Organophosphorus flame-retardant nylon composite material with permanent antistatic property, high impact resistance and damp-heat precipitation resistance and preparation method of organophosphorus flame-retardant nylon composite material

Abstract

The invention discloses an organophosphorus flame-retardant nylon composite material with permanent antistatic property, high impact resistance and damp-heat precipitation resistance. The organophosphorus flame-retardant nylon composite material is prepared from the following raw materials in parts by mass: 20-40 parts of nylon resin; 13 to 30 parts of glass fiber; 18 to 20 parts of a compound flame retardant; 20 to 30 parts of a compound antistatic agent; 0.2 to 0.4 part of a silane coupling agent; 0.1 to 0.5 part of an antioxidant; 0.1 to 1.5 parts of a lubricant; and 0.1-0.5 part of a nylon flowable agent. The problems of low impact resistance, low CTI (Comparative Tracking Index) and damp-heat precipitation of a traditional antistatic halogen-free flame-retardant nylon material are solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nylon composites, in particular to a permanent antistatic, high-impact, and moisture-resistant organic phosphorus flame-retardant nylon composite material and a preparation method thereof. BACKGROUND

[0002] With the increasingly severe global energy crisis and environmental pollution, traditional fuel vehicles have gradually transformed to clean and electric vehicles due to the problem of greenhouse gas and particulate matter pollution emissions. New energy vehicles have become a key technology path to solve energy and environmental problems due to their zero or low emission characteristics.

[0003] The three-electric system (battery, motor, and electric control) is the most core component of a new energy vehicle. Since the working environment uses a large number of high-integration circuit boards (such as BMS and inverters), the shell product needs to meet the requirements of halogen-free and flame retardation. At the same time, the vibration, friction, and electrostatic discharge in the working environment may damage micro-integrated circuit electronic components, leading to functional failure or shortened life of sensors, chips, and other components. Therefore, the plastic shell is required to have a certain electrostatic shielding effect, which puts forward higher performance requirements (antistatic, lower friction electrostatic voltage) for the material. The existing halogen-free flame-retardant nylon used in the three-electric system mainly uses ordinary organic phosphorus flame-retardant PA66+ (15~30)% GF material, which has high flame retardation, high impact resistance, and electrical insulation performance, and the surface resistance value reaches 10 12 Ω order of magnitude; while the material needs to reach the antistatic level, the surface resistance value needs to meet <10 9 Ω, which requires the material to add a certain amount of conductive filler (antistatic agent), which greatly affects the impact and CTI performance (generally <400V) of the material. In addition, the organic phosphorus material is prone to precipitation in a long-term humid and hot environment, and the acidic substances generated have corrosive damage to the components, thereby causing product failure and even fire hazards.

[0004] The existing invention patent CN 103980700A develops a kind of permanent antistatic halogen-free flame-retardant nylon engineering plastics and its preparation method, the material adopts once double-screw extrusion melt blending method, by nano graphite, polyamide resin is endowed with good antistatic effect, diethyl hypophosphite is added to realize the halogen-free flame-retardant of polyamide resin, while nano zirconium phosphate particles are added to synergistically enhance flame-retardant, but the invention does not involve material hygroscopicity and CTI performance;Invention patent CN115216142A develops a kind of permanent antistatic halogen-free flame-retardant reinforced nylon composite material and its preparation method, the material improves the compatibility and dispersion problem of poor and difficult of flame retardant and nano conductive filler by modification, improves the comprehensive performance of nylon composite material, and makes hypophosphite flame retardant, melamine polyphosphate and nano conductive carbon material form synergistic flame-retardant, further improves the flame-retardant performance of nylon composite material, but the invention does not explain the precipitation phenomenon of compounded flame retardant in high humidity environment, and nano conductive carbon material is added to greatly affect the CTI performance of material. SUMMARY

[0005] The purpose of the present application is to solve the problems of low impact resistance, low CTI and hygroscopicity of traditional antistatic halogen-free flame-retardant nylon materials. The present application uses PA66 as the base resin and selects a new type of high molecular antistatic agent. In addition, the product has better compatibility, impact resistance and antistatic ability by amination-PETS. A permanent antistatic, high impact, hygroscopicity-resistant organic phosphorus flame-retardant nylon composite material is prepared. The material can be used on BSM shell and connector.

[0006] The technical solution of the present application is as follows: A permanent antistatic, high impact, hygroscopicity-resistant organic phosphorus flame-retardant nylon composite material and its preparation method, consisting of the following mass fractions of raw materials: Nylon resin 20-40 parts; Glass fiber 13-30 parts; Compound flame retardant 18-20 parts; Compound antistatic agent 20-30 parts; Silane coupling agent 0.2-0.4 parts; Antioxidant 0.1~0.5 parts; Lubricant 0.1~1.5 parts; Nylon flow agent 0.1-0.5 parts.

[0007] The nylon resin is one or more than one mixture of PA6, PA66, PA56, PA612, PA1012 and PA12.

[0008] The glass fiber is alkali-free hydrolysis-resistant glass fiber.

[0009] The complex flame retardant is a composition of aluminum diethylphosphinate (ADP), inorganic aluminum phosphite and organic silicon flame retardant.

[0010] The complex antistatic agent is a composition of Beijing Xuyang 5502P-Z antistatic master batch and carbon black master batch; wherein 5502P-Z is a high molecular antistatic agent.

[0011] The silane coupling agent is commercially available, preferably with the trade name of KH-550.

[0012] The antioxidant is a mixture of two or more than two of hindered phenol antioxidant, thioester antioxidant and phosphite antioxidant.

[0013] The lubricant is any one of EBS, PETS and aminated PETS, preferably aminated PETS with the trade name of JNLUB101 of Juner Company.

[0014] PETS and epichlorohydrin are reacted in a potassium hydroxide alkaline solution at a reaction temperature of 80-100 DEG C for 10-12 hours to generate an epoxy propyl ether intermediate, and then the obtained intermediate is added to excess ethylenediamine for 24 hours of reaction and reduced pressure distillation to obtain aminated PETS.

[0015] The nylon flow agent is a new type of hyperbranched polymer.

[0016] A preparation method of a permanent antistatic, high impact, moisture and heat resistant separation organic phosphorus flame-retardant nylon composite material, the preparation steps of the method are as follows: Step 1: the nylon resin, the complex antistatic agent and the silane coupling agent KH-550 are stirred uniformly at a rotation speed of 30 rpm, then the complex flame retardant, the antioxidant, the lubricant and the nylon flow agent are stirred uniformly at a rotation speed of 25 rpm to obtain a mixture; Step 2: a pre-mixed material is fed from the main feeding, and glass fiber is fed from the side feeding; the screw rotation speed is set to 300 rpm, the process temperature is set according to the nylon resin processing temperature, and an extrusion granulation is performed to obtain a permanent antistatic, high impact, moisture and heat resistant separation organic phosphorus flame-retardant nylon composite material.

[0017] Compared with the prior art, the advantages of the present application are as follows: The purpose of the present application is to solve the problems of low impact resistance, low CTI and wet heat precipitation of traditional antistatic halogen-free flame-retardant nylon materials. The present application uses PA66 as the base resin and selects a new type of high molecular antistatic agent. In addition, the product has better compatibility, impact resistance and antistatic ability by amination-PETS. A permanent antistatic, high impact, and wet heat precipitation resistant organic phosphorus flame-retardant nylon composite material is prepared. The material can be used on BSM shell and connector. DETAILED DESCRIPTION

[0018] The technical solutions of the present application will be further described below in combination with specific comparative examples 1-3 and examples 1-5.

[0019] The raw materials and proportions used in the present application are shown in Table 1, but are not limited to the raw materials and proportions used in the comparative examples and examples.

[0020] The raw materials are stirred and premixed according to the proportions in Table 1, granulated by main side feeding and double screw extrusion method, to prepare a permanent antistatic, high impact, and wet heat precipitation resistant organic phosphorus flame-retardant nylon composite material.

[0021] Performance characterization and test method: The tensile strength of the composite material prepared in each of the above comparative examples and examples is measured by a universal mechanical tester according to GB / T 1040.2-2022 standard; the notched impact strength is measured by a simply supported beam impact testing machine according to GB / T 1043.1-2008 standard; the vertical burning is measured by a vertical burning tester according to GB / T 2408-2021 standard; the tracking index is measured by a tracking index tester according to GB / T 4207-2012; the surface resistivity is measured by a resistance tester according to IEC60093 standard; the oxygen index is measured by an oxygen index tester according to GB / T 2406.1-2008; and the surface precipitation is observed after the material surface is treated at 85℃ / 85%RH for 1000h.

[0022] The raw material proportions and performance test results of comparative example 1 and comparative example 2 are shown in Table 1. The antistatic agent described in comparative example 1 is a permanent type of high molecular antistatic agent.

[0023] The raw material proportions and performance test results of examples 1 and 2 and comparative example 1 are also shown in Table 1. It can be found that, compared with comparative example 1, the processing method of examples 1 and 2 changes the flame retardant from main feeding to side feeding, and the overall mechanical properties and high wet heat precipitation are significantly improved, but there are still floating fiber phenomena on the surface of the material, indicating that the glass fiber is generally infiltrated in this system. With the decrease of the amount of antistatic agent, the impact resistance of the material decreases.

[0024] Example 3 is based on Example 1, adding amino PETS to make the dispersion of antistatic agent in the plasticized substrate better, and the impact strength of the material is further improved. This is due to the thermodynamic incompatibility, the antistatic agent will be dispersed in the form of small particles or fibrous structure ("sea" island) in the matrix resin ("sea").

[0025] Example 4 and Comparative Example 2 have the same raw material ratio and performance test results as shown in Table 1. The difference is that the PETS is amino, and the results show that after adding amino PETS, the impact performance and antistatic effect of the material are slightly improved, but the material can only be colored in dark color.

[0026] The performance test results are shown in Table 1.

[0027] Table 1

[0028] It should be understood that the application of the present application is not limited to the above examples, and those skilled in the art can make improvements or modifications according to the above description, and all these improvements and modifications shall belong to the protection scope of the appended claims of the present application.

Claims

1. A permanently antistatic, high-impact, and moisture-heat-resistant organophosphorus flame-retardant nylon composite material, composed of the following raw materials in parts by weight: 20-40 parts of nylon resin; 13-30 parts glass fiber; 18-20 parts of compound flame retardant; Compound antistatic agent 20-30 parts; 0.2-0.4 parts of silane coupling agent; Antioxidant 0.1~0.5 parts; Lubricant 0.1~1.5 parts; 0.1-0.5 parts of nylon flow agent.

2. The organophosphorus flame-retardant nylon composite material with permanent antistatic properties, high impact resistance, and resistance to damp heat precipitation as described in claim 1, is characterized in that... The nylon resin is one or a mixture of more than one of PA6, PA66, PA56, PA612, PA1012 and PA12; the glass fiber is alkali-free and hydrolysis-resistant glass fiber.

3. The organophosphorus flame-retardant nylon composite material with permanent antistatic properties, high impact resistance, and resistance to damp heat precipitation as described in claim 1, is characterized in that... The compound flame retardant is a composition formed by compounding aluminum diethylphosphinate (ADP), inorganic aluminum phosphite and organosilicon flame retardant, characterized by its good dispersibility and compatibility in nylon melt.

4. The organophosphorus flame-retardant nylon composite material with permanent antistatic properties, high impact resistance, and resistance to damp heat precipitation as described in claim 1, is characterized in that... The compound antistatic agent is a combination of Beijing Xuyang 5502P-Z antistatic masterbatch and carbon black masterbatch; wherein 5502P-Z is a polymeric antistatic agent.

5. The organophosphorus flame-retardant nylon composite material with permanent antistatic properties, high impact resistance, and resistance to damp heat precipitation as described in claim 1, characterized in that, The silane coupling agent is commercially available; the antioxidant is a mixture of two or more of the following: hindered phenolic antioxidants, thioester antioxidants, and phosphite antioxidants.

6. The organophosphorus flame-retardant nylon composite material with permanent antistatic properties, high impact resistance, and resistance to damp heat precipitation as described in claim 1, is characterized in that... The lubricant is any one of EBS, PETS, or amino-modified PETS.

7. The organophosphorus flame-retardant nylon composite material with permanent antistatic properties, high impact resistance, and resistance to damp heat precipitation as described in claim 6, is characterized in that... The preparation method of the aminated PETS is as follows: PETS and epichlorohydrin are reacted in an alkaline potassium hydroxide solution at a reaction temperature of 80-100℃ for 10-12 hours to generate an epoxypropyl ether intermediate. The obtained intermediate is then added to excess ethylenediamine and reacted for 24 hours. The mixture is then distilled under reduced pressure to obtain the aminated PETS.

8. The organophosphorus flame-retardant nylon composite material with permanent antistatic properties, high impact resistance, and resistance to damp heat precipitation as described in claim 1, characterized in that, The nylon flow agent is a novel hyperbranched polymer.

9. A method for preparing a permanently antistatic, high-impact, and moisture-heat-resistant organophosphorus flame-retardant nylon composite material according to any one of claims 1 to 8, wherein the preparation steps of the method are as follows: Step 1: Mix the nylon resin, compound antistatic agent and silane coupling agent KH-550 at 30 rpm until homogeneous. Then add the compound flame retardant, antioxidant, lubricant and nylon flow agent and mix at 25 rpm until homogeneous to obtain the mixture. Step 2: Use a premixed material main feeding and glass fiber side feeding method; set the screw speed to 300 rpm, and set the process temperature according to the nylon resin processing temperature. A permanent antistatic, high impact-resistant, and moisture-heat-resistant organophosphorus flame-retardant nylon composite material can be obtained by extrusion granulation.

10. The permanent antistatic, high impact-resistant, and moisture-heat-resistant organophosphorus flame-retardant nylon composite material according to any one of claims 1 to 8 is used in BSM housings and connectors.

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