CN113969036A

CN113969036A - Preparation method of functionalized multi-walled carbon nanotube modified ABS resin

Info

Publication number: CN113969036A
Application number: CN202111418163.8A
Authority: CN
Inventors: 郝春波; 娄艳; 修忠海; 武天希; 李春晖; 栾春萌; 严成
Original assignee: North Huajin Chemical Industries Co Ltd
Current assignee: North Huajin Chemical Industries Co Ltd
Priority date: 2021-11-26
Filing date: 2021-11-26
Publication date: 2022-01-25

Abstract

The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of functionalized multi-walled carbon nanotube modified ABS resin. Firstly, preparing a functionalized multi-walled carbon nanotube to obtain a hydroxylated multi-walled carbon nanotube; and then mixing the hydroxylated multi-walled carbon nanotube and ABS resin according to different mass ratios for 10min, adding a double-screw rod to extrude and granulate, placing the mixed particles in a blast drying oven to dry for 24h, placing the dried particles in an injection molding machine to perform injection molding, performing performance test on an injection molded sample strip, and improving the mechanical property of the material because more-OH exists in the hydroxylated multi-walled carbon nanotube and the hydroxyl and-CN of the ABS can form hydrogen bonds.

Description

Preparation method of functionalized multi-walled carbon nanotube modified ABS resin

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of functionalized multi-walled carbon nanotube modified ABS resin.

Background

The ABS resin is a thermoplastic engineering plastic resin formed by combining three components of styrene, acrylonitrile and butadiene according to different proportions. The ABS resin has excellent properties such as impact resistance, corrosion resistance, high rigidity, and easy processing, and is widely used in many fields such as home appliances, automobiles, electronics, and office supplies. However, ABS resins also suffer from a number of deficiencies, such as insufficient impact properties, poor flame retardancy and transparency, etc., which have prevented ABS resins from being widely used better.

The ABS resin is modified by blending, flame retarding, heat resisting and alloying. Wherein, blending is a common modification method for toughening and improving the flame retardant property. Inorganic materials have been increasingly studied by researchers because of their ability to improve the mechanical properties of resins, their high rigidity, high modulus, and the like. At present, inorganic materials with different dimensions are blended with ABS, and the influence of the inorganic materials on the mechanical property, the heat resistance, the combustion property and the size property of the ABS is researched, such as: zero-dimensional powdery calcium carbonate and barium sulfate; one-dimensional fiber/needle-like glass fiber, wollastonite; talcum powder with a two-dimensional sheet structure, mica and graphene. On one hand, the carbon atoms in the carbon nano tube have small gaps, and the structure is not easy to have defects, so that the carbon nano tube has higher tensile strength and Young modulus. On the other hand, the dimension of the carbon nano tube is close to the size of the polymer molecular chain segment, so that the movement of the polymer molecular chain segment can be hindered, the movement capability of the polymer molecular chain and the response speed of the polymer molecular chain to temperature change can be reduced, and the heat resistance of the material can be improved. Therefore, the carbon nano tube and the ABS resin are blended and modified, and the mechanical property and the heat resistance of the ABS resin are hopeful to be improved.

The invention patent CN 108047636A discloses a graphene modified ABS resin and a preparation method thereof, melamine-diphenyl phosphoryl chloride-graphene oxide and an ABS matrix are subjected to melt blending to improve the flame retardance of the ABS resin, although the flame retardance of the ABS resin is improved by the method, the method has complex working procedures and the graphene oxide is easy to agglomerate, so that the mechanical property of the material is greatly reduced.

The invention patent CN 111825946A discloses an enhanced modified ABS resin and a preparation method thereof, wherein the ABS resin is modified by adding spherical microspheres and maleic anhydride grafted polypropylene, but the method has complex working procedures and higher filler consumption.

In the above preparation method, the inorganic filler is blended and modified to obtain the ABS resin, which has complex process, high filler consumption and difficult consideration of mechanical property and heat resistance, so research and development of an ABS resin with high mechanical property, temperature resistance and easy processing is an urgent problem to be solved at present.

Disclosure of Invention

The invention aims to provide a preparation method of a functionalized multi-walled carbon nanotube modified ABS resin, aiming at improving the mechanical property and temperature resistance of the ABS resin. The specific technical scheme is as follows:

a preparation method of functionalized multi-walled carbon nanotube modified ABS resin specifically comprises the following steps:

the method comprises the following steps: preparation of functionalized multi-walled carbon nanotubes

Adding multi-wall carbon nanotube into 80 deg.C 100mL human-eating acid solution (volume ratio of 30% H)₂O₂And 70% concentrated sulfuric acid mixed solution), stirring for 6 hours by a magnetic stirrer. Centrifuging and washing with distilled water for 3 times, centrifuging and washing with ethanol for 2 times, and drying in an air drying oven at 80 deg.C for 12h to obtain hydroxylated multiwall carbon nanotube;

step two: mixing the hydroxylated multi-walled carbon nanotube and the ABS resin for 10min according to different mass ratios, adding a double-screw rod for extrusion granulation, and controlling the cylinder temperature of the double-screw extruder in 12 sections and the temperature range of 160-220 ℃.

Step three: and (3) drying the mixed particles for 24h at the temperature of 80 ℃ in a blast drying oven, placing the dried particles into an injection molding machine for injection molding, and placing an injection molding sample strip in a constant-temperature drying oven (the temperature is 23 ℃ and the humidity is 50%) for 48 h.

Step four: and (3) carrying out performance test on the sample bars after injection molding, wherein the test of the impact performance of the simply supported beam adopts a standard GB/T1043.1-2008, the test of the bending performance adopts a standard GB/T9341-2008, the test of the tensile performance adopts a standard GB/T1040.2-2006, and the test of the heat distortion temperature adopts a standard GB/T1643.1-2019.

The invention has the technical effects that:

the preparation method of the functionalized multi-walled carbon nanotube modified ABS resin greatly improves the mechanical property and the temperature resistance of the ABS resin.

Drawings

FIG. 1 is (a-d) is a graph showing the data of mechanical properties and heat distortion temperature of hydroxylated multi-walled carbon nanotube/ABS materials with different mass ratios;

Detailed Description

The invention is further described with reference to the following figures and specific embodiments.

Comparative example 1

Adding ABS resin into a double screw rod for extrusion granulation, controlling the cylinder temperature of the double screw rod extruder in 12 sections, and controlling the temperature range to be 160-220 ℃. And (3) drying the mixed particles for 24h at the temperature of 80 ℃ in a blast drying oven, placing the dried particles into an injection molding machine for injection molding, and placing an injection molding sample strip in a constant-temperature drying oven (the temperature is 23 ℃ and the humidity is 50%) for 48 h. And (3) carrying out performance test on the sample bars after injection molding, wherein the test of the impact performance of the simply supported beam adopts a standard GB/T1043.1-2008, the test of the bending performance adopts a standard GB/T9341-2008, the test of the tensile performance adopts a standard GB/T1040.2-2006, and the test of the heat distortion temperature adopts a standard GB/T1643.1-2019.

Example 1

The preparation method comprises the following steps of (1) mixing a hydroxylated multi-wall carbon nanotube with ABS resin according to a mass ratio of 1: mixing for 10min at the mixture ratio of 100, adding a double-screw rod for extrusion granulation, controlling the cylinder temperature of the double-screw extruder in 12 sections, and controlling the temperature range to be 160-220 ℃. And (3) drying the mixed particles for 24h at the temperature of 80 ℃ in a blast drying oven, placing the dried particles into an injection molding machine for injection molding, and placing an injection molding sample strip in a constant-temperature drying oven (the temperature is 23 ℃ and the humidity is 50%) for 48 h. And (3) carrying out performance test on the sample bars after injection molding, wherein the test of the impact performance of the simply supported beam adopts a standard GB/T1043.1-2008, the test of the bending performance adopts a standard GB/T9341-2008, the test of the tensile performance adopts a standard GB/T1040.2-2006, and the test of the heat distortion temperature adopts a standard GB/T1643.1-2019.

Example 2

Mixing a hydroxylated multi-wall carbon nanotube with ABS resin according to the mass ratio of 1.5: mixing for 10min at the mixture ratio of 100, adding a double-screw rod for extrusion granulation, controlling the cylinder temperature of the double-screw extruder in 12 sections, and controlling the temperature range to be 160-220 ℃. And (3) drying the mixed particles for 24h at the temperature of 80 ℃ in a blast drying oven, placing the dried particles into an injection molding machine for injection molding, and placing an injection molding sample strip in a constant-temperature drying oven (the temperature is 23 ℃ and the humidity is 50%) for 48 h. And (3) carrying out performance test on the sample bars after injection molding, wherein the test of the impact performance of the simply supported beam adopts a standard GB/T1043.1-2008, the test of the bending performance adopts a standard GB/T9341-2008, the test of the tensile performance adopts a standard GB/T1040.2-2006, and the test of the heat distortion temperature adopts a standard GB/T1643.1-2019.

Example 3

The preparation method comprises the following steps of (1) mixing a hydroxylated multi-wall carbon nanotube with ABS resin according to a mass ratio of 3: mixing for 10min at the mixture ratio of 100, adding a double-screw rod for extrusion granulation, controlling the cylinder temperature of the double-screw extruder in 12 sections, and controlling the temperature range to be 160-220 ℃. And (3) drying the mixed particles for 24h at the temperature of 80 ℃ in a blast drying oven, placing the dried particles into an injection molding machine for injection molding, and placing an injection molding sample strip in a constant-temperature drying oven (the temperature is 23 ℃ and the humidity is 50%) for 48 h. And (3) carrying out performance test on the sample bars after injection molding, wherein the test of the impact performance of the simply supported beam adopts a standard GB/T1043.1-2008, the test of the bending performance adopts a standard GB/T9341-2008, the test of the tensile performance adopts a standard GB/T1040.2-2006, and the test of the heat distortion temperature adopts a standard GB/T1643.1-2019.

TABLE 1. hydroxylated multiwalled carbon nanotube/ABS different mass ratio material mechanical property and thermal deformation temperature data table

As shown in fig. 1 and table 1, the hydroxylated multi-walled carbon nanotubes can modify ABS in two major ways.

On one hand, as an inorganic nano material, the existence of the multi-walled carbon nano tube can improve the heat resistance of ABS.

On the other hand, more-OH exists in the hydroxylated multi-wall carbon nano-tube, and the hydroxyl and-CN of ABS can form hydrogen bonds, so that the mechanical property of the material is improved.

In conclusion, the mechanical property and the heat resistance of the ABS resin can be obviously improved by blending the multi-walled carbon nano-tube hydroxylated by edible acid with the ABS.

Claims

1. A preparation method of functionalized multi-walled carbon nanotube modified ABS resin is characterized by comprising the following steps:

Adding the multi-walled carbon nanotube into a human-eating acid solution at the temperature of 80 ℃, stirring for 6 hours by using a magnetic stirrer, centrifuging and washing by using distilled water, then centrifuging and washing by using ethanol, and drying for 12 hours in a forced air drying oven at the temperature of 80 ℃ to obtain a hydroxylated multi-walled carbon nanotube;

step two: mixing the hydroxylated multi-walled carbon nanotube and ABS resin according to different mass ratios for 10min, adding the mixture into a double-screw extruder, extruding and granulating, wherein the temperature of a machine barrel of the double-screw extruder is controlled in 12 sections, and the temperature range is controlled to be 160-220 ℃;

step three: placing the mixed particles in a forced air drying oven for drying at 80 ℃ for 24h, placing the dried particles in an injection molding machine for injection molding, and placing an injection molding sample strip in a constant-temperature drying oven at 23 ℃, with the humidity of 50% for 48 h;

step four: and (5) carrying out performance test on the sample strip after injection molding.

2. The method according to claim 1, wherein in the first step, the solution of the human acid is 30% H by volume₂O₂And 70% concentrated sulfuric acid.

3. The preparation method according to claim 1, wherein in the fourth step, the impact performance of the simple beam is measured according to standard GB/T1043.1-2008, the bending performance is measured according to standard GB/T9341-2008, the tensile performance is measured according to standard GB/T1040.2-2006, and the heat distortion temperature is measured according to standard GB/T1643.1-2019.