CN109337518A - A kind of aqueous epoxide resin paint and preparation method thereof - Google Patents
A kind of aqueous epoxide resin paint and preparation method thereof Download PDFInfo
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- CN109337518A CN109337518A CN201811190714.8A CN201811190714A CN109337518A CN 109337518 A CN109337518 A CN 109337518A CN 201811190714 A CN201811190714 A CN 201811190714A CN 109337518 A CN109337518 A CN 109337518A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
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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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/65—Additives macromolecular
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Abstract
The present invention relates to a kind of aqueous epoxide resin paints and preparation method thereof, belong to technical field of coatings.The invention proposes a kind of acrylic acid modified aqueous epoxy resin emulsions, and the epoxy coating based on above-mentioned emulsion.The lotion mainly obtains the performed polymer with unsaturated bond in such a way that polyethers, siloxanes first pass through crosslinking, hydrolytic polymerization, then graft reaction occurs with epoxy resin simultaneously by performed polymer and acrylic monomers, obtains modified epoxy resin latex.This lotion weatherability more better than the acrylic acid modified aqueous epoxy resin emulsion of routine and UV resistance.
Description
Technical field
The present invention relates to a kind of aqueous epoxide resin paints and preparation method thereof, belong to technical field of coatings.
Background technique
The dirt that the volatile organic substance (VOC) that traditional solvent type coating is discharged in the production and use process generates
Dye, at present
After coming automobile, it is classified as city primary pollution source.With scientific and technological progress and rapid development of economy, resource and the energy
Scarcity caused the attention of countries in the world, section money energy conservation protects environment, is the main problem that world's paint industry faces.As
The water paint of one of solvent based coating substitute, the attention by countries in the world.Water paint is with water as solvent or to divide
The coating of dispersion media.Earliest commercialization water paint is that occur in the 1930s.Compatibility based on it to environment
And protectiveness.And have the advantages that save resource, energy saving, water paint product is acceptable to the market soon, and is gradually sent out
Spread is big.Japan, U.S.'s water paint in 1986 account for the 18% and 22% of coating total sales volume respectively, Britain's nineteen ninety-five water paint
Yield accounts for the 64.5% of national coating total output.China begins one's study water paint from the sixties, and into after the nineties, country is big
The development of power support water paint.Though current occupation rate of market be not it is very high, have vast potential for future development.
The resin that can make water paint base-material includes alkyd, epoxy, acrylic acid, polyurethane and polyester resin etc..Because of epoxy
Resin has the characteristics that adhesive force is strong, chemical resistance corrosion, and is widely used in coatings industry.But epoxy resin indissoluble
Yu Shui is dissolved only in organic solvent, therefore traditional epoxy coating is solvent type.As countries in the world are to the day of environmental protection
Benefit is paid attention to, and develops water paint to replace solvent type painting section to have become the developing direction of coatings industry.
There are mainly three types of the preparation methods of aqueous epoxy resin system: (1) direct method, that is, Mechanical Method, with ball mill, colloid
Mill, Jun Shi device etc. grind epoxy resin, emulsifier aqueous solution are then added, then disperse water for particle by mechanical stirring.
(2) phase inversion is to pass through the volume for changing water phase, and polymer is transformed into oil-in-water state from Water-In-Oil state.(3) chemical
Method, which mainly passes through to open epoxy bond introducing polarity group and react by free radical initiation grafting, introduces epoxy for polarity gene
In molecular resin skeleton, hydrophily is made it have, so as to disperse in water.Particle obtained by Mechanical Method and phase inversion
Diameter is larger, usually micron order.And particle size obtained by chemic modified method is smaller, about dozens to a few hundred nanometers, therefore change
Learn emulsion-stabilizing made from modified method.
After macromolecule resin realizes Water-borne modification, the shortcomings that often leading to some performances and process aspect.In recent years, many is ground
The person of studying carefully has carried out the compound research of various kinds of resin, i.e., using chemical reaction processes such as grafting, esterification or polymerizations by 2 kinds or more
Resin compounded is learnt from other's strong points to offset one's weaknesses, and the comprehensive performance of water-base resin is further promoted.Wherein epoxy resin and polyacrylate resin are made
For two resinoids that usage amount is big, performance complement is strong, complex technique is by extensive concern.Using the acrylic acid modified of chemical method
Epoxy resin reacts acrylic resin with epoxy resin, forms the epoxy acrylic resin containing rich acid groups, then in ammonium hydroxide
With at salt, to form water-soluble resin.
But in the prior art, acrylic acid modified aqueous epoxide resin paint is remained to some corrosivity items
Part, it is ultraviolet under the conditions of the bad disadvantage of weather resistance, affect the service life of coating.
Summary of the invention
The purpose of the present invention is: a kind of acrylic acid modified aqueous epoxy resin emulsion is proposed, and is based on above-mentioned cream
The epoxy coating of liquid.The lotion mainly obtains band not in such a way that polyethers, siloxanes first pass through crosslinking, hydrolytic polymerization
The performed polymer of saturated bond, then graft reaction is occurred with epoxy resin simultaneously by performed polymer and acrylic monomers, obtain modification
Epoxy resin latex.This lotion weatherability more better than conventional acrylic acid modified aqueous epoxy resin emulsion and resistance to ultraviolet
Performance.
Technical solution is:
A kind of water borne epoxy resin anticorrosive paint, is made of component A and B component, and wherein component A includes according to weight percent
The following component of meter: the first aqueous epoxy resin emulsion 25-35%, the second aqueous epoxy resin emulsion 8-15%, dispersing agent 0.3-
0.5%, wetting agent 0.2-0.4%, cosolvent 2-3%, filler 25-35%, pH adjusting agent 0.6-0.8%, defoaming agent 0.3-0.5%, at
Film auxiliary agent 2-2.5%, levelling agent 0.5-1.2%, anti-flash rusting agent 0.3-0.5%, preservative 0.1-0.2%, water 15-18%；B component is
Epoxy curing agent, the weight ratio between component A and B component are 10-12:1；
The preparation method of second aqueous epoxy resin emulsion, includes the following steps:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and after reaction, diatomite is added and is neutralized, is then filtered, filtrate decompression
Water and low-boiling point material is distilled off, obtains polyether polyol；Wherein, the molar ratio of glycerol, propylene oxide and KOH are 1:35-
50:0.2-0.3；
Step 2, hydroxyl substitution reaction: in parts by weight, by 20-25 parts of polyether polyol, 0.1-0.2 parts of sodium hydride, N, N-
400-500 parts of dimethylformamide are uniformly mixed, and are reacted, are filtered at room temperature after reaction, are warp in filtrate
Cross the polyether polyol of Na substitution；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
Agent 0.3-0.5 parts of connection, and reacted, after reaction, evaporating solvent under reduced pressure obtains the polysiloxane grafted polyether polyols in surface
Alcohol；
Step 4, the preparation of performed polymer: in parts by weight, by 50-65 parts polysiloxane grafted of polyether polyol of surface, eight first
0.5-1 parts of oxygen cyclotetrasiloxane, 2-2.5 parts of the dimethyl silicone polymer of ethenyl blocking, γ-three silicon oxygen of trifluoro propyl methyl ring
0.8-1.2 parts of alkane, 0.05-0.1 parts of Pt catalyst mixing, after being replaced with nitrogen, are reacted, after reaction, heating distillation
Low-boiling-point substance is removed, performed polymer is obtained；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
12-15 parts, 15-20 parts of methyl methacrylate monomer, 2-4 parts of styrene monomer, 15-18 parts of methacrylic acid monomer, propylene
4-6 parts of acid -2- ethyl hexyl acrylate monomers, 70-80 parts of E-51 epoxy resin, 10-12 parts of emulsifier, 0.5-2 parts of catalyst, deionization
320-340 parts of water, high speed dispersion is uniform, then adds 2-4 parts of seed emulsion, is warming up to 80-85 DEG C, and performed polymer 20- is added dropwise
28 parts and initiator 2-5 parts, after being added dropwise, continues insulation reaction 1-3h, then be cooled to 65-68 DEG C, t-butyl peroxy is added
Change hydrogen 1-2 parts and sodium hydrogensulfite 0.5-1 parts, after being added dropwise, continues insulation reaction 0.5-1h, be cooled to 30-35 DEG C, use ammonia
Water adjusts pH to 7.5-8, and filtering and discharging simultaneously collects filtrate, obtains the second aqueous epoxy resin emulsion.
In the step 1, reaction temperature is 105-115 DEG C, and the reaction time is 5-8h.
In the step 2, reaction is carried out at room temperature and refers to and reacts 0.5-1h at 20-30 DEG C.
In the step 3, reaction refers to reacts 2-4h under the conditions of 70-80 DEG C.
In the step 4, reaction temperature is to react 1-3h at 130-140 DEG C, and the temperature that low-boiling-point substance is distilled off is
165-170℃。
In the step 5, emulsifier is cetyl benzenesulfonic acid sodium；Catalyst be by copper chloride and stannous chloride according to
Weight ratio 1:2-3 is mixed；Initiator is ammonium persulfate.
The filler is by molybdenum modified zinc phosphate, blanc fixe, titanium oxide, bentonite according to weight ratio 1:1.5-2:
0.2-0.4:0.3-0.6 is mixed.
The preparation method of water borne epoxy resin anticorrosive paint, includes the following steps:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, high-speed stirred is uniform, obtains coating.
The high-speed stirred refers to be stirred under 1500-2000rpm revolving speed.
Beneficial effect
In aqueous epoxide resin paint provided by the invention, it is grafted the group containing siloxanes first using polyether polyol,
It is polymerize again by the siloxanes cohydrolysis with fluorine-containing siloxanes, containing unsaturated bond, is formed and contain polyethers, fluorine functional group simultaneously
And the polysiloxane pre polymers body of unsaturated bond, then by polymerization while performed polymer and acrylic monomers to aqueous epoxy resins
Lotion is modified, and builds crosslinking hybrid epoxy emulsion；The emulsion applications, can be effectively when aqueous epoxide resin paint
Polyethers is improved in hardness, the effect of flexibility for improving epoxy coating；
In aqueous epoxy emulsion of the invention, by introducing flucride siloxane in performed polymer, so that passing through silicon in hybridisation emulsion
Oxygen alkane improves the salt fog resistance of acrylic acid epoxy hybridisation emulsion.
Detailed description of the invention
Fig. 1 is the infared spectrum for the aqueous epoxy emulsion that embodiment 3 is prepared.
Fig. 2 is the grain size distribution for the aqueous epoxy emulsion that embodiment 3 is prepared.
Fig. 3 is the SEM photograph for the aqueous epoxy emulsion that embodiment 3 is prepared.
Specific embodiment
Water borne epoxy resin anticorrosive paint provided by the invention, is made of component A and B component, and wherein component A includes pressing
According to the following component of weight percent meter: the first aqueous epoxy resin emulsion 25-35%, the second aqueous epoxy resin emulsion 8-
15%, dispersing agent 0.3-0.5%, wetting agent 0.2-0.4%, cosolvent 2-3%, filler 25-35%, pH adjusting agent 0.6-0.8%, defoaming
Agent 0.3-0.5%, coalescing agent 2-2.5%, levelling agent 0.5-1.2%, anti-flash rusting agent 0.3-0.5%, preservative 0.1-0.2%, water
15-18%；B component is epoxy curing agent, and the weight ratio between component A and B component is 10-12:1；
The preparation method of second aqueous epoxy resin emulsion, includes the following steps:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and after reaction, diatomite is added and is neutralized, is then filtered, filtrate decompression
Water and low-boiling point material is distilled off, obtains polyether polyol；Wherein, the molar ratio of glycerol, propylene oxide and KOH are 1:35-
50:0.2-0.3；
Step 2, hydroxyl substitution reaction: in parts by weight, by 20-25 parts of polyether polyol, 0.1-0.2 parts of sodium hydride, N, N-
400-500 parts of dimethylformamide are uniformly mixed, and are reacted, are filtered at room temperature after reaction, are warp in filtrate
Cross the polyether polyol of Na substitution；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
Agent 0.3-0.5 parts of connection, and reacted, after reaction, evaporating solvent under reduced pressure obtains the polysiloxane grafted polyether polyols in surface
Alcohol；
Step 4, the preparation of performed polymer: in parts by weight, by 50-65 parts polysiloxane grafted of polyether polyol of surface, eight first
1-0.5 parts of oxygen cyclotetrasiloxane, 2-2.5 parts of the dimethyl silicone polymer of ethenyl blocking, γ-three silicon oxygen of trifluoro propyl methyl ring
0.8-1.2 parts of alkane, 0.05-0.1 parts of Pt catalyst mixing, after being replaced with nitrogen, are reacted, after reaction, heating distillation
Low-boiling-point substance is removed, performed polymer is obtained；
Reaction principle in this step is: the polysiloxane grafted polyether polyol in surface and eight methoxy cyclotetrasiloxanes, vinyl
The hydrolytic-polymeric reaction of alkoxy, shape occur jointly for dimethyl silicone polymer, the γ-trifluoro propyl methyl cyclotrisiloxane of sealing end
At hydridization polysiloxane pre polymers body；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
12-15 parts, 15-20 parts of methyl methacrylate monomer, 2-4 parts of styrene monomer, 15-18 parts of methacrylic acid monomer, propylene
4-6 parts of acid -2- ethyl hexyl acrylate monomers, 70-80 parts of E-51 epoxy resin, 10-12 parts of emulsifier, 0.5-2 parts of catalyst, deionization
320-340 parts of water, high speed dispersion is uniform, then adds 2-4 parts of seed emulsion, is warming up to 80-85 DEG C, and performed polymer 20- is added dropwise
28 parts and initiator 2-5 parts, after being added dropwise, continues insulation reaction 1-3h, then be cooled to 65-68 DEG C, t-butyl peroxy is added
Change hydrogen 1-2 parts and sodium hydrogensulfite 0.5-1 parts, after being added dropwise, continues insulation reaction 0.5-1h, be cooled to 30-35 DEG C, use ammonia
Water adjusts pH to 7.5-8, and filtering and discharging simultaneously collects filtrate, obtains the second aqueous epoxy resin emulsion.
The reaction principle of this step is: due to being the silicon oxygen for including ethenyl blocking in hydridization polysiloxane pre polymers body
Alkane, therefore, by that can be formed by performed polymer, third during the emulsion polymerization with acrylic monomers, epoxy resin formation
The hydridization modification by copolymerization epoxy resin that olefin(e) acid, epoxy resin are constituted.
In coating, the first aqueous epoxy resin emulsion can be using conventional some aqueous epoxy emulsions, the present invention couple
It is not particularly limited.
Below in an example, used raw material is:
First aqueous epoxy resin emulsion, Waterpoxy 1455, BASF
Seed emulsion, SSZ-132 acrylic emulsion, Guangzhou paulownia reach
Aqueous dispersion, BYK-190, Bi Ke chemistry
Aqueous wetting agent, Hydropalat WE 3650, BASF
Cosolvent, Propylene Glycol Dimethyl Ether, Shanghai connection meaning
Molybdenum modified zinc phosphate Niu Bilai pigment
Blanc fixe Shandong Zibo Boshan science popularization is gloomy
The Nanjing titanium oxide NA200 titanium white chemical industry
Bentonite Zhangjiakou is permanent safe
PH adjusting agent triethylamine Changzhou Lear chemical industry
Defoaming agent NXZ Japan Nuo Puke chemical industry
12 Guangzhou perseverance space chemical industry of coalescing agent alcohol ester
Firm gram of chemistry of levelling agent YCK-1520
Anti- flash rusting agent DH-7940 SUZHOUQING(sic) field chemical industry
The Foshan preservative CL-149 Li Yuan chemical industry
801 BASF of epoxy curing agent Waterpoxy
Embodiment 1
The preparation of the second aqueous epoxy resin emulsion used in coating:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and reaction temperature is 105 DEG C, and the reaction time is 5h, after reaction, diatomite is added
It is neutralized, is then filtered, water and low-boiling point material is distilled off in filtrate decompression, obtains polyether polyol；Wherein, sweet
The molar ratio of oil, propylene oxide and KOH is 1:35:0.2；
Step 2, hydroxyl substitution reaction: in parts by weight, by 20 parts of polyether polyol, 0.1 part of sodium hydride, N, N- dimethyl methyl
400 parts of amide are uniformly mixed, and 0.5h is reacted at 20 DEG C, is filtered after reaction, the polyethers replaced in filtrate by Na
Polyalcohol；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
0.3 part of agent of connection, and reacted, 2h is reacted under the conditions of 70 DEG C, after reaction, evaporating solvent under reduced pressure obtains surface siloxanes
The polyether polyol of grafting；
Step 4, the preparation of performed polymer: in parts by weight, by 50 parts polysiloxane grafted of polyether polyol of surface, eight cyclohexyl methoxies
1 part of tetrasiloxane, 2 parts of the dimethyl silicone polymer of ethenyl blocking, γ -0.8 part of trifluoro propyl methyl cyclotrisiloxane, Pt are urged
0.05 part of agent mixing, after being replaced with nitrogen, reacts 1h, after reaction, is warming up to 165 DEG C and low boiling is distilled off at 130 DEG C
Object obtains performed polymer；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
12 parts, 15 parts of methyl methacrylate monomer, 2 parts of styrene monomer, 15 parts of methacrylic acid monomer, acrylic acid-2-ethyl oneself
4 parts of ester monomer, 70 parts of E-51 epoxy resin, 10 parts of emulsifier cetyl benzenesulfonic acid sodium, catalyst (copper chloride and stannous chloride
Mixed according to weight ratio 1:2) 0.5 part, 320 parts of deionized water, high speed dispersion is uniform, then adds water soluble acrylic acid kind
2 parts of sub- lotion is warming up to 80 DEG C, is added dropwise 20 parts and 2 parts of initiator ammonium persulfate of performed polymer, after being added dropwise, it is anti-to continue heat preservation
1h is answered, then is cooled to 65 DEG C, 1 part and 0.5 part of sodium hydrogensulfite of tert-butyl hydroperoxide is added, after being added dropwise, continues to keep the temperature
0.5h is reacted, is cooled to 30 DEG C, adjusts pH to 7.5-8 with ammonium hydroxide, filtering and discharging simultaneously collects filtrate, obtains the second water-base epoxy tree
Fat liquor.
The filler used in coating is by molybdenum modified zinc phosphate, blanc fixe, titanium oxide, bentonite according to weight ratio 1:
1.5:0.2:0.3 mixing.
Water borne epoxy resin anticorrosive paint is made of component A and B component, and wherein component A includes in parts by weight
Following component: the first 30 parts of aqueous epoxy resin emulsion, 15 parts of the second aqueous epoxy resin emulsion, 0.5 part of dispersing agent, wetting agent
0.4 part, 3 parts of cosolvent, 32.1 parts of filler, 0.8 part of pH adjusting agent, 0.3 part of defoaming agent, 2 parts of coalescing agent, 0.5 part of levelling agent,
0.3 part of anti-flash rusting agent, 0.1 part of preservative, 15 parts of water；B component is epoxy curing agent, the weight between component A and B component
Than being 11:1；
The preparation of water borne epoxy resin anticorrosive paint:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water 1500-2000rpm high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, 1500-2000rpm high-speed stirred is uniform, obtains coating.
Embodiment 2
The preparation of the second aqueous epoxy resin emulsion used in coating:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and reaction temperature is 115 DEG C, and the reaction time is 8h, after reaction, diatomite is added
It is neutralized, is then filtered, water and low-boiling point material is distilled off in filtrate decompression, obtains polyether polyol；Wherein, sweet
The molar ratio of oil, propylene oxide and KOH is 1:50:0.3；
Step 2, hydroxyl substitution reaction: in parts by weight, by 25 parts of polyether polyol, 0.2 part of sodium hydride, N, N- dimethyl methyl
500 parts of amide are uniformly mixed, and 1h is reacted at 30 DEG C, is filtered after reaction, and the polyethers replaced in filtrate by Na is more
First alcohol；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
0.5 part of agent of connection, and reacted, 4h is reacted under the conditions of 80 DEG C, after reaction, evaporating solvent under reduced pressure obtains surface siloxanes
The polyether polyol of grafting；
Step 4, the preparation of performed polymer: in parts by weight, by 65 parts polysiloxane grafted of polyether polyol of surface, eight cyclohexyl methoxies
0.5 part of tetrasiloxane, 2.5 parts of the dimethyl silicone polymer of ethenyl blocking, γ -1.2 parts of trifluoro propyl methyl cyclotrisiloxane,
0.1 part of Pt catalyst mixing, after being replaced with nitrogen, reacts 3h, after reaction, is warming up to 170 DEG C and is distilled off at 140 DEG C
Low-boiling-point substance obtains performed polymer；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
15 parts, 20 parts of methyl methacrylate monomer, 4 parts of styrene monomer, 18 parts of methacrylic acid monomer, acrylic acid-2-ethyl oneself
6 parts of ester monomer, 80 parts of E-51 epoxy resin, 12 parts of emulsifier cetyl benzenesulfonic acid sodium, catalyst (copper chloride and stannous chloride
Mixed according to weight ratio 1:3) 2 parts, 340 parts of deionized water, high speed dispersion is uniform, then adds water soluble acrylic acid seed
4 parts of lotion, 85 DEG C are warming up to, 28 parts and 5 parts of initiator ammonium persulfate of performed polymer, after being added dropwise is added dropwise, continues insulation reaction
3h, then 68 DEG C are cooled to, 2 parts and 1 part of sodium hydrogensulfite of tert-butyl hydroperoxide, after being added dropwise are added, insulation reaction is continued
1h is cooled to 35 DEG C, adjusts pH to 8 with ammonium hydroxide, filtering and discharging simultaneously collects filtrate, obtains the second aqueous epoxy resin emulsion.
The filler used in coating is by molybdenum modified zinc phosphate, blanc fixe, titanium oxide, bentonite according to weight ratio 1:
2:0.4:0.6 mixing.
Water borne epoxy resin anticorrosive paint is made of component A and B component, and wherein component A includes in parts by weight
Following component: the first 28 parts of aqueous epoxy resin emulsion, 12 parts of the second aqueous epoxy resin emulsion, 0.5 part of dispersing agent, wetting agent
0.4 part, 3 parts of cosolvent, 32.4 parts of filler, 0.8 part of pH adjusting agent, 0.5 part of defoaming agent, 2.5 parts of coalescing agent, levelling agent 1.2
Part, 0.5 part of anti-flash rusting agent, 0.2 part of preservative, 18 parts of water；B component is epoxy curing agent, between component A and B component
Weight ratio is 12:1；
The preparation of water borne epoxy resin anticorrosive paint:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water 1500-2000rpm high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, 1500-2000rpm high-speed stirred is uniform, obtains coating.
Embodiment 3
The preparation of the second aqueous epoxy resin emulsion used in coating:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and reaction temperature is 110 DEG C, and the reaction time is 6h, after reaction, diatomite is added
It is neutralized, is then filtered, water and low-boiling point material is distilled off in filtrate decompression, obtains polyether polyol；Wherein, sweet
The molar ratio of oil, propylene oxide and KOH is 1:40:0.25；
Step 2, hydroxyl substitution reaction: in parts by weight, by 22 parts of polyether polyol, 0.15 part of sodium hydride, N, N- dimethyl
450 parts of formamide are uniformly mixed, and 0.7h is reacted at 25 DEG C, is filtered after reaction, replace in filtrate by Na poly-
Ethoxylated polyhydric alcohol；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
0.4 part of agent of connection, and reacted, 3h is reacted under the conditions of 75 DEG C, after reaction, evaporating solvent under reduced pressure obtains surface siloxanes
The polyether polyol of grafting；
Step 4, the preparation of performed polymer: in parts by weight, by 55 parts polysiloxane grafted of polyether polyol of surface, eight cyclohexyl methoxies
0.8 part of tetrasiloxane, 2.2 parts of the dimethyl silicone polymer of ethenyl blocking, γ -1.1 parts of trifluoro propyl methyl cyclotrisiloxane,
0.07 part of Pt catalyst mixing, after being replaced with nitrogen, reacts 2h, after reaction, is warming up to 168 DEG C and is distilled off at 135 DEG C
Low-boiling-point substance obtains performed polymer；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
13 parts, 17 parts of methyl methacrylate monomer, 3 parts of styrene monomer, 16 parts of methacrylic acid monomer, acrylic acid-2-ethyl oneself
5 parts of ester monomer, 75 parts of E-51 epoxy resin, 11 parts of emulsifier cetyl benzenesulfonic acid sodium, catalyst (copper chloride and stannous chloride
Mixed according to weight ratio 1:2.5) 1 part, 330 parts of deionized water, high speed dispersion is uniform, then adds water soluble acrylic acid kind
3 parts of sub- lotion is warming up to 82 DEG C, is added dropwise 23 parts and 3 parts of initiator ammonium persulfate of performed polymer, after being added dropwise, it is anti-to continue heat preservation
2h is answered, then is cooled to 67 DEG C, 1.5 parts and 0.7 part of sodium hydrogensulfite of tert-butyl hydroperoxide are added, after being added dropwise, after continuation of insurance
Temperature reaction 0.6h, is cooled to 32 DEG C, adjusts pH to 8 with ammonium hydroxide, filtering and discharging simultaneously collects filtrate, obtains the second aqueous epoxy resins
Lotion.
The filler used in coating is by molybdenum modified zinc phosphate, blanc fixe, titanium oxide, bentonite according to weight ratio 1:
1.8:0.3:0.5 mixing.
Water borne epoxy resin anticorrosive paint is made of component A and B component, and wherein component A includes in parts by weight
Following component: the first 35 parts of aqueous epoxy resin emulsion, 13.2 parts of the second aqueous epoxy resin emulsion, 0.3 part of dispersing agent, wetting
0.2 part of agent, 3 parts of cosolvent, 25 parts of filler, 0.6 part of pH adjusting agent, 0.3 part of defoaming agent, 2.5 parts of coalescing agent, levelling agent 1.2
Part, 0.5 part of anti-flash rusting agent, 0.2 part of preservative, 18 parts of water；B component is epoxy curing agent, between component A and B component
Weight ratio is 11:1；
The preparation of water borne epoxy resin anticorrosive paint:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water 1500-2000rpm high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, 1500-2000rpm high-speed stirred is uniform, obtains coating.
Reference examples 1
Difference with embodiment 3 is: polyether polyol with siloxane polymerization, but is not added in polymerizeing with acrylic emulsion.
The preparation of the second aqueous epoxy resin emulsion used in coating:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and reaction temperature is 110 DEG C, and the reaction time is 6h, after reaction, diatomite is added
It is neutralized, is then filtered, water and low-boiling point material is distilled off in filtrate decompression, obtains polyether polyol；Wherein, sweet
The molar ratio of oil, propylene oxide and KOH is 1:40:0.25；
Step 2, the preparation of performed polymer: in parts by weight, by 1 part of KH560 silane coupling agent, eight methoxy cyclotetrasiloxanes 0.8
Part, 2.2 parts of the dimethyl silicone polymer of ethenyl blocking, γ -1.1 parts of trifluoro propyl methyl cyclotrisiloxane, Pt catalyst
0.07 part of mixing, after being replaced with nitrogen, reacts 2h, after reaction, is warming up to 168 DEG C and low-boiling-point substance is distilled off, obtain at 135 DEG C
To performed polymer；
Step 3, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
13 parts, 17 parts of methyl methacrylate monomer, 3 parts of styrene monomer, 16 parts of methacrylic acid monomer, acrylic acid-2-ethyl oneself
5 parts of ester monomer, 75 parts of E-51 epoxy resin, 11 parts of emulsifier cetyl benzenesulfonic acid sodium, catalyst (copper chloride and stannous chloride
Mixed according to weight ratio 1:2.5) 1 part, 330 parts of deionized water, high speed dispersion is uniform, then adds water soluble acrylic acid kind
3 parts of sub- lotion, is warming up to 82 DEG C, and 4 parts of performed polymer of dropwise addition, 19 parts of polyether polyol and 3 parts of initiator ammonium persulfate are added dropwise
Afterwards, continue insulation reaction 2h, then be cooled to 67 DEG C, be added 1.5 parts and 0.7 part of sodium hydrogensulfite of tert-butyl hydroperoxide, be added dropwise
After, continue insulation reaction 0.6h, be cooled to 32 DEG C, adjust pH to 8 with ammonium hydroxide, filtering and discharging simultaneously collects filtrate, obtains the
Two aqueous epoxy resin emulsions.
The filler used in coating is by molybdenum modified zinc phosphate, blanc fixe, titanium oxide, bentonite according to weight ratio 1:
1.8:0.3:0.5 mixing.
Water borne epoxy resin anticorrosive paint is made of component A and B component, and wherein component A includes in parts by weight
Following component: the first 35 parts of aqueous epoxy resin emulsion, 13.2 parts of the second aqueous epoxy resin emulsion, 0.3 part of dispersing agent, wetting
0.2 part of agent, 3 parts of cosolvent, 25 parts of filler, 0.6 part of pH adjusting agent, 0.3 part of defoaming agent, 2.5 parts of coalescing agent, levelling agent 1.2
Part, 0.5 part of anti-flash rusting agent, 0.2 part of preservative, 18 parts of water；B component is epoxy curing agent, between component A and B component
Weight ratio is 11:1；
The preparation of water borne epoxy resin anticorrosive paint:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water 1500-2000rpm high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, 1500-2000rpm high-speed stirred is uniform, obtains coating.
Reference examples 2
Difference with embodiment 3 is: γ-trifluoro propyl methyl cyclotrisiloxane being added not in polysiloxanes polymerize.
The preparation of the second aqueous epoxy resin emulsion used in coating:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and reaction temperature is 110 DEG C, and the reaction time is 6h, after reaction, diatomite is added
It is neutralized, is then filtered, water and low-boiling point material is distilled off in filtrate decompression, obtains polyether polyol；Wherein, sweet
The molar ratio of oil, propylene oxide and KOH is 1:40:0.25；
Step 2, hydroxyl substitution reaction: in parts by weight, by 22 parts of polyether polyol, 0.15 part of sodium hydride, N, N- dimethyl
450 parts of formamide are uniformly mixed, and 0.7h is reacted at 25 DEG C, is filtered after reaction, replace in filtrate by Na poly-
Ethoxylated polyhydric alcohol；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
0.4 part of agent of connection, and reacted, 3h is reacted under the conditions of 75 DEG C, after reaction, evaporating solvent under reduced pressure obtains surface siloxanes
The polyether polyol of grafting；
Step 4, the preparation of performed polymer: in parts by weight, by 55 parts polysiloxane grafted of polyether polyol of surface, eight cyclohexyl methoxies
0.07 part of 2.2 parts of dimethyl silicone polymer, Pt catalyst mixing of 0.8 part of tetrasiloxane, ethenyl blocking, is replaced with nitrogen
Afterwards, 2h is reacted at 135 DEG C, after reaction, be warming up to 168 DEG C and low-boiling-point substance is distilled off, obtain performed polymer；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
13 parts, 17 parts of methyl methacrylate monomer, 3 parts of styrene monomer, 16 parts of methacrylic acid monomer, acrylic acid-2-ethyl oneself
5 parts of ester monomer, 75 parts of E-51 epoxy resin, 11 parts of emulsifier cetyl benzenesulfonic acid sodium, catalyst (copper chloride and stannous chloride
Mixed according to weight ratio 1:2.5) 1 part, 330 parts of deionized water, high speed dispersion is uniform, then adds water soluble acrylic acid kind
3 parts of sub- lotion is warming up to 82 DEG C, is added dropwise 23 parts and 3 parts of initiator ammonium persulfate of performed polymer, after being added dropwise, it is anti-to continue heat preservation
2h is answered, then is cooled to 67 DEG C, 1.5 parts and 0.7 part of sodium hydrogensulfite of tert-butyl hydroperoxide are added, after being added dropwise, after continuation of insurance
Temperature reaction 0.6h, is cooled to 32 DEG C, adjusts pH to 8 with ammonium hydroxide, filtering and discharging simultaneously collects filtrate, obtains the second aqueous epoxy resins
Lotion.
The filler used in coating is by molybdenum modified zinc phosphate, blanc fixe, titanium oxide, bentonite according to weight ratio 1:
1.8:0.3:0.5 mixing.
Water borne epoxy resin anticorrosive paint is made of component A and B component, and wherein component A includes in parts by weight
Following component: the first 35 parts of aqueous epoxy resin emulsion, 13.2 parts of the second aqueous epoxy resin emulsion, 0.3 part of dispersing agent, wetting
0.2 part of agent, 3 parts of cosolvent, 25 parts of filler, 0.6 part of pH adjusting agent, 0.3 part of defoaming agent, 2.5 parts of coalescing agent, levelling agent 1.2
Part, 0.5 part of anti-flash rusting agent, 0.2 part of preservative, 18 parts of water；B component is epoxy curing agent, between component A and B component
Weight ratio is 11:1；
The preparation of water borne epoxy resin anticorrosive paint:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water 1500-2000rpm high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, 1500-2000rpm high-speed stirred is uniform, obtains coating.
Reference examples 3
Difference with embodiment 3 is: the dimethyl silicone polymer of ethenyl blocking being added not in polysiloxanes polymerize.
The preparation of the second aqueous epoxy resin emulsion used in coating:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and reaction temperature is 110 DEG C, and the reaction time is 6h, after reaction, diatomite is added
It is neutralized, is then filtered, water and low-boiling point material is distilled off in filtrate decompression, obtains polyether polyol；Wherein, sweet
The molar ratio of oil, propylene oxide and KOH is 1:40:0.25；
Step 2, hydroxyl substitution reaction: in parts by weight, by 22 parts of polyether polyol, 0.15 part of sodium hydride, N, N- dimethyl
450 parts of formamide are uniformly mixed, and 0.7h is reacted at 25 DEG C, is filtered after reaction, replace in filtrate by Na poly-
Ethoxylated polyhydric alcohol；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
0.4 part of agent of connection, and reacted, 3h is reacted under the conditions of 75 DEG C, after reaction, evaporating solvent under reduced pressure obtains surface siloxanes
The polyether polyol of grafting；
Step 4, the preparation of performed polymer: in parts by weight, by 55 parts polysiloxane grafted of polyether polyol of surface, eight cyclohexyl methoxies
0.8 part of tetrasiloxane, γ -1.1 parts of trifluoro propyl methyl cyclotrisiloxane, 0.07 part of Pt catalyst mixing, after being replaced with nitrogen,
2h is reacted at 135 DEG C, after reaction, is warming up to 168 DEG C and low-boiling-point substance is distilled off, obtain performed polymer；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
13 parts, 17 parts of methyl methacrylate monomer, 3 parts of styrene monomer, 16 parts of methacrylic acid monomer, acrylic acid-2-ethyl oneself
5 parts of ester monomer, 75 parts of E-51 epoxy resin, 11 parts of emulsifier cetyl benzenesulfonic acid sodium, catalyst (copper chloride and stannous chloride
Mixed according to weight ratio 1:2.5) 1 part, 330 parts of deionized water, high speed dispersion is uniform, then adds water soluble acrylic acid kind
3 parts of sub- lotion is warming up to 82 DEG C, is added dropwise 23 parts and 3 parts of initiator ammonium persulfate of performed polymer, after being added dropwise, it is anti-to continue heat preservation
2h is answered, then is cooled to 67 DEG C, 1.5 parts and 0.7 part of sodium hydrogensulfite of tert-butyl hydroperoxide are added, after being added dropwise, after continuation of insurance
Temperature reaction 0.6h, is cooled to 32 DEG C, adjusts pH to 8 with ammonium hydroxide, filtering and discharging simultaneously collects filtrate, obtains the second aqueous epoxy resins
Lotion.
The filler used in coating is by molybdenum modified zinc phosphate, blanc fixe, titanium oxide, bentonite according to weight ratio 1:
1.8:0.3:0.5 mixing.
Water borne epoxy resin anticorrosive paint is made of component A and B component, and wherein component A includes in parts by weight
Following component: the first 35 parts of aqueous epoxy resin emulsion, 13.2 parts of the second aqueous epoxy resin emulsion, 0.3 part of dispersing agent, wetting
0.2 part of agent, 3 parts of cosolvent, 25 parts of filler, 0.6 part of pH adjusting agent, 0.3 part of defoaming agent, 2.5 parts of coalescing agent, levelling agent 1.2
Part, 0.5 part of anti-flash rusting agent, 0.2 part of preservative, 18 parts of water；B component is epoxy curing agent, between component A and B component
Weight ratio is 11:1；
The preparation of water borne epoxy resin anticorrosive paint:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water 1500-2000rpm high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, 1500-2000rpm high-speed stirred is uniform, obtains coating.
Reference examples 4
Difference with embodiment 3 is: the second aqueous epoxy emulsion is not added for the component A in coating.
Water borne epoxy resin anticorrosive paint is made of component A and B component, and wherein component A includes in parts by weight
Following component: the first 48.2 parts of aqueous epoxy resin emulsion, 0.3 part of dispersing agent, 0.2 part of wetting agent, 3 parts of cosolvent, filler 25
Part, 0.6 part of pH adjusting agent, 0.3 part of defoaming agent, 2.5 parts of coalescing agent, 1.2 parts of levelling agent, 0.5 part of anti-flash rusting agent, preservative
0.2 part, 18 parts of water；B component is epoxy curing agent, and the weight ratio between component A and B component is 11:1；
The preparation of water borne epoxy resin anticorrosive paint:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water 1500-2000rpm high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, anti-flash rusting agent, preservative and remaining deionized water, 1500- is added
2000rpm high-speed stirred is uniform, obtains coating.
The solid content of second aqueous epoxy resin latex characterizes
It takes 1.0~1.5 g lotions in the weighing bottle of constant mass, dries at 105 ± 2 DEG C to constant mass, count as the following formula
Solid content: solid content=m1/m2 × 100% is calculated, wherein m1 is the quality of solid content after drying, and m2 is sample mass；
The particle diameter distribution of second aqueous epoxy resin latex
Using the second aqueous epoxy resin being prepared in 2000 laser particle analyzer of Mastersizer measurement embodiment 3
The particles size and distribution of lotion, as shown in Figure 2, it can be seen that, average grain diameter about 117nm in lotion, and be in be evenly distributed.
After lotion dilutes 20 times, seen after sampling metal spraying processing with 200 type scanning electron microscope of Quanta produced in USA
It examines, as shown in Figure 3, it can be seen that the distribution of particles in lotion is relatively narrow.
The IR Characterization of second aqueous epoxy resin latex
As shown in Figure 1, the infared spectrum of aqueous epoxy resin emulsion is obtained in embodiment 3 and reference examples 1, it can from figure
Out, 2972cm-1、2899 cm-1Place is-CH on siloxanes3Stretching vibration characteristic absorption peak, 1261 cm-1It is on siloxanes
- CH3Deformation vibration the absworption peak, 1000-1100 cm -1What is located is the stretching vibration characteristic absorption peak of Si-O-Si, is shown
Me is contained in epoxy emulsion2SiO；1244cm -1Place is the stretching vibration characteristic absorption peak of C-O in epoxy resin, 914cm -1
Place is the absorption peak of epoxy group, 1724cm -1Locate the stretching vibration characteristic absorption peak of C=O of acrylate, wherein embodiment 3 exists
3450cm -1Locate no apparent absorption peak, and has 3450cm in reference examples 1 -1There is apparent absorption peak at place, this is stretching for-OH
Contracting vibration performance absorption peak illustrates that polyether polyol is no in reference examples 1 and is polymerize, and-OH can be detected.
The dry plate spraying process of coating
The component A of coating and B component are mixed, and adjust viscosity with distilled water, to spraying on tinplate, spontaneously dries 6
It is tested after it.
Mechanical property
By the impact resistance of GB/T1732-93 test composite coating, its pencil hardness is tested by GB/T6739-96.As a result such as
Under:
As can be seen from the table, the coating that coating provided by the invention is constituted has preferable hardness and flexibility.Pass through implementation
It, can effective landform after example 3 and reference examples 1 can be seen that by the way that polyether polyol and siloxanes are first prepared performed polymer
At copolymerization hybridization network, relative to, directly by modified by polyether glycol acrylic resin, coating has preferably soft in reference examples 1
Toughness and hardness.
Resistance to UV aging
The sample of coating is put into the ultraviolet accelerated ageing case of LUV-2, is 310nm ultraviolet lamp irradiation 72h with wavelength, uses
Dataflash110 type color difference meter measures its color difference, while testing the flexibility and hardness of coating layer.
As can be seen from the above table, coating of the invention has excellent uvioresistant performance, mainly due in coating
It is crosslinked γ-trifluoro propyl methyl cyclotrisiloxane, so that coating is improved ultraviolet weatherability, by ultraviolet irradiation
Afterwards, color difference is smaller, and significant change does not occur for the hardness of coating and flexibility.
Salt spray resistance
It is tested by GB/T1771, test plate (panel) is placed in salt fog cabinet with 20 °, every 12h observes a test result, records coating table
Face visual condition.
As can be seen from the table, epoxy coating of the invention has preferable salt spray resistance, routine in reference examples 4
The salt spray resistance of aqueous epoxide resin paint be generally 200h or so, the salt-fog resistant time of the coating in the present invention can reach
To 400h or more；The comparison of embodiment 3 and reference examples 1, which can be seen that, prepares performed polymer with silicone cross-linked for polyether polyol
Afterwards, there is better salt fog resistance by the water soluble acrylic acid epoxy emulsion that emulsion polymerization obtains；Embodiment 3 and reference examples 2
Comparison can effectively improve the salt fog resistance of coating as can be seen that flucride siloxane is added；Embodiment 3 and reference examples 3
Comparison is as can be seen that can use its C=C key and propylene by the performed polymer that the siloxanes of ethenyl blocking is prepared
Acid monomers are crosslinked, and hybridisation emulsion is obtained, so that lotion has better salt spray resistance.
Claims (10)
1. a kind of water borne epoxy resin anticorrosive paint, is made of component A and B component, which is characterized in that wherein component A includes
Following component in percentage by weight: the first aqueous epoxy resin emulsion 25-35%, the second aqueous epoxy resin emulsion 8-
15%, dispersing agent 0.3-0.5%, wetting agent 0.2-0.4%, cosolvent 2-3%, filler 25-35%, pH adjusting agent 0.6-0.8%, defoaming
Agent 0.3-0.5%, coalescing agent 2-2.5%, levelling agent 0.5-1.2%, anti-flash rusting agent 0.3-0.5%, preservative 0.1-0.2%, water
15-18%；B component is epoxy curing agent, and the weight ratio between component A and B component is 10-12:1.
2. the preparation method of the second aqueous epoxy resin emulsion described in, includes the following steps:
Step 1, the preparation of polyether polyol: glycerol, KOH being added in reaction kettle, replaced with nitrogen, then vacuumize dehydration, then
Propylene oxide is added, heating is reacted, and after reaction, diatomite is added and is neutralized, is then filtered, filtrate decompression
Water and low-boiling point material is distilled off, obtains polyether polyol；Wherein, the molar ratio of glycerol, propylene oxide and KOH are 1:35-
50:0.2-0.3；
Step 2, hydroxyl substitution reaction: in parts by weight, by 20-25 parts of polyether polyol, 0.1-0.2 parts of sodium hydride, N, N-
400-500 parts of dimethylformamide are uniformly mixed, and are reacted, are filtered at room temperature after reaction, are warp in filtrate
Cross the polyether polyol of Na substitution；
The surface of step 3, polyether polyol is polysiloxane grafted: got in step 2 filtrate being continued to add KH560 silane idol
Agent 0.3-0.5 parts of connection, and reacted, after reaction, evaporating solvent under reduced pressure obtains the polysiloxane grafted polyether polyols in surface
Alcohol；
Step 4, the preparation of performed polymer: in parts by weight, by 50-65 parts polysiloxane grafted of polyether polyol of surface, eight first
1-0.5 parts of oxygen cyclotetrasiloxane, 2-2.5 parts of the dimethyl silicone polymer of ethenyl blocking, γ-three silicon oxygen of trifluoro propyl methyl ring
0.8-1.2 parts of alkane, 0.05-0.1 parts of Pt catalyst mixing, after being replaced with nitrogen, are reacted, after reaction, heating distillation
Low-boiling-point substance is removed, performed polymer is obtained；
Step 5, the preparation of acrylated epoxy lotion: in a nitrogen atmosphere, in parts by weight, by Butyl Acrylate Monomer
12-15 parts, 15-20 parts of methyl methacrylate monomer, 2-4 parts of styrene monomer, 15-18 parts of methacrylic acid monomer, propylene
4-6 parts of acid -2- ethyl hexyl acrylate monomers, 70-80 parts of E-51 epoxy resin, 10-12 parts of emulsifier, 0.5-2 parts of catalyst, deionization
320-340 parts of water, high speed dispersion is uniform, then adds 2-4 parts of seed emulsion, is warming up to 80-85 DEG C, and performed polymer 20- is added dropwise
28 parts and initiator 2-5 parts, after being added dropwise, continues insulation reaction 1-3h, then be cooled to 65-68 DEG C, t-butyl peroxy is added
Change hydrogen 1-2 parts and sodium hydrogensulfite 0.5-1 parts, after being added dropwise, continues insulation reaction 0.5-1h, be cooled to 30-35 DEG C, use ammonia
Water adjusts pH to 7.5-8, and filtering and discharging simultaneously collects filtrate, obtains the second aqueous epoxy resin emulsion.
3. water borne epoxy resin anticorrosive paint according to claim 1, which is characterized in that in the step 1, reaction temperature
Degree is 105-115 DEG C, and the reaction time is 5-8h.
4. water borne epoxy resin anticorrosive paint according to claim 1, which is characterized in that in the step 2, at room temperature
Reaction is carried out to refer to and react 0.5-1h at 20-30 DEG C.
5. water borne epoxy resin anticorrosive paint according to claim 1, which is characterized in that in the step 3, reaction is
Refer to and reacts 2-4h under the conditions of 70-80 DEG C.
6. water borne epoxy resin anticorrosive paint according to claim 1, which is characterized in that in the step 4, reaction temperature
Degree is to react 1-3h at 130-140 DEG C, and the temperature that low-boiling-point substance is distilled off is 165-170 DEG C.
7. water borne epoxy resin anticorrosive paint according to claim 1, which is characterized in that in the step 5, emulsifier
It is cetyl benzenesulfonic acid sodium；Catalyst is to be mixed by copper chloride and stannous chloride according to weight ratio 1:2-3；Initiator is
Ammonium persulfate.
8. water borne epoxy resin anticorrosive paint according to claim 1, which is characterized in that the filler is modified by molybdenum
Trbasic zinc phosphate, blanc fixe, titanium oxide, bentonite are mixed according to weight ratio 1:1.5-2:0.2-0.4:0.3-0.6.
9. the preparation method of water borne epoxy resin anticorrosive paint described in claim 1, which comprises the steps of:
By dispersing agent, wetting agent, cosolvent, filler, pH adjusting agent, defoaming agent, coalescing agent, levelling agent and a part of deionization
Water high-speed stirred is uniform, is then ground；
It is further continued for that the first aqueous epoxy resin emulsion, the second aqueous epoxy resin emulsion, anti-flash rusting agent, preservative is added and remains
Under deionized water, high-speed stirred is uniform, obtains coating.
10. the preparation method of water borne epoxy resin anticorrosive paint according to claim 8, which is characterized in that the height
Speed stirring refers to stirs under 1500-2000rpm revolving speed.
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| CN110041795A (en) * | 2019-03-22 | 2019-07-23 | 河北晨阳工贸集团有限公司 | A kind of water-base epoxy priming paint and preparation method thereof |
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| CN114891393A (en) * | 2022-05-19 | 2022-08-12 | 广东阿诺捷喷墨科技有限公司 | UV ink for tape measure, preparation method of UV ink and tape measure |
| CN115160929A (en) * | 2022-08-09 | 2022-10-11 | 任丘市嘉华电讯器材有限公司 | Corrosion-resistant steel strand and preparation method thereof |
| CN116285492A (en) * | 2023-02-01 | 2023-06-23 | 玉林师范学院 | Water-based epoxy resin black ink and preparation method thereof |
| CN117050318A (en) * | 2023-10-10 | 2023-11-14 | 络合高新材料(上海)有限公司 | Modified saturated carbon ring type epoxy resin and preparation method and application thereof |
| CN117050318B (en) * | 2023-10-10 | 2023-12-19 | 络合高新材料(上海)有限公司 | Modified saturated carbon ring type epoxy resin and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111548461A (en) | 2020-08-18 |
| CN109337518B (en) | 2020-09-01 |
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