Thermoplastic polyurethane elastomer material and method for producing the same

Abstract

The application discloses a thermoplastic polyurethane elastomer material, which comprises a thermoplastic polyurethane elastomer, a phosphorus flame retardant, a nitrogen 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 phosphorus flame retardant providing an acid source and the nitrogen flame retardant providing a gas source to synergistically flame-retardant, reducing the amount of flame retardant while improving the flame-retardant performance and mechanical properties of the thermoplastic polyurethane elastomer material. The thermoplastic polyurethane elastomer material provided by the application has excellent flame-retardant performance.

Description

Technical Field

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

[0002] Polyhedral oligomeric silsesquioxane (POSS) is a special type of organic amorphous material. It is a polycyclic organic monomer composed of a silicon framework and its intercalated oxygen atoms. It is an inorganic-organic hybrid nanomaterial. The inorganic silicon cage core in POSS decomposes upon heating to form a dense ceramic barrier layer, which isolates the release of flammable gases and the entry of 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 polyurethane elastomers (TPUs) are mainly of polyester and polyether types, with a wide hardness range. They possess excellent mechanical properties, abrasion resistance, oil resistance, and excellent elasticity. Currently, TPU materials are widely used in footwear, pipes, tires, film materials, and cable materials. In the international market, there are many low-smoke, halogen-free flame-retardant TPU cable materials that meet UL flame-retardant requirements for electrical wires. However, the overall performance of domestically produced low-smoke, halogen-free flame-retardant TPU cable materials is still far inferior to imported products. Technological monopolies have kept the price of imported high-flame-retardant TPU cable materials consistently high. With the introduction of new energy policies, my country has also begun to vigorously develop flame-retardant TPU materials. However, due to limitations in domestic flame-retardant technology, the development of high-flame-retardant TPU materials has not made significant progress. This restricts the application of TPU in China, making the development of a high-flame-retardant TPU material essential. Summary of the Invention

[0004] In view of the shortcomings of the prior art, the present invention proposes a thermoplastic polyurethane elastomer material, which aims to solve the problem of poor flame retardancy of current TPU materials.

[0005] The above-mentioned objective of this invention is achieved through the following technical solution:

[0006] In a first aspect, the present invention provides a thermoplastic polyurethane elastomer material, wherein the raw materials of the thermoplastic polyurethane elastomer material, by weight, comprise:

[0007] 70-90 parts of thermoplastic polyurethane elastomer,

[0008] 10-30 parts of phosphorus-based flame retardant

[0009] 10-30 parts of nitrogen-based flame retardant

[0010] 2-8 parts of modified polyhedral oligomeric silsesquioxanes and their derivatives as flame retardant synergists.

[0011] The structure of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is as follows:

[0012]

[0013] Wherein, R is a non-reactive group, such as isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl, and R1 is n-propyl or phenylene;

[0014] R2 is a cyclic structure with a carbon-to-hydrogen ratio greater than 1, including at least one of benzofuran group and polycyclic aromatic group.

[0015] In some embodiments of the present invention, the benzofuran group includes at least one of the benzofuran group and the dibenzofuran group;

[0016] And / or, the polycyclic aromatic group includes at least one of a naphthalene ring group, anthracene ring group, phenanthrene ring group, acenaphthene ring group, fluorene ring group and perylene ring group.

[0017] In some embodiments of the present invention, 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:

[0018]

[0019] In some embodiments of the present invention, the molar ratio of compound 1 to compound 2 is 2:1.

[0020] In some embodiments of the present invention, the preparation method of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist includes the following steps:

[0021] Compound 1 was dissolved in an organic solvent, and an aqueous solution of compound 2 was added under the action of a catalyst. After catalytic reaction, the mixture was washed and dried to obtain the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist.

[0022] The organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones, and diol derivatives.

[0023] The catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts.

[0024] In some embodiments of the present invention, the raw materials of the thermoplastic polyurethane elastomer material, by weight, include:

[0025] 70-90 parts of thermoplastic polyurethane elastomer,

[0026] 10-20 parts of phosphorus-based flame retardant

[0027] 10-20 parts of nitrogen-based flame retardant

[0028] 2-8 parts of modified polyhedral oligomeric silsesquioxane and its derivatives flame retardant synergist.

[0029] In some embodiments of the present invention, the thermoplastic polyurethane elastomer includes a polyether-type or polyester-type thermoplastic polyurethane elastomer.

[0030] In some embodiments of the present invention, the phosphorus-based flame retardant includes an inorganic phosphorus flame retardant or an organic phosphorus flame retardant; the inorganic phosphorus flame retardant includes at least one of red phosphorus, phosphate, and polyphosphate; the organic phosphorus flame retardant includes at least one of phosphate ester, phosphite, and phosphorus oxide.

[0031] And / or, the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0032] In some embodiments of the present invention, the raw materials of the thermoplastic polyurethane elastomer material further include at least one of a lubricant, an antioxidant, an anti-hydrolysis agent, and a matting agent; wherein, by weight, the raw materials are: 0.5-1 parts of the lubricant, 0.5-2 parts of the antioxidant, 0.5-2 parts of the anti-hydrolysis agent, and 2-10 parts of the matting agent.

[0033] In a second aspect, the present invention provides a method for preparing the above-mentioned thermoplastic polyurethane elastomer material, comprising the following steps: mixing the raw materials evenly, extruding and granulating them through an extruder to obtain granules, namely the thermoplastic polyurethane elastomer material.

[0034] In some embodiments of the present invention, the raw materials further include at least one of lubricant, antioxidant, anti-hydrolysis agent, and matting agent;

[0035] And / or, the extruder is a twin-screw extruder, the extrusion temperature is 160-180℃, and the screw speed is 150-170 r / min.

[0036] The thermoplastic polyurethane elastomer material of the present invention includes thermoplastic polyurethane elastomer, phosphorus-based flame retardant, nitrogen-based flame retardant, and modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists. Because the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists contain boron, a cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1, and two inorganic silicon cage cores, the boron forms boric acid during combustion, which dehydrates and carbonizes the material surface, forming a carbon layer. The two inorganic silicon cage cores decompose 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 R2 with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio, and the benzofuran group and polycyclic aromatic groups contain a large amount of carbon. During combustion, the 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. At the same time, 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. Furthermore, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist works in conjunction with the phosphorus-based flame retardant providing the acid source and the nitrogen-based flame retardant providing the gas source, synergistically enhancing flame retardancy while reducing the amount of flame retardant required. The thermoplastic polyurethane elastomer material provided by this invention exhibits excellent flame retardant properties. Attached Figure Description

[0037] Figure 1 This is a molecular structure diagram of the modified POSS flame retardant synergist 1 of the present invention;

[0038] Figure 2 This is a molecular structure diagram of the modified POSS flame retardant synergist 2 of the present invention. Detailed Implementation

[0039] 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.

[0040] Unless otherwise specified, all technical and scientific terms used herein have their usual meaning within the field to which the subject matter is claimed.

[0041] Polyhedral oligomeric silsesquioxane (POSS) is a special type of organic amorphous material. It is a polycyclic organic monomer composed of a silicon framework and its intercalated oxygen atoms. It is an inorganic-organic hybrid nanomaterial. The inorganic silicon cage core in POSS decomposes upon heating to form a dense ceramic barrier layer, which isolates the release of flammable gases and the entry of external heat into the interior, thereby delaying further decomposition of the material. POSS shows great application potential in the field of flame retardants.

[0042] Thermoplastic polyurethane elastomers (TPUs) are mainly of polyester and polyether types, with a wide hardness range. They possess excellent mechanical properties, abrasion resistance, oil resistance, and excellent elasticity. Currently, TPU materials are widely used in footwear, pipes, tires, film materials, and cable materials. In the international market, there are many low-smoke, halogen-free flame-retardant TPU cable materials that meet UL flame-retardant requirements for electrical wires. However, the overall performance of domestically produced low-smoke, halogen-free flame-retardant TPU cable materials is still far inferior to imported products. Technological monopolies have kept the price of imported high-flame-retardant TPU cable materials consistently high. With the introduction of new energy policies, my country has also begun to vigorously develop flame-retardant TPU materials. However, due to limitations in domestic flame-retardant technology, the development of high-flame-retardant TPU materials has not made significant progress. This restricts the application of TPU in China, making the development of a high-flame-retardant TPU material essential.

[0043] To address the aforementioned problems, in a first aspect, the present invention provides a thermoplastic polyurethane elastomer material, wherein the raw materials of the thermoplastic polyurethane elastomer material, by weight, comprise:

[0044] 70-90 parts of thermoplastic polyurethane elastomer,

[0045] 10-30 parts of phosphorus-based flame retardant

[0046] 10-30 parts of nitrogen-based flame retardant

[0047] 2-8 parts of modified polyhedral oligomeric silsesquioxanes and their derivatives as flame retardant synergists.

[0048] The structure of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is as follows:

[0049]

[0050] Wherein, R is a non-reactive group, such as isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl, or phenyl, and R1 is n-propyl or phenylene;

[0051] R2 is a cyclic structure with a carbon-to-hydrogen ratio greater than 1, including at least one of benzofuran group and polycyclic aromatic group.

[0052] Understandably, the thermoplastic polyurethane elastomer is any number of parts between 70 and 90, such as 70, 75, 80, 85, and 90; the phosphorus-based flame retardant is any number of parts between 10 and 30, such as 10, 15, 20, 25, and 30; the nitrogen-based flame retardant is any number of parts between 10 and 30, such as 10, 15, 20, 25, and 30; and the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists are any number of parts between 2 and 8, such as 2, 4, 6, and 8.

[0053] Understandably, when R1 connected to Si in the inorganic silicon cage core is a phenylene ring, the phenylene ring contains a benzene ring with a high carbon-hydrogen ratio and high carbon content. During combustion, it works together with the large amount of Si in the inorganic silicon cage core to further improve the flame retardant properties of the inorganic silicon cage core, thereby improving the flame retardant properties of the modified polyhedral oligomeric silsesquioxane flame retardant synergist.

[0054] Understandably, phosphorus-based flame retardants decompose during combustion to form a non-flammable liquid film of phosphoric acid. Simultaneously, the phosphoric acid further dehydrates to form metaphosphoric acid, which then polymerizes to form polymetaphosphoric acid. In this process, not only does the coating layer formed by the phosphoric acid provide a covering effect, but the resulting polymetaphosphoric acid, being a strong acid and a powerful dehydrating agent, dehydrates and carbonizes the polymer, altering the combustion process and forming a carbon film on its surface to isolate it from air, thus exerting a stronger flame-retardant effect. Furthermore, phosphorus-based flame retardants are also free radical scavengers. Mass spectrometry has revealed that any phosphorus-containing compound forms PO· during polymer combustion. This PO· can combine with hydrogen atoms in the flame region, inhibiting flame spread. In addition, the moisture generated during the flame retardant process of phosphorus-based flame retardants can lower the temperature of the condensed phase and dilute the concentration of combustibles in the gas phase, thus playing a better role in flame retardancy. Nitrogen-based flame retardants decompose at high temperatures to produce non-flammable gases such as ammonia, water vapor, and nitrogen. These gases can dilute the concentration of combustibles in the gas phase and inhibit combustion. The synergistic effect of both in the condensed and gas phases can improve the char formation rate, form a more stable and uniform char layer, and improve the flame retardant effect. In the modified polyhedral oligomeric silsesquioxane and its derivatives synergistic flame retardant, boron forms boric acid during combustion, which dehydrates and carbonizes the material surface, forming a carbon layer. Two inorganic silicon cages 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 R2, with a carbon-to-hydrogen ratio greater than 1, possesses a high carbon-to-hydrogen ratio. The benzofuran and polycyclic aromatic groups contain a large amount of carbon, which forms a glassy protective film or a heat-insulating coke layer during combustion. These protective films or coke layers 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, significantly improve the anti-dripping effect. Simultaneously, they isolate heat and oxygen transfer, reducing the release of combustible gases. The combined effect of these multiple mechanisms significantly enhances the flame retardant performance of the material. Modified polyhedral oligomeric silsesquioxanes and their derivatives, as synergistic flame retardants, contain abundant silicon and oxygen. During polymer combustion, they react with the acidic gases produced by phosphorus-based flame retardants to form phosphates, promoting the reaction between phosphorus and the polymer and rapidly forming a char layer. The SiO2 generated after combustion of the modified polyhedral oligomeric silsesquioxanes and their derivatives interpenetrates 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. The boron in the modified polyhedral oligomeric silsesquioxanes and their derivatives possesses a 2Pz empty orbital that can accept lone pairs of electrons, and its coordination with phosphorus produces a synergistic effect. The synergistic effect of boron and phosphorus further accelerates the aforementioned reaction.Simultaneously, the combustion of nitrogen-based flame retardants generates a large amount of non-combustible gas. This non-combustible gas causes the incompletely carbonized TPU 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 carbon layer.

[0055] The thermoplastic polyurethane elastomer material of the present invention includes thermoplastic polyurethane elastomer, phosphorus-based flame retardant, nitrogen-based flame retardant, and modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists. Because the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists contain boron, a cyclic structure R2 with a carbon-to-hydrogen ratio greater than 1, and two inorganic silicon cage cores, the boron forms boric acid during combustion, which dehydrates and carbonizes the material surface, forming a carbon layer. The two inorganic silicon cage cores decompose 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 R2 with a carbon-to-hydrogen ratio greater than 1 has a high carbon-to-hydrogen ratio, and the benzofuran group and polycyclic aromatic groups contain a large amount of carbon. During combustion, the 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. At the same time, 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. Furthermore, the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist works in conjunction with the phosphorus-based flame retardant providing the acid source and the nitrogen-based flame retardant providing the gas source, synergistically enhancing flame retardancy while reducing the amount of flame retardant required. The thermoplastic polyurethane elastomer material provided by this invention exhibits excellent flame retardant properties.

[0056] In some embodiments, the benzofuran group includes at least one of the benzofuran group and the dibenzofuran group.

[0057] Phenyl groups have a high carbon-to-hydrogen ratio and a high carbon content, which can slow down the spread of flames during combustion. They can also self-extinguish quickly after the flames are removed, reducing the duration and intensity of combustion. Furan groups, while having a high carbon content, also contain oxygen elements that do not participate in combustion. The combination of these two groups forms benzofuran groups or dibenzofuran groups, which have both a high carbon-to-hydrogen ratio and low combustion elements. Together, they form a glassy protective film or heat-insulating coke layer during combustion. These protective films or coke layers can isolate air, prevent heat transfer, reduce the content of combustibles, and indirectly promote char formation.

[0058] In some embodiments, R2 is a benzofuran group.

[0059] In some embodiments, the polycyclic aromatic group includes at least one of a naphthalene ring group, anthracene ring group, phenanthrene ring group, acenaphthene ring group, fluorene ring group, and perylene ring group.

[0060] Naphthyl ring groups, anthracene ring groups, phenanthrene ring groups, acenaphthene ring groups, fluorene ring groups, and perylene ring groups have a high hydrocarbon ratio and contain a large amount of carbon, making them more likely to form a glassy protective film or heat-insulating coke layer during combustion.

[0061] In some embodiments, R2 is a naphthalene ring group.

[0062] In some embodiments, 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:

[0063]

[0064] In some embodiments, the molar ratio of compound 1 to compound 2 in the above reaction process is 2:1.

[0065] Compound 1, a polyhedral oligomeric silsesquioxane, has a relatively large spatial structure. During the reaction, compound 2 needs to have sufficiently small steric hindrance to react with compound 1 and yield compound 3, a modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist. In the reaction, each compound 2 is connected to two compounds 1, meaning the molar ratio of compound 1 to compound 2 is 2:1. This ensures sufficient space for compound 3 and achieves structural stability. Compound 2 contains two hydroxyl groups. The two hydroxyl groups of one compound 2 react with one amino group from each of the two compounds 1 to undergo a dehydration reaction, yielding compound 3. The overall reaction requires only a single substance, is simple to operate, and is easy to implement.

[0066] In some embodiments, compound 1 is aminopropylheptaisobutyl cage-like polysilsesquioxane.

[0067] In some embodiments, compound 1 is aminophenyl heptaisobutyl cage-like polysilsesquioxane.

[0068] In some embodiments, compound 2 is benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid.

[0069] In some embodiments, compound 2 is dibenzofuran-3-boronic acid.

[0070] In some embodiments, the structural formula of compound 3 is:

[0071]

[0072] The following is counted as modified POSS flame retardant synergist 1.

[0073] In some embodiments, the structural formula of compound 3 is:

[0074]

[0075] The following is counted as modified POSS flame retardant synergist 2.

[0076] In some embodiments, the preparation method of compound 3 includes the following steps:

[0077] Compound 1 was dissolved in an organic solvent, and an aqueous solution of compound 2 was added under the action of a catalyst. After catalytic reaction, the mixture was washed and dried to obtain compound 3.

[0078] The organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones, and diol derivatives.

[0079] The catalyst includes at least one of acidic catalysts, metal catalysts, and basic catalysts.

[0080] In some embodiments, the catalyst is acetic acid.

[0081] In some implementations, the solvent is ethanol.

[0082] In some embodiments, the raw materials of the thermoplastic polyurethane elastomer material, by weight, include:

[0083] 70-90 parts of thermoplastic polyurethane elastomer,

[0084] 10-20 parts of phosphorus-based flame retardant

[0085] 10-20 parts of nitrogen-based flame retardant

[0086] 2-8 parts of modified polyhedral oligomeric silsesquioxane and its derivatives flame retardant synergist.

[0087] Reducing the amount of phosphorus-based and nitrogen-based flame retardants can further improve the mechanical properties of thermoplastic polyurethane elastomer materials.

[0088] In some embodiments, the thermoplastic polyurethane elastomer includes polyether-type or polyester-type thermoplastic polyurethane elastomers.

[0089] In some embodiments, the phosphorus-based flame retardant includes inorganic phosphorus flame retardants or organic phosphorus flame retardants; the inorganic phosphorus flame retardant includes at least one of red phosphorus, phosphate, and polyphosphate; the organic phosphorus flame retardant includes at least one of phosphate ester, phosphite, and phosphorus oxide flame retardant.

[0090] And / or, the nitrogen-based flame retardant includes at least one of melamine urate, melamine phosphate, melamine inorganic acid salt, dicyandiamide, and melamine.

[0091] Understandably, phosphorus-based flame retardants include, but are not limited to, aluminum hypophosphite, calcium hypophosphite, diethyl aluminum hypophosphite, methyl ethyl aluminum hypophosphite, and phenyl aluminum hypophosphite.

[0092] In some embodiments, the phosphorus-based flame retardant is diethylaluminum hypophosphite.

[0093] In some embodiments, the nitrogen-based flame retardant is melamine urate.

[0094] In some embodiments, the raw materials of the thermoplastic polyurethane elastomer material further include at least one of a lubricant, an antioxidant, an anti-hydrolysis agent, and a matting agent; wherein, by weight, the raw materials are 0.5-1 parts of the lubricant, 0.5-2 parts of the antioxidant, 0.5-2 parts of the anti-hydrolysis agent, and 2-10 parts of the matting agent.

[0095] In some embodiments, antioxidants include, but are not limited to, asymmetric hindered phenolic antioxidants, aromatic amine antioxidants, thioether antioxidants, and phosphite antioxidants.

[0096] Hindered phenolic antioxidants include, but are not limited to, antioxidant 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]), BHT (2,6-di-tert-butyl-p-cresol), and antioxidant 1076 (octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate).

[0097] Aromatic amine antioxidants include, but are not limited to, diphenylamine, p-phenylenediamine, and dihydroquinoline and their derivatives or polymers, such as antioxidant 445 (4,4'-bis(α.α-dimethylbenzyl)diphenylamine);

[0098] Thioether antioxidants include, but are not limited to, DLTP (dilauryl thiodipropionate), DSTDP (thiodipropionate distearate), and DSTP (octadecyl thiodipropionate).

[0099] Phosphite antioxidants include, but are not limited to, antioxidant 168 (tris[2,4-di-tert-butylphenyl]phosphite), antioxidant 618 (pentaerythritol diphosphite bis(octadecyl)ester), and antioxidant 626 (bis[2,4-di-tert-butylphenyl]pentaerythritol diphosphite).

[0100] Adding antioxidants can improve the antioxidant properties and aging resistance of polymer materials, thereby extending their service life.

[0101] In some embodiments, the lubricant includes, but is not limited to, PTFE powder, zinc stearate, magnesium stearate, silicone, calcium stearate, or ethylene bis-stearamide. Adding a lubricant helps to promote more uniform mixing of various raw materials, improves the flowability of the polymer resin, reduces the coefficient of friction, makes the surface of the product smoother, improves processing efficiency, and also improves the transparency and gloss of the plastic.

[0102] In some embodiments, anti-hydrolysis agents include, but are not limited to, carbodiimide-type anti-hydrolysis stabilizers, isocyanates, epoxy resins, oxazoline and anhydride anti-hydrolysis agents, polyethers, polyesters, polyurethanes, polyamides, and polyether esters. By adding anti-hydrolysis agents, hydrolysis reactions can be prevented, improving the processing and mechanical properties of the polymer, and extending the polymer's service life and performance.

[0103] In some embodiments, the matting agent includes inorganic and organic matting agents. Inorganic matting agents include, but are not limited to, silica, alumina, and calcium carbonate, while organic matting agents include, but are not limited to, metal soaps, waxes, diatomaceous earth, and synthetic silica. By adding matting agents, the surface roughness of the polymer can be altered, reducing surface gloss and thus decreasing light reflection, resulting in a softer polymer gloss.

[0104] In a second aspect, the present invention provides a method for preparing the above-mentioned thermoplastic polyurethane elastomer material, comprising the following steps: uniformly mixing the raw materials, namely thermoplastic polyurethane elastomer, phosphorus-based flame retardant, nitrogen-based flame retardant and modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist, and extruding and granulating the mixture through an extruder to obtain granular material, namely the thermoplastic polyurethane elastomer material.

[0105] In some embodiments, the raw material further includes at least one of lubricant, antioxidant, anti-hydrolysis agent, and matting agent;

[0106] And / or, the extruder is a twin-screw extruder, the extrusion temperature is 160-180℃, and the screw speed is 150-170 r / min.

[0107] The following specific embodiments and data explain the content of the present invention.

[0108] Information on the raw materials involved in the specific implementation method is shown in Table 1:

[0109] Table 1 Information on raw materials for the examples and comparative examples.

[0110]

[0111]

[0112] Preparation method of modified POSS flame retardant synergist 1

[0113] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was rotary evaporated under reduced pressure, washed with water, and dried to obtain benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 1.

[0114] Preparation method of modified POSS flame retardant synergist 2

[0115] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of dibenzofuran-3-boric acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was rotary evaporated under reduced pressure, washed with water, and dried to obtain dibenzofuran-3-boric acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 2.

[0116] Preparation method of modified POSS flame retardant synergist 3

[0117] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of methylboric acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was then rotary evaporated under reduced pressure, washed with water, and dried to obtain methylboric acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 3.

[0118] Preparation method of modified POSS flame retardant synergist 4

[0119] 2 mol of aminopropyl heptaisobutyl cage-like polysilsesquioxane was dissolved in 100 mL of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 1 mol of phenylboronic acid was added under stirring. The reaction was stirred for 2-4 h, then stopped. The mixture was then rotary evaporated under reduced pressure, washed with water, and dried to obtain phenylboronic acid-modified aminopropyl heptaisobutyl cage-like polysilsesquioxane, i.e., modified POSS flame retardant synergist 4.

[0120] Example 1:

[0121] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0122] 90 parts of polyether-type TPU;

[0123] 10 parts of aluminum diethylphosphite;

[0124] 10 parts of melamine urate;

[0125] 15 parts of modified POSS flame retardant synergist;

[0126] 0.5 parts PE wax;

[0127] Antioxidant 10100.5 parts;

[0128] 1 part carbodiimide;

[0129] 5 parts silicon dioxide;

[0130] The preparation method is as follows:

[0131] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0132] Example 2:

[0133] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0134] 70 parts of polyether-type TPU;

[0135] 15 parts of aluminum diethylphosphite;

[0136] 10 parts of melamine urate;

[0137] 18 parts of modified POSS flame retardant synergist;

[0138] 0.5 parts PE wax;

[0139] Antioxidant 10100.5 parts;

[0140] 1 part carbodiimide;

[0141] 5 parts silicon dioxide;

[0142] The preparation method is as follows:

[0143] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0144] Example 3:

[0145] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0146] 90 parts of polyether-type TPU;

[0147] 10 parts of aluminum diethylphosphite;

[0148] 30 parts of melamine urate;

[0149] 12 parts of modified POSS flame retardant synergist;

[0150] 0.5 parts PE wax;

[0151] Antioxidant 10100.5 parts;

[0152] 1 part carbodiimide;

[0153] 5 parts silicon dioxide;

[0154] The preparation method is as follows:

[0155] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0156] Example 4:

[0157] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0158] 80 parts of polyether-type TPU;

[0159] 30 parts of diethylaluminum hypophosphite;

[0160] 22 parts of melamine urate;

[0161] 15 parts of modified POSS flame retardant synergist;

[0162] 0.5 parts PE wax;

[0163] Antioxidant 10100.5 parts;

[0164] 1 part carbodiimide;

[0165] 5 parts silicon dioxide;

[0166] The preparation method is as follows:

[0167] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0168] Example 5:

[0169] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0170] 90 parts of polyether-type TPU;

[0171] 20 parts of diethylaluminum hypophosphite;

[0172] 20 parts of melamine urate;

[0173] 18 parts of modified POSS flame retardant synergist;

[0174] 0.5 parts PE wax;

[0175] Antioxidant 10100.5 parts;

[0176] 1 part carbodiimide;

[0177] 5 parts silicon dioxide;

[0178] The preparation method is as follows:

[0179] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0180] Example 6:

[0181] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0182] 70 parts of polyether-type TPU;

[0183] 20 parts of diethylaluminum hypophosphite;

[0184] 20 parts of melamine urate;

[0185] 18 parts of modified POSS flame retardant synergist;

[0186] 0.5 parts PE wax;

[0187] Antioxidant 10100.5 parts;

[0188] 1 part carbodiimide;

[0189] 5 parts silicon dioxide;

[0190] The preparation method is as follows:

[0191] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0192] Example 7:

[0193] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0194] 80 parts of polyether-type TPU;

[0195] 15 parts of aluminum diethylphosphite;

[0196] 15 parts of melamine urate;

[0197] 15 parts of modified POSS flame retardant synergist;

[0198] 0.5 parts PE wax;

[0199] Antioxidant 10100.5 parts;

[0200] 1 part carbodiimide;

[0201] 5 parts silicon dioxide;

[0202] The preparation method is as follows:

[0203] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0204] Example 8:

[0205] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0206] 80 parts of polyester-based TPU;

[0207] 15 parts of aluminum diethylphosphite;

[0208] 15 parts of melamine urate;

[0209] 15 parts of modified POSS flame retardant synergist;

[0210] 0.5 parts PE wax;

[0211] Antioxidant 10100.5 parts;

[0212] 1 part carbodiimide;

[0213] 5 parts silicon dioxide;

[0214] The preparation method is as follows:

[0215] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0216] Example 9:

[0217] Please refer to Tables 1 and 2. This embodiment includes the following parts by weight of raw materials:

[0218] 80 parts of polyether-type TPU;

[0219] 15 parts of aluminum diethylphosphite;

[0220] 15 parts of melamine urate;

[0221] 25 parts of modified POSS flame retardant synergist;

[0222] 0.5 parts PE wax;

[0223] Antioxidant 10100.5 parts;

[0224] 1 part carbodiimide;

[0225] 5 parts silicon dioxide;

[0226] The preparation method is as follows:

[0227] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 1:

[0228] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0229] 80 parts of polyether-type TPU;

[0230] 10 parts of aluminum diethylphosphite;

[0231] 15 parts of melamine urate;

[0232] 110 parts of modified POSS flame retardant synergist;

[0233] 0.5 parts PE wax;

[0234] Antioxidant 10100.5 parts;

[0235] 1 part carbodiimide;

[0236] 5 parts silicon dioxide;

[0237] The preparation method is as follows:

[0238] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 2:

[0239] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0240] 80 parts of polyether-type TPU;

[0241] 20 parts of diethylaluminum hypophosphite;

[0242] 15 parts of melamine urate;

[0243] 0.5 parts PE wax;

[0244] Antioxidant 10100.5 parts;

[0245] 1 part carbodiimide;

[0246] 5 parts silicon dioxide;

[0247] The preparation method is as follows:

[0248] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 3:

[0249] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0250] 80 parts of polyether-type TPU;

[0251] 30 parts of melamine urate;

[0252] 15 parts of modified POSS flame retardant synergist;

[0253] 0.5 parts PE wax;

[0254] Antioxidant 10100.5 parts;

[0255] 1 part carbodiimide;

[0256] 5 parts silicon dioxide;

[0257] The preparation method is as follows:

[0258] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 4:

[0259] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0260] 80 parts of polyether-type TPU;

[0261] 30 parts of diethylaluminum hypophosphite;

[0262] 15 parts of modified POSS flame retardant synergist;

[0263] 0.5 parts PE wax;

[0264] Antioxidant 10100.5 parts;

[0265] 1 part carbodiimide;

[0266] 5 parts silicon dioxide;

[0267] The preparation method is as follows:

[0268] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 5:

[0269] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0270] 80 parts of polyether-type TPU;

[0271] 135 parts of modified POSS flame retardant synergist;

[0272] 0.5 parts PE wax;

[0273] Antioxidant 10100.5 parts;

[0274] 1 part carbodiimide;

[0275] 5 parts silicon dioxide;

[0276] The preparation method is as follows:

[0277] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 6:

[0278] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0279] 80 parts of polyether-type TPU;

[0280] 35 parts of diethylaluminum hypophosphite;

[0281] 0.5 parts PE wax;

[0282] Antioxidant 10100.5 parts;

[0283] 1 part carbodiimide;

[0284] 5 parts silicon dioxide;

[0285] The preparation method is as follows:

[0286] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 7:

[0287] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0288] 80 parts of polyether-type TPU;

[0289] 35 parts of melamine urate;

[0290] 0.5 parts PE wax;

[0291] Antioxidant 10100.5 parts;

[0292] 1 part carbodiimide;

[0293] 5 parts silicon dioxide;

[0294] The preparation method is as follows:

[0295] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 8:

[0296] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0297] 80 parts of polyether-type TPU;

[0298] 15 parts of aluminum diethylphosphite;

[0299] 15 parts of melamine urate;

[0300] 5 parts of benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid;

[0301] 0.5 parts PE wax;

[0302] Antioxidant 10100.5 parts;

[0303] 1 part carbodiimide;

[0304] 5 parts silicon dioxide;

[0305] The preparation method is as follows:

[0306] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 9:

[0307] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0308] 80 parts of polyether-type TPU;

[0309] 15 parts of aluminum diethylphosphite;

[0310] 15 parts of melamine urate;

[0311] 5 parts of aminopropyl heptaisobutyl cage-like polysilsesquioxane;

[0312] 0.5 parts PE wax;

[0313] Antioxidant 10100.5 parts;

[0314] 1 part carbodiimide;

[0315] 5 parts silicon dioxide;

[0316] The preparation method is as follows:

[0317] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 10:

[0318] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0319] 80 parts of polyether-type TPU;

[0320] 15 parts of aluminum diethylphosphite;

[0321] 15 parts of melamine urate;

[0322] 1.6 parts of benzo[B]naphtho[2,3-D]furan-2-hydroxyboronic acid;

[0323] 3.4 parts of aminopropyl heptaisobutyl cage-like polysilsesquioxane;

[0324] 0.5 parts PE wax;

[0325] Antioxidant 10100.5 parts;

[0326] 1 part carbodiimide;

[0327] 5 parts silicon dioxide;

[0328] The preparation method is as follows:

[0329] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 11:

[0330] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0331] 80 parts of polyether-type TPU;

[0332] 15 parts of aluminum diethylphosphite;

[0333] 15 parts of melamine urate;

[0334] 35 parts of modified POSS flame retardant synergist;

[0335] 0.5 parts PE wax;

[0336] Antioxidant 10100.5 parts;

[0337] 1 part carbodiimide;

[0338] 5 parts silicon dioxide;

[0339] The preparation method is as follows:

[0340] The above raw materials were weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture was extruded and granulated at 170°C and a screw speed of 160 r / min to obtain a thermoplastic polyurethane elastomer material. Comparative Example 12:

[0341] Please refer to Tables 1 and 2. This comparative example includes the following parts by mass of raw materials:

[0342] 80 parts of polyether-type TPU;

[0343] 15 parts of aluminum diethylphosphite;

[0344] 15 parts of melamine urate;

[0345] 45 parts of modified POSS flame retardant synergist;

[0346] 0.5 parts PE wax;

[0347] Antioxidant 10100.5 parts;

[0348] 1 part carbodiimide;

[0349] 5 parts silicon dioxide;

[0350] The preparation method is as follows:

[0351] The above raw materials are weighed according to weight, mixed evenly using a high-speed mixer, and then fed into a twin-screw granulator. The mixture is extruded and granulated at 170°C and a screw speed of 160 r / min to obtain thermoplastic polyurethane elastomer material.

[0352] The thermoplastic polyurethane elastomer materials prepared in the above embodiments and comparative examples were injection molded or molded into sheets, and subjected to flame retardancy rating, oxygen index, tensile strength, elongation at break, thermal shock at 110°C, thermal shock at 130°C, and thermal shock at 150°C, according to the following test standards:

[0353] (1) Flame retardant rating

[0354] The test was conducted according to UL94 standards, with a sample thickness of 3 mm and a test temperature of 23±2℃. Three samples were tested using the UL94 vertical burning test apparatus from Jiangsu Zhengrui Taibang Electronics Co., Ltd., while observing for any dripping.

[0355] (2) Oxygen Index

[0356] 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 of three samples was tested using an oxygen index tester manufactured by Nanjing Jiangning District Fangshang Analytical Instrument Equipment Factory, and the results were averaged.

[0357] (3) Tensile strength and elongation at break

[0358] 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 three 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.

[0359] (4) Thermal shock at 110-150℃

[0360] The test was conducted according to Appendix A of GB / T 32129-2015 standard, with a test temperature of 23±2℃ and a weight of 2kg. Using the thermal shock resistance testing equipment from Hebei Zhongke Beigong Test Instrument Co., Ltd., three samples were tested at each temperature, and the average value was taken.

[0361] The test results are detailed in Table 3.

[0362] Table 2. Formulations of embodiments and comparative examples of the present invention.

[0363]

[0364]

[0365]

[0366] Table 3 Performance test table of embodiments and comparative examples of the present invention

[0367]

[0368] As shown in Table 3, the polyether-type TPU and polyester-type TPU injection molded sheets in Examples 1-9 exhibit good flame retardant properties, all reaching a flame retardant rating of V0. During the V0 rating test, none of them dripped, and their oxygen indices were all >25%, thus demonstrating that the TPU material of this invention possesses good flame retardant properties. Examples 5, 6, and 8 show that the polyether-type TPU and polyester-type TPU injection molded sheets also exhibit good flame retardant properties, all reaching a flame retardant rating of V0. During the V0 rating test, none of them dripped, and their oxygen indices were all >25%. Simultaneously, they possess good mechanical properties, with tensile strengths all >20 MPa, elongation at break all >500%, and no cracking during thermal shock at 110℃-150℃, thus demonstrating that the TPU material of this invention possesses good flame retardant and mechanical properties. Examples 7 and Comparative Example 1 show that when the modified POSS flame retardant synergist is used in excessive amounts, the flame retardant rating is V1, the flame retardant performance is substandard, the oxygen index decreases, mechanical properties decrease, and tensile strength and elongation at break both decrease. Examples 7 and Comparative Example 2 show that when modified POSS flame retardant synergist is not added, the flame retardant rating is V2, there is dripping, the flame retardant performance is substandard, the oxygen index decreases, and the tensile strength decreases. Examples 7 and Comparative Example 3 show that when phosphorus-based flame retardant diethylaluminum hypophosphite is not added, the flame retardant rating is V2, there is dripping, the flame retardant performance is substandard, the oxygen index decreases, and the tensile strength decreases. Examples 7 and Comparative Example 4 show that when nitrogen-based flame retardant melamine urate (MCA) is not added, the flame retardant rating is V2, the flame retardant performance is substandard, the oxygen index decreases, and the tensile strength decreases. Examples 7 and Comparative Example 5 show that... It can be seen that when only modified POSS flame retardant synergist 1 is used as a flame retardant, the flame retardant rating is V2, the flame retardant performance is substandard, the oxygen index is reduced, and the tensile strength and elongation at break are both reduced. Examples 7 and 6 show that when only the phosphorus-based flame retardant diethyl aluminum hypophosphite is used, the flame retardant rating is V2, there is dripping, the flame retardant performance is substandard, the oxygen index is reduced, and the tensile strength is reduced. Examples 7 and 7 also show that when only the nitrogen-based flame retardant melamine urate (MCA) is used, the flame retardant rating is V2, there is dripping, the flame retardant performance is substandard, the oxygen index is low, and the tensile strength and elongation at break are both reduced. This demonstrates that modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergists have a synergistic flame retardant effect with phosphorus-based and nitrogen-based flame retardants, improving the flame retardant and mechanical properties of TPU materials while reducing the amount of various flame retardants used.Examples 7 and Comparative Example 8 show that modified POSS flame retardant synergist 1, compared with benzo[B]naphtho[2,3-D]furan-2-hydroxyboric acid flame retardant, exhibits improved anti-dripping performance, oxygen index, tensile strength, and elongation at break. Examples 7 and Comparative Example 9 show that modified POSS flame retardant synergist 1, compared with aminopropylheptaisobutyl cage-like polysilsesquioxane flame retardant, exhibits improved flame retardant rating, anti-dripping performance, oxygen index, tensile strength, and elongation at break. Examples 7 and Comparative Example 10 show that modified POSS flame retardant synergist 1, compared with the flame retardant mixture of aminopropylheptaisobutyl cage-like polysilsesquioxane and benzo[B]naphtho[2,3-D]furan-2-hydroxyboric acid, shows improved anti-dripping performance. The flame retardant rating, anti-dripping properties, oxygen index, and elongation at break were all improved. Examples 7 and 11 show that modified POSS flame retardant synergist 1, compared to modified POSS flame retardant 3 (methylboronic acid modified aminopropyl heptaisobutyl cage-like polysilsesquioxane flame retardant), exhibits improved flame retardant rating, anti-dripping performance, oxygen index, and tensile strength. Examples 7 and 12 show that modified POSS flame retardant synergist 1, compared to modified POSS flame retardant 4 (phenylboronic acid modified aminopropyl heptaisobutyl cage-like polysilsesquioxane flame retardant), exhibits improved flame retardant rating, anti-dripping performance, oxygen index, and tensile strength. This demonstrates that the polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist of the present invention possesses excellent flame retardant properties.

[0369] 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 polyurethane elastomer material, characterized in that, The raw materials of the thermoplastic polyurethane elastomer material, by weight, include: 70-90 parts of thermoplastic polyurethane elastomer, 10-30 parts of phosphorus-based flame retardant 10-30 parts of nitrogen-based flame retardant 2-8 parts of modified polyhedral oligomeric silsesquioxanes and their derivatives as flame retardant synergists. The modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist is prepared by reacting compound 1 and compound 2 under the action of an acidic catalyst, wherein the molar ratio of compound 1 to compound 2 is 2:1, and the structural formula of compound 1 is as follows. The structural formula of compound 2 is as follows: ; Wherein, R is a non-reactive group, which is isobutyl, isooctyl, ethyl, cyclohexyl, cyclopentyl or phenyl, and R1 is propylene or phenylene; R2 is a cyclic structure with a carbon-to-hydrogen ratio greater than 1, including at least one of benzofuran group and polycyclic aromatic group.

2. The thermoplastic polyurethane elastomer material as described in claim 1, characterized in that, The polycyclic aromatic groups include at least one of the following: naphthyl ring group, anthracene ring group, phenanthrene ring group, acenaphthene ring group, fluorene ring group, perylene ring group, and dibenzofuran group.

3. The thermoplastic polyurethane elastomer material as described in claim 1, characterized in that, The preparation method of the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist includes the following steps: Compound 1 was dissolved in an organic solvent, and compound 2 was added under the action of a catalyst. After catalytic reaction, the mixture was washed and dried to obtain the modified polyhedral oligomeric silsesquioxane and its derivative flame retardant synergist. The organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and ketones.

4. The thermoplastic polyurethane elastomer material as described in claim 1, characterized in that, The raw materials of the thermoplastic polyurethane elastomer material, by weight, include: 70-90 parts of thermoplastic polyurethane elastomer, 10-20 parts of phosphorus-based flame retardant 10-20 parts of nitrogen-based flame retardant 2-8 parts of modified polyhedral oligomeric silsesquioxane and its derivatives flame retardant synergist.

5. The thermoplastic polyurethane elastomer material as described in claim 1, characterized in that, The thermoplastic polyurethane elastomer includes polyether-type or polyester-type thermoplastic polyurethane elastomers.

6. The thermoplastic polyurethane elastomer material as described in claim 1, characterized in that, The phosphorus-based flame retardant includes inorganic phosphorus flame retardants or organic phosphorus flame retardants. The inorganic phosphorus flame retardant includes at least one of red phosphorus, phosphate, and polyphosphate. The organic phosphorus flame retardant includes at least one of phosphate ester, phosphite, and diethylaluminum hypophosphite. And / or, the nitrogen-based flame retardant includes at least one of melamine cyanurate, melamine inorganic acid salt, dicyandiamide, and melamine.

7. The thermoplastic polyurethane elastomer material as described in claim 1, characterized in that, The raw materials of the thermoplastic polyurethane elastomer material also include at least one of lubricant, antioxidant, anti-hydrolysis agent, and matting agent; wherein, by weight, the raw materials are 0.5-1 parts of lubricant, 0.5-2 parts of antioxidant, 0.5-2 parts of anti-hydrolysis agent, and 2-10 parts of matting agent.

8. A method for preparing the thermoplastic polyurethane 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 polyurethane elastomer materials.

9. The method for preparing the thermoplastic polyurethane elastomer material as described in claim 8, characterized in that, The raw materials also include at least one of lubricant, antioxidant, anti-hydrolysis agent, and matting agent; And / or, the extruder is a twin-screw extruder, the extrusion temperature is 160-180℃, and the screw speed is 150-170 r / min.

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