CN103772975B - Graphene/composite conducting polymer material - Google Patents

Graphene/composite conducting polymer material Download PDF

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Publication number
CN103772975B
CN103772975B CN201210411231.2A CN201210411231A CN103772975B CN 103772975 B CN103772975 B CN 103772975B CN 201210411231 A CN201210411231 A CN 201210411231A CN 103772975 B CN103772975 B CN 103772975B
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graphene
graphite oxide
polymer
temperature
ester
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CN103772975A (en
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高艳
翟春熙
刘畅
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Heilongjiang Xinda Enterprise Group Co Ltd
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Heilongjiang Xinda Enterprise Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Abstract

The invention belongs to engineering materials field, be specifically related to a kind of high-performance high connductivity, thermal conductivity graphene/polymer composites preparation method.Matrix material contains the single or multiple lift Graphene containing 80-95wt% high molecular polymer, 0-15wt%, 0.1-2wt% oxidation inhibitor, the softening agent of 0.1-3wt%.Obtained matrix material has excellent conductivity, and higher heat-drawn wire and good mechanical property, can be widely used in ultracapacitor, automobile anti-electrostatic mud guard, door handle, mirror case and Turnover Box.

Description

Graphene/composite conducting polymer material
Technical field
The invention belongs to engineering materials field, be specifically related to a kind of high-performance high connductivity, thermal conductivity graphene/polymer composites and preparation method thereof.
Background technology
Graphene is that one has sp 2the carbonaceous novel material of the bi-dimensional cellular shape crystalline network that the carbon atom of hydridization is tightly packed, thickness is one or more atomic shell.Graphene shows excellent electron transport ability, and under room temperature, its electronic mobility is up to 15000cm 2/ VS.
The key of preparation High-performance graphene/composite conducting polymer material is to obtain the single Graphene of the number of plies and Graphene in the polymer dispersed.Up to the present, Graphene obtains by once four kinds of methods: chemical vapor deposition method, epitaxial growth method, mechanically peel method and oxidation reduction process, only has oxidation reduction process to make a large amount of Graphene be applied to matrix material.Graphene/polymer composites can realize mutual supplement with each other's advantages and the reinforcement of material, and Graphene greatly can improve the mechanical property of polymer materials, and this is because Graphene has high specific surface area, strong nano material-basal body interface effect and sp 2the excellent mechanical properties of hydridization.Graphene/polymer composites has good electroconductibility, can be widely used in ultracapacitor, automobile anti-electrostatic mud guard, door handle, mirror case and Turnover Box etc.The preparation method of current Graphene/polymer composites can adopt melting, solution and local reduction way, but only have the method for melt blending to realize suitability for industrialized production, consequent problem is Graphene from agglomeration traits, can affect its specific conductivity like this, conductivity can not get fully playing.
Summary of the invention
The invention provides a kind of preparation method of effective Graphene/polymer composites, be characterized in taking natural flake graphite as raw material, by improve Hummers legal system for graphite oxide, surface modification is carried out by the compound with hydrophobic functional group, improve its lipophilicity, ultrasonic stripping modified graphite oxide, then reductive agent is utilized to reduce, conjugated system is recovered, electroconductibility is recovered, retain small portion solvent, make it disperse in a solvent, adopt the mode of the melt blending such as twin screw, singe screw to obtain final matrix material.
Technical scheme of the present invention is such: the preparation of Graphene/composite conducting polymer material, and its step is as follows:
(1) preparation of graphite oxide (GO)
Ice-water bath or there is condensing equipment reactor in add the appropriate vitriol oil, and slowly add Graphite Powder 99 and SODIUMNITRATE solid when stirring, gradation adds potassium permanganate again, control temperature is within the scope of 0-20 DEG C, then continue to stir, heat up subsequently, temperature must not more than 40 DEG C, react 30-80min under agitation, with appropriate deionized water dilute reaction solution, then with reductive agent by unreacted oxidant reduction, finally solid-liquid mixed solution to be separated with whizzer with a large amount of deionized water wash, remove supernatant liquid and obtain graphite oxide (GO).
(2) graphite oxide (GO) modification
Graphite oxide and the amine containing aliphatic chain or aromatic base, carboxylic-acid and ester class are dispersed or dissolved in suitable organic solvent, as DMSO, benzene, toluene, acetone, hexanaphthene, DMF etc., then react 0-5h under acid or alkaline conditions, obtain modified graphite oxide dispersion liquid.
(3) reduction of graphite oxide (GO)
By graphite oxide dispersion at ultrasonic power 10-50000W, frequency is 10-100000Hz, and temperature is 20-250 DEG C, ultrasonic disperse 10-400min, add reductive agent 0.1-150wt% again, continue ultrasonic 10-20h, obtain homodisperse single or multiple lift graphene solution.Wherein reductive agent is at least one in hydrazine hydrate, sodium borohydride, vitamins C and natrium hydrocitricum.
(4) preparation of Graphene/polymkeric substance
By the single or multiple lift Graphene of 80-95wt% high molecular polymer, 0-15wt%, 0.1-2wt% oxidation inhibitor, the softening agent of 0.1-3wt% joins in singe screw or twin screw extruder, melt blending 1-30min in temperature 10-380 DEG C, extruded stock grain, injection moulding, obtains the preparation of polymer/graphene conducing composite material.Wherein singe screw or twin screw extruder are through transformation, make it have ultrasound functions, advantageously in Graphene dispersion in the polymer, prevent Graphene from reuniting.
Polymkeric substance in above-mentioned steps is at least one in nylon 6, nylon66 fiber, polyaniline, polymeric amide, polypropylene, urethane, polyvinyl chloride, poly(lactic acid), ABS, PC, resol, epoxy resin.
Oxidation inhibitor in above-mentioned steps is at least one in tetramethylolmethane, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, three (2,4-di-tert-butyl-phenyl) ester, the positive octadecanol ester of propionic acid, tricresyl phosphite (2,4-di-t-butyl) ester.
Softening agent in above-mentioned steps is at least one in stearic acid, phthalic ester and aliphatics dicarboxylic acid esters.
Embodiment
Following instance belongs to field of the present invention, but the present invention is not limited to example.
Embodiment 1:
(1) first before extruding pelletization, by nylon 66 material 60-80 DEG C of forced air drying 10 hours.
(2) each component and press 100wt% calculate, the pretreated nylon 66 material 95-98wt% of precise also adds 1-2wt% oxidation inhibitor N-sec.-propyl-N '-diphenyl-para-phenylene diamine, the softening agent stearic acid of 1-3wt%.Mixture is mixed on high mixer, then melt blending on the twin screw extruder, through extruding dies traction slivering, be cooled with circulating water cooling in the sink, after directly drawing, be cut into particle by dicing machine, and injection moulding on injection moulding machine.
(3) extrusion temperature is at 180-300 DEG C, obtains nylon 66 material pelletizing, and injection temperature is 200-350 DEG C, and die temperature is 150-200 DEG C, obtains the mould of detectability energy.
Embodiment 2:
(1) first before extruding pelletization, by nylon 66 material 60-80 DEG C of forced air drying 10 hours.
(2) ice-water bath or there is condensing equipment reactor in add the appropriate vitriol oil, and the SODIUMNITRATE solid of natural flake graphite 3g and q.s is slowly added when stirring, gradation adds potassium permanganate again, control temperature is within the scope of 0-20 DEG C, then continue to stir, heat up subsequently, temperature must not more than 40 DEG C, react 30-80min under agitation, with appropriate deionized water dilute reaction solution, then with reductive agent by unreacted oxidant reduction, finally solid-liquid mixed solution to be separated with whizzer with a large amount of deionized water wash, remove supernatant liquid and obtain graphite oxide (GO).
(3) graphite oxide and the isocyanic ester containing phenyl ring are dissolved in DMF by stirring, then react 3-5h in the basic conditions, obtain modified graphite oxide dispersion liquid.
(4) by graphite oxide dispersion at ultrasonic power 40000-50000W, frequency is 80000-100000Hz, and temperature is 50-80 DEG C, ultrasonic disperse 300-400min, add reductive agent hydrazine hydrate 110-150wt% again, continue ultrasonic 10-14h, obtain homodisperse single or multiple lift graphene solution.
(5) by the modified graphene of 80-95wt% high molecular polymer, 0.1-0.2wt%, 0.1-2wt% oxidation inhibitor N-sec.-propyl-N '-diphenyl-para-phenylene diamine, the softening agent stearic acid of 0.1-3wt% joins in twin screw extruder, wherein twin screw extruder does not have ultrasound functions, melt blending 1-30min in temperature 180-300 DEG C, extruded stock grain, injection temperature is 200-350 DEG C, die temperature is 150-200 DEG C, injection moulding, obtains polymer/graphene conducing composite material.
Embodiment 3:
(1) first before extruding pelletization, by nylon 66 material 60-80 DEG C of forced air drying 10 hours.
(2) ice-water bath or there is condensing equipment reactor in add the appropriate vitriol oil, and the SODIUMNITRATE solid of natural flake graphite 3g and q.s is slowly added when stirring, gradation adds potassium permanganate again, control temperature is within the scope of 0-20 DEG C, then continue to stir, heat up subsequently, temperature must not more than 40 DEG C, react 30-80min under agitation, with appropriate deionized water dilute reaction solution, then with reductive agent by unreacted oxidant reduction, finally solid-liquid mixed solution to be separated with whizzer with a large amount of deionized water wash, remove supernatant liquid and obtain graphite oxide (GO).
(3) graphite oxide and the isocyanic ester containing phenyl ring are dissolved in DMF by stirring, then react 3-5h in the basic conditions, obtain modified graphite oxide dispersion liquid.
(4) by graphite oxide dispersion at ultrasonic power 40000-50000W, frequency is 80000-100000Hz, and temperature is 50-80 DEG C, ultrasonic disperse 300-400min, add reductive agent hydrazine hydrate 110-150wt% again, continue ultrasonic 10-14h, obtain homodisperse single or multiple lift graphene solution.
(5) by the modified graphene of 80-95wt% high molecular polymer, 0.1-0.2wt%, 0.1-2wt% oxidation inhibitor N-sec.-propyl-N '-diphenyl-para-phenylene diamine, the softening agent stearic acid of 0.1-3wt% joins in twin screw extruder, wherein twin screw extruder makes it have ultrasound functions through our transformation, melt blending 1-30min in temperature 180-300 DEG C, extruded stock grain, injection temperature is 200-350 DEG C, die temperature is 150-200 DEG C, injection moulding, obtains polymer/graphene conducing composite material.
Test performance of the present invention is as shown in table 1
Test event Testing standard Embodiment 1 Embodiment 2 Embodiment 3
Tensile strength (MPa) GB/T 1040-2006 37 35 50
Modulus in flexure (GPa) GB/T 1843-2008 0.8 1.3 1.6
Second-order transition temperature (DEG C) GB/T 1634.2-2004 0 6 31
Specific conductivity (S/m) 10 -8 10 -6 10 -4

Claims (4)

1. a high-performance high connductivity, thermal conductivity graphene/polymer composites, it is characterized in that: each component calculates by 100wt%, containing the single or multiple lift Graphene of 80-95wt% high molecular polymer, 0-15wt%, 0.1-2wt% oxidation inhibitor, the softening agent of 0.1-3wt%;
The preparation method of described matrix material, comprises the following steps:
(1) preparation of graphite oxide, ice-water bath or there is condensing equipment reactor in add the appropriate vitriol oil, and slowly add Graphite Powder 99 and SODIUMNITRATE solid when stirring, gradation adds potassium permanganate again, control temperature is within the scope of 0-20 DEG C, then continue to stir, heat up subsequently, temperature must not more than 40 DEG C, react 30-80min under agitation, with appropriate deionized water dilute reaction solution, then with reductive agent by unreacted oxidant reduction, finally solid-liquid mixed solution to be separated with whizzer with a large amount of deionized water wash, remove supernatant liquid and obtain graphite oxide,
(2) graphite oxide modification, is dispersed or dissolved in graphite oxide in suitable organic solvent with the amine containing aliphatic chain or aromatic base, carboxylic-acid and ester class and then reacts 0-5h under acid or alkaline conditions, obtain modified graphite oxide dispersion liquid; Wherein, described organic solvent is at least one in DMSO, benzene, toluene, acetone, hexanaphthene and DMF;
(3) reduction of graphite oxide, by graphite oxide dispersion at ultrasonic power 10-50000W, frequency is 10-100000Hz, temperature is 20-250 DEG C, ultrasonic disperse 10-400min, then add reductive agent 0.1-150wt%, continue ultrasonic 10-20h, obtain homodisperse single or multiple lift graphene solution, wherein reductive agent is at least one of hydrazine hydrate, sodium borohydride, vitamins C and natrium hydrocitricum;
(4) preparation of Graphene/polymkeric substance, by the single or multiple lift Graphene of 80-95wt% high molecular polymer, 0-15wt%, 0.1-2wt% oxidation inhibitor, the softening agent of 0.1-3wt% joins in singe screw or twin screw extruder, melt blending 1-30min in temperature 10-380 DEG C, extruded stock grain, injection moulding, obtain polymer/graphene conducing composite material, wherein singe screw or twin screw extruder are through transformation, make it have ultrasound functions, advantageously in Graphene dispersion in the polymer, prevent Graphene from reuniting.
2. high-performance high connductivity, thermal conductivity graphene/polymer composites as claimed in claim 1, is characterized in that polymkeric substance is at least one in polyaniline, polymeric amide, polypropylene, urethane, polyvinyl chloride, poly(lactic acid), ABS, PC, resol, epoxy resin.
3. high-performance conductive, thermal conductivity graphene/polymer composites as claimed in claim 1, it is characterized in that oxidation inhibitor is at least one in tetramethylolmethane, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, three (2,4-di-tert-butyl-phenyl) ester, the positive octadecanol ester of propionic acid, tricresyl phosphite (2,4-di-t-butyl) ester.
4. high-performance high connductivity, thermal conductivity graphene/polymer composites as claimed in claim 1, is characterized in that softening agent is at least one in stearic acid, phthalic ester and aliphatics dicarboxylic acid esters.
CN201210411231.2A 2012-10-25 2012-10-25 Graphene/composite conducting polymer material Expired - Fee Related CN103772975B (en)

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