阅读说明：本技术 一种碳纳米管改性聚苯乙烯导电材料的制法和应用 (Preparation method and application of carbon nanotube modified polystyrene conductive material ) 是由 沈洁芹 于 2020-12-15 设计创作，主要内容包括：本发明涉及聚苯乙烯复合材料技术领域,且公开了一种碳纳米管改性聚苯乙烯导电材料,以2-溴代丁二酸二丙炔醇酯作为ATRP引发剂,引发苯乙烯聚合,制得端炔基聚苯乙烯,在溴化亚铜和二乙烯三胺的催化体系中,基于叠氮-炔点击反应,使叠氮化碳纳米管和端炔基聚苯乙烯进行简单温和的点击化反应,从而通过化学键共价接枝,使聚苯乙烯与碳纳米管有机结合,提高了两者之间的界面作用力和相容性,克服了碳纳米管发生团聚的现象,高度分散的碳纳米管在聚苯乙烯中产生良好的渗流阈值,形成三维导电通路和导电网络,提高了聚苯乙烯复合材料的电导率和导电性,并且碳纳米管的引入有利于增强聚苯乙烯材料的抗冲击性和韧性。(The invention relates to the technical field of polystyrene composite materials, and discloses a carbon nano tube modified polystyrene conductive material, which uses 2-bromosuccinic acid dipropargyl alcohol ester as an ATRP initiator to initiate styrene polymerization to prepare terminal alkynyl polystyrene, and makes the azide carbon nano tube and the terminal alkynyl polystyrene perform simple and mild click reaction based on azide-alkyne click reaction in a catalytic system of cuprous bromide and diethylenetriamine, so that the polystyrene and the carbon nano tube are organically combined through covalent grafting of chemical bonds, the interface acting force and compatibility between the polystyrene and the carbon nano tube are improved, the phenomenon of agglomeration of the carbon nano tube is overcome, the highly dispersed carbon nano tube generates a good percolation threshold value in the polystyrene, a three-dimensional conductive path and a conductive network are formed, and the conductivity and the electrical conductivity of the polystyrene composite material are improved, and the introduction of the carbon nano tube is beneficial to enhancing the impact resistance and the toughness of the polystyrene material.)

1. A carbon nano tube modified polystyrene conductive material is characterized in that: the preparation method of the carbon nano tube modified polystyrene conductive material comprises the following steps:

(1) adding an N, N-dimethylformamide solvent, an aminated carbon nanotube and 4-azidobenzoic acid into a constant-temperature reaction device, uniformly dispersing, adding a catalyst and an activating agent, carrying out constant-temperature reaction, carrying out suction filtration and washing to obtain an azido carbon nanotube;

(2) adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the steps of freezing treatment, vacuum treatment and unfreezing treatment for 3-5 times, heating to 120 ℃, reacting for 3-6h, extracting and purifying to obtain terminal alkynyl polystyrene;

(3) adding N, N-dimethylformamide solvent, carbon nano-tube azide and terminal alkynyl polystyrene into a constant-temperature reaction device, uniformly dispersing, adding catalyst and activating agent under the protection of nitrogen, reacting for 12-36h at 20-40 ℃, extracting, purifying, distilling under reduced pressure, drying, defoaming and pressing to form a film to prepare the carbon nano-tube modified polystyrene conductive material, which is applied to a polystyrene conductive material.

2. The carbon nanotube-modified polystyrene conductive material of claim 1, wherein: the constant temperature reaction device comprises an oil bath pot, a heat preservation shell is fixedly connected to the outer side of the oil bath pot, a motor is fixedly connected to the lower portion of the inner portion of the oil bath pot, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disk, a clamping groove is formed in the surface of the rotating disk, and a beaker is arranged in the.

3. The carbon nanotube-modified polystyrene conductive material of claim 1, wherein: the catalyst in the step (1) is 4-dimethylamino pyridine, and the activating agent is dicyclohexyl carbodiimide.

4. The carbon nanotube-modified polystyrene conductive material of claim 1, wherein: the mass ratio of the aminated carbon nanotube, the 4-azidobenzoic acid, the 4-dimethylaminopyridine and the dicyclohexylcarbodiimide in the step (1) is 10:15-35:0.5-2: 4-10.

5. The carbon nanotube-modified polystyrene conductive material of claim 1, wherein: the catalyst in the step (3) is cuprous bromide, and the activating agent is diethylenetriamine.

6. The carbon nanotube-modified polystyrene conductive material of claim 1, wherein: the mass ratio of the carbon azide nanotubes, the terminal alkynyl polystyrene, the cuprous bromide and the diethylenetriamine in the step (3) is 100:1-3:0.4-1: 0.6-1.5.

Technical Field

The invention relates to the technical field of polystyrene composite materials, in particular to a preparation method and application of a carbon nano tube modified polystyrene conductive material.

Background

Polystyrene is a common high polymer material, has good insulating property, optical property and mechanical property, has good corrosion resistance, can be prepared into impact-resistant polystyrene, styrene acrylonitrile composite materials and the like, and is widely applied to sound-insulating and heat-insulating materials, vessel containers and packaging materials, so that the comprehensive properties of the polystyrene such as conductivity, impact strength and the like need to be improved to expand the application field and practical application of the polystyrene material.

The conductive material has the functions of conveying and conducting current, has large internal resistance and strong conductivity, such as conductive plastic, conductive rubber, conductive paint and the like, and is generally prepared by physically blending conductive agents such as graphite powder, carbon black, conductive metal particles and the like with a high polymer to prepare a composite material, so that the conductivity and the conductivity of the composite material are improved.

The carbon nano tube has unique electrochemical properties, mechanical properties and other properties, is an excellent nano filler, is widely applied to high polymer materials such as polyurethane, acrylic resin and the like, has great enhancement effects on the mechanical strength, the electrical properties and the thermodynamics of the materials, but has small interface acting force and poor compatibility between the carbon nano tube and polystyrene, and has strong van der waals force among carbon nano tube particles, easy agglomeration occurs, and the enhancement effect of the carbon nano tube is difficult to exert to the maximum extent.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a preparation method and application of a carbon nano tube modified polystyrene conductive material, and solves the problems of poor conductivity of polystyrene and low mechanical properties such as impact resistance, toughness and the like.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a carbon nanotube modified polystyrene conductive material comprises the following steps:

(1) adding an N, N-dimethylformamide solvent, an aminated carbon nanotube and 4-azidobenzoic acid into a constant-temperature reaction device, uniformly dispersing, adding a catalyst and an activating agent, carrying out constant-temperature reaction, carrying out suction filtration, washing with distilled water and ethanol, and thus obtaining the azido carbon nanotube.

(2) Adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the processes of freezing treatment, vacuum treatment and unfreezing treatment for 3-5 times, heating to the temperature of 100 ℃ and 120 ℃, reacting for 3-6h, and adding distilled water and a toluene solvent for extraction and purification to prepare the terminal alkynyl polystyrene.

(3) Adding N, N-dimethylformamide solvent, carbon nano-tube azide and terminal alkynyl polystyrene into a constant-temperature reaction device, uniformly dispersing, adding catalyst and activating agent under the protection of nitrogen, reacting for 12-36h at 20-40 ℃, adding distilled water and toluene, extracting and purifying, taking a toluene organic phase, carrying out reduced pressure distillation, drying, defoaming and pressing to form a film, thus obtaining the carbon nano-tube modified polystyrene conductive material, which is applied to the polystyrene conductive material.

Preferably, the constant temperature reaction device comprises an oil bath pot, a heat preservation shell is fixedly connected to the outer side of the oil bath pot, a motor is fixedly connected to the lower portion of the inner portion of the oil bath pot, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disk, a clamping groove is formed in the surface of the rotating disk, and a beaker is arranged in the clamping.

Preferably, the catalyst in the step (1) is 4-dimethylaminopyridine, and the activating agent is dicyclohexylcarbodiimide.

Preferably, the mass ratio of the aminated carbon nanotube, the 4-azidobenzoic acid, the 4-dimethylaminopyridine and the dicyclohexylcarbodiimide in the step (1) is 10:15-35:0.5-2: 4-10.

Preferably, the catalyst in the step (3) is cuprous bromide, and the activating agent is diethylenetriamine.

Preferably, the mass ratio of the carbon azide nanotubes, the alkynyl-terminated polystyrene, the cuprous bromide and the diethylenetriamine in the step (3) is 100:1-3:0.4-1: 0.6-1.5.

Drawings

FIG. 1 is a schematic view of a structure of a constant temperature reaction apparatus;

fig. 2 is a schematic top view of a rotating disk structure.

1-constant temperature reaction device; 2-oil bath pan; 3-insulating shell; 4-a motor; 5-a rotating shaft; 6-connecting rod; 7-a rotating gear; 8-rotating the disc; 9-a card slot; 10-beaker.

(III) advantageous technical effects

Compared with the prior art, the invention has the following chemical experiment principle and beneficial technical effects:

the carbon nanotube modified polystyrene conductive material is prepared by performing amidation reaction on carboxyl of 4-azidobenzoic acid and amino of a carbon nanotube under the activation action of 4-dimethylaminopyridine and dicyclohexylcarbodiimide to prepare the azido carbon nanotube, so that the functional modification of the carbon nanotube is realized.

The carbon nano tube modified polystyrene conductive material takes 2-dipropynyl-bromosuccinate containing alkynyl as an ATRP initiator, styrene polymerization is initiated through an atom transfer radical polymerization process to prepare alkynyl-terminated polystyrene, the simple and mild click reaction is carried out on the carbon nano tube azide and the alkynyl-terminated polystyrene based on the azide-alkyne click reaction in a catalytic system of cuprous bromide and diethylenetriamine, so that the polystyrene and the carbon nano tube are organically combined through covalent grafting of chemical bonds, the interfacial force and the compatibility between the polystyrene and the carbon nano tube are greatly improved, the phenomenon that the carbon nano tube is agglomerated on a polystyrene matrix is overcome, the highly dispersed carbon nano tube generates a good percolation threshold value in the polystyrene, a three-dimensional conductive path and a conductive network are formed, and the conductivity and the electrical conductivity of the polystyrene composite material are obviously improved, and the introduction of the carbon nano tube is beneficial to enhancing the impact resistance and the toughness of the polystyrene material.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: a carbon nano tube modified polystyrene conductive material is prepared by the following steps:

(1) adding an N, N-dimethylformamide solvent into a constant-temperature reaction device, wherein the constant-temperature reaction device comprises an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat-preservation shell, the lower part of the inner part of the oil bath pot is fixedly connected with a motor, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disc, the surface of the rotating disc is provided with a clamping groove, a beaker is arranged in the clamping groove, then adding an amino carbon nanotube, 4-azidobenzoic acid, a catalyst 4-dimethylaminopyridine and an activator dicyclohexylcarbodiimide with the mass ratio of 10:15-35:0.5-2:4-10, carrying out constant-temperature reaction for 10-20h at 15-35 ℃, carrying.

(2) Adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the processes of freezing treatment, vacuum treatment and unfreezing treatment for 3-5 times, heating to the temperature of 100 ℃ and 120 ℃, reacting for 3-6h, and adding distilled water and a toluene solvent for extraction and purification to prepare the terminal alkynyl polystyrene.

(3) Adding N, N-dimethylformamide solvent, carbon azide nanotube and terminal alkynyl polystyrene into a constant-temperature reaction device, uniformly dispersing, adding cuprous bromide catalyst and diethylenetriamine activator in a mass ratio of 100:1-3:0.4-1:0.6-1.5 under the protection of nitrogen, reacting for 12-36h at 20-40 ℃, adding distilled water and toluene, extracting and purifying, taking a toluene organic phase, distilling under reduced pressure, drying, defoaming, and pressing to form a film to obtain the carbon nanotube modified polystyrene conductive material.

Example 1

(1) Adding an N, N-dimethylformamide solvent into a constant-temperature reaction device, wherein the constant-temperature reaction device comprises an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat-insulating shell, the lower part of the inner part of the oil bath pot is fixedly connected with a motor, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disc, the surface of the rotating disc is provided with a clamping groove, a beaker is arranged in the clamping groove, then adding an amino carbon nano tube, 4-azidobenzoic acid, a catalyst, 4-dimethylaminopyridine and an activator dicyclohexylcarbodiimide with the mass ratio of 10:15:0.5:4, reacting for 10 hours at 15 ℃, and performing suction.

(2) Adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the steps of freezing treatment, vacuum treatment and unfreezing treatment for 3 times, heating to 100 ℃, reacting for 3 hours, and adding distilled water and a toluene solvent for extraction and purification to obtain the terminal alkynyl polystyrene.

(3) Adding N, N-dimethylformamide solvent, carbon nano-tubes azide and alkynyl-terminated polystyrene into a constant-temperature reaction device, uniformly dispersing, adding cuprous bromide catalyst and diethylenetriamine activator in a mass ratio of 100:1:0.4:0.6 under the protection of nitrogen, reacting for 12 hours at 20 ℃, adding distilled water and toluene, extracting and purifying, taking a toluene organic phase, carrying out reduced pressure distillation, drying, defoaming and pressing to form a film, thus obtaining the carbon nano-tube modified polystyrene conductive material.

Example 2

(1) Adding an N, N-dimethylformamide solvent into a constant-temperature reaction device, wherein the constant-temperature reaction device comprises an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat-insulating shell, the lower part of the inner part of the oil bath pot is fixedly connected with a motor, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disk, the surface of the rotating disk is provided with a clamping groove, a beaker is arranged in the clamping groove, then adding an amino carbon nanotube, 4-azidobenzoic acid, a catalyst 4-dimethylaminopyridine and an activator dicyclohexylcarbodiimide in a mass ratio of 10:20:1:6, reacting for 10 hours at 30 ℃, and performing suction filtration.

(2) Adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the steps of freezing treatment, vacuum treatment and unfreezing treatment for 5 times, heating to 120 ℃, reacting for 4 hours, and adding distilled water and a toluene solvent for extraction and purification to obtain the terminal alkynyl polystyrene.

(3) Adding N, N-dimethylformamide solvent, carbon azide nanotube and terminal alkynyl polystyrene into a constant-temperature reaction device, uniformly dispersing, adding cuprous bromide catalyst and diethylenetriamine activator in a mass ratio of 100:1.5:0.6:0.9 under the protection of nitrogen, reacting for 36 hours at 35 ℃, adding distilled water and toluene, extracting and purifying, taking a toluene organic phase, carrying out reduced pressure distillation, drying, defoaming and pressing to form a film, thus obtaining the carbon nanotube modified polystyrene conductive material.

Example 3

(1) Adding an N, N-dimethylformamide solvent into a constant-temperature reaction device, wherein the constant-temperature reaction device comprises an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat-insulating shell, the lower part of the inner part of the oil bath pot is fixedly connected with a motor, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disc, the surface of the rotating disc is provided with a clamping groove, a beaker is arranged in the clamping groove, then adding an amino carbon nano tube, 4-azidobenzoic acid, a catalyst, 4-dimethylaminopyridine and an activator dicyclohexylcarbodiimide with the mass ratio of 10:28:1.5:8, reacting for 15 hours at 30 ℃, and performing suction.

(2) Adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the steps of freezing treatment, vacuum treatment and unfreezing treatment for 4 times, heating to 110 ℃, reacting for 5 hours, and adding distilled water and a toluene solvent for extraction and purification to obtain the terminal alkynyl polystyrene.

(3) Adding N, N-dimethylformamide solvent, carbon azide nanotube and terminal alkynyl polystyrene into a constant-temperature reaction device, uniformly dispersing, adding cuprous bromide catalyst and diethylenetriamine activator in a mass ratio of 100:2.2:0.8:1.2 under the protection of nitrogen, reacting for 24 hours at 30 ℃, adding distilled water and toluene, extracting and purifying, taking a toluene organic phase, carrying out reduced pressure distillation, drying, defoaming and pressing to form a film, thus obtaining the carbon nanotube modified polystyrene conductive material.

Example 4

(1) Adding an N, N-dimethylformamide solvent into a constant-temperature reaction device, wherein the constant-temperature reaction device comprises an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat-insulating shell, the lower part of the inner part of the oil bath pot is fixedly connected with a motor, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disk, the surface of the rotating disk is provided with a clamping groove, a beaker is arranged in the clamping groove, then adding an amino carbon nanotube, 4-azidobenzoic acid, a catalyst 4-dimethylaminopyridine and an activator dicyclohexylcarbodiimide with the mass ratio of 10:35:2:10, reacting for 20 hours at 35 ℃, and performing suction filtration.

(2) Adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the steps of freezing treatment, vacuum treatment and unfreezing treatment for 5 times, heating to 120 ℃, reacting for 6 hours, and adding distilled water and a toluene solvent for extraction and purification to obtain the terminal alkynyl polystyrene.

(3) Adding N, N-dimethylformamide solvent, carbon nano-tube azide and terminal alkynyl polystyrene into a constant-temperature reaction device, uniformly dispersing, adding cuprous bromide catalyst and diethylenetriamine activator in a mass ratio of 100:3:1:1.5 under the protection of nitrogen, reacting for 36 hours at 40 ℃, adding distilled water and toluene, extracting and purifying, taking a toluene organic phase, carrying out reduced pressure distillation, drying, defoaming and pressing to form a film, thus obtaining the carbon nano-tube modified polystyrene conductive material.

Comparative example 1

(1) Adding an N, N-dimethylformamide solvent into a constant-temperature reaction device, wherein the constant-temperature reaction device comprises an oil bath pot, the outer side of the oil bath pot is fixedly connected with a heat-insulating shell, the lower part of the inner part of the oil bath pot is fixedly connected with a motor, the motor is movably connected with a rotating shaft, the rotating shaft is movably connected with a connecting rod, the connecting rod is movably connected with a rotating gear, the rotating gear is movably connected with a rotating disc, the surface of the rotating disc is provided with a clamping groove, a beaker is arranged in the clamping groove, then adding an amino carbon nano tube, 4-azidobenzoic acid, a catalyst, 4-dimethylaminopyridine and an activator dicyclohexylcarbodiimide with the mass ratio of 10:10:0.2:2, reacting for 15 hours at 40 ℃, and performing suction.

(2) Adding 2-bromosuccinic acid dipropargyl alcohol ester, a catalyst cuprous bromide and a ligand 2, 2-bipyridine into a constant-temperature reaction device, repeating the steps of freezing treatment, vacuum treatment and unfreezing treatment for 3 times, heating to 110 ℃, reacting for 6 hours, and adding distilled water and a toluene solvent for extraction and purification to obtain the terminal alkynyl polystyrene.

(3) Adding N, N-dimethylformamide solvent, carbon azide nanotube and terminal alkynyl polystyrene into a constant-temperature reaction device, uniformly dispersing, adding cuprous bromide catalyst and diethylenetriamine activator in a mass ratio of 100:0.5:0.2:0.2 under the protection of nitrogen, reacting for 12 hours at 40 ℃, adding distilled water and toluene, extracting and purifying, taking a toluene organic phase, carrying out reduced pressure distillation, drying, defoaming and pressing to form a film, thus obtaining the carbon nanotube modified polystyrene conductive material.

The conductivity and the conductivity of the carbon nanotube modified polystyrene conductive material are tested by using a DDB-303A conductivity tester, and the test standard is GB/T1550-.

The impact strength of the carbon nano tube modified polystyrene conductive material is tested by using an OK-S impact tester, and the test standard is GB/T37198-.