KR102487713B1 - Method for preparing dmpa modified waterborne alkyd resin - Google Patents

Abstract

The present invention discloses a method for producing a DMPA-modified aqueous alkyd resin, according to which 70-90 parts by weight of flax oil and 10-30 parts by weight of maleic anhydride are mixed at room temperature, the temperature is raised to 240-250 ° C, and the temperature is raised to 7-9 hours. Obtaining a first product by maintaining the temperature while; Mixing 30-40 parts by weight of soybean oil, 10-20 parts by weight of polyalcohol, and 0.005-0.01 parts by weight of potassium hydroxide to raise the temperature to 240-250 ° C. and maintain the temperature for 1-1.5 hours; The temperature of the reaction product obtained in step 2 was lowered to 170-190 ° C, 20-30 parts by weight of phthalic anhydride, 8-15 parts by weight of DMPA, and 5-10 parts by weight of benzoic acid were added, and the additionally added xylene was refluxed ( refluxing), raising the temperature to 170-190 ° C, maintaining the temperature for 0.5-1.5 hours, raising the temperature again to 200-210 ° C and maintaining the temperature for 6-8 hours to obtain a second product; And 40-60 parts by weight of butyl ether and the first product are mixed, the second product is added, the temperature is lowered to 95-105 ° C, and an amine neutralizer is added so that the pH value of the mixture is 8.5-9 to DMPA (dimethylol propionic acid) ; dimethylol propionic acid) to obtain a modified aqueous alkyd resin. The water-based alkyd resin according to the present invention is greatly improved in safety and eco-friendliness, clearly showing a safe and eco-friendly aspect.

Description

Method for producing DMPA-modified aqueous alkyd resin {METHOD FOR PREPARING DMPA MODIFIED WATERBORNE ALKYD RESIN}

The present invention relates to the field of paint chemistry, and more particularly, to a method for preparing a dimethylol propionic acid (DMPA)-modified water-based alkyd resin for water-based paints.

In general, alkyd resin is a resin produced through high-temperature polymerization of soybean oil, phthalic anhydride, glycerin, pentaerythritol, and solvent oil No. 200, and has excellent weather resistance, but has a low safety factor due to high VOC emissions during production and use. , It is also a hazardous chemical substance because it is flammable and explosive during use and transportation, and it is a product that is being phased out nationally due to its large environmental pollution.

In order to solve such problems of the prior art, the present invention aims to provide a modified aqueous alkyd resin and a method for producing the same.

In one aspect, the present invention provides a DMPA-modified aqueous alkyd resin prepared from raw materials having the following weight composition ratio:

70-90 parts flax oil

Maleic anhydride 10-30 parts

30-40 parts soybean oil

10-20 parts polyalcohol

Potassium hydroxide 0.005-0.01 part

Phthalic anhydride 20-30 parts

DMPA Parts 8-15

Benzoic acid 5-10 parts

Butyl ether 40-60 parts.

Optionally, according to the aqueous alkyd resin according to the present invention, the polyalcohol may be pentaerythritol and/or glycerin.

In another aspect, the present invention provides a method for preparing an aqueous alkyd resin comprising the steps of:

Step 1: mixing 70-90 parts by weight of flax oil and 10-30 parts by weight of maleic anhydride at room temperature to raise the temperature to 240-250 ° C. and maintain the temperature for 7-9 hours to obtain a first product;

Step 2: mixing 30-40 parts by weight of soybean oil, 10-20 parts by weight of polyalcohol, and 0.005-0.01 parts by weight of potassium hydroxide to raise the temperature to 240-250 ° C. and maintain the temperature for 1-1.5 hours;

Step 3: The temperature of the reaction product obtained in step 2 is lowered to 170-190 ° C, 20-30 parts by weight of phthalic anhydride, 8-15 parts by weight of DMPA, and 5-10 parts by weight of benzoic acid are added, and xylene is further added. refluxing, raising the temperature to 170-190 ° C, maintaining the temperature for 0.5-1.5 hours, then raising the temperature to 200-210 ° C and maintaining the temperature for 6-8 hours to obtain a second product; and

Step 4: Mix 40-60 parts by weight of butyl ether with the first product, add the second product, lower the temperature to 95-105 ° C, add an amine neutralizer so that the pH value of the mixture is 8.5-9, and DMPA (dimethylol obtaining a modified aqueous alkyd resin.

Optionally, according to the manufacturing method according to the present invention, the manufacturing method further includes step 5, that is, diluting the dimethylol propionic acid (DMPA)-modified aqueous alkyd resin with water.

Optionally, according to the production method according to the present invention, the addition amount of the amine neutralizing agent is 5-10 parts by weight.

Optionally, according to the production method according to the present invention, the amine neutralizing agent is triethylamine or AMP-95.

The water-based alkyd resin according to the present invention has no benzene, reduces the emission of VOCs, and has a high safety factor during transportation and use, not only satisfies the requirements of oil-based resins in terms of technology, but also greatly improves safety and eco-friendliness. It clearly shows the safe and eco-friendly aspect.

Upon reading the following detailed description of the preferred embodiments, various and other features and advantages will become apparent to those skilled in the art. The accompanying drawings are used only to present preferred embodiments and are not intended to limit the present invention. From the accompanying drawings,
1 is a flow chart of a method for producing a DMPA-modified aqueous alkyd resin according to the present invention.

The present invention provides a number of applicable inventive concepts, and such inventive concepts can be specifically implemented in large quantities in context. Specific examples of implementation methods according to the present invention to be described later are only for explaining specific examples of the present invention and do not limit the scope of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.

In one aspect, the present invention provides a DMPA-modified aqueous alkyd resin prepared from raw materials having the following weight composition ratio:

70-90 parts flax oil

Maleic anhydride 10-30 parts

30-40 parts soybean oil

10-20 parts polyalcohol

Potassium hydroxide 0.005-0.01 part

Phthalic anhydride 20-30 parts

DMPA Parts 8-15

Benzoic acid 5-10 parts

Butyl ether 40-60 parts.

Here, the polyalcohol used in the present invention may be a tricarbon sugar and/or a satanic sugar, and may be, for example, pentaerythritol, glycerin, or a mixture thereof.

In another aspect, the present invention provides a method for preparing the aqueous alkyd resin. In FIG. 1, a flowchart of the method for preparing the aqueous alkyd resin according to the present invention is shown. As shown in Figure 1, the manufacturing method includes the following steps:

Step 1: mixing 70-90 parts by weight of flax oil and 10-30 parts by weight of maleic anhydride at room temperature to raise the temperature to 240-250 ° C. and maintain the temperature for 7-9 hours to obtain a first product;

Step 2: mixing 30-40 parts by weight of soybean oil, 10-20 parts by weight of polyalcohol, and 0.005-0.01 parts by weight of potassium hydroxide to raise the temperature to 240-250 ° C. and maintain the temperature for 1-1.5 hours;

Step 3: The temperature of the reaction product obtained in Step 2 is lowered to 170-190 ° C, 20-30 parts by weight of phthalic anhydride, 8-15 parts by weight of DMPA, and 5-10 parts by weight of benzoic acid are added and further added xylene. refluxing, raising the temperature to 170-190 ° C, maintaining the temperature for 0.5-1.5 hours, then raising the temperature to 200-210 ° C and maintaining the temperature for 6-8 hours to obtain a second product; and

Step 4: Mix 40-60 parts by weight of butyl ether with the first product, add the second product, lower the temperature to 95-105 ° C, add an amine neutralizer so that the pH value of the mixture is 8.5-9, and DMPA (dimethylol obtaining a modified aqueous alkyd resin.

Here, according to step 2, the alcohol decomposition reaction occurs at 240-250 ° C. The end point of the alcohol decomposition reaction can be determined by measuring the ethanol acceptance range. According to a specific operation method, the reaction product obtained in step 2 is taken out and mixed with 95% ethanol in a volume ratio of 1:5 at 25°C. When the mixture becomes clear, it means that the end point of the alcohol decomposition reaction has been reached.

In step 4, an amine neutralizing agent is added to adjust the pH value of the resin so that the pH value of the final product is 8.5-9. The amine neutralizing agent used may be a product such as triethylamine or MPA-95, and the added amount is 5-10 parts by weight. Among them, AMP-95, whose chemical name is 2-amino group-2-methyl-1-propanol, is a multifunctional amine auxiliary agent that regulates and stabilizes the pH value of lotion adhesives, and also has wetting and dispersing effects, making it suitable for production, storage, It is helpful at each stage of a paint's entire lifecycle, including transport, application, and final film formation.

In addition, the manufacturing method according to the present invention further includes step 5. That is, the synthesized aqueous alkyd resin is diluted. According to a specific operation method, water is added to the DMPA (dimethylol propionic acid)-modified aqueous alkyd resin to dilute it, and the amount of water added is the resin solid content required for production. can be adjusted according to Water-based alkyd resins produced through dilution treatment facilitate preservation and future use.

Various embodiments can be designed because there are many selectable elements according to the aqueous alkyd resin and the manufacturing method of the aqueous alkyd resin provided in the present invention. Therefore, the specific embodiments are merely examples of specific implementation methods according to the present invention, and do not limit the scope of the present invention. To describe the present invention in detail, an illustrative description will be made using the following examples.

Example 1

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 70 parts of flax oil, 10 parts of maleic anhydride, 30 parts of soybean oil, 10 parts of pentaerythritol, 0.005 part of potassium hydroxide, 20 parts of phthalic anhydride, 8 parts of DMPA, 5 parts of benzoic acid, and 40 parts of butyl ether.

According to the method for producing an alkyd resin according to this embodiment,

Step 1: mixing flax oil and maleic anhydride at room temperature, raising the temperature to 240° C. and maintaining the temperature for 7 hours to obtain a first product;

Step 2: mixing soybean oil, pentaerythritol, and potassium hydroxide to raise the temperature to 240° C. and hold the temperature for 1 hour to cause an alcohol decomposition reaction;

Step 3: The temperature of the reaction product obtained in Step 2 is lowered to 170°C, phthalic anhydride, DMPA, and benzoic acid are added, and the additionally added xylene is refluxed, and the temperature is raised to 170°C for 0.5 hour. and, raising the temperature again to 200° C., maintaining the temperature for 6 hours to obtain a second product;

Step 4: Mix butyl ether and the first product, add the second product, lower the temperature to 95 ° C, add 8 parts by weight of triethylamine to adjust the pH value of the mixture to 8.5-9, and obtain DMPA (dimethylol propionic acid; dimethylol propionic acid) to obtain a modified aqueous alkyd resin;

Step 5: Add an appropriate amount of tap water to DMPA (dimethylol propionic acid) modified aqueous alkyd resin to obtain the resin solid content required for production, and then pour into a barrel.

Example 2

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 90 parts of flax oil, 30 parts of maleic anhydride, 40 parts of soybean oil, 20 parts of pentaerythritol, 0.01 part of potassium hydroxide, 30 parts of phthalic anhydride, 15 parts of DMPA, 10 parts of benzoic acid, and 60 parts of butyl ether.

The method for producing the alkyd resin according to this embodiment is the same as in Example 1.

Example 3

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 80 parts of flax oil, 20 parts of maleic anhydride, 33 parts of soybean oil, 13 parts of pentaerythritol, 0.008 parts of potassium hydroxide, 25 parts of phthalic anhydride, 12 parts of DMPA, 7 parts of benzoic acid, and 50 parts of butyl ether.

The method for producing the alkyd resin according to this embodiment is the same as in Example 1.

Example 4

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 70 parts of flax oil, 10 parts of maleic anhydride, 30 parts of soybean oil, 10 parts of glycerin, 0.005 part of potassium hydroxide, 20 parts of phthalic anhydride, 8 parts of DMPA, 5 parts of benzoic acid, and butyl 40 parts of ether.

According to the method for producing an alkyd resin according to this embodiment,

Step 1: mixing flax oil and maleic anhydride at room temperature, raising the temperature to 250° C. and maintaining the temperature for 8 hours to obtain a first product;

Step 2: mixing soybean oil, pentaerythritol, and potassium hydroxide to raise the temperature to 245° C. and hold the temperature for 1.5 hours to cause an alcohol decomposition reaction;

Step 3: The temperature of the reaction product obtained in step 2 is lowered to 180°C, phthalic anhydride, DMPA, and benzoic acid are added, and the additionally added xylene is refluxed, and the temperature is raised to 180°C for 1 hour. and, raising the temperature again to 210° C., maintaining the temperature for 7 hours to obtain a second product;

Step 4: Mix butyl ether and the first product, add the second product, lower the temperature to 100 ° C, add 10 parts by weight of triethylamine so that the pH value of the mixture is 8.5-9, and DMPA (dimethylol propionic acid; dimethylol propionic acid) to obtain a modified aqueous alkyd resin;

Step 5: Add an appropriate amount of tap water to DMPA (dimethylol propionic acid) modified aqueous alkyd resin to obtain the resin solid content required for production, and then pour into a barrel.

Example 5

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 80 parts of flax oil, 20 parts of maleic anhydride, 33 parts of soybean oil, 13 parts of glycerin, 0.008 parts of potassium hydroxide, 25 parts of phthalic anhydride, 12 parts of DMPA, 7 parts of benzoic acid, and butyl 50 parts of ether.

The method for producing the alkyd resin according to this embodiment is the same as in Example 4.

Example 6

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 90 parts of flax oil, 30 parts of maleic anhydride, 40 parts of soybean oil, 20 parts of glycerin, 0.01 part of potassium hydroxide, 30 parts of phthalic anhydride, 15 parts of DMPA, 10 parts of benzoic acid, and butyl 60 parts of ether.

The method for producing the alkyd resin according to this embodiment is the same as in Example 4.

Example 7

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 80 parts of flax oil, 20 parts of maleic anhydride, 33 parts of soybean oil, 13 parts of a mixture of glycerin and pentaerythritol, 0.008 parts of potassium hydroxide, 25 parts of phthalic anhydride, 12 parts of DMPA, 7 parts of benzoic acid, and 50 parts of butyl ether.

According to the method for producing an alkyd resin according to this embodiment,

Step 1: mixing flax oil and maleic anhydride at room temperature, raising the temperature to 245° C. and maintaining the temperature for 9 hours to obtain a first product;

Step 2: mixing soybean oil, pentaerythritol, and potassium hydroxide to raise the temperature to 245° C. and hold the temperature for 1 hour to cause an alcohol decomposition reaction;

Step 3: The temperature of the reaction product obtained in step 2 is lowered to 190°C, phthalic anhydride, DMPA, and benzoic acid are added, and the additionally added xylene is refluxed, and the temperature is raised to 190°C for 1.5 hours. while maintaining, and raising the temperature again to 205 ° C. to maintain the temperature for 8 hours to obtain a second product;

Step 4: Mix butyl ether and the first product, add the second product, lower the temperature to 105 ° C, add 5 parts by weight of triethylamine to adjust the pH value of the mixture to 8.5-9, and obtain DMPA (dimethylol propionic acid; dimethylol propionic acid) to obtain a modified aqueous alkyd resin;

Step 5: Add an appropriate amount of tap water to DMPA (dimethylol propionic acid) modified aqueous alkyd resin to obtain the resin solid content required for production, and then pour into a barrel.

Example 8

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 90 parts of flax oil, 30 parts of maleic anhydride, 40 parts of soybean oil, 20 parts of a mixture of glycerin and pentaerythritol, 0.01 part of potassium hydroxide, 30 parts of phthalic anhydride, 15 parts of DMPA, Benzoic acid 10 parts, and butyl ether 60 parts.

The method for producing the alkyd resin according to this embodiment is the same as in Example 7.

Example 9

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 70 parts of flax oil, 10 parts of maleic anhydride, 30 parts of soybean oil, 10 parts of a mixture of glycerin and pentaerythritol, 0.005 part of potassium hydroxide, 20 parts of phthalic anhydride, 8 parts of DMPA, Benzoic acid 5 parts, and butyl ether 40 parts.

The method for producing the alkyd resin according to this embodiment is the same as in Example 7.

The present applicant measured the appearance, color, and acid value indicators of the aqueous alkyd resin prepared in Example 1 of the present invention, and the specific indicators and actual values are shown in Table 1.

metrics technical indicator actual value Exterior water white, transparent water white, transparent Color (Fe-Co method)/ Arc ≤9 ≤10 acid value/mgKOH/g ≤20 ≤20

According to the measured values in Table 1, it can be seen that the quality of the water-based alkyd resin according to the present invention is good and is superior to the performance of the oil-based resin. Since the measurement results of other embodiments are similar to those of Table 1, the description thereof will be omitted.

It should be noted that the above examples are merely illustrative of the present invention and are not intended to limit the present invention. Persons skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. Any reference sign between parentheses in the claim shall not limit the claim. The term "comprising" does not exclude the presence of elements or steps not listed in a claim. The use of 1st, 2nd, 3rd, etc. does not imply any order, just interpret them as names.

Claims (5)

As a method for producing a dimethylol propionic acid (DMPA) modified aqueous alkyd resin,
Step 1: mixing 70-90 parts by weight of flax oil and 10-30 parts by weight of maleic anhydride at room temperature to raise the temperature to 240-250 ° C. and maintain the temperature for 7-9 hours to obtain a first product;
Step 2: mixing 30-40 parts by weight of soybean oil, 10-20 parts by weight of polyalcohol, and 0.005-0.01 parts by weight of potassium hydroxide to raise the temperature to 240-250 ° C. and maintain the temperature for 1-1.5 hours;
Step 3: The temperature of the reaction product obtained in Step 2 is lowered to 170-190 ° C, 20-30 parts by weight of phthalic anhydride, 8-15 parts by weight of DMPA, and 5-10 parts by weight of benzoic acid are added and further added xylene. refluxing, raising the temperature to 170-190 ° C, maintaining the temperature for 0.5-1.5 hours, then raising the temperature to 200-210 ° C and maintaining the temperature for 6-8 hours to obtain a second product; and
Step 4: Mix 40-60 parts by weight of butyl ether with the first product, add the second product, lower the temperature to 95-105 ° C, add an amine neutralizer so that the pH value of the mixture is 8.5-9, and DMPA (dimethylol A process comprising obtaining a modified aqueous alkyd resin. According to claim 1,
The manufacturing method further comprises step 5, that is, adding water to the DMPA (dimethylol propionic acid)-modified aqueous alkyd resin to dilute it. According to claim 1 or 2,
The manufacturing method, characterized in that the addition amount of the amine neutralizing agent is 5-10 parts by weight. According to claim 1 or 2,
The method of claim 1, wherein the amine neutralizing agent is triethylamine or 2-amino group-2-methyl-1-propanol. According to claim 1,
The production method, characterized in that the polyalcohol is pentaerythritol and / or glycerin.

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