CN110183773A - The preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material - Google Patents
The preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material Download PDFInfo
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- CN110183773A CN110183773A CN201910592317.1A CN201910592317A CN110183773A CN 110183773 A CN110183773 A CN 110183773A CN 201910592317 A CN201910592317 A CN 201910592317A CN 110183773 A CN110183773 A CN 110183773A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention discloses a kind of preparation methods of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material, and GTA and chitosan are dissolved in deionized water, pH value is adjusted after reaction, vacuum distillation, centrifuge washing, and vacuum drying obtains chitosan quaternary ammonium salt；Ultrasonic disperse, strong mixing, washing to no chloride ion exist in deionized water for chitosan quaternary ammonium salt and montmorillonite, and vacuum drying obtains orgnic-intercalation modification montmorillonite；Dicyanodiamine and boric acid are dissolved in water, and stirring to solvent is evaporated, and drying calcining obtains g-C3N4；Mix g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, stirring is washed to neutrality, and drying and grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.The preparation method is by the montmorillonite of chitosan quaternary ammonium salt organic intercalation and g-C3N4It is compound, after montmorillonite orgnic-intercalation modification with g-C3N4Compound, for oxygen index (OI) up to 31.5%, flame retardant property is preferable, improves the flame retardant effect of polymer.
Description
Technical field
The invention belongs to fire proofings and polymeric material field, are related to a kind of chitosan quaternary ammonium salt organic intercalation montmorillonite
The preparation method of composite material；The invention further relates to a kind of applications of composite material.
Background technique
Natural polymer all has various active functional group, using the modification of some physics or chemical method, Ke Yifu
Their more excellent performances are given, its application field is further expanded.Natural polymer such as chitosan, starch etc., by
To the close attention of numerous researchers.Chitosan is a kind of positively charged natural macromolecule amylose, in nature content ten
Divide and enrich, is used widely in fields such as food chemistry, biotechnology, agricultural, environmental protection.
It is also easy to produce molten drop when traditional polymer combustion, and is accompanied by the release of black smoke and toxic gas, in application field
It is inside restricted, the anti-flammability for improving material is always that many scientific research personnel are of interest.Montmorillonite is a kind of day of silicate
Right mineral, structural formula are (Al, Mg)2〔SiO10〕(OH)2·nH2O.With good dispersion performance, it can be used for nanometer polymer
The additive of high molecular material improves shock resistance, stability, gas barrier property, while improving materiel machining performance, and enhancing is poly-
Close object physical property.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material, systems
It is standby to have compared with high flame retardant, using unrestricted polymer.
It is a further object to provide a kind of applications of composite material made from above-mentioned preparation method.
To achieve the above object, the technical scheme adopted by the invention is that: a kind of chitosan quaternary ammonium salt organic intercalation covers de-
The preparation method of soil composite material, specifically sequentially includes the following steps:
1) preparation of chitosan quaternary ammonium salt (HTCC)
1 ︰ 0.72~3.5 in mass ratio takes 2,3- epoxypropyltrimethylchloride chloride (GTA) and chitosan (CS) respectively, dissolution
In deionized water, in 60~100 DEG C of at a temperature of 8~12h of reaction, mixed liquor is obtained, the pH value of mixed liquor is adjusted with glacial acetic acid
It is 4~8, is then evaporated under reduced pressure, to remove most solvents, obtain concentrate, dehydrated alcohol is added in concentrate, removing is not joined
With the GTA reacted, washed with dehydrated alcohol repeated centrifugation, vacuum drying 8~for 24 hours, obtain the chitosan quaternary ammonium of pale yellow powder shape
Salt (HTCC)；
2) chitosan quaternary ammonium salt modified montmorillonoid (MMT)
1 ︰ 1~5 in mass ratio takes chitosan quaternary ammonium salt and montmorillonite (MMT) respectively, is added in deionized water, ultrasonic disperse,
Then 1~6h of strong mixing at a temperature of 20~100 DEG C is washed repeatedly to silver nitrate solution with deionized water and is examined without white
Precipitating checks whether that, with the presence of chloride ion, vacuum drying obtains orgnic-intercalation modification montmorillonite (HTCC intercalated montmorillonite)；
3) 1 ︰ 0.2~1.3 in mass ratio, takes dicyanodiamine and boric acid respectively, completely soluble in water, in 60~100 DEG C of temperature
Lower stirring, until solvent evaporating completely, drying, then in 400~700 DEG C of 2~6h of temperature lower calcination, obtain g-C3N4；
4) modified montmorillonoid and g-C3N4It is compound
1 ︰ 0.2~7 in mass ratio, takes g-C respectively3N4With orgnic-intercalation modification montmorillonite, then the g-C by 1g3N4It need to be rubbed with 30mL
The ratio for the sulfuric acid solution that your volumetric concentration is 5mol/L, takes sulfuric acid solution, first mixes g-C3N4It is covered with orgnic-intercalation modification de-
Soil, adds sulfuric acid solution, and stirring 10 under room temperature~for 24 hours, deionized water is washed to neutrality, and dry, grinding obtains chitosan quaternary ammonium
Salt organic intercalation montmorillonite composite material (g-C3N4@HTCC intercalated montmorillonite).
It is in order to g-C that sulfuric acid solution, which is added,3N4Delamination is carried out, it can be more preferable compound.
Another technical solution of the present invention is: chitosan quaternary ammonium salt made from a kind of above-mentioned preparation method is organic
Intercalated montmorillonite composite material and ethylene-vinyl acetate copolymer (EVA) Material cladding prepare fire proofing.
Preparation method of the present invention is by the montmorillonite of chitosan quaternary ammonium salt organic intercalation and g-C3N4Compound obtained fire retardant covers
After de- soil orgnic-intercalation modification with g-C3N4It is relatively preferable that its compound oxygen index (OI) can reach 31.5% flame retardant property, improves polymer
Flame retardant effect.This method of modifying can be used for industrial production, and lay the foundation for subsequent organic modification montmonrillonite.
Detailed description of the invention
Fig. 1 is the infrared comparison diagram of chitosan and hydroxypropyltrimethylammonium chloride chitosan.
Fig. 2 is organic intercalation montmorillonite and g-C3N4The infrared comparison diagram of@MMT.
Fig. 3 is the plane of disruption scanning electron microscope (SEM) photograph of composite flame-proof material produced by the present invention.
Specific embodiment
The present invention is described in detail below by the drawings and specific embodiments.
Embodiment 1
Weigh 2,3- epoxypropyltrimethylchloride chloride 4g and chitosan 7g, be dissolved in deionized water, 80 DEG C at a temperature of
10h is reacted, mixed liquor is obtained, is 4 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove most solvents,
Concentrate is obtained, dehydrated alcohol is added, the GTA for having neither part nor lot in reaction is removed, chitosan quaternary ammonium salt is precipitated from solution, with anhydrous second
The washing of alcohol repeated centrifugation, is dried in vacuo 8h, obtains the chitosan quaternary ammonium salt (HTCC) of pale yellow powder shape；1 ︰ 1 in mass ratio, respectively
Chitosan quaternary ammonium salt and montmorillonite (MMT) are taken, is added in deionized water, ultrasonic disperse is gone in 20 DEG C of at a temperature of strong mixing 6h
Ionized water repeatedly washs to silver nitrate solution and examines no white precipitate, and vacuum drying obtains orgnic-intercalation modification montmorillonite
(HTCC)；Weigh bis- diammonium hydrogen of 5g and 1g boric acid, it is completely soluble in water, 80 DEG C at a temperature of stir, until solvent steams completely
Hair, drying, then in 550 DEG C of temperature lower calcination 4h, obtains g-C3N4；1 ︰ 0.2 in mass ratio, takes g-C respectively3N4And have the machine transplanting of rice
Layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid
Solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 10h, deionization washing are stirred under room temperature
It washs to neutrality, dry, grinding, obtained chitosan quaternary ammonium salt organises intercalated montmorillonite composite material (g-C3N4@HTCC intercalation covers
De- soil).
By a certain percentage by composite material made from embodiment 1 and basis material ethylene-vinyl acetate copolymer (EVA)
It is kneaded, obtains fire proofing, carry out flame retardant property test.
The structure of MMT and performance evaluation explanation after organic intercalation.
1. infrared analysis
Fig. 1 show the infrared spectrum of CS and HTCC, 1560cm in CS spectrogram-1The absorption peak at place is the in-plane bending of primary amine N-H
Deformation vibration disappears in the HTCC spectrogram obtained after modification, illustrates that the H atom in N-H key is substituted.HTCC is in 3400cm-1
The absorption peak at place obviously broadens, and the absorption peak of hydroxyl becomes strong, illustrates that the amino in chitosan molecule replaces.
Fig. 2 is montmorillonite, orgnic-intercalation modification montmorillonite, g-C3N4And g-C3N4The INFRARED SPECTRUM of@HTCC intercalated montmorillonite
Figure, montmorillonite is in 1380cm-1There is no peak and occur new peak herein after intercalation, illustrates long-chain and the montmorillonite of intercalator
Combination has occurred in surface.g-C3N4In 808 cm-1The bending absorption peak at place is C-N triazine ring, in 1015~1515cm-1In range
Absorption peak, C-N absorption peak is in 1640cm respectively on carbon azacyclo--1The peak at place is the compression absorption peak of C=N,.g-C3N4@
HTCC intercalated montmorillonite is in 3000~3500cm-1Broadband be to be generated by N-H stretching vibration and interaction of hydrogen bond, and C-N
Certain red shift has occurred in the position of characteristic peak.
2. Analysis of Compatibility
Fig. 3 is the surface topography map of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material made from embodiment 1.It can from Fig. 3
To find out, the montmorillonite composite material surface of HTCC organic intercalation forms uniform fine and close carbon-coating, illustrates HTCC organic intercalation
Montmorillonite has good compatibility in basis material, and fire retardant is made to be capable of forming uniform mixed system, reduces agglomeration.
3. fire retardant mechanism is analyzed
There is more reaction hydroxyl in chitosan structure, carbon can be catalyzed into, promote the formation of layer of charcoal, can be used as a kind of novel carbon
Source uses.Montmorillonite is a kind of silicate clay of layer structure, using its layer structure, using chitosan quaternary ammonium salt as intercalation
Agent organise the lamella of intercalation processing peel montmorillonite to montmorillonite, increases cheating engaging layer spacing, increase montmorillonite
Water swellability, polymolecularity, adsorptivity etc., and montmorillonite or good carbon forming agent.In combustion, composite material
g-C3N4Fire retardant ammonia is generated, imflammable gas can be diluted, progress gas phase is fire-retardant, may advantageously facilitate the extinguishing of flame.
The structure and flame retardant property of product are analyzed using infrared spectroscopy (IR) and oxygen index (OI), intercalated montmorillonite
TGA the result shows that, organic intercalation montmorillonite is added in polymer, and the flame retardant property of polymer can be improved.
Embodiment 2
Weigh 2,3- epoxypropyltrimethylchloride chloride 4g and chitosan 8g, be dissolved in deionized water, 60 DEG C at a temperature of
Reaction response 12h, obtains mixed liquor, is 8 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added, and removes the GTA for having neither part nor lot in reaction, chitosan quaternary ammonium salt is precipitated from solution, uses
After the washing of dehydrated alcohol repeated centrifugation, vacuum drying for 24 hours, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 5 in mass ratio,
Chitosan quaternary ammonium salt and montmorillonite are taken respectively, is added in deionized water, ultrasonic disperse, in 100 DEG C of at a temperature of strong mixing 1h, are used
Deionized water washes repeatedly to silver nitrate solution and examines no white precipitate, and vacuum drying obtains orgnic-intercalation modification montmorillonite；
Bis- diammonium hydrogen of 6g and 1.2g boric acid are weighed, it is completely soluble in water, it is stirred in 100 DEG C of temperature, until solvent evaporating completely, dries
It is dry, in 400 DEG C of temperature lower calcination 6h, obtain g-C3N4；1 ︰ 7 in mass ratio, takes g-C respectively3N4It is covered with orgnic-intercalation modification de-
Soil, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid solution, first mixes
Close g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 10h is stirred under room temperature, deionized water is washed to neutrality,
Dry, grinding, obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
2 composite material of embodiment and basis material ethylene-vinyl acetate copolymer (EVA) are kneaded by a certain percentage,
Fire proofing is obtained, flame retardant property test is carried out.
Embodiment 3
Weigh 2,3- epoxypropyltrimethylchloride chloride 4g and chitosan 7g, be dissolved in deionized water, 60 DEG C at a temperature of
12h is reacted, mixed liquor is obtained, is 6 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove most solvents,
Dehydrated alcohol is added into concentrate, removes the GTA for having neither part nor lot in reaction, chitosan quaternary ammonium salt is precipitated from solution, anhydrous second
The washing of alcohol repeated centrifugation, is dried in vacuo 16h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 3 in mass ratio, takes shell respectively
Glycan quaternary ammonium salt and montmorillonite are added in deionized water, then ultrasonic disperse is spent in 60 DEG C of at a temperature of strong mixing 3.5h
Ionized water washes repeatedly to silver nitrate solution and examines no white precipitate, and vacuum drying obtains orgnic-intercalation modification montmorillonite；Claim
Take bis- diammonium hydrogen of 6g and 2g boric acid, it is completely soluble in water, 80 DEG C at a temperature of stir, until solvent evaporating completely, drying, so
Afterwards in 700 DEG C of temperature lower calcination 2h, g-C is obtained3N4；1 ︰ 3.6 in mass ratio, takes g-C respectively3N4It is covered with orgnic-intercalation modification de-
Soil, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid solution, first mixes
Close g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 17h is stirred under room temperature, deionized water is washed to neutrality,
Dry, grinding, obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
3 composite material of embodiment and basis material ethylene-vinyl acetate copolymer (EVA) are kneaded by a certain percentage,
Fire proofing is obtained, flame retardant property test is carried out.
Embodiment 4
2,3- epoxypropyltrimethylchloride chloride 4.2g and chitosan 7.5g are weighed, is dissolved in deionized water, at 100 DEG C
At a temperature of react 8h, obtain mixed liquor, with glacial acetic acid adjust mixed liquor pH value be 5, be then evaporated under reduced pressure, to remove the overwhelming majority
Dehydrated alcohol is added into concentrate for solvent, removes the GTA for having neither part nor lot in reaction, chitosan quaternary ammonium salt is precipitated from solution, nothing
The washing of water-ethanol repeated centrifugation, is dried in vacuo 9h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 2 in mass ratio, takes respectively
Chitosan quaternary ammonium salt and montmorillonite are added in deionized water, then ultrasonic disperse is spent in 30 DEG C of at a temperature of strong mixing 5h
Ionized water washes repeatedly to silver nitrate solution and examines no white precipitate, and vacuum drying obtains orgnic-intercalation modification montmorillonite；Claim
Take bis- diammonium hydrogen of 6.5g and 1.3g boric acid, it is completely soluble in water, 70 DEG C at a temperature of stir, until solvent evaporating completely, dry
It is dry, then in 500 DEG C of temperature lower calcination 5h, obtain g-C3N4；1 ︰ 1 in mass ratio, takes g-C respectively3N4It is covered with orgnic-intercalation modification
De- soil, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid solution, first
Mix g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, is stirred under room temperature for 24 hours, deionized water is washed into
Property, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
4 composite material of embodiment and basis material ethylene-vinyl acetate copolymer (EVA) are kneaded by a certain percentage,
Fire proofing is obtained, flame retardant property test is carried out.
Embodiment 5
2,3- epoxypropyltrimethylchloride chloride 4.2g and chitosan 7.5g are weighed, is dissolved in deionized water, in 70 DEG C of temperature
Degree is lower to react 9h, obtains mixed liquor, is 7 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, molten to remove the overwhelming majority
Agent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation,
It is dried in vacuo 10h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 4 in mass ratio, takes chitosan quaternary ammonium salt and Meng Tuo respectively
Soil is added in deionized water, then ultrasonic disperse is washed repeatedly with deionized water to use in 40 DEG C of at a temperature of strong mixing 4h
Silver nitrate solution examines no white precipitate, checks whether that it is de- to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
Soil；Weigh two diammonium hydrogens and 1.4g boric acid of 6.5g, it is completely soluble in water, 60 DEG C at a temperature of stir, until solvent is complete
Evaporation, drying, then in 600 DEG C of temperature lower calcination 3h, obtains g-C3N4；1 ︰ 2 in mass ratio, takes g-C respectively3N4And have the machine transplanting of rice
Layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid
Solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 11h, deionization washing are stirred under room temperature
It washs to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By a certain percentage by composite material made from embodiment 5 and basis material ethylene-vinyl acetate copolymer (EVA)
It is kneaded, obtains fire proofing, carry out flame retardant property test.
Embodiment 6
2,3- epoxypropyltrimethylchloride chloride 4.2g and chitosan 8.5g are weighed, is dissolved in deionized water, in 90 DEG C of temperature
Degree is lower to react 11h, obtains mixed liquor, is 4.5 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove big portion absolutely
Divide solvent, obtain concentrate, dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 23h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 1.5 in mass ratio, takes chitosan quaternary ammonium salt respectively
And montmorillonite, it is added in deionized water, ultrasonic disperse, in 50 DEG C of at a temperature of strong mixing 3h, then repeats to wash with deionized water
It washs to silver nitrate solution and examines no white precipitate, check whether that, with the presence of chloride ion, vacuum drying obtains orgnic-intercalation modification
Montmorillonite；Weigh bis- diammonium hydrogen of 5.5g and 1.6g boric acid, it is completely soluble in water, 90 DEG C at a temperature of stir, until solvent is complete
Pervaporation, drying, then in 450 DEG C of temperature lower calcination 2.5h, obtains g-C3N4；1 ︰ 3 in mass ratio, takes g-C respectively3N4And have
Machine transplanting of rice layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes
Sulfuric acid solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 12h, deionization are stirred under room temperature
Water washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material
Composite material made from embodiment 6 and basis material ethylene-vinyl acetate copolymer (EVA) are mixed by a certain percentage
Refining obtains fire proofing, carries out flame retardant property test.
Embodiment 7
2,3- epoxypropyltrimethylchloride chloride 5g and chitosan 8.2g are weighed, is dissolved in deionized water, in 65 DEG C of temperature
Lower reaction 8.5h, obtains mixed liquor, is 5.5 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 22h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 2.5 in mass ratio, takes chitosan quaternary ammonium salt respectively
And montmorillonite, it is added in deionized water, then ultrasonic disperse is repeated in 70 DEG C of at a temperature of strong mixing 4.5h with deionized water
Washing examines no white precipitate to silver nitrate solution, checks whether that, with the presence of chloride ion, vacuum drying obtains organic intercalation and changes
Property montmorillonite；Weigh bis- diammonium hydrogen of 8.5g and 2.5g boric acid, it is completely soluble in water, 75 DEG C at a temperature of stir, until solvent
Evaporating completely, drying, then in 650 DEG C of temperature lower calcination 2h, obtains g-C3N4；1 ︰ 4 in mass ratio, takes g-C respectively3N4And have
Machine transplanting of rice layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes
Sulfuric acid solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 22h, deionization are stirred under room temperature
Water washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By a certain percentage by composite material made from embodiment 7 and basis material ethylene-vinyl acetate copolymer (EVA)
It is kneaded, obtains fire proofing, carry out flame retardant property test.
Embodiment 8
2,3- epoxypropyltrimethylchloride chloride 5.6g and chitosan 8.7g are weighed, is dissolved in deionized water, in 75 DEG C of temperature
Degree is lower to react 9.5h, obtains mixed liquor, is 6.5 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove big portion absolutely
Divide solvent, obtain concentrate, dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 21h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 3.5 in mass ratio, takes chitosan quaternary ammonium salt respectively
And montmorillonite, it is added in deionized water, then ultrasonic disperse is repeated in 80 DEG C of at a temperature of strong mixing 2.5h with deionized water
Washing examines no white precipitate to silver nitrate solution, checks whether that, with the presence of chloride ion, vacuum drying obtains organic intercalation and changes
Property montmorillonite；Weigh bis- diammonium hydrogen of 8.7g and 2.7g boric acid, it is completely soluble in water, 85 DEG C at a temperature of stir, until solvent
Evaporating completely, drying, then in 400 DEG C of temperature lower calcination 5.5h, obtains g-C3N4；1 ︰ 5 in mass ratio, takes g-C respectively3N4With
Orgnic-intercalation modification montmorillonite, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration,
Sulfuric acid solution is taken, g-C is first mixed3N4With orgnic-intercalation modification montmorillonite, add sulfuric acid solution, stir 21h under room temperature, go from
Sub- water washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By a certain percentage by composite material made from embodiment 8 and basis material ethylene-vinyl acetate copolymer (EVA)
It is kneaded, obtains fire proofing, carry out flame retardant property test.
Embodiment 9
2,3- epoxypropyltrimethylchloride chloride 5.7g and chitosan 8.9g are weighed, is dissolved in deionized water, in 85 DEG C of temperature
Degree is lower to react 10h, obtains mixed liquor, is 7.5 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove big portion absolutely
Divide solvent, obtain concentrate, dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 20h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 4.5 in mass ratio, takes chitosan quaternary ammonium salt respectively
And montmorillonite, it is added in deionized water, then ultrasonic disperse is repeated in 90 DEG C of at a temperature of strong mixing 5.5h with deionized water
Washing examines no white precipitate to silver nitrate solution, checks whether that, with the presence of chloride ion, vacuum drying obtains organic intercalation and changes
Property montmorillonite；Weigh bis- diammonium hydrogen of 6.7g and 3g boric acid, it is completely soluble in water, 65 DEG C at a temperature of stir, until solvent is complete
Pervaporation, drying, then in 500 DEG C of temperature lower calcination 5.5h, obtains g-C3N4；1 ︰ 6 in mass ratio, takes g-C respectively3N4And have
Machine transplanting of rice layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes
Sulfuric acid solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 20h, deionization are stirred under room temperature
Water washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By a certain percentage by composite material made from embodiment 9 and basis material ethylene-vinyl acetate copolymer (EVA)
It is kneaded, obtains fire proofing, carry out flame retardant property test.
Embodiment 10
2,3- epoxypropyltrimethylchloride chloride 6g and chitosan 9g are weighed, is dissolved in deionized water, in 100 DEG C of temperature
Lower reaction 8h, obtains mixed liquor, is 4 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, molten to remove the overwhelming majority
Agent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation,
It is dried in vacuo 15h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 1.5 in mass ratio, takes chitosan quaternary ammonium salt and illiteracy respectively
De- soil, is added in deionized water, ultrasonic disperse, in 20 DEG C of at a temperature of strong mixing 6h, then with deionized water wash repeatedly to
No white precipitate is examined with silver nitrate solution, checks whether that it is de- to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
Soil；Weigh bis- diammonium hydrogen of 8.9g and 3.5g boric acid, it is completely soluble in water, 60 DEG C at a temperature of stir, until solvent steams completely
Hair, drying, then in 700 DEG C of temperature lower calcination 2h, obtains g-C3N4；1 ︰ 7 in mass ratio, takes g-C respectively3N4And organic intercalation
Modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid molten
Liquid first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 14h, deionized water washing are stirred under room temperature
To neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 10 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, oxygen determination index is analyzed.
Embodiment 11
2,3- epoxypropyltrimethylchloride chloride 6.5g and chitosan 9g are weighed, is dissolved in deionized water, in 70 DEG C of temperature
Lower reaction 11.5h, obtains mixed liquor, is 8 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 15h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 2 in mass ratio, take respectively chitosan quaternary ammonium salt and
Montmorillonite is added in deionized water, then ultrasonic disperse is washed repeatedly in 90 DEG C of at a temperature of strong mixing 2h with deionized water
No white precipitate is examined to silver nitrate solution, checks whether to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
De- soil；Weigh bis- diammonium hydrogen of 6.5g and 3g boric acid, it is completely soluble in water, 80 DEG C at a temperature of stir, until solvent steams completely
Hair, drying, then in 600 DEG C of temperature lower calcination 4h, obtains g-C3N4；1 ︰ 0.5 in mass ratio, takes g-C respectively3N4And have the machine transplanting of rice
Layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid
Solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 18h, deionization washing are stirred under room temperature
It washs to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 11 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 12
2,3- epoxypropyltrimethylchloride chloride 5.7g and chitosan 9.5g are weighed, is dissolved in deionized water, in 70 DEG C of temperature
Degree is lower to react 8.5h, obtains mixed liquor, is 7 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 18h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 1 in mass ratio, take respectively chitosan quaternary ammonium salt and
Montmorillonite is added in deionized water, ultrasonic disperse, in 60 DEG C of at a temperature of strong mixing 3.5h, then repeats to wash with deionized water
It washs to silver nitrate solution and examines no white precipitate, check whether that, with the presence of chloride ion, vacuum drying obtains orgnic-intercalation modification
Montmorillonite；Weigh bis- diammonium hydrogen of 9.5g and 4g boric acid, it is completely soluble in water, 80 DEG C at a temperature of stir, until solvent is complete
Evaporation, drying, then in 450 DEG C of temperature lower calcination 3h, obtains g-C3N4；1 ︰ 0.8 in mass ratio, takes g-C respectively3N4With it is organic
Intercalation modifying montmorillonite, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulphur
Acid solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 13h, deionized water are stirred under room temperature
Washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 12 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 13
2,3- epoxypropyltrimethylchloride chloride 5.5g and chitosan 10g are weighed, is dissolved in deionized water, in 100 DEG C of temperature
Degree is lower to react 8h, obtains mixed liquor, is 8 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, molten to remove the overwhelming majority
Agent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation,
It is dried in vacuo 18h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 3 in mass ratio, takes chitosan quaternary ammonium salt and Meng Tuo respectively
Soil, be added deionized water in, ultrasonic disperse, in 70 DEG C of at a temperature of strong mixing 4.5h, then with deionized water wash repeatedly to
No white precipitate is examined with silver nitrate solution, checks whether that it is de- to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
Soil；Weigh bis- diammonium hydrogen of 10g and 6g boric acid, it is completely soluble in water, 70 DEG C at a temperature of stir, until solvent evaporating completely,
Drying, then in 600 DEG C of temperature lower calcination 5.5h, obtains g-C3N4；1 ︰ 0.3 in mass ratio, takes g-C respectively3N4And organic intercalation
Modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid molten
Liquid first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 16h, deionized water washing are stirred under room temperature
To neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 13 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 14
2,3- epoxypropyltrimethylchloride chloride 7g and chitosan 10g are weighed, is dissolved in deionized water, in 65 DEG C of temperature
Lower reaction 11.5h, obtains mixed liquor, is 4 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 8h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 5 in mass ratio, takes chitosan quaternary ammonium salt and illiteracy respectively
De- soil, is added in deionized water, ultrasonic disperse, in 30 DEG C of at a temperature of strong mixing 5h, then with deionized water wash repeatedly to
No white precipitate is examined with silver nitrate solution, checks whether that it is de- to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
Soil；Weigh bis- diammonium hydrogen of 9g and 4g boric acid, it is completely soluble in water, 80 DEG C at a temperature of stir, until solvent evaporating completely, dry
It is dry, then in 400 DEG C of temperature lower calcination 6h, obtain g-C3N4；1 ︰ 7 in mass ratio, takes g-C respectively3N4It is covered with orgnic-intercalation modification
De- soil, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid solution, first
Mix g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 10h is stirred under room temperature, deionized water is washed into
Property, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 14 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 15
2,3- epoxypropyltrimethylchloride chloride 7.5g and chitosan 10g are weighed, is dissolved in deionized water, in 80 DEG C of temperature
Degree is lower to react 11h, obtains mixed liquor, is 6 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 17h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 4 in mass ratio, take respectively chitosan quaternary ammonium salt and
Montmorillonite is added in deionized water, ultrasonic disperse, in 90 DEG C of at a temperature of strong mixing 1.5h, then repeats to wash with deionized water
It washs to silver nitrate solution and examines no white precipitate, check whether that, with the presence of chloride ion, vacuum drying obtains orgnic-intercalation modification
Montmorillonite；Weigh bis- diammonium hydrogen of 10g and 7.5g boric acid, it is completely soluble in water, 60 DEG C at a temperature of stir, until solvent is complete
Evaporation, drying, then in 700 DEG C of temperature lower calcination 2h, obtains g-C3N4；1 ︰ 0.6 in mass ratio, takes g-C respectively3N4With it is organic
Intercalation modifying montmorillonite, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulphur
Acid solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, is stirred under room temperature for 24 hours, deionized water
Washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 15 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 16
2,3- epoxypropyltrimethylchloride chloride 7.5g and chitosan 10.5g are weighed, is dissolved in deionized water, in 70 DEG C of temperature
Degree is lower to react 11h, obtains mixed liquor, is 8 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 8h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 4 in mass ratio, takes chitosan quaternary ammonium salt and illiteracy respectively
De- soil, is added in deionized water, ultrasonic disperse, in 60 DEG C of at a temperature of strong mixing 4h, then with deionized water wash repeatedly to
No white precipitate is examined with silver nitrate solution, checks whether that it is de- to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
Soil；Weigh bis- diammonium hydrogen of 12g and 4g boric acid, it is completely soluble in water, 60 DEG C at a temperature of stir, until solvent evaporating completely,
Drying, then in 500 DEG C of temperature lower calcination 3.5h, obtains g-C3N4；1 ︰ 0.7 in mass ratio, takes g-C respectively3N4And organic intercalation
Modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid molten
Liquid first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 20h, deionized water washing are stirred under room temperature
To neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 16 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 17
2,3- epoxypropyltrimethylchloride chloride 8g and chitosan 11g are weighed, is dissolved in deionized water, in 80 DEG C of temperature
Lower reaction 9h, obtains mixed liquor, is 7 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, molten to remove the overwhelming majority
Agent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation,
Vacuum drying for 24 hours, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 1 in mass ratio, takes chitosan quaternary ammonium salt and Meng Tuo respectively
Soil is added in deionized water, then ultrasonic disperse is washed repeatedly with deionized water to use in 100 DEG C of at a temperature of strong mixing 1h
Silver nitrate solution examines no white precipitate, checks whether that it is de- to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
Soil；Weigh bis- diammonium hydrogen of 12g and 4.5g boric acid, it is completely soluble in water, 70 DEG C at a temperature of stir, until solvent steams completely
Hair, drying, then in 550 DEG C of temperature lower calcination 4h, obtains g-C3N4；1 ︰ 7 in mass ratio, takes g-C respectively3N4And organic intercalation
Modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid molten
Liquid first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, is stirred under room temperature for 24 hours, deionized water washing
To neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 17 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, carries out flame retardant property test.
Embodiment 18
2,3- epoxypropyltrimethylchloride chloride 8.5g and chitosan 11.5g are weighed, is dissolved in deionized water, in 60 DEG C of temperature
Degree is lower to react 12h, obtains mixed liquor, is 4 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove the overwhelming majority
Solvent obtains concentrate, and dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, is washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 14h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 4 in mass ratio, take respectively chitosan quaternary ammonium salt and
Montmorillonite is added in deionized water, then ultrasonic disperse is washed repeatedly in 40 DEG C of at a temperature of strong mixing 4h with deionized water
No white precipitate is examined to silver nitrate solution, checks whether to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
De- soil；Weigh bis- diammonium hydrogen of 12.5g and 5g boric acid, it is completely soluble in water, 80 DEG C at a temperature of stir, until solvent steams completely
Hair, drying, then in 650 DEG C of temperature lower calcination 2.5h, obtains g-C3N4；1 ︰ 5 in mass ratio, takes g-C respectively3N4And have the machine transplanting of rice
Layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid
Solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 19h, deionization washing are stirred under room temperature
It washs to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 18 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 19
Weigh 2,3- epoxypropyltrimethylchloride chloride 9g and chitosan 12g, be dissolved in deionized water, 90 DEG C at a temperature of
9h is reacted, mixed liquor is obtained, is 8 with the pH value that glacial acetic acid adjusts mixed liquor, is then evaporated under reduced pressure, to remove most solvents,
Concentrate is obtained, dehydrated alcohol is added in concentrate, the GTA for having neither part nor lot in reaction is removed, is washed with dehydrated alcohol repeated centrifugation, vacuum
Dry 8h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 2 in mass ratio, takes chitosan quaternary ammonium salt and montmorillonite respectively, adds
Enter in deionized water, ultrasonic disperse, in 60 DEG C of at a temperature of strong mixing 6h, is then washed repeatedly with deionized water to using silver nitrate
Solution examines no white precipitate, checks whether that, with the presence of chloride ion, vacuum drying obtains orgnic-intercalation modification montmorillonite；It weighs
Bis- diammonium hydrogen of 13g and 5.5g boric acid, it is completely soluble in water, 60 DEG C at a temperature of stir, until solvent evaporating completely, drying,
Then in 400 DEG C of temperature lower calcination 6h, g-C is obtained3N4；1 ︰ 3 in mass ratio, takes g-C respectively3N4It is covered with orgnic-intercalation modification de-
Soil, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulfuric acid solution, first mixes
Close g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, is stirred under room temperature for 24 hours, deionized water is washed to neutrality,
Dry, grinding, obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 19 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 20
2,3- epoxypropyltrimethylchloride chloride 9.5g and chitosan 33.25g are weighed, is dissolved in deionized water, at 70 DEG C
At a temperature of react 10h, obtain mixed liquor, with glacial acetic acid adjust mixed liquor pH value be 7, be then evaporated under reduced pressure, with remove absolutely big portion
Divide solvent, obtain concentrate, dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, washed with dehydrated alcohol repeated centrifugation
It washs, is dried in vacuo 8h, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 4 in mass ratio, takes chitosan quaternary ammonium salt and illiteracy respectively
De- soil, is added in deionized water, ultrasonic disperse, in 50 DEG C of at a temperature of strong mixing 5h, then with deionized water wash repeatedly to
No white precipitate is examined with silver nitrate solution, checks whether that it is de- to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
Soil；Weigh two diammonium hydrogens and 17.42g boric acid of 13.4g, it is completely soluble in water, 100 DEG C at a temperature of stir, until solvent
Evaporating completely, drying, then in 700 DEG C of temperature lower calcination 2h, obtains g-C3N4；1 ︰ 5 in mass ratio, takes g-C respectively3N4And have
Machine transplanting of rice layer modified montmorillonoid, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes
Sulfuric acid solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 10h, deionization are stirred under room temperature
Water washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 20 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
Embodiment 21
2,3- epoxypropyltrimethylchloride chloride 9.7g and chitosan 20.467g are weighed, is dissolved in deionized water, at 100 DEG C
At a temperature of react 8h, obtain mixed liquor, with glacial acetic acid adjust mixed liquor pH value be 4, be then evaporated under reduced pressure, with remove absolutely big portion
Divide solvent, obtain concentrate, dehydrated alcohol is added in concentrate, removes the GTA for having neither part nor lot in reaction, washed with dehydrated alcohol repeated centrifugation
It washs, vacuum drying for 24 hours, obtains the chitosan quaternary ammonium salt of pale yellow powder shape；1 ︰ 1 in mass ratio, take respectively chitosan quaternary ammonium salt and
Montmorillonite is added in deionized water, then ultrasonic disperse is washed repeatedly in 80 DEG C of at a temperature of strong mixing 4h with deionized water
No white precipitate is examined to silver nitrate solution, checks whether to obtain orgnic-intercalation modification illiteracy with the presence of chloride ion, vacuum drying
De- soil；Weigh bis- diammonium hydrogen of 14g and 10.5g boric acid, it is completely soluble in water, 100 DEG C at a temperature of stir, until solvent is complete
Evaporation, drying, then in 400 DEG C of temperature lower calcination 6h, obtains g-C3N4；1 ︰ 0.2 in mass ratio, takes g-C respectively3N4With it is organic
Intercalation modifying montmorillonite, then press the g-C of 1g3N4The ratio for the sulfuric acid solution that need to be 5mol/L with 30mL molal volume concentration, takes sulphur
Acid solution first mixes g-C3N4With orgnic-intercalation modification montmorillonite, sulfuric acid solution is added, 10h, deionized water are stirred under room temperature
Washing to neutrality, dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite composite material.
By composite material made from embodiment 21 and basis material ethylene-vinyl acetate copolymer (EVA) by certain ratio
Example is kneaded, and obtains fire proofing, carries out flame retardant property test.
(HCCT) the orgnic-intercalation modification montmorillonite of chitosan quaternary ammonium salt made from the various embodiments described above (MMT) and g-C3N4It is multiple
It is applied in ethylene-vinyl acetate copolymer (EVA) basis material after matching as fire retardant, the LOI of obtained composite material
Value, as shown in table 1.
The LOI data of 1 EVA of table and EVA composite material
EVA and fire retardant are weighed by different proportion, is kneaded on kneading machine, the test of oxygen index (OI) is then carried out, it can by table 1
Know: g-C being added in EVA3N4, MMT, MMT-HTCC(HTCC intercalated montmorillonite), MMT-HTCC@g-C3N4(HTCC intercalation covers de-
Native composite graphite phase carbon nitride), EG(expansible graphite) can all oxygen index (OI) be made to increase, wherein EVA/MMT-HTCC@g-C3N4/EG
(1/7) oxygen index (OI) of (mass ratio of fire retardant and expansible graphite is 1 ︰ 7, and the meaning of other ratios is identical with this in table 1) reaches
To 31.5%, oxygen index (OI) is higher, illustrates that the anti-flammability of composite material made from preparation method of the present invention is relatively preferable.
Claims (4)
1. a kind of preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material, which is characterized in that specifically by following
Step carries out:
1) 1 ︰ 0.72~3.5 in mass ratio, takes 2,3- epoxypropyltrimethylchloride chloride and chitosan respectively, is dissolved in deionized water
In, in 60~100 DEG C of at a temperature of 8~12h of reaction, mixed liquor is obtained, adjusting mixed liquor pH value with glacial acetic acid is 4~8, and decompression is steamed
It evaporates, obtains concentrate, removed with dehydrated alcohol and have neither part nor lot in 2, the 3- epoxypropyltrimethylchloride chloride of reaction, then with dehydrated alcohol weight
Multiple centrifuge washing, vacuum drying obtain chitosan quaternary ammonium salt；
2) 1 ︰ 1~5 in mass ratio takes chitosan quaternary ammonium salt and montmorillonite respectively, is added in deionized water, ultrasonic disperse, 20
1~6h of strong mixing at a temperature of~100 DEG C, it is heavy without white to being examined with silver nitrate solution then to be washed repeatedly with deionized water
It forms sediment, vacuum drying obtains orgnic-intercalation modification montmorillonite；
3) 1 ︰ 0.2~1.3 in mass ratio, takes dicyanodiamine and boric acid respectively, completely soluble in water, and stirring is steamed completely to solvent
Hair is dried, and calcining obtains g-C3N4；
4) 1 ︰ 0.2~7 in mass ratio, takes g-C respectively3N4With orgnic-intercalation modification montmorillonite, after mixing, sulfuric acid solution is added, often
The lower stirring of temperature 10~for 24 hours, deionized water is washed to neutrality, and dry, grinding obtains chitosan quaternary ammonium salt organic intercalation montmorillonite Composite
Material.
2. the preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material according to claim 1, feature
Be, in the step 3), 60~100 DEG C at a temperature of stirring to solvent evaporating completely.
3. the preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material according to claim 1, feature
It is, in the step 3), in 400~700 DEG C of 2~6h of temperature lower calcination, obtains g-C3N4。
4. the preparation method of chitosan quaternary ammonium salt organic intercalation montmorillonite composite material according to claim 1, feature
It is, in the step 4), the molal volume concentration of sulfuric acid solution is 5mol/L, the dosage of sulfuric acid solution are as follows: the g-C of 1g3N4It needs
With the 30mL sulfuric acid solution.
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| CN114316378A (en) * | 2021-12-09 | 2022-04-12 | 浙江树人学院（浙江树人大学） | Chitosan/epsilon-polylysine intercalated montmorillonite antibacterial packaging film and preparation method and application thereof |
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| CN111320771A (en) * | 2020-04-03 | 2020-06-23 | 蚌埠学院 | Preparation method of chitosan/montmorillonite hybrid microspheres and application of chitosan/montmorillonite hybrid microspheres in sustained release of methacycline hydrochloride |
| CN112316970A (en) * | 2020-11-03 | 2021-02-05 | 陕西科技大学 | Preparation method and application of multi-defect graphite-phase carbon nitride photocatalyst |
| CN113512299A (en) * | 2021-05-19 | 2021-10-19 | 广西荣昇新材料有限公司 | Preparation method of lignin/chitosan/montmorillonite composite material |
| CN113214620A (en) * | 2021-05-25 | 2021-08-06 | 湖北工业大学 | Preparation method and application of epoxy group organic modified montmorillonite |
| CN114316378A (en) * | 2021-12-09 | 2022-04-12 | 浙江树人学院（浙江树人大学） | Chitosan/epsilon-polylysine intercalated montmorillonite antibacterial packaging film and preparation method and application thereof |
| CN114316378B (en) * | 2021-12-09 | 2023-06-02 | 浙江树人学院（浙江树人大学） | Chitosan/epsilon-polylysine intercalated montmorillonite antibacterial packaging film and preparation method and application thereof |
| CN114949243A (en) * | 2022-06-07 | 2022-08-30 | 湖北科技学院 | g-C 3 N 4 Dark-light dual-mode antibacterial material and grafting method thereof |
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