CN105802436B - A kind of nanometer expansion-type transparent fire-retardant coating and preparation method thereof - Google Patents
A kind of nanometer expansion-type transparent fire-retardant coating and preparation method thereof Download PDFInfo
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- CN105802436B CN105802436B CN201610327820.0A CN201610327820A CN105802436B CN 105802436 B CN105802436 B CN 105802436B CN 201610327820 A CN201610327820 A CN 201610327820A CN 105802436 B CN105802436 B CN 105802436B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/32—Modified amine-aldehyde condensates
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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
- C08K3/346—Clay
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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
- C08K3/36—Silica
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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
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
- C09D5/185—Intumescent paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of nanometer expansion-type transparent fire-retardant coating and preparation method thereof, the coating includes component A and B component；Component A includes Nano filling grafting phosphate ester acid, and B component includes melmac.The beneficial effects of the invention are as follows：Nano silicon and organo montmorillonite are chemically grafted on phosphate ester acid by coating of the present invention so that and Nano filling is uniformly dispersed in the coating, and the problems such as effectively avoid coating transparent caused by physical blending, migration and compatibility;Nano filling, phosphate ester acid and amino resins are incorporated among transparent fire-resisting paint; the foamed char structure of densification can be formed; there is preferable flameproof protection effect to base material; wherein nano silicon and organo montmorillonite have synergistic effect with expanding fire retardant, can significantly improve the flameproof protection effect of foamed char;The raw material sources of nanometer expansion-type transparent fire-retardant coating of the present invention are extensive, cost is cheap, easy to operate.
Description
Technical field
The present invention relates to the fire proofing material field of Chemical Engineering Technology, more particularly to a kind of nanometer expansion-type transparent fire-retardant coating and
Its preparation method.
Background technology
In the scientific and technical fast-developing field such as today, modern architecture, ancient building, structural timber to decorative coveringn
Fire protection requirement more and more higher, traditional fireproof coating and decorative paint can not meet that modern architecture and ancient building are being prevented fires and filled
Demand in terms of decorations.Transparent fire-resisting paint can keep the base material texture, character pattern, quality aesthetic feeling of engineering structure, fire protecting performance
It is excellent, it can be widely applied to the fields such as ancient building, modern architecture, historical relic's protection and high-grade decoration.Expansion-type transparent fire-retardant coating
Fire protecting performance compared with non-expansion type more preferably, be at present both at home and abroad research work emphasis.
On the existing many reports of expansion-type transparent fire-retardant coating.Patent publication No. is CN104046201A patent document
Disclose a kind of flexible phosphate ester acid and methyl ether prepared using polyethylene glycol, polyphosphoric acids, butanediol, pentaerythrite as raw material
Change the Flexible intumescent transparent fire-resisting paint that amino resins compounding forms, pliability, crack resistance and the fire resistance of the coating
Preferably, and can cold curing.Patent publication No. is disclosed one kind for CN102746764A patent document and is grafted with polyethylene glycol
Condensed phosphate be component A and water-compatible amino resin is the transparent facing type fireproofing of two-component prepared by B component blending and stirring
Coating, wherein polyethylene glycol grafting condensed phosphate pass through solution using polyphosphoric acids, pentaerythrite, polyethylene glycol as raw material
Prepared by synthetic method, the transparent fire-resisting paint has preferable fire protecting performance and pliability concurrently.Patent publication No. is CN101503581's
Patent document discloses a kind of radiation curable expansion type transparent anti-flaming nano composite coating and preparation method thereof, the coating with
60%-70% acrylic resin, 30%-40% expansion type flame-retarding resin, 2%-6% light trigger, 0.5%-2% levelling helps
Agent, 0.5%-2% antifoam additives stir under the conditions of 40-60 DEG C, add 1%-10% organically-modified laminated metal afterwards
Compound, ultrasonic disperse prepare transparent flame-retardant coating into matrix resin, and the coating has preferable fire resistance and mechanicalness
Energy.Patent publication No. is that CN104693923A patent document discloses a kind of Nano-meter SiO_22Ultrathin water-based expansion fire-proof steel
Nano silicon that the main component of the preparation method of material, wherein fireproof coating is 10%, 50% APP, 10% it is poly-
Oxygen ethene polyoxypropylene pentaerythrite ether, 5% melamine, 5% titanium dioxide, 10% chlorine partial emulsion and acrylic emulsion.Specially
Sharp Publication No. CN101914333A patent document discloses a kind of water super-thin steel structure fire-proof paint and its preparation side
Method, be using in-situ emulsion polymerization method prepare phyllosilicate nano complex emulsions as film forming binder, add according to a certain percentage
Add carbonifying catalyst, carbon forming agent, foaming agent, filler, auxiliary agent and suitable quantity of water with fire protection flame retarding effect, be fully ground mixed
Conjunction forms, and the coating can form uniform and stable expanded charred layer after by fire, has preferable flameproof effect.Patent publication No. is
CN1346855A patent document discloses a kind of preparation method of high-temp.-resisting fire-proof composite nano paint, and the coating is by nano-sized carbon
SiClx, nano silicate clay etc. with the nano-particles such as phosphate, oxide and nanometer aluminium silicate add nanometer it is organic high
Molecular material is formed by physical blending.Patent publication No. is that CN103805056A patent document discloses a kind of nanometer fireproof
Coating and preparation method thereof, the coating is by inorganic nano-filler, film forming agent, coalescents, plasticizer, crosslinking agent and drier group
Into wherein inorganic nano-filler is the modified Nano compound particle for the inorganic nano-particle that surface is covered with silica.Patent is public
The number of opening is that CN103435952B patent document discloses a kind of Phosphate nano composite flame-retardant masterbatch and preparation method thereof, the resistance
It is double by benzenediol to fire masterbatch（Diphenyl phosphoester）Coupling agent modified organic clay is existed by physical blending method with KH550
High-speed stirred 5h is made at 100 DEG C, and phosphate is blended by simple physical with organic clay and prepared in the flame-retardant master batch, and product is saturating
Bright property is poor.Patent publication No. is that CN101092503A patent document discloses a kind of fire-retardant ring of salt of phosphate bi melamine
Epoxy resin nano composite material, the material are total to by organo montmorillonite, salt of phosphate bi melamine and epoxy resin by physics
Mixed to be prepared, organo montmorillonite is present among composite with physical form.Patent publication No. is CN104861497A's
Patent document discloses a kind of phosphate flame retardant and nano imvite blending and modifying PTT polymer blends, the compound by
Triphenyl phosphate ester（TPP）, bisphenol-A-bis-（Diphenyl phosphate）, nano imvite and PTT polymer blends pass through physical blending system
Standby, wherein montmorillonite is present in compound with physical form.The patent document that patent publication No. is CN104194504A is announced
A kind of nano fire-retardant coating and its preparation method and application, the nano fire-retardant coating is by nano silicon, ethene-acetic acid
Vinyl ester copolymers, melamine pyrophosphoric ester and talcum powder etc. are prepared by physical blending, and nano silicon is with thing
Reason form is present among fireproof coating.
Organo montmorillonite and nano silicon are usually white powder, and the organo montmorillonite prepared by physical blending
It is poor with the nano composite material transparency of nano silicon, it is not used to prepare transparent material.In existing report, nanometer two
The application of silica and organo montmorillonite in fireproof coating is concentrated mainly on nontransparent fireproof coating field, and is filled out on nanometer
Expect that the application study of synergistic enhancing transparent fire-resisting paint is also less.In addition, nano silicon and organic illiteracy in existing report
Among de- soil is mainly added to nano fire-retardant coating by physical blending form, and use simple physical blending form addition nanometer
Filler can increase the masking power of fireproof coating, cause transparent fire-resisting paint decorative effect to be deteriorated, can not meet transparent fire-resisting paint
Application demand.
Nano filling chemical graft is prepared the fire prevention of nanometer expansion-type transparent on phosphate ester acid strand and applied by the present invention
Material, while coating transparent is kept, strengthens the fire-retardant and smoke suppressing of transparent fire-resisting paint.
The content of the invention
In order to improve the fire protecting performance of expansion-type transparent fire-retardant coating, the invention provides a kind of nanometer expansion-type transparent to prevent
Fiery coating and preparation method thereof.Nano filling is grafted on phosphate ester acid strand saturating to prepare nanometer intumescent by the present invention
Bright fireproof coating, on the basis of the transparency of coating is ensured, improve the fire-retardant and smoke suppressing of coating.
In order to realize foregoing invention purpose, the invention provides a kind of nanometer expansion-type transparent fire-retardant coating, the coating
Including component A and B components；The component A includes Nano filling grafting phosphate ester acid, and B component includes melmac.
Nano filling is grafted phosphate ester acid in the coating：Melmac mass ratio is 1:1-2.
The melmac is methyl-etherified melmac or butylated melamine resins.
Wherein melmac is also known as melamine resin,
Methyl-etherified melmac is also known as methyl-etherified melamine resin,
Butylated melamine resins are also known as butylated melamine-formaldehyde resin.
The Nano filling grafting phosphate ester acid is that nano organic montmorillonite is grafted phosphate ester acid or nanometer titanium dioxide
Silicon is grafted phosphate ester acid or nano organic montmorillonite and nano silicon is grafted phosphate ester acid jointly;
The component A is the aqueous solution that Nano filling is grafted phosphate ester acid.
The B components are the aqueous solution of melmac.
In order to which goal of the invention is better achieved, the present invention provides the preparation side of a kind of nanometer of expansion-type transparent fire-retardant coating
Method, the preparation method comprise the following steps：
（1）The Nano filling grafting phosphate ester acid is that nano organic montmorillonite is grafted phosphate ester acid or nano-silica
SiClx is grafted phosphate ester acid or nano organic montmorillonite and nano silicon is grafted phosphate ester acid jointly;
Nano filling is grafted the preparation of phosphate ester acid：
A. the preparation of nano organic montmorillonite grafting phosphate ester acid：
By nano imvite Na+- MMT is placed in the deionized water of nano imvite 2-3 mass times and nano imvite is made
Suspension, the cetyl trimethylammonium bromide CTAB of nano imvite 2-3 mass times is then completely dissolved in deionized water
In be prepared into solution one, suspension is heated under water bath with thermostatic control and stirs 0.5h-1h, heating-up temperature be 70 DEG C -90 DEG C, then
Add solution one to be reacted, after reacting 3h-5h, stop heating, after standing 24h, remove the product after upper solution and filter, wash
Wash repeatedly into product without Br-Afterwards（Use AgNO3Examine without light-yellow precipitate）, 72h is dried at 80 DEG C, and use ball mill grinding
Into the mesh powder of 150 mesh -300, nano organic montmorillonite OMMT is made；
Then, nano organic montmorillonite OMMT, pentaerythrite, phosphoric acid and n-butanol are mixed at 120 DEG C -140 DEG C anti-
3h-6h is answered, obtains flaxen nano organic montmorillonite grafting acidic phosphate ester compounds, each component quality wherein in reactant
Percentage is that nano organic montmorillonite accounts for 2%-8%, pentaerythrite accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butanol accounts for 4%-5%,
Each component gross mass percentage is 100%；
B. or nano silicon is grafted the preparation of phosphate ester acid：
90-110g nano silicons drying >=24h at 100-110 DEG C is weighed, is then added in container, to container
Middle addition 500-600ml toluene and 5g-10g KH-550（The 5%-10% of nano silicon dosage）In 110 DEG C of -130 DEG C of heating
1h-3h is stirred, product is cooled down afterwards, filtered, is washed with absolute ethyl alcohol（Washed 3-5 times using absolute ethyl alcohol, each anhydrous second
Alcohol amount is 500ml）, then in 100-120 DEG C of dry 8-12h, obtain being alkylated nano silicon；
Then, alkylation nano silicon, pentaerythrite, phosphoric acid and n-butanol are mixed instead at 120 DEG C -140 DEG C
3h-6h is answered, obtains flaxen nano silicon grafting acidic phosphate ester compounds, wherein reactant each component quality percentage
For alkylation, nano silicon accounts for 2%-8% to number, pentaerythrite accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butanol accounts for 4%-5%,
Each component gross mass percentage is 100%；
C. or nano organic montmorillonite and nano silicon are grafted the preparation of phosphate ester acid jointly：
Alkylation nano silicon prepared by nano organic montmorillonite OMMT and b step prepared by a steps, with season penta
Tetrol, phosphoric acid and n-butanol the hybrid reaction 3h-6h at 120 DEG C -140 DEG C, obtain flaxen nano organic montmorillonite and receive
Rice silica is grafted acid phosphate jointly, and wherein reactant each component mass percent accounts for for alkylation nano silicon
1%-5%, nano organic montmorillonite OMMT account for 2%-6%, pentaerythrite accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butanol accounts for 4%-
5%, each component gross mass percentage is 100%.
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
By step（1）Nano filling prepared by middle a or b or step c is grafted phosphate ester acid respectively as component A, by three
Component A and B component are made into the aqueous solution by cymel respectively as B component；And it is grafted acid phosphate according to Nano filling
Ester:Melmac mass ratio 1:1-2 ratio is uniform by the aqueous solution blending and stirring of component A and B component, that is, is received
Rice expansion-type transparent fire-retardant coating；
Or by step（1）The solution that Nano filling grafting acid phosphide prepared by middle a or b or step c is each configured to is made
For component A, using the solution of melmac as B component, and phosphate ester acid is grafted according to Nano filling:Melamine
Resin quality is than 1:1-2 ratio is uniform by component A and B component blending and stirring, that is, obtains a nanometer expansion-type transparent fire-retardant coating.
By step（1）Nano filling prepared by middle a or b or step c is grafted acid phosphate respectively as component A, is configured to
The mass percent of component A in aqueous is 60% during the aqueous solution.
Using melmac as B component, wherein B component is in aqueous when melmac is made into the aqueous solution
Mass percent is 60%.
The melmac includes methyl-etherified melmac, butylated melamine resins.
Nano organic montmorillonite is grafted phosphate ester acid and the infrared spectrum of phosphate ester acid is shown in Figure 1, wherein receiving
Rice organo montmorillonite is grafted phosphate ester acid in 800-1400cm-1Between the obvious of absworption peak broaden and strengthen, show that nanometer has
Machine montmorillonite has been grafted on phosphate ester acid strand.
As shown in Figure 2, wherein nano silicon is grafted the infrared spectrum ginseng of nano silicon grafting phosphate ester acid
Phosphate ester acid is in 800-1400cm-1Between absworption peak substantially broaden and strengthen, 1100cm-1Nearby there is the anti-of Si-O-Si
Symmetrical stretching vibration peak, this shows Nano-meter SiO_22It has been grafted on phosphate ester acid strand.
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
（1）Nano silicon and organo montmorillonite are chemically grafted to acid by nanometer expansion-type transparent fire-retardant coating of the present invention
On formula phosphate so that Nano filling is uniformly dispersed in the coating, and effectively avoids coating transparent caused by physical blending, moves
The problems such as shifting property and compatibility.
（2）Nano filling, phosphate ester acid and amino resins are incorporated into by nanometer expansion-type transparent fire-retardant coating of the present invention
Among transparent fire-resisting paint, the foamed char structure of densification can be formed, has preferable flameproof protection effect to base material, wherein receiving
Rice silica and organo montmorillonite have synergistic effect with expanding fire retardant, can significantly improve the flameproof protection effect of foamed char
Fruit.
（3）The raw material sources of nanometer expansion-type transparent fire-retardant coating of the present invention are extensive, cost is cheap, easy to operate.
Brief description of the drawings
Fig. 1 is the infrared spectrum that nano organic montmorillonite is grafted phosphate ester acid and non-grafted phosphate ester acid.
Fig. 2 is the infrared spectrum that nano silicon is grafted phosphate ester acid and non-grafted phosphate ester acid.
Embodiment
Following examples are the further explanations to the present invention, and specific details are as follows：
Na+- MMT montmorillonites, Zhejiang Feng Hong clays Chemical Co., Ltd., CAS No. 1318-93-0
Cetyl trimethylammonium bromide CTAB, Shanghai Audemars Pigeut chemical reagents corporation, AR CAS No.57-09-0
AgNO3, silver nitrate, Xiamen seamark Science and Technology Ltd., CAS No. 7761-88-8
Pentaerythrite, purity >=98%, Shanghai is by force along chemical reagent Co., Ltd, CAS No.115-77-5
Phosphoric acid, content >=85%, Hunan Hui Hong reagents Co., Ltd, CAS No.7664-38-2
N-butanol, Chemical Reagent Co., Ltd., Sinopharm Group, AR CAS No.71-36-3
Methyl-etherified melmac Xinhua Resin Factory, Shanghai, model 5386-60
Nano-meter SiO_22, purity 99.5%, 15 ± 5nm of particle diameter, Chengdu Gracia chemical technology Co., Ltd, CAS
No.7631-86-9
KH-550, silane coupler, Jinan multidimensional bridge Co., Ltd, CAS No.919-30-2
Absolute ethyl alcohol, Chemical Reagent Co., Ltd., Sinopharm Group, CAS No.64-17-5
Butylated melamine resins Xinhua Resin Factory, Shanghai, model 582-2
Embodiment 1：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）Nano organic montmorillonite is grafted the preparation of phosphate ester acid
By 100g nano imvites Na among 1L three-necked flask+- MMT, which is placed in 200g deionized water to be made to cover, to be taken off
The suspension of soil, then it is that 200g cetyl trimethylammonium bromide CTAB is completely dissolved in again by the mass of nano imvite 2
Solution one is prepared into ionized water, suspension is heated under 90 DEG C of waters bath with thermostatic control and stirs 0.5h, solution one is then added and enters
Row reaction, after reacting 3h, stopping heating, after standing 24h, remove the product after upper solution and filter, wash repeatedly into product
Without Br-Afterwards（Examined with AgNO3 without light-yellow precipitate）, 72h is dried at 80 DEG C, and with ball mill grinding into 150 mesh powders,
Nano organic montmorillonite OMMT is made；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, the organic illiteracy of nanometer is taken off
Native OMMT, pentaerythrite, phosphoric acid and n-butanol the hybrid reaction 6h at 120 DEG C, obtain flaxen nano organic montmorillonite and connect
Branch acidic phosphate ester compounds, wherein each component mass percent account for 2%, pentaerythrite for nano organic montmorillonite and account for 26%, phosphorus
Acid accounts for 67%, n-butanol and accounts for 5%, and each component gross mass percentage is 100%；
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, phosphate ester acid and the methyl-etherified melamine of B component are grafted by component A nano organic montmorillonite
Resin is according to mass ratio 1:2 blendings form, and wherein component A is made into the organo montmorillonite grafting acid phosphate of mass percent 60%
Aqueous solution of ester, B component are made into the aqueous solution for the methyl-etherified melmac that mass percent is 60%, two kinds of aqueous solution are pressed
According to 1：2 blending and stirrings are uniform.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.92g, char volume 2.95cm3, foamed char be highly
13.50mm, flame propagation ratio 13.56, smoke density grade 6.01%.
Embodiment 2：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）Nano organic montmorillonite is grafted the preparation of phosphate ester acid
By 100g nano imvites Na among 1L three-necked flask+- MMT, which is placed in 300g deionized water to be made to cover, to be taken off
The suspension of soil, then it is that 300g cetyl trimethylammonium bromide CTAB is completely dissolved in deionization again by the mass of montmorillonite 3
Solution one is prepared into water, suspension is heated under 70 DEG C of waters bath with thermostatic control and stirs 1h, solution one is then added and is reacted,
After reacting 5h, stop heating, after standing 24h, remove the product after upper solution and filter, wash repeatedly into product without Br-Afterwards
（Examined with AgNO3 without light-yellow precipitate）, 72h is dried at 80 DEG C, and be made and received into 300 mesh powders with ball mill grinding
Rice organo montmorillonite OMMT；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, the organic illiteracy of nanometer is taken off
Native OMMT, pentaerythrite, phosphoric acid and n-butanol the hybrid reaction 3h at 140 DEG C, obtain flaxen nano organic montmorillonite and connect
Branch acidic phosphate ester compounds, wherein each component mass percent account for 8%, pentaerythrite for nano organic montmorillonite and account for 24%, phosphorus
Acid accounts for 63%, n-butanol and accounts for 5%, and each component gross mass percentage is 100%；
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, phosphate ester acid and the methyl-etherified melamine of B component are grafted by component A nano organic montmorillonite
Resin is according to mass ratio 1:1 blending forms, and wherein component A is made into the organo montmorillonite grafting acid phosphate of mass percent 60%
Aqueous solution of ester, B component are made into the aqueous solution for the methyl-etherified melmac that mass percent is 60%；Two kinds of aqueous solution are pressed
According to 1：2 blending and stirrings are uniform.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.31g, char volume 1.30cm3, foamed char be highly
15.50mm, flame propagation ratio 8.56, smoke density grade 3.92%.
Embodiment 3：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）Nano organic montmorillonite is grafted the preparation of phosphate ester acid
100g nano imvites Na+-MMT is placed in 250g deionized water to be made to cover among 1L three-necked flask and taken off
The suspension of soil, the i.e. 200g cetyl trimethylammonium bromides CTAB of the mass times of montmorillonite 2 is then completely dissolved in deionization
Solution one is prepared into water, suspension is heated under 80 DEG C of waters bath with thermostatic control and stirs 1h, solution one is then added and is reacted,
After reacting 4h, stop heating, after standing 24h, remove the product after upper solution and filter, wash repeatedly into product without Br-Afterwards
（Examined with AgNO3 without light-yellow precipitate）, 72h is dried at 80 DEG C, and be made and received into 200 mesh powders with ball mill grinding
Rice organo montmorillonite OMMT；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, the organic illiteracy of nanometer is taken off
Native OMMT, pentaerythrite, phosphoric acid and n-butanol the hybrid reaction 4h at 130 DEG C, obtain flaxen nano organic montmorillonite and connect
Branch acidic phosphate ester compounds, wherein each component mass percent account for 5%, pentaerythrite for nano organic montmorillonite and account for 25%, phosphorus
Acid accounts for 66%, n-butanol and accounts for 4%, and each component gross mass percentage is 100%；
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, phosphate ester acid and the butylated melamines of B component are grafted by component A nano organic montmorillonite
Resin is according to mass ratio 1:1.5 blendings form, and wherein component A is made into the organo montmorillonite grafting acid phosphorus of mass percent 60%
The acid esters aqueous solution, B component is made into the aqueous solution for the butylated melamine resins that mass percent is 60%, by two kinds of aqueous solution
According to 1：1.5 blending and stirrings are uniform.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.52g, char volume 1.71cm3, foamed char be highly
14.67mm, flame propagation ratio 10.56, smoke density grade 4.25%.
Embodiment 4：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）Nano silicon is grafted the preparation of phosphate ester acid
Weigh 90g nano silicons and 24h is dried at 100 DEG C, be then added to thermometer, agitator and Fen Shui
In the 1000mL three-necked flask containers of device, 500ml toluene and 5g KH-550 are added into container in 110 DEG C of heating stirring 3h,
Product is cooled down afterwards, filtered, is washed with absolute ethyl alcohol（Washed 3 times using absolute ethyl alcohol, each absolute ethyl alcohol amount is
500ml）, then in 100 DEG C of dry 12h, obtain being alkylated nano silicon；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, will be alkylated nanometer two
Silica, pentaerythrite, phosphoric acid and n-butanol the hybrid reaction 6h at 120 DEG C, obtain flaxen nano silicon grafting
Acidic phosphate ester compounds, wherein reactant each component mass percent account for 2%, pentaerythrite for alkylation nano silicon
Account for 26%, phosphoric acid and account for 67%, n-butanol and account for 5%, each component gross mass percentage is 100%；
Again by nano silicon grafting phosphate ester acid be dissolved in be made into distilled water mass percent be 60% it is water-soluble
Liquid, as component A.
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, by component A and B component according to mass ratio 1:2 blendings form, and wherein component A is mass percent
60% nano silicon grafting acid phosphate aqueous solution of ester, B component is the methyl-etherified melamine that mass percent is 60%
The aqueous solution of resin.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.85g, char volume 2.10cm3, foamed char be highly
13.00mm, flame propagation ratio 12.79, smoke density grade 4.54%.
Embodiment 5：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）Nano silicon is grafted the preparation of phosphate ester acid
Weigh 110g nano silicons and 24h is dried at 110 DEG C, be then added to thermometer, agitator and divide
In the 1000mL three-necked flask containers of water installations, 600ml toluene and 10g KH-550 are added into container in 130 DEG C of heating stirrings
1h, product is cooled down afterwards, filtered, is washed with absolute ethyl alcohol（Washed 5 times using absolute ethyl alcohol, each absolute ethyl alcohol amount is
500ml）, then in 120 DEG C of dry 8h, obtain being alkylated nano silicon；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, will be alkylated nanometer two
Silica, pentaerythrite, phosphoric acid and n-butanol the hybrid reaction 3h at 140 DEG C, obtain flaxen nano silicon grafting
Acidic phosphate ester compounds, wherein reactant each component mass percent account for 8%, pentaerythrite for alkylation nano silicon
Account for 24%, phosphoric acid and account for 63%, n-butanol and account for 5%, each component gross mass percentage is 100%；
Again by nano silicon grafting phosphate ester acid be dissolved in be made into distilled water mass percent be 60% it is water-soluble
Liquid, as component A.
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, by component A and B component according to mass ratio 1:1 blending forms, and wherein component A is mass percent
60% nano silicon grafting acid phosphate aqueous solution of ester, B component is the methyl-etherified melamine that mass percent is 60%
The aqueous solution of resin.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.35g, char volume 1.45cm3, foamed char be highly
14.50mm, flame propagation ratio 9.39, smoke density grade 3.95%.
Embodiment 6：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）Nano silicon is grafted the preparation of phosphate ester acid
Weigh 100g nano silicons and 24h is dried at 105 DEG C, be then added to thermometer, agitator and divide
In the 1000mL three-necked flask containers of water installations, 550ml toluene and 6g KH-550 are added into container in 110 DEG C of heating stirrings
2h, product is cooled down afterwards, filtered, is washed with absolute ethyl alcohol（Washed 4 times using absolute ethyl alcohol, each absolute ethyl alcohol amount is
500ml）, then in 110 DEG C of dry 10h, obtain being alkylated nano silicon；
Then, equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, will be alkylated nanometer two
Silica, pentaerythrite, phosphoric acid and n-butanol the hybrid reaction 4h at 130 DEG C, obtain flaxen nano silicon grafting
Acidic phosphate ester compounds, wherein reactant each component mass percent account for 5%, pentaerythrite for alkylation nano silicon
Account for 25%, phosphoric acid and account for 66%, n-butanol and account for 4%, each component gross mass percentage is 100%；
Again by nano silicon grafting phosphate ester acid be dissolved in be made into distilled water mass percent be 60% it is water-soluble
Liquid, as component A.
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, component A：B component mass ratio 1:1.5, wherein component A is to be grafted acid for nano silicon
Phosphate, B component are butylated melamine resins, by component A and B component be each configured to mass fraction be 60% it is water-soluble
Liquid, by two kinds of aqueous solution according to mass ratio 1:1.5 it is mixed evenly.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.57g, char volume 1.80cm3, foamed char be highly
14.00mm, flame propagation ratio 10.39, smoke density grade 4.24%.
Embodiment 7：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）The preparation of nano silicon and organo montmorillonite grafting phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, by embodiment 1 and embodiment 4
The nano organic montmorillonite and alkylation nano silicon of middle preparation exist as raw material with pentaerythrite, phosphoric acid and n-butanol
Hybrid reaction 6h at 120 DEG C, obtain flaxen nano organic montmorillonite and nano silicon and be grafted phosphate ester acid jointly
Nano organic montmorillonite accounts for 2%, alkylation nano silicon and accounts for 5%, pentaerythrite and account for 24%, phosphorus in mixture, wherein reactant
Acid accounts for 65%, n-butanol and accounts for 4%.And then nano silicon grafting acid phosphate is dissolved in distilled water and is made into quality percentage
Number is 60% aqueous solution, as component A.
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, phosphate ester acid is grafted by the nano organic montmorillonite and nano silicon of component A jointly
The aqueous solution of the aqueous solution and the methyl-etherified melmac of B component is according to mass ratio 1:2 blendings form, and wherein component A is matter
The aqueous solution of percentage 60% is measured, B component is the aqueous solution for the methyl-etherified melmac that mass percent is 60%.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.26g, char volume 1.35cm3, foamed char be highly
15.00mm, flame propagation ratio 8.59, smoke density grade 3.66%.
Embodiment 8：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）The preparation of nano silicon and organo montmorillonite grafting phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, by embodiment 2 and embodiment 5
The nano organic montmorillonite and alkylation nano silicon of middle preparation exist as raw material with pentaerythrite, phosphoric acid and n-butanol
Hybrid reaction 3h at 140 DEG C, obtain flaxen nano organic montmorillonite and nano silicon and be grafted phosphate ester acid jointly
Nano organic montmorillonite accounts for 6%, alkylation nano silicon and accounts for 1%, pentaerythrite and account for 26%, phosphorus in mixture, wherein reactant
Acid accounts for 63%, n-butanol and accounts for 4%.And then nano silicon grafting acid phosphate is dissolved in distilled water and is made into quality percentage
Number is 60% aqueous solution, as component A.
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, phosphate ester acid is grafted by the nano organic montmorillonite and nano silicon of component A jointly
The aqueous solution of mixture and the aqueous solution of the butylated melamine resins of B component are according to mass ratio 1:1 blending forms, wherein A
Component is the aqueous solution of mass percent 60%, and B component is the water-soluble of the butylated melamine resins that mass percent is 60%
Liquid.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.15g, char volume 1.15cm3, foamed char be highly
15.80mm, flame propagation ratio 7.85, smoke density grade 3.45%.
Embodiment 9：
In the present embodiment, the preparation method of nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）The preparation of nano silicon and organo montmorillonite grafting phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, by embodiment 3 and embodiment 6
The nano organic montmorillonite and alkylation nano silicon of middle preparation exist as raw material with pentaerythrite, phosphoric acid and n-butanol
Hybrid reaction 4h at 130 DEG C, obtain flaxen nano organic montmorillonite and nano silicon and be grafted phosphate ester acid jointly
Nano organic montmorillonite accounts for 2%, alkylation nano silicon and accounts for 2%, pentaerythrite and account for 24%, phosphorus in mixture, wherein reactant
Acid accounts for 67%, n-butanol and accounts for 5%.And then nano silicon grafting acid phosphate is dissolved in distilled water and is made into quality percentage
Number is 60% aqueous solution, as component A.
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
In the present embodiment, the nano organic montmorillonite and nano silicon of component A are grafted the mixed of phosphate ester acid jointly
The methyl-etherified melmac mass ratio 1 of compound and B component:1.5, wherein component A is configured to the water of mass percent 60%
Solution, B component be configured to mass percent be 60% methyl-etherified melmac the aqueous solution, by two kinds of aqueous solution according to
Mass ratio 1:1.5 blending and stirrings are uniform.
（3）Nanometer expansion-type transparent fire-retardant coating performance characterization
Using GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of nanometer expansion-type transparent fire-retardant coating to being prepared in the present embodiment enters
Row measure：Mass loss of the coating in cell method is 2.45g, char volume 1.80cm3, foamed char be highly
14.95mm, flame propagation ratio 10.15, smoke density grade 3.85%.
Comparative example 1
In the present embodiment, by the methyl-etherified melmac in the phosphate ester acid and B component in component A according to quality
Than 1:1.5 blendings form, and wherein component A is the acid phosphate aqueous solution of ester of mass percent 60%, and B component is mass percent
For the aqueous solution of 60% methyl-etherified melmac.
（1）The preparation of phosphate ester acid
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, by phosphoric acid, pentaerythrite, just
Butanol reacts 4h at 130 DEG C, obtains flaxen phosphate ester acid product liquid, and wherein pentaerythrite accounts for 26.3%, phosphoric acid and accounted for
68.4%th, n-butanol accounts for 5.3%.Afterwards, phosphate ester acid is dissolved in the aqueous solution for preparing that mass percent is 60% in distilled water,
As component A.
（2）The preparation of expansion-type transparent fire-retardant coating
By component A and B component with mass ratio 1:1.5 blendings uniformly prepare expansion-type transparent fire-retardant coating, and wherein B component is
Mass percent is the aqueous solution of 60% methyl ether melmac.
（3）Expansion-type transparent fire-retardant coating performance characterization
According to GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of expansion-type transparent fire-retardant coating to being prepared in the present embodiment is surveyed
It is fixed：In cell method mass loss be 4.07g, char volume 5.84cm3, layer of charcoal be highly 2.50mm, flame propagation ratio is
23.31, smoke density grade 17.97%.
In conjunction with the embodiments and comparative example 1 is it can be found that between nano silicon and organo montmorillonite and phosphate ester acid
There is preferable cooperative flame retardant effect, the fire-retardant and smoke suppressing of transparent fire-resisting paint can be significantly improved.
Comparative example 2
In the present embodiment, by A, B component according to mass ratio 1:1.5 blending form, wherein component A by phosphate ester acid with not
Modified montmorillonite is formed by physical blending, and B component is methyl-etherified melmac.
（1）Montmorillonite and the preparation of acid phosphate ester blend
Equipped with agitator, thermometer, reflux condensing tube, water knockout drum three-necked flask in, by pentaerythrite, phosphoric acid and just
Butanol hybrid reaction 4h at 130 DEG C, obtains flaxen acidic phosphate ester compounds；Afterwards, unmodified montmorillonite is added
Physical blending is carried out at room temperature, obtains the phosphate ester acid of milky montmorillonoid-containing, and wherein montmorillonite accounts for 5%, pentaerythrite
Account for 25%, phosphoric acid and account for 65%, n-butanol and account for 5%.And then the phosphate ester acid of montmorillonoid-containing is dissolved in distilled water and is made into quality
Percentage is 60% aqueous solution, as component A.Because montmorillonite is distributed in phosphate ester acid with physical form, product is in breast
White.
（2）The preparation of expansion-type transparent fire-retardant coating
By component A and B component with mass ratio 1:1.5 blendings uniformly prepare expansion-type transparent fire-retardant coating, and wherein B component is
Mass percent is the aqueous solution of 60% methyl ether melmac.The intumescent of the montmorillonoid-containing prepared with physical blending is saturating
The transparency decline of bright fireproof coating, it is impossible to apply.
（3）Expansion-type transparent fire-retardant coating performance characterization
According to GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of expansion-type transparent fire-retardant coating to being prepared in the present embodiment is surveyed
It is fixed：In cell method mass loss be 3.98g, char volume 3.96cm3, layer of charcoal be highly 8.33mm, flame propagation ratio is
20.35, smoke density grade 15.35%.
There is synergistic fire retardation it can be seen from comparative example 1 and comparative example 2 between montmorillonite and phosphate ester acid, can
To improve the fire-retardant and smoke suppressing of transparent fire-resisting paint, but cooperative flame retardant efficiency and the transparency connect significantly lower than organo montmorillonite
Transparent fire-resisting paint prepared by branch phosphate ester acid, and the product transparency is also decreased obviously, it is impossible to apply.
Comparative example 3
In the present embodiment, by A, B component according to mass ratio 1:1.5 blending form, wherein component A by phosphate ester acid with receiving
Rice silica is formed by physical blending, and B component is methyl-etherified melmac.
（1）The preparation of nano silicon and acid phosphate ester blend
Equipped with magnetic stir bar, thermometer, reflux condensing tube, water knockout drum three-necked flask in, by pentaerythrite, phosphoric acid
With n-butanol at 130 DEG C hybrid reaction 4h, obtain flaxen acidic phosphate ester compounds；Afterwards, unmodified receive is added
Rice silica carries out physical blending at room temperature, the phosphate ester acid of milky nano-silica-containing is obtained, wherein receiving
Rice silica, which accounts for 5%, pentaerythrite and accounts for 25%, phosphoric acid and account for 65%, n-butanol, accounts for 5%.And then the acid by nano-silica-containing
Formula phosphate is dissolved in the aqueous solution for being made into that mass percent is 60% in distilled water, as component A.Due to nano silicon with
Physical form is distributed in phosphate ester acid, and product is creamy white.
（2）The preparation of expansion-type transparent fire-retardant coating
By component A and B component with mass ratio 1:1.5 blendings uniformly prepare expansion-type transparent fire-retardant coating, and wherein B component is
Mass percent is the aqueous solution of 60% methyl ether melmac.With the swollen of the nano-silica-containing of physical blending preparation
The transparency decline of swollen type transparent fire-resisting paint, is not suitable for application.
（3）Expansion-type transparent fire-retardant coating performance characterization
According to GB12441-2005《Finishing fire retardant paint》With GB/T 8626-2007《Construction material burn or decompose
Smoke density test method》The fire-retardant and smoke suppressing of expansion-type transparent fire-retardant coating to being prepared in the present embodiment is surveyed
It is fixed：In cell method mass loss be 3.84g, char volume 4.41cm3, layer of charcoal be highly 9 mm, flame propagation ratio is
18.05, smoke density grade 14.45%.
There is association it can be seen from comparative example 1 and comparative example 3 and embodiment between nano silicon and phosphate ester acid
Fire retardation is imitated, the fire-retardant and smoke suppressing of transparent fire-resisting paint can be improved, but cooperative flame retardant efficiency and the transparency are obvious low
In transparent fire-resisting paint prepared by nano silicon grafting phosphate ester acid, and the product transparency is also decreased obviously, it is impossible to
Using.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (3)
1. a kind of nanometer expansion-type transparent fire-retardant coating, it is characterised in that the coating includes component A and B components；The A groups
Part is grafted phosphate ester acid for Nano filling, and B component is melmac；Nano filling is grafted acid phosphate in the coating
Ester：Melmac mass ratio is 1:1-2；The melmac is methyl-etherified melmac or butylation trimerization
Melamine resin；The Nano filling grafting phosphate ester acid is that nano organic montmorillonite is grafted phosphate ester acid；
Or nano silicon grafting phosphate ester acid；
Or nano organic montmorillonite and nano silicon are grafted phosphate ester acid jointly；
The preparation method of the nanometer expansion-type transparent fire-retardant coating comprises the following steps：
（1）The Nano filling grafting phosphate ester acid is that nano organic montmorillonite is grafted phosphate ester acid；Or nanometer titanium dioxide
Silicon is grafted phosphate ester acid；Or nano organic montmorillonite and nano silicon are grafted phosphate ester acid jointly；
A. the preparation of nano organic montmorillonite grafting phosphate ester acid：
By nano imvite Na+- MMT is placed in the deionized water of nano imvite 2-3 mass times the suspension that nano imvite is made
Liquid, then the cetyl trimethylammonium bromide CTAB of nano imvite 2-3 mass times is completely dissolved in deionized water and prepared
Into solution one, suspension is heated under water bath with thermostatic control and stirs 0.5h-1h, heating-up temperature is 70 DEG C -90 DEG C, is then added molten
Liquid one is reacted, and after reacting 3h-5h, stops heating, and after standing 24h, the product after removing upper solution filters, washing is multiple
Into product without Br-Afterwards, 72h is dried at 80 DEG C, and with ball mill grinding into the mesh powder of 150 mesh -300, nanometer, which is made, to be had
Machine montmorillonite OMMT；
Then, by nano organic montmorillonite OMMT, pentaerythrite, phosphoric acid and n-butanol at 120 DEG C -140 DEG C hybrid reaction 3h-
6h, nano organic montmorillonite grafting acidic phosphate ester compounds are obtained, each component mass percent is nanometer wherein in reactant
Organo montmorillonite accounts for 2%-8%, pentaerythrite accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butanol accounts for 4%-5%, each component gross mass
Percentage is 100%；
B. or nano silicon is grafted the preparation of phosphate ester acid：
90-110g nano silicons drying >=24h at 100-110 DEG C is weighed, is then added in container, is added into container
Enter 500-600ml toluene and 5g-10g KH-550 in 110 DEG C of -130 DEG C of heating stirring 1h-3h, product is cooled down afterwards, filtered,
Washed with absolute ethyl alcohol, then in 100-120 DEG C of dry 8-12h, obtain being alkylated nano silicon；
Then, by alkylation nano silicon, pentaerythrite, phosphoric acid and n-butanol the hybrid reaction 3h- at 120 DEG C -140 DEG C
6h, obtains nano silicon grafting acidic phosphate ester compounds, and wherein reactant each component mass percent is received for alkylation
Silica accounts for 2%-8% to rice, pentaerythrite accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butanol accounts for 4%-5%, each component gross mass
Percentage is 100%；
C. or nano organic montmorillonite and nano silicon are grafted the preparation of phosphate ester acid jointly：
Alkylation nano silicon prepared by nano organic montmorillonite OMMT and b step prepared by a steps, with Ji Wusi
Alcohol, phosphoric acid and n-butanol the hybrid reaction 3h-6h at 120 DEG C -140 DEG C, obtain nano organic montmorillonite and nano silicon
Common grafting phosphate ester acid, wherein reactant each component mass percent account for 1%-5%, nanometer for alkylation nano silicon
Organo montmorillonite OMMT accounts for 2%-6%, pentaerythrite accounts for 24%-26%, phosphoric acid accounts for 63%-67%, n-butanol accounts for 4%-5%, and each component is total
Mass percent is 100%；
（2）The preparation of nanometer expansion-type transparent fire-retardant coating
By step（1）Nano filling prepared by middle a or b or step c is grafted phosphate ester acid respectively as component A, by melamine
Component A and B component are made into the aqueous solution by polyimide resin respectively as B component；And it is grafted phosphate ester acid according to Nano filling:Three
Cymel mass ratio 1:1-2 ratio is uniform by the aqueous solution blending and stirring of component A and B component, that is, obtains nanometer expansion
Type transparent fire-resisting paint.
2. according to claim 1 nanometer of expansion-type transparent fire-retardant coating, it is characterised in that by step（1）Prepared by a receives
Rice organo montmorillonite grafting phosphate ester acid or step（1）Nano silicon grafting phosphate ester acid or step prepared by b
（1）Nano organic montmorillonite and nano silicon prepared by c is grafted component A when phosphate ester acid is configured to the aqueous solution and existed jointly
Mass percent in the aqueous solution is 60%.
3. according to claim 1 nanometer of expansion-type transparent fire-retardant coating, it is characterised in that using melmac as
B component, when melmac is made into the aqueous solution, wherein the mass percent of B component in aqueous is 60%.
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