Thermoplastic elastomer material and preparation method thereof

Abstract

The invention discloses a thermoplastic elastomer material, which comprises 15-22 parts of polypropylene PP, 20-30 parts of SEBS, 20-30 parts of a plasticizer, 3-8 parts of a compatilizer, 5-10 parts of a P-series flame retardant, 5-10 parts of an N-series flame retardant, and 15-30 parts of a modified polysilsesquioxane flame retardant, the modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, a compound B and a catalyst in an alkaline environment, the silsesquioxane A comprises at least one epoxy group D, and the compound B contains a phosphorus element P and a nitrogen element N and at least comprises a halogen end group X. The thermoplastic elastomer material provided by the invention is excellent in flame retardant property and dielectric property, has good processability and mechanical property, greatly improves the anti-cracking property and anti-dripping effect of the thermoplastic elastomer material, and is safe and environment-friendly.

Description

Technical Field

[0001] This invention relates to the field of materials, specifically to a thermoplastic elastomer material and its preparation method. Background Technology

[0002] Silsesquioxanes are a class of compounds with an organic-inorganic hybrid structure, consisting of a silicon framework and intercalated oxygen atoms. Their structure comprises Si-O bonded silicon-oxygen chains with long bond spacing, large bond angles, and high bond energies. They are very flexible and have a very low viscous flow activation energy. In addition, the mutual compensation of dppp bonds between Si-O bonds and the mutual compensation between Si-O dipoles causes the Si-O bonds to form a helical structure. This special composition and molecular structure endow them with many excellent properties such as resistance to high and low temperatures, weather resistance, electrical insulation, hydrophobicity, non-toxicity, and non-corrosiveness.

[0003] Thermoplastic elastomer (TPS) materials are mainly made of SEBS, white oil, PP, and with the addition of certain plasticizers and antioxidants. They have a wide hardness range, excellent hand feel, low-temperature resistance, low price, and excellent elasticity. In the international market, there are many types of low-smoke, halogen-free flame-retardant TPS cable materials that meet UL's requirements for electrical wire flame retardancy. However, the overall performance of domestically produced low-smoke, halogen-free flame-retardant TPS cable materials is far inferior to that of imported products. Due to the limitations of domestic flame retardant technology, the development of TPS materials with high flame retardancy, high mechanical properties, and crack resistance has not made significant progress. Therefore, it is essential to develop a new thermoplastic elastomer material that possesses halogen-free high flame retardancy, anti-dripping effect, high physical and mechanical properties, and crack resistance. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention proposes a thermoplastic elastomer material and its preparation method, aiming to solve the problems of poor flame retardancy, poor physical and mechanical properties, and dripping during combustion of current TPS materials.

[0005] To achieve the above objectives, the present invention proposes a thermoplastic elastomer material. The raw materials of the thermoplastic elastomer material, by weight, include 15-22 parts of polypropylene (PP), 20-30 parts of SEBS, 20-30 parts of plasticizer, 3-8 parts of compatibilizer, 5-10 parts of phosphorus-based flame retardant, 5-10 parts of nitrogen-based flame retardant, and 15-30 parts of modified polysilsesquioxane flame retardant. The modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, compound B, and a catalyst under an alkaline environment. Silsesquioxane A includes at least one epoxy group D, and compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen end group X.

[0006] Optionally, the structure of silsesquioxane A includes at least one of fully cage-like silsesquioxanes, and its structural formula includes at least one... , Where 6≥n≥1, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

[0007] Optionally, the compound B includes at least one cyclic structure E with a carbon-hydrogen ratio of not less than 1, and the halogen end group X is not directly connected to the cyclic structure E.

[0008] Optionally, the cyclic structure E with a carbon-to-hydrogen ratio of not less than 1 includes at least one of a benzene ring group and an imidazole group.

[0009] Optionally, the modified polysilsesquioxane flame retardant is synthesized by a nucleophilic substitution reaction of silsesquioxane A and compound B under the action of a catalyst after ring-opening, characterized by the following reaction route: .

[0010] Optionally, the method for synthesizing the modified polysilsesquioxane flame retardant includes the following steps: (1) First, dissolve silsesquioxane A in an organic solvent solution, then add a catalyst. Under the action of the catalyst, stir evenly and add a small amount of water. Continue stirring for 4-8 hours, then place the whole thing in an ice-water bath and stir. (2) Dissolve compound B in an organic solution, and slowly add the organic solution of compound B to step (1) through a constant pressure dropping funnel, while slowly adding an alkaline agent. Under alkaline conditions, the epoxy group D in silsesquioxane A undergoes a nucleophilic ring-opening substitution reaction with the halogen end group X in compound B to obtain the modified polysilsesquioxane flame retardant preproduct. (3) The reaction preproduct in step (2) is rotary evaporated to remove the organic solvent. Then it is washed with saturated sodium chloride solution, filtered and dried to obtain the modified polysilsesquioxane flame retardant.

[0011] Optionally, the molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:1.

[0012] Optionally, the catalyst includes at least one of an acidic catalyst, a metal catalyst, and a basic catalyst; the organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones; and the basic agent is at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium phosphate, and sodium silicate.

[0013] Optionally, the raw materials of the thermoplastic elastomer material, by weight, include 15-20 parts of polypropylene (PP), 20-25 parts of SEBS, 20-30 parts of plasticizer, 3-8 parts of compatibilizer, 5-8 parts of P-based flame retardant, 5-8 parts of N-based flame retardant, and 15-25 parts of modified polysilsesquioxane flame retardant.

[0014] Optionally, the plasticizer includes at least one of white oil, naphthenic oil, and paraffin oil; the compatibilizer includes at least one of PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride; the phosphorus-based flame retardant includes inorganic phosphorus flame retardant or organic phosphorus flame retardant, the inorganic phosphorus flame retardant includes at least one of red phosphorus, phosphate, and polyphosphate, and the organic phosphorus flame retardant includes at least one of phosphate ester, phosphite ester, and phosphine oxide; the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, and melamine inorganic acid salt.

[0015] Optionally, the raw materials of the thermoplastic elastomer material further include at least one of a lubricant, an antioxidant, and a light stabilizer; wherein, by weight, the raw materials are 0.2-1 parts of the lubricant, 0.5-2 parts of the antioxidant, and 0.2-1 parts of the light stabilizer.

[0016] This invention provides a method for preparing a thermoplastic elastomer material, comprising the following steps: mixing the raw materials evenly, extruding and granulating them through an extruder to obtain granules, i.e., the thermoplastic elastomer material.

[0017] Optionally, the raw materials may also include at least one of lubricant, antioxidant, and light stabilizer.

[0018] In this invention, the thermoplastic elastomer material includes SEBS, PP, plasticizer, compatibilizer, phosphorus-based flame retardant, nitrogen-based flame retardant, and modified polysilsesquioxane flame retardant. Because the modified polysilsesquioxane flame retardant contains phosphorus (P), nitrogen (N), a cyclic structure D with a carbon-to-hydrogen ratio greater than 1, and at least one inorganic silicon cage core, the inorganic silicon cage core decomposes upon heating to form a dense ceramic barrier layer, isolating the release of combustible gases and the entry of external heat into the interior. The cyclic structure D with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio and contains a large amount of carbon. During combustion, this large amount of carbon forms a glassy protective film or a heat-insulating coke layer. These protective films or coke layers can isolate air, prevent heat transfer, and reduce the release of combustible gases. These structures, through the formation of protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating coke layers during combustion, greatly improve the anti-dripping effect. Simultaneously, they isolate heat and oxygen transfer and reduce the release of combustible gases. The combined effect of these multiple mechanisms significantly improves the flame-retardant performance of the material. Simultaneously, the numerous Si-O bonds decompose upon heating to form a dense ceramic barrier layer. The P element in the modified polysilsesquioxane flame retardant, together with the P-based flame retardant, provides an acid source, while the N element and the N-based flame retardant provide non-combustible gases, resulting in stronger flame retardancy. The abundant hydroxyl groups in the modified polysilsesquioxane flame retardant can absorb a large amount of heat, thereby inhibiting combustion. The various flame-retardant elements work together synergistically to reduce the amount of flame retardant required while improving the flame retardant, dielectric, and mechanical properties of the thermoplastic elastomer material. The thermoplastic elastomer material provided by this invention exhibits excellent flame retardant and dielectric properties, as well as good processing and mechanical properties. It also significantly improves the crack resistance and anti-dripping effect of the thermoplastic elastomer material, making it safe and environmentally friendly. Attached Figure Description

[0019] Figure 1 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 1 of the present invention; Figure 2 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 2 of the present invention; Figure 3 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 3 of the present invention; Figure 4 This is another molecular structure diagram of the modified polysilsesquioxane flame retardant 3 of the present invention; Figure 5 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 4 of the present invention; Figure 6 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 5 of the present invention; Figure 7 This is another molecular structure diagram of the modified polysilsesquioxane flame retardant 5 of the present invention; Figure 8 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 6 of the present invention; Figure 9 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 7 of the present invention; Figure 10 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 8 of the present invention; Figure 11 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 9 of the present invention; Figure 12 This is another molecular structure diagram of the modified polysilsesquioxane flame retardant 9 of the present invention; Figure 13 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 10 of the present invention; Figure 14 This is a molecular structure diagram of the modified polysilsesquioxane flame retardant 11 of the present invention; Figure 15 This is a molecular structure diagram of the glycidyl etheroxypropyl-isooctyl polysilsesquioxane in this invention. Figure 16 This is a molecular structure diagram of bis(4-nitrophenyl)phosphochloride in this invention. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0021] Unless otherwise specified, all technical and scientific terms used herein have their usual meaning within the field to which the subject matter is claimed.

[0022] To facilitate understanding of this embodiment, the symbols, instruments, and terms are explained below: Polypropylene (PP) is a general-purpose thermoplastic polymerized from propylene monomers, with the chemical formula (C3H6)n. It is one of the world's most produced and widely used plastics, renowned for its excellent overall performance, low density, high heat resistance, superior chemical resistance, and ease of processing.

[0023] SEBS (Styrene Ethylene Butylene Styrene) is a linear triblock copolymer with polystyrene as the end block and ethylene-butene copolymer (obtained by hydrogenating polybutadiene) as the middle elastic block. SEBS exhibits good stability and aging resistance because its molecular chain does not contain unsaturated double bonds, which makes it exhibit excellent aging resistance in photo-oxidative and ozone environments.

[0024] EMA-grafted maleic anhydride (EMA-g-MAH) is an important polymer modification material. It is made by grafting maleic anhydride (MAH) active functional groups onto the molecular chain of ethylene-methyl acrylate copolymer (EMA) as the matrix through a chemical reaction. With its balanced flexibility, polarity and processing performance, EMA-g-MAH plays a key role in the fields of automotive parts, packaging materials, polymer alloys and adhesives.

[0025] POE-grafted maleic anhydride (POE-g-MAH) is a high-performance polymer material prepared through chemical modification. It uses polyolefin elastomer (POE) as the main chain and introduces highly active maleic anhydride (MAH) functional groups into the molecular chain through a grafting reaction. This not only retains the high elasticity, excellent impact resistance and low-temperature toughness of the POE matrix, but also significantly improves its compatibility and adhesion with polar materials through the polar MAH groups.

[0026] Silsesquioxanes are a class of compounds with an organic-inorganic hybrid structure, consisting of a silicon framework and intercalated oxygen atoms. Their structure comprises Si-O bonded silicon-oxygen chains with long bond distances, large bond angles, and high bond energies. They are very flexible and have very low viscous flow activation energies. In addition, the mutual compensation of dppp bonds between Si-O bonds and the mutual compensation between Si-O dipoles causes the Si-O bonds to form a helical structure. This special composition and molecular structure endow them with many excellent properties such as resistance to high and low temperatures, weather resistance, electrical insulation, hydrophobicity, non-toxicity, and non-corrosiveness.

[0027] Thermoplastic elastomer (TPS) materials are mainly made of SEBS, white oil, PP, and with the addition of certain plasticizers and antioxidants. They have a wide hardness range, excellent hand feel, low-temperature resistance, low price, and excellent elasticity. In the international market, there are many types of low-smoke, halogen-free flame-retardant TPS cable materials that meet UL's requirements for electrical wire flame retardancy. However, the overall performance of domestically produced low-smoke, halogen-free flame-retardant TPS cable materials is far inferior to that of imported products. Due to the limitations of domestic flame retardant technology, the development of TPS materials with high flame retardancy, high mechanical properties, and crack resistance has not made significant progress. Therefore, it is essential to develop a new thermoplastic elastomer material that possesses halogen-free high flame retardancy, anti-dripping effect, high physical and mechanical properties, and crack resistance.

[0028] To address the aforementioned problems, in a first aspect, this invention provides a thermoplastic elastomer material. The raw materials of the thermoplastic elastomer material, by weight, include 15-22 parts of polypropylene (PP), 20-30 parts of SEBS, 20-30 parts of plasticizer, 3-8 parts of compatibilizer, 5-10 parts of phosphorus-based flame retardant, 5-10 parts of nitrogen-based flame retardant, and 15-30 parts of modified polysilsesquioxane flame retardant. The modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, compound B, and a catalyst under an alkaline environment. Silsesquioxane A includes at least one epoxy group D, and compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen end group X.

[0029] Understandably, in thermoplastic elastomer materials, polypropylene (PP) is used in any number of parts between 15 and 22, such as 15, 18, 20, or 22; SEBS is used in any number of parts between 20 and 30, such as 20, 25, 28, or 30; P-based flame retardants are used in any number of parts between 5 and 10, such as 5, 6, 7, 8, 9, or 10; N-based flame retardants are used in any number of parts between 5 and 10, such as 5, 6, 7, 8, 9, or 10; and modified polysilsesquioxane flame retardants are used in any number of parts between 15 and 30, such as 15, 20, 25, or 30.

[0030] Understandably, modified polysilsesquioxane flame retardants are prepared from raw materials including silsesquioxane A, compound B, and a catalyst under an alkaline environment. Silsesquioxane A includes at least one epoxy group D, and compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen end group X. Under the catalysis of the catalyst, epoxy group D, due to ring strain, is easily subjected to nucleophilic attack and ring-opening. Under trace amounts of water and acidic or alkaline conditions, the epoxy group undergoes a ring-opening reaction, generating a diol structure with primary and secondary alcohols. The more reactive primary alcohol on the silsesquioxane acts as a nucleophile to attack the P atom with the halogen end group X, removing the HX molecule and generating the modified polysilsesquioxane flame retardant. Therefore, the modified polysilsesquioxane flame retardant contains a large number of Si-O bonds from silsesquioxane A and phosphorus (P) and nitrogen (N) from compound B, and also contains hydroxyl groups obtained after the ring-opening of the epoxy group.

[0031] Modified polysilsesquioxane flame retardants contain a large number of Si-O bonds, which decompose upon heating to form a dense ceramic barrier layer. This layer isolates the release of combustible gases and the entry of external heat into the interior. Simultaneously, the dense ceramic barrier layer significantly improves the material's anti-dripping effect and flame retardant performance. During combustion, the phosphorus element in the modified polysilsesquioxane flame retardant decomposes to produce highly dehydrating substances such as phosphoric acid and polyphosphoric acid, promoting carbonization on the material surface to form a heat-insulating layer (condensation mechanism). It also releases phosphorus-containing free radicals, capturing the H• and OH• free radicals necessary for combustion in the gas phase, interrupting the combustion chain reaction. This dual effect results in very high flame retardant efficiency. The nitrogen element itself decomposes upon combustion to provide a large amount of non-combustible gas, which, in conjunction with the phosphorus element, causes the forming viscous char layer to foam, forming a porous, dense, and robust expanded char layer.

[0032] Meanwhile, the modified polysilsesquioxane flame retardant contains a large number of hydroxyl groups. During the initial and subsequent combustion phases, these hydroxyl groups absorb a significant amount of heat, substantially reducing the surface temperature of the polymer material and slowing down its thermal decomposition rate, thus inhibiting combustion. The water vapor produced by the combustion of hydroxyl groups effectively dilutes the concentration of combustible gases and oxygen near the material surface, weakening or extinguishing the combustion reaction due to lack of fuel and oxygen.

[0033] Modified polysilsesquioxane flame retardants contain abundant silicon, oxygen, phosphorus, and nitrogen elements. During polymer combustion, they rapidly form a char layer. The SiO2 generated after combustion intercalates within the char layer, similar to the role of sand in cement, making the char layer more stable. The char layer makes it difficult for heat to penetrate the condensed phase, preventing oxygen from entering the combustion zone and preventing gaseous or liquid products from degradation from overflowing the material surface. Simultaneously, the combustion of nitrogen produces a large amount of non-combustible gas, which causes the incompletely carbonized TPS portion of the system to foam in the molten state, resulting in numerous pores in the burning polymer. Meanwhile, organic matter continues to react, dehydrate, and carbonize, forming inorganic matter and residual carbon. Upon completion of the reaction, the system gels and solidifies, ultimately forming a porous foamed char layer.

[0034] Thermoplastic elastomer materials include polypropylene, SEBS, phosphorus-based flame retardants, nitrogen-based flame retardants, and modified polysilsesquioxane flame retardants. Modified polysilsesquioxane flame retardants contain phosphorus (P), nitrogen (N), a cyclic structure D with a carbon-to-hydrogen ratio greater than 1, and at least one inorganic silica cage core. The inorganic silica cage core decomposes upon heating to form a dense ceramic barrier layer, isolating the release of flammable gases and preventing external heat from entering the interior. The cyclic structure D with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio and contains a large amount of carbon. During combustion, this large amount of carbon forms a glassy protective film or a heat-insulating char layer. These protective films or char layers can isolate air, prevent heat transfer, and reduce the release of flammable gases. These structures, through the formation of protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating char layers during combustion, significantly improve the anti-dripping effect. Simultaneously, they isolate heat and oxygen transfer and reduce the release of flammable gases. The combined effect of these multiple mechanisms significantly improves the flame-retardant performance of the material. Simultaneously, the numerous Si-O bonds decompose upon heating to form a dense ceramic barrier layer. The P element in the modified polysilsesquioxane flame retardant, together with the P-based flame retardant, provides an acid source, while the N element, together with the N-based flame retardant, provides non-combustible gas, resulting in stronger flame retardancy. The abundant hydroxyl groups in the modified polysilsesquioxane flame retardant can absorb a large amount of heat, thereby inhibiting combustion. The various flame-retardant elements work together synergistically to retard flames, reducing the amount of flame retardant required while improving the flame retardant, dielectric, and mechanical properties of the thermoplastic elastomer material. The thermoplastic elastomer material provided by this invention exhibits excellent flame retardant and dielectric properties, as well as good processing and mechanical properties. It also significantly improves the crack resistance and anti-dripping effect of the thermoplastic elastomer material, making it safe and environmentally friendly.

[0035] Furthermore, the structure of silsesquioxane A includes at least one of fully cage-like silsesquioxanes, and its structural formula includes at least one... , Where 6≥n≥1, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

[0036] Silsesquioxane A includes at least one of fully caged silsesquioxanes. Fully caged silsesquioxanes are hollow and have a closed structure, with all three dimensions within the nanoscale range. They possess a hexahedral inorganic framework core with a nanostructure, exhibiting unique thermodynamic properties. As the main component of the molecular skeleton of hybrid materials, fully caged silsesquioxanes, due to their large volume effect, effectively control the chain movement of the matrix material, significantly increasing the glass transition temperature (Tg). When the temperature of the silsesquioxane organic polymer rises to the point where the polymer begins to melt, the silsesquioxane molecular structure remains unchanged. When the organic molecules on its surface are oxidized at high temperatures, the silsesquioxane, due to its oxygen stability, can fix the oxidized organic molecules, forming a refractory layer and providing structural support. After the monomers of fully caged silsesquioxane macromolecules containing epoxy groups are cured, they have a high decomposition temperature and can form a high-temperature resistant cured layer.

[0037] In some embodiments, silsesquioxane A is preferably at least one of glycidyl etheroxypropylcyclotetrasiloxane, octa[(3-glycidyloxypropyl)dimethylsiloxy]-substituted PSS, 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane, acryloyloxypropyl-glycidyl etheroxypropyl cage-like polysilsesquioxane, glycidyl etheroxypropyl-isooctyl polysilsesquioxane, glycidyl etheroxypropyl cage-like polysilsesquioxane, cyclohexyloxypropyl-glycidyl etheroxypropyl cage-like polysilsesquioxane, and octacyclohexyloxypropyl cage-like polysilsesquioxane.

[0038] Understandably, the structural formula of glycidyl etheroxypropylcyclotetrasiloxane is... , where n is 1, and R1, R2, R3, R4, R5, R6, R7, and R8 include 4 epoxy groups D.

[0039] Understandably, the structural formula of PSS substituted with [3-oxyglycidylpropyl)dimethylsiloxy] is... , where n is 2, and R1, R2, R3, R4, R5, R6, R7, and R8 include 7 epoxy groups D.

[0040] Understandably, the structural formula of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane is... , where n is 3, and R1, R2, R3, R4, R5, R6, R7, and R8 include 3 epoxy groups D.

[0041] Understandably, the structural formula of acryloyloxypropyl-glycidyloxypropyl cage-type polysilsesquioxane is as follows: , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include one epoxy group D.

[0042] Understandably, the structural formula of glycidyl etheroxypropyl-isooctyl polysilsesquioxane is... , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 4 epoxy groups D.

[0043] Understandably, the structural formula of glycidyl etheroxypropyl cage-like polysilsesquioxane is... , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 8 epoxy groups D.

[0044] Understandably, the structural formula of epoxycyclohexylethyl-glycidyloxypropyl cage-like polysilsesquioxane is as follows: , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 8 epoxy groups D.

[0045] Understandably, the structural formula of octacyclohexylethyl cage-like polysilsesquioxane is... , where n is 6, and R1, R2, R3, R4, R5, R6, R7, and R8 include 8 epoxy groups D.

[0046] Understandably, each specific n represents a specific silsesquioxane. When n is the same, the R1, R2, R3, R4, R5, R6, R7, and R8 groups on the specific silsesquioxane structure can include different groups, including but not limited to oxypropyl, isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl.

[0047] Furthermore, compound B includes at least one cyclic structure E with a carbon-to-hydrogen ratio of not less than 1, and the halogen end group X is not directly connected to the cyclic structure E.

[0048] Modified polysilsesquioxane flame retardants contain fully cage-like silsesquioxanes and cyclic groups with a carbon-to-hydrogen ratio of not less than 1, as well as phosphorus and nitrogen elements. The fully cage-like silsesquioxanes decompose upon heating to form a dense ceramic barrier layer, isolating the release of combustible gases and preventing external heat from entering the interior. The cyclic structure with a carbon-to-hydrogen ratio of not less than 1 has a high carbon-to-hydrogen ratio and a large amount of carbon. During combustion, this large amount of carbon forms a heat-insulating coke layer. This coke layer isolates air, prevents heat transfer, and reduces the release of combustible gases. This structure, through the formation of carbon during combustion... Protective layers such as ceramic barrier layers, protective films, or heat-insulating coke layers greatly improve the anti-dripping effect. At the same time, they isolate heat and oxygen transfer and reduce the release of flammable gases. The combined effect of multiple mechanisms significantly improves the flame retardant performance of the material. On the other hand, when halogen end groups are directly connected to the cyclic structure E, the high bond energy makes it difficult to break and nucleophilic substitution is difficult. Direct nucleophilic substitution requires the formation of a high-energy carbanion intermediate, which is extremely difficult to carry out. Halogens will stably connect to the cyclic structure E, resulting in the presence of halogens in the modified polysilsesquioxane flame retardant, which affects the environmental performance of thermoplastic elastomer materials.

[0049] In some embodiments, compound B comprises a cyclic structure with a carbon-hydrogen ratio of not less than 1. It is understood that cyclic structures with a carbon-hydrogen ratio (C / H) greater than 1 are very common. The structure has relatively few hydrogen atoms, indicating that the structure includes unsaturated hydrocarbons (containing double or triple bonds) or is a fused-ring aromatic hydrocarbon, or a carbon allotrope composed entirely of carbon.

[0050] In some embodiments, compound B comprises two cyclic structures with a carbon-to-hydrogen ratio of not less than 1. It is understood that compound B may contain two benzene ring groups. The stability of compound B can be achieved by setting symmetrical benzene ring groups. At the same time, the two benzene ring groups increase the carbon content in the generated modified polysilsesquioxane flame retardant, thereby increasing the content of the heat-insulating coke layer formed by carbon during combustion, isolating heat and oxygen, and further improving the flame retardancy and anti-dripping performance of the material.

[0051] Furthermore, the cyclic structure E with a carbon-to-hydrogen ratio of not less than 1 includes at least one of a benzene ring group and an imidazole group.

[0052] Understandably, compound B is preferably at least one of bis(4-nitrophenyl)phosphochloride, bis(4-nitrobenzyl)chlorophosphate, di[2-(p-nitrophenyl)ethyl]chlorophosphate, 2-(4-nitrophenyl)ethylhydro(5-chloropentyl)phosphonate, Bis(3-chloropropyl) p-nitrophenyl phosphate, DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE, and N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphochloride.

[0053] Understandably, the structural formula of bis(4-nitrophenyl)phosphochloride is... .

[0054] Understandably, the structural formula of bis(4-nitrobenzyl)chlorophosphate is... .

[0055] Understandably, the structural formula of di[2-(p-nitrophenyl)ethyl]chlorophosphate is... .

[0056] Understandable, 3-nitro-N-(2,2,2-trichloro-1- The structural formula of Diethoxy-phosphorylethyl)benzamide is: .

[0057] Understandably, the structural formula of Bis(3-chloropropyl)p-nitrophenyl phosphate is... .

[0058] Understandably, the structural formula of DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE is... .

[0059] Understandably, the structural formula of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryldichloro is... .

[0060] Compound B contains phosphorus (P) and nitrogen (N), and includes at least one halogen terminal group X and at least one cyclic structure E with a carbon-to-hydrogen ratio of not less than 1. The halogen terminal group X includes -Cl, -Br, and -F. The halogen terminal group undergoes a nucleophilic substitution reaction with an epoxy group. It is understood that when compound B has only one halogen terminal group, one epoxy group is attached to compound B; when compound B has two halogen terminal groups, two epoxy groups are attached to compound B. That is, when silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane and compound B is preferably Bis(3-chloropropyl) p-nitrophenyl phosphate, Bis(3-chloropropyl) p-nitrophenyl The two chlorine-terminal groups in phosphate react with the two epoxy groups in glycidyl etheroxypropylcyclotetrasiloxane via nucleophilic substitution to form a new cyclic structure. Similarly, when compound B has only one cyclic structure E with a carbon-hydrogen ratio of not less than 1, cyclic structure E can be a benzene ring or an imidazole ring, possessing a high carbon-hydrogen ratio. This allows it to form a protective layer during combustion, improving flame retardancy and anti-dripping effects. When compound B has two benzene ring structures, the carbon-hydrogen ratio of cyclic structure E in compound B increases, making the flame retardancy and anti-dripping effects more pronounced.

[0061] Furthermore, a method for synthesizing a modified polysilsesquioxane flame retardant involves a nucleophilic substitution reaction between silsesquioxane A and compound B under the action of a catalyst after ring-opening. The reaction route is as follows: .

[0062] After hydrolysis and ring opening, silsesquioxane A forms a structure with two alcoholic hydroxyl groups, generating a diol structure containing a primary alcohol and a secondary alcohol. The more reactive primary alcohol on the silsesquioxane acts as a nucleophile to attack the P atom with a halogenated end group X, removing the HX molecule and generating a modified polysilsesquioxane flame retardant.

[0063] The synthesis method of modified polysilsesquioxane flame retardants includes the following steps: (1) First, dissolve silsesquioxane A in an organic solvent solution, then add a catalyst. Under the action of the catalyst, stir evenly and add a small amount of water. Continue stirring for 4-8 hours, then place the whole thing in an ice-water bath and stir. (2) Dissolve compound B in an organic solution, and slowly add the organic solution of compound B to step (1) through a constant pressure dropping funnel, while slowly adding an alkaline agent. Under alkaline conditions, the primary alcohol after ring opening in silsesquioxane A undergoes a nucleophilic ring-opening substitution reaction with the halogen end group X in compound B to obtain the modified polysilsesquioxane flame retardant preproduct. (3) The reaction preproduct in step (2) is rotary evaporated to remove the organic solvent. Then it is washed with saturated sodium chloride solution, filtered and dried to obtain the modified polysilsesquioxane flame retardant.

[0064] In some embodiments, silsesquioxane A is first dissolved in an organic solvent solution, then a catalyst is added. Under the action of the catalyst, the mixture is stirred evenly and a trace amount of water is added. After stirring continuously for 6 hours, the whole mixture is placed in an ice-water bath and stirred.

[0065] Furthermore, the molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:1.

[0066] The spatial structure of silsesquioxane A is relatively large. Sufficiently small steric hindrance is required during the reaction to obtain the modified polysilsesquioxane flame retardant. During the reaction, each epoxy group D is attached to one halogen group X, meaning the molar ratio of epoxy group D to halogen end group X is 1:1. This ensures sufficient space for silsesquioxane A and achieves structural stability in the modified polysilsesquioxane flame retardant. The primary alcohol groups formed after ring opening of each epoxy group undergo nucleophilic substitution reactions with halogens, thus yielding the modified polysilsesquioxane flame retardant. The overall reaction requires only a single substance, is simple to operate, and is easy to implement.

[0067] like Figure 1 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 1, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably di(4-nitrophenyl)phosphoryl chloride.

[0068] like Figure 2 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 2, silsesquioxane A is preferably octa[(3-glycidylpropyl)dimethylsiloxy]-substituted PSS and di[2-(p-nitrophenyl)ethyl]chlorophosphate.

[0069] like Figure 3 and Figure 4As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 3, silsesquioxane A is preferably 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane, and compound B is preferably DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROME) [THYL)BENZOHYDRAZONOYL]PHOSPHONATE; Understandably, this compound B contains three F-terminal groups, in 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane and DIETHYL[2-(2,4-DINITROPHENYL)- During the reaction of 3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE, the three epoxy groups in 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane in one molecule can react with DIETHYL[2-(2,4-DINITROPHENYL)-3- The three F-terminal groups in [TRIFLUOROMETHYL]BENZOHYDRAZONOYL]PHOSPHONATE react one-to-one to form a modified polysilsesquioxane flame retardant 3 with a three-ring structure; similarly, the three epoxy groups in one molecule of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane can react with three different molecules of DIETHYL[2-(2,4-DINITROPHENYL)-3- In (TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE, one F-terminal group corresponds to the reaction link, thereby forming a modified polysilsesquioxane flame retardant 3, which is a polymeric network. Both of the above structures can exist in the modified polysilsesquioxane flame retardant 3. Similarly, 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3].The three epoxy groups of [15,11] heptasiloxane can react with the two F-terminal groups in the same DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL) BENZOHYDRAZONOYL]PHOSPHONATE molecule and another different DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)] PHOSPHONATE molecule. In the [BENZOHYDRAZONOYL]PHOSPHONATE molecule, one F-terminal group reacts to form both a cyclic structure and a polymeric network structure. This structure is also present in modified polysilsesquioxane flame retardant 3, where one molecule of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane can connect 1-3 DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL) BENZOHYDRAZONOYL]PHOSPHONATE molecules. The specific molecular structure of modified polysilsesquioxane flame retardant 3 is not specifically limited here.

[0070] like Figure 5 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 4, silsesquioxane A is preferably acryloyloxypropyl-glycidyloxypropyl cage-type polysilsesquioxane, and compound B is preferably bis(4-nitrobenzyl)chlorophosphate.

[0071] like Figure 6 and Figure 7As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 5, silsesquioxane A is preferably glycidyl etheroxypropyl-isooctyl polysilsesquioxane, and compound B is preferably Bis(3-chloropropyl) p-nitrophenyl phosphate. It is understood that this compound B contains two Cl-terminal groups. During the reaction of glycidyl etheroxypropyl-isooctyl polysilsesquioxane with Bis(3-chloropropyl) p-nitrophenyl phosphate, one glycidyl etheroxypropyl-isooctyl polysilsesquioxane molecule contains four epoxy groups. One molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane corresponds to two molecules of Bis(3-chloropropyl) p-nitrophenyl phosphate. The four epoxy groups in one molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane can react with two molecules of Bis(3-chloropropyl) p-nitrophenyl phosphate. The Cl-terminal groups of phosphate are reacted one-to-one to form a modified polysilsesquioxane flame retardant 5 with two cyclic groups. Similarly, one molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane can react with one Cl-terminal group of four different Bis(3-chloropropyl) p-nitrophenyl phosphate molecules, forming a polymeric network of modified polysilsesquioxane flame retardant 5. Both of these structures exist in modified polysilsesquioxane flame retardant 5. Likewise, during the reaction, one glycidyl etheroxypropyl-isooctyl polysilsesquioxane molecule can react with two Cl-terminal groups of the same Bis(3-chloropropyl) p-nitrophenyl phosphate molecule and another different Bis(3-chloropropyl) p-nitrophenyl One Cl terminal group in the phosphate molecule reacts and connects to form both a cyclic structure and a polymeric network structure. This structure also exists in the modified polysilsesquioxane flame retardant 5, that is, one molecule of glycidyl etheroxypropyl-isooctyl polysilsesquioxane can connect 2-4 Bis(3-chloropropyl) p-nitrophenyl phosphate molecules. The specific molecular structure of the modified polysilsesquioxane flame retardant 3 is not specifically limited here.

[0072] like Figure 8As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 6, silsesquioxane A is preferably epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane, and compound B is preferably N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride. The epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane contains eight epoxy groups, and the N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride contains two Cl-terminal groups. It is understood that the N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride contains two Cl-terminal groups. The two Cl terminal groups in phosphoryl dichloride can react and connect with two groups in the same epoxycyclohexyl ethyl-glycidyl oxypropyl cage polysilsesquioxane molecule, or react and connect with epoxy groups in two different epoxycyclohexyl ethyl-glycidyl oxypropyl cage polysilsesquioxane molecules. This can simultaneously form a cyclic structure and a polymeric network structure. That is, one molecule of epoxycyclohexyl ethyl-glycidyl oxypropyl cage polysilsesquioxane can connect 4-8 N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride molecules. The specific molecular structure of the modified polysilsesquioxane flame retardant 6 is not specifically limited here.

[0073] like Figure 9 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 7, silsesquioxane A is preferably octacyclooxycyclohexylethyl cage-like polysilsesquioxane, and compound B is preferably di(4-nitrophenyl)phosphoryl chloride.

[0074] like Figure 10 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 8, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably dibenzylphosphoyl chloride.

[0075] like Figure 11 and Figure 12 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 9, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably cyclophosphamide.

[0076] like Figure 13 As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 10, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably Ethyl 3-(3-chloropropyl)-5-nitrophenylacetate.

[0077] like Figure 14As shown, in some embodiments, in the modified polysilsesquioxane flame retardant 11, silsesquioxane A is preferably glycidyl etheroxypropylcyclotetrasiloxane, and compound B is preferably bis(2-chlorophenyl)phosphoryl chloride.

[0078] Furthermore, the catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts; the organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones; and the basic agent is at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium phosphate, and sodium silicate.

[0079] Catalysts can precisely control the selectivity and reaction pathway of a reaction, while lowering the activation energy, increasing the reaction rate, and controlling the three-dimensional configuration of the product molecules. Basic agents keep the reaction in an alkaline environment, absorbing the acidic substances generated by the reaction of primary alcohol groups with halogen end groups X, thereby ensuring that the nucleophilic substitution reaction can continue to occur.

[0080] In some embodiments, the catalyst is preferably sodium hydroxide.

[0081] In some embodiments, the organic solvent is preferably ethanol.

[0082] In some embodiments, the alkaline agent is preferably triethylamine.

[0083] Furthermore, the raw materials of the thermoplastic elastomer material, by weight, include 15-20 parts of polypropylene (PP), 20-25 parts of SEBS, 20-30 parts of plasticizer, 3-8 parts of compatibilizer, 5-8 parts of P-based flame retardant, 5-8 parts of N-based flame retardant, and 15-25 parts of modified polysilsesquioxane flame retardant.

[0084] Reducing the proportions of polypropylene (PP) and SEBS in thermoplastic elastomers can further improve their mechanical and flame-retardant properties.

[0085] Furthermore, the plasticizer includes at least one of white oil, naphthenic oil, and paraffin oil; the compatibilizer includes at least one of PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride; the phosphorus-based flame retardant includes inorganic phosphorus flame retardant or organic phosphorus flame retardant, the inorganic phosphorus flame retardant includes at least one of red phosphorus, phosphate, and polyphosphate, and the organic phosphorus flame retardant includes at least one of phosphate ester, phosphite ester, and phosphine oxide; the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, and melamine inorganic acid salt.

[0086] In some embodiments, plasticizers include, but are not limited to, phthalates, fatty acid diesters, fatty acid esters, phosphate esters, polyesters, epoxy resins, and paraffin oils. Phthalate plasticizers include, but are not limited to, dibutyl phthalate (DBP) and dioctyl phthalate (DOP). These plasticizers improve the flexural strength, adhesion, and low-temperature resistance of rubber compounds. Fatty acid diester plasticizers include, but are not limited to, dioctyl adipate (DOA), dioctyl azelate (DOZ), and dioctyl sebacate (DOS). These plasticizers have excellent cold resistance. Fatty acid ester plasticizers include, but are not limited to, oleate esters, pentaerythritol fatty acid esters, and citrate esters. These plasticizers have superior cold resistance and water resistance. Phosphate ester plasticizers include, but are not limited to, tricresyl phosphate (TCP) and trioctyl phosphate (TOP). These plasticizers are mainly used to improve flame retardancy. Epoxy plasticizers include, but are not limited to, epoxidized oils, epoxidized fatty acid monoesters, and epoxidized tetrahydrophthalates. These plasticizers have good heat and light resistance. Paraffin oil is mainly used to reduce hardness. The type of plasticizer is not limited here. Those skilled in the art can select it according to the specific application requirements and performance requirements of TPV in order to improve processing performance, reduce hardness, improve cold resistance, oil resistance or flame retardancy, etc.

[0087] In some embodiments, the plasticizer is preferably paraffin oil.

[0088] In some embodiments, the compatibilizer is maleic anhydride-grafted polypropylene (PP-g-MAH). PP-g-MAH, containing both non-polar PP segments and polar maleic anhydride segments, can be used to improve the compatibility between the flame retardant and the matrix material. Preferably, the PP-g-MAH has a grafting rate of 1.2% and a melt index (230°C, 2.16 kg) greater than 50 g / 10 min.

[0089] In some embodiments, the P-based flame retardant is preferably diethyl aluminum hypophosphite.

[0090] In some embodiments, N-based flame retardants include MCA flame retardants.

[0091] Furthermore, the raw materials for thermoplastic elastomer materials also include at least one of lubricant, antioxidant, and light stabilizer; wherein, by weight, the raw materials are 0.2-1 parts lubricant, 0.5-2 parts antioxidant, and 0.2-1 parts light stabilizer.

[0092] Lubricants improve the flowability of thermoplastic elastomer resins, reduce the coefficient of friction, make the surface of products smoother, improve processing efficiency, and also improve the transparency and gloss of plastics. Antioxidants effectively reduce the oxidation rate of materials during processing and use by capturing free radicals, decomposing peroxides, and complexing metal ions, thereby delaying or preventing oxidation or auto-oxidation processes, protecting plastic products from oxidation, and thus extending their service life. By adding light stabilizers, multiple mechanisms are used to protect materials, including shielding or reflecting ultraviolet rays, absorbing ultraviolet rays and converting them into heat energy, quenching molecules or groups excited by ultraviolet rays, and capturing free radicals generated by photo-oxidation and reduction, thereby preventing photo-oxidation reactions, protecting polymer materials from photoaging, extending their service life, and reducing maintenance costs.

[0093] In some embodiments, the lubricant is at least one of silicone lubricant, PE wax, PP wax, fatty acid and fatty acid salt, and the lubricant is preferably PE wax.

[0094] In some embodiments, the antioxidant is at least one of asymmetric hindered phenolic antioxidants, aromatic amine antioxidants, thioether antioxidants, and phosphite antioxidants, and the antioxidant is preferably antioxidant 1010.

[0095] In some embodiments, the light stabilizer is at least one selected from carbon black, zinc oxide, benzotriazoles, and triazines, with carbon black being the preferred light stabilizer.

[0096] To address the above problems, this invention also proposes a method for preparing a thermoplastic elastomer material, comprising the following steps: S1: Substitution reaction yields modified polysilsesquioxane flame retardant; S2: Mix the raw materials evenly and granulate them by twin-screw extrusion to obtain granules; dry the granules to obtain thermoplastic elastomer materials.

[0097] In some embodiments, extrusion granulation is achieved using a twin-screw extruder.

[0098] The processing temperatures of each zone of the extruder are as follows: Zone 1 90-100℃, Zone 2 160-180℃, Zone 3 190-200℃, Zone 4 190-220℃, Zone 5 190-220℃, Zone 6 190-220℃, Zone 7 190-220℃, Zone 8 190-220℃, Zone 9 180-200℃, Zone 10 180-200℃, Zone 11 200-210℃, and the die head 200-210℃. The main machine speed is 400-600 r / min, and the feeding speed is 30-60 r / min.

[0099] In some embodiments, the temperature at which the thermoplastic elastomer material is obtained by extrusion granulation is 170°C-190°C.

[0100] In some embodiments, the drying time is preferably 8-12 hours.

[0101] Furthermore, the raw materials also include at least one of lubricant, antioxidant, and light stabilizer.

[0102] The following specific embodiments and data explain the content of the present invention.

[0103] Information on the raw materials involved in the specific implementation method is shown in Table 1: Table 1 Information on raw materials for the examples and comparative examples Information on the raw materials involved in the specific implementation method is shown in Table 1:

[0104]

[0105] Example 1: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath for stirring. 4 mol of bis(4-nitrophenyl)phosphoryl chloride was dissolved in ethanol solution. The organic solution of bis(4-nitrophenyl)phosphoryl chloride was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 1. 15 parts PP, 30 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 15 parts P-based flame retardant, 15 parts N-based flame retardant, 15 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0106] Example 2: The preparation method is the same as in Example 1, except that: 18 parts PP, 20 parts SEBS, 20 parts plasticizer, 3 parts compatibilizer, 10 parts P-based flame retardant, 25 parts N-based flame retardant, 25 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0107] Example 3: The preparation method is the same as in Example 1, except that: 20 parts PP, 28 parts SEBS, 25 parts plasticizer, 8 parts compatibilizer, 25 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0108] Example 4: The preparation method is the same as in Example 1, except that: 22 parts PP, 25 parts SEBS, 30 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 25 parts N-based flame retardant, 30 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black were mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material was obtained.

[0109] Example 5: 1 mol of octa[(3-glycidyl oxydimethylsiloxy)-substituted PSS] was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The mixture was then placed in an ice-water bath and stirred. 8 mol of di[2-(p-nitrophenyl)ethyl]chlorophosphate was dissolved in ethanol solution. The organic solution of di[2-(p-nitrophenyl)ethyl]chlorophosphate was slowly added dropwise through a constant-pressure dropping funnel to the ethanol solution of octa[(3-glycidyl oxydimethylsiloxy)-substituted PSS, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 2. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0110] Example 6: 1 mol of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring thoroughly with the catalyst, a small amount of water was added. The mixture was stirred continuously for 4-8 hours, and then the entire mixture was placed in an ice-water bath and stirred. 1 mol... DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE was dissolved in an ethanol solution. DIETHYL[2-(2,4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL]PHOSPHONATE was then slowly added dropwise through a constant-pressure dropping funnel to an ethanol solution of 3,7,14-tris{[3-(epoxypropoxy)propyl]dimethylsiloxy}-1,3,5,7,9,11,14-heptacyclopentyltricyclo[7.3.3.15,11]heptasiloxane. An organic solution of PHOSPHONATE (4-DINITROPHENYL)-3-(TRIFLUOROMETHYL)BENZOHYDRAZONOYL)PHOSPHONATE was prepared by slowly adding sodium hydroxide solution to create an alkaline environment, resulting in a pre-product of modified polysilsesquioxane flame retardant. The pre-product was then subjected to rotary evaporation to remove the organic solvent, followed by washing with saturated sodium chloride solution. After filtration and drying, modified polysilsesquioxane flame retardant 3 was obtained. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0111] Example 7: 1 mol of acryloyloxypropyl-glycidyl etheroxypropyl cage-type polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The entire mixture was then placed in an ice-water bath for further stirring. 1 mol of bis(4-nitrobenzyl)chlorophosphate was dissolved in ethanol solution. The organic solution of bis(4-nitrobenzyl)chlorophosphate was slowly added dropwise to the ethanol solution of acryloyloxypropyl-glycidyl etheroxypropyl cage-type polysilsesquioxane through a constant pressure dropping funnel. Simultaneously, sodium hydroxide solution was slowly added dropwise to maintain an alkaline environment, yielding a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 4. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0112] Example 8: 1 mol of glycidyl etheroxypropyl-isooctyl polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The entire mixture was then placed in an ice-water bath for stirring. 4 mol of Bis(3-chloropropyl) p-nitrophenyl phosphate was dissolved in ethanol solution. The organic solution of Bis(3-chloropropyl) p-nitrophenyl phosphate was slowly added dropwise to the ethanol solution of glycidyl etheroxypropyl-isooctyl polysilsesquioxane through a constant pressure dropping funnel, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 5. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0113] Example 9: 1 mol of epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring thoroughly under the action of the catalyst, a trace amount of water was added. The mixture was stirred continuously for 4-8 hours, and then the entire mixture was placed in an ice-water bath for stirring. 4 mol of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride was dissolved in ethanol solution and added to the epoxycyclohexylethyl-glycidyl oxypropyl cage-like polysilsesquioxane through a constant pressure dropping funnel. An organic solution of N-(4,5-dihydro-1-methyl-4-oxo-1H-imidazol-2-yl)aminophosphoryl dichloride was slowly added dropwise to an ethanol solution of a cage-like polysilsesquioxane, while sodium hydroxide solution was slowly added dropwise to maintain an alkaline environment, thus obtaining a pre-product of a modified polysilsesquioxane flame retardant. The obtained pre-product of the modified polysilsesquioxane flame retardant was subjected to rotary evaporation to remove the organic solvent, followed by washing with a saturated sodium chloride solution, and then filtered and dried to obtain modified polysilsesquioxane flame retardant 6.

[0114] 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0115] Example 10: 1 mol of octacyclohexylethyl cage-like polysilsesquioxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The mixture was then placed in an ice-water bath for further stirring. 8 mol of bis(4-nitrophenyl)phosphoryl chloride was dissolved in ethanol solution. The organic solution of bis(4-nitrophenyl)phosphoryl chloride was slowly added dropwise through a constant-pressure dropping funnel to the ethanol solution of octacyclohexylethyl cage-like polysilsesquioxane, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 7. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0116] Comparative Example 1: The preparation method is the same as in Example 1, except that: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 40 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0117] Comparative Example 2: The preparation method is the same as in Example 1, except that: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 5 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0118] Comparative Example 3: The preparation method is the same as in Example 1, except that: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 35 parts P-based flame retardant, 35 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0119] Comparative Example 4: The preparation method is the same as in Example 1, except that: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 3 parts P-based flame retardant, 3 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0120] Comparative Example 5: The preparation method is the same as in Example 1, except that: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 3 parts P-based flame retardant, 3 parts N-based flame retardant, 5 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0121] Comparative Example 6: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath for stirring. 4 mol of dibenzyl phosphoric acid chloride was dissolved in ethanol solution. The organic solution of dibenzyl phosphoric acid chloride was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 8. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0122] Comparative Example 7: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath and stirred. 2 mol of cyclophosphamide was dissolved in ethanol solution. The organic solution of cyclophosphamide was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 9. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0123] Comparative Example 8: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution, and the mixture was stirred until homogeneous under the action of the catalyst. A small amount of water was then added, and the mixture was stirred continuously for 4-8 hours. The mixture was then placed in an ice-water bath and stirred. 4 mol of Ethyl 3-(3-chloropropyl)-5-nitrophenylacetate was dissolved in ethanol solution. The organic solution of Ethyl 3-(3-chloropropyl)-5-nitrophenylacetate was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane using a constant pressure dropping funnel, while simultaneously adding sodium hydroxide solution dropwise to maintain an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 10. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0124] Comparative Example 9: 1 mol of glycidyl etheroxypropylcyclotetrasiloxane was dissolved in 100 ml of ethanol solution. 0.2 mol of catalyst was added to the solution. After stirring evenly under the action of the catalyst, a trace amount of water was added. After stirring continuously for 4-8 hours, the whole mixture was placed in an ice-water bath for stirring. 4 mol of bis(2-chlorophenyl)phosphoryl chloride was dissolved in ethanol solution. The organic solution of bis(2-chlorophenyl)phosphoryl chloride was slowly added dropwise to the ethanol solution of glycidyl etheroxypropylcyclotetrasiloxane through a constant pressure dropping funnel. At the same time, sodium hydroxide solution was slowly added dropwise to keep the reaction solution in an alkaline environment, thus obtaining a modified polysilsesquioxane flame retardant preproduct. The obtained modified polysilsesquioxane flame retardant preproduct was subjected to rotary evaporation to remove the organic solvent. It was then washed with saturated sodium chloride solution, filtered, and dried to obtain modified polysilsesquioxane flame retardant 11. 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts modified polysilsesquioxane flame retardant, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0125] Comparative Example 10: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts glycidyl ether oxypropyl-isooctyl polysilsesquioxane, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0126] Comparative Example 11: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 20 parts P-based flame retardant, 20 parts N-based flame retardant, 20 parts di(4-nitrophenyl)phosphoyl chloride, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a high flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0127] Comparative Example 12: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 60 parts glycidyl etheroxypropyl-isooctyl polysilsesquioxane, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a highly flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0128] Comparative Example 13: 20 parts PP, 25 parts SEBS, 25 parts plasticizer, 5 parts compatibilizer, 60 parts di(4-nitrophenyl)phosphoyl chloride, 0.5 parts lubricant, 0.5 parts antioxidant, and 0.5 parts carbon black are mixed evenly and granulated by twin-screw extrusion at 180°C to obtain a thermoplastic elastomer material preform. After drying at 80°C, a highly flame-retardant and crack-resistant thermoplastic elastomer material is obtained.

[0129] Table 2 summarizes the components and key preparation variables of Examples 1-10 and Comparative Examples 1-13.

[0130] The thermoplastic elastomer materials prepared in the above embodiments and comparative examples were injection molded or pressed into sheets, and then subjected to tests for flame retardancy rating, oxygen index, tensile strength, elongation at break, thermal shock at 110°C, thermal shock at 130°C, thermal shock at 150°C, and halogen acid gas content. The test standards are as follows: (1) Flame retardancy rating test According to GB / T 5455-2014, the samples were subjected to vertical flammability testing. The samples were cut to the specified dimensions and tested under the specified conditions, and key parameters such as flammability time and residual substances were monitored.

[0131] (2) Does it drip when testing flame retardancy rating? To determine whether dripping occurs during flame retardancy rating testing, the test was conducted according to UL94 standards. The sample thickness was 3mm, and the test temperature was 23±2℃. The test was performed using the UL94 vertical burning test apparatus from Jiangsu Zhengrui Taibang Electronics Co., Ltd.

[0132] (3) Oxygen index According to GB / T 2406.2-2009, the sample size was prepared according to Type IV sample size. The test was conducted according to Method A - Top Surface Ignition Method. The oxygen index tester was performed using a device from Nanjing Jiangning District Fangshang Analytical Instrument Equipment Factory.

[0133] (4) Tensile strength and elongation at break The test was conducted according to Clause 9 of GB 1040—2008, with a test temperature of 23±2℃. The tensile test used a standard dumbbell-shaped specimen with a tensile speed of 250 mm / min. The tensile strength and elongation at break of five specimens were tested using a micro-controlled electronic universal tensile testing machine from Dongguan High-Speed ​​Railway Testing Co., Ltd., and the average value of the results was taken.

[0134] (5) Thermal shock at 110-150℃ The tests were conducted according to Appendix A of GB / T 32129-2015 standard, with a test temperature of 23±2℃ and a weight of 2kg. Three samples were tested at each temperature using the thermal shock resistance testing apparatus from Hebei Zhongke Beigong Testing Instrument Co., Ltd.

[0135] (6) Halogen acid gas content The test shall be conducted in accordance with Part 7 of GB / T 17650-1-2021 standard, and the content of halogen acid gas shall be ≤5mg / g in accordance with the requirements for halogen-free materials in IEC62821-1.

[0136] The test results are detailed in Table 3.

[0137] Table 2 shows the components of Examples 1-10 and Comparative Examples 1-13 of the present invention.

[0138]

[0139]

[0140] According to the specifications in GB / T 1040-2008, GB / T 5455, GB / T 2406.2, GB / T32129, UL94, and GB / T 17650-1-2021, the thermoplastic elastomer materials in Examples 1-10 and Comparative Examples 1-13 were tested for tensile strength, elongation at break, flame retardancy rating, oxygen index, thermal shock at 110°C, thermal shock at 130°C, thermal shock at 150°C, dripping during combustion, and halogen acid gas content. The test results are recorded in Table 3 below: Table 3 Performance test table of Examples 1-10 and Comparative Examples 1-13 of the present invention Tensile strength / MPa Elongation at break (%) Flame retardant rating Oxygen index (%) Does it drip? 110℃ thermal shock 130℃ thermal shock 150℃ thermal shock Halogen-free environmental protection requirements Precipitation status Example 1 11.4 530 V0 26 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 2 13.4 460 V0 29 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 3 14.3 480 V0 31 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 4 13.2 530 V0 33 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 5 12.8 520 V0 30 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 6 11.6 540 V0 28 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 7 13.4 490 V0 26 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 8 13.8 486 V0 30 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 9 12.9 504 V0 31 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Example 10 14.2 487 V0 33 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 1 9.4 654 V0 35 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 2 14.8 430 V2 26 dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 3 8.4 296 V0 35 No dripping cracking cracking cracking Environmental friendly No precipitation Comparative Example 4 13.9 560 V1 27 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 5 16.2 390 V2 24 dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 6 12.4 510 V1 29 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 7 11.6 540 V2 27 dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 8 13.8 515 V2 24 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 9 14.2 524 V0 28 No dripping No cracks No cracks No cracks Not environmentally friendly No precipitation Comparative Example 10 12.6 530 V2 26 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 11 7.3 843 V2 31 dripping No cracks No cracks No cracks Not environmentally friendly Precipitation Comparative Example 12 8.6 680 V2 28 No dripping No cracks No cracks No cracks Environmental friendly No precipitation Comparative Example 13 4.2 1230 V2 35 dripping No cracks No cracks No cracks Not environmentally friendly Precipitation Based on the test results above, it can be seen that in Examples 1-4, the modified polysilsesquioxane flame retardant 1 of the present invention was added, and the flame retardant rating was V0, with an oxygen index of 26-33%. Examples 1-4 exhibited good flame retardancy and high flame retardant efficiency. Example 5 added modified polysilsesquioxane flame retardant 2, Example 6 added modified polysilsesquioxane flame retardant 3, Example 7 added modified polysilsesquioxane flame retardant 4, Example 8 added modified polysilsesquioxane flame retardant 5, Example 9 added modified polysilsesquioxane flame retardant 6, and Example 10 added modified polysilsesquioxane flame retardant 7. The components of modified polysilsesquioxane flame retardants 2 to 7 all contain P, N elements, a Si-O skeleton, and a cyclic structure with a carbon-hydrogen ratio of not less than 1. The thermoplastic elastomer materials obtained in Examples 5 to 10 all possess… The thermoplastic elastomers obtained in Examples 5 to 10 exhibit high tensile strength and elongation at break, demonstrating good physical and mechanical properties. Furthermore, the thermoplastic elastomers obtained in Examples 5 to 10 exhibit excellent flame retardant properties, indicating that changes in the substrate and the type of modified polysilsesquioxane flame retardant do not affect the performance of the prepared thermoplastic elastomers. The modified polysilsesquioxane flame retardant provided by this invention can stably improve the flame retardancy of the prepared materials. The thermoplastic elastomers obtained in Examples 5 to 10 did not exhibit dripping during flame retardancy rating tests, and did not crack during thermal shock tests at 110°C, 130°C, and 150°C. This indicates that the thermoplastic elastomers prepared with the added modified polysilsesquioxane flame retardant have excellent adaptability and reliability under rapidly changing temperature conditions, providing assurance for use in harsh environments.

[0141] In Comparative Example 1, the amount of the modified polysilsesquioxane flame retardant of the present invention was increased to 40 parts, while in Comparative Example 2, the amount of the modified polysilsesquioxane flame retardant of the present invention was reduced to 5 parts. In both comparative examples, the amount of modified polysilsesquioxane flame retardant was outside the range proposed in the present invention. Experimental data shows that the thermoplastic elastomer material prepared in Comparative Example 1 had a tensile strength of less than 10 MPa, indicating that when the amount of modified polysilsesquioxane flame retardant exceeded the range proposed in the present invention, it indicated an excessive amount of modified polysilsesquioxane. The excessive plasticizing effect of the silsesquioxane flame retardant on the raw materials of thermoplastic elastomers weakens the entanglement between molecules in the thermoplastic elastomer and disrupts the effective aggregation between the hard segments of the molecules, reducing crystallization and thus reducing the mechanical properties of the prepared thermoplastic elastomer. In contrast, the thermoplastic elastomer prepared in Comparative Example 2 all had a flame retardancy rating of V2, indicating that when the amount of modified polysilsesquioxane flame retardant added is too small, the flame retardant performance of the prepared thermoplastic elastomer is insufficient.

[0142] Comparative Example 3 contained 35 parts of P-based flame retardant and 35 parts of N-based flame retardant. The proportions of P-based and N-based flame retardants exceeded the range proposed in this invention. Experimental data showed that Comparative Example 3 had a flame retardancy rating of V0 and an oxygen index of 35%, indicating excellent flame retardant performance. However, due to the excessive addition of P-based and N-based flame retardants, the mechanical properties of Comparative Example 3 decreased, with a tensile strength less than 10 MPa. Furthermore, cracking occurred in thermal shock tests at 110°C, 130°C, and 150°C. Comparative Example 4 contained 3 parts of P-based flame retardant and 3 parts of N-based flame retardant. The proportions of P-based and N-based flame retardants were below the range proposed in this invention. Experimental data showed that Comparative Example 4 had a flame retardancy rating of V1. The insufficient flame retardant capacity indicates that the P and N elements provided by the modified polysilsesquioxane flame retardant are insufficient to support the flame retardant properties of the TPS resin during combustion. This reflects that the synergistic effect of the modified polysilsesquioxane flame retardant, P-based flame retardant, and N-based flame retardant ensures the excellent flame retardant effect of the prepared thermoplastic elastomer material. In Comparative Example 5, 3 parts of P-based flame retardant, 3 parts of N-based flame retardant, and 3 parts of modified polysilsesquioxane flame retardant were added. In Comparative Example 5, the proportions of P-based flame retardant, N-based flame retardant, and modified polysilsesquioxane flame retardant were all lower than the range proposed in this invention. The experimental data shows that the flame retardant component in the thermoplastic elastomer material prepared in Comparative Example 5 was too low, which affected the flame retardant properties of the prepared thermoplastic elastomer material. Its flame retardant properties were poor, and dripping occurred during combustion.

[0143] The modified polysilsesquioxane flame retardant 8 added in Comparative Example 6 contains no nitrogen (N) element, and the modified polysilsesquioxane flame retardant 10 added in Comparative Example 8 contains no phosphorus (P) element. Experimental data shows that the flame retardancy rating of Comparative Example 6 is V1, and that of Comparative Example 8 is V2, indicating poor flame retardancy for both. The modified polysilsesquioxane flame retardant 9 added in Comparative Example 7 lacks cyclic structures with a carbon-to-hydrogen ratio of not less than 1, such as benzene rings. During combustion, it cannot rapidly generate a large number of Si-C bonds, resulting in insufficient char layer and dripping during flame retardancy rating testing. The modified polysilsesquioxane flame retardant 11 added in Comparative Example 9 contains no nitrogen element and has excess halogens. The flame retardant material produced halogenated acid gas during combustion, which is not environmentally friendly. Comparative Example 10 added glycidyl etheroxypropyl-isooctyl polysilsesquioxane to replace the modified polysilsesquioxane flame retardant as the flame retardant component. While glycidyl etheroxypropyl-isooctyl polysilsesquioxane has a large number of Si-O bonds, it does not contain P, N elements, or a cyclic structure with a carbon-to-hydrogen ratio of not less than 1. Experimental data shows that the flame retardant performance of the thermoplastic elastomer material prepared in Comparative Example 10 is insufficient. Comparative Example 11 added bis(4-nitrophenyl)phosphoryl chloride to replace the modified polysilsesquioxane flame retardant as the flame retardant component. bis(4-nitrophenyl)phosphoryl chloride contains P and N elements... The compound contains halogens and a cyclic structure with a carbon-to-hydrogen ratio of not less than 1. However, during combustion, bis(4-nitrophenyl)phosphoryl chloride cannot form a char layer. Experimental data shows that Comparative Example 11 has poor flame retardant performance and drips during combustion. Furthermore, because it contains halogens, it produces halogen acid gas during combustion, which is environmentally unfriendly. After a period of time, precipitation occurs. Comparative Example 13 only adds 60 parts of glycidyl etheroxypropyl-isooctyl polysilsesquioxane as a flame retardant component to replace the flame retardant component of this invention. Experimental data shows that because glycidyl etheroxypropyl-isooctyl polysilsesquioxane cannot provide an acid source and gas... To achieve flame retardancy, Comparative Example 12 only added glycidyl etheroxypropyl-isooctyl polysilsesquioxane as a flame retardant component. The flame retardant performance of the prepared thermoplastic elastomer materials was insufficient, and their flame retardant ratings were all V2. This indicates that under the same addition amount of flame retardant component, glycidyl etheroxypropyl-isooctyl polysilsesquioxane alone cannot achieve the flame retardant effect shown by the combination of P-series flame retardants, N-series flame retardants and modified polysilsesquioxane flame retardants in this invention. Comparative Example 13 only added di(4-nitrophenyl)phosphoryl chloride as a flame retardant component. As can be seen from the experimental data, the flame retardant performance of Comparative Example 13 was insufficient, and dripping occurred during the combustion process.

[0144] Therefore, this invention verifies that modifying polysilsesquioxane flame retardants improves the flame retardancy of thermoplastic elastomer materials, giving them excellent physical and mechanical properties and excellent anti-dripping effect during combustion. It is also safe and environmentally friendly, has extremely high industrial value, and can be widely applied and promoted.

[0145] The above are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the patent protection scope of the present invention.

Claims

1. A thermoplastic elastomer material, characterized in that, The raw materials of the thermoplastic elastomer material, by weight, include: Polypropylene (PP) 15-22 parts 20-30 SEBS copies Plasticizer 20-30 parts, 3-8 parts compatibilizer 5-10 parts of P-series flame retardant 5-10 parts of N-series flame retardant 15-30 parts of modified polysilsesquioxane flame retardant, The modified polysilsesquioxane flame retardant is prepared from raw materials including silsesquioxane A, compound B, and catalyst under an alkaline environment. The silsesquioxane A includes at least one epoxy group D, and the compound B contains phosphorus P and nitrogen N, and includes at least one halogen end group X.

2. The thermoplastic elastomer material as described in claim 1, characterized in that, The structure of the silsesquioxane A includes at least one of the fully cage-like silsesquioxanes, and its structural formula includes at least one ， Where 6≥n≥1, n is an integer, and R1, R2, R3, R4, R5, R6, R7, and R8 include at least one epoxy group D.

3. The thermoplastic elastomer material as described in claim 1, characterized in that, The compound B includes at least one cyclic structure E with a carbon-hydrogen ratio of not less than 1, and the halogen end group X is not directly connected to the cyclic structure E.

4. The thermoplastic elastomer material as described in claim 3, characterized in that, The cyclic structure E with a carbon-to-hydrogen ratio of not less than 1 includes at least one of a benzene ring group and an imidazole group.

5. The thermoplastic elastomer material as described in claim 1, characterized in that, The modified polysilsesquioxane flame retardant is synthesized by a nucleophilic substitution reaction of silsesquioxane A and compound B under the action of a catalyst after ring-opening, characterized by the following reaction route: .

6. The thermoplastic elastomer material as described in claim 5, characterized in that, The method for synthesizing the modified polysilsesquioxane flame retardant includes the following steps: (1) First, dissolve silsesquioxane A in an organic solvent solution, then add a catalyst. Under the action of the catalyst, stir evenly and add a small amount of water. Continue stirring for 4-8 hours, then place the whole thing in an ice-water bath and stir. (2) Dissolve compound B in an organic solution, and slowly add the organic solution of compound B to step (1) through a constant pressure dropping funnel, while slowly adding an alkaline agent. Under alkaline conditions, the epoxy group D in silsesquioxane A undergoes a nucleophilic ring-opening substitution reaction with the halogen end group X in compound B to obtain the modified polysilsesquioxane flame retardant preproduct. (3) The reaction preproduct in step (2) is rotary evaporated to remove the organic solvent. Then it is washed with saturated sodium chloride solution, filtered and dried to obtain the modified polysilsesquioxane flame retardant.

7. The thermoplastic elastomer material as described in claim 1, characterized in that, The molar ratio of epoxy group D in silsesquioxane A to halogen end group X in compound B is 1:

1.

8. The thermoplastic elastomer material as described in claim 6, characterized in that, The catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts; the organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones; and the basic agent is at least one of triethylamine, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium phosphate, and sodium silicate.

9. The thermoplastic elastomer material as described in claim 1, characterized in that, The raw materials of the thermoplastic elastomer material, by weight, include: Polypropylene (PP) 15-20 parts SEBS 20-25 copies, Plasticizer 20-30 parts, 3-8 parts compatibilizer 5-8 parts of P-series flame retardant 5-8 parts of N-series flame retardant 15-25 parts of modified polysilsesquioxane flame retardant.

10. The thermoplastic elastomer material as described in claim 1, characterized in that, The plasticizer includes at least one of white oil, naphthenic oil, and paraffin oil; the compatibilizer includes at least one of PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride; the phosphorus-based flame retardant includes inorganic phosphorus flame retardant or organic phosphorus flame retardant, the inorganic phosphorus flame retardant includes at least one of red phosphorus, phosphate, and polyphosphate, and the organic phosphorus flame retardant includes at least one of phosphate ester, phosphite ester, and phosphine oxide; the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, and melamine inorganic acid salt.

11. The thermoplastic elastomer material as described in claim 1, characterized in that, The raw materials of the thermoplastic elastomer material also include at least one of lubricant, antioxidant, and light stabilizer; wherein, by weight, the lubricant is 0.2-1 parts, the antioxidant is 0.5-2 parts, and the light stabilizer is 0.2-1 parts.

12. A method for preparing the thermoplastic elastomer material as described in claim 1, characterized in that, The process includes the following steps: mixing the raw materials evenly, extruding and granulating them through an extruder to obtain granules, which are the thermoplastic elastomer materials.

13. The method for preparing the thermoplastic elastomer material according to claim 12, characterized in that, The raw materials also include at least one of lubricant, antioxidant, and light stabilizer.

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