A polysulfone composite material for extremely high temperature resistant safety helmets and its preparation method and application

Abstract

The present invention belongs to the technical field of modified special plastics, and provides a polysulfone composite material for extremely high temperature resistant safety helmets, and a preparation method and application thereof, which comprises 24-40% bisphenol A type polysulfone resin, and the melt index of the bisphenol A type polysulfone resin is greater than 5g / 10min and the oxygen index is greater than 30 under the test of 343°C and 2.16kg; 20-35% nylon resin, and the glass transition temperature of the nylon resin is greater than or equal to 130°C, and the relative viscosity is 1.8-2.2; 3-6% compatibilizer; 5-10% maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer; 25-35% glass fiber; 0.3-0.7% antioxidant; and 0.3-0.7% lubricant. The present invention adopts the above raw materials to prepare the composite material, and the safety helmet prepared by the composite material has excellent comprehensive mechanical properties, such as combustion resistance, 150°C bending strength, impact absorption and maximum deformation of lateral rigidity at 150°C.

Description

Technical Field

[0001] The invention belongs to the technical field of modified special plastics, and in particular relates to a polysulfone composite material for an extremely high temperature resistant safety helmet, and a preparation method and application thereof. Background Art

[0002] Fire helmets are essential personal protective equipment for firefighters. They come in many types and models with different shapes and structures. However, all fire helmets have similar characteristics and must be produced according to similar performance specifications. Fire helmets usually need to meet the requirements of high temperature resistance, flame retardancy, high strength and impact resistance. Fire helmets are generally made of glass fiber reinforced polyamide material with flame retardant added by injection molding, but the mechanical properties of the product will change at extremely high temperatures (150°C) and cannot meet the test requirements. Summary of the invention

[0003] In view of this, the object of the present invention is to provide a polysulfone composite material for an extremely high temperature resistant safety helmet and a preparation method and application thereof, wherein the composite material has excellent comprehensive mechanical properties.

[0004] The present invention provides a polysulfone composite material for an extremely high temperature resistant safety helmet, which comprises the following raw materials by mass fraction:

[0005] Bisphenol A type polysulfone resin 24~40%, under the test conditions of 343℃ and 2.16kg, the melt index of bisphenol A type polysulfone resin is>5g / 10min, and the oxygen index is>30;

[0006] Nylon resin 20~35%, glass transition temperature of nylon resin ≥130℃, relative viscosity 1.8~2.2;

[0007] Compatibilizer 3~6%;

[0008] Maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer 5~10%;

[0009] Glass fiber 25~35%;

[0010] Antioxidant 0.3~0.7%;

[0011] Lubricant 0.3~0.7%.

[0012] Preferably, the nylon resin is selected from one or more of PA6T / 6I / 66, PA6T / M5T and PA6T / XT.

[0013] Preferably, the compatibilizer is selected from one or more of ethylene-methyl acrylate-glycidyl methacrylate terpolymer, ethylene-methacrylic acid copolymer and ethylene-acrylate copolymer.

[0014] Preferably, the mass ratio of the bisphenol A type polysulfone resin to the nylon resin is (2:1) to (3:4).

[0015] Preferably, the glass fiber is alkali-free high-strength chopped glass fiber, the diameter of the glass fiber is 10-13 μm, and the elastic modulus is >90 GPa.

[0016] Preferably, the antioxidant is selected from one or more of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, bis(2,4-dicumylphenyl)pentaerythritol diphosphite and inorganic phosphates;

[0017] The lubricant is selected from partially saponified ester wax and / or montanic acid ester containing multifunctional alcohol.

[0018] The present invention provides a method for preparing the polysulfone composite material for an extremely high temperature resistant safety helmet according to the above technical solution, comprising the following steps:

[0019] Bisphenol A type polysulfone resin, nylon resin, compatibilizer, maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer, glass fiber, antioxidant and lubricant are mixed, melted, kneaded, extruded, cooled and granulated to obtain a polysulfone composite material for an extremely high temperature resistant safety helmet.

[0020] Preferably, during extrusion, the temperatures of heating zones 1# to 10# and the die are 310°C, 330°C, 330°C, 330°C, 330°C, 325°C, 325°C, 325°C, and 330°C, respectively.

[0021] The present invention provides an application of the polysulfone composite material for an extremely high temperature resistant safety helmet in preparing an extremely high temperature resistant safety helmet.

[0022] The present invention provides a polysulfone composite material for an extremely high temperature resistant safety helmet, which comprises the following raw materials by mass fraction: 24-40% bisphenol A type polysulfone resin, under the test conditions of 343°C and 2.16kg, the melt index of the bisphenol A type polysulfone resin is greater than 5g / 10min, and the oxygen index is greater than 30; 20-35% nylon resin, the glass transition temperature of the nylon resin is greater than or equal to 130°C, and the relative viscosity is 1.8-2.2; 3-6% compatibilizer; 5-10% maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer; 25-35% glass fiber; 0.3-0.7% antioxidant; and 0.3-0.7% lubricant. The present invention adopts the above-mentioned types and amounts of raw materials to prepare the composite material, and the safety helmet prepared by the composite material has excellent comprehensive mechanical properties, such as combustion resistance, bending strength at 150°C, impact absorption, and maximum deformation of lateral rigidity at 150°C. DETAILED DESCRIPTION

[0023] The present invention provides a polysulfone composite material for an extremely high temperature resistant safety helmet, which comprises the following raw materials by mass fraction:

[0024] Bisphenol A type polysulfone resin 24~40%; under the test conditions of 343℃ and 2.16kg, the melt index of bisphenol A type polysulfone resin is >5g / 10min, and the oxygen index is >30;

[0025] Nylon resin 20~35%, glass transition temperature of nylon resin ≥130℃, relative viscosity 1.8~2.2;

[0026] Compatibilizer 3~6%;

[0027] Maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer 5~10%;

[0028] Glass fiber 25~35%;

[0029] Antioxidant 0.3~0.7%;

[0030] Lubricant 0.3~0.7%.

[0031] The raw materials for preparing the polysulfone composite material for extremely high temperature resistant safety helmets provided by the present invention include 24-40% bisphenol A type polysulfone resin (PSU); the specific amount is 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%. Under the test conditions of 343°C and 2.16kg, the melt index of the bisphenol A type polysulfone resin in the present invention is >5g / 10min, and the oxygen index is >30. The present invention uses the PSU with the above melt index and oxygen index as raw material, which can make the helmet prepared from the composite material have excellent flame retardancy. The specific models of PSU used in the embodiments of the present invention are PSU P-1720 and PSU F3250.

[0032] The raw materials for preparing the polysulfone composite material for the extremely high temperature resistant safety helmet provided by the present invention include 20-35% nylon resin, and the specific amount is 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35%; the glass transition temperature of the nylon resin is ≥130°C, and the relative viscosity is 1.8-2.2. The nylon resin described in the present invention is specifically selected from one or more of PA6T / 6I / 66, PA6T / M5T and PA6T / XT. In a specific embodiment of the present invention, the nylon resin is selected from models PPA 1357, PPA HTN 501 and PPA SH560.

[0033] The mass ratio of the bisphenol A type polysulfone resin to the nylon resin in the present invention is (2:1) to (3:4). The bisphenol A type polysulfone resin and the nylon resin in the present invention have more excellent comprehensive mechanical properties within the above mass ratio range, such as notched impact strength at room temperature, notched impact strength at 150°C, flame resistance, impact absorption and maximum deformation performance of lateral rigidity at 150°C.

[0034] The raw materials for preparing the polysulfone composite material for extremely high temperature resistant safety helmets provided by the present invention include 3-6% of a compatibilizer, and the specific amount is 3%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5% or 6%. The compatibilizer is preferably selected from one or more of ethylene-methyl acrylate-glycidyl methacrylate terpolymer, ethylene-methacrylic acid copolymer and ethylene-acrylate copolymer, preferably from ethylene-methyl acrylate-glycidyl methacrylate terpolymer and / or ethylene-methacrylic acid copolymer. The present invention adopts the above-mentioned types of compatibilizers to make the compatibility of bisphenol A type polysulfone resin and nylon resin better, thereby exerting better mechanical properties. In a specific embodiment, the compatibilizer ethylene-methyl acrylate-glycidyl methacrylate terpolymer is selected from model AX8900, and the ethylene-methacrylic acid copolymer is selected from model 925.

[0035] The raw materials for preparing the polysulfone composite material for the extremely high temperature resistant safety helmet provided by the present invention include 5-10% of maleic anhydride (POE) grafted styrene-ethylene-butylene-styrene (SEBS) block copolymer; the specific amount is 5%, 5.5%, 6.0%, 6.5%, 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5% or 10%; and the grafting rate is 1.0-2.0%. When the processing temperature is high, such as 330°C, maleic anhydride grafted POE is prone to cross-linking reaction, which will affect the processing performance, and the toughening effect is general. SEBS that has not been polar modified has poor compatibility and poor toughening effect; while maleic anhydride grafted SEBS has better high temperature resistance, does not affect processability, and has a better toughening effect.

[0036] The raw materials for preparing the polysulfone composite material for the extremely high temperature resistant safety helmet provided by the present invention include 25-35% of glass fiber, and the specific amount is 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35%. The glass fiber described in the present invention is alkali-free high-strength chopped glass fiber, the diameter of the glass fiber is 10-13 μm, and the elastic modulus is >90Gpa. In a specific embodiment of the present invention, the model of the glass fiber is short glass fiber HMG-435TM.

[0037] The raw materials for preparing the polysulfone composite material for the extremely high temperature resistant safety helmet provided by the present invention include 0.3-0.7% antioxidant, and the specific amount is 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65% or 0.7%. The antioxidant in the present invention is selected from one or more of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine, bis(2,4-dicumylphenyl)pentaerythritol diphosphite and inorganic phosphate.

[0038] The raw materials for preparing the polysulfone composite material for the extremely high temperature resistant safety helmet provided by the present invention include 0.3-0.7% lubricant, and the specific amount is 0.3%, 0.35%, 0.40%, 0.45%, 0.50%, 0.55%, 0.60%, 0.65% or 0.7%. The lubricant in the present invention is selected from partially saponified ester wax and / or montanic acid ester containing multifunctional alcohol.

[0039] In a specific embodiment of the present invention, the raw materials for preparing the polysulfone composite material for the extremely high temperature resistant safety helmet include 30% PSU P-1720, 26% PPA 1357, 8% toughening agent FG1901G, 5% compatibilizer AX8900, 30% short glass fiber HMG-435TM, 0.3% antioxidant 1098, 0.2% antioxidant 9228 and 0.5% lubricant E wax;

[0040] Or including 27% PSU P-1720, 35% PPA 1357, 7% toughening agent FG1901G, 5% compatibilizer 925, 25% short glass fiber HMG-435TM, 0.2% antioxidant 1098, 0.2% antioxidant 330, 0.3% antioxidant 9228 and 0.3% lubricant E wax;

[0041] Or including 24% PSU F3250, 29% PPA HTN 501, 5% toughening agent FG1901G, 3% compatibilizer AX8900, 3% compatibilizer 925, 35% short glass fiber HMG-435TM, 0.3% antioxidant 1098, 0.2% antioxidant H10 and 0.5% lubricant OP wax;

[0042] Or including 35% PSU P-1720, 24% PPA HTN 501, 8% toughening agent FG1901G, 4% compatibilizer AX8900, 28% short glass fiber HMG-435TM, 0.4% antioxidant 330, 0.2% antioxidant 9228 and 0.4% lubricant E wax;

[0043] Or including 40% PSU F3250, 20% PPA SH560, 9% toughening agent FG1901G, 3% compatibilizer 925, 27% short glass fiber HMG-435TM, 0.2% antioxidant 330, 0.1% antioxidant H10 and 0.7% lubricant OP wax;

[0044] Or including 32% PSU P-1720, 23% PPA SH560, 5% toughening agent FG1901G, 6% compatibilizer 925, 33% short glass fiber HMG-435TM, 0.2% antioxidant 1098, 0.3% antioxidant 9228 and 0.5% lubricant OP wax;

[0045] Or include 25% PSU P-1720, 25% PPA HTN 501, 10% toughening agent FG1901G, 4% compatibilizer AX8900, 35% short glass fiber HMG-435TM, 0.3% antioxidant 1098, 0.2% antioxidant H10 and 0.5% lubricant OP wax.

[0046] The present invention provides a method for preparing the polysulfone composite material for an extremely high temperature resistant safety helmet according to the above technical solution, comprising the following steps:

[0047] Bisphenol A type polysulfone resin, nylon resin, compatibilizer, maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer, glass fiber, antioxidant and lubricant are mixed, melted, kneaded, extruded, cooled and granulated to obtain a polysulfone composite material for an extremely high temperature resistant safety helmet.

[0048] During extrusion of the present invention, the temperatures of the 1#~10# heating zones and the die are 310°C, 330°C, 330°C, 330°C, 330°C, 330°C, 325°C, 325°C, 325°C, 330°C and 330°C respectively.

[0049] The present invention provides an application of the polysulfone composite material for an extremely high temperature resistant safety helmet described in the above technical solution in preparing an extremely high temperature resistant safety helmet.

[0050] The safety helmet provided by the present invention maintains high bending strength and notched impact strength, has low maximum deformation of lateral rigidity at high temperature (150° C.), low impact absorption capacity and excellent flame retardancy.

[0051] In order to further illustrate the present invention, a polysulfone composite material for an extremely high temperature resistant safety helmet provided by the present invention, a preparation method thereof and an application thereof are described in detail below in conjunction with embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0052] The raw materials used in the following examples and comparative examples are shown in Table 1:

[0053] Table 1 Specifications and manufacturers of various raw materials

[0054]

[0055] In order to verify the reliability of the effect of the present invention, the present invention is described below in conjunction with Examples 1 to 7, and compared with Comparative Examples 1 to 9. The mass percentage of each component of Examples 1 to 7 is specifically shown in Table 2, and the mass percentage of each component of Comparative Examples 1 to 9 is specifically shown in Table 3:

[0056] Table 2

[0057]

[0058] Table 3

[0059]

[0060] The present invention performs the following performance tests on the polysulfone composite materials prepared in Examples 1 to 7 and Comparative Examples 1 to 9, and the test methods are as follows:

[0061] (1) Mechanical properties of polysulfone composite materials: The composite materials prepared in Examples 1 to 7 and Comparative Examples 1 to 9 were dried and then injection molded into standard specimens according to ISO standards, and their flexural strength and notched impact strength at 150° C. were tested.

[0062] (2) Safety helmet performance test: The composite materials prepared in Examples 1 to 7 and Comparative Examples 1 to 9 were dried and then injection molded into safety helmets. According to the requirements of XF44-2015 and GB 2811-2019, the combustion resistance, impact absorption and maximum deformation of lateral rigidity at 150°C were tested respectively. The standard requirements are: combustion time <5S, impact absorption <3780N, and maximum deformation of lateral rigidity <40mm. The test results are shown in Table 4 and Table 5 respectively:

[0063] Table 4 Performance test results of materials prepared in Examples 1 to 7

[0064]

[0065] Table 5 Performance test results of materials prepared in Comparative Examples 1 to 9

[0066]

[0067] From the above embodiments, it can be seen that the present invention provides a polysulfone composite material for extremely high temperature resistant safety helmets, which includes the following raw materials by mass fraction: 24-40% bisphenol A type polysulfone resin, under the test conditions of 343°C and 2.16kg, the melt index of bisphenol A type polysulfone resin is>5g / 10min, and the oxygen index is>30; 20-35% nylon resin, the glass transition temperature of nylon resin is ≥130°C, and the relative viscosity is 1.8-2.2; compatibilizer 3-6%; maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer 5-10%; glass fiber 25-35%; antioxidant 0.3-0.7%; lubricant 0.3-0.7%. The present invention adopts the above-mentioned types and amounts of raw materials to prepare composite materials, and the safety helmet prepared by the composite material has excellent comprehensive mechanical properties, such as combustion resistance, bending strength at 150°C, impact absorption and maximum deformation of lateral rigidity at 150°C. The test results show that the notched impact strength of the polysulfone composite materials of Examples 1 to 7 is 23.2 to 30.6 kJ / m 2 The bending strength at 150°C is 153.4~170.2Mpa; the burning resistance of the extremely high temperature safety helmet is 1.6~3.8S, the impact absorption capacity is 2650~3180N, and the maximum lateral rigidity deformation at 150°C is 30.3~37.6mm.

[0068] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. Application of a polysulfone composite material for an extremely high temperature resistant safety helmet in the preparation of an extremely high temperature resistant safety helmet; The polysulfone composite material for extremely high temperature resistant safety helmet comprises the following raw materials by mass fraction: 32% bisphenol A type polysulfone resin PSU P-1720, 23% PPA SH560, 5% toughening agent maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer FG1901G, 6% compatibilizer ethylene-methacrylic acid copolymer 925, 33% short glass fiber HMG-435TM, 0.2% antioxidant 1098, 0.3% antioxidant 9228 and 0.5% lubricant OP wax; Bisphenol A polysulfone resin PSU P-1720 has a melt index of >5g / 10min and an oxygen index of >30 under the test conditions of 343°C and 2.16kg. The glass transition temperature of the nylon resin PPA SH560 is ≥130°C, and the relative viscosity is 1.8-2.2; the glass fiber is an alkali-free high-strength chopped glass fiber, the diameter of the glass fiber is 10-13 μm, and the elastic modulus is >90 Gpa.

2. The use according to claim 1, characterized in that: The method for preparing the polysulfone composite material for an extremely high temperature resistant safety helmet comprises the following steps: Bisphenol A type polysulfone resin, nylon resin, compatibilizer, maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer, glass fiber, antioxidant and lubricant are mixed, melted, kneaded, extruded, cooled and granulated to obtain a polysulfone composite material for an extremely high temperature resistant safety helmet.

3. The use according to claim 2, characterized in that: During extrusion, the temperatures of 1#~10# heating zones and the die heads are 310°C, 330°C, 330°C, 330°C, 330°C, 325°C, 325°C, 325°C, 330°C and 330°C respectively.

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