CN113549297A - Preparation method of metal-complexed hydroxylated graphite carbon nitride-based trimer flame-retardant epoxy resin - Google Patents

Preparation method of metal-complexed hydroxylated graphite carbon nitride-based trimer flame-retardant epoxy resin Download PDF

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CN113549297A
CN113549297A CN202110502845.0A CN202110502845A CN113549297A CN 113549297 A CN113549297 A CN 113549297A CN 202110502845 A CN202110502845 A CN 202110502845A CN 113549297 A CN113549297 A CN 113549297A
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epoxy resin
carbon nitride
hydroxylated
flame
metal
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CN113549297B (en
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喻源
陈忠伟
李昌新
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Nanjing Tech University
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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
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0605—Binary compounds of nitrogen with carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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 discloses a preparation method of metal-complexed terpolymer flame-retardant epoxy resin based on hydroxylated graphite carbon nitride. The preparation method comprises the steps of taking a metal-complexed hydroxylated graphite carbon nitride-based trimer as a flame retardant, taking epoxy resin as a matrix, taking a curing agent as a curing agent, and preparing the flame-retardant epoxy resin composite material through physical stirring. The flame retardant and the flame-retardant epoxy resin composite material are tested and characterized by adopting a limiting oxygen index, a Fourier infrared spectrum, an X-ray diffraction spectrum, an X-ray photoelectron spectroscopy, bending performance and an electronic scanning microscope analysis method. The invention has the advantages that: the terpolymer and the epoxy resin prepared by the method have good dispersibility, and the section form of the terpolymer and the section form of the pure epoxy resin are basically consistent. Compared with pure epoxy resin, the epoxy resin composite material obtained by the preparation method has the limit oxygen index of 31.2% only by adding 1 g. The bending property of the epoxy resin composite material provided by the invention is improved by 9% compared with that of pure epoxy resin.

Description

Preparation method of metal-complexed hydroxylated graphite carbon nitride-based trimer flame-retardant epoxy resin
Technical Field
The invention belongs to the technical field of flame-retardant polymers, and particularly relates to a preparation method of metal-complexed hydroxylated graphite carbon nitride-based trimeric flame-retardant epoxy resin.
Background
In recent decades, with the vigorous development of industry, the application range of epoxy resins has been rapidly expanded. From the first use as adhesives and coatings to the present era of advanced technology flooring and circuit boards, epoxy resins have become one of the most widely used thermosetting resins. However, due to the inherent flammability of epoxy resin, it is necessary to add a proper flame retardant to achieve a certain flame retardant effect. However, due to the harmfulness of halogen elements to the environment and human body and the high load of metal compounds, the industry is prompted to pay attention to novel two-dimensional nano flame retardants.
From this point of view, new two-dimensional nanomaterials including graphitic carbon nitride, graphene oxide, black phosphorus and transition metal carbon/nitrides have received much attention. Wherein, the graphite carbon nitride obtained by only using cheap nitrogen source to carry out temperature programming self-polymerization has more obvious advantages than other three in scale production. In addition, it has been confirmed that hydroxylated graphite carbonitride can be synthesized by various methods, such as hydrothermal reaction of graphite carbonitride with water, or polycondensation reaction of melamine, potassium chloride and sodium hydroxide by mixing and then raising the temperature by a program. The invention firstly utilizes the latter method to obtain hydroxylated graphite carbon nitride, and develops a preparation method of the metal-complexed hydroxylated graphite carbon nitride-based trimer flame-retardant epoxy resin on the basis of the hydroxylated graphite carbon nitride.
Patent publication No. CN105670231A discloses a method for preparing expandable carbon nitride flame-retardant epoxy resin. When the addition amount of the flame retardant is 10%, the limit oxygen index of the corresponding epoxy resin composite material reaches 30.2%. However, the addition of 10% may cause a decrease in mechanical properties. Therefore, it is necessary to develop a flame retardant with an addition amount of less than 5% or even 1% to achieve a flame resistance level while improving the mechanical properties of the composite.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a preparation method of metal-complexed hydroxylated graphite carbon nitride-based trimer flame-retardant epoxy resin.
The invention comprises the following steps:
(1) uniformly mixing a nitrogen-containing compound, potassium chloride and sodium hydroxide, calcining at high temperature, crushing, washing with distilled water, and drying to obtain particles A;
(2) dispersing polyphenol in a mixed solution of triethylamine and acetonitrile, and performing ultrasonic treatment to obtain a solution A;
(3) stirring the particles A and hexachlorocyclotriphosphazene in acetonitrile to obtain a solution B;
(4) pouring the solution B into the solution A, continuing to perform ultrasonic treatment, centrifugally washing with ethanol and deionized water after the ultrasonic treatment is finished, and drying to obtain particles B;
(5) stirring and dissolving metal salt in methanol to obtain a solution C;
(6) adding the particles B into the solution C, stirring, centrifugally washing with ethanol and deionized water after the stirring is finished, and drying to obtain a metal-complexed hydroxylated graphite carbon nitride-based trimer;
(7) and adding the terpolymer based on hydroxylated graphite carbon nitride, which is subjected to metal complexation, into the epoxy resin, adding the curing agent after stirring, then stirring, pouring the mixture into a mold, and placing the mold into an oven to be cured to obtain the terpolymer flame-retardant epoxy resin composite material based on hydroxylated graphite carbon nitride.
The polyphenol is one of chlorogenic acid, tannic acid, gallic acid, quercetin, rutin, and resveratrol.
The metal salt is one or two of cobalt nitrate hexahydrate, copper nitrate trihydrate, cobalt chloride dihydrate, zinc acetate dihydrate and iron acetylacetonate.
The nitrogen-containing compound is one of melamine, urea, melamine cyanurate, graphitic carbon nitride, and hydroxylated graphitic carbon nitride.
Further, in the step (1), the nitrogen-containing compound, potassium chloride and sodium hydroxide are uniformly mixed according to the mass ratio of 1.0-1.5: 7.0-7.5: 0.01-0.05, and the mixture is heated at 520-550 ℃ for 2-4 hours to obtain the particles A.
In the steps (2) and (3), the mass ratio of the polyphenol, the hexachlorocyclotriphosphazene and the particles A is 0.6-6: 0.5-5.
The temperature of the ultrasonic treatment in the steps (2) and (4) is 30-40 ℃, and the treatment time is 30-120 min.
The stirring in the steps (3), (5), (6) and (7) is magnetic stirring, and the stirring time is 10 min-16 h.
And (3) in the steps (4) and (6), the centrifugal rotating speed is 6000-9000 r/min, and the centrifugal time is 3-5 min.
And (3) drying in the steps (4) and (6) at the temperature of 50-80 ℃ for 8-24 hours.
And (3) in the step (5), the mixing ratio of the metal salt to the methanol is 3-6 g: 100 mL.
In the step (7), the mixing mass ratio of the epoxy resin, the curing agent and the metal complexing hydroxylated graphite carbon nitride-based trimer is 70-80: 19-20: 0.1-1.
The curing temperature in the step (7) is 80-180 ℃, and the curing time is 30 min-4 h.
Compared with the prior art, the invention has the following advantages:
(1) the invention provides a preparation method of a terpolymer based on hydroxylated graphite carbon nitride, the terpolymer and epoxy resin prepared by the method have good dispersibility, and the section form of the terpolymer is basically consistent with that of pure epoxy resin.
(2) Compared with pure epoxy resin, the epoxy resin composite material prepared by the preparation method only needs 1 wt% of addition amount to reach the limit oxygen index of 31.2%. Compared with other methods, the epoxy resin composite material obtained by the invention has the highest limit oxygen index and the lowest addition amount of the flame retardant.
(3) The terpolymer based on hydroxylated graphite carbon nitride provided by the invention simultaneously improves the bending property of epoxy resin to 127MPa, and is improved by 9% compared with pure epoxy resin. Compared with other methods, the bending performance of the flame-retardant epoxy resin composite material based on graphite carbon nitride obtained by the invention is improved.
Drawings
FIG. 1 is a Fourier infrared spectrum of example 1.
FIG. 2 is an X-ray photoelectron spectroscopy analysis chart of example 1.
FIG. 3 is an X-ray powder diffraction pattern of example 1.
Fig. 4 is a scanning electron microscope image of graphitic carbon nitride.
FIG. 5 is a scanning electron microscope photograph of hydroxylated graphite carbon nitride.
Fig. 6 is a scanning electron microscope image of a terpolymer based on hydroxylated graphite carbon nitride.
Figure 7 is a scanning electron microscope image of a metal-complexed hydroxylated graphitic carbon nitride-based trimer.
FIG. 8 is a scanning electron microscope image of a cross section of epoxy resin.
FIG. 9 is a scanning electron microscope photograph of a cross section of example 2.
FIG. 10 is a graph of an epoxy resin and a limiting oxygen index for example 2.
FIG. 11 shows the flexural properties of epoxy resins and example 2.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The technical scheme adopted by the invention is further explained by combining the drawings and the embodiment.
Example 1
The preparation method of the metal complex hydroxylated graphite carbon nitride-based trimer specifically comprises the following steps:
15g of melamine, 75g of potassium chloride and 0.5g of sodium hydroxide were mixed thoroughly with a ceramic mortar and then transferred into a clean covered alumina crucible and then calcined in a muffle furnace at 550 ℃ for 4h in an air atmosphere. And (3) cooling to room temperature, crushing the blocks into powder, and then carrying out vacuum auxiliary washing with deionized water for three times to obtain the hydroxylated graphite carbon nitride (sample 2). To compare the successful preparation of hydroxylated graphitic carbon nitrides, graphitic carbon nitrides were prepared as follows. 20 grams of melamine was placed in a clean alumina crucible with a lid and then calcined in a muffle furnace in air at 550 ℃ for 4 hours. After cooling to room temperature, the resulting cake was ground to a fine powder to obtain graphite carbon nitride (sample 1).
20mL of triethylamine was dissolved in 200mL of acetonitrile, and then 6g of tannic acid was dispersed, followed by sonication at 30-35 ℃ for 45 min. Subsequently, 300mL of acetonitrile in which 5g of hexachlorocyclotriphosphazene was dissolved was poured into the above solution, and 5g of hydroxylated graphite carbon nitride was added to the solution. The polycondensation reaction was further carried out in the ultrasonic bath for 90min under the same conditions. The precipitate was collected by centrifugation (8000rpm, 5min), washed three times with ethanol and deionized water, respectively, and dried in vacuo at 60 ℃ overnight to give a hydroxylated graphite carbon nitride based trimer (sample 3).
6g of cobalt nitrate hexahydrate and 6g of copper nitrate trihydrate were dissolved in 200mL of methanol. Then 8g of a terpolymer based on hydroxylated graphite carbon nitride was added to the solution with continuous stirring, followed by stirring at room temperature for 16 h. The resulting product was collected by centrifugation (8000rpm, 5min), washed 3 times with deionized water, and dried overnight in vacuo at 60 ℃ to give a metal-complexed hydroxylated graphite carbon nitride-based trimer (sample 4).
As can be seen from FIG. 1, the signal is located at 1200-1600cm-1Characteristic peak related to N ═ C-N and 3200cm-1Near by-NH2The characteristic peaks of (A) represent successful preparation of graphitic carbon nitride. 3415 and 991 cm newly appeared in hydroxylated graphite carbon nitride-1Left and right-OH groups and 2175cm-1The cyano group in (A) is substituted successfully-NH in example 12A group. In the metal-complexed hydroxylated graphitic carbon nitride-based trimer and the hydroxylated graphitic carbon nitride-based trimer, the newly-appeared peaks associated with phosphorus were 1203, 1036 and 1090cm, respectively-1Here, it is possible to assign it to P ═ N tensile vibration of the hexachlorocyclotriphosphazene skeleton, hydroxylating the C — O — P group between graphite carbon nitride, tannic acid and hexachlorocyclotriphosphazene, revealing the success of the polymerization. In addition, the C ═ O double bond in the tannic acid was 1718cm-1To (3).
The presence of a peak representing (002) inter-planar stacking at 27.4 ° shown in the XRD patterns of graphitic carbon nitride, hydroxylated graphitic carbon nitride and trimer of fig. 2 demonstrates that the main structure of graphitic carbon nitride has not changed among the three. The XRD spectrum of the hydroxylated graphitic carbon nitride showed that the peak representing (002) plane inter-layer stacking at 27.4 ° shifted to the peak associated with the in-plane repeat unit of (100) plane at 28.3 ° and 12.5 ° disappeared, indicating that hydroxylation decreased inter-layer stacking spacing within the structure, which is another evidence of successful hydroxylation. The XRD patterns of the trimer and metal-complexed trimer were shifted to 27.9 ° and 28.0 ° in the (002) plane, respectively, as a result of the polymerization and metallization occurring. Meanwhile, the characteristic peaks at 19.0 ° and 23.2 ° newly appeared in the XRD spectrum of the metal-complexed trimer are due to intercalation of the metal.
A clear change in C can be observed in the XPS plot of FIG. 31s、N1s，O1sAnd P2pPeak strength, which is evidence of hydroxylation and polycondensation. Also, Cu was observed only in the metal-complexed trimer2pAnd Co2pThe binding energy peak of (a) also indicates the success of metal complexation. The microscopic morphology of fig. 6 and 7, which is distinct from fig. 4 and 5, also illustrates the occurrence of polymerization and metal complexation.
Example 2
The preparation method of the metal-complexed hydroxylated graphite carbon nitride-based trimer flame-retardant epoxy resin specifically comprises the following steps:
80g of epoxy resin was added to 1g of a terpolymer based on hydroxylated graphite carbon nitride, and after stirring for 30 minutes in a water bath at 60 ℃, 20g of 4, 4-diaminodiphenylmethane was added, and further stirring was continued for 10 minutes, and then the mixture was poured into a silicone oil-coated polytetrafluoroethylene mold of a standard size, and after curing in an oven, the mold was cooled and released to obtain example 2. For comparison, a pure epoxy resin based on a terpolymer of hydroxylated graphite carbon nitride without metal complexing was prepared. Adding 80g of epoxy resin into 20g of 4, 4-diaminodiphenylmethane, stirring for 10min under the condition of heating in a water bath at 60 ℃, then pouring the mixture into a polytetrafluoroethylene mold with standard size and coated with silicone oil, placing the polytetrafluoroethylene mold into an oven for curing, cooling and demolding to obtain the pure epoxy resin.
As can be seen from fig. 8 and 9, the cross section of the flame retardant epoxy resin to which the metal-complexed hydroxylated graphite carbon nitride-based terpolymer was added was almost not different from that of the pure epoxy resin, indicating excellent dispersion properties of the metal-complexed hydroxylated graphite carbon nitride-based terpolymer in the epoxy resin. As can be seen from fig. 10, the limiting oxygen index of the neat epoxy is only 24.8% and does not reach the flame retardant rating. The limited oxygen index of the epoxy resin composite material added with 1 wt% of metal complex trimer is up to 31.2%, which is 6.4% higher than that of pure epoxy resin, and is the highest limited oxygen index of all flame-retardant epoxy resins added with the carbon nitride-based flame retardant alone, as shown in table 1. In addition, as can be seen from fig. 11, the bending property of the epoxy resin composite material added with 1 wt% of the terpolymer is improved from 116.5MPa of the pure epoxy resin to 127MPa, which is improved by 9%, and is the highest bending property of the flame-retardant epoxy resin added with the carbon nitride-based flame retardant. In conclusion, the metal-complexed hydroxylated graphite carbon nitride-based terpolymer can improve the flame retardant performance and the bending performance of the epoxy resin.
TABLE 1 comparison of the oxygen index and bending Properties of the invention with other working limits
Figure BSA0000241498080000051

Claims (7)

1. A preparation method of a metal-complexed hydroxylated graphite carbon nitride-based terpolymer flame-retardant epoxy resin composite material is characterized by comprising the following steps of:
(1) uniformly mixing a nitrogen-containing compound, potassium chloride and sodium hydroxide, calcining at high temperature, crushing, washing with distilled water, and drying to obtain particles A;
(2) dispersing polyphenol in a mixed solution of triethylamine and acetonitrile, and performing ultrasonic treatment to obtain a solution A;
(3) stirring the particles A and hexachlorocyclotriphosphazene in acetonitrile to obtain a solution B;
(4) pouring the solution B into the solution A, continuing to perform ultrasonic treatment, centrifugally washing with ethanol and deionized water after the ultrasonic treatment is finished, and drying to obtain particles B;
(5) stirring and dissolving metal salt in methanol to obtain a solution C;
(6) adding the particles B into the solution C, stirring, centrifugally washing with ethanol and deionized water after the stirring is finished, and drying to obtain a metal-complexed hydroxylated graphite carbon nitride-based trimer;
(7) and adding the terpolymer based on hydroxylated graphite carbon nitride, which is subjected to metal complexation, into the epoxy resin, adding the curing agent after stirring, then stirring, pouring the mixture into a mold, and placing the mold into an oven to be cured to obtain the terpolymer flame-retardant epoxy resin composite material based on hydroxylated graphite carbon nitride.
2. The method according to claim 1, wherein the nitrogen-containing compound, the potassium chloride and the sodium hydroxide are uniformly mixed in the step (1) according to a mass ratio of 1.0-1.5: 7.0-7.5: 0.01-0.05, and the mixture is heated at 520-550 ℃ for 2-4 hours to obtain the particles A.
3. The method according to claim 1, wherein the ultrasonic treatment in the steps (2), (3), (4), (5), (6) and (7) is carried out at a temperature of 30 to 40 ℃ for a treatment time of 30 to 120 min; the stirring time is 10min to 16 h; the centrifugal speed is 6000 to 9000r/min, and the centrifugal time is 3 to 5 min; the drying temperature is 50-80 ℃, and the drying time is 8-24 h; the curing temperature is 80-180 ℃, and the curing time is 30 min-4 h.
4. The method according to claim 1, wherein the mass ratio of the polyphenol, the hexachlorocyclotriphosphazene and the particles A in the steps (2) and (3) is 0.6-6: 0.5-5.
5. The method according to claim 1, wherein the mixing ratio of the metal salt and the methanol in the step (5) is 3-6 g: 100 mL.
6. The method according to claim 1, wherein the epoxy resin, the curing agent and the metal-complexed hydroxylated graphite carbon nitride-based trimer in the step (7) are mixed in a mass ratio of 70-80: 19-20: 0.1-1.
7. The flame retardant epoxy composite of claim 1, wherein the polyphenol is one of chlorogenic acid, tannic acid, gallic acid, quercetin, rutin, resveratrol; the metal salt is one or two of cobalt nitrate hexahydrate, copper nitrate trihydrate, cobalt chloride dihydrate, zinc acetate dihydrate and iron acetylacetonate; the nitrogen-containing compound is one of melamine, urea, melamine cyanurate, graphitic carbon nitride, and hydroxylated graphitic carbon nitride.
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CN110876953A (en) * 2019-12-05 2020-03-13 常州工学院 P and S co-doped carbon nitride homotype heterojunction composite photocatalyst
CN112090440A (en) * 2020-09-22 2020-12-18 海南师范大学 Oxygen-deficient titanium dioxide material of composite hydroxylated carbon nitride and preparation method thereof
CN112357897A (en) * 2020-11-06 2021-02-12 中山大学 Preparation method and application of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane

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Publication number Priority date Publication date Assignee Title
CN110876953A (en) * 2019-12-05 2020-03-13 常州工学院 P and S co-doped carbon nitride homotype heterojunction composite photocatalyst
CN112090440A (en) * 2020-09-22 2020-12-18 海南师范大学 Oxygen-deficient titanium dioxide material of composite hydroxylated carbon nitride and preparation method thereof
CN112357897A (en) * 2020-11-06 2021-02-12 中山大学 Preparation method and application of phosphorus-doped carbon nitride two-dimensional nanoparticles for preparing flame-retardant waterborne polyurethane

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