阅读说明：本技术 一种耐水解水性醇酸树脂 (Hydrolysis-resistant water-based alkyd resin ) 是由 董永强 耿若愚 耿军生 陈茵 张海峰 于 2021-06-21 设计创作，主要内容包括：一种耐水解水性醇酸树脂,其中,脂肪酸采用豆油酸；豆油酸用量为183.69；二元酸采用苯酐和偏苯三酸酐；苯酐和偏苯三酸酐用量为155.33；多元醇采用三羟甲基丙烷；三羟甲基丙烷用量为145.04；阻剂采用新戊二醇；新戊二醇的用量为三羟甲基丙烷的15％,即21.756。本发明为提高水性醇酸树脂的耐水解性,利用新戊二醇的位阻效应提高酯键的耐水解性能,通过实验新戊二醇的最佳用量为三羟甲基丙烷的15％,这样既能保证醇酸树脂的水溶性和成膜综合性能,同时可以大幅提高醇酸树脂的耐水解性能；同时为了避免醇酸树脂在后期使用过程中发生粘度过高的情况,在醇酸树脂中加醇酸漆稀释剂,从而降低干性醇酸树脂水溶为水性醇酸树脂后的粘度,满足醇酸树脂水性涂料的市场需求。(A hydrolysis-resistant water-based alkyd resin is provided, wherein fatty acid adopts soya-oil acid; the using amount of the soya oil acid is 183.69; the dibasic acid is selected from phthalic anhydride and trimellitic anhydride; the use amount of the phthalic anhydride and the trimellitic anhydride is 155.33; the polyalcohol adopts trimethylolpropane; the dosage of the trimethylolpropane is 145.04; neopentyl glycol is adopted as the resistance agent; neopentyl glycol was used at 15% of trimethylolpropane, 21.756. In order to improve the hydrolysis resistance of the water-based alkyd resin, the hydrolysis resistance of an ester bond is improved by utilizing the steric effect of neopentyl glycol, and the optimal dosage of the neopentyl glycol is 15 percent of that of trimethylolpropane through experiments, so that the water solubility and the film forming comprehensive performance of the alkyd resin can be ensured, and the hydrolysis resistance of the alkyd resin can be greatly improved; meanwhile, in order to avoid the situation that the viscosity of the alkyd resin is too high in the later use process, the alkyd resin is added with the alkyd paint diluent, so that the viscosity of the dry alkyd resin after the dry alkyd resin is dissolved into water-based alkyd resin is reduced, and the market demand of the alkyd resin water-based paint is met.)

1. A hydrolysis-resistant water-based alkyd resin is characterized in that the alkyd resin is prepared by reacting fatty acid, dibasic acid, polyalcohol and a resistance agent;

wherein the fatty acid is soya oil acid; the using amount of the soya oil acid is 183.69; the dibasic acid is selected from phthalic anhydride and trimellitic anhydride; the use amount of the phthalic anhydride and the trimellitic anhydride is 155.33; the polyalcohol adopts trimethylolpropane; the dosage of the trimethylolpropane is 145.04; neopentyl glycol is adopted as the resistance agent; the amount of neopentyl glycol used was 15% of trimethylolpropane, i.e. 21.756;

the synthesis of the water-based alkyd resin is divided into two steps, wherein the first step is the synthesis of hydroxy alkyd resin; secondly, introducing water-soluble functional groups into the hydroxy alkyd resin; the acid value of the mixture in the first step is controlled to be 8-12; secondly, adding trimellitic anhydride to obtain resin with an acid value of 50-60;

adding alkyd paint thinner or mixed solvent of No. 200 solvent and xylene into the synthesized waterborne alkyd resin.

2. The hydrolysis-resistant waterborne alkyd resin of claim 1, wherein the ratio of phthalic anhydride to trimellitic anhydride is 5: 1.

3. The hydrolysis-resistant waterborne alkyd resin of claim 1, wherein the esterification temperature of the first step is 220 ℃ to 240 ℃.

4. The hydrolysis-resistant waterborne alkyd resin of claim 1, wherein the esterification temperature of the second step is from 210 ℃ to 220 ℃.

5. The hydrolysis-resistant waterborne alkyd resin of claim 1, wherein the neutralizing agent triethylamine is added to the soya oil acid.

6. The hydrolysis-resistant water-based alkyd resin of claim 1, wherein the water-based alkyd resin has an oil content of 40%, and an optimal alcohol content of 25%; the oil content of the waterborne alkyd resin is 45 percent, and the optimal alcohol excess is 20 percent; the oil content of the waterborne alkyd resin is 50 percent, and the optimal alcohol excess is 15 percent; the oil content of the waterborne alkyd resin is 55 percent, and the optimal alcohol excess is 10 percent.

7. The hydrolysis-resistant water-based alkyd resin of claim 6, wherein the performance of the water-based alkyd resin is optimal when the oil degree is 45%.

8. A hydrolysis-resistant waterborne alkyd resin according to claims 1-7, characterized in that it is prepared by the following steps:

s1, adding the soya-bean oil acid and the trimethylolpropane in the formula amount into a reaction kettle, introducing nitrogen, starting stirring, and heating; heating to 220-240 ℃, starting esterification reaction, and keeping the temperature for 3 hours;

s2, when the first-step reaction is finished, carrying out acid value measurement to ensure that the acid value is 8-12;

s3, adding phthalic anhydride, trimellitic anhydride and neopentyl glycol; rapidly cooling to maintain the temperature of the reaction kettle at 210-220 ℃ and preserving the heat for 3 hours;

s4, acid value measurement is carried out after the second reaction step is finished, so that the acid value is 50-60;

and S5, cooling, stirring for 10 minutes, and discharging to obtain the water-based alkyd resin.

Technical Field

The invention relates to the technical field of alkyd resin, in particular to hydrolysis-resistant water-based alkyd resin.

Background

The alkyd resin is successfully developed in 1927, the alkyd resin is rapidly developed due to the unique performance of the alkyd resin, the consumption of the alkyd resin accounts for about 40% of all synthetic resins in the 80 s abroad, particularly the consumption in North America is larger, and the proportion of the alkyd resin in China is 27%, but along with the rise of the global environment protection hot tide, the pollution of the coating to the environment is more and more highly emphasized, so that the oil-soluble coating is gradually replaced by the water-based coating.

The chemical substances can be subjected to hydrolysis reaction after being dissolved in water; for example, chlorine gas is dissolved in water to generate hydrogen chloride and hypochlorous acid, and ethyl acetate is dissolved in water to generate ethanol and acetic acid; this property is called hydrolysis, and hydrolysis resistance is a property in which hydrolysis does not easily occur; in order to improve hydrolysis resistance, the conventional alkyd resin is usually added with an auxiliary agent and a production process is controlled; although the addition of the auxiliary agent helps to improve the hydrolysis resistance of the alkyd resin, the addition of the auxiliary agent also causes the alkyd resin to generate a bleeding phenomenon or a situation of high viscosity in the later use process.

Disclosure of Invention

Objects of the invention

In order to solve the technical problems in the background art, the invention provides a hydrolysis-resistant water-based alkyd resin, in order to improve the hydrolysis resistance of the water-based alkyd resin, the hydrolysis resistance of an ester bond is improved by utilizing the steric effect of neopentyl glycol, and the optimal dosage of the neopentyl glycol is 15% of trimethylolpropane through experiments, so that the water solubility and the film forming comprehensive performance of the alkyd resin can be ensured, and the hydrolysis resistance of the alkyd resin can be greatly improved; meanwhile, in order to avoid the situation that the viscosity of the alkyd resin is too high in the later use process, an alkyd paint diluent is added in the use process of the alkyd resin, or the viscosity is adjusted by using a mixed solvent of a No. 200 solvent and xylene, so that the viscosity of the drying alkyd resin after the drying alkyd resin is dissolved in water to be the water-based alkyd resin is reduced, the economic benefit of the water-based paint is improved, and the market demand of the alkyd resin water-based paint is met.

(II) technical scheme

The invention provides a hydrolysis-resistant water-based alkyd resin, which is prepared by reacting fatty acid, dibasic acid, polyalcohol and a resistance agent; wherein the fatty acid is soya oil acid; the using amount of the soya oil acid is 183.69; the dibasic acid is selected from phthalic anhydride and trimellitic anhydride; the use amount of the phthalic anhydride and the trimellitic anhydride is 155.33; the polyalcohol adopts trimethylolpropane; the dosage of the trimethylolpropane is 145.04; neopentyl glycol is adopted as the resistance agent; the amount of neopentyl glycol used was 15% of trimethylolpropane, i.e. 21.756; the synthesis of the water-based alkyd resin is divided into two steps, wherein the first step is the synthesis of hydroxy alkyd resin; secondly, introducing water-soluble functional groups into the hydroxy alkyd resin; the acid value of the mixture in the first step is controlled to be 8-12; secondly, adding trimellitic anhydride to obtain resin with an acid value of 50-60; adding alkyd paint thinner or mixed solvent of No. 200 solvent and xylene into the synthesized waterborne alkyd resin.

Preferably, the ratio of phthalic anhydride to trimellitic anhydride is 5: 1.

Preferably, the esterification temperature of the first step is from 220 ℃ to 240 ℃.

Preferably, the esterification temperature in the second step is from 210 ℃ to 220 ℃.

Preferably, the neutralizing agent triethylamine is added to the soya oil acid.

Preferably, the oil degree of the waterborne alkyd resin is 40%, and the optimal alcohol excess is 25%; the oil content of the waterborne alkyd resin is 45 percent, and the optimal alcohol excess is 20 percent; the oil content of the waterborne alkyd resin is 50 percent, and the optimal alcohol excess is 15 percent; the oil content of the waterborne alkyd resin is 55 percent, and the optimal alcohol excess is 10 percent.

Preferably, the performance is best when the oil degree of the waterborne alkyd resin is 45%.

The preparation process comprises the following steps:

s1, adding the soya-bean oil acid and the trimethylolpropane in the formula amount into a reaction kettle, introducing nitrogen, starting stirring, and heating; heating to 220-240 ℃, starting esterification reaction, and keeping the temperature for 3 hours;

s2, when the first-step reaction is finished, carrying out acid value measurement to ensure that the acid value is 8-12;

s3, adding phthalic anhydride, trimellitic anhydride and neopentyl glycol; rapidly cooling to maintain the temperature of the reaction kettle at 210-220 ℃ and preserving the heat for 3 hours;

s4, acid value measurement is carried out after the second reaction step is finished, so that the acid value is 50-60;

and S5, cooling, stirring for 10 minutes, and discharging to obtain the water-based alkyd resin.

Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects: in order to improve the hydrolysis resistance of the water-based alkyd resin, the steric effect of neopentyl glycol is utilized to improve the hydrolysis resistance of an ester bond, and the optimal dosage of the neopentyl glycol is 15% of trimethylolpropane through experiments, so that the water solubility and the film forming comprehensive performance of the alkyd resin can be ensured, and the hydrolysis resistance of the alkyd resin can be greatly improved; meanwhile, in order to avoid the situation that the viscosity of the alkyd resin is too high in the later use process, an alkyd paint diluent is added in the use process of the alkyd resin, or the viscosity is adjusted by using a mixed solvent of a No. 200 solvent and xylene, so that the viscosity of the drying alkyd resin after the drying alkyd resin is dissolved in water to be the water-based alkyd resin is reduced, the economic benefit of the water-based paint is improved, and the market demand of the alkyd resin water-based paint is met.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.

The invention provides a hydrolysis-resistant water-based alkyd resin, which is prepared by reacting fatty acid, dibasic acid, polyalcohol and a resistance agent; wherein the fatty acid is soya oil acid; the using amount of the soya oil acid is 183.69; the dibasic acid is selected from phthalic anhydride and trimellitic anhydride; the use amount of the phthalic anhydride and the trimellitic anhydride is 155.33; the polyalcohol adopts trimethylolpropane; the dosage of the trimethylolpropane is 145.04; neopentyl glycol is adopted as the resistance agent; the amount of neopentyl glycol used was 15% of trimethylolpropane, i.e. 21.756; thus, the water solubility and the film-forming property of the alkyd resin can be ensured, and the optimal film-forming comprehensive property of the alkyd resin can also be ensured; the synthesis of the water-based alkyd resin is divided into two steps, wherein the first step is the synthesis of hydroxy alkyd resin; secondly, introducing water-soluble functional groups into the hydroxy alkyd resin; the acid value of the mixture in the first step is controlled to be 8-12; secondly, adding trimellitic anhydride to obtain resin with an acid value of 50-60; adding alkyd paint thinner or mixed solvent of No. 200 solvent and xylene into the synthesized waterborne alkyd resin.

In an alternative embodiment, the ratio of phthalic anhydride to trimellitic anhydride is 5: 1.

In an alternative embodiment, the esterification temperature of the first step is from 220 ℃ to 240 ℃.

In an alternative embodiment, the esterification temperature of the second step is from 210 ℃ to 220 ℃.

In an alternative embodiment, the neutralizing agent triethylamine is added to the soya oil acid; according to the water-based alkyd resin synthesized by different oleic acids, the material and the theoretical dosage of a neutralizer need to be determined experimentally.

In an alternative embodiment, the waterborne alkyd resin has an oil content of 40%, and an optimal alcohol excess of 25%; the oil content of the waterborne alkyd resin is 45 percent, and the optimal alcohol excess is 20 percent; the oil content of the waterborne alkyd resin is 50 percent, and the optimal alcohol excess is 15 percent; 55% of oil content of the waterborne alkyd resin, and 10% of optimal alcohol excess; meanwhile, the optimal alcohol excess of the water-based alkyd resin along with the difference of oil degrees is calculated by referring to a method for calculating the alcohol excess of the solvent-based alkyd resin according to the K value, and the theoretical calculation is consistent with the experimental structure.

In an alternative embodiment, the performance is best when the waterborne alkyd resin has an oil degree of 45%.

The preparation process comprises the following steps: adding the soya-bean oil acid and the trimethylolpropane in the formula amount into a reaction kettle, introducing nitrogen, starting stirring, and heating; heating to 220-240 ℃, starting esterification reaction, and keeping the temperature for 3 hours; when the first-step reaction is finished, carrying out acid value measurement to ensure that the acid value is 8-12; adding phthalic anhydride, trimellitic anhydride and neopentyl glycol; rapidly cooling to maintain the temperature of the reaction kettle at 210-220 ℃ and preserving the heat for 3 hours; when the second reaction step is finished, acid value measurement is carried out, so that the acid value is 50-60; cooling, stirring for 10 minutes, and discharging to obtain the water-based alkyd resin.

According to the analysis of paint preparation cost, the cost of the paint prepared from the water-based alkyd resin synthesized by the soya oil acid and the paint material prepared from the traditional solvent-based alkyd resin is higher than the original cost per ton, but the factor of diluting the solvent during construction is considered, and the construction cost of the paint prepared from the water-based alkyd resin and the solvent is basically almost the same. The water-based alkyd resin synthesized by the soya-bean oil acid has wide application prospect.

It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.