Halogen-free flame-retardant TPU cable material and preparation method thereof

Abstract

The invention discloses a halogen-free flame-retardant TPU (thermoplastic polyurethane) cable material and a preparation method thereof, belongs to the technical field of TPU processing, and aims to solve the technical problem that the wear resistance and flame retardance of a TPU cable material in the prior art need to be further improved. The TPU cable material is prepared from the following raw material components in parts by weight: 80 to 100 parts of polyurethane elastomer, 1 to 2 parts of antioxidant, 1 to 3 parts of stabilizer, 10 to 15 parts of plasticizer, 10 to 20 parts of filler and 5 to 10 parts of flame-retardant glass powder. The TPU cable material is obtained by blending, melting and extruding the polyurethane elastomer, the flame-retardant glass powder and auxiliary materials; during combustion, flame-retardant groups in the polyurethane elastomer and the flame-retardant glass powder are decomposed to promote carbonization of triazine groups in the polyurethane elastomer to obtain a flame-retardant layer, and the TPU cable material is flame-retardant, wear-resistant, stretch-resistant, high-temperature-resistant and more environment-friendly through crosslinking of organic chain segments and synergistic cooperation of functional groups.

Description

Technical Field

[0001] The invention relates to the technical field of TPU processing, and in particular to a halogen-free flame-retardant TPU cable material and a preparation method thereof. Background Art

[0002] The research on halogen-free TPU cable materials began with concerns about the environmental impact and safety issues of the halogen content in traditional TPU materials. The earliest halogen-free formulations focused on reducing halogen compounds to meet regulatory and environmental requirements.

[0003] With the tightening of environmental protection regulations, halogen-free TPU materials have begun to gain widespread attention. The use of halogen-free flame retardants in the preparation process has improved the flame retardancy and high temperature resistance of the material, while maintaining the excellent flexibility and wear resistance of TPU. In recent years, halogen-free TPU cable materials have been widely used in electronics, automobiles, construction and other fields. Its environmental protection and safety performance make it the preferred material in application scenarios with high environmental protection requirements. At present, halogen-free TPU cable materials continue to make progress in material performance and environmental protection. New halogen-free flame retardants and improved production processes make halogen-free TPU cable materials perform better in applications requiring flexibility, high performance and long life.

[0004] Prior art CN113861664A discloses a wear-resistant and flame-retardant TPU material and a preparation method thereof, which is made of the following raw materials in parts by weight: 60-100 parts of polyurethane, 15-30 parts of epoxy resin, 3-10 parts of dichlorodiphenylamine methane, 20-50 parts of polyethylene, 10-28 parts of modified calcium sulfate dihydrate whiskers, 10-28 parts of a composite flame retardant, and 2-6 parts of silicone oil; the silicone oil and the modified calcium sulfate dihydrate whiskers are mixed evenly to obtain a mixture A, and then the polyurethane, epoxy resin, dichlorodiphenylamine methane, and polyethylene are mixed evenly to obtain a mixture B, and then the composite flame retardant is added to the mixture B, stirred evenly to obtain a mixture C, and finally the mixture A and the mixture C are mixed evenly to obtain the wear-resistant and flame-retardant TPU material.

[0005] That is, a modified calcium sulfate dihydrate whisker is prepared and blended with silicone oil, and a flame-retardant and wear-resistant TPU material is obtained by blending a large amount of auxiliary materials. However, this scheme improves the wear resistance and flame retardancy of TPU cable materials by enriching the raw material components of TPU cables. During the processing, due to the strong polarity of the modified calcium sulfate dihydrate whisker, it has poor compatibility with organic polyurethane. The incompatibility between the components will cause the wear resistance of the material to be significantly reduced. The obtained modified calcium sulfate dihydrate whisker will cause the TPU cable material to produce a wick effect during the combustion process, so that the molten resin under the carbon layer is drained to the combustion area, so that its flame retardancy is significantly reduced. At the same time, the low compatibility of inorganic materials and organic materials further aggravates the wick effect, so that the flame retardancy is further reduced.

[0006] In view of the technical defects in this aspect, a solution is now proposed. Summary of the invention

[0007] The object of the present invention is to provide a halogen-free flame-retardant TPU cable material and a preparation method thereof, so as to solve the technical problem that the wear resistance and flame retardancy of the TPU cable material in the prior art need to be further improved.

[0008] The object of the present invention can be achieved by the following technical scheme: a halogen-free flame-retardant TPU cable material, comprising the following raw material components in parts by weight: 80-100 parts of a polyurethane elastomer, 1-2 parts of an antioxidant, 1-3 parts of a stabilizer, 10-15 parts of a plasticizer, 10-20 parts of a filler and 5-10 parts of a flame-retardant glass powder;

[0009] The polyurethane elastomer is processed by the following steps:

[0010] A1. By weight, 1-3 parts of hydroxy silicone oil, 5-7 parts of 1,3,5-triazine-2,4-diol-6-amino, 0.5-0.8 parts of triethanolamine and 30-40 parts of dimethyl sulfoxide are added to a reactor and stirred. The temperature of the reactor is raised to 50-60° C., the stirring rate is 120-180 rpm, and after heat preservation and stirring for 10-15 minutes, 5-7 parts of p-phenylene diisocyanate are added to the reactor, and after heat preservation and reaction for 40-60 minutes, post-treatment is performed to obtain a polyurethane elastomer precursor;

[0011] A2. By weight, 10-20 parts of polyurethane elastomer precursor and 5-8 parts of chain extender are added to a reactor, the temperature of the reactor is raised to 50-60°C, and the reaction is kept warm for 20-40 minutes. Then, 3-5 parts of end-capping agent are added to the reactor, and the reaction is kept warm for 15-30 minutes, and then post-processed to obtain a polyurethane elastomer.

[0012] The reaction equation for preparing polyurethane elastomer is:

[0013]

[0014] Where:

[0015]

[0016]

[0017] The reaction principle for preparing the polyurethane elastomer is as follows: under the action of the catalyst triethanolamine, p-phenylene diisocyanate is used as a crosslinking agent, and the isocyanate group on the p-phenylene diisocyanate is used as an active group to polymerize with the hydroxyl groups on the hydroxyl silicone oil and the 1,3,5-triazine-2,4-diol-6-amino group to form a polyurethane elastomer precursor having a hydroxyl silicone oil segment and a 1,3,5-triazine-2,4-diol-6-amino segment. Further, a chain extender having a large number of hydroxyl groups is added to further react with the isocyanate groups on the polyurethane elastomer precursor, so that the polyurethane elastomer precursor is further crosslinked, and then a capping group is added, and finally the polyurethane elastomer is prepared by reaction.

[0018] Furthermore, in step A1, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80-100°C, and the reaction liquid is distilled under reduced pressure until no liquid is extracted to obtain a polyurethane elastomer precursor; in step A2, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80-100°C, and the reaction liquid is distilled under reduced pressure until no liquid is extracted to obtain a polyurethane elastomer.

[0019] Furthermore, in step A2, the preparation method of the chain extender is as follows: by weight, 8-12 parts of glycidyl ether, 2-4 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.5-0.8 parts of triethylamine and 40-50 parts of N,N-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 60-80°C, the reaction is kept warm for 1-3 hours, and the chain extender is obtained by post-treatment.

[0020] The reaction equation for preparing the chain extender is:

[0021]

[0022] Where:

[0023] The reaction principle for preparing the chain extender is: under alkaline conditions, the epoxy group in the glycidyl ether and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide undergo a ring-opening reaction, and finally a chain extender with a large number of polyhydroxyl groups is prepared.

[0024] Furthermore, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added into a rotary evaporator with a water bath temperature of 80-100° C., and the reaction liquid is distilled under reduced pressure until no liquid is extracted to obtain a chain extender.

[0025] Furthermore, in step A2, the preparation method of the end-capping agent is as follows: by weight, 10-15 parts of the end-capping group precursor, 3-4 parts of trimethoxysilane, 0.5-0.8 parts of chloroplatinic acid and 20-25 parts of xylene are added to a reactor, the temperature of the reactor is increased to 50-60° C., and the end-capping agent is obtained by post-treatment.

[0026] The reaction equation for preparing the capping agent is:

[0027]

[0028] Where:

[0029] The reaction principle for preparing the end-capping agent is: under the catalytic action of chloroplatinic acid, the unsaturated double bonds in the chain extender precursor and the silicon-hydrogen bonds in trimethoxysilane undergo a silicon-hydrogen addition reaction to prepare an end-capping agent with a single hydroxyl group.

[0030] Furthermore, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added into a rotary evaporator with a water bath temperature of 80-100° C., and the reaction liquid is distilled under reduced pressure until no liquid is extracted to obtain a capping agent.

[0031] Furthermore, the preparation method of the capping agent precursor is as follows: by weight, 6-8 parts of phosphated triazine derivatives, 2-4 parts of acetaldehyde, 1-2 parts of aluminum chloride and 40-60 parts of N,N-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 70-90°C, the reaction is kept warm for 1-3 hours, and the capping agent precursor is obtained by post-treatment.

[0032] The reaction equation for preparing the capping agent precursor is:

[0033]

[0034] The reaction principle for preparing the capping agent precursor is as follows: under the catalysis of Lewis acid, the secondary amino group in the aminated triazine derivative acts as a nucleophilic reagent to attack the carbonyl group in acetaldehyde, forming enamino groups, and finally obtaining a capping agent precursor with a large number of carbon-carbon double bonds.

[0035] Furthermore, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added into a rotary evaporator with a water bath temperature of 80-100° C., and distilled under reduced pressure until no liquid is extracted to obtain a capping agent precursor.

[0036] Furthermore, the preparation method of the phosphated triazine derivative is as follows: by weight, 3-4 parts of a modified triazine derivative, 4-8 parts of ethyl phenyl phosphate, 0.1-0.3 parts of chloroplatinic acid and 20-30 parts of NN-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 40-50°C, the reaction is kept warm for 1-2 hours, and post-processing is performed to obtain the phosphated triazine derivative.

[0037] The reaction equation for preparing phosphated triazine derivatives is:

[0038]

[0039] Where:

[0040] The reaction principle for preparing the phosphated triazine derivative is as follows: under the catalytic condition of chloroplatinic acid, the phosphorus-hydrogen bond in ethyl phenyl phosphate undergoes a phosphorus-hydrogen addition reaction and reacts with the imine bond in the modified triazine derivative to finally obtain the phosphated triazine derivative.

[0041] Furthermore, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added into a rotary evaporator with a water bath temperature of 80-100° C., and distilled under reduced pressure until no liquid is extracted to obtain a phosphorus triazine derivative.

[0042] Furthermore, the preparation method of the modified triazine derivative is as follows: by weight, 5-6 parts of triazine derivative, 12-16 parts of 2-methoxyphenylacetaldehyde, 1-2 parts of aluminum chloride and 40-60 parts of N,N-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 70-90° C., the reaction is kept warm for 1-3 hours, and the modified triazine derivative is obtained by post-treatment.

[0043] The reaction equation for preparing modified triazine derivatives is:

[0044]

[0045] Where:

[0046] The reaction principle for preparing modified triazine derivatives is as follows: under the catalysis of Lewis acid, the secondary amino group in the triazine derivative acts as a nucleophilic reagent to attack the carbonyl group in 2-methoxyphenylacetaldehyde to form an imine bond, and finally a modified triazine derivative with a large number of imine bonds is obtained.

[0047] Furthermore, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added into a rotary evaporator with a water bath temperature of 80-100° C., and the reaction liquid is distilled under reduced pressure until no liquid is extracted to obtain a modified triazine derivative.

[0048] Furthermore, the preparation method of the triazine derivative is as follows: by weight, 8-12 parts of 2-chloro-4,6-diamino-1,3,5-triazine, 4-6 parts of 1,3-diamino-2-hydroxypropane, 0.5-0.8 parts of sodium hydroxide powder and 40-50 parts of N,N-dimethylformamide are added to a reactor, the temperature of the reactor is lowered to 0-3°C, the reaction is kept warm for 2-3 hours, and the triazine derivative is obtained by post-treatment.

[0049] The reaction equation for preparing triazine derivatives is:

[0050]

[0051] The reaction principle for preparing triazine derivatives is as follows: under alkaline conditions, the amino group of 1,3-diamino-2-hydroxypropane acts as a nucleophile to replace the chlorine group on 2-chloro-4,6-diamino-1,3,5-triazine. At the same time, the lower reaction temperature limits the activity of the remaining side chains of triazine organic matter, blocking the occurrence of self-polymerization reaction, and finally the triazine derivatives are prepared. During the experiment, the structure of the triazine derivatives was determined by mass spectrometry analysis. The mass spectrometry analysis data of the triazine derivatives are: m / z: 308.16 (100.0%), 309.16 (10.0%), 309.15 (4.4%), 310.16 (1.1%).

[0052] Furthermore, the post-treatment includes: after the reactor is cooled to room temperature, the reaction liquid is added into a rotary evaporator with a water bath temperature of 80-100° C., and the mixture is distilled under reduced pressure until no liquid is extracted to obtain a triazine derivative.

[0053] Furthermore, the method for preparing the flame retardant glass powder comprises the following steps:

[0054] B1. Place glass powder in a tube furnace, introduce air, and heat the tube furnace to 400-600°C at a heating rate of 5°C / min, and keep the temperature for 1-2 hours. After the tube furnace is naturally cooled to room temperature, take out the glass powder, wash it with deionized water for 3-5 times, and air dry it naturally to obtain a modified glass powder precursor;

[0055] The reaction principle for preparing the modified glass powder precursor is as follows: calcining the glass powder at high temperature in air as the atmosphere promotes the oxidation reaction between the oxygen component in the air and the surface of the glass powder, increases the hydroxyl group on the surface of the glass powder, and removes the sizing agent on the surface of the glass powder, making the surface of the glass powder purer.

[0056] B2. Add 5-8 parts of modified glass powder precursor, 1-2 parts of vinyltrimethoxysilane, 10-15 parts of 1-3wt% sodium hydroxide solution and 20-30 parts of ethanol solution into a reactor by weight, raise the temperature of the reactor to 60-80° C., keep the reaction temperature for 1-2 hours, and post-treat to obtain modified glass powder;

[0057] The reaction principle for preparing the modified glass powder is as follows: under alkaline conditions, the siloxy groups of the silane coupling agent vinyltrimethoxysilane are hydrolyzed and react with the hydroxyl groups on the surface of the modified glass powder precursor to obtain the modified glass powder.

[0058] B3. By weight, 5-8 parts of modified glass powder, 2-3 parts of ethyl phenyl phosphate, 0.1-0.3 parts of chloroplatinic acid and 20-30 parts of NN-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 40-50°C, the reaction is kept warm for 1-2 hours, and flame-retardant glass powder is obtained by post-treatment.

[0059] The reaction principle for preparing the flame-retardant glass powder is as follows: under the catalytic conditions of chloroplatinic acid, the phosphorus-hydrogen bonds in ethyl phenyl phosphate undergo a phosphorus-hydrogen addition reaction and react with the carbon-carbon double bonds in the modified glass powder to finally obtain the flame-retardant glass powder.

[0060] Furthermore, in step B2, post-treatment includes: after the temperature of the reactor is lowered to room temperature, the reaction liquid is filtered to collect the filter cake, the filter cake is placed in a drying oven at a temperature of 80°C for vacuum drying, and the filter cake is dried until the filter cake has a constant weight to obtain a modified glass powder; in step B3, post-treatment includes: after the temperature of the reactor is lowered to room temperature, the reaction liquid is filtered to collect the filter cake, the filter cake is placed in a drying oven at a temperature of 80°C for vacuum drying, and the filter cake is dried until the filter cake has a constant weight to obtain a flame-retardant glass powder.

[0061] The present invention also provides a method for preparing a halogen-free flame-retardant TPU cable material, comprising the following steps:

[0062] S1. Evenly mix the polyurethane elastomer, antioxidant, stabilizer, plasticizer, filler and flame retardant glass powder to obtain a mixture;

[0063] S2. Add the mixed material into a twin-screw extruder. The temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 170°C, 175°C, 175°C, 180°C, 180°C, 190°C, and 190°C, respectively. The main engine speed of the twin-screw extruder is 80-120rpm, and the pressure is 100-150bar to obtain TPU cable material through melt extrusion.

[0064] Furthermore, the antioxidant is one or more of bis(2,4-di-tert-butylphenyl)ketone, hydrogenated dibenzothiophene and tri(3,5-di-tert-butyl-4-hydroxyphenyl)phosphate; the stabilizer is one or more of diphenyl(2,4-di-tert-butyl)pyran, bis(2,4-di-tert-butylphenyl)benzothiophene and 2,4-dichlorophenylfluorinated benzophenone; the plasticizer is one or more of di(2-ethylhexyl)phthalate, dibutylphthalate and di(2-ethylhexyl)phthalate; the filler is one or more of talc, calcium carbonate and kaolin.

[0065] The present invention has the following beneficial effects:

[0066] 1. In the process of preparing a halogen-free flame-retardant TPU cable material, the present invention first prepares a chain extender, which enriches the spatial structure of the polyurethane and enhances its tensile strength while introducing a phosphoric acid group to enhance the high temperature resistance of the polyurethane, and decomposes under the high temperature state of combustion to promote the dehydration of the triazine group on the polyurethane elastomer precursor to form a molten carbon layer, and the amino group on the triazine group decomposes to generate gas to promote the foaming of the carbon layer to obtain a flame-retardant carbon layer, thereby improving the flame retardant performance of the TPU cable material; the end-capping agent prepared further forms a stable structure at the end of the polyurethane elastomer precursor to obtain a polyurethane elastomer, thereby improving the fluidity of the polyurethane elastomer in the preparation process, reducing the internal unevenness, and further Improve its wear resistance, and the internal phosphate group improves its high temperature resistance and cooperates with the triazine group to obtain a flame-retardant carbon layer, further improving its high temperature resistance. The capping agent modified with a silane coupling agent improves its compatibility with inorganic auxiliary materials, further improving its wear resistance. Furthermore, the flame-retardant glass powder obtained by high-temperature calcination, silane coupling agent modification and modified flame retardant improves its cross-linking ability with polyurethane, while allowing molten polyurethane and other organic materials to form a carbon layer on the glass powder, thereby improving the flame retardant ability of the TPU cable material and enhancing its wear resistance. In summary, a wear-resistant, tensile-resistant, flame-retardant, environmentally friendly, and high-temperature resistant halogen-free TPU cable material is prepared through the synergistic cooperation between the components.

[0067] 2. In the process of preparing a polyurethane elastomer, the present invention selects hydroxy silicone oil, 1,3,5-triazine-2,4-diol-6-amino and p-phenylene diisocyanate as reaction monomers, wherein the siloxy group in the hydroxy silicone oil and the benzene ring in p-phenylene diisocyanate cooperate with each other to improve the high temperature resistance of the material and the wear resistance of the material, and the triazine group in 1,3,5-triazine-2,4-diol-6-amino is used as a flame retardant group to improve the flame retardancy of the material; in the process of preparing the end group, the present invention first obtains a triazine derivative by polymerizing 2-chloro-4,6-diamino-1,3,5-triazine and 1,3-diamino-2-hydroxypropane, and the triazine group is used as a flame retardant group to improve the flame retardancy of the material, and further The first step is to react with 2-methoxyphenylacetaldehyde to introduce a large number of ether bonds and imino groups into the chain segment. The ether bond improves the wear resistance and high temperature resistance of the chain segment, and the imine bond provides a functional group basis for further modification. The imine bond reacts with ethyl phenyl phosphate to introduce a phosphate group and a benzene ring into the chain segment. While the phosphate group cooperates with the benzene ring to improve the high temperature resistance of the organic chain segment, it decomposes under the combustion state to promote the carbonization of the triazine group in the chain segment to improve the flame retardant properties of the TPU cable material, and then further reacts with acetaldehyde to form an ene-amino bond. The ene-amino bond reacts with trimethoxysilane to introduce a silicon-oxygen bond into the chain segment to obtain a capping agent. While the silicon-oxygen bond improves the high temperature resistance of the organic chain segment, it also improves the compatibility of other inorganic materials, thereby further improving the wear resistance of the TPU cable material.

[0068] 3. In the process of preparing a polyurethane elastomer, the present invention obtains a chain extender with polyhydroxyl groups by polymerizing glycidyl ether and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which enhances the spatial structural complexity of the polyurethane elastomer, and the cross-linked flame retardant groups in the chain segments enhance the flame retardancy of the TPU cable material, and the large number of ether bonds inside enhance the high temperature resistance of the TPU cable material; in the process of preparing a flame retardant glass powder, the present invention first obtains a clean and surface-rich hydroxyl group by high-temperature calcination in an air atmosphere. The modified glass powder precursor is prepared by using a silane coupling agent to cross-link with the modified glass powder precursor under alkaline conditions to enhance its compatibility with organic materials. The alkaline conditions promote the hydrolysis of the silane coupling agent and react with the surface of the glass powder to enrich its surface structure and further modify the flame retardant functional groups. The molten organic material forms a carbon layer during the flow process, which prevents it from igniting the unburned part of the TPU cable and makes the flame retardant carbon layer more efficient and uniform. While enhancing the wear resistance of the TPU cable material, its flame retardant ability is further enhanced. DETAILED DESCRIPTION

[0069] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than 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.

[0070] The hydroxy silicone oil used in the present invention is purchased from Shandong Longhui Chemical Co., Ltd. and has a molecular weight of 500-600;

[0071] The glass powder used in the present invention is purchased from Hebei Jinghang Mineral Products Co., Ltd., and the product number is 52-965.

[0072] Example 1

[0073] This embodiment is used to provide a method for preparing a halogen-free flame-retardant TPU cable material, comprising the following steps:

[0074] S1. Preparation of chain extender

[0075] Weigh: 24.0g of glycidyl ether, 8.0g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1.2g of triethylamine and 90.0g of N,N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 60°C, keep the reaction for 1h, cool the reactor to room temperature, add the reaction solution into a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is extracted to obtain a functional cross-linking agent.

[0076] S2. Preparation of end-capping agent

[0077] Weigh: 4.0 g 2-chloro-4,6-diamino-1,3,5-triazine, 2.0 g 1,3-diamino-2-hydroxypropane, 0.2 g sodium hydroxide powder and 20.0 g N,N-dimethylformamide and add them into a reactor, lower the temperature of the reactor to 3°C, keep the temperature for 2 hours, cool the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is produced to obtain a triazine derivative;

[0078] Weigh: 3.0 g of a triazine derivative, 7.0 g of 2-methoxyphenylacetaldehyde, 0.6 g of aluminum chloride and 24.0 g of N,N-dimethylformamide and add them to a reactor. The temperature of the reactor is raised to 70° C. and the reaction is kept warm for 1 hour. After the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80° C. and distilled under reduced pressure until no liquid is produced to obtain a modified triazine derivative;

[0079] Weigh: 8.0 g of modified triazine derivative, 12.0 g of ethyl phenyl phosphate, 0.4 g of chloroplatinic acid and 50.0 g of N.N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 40°C, keep the temperature for 1 hour, cool the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is produced to obtain a phosphorylated triazine derivative;

[0080] Weigh: 16.0 g of a phosphorus triazine derivative, 4.0 g of acetaldehyde, 2.0 g of aluminum chloride and 80.0 g of N,N-dimethylformamide and add them to a reactor. The temperature of the reactor is raised to 70° C. and the reaction is kept warm for 1 hour. After the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80° C. and distilled under reduced pressure until no liquid is produced to obtain a capping agent precursor;

[0081] Weigh: 16.8g of chain extender precursor, 4.2g of trimethoxysilane, 0.8g of chloroplatinic acid and 30.0g of xylene are added to a reactor, the temperature of the reactor is raised to 50°C, and after the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 80°C, and distilled under reduced pressure until no liquid is extracted to obtain a capping agent.

[0082] S3. Preparation of polyurethane elastomer

[0083] Weigh: 8.0g hydroxy silicone oil, 32.0g 1,3,5-triazine-2,4-diol-6-amino, 2.4g triethanolamine and 120.0g dimethyl sulfoxide, add to the reactor and stir, the temperature of the reactor is raised to 50°C, the stirring rate is 120rpm, after stirring for 10min, add 32.0g p-phenylene diisocyanate to the reactor, keep warm and react for 40min, after the reactor is cooled to room temperature, add the reaction liquid to a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is extracted to obtain a polyurethane elastomer precursor;

[0084] Weigh: 60.0g of polyurethane elastomer precursor and 30.0g of chain extender are added to the reactor, the temperature of the reactor is raised to 50°C, and the reaction is kept warm for 20 minutes. Then, 18.0g of end-capping agent is added to the reactor. After the reaction is kept warm for 15 minutes, the reactor is cooled to room temperature, and the reaction liquid is added to a rotary evaporator with a water bath temperature of 80°C, and distilled under reduced pressure until no liquid is extracted to obtain a polyurethane elastomer.

[0085] S4. Preparation of flame-retardant glass powder

[0086] Weigh: 10.0 g of glass powder is placed in a tube furnace, air is introduced, and the temperature of the tube furnace is increased to 400° C. at a heating rate of 5° C. / min, and the temperature is kept for 1 hour. After the tube furnace is naturally cooled to room temperature, the glass powder is taken out and washed with deionized water for 3 times to obtain a modified glass powder precursor;

[0087] Weigh: 7.5g of modified glass powder precursor, 1.5g of vinyltrimethoxysilane, 10.0g of 1wt% sodium hydroxide solution and 20.0g of ethanol solution, add them into a reactor, raise the temperature of the reactor to 60°C, keep the temperature for 1h, lower the temperature of the reactor to room temperature, filter the reaction liquid to collect the filter cake, place the filter cake in a drying oven at 80°C for vacuum drying, and dry until the filter cake has a constant weight to obtain a modified glass powder;

[0088] Weigh: 6.9g modified glass powder, 4.1g ethyl phenyl phosphate, 0.3g chloroplatinic acid and 35.0g N.N-dimethylformamide, add into the reactor, raise the temperature of the reactor to 40°C, keep warm for 1h, lower the temperature of the reactor to room temperature, filter the reaction liquid and collect the filter cake, place the filter cake in a drying oven at 80°C for vacuum drying, dry until the filter cake has constant weight, and obtain flame-retardant glass powder.

[0089] S5. Preparation of TPU cable material

[0090] Weigh: 90.0 g of polyurethane elastomer, 1.5 g of bis(2,4-di-tert-butylphenyl)ketone, 2.4 g of diphenyl(2,4-di-tert-butyl)pyran, 12.0 g of diisooctyl phthalate, 12.0 g of talc and 8.0 g of flame-retardant glass powder, add into a reaction kettle and mix evenly to obtain a mixture;

[0091] The mixed material is added into a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed port toward the discharge port are 170°C, 175°C, 175°C, 180°C, 180°C, 190°C, and 190°C, respectively. The main engine speed of the twin-screw extruder is 80 rpm, and the pressure is 100 bar. TPU cable material is obtained by melt extrusion.

[0092] Example 2

[0093] This embodiment is used to provide a method for preparing a halogen-free flame-retardant TPU cable material, comprising the following steps:

[0094] S1. Preparation of chain extender

[0095] Weigh: 20.0g of glycidyl ether, 8.0g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1.2g of triethylamine and 80.0g of N,N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 80°C, and keep the reaction for 3h. After the reactor is cooled to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is extracted to obtain a functional cross-linking agent.

[0096] S2. Preparation of end-capping agent

[0097] Weigh: 2.0 g 2-chloro-4,6-diamino-1,3,5-triazine, 1.0 g 1,3-diamino-2-hydroxypropane, 0.1 g sodium hydroxide powder and 10.0 g N,N-dimethylformamide and add them into a reactor, lower the temperature of the reactor to 1°C, keep the temperature for 3 hours, cool the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is produced to obtain a triazine derivative;

[0098] Weigh: 1.5 g of a triazine derivative, 4.5 g of 2-methoxyphenylacetaldehyde, 0.5 g of aluminum chloride and 18.0 g of N,N-dimethylformamide, add them into a reactor, raise the temperature of the reactor to 90°C, keep the temperature for 3 hours, cool the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is produced to obtain a modified triazine derivative;

[0099] Weigh: 4.5 g of modified triazine derivative, 10.5 g of ethyl phenyl phosphate, 0.4 g of chloroplatinic acid and 36.0 g of N.N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 50°C, keep the temperature for 2 hours, cool the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 100°C, and distill under reduced pressure until no liquid is produced to obtain a phosphorylated triazine derivative;

[0100] Weigh: 10.8 g of a phosphorus triazine derivative, 7.2 g of acetaldehyde, 2.7 g of aluminum chloride and 90.0 g of N,N-dimethylformamide and add them to a reactor. The temperature of the reactor is raised to 90° C. and the reaction is kept warm for 3 hours. After the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 100° C. and distilled under reduced pressure until no liquid is produced to obtain a capping agent precursor;

[0101] Weigh: 15.0g of chain extender precursor, 5.0g of trimethoxysilane, 0.8g of chloroplatinic acid and 30.0g of xylene are added to a reactor, the temperature of the reactor is raised to 60°C, and after the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 100°C, and distilled under reduced pressure until no liquid is extracted to obtain a capping agent.

[0102] S3. Preparation of polyurethane elastomer

[0103] Weigh: 9.0g hydroxy silicone oil, 31.5g 1,3,5-triazine-2,4-diol-6-amino, 0.8g triethanolamine and 157.5g dimethyl sulfoxide, add to the reactor and stir, the temperature of the reactor is raised to 60°C, the stirring rate is 180rpm, after stirring for 15min, add 31.5g p-phenylene diisocyanate to the reactor, keep warm and react for 60min, after the reactor is cooled to room temperature, add the reaction liquid to a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is produced to obtain a polyurethane elastomer precursor;

[0104] Weigh: 64.8g of polyurethane elastomer precursor and 26.0g of chain extender are added to the reactor, the temperature of the reactor is raised to 60°C, and the reaction is kept warm for 40 minutes. Then, 17.2g of end-capping agent is added to the reactor. After the reaction is kept warm for 30 minutes, the reactor is cooled to room temperature, and the reaction liquid is added to a rotary evaporator with a water bath temperature of 100°C, and distilled under reduced pressure until no liquid is extracted to obtain a polyurethane elastomer.

[0105] S4. Preparation of flame-retardant glass powder

[0106] Weigh: 10.0 g of glass powder is placed in a tube furnace, air is introduced, and the tube furnace is heated to 600° C. at a heating rate of 5° C. / min and kept warm for 2 h. After the tube furnace is naturally cooled to room temperature, the glass powder is taken out and washed with deionized water for 5 times to obtain a modified glass powder precursor;

[0107] Weigh: 9.6 g of modified glass powder precursor, 2.4 g of vinyltrimethoxysilane, 15.0 g of 3 wt% sodium hydroxide solution and 24.0 g of ethanol solution, add them into a reactor, raise the temperature of the reactor to 90° C., keep the temperature for 2 h, lower the temperature of the reactor to room temperature, filter the reaction liquid to collect the filter cake, place the filter cake in a drying oven at 80° C. and dry it under vacuum until the filter cake has a constant weight, to obtain a modified glass powder;

[0108] Weigh: 9.6g modified glass powder, 2.4g ethyl phenyl phosphate, 0.3g chloroplatinic acid and 24.0g N.N-dimethylformamide, add into the reactor, raise the temperature of the reactor to 50°C, keep warm for 2h, lower the temperature of the reactor to room temperature, filter the reaction liquid and collect the filter cake, place the filter cake in a drying oven at 80°C for vacuum drying, dry until the filter cake has constant weight, and obtain flame-retardant glass powder.

[0109] S5. Preparation of TPU cable material

[0110] Weigh 85.0 g of polyurethane elastomer, 1.6 g of bis(2,4-di-tert-butylphenyl)ketone, 2.4 g of diphenyl(2,4-di-tert-butyl)pyran, 12.0 g of diisooctyl phthalate, 16.0 g of talc and 8.4 g of flame-retardant glass powder, add them into a reaction kettle and mix them evenly to obtain a mixture;

[0111] The mixed material is added into a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed port toward the discharge port are 170°C, 175°C, 175°C, 180°C, 180°C, 190°C, and 190°C, respectively. The main engine speed of the twin-screw extruder is 120 rpm and the pressure is 150 bar. TPU cable material is obtained by melt extrusion.

[0112] Example 3

[0113] This embodiment is used to provide a method for preparing a halogen-free flame-retardant TPU cable material, comprising the following steps:

[0114] S1. Preparation of chain extender

[0115] Weigh: 27.0g of glycidyl ether, 9.0g of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 1.8g of triethylamine and 120.0g of N,N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 70°C, and keep the reaction for 2h. After the reactor is cooled to room temperature, add the reaction solution into a rotary evaporator with a water bath temperature of 90°C, and distill under reduced pressure until no liquid is extracted to obtain a functional cross-linking agent.

[0116] S2. Preparation of end-capping agent

[0117] Weigh: 2.5 g 2-chloro-4,6-diamino-1,3,5-triazine, 1.5 g 1,3-diamino-2-hydroxypropane, 0.2 g sodium hydroxide powder and 12.5 g N,N-dimethylformamide and add them into a reactor, lower the temperature of the reactor to 0°C, keep the temperature for 3 hours, cool the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 90°C, and distill under reduced pressure until no liquid is produced to obtain a triazine derivative;

[0118] Weigh: 2.4 g of a triazine derivative, 5.6 g of 2-methoxyphenylacetaldehyde, 0.4 g of aluminum chloride and 20.0 g of N,N-dimethylformamide and add them to a reactor, raise the temperature of the reactor to 80°C, and keep the temperature for 2 hours. After the reactor is cooled to room temperature, add the reaction liquid to a rotary evaporator with a water bath temperature of 90°C, and distill under reduced pressure until no liquid is produced to obtain a modified triazine derivative;

[0119] Weigh: 6.0 g of modified triazine derivative, 9.0 g of ethyl phenyl phosphate, 0.4 g of chloroplatinic acid and 36.0 g of N.N-dimethylformamide and add them into a reactor, raise the temperature of the reactor to 45°C, keep the temperature for 1 hour, cool the reactor to room temperature, add the reaction liquid into a rotary evaporator with a water bath temperature of 90°C, and distill under reduced pressure until no liquid is produced to obtain a phosphorylated triazine derivative;

[0120] Weigh: 12.0 g of a phosphorus triazine derivative, 6.0 g of acetaldehyde, 1.2 g of aluminum chloride and 80.0 g of N,N-dimethylformamide and add them to a reactor. The temperature of the reactor is raised to 80° C. and the reaction is kept warm for 2 hours. After the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 90° C. and distilled under reduced pressure until no liquid is produced to obtain a capping agent precursor;

[0121] Weigh: 14.0g of chain extender precursor, 4.0g of trimethoxysilane, 0.6g of chloroplatinic acid and 24.0g of xylene are added to a reactor, the temperature of the reactor is raised to 55°C, and after the reactor is cooled to room temperature, the reaction liquid is added to a rotary evaporator with a water bath temperature of 90°C, and distilled under reduced pressure until no liquid is extracted to obtain a capping agent.

[0122] S3. Preparation of polyurethane elastomer

[0123] Weigh: 8.0g hydroxy silicone oil, 28.0g 1,3,5-triazine-2,4-diol-6-amino, 1.2g triethanolamine and 72.0g dimethyl sulfoxide, add to the reactor and stir, the temperature of the reactor is raised to 55°C, the stirring rate is 150rpm, after stirring for 12min, add 28.0g p-phenylene diisocyanate to the reactor, keep warm and react for 50min, after the reactor is cooled to room temperature, add the reaction liquid to a rotary evaporator with a water bath temperature of 80°C, and distill under reduced pressure until no liquid is extracted to obtain a polyurethane elastomer precursor;

[0124] Weigh: 60.0g of polyurethane elastomer precursor and 32.0g of chain extender are added to the reactor, the temperature of the reactor is raised to 55°C, and the reaction is kept warm for 30 minutes. Then, 16.0g of end-capping agent is added to the reactor. After the reaction is kept warm for 24 minutes, the reactor is cooled to room temperature, and the reaction liquid is added to a rotary evaporator with a water bath temperature of 90°C, and distilled under reduced pressure until no liquid is extracted to obtain a polyurethane elastomer.

[0125] S4. Preparation of flame-retardant glass powder

[0126] Weigh: 10.0 g of glass powder is placed in a tube furnace, air is introduced, and the tube furnace is heated to 500° C. at a heating rate of 5° C. / min and kept warm for 2 h. After the tube furnace is naturally cooled to room temperature, the glass powder is taken out and washed with deionized water for 4 times to obtain a modified glass powder precursor;

[0127] Weigh: 8.0 g of modified glass powder precursor, 2.0 g of vinyltrimethoxysilane, 12.0 g of 2 wt% sodium hydroxide solution and 24.0 g of ethanol solution, add them into a reactor, raise the temperature of the reactor to 70° C., keep the temperature for 2 h, lower the temperature of the reactor to room temperature, filter the reaction liquid to collect the filter cake, place the filter cake in a drying oven at 80° C. and dry it under vacuum until the filter cake has a constant weight, to obtain a modified glass powder;

[0128] Weigh: 8.4g modified glass powder, 3.6g phenyl ethyl phosphate, 0.2g chloroplatinic acid and 36.0g N.N-dimethylformamide, add into the reactor, raise the temperature of the reactor to 45°C, keep warm for 2h, lower the temperature of the reactor to room temperature, filter the reaction liquid and collect the filter cake, place the filter cake in a drying oven at 80°C for vacuum drying, dry until the filter cake has constant weight, and obtain flame retardant glass powder.

[0129] S5. Preparation of TPU cable material

[0130] Weigh: 100.0 g of polyurethane elastomer, 1.8 g of bis(2,4-di-tert-butylphenyl)ketone, 2.4 g of diphenyl(2,4-di-tert-butyl)pyran, 12.0 g of diisooctyl phthalate, 16.0 g of talc and 10.0 g of flame-retardant glass powder, add into a reaction kettle and mix evenly to obtain a mixture;

[0131] The mixed material is added into a twin-screw extruder. The temperatures of the eight temperature zones of the twin-screw extruder from the feed port toward the discharge port are 170°C, 175°C, 175°C, 180°C, 180°C, 190°C, and 190°C, respectively. The main engine speed of the twin-screw extruder is 100 rpm and the pressure is 120 bar. TPU cable material is obtained by melt extrusion.

[0132] Comparative Example 1

[0133] The difference between this comparative example and Example 3 is that step S1 is omitted, and in step S3, the use of a chain extender is omitted.

[0134] Comparative Example 2

[0135] The difference between this comparative example and Example 3 is that step S2 is eliminated, and in step S3, the use of the end-capping agent is eliminated.

[0136] Comparative Example 3

[0137] The difference between this comparative example and Example 3 is that step S4 is eliminated, and in step S5, an equal amount of glass powder is used to replace the flame-retardant glass powder.

[0138] Performance Testing:

[0139] The volume abrasion loss of the TPU cable materials prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 9867-2008 "Determination of wear resistance of vulcanized rubber or thermoplastic rubber (rotating roller abrader method)";

[0140] The vertical burning grade and smoke density grade of the TPU cable materials prepared in Examples 1-3 and Comparative Examples 1-3 were measured with reference to the standard GB / T 26526-2011 "Specification for Low-smoke Halogen-free Flame-retardant Materials of Thermoplastic Elastomers";

[0141] The limiting oxygen index of the TPU cable materials prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 26526-2011 "Determination of Combustion Behavior of Plastics by Oxygen Index Method Part 2: Room Temperature Test";

[0142] The strip TPU cable material was placed in a drying oven at a temperature of 160 degrees Celsius for 120 hours, and then the strip TPU cable material was used to wrap the plastic tube to measure the number of windings. The TPU cable material was placed in a drying oven at a temperature of 120°C and heat-treated for 36 days, and then the cracking of the TPU cable material was checked. The high temperature resistance of the TPU cable materials prepared in Examples 1-3 and Comparative Examples 1-3 was tested.

[0143] The tensile strength of the TPU cable materials prepared in Examples 1-3 and Comparative Examples 1-3 was tested with reference to the standard GB / T 528-2009 “Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber”. The specific results are shown in Table 1.

[0144] Table 1-Performance test data of each sample

[0145]

[0146] Data Analysis:

[0147] Comparing and analyzing the data in Table 1 above, the volume wear of the TPU cable material prepared by the present invention is 43mm 3 , the limiting oxygen index is 39.3%, the vertical combustion level is V-0, the smoke density level is 32.4, the number of windings after high temperature treatment is 7, and the tensile strength reaches 54.5MPa without cracking after 120℃ insulation treatment for 36 days. All data are better than the comparative example;

[0148] It is explained that the chain extender prepared from glycidyl ether and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide in the present invention enhances the spatial complexity of the organic chain segment, and the decomposition of the flame retardant groups on the chain segment under the combustion state promotes the carbonization of the end groups and the triazine groups on the polyurethane elastomer, thereby enhancing the flame retardancy of the TPU cable. The flame retardant glass powder obtained by modifying the glass powder also cooperates with the polyurethane elastomer to enhance the flame retardancy and wear resistance of the TPU cable material, and finally a wear-resistant, tensile-resistant, flame-retardant, environmentally friendly, and high-temperature resistant halogen-free TPU cable is prepared.

[0149] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

[0150] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0151] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A halogen-free flame-retardant TPU cable material, characterized in that: The invention comprises the following raw material components in parts by weight: 80-100 parts of polyurethane elastomer, 1-2 parts of antioxidant, 1-3 parts of stabilizer, 10-15 parts of plasticizer, 10-20 parts of filler and 5-10 parts of flame retardant glass powder; The polyurethane elastomer is processed by the following steps: A1. By weight, 1-3 parts of hydroxy silicone oil, 5-7 parts of 1,3,5-triazine-2,4-diol-6-amino, 0.5-0.8 parts of triethanolamine and 30-40 parts of dimethyl sulfoxide are added to a reactor and stirred. The temperature of the reactor is raised to 50-60° C., the stirring rate is 120-180 rpm, and after stirring for 10-15 minutes, 5-7 parts of p-phenylene diisocyanate are added to the reactor, and the reaction is carried out for 40-60 minutes. The polyurethane elastomer precursor is obtained by post-treatment; A2. By weight, 10-20 parts of polyurethane elastomer precursor and 5-8 parts of chain extender are added to a reactor, the temperature of the reactor is raised to 50-60°C, and the reaction is kept warm for 20-40 minutes. Then, 3-5 parts of end-capping agent are added to the reactor, and the reaction is kept warm for 15-30 minutes, and then post-processed to obtain a polyurethane elastomer.

2. The halogen-free flame-retardant TPU cable material according to claim 1, characterized in that: In step A2, the preparation method of the chain extender is as follows: by weight, 8-12 parts of glycidyl ether, 2-4 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.5-0.8 parts of triethylamine and 40-50 parts of N,N-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 60-80° C., the reaction is kept warm for 1-3 hours, and the chain extender is obtained by post-treatment.

3. The halogen-free flame-retardant TPU cable material according to claim 1, characterized in that: In step A2, the preparation method of the end-capping agent is as follows: by weight, 10-15 parts of the end-capping group precursor, 3-4 parts of trimethoxysilane, 0.5-0.8 parts of chloroplatinic acid and 20-25 parts of xylene are added to a reactor, the temperature of the reactor is increased to 50-60° C., and the end-capping agent is obtained by post-treatment.

4. The halogen-free flame-retardant TPU cable material according to claim 3, characterized in that: The preparation method of the capping agent precursor is as follows: by weight, 6-8 parts of phosphated triazine derivatives, 2-4 parts of acetaldehyde, 1-2 parts of aluminum chloride and 40-60 parts of N,N-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 70-90°C, the reaction is kept warm for 1-3 hours, and the capping agent precursor is obtained by post-treatment.

5. The halogen-free flame-retardant TPU cable material according to claim 4, characterized in that: The preparation method of the phosphorylated triazine derivative is as follows: by weight, 3-4 parts of a modified triazine derivative, 4-8 parts of ethyl phenyl phosphate, 0.1-0.3 parts of chloroplatinic acid and 20-30 parts of NN-dimethylformamide are added to a reaction kettle, the temperature of the reaction kettle is increased to 40-50° C., the reaction is kept warm for 1-2 hours, and the phosphorylated triazine derivative is obtained by post-treatment.

6. The halogen-free flame-retardant TPU cable material according to claim 5, characterized in that: The preparation method of the modified triazine derivative is as follows: by weight, 5-6 parts of triazine derivative, 12-16 parts of 2-methoxyphenylacetaldehyde, 1-2 parts of aluminum chloride and 40-60 parts of N,N-dimethylformamide are added into a reaction kettle, the temperature of the reaction kettle is increased to 70-90° C., the reaction is kept warm for 1-3 hours, and the modified triazine derivative is obtained by post-treatment.

7. The halogen-free flame-retardant TPU cable material according to claim 6, characterized in that: The preparation method of the triazine derivative is as follows: by weight, 8-12 parts of 2-chloro-4,6-diamino-1,3,5-triazine, 4-6 parts of 1,3-diamino-2-hydroxypropane, 0.5-0.8 parts of sodium hydroxide powder and 40-50 parts of N,N-dimethylformamide are added into a reaction kettle, the temperature of the reaction kettle is lowered to 0-3°C, the reaction is kept warm for 2-3 hours, and the triazine derivative is obtained by post-treatment.

8. The halogen-free flame-retardant TPU cable material according to claim 1, characterized in that: The method for preparing the flame retardant glass powder comprises the following steps: B1. Place glass powder in a tube furnace, introduce air, and heat the tube furnace to 400-600°C at a heating rate of 5°C / min, and keep the temperature for 1-2 hours. After the tube furnace is naturally cooled to room temperature, take out the glass powder, wash it with deionized water for 3-5 times, and air dry it naturally to obtain a modified glass powder precursor; B2. Add 5-8 parts of modified glass powder precursor, 1-2 parts of vinyltrimethoxysilane, 10-15 parts of 1-3wt% sodium hydroxide solution and 20-30 parts of ethanol solution into a reactor by weight, raise the temperature of the reactor to 60-80°C, keep the reaction temperature for 1-2h, and post-treat to obtain modified glass powder; B3. By weight, 5-8 parts of modified glass powder, 2-3 parts of ethyl phenyl phosphate, 0.1-0.3 parts of chloroplatinic acid and 20-30 parts of NN-dimethylformamide are added to a reactor, the temperature of the reactor is increased to 40-50°C, the reaction is kept warm for 1-2 hours, and flame-retardant glass powder is obtained by post-treatment.

9. A halogen-free flame-retardant TPU cable material and a preparation method thereof as claimed in any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Evenly mixing a polyurethane elastomer, an antioxidant, a stabilizer, a plasticizer, a filler and a flame retardant glass powder to obtain a mixture; S2. Add the mixed material into a twin-screw extruder. The temperatures of the eight temperature sections of the twin-screw extruder from the feed port to the discharge port are 170°C, 175°C, 175°C, 180°C, 180°C, 190°C, and 190°C, respectively. The main engine speed of the twin-screw extruder is 80-120rpm, and the pressure is 100-150 bar to obtain TPU cable material through melt extrusion.

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