CN112661936A - Preparation method of water-based epoxy curing agent - Google Patents
Preparation method of water-based epoxy curing agent Download PDFInfo
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- CN112661936A CN112661936A CN201910983969.8A CN201910983969A CN112661936A CN 112661936 A CN112661936 A CN 112661936A CN 201910983969 A CN201910983969 A CN 201910983969A CN 112661936 A CN112661936 A CN 112661936A
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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 hydrophilic epoxy active diluent and a hydrophilic modified epoxy resin mixture into the mixed solution, controlling the reaction temperature to be 20-90 ℃ for reaction, and adjusting the amine hydrogen equivalent after the reaction is finished 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 water-based epoxy curing agent, in particular to a method for preparing a water-based epoxy curing agent with simple steps and zero VOC (volatile organic compounds), belonging to the field of epoxy resin coatings and adhesives.
Background
The existing waterborne epoxy curing agent is modified by epoxy compounds, and the viscosity of reactants is increased because epoxy groups and amine curing agents are easy to generate polymerization reaction in the modification process. To reduce the viscosity, the skilled worker often employs an excess of amine and more solvent for dilution. However, the introduction of solvent increases the VOC of the curing agent, and in order to reduce VOC and remove excess amine, reduced pressure distillation is often used, on one hand, the increase of viscosity cannot be avoided in the later stage of distillation, and the distilled solvent and the excess amine mixture are not easy to separate and recycle, and on the other hand, reduced pressure distillation also increases energy consumption.
Chinese patent (CN104356357A) introduces a synthesis method of a non-ionic waterborne epoxy hardener, propylene glycol methyl ether is added as a solvent in the reaction, the reaction is divided into three steps, and in the first step, the addition of triethylene tetramine and polyether glycol diglycidyl ether is obtained by dropping polyether glycol diglycidyl ether into a propylene glycol methyl ether solution of triethylene tetramine for reaction; secondly, carrying out reduced pressure distillation on the product obtained in the first step to remove residual triethylene tetramine; and thirdly, dropwise adding liquid epoxy resin into the propylene glycol methyl ether solution of the product obtained in the second step, and reacting to obtain the product, namely the waterborne epoxy curing agent. There are five disadvantages to this technique: firstly, in order to reduce the reaction viscosity, excessive triethylene tetramine is added in the first step of reaction, the residual triethylene tetramine needs reduced pressure distillation, the boiling point of the triethylene tetramine is 266-267 ℃, and high energy consumption is needed; secondly, the process of removing the residual triethylene tetramine is bound to be carried out at a higher temperature, and the reactant is easy to gel; thirdly, the solvent consumption is large, propylene glycol methyl ether must be distilled out in the process of removing triethylene tetramine by reduced pressure distillation after the first step of reaction is finished, and therefore, propylene glycol methyl ether must be added again before the liquid epoxy resin is dripped in the third step of reaction; fourthly, the distilled solvent and the redundant amine mixture are not easy to separate and recycle; fifthly, propylene glycol methyl ether is not removed after the third step reaction, and VOC exists in the product.
Chinese patent (CN106117519A) provides an environment-friendly low-odor zero-VOC aqueous epoxy curing agent method, which comprises four steps, wherein an emulsifier (span-20, Tween-85 and the like) is used for preparing epoxy resin into an aqueous epoxy resin emulsion, a product obtained in the first step is dripped into a polyamine aqueous solution for reaction, a monofunctional glycidyl ether is dripped into a product obtained in the second step for end capping, glacial acetic acid is added for neutralization to form an aqueous curing agent, and finally water is added for dilution to obtain the product. The technology has the disadvantages of multiple process steps, long working hours and low production efficiency; and the process is complex and the control difficulty is high. The second step and the third step have serious reaction heat release, are easy to gel, and must be divided into two steps and slowly dripped for better temperature control, and the monofunctional glycidyl ether of the end capping agent has poor compatibility with the aqueous emulsion, the polyamine and the water, so the dripping reaction must be separated, thereby increasing the steps and prolonging the working hours. The technology has the further disadvantage that the performance of the cured product is poor, and the used emulsifier is non-reactive, does not participate in the synthetic reaction of the curing agent and the curing reaction of the epoxy resin, is dissociated in the cured product, and influences the performance of the cured product, particularly the water resistance and some chemical resistance; finally, the emulsifying property is improved by acid neutralization, because the addition of the acid limits the selection of the filler in the use engineering of the curing agent, the compatibility with an alkaline filler is poor, the curing agent is easy to agglomerate, and the alkali resistance of a 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 the preparation method of the zero-VOC waterborne epoxy curing agent, which has simple steps and good reaction uniformity.
In order to achieve the technical purpose, 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 hydrophilic epoxy active diluent and a hydrophilic modified epoxy resin mixture into the mixed solution, controlling the reaction temperature to be 20-90 ℃ for reaction, and after the reaction is finished, adjusting the amine hydrogen equivalent to obtain the water-based epoxy curing agent.
Preferably, the polyamine includes at least one of aliphatic polyamine, polyether polyamine, alicyclic polyamine and aromatic polyamine. These polyamines are amine-based curing agents common 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 mpa-12000 mpa-s at the temperature of 25 ℃. The hydrophilic modified epoxy resin can be directly purchased from the Balng 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.
In a preferred embodiment, 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 adopting the hydrophilic epoxy activity, 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 activity diluent has good water solubility, so that the reaction is uniform.
In a preferred embodiment, the phase transfer catalyst comprises a quaternary ammonium salt type transfer catalyst and/or a polyether type transfer catalyst. The modification reaction rate can be improved and the modification time can be shortened by adopting the phase transfer catalyst.
In a more preferred embodiment, the quaternary ammonium salt-based transfer catalyst comprisesBenzyl triethyl ammonium chlorideTetrabutylammonium bromide,Tetrabutyl ammonium chloride、Tetrabutylammonium hydrogen sulfate、Trioctyl methyl ammonium chlorideAt least one of dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride.
In a more preferred embodiment, the polyether transfer catalyst comprises at least one of polyethylene glycol, polyethylene glycol dialkyl ether, and polypropylene glycol.
In a preferable scheme, the molar ratio of the polyamine to the epoxy group in the hydrophilic 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 property of the curing agent is improved to a certain extent.
In a preferable scheme, the mass ratio of the hydrophilic epoxy reactive diluent to the hydrophilic modified epoxy resin is 10-150: 100.
Preferably, the mass of the water is 10-60% of the mass of the polyamine.
In a preferable scheme, the mass of the phase transfer catalyst is 0.05-1% of that of the polyamine.
In a preferred scheme, the hydrophilic modified epoxy resin is dissolved and diluted by a hydrophilic epoxy active diluent in advance for later use.
The preparation method of the waterborne epoxy curing agent takes water as a diluent, takes hydrophilic modified epoxy resin and hydrophilic epoxy active diluent as raw materials, and modifies polyamine curing agent under the action of a phase transfer catalyst to obtain the waterborne curing agent. In the prior art, because the epoxy resin has hydrophobicity and most of the active diluents do not have hydrophilicity or water solubility, when the non-hydrophilic epoxy resin component is added into the amine aqueous solution for reaction, the compatibility of the epoxy resin component and the amine aqueous solution is poor, the reaction effect is influenced, the reaction is easy to cause uneven reaction, in addition, the water solubility of the modified amine curing agent is reduced, the water solubility is poor, the emulsifying property is poor, and the modified amine curing agent is difficult to be matched with the hydrophobic liquid epoxy resin for use. The invention adopts hydrophilic modified epoxy resin and diluent with hydrophilic epoxy activity, and uses phase transfer catalyst simultaneously, so that the compatibility of epoxy component and amine aqueous solution reaction system is good, the reaction is uniform, the obtained modified amine curing agent really belongs to water-soluble curing agent (zero VOC), the compatibility with water-based epoxy resin is good, and the modified amine curing agent can be matched with hydrophobic liquid epoxy resin to be used as water-based epoxy resin system, and has the emulsification 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 waterborne epoxy curing agent, the hydrophilic epoxy active diluent and the hydrophilic modified epoxy resin are added together, and the hydrophilic epoxy active 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 the waterborne epoxy resin modified polyamine can be completed by only one-step reaction, the process steps are few, the reaction time is short, the preparation process is simple, the production energy consumption can be reduced, and the device productivity can be improved.
3. In the process of preparing the waterborne epoxy curing agent, water is used as a reaction diluent, an organic solvent is avoided, high environmental protection performance is achieved, meanwhile, the latent heat of evaporation of the water is 44kJ/mol, which is the highest of all known solvents, the effect of regulating and controlling the reaction temperature can be achieved, the heating rate is reduced, the reaction tends to be more stable, the control is easy, and the gel risk is reduced.
4. The invention adopts the phase transfer catalyst in the process of preparing the waterborne epoxy hardener, can better transfer epoxy components (hydrophilic modified epoxy resin and hydrophilic epoxy active diluent) to amine components with water solubility, improves the compatibility and collision probability among reactants and is beneficial to the smooth operation of reaction.
5. In the process of preparing the waterborne epoxy hardener, water can also be used as a polymerization inhibitor in a reaction system to prevent an epoxy group and amines from excessively reacting to form macromolecular substances, so that the particle size of the product is more uniform.
6. The waterborne 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 will be further illustrated and described with reference to examples of the invention, which are not intended to limit 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-mouth 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 of deionized water, 80g of triethylene tetramine and 0.08g of deionized waterBenzyl triethyl ammonium chlorideAnd sequentially putting into the four reaction bottles, stirring, heating to 38 ℃ to form a uniform solution, dropwise adding the resin solution in a dropping funnel, controlling the temperature to be below 75 ℃, keeping the reaction at 65-75 ℃ for 2 hours after dropwise adding is finished for 1 hour, adding 195g of water, and uniformly stirring to obtain the light yellow transparent 0VOC (volatile organic compound) waterborne epoxy curing agent with the solid content of 50%.
The whole synthesis process is very simple, the use time is 3.5 hours, and the curing agent does not contain an organic solvent and a free emulsifier. The compounding ratio of the epoxy resin to the epoxy resin CYDW-100(P) is 1:1, and the performance of the water-based epoxy paint film formed after compounding is tested. Respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating on a galvanized iron plate subjected to surface treatment to form a film, curing, and performing performance test. The performance test results are as follows:
| item | |
| Adhesion force | 0-1 stage |
| Hardness of pencil | 4H |
| Impact resistance | >70cm/Kg.f |
| Water-resistant | Good after 90 days |
| 5% sodium hydroxide | Good quality for 30 days |
| 5% sulfuric acid | Good quality in 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-mouth 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 0.06g ofTetrabutyl ammonium chlorideAnd sequentially putting the materials into the four reaction bottles, stirring, heating to 50 ℃ to form a uniform solution, dropwise adding the resin solution in a dropping funnel, controlling the temperature to be below 75 ℃, keeping the reaction at 70-75 ℃ for 2 hours after dropwise adding is finished for 1 hour, adding 325g of water, and uniformly stirring to obtain the light yellow transparent 0VOC (volatile organic compound) waterborne epoxy curing agent with the solid content of 50%.
The whole synthesis process is very simple, the curing agent does not contain organic solvent or free emulsifier after 3.5 hours of use, the compounding ratio of the curing agent to the epoxy resin CYD-128 is 1:2, and the performance of a water-based epoxy paint film formed after compounding is tested. Respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating on a galvanized iron plate 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: putting 20g of glycerol glycidyl ether and 200g of CYDW-125 into a four-mouth reaction bottle provided with a condenser tube, a thermometer and a stirrer, uniformly stirring, and pouring into a constant-pressure funnel for later use.
(2) And (3) synthesizing a curing agent: 50g of deionized water, 20g of diethylenetriamine, 40g of D-230, 20g of IPDA and 0.06g of IPDAFour-piece food Ammonium chlorideAnd 0.5g of polypropylene glycol are sequentially put into the four-mouth reaction bottle, stirred and heated to 40 ℃ to form a uniform solution, then the resin solution in the dropping funnel is dripped, the temperature is controlled below 75 ℃, after dripping is finished within 1 hour, the reaction is maintained for 2 hours at 65-75 ℃, 250g of water is added, and the mixture is stirred uniformly to obtain the light yellow transparent 0VOC aqueous epoxy curing agent with the solid content of 50 percent.
The whole synthesis process is very simple, the curing agent does not contain organic solvent or free emulsifier after 3.5 hours of use, the compounding ratio of the curing agent to the epoxy resin CYD-128 is 1:1.5, and the performance of a water-based epoxy paint film formed after compounding is tested. Respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating on a galvanized iron plate subjected to surface treatment to form a film, curing, and performing performance test. The performance test results are as follows:
| item | |
| Adhesion force | 0-1 stage |
| Hardness of pencil | 2H |
| Impact resistance | >70cm/Kg.f |
| Water-resistant | Good after 90 days |
| 5% sodium hydroxide | Good quality for 30 days |
| 5% sulfuric acid | Good quality in 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-mouth 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 of deionized water, 40g of D-230, 65g of m-phenylenediamine and 0.15g of dodecyl trimethyl ammonium chloride are sequentially put into the four-mouth reaction bottle, stirring is started, the temperature is raised to 40 ℃ to form a uniform solution, then the resin solution in the dropping funnel is dripped, the temperature is controlled below 90 ℃, 1 hour of dripping is finished, the reaction is maintained at 75-85 ℃ for 2 hours, 253g of water is added, and stirring is uniformly carried out to obtain the brown transparent 0VOC aqueous epoxy curing agent with the solid content of 50%.
The whole synthesis process is very simple, the curing agent does not contain organic solvent or free emulsifier after 3.5 hours of use, the compounding ratio of the curing agent to the epoxy resin CYD-125 is 1:1.4, and the performance of a water-based epoxy paint film formed after compounding is tested. Respectively weighing the resin and the curing agent according to a proper proportion, uniformly stirring, uniformly coating on a galvanized iron plate 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:
| item | |
| Adhesion force | 0-1 stage |
| Hardness of pencil | 5H |
| Impact resistance | >70cm/Kg.f |
| Water-resistant | Good after 90 days |
| 5% sodium hydroxide | Good quality for 30 days |
| 5% sulfuric acid | Good quality in 7 days |
Claims (7)
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 mixture of a hydrophilic epoxy active diluent and a hydrophilic modified epoxy resin into the mixed solution, controlling the reaction temperature to be 20-90 ℃ for reaction, and after the reaction is finished, adjusting the amine hydrogen equivalent to obtain the waterborne epoxy curing agent.
2. The method for preparing the water-based epoxy curing agent according to claim 1, wherein: the polyamine comprises at least one of aliphatic polyamine, polyether polyamine, alicyclic polyamine and aromatic polyamine.
3. The method for preparing the water-based epoxy curing agent according to claim 1, wherein: the hydrophilic modified epoxy resin is CYDW-125, the epoxy equivalent is 200-250 g/eq, and the viscosity is 8000 mpa-s-12000 mpa-s at the temperature of 25 ℃.
4. The method for preparing the water-based epoxy curing agent according to claim 1, wherein: the hydrophilic epoxy reactive diluent comprises at least one of polyethylene glycol glycidyl ether, polypropylene glycol glycidyl ether and glycerol glycidyl ether.
5. The method for preparing the water-based epoxy curing agent according to claim 1, wherein: the phase transfer catalyst comprises a quaternary ammonium salt transfer catalyst and/or a polyether transfer catalyst.
6. The method for preparing the water-based epoxy curing agent according to claim 5, wherein: the quaternary ammonium salt transfer catalyst comprises at least one of benzyltriethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride; the polyether transfer catalyst comprises at least one of polyethylene glycol, polyethylene glycol dialkyl ether and polypropylene glycol.
7. The method for preparing a water-based epoxy curing agent according to any one of claims 1 to 6, wherein the method comprises the following steps:
the molar ratio of the polyamine to the epoxy group in the hydrophilic modified epoxy resin is 1: 0.5-2.5;
the mass ratio of the hydrophilic epoxy active diluent to the hydrophilic modified epoxy resin is 10-150: 100;
the mass of the water is 10-60% of that of the polyamine;
the mass of the phase transfer catalyst is 0.05-1% of that of the polyamine.
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2019
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