CN111349305A - Polyformaldehyde/graphene nanocomposite and preparation method and application thereof - Google Patents
Polyformaldehyde/graphene nanocomposite and preparation method and application thereof Download PDFInfo
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- CN111349305A CN111349305A CN202010078748.9A CN202010078748A CN111349305A CN 111349305 A CN111349305 A CN 111349305A CN 202010078748 A CN202010078748 A CN 202010078748A CN 111349305 A CN111349305 A CN 111349305A
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- 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
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention discloses a polyformaldehyde/graphene nanocomposite and a preparation method and application thereof, wherein the preparation method comprises the following steps: dispersing graphene oxide in a composite solvent, adding an amino compound, uniformly mixing, adding an amino fluorine-containing polyether or a hydroxyl fluorine-containing polyether, uniformly dispersing, and drying to obtain the graphene oxide subjected to coupling treatment; uniformly mixing polyformaldehyde, an antioxidant and the coupled graphene oxide, and then melting and mixing to obtain the polyformaldehyde/graphene nanocomposite. Prepared polyoxymethylene/graphene nanocomposite material, which is prepared byThe thermal weight loss rate of 1 hour heated at 230 ℃ under vacuum is reduced by 60-80 percent relative to pure polyformaldehyde, the tensile strength can reach 50-60 MPa, and the notch impact strength can reach 7-9 KJ/m2The elongation at break can reach 40-50%, and the friction coefficient can reach 0.12-0.2.
Description
Technical Field
The invention belongs to the field of processing of high polymer materials, and particularly relates to a polyformaldehyde/graphene nanocomposite and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Polyoxymethylene (POM) is [ -CH2-O-]The thermoplastic engineering plastic is a main chain, has no branching, high melting point, high density and high crystallization, has high strength and rigidity, excellent creep resistance, fatigue resistance, inherent lubricity, wear resistance, chemical resistance and the like, is the closest metal variety in the engineering plastic, can replace nonferrous metals such as copper, aluminum, zinc and the like and alloy products, and is widely applied to the fields of electronics and electricity, automobiles, light industry, machinery, chemical industry, building materials and the like. The graphene is a carbon material formed by tightly stacking sp2 hybridized carbon atoms into a single-layer two-dimensional honeycomb lattice structure, has excellent mechanical, thermal and electrical properties, wear-resisting self-lubricating property and extremely large specific surface area, and can be used for formaldehyde and formic acidAnd the degradation products have better adsorption effect. Therefore, the graphene is compounded with the polyformaldehyde, so that the mechanical property, the wear-resistant self-lubricating property, the thermal stability, the aging resistance and the like of the polyformaldehyde can be further improved, the application of the polyformaldehyde in the fields of aerospace, automobiles, electronics and the like is widened, and the actual higher application requirements are met.
Research work related to the polyformaldehyde/graphene nanocomposite material is preliminarily carried out. The inventor finds that related reports on the research of the polyformaldehyde/graphene nanocomposite are few at present, because polyformaldehyde molecular chains are regular, have no polarity, have high crystallinity and have poor compatibility with other resins or fillers; the graphene with a complete structure consists of benzene rings, so that the chemical stability is high, the surface is inert, the effect with other media is weak, strong van der Waals force exists between graphene sheets, the aggregation is easy, and the research and application of the graphene are greatly limited.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention aims to provide a polyformaldehyde/graphene nanocomposite and a preparation method and application thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a polyformaldehyde/graphene nanocomposite material comprises the following steps:
dispersing graphene oxide in a composite solvent, adding an amino compound, uniformly mixing, adding an amino fluorine-containing polyether or a hydroxyl fluorine-containing polyether, uniformly dispersing, and drying to obtain the graphene oxide subjected to coupling treatment;
uniformly mixing polyformaldehyde, an antioxidant and the coupled graphene oxide, and then melting and mixing to obtain the polyformaldehyde/graphene nanocomposite.
Grafting a formaldehyde absorbent-amino compound of polyformaldehyde on graphene oxide molecules, and further intercalating amine-terminated or hydroxyl-terminated fluorine-containing polyether between graphene layers, wherein the fluorine-containing polyether compound is not only a high-efficiency lubricant, but also has a similar molecular structure as polyformaldehyde; meanwhile, the formaldehyde absorbent-amino compound can be riveted on the surface of the graphene to stabilize and improve the migration resistance, and has a strong intermolecular action with polyformaldehyde molecules, so that the dispersibility of the graphene in a polyformaldehyde matrix can be improved, the polyformaldehyde/graphene nanocomposite can be prepared by conventional extrusion, injection molding, hot pressing and other processing methods, and the thermal stability, wear resistance and self-lubricity of the polyformaldehyde are effectively improved.
In some embodiments, the amine based compound is melamine, dicyandiamide, or urea.
In some embodiments, the composite solvent is a deionized water-methanol composite solvent, and the volume ratio of deionized water to methanol is 1: 1. The formaldehyde absorbent can only be dissolved in the composite solvent with the proportion.
In some embodiments, the amino-terminated fluoropolyether has a viscosity index of 30 to 200 and the amino-terminated fluoropolyether has a viscosity index of 30 to 200.
In some embodiments, the antioxidant is pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (Irganox1010), N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine (Irganox1098), octadecyl β - (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (Irganox 1076), or 2, 6-di-tert-butyl-4-methylphenol (BHT (264)).
In some embodiments, the mass ratio of the polyformaldehyde to the graphene oxide to the antioxidant to the amino compound to the fluoropolyether is 100:0.1-20:0.05-5:0.05-10: 0.5-20.
Further, the melt index of the polyformaldehyde is 9-27g/10 min.
The polyformaldehyde/graphene nanocomposite prepared by the preparation method of the polyformaldehyde/graphene nanocomposite.
The polyformaldehyde/graphite fine nano composite material is applied to the fields of aerospace, automobiles and electronics and electricity.
The invention has the beneficial effects that:
aiming at the problems that the compatibility of polyformaldehyde and other resins or fillers is poor, strong van der Waals force exists between graphene sheets, and the graphene sheets are easy to agglomerate and difficult to disperse, the formaldehyde absorbent is grafted on the graphene oxide molecules by utilizing the reaction of amine groups on the formaldehyde absorbent molecules of polyformaldehyde and carboxyl groups and epoxy groups on the graphene oxide molecules, so that the migration resistance of the low-molecular-weight formaldehyde absorbent can be improved, the volatilization loss in processing and application is reduced, the dispersibility of the graphene in a polyformaldehyde matrix can be improved by the strong action of the formaldehyde absorbent and the polyformaldehyde molecules, and the alkaline formaldehyde absorbent has certain reducibility on the graphene oxide and can improve the wear resistance of the graphene oxide.
The amino-terminated or hydroxyl-terminated fluoropolyether is further intercalated between the graphene layers, and the fluoropolyether compound is not only a high-efficiency lubricant, but also can be used for promoting the wear-resistant self-lubricating property of polyformaldehyde in cooperation with graphene and has a similar molecular structure with polyformaldehyde, so that the dispersibility of the graphene in a polyformaldehyde matrix can be further improved, the polyformaldehyde/graphene nanocomposite can be prepared by conventional extrusion, injection molding, hot pressing and other processing methods, the thermal stability, the wear-resistant self-lubricating property, the antistatic property/electrical conductivity and the like of the polyformaldehyde are effectively promoted, the polyformaldehyde/graphene nanocomposite with excellent comprehensive performance is obtained, and the application prospect is good.
The thermal weight loss rate of the prepared polyformaldehyde/graphene nanocomposite material heated at 230 ℃ for 1 hour under vacuum is reduced by 60-80% relative to pure polyformaldehyde, the tensile strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 50-60 MPa, and the notch impact strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 7-9 KJ/m2The elongation at break can reach 40-50%, and the friction coefficient can reach 0.12-0.2.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example 1
Dispersing 10g of graphene oxide in 2000g of deionized water/methanol composite solvent with the volume ratio of 1:1, adding 10g of melamine to dissolve at room temperature, uniformly stirring, dispersing for 60min by adopting ultrasonic waves, further adding 20g of hydroxyl-terminated fluorine-containing polyether with the viscosity index of 100, and performing ultrasonic dispersion for 80min, wherein the ultrasonic power is 2000w and the ultrasonic temperature is 50 ℃; filtering the product, washing with distilled water/methanol, and drying at 90 deg.C for 8 hr to constant weight;
adding 1Kg of polyformaldehyde, 3g of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (namely Irganox1010) and 10g of coupling-treated graphene oxide into a high-speed mixer, uniformly mixing, melting and mixing by using a double-screw extruder, extruding and granulating, wherein the rotating speed of a screw is 50-200 revolutions per minute, and the temperature of a charging barrel is 140-220 ℃, so as to obtain the polyformaldehyde/graphene nanocomposite.
The thermal weight loss rate of the prepared polyformaldehyde/graphene nanocomposite material heated at 230 ℃ for 1 hour under vacuum is reduced by 80 percent relative to pure polyformaldehyde, the tensile strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 60MPa, and the notch impact strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 9KJ/m2The elongation at break can reach 45%, and the friction coefficient can reach 0.2.
Example 2
Dispersing 50g of graphene oxide in 5000g of deionized water/methanol composite solvent with the volume ratio of 1:1, adding 40g of urea to dissolve at room temperature, uniformly stirring, dispersing for 90min by adopting ultrasonic waves, further adding 50g of amino-terminated fluoropolyether with the viscosity index of 80, and dispersing for 90min by adopting ultrasonic waves, wherein the ultrasonic wave power is 2500w, and the ultrasonic temperature is 65 ℃; filtering the product, washing with distilled water/methanol, and drying at 90 deg.C for 8 hr to constant weight;
adding 1Kg of polyformaldehyde, 5g N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine (Irganox1098) and 50g of coupling-treated graphene oxide into a high-speed mixer, uniformly mixing, melting and mixing by using a double-screw extruder, extruding and granulating, wherein the rotating speed of a screw is 50-200 revolutions per minute, and the temperature of a charging barrel is 140-220 ℃, so as to obtain the polyformaldehyde/graphene nanocomposite.
The thermal weight loss rate of the prepared polyformaldehyde/graphene nanocomposite material heated at 230 ℃ for 1 hour under vacuum is reduced by 70 percent relative to pure polyformaldehyde, the tensile strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 55MPa, and the notch impact strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 8KJ/m2The elongation at break can reach 50%, and the friction coefficient can reach 0.14.
Example 3
Dispersing 5g of graphene oxide in 1000g of deionized water/methanol composite solvent with the volume ratio of 1:1, adding 7g of dicyandiamide to dissolve at room temperature, uniformly stirring, dispersing for 60min by adopting ultrasonic waves, further adding 40g of amino-terminated fluorine-containing polyether with the viscosity index of 120, and ultrasonically dispersing for 60min, wherein the ultrasonic power is 1000w, and the ultrasonic temperature is 60 ℃; filtering the product, washing with distilled water/methanol, and drying at 90 deg.C for 8 hr to constant weight;
adding 1Kg of polyformaldehyde, 4g of β - (4-hydroxy-3, 5-di-tert-butylphenyl) octadecyl propionate (Irganox 1076) and 5g of graphene oxide subjected to coupling treatment into a high-speed mixer, uniformly mixing, melting and mixing by using a double-screw extruder, and carrying out extrusion granulation at a screw rotation speed of 50-200 r/min and a cylinder temperature of 140-220 ℃ to obtain the polyformaldehyde/graphene nanocomposite.
The thermal weight loss rate of the prepared polyformaldehyde/graphene nanocomposite material heated at 230 ℃ for 1 hour under vacuum is reduced by 60 percent relative to pure polyformaldehyde, the tensile strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 50MPa, and the notch impact strength of the prepared polyformaldehyde/graphene nanocomposite material can reach 7KJ/m2The elongation at break can reach 40%, and the friction coefficient can reach 0.15.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a polyformaldehyde/graphene nanocomposite material is characterized by comprising the following steps: the method comprises the following steps:
dispersing graphene oxide in a composite solvent, adding an amino compound, uniformly mixing, adding an amino fluorine-containing polyether or a hydroxyl fluorine-containing polyether, uniformly dispersing, and drying to obtain the graphene oxide subjected to coupling treatment;
uniformly mixing polyformaldehyde, an antioxidant and the coupled graphene oxide, and then melting and mixing to obtain the polyformaldehyde/graphene nanocomposite.
2. The method for preparing a polyoxymethylene/graphene nanocomposite as claimed in claim 1, wherein: the amino compound is melamine, dicyandiamide or urea.
3. The method for preparing a polyoxymethylene/graphene nanocomposite as claimed in claim 1, wherein: the composite solvent is a deionized water-methanol composite solvent.
4. The method for preparing a polyoxymethylene/graphene nanocomposite as claimed in claim 3, wherein: the volume ratio of deionized water to methanol was 1: 1.
5. The method for preparing a polyoxymethylene/graphene nanocomposite as claimed in claim 1, wherein: the viscosity index of the amino-terminated fluoropolyether is 30-200, and the viscosity index of the amino-terminated fluoropolyether is 30-200.
6. The method for preparing a polyoxymethylene/graphene nanocomposite according to claim 1, wherein the antioxidant is pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (Irganox1010), N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexanediamine (Irganox1098), octadecyl β - (4-hydroxy-3, 5-di-tert-butylphenyl) propionate (Irganox 1076), or 2, 6-di-tert-butyl-4-methylphenol (BHT (264)).
7. The method for preparing a polyoxymethylene/graphene nanocomposite as claimed in claim 1, wherein: the mass ratio of the polyformaldehyde to the graphene oxide to the antioxidant to the amino compound to the fluorine-containing polyether is 100:0.1-20:0.05-5:0.05-10: 0.5-20.
8. The method for preparing a polyoxymethylene/graphene nanocomposite as claimed in claim 7, wherein: the melt index of the polyformaldehyde is 9-27g/10 min.
9. A polyoxymethylene/graphene nanocomposite material prepared by the method for preparing a polyoxymethylene/graphene nanocomposite material as set forth in any one of claims 1 to 8.
10. Use of the polyoxymethylene/graphite fine nanocomposite as claimed in claim 9 in aerospace, automotive and electronic and electrical fields.
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