阅读说明：本技术 在外磁场条件下定向排列的尼龙的制备方法 (Preparation method of nylon directionally arranged under external magnetic field condition ) 是由 丁玉婕 何大方 史小军 于 2021-01-22 设计创作，主要内容包括：本发明涉及尼龙制备方法领域,尤其是在外磁场条件下定向排列的尼龙的制备方法。该制备方法的步骤为：A、通过水热法制备出纳米Fe-3O-4颗粒,再将氨基化改性后的Fe-3O-4加入氧化石墨烯水溶液中,最后通过离心、干燥后制备得出石墨烯/Fe-3O-4复合填料；B、将石墨烯/Fe-3O-4复合填料与二元胺在水溶液中超声,反应完全后进行抽滤,水洗,最后置于真空干燥箱中干燥,得到羧酸铵盐；该发明通过构筑氧化石墨烯包覆Fe-3O-4结构,通过将Fe-3O-4沉积到氧化石墨烯上,使得纳米粒子具有磁性,在磁性条件下快速有效的响应特征,从而可以使得氧化石墨烯在尼龙基体中定向排列,实现尼龙的高导热性能。(The invention relates to the field of nylon preparation methods, in particular to a preparation method of nylon which is directionally arranged under the condition of an external magnetic field. The preparation method comprises the following steps: A. preparing nano Fe by a hydrothermal method 3 O 4 Particles of Fe modified by amination 3 O 4 Adding the mixture into a graphene oxide aqueous solution, and finally centrifuging and drying the mixture to obtain graphene/Fe 3 O 4 Composite filler; B. mixing graphene/Fe 3 O 4 Carrying out ultrasonic treatment on the composite filler and diamine in an aqueous solution, carrying out suction filtration after complete reaction, washing with water, and finally drying in a vacuum drying oven to obtain ammonium carboxylate; the method is characterized in that the Fe is coated by the constructed graphene oxide 3 O 4 Structure by mixing Fe 3 O 4 The graphene oxide nanoparticles are deposited on the graphene oxide, so that the nanoparticles have magnetism and quick and effective response characteristics under the magnetic condition, the graphene oxide can be directionally arranged in a nylon matrix, and the high heat-conducting property of nylon is realized.)

1. A preparation method of nylon directionally arranged under the condition of an external magnetic field is characterized by comprising the following steps:

A. preparing nano Fe by a hydrothermal method₃O₄Particles of Fe modified by amination₃O₄Adding the mixture into a graphene oxide aqueous solution, and finally centrifuging and drying the mixture to obtain graphene/Fe₃O₄Composite filler;

B. mixing graphene/Fe₃O₄Carrying out ultrasonic treatment on the composite filler and diamine in an aqueous solution, carrying out suction filtration after complete reaction, washing with water, and finally drying in a vacuum drying oven to obtain ammonium carboxylate;

C. mixing ammonium carboxylate and a prepolymer of nylon, placing the mixture into a mold, placing the mold into a vacuum drying oven, heating to 230-250 ℃, and simultaneously applying a strong magnetic field to two sides of the mold to obtain a sample;

D. and (3) putting the sample into a reaction kettle, introducing protective gas, gradually raising the temperature to 285 ℃, continuously discharging water vapor, and extruding and drying the sample after the reaction is finished to obtain the nylon composite resin.

2. The method for preparing nylon directionally arranged under the condition of an external magnetic field as claimed in claim 1, wherein the nylon comprises the following components in parts by weight: fe₃O₄1.54-7.7 parts of particles, 0.5 part of graphene oxide aqueous solution, 21-66.5 parts of diamine and 14.3-42.9 parts of dibasic acid.

3. The method according to claim 1, wherein the dibasic acid is at least one of adipic acid, oxalic acid, succinic acid, sebacic acid, and dodecanedioic acid.

4. The method as claimed in claim 1, wherein the hydrothermal reaction temperature in step A is 65-125 ℃.

5. The method for preparing nylon oriented under external magnetic field according to claim 1, wherein in step C, the magnetic field strength is 5-10T, and the reaction time in the mold is 2-3 hours.

6. The method as claimed in claim 1, wherein the Fe is in the form of Fe₃O₄The particles being made of FeCl_3·6H₂O and FeCl_3·4H₂And O is mixed to prepare the composition.

7. The method as claimed in claim 6, wherein the Fe is in the form of Fe₃O₄The weight ratio of each component of the granule is as follows: FeCl_3·6H₂1.12-5.6 parts of O and FeCl_3·4H₂0.42 to 2.1 portions of O.

Technical Field

The invention relates to the field of nylon preparation methods, in particular to a preparation method of nylon which is directionally arranged under the condition of an external magnetic field.

Background

The use of plastics to replace steel and the use of plastics to replace wood has become a popular trend in the market, and nylon engineering plastics are widely applied to industries such as electronics and electricity, automobiles, buildings, office equipment, machinery, aerospace and the like due to the high performance advantages of the nylon engineering plastics in the aspects of mechanical performance, durability, corrosion resistance, heat resistance and the like. However, polymers are generally thermally insulating, and nylon has a thermal conductivity of 0.2-0.3W/(m.K), which limits the application of nylon materials in specific industries.

In order to improve the heat conduction, it is most effective to construct a heat-conducting network in a nylon matrix, and to improve the material system, various heat-conducting fillers are added in the matrix gaps, such as: metal oxide, metal nitride, carbon-based composite filler. However, the filler is usually added in a large amount, which not only increases the material cost, but also affects the mechanical strength of the polymer itself; also, once the filler is mixed with the polymer, an interface is formed, resulting in the generation of interface thermal resistance.

Disclosure of Invention

In order to overcome the defect of poor performance of the existing nylon, the invention provides a preparation method of nylon which is directionally arranged under the condition of an external magnetic field.

The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of nylon directionally arranged under the condition of an external magnetic field comprises the following steps:

A. preparing nano Fe by a hydrothermal method₃O₄Particles of Fe modified by amination₃O₄Adding the mixture into a graphene oxide aqueous solution, and finally centrifuging and drying the mixture to obtain graphene/Fe₃O₄Composite filler;

B. will be provided withgraphene/Fe₃O₄Carrying out ultrasonic treatment on the composite filler and diamine in an aqueous solution, carrying out suction filtration after complete reaction, washing with water, and finally drying in a vacuum drying oven to obtain ammonium carboxylate;

C. mixing ammonium carboxylate and a prepolymer of nylon, placing the mixture into a mold, placing the mold into a vacuum drying oven, heating to 230-250 ℃, and simultaneously applying a strong magnetic field to two sides of the mold to obtain a sample;

D. and (3) putting the sample into a reaction kettle, introducing protective gas, gradually raising the temperature to 285 ℃, continuously discharging water vapor, and extruding and drying the sample after the reaction is finished to obtain the nylon composite resin.

According to another embodiment of the invention, the nylon further comprises the following components in parts by weight: fe₃O₄1.54-7.7 parts of particles, 0.5 part of graphene oxide aqueous solution, 21-66.5 parts of diamine and 14.3-42.9 parts of dibasic acid.

According to another embodiment of the present invention, it further comprises that the dibasic acid is at least one of adipic acid, oxalic acid, succinic acid, sebacic acid, and dodecanedioic acid.

According to another embodiment of the invention, the reaction temperature of the hydrothermal method in the step A is 65-125 ℃.

According to another embodiment of the invention, the method further comprises the step C, wherein the magnetic field intensity is 5-10T, and the reaction time in the mold is 2-3 hours.

According to another embodiment of the present invention, further comprising said Fe₃O₄The particles being made of FeCl_3·6H₂O and FeCl_3·4H₂And O is mixed to prepare the composition.

According to another embodiment of the present invention, further comprising said Fe₃O₄The weight ratio of each component of the granule is as follows: FeCl_3·6H₂1.12-5.6 parts of O and FeCl_3·4H₂0.42 to 2.1 portions of O.

The preparation method has the beneficial effects that the Fe is coated by constructing the graphene oxide₃O₄Structure by mixing Fe₃O₄Deposition onto graphene oxideIn addition, the nano particles have magnetism and quick and effective response characteristics under the magnetic condition, so that the graphene oxide can be directionally arranged in the nylon matrix, and the high heat-conducting property of nylon is realized.

Detailed Description

A preparation method of nylon directionally arranged under the condition of an external magnetic field comprises the following steps:

A. preparing nano Fe by a hydrothermal method₃O₄Particles of Fe modified by amination₃O₄Adding the mixture into a graphene oxide aqueous solution, and finally centrifuging and drying the mixture to obtain graphene/Fe₃O₄Composite filler;

B. mixing graphene/Fe₃O₄Carrying out ultrasonic treatment on the composite filler and diamine in an aqueous solution, carrying out suction filtration after complete reaction, washing with water, and finally drying in a vacuum drying oven to obtain ammonium carboxylate;

C. mixing ammonium carboxylate and a prepolymer of nylon, placing the mixture into a mold, placing the mold into a vacuum drying oven, heating to 230-250 ℃, and simultaneously applying a strong magnetic field to two sides of the mold to obtain a sample;

D. and (3) putting the sample into a reaction kettle, introducing protective gas, gradually raising the temperature to 285 ℃, continuously discharging water vapor, and extruding and drying the sample after the reaction is finished to obtain the nylon composite resin.

The nylon comprises the following components in parts by weight: fe₃O₄1.54-7.7 parts of particles, 0.5 part of graphene oxide aqueous solution, 21-66.5 parts of diamine and 14.3-42.9 parts of dibasic acid. The dibasic acid is at least one of adipic acid, oxalic acid, succinic acid, sebacic acid and dodecanedioic acid. In the step A, the reaction temperature of the hydrothermal method is 65-125 ℃. In the step C, the magnetic field intensity is 5-10T, and the reaction time in the mold is 2-3 hours. Fe₃O₄The particles being made of FeCl_3·6H₂O and FeCl_3·4H₂And O is mixed to prepare the composition. Fe₃O₄The weight ratio of each component of the granule is as follows: FeCl_3·6H₂1.12-5.6 parts of O and FeCl_3·4H₂0.42 to 2.1 portions of O.

Example 1:

A. 0.5g of graphite oxide and 1.12g of FeCl_3·6H₂O、0.42gFeCl_3·4H₂O is mixed in methanol; mechanically stirring for 20min to obtain black flocculate; gradually dropwise adding 10g of pentamethylene diamine into the black flocculate until the pH is = 9; placing the mixed solution in a microwave hydrothermal reactor, and controlling the reaction temperature at 65 ℃; after reacting for 1.5 hours, centrifuging and drying the precipitate to obtain the graphene/Fe₃O₄A composite material;

B. 5g of graphene/Fe₃O₄Carrying out ultrasonic treatment on the composite material and 1g of pentamethylene diamine in an aqueous solution, controlling the temperature at 40 ℃ and the concentration of dissolved salt at 30 wt%; performing ultrasonic reaction for 20min, then performing suction filtration, washing with water, and finally drying in a vacuum drying oven at 40 ℃ to obtain ammonium carboxylate;

C. an aqueous solution of 10g of pentamethylenediamine was slowly added to 14.3g of adipic acid while controlling the temperature in the polymerization reactor at 240 c,

controlling the pressure at 0.1MPa, and using nitrogen for protection in the polymerization process to obtain a nylon prepolymer;

mixing 5g of ammonium carboxylate and 200g of nylon prepolymer, placing the mixture into a mold, placing the mold into a vacuum drying oven, heating to 230 ℃, simultaneously placing an external magnetic field with the strength of 5T on two sides of the mold, and reacting for 2 hours to obtain a sample.

D. And (3) putting the sample into a reaction kettle, introducing nitrogen, gradually increasing the temperature to 280 ℃, continuously discharging water vapor, reacting for 0.5h, extruding and drying the materials to obtain the nylon composite resin.

The nylon prepared in example 1 was tested to have a tensile strength of 102MPa and a thermal conductivity of 1.2W/(m.K).

Example 2:

A. 0.5g of graphite oxide and 2.24g of FeCl_3·6H₂O、0.83gFeCl_3·4H₂O is mixed in methanol; mechanically stirring for 20min to obtain black flocculate; gradually dropwise adding 15g of pentamethylene diamine into the black flocculate until the pH is = 9; placing the mixed solution in a microwave hydrothermal reactor, and controlling the reaction temperature at 70 ℃; after reacting for 1.5 hours, centrifuging and drying the precipitate to obtain the stonegraphene/Fe₃O₄A composite material;

B. 5g of graphene/Fe₃O₄Carrying out ultrasonic treatment on the composite material and 1.5g of pentamethylene diamine in an aqueous solution, controlling the temperature at 40 ℃ and the concentration of dissolved salt at 30 wt%; performing ultrasonic reaction for 20min, then performing suction filtration, washing with water, and finally drying in a vacuum drying oven at 40 ℃ to obtain ammonium carboxylate;

C. an aqueous solution of 15g of pentamethylenediamine was slowly added to 21.45g of adipic acid, and the temperature in the polymerization reactor was controlled to be

Controlling the pressure at 240 ℃ and 0.1MPa, and using nitrogen for protection in the polymerization process to obtain a nylon prepolymer;

mixing 5g of ammonium carboxylate and 200g of nylon prepolymer, placing the mixture into a mold, placing the mold into a vacuum drying oven, heating to 230 ℃, simultaneously placing an external magnetic field with the strength of 6T on two sides of the mold, and reacting for 2 hours to obtain a sample.

D. And (3) putting the sample into a reaction kettle, introducing nitrogen, gradually increasing the temperature to 280 ℃, continuously discharging water vapor, reacting for 0.5h, extruding and drying the materials to obtain the nylon composite resin.

The nylon prepared in example 2 was tested to have a tensile strength of 115MPa and a thermal conductivity of 1.5W/(m.K).

Example 3:

A. 0.5g of graphite oxide and 3.36g of FeCl_3·6H₂O、1.25gFeCl_3·4H₂O is mixed in methanol; mechanically stirring for 40min to obtain black flocculate; gradually dropping 20g of pentamethylene diamine into the black flocculate until the pH is = 9; placing the mixed solution in a microwave hydrothermal reactor, and controlling the reaction temperature at 105 ℃; after reacting for 1.5 hours, centrifuging and drying the precipitate to obtain the graphene/Fe₃O₄A composite material;

B. 5g of graphene/Fe₃O₄Carrying out ultrasonic treatment on the composite material and 2.5g of pentamethylene diamine in an aqueous solution, controlling the temperature at 60 ℃ and the concentration of dissolved salt at 50 wt%; carrying out suction filtration and water washing after the ultrasonic reaction is carried out for 40min, and finally drying in a vacuum drying oven at 40 ℃ to obtain ammonium carboxylate;

C. an aqueous solution of 23g of pentamethylenediamine was slowly added to 28.6g of adipic acid, and the temperature in the polymerization reactor was controlled to be

Controlling the pressure at 230 ℃ and 1MPa, and using nitrogen for protection in the polymerization process to obtain a nylon prepolymer;

mixing 5g of ammonium carboxylate and 300g of nylon prepolymer, placing the mixture into a mold, placing the mold into a vacuum drying oven, heating to 250 ℃, simultaneously placing an external magnetic field with the strength of 7T on two sides of the mold, and reacting for 3 hours to obtain a sample.

D. And (3) putting the sample into a reaction kettle, introducing nitrogen, gradually increasing the temperature to 280 ℃, continuously discharging water vapor, reacting for 1h, extruding and drying the materials to obtain the nylon composite resin.

The nylon prepared in example 3 was tested to have a tensile strength of 102MPa and a thermal conductivity of 2.1W/(m.K).

Example 4:

A. 0.5g of graphite oxide and 4.48g of FeCl_3·6H₂O、1.65gFeCl_3·4H₂O is mixed in methanol; mechanically stirring for 40min to obtain black flocculate; gradually dropwise adding 25g of pentamethylene diamine into the black flocculate until the pH is = 9; placing the mixed solution in a microwave hydrothermal reactor, and controlling the reaction temperature at 110 ℃; after reacting for 1.5 hours, centrifuging and drying the precipitate to obtain the graphene/Fe₃O₄A composite material;

B. 5g of graphene/Fe₃O₄Carrying out ultrasonic treatment on the composite material and 2.5g of pentamethylene diamine in an aqueous solution, controlling the temperature at 60 ℃ and the concentration of dissolved salt at 50 wt%; carrying out suction filtration and water washing after the ultrasonic reaction is carried out for 40min, and finally drying in a vacuum drying oven at 40 ℃ to obtain ammonium carboxylate;

C. an aqueous solution of 28g of pentamethylenediamine was slowly added to 35.75g of adipic acid, and the temperature in the polymerization reactor was controlled to be

Controlling the pressure at 230 ℃ and 1MPa, and using nitrogen for protection in the polymerization process to obtain a nylon prepolymer;

5g of ammonium carboxylate and 350g of nylon prepolymer are mixed and placed in a mould, the mould is placed in a vacuum drying oven, the temperature is raised to 250 ℃, and simultaneously an external magnetic field with the strength of 8T is placed on two sides of the mould to react for 3 hours, so that a sample is obtained.

D. And (3) putting the sample into a reaction kettle, introducing nitrogen, gradually increasing the temperature to 280 ℃, continuously discharging water vapor, reacting for 1h, extruding and drying the materials to obtain the nylon composite resin.

The nylon prepared in example 4 was tested to have a tensile strength of 112MPa and a thermal conductivity of 2.7W/(m.K).

Example 5:

A. 0.5g of graphite oxide and 5.6g of FeCl_3·6H₂O、2.1gFeCl_3·4H₂O is mixed in methanol; mechanically stirring for 40min to obtain black flocculate; gradually dropwise adding 30g of pentamethylene diamine into the black flocculate until the pH is = 9; placing the mixed solution in a microwave hydrothermal reactor, and controlling the reaction temperature to be 125 ℃; after reacting for 1.5 hours, centrifuging and drying the precipitate to obtain the graphene/Fe₃O₄A composite material;

B. 5g of graphene/Fe₃O₄Carrying out ultrasonic treatment on the composite material and 2.5g of pentamethylene diamine in an aqueous solution, controlling the temperature at 60 ℃ and the concentration of dissolved salt at 50 wt%; carrying out suction filtration and water washing after the ultrasonic reaction is carried out for 40min, and finally drying in a vacuum drying oven at 40 ℃ to obtain ammonium carboxylate;

C. an aqueous solution of 34g of pentamethylenediamine was slowly added to 42.9g of adipic acid, and the temperature in the polymerization vessel was controlled to be

Controlling the pressure at 230 ℃ and 1MPa, and using nitrogen for protection in the polymerization process to obtain a nylon prepolymer;

mixing 5g of ammonium carboxylate and 400g of nylon prepolymer, placing the mixture into a mold, placing the mold into a vacuum drying oven, heating to 250 ℃, simultaneously placing an external magnetic field with the strength of 9T on two sides of the mold, and reacting for 3 hours to obtain a sample.

D. And (3) putting the sample into a reaction kettle, introducing nitrogen, gradually increasing the temperature to 280 ℃, continuously discharging water vapor, reacting for 1h, extruding and drying the materials to obtain the nylon composite resin.

The nylon prepared in example 5 was tested to have a tensile strength of 116MPa and a thermal conductivity of 1.8W/(m.K).