CN107629191B - Epoxy ester prepolymer, preparation method thereof, prepared waterborne epoxy ester resin and method - Google Patents
Epoxy ester prepolymer, preparation method thereof, prepared waterborne epoxy ester resin and method Download PDFInfo
- Publication number
- CN107629191B CN107629191B CN201711064961.9A CN201711064961A CN107629191B CN 107629191 B CN107629191 B CN 107629191B CN 201711064961 A CN201711064961 A CN 201711064961A CN 107629191 B CN107629191 B CN 107629191B
- Authority
- CN
- China
- Prior art keywords
- epoxy ester
- fatty acid
- resin
- parts
- ester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Epoxy Resins (AREA)
- Paints Or Removers (AREA)
Abstract
Epoxy ester prepolymer, preparation method and waterborne epoxy ester resin and method prepared by the epoxy ester prepolymer, wherein the epoxy ester prepolymer comprises bisphenol A epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, terpene diol diglycidyl ether, drying oil fatty acid, semi-drying oil fatty acid, saturated fatty acid anhydride, unsaturated fatty acid anhydride, esterification catalyst and organic solvent. The invention also discloses a preparation method of the composition. The waterborne epoxy ester resin comprises a vinyl monomer, an initiator, the epoxy ester prepolymer, a cosolvent, a neutralizer and water. The invention also discloses a preparation method of the composition. The epoxy ester prepolymer has the advantages of excellent weather resistance, high drying speed and high impact strength; the waterborne epoxy ester resin provided by the invention has the advantages that the glass transition temperature, the corrosion resistance and the storage stability are obviously improved, and the waterborne epoxy ester resin can be used for an anticorrosive primer and a protective finish; the preparation method has simple and stable process and is suitable for industrial production.
Description
Technical Field
The invention relates to an epoxy ester prepolymer, a preparation method thereof, a prepared waterborne epoxy ester resin and a method thereof, and particularly relates to an epoxy ester prepolymer, a preparation method thereof, a prepared waterborne epoxy ester resin for single-component self-drying paint and a method thereof.
Background
Epoxy ester resins generally have excellent adhesion, salt spray resistance and good self-drying properties, but have poor weather resistance; in addition, the water-based epoxy ester resin is easy to hydrolyze in an alkaline environment, which affects the storage stability of the coating. The vinyl modified epoxy ester improves the storage stability of the coating and the weather resistance of a coating, but has slow self-drying speed and slow development of the hardness of the coating, and influences the construction efficiency; and low gloss and unsuitability as a topcoat.
CN101717490A discloses a rosin modified epoxy ester resin and a preparation method thereof, wherein the rosin modified epoxy ester resin is prepared by reacting epoxy resin with a toughening agent, a chain extender and unsaturated fatty acid rosin. Although the prepared epoxy ester resin has higher glass state temperature, quick drying, good mechanical property and excellent chemical medium resistance, and can be used as a film forming substance of anticorrosive paint. However, the rosin has complex components and unstable quality, so that the quality of the prepared epoxy ester resin is difficult to control, and the resin prepared by the scheme has poor weather resistance and is not suitable for finishing paint.
CN102391439A discloses an epoxy ester modified waterborne alkyd resin and a preparation method thereof, wherein the epoxy ester modified waterborne alkyd resin comprises the following steps: the preparation of alkyd resin, the synthesis of epoxy ester and the synthesis of epoxy ester modified alkyd resin are carried out by stirring and mixing epoxy ester with the mass ratio of 0.2: 1-0.5: 1, basic alkyd resin, 1-3 parts of organic tin catalyst and 5-15 parts of xylene, and carrying out reflux reaction at 180 ℃ for 1-2 h until the measured acid value is lower than 7 mgKOH/g; also includes the aquosity of the modified alkyd resin. The product obtained by the method not only keeps excellent performances of paint dryness, glossiness, durability, flexibility, hardness, better solubility and the like of alkyd resin, but also has excellent cohesiveness, salt fog resistance and good self-drying property of epoxy ester, and can ensure that a coating film has excellent solvent resistance and chemical resistance. However, this solution is not suitable for use in aqueous coating systems because the alkaline conditions after aqueous curing lead to hydrolysis of the alkyd resin and the epoxy ester resin, which results in poor storage stability.
CN104479087A discloses a quick-drying water-based epoxy ester emulsion and a preparation method and application thereof, which is to esterify epoxy resin, vegetable oil and 2/3 parts by mass of unsaturated fatty acid at high temperature to a designed acid value range, add the rest 1/3 parts by mass of unsaturated fatty acid to prepare epoxy ester resin, and then add a mixture of vinyl monomer and initiator dropwise for modification; after the reaction is finished, cooling, adding cosolvent and neutralizer, and finally diluting with deionized water. Although the resin can be used for an anti-rust primer, the vegetable oil belongs to fatty glyceride, cannot react with epoxy resin, only can carry out addition reaction with unsaturated fatty acid, is not easy to control in the process and is easy to gel.
CN106674441A discloses a water-soluble acrylic acid modified epoxy ester resin and a preparation method thereof, which is to carry out graft copolymerization reaction on an organic silicon modified epoxy ester prepolymer and a vinyl monomer. However, the resin contains silicon materials, so that the surface energy of the prepared coating after film formation is lower, and the recoatability is poor, and the resin is only suitable for protective finish paint.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing the epoxy ester prepolymer with excellent weather resistance, high drying speed and high impact strength.
The present invention further aims to solve the technical problem of overcoming the above defects of the prior art, and to provide a preparation method of an epoxy ester prepolymer, which is simple and stable in process and suitable for industrial production.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide the water-based epoxy ester resin which has the advantages of high coating film drying speed, high coating film hardness development speed, excellent corrosion resistance and high coating film gloss and can be used for an anticorrosive primer and a protective finish paint.
The invention further aims to solve the technical problem of overcoming the defects in the prior art and provide a preparation method of the waterborne epoxy ester resin, which is simple and stable in process and suitable for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows: an epoxy ester prepolymer comprising bisphenol a epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, terpene diol diglycidyl ether, drying oil fatty acids, semi-drying oil fatty acids, saturated fatty anhydrides, unsaturated fatty anhydrides, an esterification catalyst, and an organic solvent. The bisphenol A epoxy resin and the terpene glycol diglycidyl ether are favorable for improving the corrosion resistance of the product; dicyclopentadiene dimethanol diglycidyl ether, terpene glycol diglycidyl ether and drying oil fatty acid are beneficial to improving the glass transition temperature of a resin film-forming substance and accelerating the drying speed and the hardness development speed of a coating; dicyclopentadiene dimethanol diglycidyl ether, terpene glycol diglycidyl ether and fatty acid contribute to enhancing the weather resistance of the resin coating film; the fatty acid and the saturated fatty acid anhydride contribute to the improvement of the gloss of the resin coating film.
Preferably, the epoxy ester prepolymer comprises the following components in parts by weight: 155-175 parts of bisphenol A epoxy resin, 10-30 parts of dicyclopentadiene dimethanol diglycidyl ether, 10-30 parts of terpene diol diglycidyl ether, 95-105 parts of drying oil fatty acid, 95-105 parts of semi-drying oil fatty acid, 1-5 parts of saturated fatty acid anhydride, 1-3 parts of unsaturated fatty acid anhydride, 0.10-0.30 part of esterification catalyst and 170-210 parts of organic solvent.
Preferably, the bisphenol A epoxy resin is one or more of E-51 type, E-44 type, E-20 type or E-12 type epoxy resin and the like.
Preferably, the drying oil fatty acid is one or two of linoleic acid, eleostearic acid, high iodine value tall oil fatty acid or dehydrated castor oil fatty acid and the like. The iodine value range of the tall oil fatty acid with the high iodine value is 150-160.
Preferably, the semi-drying oil fatty acid is soybean oil fatty acid and/or low iodine value tall oil fatty acid and the like. The iodine value range of the low-iodine tall oil fatty acid is 120-135.
Preferably, the saturated fatty acid anhydride is one or more of hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride or nadic anhydride.
Preferably, the unsaturated fatty acid anhydride is maleic anhydride and/or fumaric anhydride, and the like.
Preferably, the esterification catalyst is zinc oxide or n-butyl tin oxide or the like.
Preferably, the organic solvent is one or more of propylene glycol methyl ether, propylene glycol propyl ether or propylene glycol butyl ether.
The technical scheme adopted for further solving the technical problems is as follows: a process for preparing epoxy ester prepolymer includes such steps as mixing bisphenol A epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, terpene diol diglycidyl ether, drying oil fatty acid and semi-drying oil fatty acid, stirring, heating while cooling, adding saturated fatty acid anhydride, unsaturated fatty acid anhydride and esterifying catalyst, stirring, heating while cooling, and adding organic solvent. The preparation process of the epoxy ester prepolymer has addition esterification reaction and condensation esterification reaction, and the addition esterification reaction process does not generate water, is easy to carry out and is beneficial to shortening the process flow.
Preferably, the temperature of the first heating reaction is 180-200 ℃ and the time is 1-3 h.
Preferably, after the first heating reaction, the temperature is reduced to 145-155 ℃.
Preferably, the temperature of the second heating reaction is 190-210 ℃, and the reaction is carried out until the acid value is less than or equal to 10 mgKOH/g.
Preferably, after the second heating reaction, the temperature is reduced to 80-100 ℃.
The invention further solves the technical problems by adopting the following technical scheme: a waterborne epoxy ester resin comprising a vinyl monomer, an initiator, the epoxy ester prepolymer, a cosolvent, a neutralizer and water. The epoxy ester prepolymer can enhance the corrosion resistance of the resin without affecting the storage stability; the acrylic resin part formed by graft copolymerization of the vinyl monomer and the prepolymer protects ester bonds of epoxy ester resin through a coating effect, so that the storage stability of the resin is obviously improved, and the resin coating film has better hardness and corrosion resistance due to the vinyl monomer containing the nitro group; the initiator can promote the graft polymerization reaction of the vinyl monomer and the epoxy ester; the cosolvent belongs to a hydrophilic organic solvent, can improve the dissolution degree of the resin, has weak emulsification effect, and improves the storage stability of the resin; the neutralizing agent neutralizes the resin to form salt, and water solubility is obtained.
Preferably, the waterborne epoxy ester resin comprises the following components in parts by weight: 200-260 parts (more preferably 220-240 parts) of vinyl monomer, 18-26 parts (more preferably 19-22 parts) of initiator, 500-550 parts (more preferably 510-540 parts) of epoxy ester prepolymer, 95-105 parts (more preferably 96-102 parts) of cosolvent, 10-20 parts (more preferably 12-19 parts) of neutralizer and 770-790 parts (more preferably 772-780 parts) of water. If the amount of the vinyl monomer is too much, a large amount of the vinyl monomer reacts with unsaturated double bonds in the epoxy ester prepolymer, the molecular weight of the prepared resin is large, the viscosity is remarkably increased, the production process is difficult to control, and gelation may occur, and if the amount of the vinyl monomer is too little, the graft copolymer is not enough to form a protection effect on a main chain ester bond, the storage stability of the resin is influenced, and the molecular weight of the resin is too low, so that the drying speed of the prepared coating is reduced; if the amount of the initiator is too large, the production process control and the color and quality control of the resin are not facilitated, residual substances generated after the initiator is decomposed can cause adverse effects on the coating, and if the amount of the initiator is too small, the conversion rate of the vinyl monomer graft copolymerization reaction is low, the molecular weight of the resin is low, and the film forming rate and the dry film hardness of the resin are influenced; if the dosage of the epoxy ester prepolymer is too small, the corrosion resistance of the prepared coating film is difficult to be effectively ensured, and if the dosage of the epoxy ester prepolymer is too large, the graft polymer formed by the introduced vinyl monomer is difficult to form effective coating and protection effects on ester bonds in epoxy ester; if the amount of the cosolvent is too large, the gloss of the prepared coating film is reduced, and the initial water resistance is poor, and if the amount of the cosolvent is too small, the storage stability and the film-forming property of the resin are affected; if the amount of the neutralizing agent is too large, the viscosity of the resin is significantly increased, which affects the dilution rate of the resin with water during paint mixing, and if the amount of the neutralizing agent is too small, the initial water resistance of the resulting coating film is lowered.
Preferably, the vinyl monomer comprises styrene, methacrylic acid, methyl methacrylate, polyethylene glycol methacrylate and nitro-substituted vinyl monomer, and the mixing mass ratio of the styrene, the methacrylic acid, the methyl methacrylate, the polyethylene glycol methacrylate and the nitro-substituted vinyl monomer is 96-126: 12-38: 45-75: 21-39: 6-12 (more preferably 100-120: 15-35: 50-60: 25-35: 8-10). The introduction of the polyethylene glycol methacrylate enables the waterborne epoxy ester resin to have certain self-emulsifying property, so that the dosage of a methacrylic acid monomer can be properly reduced, and the storage stability of the resin and the initial water resistance of a coating film can be enhanced; the nitro-substituted vinyl monomer can improve the hardness development speed of the waterborne epoxy ester resin coating and enhance the corrosion resistance.
Preferably, in the polyethylene glycol methacrylate, the relative molecular weight of the polyethylene glycol segment is 300-800 (more preferably 350-600).
Preferably, the nitro-substituted vinyl monomer is 2-methyl-2-nitropropyl methacrylate and/or p-nitrostyrene, etc.
Preferably, the initiator is one or more of benzoyl peroxide, tert-butyl peroxybenzoate, lauroyl peroxide and the like.
Preferably, the cosolvent is one or more of isopropanol, n-butanol, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether or methyl isobutyl ketone.
Preferably, the neutralizing agent is one or more of ammonia, triethylamine, dimethylethanolamine or meglumine.
The technical scheme adopted by the invention for further solving the technical problems is as follows: a preparation method of a water-based epoxy ester resin comprises the following steps:
(1) under the reflux state of a reaction system, dropwise adding a mixed solution of a vinyl monomer and a part of initiator into a mixed solution of the epoxy ester prepolymer and a part of cosolvent, after dropwise adding, carrying out heat preservation reaction, dropwise adding a mixed solution of the rest of initiator and the rest of cosolvent, after dropwise adding, carrying out heat preservation reaction, and cooling to obtain acrylic acid modified epoxy ester resin;
(2) and (2) adding a neutralizing agent into the acrylic acid modified epoxy ester resin obtained in the step (1), uniformly stirring, and adding water to obtain the waterborne epoxy ester resin.
The acid value of the acrylic acid modified epoxy ester resin obtained in the step (1) is 22-36 mgKOH/g, and the solid content is 78-82%.
The solid content of the waterborne epoxy ester resin obtained in the step (2) is 38-42%, and the pH value is 7.5-9.0. The obtained resin can ensure that the resin has enough water solubility under the acid value, and is convenient to add water for dilution in the construction process; the obtained resin can ensure that the resin has enough film forming substances under the solid content.
Preferably, in the step (1), the reflux temperature is 110-130 ℃. The cosolvent belongs to a hydrophilic organic solvent and is helpful for reflux heat dissipation in the synthesis process.
Preferably, in the step (1), the dropping speed of the two times is 200-300 kg/h. At the stated dropping rate, elimination of residual monomers is facilitated.
Preferably, in the step (1), the time for the two heat preservation reactions is 1-2 h. The elimination of residual monomers is further facilitated during the incubation time.
Preferably, in the step (1), the mass ratio of the successively dropped initiators is 3.5-4.5: 1.
Preferably, in the step (1), the mass ratio of the rest of the initiator to the rest of the cosolvent is 1: 6-12 (more preferably 1: 7-9). More preferably, the remaining portion of the initiator added afterwards is in liquid state; the remaining part of the cosolvent added later is propylene glycol methyl ether and/or methyl isobutyl ketone. The purpose of adding the initiator is to eliminate residual monomers in the reaction system, remove peculiar smell, facilitate the stability of the resin and facilitate the use of users.
Preferably, in the step (1), the temperature is reduced to 50-60 ℃.
The invention has the following beneficial effects:
(1) the artificial weathering time of the epoxy ester prepolymer is more than or equal to 110h, the surface drying time is less than or equal to 30min, and the positive impact strength is more than or equal to 50 kg cm-1The weather resistance is excellent, the drying speed is high, and the impact strength is high;
(2) the glass transition temperature of the waterborne epoxy ester resin is more than or equal to 67 ℃, the salt spray corrosion resistant time is more than or equal to 168h, the storage stability is more than or equal to 12 months, and the comprehensive performance is superior to that of the waterborne epoxy ester resin sold on the market, which shows that the waterborne epoxy ester resin provided by the invention has obvious improvement on the glass transition temperature, the corrosion resistance and the storage stability, and can be used for an anticorrosive primer and a protective finishing coat;
(3) the preparation method of the epoxy ester prepolymer and the preparation method of the waterborne epoxy ester resin have simple and stable processes and are suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples.
The tall oil fatty acid with high iodine value used in the embodiment of the invention is sold in the market, the iodine value is 156, the tall oil fatty acid with low iodine value used is sold in the market, and the iodine value is 128; in the used polyethylene glycol methacrylate, the relative molecular mass of a polyethylene glycol chain segment is 400; the chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Examples 1 to 3 of epoxy ester prepolymer
The amounts of the raw materials used in the epoxy ester prepolymer examples 1 to 3 are shown in table 1:
TABLE 1 dosage of raw materials for epoxy ester prepolymer examples 1-3
Note: in the table, "-" indicates no addition.
Preparation of epoxy ester prepolymer example 1
According to the mass of each raw material in the example 1 in the table 1, bisphenol A epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, terpene glycol diglycidyl ether, drying oil fatty acid and semi-drying oil fatty acid are mixed and stirred, the first heating reaction is carried out for 1.5h at the temperature of 200 ℃, saturated fatty acid anhydride, unsaturated fatty acid anhydride and esterification catalyst are added for mixing and stirring after the temperature is reduced to 150 ℃, the second heating reaction is carried out at the temperature of 200 ℃ until the acid value is less than 10mgKOH/g, the temperature is reduced to 80 ℃, and finally organic solvent is added, so that epoxy ester prepolymer A1 is obtained.
Preparation of epoxy ester prepolymer example 2
According to the quality of each raw material in the example 2 in the table 1, bisphenol A epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, terpene glycol diglycidyl ether, drying oil fatty acid and semi-drying oil fatty acid are mixed and stirred, the first heating reaction is carried out for 2 hours at 190 ℃, after the temperature is reduced to 155 ℃, saturated fatty acid anhydride, unsaturated fatty acid anhydride and esterification catalyst are added for mixing and stirring, the second heating reaction is carried out at 195 ℃ until the acid value is less than 10mgKOH/g, the temperature is reduced to 90 ℃, and finally organic solvent is added, so that epoxy ester prepolymer A2 is obtained.
Preparation of epoxy ester prepolymer example 3
According to the quality of each raw material in the example 3 in the table 1, bisphenol A epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, terpene glycol diglycidyl ether, drying oil fatty acid and semi-drying oil fatty acid are mixed and stirred, the first heating reaction is carried out for 3 hours at 185 ℃, after the temperature is reduced to 146 ℃, saturated fatty acid anhydride, unsaturated fatty acid anhydride and esterification catalyst are added for mixing and stirring, the second heating reaction is carried out at 210 ℃ until the acid value is less than 10mgKOH/g, the temperature is reduced to 95 ℃, and finally organic solvent is added, so that epoxy ester prepolymer A3 is obtained.
The weather resistance, drying speed and impact strength of the epoxy ester prepolymer examples 1-3 were tested according to the national standard test method, and the results are shown in table 2.
TABLE 2 epoxy ester prepolymer examples 1-3 Performance test results Table
As can be seen from Table 2, the artificial weathering time of the epoxy ester prepolymers of examples 1 to 3 of the present invention is not less than 110 hours, the apparent drying time is not more than 30 minutes, and the forward impact resistance is not less than 50 kg cm-1The epoxy ester prepolymer of the invention has the advantages of excellent weather resistance, high drying speed and high impact strength.
Examples 1 to 3 of Water-based epoxy ester resin
The dosage of each raw material of the waterborne epoxy ester resin in the examples 1-3 is shown in Table 3:
TABLE 3 dosage of raw materials for waterborne epoxy ester resin examples 1-3
Note: in the table, "-" indicates no addition; wherein, the initiator 1 and the initiator 2 respectively represent the dosage of the initiators added in the step (1) of the embodiment of the method; cosolvent 1 and cosolvent 2 represent the amounts of the cosolvents added successively in step (1) of the method example, respectively.
Preparation of waterborne epoxy ester resin example 1
(1) According to the mass of each raw material in the example 1 in the table 3, under the reflux state of the reaction system temperature of 120 ℃, dropwise adding the mixed solution of the vinyl monomer and the initiator 1 into the mixed solution of the epoxy ester prepolymer A1 and the cosolvent 1 at the speed of 260kg/h, after the dropwise adding is completed, carrying out heat preservation reaction for 1h, then dropwise adding the mixed solution of the initiator 2 and the cosolvent 2 at the speed of 220kg/h, after the dropwise adding is completed, carrying out heat preservation reaction for 1h, and cooling to 50 ℃ to obtain the acrylic acid modified epoxy ester resin;
(2) according to the mass of each raw material in the example 1 in the table 3, a neutralizing agent is added into the acrylic modified epoxy ester resin obtained in the step (1), and after the mixture is uniformly stirred, water is added to obtain the water-based epoxy ester resin B1.
Through detection, the acid value of the acrylic acid modified epoxy ester resin obtained in the step (1) is 23mgKOH/g, and the solid content is 78%; the solid content of the waterborne epoxy ester resin B1 obtained in the step (2) is 40%, and the pH value is 7.9.
Preparation of waterborne epoxy ester resin example 2
(1) According to the mass of each raw material in the example 2 in the table 3, under the reflux state of the reaction system temperature of 115 ℃, dropwise adding the mixed solution of the vinyl monomer and the initiator 1 into the mixed solution of the epoxy ester prepolymer A2 and the cosolvent 1 at the speed of 210kg/h, after the dropwise adding is completed, carrying out heat preservation reaction for 1.5h, then dropwise adding the mixed solution of the initiator 2 and the cosolvent 2 at the speed of 280kg/h, after the dropwise adding is completed, carrying out heat preservation reaction for 1.5h, and cooling to 55 ℃ to obtain the acrylic acid modified epoxy ester resin;
(2) according to the mass of each raw material in the example 2 in the table 3, a neutralizing agent is added into the acrylic modified epoxy ester resin obtained in the step (1), and after the mixture is uniformly stirred, water is added to obtain the water-based epoxy ester resin B2.
Through detection, the acid value of the acrylic acid modified epoxy ester resin obtained in the step (1) is 26mgKOH/g, and the solid content is 79.1%; the solid content of the waterborne epoxy ester resin B2 obtained in the step (2) is 40%, and the pH value is 8.5.
Preparation of waterborne epoxy ester resin method example 3
(1) According to the mass of each raw material in the embodiment 3 shown in the table 3, under the reflux state of the reaction system temperature of 125 ℃, dropwise adding the mixed solution of the vinyl monomer and the initiator 1 into the mixed solution of the epoxy ester prepolymer A3 and the cosolvent 1 at the speed of 290kg/h, after the dropwise adding is completed, carrying out heat preservation reaction for 1.5h, then dropwise adding the mixed solution of the initiator 2 and the cosolvent 2 at the speed of 240kg/h, after the dropwise adding is completed, carrying out heat preservation reaction for 1.5h, and cooling to 60 ℃ to obtain the acrylic acid modified epoxy ester resin;
(2) according to the mass of each raw material in the example 3 in the table 3, a neutralizing agent is added into the acrylic modified epoxy ester resin obtained in the step (1), and after the mixture is uniformly stirred, water is added to obtain the water-based epoxy ester resin B3.
Through detection, the acid value of the acrylic acid modified epoxy ester resin obtained in the step (1) is 32mgKOH/g, and the solid content is 80.3%; the solid content of the waterborne epoxy ester resin B3 obtained in the step (2) is 40%, and the pH value is 8.5.
The results of examining the glass transition temperature, storage stability and salt spray resistance of the water-soluble epoxy ester resins of examples 1 to 3 and commercially available water-based epoxy ester resins are shown in Table 4.
TABLE 4 Performance test results of examples 1 to 3 of waterborne epoxy ester resins
As can be seen from Table 4, the glass transition temperature of the waterborne epoxy ester resin of the invention in the examples 1-3 is not less than 67 ℃, the salt spray corrosion resistant time is not less than 168h, the storage stability is not less than 12 months, and the comprehensive performance is superior to that of the waterborne epoxy ester resin sold on the market, which shows that the waterborne epoxy ester resin of the invention has significant improvement on the glass transition temperature, the corrosion resistance and the storage stability.
Claims (9)
1. An epoxy ester prepolymer, characterized by comprising the following components by weight: 155-175 parts of bisphenol A epoxy resin, 10-30 parts of dicyclopentadiene dimethanol diglycidyl ether, 10-30 parts of terpene glycol diglycidyl ether, 95-105 parts of dry oil fatty acid, 95-105 parts of semi-dry oil fatty acid, 1-5 parts of saturated fatty acid anhydride, 1-3 parts of unsaturated fatty acid anhydride, 0.10-0.30 part of esterification catalyst and 170-210 parts of organic solvent;
the preparation method of the epoxy ester prepolymer comprises the following steps: mixing and stirring bisphenol A epoxy resin, dicyclopentadiene dimethanol diglycidyl ether, terpene glycol diglycidyl ether, dry oil fatty acid and semi-dry oil fatty acid, carrying out a first heating reaction, cooling, then adding saturated fatty acid anhydride, unsaturated fatty acid anhydride and an esterification catalyst, mixing and stirring, carrying out a second heating reaction, cooling, and finally adding an organic solvent.
2. The epoxy ester prepolymer of claim 1, wherein: the bisphenol A epoxy resin is one or more of E-51 type, E-44 type, E-20 type or E-12 type epoxy resin; the drying oil fatty acid is one or two of linoleic acid, eleostearic acid, high iodine value tall oil fatty acid or dehydrated castor oil fatty acid; the semi-dry oil fatty acid is soybean oil fatty acid and/or low-iodine-value tall oil fatty acid; the saturated fatty acid anhydride is one or more of hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride or nadic anhydride; the unsaturated fatty acid anhydride is maleic anhydride and/or fumaric anhydride; the esterification catalyst is zinc oxide or n-butyl tin oxide; the organic solvent is one or more of propylene glycol methyl ether, propylene glycol propyl ether or propylene glycol butyl ether.
3. The epoxy ester prepolymer of claim 1 or 2, characterized by: in the preparation method, the temperature of the first heating reaction is 180-200 ℃, and the time is 1-3 h; after the first heating reaction, cooling to 145-155 ℃; the temperature of the second heating reaction is 190-210 ℃, and the reaction is carried out until the acid value is less than or equal to 10 mgKOH/g; and after the second heating reaction, cooling to 80-100 ℃.
4. The epoxy ester prepolymer of claim 3, wherein: in the preparation method, the temperature of the first heating reaction is 180-200 ℃, and the time is 1-3 h; after the first heating reaction, cooling to 145-155 ℃; the temperature of the second heating reaction is 190-210 ℃, and the reaction is carried out until the acid value is less than or equal to 10mg KOH/g; and after the second heating reaction, cooling to 80-100 ℃.
5. A waterborne epoxy ester resin is characterized in that: comprising a vinyl monomer, an initiator, the epoxy ester prepolymer of any one of claims 1 to 4, a co-solvent, a neutralizing agent and water.
6. The waterborne epoxy ester resin of claim 5, wherein the weight parts of the components are as follows: 200-260 parts of vinyl monomer, 18-26 parts of initiator, 500-550 parts of epoxy ester prepolymer as described in any one of claims 1-4, 95-105 parts of cosolvent, 10-20 parts of neutralizer and 770-790 parts of water.
7. The waterborne epoxy ester resin of claim 5 or 6, wherein: the vinyl monomer comprises styrene, methacrylic acid, methyl methacrylate, polyethylene glycol methacrylate and a nitro-substituted vinyl monomer, and the mass ratio of the vinyl monomer to the nitro-substituted vinyl monomer is 96-126: 12-38: 45-75: 21-39: 6-12; in the polyethylene glycol methacrylate, the relative molecular weight of a polyethylene glycol chain segment is 300-800; the nitro-substituted vinyl monomer is 2-methyl-2-nitropropyl methacrylate and/or p-nitrostyrene; the initiator is one or more of benzoyl peroxide, tert-butyl peroxybenzoate or lauroyl peroxide; the cosolvent is one or more of isopropanol, n-butanol, propylene glycol methyl ether, propylene glycol propyl ether, propylene glycol butyl ether, dipropylene glycol butyl ether or methyl isobutyl ketone; the neutralizing agent is one or more of ammonia water, triethylamine, dimethylethanolamine or meglumine.
8. A method for preparing the waterborne epoxy ester resin according to any one of claims 5 to 7, comprising the steps of:
(1) under the reflux state of a reaction system, dropwise adding a mixed solution of a vinyl monomer and a part of initiator into a mixed solution of the epoxy ester prepolymer and a part of cosolvent according to any one of claims 1 to 3, after dropwise adding, carrying out heat preservation reaction, then dropwise adding a mixed solution of the rest of initiator and the rest of cosolvent, after dropwise adding, carrying out heat preservation reaction, and cooling to obtain acrylic acid modified epoxy ester resin;
(2) and (2) adding a neutralizing agent into the acrylic acid modified epoxy ester resin obtained in the step (1), uniformly stirring, and adding water to obtain the waterborne epoxy ester resin.
9. The method for preparing the aqueous epoxy ester resin according to claim 8, wherein: in the step (1), the reflux temperature is 110-130 ℃; the dripping speed of the two times is 200-300 kg/h; the time of the two heat preservation reactions is 1-2 h; the mass ratio of the successively dropped initiators is 3.5-4.5: 1; the mass ratio of the rest part of initiator to the rest part of cosolvent is 1: 6-12; and cooling to 50-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711064961.9A CN107629191B (en) | 2017-11-02 | 2017-11-02 | Epoxy ester prepolymer, preparation method thereof, prepared waterborne epoxy ester resin and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711064961.9A CN107629191B (en) | 2017-11-02 | 2017-11-02 | Epoxy ester prepolymer, preparation method thereof, prepared waterborne epoxy ester resin and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107629191A CN107629191A (en) | 2018-01-26 |
| CN107629191B true CN107629191B (en) | 2020-04-17 |
Family
ID=61107133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711064961.9A Active CN107629191B (en) | 2017-11-02 | 2017-11-02 | Epoxy ester prepolymer, preparation method thereof, prepared waterborne epoxy ester resin and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107629191B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112029368B (en) * | 2020-09-08 | 2021-09-21 | 湘江涂料科技有限公司 | Bottom-surface-in-one type water-based epoxy ester coating for tower crane standard part and preparation method thereof |
| CN113980539B (en) * | 2021-11-16 | 2022-05-03 | 湘江涂料科技有限公司 | Low-gloss water-based epoxy ester coating for steel structure and preparation method thereof |
| JP2023122103A (en) * | 2022-02-22 | 2023-09-01 | Dic株式会社 | Epoxy ester resin, vinyl-modified epoxy ester resin, resin composition, coating material and article coated with the coating material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864044B (en) * | 2010-07-02 | 2012-03-14 | 湖南湘江涂料集团有限公司 | Aqueous acrylic modified epoxy ester resin and synthesizing method thereof |
| CN102504668B (en) * | 2011-11-18 | 2014-01-01 | 浙江传化涂料有限公司 | Water-based primer-topcoat synthetic anti-corrosive paint for coating automobile spare parts and preparation method thereof |
| CN103319665B (en) * | 2013-06-13 | 2015-06-03 | 华南理工大学 | Single-component room-temperature multiple-self-crosslinking aqueous epoxy acrylate resin emulsion and preparation method thereof |
-
2017
- 2017-11-02 CN CN201711064961.9A patent/CN107629191B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107629191A (en) | 2018-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1116773A (en) | Surfactant-free polymer emulsion coating composition and two-stage method for preparing same | |
| CN107629191B (en) | Epoxy ester prepolymer, preparation method thereof, prepared waterborne epoxy ester resin and method | |
| CN107434842B (en) | Core-shell structure hydroxyl acrylic resin emulsion and preparation method and application thereof | |
| CN104356320B (en) | Waterborne epoxy ester-acrylic hybrid resin and preparation method thereof | |
| KR101011337B1 (en) | Water soluble acrylic - modified epoxy ester resin composition and method of preparing the same | |
| CN111138603B (en) | Water-based alkyd-acrylate dispersion and preparation method and application thereof | |
| KR101474056B1 (en) | Aqueous coating composition | |
| CA1101576A (en) | Aqueous coating composition of an acrylic-vinyl oxazoline ester polymer | |
| CN114044881B (en) | Phosphate modified waterborne epoxy ester resin, antirust primer thereof and preparation method thereof | |
| CN112979889A (en) | Waterborne acrylic modified epoxy ester resin and preparation method and application thereof | |
| CN104449291A (en) | Coating composition comprising autoxidisable component | |
| CN109503738B (en) | Phosphoric acid modified polyisoprene rubber, polyisoprene rubber modified acrylate resin dispersion, preparation method and application | |
| JPS6210269B2 (en) | ||
| CN103709333B (en) | A kind of vehicle bridge is used from phosphatization aqueous polyurethane acrylate resin and preparation method thereof | |
| JPS595224B2 (en) | Aqueous coating composition | |
| JPS6155540B2 (en) | ||
| CN111732686A (en) | Hydroxyl acrylic acid dispersion composition for water-based amino baking paint and preparation method thereof | |
| CN111995945A (en) | Quick-drying type water-based acrylic acid-polyurethane-epoxy ester ternary anti-corrosion emulsion and preparation method thereof | |
| CN112759720B (en) | Boiling-resistant phosphorus-containing waterborne acrylic modified polyester dispersion resin and preparation method and application thereof | |
| CN1405254A (en) | Water-based acrylic acid modified alcoholic acid amino baking paint | |
| CN111116831A (en) | Preparation method of hydroxyl acrylic emulsion | |
| CN116082597A (en) | Polyurethane-acrylic ester-alkyd aqueous dispersion, preparation method and application thereof | |
| CN113045948A (en) | Preparation method of water-based acrylic amino baking paint | |
| JPS6038427B2 (en) | Aqueous coating composition | |
| CN109456447B (en) | Preparation method of waterborne epoxy ester modified petroleum resin and dispersion thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Epoxy ester prepolymer, preparation method, waterborne epoxy ester resin and method for preparation Effective date of registration: 20230731 Granted publication date: 20200417 Pledgee: Agricultural Bank of China Limited Changsha Wangcheng District sub branch Pledgor: XIANGJIANG PAINT TECHNOLOGY CO.,LTD. Registration number: Y2023980050457 |