CN100503754C - Aqueous epoxy nano-composite corrosion proof paint and its preparation method - Google Patents
Aqueous epoxy nano-composite corrosion proof paint and its preparation method Download PDFInfo
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Abstract
The present invention relates to a water epoxy nano composite coating and its preparation method. Said coating is formed from two portions of liquid epoxy resin or epoxy resin solution and water epoxy nano composite solidifying agent, in which the solidifying agent it made up by using epoxy resin room temperature solidifying agent polyamine through the processes of end-capping, addition, salt-forming and modification. The molecular chain segment of the obtained nano composite solidifying agent not only contains hydrophilic group, but also contains oleophilic group, so that it has emulsifying function, and can directly emulsify epoxy resin or its solution. Said water epoxy nano composite solidifying agent and expoxy resin or its solution are mixed according to a certain ratio so as to obtain the invented water epoxy nano composite coating.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to double-component aqueous epoxy nano composite coating of a kind of high-performance and preparation method thereof.
Background technology
Epoxypaint has the sticking power height, chemical-resistant resistance and solvent nature excellence, and the hardness height, wear resistance is good, and alkali resistance, characteristics that salt fog resistance is good etc. are used widely industrial having obtained.Present most epoxypaint is a solvent based coating, contains a large amount of volatilizable organic compound (VOC), and is poisonous, inflammable, and environment and human body have been caused harm.Along with requirement on environmental protection is improved day by day, the cry that attenuating VOC is not even contained the coating of VOC grows to even greater heights.Nanoparticle is a kind of new states of matter, nano science is come out so far the only more than ten years, but because nano material has the not available unusual characteristic of conventional fines, and the small-size effect of nano material, surface interface effect, quantum size effect and macro quanta tunnel effect and its special light, electrical characteristic, high magnetic resistance phenomenon, non-linear resistance phenomenon and at high temperature still have characteristics such as high-strength, high-ductility, excellent stability, make it have wide Application Areas.Inorganic nanoparticles is applied to coating, and the pigment suspension, cohesive strength of whole coating system, functional, ageing resistance, wear resistance, erosion resistance and the feature of environmental protection etc. are obviously improved.
Abroad from last century the nineties develop some water-base epoxy products successively, as the epoxy emulsion EPI-REZ 3520-WY-55 and the aqueous epoxy curing agent EPI-CURE 8290-Y-60 of U.S. Shell company, the epoxy emulsion PZ 3961 of the Waterpoxy140 of Henkel companies such as the epoxy emulsion PZ 3961 of Air Products company and aqueous epoxy curing agent HZ 340, Air Products company and aqueous epoxy curing agent HZ340 etc.Domestic research also concentrates on above the preparation of aqueous epoxy emulsion.Quite popular to the research of nano composite dope in recent years both at home and abroad.Nanophase Technologies company is mixed nano aluminium oxide with transparent varnish, improve hardness, scratch resistance and the wear resistance of coating greatly.The said firm also produces oneself Nano filling slurries scattered, that can be directly used in coating.Degussa company develops the anti-scratch acrylic coating based on siloxanes embedded nano silicon dioxide granule.The anti-scratch performance of this coating is good especially, and its wear resistance is ten times of conventional acrylic system, and construction easily, and is of many uses, is environmentally friendly radiation curing and solvent-free system.Many U.S., Europe, Japanese Patent introduction utilize nano silicon, nano titanium oxide etc. or its mixture nano material that the surface is carried out being scattered in after the modification to prepare transparent wear-resistant coating in the polymer resin matrix.Domestic also someone studies nano composite dope, and Xue Lili etc. add nano titanium oxide in Resins, epoxy and the solvent to, has improved coating mechanical property and erosion resistance.Sun Jinyu etc. are dispersed in the water-based epoxy resin with nano silicon, prepare the water based epoxy nano composite dope, and the result shows that the coating of being developed has good corrosion resistance.
Summary of the invention
The objective of the invention is to propose a kind of non-environmental-pollution and do not have high-performance water-based epoxy nano composite dope of harm and preparation method thereof.
The high-performance water-based epoxy nano composite dope that the present invention proposes is made up of liquid epoxies or Resins, epoxy ethereal solution and two components of aqueous epoxy nano composite curing agent, is a kind of two-component coating.
Wherein the aqueous epoxy nano composite curing agent adds nanoparticle by polyamines class solidifying agent through end-blocking, addition, salify process modification and in modifying process and obtains, solid content is 25-35%, existing hydrophilic radical in this nano combined solidifying agent molecule segment, lipophilic group is arranged again, has emulsification function, directly emulsion epoxy resin.
Among the present invention, the consumption of above-mentioned aqueous epoxy nano composite curing agent (first component) and Resins, epoxy or its solution (component B) is that 1.5:1-1:1.5 calculates by the mol ratio of amine hydrogen and epoxy group(ing), makes aqueous epoxy nano composite coating varnish.Wherein can add proper quantity of defoaming agent in the first component, the bubble that generates when mixing to eliminate.The defoamer that adds can be SPA-202 (China), EGITAN760 (German Munzing company) etc.
The preparation method of the high-performance water-based epoxy nano composite dope that the present invention proposes is as follows:
1. prepare the aqueous epoxy nano composite curing agent
Two-Component Waterborne Epoxy Resin Coating requires at room temperature to solidify.Polyethylene polyamine class solidifying agent and adduct thereof are the self-vulcanizing epoxy curing agents of using always, it is applicable to the solvent-borne type system and is not suitable for the water-base epoxy system, because it not only can not be dispersed in and form stable dispersion in the epoxy resin latex, can cause the destruction of emulsion on the contrary, it two is separated, coating curing is bad, even can not solidify.The solidifying agent that uses in the water-base epoxy system must satisfy following condition:
1. compatible with epoxy resin latex, can be evenly dispersed in and form uniformly film forming solidified dispersion at room temperature in the emulsion;
2. with Resins, epoxy consistency is preferably arranged behind the moisture evaporation in emulsion, can form the homogeneous wet film, thereby can fully and fully solidify, obtain filming of excellent property;
3. the speed of response with Resins, epoxy is moderate, to guarantee enough working lives (2-4 hours).
Satisfy above-mentioned requirements, need polyethylene polyamine is carried out modification, and in the process of modification nano particle is added wherein, thereby make the nano combined aqueous epoxy curing agent that gets, concrete modification procedure is:
(1) dispersion of nanoparticle
Nanoparticle joins in the mono-epoxy compounds, and high-speed stirring is carried out ultra-sonic dispersion again.
Nanoparticle can adopt a kind of of the lamellated polynite of nanometer sheet, granulous silicon-dioxide, titanium dioxide etc.Addition is the 1-15% of mono-epoxy compounds weight.After organically-modified, can be scattered in the organism.
Mono-epoxy compounds can adopt aliphatic group glycidyl ether (as butylglycidyl ether, alkyl glycidyl ether) or arylolycidyl ethers (as phenyl glycidyl ether, benzyl glycidyl ether), or the mixture of aliphatic group glycidyl ether and arylolycidyl ethers.
Take by weighing the certain amount of nano particle, add to and carry out high-speed stirring (general 500-1000 rev/min) in the mono-epoxy compounds, after the stirring, carried out ultrasonic 20-40 minutes, obtain the mono-epoxy compounds of nano-dispersed.
(2) polyethylene polyamine end capping
Polyethylene polyamine can adopt diethylenetriamine, triethylene tetramine, tetrem alkene hexamine or different Fu Er ketone diamines etc.Because their end groups contain primary amine hydrogen, be higher than secondary amine hydrogen with the reactive behavior of epoxy group(ing), therefore to prolong working life, need with mono-epoxy compounds and primary amine H-H reaction generation secondary amine hydrogen.
Adopt polyethylene polyamine and disperseed the mono-epoxy compounds of nano particle to react, temperature of reaction is controlled at 50-70 ℃, and time 1.5-2.5 hour, the raw material consumption was that 1:1.5-1.5:1 calculates by the mol ratio of polyethylene polyamine and mono-epoxy compounds epoxy group(ing); Because reaction is thermopositive reaction, should slowly drip the mono-epoxy compounds of nano-dispersed to polyethylene polyamine, prevent sudden and violent poly-.
(3) diepoxides addition reaction
Still contain primary amine hydrogen through end capped polyethylene polyamine, and bad,, introduce the Resins, epoxy segment, improve with the consistency of Resins, epoxy and reduce the activity of its primary amine hydrogen at molecule segment by with it and diepoxides addition with epoxy resin compatibility.
Diepoxides can adopt bisphenol A type epoxy resin or bisphenol f type epoxy resin, as Resins, epoxy such as 601,6101 and 618.Proportioning raw materials is that 1:1.5-1.5:1 calculates by the mol ratio of the epoxy group(ing) of end-blocking product and diepoxides, and temperature of reaction is controlled at 80-120 ℃, and the time is 0.5-1.5 hour; Only contain secondary amine hydrogen in the solidifying agent that makes thus, moderate with the reactive behavior of Resins, epoxy, thus have certain working life.Consistency with the epoxy branch also is improved simultaneously.
(4) organic acid salt-forming reaction
The polyethylene polyamine solidifying agent itself is water miscible, and wetting ability descends after mono-epoxy compounds end-blocking and Resins, epoxy addition, therefore by salt-forming reaction, improves its wetting ability.
Salify adopts organic acid, as acetate, formic acid etc., the equivalence ratio of remaining amine hydrogen is 1:2.5-1:5 after organic acid and end-blocking and the addition, and the salify rate is 20-40%, and temperature of reaction is 80-100 ℃, time is 0.5-1.5 hours, salt-forming reaction adds entry after finishing, and regulates the solid content of solidifying agent, obtains water miscible solidifying agent, its solid content is faint yellow viscous liquid at 25-35%.The solidifying agent that obtains like this has hydrophilic-lipophilic balance preferably, can be dispersed in the water, with Resins, epoxy or epoxy resin solution consistency is preferably arranged again.
2. prepare the aqueous epoxy nano composite coating
The first component: the aqueous epoxy nano composite curing agent adds proper quantity of defoaming agent, as SPA-202 (China), EGITAN760 (German Munzing company), fully disperses the back as the first component.
Component B: liquid epoxies or epoxy resin solution.Preferably adopt low molecular weight material.
Is that the consumption of 1:1.5-1.5:1 mixes with first component and second component by the amine hydrogen and the mol ratio of epoxy group(ing), stirs promptly.
The performance of gained nano composite dope:
The median size of emulsive Resins, epoxy:＜2 μ m;
Surface drying time (fingers-touch method): about 1 hour (GB/T 1728-79);
Working life: about 3 hours (glossiness drop to original 75%);
Hardness of film (fork method):〉0.85 (GB/T 1730-93);
Sticking power (drawing the circle method): 1 grade;
Glossiness: 90%;
Water tolerance: 25 ℃, distilled water immersion, 50 days, non-foaming, (GB/T 1733-99) do not come off;
Acid resistance: 25 ℃, 5%H
2SO
4Solution soaking, 8 days, non-foaming, (GB 1763-79) do not come off;
Alkali resistance: 25 ℃, the 5%NaOH solution soaking, 8 days, non-foaming, (GB 1763-79) do not come off.
The present invention is by modification room temperature epoxy hardener, obtain nano combined aqueous epoxy curing agent with emulsification function, coating with Resins, epoxy is mixed with except the characteristics that aqueous epoxy coating is arranged, also has construction technology and simply reaches advantages such as performance functionization.The aqueous epoxy nano composite coating of performance functionization will have good industrial prospect and produce huge economic benefit, can be used for the metallic surface, surface of vehicle, glass surface, external and internal wall surface, surface, playground; Have, wear resistance is good, transparency is high, reflectivity is good, noise resistance, anti-aging or the like, can give full play to the effect of its functionalization.
Embodiment
Embodiment 1
(1) the aqueous epoxy nano composite curing agent is synthetic
(a) dispersion of nanoparticle
Take by weighing the 150g phenyl glycidyl ether, pour beaker into and take by weighing 7.9g lamella nano imvite again, carried out high-speed stirring 5 minutes, carried out again ultrasonic 30 minutes after preliminary the dispersion.
(b) polyethylene polyamine end capping
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, slowly drip nano imvite dispersive 150g phenyl glycidyl ether again, control reaction temperature is 60 ℃, and in 2.5 hours reaction times, product is light yellow viscous liquid.
(c) diepoxides addition reaction
In four-necked bottle, add 601 Resins, epoxy 42g, be heated to 90 ℃, treat to add the 30g ethylene glycol monoethyl ether again after its fusion, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 25.5g again, slowly heat up, control and maintenance temperature of reaction are about 90 ℃, react 1.5 hours.
(d) organic acid salt-forming reaction
5g acetic acid is joined in the reactant, be carried out to reactant salt, the salify rate is 25%, and holding temperature was reacted 1.5 hours about 90 ℃ again.
(e) be dissolved in water
In the time of 90 ℃, add 150g water, be stirred to the formation yellow solution.
Solid content: 27%
Viscosity: about 5,500mPa.s
Amine hydrogen equivalent: 730
(2) preparation of bi-component aqueous epoxy resinous varnish
The first component: add 0.2% SPA-202 defoamer in the property epoxy nano composite curing agent, height stirs and is uniformly dispersed.
Second component: low molecular weight liquid epoxy
With the first component: the mixed of second component=4:1, stir by hand, be coated on sheet glass and the tinplate sheet with brush.Form transparent wet film behind the moisture evaporation, surface drying time is 70 minutes, film performance:
Hardness (fork method) 0.85
Glossiness 85%
1 grade of sticking power
25 ℃ of water tolerance, 50 days: non-foaming, do not peel off;
25 ℃ of acid resistances, 8 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off;
25 ℃ of alkali resistances, 8 days, the 5%NaOH solution soaking, non-foaming, do not come off.
Embodiment 2
(1) the aqueous epoxy nano composite curing agent is synthetic
(a) dispersion of nanoparticle
Take by weighing the 164g benzyl glycidyl ether, pour beaker into and take by weighing the 15.8g nano silicon again, carried out high-speed stirring 5 minutes, carried out again ultrasonic 30 minutes after preliminary the dispersion.
(b) polyethylene polyamine end capping
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, slowly drip nano silicon dispersive 179.8g benzyl glycidyl ether again, control reaction temperature is 60 ℃, and in 2 hours reaction times, product is light yellow viscous liquid.
(c) diepoxides addition reaction
In four-necked bottle, add 618 Resins, epoxy 16.5g, be heated to 90 ℃, treat to add the 6g ethylene glycol monoethyl ether again after its fusion, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 27.4g again, slowly heat up, control and maintenance temperature of reaction are about 90 ℃, react 2 hours.
(d) organic acid salt-forming reaction
5g acetic acid is joined in the reactant, be carried out to reactant salt, the salify rate is 25%, and holding temperature was reacted 1 hour about 90 ℃ again.
(e) be dissolved in water
In the time of 90 ℃, add 120g water, be stirred to the formation yellow solution.
Solid content: 27%
Viscosity: about 3,500mPa.s
Amine hydrogen equivalent: 488
(2) add 0.2% SPA-202 defoamer in the preparation of bi-component aqueous epoxy resinous varnish, height stirs and is uniformly dispersed.
The first component:: the aqueous epoxy nano composite curing agent
Second component: liquid epoxies
With the first component: the mixed of second component=4:1, stir by hand, be coated on sheet glass and the tinplate sheet with brush.Form transparent wet film behind the moisture evaporation, surface drying time is 60 minutes, film performance:
Hardness (fork method) 0.85
Glossiness 75%
1 grade of sticking power
25 ℃ of water tolerance, 45 days: non-foaming, do not peel off;
25 ℃ of acid resistances, 6 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off;
25 ℃ of alkali resistances, 8 days, the 5%NaOH solution soaking, non-foaming, do not come off.
Embodiment 3
(1) the aqueous epoxy nano composite curing agent is synthetic
(a) dispersion of nanoparticle
Take by weighing the 130g butylglycidyl ether, pour beaker into and take by weighing 7.9g lamella nano titanium oxide again, carried out high-speed stirring 5 minutes, carried out again ultrasonic 30 minutes after preliminary the dispersion.
(b) polyethylene polyamine end capping
On four-necked bottle, equip whipping appts, thermometer and reflux.Add 145g triethylene tetramine (TETA, 1 mole) earlier, slowly drip nano imvite dispersive 130g phenyl glycidyl ether again, control reaction temperature is 60 ℃, and in 2 hours reaction times, product is light yellow viscous liquid.
(c) diepoxides addition reaction
In four-necked bottle, add 601 Resins, epoxy 42g, be heated to 90 ℃, treat to add the 30g ethylene glycol monoethyl ether again after its fusion, resin is dissolved fully.Resin solution is cooled to about 40 ℃, adds the above-mentioned end-blocking product of 23.8g again, slowly heat up, control and maintenance temperature of reaction are about 90 ℃, react 2 hours.
(d) organic acid salt-forming reaction
5g acetic acid is joined in the reactant, be carried out to reactant salt, the salify rate is 25%, and holding temperature was reacted 1 hour about 90 ℃ again.
(e) be dissolved in water
In the time of 90 ℃, add 150g water, be stirred to the formation yellow solution.
Solid content: 27%
Viscosity: about 3,500mPa.s
Amine hydrogen equivalent: 732
(2) preparation Resins, epoxy ethereal solution
Add cosolvent ethylene glycol monoethyl ether 10g in 100g Resins, epoxy 6101, make the Resins, epoxy dissolving, to reduce the viscosity of Resins, epoxy, the add-on of cosolvent ethylene glycol monoethyl ether is 10% of a weight epoxy.(3) preparation of bi-component aqueous epoxy resinous varnish
The first component:: the aqueous epoxy nano composite curing agent
Second component: Resins, epoxy ethereal solution
With the first component: the mixed of second component=3.8:1, stir by hand, be coated on sheet glass and the tinplate sheet with brush.Form transparent wet film behind the moisture evaporation, surface drying time is 55 minutes, film performance:
Hardness (fork method) 0.80
Glossiness 80%
1 grade of sticking power
25 ℃ of water tolerance, 38 days: non-foaming, do not peel off;
25 ℃ of acid resistances, 6 days, 5%H
2SO
4Solution soaking, non-foaming, do not come off;
25 ℃ of alkali resistances, 6 days, the 5%NaOH solution soaking, non-foaming, do not come off.
Claims (5)
1, a kind of aqueous epoxy nano composite coating, it is characterized in that forming by liquid epoxies or Resins, epoxy ethereal solution and two components of aqueous epoxy nano composite curing agent, wherein, the aqueous epoxy nano composite curing agent for by polyamines class solidifying agent through end-blocking, addition, salify process modification and add nanoparticle and obtain, solid content is 25-35%; Existing hydrophilic radical in this solidifying agent molecule segment has lipophilic group again, directly emulsion epoxy resin; The consumption of aqueous epoxy nano composite curing agent and liquid epoxies or Resins, epoxy ethereal solution is that 1.5:1-1:1.5 calculates by the mol ratio of amine hydrogen and epoxy group(ing); Wherein, described aqueous epoxy nano composite curing agent for by polyamines class solidifying agent through end-blocking, addition, salify process modification and to add the process that nanoparticle obtains as follows:
(a) dispersion of nanoparticle
The mono-epoxy compounds high speed that joins nano particle is carried out ultra-sonic dispersion after stirring again;
(b) polyethylene polyamine end capping
With polyethylene polyamine and the mono-epoxy compounds reaction that has disperseed nano particle, the raw material consumption is that 1:1.5-1.5:1 calculates by the mol ratio of the epoxy group(ing) of polyethylene polyamine and mono-epoxy compounds, and temperature of reaction is 50-70 ℃, time 1.5-2.5 hour;
(c) diepoxides addition reaction
With end capped polyethylene polyamine and diepoxides addition reaction, the raw material consumption is that 1:1.5-1.5:1 calculates by the mol ratio of the epoxy group(ing) of end-blocking product and diepoxides, and temperature of reaction 80-120 ℃, the time is 0.5-1.5 hour;
(d) organic acid salt-forming reaction
Salify adopts organic acid, and the equivalence ratio of remaining amine hydrogen is 1:2.5-1:5 after organic acid and end-blocking and the addition, and the salify rate is 20%-40%, and temperature of reaction is 80-100 ℃, and the time is 0.5-1.5 hours; Salt-forming reaction adds entry after finishing, and obtains water miscible solidifying agent, and it is 25-35% for solid content;
Wherein, described mono-epoxy compounds adopts aliphatic group glycidyl ether or arylolycidyl ethers, perhaps both mixtures.
2, the preparation method of aqueous epoxy nano composite coating according to claim 1 is characterized in that concrete steps are:
(1) preparation aqueous epoxy nano composite curing agent:
(a) dispersion of nanoparticle
The mono-epoxy compounds high speed that joins nano particle is carried out ultra-sonic dispersion after stirring again;
(b) polyethylene polyamine end capping
With polyethylene polyamine and the mono-epoxy compounds reaction that has disperseed nano particle, the raw material consumption is that 1:1.5-1.5:1 calculates by the mol ratio of the epoxy group(ing) of polyethylene polyamine and mono-epoxy compounds, and temperature of reaction is 50-70 ℃, time 1.5-2.5 hour;
(c) diepoxides addition reaction
With end capped polyethylene polyamine and diepoxides addition reaction, the raw material consumption is that 1:1.5-1.5:1 calculates by the mol ratio of the epoxy group(ing) of end-blocking product and diepoxides, and temperature of reaction 80-120 ℃, the time is 0.5-1.5 hour;
(d) organic acid salt-forming reaction
Salify adopts organic acid, and the equivalence ratio of remaining amine hydrogen is 1:2.5-1:5 after organic acid and end-blocking and the addition, and the salify rate is 20%-40%, and temperature of reaction is 80-100 ℃, and the time is 0.5-1.5 hours; Salt-forming reaction adds entry after finishing, and obtains water miscible solidifying agent, and it is 25-35% for solid content;
(2) preparation composite coating:
The aqueous epoxy nano composite curing agent of gained is added proper quantity of defoaming agent, as the first component, liquid epoxies or Resins, epoxy ethereal solution be as component B, and first component and component B are that the consumption of 1:1.5-1.5:1 mixes by the amido and the mol ratio of epoxy group(ing), stir;
Wherein, described mono-epoxy compounds adopts aliphatic group glycidyl ether or arylolycidyl ethers, perhaps both mixtures.
3, the preparation method of aqueous epoxy nano composite coating according to claim 2, it is characterized in that described nano particle is a kind of in the lamellated polynite of nanometer sheet, granulous silicon-dioxide, the titanium dioxide, addition is the 1%-15% of mono-epoxy compounds weight.
4, the preparation method of aqueous epoxy nano composite coating according to claim 2 is characterized in that the diepoxides that adopts is bisphenol A type epoxy resin or bisphenol f type epoxy resin.
5, the preparation method of aqueous epoxy nano composite coating according to claim 2 is characterized in that described organic acid is acetate or formic acid.
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| CN103897347A (en) * | 2012-12-25 | 2014-07-02 | 比亚迪股份有限公司 | Thermosetting resin composition, and prepreg and laminated board prepared from the resin composition |
| CN103087611B (en) * | 2013-01-22 | 2015-08-19 | 四川大学 | A kind of aqueous epoxide resin paint and preparation method thereof |
| CN105602400B (en) * | 2016-01-05 | 2018-05-15 | 滁州金桥德克新材料有限公司 | A kind of preparation method of environment-friendly water-based metal color steel tile coating coating |
| CN106046325B (en) * | 2016-06-15 | 2018-08-03 | 石家庄市金达特种涂料有限公司 | A kind of aqueous epoxy curing agent and water-base epoxy vehicle frame paint |
| CN106189827A (en) * | 2016-08-26 | 2016-12-07 | 安徽建邦建材有限公司 | A kind of wear-resisting epoxy coating of insulated wall |
| CN113025102B (en) * | 2021-02-26 | 2022-01-14 | 中科院广州化学有限公司 | Amphiphilic polyether amine nano composite supramolecular antibacterial coating and preparation method and application thereof |
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