterized in that: The highly flame-retardant polyether TPU material is composed of the following components: modified polyether TPU, phosphorus-based flame retardant, dopamine-based flame retardant and silane coupling agent KH-560; The modified polyether TPU is prepared with amino nano-silicon dioxide, phosphorus-based flame retardant, polyethylene glycol, toluene diisocyanate and 1,4-butanediol as raw materials; The phosphorus-based flame retardant is prepared using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and p-hydroxybenzaldehyde as raw materials; The preparation method of phosphorus-based flame retardant is: Under nitrogen protection, 5 g of bisphenol fluorene and 1 mL of triethylamine were added to 50 mL of dichloromethane, and stirred at 500 r / min for 10 min in a water bath at 10°C. Then, 1.5 g of phenylphosphoryl dichloride was added and stirred at 200 r / min for 10 h. The obtained white solid was placed in an oven at 50°C and dried for 2 h, and then ground through a 200-mesh sieve to obtain a phosphorus-based flame retardant. The preparation method of the dopamine type flame retardant is: To 200g of deionized water, add 0.2g of nano-silicon dioxide, 0.25g of dopamine hydrochloride and 0.4g of tris(hydroxymethyl)aminomethane, mix thoroughly, then add 10% by mass sodium hydroxide solution to adjust the pH value to 9. After ultrasonic dispersion, place it at a constant temperature of 28°C and stir it mechanically for 8h. After centrifugation to remove the filtrate, rinse it with deionized water 3 times, and dry it to obtain a dopamine flame retardant.

2. A highly flame retardant polyether TPU material according to claim 1, characterized in that: The preparation method of the amino-modified nano-silicon dioxide is as follows: 1 g of nano-silica was dispersed in 300 mL of anhydrous ethanol, and ultrasonically dispersed at a frequency of 26 kHz for 30 min, and then 2 mL of 3-aminopropyltriethoxysilane was added at a drop rate of 2 drops / s. After ultrasonic dispersion at a frequency of 27 kHz for 30 min, the mixture was placed in an oil bath at 60°C and stirred at a speed of 200 r / min for 6 h. The filtrate was removed by vacuum filtration and washed with anhydrous ethanol for 5 times. The mixture was placed in a vacuum oven at 60°C and dried for 24 h, and the result was recorded as amino-nano-silica.

3. A highly flame retardant polyether TPU material according to claim 1, characterized in that: The preparation steps of the modified polyether TPU are: Step 1, place 60g of polyethylene glycol at a temperature of 110-120°C and a vacuum degree of 133.3Pa for vacuum dehydration for 2h, cool to 70°C, pour into a flask, add 155g of toluene diisocyanate dropwise at a rate of 1 drop / s under stirring, keep constant temperature in a water bath at 80°C for 2h after the addition is completed, and the obtained result is recorded as the reaction component; Step 2: Add 0.2 g of amino-modified nano-silica and 0.1 g of phosphorus-based flame retardant to 30 g of 1,4-butanediol, disperse evenly by ultrasonication, and add to the reaction components heated to 100°C and under vigorous stirring conditions. After the addition, continue stirring for 10 minutes, pour into a mold, and place in an oven at 110°C for aging for 10 hours to obtain a modified polyether TPU.

4. A highly flame retardant polyether TPU material according to claim 3, characterized in that: The stirring speed in the stirring condition in step 1 is 200 r / min, the operation method for uniform ultrasonic dispersion in step 2 is ultrasonic dispersion at a frequency of 28 kHz for 30 minutes, and the stirring speed in the vigorous stirring condition in step 2 is 600 r / min.

5. A highly flame retardant polyether TPU material according to claim 1, characterized in that: The preparation steps of the phosphorus-based flame retardant are: Step A, weigh 13 g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and dissolve it in 100 mL of dichloromethane, stir and dissolve it as the first component, weigh 6 g of p-hydroxybenzaldehyde and dissolve it in 50 mL of dichloromethane, ultrasonically dissolve it as the second component; Step B, pour the second component into the first component and mix evenly, and react for 4 hours in a water bath at 80°C. After the reaction is completed, pour into a beaker, seal it, let it stand, stratify and dry in the shade, and the result is a phosphorus-based flame retardant.

6. A highly flame retardant polyether TPU material according to claim 5, characterized in that: The stirring and dissolving operation method in step A is stirring at a speed of 500 r / min for 30 min, the ultrasonic dissolution operation method in step A is ultrasonic dispersion at a frequency of 28 kHz for 10 min, and the uniform mixing operation method in step B is stirring at a speed of 300 r / min for 5 min.

7. A highly flame retardant polyether TPU material according to claim 1, characterized in that: In the preparation method of the dopamine flame retardant, the method of fully mixing is stirring at a speed of 300 r / min for 30 minutes, the method of ultrasonic dispersion is ultrasonic dispersion at a frequency of 23 kHz for 5 minutes, the speed of mechanical stirring is 200 r / min, the method of centrifugation is centrifugation at a speed of 6000 r / min for 5 minutes, and the method of drying is drying in an oven at 55°C for 3 hours.

8. A method for preparing a highly flame-retardant polyether TPU material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: Pour 100 parts by weight of modified polyether TPU into a double-roll mill, and grind for 2-3 minutes at the conditions where the front and rear roller temperatures are 110°C and 100°C respectively. Add 5-8 parts by weight of phosphorus flame retardant, 6-10 parts by weight of dopamine flame retardant and 1-2 parts by weight of silane coupling agent KH-560, and continue to grind for 10 minutes. Make triangle packages 10 times and then discharge the material. Finally, preheat on a flat vulcanizer at 170°C for 5 minutes, then hot press for 3 minutes, and then cold press for 2 minutes to remove from the mold. The resulting material is a highly flame-retardant polyether TPU material.

Images