阅读说明：本技术 一种高导电的石墨烯原位接枝聚氨酯材料及其制法 (High-conductivity graphene in-situ grafted polyurethane material and preparation method thereof ) 是由 许廷海 于 2020-05-20 设计创作，主要内容包括：本发明涉及聚氨酯技术领域,且公开了一种高导电的石墨烯原位接枝聚氨酯材料,包括以下配方原料及组分：功能化石墨烯、异氰酸酯单体、聚酯多元醇、二月桂酸二丁基锡、小分子扩链剂、苯胺、过硫酸铵。该一种高导电的石墨烯原位接枝聚氨酯材料,通苯胺与聚氨酯链端的异氰酸酯基团反应,生成活性较高的芳酰胺基,过硫酸钾作为引发剂,与苯胺进行自由基聚合过程形成聚苯胺-聚氨酯共聚物,聚苯胺中的链端氨基与功能化石墨烯的环氧基团反应,使聚苯胺-聚氨酯在石墨烯表面原位共聚,改善了石墨烯与聚氨酯的相容性,导电性能优异的聚苯胺分子和石墨烯纳米粒子,形成连续的三维导电通路,提高了聚氨酯材料的电导率和导电性能。(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.)

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.

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.