CN113956597A - Nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer and preparation method thereof - Google Patents
Nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer and a preparation method thereof, wherein the thermoplastic elastomer comprises the following components in percentage by weight: 2-20 parts of a phosphorus and nitrogen containing tetrafunctional acrylate; 10-45 parts of styrene block copolymer; 20-60 parts of filling oil, 5-20 parts of polypropylene, 5-10 parts of maleic anhydride grafted styrene block copolymer and 0.1-2 parts of stabilizer; 20-40 parts of thermoplastic polyurethane, 10-30 parts of an organic silicon and polyurethane block copolymer and 1-5 parts of silicone master batch. The preparation method comprises the steps of weighing the raw materials according to the proportion, mixing the raw materials in a high-speed stirrer, putting the mixture into a double-screw extruder for melt extrusion, cooling, drying and granulating the extruded mixture to obtain the finished product. According to the invention, the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant is adopted to prepare the thermoplastic elastomer with excellent flame retardant property, so that the mechanical property and the smoothness of the material are not sacrificed while the flame retardant property of the material is greatly improved. The flame-retardant thermoplastic elastomer is suitable for the fields of automobile parts, sealing strips, wires and cables, medical instruments and the like.
Description
Technical Field
The invention belongs to the technical field of polymer synthesis, modification and processing, and particularly relates to a nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer and a preparation method thereof.
Background
The thermoplastic elastomer is abbreviated as TPE/TPR, also called artificial rubber or synthetic rubber. The product has excellent performances of high elasticity, aging resistance and the like of the traditional cross-linked vulcanized rubber at normal temperature, can be plasticized and formed at high temperature, and has the characteristics of more common plastic processing methods and wide processing modes. The material can be produced by processing modes such as injection molding, extrusion, blow molding and the like, the 100 percent of the crushed edges and corners of the water gap can be directly used for the second time, and the material has no unpleasant smell during processing, and is a novel environment-friendly material. The TPE/TPR material is a latest material replacing traditional rubber, is environment-friendly, nontoxic, comfortable in hand feeling and exquisite in appearance, enables products to be more creative, and is widely applied to the fields of automobile accessories, sealing strips, wires and cables, medical instruments and the like.
At present, fire frequently occurs due to the inflammability of high polymer materials, and people sometimes suffer immeasurable loss of lives and properties. Many countries have in many fields of application clearly requested the use of flame retardant polymeric materials in order to reduce the fire loss. Therefore, as a polymer material closely related to the life of people, the thermoplastic elastomer also has very good flame retardant property.
The Chinese patent application 202010003254.4 discloses an ethylene-butylene elastomer, polypropylene, a cross-linking agent, lipophilic silicon dioxide, polyethylene wax, an auxiliary cross-linking agent, a halogenated flame retardant, a flame retardant auxiliary agent, an anti-dripping agent, a lubricant and an antioxidant, and the ethylene-butylene elastomer is prepared by the steps of excellent flame retardant property and can still reach the flame retardant V0 level under the thickness of 0.8 mm. However, when the halogen-containing flame retardant is used, toxic and corrosive gases are generated during ignition, and secondary damage to a human body is easily caused.
The Chinese patent with publication number CN106589756A discloses a preparation method of a thermoplastic elastomer, which comprises 30-45 parts of a styrene thermoplastic elastomer, 22-29 parts of polypropylene, 25-34 parts of SEBS, 10-16 parts of argil, 7-14 parts of talcum powder, 5-9 parts of barium sulfate, 3-8 parts of ABS resin, 11-19 parts of polyimide resin, 1-4 parts of an adhesive, 12-28 parts of an anti-thermal-oxidative aging agent, 9-18 parts of an additive, 22-30 parts of a flame retardant, 28-35 parts of a toughening agent, 3-9 parts of an emulsifier, 11-18 parts of dimethyl phthalate, 13-21 parts of dioctyl phthalate and 2-8 parts of a gum base. The formula aims to enable the flame retardance of the thermoplastic elastomer to meet the requirement, wherein the dosage of the flame retardant is large, and the weather resistance and the mechanical property of the thermoplastic elastomer are adversely affected by the large-proportion split filler.
Chinese patent publication No. CN107418126A discloses a wear-resistant high-flame-retardant halogen-free flame-retardant thermoplastic elastomer for wires and cables, which comprises 20-40% of SEBS, 20-40% of white oil, 10-30% of nylon, 5-10% of maleic anhydride SEBS, 10-20% of aluminum diethylphosphinate, 10-20% of melamine urate and 1-5% of other additives. Although the flame retardancy of the thermoplastic elastomer is improved, the abrasion resistance of the thermoplastic elastomer is poor.
Chinese patent publication No. CN103756121A discloses a temperature-resistant oil-resistant low-smoke halogen-free flame-retardant radiation-crosslinked polyolefin composite material, which mainly comprises the following components: 50-60 parts of polyolefin, 0.5-5 parts of flame retardant synergist, 40-50 parts of hyperbranched triazine charring agent microencapsulated inorganic flame retardant, 0.5-5 parts of multifunctional cross-linking agent and 0.1-1 part of antioxidant. The technical scheme has specific requirements on the shape and the composition of the flame retardant, the inorganic flame retardant needs to be subjected to microencapsulation treatment, the surface polarity of the inorganic flame retardant is reduced, the agglomeration of the inorganic flame retardant in the processing process is reduced, and the dispersibility and the interface compatibility of the inorganic flame retardant in a polyolefin material are improved, so that the mechanical property of the polyolefin composite material is improved, and the flame retardant property of the polyolefin composite material is improved by the matched use of the hyperbranched triazine charring agent microencapsulated inorganic flame retardant and the flame retardant synergist. However, the whole treatment process is complicated and difficult to realize large-scale industrialization.
With the research of flame retardant polymers getting deeper and deeper, people gradually develop a novel polymer flame retardant system with phosphorus-nitrogen synergistic flame retardant and phosphorus-silicon synergistic flame retardant. In a phosphorus-nitrogen synergistic flame-retardant system, organic phosphorus is degraded to generate a phosphoric acid derivative, so that the dehydration and carbonization of high molecules are promoted, and the condensed phase flame-retardant effect is exerted; degrading organic nitrogen to generate a flame-retardant gas, diluting and thermally degrading the concentration of free radicals, disturbing the chain reaction of the free radicals, and performing the gas-phase flame-retardant effect; the generated flame-retardant gas acts on the glassy carbon oxide layer, so that the area of the carbon layer is increased, and the synergistic flame-retardant effect of the gas phase and the condensed phase is exerted. In a phosphorus-silicon synergistic flame-retardant system, during combustion, organic silicon is firstly degraded, organic phosphorus is catalyzed to be degraded into acid due to the fact that the surface tension of the organic silicon is small and the organic silicon migrates to the surface of a material, macromolecule dehydration and carbonization are promoted, a formed carbon layer is polymerized with silicon oxide with low viscosity, the strength and the density of the carbon layer are increased, fragments or gas and the like generated by macromolecule degradation are coated, a compact heat-insulating layer for insulating heat, air and the like is formed, and the combustion of the macromolecule material is stopped or slowed down, so that the flame retardance of the material is improved.
Aiming at the defects of the existing flame-retardant thermoplastic elastomer material and the advantages of the novel polymer flame-retardant system based on phosphorus-nitrogen synergistic flame-retardant and phosphorus-silicon synergistic flame-retardant, the invention discloses a nitrogen-phosphorus-silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer and a preparation method thereof, and particularly relates to a novel nitrogen-phosphorus-silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer which is prepared by synthesizing a tetrafunctional acrylate containing phosphorus and nitrogen, and then adding the tetrafunctional acrylate into a styrene block copolymer, filling oil, polypropylene, maleic anhydride grafted styrene block copolymer, a stabilizer, thermoplastic polyurethane, an organosilicon and polyurethane block copolymer and silicone master batch composite system, so that the flame retardance of the material is greatly improved without sacrificing the mechanical property and the smoothness of the material. The flame-retardant thermoplastic elastomer is suitable for the fields of automobile parts, sealing strips, wires and cables, medical instruments and the like.
Disclosure of Invention
The invention provides a nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer and a preparation method thereof. The flame-retardant thermoplastic elastomer is suitable for the fields of automobile parts, sealing strips, wires and cables, medical instruments and the like.
The invention adopts the following technical scheme:
a nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer comprises the following raw materials in percentage by weight:
preferably, the block styrene copolymer is at least one of a styrene-butadiene-styrene block copolymer or a hydrogenated product thereof, a styrene-isoprene-styrene block copolymer or a hydrogenated product thereof, specifically, G1651, G1654, G1633 of KRATON, japan, 4055, 4044 of gory, 6151, 6154, 6159 of taiwan rubber corporation, 2315, 2314 of angoni, italy, and CH-6170 of Dynasol, spain.
The extender oil is at least one of linear saturated alkane oil and naphthenic oil, such as 150 from Sun stone corporation (SUNPAR), 150SN from Dowanese corporation, KN4010 from Clay oil refinery in Xinjiang, etc.
The polypropylene is homo-or co-polypropylene, and the melt index (230 ℃, 2.16kg) is required to be 1-50. If the melt index of the polypropylene is lower than 1, the processing fluidity is reduced, patterns are easy to appear on the surface of the product, and if the melt index of the polypropylene is higher than 50, the fluidity of the melt is overlarge, the melt strength is poor, and the injection molding process is not easy to control. Such as Daqing T30S.
The maleic anhydride grafted styrene block copolymer is specifically FG1901 and FG1924 from KRATON, usa.
The stabilizer is benzophenone, hindered phenol, phosphite or mixture composed according to certain proportion, such as Irganox 1010, Irganox 168, Irganox1076, UV531, UV327, etc. of Ciba extract.
The lubricant is at least one of zinc stearate and calcium stearate.
Thermoplastic polyurethane TPUs such as hensman a85G4819, kesichu 385, and the like.
The silicone masterbatch is prepared from Dow Corning MB50-001, MB50-002, etc.
A preparation method of a nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer comprises the following steps: mixing the raw materials in a high-speed mixer for 30min according to the proportion, uniformly mixing, mixing in a low-speed mixer for 20min, adding the uniformly mixed materials into a double-screw extruder by a metering feeder, setting the temperature at 170-200 ℃, setting the rotating speed of a main machine at 320rpm/min, and setting the frequency of the feeder at 28 Hz. The mixed raw materials are subjected to high-temperature shearing, melting, plasticizing and mixing by a double-screw extruder, and water ring granulation to obtain the material.
Preferably, the phosphorous and nitrogen containing tetrafunctional acrylates are prepared as follows: the reaction route is as shown in figure 1, under the protection of nitrogen, adding phosphorus oxychloride and a solvent into a dry clean three-neck flask with a thermometer, then dropwise adding a mixture of hydroxyl-containing monofunctional acrylic acid, triethylamine and the solvent at a set reaction temperature of 0-40 ℃, reacting at room temperature for 4-24 hours after dropwise adding, then dissolving piperazine in the solvent, slowly dropwise adding a piperazine solution into a reaction system, and continuing to react at room temperature for 8-24 hours after dropwise adding; after the reaction is finished, filtering to remove triethylamine salt, washing the product to be neutral by using a 10% hydrochloric acid solution and a saturated sodium bicarbonate solution respectively, drying by using a drying agent, and removing the solvent under reduced pressure to obtain yellow oily phosphorus and nitrogen-containing tetrafunctional acrylate.
Preferably, the solvent is one or a mixture of more of tetrahydrofuran, toluene, xylene, petroleum ether and dichloroethane; the mass ratio of the phosphorus oxychloride to the solvent is 1: 3-2: 1, and the mass ratio of the piperazine to the solvent is 1: 4-1: 1. Preferably, the solvent used for preparing the tetrafunctional acrylate containing phosphorus and nitrogen is one or a mixture of tetrahydrofuran, toluene and petroleum ether. The mass ratio of the phosphorus oxychloride to the solvent is 1: 2-1: 1, and the mass ratio of the piperazine to the solvent is 1: 2-1: 1.
Preferably, the hydroxyl-containing monofunctional acrylic acid is one or a mixture of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate. Preferably, the hydroxyl-containing monofunctional acrylic acid is one or a mixture of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate. The molar ratio of the hydroxyl-containing monofunctional acrylic acid to phosphorus oxychloride is 1:1, the molar ratio of triethylamine to phosphorus oxychloride is 3: 1-4: 1, and the molar ratio of piperazine to phosphorus oxychloride is 1: 2.
Preferably, the drying agent is one of anhydrous magnesium sulfate and anhydrous calcium chloride, and the dosage of the drying agent is 10-30% of the total mass of the product solution.
Preferably, the silicone polyurethane block copolymer is prepared by the following method: firstly heating hydroxyl silicone oil and polyether polyol with hydroxyl groups at two ends to 100 ℃ under 120mmHg, removing water for 2 hours, cooling to 30-70 ℃, dropwise adding diisocyanate by using an anhydrous oxygen-free constant-pressure dropping funnel, reacting at 30-70 ℃ for 0.5-4 hours after dropwise adding, dropwise adding 0.05-1 wt% of dibutyltin dilaurate catalyst, and reacting at 60-90 ℃ for 1-8 hours to obtain the light yellow viscous organic silicon polyurethane block copolymer.
Preferably, the hydroxyl silicone oil is at least one of dimethyl silicone oil with hydroxyl at two ends, a copolymer of dimethyl polysiloxane and methyl phenyl polysiloxane with hydroxyl at two ends, a copolymer of dimethyl polysiloxane and diphenyl polysiloxane with hydroxyl at two ends, and a copolymer of dimethyl polysiloxane and methyl trifluoro propyl polysiloxane with hydroxyl at two ends; the polyether polyol with hydroxyl groups at two ends is at least one of polyoxyethylene ether, polypropylene oxide ether and a copolymer of the epoxy vinyl ether and the polypropylene oxide ether; the isocyanate is at least one of toluene 2, 6-diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
Preferably, the viscosity of the hydroxyl silicone oil is 20-4000 mPa & s, and the molecular weight of polyether polyol with hydroxyl groups at two ends is 200-2000; preferably, the viscosity of the hydroxyl silicone oil is 20-1000 mPa & s, and the molecular weight of polyether polyol with hydroxyl groups at two ends is 600-2000; the molar ratio of the hydroxyl silicone oil to the polyether of the hydroxyl at two ends is 20: 80-70: 30, and the molar ratio of the isocyanate to the hydroxyl is 0.85: 1-0.97: 1.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
the addition of non-reactive flame retardants to thermoplastic elastomers, which are present in the form of plasticizers within the thermoplastic elastomer material, reduces the mechanical properties of the material, and, with prolonged storage time, these flame retardants can migrate to the surface of the material, further affecting the properties of the material. The reactive type four-functional acrylate containing phosphorus and nitrogen is used as the flame retardant, and the flame retardant reacts with the thermoplastic elastomer matrix polymer in a chemical bond form through dynamic vulcanization in the processing process of the thermoplastic elastomer, so that the mechanical property of the thermoplastic elastomer cannot be reduced, and the flame retardant cannot migrate to the surface of the thermoplastic elastomer along with the prolonging of the storage time. The nitrogen-containing part is heated and decomposed in the combustion process to release ammonia gas, nitrogen oxide, water vapor and other flame-retardant compounds, most of heat can be taken away by the formation of the gas and the conversion endothermic reaction of the flame retardant, and the temperature on the surface of the thermoplastic elastomer is reduced, so that the flame retardant effect is achieved. The phosphorus-containing moiety promotes dehydration and carbonization of the polymer at the decomposition stage of the thermoplastic elastomer in the early stage of a fire, thereby reducing the amount of combustible gas generated by thermal decomposition of the thermoplastic elastomer, and the resulting carbon film can also insulate the outside air and heat. The organic silicon polyurethane block copolymer and the silicone master batch have the effects of temperature resistance, flame retardance, oxidation resistance and the like, and a compact carbon layer and silicon dioxide are generated in the combustion process to form an oxygen-isolating and heat-insulating protective layer. Therefore, the reactive type phosphorus and nitrogen containing tetrafunctional acrylate, the organic silicon polyurethane block copolymer and the silicone master batch are adopted to play a good flame retardant role together with the polysiloxane in the thermoplastic elastomer in a synergistic flame retardant manner.
In the thermoplastic elastomer, the styrene block copolymer, the polypropylene, the maleic anhydride grafted styrene block copolymer, the thermoplastic polyurethane and the silicone polyurethane block copolymer provide good mechanical strength to the thermoplastic elastomer. The silicone polyurethane segmented copolymer, the silicone master batch, the filling oil and the lubricant are combined together, so that the smoothness of the thermoplastic elastomer is improved. By adopting the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant, the flame retardance of the material can be greatly improved without sacrificing the mechanical property and the smoothness of the material.
Drawings
FIG. 1 is a reaction scheme of a phosphorous and nitrogen containing tetrafunctional acrylate;
FIG. 2 is an infrared spectrum of a phosphorous and nitrogen containing tetrafunctional acrylate prepared with hydroxyethyl methacrylate.
FIG. 3 is a tetrafunctional acrylate containing phosphorus and nitrogen prepared with hydroxyethyl methacrylate1H-NMR spectrum.
Detailed Description
Preparation of phosphorous and nitrogen containing tetrafunctional acrylates with hydroxyethyl acrylate:
under the protection of nitrogen, 153.3g of phosphorus oxychloride and 306.6g of tetrahydrofuran are added into a dry clean 1000ml three-neck flask with a thermometer, then a mixture of 116.12g of hydroxyethyl acrylate and 303.57g of triethylamine is added dropwise at 5 ℃, the mixture reacts at room temperature for 20 hours after the addition, 43.0678g of piperazine is dissolved in 86.1g of tetrahydrofuran, the piperazine solution is slowly added dropwise into the reaction system, and the reaction at room temperature is continued for 24 hours after the addition. And after the reaction is finished, filtering to remove triethylamine salt, washing the product to be neutral by using a 10% hydrochloric acid solution and a saturated sodium bicarbonate solution respectively, drying by using a drying agent, and removing the solvent under reduced pressure to obtain the phosphorus and nitrogen containing tetrafunctional hydroxyethyl acrylate compound.
Preparation of phosphorous and nitrogen containing tetrafunctional acrylates with hydroxypropyl acrylate:
under the protection of nitrogen, 153.3g of phosphorus oxychloride and 153.3g of xylene are added into a dry clean 1000ml three-neck flask with a thermometer, then a mixture of 130.14g of hydroxypropyl acrylate and 303.57g of triethylamine is added dropwise at 0 ℃, after the dropwise addition, the reaction is carried out at room temperature for 12 hours, 43.0678g of piperazine is dissolved in 43.05g of xylene, the piperazine solution is slowly added dropwise into the reaction system, and after the dropwise addition, the reaction is carried out at room temperature for 12 hours. After the reaction is finished, filtering to remove triethylamine salt, washing the product to be neutral by using a 10% hydrochloric acid solution and a saturated sodium bicarbonate solution respectively, drying by using a drying agent, and removing the solvent under reduced pressure to obtain the phosphorus and nitrogen containing tetrafunctional hydroxypropyl acrylate compound.
Preparation of phosphorous and nitrogen containing tetra functional acrylates with hydroxypropyl methacrylate:
under the protection of nitrogen, 153.3g of phosphorus oxychloride, 153.3g of tetrahydrofuran and 153.3g of toluene are added into a dry clean 1000ml three-neck flask with a thermometer, then a mixture of 130.14g of hydroxyethyl methacrylate and 404.76g of triethylamine is added dropwise at 40 ℃, after the dropwise addition, the reaction is carried out at room temperature for 4 hours, then 43.0678g of piperazine is dissolved in 43.05g of tetrahydrofuran and 43.05g of toluene, the piperazine solution is slowly added dropwise into the reaction system, and the reaction is continued at room temperature for 8 hours after the dropwise addition is finished. And after the reaction is finished, filtering to remove triethylamine salt, washing the product to be neutral by using a 10% hydrochloric acid solution and a saturated sodium bicarbonate solution respectively, drying by using a drying agent, and removing the solvent under reduced pressure to obtain the phosphorus and nitrogen containing tetrafunctional hydroxyethyl methacrylate compound.
Prepared from hydroxyethyl methacrylate as shown in FIG. 2Tetrafunctional acrylates containing phosphorus and nitrogen1H-NMR spectrum at 1726cm-1、1637cm-1And 1410cm-1The strong absorption peak is the characteristic absorption peak of the acrylate group, and 1550cm-1The characteristic peak of nearby-NH-disappears, which shows that piperazine completely participates in the reaction, and the target product is successfully synthesized.
The tetrafunctional acrylate containing phosphorus and nitrogen prepared with hydroxyethyl methacrylate as shown in FIG. 31H-NMR spectrum. 3.38 to 3.55 belong to the group-N (CH)2)2Chemical shift of N-upper hydrogen atom, 4.45-4.77 belongs to (-OCH)2CH2Chemical shift of the hydrogen atom on O-.
Preparation of an organosilicone polyurethane Block copolymer (SiPU)The specific components and reaction conditions are shown in table 1.
Table 1: different silicone polyurethane block copolymers.
Example 1
The preparation method comprises the steps of mixing the components of phosphorus-and-nitrogen-containing tetrafunctional acrylate prepared from hydroxyethyl acrylate, a block styrene copolymer, filling oil, polypropylene, a maleic anhydride grafted styrene block copolymer, an organic silicon polyurethane block copolymer, thermoplastic polyurethane, a lubricant, a stabilizer, silicone master batches and the like for 30min in a high-speed mixer according to the following weight ratio, uniformly mixing, mixing for 20min in a low-speed mixer, adding the uniformly mixed materials into a double-screw extruder from a metering feeder, setting the temperature to be 170-200 ℃, setting the rotating speed of a main engine to be 320rpm/min, and setting the frequency of the feeder to be 28 Hz. The mixed raw materials are subjected to high-temperature shearing, melting, plasticizing and mixing by a double-screw extruder, and water ring granulation to obtain the material. The concrete components are as follows:
example 2
The pellets were produced according to the production process of example 1 and the following raw material weight ratios.
Example 3
Example 4
Comparative example 1
Comparative example 2
Comparative example 3
The results of the physical property tests of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 2.
Table 2: results of physical property tests of examples and comparative examples.
The nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer has good flame retardant property, basically does not damage the mechanical property of the thermoplastic elastomer, has good silky feel, high melt index and good fluidity, and has good ABS coating effect.
The above is only a specific embodiment of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions or modifications made on the basis of the present invention to solve the same technical problems and achieve the same technical effects are all covered in the protection scope of the present invention.
Claims (10)
1. The nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer is characterized by comprising the following raw materials in percentage by weight:
2. the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer as claimed in claim 1, is characterized in that: the block styrene copolymer is at least one of a styrene-butadiene-styrene block copolymer or a hydride thereof, a styrene-isoprene-styrene block copolymer or a hydride thereof; the filling oil is at least one of straight-chain saturated alkane oil and naphthenic oil; the stabilizer is at least one of benzophenone, hindered phenol and phosphite; the lubricant is at least one of zinc stearate and calcium stearate; the polypropylene is homopolymerized or copolymerized polypropylene; the lubricant is at least one of zinc stearate and calcium stearate.
3. The preparation method of the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame-retardant thermoplastic elastomer as claimed in claim 1 or 2, characterized by comprising the following steps:
the raw materials are uniformly mixed in a high-speed mixer and then mixed in a low-speed mixer, the uniformly mixed materials are added into a double-screw extruder through a metering feeder, and the mixed raw materials are subjected to high-temperature shearing, melting, plasticizing and mixing of the double-screw extruder and water ring granulation to obtain the high-performance high-temperature-resistant high-performance high-temperature-resistant high-performance high-temperature-resistant high-speed-resistant high-temperature-resistant high-performance high-temperature-performance high-melting plastic mixing material.
4. The method for preparing the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer as claimed in claim 3, is characterized in that the method for preparing the phosphorus and nitrogen containing tetrafunctional acrylate is as follows: under the protection of nitrogen, adding phosphorus oxychloride and a solvent into a dry clean three-neck flask with a thermometer, dropwise adding a mixture of hydroxyl-containing monofunctional acrylic acid, triethylamine and the solvent at the reaction temperature of 0-40 ℃, reacting at room temperature for 4-24 hours after dropwise adding, dissolving piperazine in the solvent, slowly dropwise adding a piperazine solution into a reaction system, and continuing to react at room temperature for 8-24 hours after dropwise adding; after the reaction is finished, filtering to remove triethylamine salt, washing the product to be neutral by using a 10% hydrochloric acid solution and a saturated sodium bicarbonate solution respectively, drying by using a drying agent, and removing the solvent under reduced pressure to obtain yellow oily phosphorus and nitrogen-containing tetrafunctional acrylate.
5. The preparation method of the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer is characterized in that: the solvent is one or a mixture of more of tetrahydrofuran, toluene, xylene, petroleum ether and dichloroethane; the mass ratio of the phosphorus oxychloride to the solvent is 1: 3-2: 1, and the mass ratio of the piperazine to the solvent is 1: 4-1: 1.
6. The preparation method of the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer is characterized in that: the monofunctional acrylic acid containing hydroxyl is one or a mixture of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate; the molar ratio of the hydroxyl-containing monofunctional acrylic acid to phosphorus oxychloride is 1:1, the molar ratio of triethylamine to phosphorus oxychloride is 3: 1-4: 1, and the molar ratio of piperazine to phosphorus oxychloride is 1: 2.
7. The preparation method of the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer is characterized in that: the drying agent is one of anhydrous magnesium sulfate and anhydrous calcium chloride, and the consumption of the drying agent is 10-30% of the total mass of the product solution.
8. The method for preparing the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer as claimed in claim 3, wherein the preparation method of the organic silicon polyurethane block copolymer is as follows: firstly heating hydroxyl silicone oil and polyether polyol with hydroxyl groups at two ends to 100 ℃ under 120mmHg, removing water for 2 hours, cooling to 30-70 ℃, dropwise adding diisocyanate by using an anhydrous oxygen-free constant-pressure dropping funnel, reacting at 30-70 ℃ for 0.5-4 hours after dropwise adding, dropwise adding 0.05-1 wt% of dibutyltin dilaurate catalyst, and reacting at 60-90 ℃ for 1-8 hours to obtain the light yellow viscous organic silicon polyurethane block copolymer.
9. The preparation method of the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer is characterized in that: the hydroxyl silicone oil is at least one of dimethyl silicone oil with hydroxyl at two ends, a copolymer of dimethyl polysiloxane and methyl phenyl polysiloxane with hydroxyl at two ends, a copolymer of dimethyl polysiloxane and diphenyl polysiloxane with hydroxyl at two ends and a copolymer of dimethyl polysiloxane and methyl trifluoropropyl polysiloxane with hydroxyl at two ends; the polyether polyol with hydroxyl groups at two ends is at least one of polyoxyethylene ether, polypropylene oxide ether and a copolymer of epoxy vinyl ether and polypropylene oxide ether; the isocyanate is at least one of toluene 2, 6-diisocyanate, 1, 6-hexamethylene diisocyanate and isophorone diisocyanate.
10. The preparation method of the nitrogen, phosphorus and silicon ternary halogen-free synergistic flame retardant thermoplastic elastomer is characterized in that: the viscosity of the hydroxyl silicone oil is 20-4000 mPa & s, and the molecular weight of polyether polyol with hydroxyl groups at two ends is 200-2000; the molar ratio of the hydroxyl silicone oil to the polyether of the hydroxyl at two ends is 20: 80-70: 30, and the molar ratio of the isocyanate to the hydroxyl is 0.85: 1-0.97: 1.
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