CN101613460A - Aqueous epoxy curing agent and water-base epoxy membrane-forming agent and preparation method thereof - Google Patents
Aqueous epoxy curing agent and water-base epoxy membrane-forming agent and preparation method thereof Download PDFInfo
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- CN101613460A CN101613460A CN200910089899A CN200910089899A CN101613460A CN 101613460 A CN101613460 A CN 101613460A CN 200910089899 A CN200910089899 A CN 200910089899A CN 200910089899 A CN200910089899 A CN 200910089899A CN 101613460 A CN101613460 A CN 101613460A
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Abstract
The present invention relates to a kind of aqueous epoxy curing agent and water-base epoxy membrane-forming agent and preparation method thereof.The preparation method of aqueous epoxy curing agent comprises: step 11. is added drop-wise to the bis-epoxy long-chain compound in the mixed solution of polyethylene polyamine and organic solvent, be added dropwise to complete temperature of reaction 2h～3h that the back keeps 45 ℃～75 ℃, the mol ratio of bis-epoxy long-chain compound and polyethylene polyamine is 1: 1.5～6; Step 12. is added drop-wise to the solution that step 11 prepares with the Resins, epoxy diluent that Resins, epoxy adopts thinner to obtain, and is added dropwise to complete temperature of reaction 2h～3h that the back keeps 45 ℃～75 ℃, and the mol ratio of Resins, epoxy and polyethylene polyamine is 1: 2.5～4; Step 13. adopts the mode of underpressure distillation to remove organic solvent and thinner, obtains aqueous epoxy curing agent.The preparation technology of aqueous epoxy curing agent of the present invention and water-base epoxy membrane-forming agent is simple, easy to operate, environmentally safe, cost are low.
Description
Technical field
The present invention relates to technical field of coatings, particularly relate to a kind of aqueous epoxy curing agent and water-base epoxy membrane-forming agent and preparation method thereof.
Background technology
Traditional solvent epoxy varnish membrane-forming agent, have that adhesion property is good, shrinking percentage is little, mechanical property is good, acid and alkali-resistance, advantage such as wear-resisting, but, therefore, have shortcomings such as harm operator safety, environmental pollution be serious because of it contains a large amount of volatile organic solvent (as: VOC).The aqueous epoxy resins membrane-forming agent had both had the advantage of traditional solvent epoxy varnish membrane-forming agent, simultaneously again can compliance with environmental protection requirements, therefore, become the development trend of coating industry.
Prior art one: patent publication No. is the preparation method that the Chinese patent application of CN1752163A discloses a kind of aqueous epoxide resin paint, aqueous epoxy curing agent wherein is through the mono-epoxy compounds end-blocking by polyethylene polyamine, the diepoxides addition is made by the organic acid salify at last.The polyethylene polyamine molecule segment expanded even through a step, and existing hydrophilic radical has lipophilic group again, so have emulsifying effect.
Prior art two: patent publication No. is that the Chinese patent application of CN1958639A discloses a kind of polyethylene polyamine prepares aqueous epoxy curing agent through two step chain extensions method, this method is at first carried out chain extending reaction with polyether Glycols to Resins, epoxy, with the chain extension product polyethylene polyamine is carried out the secondary chain extension reaction again, use the vinyl cyanide end-blocking then, monobasic organic acid salify is prepared the aqueous epoxy curing agent with soft segment.
Above-mentioned prior art one and prior art two add the organic acid salify and regulate wetting ability in the preparation aqueous epoxy curing agent, make it have emulsification function and curing function simultaneously, but the organic acid adding not only can pollute environment, the film forming properties of coating is descended, be used in easily to produce on the metal and dodge rust.Therefore, the not salifiable environmental protection direction of aqueous epoxide resin paint forward develops.
Prior art three: patent publication No. is the preparation method that the Chinese patent application of CN101220237A discloses non-ionic self-emulsifying aqueous epoxy cold coating a kind of environment-friendly type, that be made up of aqueous epoxy resins and waterborne curing agent. in this method, aqueous epoxy resins is to react by Resins, epoxy and alpha-amino group-ω-alkyl oxide to make, and waterborne curing agent adopts the amine curing agent of epoxy resin modification.
And in the prior art three, alpha-amino group-ω-alkyl oxide building-up process is very complicated, has limited its application.As seen, how from the relation of molecular structure and performance, by the non-ion aqueous epoxy hardener that molecule design method is prepared, make its function, thereby preparation water-base epoxy membrane-forming agent becomes present urgent problem with good emulsifying liquid epoxies.
Summary of the invention
The invention provides a kind of aqueous epoxy curing agent and water-base epoxy membrane-forming agent and preparation method thereof, complicacy in order to the aqueous epoxy curing agent preparation that reduces non-ionic type, can synthesize multiple suitable varying environment based on aqueous epoxy curing agent, the water-base epoxy membrane-forming agent of different working conditionss helps enlarging the range of application of water-base epoxy membrane-forming agent.
The invention provides a kind of aqueous epoxy curing agent, this aqueous epoxy curing agent is made through bis-epoxy long-chain compound and Resins, epoxy chain extension are synthetic by polyethylene polyamine, the mol ratio of described bis-epoxy long-chain compound and polyethylene polyamine is 1: 1.5～6, and the mol ratio of Resins, epoxy and polyethylene polyamine is 1: 2.5～4.
The present invention also provides a kind of water-base epoxy membrane-forming agent that comprises above-mentioned aqueous epoxy curing agent, the water-base epoxy membrane-forming agent also comprises second Resins, epoxy and deionized water, the mass percent of described aqueous epoxy curing agent is 21%～39%, the mass percent of described second Resins, epoxy is 19%～37%, and the mass percent of described deionized water is 35%～55%.
The present invention also provides a kind of preparation method who comprises above-mentioned aqueous epoxy curing agent, comprising:
The mode of step 13, employing underpressure distillation is removed described organic solvent and described thinner, obtains aqueous epoxy curing agent.
The present invention also provides a kind of preparation method of above-mentioned water-base epoxy membrane-forming agent, comprising:
The present invention adopts the get everything ready normal temperature aqueous epoxy curing agent of emulsification function of continuous two step chain extension legal systems, and prepare the water-base epoxy membrane-forming agent based on aqueous epoxy curing agent, its preparation technology is simple, easy to operate, environmentally safe, cost are low, has very big prospects for commercial application.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art, to do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below, apparently, accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is preparation method's schema of aqueous epoxy curing agent of the present invention;
Fig. 2 is preparation method's schema of water-base epoxy membrane-forming agent of the present invention;
Fig. 3 is the infrared test spectrogram of aqueous epoxy curing agent of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
The invention provides a kind of aqueous epoxy curing agent, this aqueous epoxy curing agent is through bis-epoxy long-chain compound and synthetic the making of two step of Resins, epoxy continuous processing chain extension by polyethylene polyamine, the mol ratio of bis-epoxy long-chain compound and polyethylene polyamine is 1: 1.5～6, and the mol ratio of Resins, epoxy and polyethylene polyamine is 1: 2.5～4.In the technique scheme, described bis-epoxy long-chain compound is the polyether glycol diglycidylether, and described polyether glycol diglycidylether comprises: polyethyleneglycol diglycidylether, or polypropylene glycol diglycidyl ether, or the mixture of the two.Described Resins, epoxy is bisphenol A type epoxy resin, and described bisphenol A type epoxy resin can be selected for use: the bisphenol A type epoxy resin of 828,834,618,637,638, the 6101 domestic and international trades mark such as grade.Described polyethylene polyamine is for comprising: diethylenetriamine, triethylene tetramine, tetraethylene pentamine, m-xylene diamine, or a benzene two methanediamines.
The present invention also provides a kind of water-base epoxy membrane-forming agent that comprises above-mentioned aqueous epoxy curing agent, concrete, this water-base epoxy membrane-forming agent comprises: above-mentioned aqueous epoxy curing agent, Resins, epoxy is (in order to distinguish with above-mentioned Resins, epoxy, below will be called second Resins, epoxy with aqueous epoxy curing agent blended Resins, epoxy) and deionized water, the mass percent of aqueous epoxy curing agent is 21%～39%, the mass percent of second Resins, epoxy is 19%～37%, and the mass percent of deionized water is 35%～55%.Wherein, second Resins, epoxy can comprise: the bisphenol A-type liquid-state epoxy resin, it as the Chinese trade mark 6002 bisphenol A-type liquid-state epoxy resin, perhaps, select E-51 for use, E-44, E-42, E-35, E-31 etc. be the bisphenol A type epoxy resin of the trade mark both at home and abroad, or the mixture that makes up in twos of above-mentioned trade mark product.
Fig. 1 is preparation method's schema of aqueous epoxy curing agent of the present invention.The present invention adopts the get everything ready method of normal temperature aqueous epoxy curing agent of emulsification function of continuous two step chain extension legal systems, carries out continuously under same reaction device (being the confined reaction chamber), same reaction temperature, and temperature of reaction is controlled at 45～75 ℃.8min～12min is to the logical nitrogen in confined reaction chamber before the reaction, and preferred, 10min afterwards, carries out preparation method's flow process of aqueous epoxy curing agent as shown in Figure 1 to the logical nitrogen in confined reaction chamber before the reaction, comprising:
The mode of step 13, employing underpressure distillation is removed described organic solvent and described thinner, obtains aqueous epoxy curing agent.
Fig. 2 is preparation method's schema of water-base epoxy membrane-forming agent of the present invention.As shown in Figure 2, the preparation method of above-mentioned water-base epoxy membrane-forming agent comprises:
The fundamental property of the water-base epoxy membrane-forming agent that the employing method for preparing obtains is as shown in table 1.
The fundamental property of table 1 water-base epoxy membrane-forming agent
| Test event | Performance | Testing method |
| The membrane-forming agent outward appearance | Light yellow, little thick liquid | ??- |
| Surface drying time | ??1h | ??- |
| The completely solidified time | ??7D | ??- |
| Hardness | ??2～3H | ??GB/T?6739-2006 |
| Sticking power (method of drawing a circle) | 1～2 grade | ??GB1720-79 |
| Snappiness | ??1～2mm | ??GB1731-79 |
| Shock-resistant | ??＞65kg.cm | ??GB1732-79 |
Based on the analysis of technique scheme as can be known, the present invention has following advantage:
1, in two step chain extension processes of polyethylene polyamine, owing to be continuous reaction in closed reactor, only need therefore shorten the time that feeds nitrogen greatly at the logical nitrogen of reaction precontract 10min, help industrial applications.
2, in two step chain extension processes of polyethylene polyamine, adopt the continuous processing reaction, polyethylene polyamine is all by chain extending reaction, avoided contacting of the bigger low molecule amine of operator and toxicity, reduced environmental pollution.
3, adopt molecule design method, the soft segment of bis-epoxy long-chain compound is introduced in the solidifying agent, can increase the toughness of Resins, epoxy membrane-forming agent, improve impact strength.
4, this membrane-forming agent has good adhesion to multiple base material, anti-anticorrosion and good characteristics such as application property, and environmentally safe, and cured film reality is nontoxic.
In a word, technology of the present invention is simple, easy to operate, cost is low, has very big prospects for commercial application.
In order to understand the present invention better, the present invention will be further explained below in conjunction with specific embodiment, but will be clear that the scope of protection of the invention is not limited to the scope that embodiment represents.Respectively describe in detail among the embodiment following, for ease of statement, below only represent the Resins, epoxy selected for use in the concrete enforcement with the product grade of Resins, epoxy, as representing with 828: the trade mark is 828 bisphenol A type epoxy resin.
Embodiment one
(1) preparation of aqueous epoxy curing agent
In the present embodiment, in the required component of preparation aqueous epoxy curing agent, organic solvent and thinner are all selected propylene glycol monomethyl ether for use, and the bis-epoxy long-chain compound is selected polyethyleneglycol diglycidylether for use, polyethylene polyamine is selected triethylene tetramine for use, and Resins, epoxy selects 828 for use.The preparation process of aqueous epoxy curing agent is as follows:
Add the 70ml propylene glycol monomethyl ether in the 500ml four-hole bottle of prolong, stirring rake is housed, starts stirring, the triethylene tetramine with 0.4mol under nitrogen protection adds in the four-hole bottle.Stirring velocity is 550r/min, adopts heating in water bath, and temperature is set at 60 ℃.Begin to drip polyethyleneglycol diglycidylether 0.2mol when temperature reaches set(ting)value, rate of addition is 0.5ml/min, behind the dropping beginning 10min, stops logical nitrogen, is incubated 2.5h after being added dropwise to complete again.After insulation finishes, dripping the Resins, epoxy 828 of 0.15mol with the speed of 1ml/min, is viscosity and the controls reaction speed that reduces Resins, epoxy, with the propylene glycol monomethyl ether of 40ml 828 dilution backs is dripped, and is added dropwise to complete back insulation 2.5h.Reaction is finished postcooling to the room temperature discharging, in 70～90 ℃ of intervals products therefrom is carried out underpressure distillation, removes the organic solvent propylene glycol monomethyl ether, obtains the epoxy hardener of oyster transparent and homogeneous.
Fig. 3 is the infrared test spectrogram of aqueous epoxy curing agent of the present invention, and in the infrared spectrogram shown in Figure 3, X-coordinate is represented wavelength, and the ordinate zou (not shown) is represented the relative intensity of each crest.By analysis chart 3 as can be known, at 3300cm
-1-3500cm
-1About the charateristic avsorption band of polyamines has appearred; 1580cm
-1, 1508cm
-1, 1458cm
-1The place is the vibration performance absorption peak of phenyl ring, has only Resins, epoxy that phenyl ring is arranged in the raw material, illustrates that the Resins, epoxy segment is present in the chain extension product; 1100cm
-1About locate charateristic avsorption band into polyethers, illustrating has the Aethoxy Sklerol segment in the product; 830cm
-1, 770cm
-1The place is the absorption peak of phenyl ring to two replacements, and further illustrating product is the result of 828 chain extensions.In following embodiment, the infrared figure of product is similar to embodiment one, and the back no longer specifically describes.
(2) preparation of water-base epoxy membrane-forming agent
A component: second Resins, epoxy;
B component: aqueous epoxy curing agent.
The preparation process of water-base epoxy membrane-forming agent is as follows:
With the A component: the mixed of B component=1: 1 (mass ratio), the manual stirring, add deionized water while stirring, make the solid content of membrane-forming agent reach 50%, be coated on sheet glass and the tinplate sheet with brush after stirring, form transparent wet film behind the moisture evaporation, surface drying time is 1h, film performance:
Hardness 2H;
1 grade of sticking power (method of drawing a circle);
Snappiness 1mm;
Shock-resistant 68kg.cm.
Embodiment two
(1) preparation of aqueous epoxy curing agent
In the present embodiment, in the required component of preparation aqueous epoxy curing agent, organic solvent and thinner are all selected propylene glycol monomethyl ether for use, and the bis-epoxy long-chain compound is selected polyethyleneglycol diglycidylether for use, polyethylene polyamine is selected diethylenetriamine for use, and Resins, epoxy selects 618 for use.The preparation process of aqueous epoxy curing agent is as follows:
Add the 60ml propylene glycol monomethyl ether in the 500ml four-hole bottle of prolong, stirring rake is housed, starts stirring, the diethylenetriamine with 0.4mol under nitrogen protection adds in the four-hole bottle.Stirring velocity is 500r/min, adopts heating in water bath, and temperature is set at 50 ℃.Begin to drip polyethyleneglycol diglycidylether 0.2mol when temperature reaches set(ting)value, rate of addition is 0.5ml/min, behind the dropping beginning 10min, stops logical nitrogen, is added dropwise to complete back insulation 2.5h.After insulation finishes, dripping the Resins, epoxy 618 of 0.10mol with the speed of 1ml/min, is viscosity and the controls reaction speed that reduces Resins, epoxy, drips together after to 618 dilutions with the propylene glycol monomethyl ether of 45ml, is added dropwise to complete back insulation 2.5h.Reaction is finished postcooling to the room temperature discharging, in 70～90 ℃ of intervals products therefrom is carried out underpressure distillation, removes the organic solvent propylene glycol monomethyl ether.
(2) preparation of water-base epoxy membrane-forming agent
A component: second Resins, epoxy;
B component: aqueous epoxy curing agent.
The preparation process of water-base epoxy membrane-forming agent is as follows:
With the A component: the mixed of B component=1: 1.3 (mass ratio), the manual stirring, add deionized water while stirring, make the solid content of membrane-forming agent reach 50%, be coated on sheet glass and the tinplate sheet with brush after stirring, form transparent wet film behind the moisture evaporation, surface drying time is 1h, film performance:
Hardness 3H;
1 grade of sticking power (method of drawing a circle);
Snappiness 2mm;
Shock-resistant 67kg.cm.
Embodiment three
(1) preparation of aqueous epoxy curing agent
In the present embodiment, in the required component of preparation aqueous epoxy curing agent, organic solvent and thinner are all selected propylene glycol monomethyl ether for use, and the bis-epoxy long-chain compound is selected polypropylene glycol diglycidyl ether for use, polyethylene polyamine is selected triethylene tetramine for use, and Resins, epoxy selects 6101 for use.The preparation process of aqueous epoxy curing agent is as follows:
Add the 75ml propylene glycol monomethyl ether in the 500ml four-hole bottle of prolong, stirring rake is housed, starts stirring, the triethylene tetramine with 0.4mol under nitrogen protection adds in the four-hole bottle.Stirring velocity is 550r/min, adopts heating in water bath, and temperature is set at 65 ℃.Begin to drip polypropylene glycol diglycidyl ether 0.2mol when temperature reaches set(ting)value, rate of addition is 0.5ml/min, behind the dropping beginning 10min, stops logical nitrogen.Be added dropwise to complete back insulation 3h.After insulation finishes, dripping the Resins, epoxy 6101 of 0.15mol with the speed of 1ml/min, is viscosity and the controls reaction speed that reduces Resins, epoxy, drips together after to 6101 dilutions with the propylene glycol monomethyl ether of 50ml, is added dropwise to complete back insulation 2.5h.Reaction is finished postcooling to the room temperature discharging, in 70～90 ℃ of intervals products therefrom is carried out underpressure distillation, removes the organic solvent propylene glycol monomethyl ether.
(2) preparation of water-base epoxy membrane-forming agent
A component: second Resins, epoxy;
B component: oil-in-water type aqueous epoxy curing agent.
The preparation process of water-base epoxy membrane-forming agent is as follows:
With the A component: the mixed of B component=1: 1.1 (mass ratio), the manual stirring, add deionized water while stirring, make the solid content of membrane-forming agent reach 55%, be coated on sheet glass and the tinplate sheet with brush after stirring, form transparent wet film behind the moisture evaporation, surface drying time is 1h, film performance:
Hardness 2H;
1 grade of sticking power (method of drawing a circle);
Snappiness 2mm;
Shock-resistant 68kg.cm.
Embodiment four
(1) preparation of aqueous epoxy curing agent
In the present embodiment, in the required component of preparation aqueous epoxy curing agent, organic solvent and thinner are all selected propylene glycol monomethyl ether for use, and the bis-epoxy long-chain compound is selected polyethyleneglycol diglycidylether for use, polyethylene polyamine is selected triethylene tetramine for use, and Resins, epoxy selects 834 for use.The preparation process of aqueous epoxy curing agent is as follows:
Add the 75ml propylene glycol monomethyl ether in the 500ml four-hole bottle of prolong, stirring rake is housed, starts stirring, the triethylene tetramine with 0.4mol under nitrogen protection adds in the four-hole bottle.Stirring velocity is 550r/min, adopts heating in water bath, and temperature is set at 60 ℃.Begin to drip polyethyleneglycol diglycidylether 0.2mol when temperature reaches set(ting)value, rate of addition is 0.5ml/min, behind the dropping beginning 10min, stops logical nitrogen.Be added dropwise to complete back insulation 2h.After insulation finishes, dripping the Resins, epoxy 834 of 0.20mol with the speed of 1ml/min, is viscosity and the controls reaction speed that reduces Resins, epoxy, drips together after to 834 dilutions with the propylene glycol monomethyl ether of 50ml, is added dropwise to complete back insulation 2.5h.Reaction is finished postcooling to the room temperature discharging, in 70～90 ℃ of intervals products therefrom is carried out underpressure distillation, removes the organic solvent propylene glycol monomethyl ether, obtains the epoxy hardener of oyster transparent and homogeneous.
(2) preparation of water-base epoxy membrane-forming agent
A component: second Resins, epoxy;
B component: oil-in-water type aqueous epoxy curing agent.
The preparation process of water-base epoxy membrane-forming agent is as follows:
With the A component: the mixed of B component=1: 1.2 (mass ratio), the manual stirring, add deionized water while stirring, make the solid content of membrane-forming agent reach 55%, be coated on sheet glass and the tinplate sheet with brush after stirring, form transparent wet film behind the moisture evaporation, surface drying time is 1h, film performance:
Hardness 3H;
2 grades of sticking power (method of drawing a circle);
Snappiness 2mm;
Shock-resistant 69kg.cm.
Embodiment five
(1) preparation of aqueous epoxy curing agent
In the present embodiment, in the required component of preparation aqueous epoxy curing agent, organic solvent and thinner are all selected propylene glycol monomethyl ether for use, and the bis-epoxy long-chain compound is selected polyethyleneglycol diglycidylether for use, polyethylene polyamine is selected m-xylene diamine for use, and Resins, epoxy selects 618 for use.The preparation process of aqueous epoxy curing agent is as follows:
Add the 75ml propylene glycol monomethyl ether in the 500ml four-hole bottle of prolong, stirring rake is housed, starts stirring, the m-xylene diamine with 0.4mol under nitrogen protection adds in the four-hole bottle.Stirring velocity is 550r/min, adopts heating in water bath, and temperature is set at 65 ℃.Begin to drip polyethyleneglycol diglycidylether 0.2mol when temperature reaches set(ting)value, rate of addition is 0.5ml/min, behind the dropping beginning 10min, stops logical nitrogen.Be incubated 3h after being added dropwise to complete again.After insulation finishes, dripping the Resins, epoxy 618 of 0.10mol with the speed of 1ml/min, is viscosity and the controls reaction speed that reduces Resins, epoxy, drips together after to 618 dilutions with the propylene glycol monomethyl ether of 40ml, is added dropwise to complete back insulation 2.5h.Reaction is finished postcooling to the room temperature discharging, in 70～90 ℃ of intervals products therefrom is carried out underpressure distillation, removes the organic solvent propylene glycol monomethyl ether.
(2) preparation of water-base epoxy membrane-forming agent
A component: second Resins, epoxy;
B component: oil-in-water type aqueous epoxy curing agent.
The preparation process of water-base epoxy membrane-forming agent is as follows:
With the A component: the mixed of B component=1: 1.3 (mass ratio), the manual stirring, add deionized water while stirring, make the solid content of membrane-forming agent reach 55%, be coated on sheet glass and the tinplate sheet with brush after stirring, form transparent wet film behind the moisture evaporation, surface drying time is 1h, film performance:
Hardness 3H;
2 grades of sticking power (method of drawing a circle);
Snappiness 3mm;
Shock-resistant 75kg.cm.
Embodiment six
(1) preparation of aqueous epoxy curing agent
In the present embodiment, in the required component of preparation aqueous epoxy curing agent, organic solvent and thinner are all selected propylene glycol monomethyl ether for use, and the bis-epoxy long-chain compound is selected polypropylene glycol diglycidyl ether for use, polyethylene polyamine is selected a benzene two methanediamines for use, and Resins, epoxy selects 828 for use.The preparation process of aqueous epoxy curing agent is as follows:
In the 500ml four-hole bottle of prolong, stirring rake is housed, add the 75ml propylene glycol monomethyl ether, start stirring, under nitrogen protection with 0.4mol between benzene two methanediamines add in the four-hole bottle.Stirring velocity is 550r/min, adopts heating in water bath, and temperature is set at 65 ℃.Begin to drip polypropylene glycol diglycidyl ether 0.2mol when temperature reaches set(ting)value, rate of addition is 0.5ml/min, behind the dropping beginning 10min, stops logical nitrogen.Be incubated 3h after being added dropwise to complete again.After insulation finishes, dripping the Resins, epoxy 828 of 0.15mol with the speed of 1ml/min, is viscosity and the controls reaction speed that reduces Resins, epoxy, drips together after to 828 dilutions with the propylene glycol monomethyl ether of 50ml, is added dropwise to complete back insulation 2.5h.Reaction is finished postcooling to the room temperature discharging, in 70～90 ℃ of intervals products therefrom is carried out underpressure distillation, removes the organic solvent propylene glycol monomethyl ether.
(2) preparation of water-base epoxy membrane-forming agent
A component: second Resins, epoxy;
B component: oil-in-water type aqueous epoxy curing agent.
The preparation process of water-base epoxy membrane-forming agent is as follows:
With the A component: the mixed of B component=1: 1.5 (mass ratio), the manual stirring, add deionized water while stirring, make the solid content of membrane-forming agent reach 55%, be coated on sheet glass and the tinplate sheet with brush after stirring, form transparent wet film behind the moisture evaporation, surface drying time is 1h, film performance:
Hardness 3H;
2 grades of sticking power (method of drawing a circle);
Snappiness 2mm;
Shock-resistant 72kg.cm.
The actual use show, the preparation technology of aqueous epoxy curing agent of the present invention and water-base epoxy membrane-forming agent is simple, easy to operate, environmentally safe, cost are low, has very big prospects for commercial application.
It should be noted that at last: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that previous embodiment is put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of embodiment of the invention technical scheme.
Claims (10)
1, a kind of aqueous epoxy curing agent, it is characterized in that, described aqueous epoxy curing agent is made through bis-epoxy long-chain compound and Resins, epoxy chain extension are synthetic by polyethylene polyamine, the mol ratio of described bis-epoxy long-chain compound and polyethylene polyamine is 1: 1.5～6, and the mol ratio of Resins, epoxy and polyethylene polyamine is 1: 2.5～4.
2, aqueous epoxy curing agent according to claim 1, it is characterized in that, described bis-epoxy long-chain compound is the polyether glycol diglycidylether, described polyether glycol diglycidylether comprises: polyethyleneglycol diglycidylether, or polypropylene glycol diglycidyl ether, or the mixture of the two.
3, aqueous epoxy curing agent according to claim 1 is characterized in that, described Resins, epoxy is bisphenol A type epoxy resin.
4, aqueous epoxy curing agent according to claim 1 is characterized in that, described polyethylene polyamine is for comprising: diethylenetriamine, triethylene tetramine, tetraethylene pentamine, m-xylene diamine, or a benzene two methanediamines.
5, a kind of water-base epoxy membrane-forming agent that comprises the arbitrary described aqueous epoxy curing agent of claim 1～4, it is characterized in that, also comprise second Resins, epoxy and deionized water, the mass percent of described aqueous epoxy curing agent is 21%～39%, the mass percent of described second Resins, epoxy is 19%～37%, and the mass percent of described deionized water is 35%～55%.
6, water-base epoxy membrane-forming agent according to claim 5 is characterized in that, described second Resins, epoxy comprises: the bisphenol A-type liquid-state epoxy resin.
7, the preparation method of the arbitrary described aqueous epoxy curing agent of a kind of claim 1～4 is characterized in that, comprising:
Step 11, the bis-epoxy long-chain compound is added drop-wise in the mixed solution of polyethylene polyamine and organic solvent, be added dropwise to complete temperature of reaction 2h～3h that the back keeps 45 ℃～75 ℃, the mol ratio of described bis-epoxy long-chain compound and described polyethylene polyamine is 1: 1.5～6;
Step 12, the Resins, epoxy diluent that adopts thinner to obtain Resins, epoxy are added drop-wise to the solution that step 11 prepares, be added dropwise to complete temperature of reaction 2h～3h that the back keeps 45 ℃～75 ℃, the mol ratio of described Resins, epoxy and described polyethylene polyamine is 1: 2.5～4;
The mode of step 13, employing underpressure distillation is removed described organic solvent and described thinner, obtains aqueous epoxy curing agent.
8, according to the preparation method of the described aqueous epoxy curing agent of claim 7, it is characterized in that, described step 11 and described step 12 are carried out under same reaction device, same reaction temperature continuously, also comprise: at the logical nitrogen in described reaction unit of 8min～12min before the performing step 11.
9, the preparation method of aqueous epoxy curing agent according to claim 7 is characterized in that, described organic solvent and described thinner are propylene glycol monomethyl ether.
10, the preparation method of a kind of claim 5 or 6 described water-base epoxy membrane-forming agents is characterized in that, comprising:
Step 21, preparation aqueous epoxy curing agent, comprise: the bis-epoxy long-chain compound is added drop-wise in the mixed solution of polyethylene polyamine and organic solvent, be added dropwise to complete temperature of reaction 2h～3h that the back keeps 45 ℃～75 ℃, the mol ratio of described bis-epoxy long-chain compound and described polyethylene polyamine is 1: 1.5～6; The Resins, epoxy diluent that adopts thinner to obtain Resins, epoxy is added drop-wise to the solution that step 1 prepares, and is added dropwise to complete temperature of reaction 2h～3h that the back keeps 45 ℃～75 ℃, and the mol ratio of described Resins, epoxy and described polyethylene polyamine is 1: 2.5～4; Adopt the mode of underpressure distillation, remove described organic solvent and described thinner, obtain aqueous epoxy curing agent;
Step 22, be 21%～39% described aqueous epoxy curing agent with mass percent, mass percent is that 19%～37% second Resins, epoxy and mass percent are 35%～55% deionized water uniform mixing, obtains the water-base epoxy membrane-forming agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100898998A CN101613460B (en) | 2009-07-27 | 2009-07-27 | Waterborne epoxy curing agent, waterborne epoxy film-forming agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100898998A CN101613460B (en) | 2009-07-27 | 2009-07-27 | Waterborne epoxy curing agent, waterborne epoxy film-forming agent and preparation method thereof |
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| CN107286324A (en) * | 2017-06-07 | 2017-10-24 | 常州兆威不锈钢有限公司 | A kind of preparation method of modified aqueous epoxy resin curing agent |
| CN111821942A (en) * | 2020-06-28 | 2020-10-27 | 瀚蓝绿电固废处理(佛山)有限公司 | High-efficiency dioxin adsorbent for waste incineration and preparation method and application thereof |
| CN112062968A (en) * | 2020-09-01 | 2020-12-11 | 邹华智 | Epoxy resin curing agent and preparation method thereof |
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| CN113583538B (en) * | 2021-07-15 | 2022-07-26 | 海洋化工研究院有限公司 | Solvent-free nontoxic anticorrosive paint for marine culture cabin |
| CN114591672A (en) * | 2022-03-24 | 2022-06-07 | 厦门百安兴新材料有限公司 | Odor-removing and aldehyde-removing paint and preparation method and application thereof |
| CN114940651A (en) * | 2022-07-01 | 2022-08-26 | 中南大学 | Wet bonding curing agent and preparation method and application thereof |
| CN114940651B (en) * | 2022-07-01 | 2023-12-22 | 中南大学 | Wet bonding curing agent and preparation method and application thereof |
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