Thermoplastic elastomer material and process for the preparation thereof

Abstract

The application discloses a thermoplastic elastomer material, which comprises PP, SEBS, a plasticizer, a compatibilizer, a P-series flame retardant, an N-series flame retardant, an inorganic flame retardant and a modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist. The modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist contains boron elements, a cyclic structure R2 with a carbon-hydrogen ratio greater than 1 and two inorganic silicon cage cores. These structures form protective layers such as carbon layers, ceramic barrier layers, protective films or heat-insulating coke layers during combustion, greatly improving the drip-proof effect. At the same time, the heat and oxygen transmission are isolated, and the release of flammable gas is reduced. Multiple mechanisms work together to significantly improve the flame-retardant performance of the material. Further, the modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist cooperates with the P-series flame retardant, the N-series flame retardant and the inorganic flame retardant to synergistically flame-retardant, reduces the amount of flame retardant and improves the flame-retardant performance of the thermoplastic elastomer material. The thermoplastic elastomer material provided by the application has excellent flame-retardant performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of materials, in particular to a thermoplastic elastomer material and a preparation method thereof. BACKGROUND

[0002] Polyhedral oligomeric silsesquioxane (POSS) is a special organic amorphous material, which is a polycyclic organic monomer composed of a silicon framework and its embedded oxygen atoms, and is an inorganic-organic hybrid nanomaterial. The inorganic silicon cage core in POSS decomposes to form a dense ceramic barrier layer when heated, which insulates the release of combustible gases and external heat into the interior, thereby delaying further decomposition of the material. POSS shows great application potential in the field of flame retardants.

[0003] Thermoplastic elastomer (TPS) material is mainly made of SEBS, white oil, PP, and added plasticizer, antioxidant, etc. It has a wide range of hardness, excellent hand feeling, low temperature resistance, low price and excellent elasticity. There are many low smoke and halogen-free flame-retardant TPS cable materials on the foreign market that can meet the UL wire flame-retardant requirements. The comprehensive performance of domestic low smoke and halogen-free flame-retardant TPS cable materials is far behind 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 necessary to develop a halogen-free TPS material with high flame retardancy, crack resistance and anti-dripping. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides a thermoplastic elastomer material, which aims to solve the problem of poor flame retardancy of the current TPS material.

[0005] The above-mentioned purpose of the present application is realized by the following technical solutions:

[0006] In the first aspect of the present application, a thermoplastic elastomer material is provided, and the raw materials of the thermoplastic elastomer material include, by weight:

[0007] PP 15-22 parts,

[0008] SEBS 20-30 parts,

[0009] Plasticizer 20-30 parts,

[0010] Compatibility agent 3-8 parts,

[0011] P-based flame retardant 10-25 parts,

[0012] N-based flame retardant 10-25 parts,

[0013] inorganic flame retardant 10-15 parts,

[0014] modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist 2-15 parts,

[0015] The structure of the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist is as follows:

[0016]

[0017] R is a non-reactive group, such as isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl, etc., R1 is n-propyl or phenylene;

[0018] R2 is a cyclic structure with a carbon-hydrogen ratio greater than 1, including at least one of a benzofuran group and a polycyclic aromatic group.

[0019] In some embodiments of the present application, the benzofuran group includes at least one of a benzofuran group and a dibenzofuran group;

[0020] And / or, the polycyclic aromatic group includes at least one of a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, an acenaphthene ring group, a fluorene ring group, and a perylene ring group.

[0021] In some embodiments of the present application, the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist is prepared by dehydration reaction of compound 1 and compound 2 under the action of a catalyst, and the reaction route is as follows:

[0022]

[0023] In some embodiments of the present application, the molar ratio of the compound 1 to the compound 2 is 2:1.

[0024] In some embodiments of the present application, the preparation method of the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist includes the following steps:

[0025] Compound 1 is dissolved in an organic solvent, compound 2 aqueous solution is added under the action of a catalyst, and the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist is obtained after catalytic reaction, washing and drying;

[0026] The organic solvent includes at least one of an alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, an ether, a ketone, and a diol derivative.

[0027] The catalyst includes at least one of an acidic catalyst, a metal catalyst, and a basic catalyst.

[0028] In some embodiments of the present application, the raw materials of the thermoplastic elastomer material include, by weight fraction:

[0029] PP 15-22 parts,

[0030] SEBS 20-30 parts,

[0031] Plasticizer 20-30 parts,

[0032] Compatibilizer 3-8 parts,

[0033] P-based flame retardant 10-15 parts,

[0034] N-based flame retardant 10-15 parts,

[0035] Inorganic flame retardant 10-12 parts,

[0036] Modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist 2-15 parts.

[0037] In some embodiments of the present application, the plasticizer includes at least one of white oil, naphthenic oil, paraffin oil.

[0038] In some embodiments of the present application, the compatibilizer includes at least one of PE grafted maleic anhydride, POE grafted maleic anhydride, PP grafted maleic anhydride, EMA grafted maleic anhydride.

[0039] In some embodiments of the present application, the P-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, polyphosphate; the organic phosphorus flame retardant includes at least one of phosphate ester, phosphite, phosphine oxide; and / or, the N-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt

[0040] In some embodiments of the present application, the inorganic flame retardant includes at least one of magnesium hydroxide, aluminum hydroxide, calcium carbonate.

[0041] In some embodiments of the present application, the raw materials of the thermoplastic elastomer material further include at least one of lubricant, antioxidant, light stabilizer; wherein, by weight fraction, the lubricant is 0.2-1 parts, the antioxidant is 0.5-2 parts, and the light stabilizer is 0.2-1 parts.

[0042] In the second aspect of the present application, a preparation method of the above-mentioned thermoplastic elastomer material is provided, including the following steps: uniformly mixing the raw materials, extruding and granulating through an extruder to obtain granules, i.e. the thermoplastic elastomer material.

[0043] In some embodiments of the application, the raw material further comprises at least one of a lubricant, an antioxidant, a light stabilizer.

[0044] The thermoplastic elastomer material comprises PP, SEBS, a plasticizer, a compatibilizer, a P-based flame retardant, an N-based flame retardant, an inorganic flame retardant, and a modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist. The modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist contains boron elements, a cyclic structure R2 with a carbon-hydrogen ratio greater than 1, and two inorganic silicon cage cores. In the combustion process, boron elements form boric acid, which dehydrates and carbonizes the surface of the material to form a carbon layer. The two inorganic silicon cage cores decompose to form a dense ceramic barrier layer that insulates the release of flammable gas and the entry of external heat into the interior. The cyclic structure R2 with a carbon-hydrogen ratio greater than 1 has a high carbon-hydrogen ratio, and the benzofuran group and polycyclic aromatic group contain a large amount of carbon elements. A large amount of carbon elements form a glassy protective film or heat-insulating coke layer during combustion, which can insulate air and prevent heat transfer and reduce the release of flammable gas. These structures form protective layers such as carbon layers, ceramic barrier layers, protective films, or heat-insulating coke layers during combustion, greatly improving the drip-proof effect. At the same time, the transfer of heat and oxygen is blocked, and the release of flammable gas is reduced. The combination of multiple mechanisms significantly improves the flame-retardant performance of the material. The modified POSS and its derivative flame-retardant synergist, the P-based flame retardant, the N-based flame retardant, and the inorganic flame retardant together serve as the main flame-retardant components of the thermoplastic elastomer material. Each component cooperates and synergizes with the others. In the combustion process, Si elements and C elements in the R2 group can rapidly react to form a large number of Si-C bonds, accompanied by the formation of a glass film on the surface of the thermoplastic elastomer material by B elements. The generated boric acid rapidly dehydrates the polymer to produce a carbon layer. The B elements in the modified POSS and its derivative flame-retardant synergist can also coordinate with P elements in the system to produce a synergistic effect, thereby improving the flame-retardant effect. By adding the modified POSS and its derivative flame-retardant synergist and the P-based and N-based flame retardants, a hard carbon layer is quickly formed to prevent the thermoplastic elastomer from burning and dripping, and air is blocked to improve the flame resistance of the thermoplastic elastomer material. The P-based flame retardant provides an acid source, the N-based flame retardant provides a gas source, and the modified POSS and its derivative flame-retardant synergist provides a rich carbon source, making the P-based and N-based flame retardants more effective. Furthermore, the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist cooperates with the inorganic flame retardant to synergistically flame-retardant, thereby ensuring that the prepared thermoplastic elastomer material has good processing performance, elasticity, and flame resistance, and improving the crack resistance, flame resistance, and physical and mechanical properties of the thermoplastic elastomer material. The thermoplastic elastomer material provided by the present application has excellent flame resistance and crack resistance, and can prevent dripping during combustion. The modified POSS and its derivative flame-retardant synergist is a colorless viscous liquid, has little effect on the performance of the thermoplastic elastomer material, and can obtain a thermoplastic elastomer material with excellent flame resistance without a high addition amount. BRIEF DESCRIPTION OF DRAWINGS

[0045] Figure 1 Molecular structure diagram of modified POSS flame retardant synergist 1 of the present application;

[0046] Figure 2 Molecular structure diagram of modified POSS flame retardant synergist 2 of the present application. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. It should be understood that the following embodiments are only used to explain the present application and are not used to limit the present application.

[0048] Unless otherwise defined, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.

[0049] PP: Polypropylene, is a semi-crystalline thermoplastic polymer made from propylene monomers through polyaddition reaction, polypropylene has the characteristics of lightness, wear resistance, antibacterial property and easy dyeing, etc., and is widely used in fiber products such as clothing, blankets, etc.; has good insulation performance, and is used to manufacture the shell and parts of refrigerator, washing machine, air conditioner, television, etc.; has good chemical stability, heat resistance, transparency and mechanical properties, and is used to manufacture medical devices; has good corrosion resistance, weather resistance and plasticity, and is used to manufacture building and building materials products.

[0050] SEBS: Styrene Ethylene Butylene Styrene, is a linear three-embedded copolymer, with polystyrene as the terminal segment, and ethylene-butene copolymer obtained by hydrogenation of polybutadiene as the middle elastic segment. SEBS has good stability and aging resistance, because its molecular chain does not contain unsaturated double bonds, which makes it show excellent aging resistance in light oxygen and ozone environment.

[0051] Polyhedral oligomeric silsesquioxane (POSS) is a special organic amorphous material, which is a polycyclic organic monomer composed of silicon framework and its embedded oxygen atoms, and is an inorganic-organic hybrid nanomaterial. The inorganic silicon cage core in POSS decomposes to form a dense ceramic barrier layer when heated, which isolates the release of combustible gas and external heat into the interior, thereby delaying further decomposition of the material. POSS shows great application potential in the field of flame retardants.

[0052] Thermoplastic elastomer (TPS) material is mainly made of SEBS, white oil, PP, adding certain plasticizer, antioxidant and the like, has a wide hardness range, has excellent hand feeling, low temperature resistance, low price and excellent elasticity, and the TPS cable material has many kinds of low smoke, halogen-free flame-retardant TPS cable material meeting the UL wire flame-retardant requirements in the foreign market, and the comprehensive performance of the low smoke halogen-free flame-retardant TPS cable material produced in China is far from that of the imported product, due to the limitation of the domestic flame-retardant technology, the development of the high flame-retardant, high mechanical property and anti-cracking TPS material has not made obvious progress, and therefore it is necessary to develop a halogen-free TPS material with high flame-retardant, anti-cracking and anti-dripping properties.

[0053] To solve the above problems, the first aspect of the present application provides a thermoplastic elastomer material, the raw materials of the thermoplastic elastomer material include, by weight:

[0054] PP 15-22 parts,

[0055] SEBS 20-30 parts,

[0056] Plasticizer 20-30 parts,

[0057] Compatibility agent 3-8 parts,

[0058] P flame retardant 10-25 parts,

[0059] N flame retardant 10-25 parts,

[0060] Inorganic flame retardant 10-15 parts,

[0061] Modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist 2-15 parts,

[0062] The structure of the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist is:

[0063]

[0064] Wherein, R is a non-reactive group, isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl, etc., R1 is n-propyl or phenylene;

[0065] R2 is a cyclic structure with a carbon-hydrogen ratio greater than 1, including at least one of a benzofuran group and a polycyclic aromatic group.

[0066] It can be understood that when R1 connected to Si in the inorganic silicon cage core is phenylene, because the phenylene contains a benzene ring, the carbon-hydrogen ratio and the carbon content of the benzene ring are relatively high, and during combustion, the inorganic silicon cage core containing a large amount of Si together, further improves the flame-retardant performance of the inorganic silicon cage core, thereby improving the flame-retardant performance of the modified polyhedral oligomeric silsesquioxane flame-retardant synergist.

[0067] The thermoplastic elastomer material of the present application comprises PP, SEBS, plasticizer, compatibilizer, P-based flame retardant, N-based flame retardant, inorganic flame retardant and modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist. Because the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist contains boron elements, cyclic structures R2 with a carbon-hydrogen ratio greater than 1 and two inorganic silicon cage cores, the boron elements form boric acid in the combustion process, which dehydrates and carbonizes the surface of the material to form a carbon layer; the two inorganic silicon cage cores decompose to form a dense ceramic barrier layer that insulates the release of flammable gas and the entry of external heat into the interior; the cyclic structure R2 with a carbon-hydrogen ratio greater than 1 has a high carbon-hydrogen ratio, and the benzofuran group and polycyclic aromatic group contain a large amount of carbon elements, which form a glassy protective film or heat-insulating coke layer in the combustion process. These protective films or coke layers can insulate air and prevent the transfer of heat, reducing the release of flammable gas. These structures form protective layers such as carbon layers, ceramic barrier layers, protective films or heat-insulating coke layers in the combustion process, greatly improving the drip-proof effect, and at the same time, insulating heat and oxygen transfer and reducing the release of flammable gas. The various mechanisms work together to significantly improve the flame retardant performance of the material. The modified POSS and its derivative flame-retardant synergist, P-based flame retardant, N-based flame retardant and inorganic flame retardant together serve as the main flame-retardant components of the thermoplastic elastomer material, and each component cooperates and synergizes with the others. In the combustion process, Si elements and C elements in the R2 group can rapidly react to form a large amount of Si-C bonds, accompanied by the formation of a glass film on the surface of the thermoplastic elastomer material by B elements, and the generated boric acid rapidly dehydrates the polymer to produce a carbon layer. The B elements in the modified POSS and its derivative flame-retardant synergist can also coordinate with the P elements in the system to produce a synergistic effect, thereby improving the flame-retardant effect. By adding the modified POSS and its derivative flame-retardant synergist and the P-based and N-based flame retardants, a relatively hard carbon layer is rapidly formed to prevent the thermoplastic elastomer from burning and dripping, and air is insulated to improve the flame retardancy of the thermoplastic elastomer material. The P-based flame retardant provides an acid source, the N-based flame retardant provides a gas source, and the modified POSS and its derivative flame-retardant synergist provides abundant carbon sources, enabling the P-based and N-based flame retardants to exhibit stronger flame retardancy. Furthermore, the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist cooperates with the inorganic flame retardant to synergize flame retardation, so that the prepared thermoplastic elastomer material can ensure the original good processing performance, elasticity and flame retardancy of the thermoplastic elastomer, and improve the crack resistance, flame retardancy and physical and mechanical properties of the thermoplastic elastomer material. The thermoplastic elastomer material provided by the present application has excellent flame retardancy and crack resistance, and can prevent dripping during combustion. The modified POSS and its derivative flame-retardant synergist is a colorless viscous liquid, has little effect on the performance of the thermoplastic elastomer material, and can obtain a thermoplastic elastomer material with excellent flame retardancy without a high addition amount.

[0068] Further, the benzofuran group includes at least one of a benzofuran group and a dibenzofuran group.

[0069] The carbon-hydrogen ratio and the carbon content in the phenyl group are high, which can slow down the spread of the flame during combustion, and the flame can self-extinguish quickly after the flame moves away, reducing the duration and intensity of combustion. The furan group has a high carbon content while having oxygen elements that do not participate in combustion. The combination of the two forms a benzofuran group or a dibenzofuran group, which has both a high carbon-hydrogen ratio and a low combustion element. The two work together to form a glassy protective film or a heat-insulating coke layer during combustion. These protective films or coke layers can insulate air, prevent heat transfer, and reduce the content of combustible materials, and can indirectly promote carbonization.

[0070] In some embodiments, R2 is a benzofuran group.

[0071] In some embodiments, the polycyclic aromatic group includes at least one of a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, an acenaphthene ring group, a fluorene ring group, and a perylene ring group.

[0072] The carbon-hydrogen ratio of the naphthalene ring group, the anthracene ring group, the phenanthrene ring group, the acenaphthene ring group, the fluorene ring group, and the perylene ring group is high, and they contain a large amount of carbon elements, which are more likely to form a glassy protective film or a heat-insulating coke layer during combustion.

[0073] In some embodiments, R2 is a naphthalene ring group.

[0074] Further, the modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist is prepared by dehydration reaction of compound 1 and compound 2 under the action of a catalyst, and the reaction route is as follows:

[0075]

[0076] Further, the molar ratio of compound 1 to compound 2 in the above reaction process is 2:1.

[0077] The space structure of compound 1 polyhedral oligomeric silsesquioxane is large, and it is necessary to ensure that compound 2 has a small enough steric hindrance to react with compound 1 to obtain compound 3 modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist. In the reaction process, each compound 2 connects 2 compound 1, i.e. the molar ratio of compound 1 to compound 2 is 2:1, which ensures the sufficient space of compound 3 and realizes the structure stability of compound 3; compound 2 contains 2 hydroxyl groups, and 2 hydroxyl groups of 1 compound 2 combine with 1 amino group of 2 compound 1 to carry out dehydration reaction to obtain compound 3. The overall reaction needs only one substance, the operation is simple, and it is easy to realize.

[0078] In some embodiments, the compound 1 is aminopropyl heptaisobutylcage polysilsesquioxane.

[0079] In some embodiments, the compound 1 is aminopropyl heptaisobutylcage polysilsesquioxane.

[0080] In some embodiments, the compound 2 is benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid.

[0081] In some embodiments, the compound 2 is benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid.

[0082] In some embodiments, the compound 3 has the following structural formula:

[0083]

[0084] The following is a modified POSS flame retardant synergist 1.

[0085] In some embodiments, the compound 3 has the following structural formula:

[0086]

[0087] The following is a modified POSS flame retardant synergist 2.

[0088] Further, the preparation method of the compound 3 comprises the following steps:

[0089] Compound 1 is dissolved in an organic solvent, and compound 2 aqueous solution is added under the action of a catalyst, and after catalytic reaction, washing and drying, compound 3 is obtained;

[0090] The organic solvent includes at least one of alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, alicyclic hydrocarbon, ether, ketone and diol derivative;

[0091] The catalyst includes at least one of an acidic catalyst, a metal catalyst and a basic catalyst.

[0092] In some embodiments, the catalyst is acetic acid.

[0093] In some embodiments, the solvent is ethanol.

[0094] Further, the raw material of the thermoplastic elastomer material includes, by weight:

[0095] PP 15-22 parts,

[0096] SEBS 20-30 parts,

[0097] Plasticizer 20-30 parts,

[0098] Compatibilizer 3-8 parts,

[0099] P flame retardant 10-15 parts,

[0100] N flame retardant 10-15 parts,

[0101] Inorganic flame retardant 10-12 parts,

[0102] Modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist 2-15 parts.

[0103] Reducing the number of P flame retardant, N flame retardant and inorganic flame retardant can further improve the mechanical properties of the thermoplastic elastomer material.

[0104] Further, the plasticizer includes at least one of white oil, naphthenic oil, paraffin oil.

[0105] The plasticizer is used to improve the flowability of the thermoplastic elastomer and improve the processability of the thermoplastic elastomer.

[0106] In some embodiments, the plasticizer is preferably white oil.

[0107] Further, the compatibilizer includes at least one of PE grafted maleic anhydride, POE grafted maleic anhydride, PP grafted maleic anhydride, EMA grafted maleic anhydride.

[0108] The compatibilizer improves the interfacial compatibility and adhesion between the base resin and the flame retardant by forming a bridge between them, so that the flame retardant can be more uniformly dispersed in the matrix, thereby improving the filling rate and flame retardant effect, improving the overall performance of the cable, and the compatibilizer can reduce the incompatibility problem in the production process, thereby improving the production process and improving the production efficiency.

[0109] Further, the P 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, polyphosphate; the organic phosphorus flame retardant includes at least one of phosphate ester, phosphite, phosphine oxide; and / or, the N flame retardant includes at least one of melamine cyanurate, melamine phosphate, melamine inorganic acid salt.

[0110] It can be understood that the phosphorus flame retardant includes but is not limited to aluminum hypophosphite, calcium hypophosphite, aluminum diethyl hypophosphite, methyl ethyl hypophosphite and phenyl hypophosphite.

[0111] In some embodiments, the P flame retardant is preferably aluminum diethyl hypophosphite.

[0112] In some embodiments, the N flame retardant is preferably melamine cyanurate.

[0113] Further, the inorganic flame retardant includes at least one of magnesium hydroxide, aluminum hydroxide, calcium carbonate.

[0114] It can be understood that the inorganic flame retardant includes but is not limited to magnesium hydroxide, aluminum hydroxide, calcium carbonate.

[0115] In some embodiments, the inorganic flame retardant is preferably aluminum hydroxide.

[0116] Further, the raw materials of the thermoplastic elastomer material further include at least one of a lubricant, an antioxidant, and a light stabilizer; wherein the raw materials are in parts 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.

[0117] In some embodiments, the antioxidant includes but is not limited to an unsymmetrical hindered phenolic antioxidant, an aromatic amine antioxidant, a sulfide antioxidant, and a phosphite antioxidant.

[0118] The hindered phenolic antioxidant includes but is not limited to antioxidant 1010 (tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester), BHT (2,6-di-tert-butyl-p-cresol), antioxidant 1076 (β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl ester);

[0119] The aromatic amine antioxidant includes but is not limited to diphenylamine, p-phenylenediamine, and dihydroquinoline and its derivatives or polymers, such as: antioxidant 445 (4,4'-bis(α.α-dimethylbenzyl)diphenylamine);

[0120] The sulfide antioxidant includes but is not limited to DLTP (dilauryl thiodipropionate), DSTDP (distearyl thiodipropionate), and DSTP (octadecyl thiodipropionate);

[0121] The phosphite antioxidant includes but is not limited to antioxidant 168 (tris[2.4-di-tert-butylphenyl]phosphite), antioxidant 618 (dilauryl pentaerythritol diphosphite), and antioxidant 626 (bis[2.4-di-tert-butylphenyl]pentaerythritol diphosphite).

[0122] By adding the antioxidant, the antioxidant performance and aging resistance of the polymer material are improved, and the service life of the polymer material is prolonged.

[0123] In some embodiments, the lubricant includes but is not limited to PTFE powder, zinc stearate, magnesium stearate, silicone, calcium stearate, or ethylene bis-stearamide. By adding the lubricant, the mixing of various raw materials is facilitated, the flowability of the polymer resin is improved, the friction coefficient is reduced, the surface of the product is smoother, the processing efficiency is improved, and the transparency and gloss of the plastic are also improved.

[0124] In some embodiments, the light stabilizer includes, but is not limited to, carbon black, zinc oxide, benzotriazole, triazine. By adding light stabilizers, the material is protected by various mechanisms, including shielding or reflecting ultraviolet light, absorbing ultraviolet light and converting it into heat energy, quenching molecules or groups excited by ultraviolet light, and capturing free radicals generated by photooxidation, thereby preventing photooxidation, protecting high molecular materials from light aging, and prolonging their service life.

[0125] In a second aspect of the present application, a method for preparing the thermoplastic elastomer material is provided, comprising the following steps: uniformly mixing raw materials, i.e. PP, SEBS, plasticizer, compatibilizer, P-based flame retardant, N-based flame retardant, inorganic flame retardant, and modified polyhedral oligomeric silsesquioxane and its derivative flame-retardant synergist, and then extruding and granulating through an extruder to obtain granules, i.e. thermoplastic elastomer material.

[0126] Further, the raw materials further include at least one of a lubricant, an antioxidant, and a light stabilizer.

[0127] The content of the present application is explained below through specific examples and data.

[0128] The information of the raw materials involved in the specific implementation part is shown in Table 1:

[0129] Table 1 Information of raw materials of examples and comparative examples

[0130]

[0131]

[0132] The thermoplastic polyurethane elastomer material prepared in the above examples and comparative examples is subjected to injection molding or compression molding, and tests of flame retardant grade, oxygen index, tensile strength, elongation at break, 110℃ thermal shock, 130℃ thermal shock, and 150℃ thermal shock are carried out, and the test standards are as follows:

[0133] (1) Flame retardant grade test

[0134] According to GB / T 5455-2014, the sample is subjected to vertical combustion grade test, the sample is cut according to the specified size, and the test is carried out under the conditions, and the key parameters such as burning time and residual material are monitored.

[0135] (2) Whether to drop during the test of flame retardant grade

[0136] Whether to drop during the test of flame retardant grade is tested according to the UL94 standard, the sample thickness is 3mm, and the test temperature is 23±2℃. The UL94 vertical combustion test device of Jiangsu Zhengruitai Bang Electronics Co., Ltd. is used for testing.

[0137] (3) Oxygen index

[0138] According to GB / T 2406.2-2009, the sample size is prepared according to type IV sample. The test is carried out according to method A-top surface ignition method. The oxygen index tester device of Nanjing Jiangning Fangshang Analytical Instrument Equipment Factory is used for testing.

[0139] (4) Tensile strength and elongation at break

[0140] According to the 9th clause of GB 1040-2008, the test temperature is 23±2℃, and the tensile test uses standard dumbbell-shaped sample with a tensile speed of 250mm / min. The tensile strength and elongation at break of 5 samples are tested by the micro-controlled electronic universal material tension machine of Dongguan Gao Tie Detection Co., Ltd., and the average value is taken.

[0141] (5) 110-150℃ thermal shock

[0142] According to the appendix A of GB / T 32129-2015 standard, the test temperature is 23±2℃, and the weight of the weight is 2kg. The thermal shock resistance test device of Hebei Zhongkebei Gong Test Instrument Co., Ltd. is used to test 3 samples at each temperature.

[0143] (6) Pants-type tear

[0144] According to GB / T 3917.2-2009 standard, the sample is cut according to the specified size, and then the two legs of the pants-shaped sample are clamped, so that the cut line of the sample is straight between the two clamps. Turn on the instrument to apply tension to the cut direction, record the tear strength until the tear reaches the specified length, calculate the average value of the highest peak and the lowest peak in the specified area, and measure the tear strength.

[0145] The test results are shown in Table 3.

[0146] Example 1:

[0147] 2mol of aminopropyl heptaisobutyl cage polysilsesquioxane is dissolved in 100ml of tetrahydrofuran solution, 0.2mol of acetic acid catalyst is added to the solution, and 1mol of benz[B]naphtho[2,3-D]furan-2-hydroxyboric acid is added under stirring. Stirring for 2-4h, stop the reaction, rotary evaporation under reduced pressure, wash with water, dry, and obtain modified POSS flame retardant synergist 1;

[0148] Mix 22 parts of PP, 30 parts of SEBS, 30 parts of white oil, 8 parts of PE grafted maleic anhydride, 10 parts of modified POSS flame-retardant synergist 1, 10 parts of aluminum diethyl phosphinate, 10 parts of MCA flame retardant, 10 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer uniformly, and then extrude and pelletize through a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, and halogen-free thermoplastic elastomer material.

[0149] Example 2:

[0150] The preparation method is the same as that in Example 1, except that:

[0151] Mix 15 parts of PP, 20 parts of SEBS, 20 parts of white oil, 3 parts of PE grafted maleic anhydride, 15 parts of modified POSS flame-retardant synergist 1, 15 parts of aluminum diethyl phosphinate, 10 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer uniformly, and then extrude and pelletize through a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, and halogen-free thermoplastic elastomer material.

[0152] Example 3:

[0153] The preparation method is the same as that in Example 1, except that:

[0154] Mix 22 parts of PP, 30 parts of SEBS, 30 parts of white oil, 8 parts of PE grafted maleic anhydride, 2 parts of modified POSS flame-retardant synergist 1, 10 parts of aluminum diethyl phosphinate, 25 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer uniformly, and then extrude and pelletize through a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, and halogen-free thermoplastic elastomer material.

[0155] Example 4:

[0156] The preparation method is the same as that in Example 1, except that:

[0157] Mix 20 parts of PP, 25 parts of SEBS, 25 parts of white oil, 5 parts of PE grafted maleic anhydride, 10 parts of modified POSS flame-retardant synergist 1, 15 parts of aluminum diethyl phosphinate, 20 parts of MCA flame retardant, 15 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer uniformly, and then extrude and pelletize through a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, and halogen-free thermoplastic elastomer material.

[0158] Example 5:

[0159] The preparation method is the same as that of Example 1, except that:

[0160] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 12 parts of modified POSS flame-retardant synergist 1, 25 parts of aluminum diethyl phosphinate, 20 parts of MCA flame retardant, 15 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated through a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant and crack-resistant halogen-free thermoplastic elastomer material.

[0161] Example 6:

[0162] The preparation method is the same as that of Example 1, except that:

[0163] 22 parts of PP, 30 parts of SEBS, 30 parts of white oil, 8 parts of PE grafted maleic anhydride, 15 parts of modified POSS flame-retardant synergist 1, 15 parts of aluminum diethyl phosphinate, 15 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated through a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant and crack-resistant halogen-free thermoplastic elastomer material.

[0164] Example 7:

[0165] The preparation method is the same as that of Example 1, except that:

[0166] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 15 parts of modified POSS flame-retardant synergist 1, 15 parts of aluminum diethyl phosphinate, 15 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated through a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant and crack-resistant halogen-free thermoplastic elastomer material.

[0167] Example 8:

[0168] The preparation method is the same as that of Example 1, except that:

[0169] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhyt, 12 parts of modified POSS flame-retardant synergist 1, 12 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant and crack-resistant halogen-free thermoplastic elastomer material.

[0170] Example 9

[0171] The preparation method is the same as that of Example 1, except that:

[0172] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhyt, 12 parts of modified POSS flame-retardant synergist 1, 12 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant and crack-resistant halogen-free thermoplastic elastomer material.

[0173] Example 10

[0174] 2 mol of aminopropyl heptaisobutyl cage polysilsesquioxane is dissolved in 100 ml of tetrahydrofuran solution, 0.2 mol of acetic acid catalyst is added to the solution, and 1 mol of dibenzofuran-3-boronic acid is added under stirring. Stirring is performed for 2-4 h, the reaction is stopped, and vacuum rotary evaporation is performed. Water is added for washing, and drying is performed to obtain modified POSS flame-retardant synergist 2.

[0175] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhyt, 12 parts of modified POSS flame-retardant synergist 2, 4 parts of aluminum diethyl phosphinate, 20 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant and crack-resistant halogen-free thermoplastic elastomer material.

[0176] Comparative Example 1

[0177] The preparation method is the same as that of Example 1, except that:

[0178] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 18 parts of modified POSS flame-retardant synergist 1, 12 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0179] Comparative Example 2:

[0180] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 16 parts of aluminum diethyl phosphinate, 16 parts of MCA flame retardant, 16 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0181] The preparation method is the same as that of Example 1, except that:

[0182] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 12 parts of modified POSS flame-retardant synergist 1, 24 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0183] Comparative Example 4:

[0184] The preparation method is the same as that of Example 1, except that:

[0185] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 12 parts of modified POSS flame-retardant synergist 1, 24 parts of aluminum diethyl phosphinate, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0186] Comparative Example 5:

[0187] The preparation method is the same as that of Example 10, except that:

[0188] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 48 parts of modified POSS flame-retardant synergist 1, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0189] Comparative Example 6:

[0190] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 48 parts of aluminum diethyl phosphinate, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0191] Comparative Example 7:

[0192] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 48 parts of aluminum diethyl phosphinate, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0193] Comparative Example 8:

[0194] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 12 parts of benz[B]naphtho[2,3-D]furan-2-hydroxyboric acid flame retardant, 12 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0195] Comparative Example 9:

[0196] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 12 parts of benz[B]naphtho[2,3-D]furan-2-hydroxyboric acid flame retardant, 12 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, and then extruded and granulated by a double-screw extruder at 180°C to obtain thermoplastic elastomer preform, which is dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0197] Comparative Example 10:

[0198] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 6 parts of benz[B] naphtho[2,3-D] furan-2-hydroxy borate flame retardant, 6 parts of aminopropyl heptaisobutyl cage polysilsesquioxane flame retardant, 12 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0199] Comparative Example 11:

[0200] 2 mol of aminopropyl heptaisobutyl cage polysilsesquioxane is dissolved in 100 ml of tetrahydrofuran solution, 0.2 mol of acetic acid catalyst is added to the solution, and 1 mol of methyl borate is added under stirring. Stirring is continued for 2-4 h, the reaction is stopped, and the product is obtained by rotary evaporation under reduced pressure, washed with water, and dried.

[0201] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 12 parts of methyl borate modified POSS flame retardant, 2 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0202] Comparative Example 12:

[0203] 2 mol of aminopropyl heptaisobutyl cage polysilsesquioxane is dissolved in 100 ml of tetrahydrofuran solution, 0.2 mol of acetic acid catalyst is added to the solution, and 1 mol of methyl borate is added under stirring. Stirring is continued for 2-4 h, the reaction is stopped, and the product is obtained by rotary evaporation under reduced pressure, washed with water, and dried.

[0204] 18 parts of PP, 22 parts of SEBS, 22 parts of white oil, 5 parts of PE grafted maleic anhydride, 12 parts of methyl borate modified POSS flame retardant, 2 parts of aluminum diethyl phosphinate, 12 parts of MCA flame retardant, 12 parts of aluminum hydroxide, 0.5 parts of lubricant, 0.5 parts of antioxidant, and 0.3 parts of light stabilizer are uniformly mixed, extruded and granulated by a double screw extruder at 180°C to obtain a thermoplastic elastomer preform, and then dried at 80°C to obtain a high-flame-retardant, crack-resistant, halogen-free thermoplastic elastomer material.

[0205] The components and important preparation variables of Examples 1-10 and Comparative Examples 1-12 are summarized in Table 2. Table 2. Components of Examples 1-10 and Comparative Examples 1-12 of the present application

[0206] Table 2. Formulations of Examples and Comparative Examples of the present application

[0207]

[0208]

[0209] The thermoplastic elastomer materials in Examples 1-10 and Comparative Examples 1-12 above were tested for tensile strength, elongation at break, flame retardant rating, oxygen index, 110°C heat shock, 130°C heat shock, 150°C heat shock, dripping during combustion, and trouser tear, according to the provisions of GB / T 1040-2008, GB / T 5455, GB / T 2406.2, GB / T 32129, UL94, and GB / T 3917.2-2009, and the test results are recorded in Table 3 below:

[0210] Table 3. Performance test table of Examples 1-10 and Comparative Examples 1-12 of the present application

[0211]

[0212]

[0213] As can be seen from Table 3, the flame-retardant properties of the thermoplastic elastomer injection-molded sheets of Examples 1-9 are high, and the flame-retardant grades all reach V0 level, and the V0 level tests all do not drip, and the oxygen indexes are all >25. In Example 9, the amount of N-series flame retardant is 4 parts, and relative to Example 8, the physical and mechanical properties decrease, and in Example 10, the amount of P-series flame retardant is 4 parts, and relative to Example 8, the flame-retardant grade of Example 10 is V1, indicating that the flame-retardant property decreases. It can be seen that the modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist has a synergistic flame-retardant effect with the P-series flame retardant and the N-series flame retardant, and can further improve the flame-retardant properties and physical and mechanical properties of the thermoplastic elastomer injection-molded sheets. In Comparative Example 2, Comparative Example 6 and Comparative Example 7, no modified POSS flame-retardant synergist is added, and relative to Example 8, dripping occurs during the combustion process of all three, and the flame-retardant properties of all three are poor, and in Comparative Example 6 and Comparative Example 7, cracking of the samples occurs during the 110℃ thermal shock test, the 130℃ thermal shock test and the 150℃ thermal shock test, indicating that the modified POSS flame-retardant synergist, the P-series flame retardant and the N-series flame retardant need to synergize together, and during the combustion process, the Si element and the C element in the R2 group can rapidly react to generate a large amount of Si-C bonds, and at the same time, the B element can form a glass film on the surface of the thermoplastic polyester elastomer material, and the generated boric acid makes the polymer rapidly dehydrate to generate a carbon layer. The B element in the modified POSS flame-retardant synergist can also coordinate with the P element in the system to produce a synergistic effect, thereby improving the flame-retardant effect, and the P-series flame retardant provides an acid source, the N-series flame retardant provides a gas source, and the modified POSS flame-retardant synergist provides abundant carbon sources, so that the P-series flame retardant and the N-series flame retardant have stronger flame-retardant properties, and the three together synergize to achieve excellent flame-retardant properties, physical and mechanical properties, anti-dripping during combustion and thermal shock resistance of the thermoplastic elastomer material. As can be seen from Example 8 and Comparative Example 8, the polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist has better anti-dripping performance than the benz[B]naphtho[2,3-D]furan-2-hydroxy borate flame retardant. As can be seen from Example 8 and Comparative Example 9, the polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist has more excellent flame-retardant properties and anti-dripping performance than the aminopropyl heptaisobutyl cage polysilsesquioxane flame retardant. As can be seen from Example 8 and Comparative Example 10, the polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist has better anti-dripping performance than the aminopropyl heptaisobutyl cage polysilsesquioxane flame retardant and the benz[B]naphtho[2,3-D]furan-2-hydroxy borate flame retardant mixed flame retardant. As can be seen from Example 8 and Comparative Examples 11 and 12, the polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist of the present application has more excellent flame-retardant properties and anti-dripping performance than other modified polyhedral oligomeric silsesquioxane flame retardants that do not contain a benzofuran group, a polycyclic aromatic group or other boric acid-modified polyhedral oligomeric silsesquioxane flame retardants, thereby indicating that the polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist of the present application has excellent flame-retardant properties and anti-dripping performance.

[0214] Therefore, the application verifies that the flame retardance of the thermoplastic elastomer material is improved by the modified POSS flame retardant synergist, the thermoplastic elastomer material has excellent physical mechanical properties and excellent combustion anti-dripping effect, has extremely high industrial value, and can be widely applied and popularized

[0215] The above is only the preferred embodiment of the application, and does not limit the patent scope of the application. For those skilled in the art, the application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principle of the application shall be included in the patent protection scope of the application.

Claims

1. A thermoplastic elastomer material, characterized in that, The raw materials of the thermoplastic elastomer material include, in parts by weight: PP 15-22 parts, SEBS 20-30 parts, Plasticizer 20-30 parts, Compatibilizer 3-8 parts, P-series flame retardant 10-25 parts, N-series flame retardant 10-25 parts, Inorganic flame retardant 10-15 parts, Modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist 2-15 parts, The structure of the modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist is: Wherein, R is isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl or phenyl, R1 is propylene or phenylene; R2 is a cyclic structure with a carbon-hydrogen ratio greater than 1, including at least one of a benzofuran group, a polycyclic aromatic group, the benzofuran group including at least one of a benzofuran group, a dibenzofuran group; the polycyclic aromatic group including at least one of a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, an acenaphthene ring group, a fluorene ring group and a perylene ring group.

2. The thermoplastic elastomer material according to claim 1, wherein The modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist is prepared by dehydration reaction of compound 1 and compound 2 under the action of a catalyst, and the reaction route is as follows: 。 3. The thermoplastic elastomer material according to claim 2, wherein The molar ratio of the compound 1 to the compound 2 is 2:

1.

4. The thermoplastic elastomer material according to claim 2, wherein The preparation method of the modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist includes the following steps: Compound 1 is dissolved in an organic solvent, and compound 2 aqueous solution is added under the action of a catalyst to carry out catalytic reaction, and then washed and dried to obtain the modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist; The organic solvent includes at least one of an alcohol, an aromatic hydrocarbon, an aliphatic hydrocarbon, a cycloaliphatic hydrocarbon, an ether and a ketone; The catalyst includes at least one of an acidic catalyst, a metal catalyst and a basic catalyst.

5. The thermoplastic elastomer material according to claim 1, wherein The raw materials of the thermoplastic elastomer material include, in parts by weight: PP 15-22 parts, SEBS 20-30 parts, Plasticizer 20-30 parts, Compatibilizer 3-8 parts, P-series flame retardant 10-15 parts, N-series flame retardant 10-15 parts, Inorganic flame retardant 10-12 parts, Modified polyhedral oligomeric silsesquioxane and derivative flame-retardant synergist 2-15 parts.

6. The thermoplastic elastomer material according to claim 1, wherein The plasticizer includes at least one of white oil, naphthenic oil and paraffin oil.

7. The thermoplastic elastomer material according to claim 1, wherein The compatibilizer includes at least one of PE grafted maleic anhydride, POE grafted maleic anhydride, PP grafted maleic anhydride and EMA grafted maleic anhydride.

8. The thermoplastic elastomer material according to claim 1, wherein The P-series flame retardant includes inorganic phosphorus flame retardant or organic phosphorus flame retardant, the inorganic phosphorus flame retardant including at least one of red phosphorus, phosphate and polyphosphate; the organic phosphorus flame retardant including at least one of phosphate ester, phosphite ester and phosphine oxide; And / or, the N-series flame retardant includes at least one of melamine urate and melamine phosphate.

9. The thermoplastic elastomer material according to claim 1, wherein, The inorganic flame retardant includes at least one of magnesium hydroxide, aluminum hydroxide and calcium carbonate.

10. The thermoplastic elastomer material according to claim 1, wherein The raw materials of the thermoplastic elastomer material further include at least one of a lubricant, an antioxidant and a light stabilizer; wherein, the raw materials include, in parts by weight, the lubricant 0.2-1 part, the antioxidant 0.5-2 parts and the light stabilizer 0.2-1 part.

11. A process for the preparation of a thermoplastic elastomeric material as claimed in claim 1, characterized in that, The method comprises the following steps: uniformly mixing the raw materials, and extruding and granulating through an extruder to obtain granules, i.e. the thermoplastic elastomer material.

12. The method of preparing a thermoplastic elastomer material according to claim 11, wherein The raw materials further comprise at least one of a lubricant, an antioxidant, and a light stabilizer.

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