Graphene composite modified flame-retardant nylon plastic

Abstract

The present application relates to a kind of graphene composite modified flame-retardant nylon plastics, belong to composite material technical field;The present application is prepared by a kind of structure with carboxyl and amino reactive flame retardant, the flame retardant can be reacted with nylon resin and be directly combined on the nylon resin molecular chain by covalent bond, effectively improve the compatibility of flame retardant and nylon resin matrix, and solve the migration problem of flame retardant, in addition, the reactive flame retardant of the present application also has quaternary ammonium salt structure, can introduce charged quaternary ammonium salt structure in the structure of nylon resin, promote the dispersion of graphene using the ion-dipole interaction with the carboxyl group on the surface of graphene, and anchor the dispersion state of graphene, inhibit the migration of graphene in the use process, under this interface interaction, graphene can form more continuous conductive / thermal network in the nylon matrix, effectively enhance the modification effect of graphene on nylon resin matrix.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of composite materials, and particularly relates to a graphene composite modified flame-retardant nylon plastic. BACKGROUND

[0002] Polyamide (PA), namely nylon, is the first fully man-made synthetic fiber in the world, has excellent mechanical strength, wear resistance, chemical resistance and self-lubricity, and is widely applied to automobile parts, electronic appliances, mechanical equipment and the like, but the nylon plastic is a flammable material, and has a low limiting oxygen index (LOI), so that a flame retardant needs to be added during preparation to overcome the flame-retardant defects of the nylon plastic, but the compatibility of the flame retardant with the nylon plastic is poor, and phase separation is prone to occur in the nylon plastic, and a large amount of addition of the flame retardant will cause a serious decrease in mechanical properties of the nylon plastic.

[0003] The use of graphene for modifying the nylon plastic can not only improve the electric conductivity and thermal conductivity of the nylon plastic, but also promote the carbonization of the flame retardant and enhance the strength and compactness of the carbon layer, effectively improves the effect of the flame retardant, and further reduces the amount of the flame retardant, based on which, the application provides a graphene composite modified flame-retardant nylon plastic. SUMMARY

[0004] The application aims to provide a graphene composite modified flame-retardant nylon plastic, and aims to solve the problems mentioned in the background.

[0005] The application can be achieved by the following technical scheme.

[0006] The graphene composite modified flame-retardant nylon plastic comprises the following raw materials in parts by mass: 100 parts of nylon resin, 1.8-2.2 parts of graphene, 8-10 parts of a reaction type flame retardant, and 0.2-0.4 parts of an antioxidant.

[0007] The reaction type flame retardant of the application has carboxyl and amino groups in the structure.

[0008] Preferably, the reaction type flame retardant can be prepared by the following preparation method.

[0009] An intermediate is obtained by Michael addition reaction of an unsaturated carboxylic acid and an organic phosphorus compound, and then a quaternary ammonium salt reaction of the intermediate and a fatty amine is performed to obtain the reaction type flame retardant.

[0010] Preferably, the unsaturated carboxylic acid is at least one of 4-chloro-2-butenoic acid and 4-bromobut-2-enoic acid.

[0011] Preferably, the organic phosphorus compound has at least one phosphinate group in the structure.

[0012] Preferably, the fatty amine is at least one of N,N-dimethylethylene diamine, N,N-diethylethylene diamine.

[0013] Preferably, the nylon resin is at least one of nylon 6, nylon 66.

[0014] Preferably, the graphene is reduced graphene oxide.

[0015] Preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 1035, antioxidant 168.

[0016] Preferably, the graphene composite modified flame-retardant nylon plastic is prepared by melt extrusion of each raw material.

[0017] Advantages of the present application:

[0018] The present application has the following advantages:

[0019] The reaction-type flame retardant of the present application has a quaternary ammonium salt structure in the structure, which can introduce a charged quaternary ammonium salt structure in the nylon resin structure after reacting with the nylon resin molecular chain, accelerate the leakage of static charge, and improve the antistatic performance of the nylon plastic.

[0020] The nylon resin molecular chain of the present application has a positively charged quaternary ammonium salt structure, which can promote the dispersion of graphene by ion-dipole interaction with the carboxyl group on the surface of graphene, and anchor the dispersion state of graphene, inhibit the migration of graphene during use. Under this interfacial interaction, graphene can form a more continuous conductive / thermal network in the nylon matrix, effectively enhancing the modification effect of graphene on the nylon resin matrix.

[0021] The present application effectively promotes the mutual attraction between graphene and the flame retardant by ion-dipole interaction, and strengthens the flame-retardant synergistic effect between graphene and the flame retardant. DETAILED DESCRIPTION

[0022] The technical solutions of the present application will be described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0023] Wherein, all raw materials of the application have no special restrictions on their sources, and can be purchased on the market or prepared according to conventional methods well known to those skilled in the art.

[0024] Example 1

[0025] A graphene composite modified flame-retardant nylon plastic, comprising the following raw materials in mass fraction: 100 parts of nylon 6 resin, 1.8 parts of reduced graphene oxide, 10 parts of reactive flame retardant, 0.2 parts of antioxidant 1010;

[0026] Wherein, the reactive flame retardant is prepared by the following preparation method:

[0027] S1, 0.1 mol of 4-chloro-2-butenoic acid, 0.12 mol of diethyl phosphite, 0.01 mol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 60 mL of tetrahydrofuran are mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at a temperature of 40°C for 3 hours. After the reaction, the reaction solution is spin-dried, and the remaining solid is washed with cold deionized water and dried to obtain an intermediate;

[0028] S2, 0.08 mol of the intermediate, 0.1 mol of N,N-dimethylethylenediamine, and 60 mL of N,N-dimethylformamide are mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at a temperature of 35°C for 24 hours. After the reaction, the reaction solution is spin-dried to obtain a reactive flame retardant;

[0029] Each raw material is added to a twin-screw extruder and melt-extruded at a temperature of 275°C to prepare a graphene composite modified flame-retardant nylon plastic.

[0030] Example 2

[0031] A graphene composite modified flame-retardant nylon plastic, comprising the following raw materials in mass fraction: 100 parts of nylon 66 resin, 2 parts of reduced graphene oxide, 9 parts of reactive flame retardant, 0.2 parts of antioxidant 1010, and 0.1 parts of antioxidant 168;

[0032] Wherein, the reactive flame retardant is prepared by the following preparation method:

[0033] S1, 0.1 mol of 4-chloro-2-butenoic acid, 0.13 mol of dimethyl phosphite, 0.01 mol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 70 mL of tetrahydrofuran are mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at a temperature of 50°C for 2.5 hours. After the reaction, the reaction solution is spin-dried, and the remaining solid is washed with cold deionized water and dried to obtain an intermediate;

[0034] S2, 0.08 mol of the intermediate, 0.11 mol of N,N-dimethylethylenediamine, 70 mL of N,N-dimethylformamide were mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at 55 DEG C for 10 h. After the reaction was completed, the reaction solution was rotary evaporated to obtain the reactive flame retardant;

[0035] The raw materials were added into a twin-screw extruder and melt-extruded at a temperature of 280 DEG C to obtain the graphene composite modified flame-retardant nylon plastic.

[0036] Example 3

[0037] A graphene composite modified flame-retardant nylon plastic, comprising the following raw materials in mass fraction: 100 parts of nylon 66 resin, 2.2 parts of reduced graphene oxide, 8 parts of reactive flame retardant, 0.3 parts of antioxidant 1035, and 0.1 parts of antioxidant 168.

[0038] The reactive flame retardant is prepared by the following preparation method:

[0039] S1, 0.1 mol of 4-bromobut-2-ene acid, 0.15 mol of diphenyl phosphite, 0.01 mol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 80 mL of tetrahydrofuran were mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at 60 DEG C for 2 h. After the reaction was completed, the reaction solution was rotary evaporated, and the remaining solid was eluted by silica gel column chromatography to obtain the intermediate.

[0040] S2, 0.08 mol of the intermediate, 0.12 mol of N,N-diethylethylenediamine, and 80 mL of N,N-dimethylformamide were mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at 75 DEG C for 6 h. After the reaction was completed, part of the solvent was removed by rotary evaporation, and the remaining reaction solution was poured into cold deionized water. The solid was separated by filtration to obtain the reactive flame retardant.

[0041] The raw materials were added into a twin-screw extruder and melt-extruded at a temperature of 285 DEG C to obtain the graphene composite modified flame-retardant nylon plastic.

[0042] Comparative Example 1

[0043] The difference between the present comparative example and Example 3 is that the reactive flame retardant is not prepared, and the commercially available flame retardant DOPO is used to replace the reactive flame retardant in the raw materials.

[0044] A graphene composite modified flame-retardant nylon plastic, comprising the following raw materials in mass fraction: 100 parts of nylon 66 resin, 2.2 parts of reduced graphene oxide, 8 parts of flame retardant DOPO, 0.3 parts of antioxidant 1035, and 0.1 parts of antioxidant 168.

[0045] The raw materials are added into a double screw extruder to melt and extrude at a temperature of 285°C to prepare the graphene composite modified flame-retardant nylon plastic.

[0046] Comparative Example 2

[0047] The difference between the present comparative example and Example 3 is that the reduced graphene oxide in the raw materials is removed and an equal amount of reactive flame retardant is used to replace the reduced graphene oxide.

[0048] A graphene composite modified flame-retardant nylon plastic, comprising the following raw materials in mass fraction: 100 parts of nylon 66 resin, 2.2 parts of reactive flame retardant, 0.3 parts of antioxidant 1035, and 0.1 part of antioxidant 168.

[0049] The reactive flame retardant is prepared by the following preparation method:

[0050] S1, 0.1 mol of 4-bromobut-2-ene acid, 0.15 mol of diphenyl phosphite, 0.01 mol of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 80 mL of tetrahydrofuran are mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at a temperature of 60°C for 2 hours. After the reaction, the reaction solution is spin-dried, and the remaining solid is eluted by silica gel column chromatography to obtain an intermediate.

[0051] S2, 0.08 mol of the intermediate, 0.12 mol of N,N-diethyl ethylenediamine, and 80 mL of N,N-dimethylformamide are mixed in a three-necked flask equipped with a thermometer and a condenser reflux device, and reacted at a temperature of 75°C for 6 hours. After the reaction, part of the solvent is removed by rotary evaporation, and the remaining reaction solution is poured into cold deionized water. The solid is separated by filtration to obtain a reactive flame retardant.

[0052] The raw materials are added into a double screw extruder to melt and extrude at a temperature of 285°C to prepare the graphene composite modified flame-retardant nylon plastic.

[0053] Experimental Example

[0054] The composite modified flame-retardant nylon plastics in Examples 1-3 and Comparative Examples 1-2 are respectively subjected to performance testing. The tensile strength of each component nylon plastic is tested in accordance with the national standard GB / T 1040.2-2006 “Determination of tensile properties of plastics”. The volume resistivity of each component nylon plastic is tested in accordance with the national standard GB / T 1410-2006 “Test method for volume and surface resistivity of solid insulating materials”. The thermal conductivity of each component nylon plastic is tested in accordance with the national standard GB / T 10297-2015 “Determination of thermal conductivity of non-metallic solid materials”. The limiting oxygen index of each component nylon plastic is tested in accordance with the national standard GB / T 2406.1-2008 “Determination of flammability of plastics by oxygen index method”. The test results are shown in Table 1.

[0055]

[0056] It can be seen from Table 1 that the nylon plastics in Examples 1-3 have higher tensile strength, but the nylon plastics in Comparative Example 1 have poor tensile properties, which indicates that the reaction type flame retardant of the application has less influence on the mechanical properties of the nylon plastics. It can be seen from Comparative Example 1 that the use of the reaction type flame retardant of the application can effectively enhance the modification effect of graphene on the nylon plastics. It can be seen from Comparative Example 2 that graphene can effectively improve the flame retardant effect of the nylon plastics.

[0057] The above description of disclosed embodiments enables one of ordinary skill in the art to make or use the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein can be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A graphene composite modified flame retardant nylon plastic, characterized in that, The application relates to a graphene composite modified flame-retardant nylon plastic, which comprises the following raw materials: a nylon resin, graphene, a reactive flame retardant and an antioxidant. The reactive flame retardant has carboxyl and amino groups in the structure. The reactive flame retardant is prepared by the following preparation method: An intermediate is obtained by Michael addition reaction of an unsaturated carboxylic acid and an organic phosphorus compound, and then quaternary ammonium salt reaction of the intermediate and a fatty amine is carried out to obtain the reactive flame retardant. The unsaturated carboxylic acid is at least one of 4-chloro-2-butenoic acid and 4-bromobut-2-enoic acid, and the organic phosphorus compound has at least one phosphite group in the structure.

2. The graphene composite modified flame-retardant nylon plastic according to claim 1, characterized in that, The nylon resin is at least one of nylon 6 and nylon 66.

3. The graphene composite modified flame-retardant nylon plastic according to claim 1, characterized in that, The graphene is reduced graphene oxide.

4. The graphene composite modified flame-retardant nylon plastic according to claim 1, characterized in that, The antioxidant is at least one of antioxidants 1010, 1035 and 168.

5. The graphene composite modified flame-retardant nylon plastic according to claim 1, characterized in that, The application also discloses a preparation method of the graphene composite modified flame-retardant nylon plastic.

6. The graphene composite modified flame-retardant nylon plastic according to claim 1, characterized in that, The fatty amine is at least one of N,N-dimethylethylenediamine and N,N-diethylethylenediamine.

7. The graphene composite modified flame-retardant nylon plastic according to claim 1, characterized in that, ​

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