A thermally conductive and wear-resistant copper alloy plug prong composite coating material and its preparation method

Abstract

This invention discloses a thermally conductive and wear-resistant copper alloy plug prong composite coating material. The components of the composite coating material, by mass percentage, are as follows: 40-60% polyaniline, 20-40% modified polyaniline, 3-7% emulsifier, 10-20% diluent, and 5-15% additive; the sum of the mass percentages of all components is 100%. The additive is an organic-inorganic composite material of graphene coated with a porous metal-organic framework. The copper alloy plug prong composite coating material of this invention not only possesses excellent electrical conductivity and oxidation resistance, but also excellent thermal conductivity, wear resistance, impact resistance, and other performance characteristics, meeting the requirements for long-term safe use of copper alloy plug prongs.

Description

Technical Field

[0001] This invention relates to the technical field of plug coatings, and more particularly to a thermally conductive and wear-resistant copper alloy plug composite coating material and its preparation method. Background Technology

[0002] A power plug is a device that connects electrical appliances and other devices to a power source. Its uses are widespread, and it's necessary for industries of all sizes. Power plugs are generally classified as 2-pin, 3-pin, and multi-pin plugs. A 2-pin plug, as the name suggests, has two prongs or two pins; a 3-pin plug, as the name suggests, has three prongs or three pins, or two prongs or two pins plus a grounding hole. Existing plug prongs typically use copper or copper alloy as the conductive substrate, and then electroplat a metal protective layer on the conductive substrate to prevent the power plug from failing to meet safety performance requirements due to oxidation and other external factors after long-term use. In addition, existing power plugs also suffer from wear, noise, and heat during frequent plugging and unplugging, leading to an unsettling experience for operators. Summary of the Invention

[0003] In view of the shortcomings of the prior art, one aspect of the present invention is to provide a thermally conductive and wear-resistant copper alloy plug prong composite coating material to solve the problem that existing copper alloy plug prong surface coating materials cannot simultaneously possess comprehensive properties such as electrical conductivity, thermal conductivity, wear resistance, impact resistance, and oxidation resistance, thereby meeting the long-term safe use requirements of copper alloy plug prongs.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A thermally conductive and wear-resistant copper alloy plug prong composite coating material, wherein the mass percentages of each component of the composite coating material are as follows: 30-50% polyaniline, 20-40% modified polyaniline, 3-7% emulsifier, 10-20% diluent, and 15-25% additive; the sum of the mass percentages of each component is 100%; the additive is an organic-inorganic composite material of porous metal-organic framework material coated with graphene.

[0006] Preferably, the modification method of the modified polyaniline is as follows: polyaniline is dissolved in methylpyrrolidone, doped with hydrochloric acid, and then an epoxy-containing polysiloxane is added. The mixture is stirred and reacted at a temperature of 30–60°C for 10–30 minutes to obtain the modified polyaniline. The polyaniline of this invention, after acid doping and modification with epoxy-containing polysiloxane, when compounded with unmodified polyaniline, not only ensures that the intrinsically conductive polyaniline film has excellent mechanical properties, but also provides good adhesion to copper alloy plug prongs, meeting the performance requirements for long-term use.

[0007] Preferably, the emulsifier is a compound of sodium dodecyl sulfonate and polyethylene glycol.

[0008] Preferably, the diluent is at least one of methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide, and sulfolane.

[0009] Preferably, the additive is prepared by: ultrasonically dispersing graphene in an aqueous solution containing metal ions, adding adamantane polyacid organic ligand, heating to 80-120°C for hydrothermal reaction, and adding epoxy alcohol to continue the reaction after a certain reaction time.

[0010] Preferably, the metal ion is at least one selected from copper ions, nickel ions, and iron ions.

[0011] Preferably, the adamantane polyacid is at least one selected from 1,3,5,7-adamantanetetracarboxylic acid, 5-ethyladamantane-1,3-dicarboxylic acid, and 1,3-adamantanedicarboxylic acid.

[0012] Preferably, the epoxy alcohol is at least one of glycidol, 2-methylglycidol, and 3,4-epoxyhexanol.

[0013] The additive of this invention is obtained by coating graphene with a porous metal-organic framework (MOF), combining the advantages of both graphene and MOF materials. This results in a composite coating material that not only possesses excellent electrical conductivity and oxidation resistance, but also excellent thermal conductivity, wear resistance, impact resistance, and other performance characteristics, meeting the long-term safe use requirements of copper alloy plug prongs. Specifically, by coating graphene with a porous MOF, graphene is uniformly dispersed in the composite coating material, improving the electrical conductivity of the copper alloy plug prongs coated with the composite coating. Furthermore, using adamantane polyacid as an organic ligand, it reacts with metal ions in a hydrothermal manner to form a network structure through molecular self-assembly. The resulting porous MOF further enhances the thermal conductivity of the composite coating material, as well as its wear resistance, impact resistance, and oxidation resistance. Simultaneously, the unique porous structure of the MOF reduces noise during long-term plugging and unplugging, improving the comfort and safety of the power plug prongs. In addition, the additive of the present invention, after the metal-organic framework material MOF is self-assembled and coated on the graphene surface, continues to react by adding a certain amount of epoxy alcohol, so that the additive has epoxy groups, thereby further improving the bonding strength between the composite coating material and the copper alloy plug piece.

[0014] Another aspect of the present invention provides a method for preparing the thermally conductive and wear-resistant copper alloy plug composite coating material as described above. The method involves weighing the following components of the composite coating material in the following mass percentages: 30-50% polyaniline, 20-40% modified polyaniline, 3-7% emulsifier, 10-20% diluent, and 15-25% additives; the sum of the mass percentages of each component is 100%; after uniform mixing, the mixture is coated onto the copper alloy plug, and after drying, the thermally conductive and wear-resistant copper alloy plug composite coating material is obtained.

[0015] The beneficial effects of this invention are:

[0016] The thermally conductive and wear-resistant copper alloy plug composite coating material of the present invention uses polyaniline combined with modified polyaniline as the main material of the protective film layer on the surface of the copper alloy plug, and is compounded with additives obtained by coating graphene with porous metal-organic framework materials. This makes the composite coating material of the present invention not only have excellent electrical conductivity and anti-oxidation properties, but also excellent thermal conductivity, wear resistance, impact resistance and other performance properties, which can meet the requirements for long-term safe use of copper alloy plugs. Detailed Implementation

[0017] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0018] Example 1

[0019] The thermally conductive and wear-resistant copper alloy plug composite coating material of this embodiment has the following mass percentage composition of each component: 30% polyaniline, 30% modified polyaniline, 5% emulsifier, 10% methylpyrrolidone and 25% additive; the sum of the mass percentages of each component is 100%; the additive is an organic-inorganic composite material of porous metal-organic framework material coated with graphene.

[0020] The modification method of the modified polyaniline is as follows: 20g of polyaniline is dissolved in 250mL of methylpyrrolidone, 15mL of a 50% hydrochloric acid aqueous solution is added for hydrochloric acid doping, and then 3g of an epoxy-containing polysiloxane is added. The mixture is stirred and reacted at 60°C for 15min to obtain the modified polyaniline. The epoxy-containing polysiloxane is obtained by hydrolyzing 3-(2,3-epoxypropoxy)propyltrimethoxysilane in an aqueous solution at pH 10.

[0021] The emulsifier is prepared by compounding sodium dodecyl sulfonate and polyethylene glycol in a mass ratio of 1:2.

[0022] The additive is prepared by ultrasonically dispersing graphene (10g) in a 25% copper nitrate aqueous solution (500mL), adding 1,3,5,7-adamantanetetracarboxylic acid organic ligand (the molar ratio of 1,3,5,7-adamantanetetracarboxylic acid to copper nitrate is 4:1), heating to 105℃ for hydrothermal reaction, and after reacting for 1h, adding glycidol (the molar ratio of glycidol to 1,3,5,7-adamantanetetracarboxylic acid is 1:10) to continue the reaction.

[0023] The preparation method of the thermally conductive and wear-resistant copper alloy plug composite coating material in this embodiment involves weighing the following components of the composite coating material in the following mass percentages: 30% polyaniline, 30% modified polyaniline, 5% emulsifier, 10% diluent, and 25% additive; the sum of the mass percentages of each component is 100%; after mixing them evenly, they are coated onto the copper alloy plug, and after drying, the thermally conductive and wear-resistant copper alloy plug composite coating material is obtained.

[0024] Example 2

[0025] The thermally conductive and wear-resistant copper alloy plug composite coating material of this embodiment has the following mass percentage composition of each component: 40% polyaniline, 22% modified polyaniline, 3% emulsifier, 15% dimethyl sulfoxide and 20% additive; the sum of the mass percentages of each component is 100%; the additive is an organic-inorganic composite material of porous metal-organic framework material coated with graphene.

[0026] The modification method of the modified polyaniline is as follows: 15g of polyaniline is dissolved in 250mL of methylpyrrolidone, 20mL of a 50% hydrochloric acid aqueous solution is added for hydrochloric acid doping, and then 2g of an epoxy-containing polysiloxane is added. The mixture is stirred and reacted at 60°C for 15min to obtain the modified polyaniline. The epoxy-containing polysiloxane is obtained by hydrolyzing 3-(2,3-epoxypropoxy)propyltrimethoxysilane in an aqueous solution at pH 10.

[0027] The emulsifier is prepared by compounding sodium dodecyl sulfonate and polyethylene glycol in a mass ratio of 2:3.

[0028] The additive is prepared by ultrasonically dispersing graphene (10g) in a 25% nickel nitrate aqueous solution (500mL), adding 5-ethyladamantane-1,3-dicarboxylic acid organic ligand (the molar ratio of 5-ethyladamantane-1,3-dicarboxylic acid to copper nitrate is 2:1), heating to 105℃ for hydrothermal reaction, reacting for 1h, and then adding 2-methylepoxypropanol (the molar ratio of 2-methylepoxypropanol to 5-ethyladamantane-1,3-dicarboxylic acid is 1:10) to continue the reaction.

[0029] The preparation method of the thermally conductive and wear-resistant copper alloy plug composite coating material in this embodiment is the same as in Embodiment 1.

[0030] Example 3

[0031] The thermally conductive and wear-resistant copper alloy plug composite coating material of this embodiment has the following mass percentage composition of each component: 50% polyaniline, 20% modified polyaniline, 5% emulsifier, 10% N,N-dimethylformamide and 15% additive; the sum of the mass percentages of each component is 100%; the additive is an organic-inorganic composite material of porous metal-organic framework material coated with graphene.

[0032] The modification method of the modified polyaniline is as follows: 25g of polyaniline is dissolved in 250mL of methylpyrrolidone, 15mL of a 50% hydrochloric acid aqueous solution is added for hydrochloric acid doping, and then 5g of an epoxy-containing polysiloxane is added. The mixture is stirred and reacted at 60°C for 15min to obtain the modified polyaniline. The epoxy-containing polysiloxane is obtained by hydrolyzing 3-(2,3-epoxypropoxy)propyltrimethoxysilane in an aqueous solution at pH 10.

[0033] The emulsifier is prepared by compounding sodium dodecyl sulfonate and polyethylene glycol in a mass ratio of 1:3.

[0034] The additive is prepared by ultrasonically dispersing graphene (10g) in a 25% ferric nitrate aqueous solution (500mL), adding 1,3-adamantanedicarboxylic acid organic ligand (the molar ratio of 1,3-adamantanedicarboxylic acid to copper nitrate is 3:1), heating to 105℃ for hydrothermal reaction, reacting for 1h, and then adding 3,4-epoxyhexanol (the molar ratio of 3,4-epoxyhexanol to 1,3-adamantanedicarboxylic acid is 1:10) to continue the reaction.

[0035] The preparation method of the thermally conductive and wear-resistant copper alloy plug composite coating material in this embodiment is the same as in Embodiment 1.

[0036] Example 4

[0037] The thermally conductive and wear-resistant copper alloy plug composite coating material of this embodiment has the following mass percentage composition of each component: 35% polyaniline, 23% modified polyaniline, 7% emulsifier, 15% sulfolane and 20% additive; the sum of the mass percentages of each component is 100%; the additive is an organic-inorganic composite material of porous metal-organic framework material coated with graphene.

[0038] The modification method of the modified polyaniline is as follows: 20g of polyaniline is dissolved in 250mL of methylpyrrolidone, 15mL of a 50% hydrochloric acid aqueous solution is added for hydrochloric acid doping, and then 3g of an epoxy-containing polysiloxane is added. The mixture is stirred and reacted at 60°C for 15min to obtain the modified polyaniline. The epoxy-containing polysiloxane is obtained by hydrolyzing 3-(2,3-epoxypropoxy)propyltrimethoxysilane in an aqueous solution at pH 10.

[0039] The emulsifier is prepared by compounding sodium dodecyl sulfonate and polyethylene glycol in a mass ratio of 1:2.

[0040] The additive is prepared by ultrasonically dispersing graphene (10g) in a 25% copper nitrate aqueous solution (500mL), adding 1,3,5,7-adamantanetetracarboxylic acid organic ligand (the molar ratio of 1,3,5,7-adamantanetetracarboxylic acid to copper nitrate is 4:1), heating to 105℃ for hydrothermal reaction, reacting for 1h, and then adding 2-methylglycidol (the molar ratio of 2-methylglycidol to 1,3,5,7-adamantanetetracarboxylic acid is 1:10) to continue the reaction.

[0041] The preparation method of the thermally conductive and wear-resistant copper alloy plug composite coating material in this embodiment is the same as in Embodiment 1.

[0042] Comparative Example 1

[0043] The raw material composition and preparation method of the comparative copper alloy plug composite coating material are basically similar to those of Example 1. The main difference is that the composite coating material does not contain additives.

[0044] Comparative Example 2

[0045] The comparative example of copper alloy plug composite coating material has a raw material composition and preparation method that are basically similar to those of Example 1. The main difference is that the additive in the composite coating material is 3,3',4,4'-biphenyltetracarboxylic acid instead of 1,3,5,7-adamantanetetracarboxylic acid.

[0046] The copper alloy plug composite coating materials prepared in Examples 1-4 and Comparative Examples 1-2 were subjected to performance tests, and the performance results are shown in Table 1.

[0047] Hardness was tested according to GB / T 6739; adhesion was tested according to GB / T 9286; impact resistance was tested according to GB / T 1732; and resistance to neutral salt spray was tested according to GB / T 1771.

[0048] Table 1

[0049]

[0050]

[0051] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A heat conductive wear resistant copper alloy plug piece composite coating material characterized by, The mass ratio of the components of the composite coating material is as follows: 30-50% polyaniline, 20-40% modified polyaniline, 3-7% emulsifier, 10-20% diluent and 15-25% additive, and the sum of the mass percentages of the components is 100%; the additive is a porous metal organic framework material coated graphene organic-inorganic composite; the modification method of the modified polyaniline is as follows: polyaniline is dissolved in methylpyrrolidone, doped with hydrochloric acid, then epoxy-containing polysiloxane is added, and stirring is carried out at a temperature of 30-60 DEG C for 10-30 min to obtain modified polyaniline; the preparation method of the additive is as follows: graphene is ultrasonically dispersed in an aqueous solution containing metal ions, adamantane polyacid organic ligand is added, the temperature is raised to 80-120 DEG C for hydrothermal reaction, and after a certain time of reaction, epoxy alcohol is added for further reaction.

2. The heat conductive wear resistant copper alloy plug piece composite coating material of claim 1 wherein, The emulsifier is obtained by compounding sodium dodecyl sulfonate and polyethylene glycol.

3. The heat conductive wear resistant copper alloy plug piece composite coating material of claim 1 wherein, The diluent is at least one of methylpyrrolidone, dimethyl sulfoxide, N,N-dimethylformamide and sulfolane.

4. The heat conducting wear resistant copper alloy plug piece composite coating material of claim 1 wherein, The metal ion is at least one of copper ion, nickel ion and iron ion.

5. The heat conducting wear resistant copper alloy plug piece composite coating material of claim 1 wherein, The adamantane polyacid is at least one of 1,3,5,7-adamantane tetracarboxylic acid, 5-ethyladamantane-1,3-dicarboxylic acid and 1,3-adamantane dicarboxylic acid.

6. The heat conducting wear resistant copper alloy plug piece composite coating material of claim 1 wherein, The epoxy alcohol is at least one of epoxypropanol, 2-methyl epoxypropanol and 3,4-epoxyhexanol.

7. A method of producing a wear resistant copper alloy plug piece composite coating material according to any one of claims 1 to 6, characterized in that The mass ratio of the components of the composite coating material is as follows: 30-50% polyaniline, 20-40% modified polyaniline, 3-7% emulsifier, 10-20% diluent and 15-25% additive, and the sum of the mass percentages of the components is 100%; the additive is a porous metal organic framework material coated graphene organic-inorganic composite; the modification method of the modified polyaniline is as follows: polyaniline is dissolved in methylpyrrolidone, doped with hydrochloric acid, then epoxy-containing polysiloxane is added, and stirring is carried out at a temperature of 30-60 DEG C for 10-30 min to obtain modified polyaniline; the preparation method of the additive is as follows: graphene is ultrasonically dispersed in an aqueous solution containing metal ions, adamantane polyacid organic ligand is added, the temperature is raised to 80-120 DEG C for hydrothermal reaction, and after a certain time of reaction, epoxy alcohol is added for further reaction.

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