A kind of aqueous epoxy resin emulsion, anticorrosive paint and preparation method thereof
Technical field
The present invention relates to a kind of aqueous epoxy resin emulsion, anticorrosive paint and preparation method thereof, belong to technical field of coatings。
Background technology
On August 12nd, 2015, after Tianjin seismic network dangerous materials explosive incident occurs, the whole nation is stricter to hazardous chemical producer, warehouse, transport, equally also further accelerate the development in water paint market simultaneously, by new " environmental law ", " consumption tax ", " effluent charge ", and phase Yingcheng City puts into effect production and the use of forbidding oil-based paints in order to administer PM2.5, again it can be seen that the development supporting and encourageing water paint coating of country's indirectly great dynamics。
In anticorrosive paint, main or epoxy systems accounts for leading, in fact aqueous epoxy resins be emulsified in the domestic developing history having had nearly 30 years, its preparation method is nothing more than three kinds: 1, direct method;2, phase inversion;3, chemical method。Owing to first two method broadly falls into additional emulsifying agent method, the latex particle of formation is relatively big, and skewness, it is easy to coagulation occurs。The appearance bin stability making aqueous epoxy resins is poor, solidify the drawbacks such as uneven, substantially superseded。Chemical method is to be incorporated in epoxy molecule by aqueous group so that it is have hydrophilic, thus can in water uniformly, stable dispersion。
Summary of the invention
A kind of aqueous epoxy resin emulsion of disclosure and utilize the anticorrosive paint that this emulsion prepares, its reaction principle make use of poly-(oxygen ethylene/oxypropylene)-2-propylamine of a kind of methoxyl group to react with epoxy resin, make the epoxy resin that originally can not be directly dissolved in water by (oxygen ethylene/oxypropylene)-2-propylamine " hydrophilic " bridge joint poly-with methoxyl group, utilize-the COOH of epoxy resin one end,-OH reacts with poly-(oxygen ethylene/oxypropylene)-2-propylamine of methoxyl group, one end generates salt, the other end of poly-(oxygen ethylene/oxypropylene)-2-propylamine of methoxyl group contains substantial amounts of hydrophilic group, so that water-fast epoxy resin extraordinary can be dissolved in water originally, react with aqueous epoxy curing agent, very excellent epoxy coating can be generated。The water corrosion-resistant epoxy paint of preparation has the advantage of very excellent adhesive force, rate of drying, salt fog resistance, chemical resistance, hardness and application property, and cost is low。
According to the first aspect of the invention:
A kind of aqueous epoxy resin emulsion, includes following component by weight percentage:
Epoxy resin: 40~50%;
Methoxyl group gathers (oxygen ethylene/oxypropylene)-2-propylamine: 4.3~8.7%;
Solvent: 4~8%;
Defoamer: 0.1~0.3%;
Nertralizer: 0.5~1.0%;
Deionized water 33~49%;
The structure of poly-(oxygen ethylene/oxypropylene)-2-propylamine of described methoxyl group is shown below:
;
Wherein, R is H or CH3, x is the arbitrary integer (being preferably 6) between 4~8;Y is the arbitrary integer (being preferably 35) between 30~40。
In one embodiment, poly-(oxygen ethylene/oxypropylene)-2-propylamine of methoxyl group is by the mixing of following two structural material:
The first:
;
The second:
。
In one embodiment, the first material is 1:2~4 with the mol ratio preferable range of the second material;It is more preferably 10:31。
According to the second aspect of the invention:
The preparation method of above-mentioned aqueous epoxy resin emulsion, comprises the steps:
1, by epoxy resin, solvent mixing, it is warming up to 50~70 DEG C, stirs;
2, add poly-(oxygen ethylene/oxypropylene)-2-propylamine of methoxyl group, adopt 50~70 DEG C of insulation 0.5~2h;
3, after cooling, add defoamer and deionized water, mix homogeneously, adopt nertralizer to adjust pH value to 8.5~9.5。
According to the third aspect of the present invention:
Anticorrosive paint containing above-mentioned aqueous epoxy resin emulsion。
Described anticorrosive paint refers to water-based epoxy zinc-rich primer, and it is made up of according to percentage by weight 1:8~12 the first component and second component;
The first described component refers to above-mentioned aqueous epoxy resin emulsion;
Described second component includes the following component according to weight percent meter:
Aqueous epoxy curing agent: 8~12%;
Zinc powder: 79~81%;
Corrosion inhibiter: 1~2%;
Aqueous zinc phosphate: 1~3%;
Dispersant: 0.2~0.5%;
Second defoamer: 0.1~0.3%;
Wetting agent: 0.1~0.3%;
Anti-sudden strain of a muscle rust agent: 0.5~0.8%;
Aqueous polyamide wax: 2~4%;
Coalescents 2~3%。
Described anticorrosive paint refers to water-soluble epoxy red ferric oxide primer, and it is made up of according to percentage by weight 1:8~12 the first component and second component;
The first described component refers to above-mentioned aqueous epoxy resin emulsion;
Described second component includes the following component according to weight percent meter:
Aqueous epoxy curing agent: 10~15%;
Iron oxide red: 15~20%;
Phlogopite: 5~10%;
Long Vermiculitum: 20~28%;
Barium sulfate: 5~10%;
Aqueous zinc phosphate: 5~8%;
Dispersant: 0.2~0.5%;
Foam inhibitor: 0.1~0.2%;
Defoamer: 0.1~0.2%;
Levelling agent: 0.1~0.2%;
Wetting agent: 0.1~0.2%;
Anti-sudden strain of a muscle rust agent: 0.3~0.5%;
Antimildew disinfectant: 0.2~0.4%;
Nertralizer: 0.3~0.6%;
Aqueous polyamide wax: 2~4%;
Hydrated magnesium silicate: 0.3~0.5%;
Corrosion inhibiter: 1~2%;
Cosolvent 1~2%;
Deionized water 15~17%。
Beneficial effect
Product has very excellent application property, anti-corrosive properties, chemical resistance, high rigidity, and production technology is very simple。
Detailed description of the invention
Below by detailed description of the invention, the present invention is described in further detail。It will be apparent, however, to one skilled in the art, that the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention。Unreceipted concrete technology or condition person in embodiment, technology or condition described by the document in this area or carry out according to product description。Agents useful for same or the unreceipted production firm person of instrument, be can pass through city available from conventional products。
In addition, the ordinal number used in the claims and specification is " first ", " second ", " the 3rd " etc. such as, for modify claim rather than due to itself containing any preferentially, the order of formerly or one claim is before another claim or performs the time sequencing of method step。But, use with difference such as with element (rather than belonging to for succession) with same names of the element of the claim of specific names and another one as just label, distinguish the element of claim。Thus, define " first ", the feature of " second " can express or implicitly include one or more these features。
Word used herein " includes ", " comprising ", " having " or its any other variant are intended to including of non-exclusionism。Such as, it is not necessarily limited by those key elements including listing the technique of key element, method, article or equipment, but can be included other and be not expressly set out or belong to the key element that this technique, method, article or equipment are intrinsic。
The numerical value as range limit not only including clearly listing should be interpreted as using the value of range format expression in a flexible way, but also include all single numerical value or the subinterval that are encompassed within the scope of this, be expressly recited out just as each numerical value and subinterval。Such as, the concentration range of " about 0.1% to about 5% " should be understood to not only to include the concentration of about 0.1% to about 5% clearly listed, also include single concentration in institute's how (as, 1%, 2%, 3% and 4%) and subinterval (such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%)。In description of the invention, percentage ratio when non-specified otherwise all referring to percentage by weight。
Methoxyl group gathers (oxygen ethylene/oxypropylene)-2-propylamine:
The methoxyl group adopted in the present invention gathers (oxygen ethylene/oxypropylene)-2-propylamine (CAS registration number 83713-01-3), is the monoamine of a copolymer chain, and its structure is as follows:
;
Wherein, R is H or CH3, x is the arbitrary integer (being preferably 6) between 4~8;Y is the arbitrary integer (being preferably 35) between 30~40。Such as can adopt the Huntsman JEFFAMINE produced?M-2070 polyetheramine is a molecular weight about 2000 single functionality primary amine。The mol ratio of its expoxy propane/oxirane (PO/EO) is 10/31。
Epoxy resin:
The epoxy resin adopted in the present invention is not particularly limited, can list such as: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, 3 trifunctional phenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, aralkyl phenolic resin varnish type epoxy resin, alicyclic epoxy resin, polyol type epoxy resin, glycidyl amine, ethylene oxidic ester, with the compound by the double bond epoxidation of butadiene etc., and the compound etc. obtained by hydroxyl organic siliconresin class and epichlorohydrin reaction。
Solvent:
The concrete example of operable solvent, it is possible to enumerate the alcohols such as the arene compounds such as the alkanes such as hexane, hexamethylene, heptane, toluene, dimethylbenzene, methanol, ethanol, isopropanol, butanol, hexanol, Hexalin。It addition, the nitrile compounds such as ester compounds, acetonitrile etc. such as the ethers such as the ketones such as butanone, methyl iso-butyl ketone (MIBK), cycloheptanone, Ketohexamethylene, ether, oxolane, dioxane, ethyl acetate, butyl acetate, methyl formate according to circumstances can also be used。
Defoamer:
Defoamer suitable in the present invention is not particularly limited, it is possible to enumerate: alcohol defoaming agent (such as 2-Ethyl Hexanol, isooctanol, isoamyl alcohol, diisobutyl carbinol (DIBC) etc.), fatty acid and fatty acid defoamer, amide-type defoamer, phosphate ester defoamer, organo-silicon compound class defoamer, halogenated organic defoamer, surfactant antifoaming agent etc.。
Nertralizer:
Nertralizer is not particularly limited, it is preferred to hydrochloric acid, acetic acid, an iodomethane, sodium hydroxide, ammonia, triethylamine, methylamine or triethanolamine etc.。
The preparation method of above-mentioned emulsion, can pass through epoxy resin, poly-(oxygen ethylene/oxypropylene)-2-propylamine of methoxyl group reacts in the solution, temperature preferable range 50~70 DEG C, realize the epoxy resin that originally can not be directly dissolved in water by (oxygen ethylene/oxypropylene)-2-propylamine " hydrophilic " bridge joint poly-with methoxyl group, utilize-the COOH of epoxy resin one end,-OH reacts with poly-(oxygen ethylene/oxypropylene)-2-propylamine of methoxyl group, one end generates salt, the other end of poly-(oxygen ethylene/oxypropylene)-2-propylamine of methoxyl group contains substantial amounts of hydrophilic group, so that water-fast epoxy resin extraordinary can be dissolved in water originally。
After having reacted, then mix with defoamer, nertralizer, deionized water, it is possible to prepare modified epoxy resin emulsion, it is preferred to use phase conversion emulsifying。First, add a small amount of water, mixing in dividing (organic solvent containing epoxy resin) to the oil adding emulsifying agent, thus can obtain w/o type emulsion。Then, being slowly added into water, while making its phase inversion, O/W type emulsion may finally be obtained。Device for mixing can enumerate the shaft mixer with rotating vane and homogenizer, homomixer, colloid mill etc.。It addition, emulsifying temperature is preferably in the scope of 10~80 DEG C, more preferably in the scope of 20~30 DEG C。There is no particular limitation for the mean diameter of epoxy resin latex, is generally about 0.01~10 μm, it is preferred to about 0.1~1 μm。The mean diameter occasion more than 10 μm, it is easy to settle, bad stability。
The above-mentioned aqueous epoxy resin emulsion prepared can prepare aqueous epoxide resin paint compositions further with other compositions including epoxy hardener。
Epoxy hardener:
The kind of epoxy hardener used here is not particularly limited, as long as can react with epoxy resin, form 3 dimension network structure, can list such as, the amide-type firming agent such as dicyandiamide, fatty polyamide, the amine curing agents such as diaminodiphenyl-methane, m-diaminobenzene., ammonia, triethylamine, diethylamine, the phenols curing agent of bisphenol-A, Bisphenol F, phenol novolak resin, cresol novalac resin, xylol phenolic novolac etc. and acid anhydride type curing agent etc. show at type firming agent, latent curing agent。They can be used alone, it is also possible to merges and uses 2 kinds or above。Such as: peaceful 751 aqueous epoxy resin curing agents of AB-HGA aqueous epoxy resin curing agent or section etc.。
In one embodiment, it is possible to prepare into water-based epoxy zinc-rich primer, it is formed as the first component and the second component proportioning containing firming agent by above-mentioned epoxy resin latex。The weight ratio of the first component and second component is preferably 1:8~12。
Second component includes following component by weight percentage:
Aqueous epoxy curing agent: 8~12%;
Zinc powder: 79~81%;
Corrosion inhibiter: 1~2%;
Aqueous zinc phosphate: 1~3%;
Dispersant: 0.2~0.5%;
Defoamer: 0.1~0.3%;
Wetting agent: 0.1~0.3%;
Anti-sudden strain of a muscle rust agent: 0.5~0.8%;
Aqueous polyamide wax: 2~4%;
Coalescents 2~3%。
In another embodiment, it is possible to prepare into water-soluble epoxy red ferric oxide primer, it is formed as the first component and the second component proportioning containing firming agent by above-mentioned epoxy resin latex。The weight ratio of the first component and second component is preferably 1:8~12。
Second component includes following component by weight percentage:
Aqueous epoxy curing agent: 10~15%;
Iron oxide red: 15~20%;
Phlogopite: 5~10%;
Long Vermiculitum: 20~28%;
Barium sulfate: 5~10%;
Aqueous zinc phosphate: 5~8%;
Dispersant: 0.2~0.5%;
Foam inhibitor: 0.1~0.2%;
Second defoamer: 0.1~0.2%;
Levelling agent: 0.1~0.2%;
Wetting agent: 0.1~0.2%;
Anti-sudden strain of a muscle rust agent: 0.3~0.5%;
Antimildew disinfectant: 0.2~0.4%;
Second nertralizer: 0.3~0.6%;
Aqueous polyamide wax: 2~4%;
Hydrated magnesium silicate: 0.3~0.5%;
Corrosion inhibiter: 1~2%;
Cosolvent 1~2%;
Deionized water 15~17%。
The coating composition prepared by such scheme goes for various base material, can list such as, the miscellaneous equipment etc. that aluminium sheet, steel plate, tin plate etc. are untreated or surface treated metallic plate and the metallic plate being coated with the priming paint such as epoxies, vinyl on these metallic plates etc., these metallic plates process。As the coating composition of the present invention being coated with the method installing on base material, it is possible to be suitable for various known methods, for instance, roller coat application, spray-coating, dipping coating, electrodeposition coating etc.。Wherein, it is preferable that roller coat application or spray-coating。Coating thickness suitably can select according to purposes, but is generally preferred to about 3~20 μm。As the drying condition of the film after application, generally it is suitably when raw-material maximum temperature reached is 120~300 DEG C and carries out 10 seconds~30 minutes, it is preferred at 200~280 DEG C in the scope of 15 seconds~10 minutes。
In order to improve hardness when epoxy resin latex prepares into coating further, in one preferred embodiment, it is also possible to add the fluorine-containing ethamine of 1~3% in second component, for instance 2,2-difluoroethylamines or 2,2,2-trifluoroethylamine。
The method for testing performance of the coating prepared in following example is as follows:
Drying time according to GB/T1728, adhesive force according to GB/T5210, impact according to GB/T1732, toughness according to GB/T1731, proportion according to GB/T6750, viscosity according to GB/T6753.3, chemical-resistance according to GB/T1763, hardness according to GB/T6739, resistance to neutral salt spray tests according to GB/T9793 containing belonging to Zn content according to GB/T1735, dry film according to GB/T9264, thermostability according to GB/T4956, not sagging build according to iron content in GB/T1771, paint film。
Embodiment 1~7 the present embodiment is for illustrating to prepare different modified epoxy resin emulsions
Raw material is as follows:
Epoxy resin 128(E51), South Asia epoxy resin
Poly-(the EO/PO)-2-propylamine of methoxyl group have employed following different A composition and B composition and their combination:
A composition:
;Wherein, x=6, y=35;
B component:
;Wherein, x=6, y=35;
Table 1: in each embodiment, methoxyl group gathers the A composition of (EO/PO)-2-propylamine and the weight ratio of B component
Defoamer (2550 BASF)
Nertralizer (DMAE engrave in sea this chemistry)
Mixed solvent (ethylene glycol monobutyl ether: ethylene glycol: acetone=40:40:20)
Table 2: embodiment 1~embodiment 7 aqueous epoxy resin emulsion formulation ratio (percentage by weight)
Preparation method:
1st step, is warming up to 60 DEG C after epoxy resin, solvent mixing, stirs;
2nd step, adds poly-(the EO/PO)-2-propylamine of methoxyl group, adopts 60 DEG C of insulation 1h;
3rd step, cools the temperature under room temperature condition, adds defoamer and deionized water, adopts nertralizer to adjust pH value。
Embodiment 8 water-based epoxy zinc-rich primer formula
First component: aqueous epoxy resin emulsion (emulsion prepared in above-described embodiment 1~7)
The raw material of second component is as follows:
High-purity zinc powder (500 height of eye purity zinc powder Jiangsu section Cheng Xinye)
Aqueous zinc phosphate (PZ04 ring fine jade chemical industry)
Dispersant (755W enlightening is high)
Second defoamer (0670 U.S. OMG)
Wetting agent (2817 U.S.'s Hexion)
Corrosion inhibiter (142DA be full of in Shanghai water)
Aqueous polyamide wax slurry (the vertical Hua of AQH-800 is prosperous)
Coalescents (ethylene glycol monobutyl ether LG-DOW)
Aqueous epoxy curing agent (EK8538-Y-68 U.S. Hexion)
Anti-dodge rust agent (AH10 be full of in Shanghai water)
Table 3: the second component formulation ratio (percentage by weight) of embodiment 8
Preparation method is:
1, aqueous epoxy curing agent, corrosion inhibiter, dispersant, the second defoamer are added in production cylinder, adopt 400~600 revs/min to stir 5~10 minutes;
2, limit employing 400~600 revs/min adds aqueous zinc phosphate, aqueous polyamide wax while stirring, adopts 600~800 revs/min to disperse 10~15 minutes, and it is less than 50 microns that addition zirconium pearl is ground to fineness;
3, add wetting agent, anti-sudden strain of a muscle rust agent, coalescents, adopt 400~600 revs/min to stir 10~15 minutes;
4, add high-purity zinc powder, adopt 600~800 revs/min to stir 15~20 minutes。
Coating dry plate realizes process: by the first component and second component=1:10 proportioning, proportioning out adopts hydrometer jar to measure paint proportion afterwards, than weight average up to more than 2.73g/ml, then deionized-distilled water is adopted to carry out the adjustment of spray viscosity, spray viscosity is adjusted to 30~40S(NK-2 cup), spray layer 2-3, dry plate is placed in 25 DEG C of calorstats from dry 48 hours detection traditional performances, ripening tested salt spray resistance after 7 days, and the dry plate film thickness of salt spray resistance controls at 80~100 μm。
The performance test data of the coating that the epoxy resin latex being respectively adopted in embodiment 1~7 prepares following (being called the 1st~7 group), and using the aqueous epoxy coating disclosed in patent CN104140738A as reference。Additionally, in order to show without modified epoxy resin performance under similarity condition, as controlled trial, emulsion preparation method in embodiment 5 will be added without poly-(the EO/PO)-2-propylamine of methoxyl group, directly being prepared emulsion by epoxy resin and other composition, then be used in the preparation method for coating preparing in the present embodiment by this comparison emulsion, preparation is without modified epoxy coating, again according to carrying out controlled trial with method, result is as follows:
Table 4: embodiment 8 dry plate and CN104140738A performance comparison
* refer to when reaching the corresponding time, the phenomenon such as coating surface occurs bubbling, comes off, cracking。
Be can be seen that by Experimental Comparison, self-control aqueous epoxy resin emulsion is adopted to make water-based epoxy zinc-rich primer, all being superior to three Chinese patents of CN104140738A, CN101775108B and CN102977338B in salt spray resistance, chemical resistance, hardness, application property etc., wherein the hardness performance of the 5th group of coating obtained is optimum。This water-based epoxy zinc-rich primer all properties is satisfied by protecting all standard requirement of application in TB/T1527-2011 railway steel bridge, can be applicable on railway steel bridge product。This kind of product has drying speed, adhesive force is good, proportion reaches 2.73g/ml, dry film metallic zinc content reaches more than 80%, and salt fog resistance can reach more than 2500 hours。
Embodiment 9 water-soluble epoxy red ferric oxide primer
First component: aqueous epoxy resin emulsion (emulsion prepared in above-described embodiment 5)
The raw material of second component is as follows:
Aqueous epoxy curing agent (8290-Y-60 U.S. Hexion)
Iron oxide red (190D span new century)
Phlogopite powder (800 order phlogopite Chuzhou lattice are sharp)
Barium sulfate (1500 order blanc fixe Jinan dawn)
Long Vermiculitum (1250 order long Vermiculitum Chuzhou lattice are sharp)
The zinc phosphate (PZ04 ring fine jade chemical industry) that water paint is special
2,2-difluoroethylamine (Wuxi City sows precious Pharmaceutical)
Dispersant (492 bright icepro chemistry)
Foam inhibitor (MD-20 U.S. aerochemistry)
Second defoamer (the peaceful chemicals of NXZ section)
Levelling agent (3300 Chongqing wheat figure)
Wetting agent (245 enlightening are high)
Aqueous polyamide wax (the vertical Hua of AQH-800 is prosperous)
Hydrated magnesium silicate (AD sea ease chemistry)
Cosolvent (ethylene glycol monobutyl ether LG-DOW)
Second nertralizer (AMP-95 engrave in sea this chemistry)
Anti-dodge rust agent (FA-179 engrave in sea this chemistry)
Antimildew disinfectant (HF-1 Clariant)
Corrosion inhibiter (142DA be full of in Shanghai water)
Table 5: the second component formulation ratio in embodiment 9
Preparation method is:
1, aqueous epoxy curing agent, a part of second nertralizer, cosolvent are added employing 400~600 revs/min and stir 5~10 minutes;
2, adopt a part of deionized water that hydrated magnesium silicate is fabricated to the pre-slurrying of 15%, adopt 600~800 revs/min to stir 15~20 minutes;
3, adopt a part of deionized water to produce adding after dispersant, foam inhibitor, anti-sudden strain of a muscle rust dilution agent in cylinder, adopt 400~600 revs/min to stir 5~10 minutes;
4, limit employing 400~600 revs/min adds iron oxide red, phlogopite, long Vermiculitum, zinc phosphate, aqueous polyamide wax, barium sulfate and the pre-slurrying of hydrated magnesium silicate while stirring, adopting 600~800 revs/min to disperse 20~30 minutes, it is 50 microns that addition zirconium pearl is ground to fineness;
5, adopt remaining deionized water to produce adding after the second defoamer, levelling agent, wetting agent, antimycotic antiseptic dilution agent in cylinder, adopt 600~800 revs/min to stir 5~10 minutes, add remaining second nertralizer and stir。
In 6th group of test, it is necessary to the 3rd step adds 2, the 2-difluoroethylamines accounting for aqueous epoxy curing agent weight 20% on the formula basis of the 1st group。
Performance test: the first component: second component=15:100 weight proportion paint, deionized-distilled water is adopted to be diluted to spray viscosity (30~40S, NK-2 cup), standard-bred mouth iron plate carries out phosphatization or grinding process, on tinplate sheet, THICKNESS CONTROL is at the thickness of 20~30 μm, does all-round property testing after 48 hours do solid work completely。Salt spray resistance and chemical resistance tested steel plate thickness control at 80~100 μm, and ripening was tested after 7 days。
Respectively the component obtained in the 1st~6 group is prepared the performance test data of epoxy coating as follows, combination property contrasts with certain oiliness iron red epoxy primer in city:
Table 6: the dry plate the performance test results realized from preparing aqueous epoxy resins
* refer to that when reaching the corresponding time, the phenomenons such as vesicle has occurred in coating surface。
By it have been experienced that, adopt the aqueous iron red epoxy primer that self-control aqueous epoxy resin emulsion makes, there is very excellent application property, quick-drying, salt fog resistance, chemical resistance, disposable spray finishing build is not sagging more than 200 microns, and this product can be widely applied to the industries such as engineering machinery, vehicle, bridge, steel structure, lathe, highway bearing, petroleum and petrochemical industry。