A wear-resistant nylon product with heat conduction function and a preparation method thereof

Abstract

This invention relates to the field of nylon technology, specifically to a wear-resistant nylon product with thermal conductivity and its preparation method. The invention first uses hexachlorocyclotriphosphazene as a raw material to prepare a cyclotriphosphazene compound with six terminal carboxyl groups. Then, using the cyclotriphosphazene compound as the core, a carboxylated nylon 6 resin with good mechanical and thermal properties is prepared. The nylon product prepared using this carboxylated nylon 6 resin exhibits excellent wear resistance. Copper plating on the carbon fiber-graphene oxide composite forms a better thermal conductivity pathway, enhancing the thermal conductivity of the nylon product.

Description

Technical Field

[0001] This invention relates to the field of nylon technology, specifically to a wear-resistant nylon product with thermal conductivity and its preparation method. Background Technology

[0002] In modern industry and consumer goods, nylon is an important engineering plastic widely used due to its excellent wear resistance, strength, and chemical corrosion resistance. However, traditional nylon materials have limitations in thermal conductivity, which restricts their application range.

[0003] Existing technologies typically improve the thermal conductivity of nylon by introducing thermally conductive fillers or additives into the nylon matrix. These fillers can be metal particles, carbon nanotubes, graphite, etc., and possess excellent thermal conductivity, thus enhancing the thermal conductivity of nylon products. However, excessive addition of fillers can lead to filler agglomeration and difficulty in dispersion, resulting in a decrease in the mechanical properties of nylon products.

[0004] To address the aforementioned issues and improve the thermal conductivity and wear resistance of nylon products, this invention provides a wear-resistant nylon product with thermal conductivity and its preparation method. Summary of the Invention

[0005] The purpose of this invention is to provide a wear-resistant nylon product with thermal conductivity and its preparation method, so as to solve the problems mentioned in the background art.

[0006] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0007] A method for preparing a wear-resistant nylon product with thermal conductivity includes the following steps:

[0008] S1: The activated aminated carbon fiber-graphene oxide composite was placed in the plating solution for chemical copper plating. The reaction time was 5-10 min. After precipitation, centrifugation, washing and drying, copper-plated aminated carbon fiber-graphene oxide composite was obtained.

[0009] S2: Take carboxylated nylon 6 resin, add nano β-silicon nitride, copper-plated aminated carbon fiber-graphene oxide composite, antioxidant, lubricant, blend, cool and granulate, and injection mold to obtain nylon products;

[0010] A more optimized method for preparing the aminated carbon fiber-graphene oxide composite is as follows: γ-aminopropyltriethoxysilane and methanol aqueous solution are mixed evenly, and the carbon fiber-graphene oxide composite is added. The mixture is heated to 65-70℃ and stirred for 1-2 hours. After filtration, washing, and drying, the pretreated carbon fiber-graphene oxide composite is obtained. Succinic anhydride and ethylene glycolamine are mixed evenly, and the pretreated carbon fiber-graphene oxide composite and p-toluenesulfonic acid are added. The mixture is heated to 105-110℃ and stirred for 4-5 hours. After filtration, washing, and drying, the aminated carbon fiber-graphene oxide composite is obtained.

[0011] A more optimized method for preparing the carbon fiber-graphene oxide composite is as follows: Carbon fiber and anhydrous ethanol are ultrasonically dispersed for 10-14 hours and dried to obtain cleaned carbon fiber; graphene oxide and deionized water are ultrasonically dispersed to obtain a graphene oxide dispersion; deionized water and anhydrous ethanol are mixed evenly, silane coupling agent KH550 is added, the temperature is raised to 40-45℃, and the mixture is stirred for 2-3 hours; the cleaned carbon fiber is added, and the mixture is stirred for 2-3 hours; the graphene oxide dispersion is added, hydrochloric acid is added dropwise, the pH value is adjusted to 3, the temperature is raised to 75-80℃, and the reaction is carried out for 2-3 hours; the mixture is washed and dried to obtain the carbon fiber-graphene oxide composite.

[0012] In a more optimized manner, the nylon product comprises the following components, by weight: 100-115 parts of carboxylated nylon 6 resin, 10-15 parts of nano-β-silicon nitride, 10-15 parts of copper-plated aminated carbon fiber-graphene oxide composite, 0.05-0.1 parts of antioxidant, and 0.05-0.1 parts of lubricant.

[0013] A more optimized method for preparing the carboxylated nylon 6 resin includes the following steps:

[0014] S1: Take hexachlorocyclotriphosphazene and tetrahydrofuran, stir evenly to obtain a mixed solution; take anhydrous potassium carbonate, p-hydroxybenzaldehyde and tetrahydrofuran, stir evenly, add to the mixed solution, heat to 65-70℃, reflux for 22-26h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene;

[0015] S2: Take hexa(4-aldehyde phenoxy)cyclotriphosphazene, sodium hydroxide, tetrahydrofuran, and distilled water, stir well, add potassium permanganate, filter, rotary evaporate, add hydrochloric acid, adjust the pH value to 3-4, precipitate, filter, wash, and dry to obtain cyclotriphosphazene compounds.

[0016] S3: Take ε-caprolactam, cyclotriphosphazene compounds, and distilled water, heat to 250-252℃ under nitrogen atmosphere, react for 3-4 hours, then vacuum for 2-2.5 hours, and then extract the material in deionized water at 100℃ for 22-26 hours, and dry to obtain carboxylated nylon 6 resin.

[0017] More preferably, the lubricant is any one or more of oleamide, glyceryl stearate, and calcium stearate.

[0018] More preferably, the antioxidant is any one or more of phosphite, 2,6-di-tert-butyl-p-cresol, and dodecyl alcohol ester.

[0019] In a more optimized manner, the preparation method of the activated aminated carbon fiber-graphene oxide composite in step one is as follows: take stannous chloride and hydrochloric acid, stir evenly to obtain a sensitizing solution; take palladium chloride and hydrochloric acid, stir evenly to obtain an activation solution; take the sensitizing solution, add the aminated carbon fiber-graphene oxide composite, stir evenly, wash and filter, add the activation solution, stir evenly, wash and filter to obtain the activated aminated carbon fiber-graphene oxide composite.

[0020] The plating solution is prepared as follows: copper sulfate pentahydrate, deionized water, and formaldehyde solution are stirred evenly to obtain solution A; anhydrous sodium carbonate, deionized water, and potassium sodium tartrate are stirred evenly to obtain solution B; solution A is added to solution B and mixed evenly to obtain the plating solution.

[0021] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0022] (1) This invention first uses hexachlorocyclotriphosphazene as a raw material to prepare a cyclotriphosphazene compound with six terminal carboxyl groups. Then, using the cyclotriphosphazene compound as the core, a carboxylated nylon 6 resin with good mechanical and thermal properties is prepared. Nylon products prepared using this carboxylated nylon 6 resin as a raw material have excellent wear resistance.

[0023] (2) This invention combines carbon fiber and graphene oxide, improving the dispersion performance of graphene oxide. Copper plating on the carbon fiber-graphene oxide composite forms a better thermal conductivity pathway, enhancing the thermal conductivity of nylon products. Amination treatment of the carbon fiber-graphene oxide composite allows the amino groups on the copper-plated aminated carbon fiber-graphene oxide composite to react with the carboxyl groups on the carboxylated nylon 6 resin, improving the dispersibility of the copper-plated aminated carbon fiber-graphene oxide composite in the matrix, thereby improving the wear resistance and thermal conductivity of nylon products. Detailed Implementation

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0025] There are no specific restrictions on the manufacturers and models of the raw materials involved in this invention. Exemplary examples include:

[0026] Nano-β-silicon nitride: Particle size: 25nm; Carbon fiber diameter: 50-200nm, length: 1-15µm, provided by Xi'an Qiyue Biotechnology Co., Ltd.; Graphite powder: Model: G616494, provided by Aladdin;

[0027] The preparation method of graphene oxide in this invention is as follows:

[0028] Take 5g of potassium permanganate, 1g of graphite powder, and 70mL of 98wt% sulfuric acid, mix them evenly, cool them to 0℃ in an ice bath, raise the temperature to 80℃, stir evenly and react for 10h, add 100mL of deionized water, stir evenly, raise the temperature to 90℃, add 200mL of deionized water and 3mL of 30wt% hydrogen peroxide, filter, take the supernatant, wash until the pH is neutral, freeze dry, and sieve to obtain graphene oxide with a thickness of 10-20nm.

[0029] Example 1: A method for preparing a wear-resistant nylon product with thermal conductivity, comprising the following steps:

[0030] Step 1: Preparation of carboxylated nylon 6 resin:

[0031] Take 50g of hexachlorocyclotriphosphazene and 100mL of tetrahydrofuran, stir well to obtain a mixture; take 140g of anhydrous potassium carbonate, 125g of p-hydroxybenzaldehyde and 500mL of tetrahydrofuran, stir well, add to the mixture, heat to 67℃, reflux for 24h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene;

[0032] Take 50g of hexa(4-aldehydephenoxy)cyclotriphosphazene, 15g of sodium hydroxide, 300mL of tetrahydrofuran, and 300mL of distilled water, stir well, add 118g of potassium permanganate, filter under vacuum, evaporate by rotary evaporation, add hydrochloric acid, adjust the pH value to 3.5, precipitate, filter under vacuum, wash, and dry to obtain cyclotriphosphazene compounds.

[0033] Take 2000g of ε-caprolactam, 50g of cyclotriphosphazene compound, and 60g of distilled water. Under nitrogen atmosphere, heat to 251℃ and react for 3.5h. Then, react under vacuum for 2.2h. Finally, extract the material in deionized water at 100℃ for 24h and dry it to obtain carboxylated nylon 6 resin.

[0034] Step 2: Preparation of carbon fiber-graphene oxide composite:

[0035] Take 2g of carbon fiber and 500mL of anhydrous ethanol, sonicate for 12h, and dry to obtain cleaned carbon fiber; take 0.2g of graphene oxide and 500mL of deionized water, sonicate to obtain graphene oxide dispersion; take 150mL of deionized water and 350mL of anhydrous ethanol, mix evenly, add 0.8g of silane coupling agent KH550, heat to 42℃, stir for 2.5h, add 2g of cleaned carbon fiber, stir for 2.5h, add graphene oxide dispersion, add hydrochloric acid dropwise, adjust the pH to 3, heat to 78℃, react for 2.5h, wash and dry to obtain carbon fiber-graphene oxide composite;

[0036] Step 3: Preparation of aminated carbon fiber-graphene oxide composite:

[0037] Take 8g of γ-aminopropyltriethoxysilane and 80g of 10% methanol aqueous solution, stir evenly, add 30g of carbon fiber-graphene oxide composite, heat to 68℃, stir for 1.5h, filter, wash and dry to obtain pretreated carbon fiber-graphene oxide composite; take 3g of succinic anhydride and 45g of ethylene glycolamine, mix evenly, add 25g of pretreated carbon fiber-graphene oxide composite and 1g of p-toluenesulfonic acid, heat to 108℃, stir for 4.5h, filter, wash and dry to obtain aminated carbon fiber-graphene oxide composite;

[0038] Step 4: Preparation of copper-plated aminated carbon fiber-graphene oxide composite:

[0039] Take 0.0075 mol / L stannous chloride and 0.15 mol / L hydrochloric acid, stir well to obtain a sensitization solution; take 0.003 mol / L palladium chloride and 0.06 mol / L hydrochloric acid, stir well to obtain an activation solution; take 100 mL of the sensitization solution, add 2 g of aminated carbon fiber-graphene oxide composite, stir well, wash and filter, add 100 mL of the activation solution, stir well, wash and filter to obtain the activated aminated carbon fiber-graphene oxide composite;

[0040] Take 5g of copper sulfate pentahydrate, 300ml of deionized water, and 8ml of 37% formaldehyde solution, and stir well to obtain solution A; take 8g of anhydrous sodium carbonate, 300ml of deionized water, and 30g of potassium sodium tartrate, and stir well to obtain solution B; add solution A to solution B, mix well, and obtain plating solution.

[0041] 2g of activated aminated carbon fiber-graphene oxide composite was placed in a plating solution for chemical copper plating. The reaction time was 5min. After precipitation, centrifugation, washing, and drying, copper-plated aminated carbon fiber-graphene oxide composite was obtained.

[0042] Step 5: Preparation of Nylon Products

[0043] Take carboxylated nylon 6 resin, add nano β-silicon nitride, copper-plated aminated carbon fiber-graphene oxide composite, antioxidant, lubricant, blend, cool and granulate, and injection mold to obtain nylon products;

[0044] The nylon product comprises the following components, by weight: 112 parts carboxylated nylon 6 resin, 12 parts nano β-silicon nitride, 13 parts copper-plated aminated carbon fiber-graphene oxide composite, 0.08 parts antioxidant, and 0.08 parts lubricant.

[0045] The lubricant is oleamide; the antioxidant is phosphite.

[0046] Example 2: A method for preparing a wear-resistant nylon product with thermal conductivity, comprising the following steps:

[0047] Step 1: Preparation of carboxylated nylon 6 resin:

[0048] Take 50g of hexachlorocyclotriphosphazene and 100mL of tetrahydrofuran, stir well to obtain a mixture; take 140g of anhydrous potassium carbonate, 125g of p-hydroxybenzaldehyde and 500mL of tetrahydrofuran, stir well, add to the mixture, heat to 65℃, reflux for 22h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene;

[0049] Take 50g of hexa(4-aldehyde phenoxy)cyclotriphosphazene, 15g of sodium hydroxide, 300mL of tetrahydrofuran, and 300mL of distilled water, stir well, add 118g of potassium permanganate, filter under vacuum, evaporate by rotary evaporation, add hydrochloric acid, adjust the pH value to 3, precipitate, filter under vacuum, wash, and dry to obtain cyclotriphosphazene compounds.

[0050] Take 2000g of ε-caprolactam, 50g of cyclotriphosphazene compound, and 60g of distilled water. Under nitrogen atmosphere, heat to 250℃ and react for 3h. Then, vacuum the reaction for 2h. Finally, extract the material in deionized water at 100℃ for 22h and dry it to obtain carboxylated nylon 6 resin.

[0051] Step 2: Preparation of carbon fiber-graphene oxide composite:

[0052] Take 2g of carbon fiber and 500mL of anhydrous ethanol, sonicate for 10h, and dry to obtain cleaned carbon fiber; take 0.2g of graphene oxide and 500mL of deionized water, sonicate to obtain graphene oxide dispersion; take 150mL of deionized water and 350mL of anhydrous ethanol, mix evenly, add 0.8g of silane coupling agent KH550, heat to 40℃, stir for 2h, add 2g of cleaned carbon fiber, stir for 2h, add graphene oxide dispersion, add hydrochloric acid dropwise, adjust the pH value to 3, heat to 75℃, react for 2h, wash and dry to obtain carbon fiber-graphene oxide composite;

[0053] Step 3: Preparation of aminated carbon fiber-graphene oxide composite:

[0054] Take 8g of γ-aminopropyltriethoxysilane and 80g of 10% methanol aqueous solution, stir evenly, add 30g of carbon fiber-graphene oxide composite, heat to 65℃, stir for 1h, filter, wash and dry to obtain pretreated carbon fiber-graphene oxide composite; take 3g of succinic anhydride and 45g of ethylene glycolamine, mix evenly, add 25g of pretreated carbon fiber-graphene oxide composite and 1g of p-toluenesulfonic acid, heat to 105℃, stir for 4h, filter, wash and dry to obtain aminated carbon fiber-graphene oxide composite.

[0055] Step 4: Preparation of copper-plated aminated carbon fiber-graphene oxide composite:

[0056] Take 0.0075 mol / L stannous chloride and 0.15 mol / L hydrochloric acid, stir well to obtain a sensitization solution; take 0.003 mol / L palladium chloride and 0.06 mol / L hydrochloric acid, stir well to obtain an activation solution; take 100 mL of the sensitization solution, add 2 g of aminated carbon fiber-graphene oxide composite, stir well, wash and filter, add 100 mL of the activation solution, stir well, wash and filter to obtain the activated aminated carbon fiber-graphene oxide composite;

[0057] Take 5g of copper sulfate pentahydrate, 300ml of deionized water, and 8ml of 37% formaldehyde solution, and stir well to obtain solution A; take 8g of anhydrous sodium carbonate, 300ml of deionized water, and 30g of potassium sodium tartrate, and stir well to obtain solution B; add solution A to solution B, mix well, and obtain plating solution.

[0058] 2g of activated aminated carbon fiber-graphene oxide composite was placed in a plating solution for chemical copper plating. The reaction time was 5min. After precipitation, centrifugation, washing, and drying, copper-plated aminated carbon fiber-graphene oxide composite was obtained.

[0059] Step 5: Preparation of Nylon Products

[0060] Take carboxylated nylon 6 resin, add nano β-silicon nitride, copper-plated aminated carbon fiber-graphene oxide composite, antioxidant, lubricant, blend, cool and granulate, and injection mold to obtain nylon products;

[0061] The nylon product comprises the following components, by weight: 100 parts carboxylated nylon 6 resin, 10 parts nano β-silicon nitride, 10 parts copper-plated aminated carbon fiber-graphene oxide composite, 0.05 parts antioxidant, and 0.05 parts lubricant.

[0062] The lubricant is glyceryl stearate; the antioxidant is 2,6-di-tert-butyl-p-cresol.

[0063] Example 3: A method for preparing a wear-resistant nylon product with thermal conductivity, comprising the following steps:

[0064] Step 1: Preparation of carboxylated nylon 6 resin:

[0065] Take 50g of hexachlorocyclotriphosphazene and 100mL of tetrahydrofuran, stir well to obtain a mixed solution; take 140g of anhydrous potassium carbonate, 125g of p-hydroxybenzaldehyde and 500mL of tetrahydrofuran, stir well, add to the mixed solution, heat to 70℃, reflux for 26h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene;

[0066] Take 50g of hexa(4-aldehydephenoxy)cyclotriphosphazene, 15g of sodium hydroxide, 300mL of tetrahydrofuran, and 300mL of distilled water, stir well, add 118g of potassium permanganate, filter under vacuum, evaporate by rotary evaporation, add hydrochloric acid, adjust the pH value to 4, precipitate, filter under vacuum, wash, and dry to obtain cyclotriphosphazene compounds.

[0067] Take 2000g of ε-caprolactam, 50g of cyclotriphosphazene compound, and 60g of distilled water. Under nitrogen atmosphere, heat to 252℃ and react for 4h. Then, vacuum the reaction for 2.5h. Finally, extract the material in deionized water at 100℃ for 26h and dry it to obtain carboxylated nylon 6 resin.

[0068] Step 2: Preparation of carbon fiber-graphene oxide composite:

[0069] Take 2g of carbon fiber and 500mL of anhydrous ethanol, sonicate for 14h, and dry to obtain cleaned carbon fiber; take 0.2g of graphene oxide and 500mL of deionized water, sonicate to obtain graphene oxide dispersion; take 150mL of deionized water and 350mL of anhydrous ethanol, mix evenly, add 0.8g of silane coupling agent KH550, heat to 45℃, stir for 3h, add 2g of cleaned carbon fiber, stir for 3h, add graphene oxide dispersion, add hydrochloric acid dropwise, adjust the pH value to 3, heat to 80℃, react for 3h, wash and dry to obtain carbon fiber-graphene oxide composite;

[0070] Step 3: Preparation of aminated carbon fiber-graphene oxide composite:

[0071] Take 8g of γ-aminopropyltriethoxysilane and 80g of 10% methanol aqueous solution, stir evenly, add 30g of carbon fiber-graphene oxide composite, heat to 70℃, stir for 2h, filter, wash and dry to obtain pretreated carbon fiber-graphene oxide composite; take 3g of succinic anhydride and 45g of ethylene glycolamine, mix evenly, add 25g of pretreated carbon fiber-graphene oxide composite and 1g of p-toluenesulfonic acid, heat to 110℃, stir for 5h, filter, wash and dry to obtain aminated carbon fiber-graphene oxide composite.

[0072] Step 4: Preparation of copper-plated aminated carbon fiber-graphene oxide composite:

[0073] Take 0.0075 mol / L stannous chloride and 0.15 mol / L hydrochloric acid, stir well to obtain a sensitization solution; take 0.003 mol / L palladium chloride and 0.06 mol / L hydrochloric acid, stir well to obtain an activation solution; take 100 mL of the sensitization solution, add 2 g of aminated carbon fiber-graphene oxide composite, stir well, wash and filter, add 100 mL of the activation solution, stir well, wash and filter to obtain the activated aminated carbon fiber-graphene oxide composite;

[0074] Take 5g of copper sulfate pentahydrate, 300ml of deionized water, and 8ml of 37% formaldehyde solution, and stir well to obtain solution A; take 8g of anhydrous sodium carbonate, 300ml of deionized water, and 30g of potassium sodium tartrate, and stir well to obtain solution B; add solution A to solution B, mix well, and obtain plating solution.

[0075] 2g of activated aminated carbon fiber-graphene oxide composite was placed in a plating solution for chemical copper plating. The reaction time was 5min. After precipitation, centrifugation, washing, and drying, copper-plated aminated carbon fiber-graphene oxide composite was obtained.

[0076] Step 5: Preparation of Nylon Products

[0077] Take carboxylated nylon 6 resin, add nano β-silicon nitride, copper-plated aminated carbon fiber-graphene oxide composite, antioxidant, lubricant, blend, cool and granulate, and injection mold to obtain nylon products;

[0078] The nylon product comprises the following components, by weight: 115 parts carboxylated nylon 6 resin, 15 parts nano β-silicon nitride, 15 parts copper-plated aminated carbon fiber-graphene oxide composite, 0.1 parts antioxidant, and 0.1 parts lubricant.

[0079] The lubricant is calcium stearate; the antioxidant is dodecyl alcohol ester.

[0080] Comparative Example 1: Copper was not plated on the carbon fiber-graphene oxide composite; all other aspects were the same as in Example 1.

[0081] Step 1: Preparation of carboxylated nylon 6 resin:

[0082] Take 50g of hexachlorocyclotriphosphazene and 100mL of tetrahydrofuran, stir well to obtain a mixture; take 140g of anhydrous potassium carbonate, 125g of p-hydroxybenzaldehyde and 500mL of tetrahydrofuran, stir well, add to the mixture, heat to 67℃, reflux for 24h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene;

[0083] Take 50g of hexa(4-aldehydephenoxy)cyclotriphosphazene, 15g of sodium hydroxide, 300mL of tetrahydrofuran, and 300mL of distilled water, stir well, add 118g of potassium permanganate, filter under vacuum, evaporate by rotary evaporation, add hydrochloric acid, adjust the pH value to 3.5, precipitate, filter under vacuum, wash, and dry to obtain cyclotriphosphazene compounds.

[0084] Take 2000g of ε-caprolactam, 50g of cyclotriphosphazene compound, and 60g of distilled water. Under nitrogen atmosphere, heat to 251℃ and react for 3.5h. Then, react under vacuum for 2.2h. Finally, extract the material in deionized water at 100℃ for 24h and dry it to obtain carboxylated nylon 6 resin.

[0085] Step 2: Preparation of carbon fiber-graphene oxide composite:

[0086] Take 2g of carbon fiber and 500mL of anhydrous ethanol, sonicate for 12h, and dry to obtain cleaned carbon fiber; take 0.2g of graphene oxide and 500mL of deionized water, sonicate to obtain graphene oxide dispersion; take 150mL of deionized water and 350mL of anhydrous ethanol, mix evenly, add 0.8g of silane coupling agent KH550, heat to 42℃, stir for 2.5h, add 2g of cleaned carbon fiber, stir for 2.5h, add graphene oxide dispersion, add hydrochloric acid dropwise, adjust the pH to 3, heat to 78℃, react for 2.5h, wash and dry to obtain carbon fiber-graphene oxide composite;

[0087] Step 3: Preparation of aminated carbon fiber-graphene oxide composite:

[0088] Take 8g of γ-aminopropyltriethoxysilane and 80g of 10% methanol aqueous solution, stir evenly, add 30g of carbon fiber-graphene oxide composite, heat to 68℃, stir for 1.5h, filter, wash and dry to obtain pretreated carbon fiber-graphene oxide composite; take 3g of succinic anhydride and 45g of ethylene glycolamine, mix evenly, add 25g of pretreated carbon fiber-graphene oxide composite and 1g of p-toluenesulfonic acid, heat to 108℃, stir for 4.5h, filter, wash and dry to obtain aminated carbon fiber-graphene oxide composite;

[0089] Step 4: Preparation of Nylon Products

[0090] Take carboxylated nylon 6 resin, add nano-β-silicon nitride, aminated carbon fiber-graphene oxide composite, antioxidant, lubricant, blend, cool and granulate, and injection mold to obtain nylon products;

[0091] The nylon product comprises the following components, by weight: 112 parts carboxylated nylon 6 resin, 12 parts nano-β-silicon nitride, 13 parts aminated carbon fiber-graphene oxide composite, 0.08 parts antioxidant, and 0.08 parts lubricant.

[0092] The lubricant is oleamide; the antioxidant is phosphite.

[0093] Comparative Example 2: The carbon fiber-graphene oxide composite was not subjected to amination treatment; all other aspects were the same as in Example 1.

[0094] Step 1: Preparation of carboxylated nylon 6 resin:

[0095] Take 50g of hexachlorocyclotriphosphazene and 100mL of tetrahydrofuran, stir well to obtain a mixture; take 140g of anhydrous potassium carbonate, 125g of p-hydroxybenzaldehyde and 500mL of tetrahydrofuran, stir well, add to the mixture, heat to 67℃, reflux for 24h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene;

[0096] Take 50g of hexa(4-aldehydephenoxy)cyclotriphosphazene, 15g of sodium hydroxide, 300mL of tetrahydrofuran, and 300mL of distilled water, stir well, add 118g of potassium permanganate, filter under vacuum, evaporate by rotary evaporation, add hydrochloric acid, adjust the pH value to 3.5, precipitate, filter under vacuum, wash, and dry to obtain cyclotriphosphazene compounds.

[0097] Take 2000g of ε-caprolactam, 50g of cyclotriphosphazene compound, and 60g of distilled water. Under nitrogen atmosphere, heat to 251℃ and react for 3.5h. Then, react under vacuum for 2.2h. Finally, extract the material in deionized water at 100℃ for 24h and dry it to obtain carboxylated nylon 6 resin.

[0098] Step 2: Preparation of carbon fiber-graphene oxide composite:

[0099] Take 2g of carbon fiber and 500mL of anhydrous ethanol, sonicate for 12h, and dry to obtain cleaned carbon fiber; take 0.2g of graphene oxide and 500mL of deionized water, sonicate to obtain graphene oxide dispersion; take 150mL of deionized water and 350mL of anhydrous ethanol, mix evenly, add 0.8g of silane coupling agent KH550, heat to 42℃, stir for 2.5h, add 2g of cleaned carbon fiber, stir for 2.5h, add graphene oxide dispersion, add hydrochloric acid dropwise, adjust the pH to 3, heat to 78℃, react for 2.5h, wash and dry to obtain carbon fiber-graphene oxide composite;

[0100] Step 3: Preparation of copper-plated carbon fiber-graphene oxide composite:

[0101] Take 0.0075 mol / L stannous chloride and 0.15 mol / L hydrochloric acid, stir well to obtain a sensitization solution; take 0.003 mol / L palladium chloride and 0.06 mol / L hydrochloric acid, stir well to obtain an activation solution; take 100 mL of the sensitization solution, add 2 g of carbon fiber-graphene oxide composite, stir well, wash and filter, add 100 mL of the activation solution, stir well, wash and filter to obtain the activated carbon fiber-graphene oxide composite;

[0102] Take 5g of copper sulfate pentahydrate, 300ml of deionized water, and 8ml of 37% formaldehyde solution, and stir well to obtain solution A; take 8g of anhydrous sodium carbonate, 300ml of deionized water, and 30g of potassium sodium tartrate, and stir well to obtain solution B; add solution A to solution B, mix well, and obtain plating solution.

[0103] 2g of activated carbon fiber-graphene oxide composite was placed in a plating solution for chemical copper plating. The reaction time was 5min. After precipitation, centrifugation, washing, and drying, copper-plated carbon fiber-graphene oxide composite was obtained.

[0104] Step 4: Preparation of Nylon Products

[0105] Take carboxylated nylon 6 resin, add nano β-silicon nitride, copper-plated carbon fiber-graphene oxide composite, antioxidant, lubricant, blend, cool and granulate, and injection mold to obtain nylon products;

[0106] The nylon product comprises the following components, by weight: 112 parts carboxylated nylon 6 resin, 12 parts nano β-silicon nitride, 13 parts copper-plated carbon fiber-graphene oxide composite, 0.08 parts antioxidant, and 0.08 parts lubricant.

[0107] The lubricant is oleamide; the antioxidant is phosphite.

[0108] Comparative Example 3: No carbon fiber added, otherwise the same as Example 1:

[0109] Step 1: Preparation of carboxylated nylon 6 resin:

[0110] Take 50g of hexachlorocyclotriphosphazene and 100mL of tetrahydrofuran, stir well to obtain a mixture; take 140g of anhydrous potassium carbonate, 125g of p-hydroxybenzaldehyde and 500mL of tetrahydrofuran, stir well, add to the mixture, heat to 67℃, reflux for 24h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene;

[0111] Take 50g of hexa(4-aldehydephenoxy)cyclotriphosphazene, 15g of sodium hydroxide, 300mL of tetrahydrofuran, and 300mL of distilled water, stir well, add 118g of potassium permanganate, filter under vacuum, evaporate by rotary evaporation, add hydrochloric acid, adjust the pH value to 3.5, precipitate, filter under vacuum, wash, and dry to obtain cyclotriphosphazene compounds.

[0112] Take 2000g of ε-caprolactam, 50g of cyclotriphosphazene compound, and 60g of distilled water. Under nitrogen atmosphere, heat to 251℃ and react for 3.5h. Then, react under vacuum for 2.2h. Finally, extract the material in deionized water at 100℃ for 24h and dry it to obtain carboxylated nylon 6 resin.

[0113] Step 2: Preparation of Aminographene:

[0114] Take 8g of γ-aminopropyltriethoxysilane and 80g of 10% methanol aqueous solution, stir evenly, add 30g of graphene oxide, heat to 68℃, stir for 1.5h, filter, wash and dry to obtain pretreated graphene; take 3g of succinic anhydride and 45g of ethylene glycolamine, mix evenly, add 25g of pretreated graphene and 1g of p-toluenesulfonic acid, heat to 108℃, stir for 4.5h, filter, wash and dry to obtain aminated graphene;

[0115] Step 3: Preparation of copper-plated graphene:

[0116] Take 0.0075 mol / L stannous chloride and 0.15 mol / L hydrochloric acid, stir well to obtain a sensitization solution; take 0.003 mol / L palladium chloride and 0.06 mol / L hydrochloric acid, stir well to obtain an activation solution; take 100 mL of the sensitization solution, add 2 g of aminated carbon fiber-graphene oxide composite, stir well, wash and filter, add 100 mL of the activation solution, stir well, wash and filter to obtain activated graphene;

[0117] Take 5g of copper sulfate pentahydrate, 300ml of deionized water, and 8ml of 37% formaldehyde solution, and stir well to obtain solution A; take 8g of anhydrous sodium carbonate, 300ml of deionized water, and 30g of potassium sodium tartrate, and stir well to obtain solution B; add solution A to solution B, mix well, and obtain plating solution.

[0118] 2g of activated graphene was placed in a plating solution for chemical copper plating. The reaction time was 5min. After precipitation, centrifugation, washing, and drying, copper-plated graphene was obtained.

[0119] Step 4: Preparation of Nylon Products

[0120] Take carboxylated nylon 6 resin, add nano β-silicon nitride, copper-plated graphene, antioxidant, and lubricant, blend, cool and granulate, and injection mold to obtain nylon products;

[0121] The nylon product comprises the following components, by weight: 112 parts carboxylated nylon 6 resin, 12 parts nano β-silicon nitride, 13 parts copper-plated graphene, 0.08 parts antioxidant, and 0.08 parts lubricant.

[0122] The lubricant is oleamide; the antioxidant is phosphite.

[0123] experiment:

[0124] The nylon products prepared using Examples 1-3 and Comparative Examples 1-3 were subjected to performance tests. The tensile strength of the nylon products was tested according to ASTM-D638; the kinetic friction coefficient of the nylon products was tested according to GB 3960-2023; and the thermal conductivity of the obtained nylon products was tested using a thermal constant analyzer. The data are shown below:

[0125]

[0126] Conclusions: In Comparative Example 1, without copper plating on the carbon fiber-graphene oxide composite, the thermal conductivity of the nylon product significantly decreased. In Examples 1-3, copper plating on the carbon fiber-graphene oxide composite created a better thermal conductivity pathway, enhancing the thermal conductivity of the nylon product. In Comparative Example 2, no amination treatment was performed on the carbon fiber-graphene oxide composite. In Examples 1-3, carbon fibers and graphene oxide were combined, improving the dispersion performance of graphene oxide. The amino groups on the copper-plated amination carbon fiber-graphene oxide composite can also react with the carboxyl groups on the carboxylated nylon 6 resin, improving the dispersion of the copper-plated amination carbon fiber-graphene oxide composite in the matrix, thereby improving the wear resistance and thermal conductivity of the nylon product. In Comparative Example 3, without the addition of carbon fiber, both the wear resistance and thermal conductivity of the nylon product decreased.

[0127] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a wear-resistant nylon product with thermal conductivity, characterized in that: Includes the following steps: Step 1: Place the activated aminated carbon fiber-graphene oxide composite into the plating solution for chemical copper plating. The reaction time is 5-10 min. After precipitation, centrifugation, washing, and drying, copper-plated aminated carbon fiber-graphene oxide composite is obtained. Step 2: Take carboxylated nylon 6 resin, add nano β-silicon nitride, copper-plated aminated carbon fiber-graphene oxide composite, antioxidant, lubricant, blend, cool and pelletize, and injection mold to obtain nylon products; The preparation method of the aminated carbon fiber-graphene oxide composite is as follows: γ-aminopropyltriethoxysilane and methanol aqueous solution are taken, stirred evenly, and carbon fiber-graphene oxide composite is added. The temperature is raised to 65-70℃, stirred for 1-2 hours, filtered, washed, and dried to obtain the pretreated carbon fiber-graphene oxide composite; succinic anhydride and ethylene glycolamine are taken, mixed evenly, and the pretreated carbon fiber-graphene oxide composite and p-toluenesulfonic acid are added. The temperature is raised to 105-110℃, stirred for 4-5 hours, filtered, washed, and dried to obtain the aminated carbon fiber-graphene oxide composite. The preparation method of the carbon fiber-graphene oxide composite is as follows: take carbon fiber and anhydrous ethanol, ultrasonically disperse for 10-14 hours, dry to obtain cleaned carbon fiber; take graphene oxide and deionized water, ultrasonically disperse to obtain graphene oxide dispersion; take deionized water and anhydrous ethanol, mix evenly, add silane coupling agent KH550, heat to 40-45℃, stir for 2-3 hours, add cleaned carbon fiber, stir for 2-3 hours, add graphene oxide dispersion, add hydrochloric acid dropwise, adjust pH value to 3, heat to 75-80℃, react for 2-3 hours, wash and dry to obtain carbon fiber-graphene oxide composite. The preparation method of the carboxylated nylon 6 resin is as follows: Includes the following steps: S1: Take hexachlorocyclotriphosphazene and tetrahydrofuran, stir evenly to obtain a mixed solution; take anhydrous potassium carbonate, p-hydroxybenzaldehyde and tetrahydrofuran, stir evenly, add to the mixed solution, heat to 65-70℃, reflux for 22-26h, filter, rotary evaporate, precipitate, filter, wash and dry to obtain hexa(4-aldehydephenoxy)cyclotriphosphazene; S2: Take hexa(4-aldehyde phenoxy)cyclotriphosphazene, sodium hydroxide, tetrahydrofuran, and distilled water, stir well, add potassium permanganate, filter, rotary evaporate, add hydrochloric acid, adjust the pH value to 3-4, precipitate, filter, wash, and dry to obtain cyclotriphosphazene compounds. S3: Take ε-caprolactam, cyclotriphosphazene compounds, and distilled water, heat to 250-252℃ under nitrogen atmosphere, react for 3-4 hours, vacuum reaction for 2-2.5 hours, then extract the material in deionized water at 100℃ for 22-26 hours, dry, and obtain carboxylated nylon 6 resin. In step one, the preparation method of the activated aminated carbon fiber-graphene oxide composite is as follows: take stannous chloride and hydrochloric acid, stir evenly to obtain a sensitization solution; take palladium chloride and hydrochloric acid, stir evenly to obtain an activation solution; take the sensitization solution, add the aminated carbon fiber-graphene oxide composite, stir evenly, wash and filter, add the activation solution, stir evenly, wash and filter to obtain the activated aminated carbon fiber-graphene oxide composite. The plating solution is prepared as follows: copper sulfate pentahydrate, deionized water, and formaldehyde solution are stirred evenly to obtain solution A; anhydrous sodium carbonate, deionized water, and potassium sodium tartrate are stirred evenly to obtain solution B; solution A is added to solution B and mixed evenly to obtain the plating solution.

2. The method for preparing a wear-resistant nylon product with thermal conductivity according to claim 1, characterized in that: The nylon product comprises the following components, by weight: 100-115 parts carboxylated nylon 6 resin, 10-15 parts nano β-silicon nitride, 10-15 parts copper-plated aminated carbon fiber-graphene oxide composite, 0.05-0.1 parts antioxidant, and 0.05-0.1 parts lubricant.

3. The method for preparing a wear-resistant nylon product with thermal conductivity according to claim 1, characterized in that: The lubricant is any one or more of oleamide, glyceryl stearate, and calcium stearate.

4. The method for preparing a wear-resistant nylon product with thermal conductivity according to claim 1, characterized in that: The antioxidant is any one or more of phosphite, 2,6-di-tert-butyl-p-cresol, and dodecyl alcohol ester.

5. A nylon product prepared by the method for preparing a thermally conductive and wear-resistant nylon product according to any one of claims 1-4.

Images