阅读说明：本技术 一种净味成膜助剂的制备工艺 (Preparation process of odor-free film-forming additive ) 是由 郑凤云 赵红阳 陈玮 吴通达 邢燕燕 陈志勇 苗淑兰 牛丽丽 张金叶 刘千河 闫 于 2020-12-31 设计创作，主要内容包括：本发明属于净味涂料制备技术领域,具体涉及一种净味成膜助剂的制备工艺。本发明利用醇类与十二或十六碳醇酯制备中残留的异丁酸反应,生成异丁酸酯,从而消除成膜助剂中的臭味；所得异丁酸酯可作为成膜助剂的有效成分。所用醇类物质的添加量大于十二或十六碳醇酯制备过程中异丁酸的产生量,从促进异丁酸与醇类物质进行酯化反应以及抑制十二/十六碳醇酯的水解,而多余的醇类可以作为成膜助剂的快干成分和防冻成分,不会影响成膜助剂的性能。(The invention belongs to the technical field of preparation of odorless coatings, and particularly relates to a preparation process of an odorless film-forming aid. The invention utilizes alcohols to react with residual isobutyric acid in the preparation of dodecyl or hexadecyl alcohol ester to generate isobutyrate, thereby eliminating the odor in the film forming additive; the resulting isobutyrate ester can be used as an active ingredient of a film-forming aid. The addition amount of the alcohol substance is larger than the generation amount of isobutyric acid in the preparation process of the dodeca-or hexadecanol ester, so that the esterification reaction of the isobutyric acid and the alcohol substance is promoted, the hydrolysis of the dodeca/hexadecanol ester is inhibited, and the redundant alcohol can be used as a quick-drying component and an antifreezing component of the film-forming additive without influencing the performance of the film-forming additive.)

1. A preparation process of an odorless film-forming aid is characterized by comprising the following steps:

1) synthesizing dodecyl alcohol ester by taking isobutyraldehyde as a raw material under an alkaline condition, and reacting at the temperature of 160-200 ℃ for 8-15 min; the mass ratio of isobutyraldehyde to alkali is 50-180: 1;

2) removing isobutyraldehyde which does not participate in the reaction in the dodecanol ester reaction solution, and then adding alcohols, wherein the mass ratio of the addition amount of the alcohols to the dodecanol ester is (0.1-1): 99-99.9, and reacting for 1-2 h; the alcohol is any one of ethylene glycol, ethanol or propanol.

2. The process of claim 1, wherein: step 1), the mass ratio of isobutyraldehyde to alkali is 50-53: 1.

3. a preparation process of an odorless film-forming aid is characterized by comprising the following steps:

1) synthesizing dodecyl alcohol ester by taking isobutyraldehyde as a raw material under an alkaline condition, and reacting at the temperature of 160-200 ℃ for 8-15 min; the mass ratio of isobutyraldehyde to alkali is 140-180: 1;

2) adding sodium percarbonate into the reaction liquid obtained in the step 1), wherein the temperature is 190-200 ℃, and the reaction time is 0.5-1 h; the adding amount of the sodium percarbonate is 18-22% of the mass of the isobutyraldehyde in the step 1);

3) continuously reacting for 0.5-1 h at 190-200 ℃ under an acidic condition to obtain a reaction solution of the hexadecanol ester;

4) adding alcohols into the reaction liquid obtained in the step 3), wherein the mass ratio of the addition amount of the alcohols to the reaction liquid is (0.1-1): 99-99.9, and reacting for 1-2 h; the alcohol is any one of ethylene glycol, ethanol or propanol.

4. An odorless film-forming additive prepared by the preparation process as claimed in any one of claims 1 to 3.

5. Use of the odor-free coalescent of claim 4 as an auxiliary component of a coating.

6. The use of claim 5, wherein: the coating is a water-based coating.

7. The use of claim 6, wherein: the water paint is any one or mixture of more than two of acrylate emulsion, styrene emulsion, vinyl acetate emulsion, polyurethane emulsion, epoxy emulsion, styrene/butadiene emulsion and acrylonitrile/butadiene/styrene emulsion in any proportion.

8. Use according to any one of claims 5 to 7, wherein: the addition amount of the odorless film-forming aid in the coating is 3% -7%.

Technical Field

The invention belongs to the technical field of preparation of odorless coatings, and particularly relates to a preparation process of an odorless film-forming aid.

Background

When the environment temperature is lower than the film-forming temperature of the emulsion, the emulsion is not easy to form a film, and the film-forming auxiliary agent can reduce the minimum film-forming temperature of the emulsion, help film formation and does not influence the characteristic of damaging a film. At present, the film forming auxiliary agents mainly used for water-based paint on the market comprise two products, namely dodecyl alcohol ester and hexadecyl alcohol ester, and the two products can effectively reduce the film forming temperature of the emulsion.

Wherein the synthesis of the cetyl alcohol ester generally comprises the steps of: 1) under the action of a basic catalyst, partial aldol condensation reaction and disproportionation reaction of isobutyraldehyde are carried out to obtain 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and reaction liquid of unreacted isobutyraldehyde; 2) removing the basic catalyst in the reaction liquid, then carrying out oxidation reaction under the action of an oxidant and an oxidation catalyst, and oxidizing unreacted isobutyraldehyde into isobutyric acid; 3) after removing the oxidation catalyst in the reaction solution, 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate and isobutyric acid are subjected to esterification reaction under the catalysis of an esterification catalyst to finally obtain 2, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate.

The synthesis process has unreacted isobutyric acid, and the synthesized product 2, 2, 4-trimethyl-1, 3-pentanediol diisobutyrate is hydrolyzed to generate isobutyric acid. Isobutyric acid has a bad smell of feet, and a very small amount can stimulate the smell. The main method for improving the odor problem of cetyl alcohol ester in the prior art is to cover the odor problem by adding essence, but the odor problem cannot be completely solved, and even in the process of adding the essence, the essence components and the coating components interact to cause the denaturation of the essence components and generate other odors.

Disclosure of Invention

In order to solve the problem that the film-forming assistant in the prior art has peculiar smell, the invention aims to provide a preparation process of the odor-free film-forming assistant, wherein the twelve or hexadecanol ester product produced by the process has the total content of more than 98 percent, meets the content quality standard of the film-forming assistant and can effectively solve the problem of peculiar smell of the product.

In order to achieve the technical purpose, the invention adopts the following technical scheme:

a preparation process of an odorless film forming aid specifically comprises the following steps:

1) synthesizing dodecyl alcohol ester by taking isobutyraldehyde as a raw material under an alkaline condition, and reacting at the temperature of 160-200 ℃ for 8-15 min; the mass ratio of isobutyraldehyde to alkali is 50-180: 1;

2) removing isobutyraldehyde which does not participate in the reaction in the dodecanol ester reaction solution, and then adding alcohols, wherein the mass ratio of the addition amount of the alcohols to the dodecanol ester is (0.1-1): 99-99.9, and reacting for 1-2 h; the alcohol is any one of ethylene glycol, ethanol or propanol.

Preferably, the mass ratio of isobutyraldehyde to base in the step 1) is 50-53: 1.

a preparation process of an odorless film forming aid specifically comprises the following steps:

1) synthesizing dodecyl alcohol ester by taking isobutyraldehyde as a raw material under an alkaline condition, and reacting at the temperature of 160-200 ℃ for 8-15 min; the mass ratio of isobutyraldehyde to alkali is 140-180: 1;

2) adding sodium percarbonate into the reaction liquid obtained in the step 1), wherein the temperature is 190-200 ℃, and the reaction time is 0.5-1 h;

the adding amount of the sodium percarbonate is 18-22% of the mass of the isobutyraldehyde in the step 1);

3) continuously reacting for 0.5-1 h at 190-200 ℃ under an acidic condition to obtain a reaction solution of the hexadecanol ester;

4) adding alcohols into the reaction liquid obtained in the step 3), wherein the mass ratio of the addition amount of the alcohols to the reaction liquid is (0.1-1): 99-99.9, and reacting for 1-2 h; the alcohol is any one of ethylene glycol, ethanol or propanol.

Based on a general inventive concept, the invention also comprises the odorless film-forming aid prepared by the preparation process.

Based on one general inventive concept, the present invention also includes the use of the above described odor-free coalescent as an auxiliary component of a coating.

Preferably, the coating is a water-based coating.

More preferably, the aqueous coating is a mixture of any one or two or more of an acrylate emulsion, a styrene emulsion, a vinyl acetate emulsion, a polyurethane emulsion, an epoxy emulsion, a styrene/butadiene emulsion, and an acrylonitrile/butadiene/styrene emulsion in any proportion.

Preferably, the addition amount of the odorless film-forming aid in the coating is 3% -7%.

The technical principle of the invention is that alcohols are used for reacting with residual isobutyric acid in the preparation of dodecyl alcohol ester or hexadecyl alcohol ester to generate isobutyrate, thereby eliminating the odor in the film-forming auxiliary agent; the resulting isobutyrate ester can be used as an active ingredient of a film-forming aid. The addition amount of the alcohol substance is larger than the generation amount of isobutyric acid in the preparation process of the dodeca-or hexadecanol ester, so that the esterification reaction of the isobutyric acid and the alcohol substance is promoted, the hydrolysis of the dodeca/hexadecanol ester is inhibited, and the redundant alcohol can be used as a quick-drying component and an antifreezing component of the film-forming additive without influencing the performance of the film-forming additive. After verification, after the film-forming additive is added into the water-based paint, the paint has no peculiar smell or the degree of the peculiar smell is obviously improved, and particularly, when the addition amount of glycol or ethanol in the film-forming additive is 0.7-1%, the peculiar smell of isobutyric acid is completely eliminated, so that the odor-free paint standard can be reached.

Compared with the prior art, the invention has the beneficial effects that:

1) according to the invention, excessive alcohol substances are added in the preparation of the twelve or sixteen carbon alcohol ester, so that residual isobutyric acid in the reaction liquid is reacted, thereby eliminating odor sources, and the generated isobutyrate can be used as an effective component of a film-forming additive, so that the performance of the film-forming additive is improved; the film-forming additive does not need to add essence or spice additionally during use, avoids the product quality problem caused by the denaturation of essence components, and can reduce the production cost;

2) by optimizing the proportion, the added redundant alcohol substances are soft in taste and can be used as quick-drying components and anti-freezing components in the film-forming auxiliary agent, and the overall performance of the film-forming auxiliary agent is not influenced.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments;

the reagents used in the present invention are either commonly available or available to one skilled in the art through published routes.

Example 1

A preparation process of an odorless film-forming aid specifically comprises the following steps:

1) adding 10kg of isobutyraldehyde into 0.2kg of sodium hydroxide aqueous solution, reacting for 10min at 180 ℃; the mass concentration of the sodium hydroxide aqueous solution is 35 percent;

2) adding 1.9kg of sodium percarbonate, stirring and reacting at the reaction temperature of 200 ℃ for 45 min;

3) both the step 1) and the step 2) can generate partial isobutyric acid, so that the reaction liquid is acidic, and the reaction is continued for 1h at the temperature of 200 ℃ to obtain the hexadecanol ester;

4) adding 9.50mL of glycol, and continuing to react for 1h to obtain the compound.

The yield of the final hexadecanol ester is about 95.02 percent based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of the ethylene glycol to the hexadecanol ester is 0.1%: 99.9 percent.

Example 2

A preparation process of an odorless film-forming aid specifically comprises the following steps:

1) adding 10kg of isobutyraldehyde into 0.15kg of sodium hydroxide aqueous solution, reacting for 10min at 180 ℃; the mass concentration of the sodium hydroxide aqueous solution is 38 percent;

2) adding 1.85kg of sodium percarbonate, stirring and reacting at the reaction temperature of 200 ℃ for 40 min;

3) both the step 1) and the step 2) can generate partial isobutyric acid, so that the reaction liquid is acidic, and the reaction is continued for 1h at the temperature of 200 ℃ to obtain the hexadecanol ester;

4) adding 27.57mL of ethanol, and continuing to react for 1.5h to obtain the compound.

The yield of the final hexadecanol ester is about 91.89% based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of the ethanol to the hexadecanol ester is 0.3%: 99.7 percent.

Example 3

A preparation process of an odorless film-forming aid specifically comprises the following steps:

1) adding 9kg of isobutyraldehyde into 0.15kg of sodium hydroxide aqueous solution, reacting for 12min at the temperature of 170 ℃; the mass concentration of the sodium hydroxide aqueous solution is 36 percent;

2) adding 1.9kg of sodium percarbonate, stirring and reacting at the reaction temperature of 200 ℃ for 40 min;

3) both the step 1) and the step 2) can generate partial isobutyric acid, so that the reaction liquid is acidic, and the reaction is continued for 1h at the temperature of 200 ℃ to obtain the hexadecanol ester;

4) adding 40.59mL of glycol, and continuing to react for 1h to obtain the compound.

The yield of the final hexadecanol ester is about 90.21% based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of the ethylene glycol to the hexadecanol ester is 0.5%: 99.5 percent.

Example 4

A process for the preparation of an odorless film forming aid, the process comprising the specific steps of referring to example 1;

the difference from the embodiment 1 is that 66.46mL of ethylene glycol is added in the step 4), and the reaction is continued for 1h to obtain the compound;

the yield of the final hexadecanol ester is about 94.95 percent based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of the ethylene glycol to the hexadecanol ester is 0.7%: 99.3 percent.

Example 5

A process for the preparation of an odorless film forming aid, the process comprising the specific steps of referring to example 2;

the difference from the embodiment 2 is that 92mL of ethanol is added in the step 4), and the reaction is continued for 1.5h to obtain the compound;

the yield of the final hexadecanol ester is about 92 percent based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of ethanol to the hexadecanol ester is 1%: 99 percent.

Example 6

A preparation process of an odorless film-forming aid specifically comprises the following steps:

1) slowly adding 3.6kg of isobutyraldehyde into 0.2kg of sodium hydroxide aqueous solution, reacting for 10min at the temperature of 180 ℃; the mass concentration of the sodium hydroxide aqueous solution is 35 percent;

2) filtering unreacted isobutyraldehyde to obtain a reaction solution with the main component of dodecyl alcohol ester; adding 2.34mL of glycol, and continuing to react for 2h to obtain the compound.

The yield of the final dodecyl alcohol ester is about 64.92 percent based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of the ethylene glycol to the lauryl alcohol ester is 0.1%: 99.9 percent.

Example 7

A preparation process of an odorless film-forming aid specifically comprises the following steps:

1) slowly adding 3kg of isobutyraldehyde into 0.15kg of sodium hydroxide aqueous solution, reacting at 180 ℃ for 10 min; the mass concentration of the sodium hydroxide aqueous solution is 38 percent;

2) filtering unreacted isobutyraldehyde after the reaction is completed to obtain reaction liquid of which the main component is dodecyl alcohol ester; adding 5.72mL of ethanol, and continuing to react for 2h to obtain the compound.

The yield of the final dodecyl alcohol ester is about 63.52 percent based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of ethanol to the dodecanol ester is 0.3%: 99.7 percent.

Example 8

A preparation process of an odorless film-forming aid specifically comprises the following steps:

1) slowly adding 3.6kg of isobutyraldehyde into 0.2kg of sodium hydroxide aqueous solution, reacting for 10min at the temperature of 180 ℃; the mass concentration of the sodium hydroxide aqueous solution is 36 percent;

2) after the reaction is completed, filtering unreacted isobutyraldehyde to obtain reaction liquid with the main component of alcohol ester twelve; adding 12.2mL of glycol, and continuing to react for 2h to obtain the product.

The yield of the final dodecyl alcohol ester is about 68.01% based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of the ethylene glycol to the lauryl alcohol ester is 0.5%: 99.5 percent.

Example 9

A process for the preparation of an odorless film forming aid, the process comprising the steps of referring to example 6;

the difference from the example 6 is that 16.16mL of ethylene glycol is added in the step 3), and the reaction is continued for 2h to obtain the compound.

The yield of the final dodecyl alcohol ester is about 64.15% based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of the ethylene glycol to the lauryl alcohol ester is 0.7%: 99.3 percent.

Example 10

A process for the preparation of an odorless coalescent, the process comprising the steps of referring to example 7;

the difference from the embodiment 7 is that 18.91mL of ethanol is added in the step 3), and the reaction is continued for 2h to obtain the compound;

the yield of the final dodecyl alcohol ester is about 63.05 percent based on the amount of isobutyraldehyde in the process; the mass concentration ratio of the addition amount of ethanol to the mass concentration of the dodecyl alcohol ester is 1%: 99 percent.

In examples 1 to 10, the yield of the dodecanol ester or hexadecanol ester and the amount ratio of the dodecanol ester or hexadecanol ester to the alcohol (ethylene glycol or ethanol) are shown in table 1;

TABLE 1 dosage ratio of film forming assistant to alcohol in examples 1 to 10

In order to show the technical effect of the invention, the film-forming assistant obtained in the embodiment 1-10 is added into the coating for effect verification, and the specific process is as follows.

Test examples

The film-forming assistant obtained in examples 1 to 10 was added to an aqueous coating material (a commercially available acrylic emulsion) in an amount of 5%; after uniform dispersion, coating a film; after standing for 48 hours, performance evaluation was performed. In the test, isobutyraldehyde is used as a raw material, a film-forming aid without adding alcohol in the preparation process is used as a control group (cetyl alcohol ester obtained in the preparation process is used as a control group 1, and lauryl alcohol ester is used as a control group 2), and a treatment group without adding the film-forming aid is used as a blank; three replicates were set for each condition and the test results averaged.

The film forming effect is measured by using a minimum film forming temperature instrument according to GB/T9267-2008 'determination of white point temperature and minimum film forming temperature of emulsion and paint for paint and polymer dispersoid for plastics', the temperature is 20 ℃, and the relative humidity is 50%; the odor was determined by olfaction with reference to GB/T15549-. The film forming effect under different conditions is compared and shown in the table 2;

TABLE 2 comparison of film-Forming Effect of acrylic emulsions under different conditions

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As can be seen from the above table, the film-forming additive obtained in examples 1 to 10 has good compatibility with acrylic emulsion; after the film is kept stand for 24h, the appearance is good, the film is formed, and the powder is not dropped off after dry wiping. It is demonstrated that the film-forming aids obtained in examples 1 to 10 do not affect the performance of the acrylic emulsion. However, from the aspect of odor, after the film-forming additive obtained in the embodiments 1 to 10 is added, the acrylic emulsion has no peculiar smell or the degree of peculiar smell is obviously improved, and particularly, when the addition amount of the glycol or the ethanol reaches 0.7 to 1 percent, the peculiar smell of the isobutyric acid is completely eliminated or covered, so that the odor-free coating standard can be reached.