High-temperature-resistant polyester composite material and preparation method thereof

Abstract

The invention discloses a high-temperature-resistant polyester composite material and a preparation method thereof, and relates to the technical field of composite materials, and the high-temperature-resistant polyester composite material is prepared from the following raw materials: PBT resin, amino-terminated hyperbranched polysiloxane liquid crystals, a functional copolymer, a catalyst, a coupling agent, a high-temperature-resistant filler, nano boron fibers, a thermoplastic polyester elastomer, an antioxidant, a lubricant and a compatilizer. The functional copolymer comprises a structural unit introduced by the following monomers: 1, 3-bis (oxirane methyl)-5-(2-propenyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone, 2-acrylamido-2-methylpropanesulfonic acid, and diphenyl (4-vinyl phenyl) phosphine oxide, and a structural unit introduced by the following monomers: 1, 3-bis (oxirane methyl)-5-(2-propenyl)-1, 3, 5-triazine-2, 4, 6 (1H, 3H, 5H)-triketone; the high-temperature-resistant filler is formed by mixing LDH coated SiO2 nanoparticles, graphene nanosheets and glass flakes. The material is good in high temperature resistance and excellent in mechanical property, toughness and flame retardance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of composite materials, and particularly relates to a high-temperature-resistant polyester composite material and a preparation method thereof. BACKGROUND

[0002] Polyester composite materials have a wide application prospect in many fields such as electronic appliances, automobile industry, aerospace, etc. due to their good mechanical properties and processing properties. However, with the increasing requirements of various industries on the performance of materials, the performance of traditional polyester composite materials has been difficult to meet the needs of some high-end application scenarios. It is particularly important to develop polyester composite materials with more excellent comprehensive performance and performance stability.

[0003] The high-temperature resistance of traditional polyester composite materials is often difficult to meet the use requirements of high-end fields due to the limitation of molecular structure. When the temperature rises to a certain extent, softening, deformation or even decomposition easily occurs, which leads to a significant decline in the mechanical properties and functional characteristics of the material, and seriously affects the normal operation of related equipment and components. At present, the methods for improving the high-temperature resistance of polyester materials mainly include chemical modification and physical blending. Although chemical modification can improve the heat resistance of polyester to a certain extent, it often requires complex synthesis process, has high cost, and may adversely affect other properties of the material. The physical blending method is relatively simple, but how to realize the uniform dispersion and good interfacial bonding of the modifier and the polyester matrix is a key problem. If the dispersion is not uniform or the interfacial bonding force is poor, the high-temperature resistance of the material cannot be effectively improved, and the mechanical properties of the material may be reduced. In addition, the mechanical properties, toughness and flame retardancy of the polyester composite materials on the market still need to be further improved.

[0004] In order to solve the above technical problems, a high-temperature-resistant polyester composite material and a preparation method thereof are disclosed in a Chinese patent with the authorization publication number CN108314796B; an organosilicon coating agent is prepared by polycondensation reaction with fluorine-containing phenyl silicone resin and silicone rubber (107 glue) as raw materials, a mixture of the organosilicon coating agent, an oxidizing agent and a diluent is coated on a polyester substrate, and a high-temperature-resistant polyester composite material is obtained by drying and curing. Since a certain amount of fluorine-containing phenyl is introduced into the structure of the product, the obtained product has excellent high-temperature resistance and bonding properties, and has the advantages of simple preparation process, low equipment requirement and suitability for industrial scale production. However, the mechanical properties, toughness and flame retardancy of the material still need to be further improved.

[0005] It can be seen that developing a high-temperature-resistant polyester composite material with good high-temperature resistance, excellent mechanical properties, toughness and flame retardancy and a preparation method thereof meets the market demand, has wide market value and application prospect, and has very important significance for promoting the further development of the polyester material field. SUMMARY

[0006] Therefore, the present application aims to provide a high-temperature-resistant polyester composite material with good high-temperature resistance, mechanical properties, toughness and flame resistance, and a preparation method thereof.

[0007] In order to achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0008] A high-temperature-resistant polyester composite material comprises the following raw materials in parts by weight: PBT resin 80 parts, amino-terminated hyperbranched polysiloxane liquid crystal 5-8 parts, functional copolymer 8-12 parts, catalyst 1-3 parts, coupling agent 1-3 parts, high-temperature-resistant filler 20-30 parts, nano boron fiber 3-5 parts, thermoplastic polyester elastomer 8-10 parts, antioxidant 0.5-1 part, lubricant 0.8-1.2 parts, and compatibility agent 1-2 parts. The functional copolymer comprises structural units introduced by the following monomers: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide.

[0009] Preferably, the PBT resin is PBT 4012G RESIN.

[0010] Preferably, the source of the amino-terminated hyperbranched polysiloxane liquid crystal has no special requirements, and in an embodiment of the present application, the amino-terminated hyperbranched polysiloxane liquid crystal is prepared according to the method of Example 1 of the Chinese Invention Patent with the authorization announcement number CN103951829B.

[0011] Preferably, the preparation method of the functional copolymer comprises the following steps: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide are added to a high-boiling-point solvent, stirred at 60-70°C for 3-5h under an inert gas atmosphere, then precipitated in water, washed with ethanol for 3-6 times, and finally dried in a vacuum drying box at 85-95°C for 5-8h to obtain the functional copolymer.

[0012] Preferably, the mass ratio of the 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator, and high-boiling-point solvent is 1:(0.8-1.2):(1-2):(0.03-0.05):(10-15).

[0013] Preferably, the initiator is azobisisobutyronitrile; the high-boiling-point solvent is any one of dimethyl sulfoxide, N,N-dimethylformamide, or N-methylpyrrolidone; and the inert gas is any one of nitrogen, helium, neon, or argon.

[0014] Preferably, the catalyst is a mixture of phosphorus pentoxide and polyphosphoric acid in a mass ratio of (1-2):1.

[0015] Preferably, the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, or silane coupling agent KH570.

[0016] Preferably, the method for preparing the LDH@SiO2 nanoparticles comprises the following steps: dissolving magnesium nitrate and aluminum nitrate in deionized water, adding 1.8-2.2 mol / L sodium hydroxide solution dropwise at 65-75°C until pH=9, adding nano-SiO2 and ultrasonically dispersing for 1-2 h, performing hydrothermal reaction for 10-12 h, centrifuging and drying to obtain the LDH@SiO2 nanoparticles.

[0017] Preferably, the molar ratio of the magnesium nitrate, aluminum nitrate, deionized water, and nano-SiO2 is 3:1:(12-20):(0.8-1.2).

[0018] Preferably, the particle size of the nano-SiO2 is 10-80 nm.

[0019] Preferably, the temperature of the hydrothermal reaction is 190-220°C.

[0020] Preferably, the graphene nanosheet has a diameter of 5-10 μm and a thickness of 3-10 nm.

[0021] Preferably, the glass flake has a flake diameter of 10-100 μm and a thickness of 3-5 μm.

[0022] Preferably, the nano-boron fiber has an average diameter of 100-300 nm and an aspect ratio of (25-30):1.

[0023] Preferably, the thermoplastic polyester elastomer is Hytrel 6356 TPEE.

[0024] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1076, antioxidant 168; the lubricant is at least one of pentaerythritol stearate, zinc stearate, ethylene bis-stearamide; the compatibilizer is compatibilizer CMG9801.

[0025] Another object of the present application is to provide a preparation method of the high-temperature-resistant polyester composite material, comprising the following steps: uniformly mixing each raw material according to weight parts, and then adding into a twin-screw extruder for melt blending extrusion to obtain the high-temperature-resistant polyester composite material.

[0026] Preferably, the temperature of the melt blending extrusion is 240-260℃, and the screw rotation speed is 200-300rpm.

[0027] The technical scheme has the beneficial effects that:

[0028] (1) The preparation method of the high-temperature-resistant polyester composite material is simple in process, convenient in operation control, low in dependence on equipment, high in preparation efficiency and product qualification rate, suitable for industrial large-scale production, and has high popularization and application value.

[0029] (2) The high-temperature-resistant polyester composite material comprises the following raw materials according to weight parts: PBT resin 80 parts, amino-terminated hyperbranched polysiloxane liquid crystal 5-8 parts, functional copolymer 8-12 parts, catalyst 1-3 parts, coupling agent 1-3 parts, high-temperature-resistant filler 20-30 parts, nano boron fiber 3-5 parts, thermoplastic polyester elastomer 8-10 parts, antioxidant 0.5-1 part, lubricant 0.8-1.2 parts, and compatibilizer 1-2 parts; through the mutual cooperation and joint action of each raw material, the prepared composite material has good high-temperature-resistant performance, excellent mechanical properties, toughness and flame retardancy.

[0030] (3) The high-temperature-resistant polyester composite material comprises the following monomers: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide; the introduced epoxy group can undergo epoxy ring-opening reaction with the amino group on the amino-terminated hyperbranched polysiloxane liquid crystal; the sulfonic acid group can undergo chemical reaction with the benzene ring on the PBT and thermoplastic polyester elastomer to form an interpenetrating network structure, effectively improving the high-temperature-resistant performance, mechanical properties, toughness and flame retardancy of the composite material. Meanwhile, the introduced triazinone, amido group, phenyl phosphine oxide, polyester and hyperbranched polysiloxane liquid crystal structure have the effects of electronic effect, steric effect and conjugation effect, so that the prepared composite material product has better high-temperature-resistant performance and more excellent mechanical properties, toughness and flame retardancy.

[0031] (4) The high-temperature-resistant polyester composite material provided by the application, the high-temperature-resistant filler is LDH@SiO2 nanoparticles, graphene nanosheets and glass flake mixed in a mass ratio of (4-9):(2-5):(1-3). The above composition forms a "nano-steel bar-concrete" reinforcing network. When the temperature rises, the water molecules between the LDH layers absorb heat through controllable release, delaying the thermal degradation of the matrix. The two-dimensional heat conduction network of graphene improves the thermal conductivity of the composite material, effectively reducing the local thermal stress. The flake structure of the glass flake is arranged in parallel on the surface of the material, forming a "labyrinth effect" to delay the penetration of oxygen / heat. The three work together so that the addition of the high-temperature-resistant filler to the composite material not only improves the mechanical properties but also effectively improves the high-temperature resistance. DETAILED DESCRIPTION

[0032] In order to enable those skilled in the art to better understand the technical solutions of the present application, and to make the above features, objects and advantages of the present application more clear and easy to understand, the present application will be further described below in conjunction with examples. The examples are only used to illustrate the present application and not to limit the scope of the present application.

[0033] Example 1

[0034] A high-temperature-resistant polyester composite material, comprising the following raw materials made by weight parts: PBT resin 80 parts, amino-terminated hyperbranched polysiloxane liquid crystal 5 parts, functional copolymer 8 parts, catalyst 1 part, coupling agent 1 part, high-temperature-resistant filler 20 parts, nano boron fiber 3 parts, thermoplastic polyester elastomer 8 parts, antioxidant 0.5 parts, lubricant 0.8 parts, and compatibility agent 1 part; the functional copolymer comprises structural units introduced by the following monomers: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide; the high-temperature-resistant filler is LDH@SiO2 nanoparticles, graphene nanosheets and glass flake mixed in a mass ratio of 4:2:1; the PBT resin is PBT 4012G RESIN; the amino-terminated hyperbranched polysiloxane liquid crystal is made by the method of Example 1 of the Chinese invention patent with the authorized announcement number CN103951829B.

[0035] The preparation method of the functional copolymer comprises the following steps: 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl) phosphine oxide, initiator are added into a high-boiling-point solvent, stirring reaction is carried out under an inert gas atmosphere at 60 DEG C for 3h, then precipitation is carried out in water, and washing is carried out with ethanol for 3 times, finally drying is carried out in a vacuum drying box at 85 DEG C for 5h to obtain the functional copolymer; the mass ratio of the 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl) phosphine oxide, initiator, high-boiling-point solvent is 1:0.8:1:0.03:10; the initiator is azobisisobutyronitrile; the high-boiling-point solvent is dimethyl sulfoxide; and the inert gas is nitrogen. Through GPC test, the M n =13870g / mol, M W n =1.361; through element analysis and weight change calculation, the mole ratio of the structural units introduced by 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl) phosphine oxide in the functional copolymer is 0.99:0.8:0.98.

[0036] The catalyst is a mixture of phosphorus pentoxide and polyphosphoric acid in a mass ratio of 1:1; and the coupling agent is silane coupling agent KH550.

[0037] The preparation method of the LDH@SiO2 nanoparticles comprises the following steps: magnesium nitrate and aluminum nitrate are dissolved in deionized water, 1.8mol / L sodium hydroxide solution is added dropwise at 65 DEG C until pH is 9, nano-SiO2 is added and ultrasonic dispersion is carried out for 1h, centrifugal drying is carried out after hydrothermal reaction for 10h to prepare LDH@SiO2 nanoparticles; the molar ratio of the magnesium nitrate, aluminum nitrate, deionized water and nano-SiO2 is 3:1:12:0.8; the particle size of the nano-SiO2 is 10nm; and the temperature of the hydrothermal reaction is 190 DEG C.

[0038] ​The diameter of the graphene nanosheet is 5-10 μm, and the thickness is 3-10 nm; the flake diameter of the glass flake is 10-100 μm, and the thickness is 3-5 μm; the average diameter of the nanometer boron fiber is 100 nm, and the aspect ratio is 25:1; the thermoplastic polyester elastomer is Hytrel 6356 TPEE; the antioxidant is antioxidant 1010; the lubricant is pentaerythritol stearate; and the compatibilizer is compatibilizer CMG9801.

[0039] A preparation method of the high-temperature-resistant polyester composite material, comprising the following steps: uniformly mixing each raw material according to the weight parts, and then adding into a double-screw extruder to perform melt blending extrusion, so as to obtain the high-temperature-resistant polyester composite material; the temperature of the melt blending extrusion is 240°C, and the screw rotation speed is 200 rpm.

[0040] Example 2

[0041] A high-temperature-resistant polyester composite material, comprising the following raw materials according to the weight parts: PBT resin 80 parts, amino-terminated hyperbranched polysiloxane liquid crystal 6 parts, functional copolymer 9 parts, catalyst 1.5 parts, coupling agent 1.5 parts, high-temperature-resistant filler 23 parts, nanometer boron fiber 3.5 parts, thermoplastic polyester elastomer 8.5 parts, antioxidant 0.6 parts, lubricant 0.9 parts, and compatibilizer 1.2 parts; the functional copolymer comprises structural units introduced by the following monomers: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide; the high-temperature-resistant filler is a mixture of LDH@SiO2 nanoparticles, graphene nanosheets, and glass flakes in a mass ratio of 5:3:1.5; the PBT resin is PBT 4012G RESIN; and the amino-terminated hyperbranched polysiloxane liquid crystal is prepared according to the method of Example 1 of the Chinese invention patent with the authorized announcement number CN103951829B.

[0042] The preparation method of the functional copolymer comprises the following steps: 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropanesulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator are added into a high-boiling-point solvent, stirring reaction is carried out under an inert gas atmosphere at 63 DEG C for 3.5 h, then precipitation is carried out in water, and washing is carried out with ethanol for 4 times, finally drying is carried out in a vacuum drying box at 87 DEG C for 6 h to obtain the functional copolymer; the mass ratio of the 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropanesulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator, high-boiling-point solvent is 1:0.9:1.2:0.035:11; the initiator is azobisisobutyronitrile; the high-boiling-point solvent is N,N-dimethylformamide; and the inert gas is helium.

[0043] The catalyst is prepared by mixing phosphorus pentoxide and polyphosphoric acid at a mass ratio of 1.2:1; and the coupling agent is silane coupling agent KH560.

[0044] The preparation method of the LDH@SiO2 nanoparticles comprises the following steps: magnesium nitrate and aluminum nitrate are dissolved in deionized water, 1.9 mol / L sodium hydroxide solution is added dropwise at 67 DEG C until pH is 9, nano-SiO2 is added and ultrasonic dispersion is carried out for 1.2 h, hydrothermal reaction is carried out for 10.5 h, then centrifugal drying is carried out to prepare the LDH@SiO2 nanoparticles; the molar ratio of the magnesium nitrate, aluminum nitrate, deionized water and nano-SiO2 is 3:1:14:0.9; the particle size of the nano-SiO2 is 30 nm; and the temperature of the hydrothermal reaction is 200 DEG C.

[0045] The diameter of the graphene nanosheet is 5-10 mu m, the thickness is 3-10 nm, the flake diameter of the glass flake is 10-100 mu m, the thickness is 3-5 mu m, the average diameter of the nano boron fiber is 150 nm, the aspect ratio is 26:1, the thermoplastic polyester elastomer is Hytrel 6356 TPEE, the antioxidant is antioxidant 1076, the lubricant is zinc stearate, and the compatibilizer is compatibilizer CMG9801.

[0046] A preparation method of the high-temperature-resistant polyester composite material comprises the following steps: after the raw materials are uniformly mixed according to weight parts, the raw materials are added into a double-screw extruder for melt blending extrusion to obtain the high-temperature-resistant polyester composite material; the temperature of the melt blending extrusion is 245 DEG C, and the screw rotation speed is 230 rpm.

[0047] Example 3

[0048] A high-temperature-resistant polyester composite material, comprising the following raw materials in parts by weight: PBT resin 80 parts, amino-terminated hyperbranched polysiloxane liquid crystal 6.5 parts, functional copolymer 10 parts, catalyst 2 parts, coupling agent 2 parts, high-temperature-resistant filler 25 parts, nano boron fiber 4 parts, thermoplastic polyester elastomer 9 parts, antioxidant 0.8 parts, lubricant 1 part, and compatibilizer 1.5 parts; the functional copolymer comprises structural units introduced by the following monomers: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide; the high-temperature-resistant filler is a mixture of LDH@SiO2 nanoparticles, graphene nanosheets, and glass flake in a mass ratio of 7:3.5:2; the PBT resin is PBT 4012G RESIN; and the amino-terminated hyperbranched polysiloxane liquid crystal is prepared according to the method of Example 1 of the Chinese patent for invention with the authorized announcement No. CN103951829B.

[0049] A preparation method of the functional copolymer, comprising the following steps: adding 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, and initiator into a high-boiling-point solvent, stirring and reacting at 65°C for 4h in an inert gas atmosphere, then precipitating in water, washing with ethanol for 5 times, and finally drying in a vacuum drying box at 90°C for 6.5h to obtain the functional copolymer; the mass ratio of 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator, and high-boiling-point solvent is 1:1:1.5:0.04:13; the initiator is azobisisobutyronitrile; the high-boiling-point solvent is N-methylpyrrolidone; and the inert gas is neon.

[0050] The catalyst is a mixture of phosphorus pentoxide and polyphosphoric acid in a mass ratio of 1.5:1; and the coupling agent is silane coupling agent KH570.

[0051] A preparation method of the LDH@SiO2 nanoparticles, comprising the following steps: dissolving magnesium nitrate and aluminum nitrate in deionized water, adding 2mol / L sodium hydroxide solution dropwise at 70°C until pH=9, ultrasonically dispersing nano SiO2 for 1.5h, and then centrifuging and drying after hydrothermal reaction for 11h to obtain the LDH@SiO2 nanoparticles; the molar ratio of magnesium nitrate, aluminum nitrate, deionized water, and nano SiO2 is 3:1:16:1; the particle size of the nano SiO2 is 50nm; and the temperature of the hydrothermal reaction is 205°C.

[0052] The diameter of the graphene nanosheet is 5-10 μm, and the thickness is 3-10 nm; the flake diameter of the glass flake is 10-100 μm, and the thickness is 3-5 μm; the average diameter of the nanometer boron fiber is 200 nm, and the aspect ratio is 27:1; the thermoplastic polyester elastomer is Hytrel 6356 TPEE; the antioxidant is antioxidant 168; the lubricant is ethylene bis-stearamide; and the compatibilizer is compatibilizer CMG9801.

[0053] A preparation method of the high-temperature-resistant polyester composite material, comprising the following steps: uniformly mixing each raw material according to the weight parts, and then adding into a double-screw extruder to perform melt blending extrusion, so as to obtain the high-temperature-resistant polyester composite material; the temperature of the melt blending extrusion is 250°C, and the screw rotation speed is 250 rpm.

[0054] Example 4

[0055] A high-temperature-resistant polyester composite material, which is made of the following raw materials according to weight parts: PBT resin 80 parts, amino-terminated hyperbranched polysiloxane liquid crystal 7.5 parts, functional copolymer 11 parts, catalyst 2.5 parts, coupling agent 2.5 parts, high-temperature-resistant filler 28 parts, nanometer boron fiber 4.5 parts, thermoplastic polyester elastomer 9.5 parts, antioxidant 0.9 parts, lubricant 1.1 parts, and compatibilizer 1.8 parts; the functional copolymer comprises structural units introduced by the following monomers: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide; the high-temperature-resistant filler is a mixture of LDH@SiO2 nanoparticles, graphene nanosheet, and glass flake according to a mass ratio of 9:5:3; the PBT resin is PBT 4012G RESIN; and the amino-terminated hyperbranched polysiloxane liquid crystal is made according to the method of Example 1 of the Chinese patent for invention with the authorized publication number CN103951829B.

[0056] The preparation method of the functional copolymer comprises the following steps: 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropanesulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator are added into a high-boiling-point solvent, stirring reaction is carried out under an inert gas atmosphere at 70 DEG C for 5h, then precipitation is carried out in water, and washing is carried out with ethanol for 6 times, finally drying is carried out in a vacuum drying box at 95 DEG C for 8h to obtain the functional copolymer; the mass ratio of the 1,3-bis(oxazolidinylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropanesulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator, high-boiling-point solvent is 1:1.2:2:0.05:15; the initiator is azobisisobutyronitrile; the high-boiling-point solvent is dimethyl sulfoxide; and the inert gas is argon.

[0057] The catalyst is prepared by mixing phosphorus pentoxide and polyphosphoric acid at a mass ratio of 2:1; and the coupling agent is prepared by mixing silane coupling agent KH550, silane coupling agent KH560 and silane coupling agent KH570 at a mass ratio of 1:2:1.

[0058] The preparation method of the LDH@SiO2 nanoparticles comprises the following steps: magnesium nitrate and aluminum nitrate are dissolved in deionized water, 2.1mol / L sodium hydroxide solution is added dropwise at 73 DEG C until pH is 9, nano-SiO2 is ultrasonically dispersed for 1.9h, hydrothermal reaction is carried out for 11.5h, then centrifugal drying is carried out to prepare the LDH@SiO2 nanoparticles; the molar ratio of the magnesium nitrate, aluminum nitrate, deionized water and nano-SiO2 is 3:1:19:1.1; the particle size of the nano-SiO2 is 70nm; and the temperature of the hydrothermal reaction is 210 DEG C.

[0059] The diameter of the graphene nanosheet is 5-10um, and the thickness is 3-10nm; the flake diameter of the glass flake is 10-100um, and the thickness is 3-5um; the average diameter of the nano boron fiber is 250nm, and the aspect ratio is 29:1; the thermoplastic polyester elastomer is Hytrel 6356TPEE; the antioxidant is prepared by mixing antioxidant 1010, antioxidant 1076 and antioxidant 168 at a mass ratio of 1:3:5; the lubricant is prepared by mixing pentaerythritol stearate, zinc stearate and ethylene bis-stearamide at a mass ratio of 1:2:1; and the compatibilizer is compatibilizer CMG9801.

[0060] A preparation method of the high-temperature-resistant polyester composite material, comprising the following steps: uniformly mixing raw materials according to weight parts, and then adding into a double-screw extruder for melt blending extrusion to obtain the high-temperature-resistant polyester composite material; the temperature of the melt blending extrusion is 255 DEG C, and the screw rotation speed is 290 rpm.

[0061] Example 5

[0062] A high-temperature-resistant polyester composite material, which is made of the following raw materials according to weight parts: PBT resin 80 parts, amino-terminated hyperbranched polysiloxane liquid crystal 8 parts, functional copolymer 12 parts, catalyst 3 parts, coupling agent 3 parts, high-temperature-resistant filler 30 parts, nano boron fiber 5 parts, thermoplastic polyester elastomer 10 parts, antioxidant 1 part, lubricant 1.2 parts, and compatibility agent 2 parts; the functional copolymer comprises structural units introduced by the following monomers: 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide; the high-temperature-resistant filler is a mixture of LDH@SiO2 nanoparticles, graphene nanosheets, and glass flake according to a mass ratio of (4-9):(2-5):(1-3); the PBT resin is PBT 4012G RESIN; and the amino-terminated hyperbranched polysiloxane liquid crystal is made according to the method of Example 1 of the Chinese patent for invention with the authorized announcement No. CN103951829B.

[0063] A preparation method of the functional copolymer, comprising the following steps: adding 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, and initiator into a high-boiling-point solvent, stirring and reacting at 70 DEG C for 5 h in an inert gas atmosphere, then precipitating in water, washing with ethanol for 6 times, and finally drying in a vacuum drying box at 95 DEG C for 8 h to obtain the functional copolymer; the mass ratio of 1,3-bis(oxymethylene methyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropane sulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator, and high-boiling-point solvent is 1:1.2:2:0.05:15; the initiator is azobisisobutyronitrile; the high-boiling-point solvent is dimethyl sulfoxide; and the inert gas is nitrogen.

[0064] The catalyst is a mixture of phosphorus pentoxide and polyphosphoric acid according to a mass ratio of 2:1; and the coupling agent is silane coupling agent KH550.

[0065] The preparation method of the LDH@SiO2 nanoparticles comprises the following steps: dissolving magnesium nitrate and aluminum nitrate in deionized water, adding 2.2 mol / L sodium hydroxide solution dropwise at 75 DEG C until pH = 9, adding nano-SiO2 and ultrasonic dispersion for 2 h, centrifugal drying after hydrothermal reaction for 12 h, and preparing LDH@SiO2 nanoparticles; the molar ratio of the magnesium nitrate, aluminum nitrate, deionized water and nano-SiO2 is 3:1:20:1.2; the particle size of the nano-SiO2 is 80 nm; and the temperature of the hydrothermal reaction is 220 DEG C.

[0066] The diameter of the graphene nanosheet is 5-10 mu m, and the thickness is 3-10 nm; the flake diameter of the glass flake is 10-100 mu m, and the thickness is 3-5 mu m; the average diameter of the nano boron fiber is 300 nm, and the aspect ratio is 30:1; the thermoplastic polyester elastomer is Hytrel 6356 TPEE; the antioxidant is antioxidant 1010; the lubricant is zinc stearate; and the compatibilizer is compatibilizer CMG9801.

[0067] A preparation method of the high-temperature-resistant polyester composite material comprises the following steps: uniformly mixing the raw materials according to weight parts, and then adding them into a double-screw extruder for melt blending extrusion to obtain the high-temperature-resistant polyester composite material; the temperature of the melt blending extrusion is 260 DEG C, and the screw rotation speed is 300 rpm.

[0068] Comparative Example 1

[0069] A high-temperature-resistant polyester composite material and a preparation method thereof are basically the same as those in Embodiment 1, except that the hyperbranched polysiloxane liquid crystal with an amino-terminated end is not added.

[0070] Comparative Example 2

[0071] A high-temperature-resistant polyester composite material and a preparation method thereof are basically the same as those in Embodiment 1, except that the functional copolymer is not added.

[0072] In order to further illustrate the unexpected positive technical effects achieved by the products of the embodiments of the present application, the functional copolymers prepared in each example are subjected to relevant performance tests, and the test results are shown in Table 1, and the test methods are as follows: an electronic universal material testing machine is used, and the test is carried out according to the standard GB / T 1040.1-2018. The sample is made into a dumbbell-shaped type I sample, and the tensile test is carried out on the testing machine at a speed of 50 mm / min. The maximum load at the breaking of the sample is recorded, and the tensile strength is calculated; a cantilever beam impact testing machine is used, and the test is carried out according to the standard GB / T 1843-2008. The sample is made into a size of 80*10*4 mm 3The notched sample is impacted by a pendulum, the energy loss before and after the pendulum impact sample is recorded, and the impact strength is calculated. Flame retardant grade test: using UL-94 standard, the sample thickness is 1.0mm. High temperature resistance Each product is placed in a 150℃ environment for 168 hours, then cooled to room temperature, and the tensile strength after the test is measured, and the retention rate of the tensile strength is used to measure the high temperature resistance, the larger the value, the better the high temperature resistance, the retention rate of the tensile strength = the tensile strength after the test / the tensile strength before the test x 100%, wherein the test after the test and the test before the test are tested according to GB / T 1040.1-2018.

[0073] Table 1 Performance test results of high temperature resistant polyester composite material

[0074]

[0075] From Table 1, it can be seen that the high temperature resistant polyester composite material disclosed in each embodiment of the present application has better mechanical properties, more excellent toughness, flame retardance and high temperature resistance than the comparative product, and the combination of the terminal amino hyperbranched polysiloxane liquid crystal and the functional copolymer is beneficial to improving the above properties.

[0076] The above shows and describes the basic principles, main features and advantages of the present application. Those skilled in the art should understand that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection required by the present application is defined by the appended claims and their equivalents.

Claims

1. A high temperature resistant polyester composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 80 parts of PBT resin, 5-8 parts of amino-terminated hyperbranched polysiloxane liquid crystal, 8-12 parts of functional copolymer, 1-3 parts of catalyst, 1-3 parts of coupling agent, 20-30 parts of high-temperature resistant filler, 3-5 parts of nano-boron fiber, 8-10 parts of thermoplastic polyester elastomer, 0.5-1 part of antioxidant, 0.8-1.2 parts of lubricant, and 1-2 parts of compatibilizer; the functional copolymer comprises structural units introduced by the following monomers: 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropanesulfonic acid, and diphenyl(4-vinylphenyl)phosphine oxide; the high-temperature resistant filler is a mixture of LDH@SiO2 nanoparticles, graphene nanosheets, and glass flakes in a mass ratio of (4-9):(2-5):(1-3).

2. The high temperature resistant polyester composite material according to claim 1, characterized in that: The PBT resin is PBT4012GRESIN.

3. The high temperature resistant polyester composite material according to claim 1, characterized in that: The preparation method of the functional copolymer comprises the following steps: adding 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropanesulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide and an initiator to a high-boiling-point solvent, stirring and reacting at 60-70°C in an inert gas atmosphere for 3-5 hours, then precipitating the copolymer in water, washing the copolymer with ethanol for 3-6 times, and finally drying the copolymer in a vacuum drying oven at 85-95°C for 5-8 hours to obtain the functional copolymer.

4. The high temperature resistant polyester composite material according to claim 3, characterized in that: The mass ratio of the 1,3-bis(oxiranylmethyl)-5-(2-propenyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2-acrylamido-2-methylpropanesulfonic acid, diphenyl(4-vinylphenyl)phosphine oxide, initiator and high boiling point solvent is 1:(0.8-1.2):(1-2):(0.03-0.05):(10-15).

5. The high temperature resistant polyester composite material according to claim 3, characterized in that: The initiator is azobisisobutyronitrile; the high boiling point solvent is any one of dimethyl sulfoxide, N,N-dimethylformamide, and N-methylpyrrolidone; and the inert gas is any one of nitrogen, helium, neon, and argon.

6. The high temperature resistant polyester composite material according to claim 1, characterized in that: The catalyst is prepared by mixing phosphorus pentoxide and polyphosphoric acid in a mass ratio of (1-2):1; the coupling agent is at least one of silane coupling agent KH550, silane coupling agent KH560, and silane coupling agent KH570.

7. The high temperature resistant polyester composite material according to claim 1, characterized in that: The preparation method of the LDH@SiO2 nanoparticles comprises the following steps: dissolving magnesium nitrate and aluminum nitrate in deionized water, adding dropwise 1.8-2.2 mol / L sodium hydroxide solution at 65-75°C to a pH of 9, adding nano-SiO2 and ultrasonically dispersing for 1-2 hours, performing a hydrothermal reaction for 10-12 hours, and then centrifuging and drying to obtain the LDH@SiO2 nanoparticles.

8. The high temperature resistant polyester composite material according to claim 7, characterized in that: The molar ratio of the magnesium nitrate, aluminum nitrate, deionized water, and nano-SiO2 is 3:1:(12-20):(0.8-1.2); the particle size of the nano-SiO2 is 10-80 nm; and the temperature of the hydrothermal reaction is 190-220°C.

9. The high temperature resistant polyester composite material according to claim 1, characterized in that: The diameter of the graphene nanosheets is 5-10 μm and the thickness is 3-10 nm; the diameter of the glass flakes is 10-100 μm and the thickness is 3-5 μm; the average diameter of the nano-boron fibers is 100-300 nm and the aspect ratio is (25-30):1; the thermoplastic polyester elastomer is Hytrel 6356 TPEE; the antioxidant is at least one of antioxidant 1010, antioxidant 1076, and antioxidant 168; the lubricant is at least one of pentaerythritol stearate, zinc stearate, and ethylene bisstearamide; and the compatibilizer is compatibilizer CMG9801.

10. A method for preparing the high temperature resistant polyester composite material according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: uniformly mixing the raw materials according to parts by weight, adding the raw materials into a twin-screw extruder for melt blending and extrusion to obtain a high-temperature resistant polyester composite material; the melt blending and extrusion temperature is 240-260°C and the screw speed is 200-300rpm.

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