CN105949987B - A kind of imine modified polyaspartic ester water proof anti-corrosive paint and preparation method and application - Google Patents
A kind of imine modified polyaspartic ester water proof anti-corrosive paint and preparation method and application Download PDFInfo
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- CN105949987B CN105949987B CN201610547533.0A CN201610547533A CN105949987B CN 105949987 B CN105949987 B CN 105949987B CN 201610547533 A CN201610547533 A CN 201610547533A CN 105949987 B CN105949987 B CN 105949987B
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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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
- C09D5/08—Anti-corrosive 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
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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
- C09D7/65—Additives macromolecular
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- 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
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Abstract
The invention discloses a kind of imine modified polyaspartic ester water proof anti-corrosive paint and preparation method and applications.The coating includes first component and component B：The composition of first component is as follows：Polyaspartic ester 46~61%, imines 38.5~53.5% and accelerating agent 0.1%~0.5%；The composition of second component is as follows：Isocyanate functional group's component 50~61%, low viscosity epoxy compound 11~15%, nano fumed silica 5~8%, filler 18~27%, pigment 1% and other auxiliary agents 2%.By the ingredient mixing in first component to get first component；By the ingredient mixing in second component to get second component；In use, by first component and second component in mass ratio 1:3~1:4.5 are uniformly mixed, you can are coated on sheet metal or concrete construction surface.Coating water-proof performance provided by the present invention is good, and adhesive property is strong, is solventless coatings.
Description
Technical field
The present invention relates to a kind of coating, more particularly to a kind of imine modified polyaspartic ester water proof anti-corrosive paint and system
Preparation Method and application.
Background technology
Concrete becomes modern infrastructure and civil buildings, sea because of its excellent robustness, durability and safety etc.
The essential construction material such as harbor work's journey, road, bridge, tunnel.However, for a long time by the physics of ambient enviroment, chemistry, biology
Effect is so that concrete volume expansion just occurs successively after the completion of concrete works after a period of time, cracking even destroys etc.
Defect drastically influences safety and the service life of concrete construction engineering.
Water is the main cause and carrier for causing concrete destruction.Moisture can lead to direct physical change such as frost and defrosting and
The tension of generation, water are also the carrier for transmitting corrosive substance such as chlorion, sour gas, poisonous substance etc..Therefore, as long as being avoided that
Concrete is in direct contact with moisture, so that it may to effectively improve concrete durability.
At present applied to concrete construction engineering water proof anti-corrosive paint mainly have modified epoxy resin mortar, polyurethane coating,
Vinyl resin paint, organosilicon alkanes, acrylate paint and carbamide paint.Polyaspartic Ester-Based Coatings are to exist in recent years
It is poly- to revolutionize tradition for a kind of novel aliphatic, long response time and the high performance two-component coating that polyurea industry field occurs
The shortcomings of gel time of urea coating is short and easy xanthochromia.Compared with conventional urethane coating, and with solid content height, hardness and coagulate
The advantages that glue time is adjustable, good corrosion resistance, thick can apply, excellent in abrasion resistance.
However, 103031045 A of patent CN1880393A, CN103788857B, CN discloses the poly- day of bi-component at present
L-aminobutanedioic acid ester polyureas elastic waterproof anti-corrosive paint, isocyanate component are divided into A, B component with polyaspartic ester group.But this
Or a little formulation for coating material occur can rapid draings but validity period is short or validity period often but the defect of slow-drying.In order to regulate and control
Reactivity, as patent CN1880393A, CN102391771A, CN103865370B disclose the blocked amine using low viscosity,
Such as ketimide and aldimine are used in mixed way with polyaspartic ester.But the imidization used in these current patents
Conjunction object content is relatively low, and effect is only limitted to the curing activity of regulation and control coating.In actual repair concrete construction engineering process,
Contain more Free water in the surface of concrete construction defect, crack, it is difficult to by it during water proof anti-corrosive paint penetrates into
Discharge, causes Polyaspartic Ester-Based Coatings after hardening and the combination on concrete construction surface is poor, be susceptible to coating
Layer and concrete cracking, especially highway, subway tunnel and high-speed railway crack apparent after being given a shock.
It is suitable for repairing the coating of concrete construction therefore, it is necessary to continue research and development.
Invention content
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of imine modified poly- lucid asparagus
Propylhomoserin ester water proof anti-corrosive paint.
Another object of the present invention is to provide the preparations of the imine modified polyaspartic ester water proof anti-corrosive paint
Method.
It is still another object of the present invention to provide the applications of the imine modified polyaspartic ester water proof anti-corrosive paint.
The purpose of the invention is achieved by the following technical solution：A kind of imine modified polyaspartic ester waterproof and anticorrosion painting
Material, including first component and component B：
First component by as follows by mass percentage at being grouped as：Polyaspartic ester 46~61%, imines 38.5
~53.5% and accelerating agent 0.1%~0.5%；
Second component by as follows by mass percentage at being grouped as：It is isocyanate functional group's component 50~61%, low viscous
Spend epoxide 11~15%, nano fumed silica 5~8%, filler 18~27%, pigment 1% and other auxiliary agents
2%.
Quality proportioning when the first component and the second component use is：First component:Second component=1:3~1:
4.5。
The polyaspartic ester is that dicarboxylic esters reacts the Michael additions generated production with primary amine through catalysis
Object, addition compound product contains secondary amine, and anti-life reacts to form cured product with isocyanates.Polyaspartic ester includes that laboratory is logical
Cross the addition compound product and other commercially available polyaspartic esters that dicarboxylic esters is prepared with primary amine reaction, preferably Bayer
One kind or at least two in F-420, F-524, F-520 and F220 is flown upward in Desmophen NH1420, NH1520, NH1220, Zhuhai
Kind.
The imines is reacted according to Mannich to be prepared：By polyamine and sealer in molar ratio 1：2 proportioning mixing, then
The catalyst of catalytic amount is added, warming while stirring is warming up to 90~120 DEG C, is stirred to react 3~5 hours；It is subsequently added into band water
Agent, shunting remove the moisture generated in reaction system, until the quality of water entrainer band water outlet reaches theoretical value；Continue to be warming up to phase
It answers near the boiling point of sealer, vacuum distillation removes the sealer for not participating in reaction in water entrainer and system, obtains imines (such as formula
Shown in I)；Its reaction process is shown below：
The imines is more preferably prepared by following specific steps：By 1 mole of polyamine and 2 moles of closing
Agent is added in the reaction kettle with division box, and 0.2~0.3 gram of catalyst is added, is while stirring raised to the temperature of system
90~120 DEG C；After stirring 3~5 hours, 100~120mL water entrainers are added, shunt the moisture generated in removing system, until
The quality of water entrainer band water outlet reaches theoretical value.Continue to be warming up near the boiling point of corresponding sealer, vacuum distillation removes band water
The sealer for not participating in reaction in agent and system, obtains imines.
The polyamine can be the low molecular weight amine compound containing two or more than two molecule of primary amine, preferably
Diethylenetriamine, triethylene tetramine, tetraethylenepentamine, hexamethylene diamine, isophorone diamine, 4,4 '-diamino-dicyclohexyl methanes
At least one of with 3,3 '-dimethyl -4,4 '-diamino-dicyclohexyl methane.
The sealer can be containing carbonyl and the organic compound that can be reacted with the anti-raw Mannich of primary amine, it is excellent
It is selected as at least one of ketone or aldehyde.
The ketone is preferably that acetone, acetophenone, cyclohexanone, cyclopentanone, bicyclo-propyl ketone, cyclopentylethanone and methyl are different
One kind in butyl ketone or at least two.
The aldehyde is preferably propionic aldehyde, butyraldehyde, aldehyde C-9, hexanal, n-octaldehyde, valeral, furtural, capraldehyde, pyroracemic aldehyde, benzene
Formaldehyde, the hendecanal, phenylacetaldehyde, the third formaldehyde of ring, phenyl-allylene aldehyde, thiophenecarboxaldehyde, benzaldehyde iodine, 2- pyridine carboxaldehydes and 5- indolecarboxaldehydes
Middle one kind or at least two.
The water entrainer is preferably one or both of hexamethylene and toluene.
The content of the accelerating agent is preferably mass percent 0.5%.
The accelerating agent is dibutyl tin laurate, stannous octoate and one kind in isooctyl acid bismuth or at least two.
Isocyanate functional group's component is main ingredient in second component, is and imines, polyaspartic ester
The co-curing ingredient for forming solidfied material, in order to balance the mobility of coating and to the cladding function of coating, isocyanate-functional
The number-average molecular weight of group's component can be 1000~15000 grams/mol, preferably 2000~8000 grams/mol；It is diisocyanate
The modifier of ester and polyether polyol, the modifier are mainly prepared by the following method：Polyether polyol is added to reaction kettle
Interior, heat temperature raising, stirring vacuumizes, and temperature is 110~120 DEG C inside, vacuum degree 133.3Pa is dehydrated 2~3h；Then 50 are cooled to
DEG C, it is added dropwise and diisocyanate cpd is added, the addition of diisocyanate cpd presses the OH groups of polyether polyol：Two is different
NCO group=molar ratio 1 of cyanate esters:1.4~1:2.3 calculating；Continue stirring after dripping 1~2 hour, addition is urged
Agent is gradually warming up to 60~80 DEG C, constant temperature 3.5~6h of clock reaction, and cooling down, vacuumizing and defoaming obtains diisocyanate
The modifier of ester and polyether polyol.
The polyether polyol is the polyalcohol that molecular weight is not higher than 2000 grams/mol, preferably polyether polyol N-
204, N-210, N-220, PTMEG (polytetramethylene ether glycol) -250, PTMEG-650, two functional group such as PTMEG-1000
One or both of polyether polyol.
The diisocyanate cpd is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, six Asias 1,6-
Methyl diisocyanate, two isocyanide of isophorone diisocyanate, benzene dimethylene diisocyanate and cyclohexanedimethyleterephthalate
One kind in acid esters or at least two.
The time of the stirring is preferably 2h.
The low viscosity epoxy compound refer to not hydroxyl, contain only the compound of epoxy group, preferably glycolylurea ring
One kind in oxygen resin, ethylene glycol diglycidylether and 1,4-butanediol diglycidyl ether or at least two, more preferably
Glycolylurea epoxide resin.
The filler is preferably titanium dioxide, silicon powder, flyash, talcum powder, sericite in powder, blanc fixe, heavy
One kind in calcium carbonate and precipitated calcium carbonate or at least two.
The pigment is preferably carbon black.
Other described auxiliary agents are that molecular formula is HO- [Si (CH3)2-O]n- H and the low molecular weight hydroxyl of polymerization degree n=6~11
Dimethyl silicone polymer, gamma-aminopropyl-triethoxy-silane or the N- phenylaminomethyl triethoxysilanes of base sealing end.
The preparation method of the imine modified polyaspartic ester water proof anti-corrosive paint, includes the following steps：
(1) polyaspartic ester, imines and accelerating agent are uniformly mixed, obtain first component；Wherein, each component presses quality
Percentages are as follows：Polyaspartic ester 46~61%, imines 38.5~53.5% and accelerating agent 0.1%~0.5%；
(2) by isocyanate functional group's component, low viscosity epoxy compound, nano fumed silica, filler, pigment and
Other auxiliary agents are uniformly mixed, and obtain second component；Wherein, each component is as follows by mass percentage：Isocyanate functional group's component
50~61%, low viscosity epoxy compound 11~15%, nano fumed silica 5~8%, filler 18~27%, pigment 1%
With other auxiliary agents 2%.
The application of the imine modified polyaspartic ester water proof anti-corrosive paint, includes the following steps：By first component
With component B in mass ratio 1:3~1:4.5 are uniformly mixed, and are coated on sheet metal or concrete construction surface.
The concrete construction is the concrete construction of humidity.
The thickness for the film that the coating is formed is preferably 1.5~2mm.
The present invention has the following advantages and effects with respect to the prior art：
(1) present invention increases the content of group with imine moiety, and not only group with imine moiety can regulate and control curing activity, moreover it is possible to it is mixed
The Free water on solidifying soil surface reacts, and reduces influence of the Free water to water proof anti-corrosive paint and the deterioration of concrete adhesive force, together
When, the carbonyl containing compound generated is reacted with water can play the role of levelling agent, enhance the apparent property of water proof anti-corrosive paint, disappear
Removing coating pin hole further increases its waterproof effect.
(2) present invention introduces a part of low viscosity epoxy compounds and polyurethane to form B component, is handed over altogether by curing reaction
It is linked in paint solidification object, further improves the bonding force of coating and concrete surface, realize the raising of coating durability.
(3) viscosity of group with imine moiety and low viscosity epoxy compound itself is very low in the present invention, can effectively improve painting
The mobility of material realizes solventless coatings, reduces the wasting of resources and environmental pollution caused by organic matter volatilization, and to construction
The damage of personnel.
(4) group with imine moiety replaces part polyaspartic ester to participate in reaction in the present invention, when the gel of formulation for coating material
Between adjustable extent it is wider, construction flexibility enhancing.
Specific implementation mode
With reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
(1) synthesis of aldimine
Equipped with blender, water knockout drum, condenser pipe there-necked flask in be added 103 grams of diethylenetriamine, be slowly added dropwise into benzene
0.3 gram of 723 cation exchange resin of catalyst is added in 212 grams of formaldehyde, and warming while stirring is reacted 3 hours to 90 DEG C.It is added
The temperature of reaction system is increased to 115 by cyclohexane 100mL when the quality of separated water is close to 36 grams of theoretical value
DEG C, it boils off and has neither part nor lot in reaction dissolvent, obtain diphenyl imine (as shown in Formula II) and its closed is stored in dry brown bottle
It is interior.
(2) preparation of first component
Polyaspartic ester DesmophenNH1420,49.5wt% structural formula that 50wt% Bayers are produced is Formula II
Diphenyl imine and the isooctyl acid bismuth of 0.5wt% be uniformly mixed at normal temperatures, stand 6 hours, obtain first component.
(3) preparation of second component
Polyether polyol N-204 is added in reaction kettle, heat temperature raising, stirring vacuumizes.Temperature is 110 DEG C, very inside
Reciprocal of duty cycle 133.3Pa is dehydrated 2h.It is cooled to 50 DEG C；It is 1 by the molar ratio of OH and NCO:2.1 are added dropwise addition toluene di-isocyanate(TDI),
Continue stirring 2 hours after dripping, catalyst dibutyltin dilaurylate is added, is gradually warming up to 60 DEG C, constant temperature clock reaction
3.5h, cooling down, vacuumizing and defoaming obtain diisocyanate and polyether polyols that molecular weight is 3000~4000 grams/mol
The modifier of alcohol.By the aforementioned modified objects of 58wt%, 12wt% glycolylurea epoxide resins (Wuxi Meihua Chemical Co., Ltd.,
MHRO70), 6wt% nano fumed silicas (wacker chemicals (China) Co., Ltd, N70, similarly hereinafter), 21wt% talcum powder
(specialty minerals Co., Ltd of the U.S., AG609, similarly hereinafter), 1wt% carbon blacks (Columbian Chemical, Raven 1255, similarly hereinafter) and
The dimethyl silicone polymer (DOW CORNING 107) of 2wt% low-molecular-weight hydroxyls sealing end is uniformly mixed by high-speed dispersion system, is obtained
Component B.
(4) preparation of water proof anti-corrosive paint
According to first component:Second component=1:4.5 stir evenly after be coated in metallic plate and moist cement concrete (humidity
Cement concrete is that " 8 " type matrix after dry solidification is complete impregnates acquisition in 7 days in pure water, similarly hereinafter) surface, film thickness control
In 1.5~2.0mm.Its testing result is as shown in table 1.
Embodiment 2
(1) synthesis of aldimine
Equipped with blender, water knockout drum, condenser pipe there-necked flask in be added 146 grams of triethylene tetramine, be slowly added dropwise into benzene
0.3 gram of 723 cation exchange resin is added in 212 grams of formaldehyde, and warming while stirring is reacted 3 hours to 90 DEG C.Hexamethylene is added
The temperature of reaction system is increased to 115 DEG C, boiled off by water entrainer 100mL when the quality of separated water is close to 36 grams of theoretical value
Reaction dissolvent is had neither part nor lot in, diphenyl imine (as shown in formula III) is obtained and closed is stored in its in dry brown bottle.
(2) preparation of first component
Polyaspartic ester DesmophenNH1520,53.5wt% structural formula that 46wt% Bayers are generated is formula III
Diphenyl imine and the isooctyl acid bismuth of 0.5wt% be uniformly mixed at normal temperatures, stand 6 hours.
(3) preparation of second component
Polyether polyol N-204 is added in reaction kettle, heat temperature raising, stirring vacuumizes.Temperature is 110 DEG C, very inside
Reciprocal of duty cycle 133.3Pa is dehydrated 2h.It is cooled to 50 DEG C；It is 1 by the molar ratio of OH and NCO:2.3 are added dropwise addition isophorone diisocyanate
Ester continues stirring 2 hours after dripping, catalyst dibutyltin dilaurylate is added, is gradually warming up to 60 DEG C, constant temperature timing is anti-
Answer 4h, cooling down, vacuumizing and defoaming, obtain isophorone diisocyanate that molecular weight is 3000~4000 grams/mol with
The modifier of polyether polyol.By the aforementioned modified objects of 61wt%, 13wt% ethylene glycol diglycidylethers (expand abundant chemical industry in Changshu City
Co., Ltd, HHY669), 5wt% nano fumed silicas, 18wt% talcum powder, 1wt% carbon blacks and 2wt% low molecular weights
Hydroxy-end capped dimethyl silicone polymer is uniformly mixed by high-speed dispersion system.
(4) preparation of water proof anti-corrosive paint
According to first component:Second component=1:3.4 stir evenly after be coated in metallic plate and moist cement concrete surface, film
Thickness control is in 1.5~2.0mm.The results are shown in Table 1 for it.
Embodiment 3
(1) synthesis of ketimide
Equipped with blender, water knockout drum, condenser pipe there-necked flask in be added 146 grams of triethylene tetramine, be slowly added dropwise into ring
0.2 gram of FeCl is added in 196 grams of hexanone3, warming while stirring is to 100 DEG C, reaction 5 hours.Water entrainer toluene 120mL is added, waits for
When the quality of separated water is close to 36 grams of theoretical value, the temperature of reaction system is increased to 125 DEG C, boils off that have neither part nor lot in reaction molten
Agent obtains diphenyl imine (as shown in formula IV) and closed is stored in its in dry brown bottle.
(2) preparation of first component
Polyaspartic ester DesmophenNH1520,38.5wt% structural formula that 61wt% Bayers are generated is formula IV
Diphenyl imine and the dibutyl tin laurate of 0.5wt% be uniformly mixed at normal temperatures, stand 6 hours.
(3) preparation of second component
Polyether polyol N-204 is added in reaction kettle, heat temperature raising, stirring vacuumizes.Temperature is 110 DEG C, very inside
Reciprocal of duty cycle 133.3Pa is dehydrated 2h.It is cooled to 50 DEG C；It is 1 by the molar ratio of OH and NCO:1.4 are added dropwise addition isophorone diisocyanate
Ester continues stirring 2 hours after dripping, catalyst dibutyltin dilaurylate is added, is gradually warming up to 80 DEG C, constant temperature timing is anti-
Answer 6h, cooling down, vacuumizing and defoaming, obtain isophorone diisocyanate that molecular weight is 5000~8000 grams/mol with
The modifier of polyether polyol.By the aforementioned modified objects of 51wt%, 15wt% glycolylurea epoxide resins, 8wt% nano-gas-phase titanium dioxides
Silicon, 23wt% talcum powder, 1wt% carbon blacks and 2wt% gamma-aminopropyl-triethoxy-silanes (the military big organosilicon new material stock in Hubei
Part Co., Ltd, WD-50, similarly hereinafter) be uniformly mixed by high-speed dispersion system.
(4) preparation of water proof anti-corrosive paint
According to first component:Second component=1:3 stir evenly after be coated in metallic plate and moist cement concrete surface, film thickness
Degree control is in 1.5~2.0mm.The results are shown in Table 1 for it.
Embodiment 4
(1) synthesis of ketimide
Equipped with blender, water knockout drum, condenser pipe there-necked flask in be added 103 grams of diethylenetriamine, be slowly added dropwise into ring
0.2 gram of FeCl is added in 196 grams of hexanone3, warming while stirring is to 100 DEG C, reaction 5 hours.Cyclohexane 100mL is added,
When the quality of separated water is close to 36 grams of theoretical value, the temperature of reaction system is increased to 115 DEG C, boils off that have neither part nor lot in reaction molten
Agent obtains diphenyl imine (shown as a formula V) and closed is stored in its in dry brown bottle.
(2) preparation of first component
It is by polyaspartic ester F520,53.5wt% structural formula that 46wt% Zhuhai Feiyang Chemical Co., Ltd produces
The diphenyl imine of Formula V and the dibutyl tin laurate of 0.5wt% are uniformly mixed at normal temperatures, stand 6 hours.
(3) preparation of second component
50wt% is modified addition product, 12wt% hydantoin epoxies according to isophorone diisocyanate prepared by embodiment 3
Resin, 8wt% nano fumed silicas, 27wt% talcum powder, 1wt% carbon blacks and 2wt% gamma-aminopropyl-triethoxy-silanes
It is uniformly mixed by high-speed dispersion system.
(4) preparation of water proof anti-corrosive paint
According to first component:Second component=1：4 stir evenly after be coated in metallic plate and moist cement concrete surface, film thickness
Degree control is in 1.5~2.0mm.The results are shown in Table 1 for it.
Embodiment 5
(1) synthesis of ketimide
Equipped with blender, water knockout drum, condenser pipe there-necked flask in be added 170 grams of isophorone diamine, be slowly added dropwise into
0.3 gram of SnCl is added in 210 grams of methyl iso-butyl ketone (MIBK)2, warming while stirring is to 90 DEG C, reaction 6 hours.Hexamethylene band water is added
The temperature of reaction system is increased to 120 DEG C, boils off and do not join by agent 100mL when the quality of separated water is close to 36 grams of theoretical value
Methyl iso-butyl ketone (MIBK) and reaction dissolvent, obtain diphenyl imine (as shown in Formula IV) and its closed be stored in dry brown
In bottle.
(2) preparation of first component
It is by polyaspartic ester F220,41wt% structural formula that 58.5wt% Zhuhai Feiyang Chemical Co., Ltd produces
The diphenyl imine of Formula IV and the dibutyl tin laurate of 0.5wt% are uniformly mixed at normal temperatures, stand 6 hours.
(3) preparation of second component
Polyether polyol PTMEG-250 is added in reaction kettle, heat temperature raising, stirring vacuumizes.Temperature is 120 inside
DEG C, vacuum degree 133.3Pa be dehydrated 3h.It is cooled to 50 DEG C；It is 1 by the molar ratio of OH and NCO:1.6 are added dropwise addition six methylenes of 1,6-
Group diisocyanate continues stirring 2 hours after dripping, catalyst dibutyltin dilaurylate is added, is gradually warming up to 65 DEG C,
It is sub- to obtain 1, the 6- six that molecular weight is 3000~5000 grams/mol for constant temperature clock reaction 4h, cooling down, vacuumizing and defoaming
Methyl diisocyanate is modified addition product.1, the 6- hexamethylene diisocyanates of 55wt% molecular weight are modified addition product,
11wt%1,4- butanediol diglycidyl ether, 6wt% nano fumed silicas, 25wt% talcum powder, 1wt% carbon blacks and
2wt%N- phenylaminomethyls triethoxysilane (Hangzhou Jesse blocks Chemical Co., Ltd., KH-ND42), passes through high speed dispersion system
System is uniformly mixed.
(4) preparation of water proof anti-corrosive paint
According to first component:Second component=1:3 stir evenly after be coated in metallic plate and moist cement concrete surface, film thickness
Degree control is in 1.5~2.0mm.The results are shown in Table 1 for it.
Comparative example 1
(1) preparation of first component
61wt% polyaspartic esters DesmophenNH1420, the 38.5wt% embodiment 3 that Bayer is generated prepares knot
Structure formula is that the imines of IV and the isooctyl acid bismuth of 0.5wt% are uniformly mixed at normal temperatures, stands 6 hours.
(2) preparation of second component
The toluene di-isocyanate(TDI) that molecular weight prepared by 68wt% embodiments 1 is 3000~4000 grams/mol, which is modified, to be added
At object, 6wt% nano fumed silicas, 23wt% talcum powder, 1wt% carbon blacks and 2wt% low-molecular-weight hydroxyls sealing end it is poly-
Dimethyl siloxane is uniformly mixed by high-speed dispersion system.
(3) preparation of water proof anti-corrosive paint
According to first component:Second component=1:4.5 stir evenly after be coated in metallic plate and moist cement concrete surface, film
Thickness control is in 1.5~2.0mm.The results are shown in Table 1 for it.
Comparative example 2
(1) preparation of first component
The isooctyl acid bismuth of 99.5wt% polyaspartic esters DesmophenNH1420,0.5wt% that Bayer generates are existed
It is uniformly mixed under room temperature, stands 6 hours.
(2) preparation of second component
The toluene di-isocyanate(TDI) that molecular weight prepared by 57wt% embodiments 1 is 3000~4000 grams/mol, which is modified, to be added
At object, 11wt% glycolylurea epoxide resins, 6wt% nano fumed silicas, 23wt% talcum powder, 1wt% carbon blacks and 2wt% are low
The components such as the dimethyl silicone polymer of molecular weight hydroxy sealing end are uniformly mixed by high-speed dispersion system.
(3) preparation of water proof anti-corrosive paint
According to first component:Second component=1:4.5 stir evenly after be coated in metallic plate and moist cement concrete surface, film
Thickness control is in 1.5~2.0mm.The results are shown in Table 1 for it.
Comparative example 3
(1) preparation of first component
Step in polyaspartic ester DesmophenNH1420,20wt% embodiment 1 that 79.5wt% Bayers are produced
(1) the isooctyl acid bismuth of the diphenyl imine and 0.5wt% that synthesize is uniformly mixed at normal temperatures, is stood 6 hours, is obtained first component.
(2) preparation of second component
The toluene di-isocyanate(TDI) that 63wt% molecular weight is 3000~4000 grams/mol is modified addition product, 5wt% glycolylureas
Epoxy resin, 6wt% nano fumed silicas, 23wt% talcum powder, 1wt% carbon blacks and 2wt% low-molecular-weight hydroxyls sealing end
Dimethyl silicone polymer by high-speed dispersion system be uniformly mixed.
(3) preparation of water proof anti-corrosive paint
According to first component:Second component=1:4.5 stir evenly after be coated in metallic plate and moist cement concrete surface, film
Thickness control is in 1.5~2.0mm.The results are shown in Table 1 for it.
As shown in Table 1, will more large content of imines and low viscosity epoxy compound collocation use, poly- day can be effectively improved
The tensile strength of L-aminobutanedioic acid ester water proof anti-corrosive paint, impact resistance, heat aging property and to metal and moist cement
The adhesive strength of concrete, while acid resistance in simple imine modified polyaspartic ester water proof anti-corrosive paint can be overcome bad
Defect.
Product performance index prepared by table 1 is：
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of imine modified polyaspartic ester water proof anti-corrosive paint, it is characterised in that including first component and component B：
First component by as follows by mass percentage at being grouped as：Polyaspartic ester 46~61%, imines 38.5~
53.5% and accelerating agent 0.1%~0.5%；
Second component by as follows by mass percentage at being grouped as：Isocyanate functional group's component 50~61%, low viscosity ring
Oxygen compound 11~15%, nano fumed silica 5~8%, filler 18~27%, pigment 1% and other auxiliary agents 2%.
2. imine modified polyaspartic ester water proof anti-corrosive paint according to claim 1, it is characterised in that：The first
Quality proportioning when component and the second component use is：First component:Second component=1:3~1:4.5.
3. imine modified polyaspartic ester water proof anti-corrosive paint according to claim 1, it is characterised in that：
The imines is reacted according to Mannich to be prepared；
Isocyanate functional group's component is diisocyanate and the modifier of polyether polyol；
The low viscosity epoxy compound refer to not hydroxyl, contain only the compound of epoxy group；
Other described auxiliary agents are that molecular formula is HO- [Si (CH3)2-O]n- H and the low-molecular-weight hydroxyl of polymerization degree n=6~11 envelope
Dimethyl silicone polymer, gamma-aminopropyl-triethoxy-silane or the N- phenylaminomethyl triethoxysilanes at end.
4. imine modified polyaspartic ester water proof anti-corrosive paint according to claim 3, it is characterised in that：
Isocyanate functional group's component is prepared by the following method：Polyether polyol is added in reaction kettle, is heated
Heating, stirring vacuumize, and temperature is 110~120 DEG C inside, vacuum degree 133.3Pa is dehydrated 2~3h；Then 50 DEG C are cooled to, is added dropwise
Diisocyanate cpd is added, the addition of diisocyanate cpd presses the OH groups of polyether polyol：Diisocyanate
NCO group=molar ratio 1 of compound:1.4~1:2.3 calculating；Continue stirring after dripping 1~2 hour, catalyst be added,
60~80 DEG C, constant temperature 3.5~6h of clock reaction are gradually warming up to, cooling down, vacuumizing and defoaming obtains diisocyanate and gathers
The modifier of ethoxylated polyhydric alcohol；
The preparation process of the imines is as follows：By polyamine and sealer in molar ratio 1：2 proportioning mixing, add catalytic amount
Catalyst, warming while stirring is warming up to 90~120 DEG C, is stirred to react 3~5 hours；It is subsequently added into water entrainer, shunting removes
The moisture generated in dereaction system, until the quality of water entrainer band water outlet reaches theoretical value；Continue to be warming up to corresponding sealer
Boiling point near, vacuum distillation removes the sealer for not participating in reaction in water entrainer and system, obtains imines；
The low viscosity epoxy compound is that glycolylurea epoxide resin, ethylene glycol diglycidylether and 1,4- butanediols two shrink
One kind in glycerin ether or at least two.
5. imine modified polyaspartic ester water proof anti-corrosive paint according to claim 4, it is characterised in that：
The polyether polyol is the polyalcohol that molecular weight is not higher than 2000 grams/mol；
The diisocyanate cpd is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, 1,6- hexa-methylenes
Diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate and cyclohexanedimethyleterephthalate diisocyanate
In one kind or at least two；
The polyamine be containing there are two or more than two molecule of primary amine low molecular weight amine compound；
The sealer is containing carbonyl and the organic compound that can be reacted with the anti-raw Mannich of primary amine.
6. imine modified polyaspartic ester water proof anti-corrosive paint according to claim 1, it is characterised in that：
The polyaspartic ester is Bayer Desmophen NH1420, Bayer Desmophen NH1520, Bayer
Desmophen NH1220, Zhuhai fly upward F-420, F-524 is flown upward in Zhuhai, F-520 is flown upward in Zhuhai and Zhuhai is flown upward one in F220
Kind or at least two.
7. imine modified polyaspartic ester water proof anti-corrosive paint according to claim 1, it is characterised in that：
The accelerating agent is dibutyl tin laurate, stannous octoate and one kind in isooctyl acid bismuth or at least two；
The filler be titanium dioxide, silicon powder, flyash, talcum powder, sericite in powder, blanc fixe, powdered whiting and
One kind in precipitated calcium carbonate or at least two.
8. the preparation method of the imine modified polyaspartic ester water proof anti-corrosive paint of claim 1~7 any one of them,
It is characterized in that including the following steps：
(1) polyaspartic ester, imines and accelerating agent are uniformly mixed, obtain first component；Wherein, each component presses quality percentage
It is as follows than counting：Polyaspartic ester 46~61%, imines 38.5~53.5% and accelerating agent 0.1%~0.5%；
(2) by isocyanate functional group's component, low viscosity epoxy compound, nano fumed silica, filler, pigment and other
Auxiliary agent is uniformly mixed, and obtains second component；Wherein, each component is as follows by mass percentage：Isocyanate functional group's component 50~
61%, low viscosity epoxy compound 11~15%, nano fumed silica 5~8%, filler 18~27%, pigment 1% and its
His auxiliary agent 2%.
9. the application of the imine modified polyaspartic ester water proof anti-corrosive paint of claim 1~7 any one of them, feature
It is to include the following steps：By first component and component B in mass ratio 1:3~1:4.5 be uniformly mixed, be coated on sheet metal or
Concrete construction surface.
10. the application of imine modified polyaspartic ester water proof anti-corrosive paint according to claim 9, feature exist
In：
The concrete construction is the concrete construction of humidity；
The thickness for the film that the coating is formed is 1.5~2mm.
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| CN106854428B (en) * | 2016-11-08 | 2019-11-05 | 山东非金属材料研究所 | A kind of flexible polyurea anticorrosive paint |
| CN106811037B (en) * | 2017-01-12 | 2019-04-23 | 广州嘉睿复合材料有限公司 | A kind of Polyaspartic Polyurea coating and its application |
| CN107556451B (en) * | 2017-08-22 | 2021-11-23 | 山西省建筑科学研究院 | Macromolecular polyaspartic acid ester and preparation method thereof |
| CN107663407B (en) * | 2017-10-25 | 2020-12-15 | 广东东方雨虹防水工程有限公司 | Polyaspartate polyurea waterproof coating, preparation method thereof and repair construction method of indoor waterproof structure |
| CN108250944B (en) * | 2017-12-28 | 2020-06-16 | 中冶建筑研究总院有限公司 | Concrete coating protection system and construction method |
| CN109467571B (en) * | 2018-09-29 | 2023-12-19 | 万华化学集团股份有限公司 | Siloxane modified aspartic acid ester and preparation method and application thereof |
| CN110527084B (en) * | 2019-05-12 | 2022-01-28 | 合肥博朗德纳米技术有限公司 | Biodegradable L-structure polyaspartic acid high-molecular dispersant and preparation method thereof |
| CN112375196B (en) * | 2020-11-12 | 2022-09-23 | 深圳飞扬骏研新材料股份有限公司 | Polyurea resin and preparation method and application thereof |
| CN113637398B (en) * | 2021-08-25 | 2022-03-08 | 黄山中邦孚而道涂料有限公司 | Bottom-surface integrated solvent-free polyaspartic acid ester heavy-duty anticorrosive paint, and preparation method and application thereof |
| CN114456691A (en) * | 2022-01-26 | 2022-05-10 | 深圳飞扬骏研新材料股份有限公司 | Method for prolonging activation period of asparagus polyurea coating and coating |
| CN114262559B (en) * | 2022-01-26 | 2022-08-23 | 深圳飞扬骏研新材料股份有限公司 | Asparagus polyurea coating and preparation method thereof |
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| DE4327853A1 (en) * | 1993-08-19 | 1995-02-23 | Bayer Ag | Process for the production of coatings |
| US6989421B2 (en) * | 2003-07-02 | 2006-01-24 | E. I. Dupont Denemours And Company | Two component coating compositions and coatings produced therefrom |
| DE102005020269A1 (en) * | 2005-04-30 | 2006-11-09 | Bayer Materialscience Ag | Binder mixtures of polyaspartic esters and sulfonate-modified polyisocyanates |
| CN101469246B (en) * | 2007-12-27 | 2011-12-21 | 上海涂料有限公司技术中心 | Preparation of polyaspartate polyurea waterproof coating material |
| DE102009007194A1 (en) * | 2009-02-03 | 2010-08-05 | Bayer Materialscience Ag | Flexible coatings |
| EP2556126A4 (en) * | 2010-04-09 | 2014-08-20 | Bayer Materialscience Llc | Two-component, polyaspartic coating compositions |
| CN103031045B (en) * | 2011-10-10 | 2015-08-19 | 珠海飞扬新材料股份有限公司 | Solvent-free polyaspartic acid ester polyurea elastic waterproof paint |
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