Highly flame retardant tpe material and preparation method thereof

Abstract

The application discloses a kind of high flame-retardant tpe materials and preparation method thereof, by polytetrahydrofuran, modified monomer and 4,4'-dicyclohexyl methane diisocyanate are reacted, chain extension is used with 1,4-butanediol, finally join flame-retardant additive, form branched structure, and the molecular structure of the pte material is branched structure, and molecular chain segment contains organic silicon composite organic phosphorus structure, when heat decomposition, can generate phosphoric acid, poly-metaphosphoric acid and other acidic substances, these acidic substances will catalyze pte molecule to occur dehydration reaction, accelerate its crosslinking, organic silicon chain segment will produce inorganic silicate or silicon-carbon, and then form a dense carbon layer on the surface of material, can heat insulation and oxygen isolation, prevent combustible gas to escape outward and oxygen diffusion inward, and slow down the further thermal decomposition of internal material, prevent carbon layer from being burnt through or collapse under high temperature, improve the durability of barrier, so that pte material has good flame-retardant effect.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of tpe material preparation, in particular to a high-flame-retardant tpe material and a preparation method thereof. BACKGROUND

[0002] With the development of modern industry, thermoplastic elastomers are widely used in various fields such as automobiles, electronics, construction, etc. due to their good physical properties and processing performance. However, traditional thermoplastic elastomers have a major problem: their flame retardant performance is poor, and they are prone to burning in high-temperature or flame environments, which not only increases the safety hazard, but also limits their expansion in certain key application fields. Therefore, developing thermoplastic elastomer materials with superior flame retardant performance has become an important research direction. Such materials not only need to maintain their original excellent physical and mechanical properties, such as good elasticity and strength, but also need to effectively suppress flame spread and reduce the amount of harmful smoke released during combustion to ensure the safety of personnel and equipment. SUMMARY

[0003] The application aims to provide a high-flame-retardant tpe material and a preparation method thereof, which solves the problem of poor flame retardant effect of tpe materials at the present stage.

[0004] The object of the application can be achieved by the following technical solutions:

[0005] A preparation method of a high-flame-retardant tpe material, specifically comprising the following steps:

[0006] Step A1: uniformly mix phosphonic acid monophenyl ester, pyridine, 4-dimethylaminopyridine and tetrahydrofuran, protect with nitrogen, stir at a rotation speed of 150-200 r / min and a temperature of 0-5 DEG C, and then add dimethylchlorosilane, heat to 50-60 DEG C, and react for 15-18 h to obtain an intermediate;

[0007] Step A2: mix the intermediate, allyl alcohol, chloroplatinic acid and DMF, protect with nitrogen, react at a rotation speed of 200-300 r / min and a temperature of 80-85 DEG C for 6-8 h to obtain a modified monomer;

[0008] Step A3: mix polytetrahydrofuran, the modified monomer and 4,4'-dicyclohexyl methane diisocyanate, react at a rotation speed of 120-150 r / min and a temperature of 80-85 DEG C for 2-3 h, then add 1,4-butanediol and continue to react for 2-3 h, add a flame retardant additive and continue to react for 4-6 h to obtain the high-flame-retardant tpe material.

[0009] Further, the molar ratio of the monophenyl phosphate, pyridine, 4-dimethylamino pyridine and dimethyl chlorosilane in step A1 is 1:2.5:0.2:2.2.

[0010] Further, the molar ratio of the intermediate and allyl alcohol in step A2 is 1:2, and the amount of chloroplatinic acid is 0.01% of the mass of the allyl alcohol.

[0011] Further, the molar ratio of the polytetrahydrofuran, modified monomer, 4,4'-dicyclohexyl methane diisocyanate, 1,4-butanediol and flame retardant additive in step A3 is 30:10:60:10:0.5.

[0012] Further, the flame retardant additive is prepared by the following steps:

[0013] Step B1: mix dimethyl vinyl silanol lithium and tetrahydrofuran uniformly, protect with nitrogen, stir at a rotation speed of 120-150 r / min and a temperature of 0°C, add tetramethylcyclotetrasiloxane, warm to 20-25°C, react for 8-10 h, add γ-chloropropyltrichlorosilane, react for 2-3 h, prepare branched polysiloxane, add DOPO to the reaction kettle, protect with nitrogen, stir at a rotation speed of 60-80 r / min and a temperature of 120-125°C, add magnolol, warm to 160-165°C, react for 20-25 h, prepare the modifier;

[0014] Step B2: mix the branched polysiloxane, modifier, triethylamine and DMF, react for 3-5 h at a rotation speed of 200-300 r / min and a temperature of 35-40°C, prepare the functionalized polysiloxane, mix 1-oxyl phosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and tetrahydrofuran uniformly, protect with nitrogen, stir at a rotation speed of 150-200 r / min and a temperature of 0-5°C, add acryloyl chloride, react for 4-6 h, prepare the modified flame retardant;

[0015] Step B3: mix the functionalized polysiloxane, thio glycerol, benzophenone and DMF uniformly, react for 2-3 h at a rotation speed of 200-300 r / min, a temperature of 20-25°C and under ultraviolet light irradiation, prepare the modified polysiloxane, mix the modified polysiloxane, modified flame retardant, chloroplatinic acid and DMF, protect with nitrogen, react for 8-10 h at a rotation speed of 150-200 r / min and a temperature of 80-85°C, prepare the flame retardant additive.

[0016] Further, the molar ratio of the Si-Cl bond on dimethylvinylsilanol lithium, tetramethylcyclotetrasiloxane and gamma-chloropropyltrichlorosilane in step B1 is 1:3:1, and the molar ratio of DOPO and magnolol is 2:1.

[0017] Further, the molar ratio of the branched polysiloxane, the modifier and triethylamine in step B2 is 2:1:2.1, and the molar ratio of 1-oxylphosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and acryloyl chloride is 1:1.1:1.2.

[0018] Further, the molar ratio of the double bond on the functionalized polysiloxane and thio glycerol in step B3 is 1:1, the amount of benzophenone is 0.1% of the mass of thio glycerol, the molar ratio of the Si-H bond on the modified polysiloxane and the modified flame retardant is 1:1, and the amount of chloroplatinic acid is 0.01% of the mass of the modified flame retardant.

[0019] The present application has the following advantages: the high flame-retardant tpe material prepared by the present application uses monophenyl phosphate as raw material and reacts with dimethylchlorosilane to make the P-OH bond on monophenyl phosphate and the Si-Cl bond on dimethylchlorosilane react, to prepare an intermediate, reacts the intermediate with allyl alcohol to make the Si-H bond on the intermediate and the double bond on allyl alcohol react, to prepare a modified monomer, reacts polytetrahydrofuran, the modified monomer and 4,4'-dicyclohexyl methane diisocyanate, then uses 1,4-butanediol to chain extend, finally adds a flame-retardant additive to form a branched structure, to prepare a tpe material.

[0020] The flame-retardant additive uses dimethylvinylsilanol lithium as an initiator, tetramethylcyclotetrasiloxane as a polymerization monomer to form a polysiloxane structure with one end being a double bond and the other end being silanol lithium, then adds gamma-chloropropyltrichlorosilane to make the Si-Cl bond on gamma-chloropropyltrichlorosilane and silanol lithium react, to prepare a branched polysiloxane, reacts DOPO and magnolol to make the P-H bond on DOPO and the double bond on magnolol react, to prepare a modifier, reacts the branched polysiloxane and the modifier to make the C-Cl on the branched polysiloxane and the phenolic hydroxyl on the modifier react, to prepare a functionalized polysiloxane, reacts 1-oxylphosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane and acryloyl chloride to make the hydroxyl on 1-oxylphosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane and the acyl chloride on acryloyl chloride react, to prepare a modified flame retardant, reacts the functionalized polysiloxane and thio glycerol under ultraviolet light to make the double bond on the functionalized polysiloxane and the mercapto group on thio glycerol react, to prepare a modified polysiloxane, and reacts the modified polysiloxane and the modified flame retardant to make the Si-H bond on the modified polysiloxane and the double bond on the modified flame retardant react, to prepare a flame-retardant additive.

[0021] The molecular structure of the PTE material is a branched structure, and the molecular chain segment contains an organic silicon composite organic phosphorus structure. When decomposed by heat, the PTE material can generate acidic substances such as phosphoric acid and poly-metaphosphoric acid. These acidic substances can catalyze the dehydration reaction of the PTE molecules, accelerate the crosslinking of the PTE molecules, and the organic silicon chain segment can generate inorganic silicate or silicon-carbon, and then form a dense carbon layer on the surface of the material. The carbon layer can isolate heat and oxygen, prevent combustible gas from escaping outward and oxygen from diffusing inward, and slow down the further thermal decomposition of the internal material, thereby preventing the carbon layer from being burned through or collapsed at high temperatures, thereby greatly improving the durability of the barrier, and making the prepared PTE material have good flame retardant effect. DETAILED DESCRIPTION

[0022] The technical solutions in the embodiments of the present application will be described below. Obviously, the described embodiments are only a part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by a person of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0023] Embodiment 1, a preparation method of a high-flame-retardant tpe material, specifically comprising the following steps:

[0024] Step A1: uniformly mix phosphonic acid monophenyl ester, pyridine, 4-dimethylaminopyridine and tetrahydrofuran, protect with nitrogen, stir at a rotation speed of 150 r / min and a temperature of 0℃, and then add dimethylchlorosilane, heat to 50℃, and react for 15 h to prepare an intermediate;

[0025] Step A2: mix the intermediate, allyl alcohol, chloroplatinic acid and DMF, protect with nitrogen, react at a rotation speed of 200 r / min and a temperature of 80℃ for 6 h to prepare a modified monomer;

[0026] Step A3: mix polytetrahydrofuran, the modified monomer and 4,4'-dicyclohexyl methane diisocyanate, react at a rotation speed of 120 r / min and a temperature of 80℃ for 2 h, then add 1,4-butanediol, continue to react for 2 h, add a flame-retardant additive, and continue to react for 4 h to prepare a high-flame-retardant tpe material.

[0027] The molar ratio of the phosphonic acid monophenyl ester, pyridine, 4-dimethylaminopyridine and dimethylchlorosilane in step A1 is 1:2.5:0.2:2.2.

[0028] The molar ratio of the intermediate and allyl alcohol in step A2 is 1:2, and the amount of chloroplatinic acid is 0.01% of the mass of allyl alcohol.

[0029] The molar ratio of polytetrahydrofuran, modified monomer, 4,4'-dicyclohexyl methane diisocyanate, 1,4-butanediol and flame retardant additive in step A3 is 30:10:60:10:0.5, and the molecular weight of polytetrahydrofuran is 1000.

[0030] The flame retardant additive is prepared by the following steps:

[0031] Step B1: uniformly mix dimethyl vinyl silanol lithium and tetrahydrofuran, protect with nitrogen, stir at a rotation speed of 120 r / min and a temperature of 0℃, add tetramethylcyclotetrasiloxane, warm up to 20℃, react for 8h, then add γ-chloropropyltrichlorosilane, react for 2h, to obtain branched polysiloxane, add DOPO into the reaction kettle, protect with nitrogen, stir at a rotation speed of 60 r / min and a temperature of 120℃, add magnolol, warm up to 160℃, react for 20h, to obtain a modifier;

[0032] Step B2: mix branched polysiloxane, modifier, triethylamine and DMF, react for 3h at a rotation speed of 200 r / min and a temperature of 35℃, to obtain functionalized polysiloxane, uniformly mix 1-oxyl phosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and tetrahydrofuran, protect with nitrogen, stir at a rotation speed of 150 r / min and a temperature of 0℃, add acryloyl chloride, react for 4h, to obtain a modified flame retardant;

[0033] Step B3: uniformly mix functionalized polysiloxane, thio-glycerol, benzophenone and DMF, react for 2h at a rotation speed of 200 r / min, a temperature of 20℃ and under ultraviolet light irradiation, to obtain modified polysiloxane, mix modified polysiloxane, modified flame retardant, chloroplatinic acid and DMF, protect with nitrogen, react for 8h at a rotation speed of 150 r / min and a temperature of 80℃, to obtain a flame retardant additive.

[0034] The molar ratio of Si-Cl bonds on dimethyl vinyl silanol lithium, tetramethylcyclotetrasiloxane and γ-chloropropyltrichlorosilane in step B1 is 1:3:1, and the molar ratio of DOPO and magnolol is 2:1.

[0035] The molar ratio of branched polysiloxane, modifier and triethylamine in step B2 is 2:1:2.1, and the molar ratio of 1-oxyl phosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and acryloyl chloride is 1:1.1:1.2.

[0036] The molar ratio of the double bond on the functionalized polysiloxane and the thio glycerol is 1:1, the amount of benzophenone is 0.1% of the mass of the thio glycerol, the molar ratio of the Si-H bond on the modified polysiloxane and the modified flame retardant is 1:1, and the amount of chloroplatinic acid is 0.01% of the mass of the modified flame retardant.

[0037] Embodiment 2, a method for preparing a high flame-retardant tpe material, specifically comprising the following steps:

[0038] Step A1: uniformly mix monophenyl phosphate, pyridine, 4-dimethylaminopyridine, and tetrahydrofuran, protect with nitrogen, stir at a rotation speed of 150 r / min and a temperature of 5℃, and then add dimethylchlorosilane, heat to 55℃, and react for 18 h to obtain an intermediate;

[0039] Step A2: mix the intermediate, allyl alcohol, chloroplatinic acid, and DMF, protect with nitrogen, react at a rotation speed of 200 r / min and a temperature of 85℃ for 7 h to obtain a modified monomer;

[0040] Step A3: mix polytetrahydrofuran, the modified monomer, and 4,4'-dicyclohexyl methane diisocyanate, react at a rotation speed of 120 r / min and a temperature of 85℃ for 2 h, then add 1,4-butanediol, continue to react for 3 h, add a flame-retardant additive, and continue to react for 5 h to obtain the high flame-retardant tpe material.

[0041] The molar ratio of the monophenyl phosphate, pyridine, 4-dimethylaminopyridine, and dimethylchlorosilane in Step A1 is 1:2.5:0.2:2.2.

[0042] The molar ratio of the intermediate and the allyl alcohol in Step A2 is 1:2, and the amount of chloroplatinic acid is 0.01% of the mass of the allyl alcohol.

[0043] The molar ratio of the polytetrahydrofuran, the modified monomer, 4,4'-dicyclohexyl methane diisocyanate, 1,4-butanediol, and the flame-retardant additive in Step A3 is 30:10:60:10:0.5, and the molecular weight of the polytetrahydrofuran is 1000.

[0044] The flame-retardant additive is prepared by the following steps:

[0045] Step B1: The lithium dimethylvinylsilanolate and tetrahydrofuran were mixed uniformly, and nitrogen was introduced for protection. The four-methylcyclosiloxane was added under the condition of 150 r / min and 0℃, and the temperature was increased to 20℃. After 9 h of reaction, the γ-chloropropyltrichlorosilane was added and reacted for 3 h to obtain the branched polysiloxane. The DOPO was added to the reaction kettle, and nitrogen was introduced for protection. The thick oolong phenol was added under the condition of 60 r / min and 125℃, and the temperature was increased to 160℃. After 25 h of reaction, the modifier was prepared.

[0046] Step B2: The branched polysiloxane, the modifier, triethylamine and DMF were mixed and reacted for 4 h under the condition of 200 r / min and 40℃ to obtain the functionalized polysiloxane. The 1-oxyl phosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and tetrahydrofuran were mixed uniformly, and nitrogen was introduced for protection. The acryloyl chloride was added under the condition of 150 r / min and 3℃, and the temperature was increased to 5 h to obtain the modified flame retardant.

[0047] Step B3: The functionalized polysiloxane, the sulfur glycerol, the benzophenone and the DMF were mixed uniformly and reacted for 2 h under the condition of 200 r / min, 25℃ and ultraviolet light irradiation to obtain the modified polysiloxane. The modified polysiloxane, the modified flame retardant, the chloroplatinic acid and the DMF were mixed and reacted for 9 h under the condition of 200 r / min and 80℃ to obtain the flame retardant additive.

[0048] The molar ratio of the Si-Cl bonds on the lithium dimethylvinylsilanolate, the four-methylcyclosiloxane and the γ-chloropropyltrichlorosilane in step B1 was 1:3:1, and the molar ratio of the DOPO and the thick oolong phenol was 2:1.

[0049] The molar ratio of the branched polysiloxane, the modifier and the triethylamine in step B2 was 2:1:2.1, and the molar ratio of the 1-oxyl phosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, the pyridine and the acryloyl chloride was 1:1.1:1.2.

[0050] The molar ratio of the double bond on the functionalized polysiloxane and the sulfur glycerol in step B3 was 1:1, the amount of the benzophenone was 0.1% of the mass of the sulfur glycerol, the molar ratio of the Si-H bond on the modified polysiloxane and the modified flame retardant was 1:1, and the amount of the chloroplatinic acid was 0.01% of the mass of the modified flame retardant.

[0051] Example 3, a method for preparing a high flame-retardant tpe material, specifically comprising the following steps:

[0052] Step A1: Phosphonic acid monophenyl ester, pyridine, 4-dimethylaminopyridine and tetrahydrofuran were mixed uniformly, and nitrogen was introduced for protection. Under the conditions of a rotation speed of 200 r / min and a temperature of 5℃, dimethylchlorosilane was stirred and added, and the reaction was carried out at 60℃ for 18 h to prepare an intermediate.

[0053] Step A2: The intermediate, allyl alcohol, chloroplatinic acid and DMF were mixed, and nitrogen was introduced for protection. Under the conditions of a rotation speed of 300 r / min and a temperature of 85℃, the reaction was carried out for 8 h to prepare a modified monomer.

[0054] Step A3: Polytetrahydrofuran, modified monomer and 4,4'-dicyclohexyl methane diisocyanate were mixed, and the reaction was carried out at a rotation speed of 150 r / min and a temperature of 85℃ for 3 h. Then 1,4-butanediol was added, and the reaction was continued for 3 h. Then a flame retardant additive was added, and the reaction was continued for 6 h to prepare a high-flame-retardant tpe material.

[0055] The molar ratio of phosphonic acid monophenyl ester, pyridine, 4-dimethylaminopyridine and dimethylchlorosilane in step A1 is 1:2.5:0.2:2.2.

[0056] The molar ratio of the intermediate and allyl alcohol in step A2 is 1:2, and the amount of chloroplatinic acid is 0.01% of the mass of allyl alcohol.

[0057] The molar ratio of polytetrahydrofuran, modified monomer, 4,4'-dicyclohexyl methane diisocyanate, 1,4-butanediol and flame retardant additive in step A3 is 30:10:60:10:0.5, and the molecular weight of polytetrahydrofuran is 1000.

[0058] The flame retardant additive is prepared by the following steps:

[0059] Step B1: Dimethylvinylsilanol lithium and tetrahydrofuran were mixed uniformly, and nitrogen was introduced for protection. Under the conditions of a rotation speed of 150 r / min and a temperature of 0℃, tetramethylcyclotetrasiloxane was stirred and added, and the reaction was carried out at 25℃ for 10 h. Then γ-chloropropyltrichlorosilane was added, and the reaction was carried out for 3 h to prepare a branched polysiloxane. DOPO was added to the reaction kettle, and nitrogen was introduced for protection. Under the conditions of a rotation speed of 80 r / min and a temperature of 125℃, magnolol was stirred and added, and the reaction was carried out at 165℃ for 25 h to prepare a modifier.

[0060] Step B2: the functionalized polysiloxane was prepared by mixing branched polysiloxane, modifier, triethylamine and DMF, and stirring at a rotation speed of 300 r / min and a temperature of 40℃ for 5 h; 1-oxylphospho-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and tetrahydrofuran were mixed uniformly, and stirred at a rotation speed of 200 r / min and a temperature of 5℃ for 6 h after acryloyl chloride was added under nitrogen protection; and the modified flame retardant was prepared.

[0061] Step B3: the modified polysiloxane was prepared by mixing the functionalized polysiloxane, thioglycerol, benzophenone and DMF uniformly, and stirring at a rotation speed of 300 r / min and a temperature of 25℃ for 3 h under ultraviolet light irradiation; the flame retardant additive was prepared by mixing the modified polysiloxane, the modified flame retardant, chloroplatinic acid and DMF, and stirring at a rotation speed of 200 r / min and a temperature of 85℃ for 10 h under nitrogen protection.

[0062] The molar ratio of lithium dimethylvinylsilanolate, tetramethylcyclotetrasiloxane and Si-Cl bond on γ-chloropropyltrichlorosilane in Step B1 was 1:3:1, and the molar ratio of DOPO and magnolol was 2:1.

[0063] The molar ratio of branched polysiloxane, modifier and triethylamine in Step B2 was 2:1:2.1, and the molar ratio of 1-oxylphospho-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and acryloyl chloride was 1:1.1:1.2.

[0064] The molar ratio of double bond on the functionalized polysiloxane and thioglycerol in Step B3 was 1:1, the amount of benzophenone was 0.1% of the mass of thioglycerol, the molar ratio of Si-H bond on the modified polysiloxane and the modified flame retardant was 1:1, and the amount of chloroplatinic acid was 0.01% of the mass of the modified flame retardant.

[0065] Comparative Example 1: the same as Example 1 except that no modified monomer was added.

[0066] Comparative Example 2: the same as Example 1 except that lithium dimethylvinylsilanolate and tetrahydrofuran were mixed uniformly, and stirred at a rotation speed of 120 r / min and a temperature of 0℃ for 8 h after tetramethylcyclotetrasiloxane was added under nitrogen protection, and then phenyltrichlorosilane was added and reacted for 2 h to prepare the product instead of the functionalized polysiloxane.

[0067] Comparative Example 3: the same as Example 1 except that mercaptoethanol was used instead of thioglycerol.

[0068] The materials prepared in Examples 1-3 and Comparative Examples 1-3 were prepared into 130mmx13mmx4mm samples according to the standard of GB / T2408-2021, and the vertical burning grade and flame extinguishing time were detected, and according to the standard of GB / T8323.2-2008, square samples with side length of 75mm and thickness of 25mm were prepared, and under the condition of no ignition flame, the smoke density was detected, and the test results are shown in Table 1. 2

[0069]

[0070] From Table 1, it can be seen that the application has good flame retardant effect.

[0071] The above is only an example and description of the concept of the present application. Those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as they do not deviate from the concept of the invention or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.​

Claims

1. A process for the preparation of a high flame retardant tpe material, characterized in that: Specifically comprising the following steps: Step A1: the phosphonic acid monophenyl ester, pyridine, 4-dimethylaminopyridine and tetrahydrofuran are mixed uniformly, nitrogen is introduced, stirring and adding dimethylchlorosilane, warming reaction, to prepare an intermediate; Step A2: the intermediate, allyl alcohol, chloroplatinic acid and DMF are mixed, nitrogen is introduced, and reaction is carried out, to prepare a modified monomer; Step A3: polytetrahydrofuran, the modified monomer and 4,4'-dicyclohexyl methane diisocyanate are mixed, after reaction, 1,4-butanediol is added, and continues to react, the flame retardant additive is added, and continues to react, to prepare a high flame retardant tpe material; The flame retardant additive is prepared by the following steps: Step B1: dimethylvinylsilanol lithium and tetrahydrofuran are mixed uniformly, nitrogen is introduced, stirring and adding tetramethylcyclotetrasiloxane, after warming reaction, γ-chloropropyltrichlorosilane is added, and reaction is carried out, to prepare a branched polysiloxane, DOPO is added into the reaction kettle, nitrogen is introduced, stirring and adding magnolol, warming reaction, to prepare a modifier; Step B2: the branched polysiloxane, the modifier, triethylamine and DMF are mixed and reacted, to prepare a functionalized polysiloxane, 1-oxyl phosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and tetrahydrofuran are mixed uniformly, nitrogen is introduced, stirring and adding acryloyl chloride, and reaction is carried out, to prepare a modified flame retardant; Step B3: the functionalized polysiloxane, thio glycerol, benzophenone and DMF are mixed and ultraviolet light irradiation is carried out, to prepare a modified polysiloxane, the modified polysiloxane, the modified flame retardant, chloroplatinic acid and DMF are mixed, nitrogen is introduced, and reaction is carried out, to prepare a flame retardant additive.

2. The process for the preparation of a high flame retardant tpe material according to claim 1, characterized by the fact that: The molar ratio of the phosphonic acid monophenyl ester, pyridine, 4-dimethylaminopyridine and dimethylchlorosilane in step A1 is 1:2.5:0.2:2.

2.

3. The process for the preparation of a high flame retardant tpe material according to claim 1, characterized by the fact that: The molar ratio of the intermediate and allyl alcohol in step A2 is 1:

2.

4. The process for preparing a high flame retardant tpe material according to claim 1, characterized in that: The molar ratio of the polytetrahydrofuran, the modified monomer, 4,4'-dicyclohexyl methane diisocyanate, 1,4-butanediol and the flame retardant additive in step A3 is 30:10:60:10:0.

5.

5. The process for preparing a high flame retardant tpe material according to claim 1, characterized in that: The molar ratio of the dimethylvinylsilanol lithium, tetramethylcyclotetrasiloxane and γ-chloropropyltrichlorosilane in step B1 is 1:3:1, and the molar ratio of DOPO and magnolol is 2:

1.

6. The process for preparing a high flame retardant tpe material according to claim 1, characterized in that: The molar ratio of the branched polysiloxane, the modifier and triethylamine in step B2 is 2:1:2.1, and the molar ratio of 1-oxyl phosphorus-4-hydroxymethyl-2,6,7-trioxa-bicyclo[2.2.2]octane, pyridine and acryloyl chloride is 1:1.1:1.

2.

7. The process for preparing a high flame retardant tpe material according to claim 1, characterized in that: The molar ratio of the double bond on the functionalized polysiloxane and thio glycerol in step B3 is 1:1, and the molar ratio of the Si-H bond on the modified polysiloxane and the modified flame retardant is 1:

1.

8. A high flame retardant tpe material characterized in that: Prepared according to the preparation method in any one of claims 1-7.

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