阅读说明：本技术 一种吡咯-噻吩共聚物接枝丙烯酸树脂导电材料及其制法 (Pyrrole-thiophene copolymer grafted acrylic resin conductive material and preparation method thereof ) 是由 黄礼辉 于 2020-05-20 设计创作，主要内容包括：本发明涉及导电丙烯酸树脂技术领域,且公开了一种吡咯-噻吩共聚物接枝丙烯酸树脂导电材料,包括以下配方原料及组分：含烯基吡咯-噻吩共聚物接枝石墨烯、甲基丙烯酸甲酯、丙烯酸丁酯、苯乙烯、过氧化二苯甲酰。该一种吡咯-噻吩共聚物接枝丙烯酸树脂导电材料,吡咯、3-乙烯基噻吩和3,4-乙烯二氧噻吩在石墨烯表面,原位共价修饰含有烯基的吡咯-噻吩共聚物,再与甲基丙烯酸甲酯等共聚,通过共价键接枝的方法将石墨烯和吡咯-噻吩共聚物引入丙烯酸树脂的分子链中,改善了导电介质与丙烯酸树脂相容性,增强了丙烯酸树脂的导电性能,力学性能优异的石墨烯,以及刚性的聚噻吩共轭分子链,可以提高丙烯酸树脂的机械强度。(The invention relates to the technical field of conductive acrylic resin, and discloses a pyrrole-thiophene copolymer grafted acrylic resin conductive material which comprises the following formula raw materials and components: alkenyl-containing pyrrole-thiophene copolymer grafted graphene, methyl methacrylate, butyl acrylate, styrene and dibenzoyl peroxide. According to the pyrrole-thiophene copolymer grafted acrylic resin conductive material, pyrrole, 3-vinyl thiophene and 3, 4-ethylenedioxythiophene are in situ covalently modified on the surface of graphene, and then are copolymerized with methyl methacrylate and the like, the graphene and the pyrrole-thiophene copolymer are introduced into a molecular chain of acrylic resin by a covalent bond grafting method, so that the compatibility of a conductive medium and the acrylic resin is improved, the conductive performance of the acrylic resin is enhanced, the graphene with excellent mechanical properties and a rigid polythiophene conjugated molecular chain are enhanced, and the mechanical strength of the acrylic resin can be improved.)

1. The pyrrole-thiophene copolymer grafted acrylic resin conductive material comprises the following raw materials and components, and is characterized in that: the alkenyl-containing pyrrole-thiophene copolymer grafted graphene, methyl methacrylate, butyl acrylate, styrene and dibenzoyl peroxide in a mass ratio of 3-20:100:20-30:15-25: 0.4-0.6.

2. The pyrrole-thiophene copolymer grafted acrylic resin conductive material according to claim 1, wherein: the preparation method of the pyrrole-thiophene copolymer grafted acrylic resin conductive material comprises the following steps:

(1) adding carboxylated graphene into an anhydrous trichloromethane solvent in a nitrogen atmosphere, placing the mixture into an ultrasonic treatment instrument for ultrasonic dispersion, adding thionyl chloride, stirring the mixture for 3 to 8 hours at the temperature of between 0 and 5 ℃, and carrying out reduced pressure distillation, washing and drying to prepare the acylchlorinated graphene;

(2) adding acylchlorinated graphene and a surfactant sodium dodecyl sulfate into an N, N-dimethylformamide solvent in a nitrogen atmosphere, adding pyrrole after uniform ultrasonic dispersion, stirring for 2-6h at 0-5 ℃, adding concentrated hydrochloric acid to adjust the pH value of the solution to 2-3, adding 3-vinyl thiophene and 3, 4-ethylene dioxythiophene, stirring for 1-2h at 25-35 ℃, adding an aqueous solution of a hydrogen peroxide component 1 and a ferric trichloride component 1, reacting for 2-4h, adding an aqueous solution of a hydrogen peroxide component 2 and a ferric trichloride component 2, reacting for 1-2h, filtering, washing and drying to prepare the alkenyl-containing pyrrole-thiophene copolymer grafted graphene;

(3) adding the alkenyl-containing pyrrole-thiophene copolymer grafted graphene, methyl methacrylate, butyl acrylate and styrene into a toluene solvent, uniformly stirring, slowly dripping the solution into a toluene solution containing initiator dibenzoyl peroxide, reacting at the temperature of 100 ℃ and 120 ℃ for 2-6h, pouring the solution into a mold, and curing to form a film to prepare the pyrrole-thiophene copolymer grafted acrylic resin conductive material.

3. The pyrrole-thiophene copolymer grafted acrylic resin conductive material according to claim 2, wherein: the ultrasonic treatment instrument in the step (1) comprises an ultrasonic probe and a water bath which is arranged in the ultrasonic treatment instrument, heating rings fixedly connected to the two sides of the ultrasonic treatment instrument and a base fixedly connected to the bottom of the ultrasonic treatment instrument, a lifting device is fixedly connected to the upper side of the base, an adjusting ball is movably connected to the lifting device, an objective table is movably connected to the adjusting ball, and a reaction bottle is arranged above the objective table.

4. The pyrrole-thiophene copolymer grafted acrylic resin conductive material according to claim 2, wherein: the carboxyl content of the carboxylated graphene in the step (2) is 3-5%, and the mass ratio of the carboxyl content to the thionyl chloride is 1: 200-300.

5. The pyrrole-thiophene copolymer grafted acrylic resin conductive material according to claim 2, wherein: the mass ratio of the acylchlorinated graphene, the sodium dodecyl sulfate, the pyrrole, the 3-vinyl thiophene, the 3, 4-ethylenedioxythiophene, the ferric trichloride component 1, the hydrogen peroxide component 1, the ferric trichloride component 2 and the hydrogen peroxide component 2 in the step (1) is 5-30:2-5:100:10-20:80-120:550-600: 200-220-300: 100-130.

Technical Field

The invention relates to the technical field of conductive acrylic resin, in particular to a pyrrole-thiophene copolymer grafted acrylic resin conductive material and a preparation method thereof.

Background

The material for transmitting and conducting current is called as conductive material, mainly comprises conductive plastic, conductive rubber and conductive film, etc., and the conductive medium of silver and aluminum, etc. and the polymer material are physically filled, compounded, surface compounded or laminated, so that the conductive material used in the field of electricians has the features of high conductivity, good mechanical performance, easy processing, corrosion resistance, etc.

Acrylic resin is generally divided into thermoplastic acrylic resin and thermosetting acrylic resin, the acrylic resin has the advantages of good light and color retention, water resistance, chemical resistance and the like, and the product is mainly used for coatings, paint and adhesives and is widely applied to the fields of building materials, transportation, electronic appliances and the like.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a pyrrole-thiophene copolymer grafted acrylic resin conductive material and a preparation method thereof, and solves the problem of poor conductivity of acrylic resin.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a pyrrole-thiophene copolymer grafted acrylic resin conductive material comprises the following raw materials and components: the mass ratio of the alkenyl-containing pyrrole-thiophene copolymer grafted graphene to methyl methacrylate to butyl acrylate to styrene to dibenzoyl peroxide is 3-20:100:20-30:15-25: 0.4-0.6.

Preferably, the preparation method of the pyrrole-thiophene copolymer grafted acrylic resin conductive material is as follows:

(1) introducing nitrogen into an atmosphere reaction bottle, adding carboxylated graphene and an anhydrous chloroform solvent, placing the mixture into an ultrasonic treatment instrument for ultrasonic dispersion, adding thionyl chloride, stirring at a constant speed of 0-5 ℃ for 3-8 hours, removing the solvent by reduced pressure distillation, washing a solid product by using anhydrous acetone, and drying to prepare the acyl chloride fossil graphene.

(2) Introducing nitrogen into an atmosphere reaction bottle, adding N, N-dimethylformamide solvent, acyl chloride graphene and surfactant sodium dodecyl sulfate, adding pyrrole after ultrasonic dispersion is uniform, stirring at 0-5 deg.C for 2-6 hr, adding concentrated hydrochloric acid to adjust pH to 2-3, adding 3-vinyl thiophene and 3, 4-ethylenedioxythiophene, stirring at a constant speed of 25-35 ℃ for 1-2h, adding an aqueous solution of a hydrogen peroxide component 1 and a ferric trichloride component 1, stirring at a constant speed for reaction for 2-4h, adding an aqueous solution of a hydrogen peroxide component 2 and a ferric trichloride component 2, stirring at a constant speed for reaction for 1-2h, filtering the solution to remove a solvent, washing a solid product with ethanol and distilled water, and drying to prepare the alkenyl-containing pyrrole-thiophene copolymer grafted graphene.

(3) Adding a toluene solvent, the alkenyl-containing pyrrole-thiophene copolymer grafted graphene, methyl methacrylate, butyl acrylate and styrene into a reaction bottle, uniformly stirring, slowly dripping the solution into a toluene solution containing initiator dibenzoyl peroxide, reacting for 2-6h at a constant speed at the temperature of 100-120 ℃, pouring the solution into a mold, and curing to form a film to prepare the pyrrole-thiophene copolymer grafted acrylic resin conductive material.

Preferably, the ultrasonic treatment instrument in the step (1) comprises an ultrasonic probe and a water bath arranged inside the ultrasonic treatment instrument, a heating ring fixedly connected to the two sides of the ultrasonic treatment instrument, and a base fixedly connected to the bottom of the ultrasonic treatment instrument, a lifting device is fixedly connected to the upper side of the base, an adjusting ball is movably connected to the lifting device, an objective table is movably connected to the adjusting ball, and a reaction bottle is arranged above the objective table.

Preferably, the carboxyl content of the carboxylated graphene in the step (1) is 3-5%, and the mass ratio of the carboxyl content to the thionyl chloride is 1: 200-300.

Preferably, the mass ratio of the acylchlorinated graphene, the sodium dodecyl sulfate, the pyrrole, the 3-vinyl thiophene, the 3, 4-ethylenedioxythiophene, the ferric trichloride component 1, the hydrogen peroxide component 1, the ferric trichloride component 2 and the hydrogen peroxide component 2 in the step (2) is 5-30:2-5:100:10-20:80-120:550-600: 200-300: 220-130-220-300-200-one-step reaction.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the pyrrole-thiophene copolymer grafted acrylic resin conductive material is prepared by reacting imino group of pyrrole with acyl chloride group of acylchlorinated graphene to covalently modify pyrrole in graphene, using pyrrole, 3-vinyl thiophene and 3, 4-ethylene dioxythiophene as comonomers by an in-situ polymerization method, covalently modifying pyrrole-thiophene copolymer containing alkenyl on the surface of graphene in situ, copolymerizing alkene free radicals, copolymerizing the graphene grafted alkenyl pyrrole-thiophene copolymer with methyl methacrylate and the like, introducing the graphene and the pyrrole-thiophene copolymer into a molecular chain of acrylic resin by a covalent bond grafting method, improving compatibility of a conductive medium of the graphene nano particles and the pyrrole-thiophene copolymer with acrylic resin, and enabling the graphene nano particles and the pyrrole-thiophene copolymer to have high conductivity, the uniformly dispersed pyrrole-thiophene copolymer grafted graphene obviously enhances the conductivity of the acrylic resin, and the graphene with excellent mechanical property and the rigid polythiophene conjugated molecular chain in the pyrrole-thiophene copolymer can improve the mechanical strength of the acrylic resin.

Drawings

FIG. 1 is a schematic front view of a constant temperature ultrasonic disperser;

FIG. 2 is an enlarged schematic view of a horizontal spring rod;

1-ultrasonic treatment instrument; 2-an ultrasonic probe; 3-water bath; 4-heating a ring; 5-a base; 6-a lifting device; 7-adjusting the ball; 8-an object stage; 9-reaction flask.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: the pyrrole-thiophene copolymer grafted acrylic resin conductive material comprises the following raw materials and components: the alkenyl-containing pyrrole-thiophene copolymer grafted graphene, methyl methacrylate, butyl acrylate, styrene and dibenzoyl peroxide in a mass ratio of 3-20:100:20-30:15-25: 0.4-0.6.

The preparation method of the pyrrole-thiophene copolymer grafted acrylic resin conductive material comprises the following steps:

(1) introducing nitrogen into an atmosphere reaction bottle, adding carboxylated graphene with 3-5% of carboxyl content and an anhydrous trichloromethane solvent, placing the mixture into an ultrasonic treatment instrument for ultrasonic dispersion, wherein the ultrasonic treatment instrument comprises an ultrasonic probe, a water bath is arranged in the ultrasonic treatment instrument, heating rings are fixedly connected to two sides of the ultrasonic treatment instrument, a base is fixedly connected to the bottom of the ultrasonic treatment instrument, a lifting device is fixedly connected to the upper part of the base, the lifting device is movably connected with an adjusting ball, the adjusting ball is movably connected with an objective table, a reaction bottle is arranged above the objective table, adding thionyl chloride, and the mass ratio of the carboxylated graphene to the carboxylated graphene is 200-300:1, stirring at 0-5 ℃ for 3-8h at constant speed, distilling under reduced pressure to remove the solvent, washing the solid product with anhydrous acetone, and drying to obtain the graphene oxychloride.

(2) Introducing nitrogen into an atmosphere reaction bottle, adding N, N-dimethylformamide solvent, chlorinated graphene oxide and surfactant sodium dodecyl sulfate, uniformly dispersing by ultrasonic, adding pyrrole, uniformly stirring at 0-5 ℃ for 2-6h, adding concentrated hydrochloric acid to adjust the pH of the solution to 2-3, adding 3-vinyl thiophene and 3, 4-ethylene dioxythiophene, uniformly stirring at 25-35 ℃ for 1-2h, adding hydrogen peroxide component 1 aqueous solution and ferric trichloride component 1, uniformly stirring to react for 2-4h, and adding hydrogen peroxide component 2 aqueous solution and ferric trichloride component 2, wherein acyl chlorinated graphene, sodium dodecyl sulfate, pyrrole, 3-vinyl thiophene, 3, 4-ethylene dioxythiophene, ferric trichloride component 1, iron trichloride component 1, The mass ratio of the hydrogen peroxide component 1, the ferric trichloride component 2 and the hydrogen peroxide component 2 is 5-30:2-5:100:10-20:80-120:550-600:200-250:220-300:100-130, the solution is stirred at a constant speed for reaction for 1-2h, the solvent is removed by filtration, the solid product is washed by ethanol and distilled water and dried, and the alkenyl-containing pyrrole-thiophene copolymer grafted graphene is prepared.

(3) Adding a toluene solvent, the alkenyl-containing pyrrole-thiophene copolymer grafted graphene, methyl methacrylate, butyl acrylate and styrene into a reaction bottle, uniformly stirring, slowly dripping the solution into a toluene solution containing initiator dibenzoyl peroxide, reacting for 2-6h at a constant speed at the temperature of 100-120 ℃, pouring the solution into a mold, and curing to form a film to prepare the pyrrole-thiophene copolymer grafted acrylic resin conductive material.