Phosphate-modified poss flame retardant, tps sheathing material and preparation method thereof, sheathing

Abstract

The application discloses a phosphate-modified POSS flame retardant, a TPS sheath material, a preparation method of the TPS sheath material and a sheath. The phosphate-modified POSS flame retardant is obtained by catalytic reaction of glycidyl ether oxygen propyl cage polysilsesquioxane and 2-amine ethyl-2,3-dihydroxypropyl-hydroxy phosphate, and the molar ratio is 1:8; and the TPS sheath material comprises, in parts by weight, the following components: 15-22 parts of polypropylene, 20-30 parts of SEBS, 20-30 parts of a plasticizer, 3-8 parts of a compatilizer, 5-30 parts of the phosphate-modified POSS flame retardant and 10-45 parts of a flame retardant. The high-flame-retardant TPS sheath material has excellent flame retardancy and physical and mechanical properties.

Description

Technical Field

[0001] This invention relates to the field of sheath materials, specifically to a phosphate ester modified POSS flame retardant, TPS sheath material, its preparation method, and a sheath. Background Technology

[0002] With the surge in sales of new energy vehicles, many domestic companies are developing US standard TPS charging cables. There are many types of TPS cable materials on the international market, including 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 significantly inferior to imported products. Due to limitations in domestic flame-retardant technology, the development of high-flame-retardant, high-performance TPS materials has not made significant progress. Thermoplastic elastomer (TPS) is mainly composed of SEBS, white oil, PP, and certain toughening agents and antioxidants. It has a wide hardness range, excellent hand feel, low-temperature resistance, low price, and excellent elasticity. Therefore, developing a flame retardant for TPS materials to achieve high flame retardancy and high performance is essential. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the present invention proposes a phosphate ester modified POSS flame retardant, a TPS sheath material and its preparation method, and a sheath, aiming to solve the problem of poor flame retardancy and physical and mechanical properties of current TPS materials.

[0004] To achieve the above objectives, this invention proposes a phosphate ester modified POSS flame retardant, a TPS sheath material, a preparation method thereof, and a sheath. A phosphate ester modified POSS flame retardant is characterized in that it is obtained by a catalytic reaction of glycidyl etheroxypropyl cage-like polysilsesquioxane and 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate.

[0005] Optionally, the molar ratio of the glycidyl etheroxypropyl cage-like polysilsesquioxane and 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate is 1:8.

[0006] The TPS sheath material comprises, by weight, 15-22 parts polypropylene, 20-30 parts SEBS, 20-30 parts plasticizer, 3-8 parts compatibilizer, 5-30 parts phosphate-modified POSS flame retardant, and 10-45 parts flame retardant.

[0007] Optionally, the polypropylene includes at least one of ethylene-propylene copolymer or propylene homopolymer, and the compatibilizer is one or more of PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride.

[0008] Optionally, the flame retardant includes 0-10 parts of P-series flame retardant, 0-10 parts of N-series flame retardant, and 10-15 parts of inorganic flame retardant.

[0009] Optionally, the TPS sheath material further includes 0.2-1 parts of lubricant, 0.3-1.5 parts of antioxidant, and 0.3-1.5 parts of light stabilizer; the lubricant includes at least one of stearic acid, calcium stearate, magnesium stearate, polyethylene wax, paraffin wax, and silicone; the antioxidant includes at least one of antioxidant 1035, antioxidant 168, antioxidant TH-412S, antioxidant 1098, and antioxidant 1010; and the light stabilizer includes at least one of zinc oxide, titanium dioxide, benzophenone, salicylic acid, and benzotriazole.

[0010] To achieve the above objectives, the present invention also proposes a method for preparing TPS sheath material, comprising the following steps: obtaining phosphate-modified POSS flame retardant through catalytic reaction; mixing SEBS and plasticizer evenly, then adding polypropylene, compatibilizer and phosphate-modified POSS flame retardant, and performing intensive mixing, extrusion granulation to obtain granules; and drying the granules to obtain the TPS sheath material.

[0011] Optionally, the catalytic reaction yields a phosphate-modified POSS flame retardant, comprising the following steps: dissolving glycidyl etheroxypropyl cage-like polysilsesquioxane in an organic solvent solution, adding 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate under the action of a catalyst, and then cleaning and drying after catalytic reaction to obtain the phosphate-modified POSS flame retardant.

[0012] Optionally, the catalyst comprises one or more organic acids and / or inorganic acids; and / or, the organic solvent comprises at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones, and diol derivatives.

[0013] To achieve the above objectives, the present invention also proposes a sheath for use in charging cables, comprising the sheath material described above.

[0014] The beneficial effects of this invention are as follows: This invention modifies POSS flame retardant by means of phosphate ester, and combines Si, P and N elements together in the phosphate ester modified POSS flame retardant through a catalytic reaction, thereby improving the flame retardant efficiency and flame retardant effect. The modified flame retardant has a large number of hydroxyl groups at the macromolecular end groups, which can be more conducive to the dispersion of the flame retardant and can effectively improve the flame retardant performance and crack resistance of the material.

[0015] This invention also applies the aforementioned flame retardant to prepare TPS sheath material. In this invention, SEBS does not contain unsaturated double bonds and has good heat resistance, ozone resistance, UV degradation resistance, acid and alkali resistance, and wear resistance. It, along with polypropylene, plasticizer, phosphate-modified POSS flame retardant, and other flame retardants, serves as the main component of TPS sheath material. The components work together synergistically to ensure that the cable sheath material can maintain the original good processing performance and elasticity of thermoplastic elastomer, while improving the crack resistance, flame retardancy, and physical and mechanical properties of TPS sheath material. Phosphate-modified POSS is a colorless viscous liquid, and its addition to TPS sheath material has little impact on the performance of TPS sheath material. Moreover, a high addition amount is not required to obtain TPS sheath material with excellent flame retardancy. Attached Figure Description

[0016] Figure 1 This is a molecular structure diagram of the phosphate ester modified POSS flame retardant of the present invention. Detailed Implementation

[0017] 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.

[0018] Unless otherwise specified, all technical and scientific terms used herein have their usual meaning within the field to which the subject matter is claimed.

[0019] To facilitate understanding of this embodiment, the symbols, instruments, and terms are explained below:

[0020] TPS: Thermal Plastic Shielding, has good thermal and dimensional stability and can maintain stable performance at high temperatures. It is widely used in electronics, automotive, aerospace and other fields to protect electronic equipment from high temperatures or electromagnetic interference.

[0021] SEBS: Styrene-Ethylene-Butylene-Styrene, SEBS is a new type of environmentally friendly polymer material with excellent performance and wide application. It has excellent weather resistance, aging resistance, heat resistance, and compression set resistance. It is widely used in polymer modification, adhesives and sealants, lubricating oil thickeners, fillers and sheathing materials for high-grade cables and wires, asphalt modification and other fields.

[0022] Phosphorus-based flame retardants: Phosphorus-based flame retardants include inorganic phosphorus-based flame retardants and organic phosphorus-based flame retardants.

[0023] N-series flame retardants: nitrogen-based flame retardants.

[0024] With the surge in sales of new energy vehicles, many domestic companies are developing US standard TPS charging cables. There are many types of TPS cable materials on the international market, including 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 significantly inferior to imported products. Due to limitations in domestic flame-retardant technology, the development of high-flame-retardant, high-performance TPS materials has not made significant progress. Thermoplastic elastomer (TPS) is mainly composed of SEBS, white oil, PP, and certain toughening agents and antioxidants. It has a wide hardness range, excellent hand feel, low-temperature resistance, low price, and excellent elasticity. Therefore, developing a high-flame-retardant, high-performance TPS material is essential.

[0025] To address the aforementioned problems, this invention proposes a phosphate-modified POSS flame retardant, which is obtained by a catalytic reaction of glycidyl etheroxypropyl cage-like polysilsesquioxane and 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate.

[0026] This invention modifies POSS flame retardant with phosphate esters. Through a catalytic reaction, the phosphate ester is incorporated into the POSS molecule, combining Si, P, and N elements in the phosphate-modified POSS flame retardant. This results in POSS possessing not only excellent char-forming properties but also highly efficient flame retardancy. It also solves the problem of phosphate esters easily precipitating due to their molecular weight. The modified flame retardant has a large number of hydroxyl groups at the macromolecular end groups, which is more conducive to the dispersion of the flame retardant and can effectively improve the flame retardant performance and crack resistance of the material.

[0027] In this scheme, 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate molecules are reacted with glycidyl etheroxypropyl cage-like polysilsesquioxane.

[0028] In some embodiments, the molar ratio of the glycidyl etheroxypropyl cage-like polysilsesquioxane to 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate is 1:8.

[0029] The present invention also uses the above-mentioned flame retardant to prepare TPS sheath material. In this scheme, the ingredients of TPS sheath material, by weight, include 15-22 parts of polypropylene, 20-30 parts of SEBS, 20-30 parts of plasticizer, 3-8 parts of compatibilizer, 5-30 parts of phosphate ester modified POSS flame retardant, and 10-45 parts of flame retardant.

[0030] In this invention, polypropylene, SEBS, plasticizer, compatibilizer, and phosphate-modified POSS flame retardant are used as the main components of TPS sheath material. The components work together synergistically to ensure that the cable sheath material can maintain the good processing performance and elasticity of the original thermoplastic elastomer, and improve the crack resistance, flame retardancy and physical and mechanical properties of TPS sheath material. The phosphate-modified POSS is a colorless viscous liquid. Its addition to TPS sheath material has little impact on the performance of TPS sheath material, and a high addition amount is not required to obtain TPS sheath material with excellent flame retardancy.

[0031] In some embodiments, the TPS sheath material is preferably composed of the following components by weight: 15-22 parts polypropylene, 20-30 parts SEBS, 20-30 parts plasticizer, 3-8 parts compatibilizer, 5-30 parts phosphate-modified POSS flame retardant, and 10-45 parts flame retardant.

[0032] In some embodiments, the polypropylene includes at least one of ethylene-propylene copolymer or propylene homopolymer, and the compatibilizer is one or more of PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride.

[0033] The copolymers mentioned above contain styrene-ethylene blocks, with styrene as the hard segment and ethylene as the soft segment. The hard styrene and polypropylene form a stable structure for the TPS sheath material. The soft ethylene segment is less prone to chain movement compared to straight-chain olefins and other structures when subjected to external forces, thus exhibiting better stability.

[0034] In some embodiments, the polypropylene includes an ethylene-propylene copolymer or a propylene homopolymer.

[0035] Preferably, the polypropylene comprises an ethylene-propylene copolymer.

[0036] Furthermore, the compatibilizer is one or more of the following: PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride. Appropriate compatibilizer content has a positive effect on the mechanical properties, molecular structure, and thermal properties of the TPS sheathing material.

[0037] In some embodiments, the compatibilizer is not specifically limited, but is preferably PP grafted with maleic anhydride, and the TPS sheath material includes 5 parts of compatibilizer.

[0038] Furthermore, the flame retardant comprises 0-10 parts of P-series flame retardant, 0-10 parts of N-series flame retardant, and 10-15 parts of inorganic flame retardant.

[0039] The flame retardant mechanism of phosphorus-nitrogen synergistic flame retardant is a combination of condensed phase flame retardancy and gas phase flame retardancy. During the combustion heating process, the flame retardant decomposes to generate inorganic acids such as phosphoric acid and polyphosphoric acid, which can form a protective film on the surface of the substrate and isolate the air. At the same time, after being heated, it easily releases non-flammable gases such as ammonia, nitrogen, water vapor and nitrogen oxides. These gases block the supply of oxygen and achieve the purpose of flame retardancy.

[0040] Aluminum hydroxide flame retardant produces no harmful substances during the entire flame retardant process, and its decomposition products can absorb harmful gases and smoke produced by the combustion of polymer materials while retardant.

[0041] In this solution, the flame retardant components form a halogen-free compound flame retardant, which allows multiple flame retardant elements to work synergistically, thereby better balancing the relationship between flame retardant dosage, performance and cost, making it more environmentally friendly and safer.

[0042] In some embodiments, the flame retardant comprises 12 parts of an inorganic flame retardant.

[0043] Furthermore, the TPS sheath material also includes 0.2-1 parts of lubricant, 0.3-1.5 parts of antioxidant, and 0.3-1.5 parts of light stabilizer. The lubricant includes at least one of stearic acid, calcium stearate, magnesium stearate, polyethylene wax, paraffin wax, and silicone. The antioxidant includes at least one of antioxidant 1035, antioxidant 168, antioxidant TH-412S, antioxidant 1098, and antioxidant 1010. The light stabilizer includes at least one of zinc oxide, titanium dioxide, benzophenone, salicylic acid, and benzotriazole. The addition of lubricant ensures better compatibility and leveling of the mixed feed in the plasticized state during the mixing process, ensuring a uniform overall appearance and smooth surface of the sheath material. The antioxidant prevents thermal oxidative degradation of the elastomer, and the light stabilizer prevents photo-oxidative degradation of the elastomer.

[0044] In some embodiments, the lubricant includes at least one of stearic acid, calcium stearate, magnesium stearate, polyethylene wax, paraffin, and silicone, preferably silicone, and the TPS sheath material is formulated with lubricant, preferably 0.5 parts.

[0045] In some embodiments, the antioxidant includes at least one of antioxidant 1035, antioxidant 168, antioxidant TH-412S, antioxidant 1098, and antioxidant 1010, preferably antioxidant 1010, and the TPS sheath material contains an antioxidant, preferably 0.5 parts.

[0046] In some embodiments, the light stabilizer includes at least one of zinc oxide, titanium dioxide, benzophenone, salicylic acid, and benzotriazole, and the TPS sheath material contains a light stabilizer, preferably 0.3 parts.

[0047] To address the above problems, this invention also proposes a method for preparing TPS sheath material, comprising the following steps:

[0048] S1: Catalytic reaction yields phosphate-modified POSS flame retardant;

[0049] In this scheme, the obtained phosphate-modified POSS flame retardant can ensure the original good processing performance and elasticity of the thermoplastic elastomer, while improving the crack resistance of the cable sheath material.

[0050] S2: Mix SEBS and plasticizer evenly, then add polypropylene, compatibilizer and phosphate-modified POSS flame retardant, and then perform intensive mixing, extrusion and granulation to obtain granules.

[0051] In some embodiments, mixing is carried out in an internal mixer.

[0052] In some embodiments, antioxidants and light stabilizers are also added.

[0053] S3: The granular material is dried to obtain a high flame-retardant and crack-resistant TPS sheath material for charging cables.

[0054] In some embodiments, extrusion granulation is achieved using a twin-screw extruder.

[0055] In some embodiments, the length-to-diameter ratio of the twin-screw extruder is (35-40):1.

[0056] In some embodiments, the temperature at which the granules are extruded to obtain TPS preforms is 170°C-190°C.

[0057] In some embodiments, the temperature at which the granules are dried is 80°C-90°C.

[0058] Further, the catalytic reaction yields a phosphate-modified POSS flame retardant, comprising the following steps:

[0059] Glycidyl etheroxypropyl cage-like polysilsesquioxane was dissolved in an organic solvent solution, and 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate was added under the action of a catalyst. After catalytic reaction, the mixture was cleaned and dried to obtain phosphate-modified POSS flame retardant.

[0060] Furthermore, the catalyst comprises one or more organic acids and / or inorganic acids; and / or, the organic solvent comprises at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones, and diol derivatives.

[0061] In some embodiments, the catalyst is not specifically limited herein, but is preferably acetic acid.

[0062] In some embodiments, the organic solvent is not specifically limited, but is preferably tetrahydrofuran. To address the above problems, the present invention also proposes a sheath for use in cables, comprising the aforementioned sheath material.

[0063] The following specific embodiments and data explain the content of the present invention.

[0064] Example 1:

[0065] 1 mol of glycidyl etheroxypropyl cage-like polysilsesquioxane was dissolved in 100 ml of tetrahydrofuran solution. 0.2 mol of acetic acid catalyst was added to the solution, and 8 mol of 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate 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 the phosphate-modified POSS flame retardant.

[0066] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0067] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 5 parts phosphate-modified POSS flame retardant, 12 parts flame retardant (0 parts P-series flame retardant, 0 parts N-series flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0068] Example 2:

[0069] The preparation method is the same as in Example 1, except that:

[0070] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0071] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 10 parts phosphate-modified POSS flame retardant, 12 parts flame retardant (0 parts P-based flame retardant, 0 parts N-based flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0072] Example 3:

[0073] The preparation method is the same as in Example 1, except that:

[0074] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0075] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 15 parts phosphate-modified POSS flame retardant, 12 parts flame retardant (0 parts P-series flame retardant, 0 parts N-series flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0076] Example 4:

[0077] The preparation method is the same as in Example 1, except that:

[0078] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0079] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 20 parts phosphate-modified POSS flame retardant, 12 parts flame retardant (0 parts P-series flame retardant, 0 parts N-series flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0080] Example 5:

[0081] The preparation method is the same as in Example 1, except that:

[0082] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0083] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 25 parts phosphate-modified POSS flame retardant, 12 parts flame retardant (0 parts P-series flame retardant, 0 parts N-series flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0084] Example 6:

[0085] The preparation method is the same as in Example 1, except that:

[0086] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0087] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 30 parts phosphate-modified POSS flame retardant, 12 parts flame retardant (0 parts P-series flame retardant, 0 parts N-series flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0088] Example 7:

[0089] The preparation method is the same as in Example 1, except that:

[0090] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0091] The mixture was thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 20 parts phosphate-modified POSS flame retardant, 22 parts flame retardant (5 parts P-based flame retardant, 5 parts N-based flame retardant, and 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture was then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheathing material for charging cables was obtained. Comparative Example 1:

[0092] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0093] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 42 parts flame retardant (30 parts P-series flame retardant, 0 parts N-series flame retardant, and 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0094] Comparative Example 2:

[0095] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0096] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 30 parts phosphate-modified POSS flame retardant, 42 parts flame retardant (0 parts P-series flame retardant, 30 parts N-series flame retardant, and 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0097] Comparative Example 3:

[0098] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0099] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 30 parts 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate, 12 parts flame retardant (0 parts P-based flame retardant, 0 parts N-based flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0100] Comparative Example 4:

[0101] Mix 15 parts plasticizer and 25 parts SEBS evenly and let stand for 2-4 hours;

[0102] The mixture is thoroughly mixed with 18 parts PP, 5 parts compatibilizer, 30 parts glycidyl ether oxypropyl cage polysilsesquioxane, 12 parts flame retardant (0 parts P-series flame retardant, 0 parts N-series flame retardant, 12 parts inorganic flame retardant), 0.5 parts lubricant, 0.5 parts antioxidant, and 0.3 parts light stabilizer. The mixture is then granulated by twin-screw extrusion at 180°C to obtain TPS preform. After drying at 80°C, a high flame-retardant and crack-resistant TPS sheath material for charging cables is obtained.

[0103] The components and key preparation variables of Examples 1-7 and Comparative Examples 1-4 are summarized in Table 1.

[0104] Table 1. Component list of Examples 1-7 and Comparative Examples 1-4 of the present invention

[0105]

[0106] According to the specifications of GB / T 1040.2, UL94, GB / T 2406.2 and GB / T33594, the TPS sheathing materials in Examples 1-7 and Comparative Examples 1-4 were tested for tensile strength, elongation at break, flame retardancy rating, oxygen index, trouser tear test, 110°C thermal shock, 130°C thermal shock, 150°C thermal shock and exudation. The test results are recorded in Table 2 below:

[0107] Table 2 Performance test table of Examples 1-7 and Comparative Examples 1-4 of the present invention

[0108]

[0109] Based on the test results above, it can be seen that in Examples 1-6, the flame retardant performance gradually improves with the increase of the amount of phosphate-modified POSS flame retardant, proving that the phosphate-modified POSS flame retardant has good flame retardancy, high flame retardant efficiency, and resistance to exudation. Examples 6 and Comparative Example 4 show that the sheath material with added phosphate-modified POSS flame retardant has better flame retardancy; Examples 6 and Comparative Example 3 show that the sheath material with added phosphate-modified POSS flame retardant has good resistance to exudation; Example 7 shows that the combination of phosphate-modified POSS flame retardant and conventional flame retardants can also produce good results; Examples 6 and Comparative Example 1 show that the phosphate-modified POSS flame retardant has better compatibility, and the flame-retardant TPS sheath material has superior physical properties; Examples 6 and Comparative Example 2 show that the phosphate-modified POSS flame retardant has better flame retardancy.

[0110] This invention verifies that the flame retardancy of TPS sheath material is improved by adding phosphate ester modified POSS flame retardant, giving it excellent physical and mechanical properties, high industrial value, and the potential for widespread application and promotion.

[0111] 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 phosphate ester modified POSS flame retardant, characterized in that, The phosphate-modified POSS flame retardant is obtained by catalytic reaction of glycidyl etheroxypropyl cage-like polysilsesquioxane and 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate, wherein the molar ratio of glycidyl etheroxypropyl cage-like polysilsesquioxane and 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate is 1:

8.

2. A TPS sheathing material, characterized in that, The TPS sheath material is formulated in parts by weight, comprising: 15-22 parts of polypropylene SEBS 20-30 copies, Plasticizer 20-30 parts, 3-8 parts compatibilizer 5-30 parts of the phosphate-modified POSS flame retardant as described in claim 1 10-45 parts of flame retardant other than phosphate-modified POSS flame retardant.

3. The TPS sheath material as described in claim 2, characterized in that, The polypropylene includes at least one of ethylene-propylene copolymer or propylene homopolymer, and the compatibilizer is one or more of PE grafted with maleic anhydride, POE grafted with maleic anhydride, PP grafted with maleic anhydride, and EMA grafted with maleic anhydride.

4. The TPS sheath material as described in claim 2, characterized in that, The flame retardants, excluding the phosphate-modified POSS flame retardant, include 0-10 parts of P-series flame retardant, 0-10 parts of N-series flame retardant, and 10-15 parts of inorganic flame retardant.

5. The TPS sheath material as described in claim 2, characterized in that, The TPS sheath material also includes 0.2-1 parts of lubricant, 0.3-1.5 parts of antioxidant, and 0.3-1.5 parts of light stabilizer. The lubricant includes at least one of stearic acid, calcium stearate, magnesium stearate, polyethylene wax, paraffin wax, and silicone. The antioxidant includes at least one of antioxidant 1035, antioxidant 168, antioxidant TH-412S, antioxidant 1098, and antioxidant 1010. The light stabilizer includes at least one of zinc oxide, titanium dioxide, benzophenone, salicylic acid, and benzotriazole.

6. A method for preparing a TPS sheath material according to any one of claims 2-5, characterized in that, Includes the following steps: The phosphate-modified POSS flame retardant was obtained by catalytic reaction; SEBS and plasticizer are mixed evenly, and then polypropylene, compatibilizer, lubricant, antioxidant, light stabilizer, flame retardant (excluding phosphate-modified POSS flame retardant) and the phosphate-modified POSS flame retardant are added. The mixture is then subjected to intensive mixing, extrusion and granulation to obtain granules. The granules are then dried to obtain the TPS sheath material.

7. The method for preparing the TPS sheath material as described in claim 6, characterized in that, The catalytic reaction yields a phosphate-modified POSS flame retardant, comprising the following steps: Glycidyl etheroxypropyl cage-like polysilsesquioxane was dissolved in an organic solvent solution, and 2-aminoethyl-2,3-dihydroxypropyl-hydroxyphosphate was added under the action of a catalyst. After catalytic reaction, the mixture was cleaned and dried to obtain phosphate-modified POSS flame retardant.

8. The method for preparing the TPS sheath material as described in claim 7, characterized in that, The catalyst includes one or more organic acids and / or inorganic acids; And / or, the organic solvent includes at least one of alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones, and diol derivatives.

9. A protective sleeve, characterized in that, Applied to charging cables, including sheathing materials as described in any one of claims 2-5 or sheathing materials obtained by the preparation method of any one of claims 6-8.

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