CN110183773B - Preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material - Google Patents
Preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses a preparation method of a chitosan quaternary ammonium salt organic intercalated montmorillonite composite material, which comprises the steps of dissolving GTA and chitosan in deionized water, adjusting the pH value after reaction, distilling under reduced pressure, centrifugally washing, and drying in vacuum to obtain chitosan quaternary ammonium salt; ultrasonically dispersing chitosan quaternary ammonium salt and montmorillonite in deionized water, strongly stirring, washing until no chloride ion exists, and drying in vacuum to obtain organic intercalation modified montmorillonite; dissolving dicyanodiamine and boric acid in water, stirring until the solvent is evaporated, drying and calcining to obtain g-C3N4(ii) a Mixing of g-C3N4Adding organic intercalation modified montmorillonite, adding sulfuric acid solution, stirring, washing to neutrality, drying and grinding to obtain chitosan quaternaryAmmonium salt organic intercalation montmorillonite composite material. The preparation method comprises organically intercalating chitosan quaternary ammonium salt with montmorillonite and g-C3N4Compounding montmorillonite modified by organic intercalation with g-C3N4The composite material has an oxygen index of 31.5%, and good flame retardant property, and improves the flame retardant effect of the polymer.
Description
Technical Field
The invention belongs to the field of flame retardant materials and high polymer materials, and relates to a preparation method of a chitosan quaternary ammonium salt organic intercalated montmorillonite composite material; the invention also relates to the use of the composite material.
Background
The natural macromolecules have various active functional groups, and can be endowed with more excellent performances by modification of some physical or chemical methods, so that the application field of the natural macromolecules is further expanded. Natural high molecular compounds such as chitosan, starch, etc. are receiving close attention from researchers. Chitosan is a natural high-molecular polysaccharide with positive charges, is rich in nature, and is widely applied to the fields of food chemical industry, biotechnology, agriculture, environmental protection and the like.
The traditional polymer is easy to generate molten drops when being burnt, and is accompanied with the release of black smoke and toxic gas, so that the application field is limited, and the improvement of the flame retardance of the material is always concerned by many researchers. Montmorillonite is a natural mineral of silicate, and has a structural formula of (Al, Mg)2〔SiO10〕(OH)2·nH2And O. Has good dispersion performance, can be used as an additive of a nano polymer high molecular material, improves the shock resistance, stability and gas barrier performance, improves the material processing performance and enhances the physical properties of the polymer.
Disclosure of Invention
The invention aims to provide a preparation method of a chitosan quaternary ammonium salt organic intercalated montmorillonite composite material, which is used for preparing a polymer with higher flame retardance and unlimited application.
The invention also aims to provide application of the composite material prepared by the preparation method.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a chitosan quaternary ammonium salt organic intercalated montmorillonite composite material specifically comprises the following steps:
1) preparation of chitosan quaternary ammonium salt (HTCC)
Dissolving 2, 3-epoxypropyltrimethylammonium chloride (GTA) and Chitosan (CS) in deionized water according to a mass ratio of 1: 0.72-3.5, reacting at 60-100 ℃ for 8-12 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 4-8 with glacial acetic acid, then distilling under reduced pressure to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution to remove GTA which does not participate in the reaction, repeatedly centrifuging and washing with absolute ethyl alcohol, and drying in vacuum for 8-24 hours to obtain a light yellow powdery chitosan quaternary ammonium salt (HTCC);
2) chitosan quaternary ammonium salt Modified Montmorillonite (MMT)
Respectively taking chitosan quaternary ammonium salt and montmorillonite (MMT) according to a mass ratio of 1: 1-5, adding the chitosan quaternary ammonium salt and the montmorillonite (MMT) into deionized water, carrying out ultrasonic dispersion, strongly stirring the mixture for 1-6 hours at a temperature of 20-100 ℃, then repeatedly washing the mixture by using the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist, and carrying out vacuum drying to obtain organic intercalated modified montmorillonite (HTCC intercalated montmorillonite);
3) respectively taking dicyandiamide and boric acid according to the mass ratio of 1: 0.2-1.3, completely dissolving dicyandiamide and boric acid in water, and stirring at the temperature of 60-100 ℃ until the solvent is dissolvedCompletely evaporating, drying, and calcining at 400-700 ℃ for 2-6 h to obtain g-C3N4；
4) Modified montmorillonite and g-C3N4Compounding
Taking g-C according to a mass ratio of 1: 0.2-7 respectively3N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4Adding the organic intercalated modified montmorillonite, adding a sulfuric acid solution, stirring for 10-24 hours at normal temperature, washing with deionized water to be neutral, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material (g-C)3N4@ HTCC intercalated montmorillonite).
The sulfuric acid solution is added for g-C3N4And stripping to ensure that the composite material can be better compounded.
The other technical scheme adopted by the invention is as follows: the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material prepared by the preparation method is compounded with an ethylene-vinyl acetate copolymer (EVA) material to prepare the flame retardant material.
The preparation method of the invention is that chitosan quaternary ammonium salt organic intercalation montmorillonite and g-C are added3N4Compounding to obtain fire retardant, modifying montmorillonite with organic intercalation, and mixing with g-C3N4The oxygen index of the composite material can reach 31.5 percent, the flame retardant property is relatively good, and the flame retardant effect of the polymer is improved. The modification method can be used for industrial production and lays a foundation for subsequent organic modification of montmorillonite.
Drawings
FIG. 1 is a graph of an infrared comparison of chitosan and hydroxypropyl trimethylammonium chloride chitosan.
FIG. 2 shows organic intercalated montmorillonite and g-C3N4Infrared contrast plot of @ MMT.
FIG. 3 is a scanning electron microscope image of the fracture surface of the composite flame retardant material prepared by the invention.
Detailed Description
The invention is explained in more detail below with reference to the figures and the embodiments.
Example 1
Weighing 4g of 2, 3-epoxypropyltrimethylammonium chloride and 7g of chitosan, dissolving in deionized water, reacting at 80 ℃ for 10 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 4 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol, removing GTA which does not participate in the reaction to separate out chitosan quaternary ammonium salt from the solution, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 8 hours to obtain light yellow powdery chitosan quaternary ammonium salt (HTCC); respectively taking chitosan quaternary ammonium salt and montmorillonite (MMT) according to a mass ratio of 1: 1, adding the chitosan quaternary ammonium salt and the montmorillonite (MMT) into deionized water, carrying out ultrasonic dispersion, strongly stirring the mixture for 6 hours at a temperature of 20 ℃, washing the mixture for multiple times by using the deionized water until no white precipitate is detected by using a silver nitrate solution, and carrying out vacuum drying to obtain organic intercalation modified montmorillonite (HTCC); weighing 5g of dihydrodiamine and 1g of boric acid, completely dissolving in water, stirring at 80 ℃ until the solvent is completely evaporated, drying, and calcining at 550 ℃ for 4h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 0.23N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4Adding organic intercalation modified montmorillonite, adding sulfuric acid solution, stirring at normal temperature for 10 hr, washing with deionized water to neutrality, drying, and grinding to obtain chitosan quaternary ammonium salt organic intercalation montmorillonite composite material (g-C)3N4@ HTCC intercalated montmorillonite).
The composite material prepared in the example 1 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant performance test is carried out.
The structure and performance analysis of MMT after organic intercalation shows.
1. Infrared analysis
FIG. 1 shows the IR spectra of CS and HTCC, 1560cm in CS spectrum-1The absorption peak is the in-plane bending deformation vibration of primary amine N-H, disappears in an HTCC spectrogram obtained after modification, and indicates that H atoms in N-H bondsIs substituted. HTCC at 3400cm-1The absorption peak is obviously widened, and the absorption peak of hydroxyl is strengthened, which indicates that amino in chitosan molecules is substituted.
FIG. 2 shows montmorillonite, organic intercalation modified montmorillonite, g-C3N4And g-C3N4Infrared spectrogram of @ HTCC intercalated montmorillonite at 1380cm-1There is no peak and a new peak appears here after intercalation, indicating that the long chain of the intercalating agent is bonded to the surface of the montmorillonite. g-C3N4At 808 cm-1The bending absorption peak is C-N triazine ring and ranges from 1015 cm to 1515cm-1Absorption peaks in the range of 1640cm for C-N on the carbon-nitrogen heterocycle-1The peak at (a) is the C = N compressive absorption peak. g-C3N4@ HTCC intercalated montmorillonite is 3000-3500 cm-1The wide band of (A) is generated by N-H stretching vibration and hydrogen bond interaction, and the position of the C-N characteristic peak generates a certain red shift.
2. Compatibility analysis
FIG. 3 is a surface topography of the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material prepared in example 1. As can be seen from fig. 3, a uniform dense carbon layer is formed on the surface of the HTCC organic intercalated montmorillonite composite material, which indicates that the HTCC organic intercalated montmorillonite has good compatibility in the matrix material, so that the flame retardant can form a uniform mixed system, and the agglomeration phenomenon is reduced.
3. Analysis of flame retarding mechanism
The chitosan structure has more reaction hydroxyl groups, can be catalyzed into carbon, promotes the formation of a carbon layer, and can be used as a novel carbon source. The montmorillonite is silicate clay with a layered structure, and the layered structure of the montmorillonite is utilized, chitosan quaternary ammonium salt is used as an intercalating agent, the montmorillonite is subjected to organic intercalation treatment to strip the sheets of the montmorillonite, so that the interlayer spacing of the montmorillonite is increased, the water-absorbing expansibility, high dispersibility, adsorbability and the like of the montmorillonite are increased, and the montmorillonite is also a good carbon forming agent. During combustion, the composite material g-C3N4The flame-retardant ammonia gas is generated, the combustible gas can be diluted, the gas-phase flame retardance is realized, and the flame extinguishment is promoted.
The structure and the flame retardant property of the product are analyzed by infrared spectroscopy (IR) and oxygen index, and the TGA result of the intercalated montmorillonite shows that the organic intercalated montmorillonite is added into the polymer to improve the flame retardant property of the polymer.
Example 2
Weighing 4g of 2, 3-epoxypropyltrimethylammonium chloride and 8g of chitosan, dissolving the 2, 3-epoxypropyltrimethylammonium chloride and the chitosan in deionized water, reacting for 12 hours at the temperature of 60 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 8 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvent to obtain a concentrated solution, adding absolute ethyl alcohol, removing GTA which does not participate in the reaction to separate out chitosan quaternary ammonium salt from the solution, repeatedly centrifuging and washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 24 hours to obtain faint yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, strongly stirring the mixture for 1 hour at the temperature of 100 ℃, repeatedly washing the mixture by using the deionized water until no white precipitate is detected by using a silver nitrate solution, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 6g of dihydrodiamine and 1.2g of boric acid, completely dissolving in water, stirring at 100 ℃ until the solvent is completely evaporated, drying, and calcining at 400 ℃ for 6h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 73N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 10 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material of the embodiment 2 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant performance test is carried out.
Example 3
Weighing 4g of 2, 3-epoxypropyltrimethylammonium chloride and 7g of chitosan, dissolving in deionized water, reacting at 60 ℃ for 12 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 6 by using glacial acetic acid, and thenDistilling under reduced pressure to remove most of solvent, adding anhydrous ethanol into the concentrated solution, removing GTA which does not participate in reaction, separating out chitosan quaternary ammonium salt from the solution, repeatedly centrifuging and washing with anhydrous ethanol, and vacuum drying for 16h to obtain yellowish powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 3, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, strongly stirring the mixture for 3.5 hours at the temperature of 60 ℃, then repeatedly washing the mixture by using the deionized water until no white precipitate is detected by using a silver nitrate solution, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 6g of dihydrodiamine and 2g of boric acid, completely dissolving in water, stirring at 80 ℃ until the solvent is completely evaporated, drying, and calcining at 700 ℃ for 2h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 3.63N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 17 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material obtained in the embodiment 3 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame-retardant material, and the flame-retardant performance test is carried out.
Example 4
Weighing 4.2g of 2, 3-epoxypropyltrimethylammonium chloride and 7.5g of chitosan, dissolving in deionized water, reacting for 8 hours at the temperature of 100 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 5 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvents, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, separating out chitosan quaternary ammonium salt from the solution, repeatedly centrifuging and washing the absolute ethyl alcohol, and carrying out vacuum drying for 9 hours to obtain faint yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 2, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, strongly stirring the mixture for 5 hours at the temperature of 30 ℃, and then repeatedly washing the mixture by using the deionized water until no white precipitate is detected by using a silver nitrate solutionVacuum drying to obtain organic intercalation modified montmorillonite; weighing 6.5g of dihydrodiamine and 1.3g of boric acid, completely dissolving in water, stirring at 70 ℃ until the solvent is completely evaporated, drying, and calcining at 500 ℃ for 5h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 13N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 24 hours at normal temperature, washing the mixture to be neutral by deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material of the embodiment 4 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant performance test is carried out.
Example 5
Weighing 4.2g of 2, 3-epoxypropyltrimethylammonium chloride and 7.5g of chitosan, dissolving in deionized water, reacting at 70 ℃ for 9 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 7 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 10 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 4, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 4 hours at the temperature of 40 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 6.5g of dihydrodiamine and 1.4g of boric acid, completely dissolving in water, stirring at the temperature of 60 ℃ until the solvent is completely evaporated, drying, and calcining at the temperature of 600 ℃ for 3h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 23N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4The proportion of 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L is required, and the sulfuric acid solution is takenLiquid, mixing g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 11 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in the example 5 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant performance test is carried out.
Example 6
Weighing 4.2g of 2, 3-epoxypropyltrimethylammonium chloride and 8.5g of chitosan, dissolving in deionized water, reacting at the temperature of 90 ℃ for 11 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 4.5 by using glacial acetic acid, then distilling under reduced pressure to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly centrifuging and washing by using the absolute ethyl alcohol, and drying in vacuum for 23 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 1.5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 3 hours at a temperature of 50 ℃, then repeatedly washing the chitosan quaternary ammonium salt and the montmorillonite with the deionized water until no white precipitate exists through a silver nitrate solution, detecting whether chloride ions exist, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 5.5g of dihydrodiamine and 1.6g of boric acid, completely dissolving in water, stirring at 90 ℃ until the solvent is completely evaporated, drying, and calcining at 450 ℃ for 2.5h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 33N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4Adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 12 hours at normal temperature, washing the mixture to be neutral by deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material
The composite material prepared in the example 6 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant performance test is carried out.
Example 7
Weighing 5g of 2, 3-epoxypropyltrimethylammonium chloride and 8.2g of chitosan, dissolving in deionized water, reacting at 65 ℃ for 8.5h to obtain a mixed solution, adjusting the pH value of the mixed solution to 5.5 by using glacial acetic acid, then distilling under reduced pressure to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly centrifuging and washing by using the absolute ethyl alcohol, and drying in vacuum for 22h to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 2.5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 4.5 hours at the temperature of 70 ℃, then repeatedly washing the chitosan quaternary ammonium salt and the montmorillonite with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 8.5g of dihydrodiamine and 2.5g of boric acid, completely dissolving in water, stirring at 75 ℃ until the solvent is completely evaporated, drying, and calcining at 650 ℃ for 2h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 43N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 22 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 7 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 8
Weighing 5.6g of 2, 3-epoxypropyltrimethylammonium chloride and 8.7g of chitosan, dissolving in deionized water, reacting at the temperature of 75 ℃ for 9.5 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 6.5 by using glacial acetic acid, then distilling under reduced pressure to remove most of solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly centrifuging and washing by using the absolute ethyl alcohol, and drying in vacuum for 21 hours to obtain faint yellow powderA chitosan quaternary ammonium salt in a form; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 3.5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 2.5 hours at the temperature of 80 ℃, then repeatedly washing the chitosan quaternary ammonium salt and the montmorillonite with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 8.7g of dihydrodiamine and 2.7g of boric acid, completely dissolving in water, stirring at 85 ℃ until the solvent is completely evaporated, drying, and calcining at 400 ℃ for 5.5h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 53N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 21 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in the example 8 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant performance test is carried out.
Example 9
Weighing 5.7g of 2, 3-epoxypropyltrimethylammonium chloride and 8.9g of chitosan, dissolving in deionized water, reacting at 85 ℃ for 10 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 7.5 by using glacial acetic acid, then distilling under reduced pressure to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly centrifuging and washing by using the absolute ethyl alcohol, and drying in vacuum for 20 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 4.5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 5.5 hours at the temperature of 90 ℃, then repeatedly washing the chitosan quaternary ammonium salt and the montmorillonite with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; 6.7g of dihydrodiamine and 3g of boric acid are weighed, completely dissolved in water and stirred at 65 ℃ until the solvent has completely evaporatedDrying, and calcining at 500 deg.C for 5.5h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 63N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 20 hours at normal temperature, washing the mixture to be neutral by deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in the example 9 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant performance test is carried out.
Example 10
Weighing 6g of 2, 3-epoxypropyltrimethylammonium chloride and 9g of chitosan, dissolving in deionized water, reacting for 8 hours at the temperature of 100 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 4 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 15 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 1.5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 6 hours at the temperature of 20 ℃, then repeatedly washing the chitosan quaternary ammonium salt and the montmorillonite with the deionized water until no white precipitate exists through a silver nitrate solution, detecting whether chloride ions exist, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 8.9g of dihydrodiamine and 3.5g of boric acid, completely dissolving in water, stirring at the temperature of 60 ℃ until the solvent is completely evaporated, drying, and calcining at the temperature of 700 ℃ for 2 hours to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 73N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4Adding organic intercalation modified montmorillonite, adding sulfuric acid solution, stirring at room temperature for 14 hr, washing with deionized water to neutral, and dryingDrying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 10 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and the flame retardant material is analyzed by measuring an oxygen index.
Example 11
Weighing 6.5g of 2, 3-epoxypropyltrimethylammonium chloride and 9g of chitosan, dissolving in deionized water, reacting at 70 ℃ for 11.5h to obtain a mixed solution, adjusting the pH value of the mixed solution to 8 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 15h to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 2, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 2 hours at the temperature of 90 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 6.5g of dihydrodiamine and 3g of boric acid, completely dissolving in water, stirring at 80 ℃ until the solvent is completely evaporated, drying, and calcining at 600 ℃ for 4h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 0.53N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 18 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 11 and a matrix material, namely ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 12
Weighing 5.7g of 2, 3-epoxypropyltrimethylammonium chloride and 9.5g of chitosan, dissolving in deionized water at 70%Reacting at the temperature of 8.5 ℃ for 8.5 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 7 by using glacial acetic acid, then distilling under reduced pressure to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly centrifuging and washing by using the absolute ethyl alcohol, and drying in vacuum for 18 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 1, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 3.5 hours at a temperature of 60 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 9.5g of dihydrodiamine and 4g of boric acid, completely dissolving in water, stirring at the temperature of 80 ℃ until the solvent is completely evaporated, drying, and calcining at the temperature of 450 ℃ for 3h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 0.83N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 13 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 12 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 13
Weighing 5.5g of 2, 3-epoxypropyltrimethylammonium chloride and 10g of chitosan, dissolving in deionized water, reacting for 8 hours at the temperature of 100 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 8 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvents to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 18 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite at a mass ratio of 1: 3, adding into deionized water, ultrasonically dispersing, and strongly stirring at 70 deg.C4.5h, repeatedly washing with deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist, and drying in vacuum to obtain the organic intercalation modified montmorillonite; weighing 10g of dihydrodiamine and 6g of boric acid, completely dissolving in water, stirring at 70 ℃ until the solvent is completely evaporated, drying, and calcining at 600 ℃ for 5.5h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 0.33N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 16 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 13 and a matrix material, namely ethylene-vinyl acetate copolymer (EVA), are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 14
Weighing 7g of 2, 3-epoxypropyltrimethylammonium chloride and 10g of chitosan, dissolving in deionized water, reacting at 65 ℃ for 11.5h to obtain a mixed solution, adjusting the pH value of the mixed solution to 4 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 8h to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 5 hours at the temperature of 30 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 9g of dihydrodiamine and 4g of boric acid, completely dissolving in water, stirring at the temperature of 80 ℃ until the solvent is completely evaporated, drying, and calcining at the temperature of 400 ℃ for 6 hours to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 73N4And organic intercalation modified montmorilloniteSoil, then 1g of g-C3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 10 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 14 and a matrix material, namely ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 15
Weighing 7.5g of 2, 3-epoxypropyltrimethylammonium chloride and 10g of chitosan, dissolving in deionized water, reacting for 11 hours at the temperature of 80 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 6 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvents to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 17 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 4, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, strongly stirring the mixture for 1.5 hours at the temperature of 90 ℃, then repeatedly washing the mixture by using the deionized water until no white precipitate exists by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 10g of dihydrodiamine and 7.5g of boric acid, completely dissolving in water, stirring at the temperature of 60 ℃ until the solvent is completely evaporated, drying, and calcining at the temperature of 700 ℃ for 2h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 0.63N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 24 hours at normal temperature, washing the mixture to be neutral by deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 15 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 16
Weighing 7.5g of 2, 3-epoxypropyltrimethylammonium chloride and 10.5g of chitosan, dissolving in deionized water, reacting for 11 hours at the temperature of 70 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 8 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 8 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 4, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 4 hours at the temperature of 60 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 12g of dihydrodiamine and 4g of boric acid, completely dissolving in water, stirring at 60 ℃ until the solvent is completely evaporated, drying, and calcining at 500 ℃ for 3.5h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 0.73N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 20 hours at normal temperature, washing the mixture to be neutral by deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 16 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 17
Weighing 8g of 2, 3-epoxypropyltrimethylammonium chloride and 11g of chitosan, dissolving in deionized water, reacting at 80 ℃ for 9h to obtain a mixed solution, adjusting the pH value of the mixed solution to 7 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of the solvent to obtain a concentrated solution, and adding anhydrous sodium chloride into the concentrated solutionRemoving GTA which does not participate in the reaction by using water ethanol, repeatedly centrifuging and washing by using absolute ethanol, and carrying out vacuum drying for 24 hours to obtain light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 1, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 1h at the temperature of 100 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 12g of dihydrodiamine and 4.5g of boric acid, completely dissolving in water, stirring at 70 ℃ until the solvent is completely evaporated, drying, and calcining at 550 ℃ for 4h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 73N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 24 hours at normal temperature, washing the mixture to be neutral by deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 17 was mixed with a base material ethylene-vinyl acetate copolymer (EVA) at a certain ratio, and a flame retardancy test was performed.
Example 18
Weighing 8.5g of 2, 3-epoxypropyltrimethylammonium chloride and 11.5g of chitosan, dissolving in deionized water, reacting at 60 ℃ for 12 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 4 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 14 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 4, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 4 hours at the temperature of 40 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; 12.5g of dihydrodiamine are weighedAnd 5g boric acid, completely dissolved in water, stirred at 80 ℃ until the solvent is completely evaporated, dried, and then calcined at 650 ℃ for 2.5h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 53N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 19 hours at normal temperature, washing the mixture to be neutral by deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 18 and a matrix material, namely ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 19
Weighing 9g of 2, 3-epoxypropyltrimethylammonium chloride and 12g of chitosan, dissolving in deionized water, reacting at 90 ℃ for 9 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 8 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of the solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 8 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 2, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 6 hours at the temperature of 60 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 13g of dihydrodiamine and 5.5g of boric acid, completely dissolving in water, stirring at the temperature of 60 ℃ until the solvent is completely evaporated, drying, and calcining at the temperature of 400 ℃ for 6 hours to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 33N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And organic intercalation modified montmorilloniteAnd adding sulfuric acid solution into the soil, stirring for 24 hours at normal temperature, washing the soil to be neutral by using deionized water, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 19 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 20
Weighing 9.5g of 2, 3-epoxypropyltrimethylammonium chloride and 33.25g of chitosan, dissolving in deionized water, reacting at 70 ℃ for 10 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 7 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvent to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 8 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 4, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 5 hours at a temperature of 50 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 13.4g of dihydrodiamine and 17.42g of boric acid, completely dissolving in water, stirring at 100 ℃ until the solvent is completely evaporated, drying, and calcining at 700 ℃ for 2h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 53N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 10 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 20 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
Example 21
WeighingDissolving 9.7g of 2, 3-epoxypropyltrimethylammonium chloride and 20.467g of chitosan in deionized water, reacting for 8 hours at the temperature of 100 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 4 by using glacial acetic acid, then carrying out reduced pressure distillation to remove most of solvents to obtain a concentrated solution, adding absolute ethyl alcohol into the concentrated solution, removing GTA which does not participate in the reaction, repeatedly carrying out centrifugal washing by using the absolute ethyl alcohol, and carrying out vacuum drying for 24 hours to obtain a light yellow powdery chitosan quaternary ammonium salt; respectively taking chitosan quaternary ammonium salt and montmorillonite according to a mass ratio of 1: 1, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, carrying out strong stirring for 4 hours at a temperature of 80 ℃, then repeatedly washing with the deionized water until no white precipitate is detected by using a silver nitrate solution, detecting whether chloride ions exist or not, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite; weighing 14g of dihydrodiamine and 10.5g of boric acid, completely dissolving in water, stirring at 100 ℃ until the solvent is completely evaporated, drying, and calcining at 400 ℃ for 6h to obtain g-C3N4(ii) a Respectively taking g-C according to the mass ratio of 1: 0.23N4And organic intercalation modified montmorillonite, and then according to g-C of 1g3N4Taking 30mL of sulfuric acid solution with the molar volume concentration of 5mol/L, mixing the sulfuric acid solution with g-C3N4And adding sulfuric acid solution into the organic intercalated modified montmorillonite, stirring for 10 hours at normal temperature, washing the mixture to be neutral by using deionized water, drying and grinding the mixture to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
The composite material prepared in example 21 and a matrix material ethylene-vinyl acetate copolymer (EVA) are mixed according to a certain proportion to obtain a flame retardant material, and a flame retardant property test is carried out.
The chitosan quaternary ammonium salt (HCCT) organic intercalation Modified Montmorillonite (MMT) and g-C prepared by the above embodiments3N4The compounded material is applied to an ethylene-vinyl acetate copolymer (EVA) matrix material as a flame retardant, and the LOI value of the obtained composite material is shown in Table 1.
TABLE 1 LOI data for EVA and EVA composites
EVA and flame retardant are weighed according to different proportions, mixed on a mixing roll, and then tested for oxygen index, as can be seen from Table 1: adding g-C into EVA3N4MMT, MMT-HTCC (HTCC intercalated montmorillonite), MMT-HTCC @ g-C3N4The oxygen index can be increased by (HTCC intercalated montmorillonite composite graphite phase carbon nitride) and EG (expandable graphite), wherein EVA/MMT-HTCC @ g-C3N4The oxygen index of EG (1/7) (the mass ratio of the flame retardant to the expandable graphite is 1: 7, and the meanings of other ratios in Table 1 are the same) reaches 31.5 percent, and the higher the oxygen index is, the better the flame retardance of the composite material prepared by the preparation method is relatively.
Claims (4)
1. A preparation method of a chitosan quaternary ammonium salt organic intercalated montmorillonite composite material is characterized by comprising the following steps:
1) respectively taking 2, 3-epoxypropyltrimethylammonium chloride and chitosan according to a mass ratio of 1: 0.72-3.5, dissolving in deionized water, reacting at the temperature of 60-100 ℃ for 8-12 hours to obtain a mixed solution, adjusting the pH value of the mixed solution to 4-8 with glacial acetic acid, carrying out reduced pressure distillation to obtain a concentrated solution, removing unreacted 2, 3-epoxypropyltrimethylammonium chloride with absolute ethyl alcohol, repeatedly carrying out centrifugal washing with absolute ethyl alcohol, and carrying out vacuum drying to obtain chitosan quaternary ammonium salt;
2) respectively taking chitosan quaternary ammonium salt and montmorillonite according to the mass ratio of 1: 1-5, adding the chitosan quaternary ammonium salt and the montmorillonite into deionized water, carrying out ultrasonic dispersion, strongly stirring the mixture for 1-6 hours at the temperature of 20-100 ℃, repeatedly washing the mixture by using the deionized water until no white precipitate is detected by using a silver nitrate solution, and carrying out vacuum drying to obtain the organic intercalation modified montmorillonite;
3) respectively taking dicyanodiamine and boric acid according to the mass ratio of 1: 0.2-1.3, completely dissolving in water, stirring until the solvent is completely evaporated, drying and calcining to obtain g-C3N4；
4) Taking g-C according to a mass ratio of 1: 0.2-7 respectively3N4Mixing with organic intercalation modified montmorillonite, adding sulfuric acid solution, stirring at normal temperature for 10-24 h, and deionizingWashing with water to neutrality, drying and grinding to obtain the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material.
2. The preparation method of the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material as claimed in claim 1, wherein in the step 3), the stirring is carried out at the temperature of 60-100 ℃ until the solvent is completely evaporated.
3. The preparation method of the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material as claimed in claim 1, wherein in the step 3), the composite material is calcined at 400-700 ℃ for 2-6 h to obtain g-C3N4。
4. The method for preparing the chitosan quaternary ammonium salt organic intercalated montmorillonite composite material as claimed in claim 1, wherein in the step 4), the molar volume concentration of the sulfuric acid solution is 5mol/L, and the dosage of the sulfuric acid solution is as follows: 1g of g-C3N430mL of the sulfuric acid solution was used.
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