阅读说明：本技术 一种丙烯酸改性水性环氧酯树脂配方及制备方法 (Formula and preparation method of acrylic acid modified waterborne epoxy ester resin ) 是由 刘风广 戴国绪 于 2019-11-18 设计创作，主要内容包括：本发明公开了一种丙烯酸改性水性环氧酯树脂及其制备方法,本发明提供的配方按重量分数计由如下组分组成；903#环氧树脂13-18份,907#环氧树脂9-13份,环氧催化剂0.1份,油酸18-22份,脱水溶剂11-13份,稀释剂21-25份,引发剂0.5-0.9份,苯乙烯6-7份,甲基丙烯酸甲酯6-7份,丙烯酸2-3份,中和剂3-4份,本发明利用接枝共聚合的方法引入亲水基团,达到水性化的目的实现环氧酯树脂的水性化,使其成为环境友好、低污染的涂料用产品,通过功能各异的丙烯酸酯类单体的配比调整来提升产品的各项性能,采用溶剂回收工艺,减少溶剂量,提升了固体分和环保性。(The invention discloses an acrylic acid modified waterborne epoxy ester resin and a preparation method thereof, wherein the formula provided by the invention comprises the following components in parts by weight; 13-18 parts of 903# epoxy resin, 9-13 parts of 907# epoxy resin, 0.1 part of epoxy catalyst, 18-22 parts of oleic acid, 11-13 parts of dehydration solvent, 21-25 parts of diluent, 0.5-0.9 part of initiator, 6-7 parts of styrene, 6-7 parts of methyl methacrylate, 2-3 parts of acrylic acid and 3-4 parts of neutralizer.)

1. The acrylic acid modified waterborne epoxy ester resin is characterized by comprising the following components in parts by weight:

903# epoxy resin 13-18 parts

907# epoxy resin 9-13 parts

0.1 part of epoxy catalyst

18-22 parts of oleic acid

11-13 parts of dehydration solvent

21-25 parts of diluent

0.5 to 0.9 portion of initiator

6-7 parts of styrene

6-7 parts of methyl methacrylate

2-3 parts of acrylic acid

3-4 parts of a neutralizing agent.

2. The acrylic-modified waterborne epoxy ester resin of claim 1, wherein: the epoxy catalyst is zinc oxide.

3. The acrylic-modified waterborne epoxy ester resin of claim 1, wherein: the oleic acid is linoleic acid with an iodine value of 180.

4. The acrylic-modified waterborne epoxy ester resin of claim 1, wherein: the dehydration solvent is methyl isobutyl ketone.

5. The acrylic-modified waterborne epoxy ester resin of claim 1, wherein: the diluent is propylene glycol methyl ether and ethylene glycol tert-butyl ether.

6. The acrylic-modified waterborne epoxy ester resin of claim 1, wherein: the initiator is azobisisobutyronitrile.

7. The acrylic-modified waterborne epoxy ester resin of claim 1, wherein: the neutralizing agent is N, N-dimethylethanolamine.

8. The preparation method of the acrylic acid modified waterborne epoxy ester resin is characterized by comprising the following steps:

s1, weighing 13-18 parts of 903# epoxy resin, 9-13 parts of 907# epoxy resin, 0.1 part of epoxy catalyst, 18-22 parts of oleic acid, 11-13 parts of dehydration solvent, 9-11 parts of propylene glycol monomethyl ether, 12-14 parts of ethylene glycol tert-butyl ether, 0.5-0.9 part of initiator, 6-7 parts of styrene, 6-7 parts of methyl methacrylate, 2-3 parts of acrylic acid and 3-4 parts of N, N-dimethylethanolamine,

s2, mixing epoxy resin and oleic acid, adding into a reactor, adding a dehydration solvent and an epoxy catalyst, fully stirring for about 1 hour at 120 ℃, heating, controlling the temperature to react for 1 hour at 130-180 ℃, preserving the heat for 1 hour, slowly heating to 200-210 ℃, reacting for 3-4 hours, checking the acid value to be 3-10mgKOH/g, finishing the reaction, cooling to below 180 ℃, extracting the dehydration solvent by a vacuum pump for 0.5-1 hour, continuously cooling to 150 ℃, adding a diluting solvent, and uniformly stirring to obtain the epoxy ester resin;

s3, heating to the temperature of 120-135 ℃, mixing the initiator, the styrene, the acrylic acid, the methyl methacrylate and other monomers in proportion, adding the mixture into the epoxy ester resin in a dropwise manner, controlling the temperature within the range of 125-135 ℃, completing dripping within about 3 hours, and keeping the temperature for 30 minutes; continuously adding the initiator, finishing dropping within 30 minutes, and keeping the temperature for 1 hour; the same steps are repeated once again, and the reaction is stopped after the heat preservation is carried out for 2 hours;

s4, cooling to 80-90 ℃, adding N, N-dimethylethanolamine for neutralization, stirring for 20-30 minutes, and discharging to obtain the acrylic acid modified waterborne epoxy ester resin.

Technical Field

The invention belongs to the technical field of resin manufacturing, and particularly relates to a formula and a preparation method of acrylic acid modified waterborne epoxy ester resin.

Background

Volatile Organic Compounds (VOCs) are one of the most important pollutants in atmospheric pollution, are themselves highly toxic and can cause haze and photochemical smog. The country has started to punch a fist, and the policy is taken as a guide to promote the transformation and upgrading of the coating industry, namely oil-to-water, and the emission of VOC is reduced more and more strictly, and the cost is higher and higher. The water-based paint takes water as a dispersion medium, has the advantages of low combustion, small smell, low toxicity, low pollution and the like, meets the low-carbon green environmental protection requirement which is widely concerned in the world at present, and becomes a mainstream research hotspot.

The direction of the water-based resin, which is the most important raw material in the coating, largely determines the trend of the water-based coating. Epoxy resin is a common and important type of resin for paint, cannot be dissolved or dispersed in water, and is often used as paint by using a large amount of organic solvent, which is expensive, volatile, harmful to the health of constructors and causes pollution and damage to the ecological environment. Therefore, the water-based epoxy resin has been the direction of the continuous development of epoxy resin coatings, and the specific embodiment is to introduce hydrophilic groups into the molecular chain of the epoxy resin to make the epoxy resin water-based. At present, more acrylic modified epoxy ester resin is used to introduce hydrophilic carboxyl into the molecule to realize the water-based property. However, the introduction of more hydrophilic groups affects the corrosion resistance of a coating film, the oxidation crosslinking speed of fatty acid is slow, and the coating film is easy to damage at the early drying stage, and more importantly, the solvents used in the water-based epoxy acrylate on the market, such as trimethylolpropane tripropionate, propylene glycol butyl ether and the like, have the defects of high toxicity, pungent smell and the like. In view of the special structure and properties of the nano-silica particles, some people can improve the scratch resistance, hardness, wear resistance and the like of the materials by using the nano-silica particles to modify organic materials, but the performances of corrosion resistance, water resistance, drying property and the like are still not satisfactory. Therefore, in order to meet the wide market demand, an environment-friendly waterborne epoxy ester resin which has excellent corrosion resistance and water resistance, good storage stability and quick drying of a coating film is to be developed.

Disclosure of Invention

In order to solve the above problems, the present invention provides the following technical solutions: the formula of the acrylic acid modified waterborne epoxy ester resin comprises the following components in parts by weight:

903# epoxy resin 13-18 parts

907# epoxy resin 9-13 parts

0.1 part of epoxy catalyst

18-22 parts of oleic acid

11-13 parts of dehydration solvent

21-25 parts of diluent

0.5 to 0.9 portion of initiator

6-7 parts of styrene

6-7 parts of methyl methacrylate

2-3 parts of acrylic acid

3-4 parts of neutralizing agent

Further, the epoxy catalyst is zinc oxide.

Further, the oleic acid is linoleic acid with an iodine value of 180.

Further, the dehydrating solvent is methyl isobutyl ketone.

Further, the diluent is propylene glycol methyl ether and ethylene glycol tert-butyl ether.

Further, the initiator is azobisisobutyronitrile.

Further, the neutralizing agent is N, N-dimethylethanolamine.

The invention provides a preparation method of acrylic acid modified waterborne epoxy ester resin, which comprises the following steps;

s1, weighing 13-18 parts of 903# epoxy resin, 9-13 parts of 907# epoxy resin, 0.1 part of epoxy catalyst, 18-22 parts of oleic acid, 11-13 parts of dehydration solvent, 9-11 parts of propylene glycol monomethyl ether, 12-14 parts of ethylene glycol tert-butyl ether, 0.5-0.9 part of initiator, 6-7 parts of styrene, 6-7 parts of methyl methacrylate, 2-3 parts of acrylic acid and 3-4 parts of N, N-dimethylethanolamine;

s2, mixing epoxy resin and oleic acid, adding into a reactor, adding a dehydration solvent and an epoxy catalyst, fully stirring for about 1 hour at 120 ℃, heating, controlling the temperature to react for 1 hour at 130-180 ℃, preserving the heat for 1 hour, slowly heating to 200-210 ℃, reacting for 3-4 hours, checking the acid value to be 3-10mgKOH/g, finishing the reaction, cooling to below 180 ℃, extracting the dehydration solvent by a vacuum pump for 0.5-1 hour, continuously cooling to 150 ℃, adding a diluting solvent, and uniformly stirring to obtain the epoxy ester resin;

s3, heating to 120-135 ℃ (the temperature is reduced to below 120 ℃ after the diluent solvent is added), mixing the initiator, the styrene, the acrylic acid, the methyl methacrylate and other monomers in proportion, adding the mixture into the epoxy ester resin in a dropwise manner, controlling the temperature within 125-135 ℃, completing the dropwise addition within about 3 hours, and keeping the temperature for 30 minutes. Continuously adding the initiator, dripping for 30 minutes, and keeping the temperature for 1 hour. The same steps are repeated once again, and the reaction is stopped after the heat preservation is carried out for 2 hours;

s4, cooling to 80-90 ℃, adding N, N-dimethylethanolamine for neutralization, stirring for 20-30 minutes, and discharging to obtain the acrylic acid modified waterborne epoxy ester resin.

According to the invention, a hydrophilic group is introduced by using a graft copolymerization method, epoxy resin reacts with fatty acid, a dehydration volume and a catalyst are added, and a dehydration solvent is extracted to achieve the purpose of water-based treatment. Various performances of the product are improved by adjusting the proportion of the acrylate monomers with different functions, the solvent recovery process is adopted, the solvent amount is reduced, the solid content and the environmental protection are improved, and the solvent amount is reduced to the lowest value.

The preparation method has the characteristics of less side reaction and high degree of linkage of operation procedures in the process, so that the prepared product has high purity, simple process, less energy consumption and low cost, and the prepared paint film has excellent performance.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.