CN113337177A - Epoxy resin coating of porous organic polymer modified carbon nano tube and preparation method thereof - Google Patents

Epoxy resin coating of porous organic polymer modified carbon nano tube and preparation method thereof Download PDF

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CN113337177A
CN113337177A CN202110569356.7A CN202110569356A CN113337177A CN 113337177 A CN113337177 A CN 113337177A CN 202110569356 A CN202110569356 A CN 202110569356A CN 113337177 A CN113337177 A CN 113337177A
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porous organic
organic polymer
epoxy resin
phosphaphenanthrene
carbon nano
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李晓云
陈明惠
李丽坤
张蓉
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Hua Bida Science And Technology Ltd S Of Shenzhen
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Hua Bida Science And Technology Ltd S Of Shenzhen
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

The invention belongs to the technical field of epoxy resin, and particularly relates to an epoxy resin coating of a porous organic polymer modified carbon nano tube and a preparation method thereof.

Description

Epoxy resin coating of porous organic polymer modified carbon nano tube and preparation method thereof
Technical Field
The invention belongs to the technical field of new epoxy resin materials, and particularly relates to an epoxy resin coating of a porous organic polymer modified carbon nanotube and a preparation method thereof.
Background
Organic compounds containing two or more Epoxy groups in the molecule are collectively called Epoxy resins (Epoxy resins), and are the most studied and important thermosetting resins at present. The limited oxygen index of the epoxy resin is only about 20 percent, and the epoxy resin has the defects of flammability, poor heat resistance, poor toughness and the like. In the actual combustion process, the epoxy resin material can release a large amount of black smoke and is accompanied with a melting and dropping phenomenon, and secondary combustion is easily caused. The disadvantage of epoxy resin also limits the practical application and development of epoxy resin in fields with higher flame retardant level requirements, such as electronic appliances, aerospace and the like. Therefore, in order to reduce or even eliminate the potential safety hazard of the epoxy resin in the use process, and simultaneously in order to widen the application range and meet the market demand, the flame retardant modification of the epoxy resin is of great practical significance.
A porous organic polymer linked by covalent bonds is a porous material with a large surface area and rich chemical groups. Currently, porous organic polymers are mainly classified into the following four categories: polymers of intrinsic microporosity, conjugated microporous polymers, hypercrosslinked polymers, and Covalent Organic Frameworks (COFs). It is reported that the porous organic polymer has many advantages such as a large specific surface area, good thermal stability, abundance of polar groups, low density and adjustable tunneling effect, etc. At present, porous organic polymers have been applied to various fields such as positive electrodes, negative electrodes, and solid electrolyte materials of lithium ion batteries.
Chinese patent CN201710491460 discloses an application of an epoxy resin cured product reinforced and functionalized by nitrogen-doped carbon nanotubes. Dispersing the nitrogen-doped carbon nano tube in epoxy resin, and constructing chemical bonds between the epoxy resin and the nitrogen-doped carbon nano tube by utilizing rich nitrogen-containing groups of the nitrogen-doped carbon nano tube, so that effective interaction is formed between the epoxy resin and the nitrogen-doped carbon nano tube, and the dispersion of the nitrogen-doped carbon nano tube in an epoxy matrix is promoted. When the formed composite material is subjected to external force, the stress can be effectively transferred from the matrix to the nitrogen-doped carbon nano tube, so that the mechanical property of the composite material is improved, and meanwhile, the composite material also has good conductive capability due to the excellent conductive performance of the nitrogen-doped carbon nano tube. But the flame retardance of the compounded epoxy resin material is not enhanced.
The existing flame retardant for the high polymer material comprises an inorganic flame retardant and an organic flame retardant, wherein the inorganic flame retardant is green and environment-friendly, but has large addition amount and influences the mechanical property of the high polymer material; the organic flame retardant has high flame retardant efficiency and good compatibility with high polymer materials, but most of the bromine-containing organic flame retardants are forbidden due to the generation of toxic gas during combustion. Therefore, the design and development of environment-friendly and high-performance flame retardant materials are the inevitable trend of flame retardant research.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the epoxy resin coating of the porous organic polymer modified carbon nano tube and the preparation method thereof, which can improve the flame retardant effect of the epoxy resin, improve the toughness and the compatibility of the epoxy resin coating and solve the problems of secondary combustion phenomenon and poor flame retardant effect existing in the existing epoxy resin coating when used as a flame retardant.
In order to achieve the purpose, the invention is realized by the following scheme:
a preparation method of epoxy resin paint of porous organic polymer modified carbon nano-tubes comprises the following steps:
(1) preparation of porous organic polymers: firstly, dissolving melamine in DMSO, then sequentially adding 1, 4-benzaldehyde and acetic acid, stirring and mixing uniformly, reacting the obtained mixture at the temperature of 130-140 ℃ for 70-80h, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate product, then sequentially washing and purifying the product by THF, acetone and methanol, and finally drying to obtain a porous organic polymer product for later use;
(2) preparation of phosphaphenanthrenated porous organic polymers: adding the porous organic polymer prepared in the step (1) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene into an N, N-dimethylformamide solvent, carrying out addition reaction in a nitrogen atmosphere, adding deionized water after the reaction is finished to separate out a precipitate, centrifugally separating to remove the solvent, washing with the deionized water and ethanol, and drying to obtain the phosphaphenanthrene-based porous organic polymer;
(3) preparation of phosphaphenanthrene-modified porous organic polymer-modified carbon nanotubes: dissolving the phosphaphenanthrene-modified porous organic polymer synthesized in the step (2) with deionized water, adding a carbon nano tube, carrying out ice-water bath ultrasonic treatment for 3-5 hours, centrifuging the obtained suspension to remove the carbon nano tube agglomerated at the bottom, centrifuging the collected upper-layer suspension again, washing the obtained precipitate with deionized water, and drying in vacuum to obtain the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube;
(4) preparing a modified epoxy resin coating: and (3) adding epoxy resin, the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube prepared in the step (3), a brightening agent and a defoaming agent into a deionized water solvent, and stirring and mixing uniformly to obtain the epoxy resin coating of the porous organic polymer modified carbon nano tube.
Preferably, in the step (1), the mass ratio of the melamine to the 1, 4-benzaldehyde is 1-3:2-6, the mass volume ratio of the melamine to the DMSO is 1g:20-40ml, the mass volume ratio of the 1, 4-benzaldehyde to the acetic acid solution is 1g:8-12ml, and the concentration of the acetic acid solution is 3 mol/L; the drying temperature is 80 ℃ and the drying time is 12 h.
Preferably, the mass ratio of the porous organic polymer to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene in step (2) is 100: 25-70.
Preferably, the temperature of the reaction in the step (2) is 100-140 ℃, and the reaction time is 24-72 h.
Preferably, the mass ratio of the phosphaphenanthrene-based porous organic polymer to the carbon nanotubes in the step (3) is 6: 1-3.
Preferably, the first centrifugation condition and the second centrifugation condition of the suspension in the step (4) are respectively 250-400rpm/10-20min and 10000-15000rpm/8-12 min.
Preferably, the mass ratio of the epoxy resin, the phosphaphenanthrene-modified porous organic polymer modified carbon nanotube, the brightener and the defoamer in the step (4) is 100: 10-15: 1.5-2.5: 0.5 to 1.
Preferably, in the step (4), the brightening agent is organic wax powder, and the defoaming agent is dimethyl silicone oil.
In addition, the invention also discloses an epoxy resin coating of the porous organic polymer modified carbon nano tube prepared by any one of the preparation methods.
Compared with the prior art, the method has the beneficial effects that:
(1) the invention combines C atom and N atom double bonds to form C-N bond through Schiff base reaction of melamine and 1, 4-benzaldehyde, thereby forming a porous organic polymer. The polymer shows good thermal stability, has large specific surface area and abundant polar functional groups, has good compatibility with epoxy resin, provides active C ═ N bonds, is convenient for further chemical modification, and can release a large amount of non-combustible gas and form a carbon layer during combustion to play a certain flame-retardant effect.
(2) On the basis of the synthesized porous organic polymer, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene is added, and a C ═ N bond is added through an addition reaction, and a P atom is introduced to form the phosphaphenanthrene-modified porous organic polymer. During combustion, the heated phosphaphenanthrene porous organic polymer can form an expanded protective carbon layer, and CO in the expanded porous polymer2、N2Filling in the pore canal to block O2Meanwhile, the phosphaphenanthrene burns to generate acidic substances such as phosphoric acid and the like, and the acidic substances react with the polymer to promote carbon formation, so that the flame retardance of the material is enhanced.
(3) According to the invention, the phosphaphenanthrene porous organic polymer modified carbon nanotube is prepared, so that the carbon nanotube and the phosphaphenanthrene porous organic polymer are combined through pi-pi bond action, the defect that the carbon nanotube is difficult to disperse in a material is solved, the heat release rate and the mass loss rate are improved, the flame retardant property of a polymer material is improved, and the epoxy resin material has higher strength and toughness.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of epoxy resin paint of porous organic polymer modified carbon nano-tubes comprises the following steps:
(1) preparation of porous organic polymers: firstly, dissolving 4g of melamine in 100mL of DMSO (dimethyl sulfoxide), then sequentially adding 6g of 1, 4-benzaldehyde and 50mL of acetic acid, stirring and mixing uniformly, then reacting the obtained mixture at 135 ℃ for 72 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate product, then sequentially washing and purifying the product by using THF (tetrahydrofuran), acetone and methanol, and finally drying to obtain a porous organic polymer product for later use;
(2) preparation of phosphaphenanthrenated porous organic polymers: adding 10g of the porous organic polymer prepared in the step (1) and 5g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene into 100ml of N, N-dimethylformamide solvent, carrying out addition reaction in a nitrogen atmosphere, wherein the reaction temperature is 100 ℃, the reaction time is 24 hours, adding deionized water after the reaction is finished to precipitate, centrifugally separating to remove the solvent, washing with the deionized water and ethanol, and drying to obtain the phosphaphenanthrene-based porous organic polymer;
(3) preparation of phosphaphenanthrene-modified porous organic polymer-modified carbon nanotubes: dissolving 6g of the phosphaphenanthrene-modified porous organic polymer synthesized in the step (2) by using deionized water, adding 2g of carbon nano tubes, carrying out ice-water bath ultrasonic treatment for 3 hours, centrifuging the obtained suspension at 300rpm/15min to remove the carbon nano tubes agglomerated at the bottom, centrifuging the collected upper-layer suspension again at 12000rpm/10min, washing the obtained precipitate by using deionized water, and drying in vacuum to obtain the phosphaphenanthrene-modified porous organic polymer modified carbon nano tubes;
(4) preparing a modified epoxy resin coating: and (3) adding 100g of epoxy resin, 10g of the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube prepared in the step (3), 1.5g of brightening agent organic micro-wax powder and 1g of defoaming agent dimethyl silicone oil into 500ml of deionized water solvent, and stirring and mixing uniformly to obtain the epoxy resin coating of the porous organic polymer modified carbon nano tube.
Example 2
A preparation method of epoxy resin paint of porous organic polymer modified carbon nano-tubes comprises the following steps:
(1) preparation of porous organic polymers: firstly, dissolving 4g of melamine in 100mL of DMSO (dimethyl sulfoxide), then sequentially adding 6g of 1, 4-benzaldehyde and 50mL of acetic acid, stirring and mixing uniformly, then reacting the obtained mixture at 135 ℃ for 72 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate product, then sequentially washing and purifying the product by using THF (tetrahydrofuran), acetone and methanol, and finally drying to obtain a porous organic polymer product for later use;
(2) preparation of phosphaphenanthrenated porous organic polymers: adding 10g of the porous organic polymer prepared in the step (1) and 5g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene into 120ml of N, N-dimethylformamide solvent, carrying out addition reaction in a nitrogen atmosphere at the reaction temperature of 110 ℃ for 30h, adding deionized water after the reaction is finished to precipitate, centrifugally separating to remove the solvent, washing with the deionized water and ethanol, and drying to obtain the phosphaphenanthrene-based porous organic polymer;
(3) preparation of phosphaphenanthrene-modified porous organic polymer-modified carbon nanotubes: dissolving 6g of the phosphaphenanthrene-modified porous organic polymer synthesized in the step (2) by using deionized water, adding 2g of carbon nano tubes, carrying out ice-water bath ultrasonic treatment for 3 hours, centrifuging the obtained suspension at 300rpm/15min to remove the carbon nano tubes agglomerated at the bottom, centrifuging the collected upper-layer suspension again at 12000rpm/10min, washing the obtained precipitate by using deionized water, and drying in vacuum to obtain the phosphaphenanthrene-modified porous organic polymer modified carbon nano tubes;
(4) preparing a modified epoxy resin coating: and (3) adding 100g of epoxy resin, 12.5g of the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube prepared in the step (3), 1.5g of brightener organic micro-wax powder and 1g of defoamer dimethyl silicone oil into 550ml of deionized water solvent, and stirring and uniformly mixing to obtain the epoxy resin coating of the porous organic polymer modified carbon nano tube.
Example 3
A preparation method of epoxy resin paint of porous organic polymer modified carbon nano-tubes comprises the following steps:
(1) preparation of porous organic polymers: firstly, dissolving 4g of melamine in 120mL of DMSO (dimethyl sulfoxide), then sequentially adding 6g of 1, 4-benzaldehyde and 50mL of acetic acid, stirring and mixing uniformly, then reacting the obtained mixture at 135 ℃ for 72 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate product, then sequentially washing and purifying the product by using THF (tetrahydrofuran), acetone and methanol, and finally drying to obtain a porous organic polymer product for later use;
(2) preparation of phosphaphenanthrenated porous organic polymers: adding 10g of the porous organic polymer prepared in the step (1) and 5g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene into 100ml of N, N-dimethylformamide solvent, carrying out addition reaction in a nitrogen atmosphere at the reaction temperature of 120 ℃ for 40h, adding deionized water after the reaction is finished to precipitate, centrifugally separating to remove the solvent, washing with the deionized water and ethanol, and drying to obtain the phosphaphenanthrene-based porous organic polymer;
(3) preparation of phosphaphenanthrene-modified porous organic polymer-modified carbon nanotubes: dissolving 6g of the phosphaphenanthrene-modified porous organic polymer synthesized in the step (2) by using deionized water, adding 2g of carbon nano tubes, carrying out ice-water bath ultrasonic treatment for 3 hours, centrifuging the obtained suspension at 300rpm/15min to remove the carbon nano tubes agglomerated at the bottom, centrifuging the collected upper-layer suspension again at 12000rpm/10min, washing the obtained precipitate by using deionized water, and drying in vacuum to obtain the phosphaphenanthrene-modified porous organic polymer modified carbon nano tubes;
(4) preparing a modified epoxy resin coating: and (3) adding 100g of epoxy resin, 15g of the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube prepared in the step (3), 1.5g of brightening agent organic micro-wax powder and 1g of defoaming agent dimethyl silicone oil into 600ml of deionized water solvent, and stirring and mixing uniformly to obtain the epoxy resin coating of the porous organic polymer modified carbon nano tube.
Comparative example 1
A preparation method of an epoxy resin coating of a porous organic polymer modified carbon nanotube comprises the following steps:
(1) preparation of porous organic polymers: firstly, dissolving 4g of melamine in 100mL of DMSO (dimethyl sulfoxide), then sequentially adding 6g of 1, 4-benzaldehyde and 50mL of acetic acid, stirring and mixing uniformly, then reacting the obtained mixture at 135 ℃ for 72 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate product, then sequentially washing and purifying the product by using THF (tetrahydrofuran), acetone and methanol, and finally drying to obtain a porous organic polymer product for later use;
(2) preparation of porous organic polymer modified carbon nanotubes: dissolving 6g of the porous organic polymer in the step (1) by using deionized water, adding 2g of carbon nano tubes, carrying out ice-water bath ultrasonic treatment for 3 hours, centrifuging the obtained suspension for 300rpm/15min to remove the carbon nano tubes agglomerated at the bottom, centrifuging the collected upper layer suspension for 12000rpm/10min again, and finally washing the obtained precipitate by using deionized water and carrying out vacuum drying to obtain the porous organic polymer modified carbon nano tubes;
(3) preparing a modified epoxy resin coating: and (3) adding 100g of epoxy resin, 12.5g of the porous organic polymer modified carbon nano tube prepared in the step (2), 1.5g of brightening agent organic micro-wax powder and 1g of defoaming agent dimethyl silicone oil into a deionized water solvent, and stirring and mixing uniformly to obtain the epoxy resin coating of the porous organic polymer modified carbon nano tube.
Comparative example 2
A preparation method of a porous organic polymer modified epoxy resin coating comprises the following steps:
(1) preparation of porous organic polymers: firstly, dissolving 4g of melamine in 100mL of DMSO (dimethyl sulfoxide), then sequentially adding 6g of 1, 4-benzaldehyde and 50mL of acetic acid, stirring and mixing uniformly, then reacting the obtained mixture at 135 ℃ for 72 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate product, then sequentially washing and purifying the product by using THF (tetrahydrofuran), acetone and methanol, and finally drying to obtain a porous organic polymer product for later use;
(2) preparation of phosphaphenanthrenated porous organic polymers: adding 10g of the porous organic polymer prepared in the step (1) and 5g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene into 110ml of N, N-dimethylformamide solvent, carrying out addition reaction in a nitrogen atmosphere at the reaction temperature of 100 ℃ for 24h, adding deionized water after the reaction is finished to precipitate, centrifugally separating to remove the solvent, washing with the deionized water and ethanol, and drying to obtain the phosphaphenanthrene-based porous organic polymer;
(3) preparing a modified epoxy resin coating: and (3) adding 100g of epoxy resin, 12.5g of the phosphaphenanthrene-modified porous organic polymer prepared in the step (2), 1.5g of brightening agent organic micro-wax powder and 1g of defoaming agent dimethyl silicone oil into a deionized water solvent, and uniformly stirring and mixing to obtain the porous organic polymer modified epoxy resin coating.
The epoxy resin coatings synthesized in examples 1 to 3 and comparative examples 1 to 2 were mixed with an epoxy curing agent by stirring, poured into a polytetrafluoroethylene mold at room temperature, air-dried and cured, demolded, cut into square sample strips, tested on a K-R2406S oxygen index analyzer, placed vertically, and ignited to measure the oxygen concentration, and the limiting oxygen index data was obtained.
Figure BDA0003082032480000101
As can be seen from the table above, for the examples 1-3, the limiting oxygen index is not only improved, and the flame retardant property is gradually enhanced, for the comparative example 1, when the addition reaction of the phosphaphenanthrene and the porous organic polymer is lacked, the limiting oxygen index is greatly reduced; for comparative example 2, the flame retardant performance was also reduced in the absence of carbon nanotube compounding, indicating that both phosphaphenanthrene-based porous organic polymers and carbon nanotubes play a crucial role in the flame retardant performance of epoxy coatings.
The coatings of examples 1-3 and comparative examples 1-2 were cured into films of 5cm diameter and 0.5mm thickness and films of 12.7cm length, 1.27cm width and 1mm thickness, and then tested for thermal conductivity and flame retardancy. The results are given in the following table:
Figure BDA0003082032480000111
the epoxy resin coatings synthesized in examples 1 to 3 and comparative examples 1 to 3 were mixed with an epoxy hardener under stirring, poured into a polytetrafluoroethylene mold at room temperature, air-dried, cured, demolded, cut into square sample bars, and subjected to a corresponding test on a WY-2000A tensile bending tester to obtain the corresponding flexural strength and flexural modulus.
Figure BDA0003082032480000112
Figure BDA0003082032480000121
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. A preparation method of an epoxy resin coating of a porous organic polymer modified carbon nanotube is characterized by comprising the following steps:
(1) preparation of porous organic polymers: firstly, dissolving melamine in DMSO, then sequentially adding 1, 4-benzaldehyde and acetic acid, stirring and mixing uniformly, reacting the obtained mixture at the temperature of 130-140 ℃ for 70-80h, cooling to room temperature after the reaction is finished, centrifuging to obtain a precipitate product, then sequentially washing and purifying the product by THF, acetone and methanol, and finally drying to obtain a porous organic polymer product for later use;
(2) preparation of phosphaphenanthrenated porous organic polymers: adding the porous organic polymer prepared in the step (1) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene into an N, N-dimethylformamide solvent, carrying out addition reaction in a nitrogen atmosphere, adding deionized water after the reaction is finished to separate out a precipitate, centrifugally separating to remove the solvent, washing with the deionized water and ethanol, and drying to obtain the phosphaphenanthrene-based porous organic polymer;
(3) preparation of phosphaphenanthrene-modified porous organic polymer-modified carbon nanotubes: dissolving the phosphaphenanthrene-modified porous organic polymer synthesized in the step (2) with deionized water, adding a carbon nano tube, carrying out ice-water bath ultrasonic treatment for 3-5 hours, centrifuging the obtained suspension to remove the carbon nano tube agglomerated at the bottom, centrifuging the collected upper-layer suspension again, washing the obtained precipitate with deionized water, and drying in vacuum to obtain the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube;
(4) preparing a modified epoxy resin coating: and (3) adding epoxy resin, the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube prepared in the step (3), a brightening agent and a defoaming agent into a deionized water solvent, and stirring and mixing uniformly to obtain the epoxy resin coating of the porous organic polymer modified carbon nano tube.
2. The method of claim 1, wherein: in the step (1), the mass ratio of melamine to 1, 4-benzaldehyde is 1-3:2-6, the mass volume ratio of melamine to DMSO is 1g:20-40ml, the mass volume ratio of 1, 4-benzaldehyde to acetic acid solution is 1g:8-12ml, and the concentration of the acetic acid solution is 3 mol/L; the drying temperature is 80 ℃ and the drying time is 12 h.
3. The method of claim 1, wherein: in the step (2), the mass ratio of the porous organic polymer to the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene is 100: 25-70.
4. The method of claim 1, wherein: the reaction temperature in the step (2) is 100-140 ℃, and the reaction time is 24-72 h.
5. The method of claim 1, wherein: the mass ratio of the phosphaphenanthrene porous organic polymer to the carbon nano tube in the step (3) is 6: 1-3.
6. The method of claim 1, wherein: the first centrifugation condition and the second centrifugation condition of the suspension in the step (4) are respectively 250-400rpm/10-20min and 10000-15000rpm/8-12 min.
7. The method of claim 1, wherein: the mass ratio of the epoxy resin, the phosphaphenanthrene-modified porous organic polymer modified carbon nano tube, the brightening agent and the defoaming agent in the step (4) is 100: 10-15: 1.5-2.5: 0.5 to 1.
8. The method of claim 1, wherein: in the step (4), the brightening agent is organic micro-wax powder, and the defoaming agent is dimethyl silicone oil.
9. An epoxy resin coating of porous organic polymer modified carbon nanotubes prepared by the preparation method of any one of claims 1 to 8.
CN202110569356.7A 2021-05-25 2021-05-25 Epoxy resin coating of porous organic polymer modified carbon nano tube and preparation method thereof Pending CN113337177A (en)

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Application publication date: 20210903