CN112898564A - Preparation method of nylon directionally arranged under external magnetic field condition - Google Patents

Preparation method of nylon directionally arranged under external magnetic field condition Download PDF

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Publication number
CN112898564A
CN112898564A CN202110088765.5A CN202110088765A CN112898564A CN 112898564 A CN112898564 A CN 112898564A CN 202110088765 A CN202110088765 A CN 202110088765A CN 112898564 A CN112898564 A CN 112898564A
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nylon
magnetic field
graphene
graphene oxide
aqueous solution
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丁玉婕
何大方
史小军
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Changzhou Changruiyuan Material Technology Co ltd
Jiangsu Jiangnan Elenyl Graphene Technology Co ltd
JIANGNAN GRAPHENE RESEARCH INSTITUTE
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Changzhou Changruiyuan Material Technology Co ltd
Jiangsu Jiangnan Elenyl Graphene Technology Co ltd
JIANGNAN GRAPHENE RESEARCH INSTITUTE
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Priority to CN202110088765.5A priority Critical patent/CN112898564A/en
Publication of CN112898564A publication Critical patent/CN112898564A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

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 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; the method is characterized in that the Fe is coated by the constructed graphene oxide3O4Structure by mixing Fe3O4The 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.

Description

Preparation method of nylon directionally arranged under external magnetic field condition
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 FeCl3·6H2O and FeCl3·4H2And 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: FeCl3·6H21.12-5.6 parts of O and FeCl3·4H20.42 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 FeCl3·6H2O and FeCl3·4H2And O is mixed to prepare the composition. Fe3O4The weight ratio of each component of the granule is as follows: FeCl3·6H21.12-5.6 parts of O and FeCl3·4H20.42 to 2.1 portions of O.
Example 1:
A. 0.5g of graphite oxide and 1.12g of FeCl3·6H2O、0.42gFeCl3·4H2O 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 FeCl3·6H2O、0.83gFeCl3·4H2O 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 FeCl3·6H2O、1.25gFeCl3·4H2O 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 FeCl3·6H2O、1.65gFeCl3·4H2O 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 FeCl3·6H2O、2.1gFeCl3·4H2O 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).

Claims (7)

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 FeCl3·6H2O and FeCl3·4H2And 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: FeCl3·6H21.12-5.6 parts of O and FeCl3·4H20.42 to 2.1 portions of O.
CN202110088765.5A 2021-01-22 2021-01-22 Preparation method of nylon directionally arranged under external magnetic field condition Pending CN112898564A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933948A (en) * 2014-04-21 2014-07-23 南华大学 Grated loading method of nano Fe3O4 and beer saccharomycete and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933948A (en) * 2014-04-21 2014-07-23 南华大学 Grated loading method of nano Fe3O4 and beer saccharomycete and application thereof

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Application publication date: 20210604