KR20160110054A - A dimethylolpropionic acid modified waterborne phenolic resin and preparation method thereof - Google Patents

Abstract

Disclosed in the present invention is a dimethylolpropionic acid-modified waterborne phenolic resin which is prepared from the following raw materials, in parts by weight: 70-90 of linseed oil, 10-30 of maleic anhydride, 30-40 of tung oil, 10-20 of polyalcohol, 0.005-0.01 of potassium hydroxide, 20-30 of phthalic anhydride, 8-15 of dimethylolpropionic acid, 5-10 of benzoic acid, 30-50 of butyl ether and 5-15 of n-butyl alcohol. Also, disclosed in the present invention is a preparation method of the waterborne phenolic resin. The waterborne phenolic resin disclosed in the present invention is benzene-free, reduces the discharge of VOC, and has high safety factors in transport and application processes; and the waterborne phenolic resin not only meets the technical requirements of oleoresin, but also is greatly improved in terms of safety and environmental friendliness, thereby having safety and environmental friendliness.

Description

TECHNICAL FIELD The present invention relates to a phenol resin modified with dimethylol propionic acid and a method for producing the phenol resin.

The present invention relates to the field of chemical coatings, and more particularly to dimethylolpropionic acid modified waterborne phenolic resins for the preparation of waterborne coatings and their preparation.

Phenolic resins are generally tung oil, phthalic anhydride, glycerol, pentaerythritol, 200 ^# are produced through high-temperature polymerization of the solvent gas (petrol), characterized by a good weather resistance, but this application and transport during large VOC emissions and lower safety factor Have; It is flammable and explosive when applied and transported and belongs to hazardous chemicals; It causes a great deal of environmental pollution and is on the list of domestic exclusion substances.

SUMMARY OF THE INVENTION The present invention aims at solving the problems of the prior art, and to provide a modified waterborne phenolic resin and a process for producing the same.

In the first embodiment, the modified water-borne phenolic resin is provided comprising the following by weight:

Linseed oil 70 to 90,

Maleic anhydride 10 to 30,

30,

Polyol 10 to 20,

Potassium hydroxide 0.005 to 0.01,

Phthalic anhydride 20 to 30,

Dimethylol propionic acid 8 to 15,

Benzoic acid 5 to 10,

Butyl ether 30 to 50,

n-butanol 5-15.

Alternatively, in the aqueous phenolic resin according to the present invention, the polyol is pentaerythritol and / or glycerol.

According to a second aspect, there is provided a process for preparing the aqueous phenolic resin, comprising:

Step 1: 70 to 90 parts by weight of linseed oil and 10 to 30 parts by weight of maleic anhydride are mixed at room temperature, heated to 240 to 250 캜 and maintained for 7 to 9 hours to obtain a first product;

Step 2: mixing 30 to 40 parts by weight of the crude oil, 10 to 20 parts by weight of polyhydric alcohol and 0.005 to 0.01 part by weight of potassium hydroxide, heating to 240 to 250 DEG C and holding for 1 to 1.5 hours;

Step 3: The product obtained in Step 2 is cooled to 170 to 190 占 폚, 20 to 30 parts by weight of phthalic anhydride, 8 to 15 parts by weight of dimethylolpropionic acid and 5 to 10 parts by weight of benzoic acid are added and heated to 170 to 190 占 폚 Refluxing the xylenes and holding for 0.5 to 1.5 hours, heating to 200 to 210 ° C and holding for 6 to 8 hours to obtain a second product;

Step 4: 30 to 50 parts by weight of butyl ether and 5 to 15 parts by weight of n-butanol are mixed with the first product, the second product is added, and the amine neutralizing agent is added when the temperature is reduced to 95 to 105 DEG C, To obtain a pH of 8.5 to 9 to obtain an aqueous phenolic resin.

Optionally, the process according to the invention further comprises the step of diluting the aqueous phenolic resin by adding water.

Alternatively, in the above production method according to the present invention, the amount of the amine neutralizing agent to be added is 5 to 10 parts by weight.

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

The aqueous phenolic resin according to the present invention is free of benzene, reduces VOC emissions, has a high safety factor in transportation and application; Not only does it reach the technical requirements of Oreo resin, but it also has significant - improved safety and environmental friendliness, resulting in significant safety and environmental friendliness.

Various other advantages and advantages of the present invention will be fully appreciated by those skilled in the art from reading the following detailed description of the preferred embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings are not intended to limit the scope of the invention, but merely to illustrate preferred embodiments thereof,
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a flow chart of a method for producing a dimethylolpropionic acid-modified water-based phenolic resin in the present invention.

The present invention provides many applicable creative concepts that can be implemented substantially in context. The following specific embodiments described herein are illustrative and not intended to be limiting of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

According to a first aspect, there is provided a modified waterborne phenolic resin comprising, by weight, the following:

Linseed oil 70 to 90,

Maleic anhydride 10 to 30,

30,

Polyol 10 to 20,

Potassium hydroxide 0.005 to 0.01,

Phthalic anhydride 20 to 30,

Dimethylol propionic acid 8 to 15,

Benzoic acid 5 to 10,

Butyl ether 30 to 50,

n-butanol 5-15.

The polyols employed in the present invention may be triols and / or tetraols such as pentaerythritol, glycerin or mixtures thereof.

According to a second aspect, a method for producing a water-soluble phenolic resin is provided, and Fig. 1 shows a flow chart of a method for producing the water-based phenolic resin of the present invention. As shown in Figure 1, the method comprises:

Step 1: Mixing 70 to 90 parts by weight of linseed oil and 10 to 30 parts by weight of maleic anhydride at room temperature, heating to 240 to 250 DEG C and holding for 7 to 9 hours to obtain a first product;

Step 2: mixing 30 to 40 parts by weight of the crude oil, 10 to 20 parts by weight of polyhydric alcohol and 0.005 to 0.01 part by weight of potassium hydroxide, heating to 240 to 250 DEG C and holding for 1 to 1.5 hours;

Step 3: The product obtained in Step 2 is cooled to 170 to 190 占 폚, 20 to 30 parts by weight of phthalic anhydride, 8 to 15 parts by weight of dimethylolpropionic acid and 5 to 10 parts by weight of benzoic acid are added and heated to 170 to 190 占 폚 Refluxing the xylene for 0.5 to 1.5 hours, heating to 200 to 210 DEG C and holding for 6 to 8 hours to obtain a second product;

Step 4: 30 to 50 parts by weight of butyl ether and 5 to 15 parts by weight of n-butanol are mixed with the first product, the second product is added, and the amine neutralizing agent is added when the temperature is reduced to 95 to 105 DEG C, To a pH of 8.5 to 9 to obtain an aqueous phenolic resin.

In the above step 2, the alcoholysis reaction is carried out at 240 to 250 ° C. The ethanol tolerance determination method can be employed to determine the end point of the alcoholysis reaction and includes the following specific operations: taking the reaction in step 2, mixing with 95% ethanol in a volume ratio of 1: 5 at 25 캜, And indicating that the alcoholysis reaction has reached an end point when the mixture becomes transparent.

In step 4 above, the amine neutralizing agent is added to adjust the pH of the resin so that the pH of the final product is 8.5 to 9. The amine neutralizer applied may be a material such as triethylamine or MPA-95, and the amount thereof added is 5 to 10 parts by weight. Here, the chemical name of AMP-95 is 2-amino-2-methyl-1-propanol, which is a polyfunctional amine additive, can control the pH of the emulsion adhesive to reach a stable state, It is useful at each stage of the entire service cycle of coating, including manufacture, storage, transportation, application and final filming.

The process according to the invention also comprises a step 5 of adding water to dilute the obtained water-based phenolic resin, which comprises a specific operation: water is added to dilute the aqueous phenolic resin, It can be controlled according to the resin solids required for production. Dilution treatment can facilitate storage and subsequent application of the water-based phenolic resin produced.

Based on the waterborne phenolic resin of the present invention and the method of preparation thereof, many elements can be chosen at will, and various embodiments can be devised, and thus the specific embodiments described herein are illustratively described, It is not meant to be.

For a detailed description of the present invention, the following illustrative examples have been selected.

Example  One

In this embodiment, the aqueous phenolic resin comprises, by weight, the following:

Flaxseed oil 70, maleic anhydride 10, tung oil 30, pentaerythritol 10, potassium hydroxide 0.005, phthalic anhydride 20, dimethylol propionic acid 8, benzoic acid 5, butyl ether 30, n-butanol 15.

The method for producing a phenolic resin in this embodiment includes the following steps:

Step 1: Mixing linseed oil and maleic anhydride at room temperature, heating to 240 占 폚 and holding for 7 hours to obtain a first product;

Step 2: Mixing the oil, pentaerythritol and potassium hydroxide, heating to 240 占 폚 and holding for 1 hour to carry out the alcoholysis reaction;

Step 3: The alcohol decomposition product obtained in Step 2 was cooled to 170 DEG C, phthalic anhydride, dimethylolpropionic acid and benzoic acid were added, and the xylene was refluxed while heating to 170 DEG C, held for 0.5 hour, heated to 200 DEG C, To obtain a second product;

Step 4: The butyl ether is mixed with the first product, the second product is added, and when the temperature is reduced to 95 캜, 8 parts by weight of triethylamine is added to adjust the pH of the mixture to 8.5 to 9, Obtaining a resin;

Step 5: adding an appropriate amount of tap water to the aqueous phenolic resin, and obtaining and bareling the resin solids required for production.

Example  2

In this embodiment, the phenolic resin comprises, by weight, the following:

Flaxseed oil 90, maleic anhydride 30, tung oil 40, pentaerythritol 20, potassium hydroxide 0.01, phthalic anhydride 30, dimethylol propionic acid 15, benzoic acid 10, butyl ether 50, n-butanol 5.

The method for producing the phenolic resin of this example is the same as that of the first embodiment.

Example  3

In this embodiment, the phenolic resin comprises, by weight, the following:

Flaxseed oil 80, maleic anhydride 20, ternary oil 33, pentaerythritol 13, potassium hydroxide 0.008, phthalic anhydride 25, dimethylolpropionic acid 12, benzoic acid 7, butyl ether 40, n-butanol 10.

The method for producing the phenolic resin of this example is the same as that of the first embodiment.

Example  4

In this embodiment, the phenolic resin comprises, by weight, the following:

Flaxseed oil 70, maleic anhydride 10, tung oil 30, glycerol 10, potassium hydroxide 0.005, phthalic anhydride 20, dimethylolpropionic acid 8, benzoic acid 5, butyl ether 30, n-butanol 15.

The method for producing a phenolic resin in this embodiment includes the following steps:

Step 1: Mixing linseed oil and maleic anhydride at room temperature, heating to 250 占 폚 and holding for 8 hours to obtain a first product;

Step 2: Mixing the oil, glycerol and potassium hydroxide, heating to 245 DEG C and holding for 1.5 hours to effect the alcoholysis reaction;

Step 3: The alcohol decomposition product obtained in step 2 was cooled to 180 DEG C, phthalic anhydride, dimethylolpropionic acid and benzoic acid were added, and the xylene was refluxed while heating to 180 DEG C, held for 1 hour, heated to 210 DEG C, To obtain a second product;

Step 4: butyl ether is mixed with the first product, the second product is added, and when the temperature is reduced to 100 占 폚, 8 parts by weight of triethylamine is added to adjust the pH of the mixture to 8.5 to 9, Obtaining a resin;

Step 5: adding an appropriate amount of tap water to the aqueous phenolic resin, and obtaining and bareling the resin solids required for production.

Example  5

In this embodiment, the phenolic resin comprises, by weight, the following:

Flaxseed oil 80, maleic anhydride 20, tung oil 33, glycerol 13, potassium hydroxide 0.008, phthalic anhydride 25, dimethylol propionic acid 12, benzoic acid 7, butyl ether 40, n-butanol 10.

The method for producing the phenolic resin of this example is the same as that of the fourth embodiment.

Example  6

In this embodiment, the phenolic resin comprises, by weight, the following:

Flaxseed oil 90, maleic anhydride 30, tung oil 40, glycerol 20, potassium hydroxide 0.01, phthalic anhydride 30, dimethylol propionic acid 15, benzoic acid 10, butyl ether 50, n-butanol 5.

The method for producing the phenolic resin of this example is the same as that of the fourth embodiment.

Example  7

In this embodiment, the phenolic resin comprises, by weight, the following:

Flaxseed oil 80, maleic anhydride 20, ternary oil 33, mixture 13 of glycerol and pentaerythritol, potassium hydroxide 0.008, phthalic anhydride 25, dimethylolpropionic acid 12, benzoic acid 7, butyl ether 40, n-butanol 10.

The method for producing a phenolic resin in this embodiment includes the following steps:

Step 1: Mixing linseed oil and maleic anhydride at room temperature, heating to 245 占 폚 and holding for 9 hours to obtain a first product;

Step 2: Mixing of a mixture of the oil, glycerol and pentaerythritol, and potassium hydroxide, heating to 245 DEG C and holding for 1 hour to carry out the alcoholysis reaction;

Step 3: The alcohol decomposition product obtained in step 2 was cooled to 190 ° C, phthalic anhydride, dimethylol propionic acid and benzoic acid were added, and the xylene was refluxed while heating to 190 ° C, held for 1.5 hours, heated to 205 ° C, To obtain a second product;

Step 4: The butyl ether was mixed with the first product, the second product was added, and when the temperature was reduced to 105 ° C, 5 parts by weight of triethylamine was added to adjust the pH of the mixture to 8.5 to 9, Obtaining a resin;

Step 5: adding an appropriate amount of tap water to the aqueous phenolic resin, and obtaining and bareling the resin solids required for production.

Example  8

In this embodiment, the phenolic resin comprises, by weight, the following:

A mixture of maleic anhydride 90, maleic anhydride 30, tung oil 40, a mixture of glycerol and pentaerythritol 20, potassium hydroxide 0.01, phthalic anhydride 30, dimethylol propionic acid 15, benzoic acid 10, butyl ether 50, n-butanol 5.

The method for producing the phenolic resin of this example is the same as that of the seventh embodiment.

Example  9

In this embodiment, the phenolic resin comprises, by weight, the following:

10 mixture of glycerol and pentaerythritol, potassium hydroxide 0.005, anhydrous phthalic acid 20, dimethylolpropionic acid 8, benzoic acid 5, butyl ether 30, n-butanol 15.

The method for producing the phenolic resin of this example is the same as that of the seventh embodiment.

The present inventors measured the appearance, color, gloss and acid value index of the water-based phenol resin prepared in Example 1, and the specific indexes and the actual detection values are shown in Table 1.

Detection item Technical indicator Actual detection value Appearance Water white, transparent Reddish brown Color and gloss
(Fe-Co method) / number (number) ≤9 13 Acid value / mg KOH / g ≤20 ≤20

As can be seen from the above measurement data, the waterborne phenolic resin of the present invention has a good quality and has a performance exceeding the quality of oleoresin.

The measurement results of the other embodiments are similar to those of Table 1, and therefore will not be described here.

It should be noted that the above-described implementations used herein are presented by way of example only and are not intended to limit the present invention. Those skilled in the art will recognize that many other alternative embodiments may be devised without departing from the spirit and scope of the appended claims. Numerals between parentheses, terms, descriptions, and numerical values used in the specification are intended to be illustrative and not restrictive. The word "comprising" does not exclude the presence of other elements or steps not listed in the claims. A word such as " first, "" second," or " third, " does not mean a sequence and can be interpreted as a name.

Claims (6)

Wherein the weight ratio of fumaric acid to fumaric acid is 70 to 90, maleic anhydride is 10 to 30, ternary 30 to 40, polyol 10 to 20, potassium hydroxide 0.005 to 0.01, phthalic anhydride 20 to 30, dimethylolpropionic acid 8 to 15, benzoic acid 5 to 10, Ether 30-50, and n-butanol 5-15. The aqueous phenolic resin modified with dimethylolpropionic acid.
The water-based phenol resin modified with dimethylolpropionic acid according to claim 1, wherein the polyol is pentaerythritol and / or glycerol.
Step 1: mixing 70 to 90 parts by weight of linseed oil and 10 to 30 parts by weight of maleic anhydride at room temperature, heating to 240 to 250 DEG C and holding for 7 to 9 hours to obtain a first product;
Step 2: mixing 30 to 40 parts by weight of the crude oil, 10 to 20 parts by weight of the polyol and 0.005 to 0.01 part by weight of potassium hydroxide, heating to 240 to 250 DEG C and holding for 1 to 1.5 hours;
Step 3: The product obtained in Step 2 is cooled to 170 to 190 占 폚, 20 to 30 parts by weight of phthalic anhydride, 8 to 15 parts by weight of dimethylolpropionic acid and 5 to 10 parts by weight of benzoic acid are added and heated to 170 to 190 占 폚 Refluxing the xylene, holding it for 0.5 to 1.5 hours, heating to 200 to 210 DEG C and holding for 6 to 8 hours to obtain a second product;
Step 4: 30 to 50 parts by weight of butyl ether and 5 to 15 parts by weight of n-butanol are mixed with the first product, the second product is added, and the amine neutralizing agent is added when the temperature is reduced to 95 to 105 DEG C, To obtain a pH of 8.5 to 9 to obtain an aqueous phenolic resin;
Wherein the water-based phenolic resin is a water-based phenolic resin.
4. The method according to claim 3, further comprising the step of adding water to dilute the aqueous phenolic resin.
The method for producing an aqueous phenol resin according to claim 3 or 4, wherein the amount of the amine neutralizing agent to be added is 5 to 10 parts by weight.
The method for producing an aqueous phenolic resin according to claim 3 or 4, wherein the amine neutralizing agent is triethylamine or AMP-95.

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