CN106752682A - A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof - Google Patents

A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof Download PDF

Info

Publication number
CN106752682A
CN106752682A CN201611037059.3A CN201611037059A CN106752682A CN 106752682 A CN106752682 A CN 106752682A CN 201611037059 A CN201611037059 A CN 201611037059A CN 106752682 A CN106752682 A CN 106752682A
Authority
CN
China
Prior art keywords
epoxy resin
agent
polyethyleneimine
component
steel construction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201611037059.3A
Other languages
Chinese (zh)
Other versions
CN106752682B (en
Inventor
戴李宗
邵志恒
柳超
黄陈
曾碧榕
许婷
许一婷
罗伟昂
袁丛辉
陈国荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN201611037059.3A priority Critical patent/CN106752682B/en
Publication of CN106752682A publication Critical patent/CN106752682A/en
Priority to PCT/CN2017/112583 priority patent/WO2018095361A1/en
Application granted granted Critical
Publication of CN106752682B publication Critical patent/CN106752682B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention discloses a kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof, belong to functional coating.This expanding fire-proof paint is made up of the component of A, B two, and wherein component A mainly includes film forming matter, carbonifying catalyst, foaming agent, carbon forming agent, auxiliary agent, solvent, color stuffing, and B component mainly includes curing agent, modified polyethyleneimine, solvent, auxiliary agent.It is fire proofing additive (PEI DEPP) and compounded technology that fireproof coating prepared by the present invention uses diethyl phosphite modified polyethyleneimine, effectively improves layer of charcoal expansion multiple and layer of charcoal quality after fireproof coating burning.The coating has excellent fire protecting performance, cohesive force, water resistance, heat resistance, corrosion resistance and resistance to acids and bases, cannot be only used for nigh-level synthesis, applies also for that extra large frock is standby and the flameproof protection of the steel construction in adverse circumstances such as petrochemical industry.

Description

A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof
Technical field
The invention belongs to fireproof coating field, it is related to a kind of epoxy resin fireproof coating, is specifically related to a kind of steel construction With epoxy resin expandable fireproof paint and preparation method thereof.
Background technology
As economic society and science and technology are continued to develop, the construction material used by the mankind is constantly updated and regenerated.Steel construction is built Build and had a clear superiority at aspects such as environmental protection, energy-conservation, efficient, factorial praluctions compared to brick-and-concrete buildingses, thus progressively take Turn into main construction style for armored concrete.According to national standard《Code for fire protection design of buildings》GB's 50016-2014 It is required that, it is necessary to flameproof protection is carried out to steel building.Expanding fire-proof paint is used as steel building extensively at present Fire prevention, expanding fire-proof paint meet fire after it is expanded foamed, play anti-flaming thermal-insulation effect, toxic gas is never discharged during foaming, Human body is protected not to be poisoned.
Expanding fire-proof paint matrix resin can be divided into two kinds of thermoplastics type and heat curing-type, and heat curing-type fireproof coating is using double groups Part system, film forming matter is generally epoxy resin or polyurethane resin.Double-component typically has preferable chemical resistance, heat-resisting Property, resistance to acids and bases and closure.Flame-retardant system is not easy to move to coating surface, and fire protecting performance is relatively stable, is difficult by the time With the influence of environment.Double-component fireproof coating foamed char intensity is high, can provide effective flameproof protection.
It is many to the report of fire-resistant coating for steel structure in recent years, but research for response type self-expanding fire proofing additive, specially Profit report is simultaneously few.Chinese patent CN102634264A has synthesized a kind of aqueous phosphate phenyl ester 2-glycidyl ester, then by this Plant compound to be used for preparing Waterborne phosphorus-containinepoxy epoxy resin fireproof coating, when coating layer thickness is 1.0mm when cured, scribbles fire prevention and apply The three-ply board of the material endurable burning time, its LOI was also up to 42 up to one hour.Chinese patent CN105585931A is by using diethanol Amine to epoxy resin modification, be then respectively adopted phosphoric acid-phosphorus pentoxide-urea, phosphoric acid-urea, ammonium polyphosphate-urea with Modified epoxy resin reaction, synthesizes a kind of water-soluble poly ammonium phosphate ester fire retardant, and be made new high-performance Fireproof coating, its resistance to combustion time is up to 60min.The fire prevention that Chinese patent CN104845490A is prepared for adding BACN is applied Material, fire retardant includes antimony oxide, ammonium sulfate, magnesium hydroxide, citric acid and diatomite.Chinese patent CN104804594A systems For a kind of fire-resistant coating for steel structure, addition type expansible graphite, chlorinated paraffin and titanium dioxide are used, worked as coating layer thickness 2.2mm its fire endurance is up to 100min.
Existing patent, the fire-resistant coating for steel structure of document report are primarily present problems with：
1) fire proofing additive for adding all is addition type, is elapsed over time, and fire proofing additive is easy to run off, thus can cause fire prevention Hydraulic performance decline.
2) fire proofing additive addition is larger, reduces the intensity and other physicochemical properties of coating.
3) fireproof coating water resistance and heat resistance, decay resistance are poor, and addition type fire proofing additive is easily settled, can shadow Ring fire protecting performance.
The content of the invention
Present invention seek to address that the deficiency of existing fire-resistant coating for steel structure, it is proposed that a kind of steel construction epoxy expansion Type fireproof coating and preparation method thereof.
The Ju Ti Pei Fang of steel construction epoxy resin expandable fireproof paint of the present invention such as table 1：
The component and mass fraction of the steel construction epoxy resin expandable fireproof paint of the invention of table 1
Component A Content (wt%) B component Content (wt%)
Epoxy resin 21~28 Curing agent 35~53
Carbonifying catalyst 25~30 Modified polyethyleneimine 18~54
Foaming agent 10~17 Auxiliary agent 0~6
Carbon forming agent 8~11 Color stuffing 0~15
Color stuffing 2~7 Solvent 5~18
Expansible graphite 2~3
Auxiliary agent 0~6
Solvent 11~18
Described epoxy resin be bisphenol A type epoxy resin or bisphenol f type epoxy resin, epoxide number be 0.1~0.56 it Between.
The carbonifying catalyst includes that mass ratio is 2~3:1 APP and melamine phosphate.
The foaming agent includes that mass ratio is 1.9~3:1 melamine and urea.
The carbon forming agent includes that mass ratio is 1.4~2:1 pentaerythrite and mannitol.
The color stuffing includes that mass ratio is 0.9~1.1:0.9~1.1:0.9~1.1 titanium dioxide, Firebrake ZB and hydrogen Aluminum oxide.
Described expansible graphite mesh number is 80~200 mesh.
The auxiliary agent according to the mass fraction, including 0~1.0 part of dispersant, 0~1.0 part of defoamer, levelling agent 0~1.0 Part, 0~0.6 part of anti-settling agent；The dispersant is the solution B YK- of German Bi Ke low-molecular-weights unsaturation polycarboxylic acid polymers P104, defoamer is Germany Bi Ke brokenly bubble polysiloxane solution BYK-066N, and levelling agent is polyether-modified dimethyl silicone polymer EVA BYK-333, anti-settling agent is Germany Bi Ke modified urea solution Bs YK-410.
The solvent is the mixing of dimethylbenzene, n-butanol and butyl acetate, wherein dimethylbenzene, n-butanol and butyl acetate Mass ratio is 2.9~3.1:1.9~2.1:1.
The curing agent viscosity is low, toughness is high, curing rate is moderate, for example curing agent from polyamide, diethylenetriamine, At least one in triethylene tetramine.
The modified polyethyleneimine (PEI-DEPP) is used as fire proofing additive therein, and its chemical structural formula is as follows：
Wherein n is the degree of polymerization, n=1~140.
The preparation method of the modified polyethyleneimine is：Polyethyleneimine, diethyl phosphite and dichloromethane are mixed Close, at 0~5 DEG C, carbon tetrachloride and triethylamine is added dropwise；The polyethyleneimine molecular weight is 600~70000, and polyethylene Amido and the mol ratio of diethyl phosphite, carbon tetrachloride, triethylamine in imines (18~20mmol/g of amine value) are 1.8~2: 0.8~1.2:1~1.4:1~1.4, preferably 1.8~2:1:1.2:1.2；The consumption of the dichloromethane is poly- in mass ratio 1.3~1.5 times of aziridine quality；After 10~24h of reaction, solvent is removed, obtain crude product；Crude product is removed into impurity, It is lyophilized, obtain final product modified polyethyleneimine.
The preparation method of the steel construction epoxy resin expandable fireproof paint, its step is as follows：
1) by the proportioning in the component A, epoxy resin is dissolved in solvent, add carbonifying catalyst, into Charcoal agent, foaming agent, expansible graphite, color stuffing, are well mixed, and add auxiliary agent, are fully ground, and obtain final product component A；
2) by the proportioning in the B component, curing agent and modified polyethyleneimine are dissolved in solvent, add face and fill out Material and auxiliary agent, are well mixed, and are fully ground, and obtain final product B component.
The steel construction epoxy resin expandable fireproof paint, it is preceding using, by A, B component in mass ratio 2~5:1 mixes Stirring is closed, the method that can be applied using spraying, brushing, trowel is constructed.
The present invention has advantages below compared with prior art：
1) modified polyethyleneimine synthesized by is a kind of Halogen and has the branched chain type macromolecular of higher phosphorous nitrogen content to prevent fires Auxiliary agent.
2) fire proofing additive (PEI-DEPP) contains multiple active amine sites, can again may be used as response type fire proofing additive As epoxy resin toughener, both strengthen coating fire protecting performance, and do not influence its mechanical performance.
3) fire proofing additive (PEI-DEPP) collection acid source, source of the gas, carbon source " three-source integrated "：Wherein polyethyleneimine is high nitrogenous Amount plays action of gas source, and " phosphorous acid structure " plays acid source the effect, " diethylester on diethyl phosphite in diethyl phosphite Group " plays carbon source effect, and the response type fire proofing additive fire protection efficiency is high, and preparation method is simple, raw material is cheap, and yield is higher, Commercial industries can be carried out.
4) in epoxy resin expandable fireproof paint of the invention, component A is added with epoxy resin as main film forming substance The intumescent system of ammonium polyphosphate, melamine phosphate, melamine, urea and pentaerythrite, mannitol composition, then add can be swollen Swollen graphite and titanium dioxide add Firebrake ZB and aluminium hydroxide as fire retardant and smoke suppressant, by dividing to improve layer of charcoal quality Powder, anti-settling agent, defoamer and levelling agent improve the bin stability of coating；B component mainly has curing agent, modified poly ethylene sub- Amine fire proofing additive, color stuffing, solvent and various auxiliary agents.When the component of A, B two is used in mixed way, can produce excellent fire protecting performance and Physicochemical property, it is adaptable to standby and steel construction the flameproof protection of the more severe extra large frock of environment.
Brief description of the drawings
The invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the fire proofing additive PEI-DEPP's of synthesis in embodiment 11HNMR nuclear magnetic spectrograms.
Fig. 2 is polyethyleneimine PEI's1HNMR nuclear magnetic spectrograms.
Fig. 3 is diethyl phosphite1HNMR nuclear magnetic spectrograms.
Fig. 4 is the contrast photo before and after the fireproof coating burning that embodiment 1 is obtained.
Specific embodiment
Present disclosure is illustrated below by embodiment：
Embodiment 1：
Step 1：Prepare modified polyethyleneimine fire proofing additive
Polyethyleneimine (PEI), 138g phosphorous acid diethyls that 100g molecular weight is 600~70000 are added in a kettle. Ester and 100ml dichloromethane, under condition of ice bath, are added dropwise 185g carbon tetrachloride and 122g triethylamines in 6h, react 24h Afterwards, revolving obtains crude product.Product is dissolved in 500ml distilled water, dialysis removes impurity, then freezes and obtain final product Modified polyethyleneimine (PEI-DEPP).
By Fig. 1's1HNMR nuclear magnetic spectrograms and the visible amine that polyethyleneimine PEI is occurred in that in 2~3ppm of Fig. 2, Fig. 3 contrast Base proton peak, 7.66ppm and 5.93ppm but P-H proton peaks without diethyl phosphite, and respectively in 1.23ppm and The methyl of diethyl phosphite and the peak of methylene are occurred in that at 3.91ppm.Illustrate the successful synthesis of fire proofing additive PEI-DEPP.
Step 2：480g epoxy resin is dissolved in the solvent that 130g dimethylbenzene, 87g n-butanols, 43g butyl acetates mix In, carbonifying catalyst i.e. 380g APPs and 190g melamine phosphates are added, foaming agent is 217g melamines With 109g ureas, carbon forming agent is 122g pentaerythrites and 82g mannitol, 41g expansible graphites, color stuffing be 40g titanium dioxide, 40g Firebrake ZBs and 40g aluminium hydroxides, mixing, are subsequently adding in material-compound tank, and the 30min that stirs is disperseed with high speed dispersor, plus Enter auxiliary agent (20g dispersant Bs YK-P104,15g defoamer BYK-066N, 15g levelling agent BYK-333,10g anti-settling agent BYK- 410), then with three-roll grinder (or ball mill or sand mill) carry out being fully ground 2h, sieved after discharging, obtain final product component A.
Step 3：The modified polyethyleneimine that 350g curing agent polyamide and 200g steps 1 are obtained is dissolved in 45g diformazans In benzene, 30g n-butanols, the solvent of 15g butyl acetates mixing, color stuffing i.e. 10g titanium dioxide, 10g Firebrake ZBs, 10g are added Aluminium hydroxide and auxiliary agent (6g dispersant Bs YK-P104,5g defoamer BYK-066N, 5g levelling agent BYK-333,4g anti-settling agent BYK- 410), then 30min is stirred in dispersion at a high speed, then carries out being fully ground 1h with three-roll grinder (or ball mill or sand mill), is gone out Sieved after material, obtain final product B component.
Step 4：The component of used time A, B two in mass ratio 4.5:1 ratio mixing, obtains final product fireproof coating, spraying, brushing or trowel Tu Junke.
Gained fireproof coating all technical presses standard GB/T 14907-2002《Fire-resistant coating for steel structure》Requirement Tested, fire protecting performance：Coating layer thickness 1.92mm (Fig. 4 is right), layer of charcoal is highly 4.32cm (Fig. 4 is left), fire resisting pole after expansion Limit 143.3min；Remaining the results are shown in Table 2.
The main performance index of the epoxy resin expandable fireproof paint of the embodiment 1 of table 2
Embodiment 2：
Step 1：Prepare modified polyethyleneimine fire proofing additive
In a kettle. add 100g molecular weight be 600~70000 polyethyleneimine, 125g diethyl phosphites and 100ml dichloromethane, under condition of ice bath, is added dropwise 185g carbon tetrachloride and 122g triethylamines in 6h, after reaction 24h, revolving Obtain crude product.Product is dissolved in 500ml distilled water, dialysis removes impurity, then freezes that to obtain final product modified poly- Aziridine.
Step 2：450g epoxy resin is dissolved in the solvent that 120g dimethylbenzene, 80g n-butanols, 40g butyl acetates mix In, carbonifying catalyst i.e. 340g APPs and 170g melamine phosphates are added, foaming agent is 190g melamines With 95g ureas, carbon forming agent is 120g pentaerythrites and 60g mannitol, and 41g expansible graphites, color stuffing is 30g titanium dioxide, 30g Firebrake ZB and 30g aluminium hydroxides, mixing, are subsequently adding in material-compound tank, and the 30min that stirs is disperseed with high speed dispersor, are added Auxiliary agent (15g dispersant Bs YK-P104,15g defoamer BYK-066N, 12g levelling agent BYK-333,6g anti-settling agent BYK-410), then Carry out being fully ground 2h with three-roll grinder (or ball mill or sand mill), sieved after discharging, obtain final product component A.
Step 3：The modified polyethyleneimine that 380g curing agent polyamide and 180g steps 1 are obtained is dissolved in 39g diformazans In benzene, 26g n-butanols, the solvent of 13g butyl acetates mixing, color stuffing i.e. 30g titanium dioxide, 30g Firebrake ZBs, 30g are added Aluminium hydroxide and auxiliary agent (8g dispersant Bs YK-P104,15g defoamer BYK-066N, 12g levelling agent BYK-333,10g anti-settling agent BYK-410), then 30min is stirred in dispersion at a high speed, then is fully ground with three-roll grinder (or ball mill or sand mill) 1h, sieves after discharging, obtains final product B component.
Step 4：The component of used time A, B two in mass ratio 4:1 ratio mixing, obtains final product fireproof coating, and spraying, brushing or trowel are applied .
Gained fireproof coating all technical presses standard GB/T 14907-2002《Fire-resistant coating for steel structure》Requirement Tested, fire protecting performance：Coating layer thickness 1.89mm, fire endurance 110.2min；Remaining the results are shown in Table 3.
The main performance index of the epoxy resin expandable fireproof paint of the embodiment 2 of table 3
Inspection project Assay
State in a reservoir Meet the requirements
Drying time (surface drying)/h 4.5
Initial dry cracking resistance Flawless
Outward appearance and color Meet the requirements
Adhesion strength/MPa 0.52
Vibration resistance Meet the requirements
Flexing resistance Meet the requirements
Hot/the h of resistance to exposure >=720 coatings without aliquation, come off, hollowing, cracking phenomena
Humidity resistance/h >=504 coatings are without aliquation, obscission
Freeze-thawing resistant cyclicity/time >=15 coatings are without ftractureing, come off, foaming phenomena
Acid resistance/h (3%HCl solution) >=360 coatings without aliquation, come off, cracking phenomena
Alkali resistance/h (3% ammonia spirit) >=360 coatings without aliquation, come off, cracking phenomena
Salt fog resistance/time >=30 coatings are without foaming, it will be apparent that rotten, ruckbildung
Fire resistance Coating layer thickness 1.89mm, fire endurance 110.2min
Embodiment 3：
Step 1：Prepare modified polyethyleneimine fire proofing additive
In a kettle. add 100g molecular weight be 600~70000 polyethyleneimine and 138g diethyl phosphites with And 100ml dichloromethane, under condition of ice bath, 185g carbon tetrachloride and 122g triethylamines are added dropwise in 6h, after reaction 24h, rotation Steaming obtains crude product.Product is dissolved in 500ml distilled water, dialysis removes impurity, then the lyophilized final product that obtains is modified Polyethyleneimine.
Step 2：600g epoxy resin is dissolved in the solvent that 141g dimethylbenzene, 94g n-butanols, 47g butyl acetates mix In, carbonifying catalyst i.e. 420g APPs and 210g melamine phosphates are added, foaming agent is 180g melamines With 90g ureas, carbon forming agent and 140g pentaerythrites and 70g mannitol, 50g expansible graphites, color stuffing is 45g titanium dioxide, 45g Firebrake ZB and 45g aluminium hydroxides, mixing, are subsequently adding in material-compound tank, and the 30min that stirs is disperseed with high speed dispersor, are added Auxiliary agent (25g dispersant Bs YK-P104,18g defoamer BYK-066N, 18g levelling agent BYK-333,14g anti-settling agent BYK-410), Carry out being fully ground 2h with three-roll grinder (or ball mill or sand mill) again, sieved after discharging, obtain final product component A.
Step 3：The modified polyethyleneimine that 150g curing agent polyamide and 180g steps 1 are obtained is dissolved in 30g diformazans In benzene, 20g n-butanols, the solvent of 10g butyl acetates mixing, color stuffing i.e. 15g titanium dioxide, 15g Firebrake ZBs, 15g are added Aluminium hydroxide and auxiliary agent (5g dispersant Bs YK-P104,5g defoamer BYK-066N, 5g levelling agent BYK-333,5g anti-settling agent BYK- 410), then 30min is stirred in dispersion at a high speed, then carries out being fully ground 1h with three-roll grinder (or ball mill or sand mill), is gone out Sieved after material, obtain final product B component.
Step 4：The component of used time A, B two in mass ratio 2.5:1 ratio mixing, obtains final product fireproof coating, spraying, brushing or trowel Tu Junke.
Gained fireproof coating all technical presses standard GB/T 14907-2002《Fire-resistant coating for steel structure》Requirement Tested, fire protecting performance：Coating layer thickness 2.04mm, fire endurance 120.8min；Remaining the results are shown in Table 4.
The main performance index of the epoxy resin expandable fireproof paint of the embodiment 3 of table 4
The above, only present pre-ferred embodiments, therefore can not according to this limit the scope of present invention implementation, i.e., according to Equivalence changes that the scope of the claims of the present invention and description are made and modification, all should still belong in the range of the present invention covers.

Claims (10)

1. a kind of steel construction epoxy resin expandable fireproof paint, it is characterised in that：Including component A and B component, wherein, A groups Divide according to the mass fraction, including：21~28 parts of epoxy resin, 25~30 parts of carbonifying catalyst, 11~17 parts of foaming agent, into 8~11 parts of charcoal agent, 2~7 parts of color stuffing, 2~3 parts of expansible graphite, 0~6 part of auxiliary agent, 11~18 parts of solvent；B component presses quality Number meter, including：35~53 parts of curing agent, 18~54 parts of modified polyethyleneimine, 0~6 part of auxiliary agent, 0~15 part of color stuffing is molten 5~18 parts of agent, the modified polyethyleneimine chemical structural formula is as follows：
Wherein, n is the degree of polymerization, n=1~140；
The component of used time A, B two in mass ratio 2~5:1 ratio is used in mixed way.
2. steel construction epoxy resin expandable fireproof paint as claimed in claim 1, it is characterised in that：The epoxy resin It is bisphenol A type epoxy resin or bisphenol f type epoxy resin, epoxide number is between 0.1~0.56.
3. steel construction epoxy resin expandable fireproof paint as claimed in claim 1, it is characterised in that described to be dehydrated into charcoal Catalyst includes that mass ratio is 2~3:1 APP and melamine phosphate；The foaming agent include mass ratio be 1.9~ 3:1 melamine and urea；The carbon forming agent includes that mass ratio is 1.4~2:1 pentaerythrite and mannitol；The color stuffing It is 0.9~1.1 including mass ratio:0.9~1.1:0.9~1.1 titanium dioxide, Firebrake ZB and aluminium hydroxide；It is described inflatable Graphite mesh number is 80~200 mesh.
4. steel construction epoxy resin expandable fireproof paint as claimed in claim 1, it is characterised in that：The auxiliary agent presses matter Amount number meter, including 0~1.0 part of dispersant, 0~1.0 part of defoamer, 0~1.0 part of levelling agent, 0~0.6 part of anti-settling agent；It is described Dispersant is the solution of low-molecular-weight unsaturation polycarboxylic acid polymers, and defoamer is brokenly bubble polysiloxane solution, and levelling agent is Polyether-modified Dimethicone Copolyol body, anti-settling agent is modified urea solution.
5. steel construction epoxy resin expandable fireproof paint as claimed in claim 1, it is characterised in that：The solvent is two The mass ratio of the mixing of toluene, n-butanol and butyl acetate, wherein dimethylbenzene, n-butanol and butyl acetate is 2.9~3.1:1.9 ~2.1:1.
6. steel construction epoxy resin expandable fireproof paint as claimed in claim 1, it is characterised in that：The curing agent is At least one in polyamide, diethylenetriamine, triethylene tetramine.
7. the preparation method of the steel construction epoxy resin expandable fireproof paint described in a kind of claim 1, it is characterised in that： Including：
1) by the proportioning in the component A, epoxy resin is dissolved in solvent, add carbonifying catalyst, carbon forming agent, Foaming agent, expansible graphite, color stuffing, are well mixed, and add auxiliary agent, are fully ground, and obtain final product component A；
2) by the proportioning in the B component, curing agent and modified polyethyleneimine are dissolved in solvent, add color stuffing and Auxiliary agent, is well mixed, and is fully ground, and obtains final product B component.
8. the preparation method of steel construction epoxy resin expandable fireproof paint according to claim 7, it is characterised in that： The preparation method of the modified polyethyleneimine is：By the polyethyleneimine of 18~20mmol/g of amine value, diethyl phosphite and Dichloromethane mixes, and at 0~5 DEG C, carbon tetrachloride and triethylamine is added dropwise；The polyethyleneimine molecular weight be 600~ Amido and the mol ratio of diethyl phosphite, carbon tetrachloride, triethylamine in 70000, and polyethyleneimine are 1.8~2:0.8 ~1.2:1~1.4:1~1.4；The consumption of the dichloromethane is 1.3~1.5 times of polyethyleneimine quality in mass ratio；Instead After answering 10~24h, solvent is removed, obtain crude product；Crude product is removed into impurity, is freezed, obtain final product modified polyethyleneimine.
9. a kind of epoxy resin expandable fireproof paint fire proofing additive, it is characterised in that：The fire proofing additive is modified poly ethylene Imines, its chemical structural formula is as follows：
Wherein, n is the degree of polymerization, n=1~140.
10. a kind of preparation method of the epoxy resin expandable fireproof paint fire proofing additive described in claim 9, its feature exists In：The polyethyleneimine of 18~20mmol/g of amine value, diethyl phosphite and dichloromethane are mixed, at 0~5 DEG C, is added dropwise Carbon tetrachloride and triethylamine；The polyethyleneimine molecular weight is amido and phosphorous in 600~70000, and polyethyleneimine Diethyl phthalate, carbon tetrachloride, the mol ratio of triethylamine are 1.8~2:0.8~1.2:1~1.4:1~1.4；The dichloromethane Consumption be in mass ratio 1.3~1.5 times of polyethyleneimine quality；After 10~24h of reaction, solvent is removed, obtain crude product； Crude product is removed into impurity, is freezed, obtain final product modified polyethyleneimine.
CN201611037059.3A 2016-11-23 2016-11-23 A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof Active CN106752682B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201611037059.3A CN106752682B (en) 2016-11-23 2016-11-23 A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof
PCT/CN2017/112583 WO2018095361A1 (en) 2016-11-23 2017-11-23 Epoxy-resin intumescent fire-resistant coating for steel structure use, and method for fabrication thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611037059.3A CN106752682B (en) 2016-11-23 2016-11-23 A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106752682A true CN106752682A (en) 2017-05-31
CN106752682B CN106752682B (en) 2019-06-14

Family

ID=58971827

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611037059.3A Active CN106752682B (en) 2016-11-23 2016-11-23 A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof

Country Status (2)

Country Link
CN (1) CN106752682B (en)
WO (1) WO2018095361A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018095361A1 (en) * 2016-11-23 2018-05-31 厦门大学 Epoxy-resin intumescent fire-resistant coating for steel structure use, and method for fabrication thereof
CN108559359A (en) * 2018-04-25 2018-09-21 中南林业科技大学 A kind of fire-resistant coating for steel structure and preparation method thereof of decalescence, expandable flame retardant
CN109749682A (en) * 2018-12-25 2019-05-14 中国人民解放军海军工程大学 A kind of flame retardant epoxy adhesive peculiar to vessel
CN115626985A (en) * 2022-09-23 2023-01-20 浙大宁波理工学院 Novel Mo-based polymer and preparation method and application thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2907062T3 (en) * 2019-03-22 2022-04-21 Hilti Ag Fire protection composition and its use
EP3712218B1 (en) * 2019-03-22 2022-01-26 Hilti Aktiengesellschaft Flame retardant compound and use of same
CN113217077B (en) * 2021-05-07 2024-03-29 湖南红森科技有限公司 Construction method of tunnel fireproof coating
CN114904739B (en) * 2022-06-16 2023-04-14 广东百安环保新材料有限公司 Water-based fireproof coating for steel structure and preparation method thereof
CN114922066A (en) * 2022-07-08 2022-08-19 上海岐海防腐工程技术有限公司 Anticorrosive fireproof bridge cable
CN116925497A (en) * 2023-07-21 2023-10-24 广州润泰新材料科技有限公司 Novel fireproof material and preparation method and application thereof
CN116970325B (en) * 2023-09-22 2023-11-24 潍坊市兴源防水材料股份有限公司 Building fireproof paint and preparation method thereof
CN117467332A (en) * 2023-11-24 2024-01-30 上海中南建筑材料有限公司 Waterproof aerogel fireproof coating and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103740231A (en) * 2013-12-26 2014-04-23 中盈长江国际新能源投资有限公司 Water-based expansive type nano fireproof coating for cable and preparation method thereof
CN103805033A (en) * 2014-02-25 2014-05-21 绵阳惠利环氧工程有限公司 Ultrathin expansion steel structure fireproof coating and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086385A (en) * 1975-11-05 1978-04-25 The United States Of America As Represented By The Secretary Of Agriculture Flame retarded textiles via deposition of polymers from oligomeric vinylphosphonate and polyamino compounds
CN103045037B (en) * 2012-12-14 2015-07-08 中盈长江国际新能源投资有限公司 Water-based expandable fireproof steel structure coating and preparation method
US20160168393A1 (en) * 2014-12-12 2016-06-16 United States Mineral Products Company Intumescent Coating
CN105368166A (en) * 2015-11-27 2016-03-02 沈阳顺风新城建筑材料有限公司 Expansion-type chlorinated rubber fire retardant coating and preparation method thereof
CN106752682B (en) * 2016-11-23 2019-06-14 厦门大学 A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103740231A (en) * 2013-12-26 2014-04-23 中盈长江国际新能源投资有限公司 Water-based expansive type nano fireproof coating for cable and preparation method thereof
CN103805033A (en) * 2014-02-25 2014-05-21 绵阳惠利环氧工程有限公司 Ultrathin expansion steel structure fireproof coating and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018095361A1 (en) * 2016-11-23 2018-05-31 厦门大学 Epoxy-resin intumescent fire-resistant coating for steel structure use, and method for fabrication thereof
CN108559359A (en) * 2018-04-25 2018-09-21 中南林业科技大学 A kind of fire-resistant coating for steel structure and preparation method thereof of decalescence, expandable flame retardant
CN108559359B (en) * 2018-04-25 2020-07-31 中南林业科技大学 Phase-change heat-absorbing and expansion flame-retardant steel structure fireproof coating and preparation method thereof
CN109749682A (en) * 2018-12-25 2019-05-14 中国人民解放军海军工程大学 A kind of flame retardant epoxy adhesive peculiar to vessel
CN115626985A (en) * 2022-09-23 2023-01-20 浙大宁波理工学院 Novel Mo-based polymer and preparation method and application thereof
CN115626985B (en) * 2022-09-23 2023-09-05 浙大宁波理工学院 Mo-based polymer and preparation method and application thereof

Also Published As

Publication number Publication date
WO2018095361A1 (en) 2018-05-31
CN106752682B (en) 2019-06-14

Similar Documents

Publication Publication Date Title
CN106752682B (en) A kind of steel construction epoxy resin expandable fireproof paint and preparation method thereof
CN104448237B (en) It is a kind of suitable for silicon nitrogen phosphorus cooperative flame retardant epoxy powder coating of steel pipe and preparation method thereof
CN106752681A (en) A kind of Water-borne inflation type refractory coating based on modified graphene oxide and preparation method thereof
CN102134432A (en) Water-borne ultrathin intumescent fireproof and anticorrosive double-function coating for steel structure and preparation method thereof
CN107099240B (en) A kind of multifunctional modification aqueous polyurethane coating material and preparation method thereof
CN105238221A (en) Flexible epoxy intumescence fire-retardant coating and preparation method thereof
CN103709899A (en) Fire retardant coating for steel structure surface of nuclear power plant
CN1786093A (en) Expansion type fire retarding epoxide resin powder paint suitable for steel structure and its preparation method
CN102559022A (en) Polyurea expanding type fireproof paint as well as preparation method and application thereof
CN102002301A (en) Fire-proof and corrosion-proof dual-function paint for water-based ultrathin expansion steel structure and preparation method thereof
CN104130671A (en) Aqueous ultrathin expansion-type fireproof coating for steel structure and preparation method thereof
CN101323727A (en) Environment-friendly aqueous expansion type fireproof coating and preparation thereof
CN102108236A (en) Fire-proof and corrosion-proof paint for ultra-thin section steel structures
CN105037808B (en) A kind of microencapsulation hypo-aluminum orthophosphate and preparation method and application
CN109705700A (en) A kind of dual cure wet-heat resisting heavy antisepsis ceramic coating
RU2764294C1 (en) Battery containing a swelling layer
CN108912909A (en) Thin section steel structure fire retardant, anticorrosive coating
CN110105528A (en) A kind of halogen-free flameproof glue and preparation method thereof
CN104356915A (en) Method for preparing flame-retardancy and waterproof aqueous polyurethane coating and adhesive
CN110105849A (en) A kind of oil well pipe Wear-resistant, high-temperature resistant powdery paints
CN101659833A (en) Fireproofing paint for steel structure and preparation method thereof
CN105384902B (en) A kind of building heat preservation novel environment friendly flame retardant polyurethane material
JP2015529714A (en) High heat resistant composition
CN107022260A (en) A kind of quick-drying flame retardant type water-repellent paint and preparation method thereof
CN105566968B (en) A kind of aqueous fire-proof coating and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant