CN112661936B - Preparation method of water-based epoxy curing agent - Google Patents
Preparation method of water-based epoxy curing agent Download PDFInfo
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- CN112661936B CN112661936B CN201910983969.8A CN201910983969A CN112661936B CN 112661936 B CN112661936 B CN 112661936B CN 201910983969 A CN201910983969 A CN 201910983969A CN 112661936 B CN112661936 B CN 112661936B
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Abstract
The invention discloses a preparation method of a water-based epoxy curing agent, which comprises the steps of uniformly stirring water, polyamine and a phase transfer catalyst to obtain a mixed solution, dropwise adding a mixture of a hydrophilic epoxy reactive diluent and a hydrophilic modified epoxy resin into the mixed solution, controlling the reaction temperature to react at 20-90 ℃, and adjusting amine-hydrogen equivalent after the reaction is completed to obtain the water-based epoxy curing agent. The method does not use any organic solvent, has simple steps and good reaction uniformity, and can obtain the curing agent with better performance.
Description
Technical Field
The invention relates to a preparation method of a waterborne epoxy curing agent, in particular to a method for preparing the waterborne epoxy curing agent, which is simple in steps and free of VOC, and belongs to the fields of epoxy resin coatings and adhesives.
Background
The existing aqueous epoxy curing agent is generally modified by adopting an epoxy compound, and the epoxy group and the amine curing agent are easy to generate polymerization reaction in the modification process, so that the viscosity of the reactant is increased. To reduce the viscosity, the person skilled in the art often uses an excess of amine and a greater amount of solvent for dilution. However, the introduction of solvents increases the VOC of the curing agent, and reduced pressure distillation is often employed in order to reduce the VOC and remove the excess amine, on the one hand, the increase in viscosity is not avoided in the latter stage of distillation, and the distilled solvent and excess amine mixture are not easily separated and recycled, on the other hand, the reduced pressure distillation also increases the energy consumption.
Chinese patent (CN 104356357A) describes a method for synthesizing a nonionic waterborne epoxy hardener, propylene glycol methyl ether is added in the reaction to serve as a solvent, the reaction is divided into three steps, and firstly, polyether polyol diglycidyl ether is dripped into propylene glycol methyl ether solution of triethylene tetramine to react to obtain an adduct of triethylene tetramine and polyether polyol diglycidyl ether; the second step is to carry out reduced pressure distillation on the product of the first step to remove the residual triethylene tetramine; and thirdly, dropwise adding the liquid epoxy resin into the propylene glycol methyl ether solution of the second-step product, and reacting to obtain the product waterborne epoxy hardener. The technology has five disadvantages: firstly, in order to reduce the reaction viscosity, adding excessive triethylene tetramine in the first step of reaction, distilling residual triethylene tetramine under reduced pressure, wherein the boiling point of the triethylene tetramine is 266-267 ℃, and high energy consumption is required; secondly, the process of removing the residual triethylene tetramine is necessarily carried out at a higher temperature, so that the gel of the reactant is very easy to cause; thirdly, the consumption of the solvent is large, and propylene glycol methyl ether is distilled out necessarily in the process of removing triethylene tetramine by reduced pressure distillation after the reaction of the first step, so that the propylene glycol methyl ether is added again before the reaction of the liquid epoxy resin is dripped in the third step; fourthly, the distilled solvent and the mixture of the redundant amine are not easy to separate and recycle; fifth, after the third step of reaction, propylene glycol methyl ether is not removed, and VOC exists in the product.
Chinese patent (CN 106117519A) provides a method for preparing an environment-friendly low-odor zero-VOC waterborne epoxy curing agent, which comprises four steps, wherein the first step is to prepare waterborne epoxy resin emulsion by using an emulsifier (span-20, tween-85 and the like), the second step is to add a product of the first step into a polyamine aqueous solution for reaction, the third step is to add monofunctional glycidyl ether into the product of the second step for blocking, the fourth step is to add glacial acetic acid for neutralization to form a waterborne curing agent, and finally water is added for dilution to obtain the product. The technology has the defects of more process steps, long working time and low production efficiency; and the process is complex and the control difficulty is high. The second and third steps have serious exothermic and easy gel reaction, and in order to better control the temperature, the end capping agent monofunctional glycidyl ether must be slowly dripped in two steps, and the end capping agent monofunctional glycidyl ether has poor compatibility with aqueous emulsion, polyamine and water, so that the dripping reaction must be separately carried out, thereby increasing the steps and prolonging the working time. The technology has the further disadvantage that the performance of the cured product is poor, the emulsifier is non-reactive, and does not participate in the synthesis reaction of the curing agent or the curing reaction of the epoxy resin, and is free in the cured product, so that the performance of the cured product, particularly the water resistance and some chemical resistance, are affected; finally, the emulsification performance is improved by acid neutralization, and the selection of the filler in the use engineering of the curing agent is limited due to the addition of the acid, the alkaline filler has poor matching property, the curing agent is easy to agglomerate, and the alkali resistance of the cured product is poor.
Disclosure of Invention
Aiming at the defects of the preparation of the waterborne epoxy curing agent in the prior art, the invention aims to provide a preparation method of the zero VOC waterborne epoxy curing agent, which has simple steps and good reaction uniformity.
In order to achieve the technical aim, the invention provides a preparation method of a water-based epoxy curing agent, which comprises the steps of uniformly stirring water, polyamine and a phase transfer catalyst to obtain a mixed solution, dropwise adding a mixture of a hydrophilic epoxy reactive diluent and a hydrophilic modified epoxy resin into the mixed solution, controlling the reaction temperature to react at 20-90 ℃, and adjusting the amine hydrogen equivalent after the reaction is completed to obtain the water-based epoxy curing agent.
In a preferred embodiment, the polyamine includes at least one of aliphatic polyamine, polyether polyamine, alicyclic polyamine, and aromatic polyamine. These polyamines are amine curing agents commonly found in the art.
In a preferred scheme, the hydrophilic modified epoxy resin is CYDW-125, the epoxy equivalent is 200-250 g/eq, and the viscosity is 8000-12000 mpa.s at 25 ℃. The hydrophilic modified epoxy resin can be directly purchased from Baling petrochemical division of China petrochemical group asset management and management Co., ltd, and the product model is CYDW-125. The invention adopts the hydrophilic modified epoxy resin, the compatibility of the epoxy resin component and the amine aqueous solution reaction system is good, the reaction is uniform, and the obtained modified amine curing agent has better water solubility.
Preferably, the hydrophilic epoxy reactive diluent comprises at least one of polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether and glycerol glycidyl ether. According to the invention, the hydrophilic epoxy resin is diluted by the hydrophilic epoxy reactive diluent, so that the hydrophilic modified epoxy resin can achieve an effective dilution effect, the use of an organic solvent is avoided, and the hydrophilic epoxy reactive diluent has good water solubility, so that the reaction is uniform.
Preferably, the phase transfer catalyst comprises a quaternary ammonium salt transfer catalyst and/or a polyether transfer catalyst. The phase transfer catalyst can raise the modifying reaction rate and shorten modifying time.
More preferred embodiments, the quaternary ammonium salt transfer catalyst comprisesBenzyl triethyl ammonium chlorideTetrabutylammonium bromide,Tetrabutylammonium chloride、Tetrabutylammonium bisulfate、Trioctylmethyl ammonium chlorideAt least one of dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
More preferably, the polyether transfer catalyst comprises at least one of polyethylene glycol, polyethylene glycol dialkyl ether and polypropylene glycol.
In a preferred embodiment, the molar ratio of polyamine to epoxy groups in the hydrophilically modified epoxy resin is 1:0.5-2.5. In the preferable proportion range, not only can the water-based curing agent with good water solubility be obtained, but also the curing film forming performance of the curing agent is improved to a certain extent.
In a preferred scheme, the mass ratio of the hydrophilic epoxy reactive diluent to the hydrophilic modified epoxy resin is 10-150:100.
In a preferred scheme, the mass of the water is 10-60% of the mass of the polyamine.
In a preferred embodiment, the mass of the phase transfer catalyst is 0.05 to 1% of the mass of the polyamine.
In a preferred scheme, the hydrophilic modified epoxy resin is dissolved and diluted in advance by adopting a hydrophilic epoxy reactive diluent for later use.
The preparation method of the aqueous epoxy curing agent adopts water as a diluent, adopts hydrophilic modified epoxy resin and hydrophilic epoxy reactive diluent as raw materials, and modifies polyamine curing agent under the action of a phase transfer catalyst to obtain the aqueous curing agent. In the prior art, the epoxy resin has hydrophobicity, most of reactive diluents also have no hydrophilicity or water solubility, so that in the reaction process of adding the non-hydrophilic epoxy resin component into the amine aqueous solution, the reaction effect is affected due to poor compatibility of the non-hydrophilic epoxy resin component and the amine aqueous solution, the reaction is easy to be uneven, in addition, the water solubility of the modified amine curing agent is also reduced, the water solubility is poor, the emulsifying property is poor, and the modified amine curing agent is difficult to be matched with hydrophobic liquid epoxy resin for use. The invention adopts hydrophilic modified epoxy resin and hydrophilic epoxy reactive diluent and phase transfer catalyst, so that the epoxy component and amine aqueous solution reaction system have good compatibility and uniform reaction, the obtained modified amine curing agent truly belongs to a water-soluble curing agent (zero VOC), has good compatibility with water-based epoxy resin, can be used as a water-based epoxy resin system by being matched with hydrophobic liquid epoxy resin, and has the emulsifying function of emulsifiable liquid epoxy resin.
Compared with the prior art, the technical scheme of the invention has the advantages that:
1. in the process of preparing the water-based epoxy curing agent, the hydrophilic epoxy reactive diluent and the hydrophilic modified epoxy resin are added together, and the hydrophilic epoxy reactive diluent is used for replacing an organic solvent to dilute the epoxy resin, so that the hydrophilic modified epoxy resin can achieve an effective dilution effect.
2. The process of modifying the polyamine by the aqueous epoxy resin can be completed by one-step reaction, the process steps are few, the reaction time is short, the preparation process is very simple, the production energy consumption can be reduced, and the productivity of the device is improved.
3. In the process of preparing the water-based epoxy curing agent, water is used as a reaction diluent, so that an organic solvent is avoided, high environmental protection performance is achieved, meanwhile, the evaporation latent heat of water is 44kJ/mol, which is the highest of all known solvents, and the water-based epoxy curing agent can play a role in regulating and controlling the reaction temperature, reduce the temperature rising rate, enable the reaction to be more stable, be easy to control and reduce the gel risk.
4. The phase transfer catalyst is adopted in the preparation process of the water-based epoxy curing agent, so that epoxy components (hydrophilic modified epoxy resin and hydrophilic epoxy reactive diluent) can be transferred into water-soluble amine components better, the compatibility and collision probability between reactants are improved, and the smooth reaction is facilitated.
5. In the process of preparing the water-based epoxy curing agent, water can also be used as a polymerization inhibitor in a reaction system to prevent epoxy groups from excessively reacting with amines to form macromolecular substances, so that the particle size of the product is more uniform.
6. The aqueous epoxy curing agent prepared by the invention has better mechanical property and corrosion resistance after being cured and molded with epoxy resin.
Detailed Description
The invention is further illustrated and described below in connection with the embodiments of the invention, but is not presently limited by the scope of the claims.
Example 1
(1) Preparing a resin solution: 95g of polyethylene glycol glycidyl ether and 60g of CYDW-125 are put into a four-port reaction bottle provided with a condenser tube, a thermometer and a stirrer, stirred uniformly and poured into a constant pressure funnel for standby.
(2) And (3) synthesizing a curing agent: 40g deionized water, 80g triethylene tetramine and 0.08gBenzyl triethyl ammonium chlorideSequentially adding into the four-port reaction bottle, stirring, heating to 38 ℃ to form uniform solution, then dropwise adding the resin solution in the dropping funnel, controlling the temperature below 75 ℃, after 1 hour of dropwise adding, maintaining the reaction at 65-75 ℃ for 2 hours, adding 195g of water, and uniformly stirring to obtain the light-yellow transparent 0VOC aqueous epoxy curing agent with 50% of solid content.
The whole synthesis process is very concise, and the curing agent does not contain an organic solvent or free emulsifying agent 3.5 hours after use. And (3) testing the performance of the water-based epoxy paint film formed after the compounding, wherein the compounding ratio of the water-based epoxy paint film and the epoxy resin CYDW-100 (P) is 1:1. And respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating the mixture on the tinplate subjected to surface treatment to form a film, curing, and performing performance test. The performance test results are as follows:
| project | |
| Adhesion force | 0-1 grade |
| Hardness of pencil | 4H |
| Impact resistance | >70cm/Kg.f |
| Waterproof | Is good for 90 days |
| 5% sodium hydroxide | Is good for 30 days |
| 5% sulfuric acid | Is good for 7 days |
Example 2:
(1) Preparing a resin solution: 150g of polypropylene glycol glycidyl ether and 120g of CYDW-125 are put into a four-port reaction bottle provided with a condenser tube, a thermometer and a stirrer, stirred uniformly and poured into a constant pressure funnel for standby.
(2) And (3) synthesizing a curing agent: 35g of deionized water, 65g of triethylene tetramine, 25g of D-230 and 0.06gTetrabutylammonium chlorideSequentially adding into the four-port reaction bottle, stirring, heating to 50 ℃ to form uniform solution, then dropwise adding the resin solution in the dropping funnel, controlling the temperature below 75 ℃, after 1 hour of dropwise adding, maintaining the reaction at 70-75 ℃ for 2 hours, adding 325g of water, and stirring uniformly to obtain the light-yellow transparent 0VOC aqueous epoxy curing agent with 50% solid content.
The whole synthesis process is very concise, the time is 3.5 hours, the curing agent does not contain an organic solvent or free emulsifying agent, the compounding ratio of the curing agent and the epoxy resin CYD-128 is 1:2, and the performance test of the water-based epoxy paint film is carried out after compounding. And respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating the mixture on the tinplate subjected to surface treatment to form a film, curing, and performing performance test. The performance test results are as follows:
example 3:
(1) Preparing a resin solution: 20g of glycerol glycidyl ether and 200g of CYDW-125 are put into a four-port reaction bottle provided with a condenser tube, a thermometer and a stirrer, stirred uniformly and poured into a constant pressure funnel for standby.
(2) And (3) synthesizing a curing agent: 50g of deionized water, 20g of diethylenetriamine, 40g of D-230, 20g of IPDA and 0.06gFour-block food Ammonium chloride baseAnd sequentially adding 0.5g of polypropylene glycol into the four-port reaction bottle, starting stirring, heating to 40 ℃ to form a uniform solution, then dripping the resin solution in a dropping funnel, controlling the temperature below 75 ℃ for 1 hour, maintaining the reaction at 65-75 ℃ for 2 hours after the dripping is completed, adding 250g of water, and uniformly stirring to obtain the light-yellow transparent 0VOC aqueous epoxy curing agent with the solid content of 50%.
The whole synthesis process is very concise, the curing agent does not contain an organic solvent or free emulsifying agent 3.5 hours after the use, the compounding ratio of the curing agent and the epoxy resin CYD-128 is 1:1.5, and the performance test of the water-based epoxy paint film formed after the compounding is performed. And respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating the mixture on the tinplate subjected to surface treatment to form a film, curing, and performing performance test. The performance test results are as follows:
| project | |
| Adhesion force | 0-1 grade |
| Hardness of pencil | 2H |
| Impact resistance | >70cm/Kg.f |
| Waterproof | Is good for 90 days |
| 5% sodium hydroxide | Is good for 30 days |
| 5% sulfuric acid | Is good for 7 days |
Example 4:
(1) Preparing a resin solution: 20g of polyethylene glycol glycidyl ether, 30g of glycerol glycidyl ether and 158g of CYDW-125 are put into a four-port reaction bottle provided with a condenser tube, a thermometer and a stirrer, stirred uniformly and poured into a constant pressure funnel for standby.
(2) And (3) synthesizing a curing agent: 60g deionized water, 40g D-230, 65g m-phenylenediamine and 0.15g dodecyl trimethyl ammonium chloride are sequentially added into the four-port reaction bottle, stirring is started, the temperature is raised to 40 ℃ to form a uniform solution, then the resin solution in a dropping funnel is added dropwise, the temperature is controlled below 90 ℃, after 1 hour dropwise addition, the reaction is maintained for 2 hours at 75-85 ℃, 253g of water is added, and the mixture is stirred uniformly to obtain the brown transparent 0VOC aqueous epoxy curing agent with 50% solid content.
The whole synthesis process is very concise, the curing agent does not contain an organic solvent or free emulsifying agent 3.5 hours after the use, the compounding ratio of the curing agent and the epoxy resin CYD-125 is 1:1.4, and the performance test of the water-based epoxy paint film formed after the compounding is performed. And respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating the mixture on the tinplate subjected to surface treatment to form a film, curing, and performing performance test. The results of the performance tests are shown in the following table:
| project | |
| Adhesion force | 0-1 grade |
| Hardness of pencil | 5H |
| Impact resistance | >70cm/Kg.f |
| Waterproof | Is good for 90 days |
| 5% sodium hydroxide | Is good for 30 days |
| 5% sulfuric acid | Is good for 7 days |
Claims (4)
1. A preparation method of a water-based epoxy curing agent is characterized by comprising the following steps: uniformly stirring water, polyamine and a phase transfer catalyst to obtain a mixed solution, dropwise adding a hydrophilic epoxy reactive diluent and a hydrophilic modified epoxy resin mixture into the mixed solution, controlling the reaction temperature to react at 20-90 ℃, and adjusting amine-hydrogen equivalent after the reaction is completed to obtain a water-based epoxy curing agent; the hydrophilic modified epoxy resin is CYDW-125, the epoxy equivalent is 200-250 g/eq, and the viscosity is 8000-12000 mpa.s at 25 ℃; the hydrophilic epoxy reactive diluent comprises at least one of polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether and glycerol glycidyl ether; the phase transfer catalyst comprises a quaternary ammonium salt transfer catalyst and/or a polyether transfer catalyst; the mass of the water is 10 to 60 percent of the mass of the polyamine.
2. The method for preparing the aqueous epoxy curing agent according to claim 1, wherein the method comprises the following steps: the polyamine comprises at least one of aliphatic polyamine, polyether polyamine, alicyclic polyamine and aromatic polyamine.
3. The method for preparing the aqueous epoxy curing agent according to claim 1, wherein the method comprises the following steps: the quaternary ammonium salt transfer catalyst comprises at least one of benzyl triethyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride; the polyether transfer catalyst comprises at least one of polyethylene glycol, polyethylene glycol dialkyl ether and polypropylene glycol.
4. A method for preparing an aqueous epoxy hardener according to any one of claims 1 to 3, characterized in that:
the molar ratio of the polyamine to the epoxy groups in the hydrophilic modified epoxy resin is 1:0.5-2.5;
the mass ratio of the hydrophilic epoxy reactive diluent to the hydrophilic modified epoxy resin is 10-150:100;
the mass of the phase transfer catalyst is 0.05-1% of the mass of the polyamine.
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