CN113462024A - Polydopamine and metal ion modified montmorillonite flame retardant and preparation method thereof - Google Patents
Polydopamine and metal ion modified montmorillonite flame retardant and preparation method thereof Download PDFInfo
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- CN113462024A CN113462024A CN202110737562.4A CN202110737562A CN113462024A CN 113462024 A CN113462024 A CN 113462024A CN 202110737562 A CN202110737562 A CN 202110737562A CN 113462024 A CN113462024 A CN 113462024A
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Abstract
The invention provides a polydopamine and metal ion modified montmorillonite flame retardant and a preparation method thereof, wherein the flame retardant is prepared by taking montmorillonite, dopamine hydrochloride and metal ions as raw materials and comprises the following steps: (1) dispersing montmorillonite with a preset solid-to-liquid ratio in deionized water, and stirring for a preset time under the condition of a preset temperature; (2) regulating the pH value of montmorillonite dispersion liquid by adopting trihydroxymethyl aminomethane, adding dopamine hydrochloride into the solution, stirring at a preset temperature for a preset time, centrifuging at a certain rotating speed, and washing with deionized water; (3) adding metal ions, stirring at a preset temperature for a preset time, centrifuging at a certain rotating speed, washing with deionized water, and drying in a vacuum oven to obtain the modified montmorillonite flame retardant. The flame retardant can be used as an additive to endow the material with excellent flame retardant performance through the synergistic effect of montmorillonite and metal ions.
Description
Technical Field
The invention relates to the field of preparation of flame retardants, in particular to a polydopamine and metal ion modified montmorillonite flame retardant and a preparation method thereof.
Background
The polymer material has the advantages of good chemical resistance, corrosion resistance, low dielectric property, excellent mechanical strength and the like, so that the polymer material has a huge application market, but most of the polymer materials have the disadvantage of flammability and directly threaten the life and property safety of people, so that the application of the polymer material in many fields with high requirements on flame retardant property, such as electronic equipment, aerospace and the like, is limited. Therefore, it is very important to improve the flame resistance of the polymer material.
The addition of flame retardants to polymeric materials has been widely used to address such problems. In recent years, inorganic fillers have attracted much attention as a novel flame retardant, and generally include layered double hydroxides, alumina, silica, kaolin, montmorillonite and the like. Wherein, montmorillonite has the advantages of larger specific surface area, chemical stability, certain flame retardance and the like, and is widely applied to a plurality of high polymer materials. However, unmodified montmorillonite has certain hydrophilicity, poor compatibility with high polymer materials, and easy agglomeration, and cannot significantly improve the flame retardance of the material. Therefore, the dispersion of the montmorillonite in the high polymer material can be effectively promoted by modifying the montmorillonite, so that the flame retardant property of the montmorillonite is better exerted.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the flame retardant is prepared by modifying montmorillonite with polydopamine and metal ions, and can improve flame retardance and heat resistance of high polymer materials.
In order to solve the technical problems, the invention adopts the technical scheme that:
a polydopamine and metal ion modified montmorillonite flame retardant has the following structural formula:
wherein R is Fe3+、Cu2+、Zn2+And Al3+One kind of (1).
In order to solve the technical problem, the invention adopts another technical scheme as follows:
a preparation method of polydopamine and metal ion modified montmorillonite flame retardant comprises the following steps:
(1) dispersing montmorillonite in deionized water according to a preset solid-liquid ratio, and stirring for a preset time under the condition of a preset temperature;
(2) regulating the pH value of montmorillonite dispersion liquid by adopting trihydroxymethyl aminomethane, adding dopamine hydrochloride into the solution, stirring at a preset temperature for a preset time, centrifuging at a preset rotating speed, and washing with deionized water;
(3) adding metal ions, stirring at a preset temperature for a preset time, centrifuging at a preset rotating speed, washing with deionized water, and drying in a vacuum oven to obtain the modified montmorillonite flame retardant.
The invention has the beneficial effects that: the invention provides a polydopamine and metal ion modified montmorillonite flame retardant which takes deionized water as a solvent in the preparation process and has the advantage of environmental friendliness.
Montmorillonite in the flame retardant has good chemical stability and is not easy to burn, and the heat resistance and the flame retardant property of the montmorillonite can be improved by adding the montmorillonite into a material; polydopamine generated by dopamine hydrochloride reaction has strong adhesion capability and is rich in various functional groups, the dispersion effect of modified montmorillonite in the material can be improved, the modified montmorillonite can be complexed with metal ions, the complexed metal ions have a catalytic carbonization effect, and the modified montmorillonite is added into the material through the synergistic effect with the montmorillonite, so that the flame retardant property of the material can be improved.
Drawings
FIG. 1 is a schematic structural diagram of a polydopamine and metal ion modified montmorillonite flame retardant in one embodiment of the invention;
FIG. 2 is a schematic structural diagram of a polydopamine and metal ion modified montmorillonite flame retardant in a second embodiment of the invention;
FIG. 3 is a schematic structural diagram of a polydopamine and metal ion modified montmorillonite flame retardant in a third embodiment of the invention;
FIG. 4 is a schematic structural diagram of a polydopamine and metal ion modified montmorillonite flame retardant in the invention;
FIG. 5 is a first reaction scheme of a polydopamine and metal ion modified montmorillonite flame retardant in the present invention;
FIG. 6 is a second reaction scheme of a polydopamine and metal ion modified montmorillonite flame retardant in the present invention.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
In order to improve the dispersibility of montmorillonite in a high polymer material, polydopamine and metal ions are introduced into the surface of montmorillonite, and the polydopamine has strong adhesive capacity and is rich in various functional groups, so that the dispersibility of modified montmorillonite is improved, and the polydopamine and metal ion modified montmorillonite flame retardant is prepared. Montmorillonite in the flame retardant has better chemical stability, and the heat resistance of the montmorillonite added into a polymer can be improved; the polydopamine has strong adhesion capability and is rich in various functional groups, not only can improve the dispersibility of the modified montmorillonite in a polymer, but also can be complexed with metal ions, the complexed metal ions have the function of catalyzing to form carbon, and the modified montmorillonite can obviously improve the flame retardant and heat resistance of the material through the synergistic effect of the montmorillonite and the metal ions.
One of the purposes of the invention is to provide a polydopamine and metal ion modified montmorillonite flame retardant, and the structure of the flame retardant is shown in figure 4. In FIG. 4, R is Fe3+、Cu2+、Zn2+、Al3+One kind of (1).
The invention also aims to provide a preparation method of the polydopamine and metal ion modified montmorillonite flame retardant, which comprises the following steps:
and dispersing montmorillonite in deionized water according to a preset solid-liquid ratio, and stirring for a preset time under the condition of a preset temperature. Wherein the solid-liquid ratio of the montmorillonite to the deionized water is 1: 50-55, the stirring temperature is 20-40 ℃, and the stirring time is 12-14 h;
(2) regulating the pH value of the montmorillonite dispersion liquid by using trihydroxymethyl aminomethane, pouring a proper amount of dopamine hydrochloride into the solution, stirring for a preset time at a preset temperature, centrifuging at a preset rotating speed, and washing by using deionized water. Wherein the pH value of the dispersion liquid is adjusted to 8-9, and the mass of the added dopamine hydrochloride is 0.008-0.010 of that of montmorillonite; the stirring temperature is 20-40 ℃, and the stirring time is 2-3 h; the centrifugal speed is 4000-6000 rpm, and the reaction formula is shown in figure 5.
(3) Adding metal ions, stirring at a preset temperature for a preset time, centrifuging at a set rotating speed, washing with deionized water, and drying in a vacuum oven to obtain the target product. Wherein the molar ratio of the metal ions to the dopamine hydrochloride is 1: 2.8-3, the stirring temperature is 15-40 ℃, the stirring time is 2-4 h, the centrifugal speed is 4000-6000 rpm, the drying temperature of the vacuum oven is 60-75 ℃, and the time is 20-24 h, and the reaction formula is shown in FIG. 6.
Example one
Preparation method of polydopamine and metal ion modified montmorillonite flame retardant (wherein R in the flame retardant is Fe)3+) The method comprises the following steps:
(1) montmorillonite (5.19g) was dispersed in deionized water at a solid-to-liquid ratio of montmorillonite to deionized water of 1:50 and stirred at 20 ℃ for 14 h.
(2) The montmorillonite dispersion was adjusted to pH 8 with tris, dopamine hydrochloride (0.042g) was added, stirred at 20 ℃ for 3h, and centrifuged at 4000rpm in a centrifuge.
(3) Adding Fe3+(0.023g) is added into the solution, stirred for 4 hours at the temperature of 15 ℃, centrifuged at the rotating speed of 4000rpm, dried for 24 hours in a vacuum oven at the temperature of 60 ℃ to obtain the modified montmorillonite flame retardant, and the structural formula of the obtained polydopamine and metal ion modified montmorillonite flame retardant is shown in figure 1.
Infrared spectrum: Si-O (1006 cm)-1)，Ph(1604cm-1)，Ar-OH(3370cm-1)，-OH(3656cm-1)， SiO2(794cm-1)，Al-O-Si(515cm-1)。
Diaminodiphenylmethane is used as a curing agent, the synthesized modified montmorillonite is used as a flame retardant, and a modified epoxy resin condensate is prepared, wherein the initial decomposition temperature of the modified epoxy resin condensate is 336.8 ℃, the residual carbon content of the condensate at 600 ℃ is 35.2%, the oxygen index is 34.4%, and the V-0 level of a vertical combustion test is reached.
Example two
Preparation method of polydopamine and metal ion modified montmorillonite flame retardant (wherein R in the flame retardant is Cu)2+) The method comprises the following steps:
(1) according to the solid-to-liquid ratio of the montmorillonite to the deionized water of 1:55, the montmorillonite (5.16g) is dispersed in the deionized water and stirred for 12h at the temperature of 40 ℃.
(2) The montmorillonite dispersion was adjusted to pH 9 with tris, dopamine hydrochloride (0.05g) was added, stirred at 40 ℃ for 2h, and centrifuged at 6000rpm in a centrifuge.
(3) Adding Cu2+(0.022g) adding the mixture into the solution, stirring for 2h at 40 ℃, centrifuging at the rotating speed of 6000rpm, drying for 20h in a vacuum oven at 75 ℃ to obtain the modified montmorillonite flame retardant, wherein the structural formula of the obtained polydopamine and metal ion modified montmorillonite flame retardant is shown in figure 2.
Infrared spectrum: Si-O (1010 cm)-1)，Ph(1618cm-1)，Ar-OH(3376cm-1)，-OH(3646cm-1)， SiO2(796cm-1)，Al-O-Si(517cm-1)。
Diaminodiphenylmethane is used as a curing agent, the synthesized modified montmorillonite is used as a flame retardant, and a modified epoxy resin condensate is prepared, wherein the initial decomposition temperature of the modified epoxy resin condensate is 327.9 ℃, the residual carbon content of the condensate at 600 ℃ is 32.8%, the oxygen index is 32.8%, and the V-0 level of a vertical combustion test is reached.
EXAMPLE III
Preparation method of polydopamine and metal ion modified montmorillonite flame retardant (wherein R in the flame retardant is Al3+) The method comprises the following steps:
(1) according to the solid-to-liquid ratio of the montmorillonite to the deionized water of 1:52, the montmorillonite (5.18g) is dispersed in the deionized water and stirred for 13h at the temperature of 30 ℃.
(2) The pH of the montmorillonite dispersion was adjusted to 8.5 with Tris, adding dopamine hydrochloride (0.05g), stirring at 30 deg.C for 2.5h, and centrifuging at 5000rpm in a centrifuge.
(3) Adding Al3+(0.021g) adding into the solution, stirring at 30 deg.C for 3h, centrifuging at 5000rpm, and drying in vacuum oven at 70 deg.C for 22h to obtain modified montmorillonite flame retardant, wherein the structural formula of the obtained polydopamine and metal ion modified montmorillonite flame retardant is shown in figure 3.
Infrared spectrum: Si-O (1019 cm)-1)，Ph(1630cm-1)，Ar-OH(3370cm-1)，-OH(3644cm-1)， SiO2(790cm-1)，Al-O-Si(510cm-1)。
Diaminodiphenylmethane is used as a curing agent, the synthesized modified montmorillonite is used as a flame retardant, and a modified epoxy resin condensate is prepared, wherein the initial decomposition temperature of the modified epoxy resin condensate is 325.5 ℃, the residual carbon content of the condensate at 600 ℃ is 31.3%, the oxygen index is 32.3%, and the V-0 level of a vertical combustion test is reached.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (5)
1. The polydopamine and metal ion modified montmorillonite flame retardant is characterized in that the structural formula of the flame retardant is as follows:
wherein R is Fe3+、Cu2+、Zn2+And Al3+One kind of (1).
2. A preparation method of polydopamine and metal ion modified montmorillonite flame retardant is characterized by comprising the following steps:
(1) dispersing montmorillonite in deionized water according to a preset solid-liquid ratio, and stirring for a preset time under the condition of a preset temperature;
(2) regulating the pH value of montmorillonite dispersion liquid by adopting trihydroxymethyl aminomethane, adding dopamine hydrochloride into the solution obtained in the step (1), stirring at a preset temperature for a preset time, centrifuging at a preset rotating speed, and washing with deionized water;
(3) adding metal ions, stirring at a preset temperature for a preset time, centrifuging at a preset rotating speed, washing with deionized water, and drying in a vacuum oven to obtain the modified montmorillonite flame retardant.
3. The preparation method of the polydopamine and metal ion modified montmorillonite flame retardant according to claim 2, wherein the solid-to-liquid ratio of montmorillonite to deionized water in the step (1) is 1: 50-55; the temperature is 20-40 ℃; the time is 12-14 h.
4. The preparation method of the polydopamine and metal ion modified montmorillonite flame retardant according to claim 2, characterized in that the pH of the dispersion liquid in the step (2) is adjusted to 8-9, the mass of dopamine hydrochloride added is 0.008-0.010 of montmorillonite, the temperature is 20-40 ℃, the time is 2-3 h, and the centrifugal rotation speed is 4000-6000 rpm.
5. The preparation method of the polydopamine and metal ion modified montmorillonite flame retardant according to claim 2, characterized in that the molar ratio of the metal ions to dopamine hydrochloride added in the step (3) is 1: 2.8-3, the stirring temperature is 15-40 ℃, the stirring time is 2-4 h, the centrifugal rotation speed is 4000-6000 rpm, the vacuum oven drying temperature is 60-75 ℃, and the time is 20-24 h.
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Cited By (3)
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| CN114044991A (en) * | 2021-11-29 | 2022-02-15 | 杨春生 | Flame-retardant PVC material and preparation method thereof |
| CN114156538A (en) * | 2021-12-21 | 2022-03-08 | 吉林大学 | Electrolyte flame-retardant additive material with triphenyl phosphate @ polydopamine microcapsule structure and synthesis method thereof |
| CN118006030A (en) * | 2024-04-08 | 2024-05-10 | 拓柔电缆(上海)有限公司 | Low-smoke halogen-free flat cable sheath and preparation method thereof |
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