CN101050300A - Self-emulsifying type aqueous latex of epoxy hardener, and preparation method - Google Patents
Self-emulsifying type aqueous latex of epoxy hardener, and preparation method Download PDFInfo
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Abstract
This invention relates to a method for preparing self-emulsifying waterborne epoxy curing agent emulsion, which is composed of: primary amine 7-20 wt.%, epoxy resin 12-27 wt.%, epoxy-terminated polyether 3-8 wt.%, epoxy active diluter 10-30 wt.%, and deionized water 35-60 wt.%. The method comprises: adding primary amine into a reactor, slowly dropping a mixture of epoxy resin and epoxy-terminated polyether, reacting at a certain temperature, slowly dropping monofunctional epoxy active diluter, reacting, adding water, and emulsifying to obtain white waterborne epoxy curing agent emulsion. The method has such advantages as simple process, low reaction temperature (below 100 deg.C), high safety and low energy consumption. The obtained waterborne epoxy curing agent emulsion has such advantages as low VOC content, high stability, high water resistance, high compatibility with epoxy resin, high impact resistance, good luster, high toughness and high adhesiveness, and can be used in paint, adhesive and polymer concrete.
Description
Technical field:
The present invention relates to aqueous epoxy curing agent and technology of preparing thereof, particularly a kind of self-emulsifying type aqueous latex of epoxy hardener and technology of preparing thereof that does not add emulsifying agent in addition.
Technical background:
Since over half a century, Resins, epoxy relies on its excellent mechanical property, adhesiveproperties, electrical insulation capability, processing characteristics and corrosion resistance nature to obtain using widely in various fields such as coating, matrix material, casting material, tackiness agent, moulding material and injecting forming materials.In Resins, epoxy was used, solidifying agent occupied crucial position.Yet traditional solidifying agent mostly is a solvent-based system, not only consumes a large amount of solvents, has wasted resource, and the physical environment that animals and plants depend on for existence is caused the threat that is on the rise.Therefore, for many years, people are striving for the Water-borne modification of epoxy hardener always, and the self-emulsifying aqueous epoxy hardener of especially zero VOC (volatile organic compounds) content is the target of people's effort especially.
At present, the solidifying agent of the water-borne epoxy systems of report use both at home and abroad is mainly three major types: one, soluble epoxide solidifying agent; Its two, add emulsifying agent emulsive aqueous latex of epoxy hardener; Its three, the solidifying agent molecule itself contains the self-emulsifying type aqueous latex of epoxy hardener of hydrophilic segment.
The soluble epoxide solidifying agent is to use a most general class solidifying agent at present, and synthetic route is mainly single polyamines and Resins, epoxy addition, adopts mono-epoxy compounds sealing primary amine hydrogen then, adds sour salify at last and realizes Water-borne modification.This class solidifying agent synthesis technique is simple, but because of the solidifying agent wetting ability is too strong, during curing and hydrophobic epoxy resin compatibility poor, cause state of cure lower, coating physicals and resistance are relatively poor; Unreacted solidifying agent causes water-resistant coating poor because of being water miscible; Especially to show as solidity to corrosion during the metal basal plane poor because of existing ionization equilibrium to make to be applied in many occasions by such solidifying agent in the acid that adds when synthetic; The water-dilutable of water soluble solid agent is relatively poor, that is to say that need adding more water just can make its viscosity obviously reduce, this drawbacks limit its application in the thick coated type aqueous epoxy coating.
Patent CN 200510050589.7 discloses a kind of emulsifying agent emulsive aqueous epoxy curing agent preparation method that adds, having adopted polyglycol ether and alkyl polyoxyethylene ether is tensio-active agent, add tensio-active agent and make that emulsifying agent trended towards migrating to coatingsurface with solidifying afterwards when solidifying agent solidified, coating is easily turned white, poor water resistance.
For self-emulsifying aqueous epoxy hardener, report all seldom both at home and abroad.U.S. Pat 6127459 discloses a kind of preparation method of self-emulsifying aqueous epoxy hardener, this patent adopts liquid epoxy and the excessive single polyamines addition of aromatic series, then add end carboxyl polyethers 200 ℃ of reactions, add toluene then and be stirred to homogeneous phase, add entry again and stir the formation curing agent emulsion.The solidifying agent that adopts this method to make has improved the consistency of itself and Resins, epoxy, improved the physicals and the resistance of coating, but building-up process has adopted 200 ℃ high temperature, not only power consumption, and be unfavorable for safety in production; On the other hand, owing to contain toxic bigger organic solvent toluene in the emulsion particle of this curing agent emulsion, do not meet environmental requirement.
Summary of the invention:
Because preparation method in the past can not obtain zero VOC, the simple self-emulsifying aqueous epoxy hardener of synthesis technique simultaneously, the object of the present invention is to provide a kind of zero VOC, synthesis technique is simple, curing performance is good and the self-emulsifying type aqueous latex of epoxy hardener of water easily dilutable and preparation method thereof, thereby open up more wide space for the development of water-borne epoxy systems.
The present invention can reach by following measure:
Step 1: get the raw materials ready
Get the raw materials ready as follows by following component and the mass percent that accounts for total inventory thereof:
Constituent mass per-cent
Basis amine 7～20%
Resins, epoxy 12～27%
End epoxy group(ing) polyethers 3～8%
Epoxy active diluent 10～30%
Deionized water 35～60%
Wherein basic amine is generally the single polyamines that contains four reactive hydrogen atoms in the molecule at least, as diethylenetriamine, triethylene tetramine, tetraethylene pentamine, isophorone diamine, m-xylene diamine, diaminodiphenyl-methane, two (4-amino-3-methylcyclohexyl) methane etc.These single polyamines molecular weight are little, high volatility, and toxicity is big; Big with Resins, epoxy reaction post-crosslinking density, cured article fragility is big, and is not shock-resistant; General single polyamines is the single polyamine curing agent reactive behavior of aliphatics height particularly, and speed of response is fast, and thermal discharge is big during reaction, and each batching can not be many, and the batching usage period is short, and construction is inconvenience very; And single fat amine can with CO in the air
2Form carbaminate, coating surface is seriously turned white; A small amount of unreacted polyamines can absorb airborne steam, makes coatingsurface " sweating ".In order to overcome the fragility of amine curing agent, bad shock-resistance, not good enough weathering resistance and toxic action must be carried out further modification to amine curing agent, so that obtain nontoxic or low toxicity, solidified amine curing agent at ambient temperature.
Resins, epoxy should select softening temperature to be lower than 70 ℃ Resins, epoxy, as oxirane value is the liquid bisphenol A type Resins, epoxy E-51 of 0.48～0.54mol/100g, oxirane value is 0.41～0.47mol/100g, softening temperature is 12～20 ℃ bisphenol A type epoxy resin E-44, oxirane value is 0.37～0.40mol/100g, softening temperature is 24～28 ℃ bisphenol A type epoxy resin E-39, oxirane value is 0.23～0.38mol/100g, softening temperature is 40～55 ℃ bisphenol A type epoxy resin E-31, oxirane value is 0.20～0.22mol/100g, softening temperature is 60～70 ℃ bisphenol A type epoxy resin E-21, oxirane value is the liquid bisphenol F type Resins, epoxy CYDF-170 of 0.56～0.63mol/100g, oxirane value is the liquid bisphenol F type Resins, epoxy 6445 of 0.42～0.48mol/100g, and oxirane value is 0.18～0.22mol/100g, softening temperature is 50～65 ℃ a bisphenol f type epoxy resin 6420 etc.Though adopting higher Resins, epoxy of softening temperature such as oxirane value is that 0.10～0.18mol/100g, softening temperature are that 76～85 ℃ bisphenol A type epoxy resin E14 or oxirane value are that 0.11～0.14mol/100g, softening temperature are snappiness and the impact resistance that 78～90 ℃ bisphenol f type epoxy resin 6412 can improve final cured product, but when synthetic, need higher temperature Resins, epoxy could be melted, make synthetic route not only consume energy but also the processing safety reduction; And because the employing of high molecular expoxy resin makes reaction system viscosity height, and the molecule activity ability reduces, and speed of response slows down, the reaction times prolongs, and has further increased energy consumption.Can help dissolved epoxy though add organic solvent, reduce temperature of reaction and system viscosity, need in the subsequent handling to remove organic solvent, make synthesis technique become complicated.
End epoxy group(ing) polyethers should select to contain at least in the molecule the dual functional active polyether of 5 ehter bonds.The epoxy equivalent (weight) that provides as Harbin City's Harbin Fine Chemical Works is the difunctionality end epoxy group(ing) polyethers E-220 of 1492g/mol, and the epoxy equivalent (weight) that India A Tu company provides is the difunctionality end epoxy group(ing) polyethers XR-19 of 320g/mol.The main chain of this active polyether generally is the product of oxyethane or propylene oxide ring-opening polymerization, also can be the product of the mixture ring-opening polymerization of the two.The introducing of hydrophilic segment is the prerequisite that solidifying agent is realized self-emulsifying, adopt the polyethers that epoxy group(ing) is contained at two ends to participate in reaction, can make and introduce hydrophilic polyether segment in the solidifying agent molecule, but ehter bond active polyether very little makes that the synthetic product wetting ability is not enough, can not realize phase reversion.
Epoxy active diluent is meant the low molecular weight epoxy compound that contains an epoxy group(ing) in the molecule.Be generally ortho-cresol glycidyl ether, p-cresol glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, p-tert-butylphenol glycidyl ether, butylglycidyl ether, glycidyl allyl ether, C12～C14 alkyl glycidyl ether, 2-ethylhexyl glycidyl ether etc., these reactive thinners are because self contain epoxy group(ing), adopt this mono-epoxy compounds to participate in reacting the primary amine hydrogen that can seal in the solidifying agent, reduce the reactive behavior of solidifying agent, prolong the working life after making solidifying agent and Resins, epoxy mixed, so that constructing operation.
Step 2: the preparation of curing agent emulsion
(1) will drop in the reactor constant temperature after making system be warming up to 70～100 ℃ under the state that stirs earlier by the basic amine 7～20% after the above-mentioned prescription metering;
(2) mixture after again will be by the Resins, epoxy 12～27% after the metering of above-mentioned prescription and end epoxy group(ing) polyethers 3～8% compatible dropped in the reactor in 30～90 minutes, waited to dropwise the back and continued isothermal reaction 2～5 hours;
(3) will in 30～90 minutes, drop in the reactor by above-mentioned prescription metering back monofunctional epoxy reactive thinner then, wait to dropwise continuation isothermal reaction 2～5 hours;
(4) in reactor, drip by the deionized water after the above-mentioned prescription metering.In the process that drips deionized water, phase reversion can take place in system.When phase reversion took place, external phase became water by oil phase, and the viscosity of system reduces suddenly, formed O/W type emulsion, continued this moment to drip remaining deionized water in the prescription, obtained setting the aqueous latex of epoxy hardener of solid content.The solid content of emulsion should not be set the stability in storage that low, low excessively solid content can reduce emulsion, and the solid content of general curing agent emulsion should be controlled at more than 40%.
The median size of emulsion particle is in 0.1～0.8 micrometer range in the prepared emulsion.
Described reactor is that the reactor that agitator, prolong, temperature are taken into account feeding device is housed.
The principal reaction formula of step 2 is expressed as follows:
Wherein R is basic amine molecule chain link, R
1Be Resins, epoxy building block, R
2Be end epoxy group(ing) pfpe molecule chain link, R
3Be monofunctional epoxy reactive thinner building block.
The present invention has following outstanding advantage compared with prior art:
1, adopts the reaction of end epoxy group(ing) polyethers and amine, hydrophilic segment with polyethers under can (being lower than 100 ℃) at a lower temperature is incorporated in the solidifying agent molecule, avoid adopting end carboxyl polyethers and amine dehydration reaction to need pyritous situation (generally being higher than 200 ℃), made synthesis technique not only simply but also energy-saving safe.
2, the hydrophilic segment in the end epoxy group(ing) polyethers is incorporated in the solidifying agent molecule with the formal bond of chemical bond, the system that not only makes need not to add emulsifying agent in addition separately just can make solidifying agent have the self-emulsifying function, and got rid of when solidifying agent solidifies and the possibility that emulsifying agent is separated out after solidifying, make the water tolerance of coating be greatly enhanced.
3, when adopting liquid-state epoxy resin to be raw material, need not to add solubility promoter, the VOC content that can make the curing agent emulsion of preparation is zero, satisfies the environmental requirement of increasingly stringent.
4, with the aqueous epoxy curing agent easily dilutable of this method preparation, only need to reduce its viscosity, can be used as the solidifying agent of water-base epoxy thick coated type coating such as waterborne epoxy self-leveling floor coating with a spot of water.
Embodiment
Embodiment 1
Step 1, get the raw materials ready by following component and the mass percent that accounts for total material thereof:
Constituent mass per-cent
Basis amine: isophorone diamine 10.5%
Resins, epoxy: 6,420 25.7%
End epoxy group(ing) polyethers: E-220 7.2%
Epoxy active diluent: phenyl glycidyl ether 16.6%
Deionized water 40%
Step 2: the preparation of curing agent emulsion
(1) 1 described isophorone diamine with metering drops into reactor, constant temperature after making system be warming up to 80 ℃ under the state that stirs set by step;
(2) mixture of 1 described 6420 Resins, epoxy that will measure after compatible with E-220 drops to reactor in 30～90 minutes minute set by step, waits to dropwise the back and continues isothermal reaction 3 hours;
(3) 1 described phenyl glycidyl ether with metering dropped in the reactor in 30～90 minutes set by step, waited to dropwise continuation isothermal reaction 2 hours;
(4) drip the deionized water that measures in reactor, system generation phase reversion promptly gets the oyster white aqueous latex of epoxy hardener.
The solid content of gained aqueous latex of epoxy hardener is 60%, the emulsion particle median size is 0.26 micron, this emulsion cooperates the back to record varnish performance under the state of national Specification with standard liquid-state epoxy resin equivalent: hardness 3H, snappiness 1mm, shock-resistance is greater than 50cm, and gloss is 98% (60 ° of glossometers).
Embodiment 2
Step 1, get the raw materials ready by following component and the mass percent that accounts for total material thereof:
Constituent mass per-cent
Basis amine: diaminodiphenyl-methane 12.8%
Resins, epoxy: E-51 16.5%
End epoxy group(ing) polyethers: XR-19 4.2%
Epoxy active diluent: ortho-cresol glycidyl ether 16.5%
Deionized water 50%
Step 2: the preparation of curing agent emulsion
(1) 1 described diaminodiphenyl-methane with metering drops into reactor, constant temperature after making system be warming up to 70 ℃ under the state that stirs set by step;
(2) the 1 described mixture of E-51 after compatible with XR-19 with metering dropped to reactor in 30～90 minutes set by step, waited to dropwise the back and continued isothermal reaction 4 hours;
(3) 1 described ortho-cresol glycidyl ether with metering dropped in the reactor in 30～90 minutes set by step, waited to dropwise continuation isothermal reaction 3 hours;
(4) in reactor, drip the deionized water that measures.Remaining deionization adding system in continuing after the system generation phase reversion fill a prescription obtains solid content and is 50% oyster white aqueous latex of epoxy hardener.
The median size of emulsion particle is 0.23 micron in the gained aqueous latex of epoxy hardener, this emulsion cooperates the back to record varnish performance under the state of national Specification with standard liquid-state epoxy resin equivalent: hardness 3H, snappiness 1mm, shock-resistance is greater than 50cm, and gloss is 100% (60 ° of glossometers).
Claims (9)
1, a kind of self-emulsifying type aqueous latex of epoxy hardener is characterized in that the component of described emulsion and mass percent thereof are:
Basis amine 7～20%
Resins, epoxy 12～27%
End epoxy group(ing) polyethers 3～8%
Epoxy active diluent 10～30%
Deionized water 35～60%.
2, a kind of self-emulsifying type aqueous latex of epoxy hardener according to claim 1 is characterized in that: basic amine is to be selected from diethylenetriamine, triethylene tetramine, tetraethylene pentamine, isophorone diamine, m-xylene diamine, diaminodiphenyl-methane, two (4-amino-3-methylcyclohexyl) methane any one or a few.
3, a kind of self-emulsifying type aqueous latex of epoxy hardener according to claim 1 is characterized in that: Resins, epoxy is to be selected from softening temperature to be lower than 70 ℃ the bifunctional bisphenol A-type or the Resins, epoxy of Bisphenol F type.
4, a kind of self-emulsifying type aqueous latex of epoxy hardener according to claim 1 is characterized in that: end epoxy group(ing) polyethers is to be selected from the dual functional active epoxy polyethers that contains 5 ehter bonds in the molecule at least.
5, a kind of self-emulsifying type aqueous latex of epoxy hardener according to claim 1, it is characterized in that: epoxy active diluent is the monocycle oxycompound, specifically is to be selected from ortho-cresol glycidyl ether, p-cresol glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, p-tert-butylphenol glycidyl ether, butylglycidyl ether, glycidyl allyl ether, C12～C14 alkyl glycidyl ether, the 2-ethylhexyl glycidyl ether any one or a few.
6, according to the described a kind of self-emulsifying type aqueous latex of epoxy hardener of claim 1～5, it is characterized in that: the solid content of emulsion can be regulated in 40～65% scopes.
7. the preparation method of the self-emulsifying type aqueous latex of epoxy hardener of a claim 1 is characterized in that this method is made up of following steps:
(1) will drop in the reactor constant temperature after making system be warming up to 70～100 ℃ under the state that stirs earlier by the basic amine 7～20% after the above-mentioned prescription metering;
(2) mixture after again will be by the Resins, epoxy 12～27% after the metering of above-mentioned prescription and end epoxy group(ing) polyethers 3～8% compatible dropped in the reactor in 30～90 minutes, waited to dropwise the back and continued isothermal reaction 2～5 hours;
(3) will in 30～90 minutes, drop in the reactor by the monofunctional epoxy reactive thinner 10～30% after the above-mentioned prescription metering then, wait to dropwise continuation isothermal reaction 2～5 hours;
(4) in reactor, drip by the deionized water after the above-mentioned prescription metering, in the process that drips deionized water, system generation phase reversion, when phase reversion took place, external phase became water by oil phase, and the viscosity of system reduces suddenly, forms O/W type emulsion; Continue this moment to drip remaining deionized water in the prescription, obtain setting the aqueous latex of epoxy hardener of solid content.
8, the preparation method of a kind of self-emulsifying type aqueous latex of epoxy hardener according to claim 7 is characterized in that: the median size of emulsion particle is in 0.1～0.8 micrometer range in the described emulsion.
9. the preparation method of a kind of self-emulsifying type aqueous latex of epoxy hardener according to claim 7 is characterized in that: described reactor is that the reactor that agitator, prolong, temperature are taken into account feeding device is housed.
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Address after: Supe Industrial Park, No. 72 Panyu District Zhong villages of Guangzhou city in Guangdong province 511495 Xie Shi Lu Patentee after: GUANGZHOU SUPER CHEMICAL COATING CO., LTD. Address before: Supe Industrial Park, No. 72 Panyu District Zhong villages of Guangzhou city in Guangdong province 511495 Xie Shi Lu Patentee before: Guangzhou Supe Chemical Co., Ltd. |