CN110343291B - Preparation method of modified hexagonal boron nitride flame retardant and water-based intumescent fire-retardant coating - Google Patents
Preparation method of modified hexagonal boron nitride flame retardant and water-based intumescent fire-retardant coating Download PDFInfo
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- C08K3/38—Boron-containing compounds
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Abstract
The invention provides a preparation method of a modified hexagonal boron nitride nano flame retardant and a water-based intumescent fire retardant coating, wherein the preparation method comprises the following steps: 1) performing mechanical ball milling and gemini surfactant liquid phase ultrasonic treatment on the hexagonal boron nitride to obtain hexagonal boron nitride nanosheets; 2) and (3) carrying out surface hydroxylation treatment on the hexagonal boron nitride nanosheet, adding a silane coupling agent, and carrying out grafting reaction to obtain the modified hexagonal boron nitride nano flame retardant. According to the preparation method of the modified hexagonal boron nitride nano flame retardant, the hexagonal boron nitride is subjected to mechanical ball milling and surfactant liquid phase ultrasonic stripping to increase the interlayer spacing, so that the hexagonal boron nitride is stripped into a lamellar nano structure, and then the surface of the nano hexagonal boron nitride nano sheet is modified by using a strong alkaline solution and a silane coupling agent, so that the obtained modified hexagonal boron nitride nano flame retardant has high flame retardance and good thermal stability.
Description
Technical Field
The invention relates to the technical field of flame retardants, in particular to a preparation method of a modified hexagonal boron nitride flame retardant and a water-based intumescent fire-retardant coating.
Background
Polymers often do not have good high flame retardancy themselves, and a great deal of research has been conducted to improve the flame retardancy of polymers. Research has shown that adding flame retardants to polymers is an effective way to effectively improve the flame retardancy of polymers. However, whether the flame retardant can be well dispersed in the polymer directly influences the performance of the flame retardant effect. The inorganic filler generally has a low surface activity of particles, resulting in poor interfacial force with the organic polymer. Therefore, the development of flame retardants with high flame retardancy is a work with important application prospects.
In recent years, layered nanomaterials have become one of the most widely studied materials in the field of nanomaterials due to their unique structures and excellent properties. Due to similar structures, the hexagonal boron nitride nanosheets and the graphene show similar attractive properties such as ideal mechanical strength, good chemical and thermal stability, high thermal conductivity, corrosion resistance, insulating property and the like, and show wide application prospects in the fields of optoelectronics, electronic industry, catalysis, energy, storage and the like.
The hexagonal boron nitride has excellent performances such as outstanding heat resistance, thermal stability and thermal conductivity, and the layered barrier effect and the catalytic carbonization effect of the hexagonal boron nitride can improve the flame retardance of the flame retardant, but the hexagonal boron nitride has very stable surface and few active groups, so that compared with other inorganic materials, the hexagonal boron nitride has higher modification application difficulty and can not catalyze polymers to form carbon efficiently, and the flame retardance efficiency is difficult to improve qualitatively. Therefore, the modification of the hexagonal boron nitride is carried out to give full play to the structural advantages of the hexagonal boron nitride, and the application of the hexagonal boron nitride in the fields of nano flame retardance, nano energy and the like is promoted.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a modified hexagonal boron nitride flame retardant, so as to solve the problem that the existing hexagonal boron nitride flame retardant is poor in flame retardant efficiency.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of a modified hexagonal boron nitride flame retardant comprises the following steps:
1) performing mechanical ball milling and gemini surfactant liquid phase ultrasonic treatment on the hexagonal boron nitride to obtain hexagonal boron nitride nanosheets;
2) and (3) carrying out surface hydroxylation treatment on the hexagonal boron nitride nanosheet, adding a silane coupling agent, and carrying out grafting reaction to obtain the modified hexagonal boron nitride flame retardant.
Optionally, the mechanical ball milling and gemini surfactant liquid phase ultrasonic treatment of the hexagonal boron nitride in the step 1) are performed to obtain a hexagonal boron nitride nanosheet, and the method comprises the following steps:
after the hexagonal boron nitride is mechanically ball-milled, adding a gemini surfactant, uniformly mixing, and carrying out liquid-phase ultrasonic treatment to obtain a dispersion A;
and standing the dispersion liquid A, then, carrying out layered centrifugation, and after the layered centrifugation is finished, washing, carrying out suction filtration and drying to obtain the hexagonal boron nitride nanosheet.
Optionally, the ball grinding agent in the mechanical ball grinding treatment is one of isopropanol and urea; in the mechanical ball milling treatment, the mass ratio of the hexagonal boron nitride to the grinding medium to the ball milling agent is 1: 3-5: 30-50; the ball milling speed in the mechanical ball milling treatment is 250rpm, and the ball milling time is 2-4 h.
Optionally, the gemini surfactant is a cyclic quaternary ammonium salt gemini surfactant, and the mass of the hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant is 1-10 g.
Optionally, after performing surface hydroxylation on the hexagonal boron nitride nanosheet in step 2), adding a silane coupling agent for a grafting reaction to obtain a modified hexagonal boron nitride flame retardant, including the following steps:
adding the hexagonal boron nitride nanosheets into a strong alkaline solution, stirring in an oil bath, carrying out surface hydroxylation reaction, cooling, washing with water, carrying out suction filtration, and drying after the surface hydroxylation reaction is finished, thereby obtaining surface hydroxylated hexagonal boron nitride nanosheets;
dissolving a silane coupling agent in an organic solvent, adding the surface hydroxylated hexagonal boron nitride nanosheet, performing ultrasonic stirring in a water bath, performing stirring in an oil bath, performing grafting reaction, and after the grafting reaction is finished, performing suction filtration, washing with water and drying to obtain the modified hexagonal boron nitride flame retardant.
Optionally, the strong alkali solution is one or more of a sodium hydroxide solution and a potassium hydroxide solution, and the concentration of the strong alkali solution is 2-5 mol/L.
Optionally, the silane coupling agent is one of aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane or N- (beta aminoethyl) -gamma-aminopropylmethyl-dimethyloxysilane; the organic solvent is one of absolute ethyl alcohol and methanol.
Optionally, the silane coupling agent accounts for 10% -20% of the mass of the surface hydroxylated hexagonal boron nitride nanosheet; the mass of the silane coupling agent in 1L of the organic solvent is 2-5 g.
Optionally, the stirring temperature of the oil bath in the surface hydroxylation reaction is 110-120 ℃, and the stirring time is 20-24 h; the water bath ultrasonic stirring water bath ultrasonic temperature is 40-60 ℃, and the water bath ultrasonic time is 1-3 h; the stirring temperature of oil bath stirring in the grafting reaction is 70-110 ℃, the stirring time is 7-12h, and the stirring speed is 200-300 rpm.
The second purpose of the invention is to provide a water-based intumescent fire-retardant coating, which comprises the following components in percentage by mass: epoxy styrene-acrylic emulsion: 22-26%, ammonium polyphosphate: 34-38%, pentaerythritol: 10-14%, melamine: 10-14%, hydroxyethyl cellulose: 0.4-0.6%, dispersant: 0.4-0.6%, defoaming agent: 0.4-0.6%, n-octanol: 0.4-0.6%, water: 8-10%, the modified hexagonal boron nitride flame retardant prepared by the preparation method of the modified hexagonal boron nitride flame retardant comprises the following steps: 3-7%.
The basic preparation principle of the modified hexagonal boron nitride flame retardant is as follows:
the hexagonal boron nitride is a multifunctional layered compound, has a stable layered structure and is easy to peel and regulate; according to the invention, mechanical ball milling and liquid phase ultrasound are used for stripping hexagonal boron nitride, so that the interlayer spacing is increased, the hexagonal boron nitride nanosheets are stripped into sheet hexagonal boron nitride nanosheets, after the hexagonal boron nitride nanosheets are subjected to surface modification by strong base, hydroxyl groups are arranged on the surfaces of the hexagonal boron nitride nanosheets to provide reaction groups for further amino modification, then, a silane coupling agent is used for carrying out grafting reaction to increase the reaction activity, the silane coupling agent and molecules on the surface of an inorganic filler form covalent bonds and are bonded with polymeric molecules to obtain good interface bonding, and at the moment, the silane coupling agent plays a role of a bridge formed by mutually connecting inorganic phases and organic phases to connect the nano hexagonal boron nitride and a polymer base material, so that the nano hexagonal boron nitride exerts the flame retardant effect, and the stability of the flame retardant is improved. The nanometer hexagonal boron nitride flame retardant can play a flame retardant role in a gas phase and a condensed phase, nitrogen of hexagonal boron nitride serves as a part of nitrogen source in the intumescent flame retardant, boron can effectively catalyze a matrix in the form of boron oxide and borate to promote char formation, and can generate a radical scavenger in the gas phase to inhibit radicals playing a chain growth role in a combustion reaction, so that the flame retardant plays a flame retardant role, the flame retardant can have an N-Si synergistic effect, so that the flame retardant has more excellent catalytic char formation performance, and particularly in the intumescent flame retardant, the flame retardant can have better thermal stability and barrier property, so that a carbon layer formed by combustion is more compact.
Compared with the prior art, the preparation method of the modified hexagonal boron nitride flame retardant has the following advantages:
1. according to the preparation method of the modified hexagonal boron nitride flame retardant, the hexagonal boron nitride is subjected to mechanical ball milling and surfactant liquid phase ultrasonic stripping to increase the interlayer spacing, so that the hexagonal boron nitride is stripped into a lamellar nano structure, and then the surface of the nano hexagonal boron nitride nanosheet is modified by using a strong alkaline solution and a silane coupling agent, so that the obtained modified hexagonal boron nitride flame retardant has high flame retardance and good thermal stability.
2. The modified hexagonal boron nitride flame retardant prepared by the invention contains a large amount of active groups such as hydroxyl, amino and the like, has large specific surface area and good dispersibility, and has wide application prospects in the aspects of intumescent flame retardants, polymer modification and the like.
3. The modified hexagonal boron nitride flame retardant prepared by the invention has the characteristics of wide applicability of the preparation method and simple and point operation process, and the preparation process is halogen-free and environment-friendly, thereby being beneficial to industrial popularization and application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a particle size distribution diagram of a modified hexagonal boron nitride flame retardant of example 1 of the present invention;
FIG. 2 is an IR spectrum of a modified hexagonal boron nitride flame retardant of example 1 of the present invention;
FIG. 3 is a thermogram of a modified hexagonal boron nitride flame retardant of example 1 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
A preparation method of a modified hexagonal boron nitride flame retardant specifically comprises the following steps:
1) respectively weighing 30g of zirconia balls (grinding media), 5g of hexagonal boron nitride with the average particle size of 2-3 microns and 150g of isopropanol (ball grinding agent), placing the mixture in a zirconia ball milling tank, carrying out ball milling at the rotating speed of 250rpm for 2 hours, after the ball milling is finished, carrying out suction filtration on milky suspension obtained by the ball milling, and placing filter residues in a drying box at the temperature of 80 ℃ for drying to obtain ball-milled hexagonal boron nitride powder;
2) adding a cyclic quaternary ammonium salt gemini surfactant G8 into ball-milled hexagonal boron nitride powder, and uniformly mixing, wherein the mass of hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant G8 is 2G, and then carrying out ultrasonic treatment by adopting 70W power in a water bath at 30 ℃ to obtain a dispersion liquid A;
3) standing the dispersion liquid A, placing the dispersion liquid A in a centrifuge, centrifuging and layering at the rotating speeds of 1000rpm, 3000rpm, 5000rpm and 7000rpm respectively, and after the centrifuging and layering are finished, washing, filtering and drying to obtain hexagonal boron nitride nanosheets;
4) adding the hexagonal boron nitride nanosheets into a sodium hydroxide solution with the concentration of 5mol/L, stirring for 24 hours in an oil bath kettle at 120 ℃, carrying out surface hydroxylation reaction, naturally cooling after the surface hydroxylation reaction is finished, washing for 2-3 times, carrying out suction filtration, and drying in a drying box at 80 ℃ to obtain surface hydroxylated hexagonal boron nitride nanosheets;
5) dissolving aminopropyltriethoxysilane in absolute ethanol, wherein the mass of the aminopropyltriethoxysilane in 1L of the absolute ethanol is 2g, then adding surface hydroxylated hexagonal boron nitride nanosheets, wherein the mass of the aminopropyltriethoxysilane is 10% of that of the surface hydroxylated hexagonal boron nitride nanosheets, simultaneously mechanically stirring and ultrasonically treating for 2h in a water bath at 40 ℃, then mechanically stirring for 7h in a 110 ℃ oil bath kettle at a stirring speed of 250rpm, carrying out grafting reaction, after the grafting reaction is finished, carrying out suction filtration, washing with ethanol for 2-3 times, washing with deionized water for 2-3 times, and after the washing is finished, drying in a drying box at 80 ℃ to obtain the modified hexagonal boron nitride flame retardant.
The structural formula of the cyclic quaternary ammonium salt gemini surfactant G8 in the embodiment is as follows:
The structural formula of the modified hexagonal boron nitride flame retardant of this example is:
from the above structural formula, the modified hexagonal boron nitride flame retardant of this example contains a large amount of active hydroxyl and amino functional groups on the surface.
The particle size of the modified hexagonal boron nitride flame retardant of this example was tested and the results are shown in figure 1.
As can be seen from FIG. 1, the modified hexagonal boron nitride flame retardant of the present embodiment has an average particle size of about 300-500nm, and the size is significantly reduced compared to that of the original hexagonal boron nitride.
The modified hexagonal boron nitride flame retardant of this example was tested by infrared spectroscopy and compared to unmodified hexagonal Boron Nitride (BN) and the results are shown in figure 2.
As can be seen from FIG. 2, unmodified hexagonal Boron Nitride (BN), hydroxylated hexagonal boron nitride (BN-OH) and silane coupling agent grafted hexagonal boron nitride (BN-NH)2) Modified hexagonal boron nitride flame retardant of this example) at 1374cm-1、814cm-1All appear flatIn-plane B-N tensile and flexural vibration peaks, hydroxylated hexagonal boron nitride at 3440cm-1The peak of B-OH appears, and a new peak appears after the reaction of the hydroxylated hexagonal boron nitride and the 3-aminopropyltriethoxysilane coupling agent, wherein the peak is 2939cm-1、2976cm-1Corresponding to CH2、NH2Vibration of the radical at 1020cm-1、1070cm-1、1125cm-1The three new peaks correspond to the vibration of Si-O-B, Si-O-Si and Si-O-C respectively, which shows that the modified hexagonal boron nitride flame retardant is successfully prepared by the invention.
The modified hexagonal boron nitride flame retardant of this example was subjected to a thermal analysis test and compared with unmodified hexagonal Boron Nitride (BN), and the results of the test are shown in fig. 3.
As can be seen from fig. 3, the residual mass of the modified hexagonal boron nitride flame retardant of the present example is as high as 92% at 800 ℃, while the residual mass of the unmodified hexagonal boron nitride is 80%, which indicates that the modified hexagonal boron nitride flame retardant of the present example has significantly improved thermal stability, and can be used as an inorganic nano flame retardant to improve the fire resistance of a polymer material.
In order to represent the practical application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiment is used as an inorganic flame retardant, the epoxy styrene-acrylic emulsion is used as a film forming material, a water-based intumescent fire-retardant coating is prepared, and the performance test of the coating is carried out.
The epoxy styrene-acrylic emulsion is prepared by the following steps:
1) preparing a seed emulsion: 1/3 aqueous solution of emulsifier and NaHCO3(about 0.4 percent of the monomer amount), and secondary distilled water is put into a flask and stirred at high speed to be dissolved and dispersed evenly; heating to 80 +/-1 ℃, dropwise adding the seed monomer, and continuing stirring and emulsifying for 15min after dropwise adding; introducing nitrogen into the bottle for 5min (attention is paid to control the air flow to slowly and smoothly blow in so as to avoid more monomer loss); reducing the stirring speed to 200-220 r/min, taking 1/3 initiator aqueous solution, and continuously dripping into a bottle within 30min (the system is in a blue-light milk white color, and marks that seed emulsion is formed); after the initiator is dripped, keeping the temperature for 15min to prepare the seed milkLiquid;
2) pre-emulsification of shell monomers: adding the rest 2/3 emulsifier aqueous solution and shell monomer into a flask, fully stirring and emulsifying, wherein the emulsified system is stable emulsion (when the room temperature is low, the emulsification effect is poor under the condition, the layering is easy, the emulsification can be carried out under the condition of heating to 35-40 ℃, or the pre-emulsification is carried out under the condition of heating by ultrasound);
3) preparation of core-shell emulsion: continuously and uniformly dripping the residual initiator aqueous solution and the shell monomer subjected to pre-emulsification treatment into the seed emulsion within 2 hours; dripping epoxy resin dissolved in acetone, and stirring for 30 min; raising the temperature to 85 +/-1 ℃, and curing for 1 hour; after the curing is finished, reducing the temperature to 60 ℃, and continuously dropping an ammonium persulfate aqueous solution accounting for 0.1 percent of the total amount of the monomers and a sodium bisulfite aqueous solution accounting for 0.1 percent of the total amount of the monomers simultaneously within half an hour; reducing the temperature to 45 ℃, and adjusting the pH value to 7-8 by using triethylamine; and (4) sieving the obtained emulsion with a 200-mesh sieve to obtain the epoxy styrene-acrylic emulsion.
The water-based intumescent fire retardant coating is prepared by the following steps:
1) weighing the components according to the mixture ratio, wherein the components and the mass percentage of the components are as follows: 24% of epoxy styrene-acrylic emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol, 9% of water and 5% of modified hexagonal boron nitride flame retardant;
2) grinding the weighed ammonium polyphosphate, pentaerythritol, melamine and hydroxyethyl cellulose into powder, adding water, fully grinding and uniformly mixing, adding a defoaming agent and a dispersing agent, continuously fully grinding, then adding a modified hexagonal boron nitride flame retardant, an epoxy styrene-acrylic emulsion and n-octanol, fully grinding and uniformly mixing to obtain the water-based intumescent fire-retardant coating.
Example 2
A preparation method of a modified hexagonal boron nitride flame retardant specifically comprises the following steps:
1) respectively weighing 30g of zirconia balls (grinding media), 5g of hexagonal boron nitride with the average particle size of 2-3 microns and 150g of urea (ball grinding agent), placing the mixture into a zirconia ball milling tank, carrying out ball milling for 2 hours at the rotating speed of 250rpm, and after the ball milling is finished, placing a milky white solid mixture obtained by the ball milling into a drying box at the temperature of 80 ℃ for drying to obtain ball-milled hexagonal boron nitride powder;
2) adding a cyclic quaternary ammonium salt gemini surfactant G10 into ball-milled hexagonal boron nitride powder, and uniformly mixing, wherein the mass of hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant G10 is 4G, and then carrying out ultrasonic treatment by adopting 70W power in a water bath at 30 ℃ to obtain a dispersion liquid A;
3) standing the dispersion liquid A, placing the dispersion liquid A in a centrifuge, centrifuging and layering at the rotating speeds of 1000rpm, 3000rpm, 5000rpm and 7000rpm respectively, and after the centrifuging and layering are finished, washing, filtering and drying to obtain hexagonal boron nitride nanosheets;
4) adding the hexagonal boron nitride nanosheets into a potassium hydroxide solution with the concentration of 5mol/L, stirring for 20 hours in an oil bath kettle at 120 ℃, carrying out surface hydroxylation reaction, naturally cooling after the surface hydroxylation reaction is finished, washing for 2-3 times, carrying out suction filtration, and drying in a drying box at 80 ℃ to obtain surface hydroxylated hexagonal boron nitride nanosheets;
5) dissolving 3-glycidoxypropyltrimethoxysilane in absolute ethyl alcohol, wherein the mass of the 3-glycidoxypropyltrimethoxysilane in 1L of absolute ethyl alcohol is 3g, then adding surface hydroxylated hexagonal boron nitride nanosheets, wherein the mass of the 3-glycidoxypropyltrimethoxysilane is 15% of that of the surface hydroxylated hexagonal boron nitride nanosheets, simultaneously mechanically stirring and ultrasonically treating the mixture in a water bath at 40 ℃ for 1h, then mechanically stirring the mixture in an oil bath kettle at 110 ℃ for 10h at a stirring speed of 250rpm, carrying out grafting reaction, after the grafting reaction is finished, carrying out suction filtration, washing the ethanol for 2-3 times, washing the mixture with deionized water for 2-3 times, and after the washing is finished, drying the mixture in a drying box at 80 ℃ to obtain the modified hexagonal boron nitride flame retardant.
The structural formula of the cyclic quaternary ammonium salt gemini surfactant G10 in the embodiment is as follows:
In order to represent the practical application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiment is used as an inorganic flame retardant, the epoxy styrene-acrylic emulsion is used as a film forming material, a water-based intumescent fire-retardant coating is prepared, and the performance test of the coating is carried out.
Wherein, the preparation methods of the epoxy styrene-acrylic emulsion and the water-based intumescent fire retardant coating are the same as the example 1.
Example 3
A preparation method of a modified hexagonal boron nitride flame retardant specifically comprises the following steps:
1) respectively weighing 42g of zirconia balls (grinding media), 7g of hexagonal boron nitride with the average particle size of 2-3 microns and 210g of isopropanol (ball grinding agent), placing the mixture in a zirconia ball milling tank, carrying out ball milling at the rotating speed of 250rpm for 4 hours, after the ball milling is finished, carrying out suction filtration on milky suspension obtained by the ball milling, and placing filter residues in a drying box at the temperature of 80 ℃ for drying to obtain ball-milled hexagonal boron nitride powder;
2) adding a cyclic quaternary ammonium salt gemini surfactant G12 into ball-milled hexagonal boron nitride powder, and uniformly mixing, wherein the mass of hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant G12 is 10G, and then carrying out ultrasonic treatment by adopting 70W power in a water bath at 40 ℃ to obtain a dispersion A;
3) standing the dispersion liquid A, placing the dispersion liquid A in a centrifuge, centrifuging and layering at the rotating speeds of 1000rpm, 3000rpm, 5000rpm and 7000rpm respectively, and after the centrifuging and layering are finished, washing, filtering and drying to obtain hexagonal boron nitride nanosheets;
4) adding the hexagonal boron nitride nanosheets into a mixed solution (1: 1) of sodium hydroxide and potassium hydroxide with the concentration of 2mol/L, stirring for 20 hours in an oil bath pan at 110 ℃, carrying out surface hydroxylation reaction, naturally cooling after the surface hydroxylation reaction is finished, washing for 2-3 times, carrying out suction filtration, and drying in a drying box at 80 ℃ to obtain surface hydroxylated hexagonal boron nitride nanosheets;
5) dissolving 3-glycidoxypropyltrimethoxysilane in absolute ethyl alcohol, wherein the mass of the 3-glycidoxypropyltrimethoxysilane in 1L of absolute ethyl alcohol is 5g, then adding surface hydroxylated hexagonal boron nitride nanosheets, wherein the mass of the 3-glycidoxypropyltrimethoxysilane is 20% of that of the surface hydroxylated hexagonal boron nitride nanosheets, simultaneously mechanically stirring and ultrasonically treating the mixture in a water bath at 40 ℃ for 1h, then mechanically stirring the mixture in an oil bath kettle at 110 ℃ for 12h at a stirring speed of 250rpm, carrying out grafting reaction, after the grafting reaction is finished, carrying out suction filtration, washing the ethanol for 2-3 times, washing the mixture with deionized water for 2-3 times, and after the washing is finished, drying the mixture in a drying box at 80 ℃ to obtain the modified hexagonal boron nitride flame retardant.
The structural formula of the cyclic quaternary ammonium salt gemini surfactant G12 in the embodiment is as follows:
In order to represent the practical application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiment is used as an inorganic flame retardant, the epoxy styrene-acrylic emulsion is used as a film forming material, a water-based intumescent fire-retardant coating is prepared, and the performance test of the coating is carried out.
Wherein, the preparation methods of the epoxy styrene-acrylic emulsion and the water-based intumescent fire retardant coating are the same as the example 1.
Example 4
A preparation method of a modified hexagonal boron nitride flame retardant specifically comprises the following steps:
1) respectively weighing 30g of zirconia balls (grinding media), 5g of hexagonal boron nitride with the average particle size of 2-3 microns and 150g of isopropanol (ball grinding agent), placing the mixture in a zirconia ball milling tank, carrying out ball milling at the rotating speed of 250rpm for 2 hours, after the ball milling is finished, carrying out suction filtration on milky suspension obtained by the ball milling, and placing filter residues in a drying box at the temperature of 80 ℃ for drying to obtain ball-milled hexagonal boron nitride powder;
2) adding a cyclic quaternary ammonium salt gemini surfactant G14 into ball-milled hexagonal boron nitride powder, and uniformly mixing, wherein the mass of hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant G14 is 4G, and then carrying out ultrasonic treatment by adopting 70W power in a water bath at 30 ℃ to obtain a dispersion liquid A;
3) standing the dispersion liquid A, placing the dispersion liquid A in a centrifuge, centrifuging and layering at the rotating speeds of 1000rpm, 3000rpm, 5000rpm and 7000rpm respectively, and after the centrifuging and layering are finished, washing, filtering and drying to obtain hexagonal boron nitride nanosheets;
4) adding the hexagonal boron nitride nanosheets into a potassium hydroxide solution with the concentration of 5mol/L, stirring for 20 hours in an oil bath kettle at 120 ℃, carrying out surface hydroxylation reaction, naturally cooling after the surface hydroxylation reaction is finished, washing for 2-3 times, carrying out suction filtration, and drying in a drying box at 80 ℃ to obtain surface hydroxylated hexagonal boron nitride nanosheets;
5) dissolving vinyl trimethoxy silane in absolute ethyl alcohol, wherein the mass of the vinyl trimethoxy silane in 1L of absolute ethyl alcohol is 3g, then adding surface hydroxylated hexagonal boron nitride nanosheets, wherein the mass of the vinyl trimethoxy silane is 15% of that of the surface hydroxylated hexagonal boron nitride nanosheets, simultaneously mechanically stirring and ultrasonically treating for 1h in a water bath at 40 ℃, then mechanically stirring for 10h at a stirring speed of 250rpm in an oil bath kettle at 110 ℃, carrying out grafting reaction, after the grafting reaction is finished, carrying out suction filtration, washing for 2-3 times with ethanol, washing for 2-3 times with deionized water, and after the washing is finished, drying in a drying box at 80 ℃ to obtain the modified hexagonal boron nitride flame retardant.
The structural formula of the cyclic quaternary ammonium salt gemini surfactant G14 in the embodiment is as follows:
In order to represent the practical application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiment is used as an inorganic flame retardant, the epoxy styrene-acrylic emulsion is used as a film forming material, a water-based intumescent fire-retardant coating is prepared, and the performance test of the coating is carried out.
Wherein, the preparation methods of the epoxy styrene-acrylic emulsion and the water-based intumescent fire retardant coating are the same as the example 1.
Example 5
A preparation method of a modified hexagonal boron nitride flame retardant specifically comprises the following steps:
1) respectively weighing 42g of zirconia balls (grinding media), 7g of hexagonal boron nitride with the average particle size of 2-3 microns and 210g of isopropanol (ball grinding agent), placing the mixture in a zirconia ball milling tank, carrying out ball milling at the rotating speed of 250rpm for 4 hours, after the ball milling is finished, carrying out suction filtration on milky suspension obtained by the ball milling, and placing filter residues in a drying box at the temperature of 80 ℃ for drying to obtain ball-milled hexagonal boron nitride powder;
2) adding a cyclic quaternary ammonium salt gemini surfactant G16 into ball-milled hexagonal boron nitride powder, and uniformly mixing, wherein the mass of hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant G16 is 10G, and then carrying out ultrasonic treatment by adopting 70W power in a water bath at 40 ℃ to obtain a dispersion A;
3) standing the dispersion liquid A, placing the dispersion liquid A in a centrifuge, centrifuging and layering at the rotating speeds of 1000rpm, 3000rpm, 5000rpm and 7000rpm respectively, and after the centrifuging and layering are finished, washing, filtering and drying to obtain hexagonal boron nitride nanosheets;
4) adding the hexagonal boron nitride nanosheets into a mixed solution (1: 1) of sodium hydroxide and potassium hydroxide with the concentration of 2mol/L, stirring for 20 hours in an oil bath pan at 110 ℃, carrying out surface hydroxylation reaction, naturally cooling after the surface hydroxylation reaction is finished, washing for 2-3 times, carrying out suction filtration, and drying in a drying box at 80 ℃ to obtain surface hydroxylated hexagonal boron nitride nanosheets;
5) dissolving N- (beta aminoethyl) -gamma-aminopropylmethyl-dimethyloxysilane in methanol, wherein the mass of the N- (beta aminoethyl) -gamma-aminopropylmethyl-dimethyloxysilane in 1L of the methanol is 5g, then adding surface hydroxylated hexagonal boron nitride nanosheets, wherein the mass of the N- (beta aminoethyl) -gamma-aminopropylmethyl-dimethyloxysilane is 20% of the mass of the surface hydroxylated hexagonal boron nitride nanosheets, simultaneously mechanically stirring and ultrasonically treating the mixture for 1h in a water bath at the temperature of 40 ℃, then mechanically stirring the mixture for 12h at the stirring speed of 250rpm in an oil bath kettle at the temperature of 110 ℃, carrying out grafting reaction, after the grafting reaction is finished, carrying out suction filtration, washing the mixture with ethanol for 2-3 times, washing the mixture with deionized water for 2-3 times, and after the washing is finished, and (3) drying in a drying oven at 80 ℃ to obtain the modified hexagonal boron nitride flame retardant.
The structural formula of the cyclic quaternary ammonium salt gemini surfactant G16 in the embodiment is as follows:
In order to represent the practical application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiment is used as an inorganic flame retardant, the epoxy styrene-acrylic emulsion is used as a film forming material, a water-based intumescent fire-retardant coating is prepared, and the performance test of the coating is carried out.
Wherein, the preparation methods of the epoxy styrene-acrylic emulsion and the water-based intumescent fire retardant coating are the same as the example 1.
Example 6
A preparation method of a modified hexagonal boron nitride flame retardant specifically comprises the following steps:
1) respectively weighing 42g of zirconia balls (grinding media), 7g of hexagonal boron nitride with the average particle size of 2-3 microns and 210g of urea (ball grinding agent), placing the mixture into a zirconia ball milling tank, carrying out ball milling for 4 hours at the rotating speed of 250rpm, and after the ball milling is finished, placing a milky white solid mixture obtained by the ball milling into a drying box at the temperature of 80 ℃ for drying to obtain ball-milled hexagonal boron nitride powder;
2) adding a cyclic quaternary ammonium salt gemini surfactant G18 into ball-milled hexagonal boron nitride powder, and uniformly mixing, wherein the mass of hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant G18 is 6G, and then carrying out ultrasonic treatment by adopting 70W power in a water bath at 40 ℃ to obtain a dispersion A;
3) standing the dispersion liquid A, placing the dispersion liquid A in a centrifuge, centrifuging and layering at the rotating speeds of 1000rpm, 3000rpm, 5000rpm and 7000rpm respectively, and after the centrifuging and layering are finished, washing, filtering and drying to obtain hexagonal boron nitride nanosheets;
4) adding hexagonal boron nitride nanosheets into a mixed solution (1: 1) of sodium hydroxide and potassium hydroxide with the concentration of 5mol/L, stirring for 24 hours in an oil bath pan at 110 ℃, carrying out surface hydroxylation reaction, naturally cooling after the surface hydroxylation reaction is finished, washing for 2-3 times, carrying out suction filtration, and drying in a drying box at 80 ℃ to obtain surface hydroxylated hexagonal boron nitride nanosheets;
5) dissolving vinyl trimethoxy silane in absolute ethyl alcohol, wherein the mass of the vinyl trimethoxy silane in 1L of absolute ethyl alcohol is 4g, then adding surface hydroxylated hexagonal boron nitride nanosheets, wherein the mass of the vinyl trimethoxy silane is 10% of that of the surface hydroxylated hexagonal boron nitride nanosheets, simultaneously mechanically stirring and ultrasonically treating for 1h in a water bath at 40 ℃, then mechanically stirring for 10h at a stirring speed of 250rpm in an oil bath pot at 110 ℃, carrying out grafting reaction, after the grafting reaction is finished, carrying out suction filtration, washing for 2-3 times with ethanol, washing for 2-3 times with deionized water, and after the washing is finished, drying in a drying box at 80 ℃ to obtain the modified hexagonal boron nitride flame retardant.
The structural formula of the cyclic quaternary ammonium salt gemini surfactant G18 in the embodiment is as follows:
In order to represent the practical application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiment is used as an inorganic flame retardant, the epoxy styrene-acrylic emulsion is used as a film forming material, a water-based intumescent fire-retardant coating is prepared, and the performance test of the coating is carried out.
Wherein, the preparation methods of the epoxy styrene-acrylic emulsion and the water-based intumescent fire retardant coating are the same as the example 1.
Comparative example 1
In order to further characterize the actual application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiments 1 to 6 of the invention is not added, the epoxy styrene-acrylic emulsion is used as a film forming material to prepare the water-based intumescent fire-retardant coating, and the performance test of the coating is carried out.
The preparation method of the epoxy styrene-acrylic emulsion in the comparative example is the same as that of example 1.
The preparation method of the aqueous intumescent fire retardant coating in the comparative example specifically comprises the following steps:
1) weighing the components according to the mixture ratio, wherein the components and the mass percentage of the components comprise: 24% of epoxy styrene-acrylic emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octyl alcohol and 14% of water;
2) grinding the weighed ammonium polyphosphate, pentaerythritol, melamine and hydroxyethyl cellulose into powder, then adding water, fully grinding and uniformly mixing, adding a defoaming agent and a dispersing agent, continuing to fully grind, then adding an epoxy styrene-acrylic emulsion and n-octanol, fully grinding and uniformly mixing to obtain the water-based intumescent fire retardant coating.
Comparative example 2
In order to further characterize the actual application effect of the modified hexagonal boron nitride flame retardant of the embodiment, the modified hexagonal boron nitride flame retardant of the embodiments 1 to 6 of the invention is not added, the epoxy styrene-acrylic emulsion is used as a film forming material to prepare the water-based intumescent fire-retardant coating, and the performance test of the coating is carried out.
The preparation method of the epoxy styrene-acrylic emulsion in the comparative example is the same as that of example 1.
The preparation method of the aqueous intumescent fire retardant coating in the comparative example specifically comprises the following steps:
1) weighing the components according to the mixture ratio, wherein the components and the mass percentage of the components comprise: 24% of epoxy styrene-acrylic emulsion, 36% of ammonium polyphosphate, 12% of pentaerythritol, 12% of melamine, 0.5% of hydroxyethyl cellulose, 0.5% of dispersing agent, 0.5% of defoaming agent, 0.5% of n-octanol, 9% of water and 5% of hexagonal boron nitride;
2) grinding the weighed ammonium polyphosphate, pentaerythritol, melamine and hydroxyethyl cellulose into powder, adding water, fully grinding and uniformly mixing, adding a defoaming agent and a dispersing agent, continuously fully grinding, then adding hexagonal boron nitride, epoxy styrene-acrylic emulsion and n-octanol, fully grinding and uniformly mixing to obtain the water-based intumescent fire-retardant coating.
The fire resistance of the aqueous intumescent fire-retardant coatings obtained in comparative examples 1 and 2 and examples 1 to 6 above was tested and the results are shown in table 1.
TABLE 1
As can be seen from table 1, compared with the aqueous intumescent fire retardant coatings of comparative example 1 and comparative example 2 without adding the modified hexagonal boron nitride fire retardant of examples 1 to 6 of the present invention, the aqueous intumescent fire retardant coatings with the modified hexagonal boron nitride fire retardant of examples 1 to 6 of the present invention have significantly improved fire endurance, and the formed intumescent carbon layer is more compact and has higher strength, which indicates that the modified hexagonal boron nitride fire retardant obtained by the present invention has good fire retardant efficiency, excellent comprehensive properties, good resin compatibility, no damage to other properties of the material, and strong applicability.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a modified hexagonal boron nitride flame retardant is characterized by comprising the following steps:
1) performing mechanical ball milling and gemini surfactant liquid phase ultrasonic treatment on the hexagonal boron nitride to obtain hexagonal boron nitride nanosheets;
2) performing surface hydroxylation treatment on the hexagonal boron nitride nanosheet, adding a silane coupling agent, and performing grafting reaction to obtain a modified hexagonal boron nitride flame retardant;
the method comprises the following steps of 1), carrying out mechanical ball milling and gemini surfactant liquid phase ultrasonic treatment on hexagonal boron nitride in step 1) to obtain hexagonal boron nitride nanosheets, wherein the method comprises the following steps:
after the hexagonal boron nitride is mechanically ball-milled, adding a gemini surfactant, uniformly mixing, and carrying out liquid-phase ultrasonic treatment to obtain a dispersion A; the gemini surfactant is a cyclic quaternary ammonium salt gemini surfactant, and the mass of the hexagonal boron nitride in 1L of the cyclic quaternary ammonium salt gemini surfactant is 1-10 g;
standing the dispersion liquid A, then, centrifugally layering, and after the centrifugal layering is finished, washing with water, performing suction filtration and drying to obtain a hexagonal boron nitride nanosheet;
performing surface hydroxylation treatment on the hexagonal boron nitride nanosheet in the step 2), adding a silane coupling agent, and performing grafting reaction to obtain the modified hexagonal boron nitride flame retardant, wherein the method comprises the following steps:
adding the hexagonal boron nitride nanosheets into a strong alkaline solution, stirring in an oil bath, carrying out surface hydroxylation reaction, cooling, washing with water, carrying out suction filtration, and drying after the surface hydroxylation reaction is finished, thereby obtaining surface hydroxylated hexagonal boron nitride nanosheets;
dissolving a silane coupling agent in an organic solvent, adding the surface hydroxylated hexagonal boron nitride nanosheet, performing ultrasonic stirring in a water bath, performing stirring in an oil bath, performing grafting reaction, and after the grafting reaction is finished, performing suction filtration, washing with water and drying to obtain a modified hexagonal boron nitride flame retardant; the silane coupling agent accounts for 10-20% of the mass of the surface hydroxylated hexagonal boron nitride nanosheet; the mass of the silane coupling agent in 1L of the organic solvent is 2-5 g.
2. The preparation method of the modified hexagonal boron nitride flame retardant of claim 1, wherein a ball milling agent in the mechanical ball milling treatment is one of isopropanol and urea; in the mechanical ball milling treatment, the mass ratio of the hexagonal boron nitride to the grinding medium to the ball milling agent is 1: 3-5: 30-50; the ball milling speed in the mechanical ball milling treatment is 250rpm, and the ball milling time is 2-4 h.
3. The preparation method of the modified hexagonal boron nitride flame retardant of claim 1, wherein the strong alkali solution is one or more of sodium hydroxide solution and potassium hydroxide solution, and the concentration of the strong alkali solution is 2-5 mol/L.
4. The method of claim 1, wherein the silane coupling agent is one of aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, or N- (β aminoethyl) - γ -aminopropylmethyl-dimethyloxysilane; the organic solvent is one of absolute ethyl alcohol and methanol.
5. The preparation method of the modified hexagonal boron nitride flame retardant of claim 1, wherein the stirring temperature of oil bath stirring in the surface hydroxylation reaction is 110-120 ℃, and the stirring time is 20-24 h; the water bath ultrasonic stirring water bath ultrasonic temperature is 40-60 ℃, and the water bath ultrasonic time is 1-3 h; the stirring temperature of oil bath stirring in the grafting reaction is 70-110 ℃, the stirring time is 7-12h, and the stirring speed is 200-300 rpm.
6. The water-based intumescent fire-retardant coating is characterized by comprising the following components in percentage by mass: epoxy styrene-acrylic emulsion: 22-26%, ammonium polyphosphate: 34-38%, pentaerythritol: 10-14%, melamine: 10-14%, hydroxyethyl cellulose: 0.4-0.6%, dispersant: 0.4-0.6%, defoaming agent: 0.4-0.6%, n-octanol: 0.4-0.6%, water: 8-10%, the modified hexagonal boron nitride flame retardant prepared by the method of any one of claims 1 to 5: 3-7%.
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| CN105504878A (en) * | 2015-11-30 | 2016-04-20 | 东华大学 | Organically modified alpha-ZrP and modification method thereof |
| CN109401456A (en) * | 2018-10-31 | 2019-03-01 | 武汉工程大学 | A kind of Water-borne inflation type refractory coating and preparation method thereof based on modified boron nitride |
| CN109943099B (en) * | 2019-03-22 | 2021-02-12 | 武汉工程大学 | Flame retardant based on modified alpha-zirconium phosphate and preparation method thereof |
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