CN108570132A - The hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin - Google Patents
The hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin Download PDFInfo
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- CN108570132A CN108570132A CN201710142499.3A CN201710142499A CN108570132A CN 108570132 A CN108570132 A CN 108570132A CN 201710142499 A CN201710142499 A CN 201710142499A CN 108570132 A CN108570132 A CN 108570132A
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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
- C08F283/105—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 on to unsaturated polymers containing more than one epoxy radical per molecule
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1472—Fatty acids
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Abstract
The present invention provides each component parts by weight in the hybridisation emulsion synthesizing formula of a kind of epoxy ester resin aqueous dispersion and acrylic resin to be：5 90 parts of epoxy ester resin aqueous dispersion, 1 50 parts of acrylic monomer, 07 parts of emulsifier, 02 parts of pH value adjustment agent, 0.05 7 parts of initiator, 0 60 parts of water.The advantages of present invention is that epoxy ester resin and acrylic resin are carried out hybrid polymer, and the resin emulsion obtained from is comprehensive and two kinds of resins, the shortcomings that overcoming two kinds of resins, have high solid low viscosity, quick-drying, preferable film forming, glossiness is high, resistance to ag(e)ing and the good feature of salt spray resistance.
Description
Technical field
The present invention relates to technical field of aqueous paint, in particular to a kind of epoxy ester resin aqueous dispersion and propylene
The hybridisation emulsion of acid resin.
Background technology
Currently, one-component is from the water paint product of dryness, there are two main classes, and one kind is the alkyd resin of solvent method synthesis,
The aqueous dispersion of epoxy ester resin, they the advantages of for film formation at low temp it is good, gloss, salt spray resistance are good, disadvantage be in water
Hydrolysis is than more serious, and resistance to ag(e)ing is poor, is limited by resin viscosity, molecular weight mostly very little, leans on oxidation cross-linked film forming, does
Dry speed is very slow, Gu containing very low；Another kind is exactly the acrylic emulsion of emulsion polymerization synthesis, and the molecular weight of molecule is very big,
Have the characteristics that high solid low viscosity, there is preferable dryness, resistance to ag(e)ing, but film formation at low temp is poor, salt spray resistance is very poor.
Invention content
It is an object of the invention to overcome the defect of above two resin, a kind of epoxy ester resin aqueous dispersion and third are provided
The hybridisation emulsion of olefin(e) acid resin, to realize the high solid low viscosity of resin, quick-drying, preferable film forming, glossiness, resistance to ag(e)ing and resistance to
It is salt fog.
On one side, the present invention proposes a kind of hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin, closes
It is at each component parts by weight in formula：5-90 parts of epoxy ester resin aqueous dispersion, 1-50 parts of acrylic monomer, emulsifier 0-7
Part, 0-2 parts of pH value adjustment agent, 0.05-7 parts of initiator, 0-60 parts of water.
Further, each in synthesizing formula in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin
Ingredients weight parts are：20-80 parts of epoxy ester resin aqueous dispersion, 2-40 parts of acrylic monomer, 0.01-5 parts of emulsifier, pH value
0-1 parts of conditioning agent, 0.1-5 parts of initiator, 5-40 parts of water.
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the acrylic compounds
Monomer is styrene, (methyl) acrylic acid, methyl methacrylate, (methyl) butyl acrylate, (methyl) isobomyl acrylate
Ester, (methyl) ethyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate and methyl propenoic acid glycidyl
At least one of ester.
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the initiator
For potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide, benzoyl peroxide, peroxidized t-butyl perbenzoate, peroxidating bay
Acyl, benzoyl peroxide/sucrose, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/sodium pyrosulfite, benzoyl peroxide
Formyl/N, accelerine, ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, hydrogen peroxide/tartaric acid,
Hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/sulfuric acid ferrous iron, benzoyl peroxide/N, N- diethylbenzenes
Amine, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, isopropyl benzene hydroperoxide/chlorination
Ferrous iron, one kind in the aziridine of potassium peroxydisulfate/frerrous chloride, hydrogen peroxide/frerrous chloride and isopropyl benzene hydroperoxide/tetra- or
Two kinds.
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the emulsifier is
Polyethylene glycol oxide carboxylic acid esters, polyalcohol carboxylic for metal carboxylate, alkylsurfuric acid salt, Sulfonates and HLB value in 9-14
At least one of esters of gallic acid, polyoxyethylated polyols carboxylic acid esters, polyoxyethylene alkyl ether class and ethyoxyl alcohols.
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the epoxy-ester tree
Each component parts by weight are in fat aqueous dispersion formula：15-40 parts of epoxy resin, 11-40 parts of aliphatic acid, acrylic monomer 2-8
Part, 4.5-35 parts of acrylic ester monomer, 0-0.1 parts of catalyst, 0.6-2 parts of initiator content, 20-40 parts of solvent, neutralizer
5-15 parts, 1-5 parts of drier, 100-200 parts of water.
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the catalyst is
Organotin or zinc class catalyst；The neutralizer is triethylamine, N, at least one in N- dimethylethanolamines and methyl morpholine
Kind；The drier is cobalt, zirconium, zinc, calcium class drier or combinations thereof object.
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the catalyst is
Zinc oxide or zinc naphthenate.
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the initiator is
Perbenzoic acid, peroxidized t-butyl perbenzoate, di-tert-butyl peroxide, two t-amyl peroxy compounds and peroxidating -2-
One or both of ethylhexanate (pentyl ester).
Further, in the hybridisation emulsion of above-mentioned epoxy ester resin aqueous dispersion and acrylic resin, the solvent is two
Butyl glycol ether, dipropylene, n-butanol, ethylene glycol monobutyl ether, propandiol butyl ether, propylene glycol monomethyl ether, ethyl alcohol, isopropanol
At least one of with sec-butyl alcohol.
The main body of the embodiment of the present invention is the hybridisation emulsion of epoxy ester resin and acrylic resin, wherein the moisture of epoxy-ester
The advantages of granular media is that film formation at low temp is good, and glossiness is high, and salt spray resistance is good, and disadvantage is to be hydrolyzed in water than more serious, resistance to old
The property changed is poor, is limited by resin viscosity, molecular weight very little, generally thousands of, leans on oxidation cross-linked film forming, rate of drying is very
Slowly, Gu containing very low；Acrylic emulsion generally arrives hundreds of thousands since the molecular weight of molecule is very big tens of thousands of, with high solid low viscosity
Feature has preferable quick-drying, resistance to ag(e)ing, but film formation at low temp is poor, salt fog poor performance, and the embodiment of the present invention is by ring
The advantages of oxygen ester resin and acrylic resin carry out hybrid polymer, and the resin emulsion obtained from combines two kinds of resins, overcomes
The shortcomings that two kinds of resins, has high solid low viscosity, and quick-drying, preferable film forming, glossiness is high, resistance to ag(e)ing and salt fog resistance
The good feature of energy.
Specific implementation mode
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention rather than to patent requirements of the present invention
Limitation.
The present invention provides a kind of hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin, lotion synthesis is matched
Each component parts by weight are in side：5-90 parts of epoxy ester resin aqueous dispersion, 1-50 parts of acrylic monomer, 0-7 parts of emulsifier, PH
It is worth 0-2 parts of conditioning agent, 0.05-7 parts of initiator, 0-60 parts of water.Preferably, the parts by weight of each component are as follows in formula：Epoxy-ester
20-80 parts of resin water dispersion, 2-40 parts of acrylic monomer, 0.01-5 parts of emulsifier, 0-1 parts of pH value adjustment agent, initiator
0.1-5 parts, 5-40 parts of water.
Wherein：Epoxy ester resin aqueous dispersion is that epoxy resin is passed through fatty acid modified and acrylic acid and esters of acrylic acid
Modified product.Each component parts by weight are in epoxy ester resin aqueous dispersion formula：15-40 parts of epoxy resin, aliphatic acid 11-
40 parts, 2-8 parts of acrylic monomer, 4.5-35 parts of acrylic ester monomer, 0-0.1 parts of catalyst, initiator content 0.6-2
Part, 20-40 parts of solvent, 5-15 parts of neutralizer, 1-5 parts of drier, 100-200 parts of water.Preferably, epoxy ester resin aqueous dispersion
Each component parts by weight are in formula：19-35 parts of epoxy resin, 12-27 parts of aliphatic acid, 2-4 parts of acrylic monomer, acrylic acid
5-30 parts of esters monomer, 0-0.08 parts of catalyst, 0.6-1.6 parts of initiator, 20-30 parts of solvent, 5-10 parts of neutralizer, drier
1-5 parts, 100-150 parts of water.
Epoxy resin in epoxy ester resin aqueous dispersion formula can be A type epoxy resin, and preferably epoxide equivalent exists
Epoxy resin within the scope of 500-3000 is one or two kinds of.Such as E12 types epoxy resin, E03 types epoxy resin, E14 type ring oxygen
At least one of resin, E51 type epoxy resin.
Aliphatic acid for being modified to epoxy resin can be unsaturated fatty acid, be specifically as follows linolenic acid,
One or more of behenic acid, linoleic acid, tall oil acid, dehydrated castor oleic acid.
Acrylic monomer for being modified to epoxy resin is the one or two of acrylic acid, methacrylic acid.
Acrylic ester monomer can be styrene, methyl methacrylate, (methyl) butyl acrylate, methacrylic acid
One or more of isobornyl thiocyanoacetate, (methyl) hydroxy-ethyl acrylate, glycidyl methacrylate.
Catalyst is organotin or zinc class catalyst, it is preferable that catalyst can be zinc oxide, one in zinc naphthenate
Kind.Initiator is perbenzoic acid, peroxidized t-butyl perbenzoate, di-tert-butyl peroxide, two t-amyl peroxy compounds,
The one or two of peroxide -2-ethyl hexanoic acid tert-butyl (pentyl ester).
Neutralizer is triethylamine, N, one or more of N- dimethylethanolamines and methyl morpholine.
Drier is cobalt, zirconium, zinc, calcium, barium class drier or combinations thereof object.Wherein, drier cobalt, zirconium are dry for main reminder
Agent can be added individually, drier activator supplemented by zinc or calcium, with (0-5):1 mass ratio and main drier are used in mixed way, such as cobalt zinc
Mixed drier, cobalt barium zinc drier etc..
Solvent is butyl, dipropylene, n-butanol, ethylene glycol monobutyl ether, propandiol butyl ether, propylene glycol
One or more of methyl ether, ethyl alcohol, isopropanol, sec-butyl alcohol.
Acrylic monomer in hybridisation emulsion formula provided in this embodiment can be acrylic compounds and its list of esters
Body.Specifically, acrylic monomer is selected from styrene, (methyl) acrylic acid, methyl methacrylate, (methyl) acrylic acid fourth
Ester, (methyl) isobornyl acrylate, (methyl) ethyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) acrylic acid hydroxypropyl
At least one of ester and glycidyl methacrylate.It should be noted that (methyl) acrylic acid includes methacrylic acid
And acrylic acid, (methyl) butyl acrylate include butyl methacrylate and butyl acrylate, (methyl) isobornyl acrylate
Including isobornyl methacrylate and isobornyl acrylate, (methyl) ethyl acrylate includes ethyl methacrylate and third
Olefin(e) acid ethyl ester, (methyl) hydroxy-ethyl acrylate include hydroxyethyl methacrylate and hydroxy-ethyl acrylate, (methyl) acrylic acid hydroxyl
Propyl ester includes hydroxy propyl methacrylate and hydroxypropyl acrylate.
Initiator in hybridisation emulsion formula is selected from potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide, benzoyl peroxide first
Acyl, peroxidized t-butyl perbenzoate, lauroyl peroxide and redox initiator, such as benzoyl peroxide/sucrose, uncle
Butylhydroperoxide/rongalite, tert-butyl hydroperoxide/sodium pyrosulfite, benzoyl peroxide/N, accelerine, mistake
Ammonium sulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, hydrogen peroxide/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, persulfuric acid
Ammonium/ferrous sulfate, hydrogen peroxide/sulfuric acid ferrous iron, benzoyl peroxide/N, N- diethylanilines, benzoyl peroxide/pyrophosphoric acid
Ferrous iron, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, isopropyl benzene hydroperoxide/frerrous chloride, potassium peroxydisulfate/frerrous chloride,
One or both of aziridine of hydrogen peroxide/frerrous chloride and isopropyl benzene hydroperoxide/tetra-.
Emulsifier in hybridisation emulsion formula is metal carboxylate, alkylsurfuric acid salt, Sulfonates and HLB value in 9-14
Polyethylene glycol oxide carboxylic acid esters, polyol carboxylate's class, polyoxyethylated polyols carboxylic acid esters, polyoxyethylene alkyl ether class
At least one of with ethyoxyl alcohols.I.e.：Emulsifier in the embodiment of the present invention can be selected from anion emulsifier (such as carboxylic acid
Salt, alkylsurfuric acid salt and Sulfonates) and HLB value 9-14 nonionic emulsifier (such as polyethylene glycol oxide carboxylic acid esters,
Polyol carboxylate's class, polyoxyethylated polyols carboxylic acid esters, polyoxyethylene alkyl ether class and ethyoxyl alcohols) at least
It is a kind of.
Any one PH conditioning agent that pH value adjustment agent in hybridisation emulsion formula is well known to those skilled in the art, example
Such as sodium bicarbonate.
The preparation method of the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin provided by the invention, including with
Lower step：
(1) epoxy ester aqueous dispersion preparation process：First step：By epoxy ester aqueous dispersion be formulated in epoxy resin,
Aliphatic acid and catalyst are added in reaction kettle, and stirring is warming up to 170-210 DEG C, keep the temperature to the acid value of material and are less than 10mg KOH/g
Fatty acid modified epoxy resin is obtained, and is cooled to 80-160 DEG C, the partial solvent being added in formula dilutes to obtain ring
Oxygen ester resin is for use.
When it is implemented, 5-7 parts of dimethylbenzene can be added into reaction kettle, on the one hand, dimethylbenzene can make epoxy resin and
Aliphatic acid adequately dispersion is in the reaction system；Another aspect dimethylbenzene circulating reflux can take the water that reaction generates out of, promote anti-
It should carry out to forward direction, when the acid value of reaction to material is less than 10mg KOH/g, can be extracted out dimethylbenzene with vacuum.
Second step, the acrylic monomer in being formulated to epoxy ester aqueous dispersion, addition portion in acrylic ester monomer
Divide initiator to be uniformly mixed, at 110-150 DEG C, was added dropwise in above-mentioned fatty acid modified epoxy ester resin, is added dropwise with 2-4 hours
Initiator is added after the completion to conversion ratio up to 95% or more, and neutralizer and drier are added into reacted material, stirring
Uniformly, add water emulsification while stirring, obtain epoxy ester aqueous dispersion.When it is implemented, reaction temperature is according to different initiators
To determine, such as with the reaction temperature of benzoyl peroxide, peroxidized t-butyl perbenzoate it is 110-130 DEG C, uses di-t-butyl
The reaction temperature of (amyl) peroxide is 140-150 DEG C, and the reaction temperature of peroxide -2-ethyl hexanoic acid tert-butyl (pentyl ester) is
130-140℃.Initiator can be added after being added dropwise to complete to conversion ratio up to 95% or more, the resinous acid value 20- obtained at this time
30mgKOH/g, at this point, neutralizer is added into reaction system, drier stirs evenly, and water emulsification is added while stirring, obtains
Lotion PH 8-10, admittedly contain 30-40%, fineness in 25um hereinafter, lotion acid value be 10-15mgKOH/g.
In addition, it can include third step, that is, depressurize solvent removal step：Epoxy ester aqueous dispersion is added to the container,
It is warming up to 30-70 DEG C, gradually opens big vacuum, deviates from most of solvent in epoxy ester aqueous dispersion under a reduced pressure, after having taken off
Water is added to be adjusted to suitably admittedly contain.Gained epoxy ester aqueous dispersion contains 30-50%, acid value 10-15mgKOH/g, VOC7% admittedly
Hereinafter, pH value is 8-10.
(2) acrylic monomer pre-emulsification step：Under room temperature, in protective atmosphere, by the epoxy of 0-90% in step (1)
The water of ester aqueous dispersion, the emulsifier of 50%-100% and 50%-100% is first added in reaction vessel, and hybridisation emulsion is formulated
In 100% acrylic monomer and the initiator elder generation mixed dissolution of 50%-100%, add reaction vessel high speed stirring
10-40 minutes, the pre-emulsion of acrylic monomer is obtained, it is spare.By high-speed stirred, acrylic monomer can be by abundant breast
Change, prepares for reaction in next step.
(3) epoxy ester resin aqueous dispersion and acrylic resin hybridisation step：In protective atmosphere, for example, entire reaction
It is all passed through nitrogen in the process, by the 5%-20% of the pre-emulsion of the acrylic monomer obtained in step (2), hybridisation emulsion formula
In in remaining emulsifier, initiator and water and step (1) in remaining epoxy ester aqueous dispersion and hybridisation emulsion formula
PH conditioning agents are added in reaction vessel, and 30-85 DEG C is warming up under stirring, react 20-60 minutes, start a dropping step
(2) remaining pre-emulsion in, time for adding are 1-8 hours, add initiator during being added dropwise, are protected at 50-90 DEG C after dripping
It is 1.5-6.5 hours warm.First plus the 5%-20% of the pre-emulsion of acrylic monomer can effectively control reaction speed, due to selecting
Initiator in contain redox initiator, can initiation reaction at a lower temperature, therefore reaction temperature can control
30-85 DEG C, the energy is saved.It is more thorough in order to make reaction carry out, it can be according to the actual conditions of reaction, when one section
Between, such as 1 hour, add an initiator.
In the above preparation method, those skilled in the art can select the technological parameter in hybridisation process.A kind of excellent
In the embodiment of choosing, in step (3), it is warming up to 75-85 DEG C under stirring, is kept the temperature at 80-85 DEG C after dripping.
In another preferred embodiment, in step (3), the time of heat preservation can be 2-5 hours.
In epoxy ester aqueous dispersion preparation process, by epoxy resin with a certain amount of fatty acid modified, after drier is added,
Performance with preferable air drying；Carry out graft copolymerization using acrylic acid (ester), using in acrylic acid and provide it is water-soluble,
It because acrylic acid is copolyreaction, avoids water soluble group and is detached from main chain, make more stable after resin Water-borne modification.
In addition the method that hybridisation process of the present invention uses emulsion polymerization, reaction process need not add solvent, be conducive to do
At low VOC (volatile organic solvent) environment-friendly products；Also, emulsion polymerisation process is used, the viscosity of lotion can be reduced, carried
The solid content of high lotion, to during manufacturing coating, the solid content of coating be improved, reduce volatile object
Matter, to energy saving.In addition, the introducing of (methyl) acrylicacidandesters, can adjust the glass transition temperature of resin, so as to
To make high glass transition temperature, high rigidity, the product of quick-dry type, solving water-base epoxy ester industrial paint, drying is very slow at normal temperatures
The problem of；Also, the epoxy ester resin dispersion due to being synthesized with solvent method carries out grafting hydridization with acrylic resin so that
Lotion after hydridization has good filming performance, and can be oxidation cross-linked in air, so making final product than one
As the paint film of acrylic emulsion that does of emulsion polymerisation process it is finer and close, water-fast, salt spray resistance is more superior.
Below in conjunction with specific embodiment, the present invention will be further described.
Embodiment 1
(1) by 280 grams of epoxy resin E12,30 grams of dehydrated castor oleic acid, 200 grams of tall oil acid, 0.5 gram of addition of zinc oxide
Stirring is warming up to 200-210 DEG C in reaction bulb, and reaction is to acid value 5mgKOH/g hereinafter, being cooled to 130 DEG C of addition n-butanols 220
Gram, 110-115 DEG C is kept the temperature at, fatty acid modified epoxy resin is obtained；
(2) by 22 grams of acrylic acid, 100 grams of mixing of methyl methacrylate are added 5 grams of peroxidized t-butyl perbenzoate, mix
It uses instill in material above after closing uniformly within 2-3 hours, adds 5 grams of peroxidized t-butyl perbenzoate after dripping in three times, most
3 hours are kept the temperature afterwards, obtain acrylic acid, fatty acid modified epoxy resin；
(3) resin of having changed property is cooled to 80 DEG C, 55 grams of triethylamines is added, 22 grams of cobalts, zinc mixed drier, stirring is
It is even, 40 DEG C of 1000 grams of distilled water is instilled in resin, emulsification obtains epoxy ester aqueous dispersion；
(4) lotion emulsified is put into there-necked flask, installs vacuum extractor, temperature is controlled at 45-50 DEG C, will be true
Sky is gradually opened greatly until there is solvent outflow, collects the quantity of solvent of abjection, and detect, until in lotion butanol content 1% hereinafter,
Finally 40-44% is contained in water consolidating for lotion of adjustment；
(5) under nitrogen atmosphere protection, 400 grams of epoxy ester aqueous dispersion made from above-mentioned steps, hybridisation emulsion formula are taken
In emulsifier AS801 (alkylol poly-alkoxyl sodium sulfate salt and methyl oxirane, ethylene oxide and single (2- ethylhexyls)
The mixture of the polymer of ether) 2.2 grams, 40 grams of water be added to the container, 60 grams of methyl methacrylate and azo-bis-isobutyl cyanide 0.8
Gram first mixed dissolution, adds container high speed and stirs 3 minutes, obtain the pre-emulsion of acrylic monomer；
(6) continue to be passed through nitrogen into reaction system, by 100 grams of remaining epoxy ester aqueous dispersion, hydridization in step (3)
1 gram of remaining emulsifier AS801 in emulsion formulations, 0.08 gram of ammonium persulfate, 0.1 gram of sodium bicarbonate in hybridisation emulsion formula,
With 22 grams of the pre-emulsion of the acrylic monomer prepared in step (5), it is added in reaction bulb, warming while stirring is to 80 DEG C, instead
It answers 30 minutes, starts the pre-emulsion of remaining acrylic monomer in a dropping step (5), be added dropwise to complete, be added dropwise with 1-2 hours
Ammonium persulfate is added according to the concrete condition of reaction in journey, 1.5-2 hours is kept the temperature at 80 DEG C after dripping, cools to 40 DEG C, mistake
Filter out material.It obtains lotion and contains 50%, viscosity 35mPa.s admittedly, after painting varnish paint film, surface drying time is 30 minutes, does solid work the time
It is 10 hours, glossiness 98%, water-fast 24 hours, salt spray resistance 196 hours.
Embodiment 2
(1) by 175 grams of epoxy resin E12,28 grams of dehydrated castor oleic acid, 112 grams of linolenic acid, 0.1 gram of zinc naphthenate plus
Enter stirring in reaction bulb and be warming up to 205-210 DEG C, reaction is to acid value 7mgKOH/g hereinafter, being cooled to 160 DEG C of addition ethylene glycol fourths
120 grams of ether.145-150 DEG C is kept the temperature at, fatty acid modified epoxy resin is obtained；
(2) by 21 grams of acrylic acid, 3 grams of di-tert-butyl peroxide is added in 90 grams of mixing of methyl methacrylate, and mixing is equal
It uses instill in material above after even within 3-4 hours, adds 1 gram of di-tert-butyl peroxide after dripping in three times, finally keep the temperature 3
A hour obtains acrylic acid, fatty acid modified epoxy resin；
(3) resin of having changed property is cooled to 80 DEG C, 25 grams of N is added, N- dimethylethanolamines stir evenly, by 40 DEG C
643 grams of distilled water instill in resins, emulsification obtains epoxy ester aqueous dispersion, adjusts solid containing to 35%；
(4) under nitrogen atmosphere protection, 360 grams of epoxy ester aqueous dispersion made from above-mentioned steps, hybridisation emulsion formula are taken
In 2.2 grams of emulsifier AEO-9 (ethoxy alcohol), 40 grams of water is added to the container, 40 grams of methyl methacrylate and metering system
2 grams of sour isobornyl thiocyanoacetate and the first mixed dissolution of 0.65 gram of azo-bis-isobutyl cyanide, add container high speed and stir 20 minutes, obtain third
The pre-emulsion of alkene acrylic monomer；
(5) continue to be passed through nitrogen into reaction system, by 40 grams of remaining epoxy ester aqueous dispersion, hydridization in step (3)
Sodium bicarbonate in emulsion formulations in 1 gram of remaining emulsifier, 0.08 gram of potassium peroxydisulfate, 10 grams of water and hybridisation emulsion formula
0.1 gram with step (4) in prepare acrylic monomer 20 grams of pre-emulsion, be added reaction bulb in, warming while stirring to 83
DEG C, it reacts 30 minutes, starts the pre-emulsion of remaining acrylic monomer in a dropping step (4), be added dropwise to complete with 2-3 hours,
Potassium peroxydisulfate is added according to the concrete condition of reaction during dropwise addition, 2-2.5 hours is kept the temperature at 83 DEG C after dripping, cools to 40
DEG C, filtering and discharging.It obtains lotion and contains 36%, viscosity 80mPa.s admittedly, after painting varnish paint film, surface drying time is 20 minutes, is done solid work
Time is 2 hours, glossiness 95%, water-fast 72 hours, salt spray resistance 96 hours.
Embodiment 3
(1) by the mixture of 175 grams of epoxy resin E12 and epoxy resin E03,28 grams of dehydrated castor oleic acid, linolenic acid
112 grams, in 0.1 gram of addition reaction bulb of mixture of zinc oxide and zinc naphthenate stirring be warming up to 180-190 DEG C, reaction to acid value
9mgKOH/g is hereinafter, be cooled to 150 DEG C of 110 grams of butyl glycol ethers of addition.130-135 DEG C is kept the temperature at, aliphatic acid is obtained
Modified epoxy resin；
(2) by 14 grams of acrylic acid, 15 grams of methyl methacrylate, 30 grams of mixing of styrene, two t-amyl peroxies of addition
3 grams of object uses instill in material above within 3-4 hours, adds di-tert-butyl peroxide 1 after dripping in three times after mixing
Gram, 3 hours finally are kept the temperature, obtain acrylic acid, fatty acid modified epoxy resin；
(3) resin of having changed property is cooled to 80 DEG C, 16 grams of N is added, N- dimethylethanolamines stir evenly, by 40 DEG C
565 grams of distilled water instill in resins, emulsification obtains epoxy ester aqueous dispersion, adjusts solid containing to 35%；
(4) under nitrogen atmosphere protection, 200 grams of epoxy ester aqueous dispersion made from above-mentioned steps, hybridisation emulsion formula are taken
In emulsifier AS801 ((alkylol poly-alkoxyl sodium sulfate salt and methyl oxirane, ethylene oxide and single (2- ethyl hexyls
Base) ether polymer mixture) with AEO-9 (ethoxy alcohol) with mass ratio be 2:The mixture of 1 mixing) 2.2 grams, 40 grams of water
It is added to the container, 40 grams of methyl methacrylate and the first mixed dissolution of 0.8 gram of azo-bis-isobutyl cyanide add container high speed and stir
It mixes 25 minutes, obtains the pre-emulsion of acrylic monomer；
(5) continue to be passed through nitrogen into reaction system, by 100 grams of remaining epoxy ester aqueous dispersion, hydridization in step (3)
1 gram of remaining emulsifier in emulsion formulations, 0.08 gram of ammonium persulfate and 0.05 gram of sodium bicarbonate in hybridisation emulsion formula, with
20 grams of the pre-emulsion of the acrylic monomer prepared in step (4) is added in reaction bulb, and warming while stirring is to 80 DEG C, reaction
40 minutes, start the pre-emulsion of remaining acrylic monomer in a dropping step (4), be added dropwise to complete with 3-4 hours, process is added dropwise
It is middle that ammonium persulfate is added according to the concrete condition of reaction, 3-3.5 hours are kept the temperature at 80-85 DEG C after dripping, cools to 40 DEG C, mistake
Filter out material.It obtains lotion and contains 37.8%, viscosity 50mPa.s admittedly, after painting varnish paint film, surface drying time is 30 minutes, when doing solid work
Between be 8 hours, glossiness 95%, water-fast 48 hours, salt spray resistance 72 hours.
Embodiment 4
(1) by 100 grams of epoxy resin E14,80 grams of behenic acid is stirred in 0.3 gram of addition reaction bulb of zinc oxide and is warming up to
190-200 DEG C, reaction is to acid value 10mgKOH/g hereinafter, being cooled to 145 DEG C of 40 grams of n-butanols of addition.Keep the temperature at 110-
118 DEG C, obtain fatty acid modified epoxy resin；
(2) by 8 grams of acrylic acid, perbenzoic acid and perbenzoic acid is added in 30 grams of mixing of methyl methacrylate
1.5 grams of the mixture of the tert-butyl ester is used instill in material above within 2-3 hours, was added in three times after dripping after mixing
1.5 grams of t-butyl perbenzoate is aoxidized, finally 3 hours is kept the temperature, obtains acrylic acid, fatty acid modified epoxy resin；
(3) resin of having changed property is cooled to 80 DEG C, 15 grams of N is added, N- dimethylethanolamines stir evenly, by 40 DEG C
265 grams of distilled water instill in resins, emulsification obtains epoxy ester aqueous dispersion, adjusts solid containing to 39%；
(4) under nitrogen atmosphere protection, 350 grams of epoxy ester aqueous dispersion made from above-mentioned steps, hybridisation emulsion formula are taken
In 3.5 grams of emulsifier NP-10 (nonylphenol polyoxyethylene ether), 30 grams of water is added to the container, 100 grams of methyl methacrylate and
The first mixed dissolution of 5 grams of azo-bis-isobutyl cyanide, adds container high speed and stirs 30 minutes, obtain the pre- breast of acrylic monomer
Liquid；
(5) continue to be passed through nitrogen into reaction system, by 150 grams of remaining epoxy ester aqueous dispersion, hydridization in step (3)
Sodium bicarbonate in emulsion formulations in 1.5 grams of remaining emulsifier, 0.08 gram of ammonium persulfate, 27 grams of water and hybridisation emulsion formula
0.04 gram with step (4) in prepare acrylic monomer 30 grams of pre-emulsion, be added reaction bulb in, warming while stirring to 70
DEG C, it reacts 45 minutes, starts the pre-emulsion of remaining acrylic monomer in a dropping step (4), be added dropwise to complete with 4-5 hours,
Ammonium persulfate is added according to the concrete condition of reaction during dropwise addition, 4.5-5 hours are kept the temperature at 70-75 DEG C after dripping, is cooled down
To 40 DEG C, filtering and discharging.It obtains lotion and contains 45%, viscosity 30mPa.s admittedly, after painting varnish paint film, surface drying time is 30 minutes,
It is 4 hours to do solid work the time, glossiness 98%, water-fast 24 hours, salt spray resistance 72 hours.
Embodiment 5
(1) by 100 grams of epoxy resin E51,120 grams of behenic acid is stirred in 0.5 gram of addition reaction bulb of zinc oxide and is warming up to
200-210 DEG C, reaction is to acid value 8mgKOH/g hereinafter, being cooled to 140 DEG C of 90 grams of propandiol butyl ethers of addition.It keeps the temperature at
130-135 DEG C, obtain fatty acid modified epoxy resin；
(2) by 14 grams of acrylic acid, 1.5 grams of peroxide -2-ethyl hexanoic acid tert-butyl, mixing is added in 30 grams of mixing of styrene
It uses instill in material above after uniformly within 2-3 hours, adds 1.5 grams of peroxidized t-butyl perbenzoate after dripping in three times, most
3 hours are kept the temperature afterwards, obtain acrylic acid, fatty acid modified epoxy resin；
(3) resin of having changed property is cooled to 80 DEG C, 18 grams of N is added, N- dimethylethanolamines stir evenly, by 40 DEG C
400 grams of distilled water instill in resins, emulsification obtains epoxy ester aqueous dispersion, adjusts solid containing to 34%；
(4) under nitrogen atmosphere protection, in taking 63 grams of epoxy ester aqueous dispersion made from above-mentioned steps, hybridisation emulsion to be formulated
Emulsifier (AS801 (alkylol poly-alkoxyl sodium sulfate salt and methyl oxirane, ethylene oxide and single (2- ethylhexyls)
The mixture of the polymer of ether) with GS7815 (natural phenol polyethenoxy ether) with mass ratio be 2:The mixture of 1 mixing)) 3.5
Gram, 50 grams of the mixture of methyl methacrylate and butyl methacrylate, 33 grams of water is added to the container high-speed stirred 35 minutes,
Obtain the pre-emulsion of acrylic monomer；
(5) continue to be passed through nitrogen into reaction system, by 27 grams of remaining epoxy ester aqueous dispersion, hydridization in step (3)
Sodium bicarbonate 0.08 in emulsion formulations in 1.5 grams of remaining emulsifier, 2.5 grams of lauroyl peroxide and hybridisation emulsion formula
Gram with step (4) in prepare acrylic monomer 8 grams of pre-emulsion, be added reaction bulb in, warming while stirring is to 75 DEG C, instead
It answers 50 minutes, starts the pre-emulsion of remaining acrylic monomer in a dropping step (4), be added dropwise to complete, be added dropwise with 5-6 hours
Lauroyl peroxide is added according to the concrete condition of reaction in journey, 5-6.5 hours is kept the temperature at 75-80 DEG C after dripping, cools to
40 DEG C, filtering and discharging.It obtains lotion and contains 44.6%, viscosity 300mPa.s admittedly, after painting varnish paint film, surface drying time is 30 points
Clock, it is 2 hours to do solid work the time, glossiness 90%, water-fast 24 hours, salt spray resistance 48 hours.
Embodiment 6
(1) by 250 grams of epoxy resin E12,50 grams of behenic acid is stirred in 0.3 gram of addition reaction bulb of zinc oxide and is warming up to
170-180 DEG C, reaction is to acid value 9mgKOH/g hereinafter, being cooled to 138 DEG C of 108 grams of n-butanols of addition.Keep the temperature at 110-
118 DEG C, obtain fatty acid modified epoxy resin；
(2) by 16 grams of acrylic acid, peroxidating -1.5 grams of 2 ethyl hexanoic acid tert-pentyl ester, mixing is added in 60 grams of mixing of styrene
It uses instill in material above after uniformly within 3-4 hours, adds 1.5 grams of peroxidized t-butyl perbenzoate after dripping in three times, most
3 hours are kept the temperature afterwards, obtain acrylic acid, fatty acid modified epoxy resin；
(3) resin of having changed property is cooled to 80 DEG C, 20 grams of N is added, N- dimethylethanolamines stir evenly, by 40 DEG C
570 grams of distilled water instill in resins, emulsification obtains epoxy ester aqueous dispersion, adjusts solid containing to 35%；
(4) under nitrogen atmosphere protection, in taking 63 grams of epoxy ester aqueous dispersion made from above-mentioned steps, hybridisation emulsion to be formulated
0.7 gram of emulsifier GS7815 (natural phenol polyethenoxy ether), 10.5 grams of methyl methacrylate is added to the container high-speed stirred
40 minutes, obtain the pre-emulsion of acrylic monomer；
(5) continue to be passed through nitrogen into reaction system, by 37 grams of remaining epoxy ester aqueous dispersion, hydridization in step (3)
0.3 gram of remaining emulsifier, benzoyl peroxide/N in emulsion formulations, 0.12 gram of accelerine and hybridisation emulsion formula
In 0.1 gram of sodium bicarbonate and the acrylic monomer prepared in step (4) 8 grams of pre-emulsion, be added in reaction bulb, side stirring
While being warming up to 30 DEG C, react 60 minutes, starts the pre-emulsion of remaining acrylic monomer in a dropping step (4), with 6-8 hours
It is added dropwise to complete, benzoyl peroxide/n,N-Dimethylaniline is added according to the concrete condition of reaction during dropwise addition, after dripping
3.5-5 hours are kept the temperature at 45-50 DEG C, cools to 40 DEG C, filtering and discharging.It obtains lotion and contains 40.8%, viscosity 50mPa.s admittedly, apply
After varnish paint film, surface drying time is 30 minutes, and it is 10 hours to do solid work the time, glossiness 98%, water-fast 24 hours, salt spray resistance
120 hours.
As can be seen that in embodiment 1-6 obtained hybridisation emulsion all have high solid low viscosity, quick-drying, preferable film forming,
The characteristics of higher glossiness, preferable water-fast and salt spray resistance, such as by the hybridisation emulsion and water in embodiment 1,2 and 6
Property epoxy ester resin aqueous dispersion is tested for the property respectively under the same test conditions with existing aqueous acrylic emulsion,
The results are shown in table below for it：
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：System of the present invention
The hybridisation emulsion of standby epoxy ester resin dispersion and acrylic resin combines the excellent of epoxy ester dispersion and acrylic emulsion
Point, the shortcomings that overcoming them, have high solid low viscosity, and quick-drying, preferable film forming, glossiness is high, resistance to ag(e)ing and salt spray resistance
The good feature of performance.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
God and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin, which is characterized in that each group in synthesizing formula
Point parts by weight are：5-90 parts of epoxy ester resin aqueous dispersion, 1-50 parts of acrylic monomer, 0-7 parts of emulsifier, pH value adjustment agent
0-2 parts, 0.05-7 parts of initiator, 0-60 parts of water.
2. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 1, which is characterized in that
Each component parts by weight are in synthesizing formula：20-80 parts of epoxy ester resin aqueous dispersion, 2-40 parts of acrylic monomer, emulsifier
0.01-5 parts, 0-1 parts of pH value adjustment agent, 0.1-5 parts of initiator, 5-40 parts of water.
3. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 1, which is characterized in that
The acrylic monomer is styrene, (methyl) acrylic acid, methyl methacrylate, (methyl) butyl acrylate, (methyl)
Isobornyl acrylate, (methyl) ethyl acrylate, (methyl) hydroxy-ethyl acrylate, (methyl) hydroxypropyl acrylate and methyl-prop
At least one of olefin(e) acid ethylene oxidic ester.
4. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 1, which is characterized in that
The initiator be potassium peroxydisulfate, ammonium persulfate, azo-bis-isobutyl cyanide, benzoyl peroxide, peroxidized t-butyl perbenzoate,
Lauroyl peroxide, benzoyl peroxide/sucrose, tert-butyl hydroperoxide/rongalite, tert-butyl hydroperoxide/pyrosulfurous acid
Sodium, benzoyl peroxide/N, accelerine, ammonium persulfate/sodium hydrogensulfite, potassium peroxydisulfate/sodium hydrogensulfite, peroxidating
Hydrogen/tartaric acid, hydrogen peroxide/sodium formaldehyde sulfoxylate, ammonium persulfate/ferrous sulfate, hydrogen peroxide/sulfuric acid ferrous iron, benzoyl peroxide/N,
N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, isopropylbenzene peroxide
Change hydrogen/frerrous chloride, potassium peroxydisulfate/frerrous chloride, the aziridine of hydrogen peroxide/frerrous chloride and isopropyl benzene hydroperoxide/tetra-
One or both of.
5. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 1, which is characterized in that
The emulsifier is the polyethylene glycol oxide carboxylate of metal carboxylate, alkylsurfuric acid salt, Sulfonates and HLB value in 9-14
In class, polyol carboxylate's class, polyoxyethylated polyols carboxylic acid esters, polyoxyethylene alkyl ether class and ethyoxyl alcohols extremely
Few one kind.
6. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to any one of claim 1 to 5,
It is characterized in that, each component parts by weight are in the epoxy ester resin aqueous dispersion formula：15-40 parts of epoxy resin, aliphatic acid
11-40 parts, 2-8 parts of acrylic monomer, 4.5-35 parts of acrylic ester monomer, 0-0.1 parts of catalyst, initiator content 0.6-
2 parts, 20-40 parts of solvent, 5-15 parts of neutralizer, 1-5 parts of drier, 100-200 parts of water.
7. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 6, which is characterized in that
The epoxy resin is bisphenol A type epoxy resin；The catalyst is organotin or zinc class catalyst；The neutralizer is three
Ethamine, N, at least one of N- dimethylethanolamines and methyl morpholine；The drier be cobalt, zirconium, zinc, calcium class drier or
Its composition.
8. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 6, which is characterized in that
The catalyst is zinc oxide or zinc naphthenate.
9. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 6, which is characterized in that
The initiator is perbenzoic acid, peroxidized t-butyl perbenzoate, di-tert-butyl peroxide, two t-amyl peroxy compounds
One or both of with peroxide -2-ethyl hexanoic acid tert-butyl (pentyl ester).
10. the hybridisation emulsion of epoxy ester resin aqueous dispersion and acrylic resin according to claim 6, feature exist
In the solvent is butyl, dipropylene, n-butanol, ethylene glycol monobutyl ether, propandiol butyl ether, propylene glycol
At least one of methyl ether, ethyl alcohol, isopropanol and sec-butyl alcohol.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111635656A (en) * | 2020-07-07 | 2020-09-08 | 锦州天壹新材科技有限公司 | Preparation of high-vitrification film-forming-temperature acrylic modified emulsion and anticorrosive paint thereof |
| CN112898479A (en) * | 2021-03-19 | 2021-06-04 | 郑州中科新兴产业技术研究院 | Unsaturated fatty acid modified water-based acrylic resin dispersion and preparation method thereof |
| CN113278114A (en) * | 2021-05-21 | 2021-08-20 | 安徽科邦树脂科技有限公司 | Functional epoxy modified acrylate emulsion and preparation method thereof |
| WO2021216435A1 (en) * | 2020-04-21 | 2021-10-28 | Ingevity South Carolina, Llc | Polymerizable thermosetting resins from tall oil |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62112603A (en) * | 1985-11-12 | 1987-05-23 | Toagosei Chem Ind Co Ltd | Production of emulsion polymer |
| JPH09278848A (en) * | 1996-04-09 | 1997-10-28 | Kansai Paint Co Ltd | Water-based coating composition |
| CN1919889A (en) * | 2006-09-05 | 2007-02-28 | 英志祥 | Organosilicon epoxide acrylate water dispersion, preparation method and application thereof |
| CN101045844A (en) * | 2007-03-30 | 2007-10-03 | 增城市裕新涂料有限公司 | Manufacturing method of epoxy modification acrylate latex automatic deposit paint |
| CN101429267A (en) * | 2008-12-25 | 2009-05-13 | 海洋化工研究院 | Preparation and uses of epoxy/acrylic acid hybridisation emulsion |
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| CN104152009A (en) * | 2014-08-26 | 2014-11-19 | 上海科罗纳精细化工有限公司 | Preparation method of epoxy acrylate antirust emulsion |
| CN104497224A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Low-acid-value and low-VOC aqueous acrylic acid and fatty acid modified epoxy resin |
| CN104513345A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Preparation method for waterborne epoxy modified acrylic resin and aqueous dispersion thereof |
| CN104513343A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Preparation method for low acid value and low VOC waterborne acrylic acid and fatty acid modified epoxy resin |
-
2017
- 2017-03-10 CN CN201710142499.3A patent/CN108570132B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62112603A (en) * | 1985-11-12 | 1987-05-23 | Toagosei Chem Ind Co Ltd | Production of emulsion polymer |
| JPH09278848A (en) * | 1996-04-09 | 1997-10-28 | Kansai Paint Co Ltd | Water-based coating composition |
| CN1919889A (en) * | 2006-09-05 | 2007-02-28 | 英志祥 | Organosilicon epoxide acrylate water dispersion, preparation method and application thereof |
| CN101045844A (en) * | 2007-03-30 | 2007-10-03 | 增城市裕新涂料有限公司 | Manufacturing method of epoxy modification acrylate latex automatic deposit paint |
| CN101429267A (en) * | 2008-12-25 | 2009-05-13 | 海洋化工研究院 | Preparation and uses of epoxy/acrylic acid hybridisation emulsion |
| CN102358815A (en) * | 2011-07-25 | 2012-02-22 | 上海电动工具研究所 | One-component self-drying acrylic acid grafted epoxy ester aqueous dispersion coating and its preparation method |
| CN104152009A (en) * | 2014-08-26 | 2014-11-19 | 上海科罗纳精细化工有限公司 | Preparation method of epoxy acrylate antirust emulsion |
| CN104497224A (en) * | 2014-12-04 | 2015-04-08 | 北京金汇利应用化工制品有限公司 | Low-acid-value and low-VOC aqueous acrylic acid and fatty acid modified epoxy resin |
| CN104513345A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Preparation method for waterborne epoxy modified acrylic resin and aqueous dispersion thereof |
| CN104513343A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Preparation method for low acid value and low VOC waterborne acrylic acid and fatty acid modified epoxy resin |
Non-Patent Citations (2)
| Title |
|---|
| MIN LIU，等: "Water and corrosion resistance of epoxy–acrylic–amine waterborne coatings: Effects of resin molecular weight, polar group and hydrophobic segment", 《CORROSION SCIENCE》 * |
| 王秋英，等: "水性环氧丙烯酸酯的制备与表征", 《化工新型材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021216435A1 (en) * | 2020-04-21 | 2021-10-28 | Ingevity South Carolina, Llc | Polymerizable thermosetting resins from tall oil |
| US12091493B2 (en) | 2020-04-21 | 2024-09-17 | Ingevity South Carolina, Llc | Polymerizable thermosetting resins from tall oil |
| CN111635656A (en) * | 2020-07-07 | 2020-09-08 | 锦州天壹新材科技有限公司 | Preparation of high-vitrification film-forming-temperature acrylic modified emulsion and anticorrosive paint thereof |
| CN112898479A (en) * | 2021-03-19 | 2021-06-04 | 郑州中科新兴产业技术研究院 | Unsaturated fatty acid modified water-based acrylic resin dispersion and preparation method thereof |
| CN113278114A (en) * | 2021-05-21 | 2021-08-20 | 安徽科邦树脂科技有限公司 | Functional epoxy modified acrylate emulsion and preparation method thereof |
| CN113278114B (en) * | 2021-05-21 | 2023-01-31 | 安徽科邦树脂科技有限公司 | Functional epoxy modified acrylate emulsion and preparation method thereof |
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