阅读说明：本技术 一种石墨烯/聚吡咯/水溶性高分子三元复合材料及其制备方法 (Graphene/polypyrrole/water-soluble polymer ternary composite material and preparation method thereof ) 是由 向萌 董爽 杨菁菁 周仕龙 王晨 孙雨 丁颖 于 2019-09-23 设计创作，主要内容包括：本发明属于聚合物复合材料技术领域,具体涉及一种石墨烯/聚吡咯/水溶性高分子三元复合材料及其制备方法,所述方法为：在水热反应釜中加入氧化石墨烯水分散液、吡咯单体、形貌控制剂、氧化剂和络合剂,超声分散处理后,加热,同时辐照处理,得到石墨烯/聚吡咯/水溶性高分子三元杂化水凝胶,然后将水凝胶进行冷冻干燥后即得到石墨烯/聚吡咯/水溶性高分子三元复合材料,本发明方法能够使石墨烯和聚吡咯在高分子基体中分散均匀,使制得的复合材料具有优异的导电性能和力学性能。(The invention belongs to the technical field of polymer composite materials, and particularly relates to a graphene/polypyrrole/water-soluble polymer ternary composite material and a preparation method thereof, wherein the method comprises the following steps: adding graphene oxide aqueous dispersion, pyrrole monomer, morphology control agent, oxidant and complexing agent into a hydrothermal reaction kettle, performing ultrasonic dispersion treatment, heating, performing irradiation treatment simultaneously to obtain graphene/polypyrrole/water-soluble polymer ternary hybrid hydrogel, and then performing freeze drying on the hydrogel to obtain the graphene/polypyrrole/water-soluble polymer ternary composite material.)

1. A preparation method of a graphene/polypyrrole/water-soluble polymer ternary composite material is characterized by comprising the following steps:

(1) adding the graphene oxide aqueous dispersion into a hydrothermal reaction kettle, adding a pyrrole monomer, a morphology control agent, an oxidant and a complexing agent into the graphene oxide aqueous dispersion, carrying out ultrasonic dispersion treatment, heating the hydrothermal reaction kettle, and carrying out irradiation treatment to obtain graphene/polypyrrole/water-soluble polymer ternary hybrid hydrogel;

(2) and (3) carrying out freeze drying on the graphene/polypyrrole/water-soluble polymer ternary hybrid hydrogel to obtain the graphene/polypyrrole/water-soluble polymer ternary composite material.

2. The preparation method of the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 1, wherein the concentration of the graphene oxide aqueous dispersion in the step (1) is 0.05-10 mg/mL, and the mass ratio of the graphene oxide aqueous dispersion to the pyrrole monomer is (0.1-30): 1.

3. The preparation method of the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 1, wherein the graphene/polypyrrole/water-soluble polymer ternary composite material is prepared by the following steps,

the water-soluble polymer matrix is one or more of carboxymethyl starch, starch acetate, hydroxymethyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide and polyacrylate, and the dosage of the water-soluble polymer matrix in the graphene oxide aqueous dispersion is 0.01-10 g/L;

the morphology control agent is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, hexadecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, benzyl triethyl ammonium chloride, sodium lignosulfonate, BYK-190 and BYK-192, and the dosage of the morphology control agent in the graphene oxide aqueous dispersion is 0.001-0.8 mol/L;

the complexing agent is one or more of polyether amine D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2003, EDR-148, T-403, T-3000 and T-5000, and the dosage of the complexing agent in the graphene oxide aqueous dispersion is 0.02-10 g/L;

the oxidant is one or more of ferric chloride, ammonium persulfate, hydrogen peroxide, potassium iodate and potassium dichromate, and the dosage of the oxidant in the graphene oxide aqueous dispersion is 0.01-8 g/L.

4. The preparation method of the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 1, wherein the heating temperature of the hydrothermal reaction kettle in the step (1) is 100-200 ℃, and the heating reaction time is 10-20 hours.

5. The preparation method of the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 1, wherein the ultrasonic power of the ultrasonic dispersion treatment in the step (1) is 200-1000W, and the ultrasonic time is 0.5-5 h.

6. The method for preparing the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 1, wherein the irradiation treatment in the step (1) is one of laser pulse treatment, microwave treatment, ultraviolet treatment, gamma ray treatment and plasma beam treatment.

7. The preparation method of the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 6, wherein the graphene/polypyrrole/water-soluble polymer ternary composite material is prepared by the following steps,

when the irradiation treatment is laser pulse treatment, the wavelength of laser is 355-1064 nm, the laser intensity is 0.0001-500J/pulse, the pulse width is 1 picosecond-100 nanosecond, and the pulse frequency is 1-100 Hz;

when the irradiation treatment is microwave treatment, the microwave frequency is 20-20000 MHZ, the time is 0.1-400 min, and the microwave output power is 50-50000W;

when the irradiation treatment is ultraviolet treatment, the wavelength of ultraviolet light is 100-400 nm, the power is 50-5000W, and the treatment time is 0.1-400 min;

when the irradiation treatment is gamma ray treatment, the dose of the gamma ray is 0.01-1000 Gy, and the treatment time is 0.1-400 min;

when the irradiation treatment is plasma beam treatment, the current intensity of the emitted plasma beam is 0.01-100A, and the treatment time is 0.1-400 min.

8. The method for preparing the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 1, wherein the freeze drying in the step (2) is one of supercritical carbon dioxide drying, directional freeze drying and non-directional freeze drying.

9. The preparation method of the graphene/polypyrrole/water-soluble polymer ternary composite material according to claim 8, wherein the freezing temperature of the directional freeze drying or the non-directional freeze drying is-196 ℃ to-2 ℃, the drying temperature is 0 ℃ to 50 ℃, the drying vacuum degree is 3Pa to 30000Pa, and the drying time is 5h to 96 h.

10. The graphene/polypyrrole/water-soluble polymer ternary composite material prepared by the preparation method according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of polymer composite materials, in particular to a graphene/polypyrrole/water-soluble polymer ternary composite material and a preparation method thereof.

Background

Graphene is a polymer made of carbon atoms in sp²The carbon atoms are regularly arranged in the honeycomb lattice structure unit. The special atomic structure of graphene makes it have many unique properties: the tensile strength reaches 130GPa, the elastic modulus reaches 1.1TPa, and the hardness reaches 4.5 multiplied by 10⁸Nm Kg^-1The strength of the material is dozens of times of that of steel, and the material is the highest in strength and hardness among known materials. It has very large specific surface area, and the specific surface area of single-layer graphene is as high as 2.6 multiplied by 10³m²g^-1(ii) a At room temperature, its carrier is in SiO₂Mobility on substrate 10⁴m²v^-1s^-1Conductivity of 10⁴S/cm, which is the material with the best conductivity at room temperature; the thermal conductivity at room temperature is 4.40 multiplied by 10³W m^-1k^-1～5.78×10³W m^-1k^-1Insofar as it is the material having the highest thermal conductivity so far.

High polymer materials such as conductive polymers have excellent structure and physicochemical properties, so that the high polymer materials become a research focus in the field of material science from the discovery. The conductive polymer has great application value in the fields of semiconductor materials, electromagnetic materials, sensors, energy sources, photoelectric devices, life sciences and the like.

Polypyrrole is a typical representative of conductive polymers, has the advantages of convenient synthesis, no need of strong acid and strong alkali environments, low polymerization potential, good air stability, good mechanical tolerance, high biocompatibility, lower cost, good conductivity, photoelectric property, thermoelectric property and the like, and is a conductive polymer with ideal overall performance. However, the solubility of graphene and polypyrrole in common polymer materials is poor, thereby limiting the wide application of graphene and polypyrrole.

In a broad sense, the conductivity is less than 10^-11The S/cm material is called as insulating material, and the conductivity is 10^-6～10^-11The material between S/cm is called antistatic material, and the conductivity is more than 10^-6The S/cm material is called a conductive material. The conductivity of the common polymer material is 10^-13-10^-15The antistatic polymer material has high insulation property between S/cm, and is easy to gather static charge after contacting or rubbing with other substances, so that normal production and work are hindered, even explosion and fire can be caused, and therefore, under the specific working environment or dynamic operation condition of industries such as coal mine underground, textile equipment, electronic and electric appliances and the like, a polymer product is required to have an antistatic function; meanwhile, with the rapid development of the electronic industry, the information technology and other industries, higher requirements are also put forward on the conductivity of the conductive material. Therefore, the polymer is subjected to antistatic and conductive functional modification, and the engineering application range of the polymer is expanded, so that the polymer has important significance.

The preparation method of the conductive polymer composite material is generally to compound conductive fillers such as graphene, polypyrrole and the like with a polymer matrix by a melt blending method, the method is time-consuming and energy-consuming, the dispersibility of the fillers in the polymer is poor due to the polarity difference between the fillers and the polymer, and the finally obtained polymer material is poor in conductivity. And the conductive fillers such as graphene and polypyrrole are easy to disperse in the solution, so that the conductive polymer composite material with uniformly dispersed fillers can be easily obtained by a solution compounding method or an in-situ polymerization method, and the conductive polymer composite material is expected to be applied to the fields of electromagnetic shielding materials, flexible sensors, wearable equipment and the like.

Disclosure of Invention

In order to solve the technical problem of poor dispersibility of the filler in the high polymer material, the invention provides the graphene/polypyrrole/water-soluble high polymer ternary composite material and the preparation method thereof.

The invention is realized by the following technical scheme:

a preparation method of a graphene/polypyrrole/water-soluble polymer ternary composite material comprises the following steps:

(1) adding a graphene oxide aqueous dispersion into a hydrothermal reaction kettle, adding a pyrrole monomer, a morphology control agent, an oxidant and a complexing agent into the graphene oxide aqueous dispersion, performing ultrasonic dispersion treatment to uniformly disperse the pyrrole monomer on a graphene oxide sheet layer, heating the hydrothermal reaction kettle, and performing laser pulse, microwave, ultraviolet ray, gamma ray or plasma beam irradiation treatment to quickly oxidize the pyrrole monomer on the graphene sheet layer into polypyrrole to obtain a graphene/polypyrrole/water-soluble polymer ternary hybrid hydrogel;

(2) and (3) carrying out freeze drying on the graphene/polypyrrole/water-soluble polymer ternary hybrid hydrogel to obtain the graphene/polypyrrole/water-soluble polymer ternary composite material.

Further, the concentration of the graphene oxide aqueous dispersion in the step (1) is 0.05-10 mg/mL, and the mass ratio of the graphene oxide aqueous dispersion to the pyrrole monomer is (0.1-30): 1;

the water-soluble polymer matrix is one or more of carboxymethyl starch, starch acetate, hydroxymethyl cellulose, carboxymethyl cellulose, hydroxypropyl methyl cellulose, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polyacrylic acid, polyacrylamide and polyacrylate, and the dosage of the water-soluble polymer matrix in the graphene oxide aqueous dispersion is 0.01-10 g/L.

The morphology control agent is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, hexadecyl trimethyl ammonium bromide, dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, benzyl triethyl ammonium chloride, sodium lignosulfonate, BYK-190 and BYK-192, and the dosage of the morphology control agent in the graphene oxide aqueous dispersion is 0.001-0.8 mol/L.

The complexing agent is one or more of polyether amine D-230, D-400, D-2000, D-4000, ED-600, ED-900, ED-2003, EDR-148, T-403, T-3000 and T-5000, and the dosage of the complexing agent in the graphene oxide aqueous dispersion is 0.02-10 g/L. The polyether amine complexing agent fixes polypyrrole particles on the graphene sheet layer through the complexing effect of the terminal amino groups.

The oxidant is one or more of ferric chloride, ammonium persulfate, hydrogen peroxide, potassium iodate and potassium dichromate, and the dosage of the oxidant in the graphene oxide aqueous dispersion is 0.01-8 g/L.

Further, in the step (1), the heating temperature of the hydrothermal reaction kettle is 100-200 ℃, and the heating reaction time is 10-20 hours.

Further, the ultrasonic power of the ultrasonic dispersion treatment in the step (1) is 200-1000W, and the ultrasonic time is 0.5-5 h.

Further, when the irradiation treatment in the step (1) is laser pulse treatment, the wavelength of the laser is 355-1064 nm, the laser intensity is 0.0001-500J/pulse, the pulse width is 1 picosecond-100 nanoseconds, and the pulse frequency is 1-100 Hz;

when the irradiation treatment is microwave treatment, the microwave frequency is 20-20000 MHZ, the time is 0.1-400 min, and the microwave output power is 50-50000W;

when the irradiation treatment is ultraviolet treatment, the wavelength of ultraviolet light is 100-400 nm, the power is 50-5000W, and the treatment time is 0.1-400 min;

when the irradiation treatment is gamma ray treatment, the dose of the gamma ray is 0.01-1000 Gy, and the treatment time is 0.1-400 min;

when the irradiation treatment is plasma beam treatment, the current intensity of the emitted plasma beam is 0.01-100A, and the treatment time is 0.1-400 min.

Further, the freeze drying in the step (2) is one of supercritical carbon dioxide drying, directional freeze drying and non-directional freeze drying, wherein the freeze temperature of the directional freeze drying or the non-directional freeze drying is-196 to-2 ℃, the drying temperature is 0 to 50 ℃, the drying vacuum degree is 3 to 30000Pa, and the drying time is 5 to 96 hours.

The invention also provides a graphene/polypyrrole/water-soluble polymer ternary composite material prepared by the method.

The beneficial technical effects are as follows:

(1) the method disclosed by the invention is used for carrying out high-temperature and high-pressure hydrothermal reaction in a closed environment, and enhancing the capability of oxidizing pyrrole by an oxidant by matching with irradiation treatment, so that pyrrole monomers dispersed on a graphene sheet layer are quickly oxidized into polypyrrole, and the polymer/graphene/polypyrrole ternary hybrid hydrogel is obtained;

the graphene oxide is used as a framework for bearing a water-soluble polymer matrix and polypyrrole due to the fact that the graphene oxide has a light porous three-dimensional network structure, the polypyrrole is generated on the graphene oxide framework in situ and penetrates through the water-soluble polymer matrix through a three-dimensional mutual lapping network structure formed by hybridization with the polypyrrole, and the conductivity of the prepared ternary composite material is remarkably improved, the conductivity of the graphene/polypyrrole/water-soluble polymer ternary composite material is 3-8 orders of magnitude higher than that of the traditional water-soluble polymer conductive composite material, because the natural network structure of the graphene oxide can load the polypyrrole on the network structure of the graphene oxide to form a prefabricated conductive network framework, a polypyrrole network with three-dimensional conjugated pi bonds on the conductive network framework and a graphene oxide network with two-dimensional conjugated bonds form a synergistic effect, and the transportation capacity of current carriers in the ternary composite material is greatly improved, thereby improving the conductivity of the ternary composite material;

in addition, the polypyrrole particle bulges generated in situ on the graphene oxide lamellar structure increase the relative sliding roughness between the graphene/polypyrrole conductive framework and the water-soluble polymer chain, so that the tensile strength and toughness of the composite material can be improved, and the problem of poor dispersibility of graphene and polypyrrole in a polymer matrix can be solved by in-situ compounding with the water-soluble polymer material.

(2) According to the invention, a water-soluble polymer matrix and other raw materials are added into the graphene oxide aqueous dispersion simultaneously, and a 'one-pot' method hydrothermal reaction is adopted to prepare the ternary hybrid hydrogel in situ, so that two steps of preparing the conductive framework and compounding the polymer matrix are combined into one, the production process is simplified, and the use of chemical reagents is reduced, thereby improving the production efficiency and reducing the environmental pollution in the preparation process of the composite material; in addition, the composite material prepared by the method has few problems of local agglomeration, and the formed composite material has high uniformity. The graphene/polypyrrole conductive framework is uniformly distributed in the composite material in a penetrating manner, so that the prepared composite material has high conductivity; meanwhile, the graphene/polypyrrole conductive framework and the water-soluble polymer matrix are mutually occluded and restrained due to interaction between the graphene/polypyrrole conductive framework and the water-soluble polymer matrix, so that the synergistic deformation resistance of the conductive framework network and the water-soluble polymer matrix is remarkably improved, the strength and toughness of the composite material are further improved, and the problem that the mechanical property of the conventional blending composite material is reduced due to separation of two phases is solved.

(3) The method has the advantages of simple operation, low cost and easy structure regulation, and can be widely applied to conductive composite materials and rigidity-toughness balance composite materials.

Detailed Description

The invention is further described below with reference to specific examples, but without limiting the scope of the invention.