CN111440330A - High-conductivity graphene in-situ grafted polyurethane material and preparation method thereof - Google Patents
High-conductivity graphene in-situ grafted polyurethane material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of polyurethane, and discloses a high-conductivity graphene in-situ grafted polyurethane material which comprises the following formula raw materials and components: the modified graphene material comprises functionalized graphene, an isocyanate monomer, polyester polyol, dibutyltin dilaurate, a micromolecular chain extender, aniline and ammonium persulfate. According to the high-conductivity graphene in-situ grafted polyurethane material, aniline reacts with an isocyanate group at the chain end of polyurethane to generate an aromatic amide group with high activity, potassium persulfate is used as an initiator and is subjected to a free radical polymerization process with aniline to form a polyaniline-polyurethane copolymer, and the amino group at the chain end of polyaniline reacts with an epoxy group of functionalized graphene to enable polyaniline-polyurethane to be copolymerized in situ on the surface of graphene, so that the compatibility of graphene and polyurethane is improved, polyaniline molecules and graphene nanoparticles with excellent conductivity form a continuous three-dimensional conductive path, and the conductivity of the polyurethane material are improved.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to a high-conductivity graphene in-situ grafted polyurethane material and a preparation method thereof.
Background
The conductive material has the characteristics of conveying and conducting current, can be divided into good conductor materials and high-resistance materials, such as conductive plastics, conductive rubber and the like, can distribute conductive media such as silver plating on glass, silver plating on aluminum, graphene and the like in a material matrix, and can be contacted with conductive particles through pressure to achieve a good conductive effect.
Polyurethane is classified into polyester type and polyether type, polyurethane has good chemical stability and mechanical property, can be made into materials such as polyurethane plastic, polyurethane fiber, polyurethane elastomer and the like, and is widely applied to the fields of household appliances, buildings, daily necessities, traffic, household appliances and the like, but polyurethane has high resistivity and poor conductivity, so that the practical application of polyurethane materials is limited, and conductive media such as nano materials such as nano silver, graphene and the like can be combined with polyurethane to enhance the conductivity of polyurethane.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a high-conductivity graphene in-situ grafted polyurethane material and a preparation method thereof, which solve the problem of low conductivity of the polyurethane material and solve the problem of poor dispersibility of graphene in polyurethane.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a high-conductivity graphene in-situ grafted polyurethane material comprises the following raw materials and components: the modified graphene-based polyurethane material comprises functionalized graphene, an isocyanate monomer, polyester polyol, dibutyltin dilaurate, a micromolecular chain extender, aniline and ammonium persulfate, wherein the isocyanate monomer is any one of isophorone diisocyanate or dimethyl biphenyl diisocyanate, and the micromolecular chain extender is any one of 1, 4-butanediol or 1, 6-hexanediol.
Preferably, the preparation method of the high-conductivity graphene in-situ grafted polyurethane material comprises the following steps:
(1) adding deionized water and graphene oxide into a reaction bottle, adding concentrated hydrochloric acid to adjust the pH value of the solution to 2-3 after uniform ultrasonic dispersion, placing the solution in a constant-temperature oil bath reactor, heating to 30-40 ℃, adding ferrous chloride after uniform stirring, stirring at a constant speed for reaction for 5-10min, slowly dropwise adding a 20-30% hydrogen peroxide aqueous solution, stirring at a constant speed for reaction for 1-2h, centrifugally separating the solution to remove the solvent, washing the solid product with dilute hydrochloric acid and deionized water in sequence, and drying to prepare the hydroxylated graphene.
(2) Adding a toluene solvent and hydroxylated graphene into a reaction bottle, adding a silane coupling agent after uniform ultrasonic dispersion, placing the reaction bottle in a constant-temperature oil bath reactor, heating to 100 ℃ and 120 ℃, stirring at a constant speed for reaction for 5-10h, carrying out reduced pressure distillation on the solution to remove the solvent, washing the solid product with deionized water and ethanol, and drying to obtain the functionalized graphene.
(3) Adding polyester polyol into a reaction bottle, heating to 65-75 ℃ in a constant-temperature oil bath reactor, adding an isocyanate monomer and a catalyst dibutyltin dilaurate, uniformly stirring for reaction for 2-3h, adding an acetone solvent for dilution, reducing the temperature to 50-60 ℃, adding a small-molecule chain extender, uniformly stirring for reaction for 2-3h, adding an aniline component 1, uniformly stirring for reaction for 2-3h, placing the reaction bottle in an ice water bath, slowly dropwise adding concentrated hydrochloric acid at 0-5 deg.C to adjust pH to 1-2, adding aniline component 2 and functionalized graphene, stirring, slowly dropwise adding aqueous solution of ammonium persulfate, stirring at constant speed for reaction for 2-4 hr, pouring the solution into a film-forming mold, and performing thermal curing film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material.
Preferably, the constant temperature oil bath reactor includes that heat preservation, heat preservation inside are provided with the oil bath groove, the inside below fixedly connected with constant temperature heating ring, the inside both sides fixedly connected with bracing piece of heat preservation, bracing piece fixedly connected with snap ring, the inside reaction flask that is provided with of snap ring, bracing piece are provided with the fixture block, fixture block swing joint have adjust the pole, adjust pole fixedly connected with stopper.
Preferably, the mass ratio of the graphene oxide, the ferrous chloride and the hydrogen peroxide in the step (1) is 1:8-15: 120-180.
Preferably, the silane coupling agent in the step (2) is any one of 3-glycidyloxypropylmethyldimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 3- (2, 3-glycidoxy) propyltrimethoxysilane, and the mass ratio of the silane coupling agent to the hydroxylated graphene is 1: 2-6.
Preferably, the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the small-molecule chain extender, the aniline component 1, the aniline component 2, the functionalized graphene and the ammonium persulfate in the step (3) is 100:40-60:4-8:0.5-1:8-15:0.5-5: 20-38.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the high-conductivity graphene in-situ grafting polyurethane material, under a ferrous chloride and hydrogen peroxide system, generated hydroxyl radicals are chemically bonded with carbon atoms on the surface of graphene oxide to obtain graphene oxide with high hydroxyl content, a large number of hydroxyl groups are easily reacted with an epoxy silane coupling agent to obtain functional graphene with high epoxy group content, aniline added in the polyurethane synthesis process reacts with isocyanate groups at the chain ends of polyurethane under the action of a catalyst to generate aromatic amide groups with high activity, the amide groups form N radical positive ions under the action of hydrochloric acid, potassium persulfate is used as an initiator, the polyaniline-polyurethane copolymer is further subjected to free radical polymerization with aniline to form polyaniline-polyurethane copolymer, and meanwhile, amino groups at the chain ends of polyaniline react with the epoxy groups of the functional graphene to enable the polyaniline-polyurethane to be copolymerized in situ on the surface of the graphene, graphene and polyurethane are organically combined through polyaniline molecules by a chemical covalent grafting method, the compatibility of the graphene and the polyurethane is obviously improved, polyaniline molecules and graphene nanoparticles with excellent conductivity are formed, a continuous three-dimensional conductive path is formed in polyurethane groups, and the graphene in-situ grafted polyurethane material shows high conductivity and excellent conductivity.
Drawings
FIG. 1 is a schematic front view of a constant temperature oil bath reactor;
FIG. 2 is a schematic top view of a snap ring;
FIG. 3 is a schematic view of adjustment lever adjustment;
fig. 4 is a scanning electron microscope SEM image of functionalized graphene;
fig. 5 is a fourier transform infrared spectrometer FT-IR plot of functionalized graphene.
1. A constant temperature oil bath reactor; 2. a heat-insulating layer; 3. an oil bath groove; 4. a constant temperature heating ring; 5. a support bar; 6. a snap ring; 7. a reaction bottle; 8. a clamping block; 9. adjusting a rod; 10 a limiting block.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a high-conductivity graphene in-situ grafted polyurethane material comprises the following raw materials and components: the modified graphene-based polyurethane material comprises functionalized graphene, an isocyanate monomer, polyester polyol, dibutyltin dilaurate, a micromolecular chain extender, aniline and ammonium persulfate, wherein the isocyanate monomer is any one of isophorone diisocyanate or dimethyl biphenyl diisocyanate, and the micromolecular chain extender is any one of 1, 4-butanediol or 1, 6-hexanediol.
The preparation method of the high-conductivity graphene in-situ grafted polyurethane material comprises the following steps:
(1) adding deionized water and graphene oxide into a reaction bottle, adding concentrated hydrochloric acid to adjust the pH value of the solution to 2-3 after ultrasonic dispersion is uniform, placing the solution into a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a heat preservation layer, an oil bath groove is arranged in the heat preservation layer, a constant-temperature heating ring is fixedly connected below the inner part of the heat preservation layer, support rods are fixedly connected to two sides of the inner part of the heat preservation layer, clamping rings are fixedly connected to the support rods, a reaction bottle is arranged in each clamping ring, each support rod is provided with a clamping block, each clamping block is movably connected with an adjusting rod, each adjusting rod is fixedly connected with a limiting block, heating is carried out to 30-40 ℃, ferrous chloride is added after stirring is uniform, stirring reaction is carried out for 5-10min at constant speed, then, a hydrogen peroxide aqueous solution with the mass fraction of, and (3) stirring at a constant speed for reaction for 1-2h, centrifugally separating the solution to remove the solvent, washing the solid product by using dilute hydrochloric acid and deionized water in sequence, and drying to prepare the hydroxylated graphene.
(2) Adding a toluene solvent and hydroxylated graphene into a reaction bottle, adding a silane coupling agent after ultrasonic dispersion is uniform, wherein the silane coupling agent is any one of 3-glycidyloxypropylmethyldimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 3- (2, 3-glycidoxy) propyltrimethoxysilane, the mass ratio of the silane coupling agent to the hydroxylated graphene is 1:2-6, placing the mixture into a constant-temperature oil bath reactor, heating to 100 ℃ and 120 ℃, stirring at a constant speed for reaction for 5-10h, distilling the solution under reduced pressure to remove the solvent, washing a solid product with deionized water and ethanol, and drying to prepare the functionalized graphene.
(3) Adding polyester polyol into a reaction bottle, heating to 65-75 ℃ in a constant-temperature oil bath reactor, adding an isocyanate monomer and a catalyst dibutyltin dilaurate, uniformly stirring for reaction for 2-3h, adding an acetone solvent for dilution, cooling to 50-60 ℃, adding a small-molecule chain extender, uniformly stirring for reaction for 2-3h, adding an aniline component 1, uniformly stirring for reaction for 2-3h, placing the reaction bottle into an ice water bath, adding slowly dropwise concentrated hydrochloric acid at 0-5 ℃ to adjust the pH of the solution to 1-2, adding an aniline component 2 and functionalized graphene, uniformly stirring, and slowly dropwise adding an aqueous solution of ammonium persulfate, wherein the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the small-molecule chain extender, the aniline component 1, the aniline component 2, the functionalized graphene to the ammonium persulfate is 100:40-60:4-8:0.5-1 8-15:0.5-5:20-38, stirring at a constant speed for reaction for 2-4h, pouring the solution into a film forming mold, and performing thermal curing film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material.
Example 1
(1) Adding deionized water and graphene oxide into a reaction bottle, adding concentrated hydrochloric acid to adjust the pH value of the solution to 2 after ultrasonic dispersion is uniform, placing the solution into a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a heat preservation layer, an oil bath groove is arranged in the heat preservation layer, a constant-temperature heating ring is fixedly connected below the inner part of the heat preservation layer, supporting rods are fixedly connected to two sides of the inner part of the heat preservation layer, clamping rings are fixedly connected to the supporting rods, a reaction bottle is arranged in each clamping ring, each supporting rod is provided with a clamping block, each clamping block is movably connected with an adjusting rod, each adjusting rod is fixedly connected with a limiting block, heating is carried out to 30 ℃, ferrous chloride is added after uniform stirring, stirring reaction is carried out at a constant speed for 5min, then, a hydrogen peroxide solution with the mass fraction of 20% is slowly dripped, and washing the solid product by using dilute hydrochloric acid and deionized water in sequence, and drying to prepare the hydroxylated graphene.
(2) Adding a toluene solvent and hydroxylated graphene into a reaction bottle, adding a silane coupling agent 3-glycidyl ether group oxypropyl methyl dimethoxysilane after uniform ultrasonic dispersion, placing the mixture and the hydroxylated graphene in a mass ratio of 1:2, heating the mixture to 100 ℃ in a constant-temperature oil bath reactor, stirring at a constant speed for reaction for 5 hours, carrying out reduced pressure distillation on the solution to remove the solvent, washing a solid product with deionized water and ethanol, and drying to prepare the functionalized graphene.
(3) Adding polyester polyol into a reaction bottle, heating to 65 ℃ in a constant-temperature oil bath reactor, adding an isocyanate monomer and a catalyst dibutyltin dilaurate, uniformly stirring for reaction for 2 hours, adding an acetone solvent for dilution, cooling to 50 ℃, adding a small molecular chain extender 1, 4-butanediol, uniformly stirring for reaction for 2 hours, adding an aniline component 1, uniformly stirring for reaction for 2 hours, placing the reaction bottle in an ice water bath, adding slowly dropwise concentrated hydrochloric acid at 5 ℃ to adjust the pH of the solution to 2, adding an aniline component 2 and functionalized graphene, uniformly stirring, slowly dropwise adding an aqueous solution of ammonium persulfate, wherein the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the small molecular chain extender, the aniline component 1, the aniline component 2, the functionalized graphene to the ammonium persulfate is 100:40:4:0.5:8:0.5:20, stirring at a constant speed for reaction for 2 hours, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material 1.
Example 2
(1) Adding deionized water and graphene oxide into a reaction bottle, adding concentrated hydrochloric acid to adjust the pH value of the solution to 3 after ultrasonic dispersion is uniform, placing the solution into a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a heat-insulating layer, an oil bath groove is arranged in the heat-insulating layer, a constant-temperature heating ring is fixedly connected below the inner part of the heat-insulating layer, supporting rods are fixedly connected to two sides of the inner part of the heat-insulating layer, clamping rings are fixedly connected to the supporting rods, a reaction bottle is arranged in each clamping ring, each supporting rod is provided with a clamping block, each clamping block is movably connected with an adjusting rod, each adjusting rod is fixedly connected with a limiting block, heating is carried out to 40 ℃, ferrous chloride is added after uniform stirring, stirring reaction is carried out at a constant speed for 5min, then, a hydrogen peroxide solution with the mass fraction of 30% is, and washing the solid product by using dilute hydrochloric acid and deionized water in sequence, and drying to prepare the hydroxylated graphene.
(2) Adding a toluene solvent and hydroxylated graphene into a reaction bottle, adding a silane coupling agent 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane after uniform ultrasonic dispersion, placing the mixture and the hydroxylated graphene in a mass ratio of 1:3 in a constant-temperature oil bath reactor, heating to 120 ℃, stirring at a constant speed for reaction for 5 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with deionized water and ethanol, and drying to prepare the functionalized graphene.
(3) Adding polyester polyol into a reaction bottle, heating the reaction bottle to 75 ℃ in a constant-temperature oil bath reactor, adding an isocyanate monomer and a catalyst dibutyltin dilaurate, uniformly stirring the mixture for reaction for 2 hours, adding an acetone solvent for dilution, cooling the temperature to 60 ℃, adding a small molecular chain extender 1, 6-hexanediol, uniformly stirring the mixture for reaction for 2 hours, adding an aniline component 1, uniformly stirring the mixture for reaction for 2 hours, placing the reaction bottle in an ice water bath, slowly dropwise adding concentrated hydrochloric acid at the temperature of 5 ℃ to adjust the pH of the solution to 2, adding an aniline component 2 and functionalized graphene, uniformly stirring the mixture, slowly dropwise adding an aqueous solution of ammonium persulfate, wherein the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the small molecular chain extender, the aniline component 1, the aniline component 2, the functionalized graphene to the ammonium persulfate is 100:45:5:0.6:10:1:25, stirring at a constant speed for reaction for 4 hours, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material 2.
Example 3
(1) Adding deionized water and graphene oxide into a reaction bottle, adding concentrated hydrochloric acid to adjust the pH value of the solution to 3 after uniform ultrasonic dispersion, placing the solution into a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a heat-insulating layer, an oil bath groove is arranged in the heat-insulating layer, a constant-temperature heating ring is fixedly connected below the inner part of the heat-insulating layer, supporting rods are fixedly connected to two sides of the inner part of the heat-insulating layer, clamping rings are fixedly connected to the supporting rods, a reaction bottle is arranged in each clamping ring, each supporting rod is provided with a clamping block, each clamping block is movably connected with an adjusting rod, each adjusting rod is fixedly connected with a limiting block, heating is carried out to 35 ℃, ferrous chloride is added after uniform stirring, the solution is stirred and reacted for 8min at a constant speed, then, a hydrogen peroxide solution with the mass fraction of 25% is slowly drippe, and washing the solid product by using dilute hydrochloric acid and deionized water in sequence, and drying to prepare the hydroxylated graphene.
(2) Adding a toluene solvent and hydroxylated graphene into a reaction bottle, adding a silane coupling agent 3- [ (2,3) -glycidoxy ] propyl methyldimethoxysilane after uniform ultrasonic dispersion, placing the mixture and the hydroxylated graphene in a mass ratio of 1:4 in a constant-temperature oil bath reactor, heating to 110 ℃, uniformly stirring for reaction for 8 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with deionized water and ethanol, and drying to prepare the functionalized graphene.
(3) Adding polyester polyol into a reaction bottle, heating to 70 ℃ in a constant-temperature oil bath reactor, adding an isocyanate monomer and a catalyst dibutyltin dilaurate, uniformly stirring for reaction for 2.5 hours, adding an acetone solvent for dilution, cooling to 55 ℃, adding a small-molecule chain extender 1, 6-hexanediol, uniformly stirring for reaction for 2 hours, adding an aniline component 1, uniformly stirring for reaction for 2.5 hours, placing the reaction bottle in an ice water bath, adding concentrated hydrochloric acid slowly dropwise at 2 ℃ to adjust the pH of the solution to 2, adding an aniline component 2 and functionalized graphene, uniformly stirring, slowly dropwise adding an aqueous solution of ammonium persulfate, wherein the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the small-molecule chain extender, the aniline component 1, the aniline component 2, the functionalized graphene to the ammonium persulfate is 100:50:6:0.8:12:2:30, stirring at a constant speed for reaction for 3 hours, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material 3.
Example 4
(1) Adding deionized water and graphene oxide into a reaction bottle, adding concentrated hydrochloric acid to adjust the pH value of the solution to 3 after ultrasonic dispersion is uniform, placing the solution into a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a heat-insulating layer, an oil bath groove is arranged in the heat-insulating layer, a constant-temperature heating ring is fixedly connected below the inner part of the heat-insulating layer, supporting rods are fixedly connected to two sides of the inner part of the heat-insulating layer, clamping rings are fixedly connected to the supporting rods, a reaction bottle is arranged in each clamping ring, each supporting rod is provided with a clamping block, each clamping block is movably connected with an adjusting rod, each adjusting rod is fixedly connected with a limiting block, heating is carried out to 30 ℃, ferrous chloride is added after uniform stirring, stirring reaction is carried out at a constant speed for 10min, then, hydrogen peroxide water solution with the mass fraction of 30% is, and washing the solid product by using dilute hydrochloric acid and deionized water in sequence, and drying to prepare the hydroxylated graphene.
(2) Adding a toluene solvent and hydroxylated graphene into a reaction bottle, adding a silane coupling agent 3- (2, 3-epoxypropoxy) propyl trimethoxy silane after uniform ultrasonic dispersion, placing the mixture and the hydroxylated graphene in a mass ratio of 1:5 in a constant-temperature oil bath reactor, heating to 120 ℃, stirring at a constant speed for reaction for 8 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with deionized water and ethanol, and drying to prepare the functionalized graphene.
(3) Adding polyester polyol into a reaction bottle, heating the reaction bottle to 75 ℃ in a constant-temperature oil bath reactor, adding an isocyanate monomer and a catalyst dibutyltin dilaurate, uniformly stirring the mixture for reaction for 2 hours, adding an acetone solvent for dilution, cooling the temperature to 60 ℃, adding a small molecular chain extender 1, 4-butanediol, uniformly stirring the mixture for reaction for 3 hours, adding an aniline component 1, uniformly stirring the mixture for reaction for 3 hours, placing the reaction bottle in an ice water bath, adding concentrated hydrochloric acid slowly dropwise at 0 ℃ to adjust the pH of the solution to 2, adding an aniline component 2 and functionalized graphene, uniformly stirring the mixture, slowly dropwise adding an aqueous solution of ammonium persulfate, wherein the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the small molecular chain extender, the aniline component 1, the aniline component 2, the functionalized graphene to the ammonium persulfate is 100:55:7:0.8:14:3.5:34, stirring at a constant speed for reaction for 4 hours, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material 4.
Example 5
(1) Adding deionized water and graphene oxide into a reaction bottle, adding concentrated hydrochloric acid to adjust the pH value of the solution to 2 after uniform ultrasonic dispersion, placing the solution into a constant-temperature oil bath reactor, wherein the constant-temperature oil bath reactor comprises a heat-insulating layer, an oil bath groove is arranged in the heat-insulating layer, a constant-temperature heating ring is fixedly connected below the inner part of the heat-insulating layer, supporting rods are fixedly connected to two sides of the inner part of the heat-insulating layer, clamping rings are fixedly connected to the supporting rods, a reaction bottle is arranged in each clamping ring, each supporting rod is provided with a clamping block, each clamping block is movably connected with an adjusting rod, each adjusting rod is fixedly connected with a limiting block, heating is carried out to 40 ℃, adding ferrous chloride after uniform stirring, carrying out uniform stirring reaction for 10min, slowly dropwise adding a hydrogen peroxide solution with the mass fraction of 30%, controlling the mass ratio of, and washing the solid product by using dilute hydrochloric acid and deionized water in sequence, and drying to prepare the hydroxylated graphene.
(2) Adding a toluene solvent and hydroxylated graphene into a reaction bottle, adding a silane coupling agent 3-glycidyl ether group oxypropyl methyl dimethoxysilane after uniform ultrasonic dispersion, placing the mixture and the hydroxylated graphene in a constant-temperature oil bath reactor with the mass ratio of 1:6, heating to 120 ℃, stirring at a constant speed for reaction for 10 hours, distilling the solution under reduced pressure to remove the solvent, washing the solid product with deionized water and ethanol, and drying to prepare the functionalized graphene.
(3) Adding polyester polyol into a reaction bottle, heating the reaction bottle to 75 ℃ in a constant-temperature oil bath reactor, adding an isocyanate monomer and a catalyst dibutyltin dilaurate, uniformly stirring the mixture for reaction for 3 hours, adding an acetone solvent for dilution, cooling the temperature to 60 ℃, adding a small molecular chain extender 1, 4-butanediol, uniformly stirring the mixture for reaction for 3 hours, adding an aniline component 1, uniformly stirring the mixture for reaction for 3 hours, placing the reaction bottle in an ice water bath, adding concentrated hydrochloric acid dropwise slowly at 0 ℃ to adjust the pH of the solution to 1, adding an aniline component 2 and functionalized graphene, uniformly stirring the mixture, slowly adding an aqueous solution of ammonium persulfate dropwise, wherein the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the small molecular chain extender, the aniline component 1, the aniline component 2, the functionalized graphene to the ammonium persulfate is 100:60:8:1:15:5:38, stirring at a constant speed for reaction for 4 hours, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material 5.
The conductivity of the highly conductive graphene in-situ grafted polyurethane materials 1-5 in the examples was tested by using an ino L ab Cond7110 conductivity meter, with the test standard GB/T29288-.
In summary, in the highly conductive graphene in-situ grafting polyurethane material, a hydroxyl radical generated in a ferrous chloride and hydrogen peroxide system is chemically bonded with a carbon atom on the surface of graphene oxide to obtain graphene oxide with high hydroxyl content, a large number of hydroxyl groups are easily reacted with an epoxy silane coupling agent to obtain functionalized graphene with high epoxy group content, aniline added in the polyurethane synthesis process reacts with an isocyanate group at the end of polyurethane chain under the action of a catalyst to generate an aromatic amide group with high activity, the amide group forms N radical positive ions under the action of hydrochloric acid, potassium persulfate is used as an initiator to further perform free radical polymerization with aniline to form a polyaniline-polyurethane copolymer, and meanwhile, the amino group at the end of the polyaniline chain is reacted with the epoxy group of the functionalized graphene, polyaniline-polyurethane is subjected to in-situ copolymerization on the surface of graphene, the graphene and the polyurethane are organically combined through polyaniline molecules by a chemical covalent grafting method, the compatibility of the graphene and the polyurethane is remarkably improved, polyaniline molecules and graphene nanoparticles with excellent conductivity are formed in a polyurethane group, and a continuous three-dimensional conductive path is formed, so that the graphene in-situ grafted polyurethane material has high conductivity and excellent conductivity.
Claims (6)
1. The high-conductivity graphene in-situ grafted polyurethane material comprises the following raw materials and components, and is characterized in that: the modified graphene-based polyurethane material comprises functionalized graphene, an isocyanate monomer, polyester polyol, dibutyltin dilaurate, a micromolecular chain extender, aniline and ammonium persulfate, wherein the isocyanate monomer is any one of isophorone diisocyanate or dimethyl biphenyl diisocyanate, and the micromolecular chain extender is any one of 1, 4-butanediol or 1, 6-hexanediol.
2. The highly conductive graphene in-situ grafted polyurethane material according to claim 1, wherein: the preparation method of the high-conductivity graphene in-situ grafted polyurethane material comprises the following steps:
(1) adding graphene oxide into deionized water, adding concentrated hydrochloric acid to adjust the pH value of the solution to 2-3 after uniform ultrasonic dispersion, placing the solution in a constant-temperature oil bath reactor, heating the solution to 30-40 ℃, adding ferrous chloride, reacting for 5-10min, slowly dropwise adding a 20-30% hydrogen peroxide aqueous solution, reacting for 1-2h, centrifugally separating, washing and drying to prepare hydroxylated graphene;
(2) adding hydroxylated graphene into a toluene solvent, adding a silane coupling agent after ultrasonic dispersion is uniform, placing the mixture into a constant-temperature oil bath reactor, heating to 120 ℃ for reaction for 5-10h, and carrying out reduced pressure distillation, washing and drying to prepare functionalized graphene;
(3) adding an isocyanate monomer and a catalyst dibutyltin dilaurate into polyester polyol, heating to 65-75 ℃ in a constant-temperature oil bath reactor, reacting for 2-3h, adding an acetone solvent, diluting, cooling to 50-60 ℃, adding a small-molecule chain extender, reacting for 2-3h, adding an aniline component 1, reacting for 2-3h, adding slowly dropwise concentrated hydrochloric acid at 0-5 ℃ to adjust the pH of the solution to 1-2, adding an aniline component 2 and functionalized graphene, slowly dropwise adding an aqueous solution of ammonium persulfate, reacting for 2-4h, pouring the solution into a film forming mold, and performing thermosetting film forming to prepare the high-conductivity graphene in-situ grafted polyurethane material.
3. The highly conductive graphene in-situ grafted polyurethane material as claimed in claim 2, wherein: the constant temperature oil bath reactor comprises a heat preservation layer, an oil bath groove arranged inside the heat preservation layer, a constant temperature heating ring fixedly connected to the inner lower portion of the heat preservation layer, supporting rods fixedly connected to the two sides inside the heat preservation layer, a clamping ring fixedly connected to the supporting rods, reaction bottles arranged inside the clamping ring, clamping blocks arranged inside the clamping ring, adjusting rods movably connected to the clamping blocks, and limiting blocks fixedly connected to the adjusting rods.
4. The highly conductive graphene in-situ grafted polyurethane material as claimed in claim 2, wherein: the mass ratio of the graphene oxide, the ferrous chloride and the hydrogen peroxide in the step (1) is 1:8-15: 120-180.
5. The highly conductive graphene in-situ grafted polyurethane material as claimed in claim 2, wherein: the silane coupling agent in the step (2) is any one of 3-glycidyloxypropylmethyldimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane and 3- (2, 3-glycidoxy) propyltrimethoxysilane, and the mass ratio of the silane coupling agent to the hydroxylated graphene is 1: 2-6.
6. The highly conductive graphene in-situ grafted polyurethane material as claimed in claim 2, wherein: the mass ratio of the polyester polyol, the isocyanate monomer, the dibutyltin dilaurate, the micromolecular chain extender, the aniline component 1, the aniline component 2, the functionalized graphene and the ammonium persulfate in the step (3) is 100:40-60:4-8:0.5-1:8-15:0.5-5: 20-38.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848173A (en) * | 2020-07-28 | 2020-10-30 | 郑州大学 | Three-dimensional porous silicon carbide ceramic aerogel and preparation method thereof |
| CN112592489A (en) * | 2020-12-15 | 2021-04-02 | 嘉兴市嘉誉科技有限公司 | High-thermal-conductivity graphene in-situ grafted polyurethane elastomer and preparation method thereof |
| CN114974737A (en) * | 2022-05-30 | 2022-08-30 | 珠海思科信电线电缆有限公司 | Corrosion-resistant high-flexibility coaxial cable and preparation process thereof |
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2020
- 2020-05-20 CN CN202010432510.1A patent/CN111440330A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848173A (en) * | 2020-07-28 | 2020-10-30 | 郑州大学 | Three-dimensional porous silicon carbide ceramic aerogel and preparation method thereof |
| CN112592489A (en) * | 2020-12-15 | 2021-04-02 | 嘉兴市嘉誉科技有限公司 | High-thermal-conductivity graphene in-situ grafted polyurethane elastomer and preparation method thereof |
| CN114974737A (en) * | 2022-05-30 | 2022-08-30 | 珠海思科信电线电缆有限公司 | Corrosion-resistant high-flexibility coaxial cable and preparation process thereof |
| CN114974737B (en) * | 2022-05-30 | 2023-01-06 | 珠海思科信电线电缆有限公司 | Corrosion-resistant high-flexibility coaxial cable and preparation process thereof |
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