KR20160110043A - Method for preparing dmpa modified waterborne alkyd resin - Google Patents

Abstract

The present invention discloses a method for preparing a DMPA-modified waterborne alkyd resin, wherein the method comprises: a step for mixing 70-90 parts by weight of flaxseed oil at room temperature and 10-30 parts by weight of maleic acid anhydride, followed by heating up to 240-250C and maintaining the temperature for 7-9 hours to obtain a first product; a step for mixing 30-40 parts by weight of soybean oil, 10-20 parts by weight of poly-alcohol, and 0.005-0.01 parts by weight of potassium hydroxide, and heating up to a temperature of 240-250C and maintaining the temperature for 1-1.5 hours; a step for lowering the temperature of the reaction product obtained in the second step down to 170-190C, and adding thereto 20-30 parts by weight of phthalic acid anhydride, 8-15 parts by weight of DMPA, and 5-10 parts by weight of benzoic acid to reflux xylene, and heating up to a temperature of 170-190C and maintaining the temperature for 0.5-1.5 hours, and further heating up to a temperature of 200-210C and maintaining the temperature for 6-8 hours to obtain a second product; and a step for mixing the first product with 40-60 parts by weight of butyl ether, adding the second product thereto, and lowering the temperature down to 95-105C, and then adding an amine neutralizer to adjust the pH value of the mixture to 8.5-9 to obtain a waterborne phenol resin. The waterborne alkyd resin according to the present invention has greatly improved safety and environmental-friendliness.

Description

METHOD FOR PREPARING DMPA MODIFIED WATERBORNE ALKYD RESIN [0002]

More particularly, the present invention relates to a process for producing dimethylol propionic acid (DMPA) modified aqueous alkyd resin of an aqueous coating material.

Generally, alkyd resin is a resin produced through high-temperature polymerization of soybean oil, phthalic anhydride, glycerin, pentaerythritol and No.200 solvent oil, and has excellent weatherability. However, since the amount of VOC emission during production and use is high, safety factor is low It is also dangerous chemical because it is flammable and explosive in use and transportation process, and it belongs to a product that has been taken over by the nation because of environmental pollution.

In order to solve the problems of the prior art, it is an object of the present invention to provide a modified aqueous alkyd resin and a process for producing the same.

In one aspect, the present invention provides a DMPA modified aqueous alkyd resin made from a starting material having the following weight ratio:

Flax oil 70-90 part

Maleic anhydride 10-30 part

Soybean oil 30-40 part

Polyalcohol 10-20 part

Potassium hydroxide 0.005-0.01 part

Phthalic anhydride 20-30 part

DMPA 8-15 part

Benzoic acid 5-10 part

Butyl ether 40-60 copies.

Alternatively, 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 process for preparing an aqueous alkyd resin comprising the steps of:

Step 1: mixing 70-90 parts by weight of flaxseed oil and 10-30 parts by weight of maleic anhydride at room temperature to raise the temperature to 240-250 占 폚 and maintaining the temperature for 7-9 hours to obtain a first product;

Step 2: 30-40 parts by weight of soybean oil, 10-20 parts by weight of polyalcohol, and 0.005-0.01 part by weight of potassium hydroxide are mixed to raise the temperature to 240-250 占 폚 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 占 폚, 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 to reflux the xylene, Increasing the temperature to 170-190 DEG C, maintaining the temperature for 0.5-1.5 hours, raising the temperature to 200-210 DEG C again and maintaining the temperature for 6-8 hours to obtain a second product; And

Step 4: 40-60 parts by weight of butyl ether and the first product are mixed and the second product is added and the temperature is lowered to 95-105 ° C, followed by the addition of an amine neutralizing agent so that the pH value of the mixture becomes 8.5-9, ≪ / RTI >

Alternatively, according to the process of the invention, the process further comprises step 5, i.e., diluting the aqueous phenolic resin with water.

Alternatively, the amine neutralizing agent may be added in an amount of 5 to 10 parts by weight based on the preparation method of the present invention.

Alternatively, according to the preparation process according to the invention, the amine neutralizing agent is triethylamine or AMP-95.

The aqueous alkyd resin according to the present invention is free of benzene, reduces VOC emissions, and has a high safety factor in the course of transportation and use. In addition to satisfying the requirements of oil-based resins from the technical viewpoint, safety and eco-friendliness are greatly improved and improved It is safe and eco-friendly.

It will be clear to those of ordinary skill in the art, after reading the following detailed description of the preferred embodiments, that various and other features and advantages will be apparent to those skilled in the art. The accompanying drawings are only used to illustrate the preferred embodiments and are not intended to limit the present invention. In 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 creative concepts, which can be implemented in large quantities in context. The embodiments of the method according to the present invention described below are only illustrative of concrete 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 made from a starting material having the following weight ratio:

Flax oil 70-90 part

Maleic anhydride 10-30 part

Soybean oil 30-40 part

Polyalcohol 10-20 part

Potassium hydroxide 0.005-0.01 part

Phthalic anhydride 20-30 part

DMPA 8-15 part

Benzoic acid 5-10 part

Butyl ether 40-60 copies.

Here, the polyalcohol used in the present invention may be a trimitol and / or a saccharide and may be, for example, pentaerythritol, glycerin, or a mixture of both.

In another aspect, the present invention provides a process for the preparation of the aqueous alkyd resin, and in FIG. 1, a flow chart of the process for producing the aqueous alkyd resin according to the invention. As shown in Fig. 1, the present manufacturing method includes the following steps:

Step 1: mixing 70-90 parts by weight of flaxseed oil and 10-30 parts by weight of maleic anhydride at room temperature to raise the temperature to 240-250 占 폚 and maintaining the temperature for 7-9 hours to obtain a first product;

Step 2: 30-40 parts by weight of soybean oil, 10-20 parts by weight of polyalcohol, and 0.005-0.01 part by weight of potassium hydroxide are mixed to raise the temperature to 240-250 占 폚 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 占 폚, 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 to reflux the xylene, Increasing the temperature to 170-190 DEG C, maintaining the temperature for 0.5-1.5 hours, raising the temperature to 200-210 DEG C again and maintaining the temperature for 6-8 hours to obtain a second product; And

Step 4: 40-60 parts by weight of butyl ether and the first product are mixed and the second product is added and the temperature is lowered to 95-105 ° C, followed by the addition of an amine neutralizing agent so that the pH value of the mixture becomes 8.5-9, ≪ / RTI >

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

In step 4, the pH value of the resin is adjusted by adding an amine neutralizing agent 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 addition amount is 5-10 parts by weight. Among them, AMP-95, whose chemical name is 2-amino-2-methyl-1-propanol, is a multifunctional amine adjuvant which stabilizes by adjusting the pH value of the lotion adhesive and has a wetting and dispersing effect, Transportation, application, and final film formation at each stage of the paint cycle.

Further, the manufacturing method according to the present invention further includes the step 5. That is, by diluting the synthesized aqueous alkyd resin, according to a specific operating method, the aqueous phenolic resin is diluted with water, and the amount of water added can be adjusted according to the resin solids content required for production. The aqueous alkyd resin prepared through dilution treatment is easy to preserve and future use.

The water-based alkyd resin and the method for producing the water-based alkyd resin provided in the present invention have many selectable elements, so that various embodiments can be designed. Accordingly, the specific embodiments are only illustrative of specific embodiments of the method according to the present invention, and do not limit the scope of the present invention. In order to explain the present invention in detail, an exemplary explanation will be made using the following embodiments.

Example 1

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 70 parts of flaxseed 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, And 40 parts of butyl ether.

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

Step 1: Mixing flaxseed and maleic anhydride at room temperature to increase the temperature to 240 < 0 > C and maintaining the temperature for 7 hours to obtain the first product;

Step 2: Soybean oil, pentaerythritol, and potassium hydroxide are mixed to raise the temperature to 240 캜 and maintain the temperature for 1 hour to cause an alcoholysis reaction;

Step 3: The temperature of the reaction product obtained in Step 2 is lowered to 170 占 폚, the xylene is refluxed by adding phthalic anhydride, DMPA, and benzoic acid, the temperature is raised to 170 占 폚 and the temperature is maintained for 0.5 hour, To maintain the temperature for 6 hours to obtain a second product;

Step 4: After adding the butyl ether and the first product, placing the second product and lowering the temperature to 95 캜, 8 parts by weight of triethylamine is added so that the pH value of the mixture becomes 8.5-9 to obtain an aqueous phenolic resin;

Step 5: Add an appropriate amount of tap water to the aqueous phenolic resin to obtain the resin solids content required for production and then pack it in a container.

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, And 60 parts of butyl ether.

The method of producing the alkyd resin according to this embodiment is the same as that of Embodiment 1. [

Example 3

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 80 parts of flaxseed 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, And 50 parts of butyl ether.

The method of producing the alkyd resin according to this embodiment is the same as that of Embodiment 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, 40 parts of ether.

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

Step 1: Mixing flaxseed and maleic anhydride at room temperature to raise the temperature to 250 < 0 > C and maintaining the temperature for 8 hours to obtain a first product;

Step 2: Soybean oil, pentaerythritol, and potassium hydroxide are mixed to raise the temperature to 245 DEG C and maintain the temperature for 1.5 hours to cause an alcoholysis reaction;

Step 3: The temperature of the reaction product obtained in Step 2 is lowered to 180 占 폚, the phthalic anhydride, DMPA, and benzoic acid are added to reflux the xylene, the temperature is raised to 180 占 폚 and the temperature is maintained for 1 hour, Maintaining the temperature for 7 hours to obtain a second product;

Step 4: After adding the butyl ether and the first product, placing the second product, lowering the temperature to 100 占 폚, adding 10 parts by weight of triethylamine to obtain a pH value of the mixture of 8.5-9 to obtain an aqueous phenolic resin;

Step 5: Add an appropriate amount of tap water to the aqueous phenolic resin to obtain the resin solids content required for production and then pack it in a container.

Example 5

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention was 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, 50 parts of ether.

The method of producing the alkyd resin according to this embodiment is the same as that of the fourth embodiment.

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, 60 parts of ether.

The method of producing the alkyd resin according to this embodiment is the same as that of the fourth embodiment.

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 glycerin and pentaerythritol, 0.008 parts of potassium hydroxide, 25 parts of phthalic anhydride, 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 the flaxseed and maleic anhydride at room temperature to raise the temperature to 245 DEG C and maintaining the temperature for 9 hours to obtain the first product;

Step 2: Soybean oil, pentaerythritol, and potassium hydroxide are mixed to raise the temperature to 245 DEG C and maintain the temperature for 1 hour to cause an alcoholysis reaction;

Step 3: The temperature of the reaction product obtained in step 2 is lowered to 190 DEG C, the xylene is refluxed by adding phthalic anhydride, DMPA, and benzoic acid, the temperature is raised to 190 DEG C and the temperature is maintained for 1.5 hours, To maintain the temperature for 8 hours to obtain a second product;

Step 4: After adding the butyl ether and the first product, placing the second product, lowering the temperature to 105 ° C, adding 5 parts by weight of triethylamine to obtain a pH value of the mixture of 8.5-9 to obtain an aqueous phenolic resin;

Step 5: Add an appropriate amount of tap water to the aqueous phenolic resin to obtain the resin solids content required for production and then pack it in a container.

Example 8

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 90 parts of flaxseed 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, 10 parts of benzoic acid, and 60 parts of butyl ether.

The method of producing the alkyd resin according to this embodiment is the same as that of the seventh embodiment.

Example 9

The raw material weight composition ratio of the aqueous alkyd resin according to the present invention is 70 parts of flaxseed 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, 5 parts of benzoic acid, and 40 parts of butyl ether.

The method of producing the alkyd resin according to this embodiment is the same as that of the seventh embodiment.

The present inventors measured the appearance, color, and acid value index of the aqueous alkyd resin prepared in Example 1 of the present invention, and the specific indices and measured values thereof are shown in Table 1.

Metrics Technical indicators Found Exterior White, transparent White, transparent Color (Fe-Co method) / No. ≤9 ≤10 Acid value / mgKOH / g ≤20 ≤20

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

It should be noted that the above embodiments are only illustrative of the present invention and are not intended to limit the present invention. Those skilled in the art will be able to design alternative embodiments without departing from the scope of the appended claims. The claims should not be limited to any reference signs within the parentheses of the claims. The term "comprising " does not exclude the presence of elements or steps not listed in a claim. The use of the first, second, third, etc. does not mean any order, but may be interpreted as a name.

Claims (5)

A process for producing a dimethylol propionic acid (DMPA) modified aqueous alkyd resin,
Step 1: mixing 70-90 parts by weight of flaxseed oil and 10-30 parts by weight of maleic anhydride at room temperature to raise the temperature to 240-250 占 폚 and maintaining the temperature for 7-9 hours to obtain a first product;
Step 2: 30-40 parts by weight of soybean oil, 10-20 parts by weight of polyalcohol, and 0.005-0.01 part by weight of potassium hydroxide are mixed to raise the temperature to 240-250 占 폚 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 占 폚, 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 to reflux the xylene, Increasing the temperature to 170-190 DEG C, maintaining the temperature for 0.5-1.5 hours, raising the temperature to 200-210 DEG C again and maintaining the temperature for 6-8 hours to obtain a second product; And
Step 4: 40-60 parts by weight of butyl ether and the first product are mixed and the second product is added and the temperature is lowered to 95-105 ° C, followed by the addition of an amine neutralizing agent so that the pH value of the mixture becomes 8.5-9, ≪ / RTI > The method according to claim 1,
Wherein the preparation method further comprises step 5, i.e., diluting the aqueous phenolic resin with water. 3. The method according to claim 1 or 2,
Wherein the amine neutralizing agent is added in an amount of 5 to 10 parts by weight. 3. The method according to claim 1 or 2,
Wherein the amine neutralizing agent is triethylamine or AMP-95. The method according to claim 1,
Wherein the polyalcohol is pentaerythritol and / or glycerin.

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