DE102016103139A1 - Dimethylolpropionic acid-modified, water-dilutable phenolic resin - Google Patents

Abstract

The invention discloses a dimethylolpropionic acid-modified, water-dilutable phenolic resin comprising by weight 70-90 linseed oil, 10-30 maleic anhydride, 30-40 tung oil, 10-20 polyol, 0.005-0.01 potassium hydroxide, 20-30 phthalic anhydride, 8-15 dimethylolpropionic acid, 5-10 g of benzoic acid, 30-50 butyl ether, 5-15 n-butanol. The water reducible phenolic resin of the present invention is benzene free, reduces VOC emissions and has a high safety factor during transportation and application; It not only meets the technical requirements of oleoresin, but also has greatly improved safety and environmental friendliness, so that it truly embodies safety and environmental friendliness.

Description

TECHNICAL AREA

The invention relates to the field of coating chemical technology, and more particularly relates to a dimethylolpropionic acid-modified, water-dilutable phenolic resin for preparing a water-thinnable paint.

BACKGROUND

Phenolic resin is a resin generally made by the high temperature polymerization of tung oil, phthalic anhydride, glycerin, pentaerythritol, and 200 # liquid gasoline. It is characterized by good weather resistance, but has a high emissivity of volatile organic compounds and a low safety factor during application and transport; it is flammable and explosive during application and transportation, is one of the dangerous chemicals; it is very harmful to the environment and is listed among household products that need to be phased out.

SUMMARY OF THE INVENTION

This invention relates to the solution of the problem encountered in the prior art and provides a modified water-reducible phenolic resin.

A first aspect of the invention provides a dimethylolpropionic acid-modified, water-dilutable phenolic resin comprising by weight:
70-90 linseed oil
10-30 maleic anhydride
30-40 tung oil
10-20 polyol
0.005-0.01 potassium hydroxide
20-30 phthalic anhydride
8-15 dimethylolpropionic acid
5-10 benzoic acid
30-50 butyl ether
515 n-butanol.

In one embodiment, the present invention may include pentaerythritol and / or glycerin as a polyol.

According to one embodiment of the invention, the dimethylolpropionic acid-modified, water-dilutable phenolic resin by weight comprises 80 linseed oil, 20 maleic anhydride, 33 tung oil, 13 pentaerythritol, 0.008 potassium hydroxide, 25 phthalic anhydride, 12 dimethylolpropionic acid, 7 benzoic acid, 40 butyl ether, 10 n-butanol.

According to one embodiment of the invention, the dimethylolpropionic acid-modified, water-dilutable phenolic resin by weight comprises 70 linseed oil, 10 maleic anhydride, 30 tung oil, 10 glycerol, 0.005 potassium hydroxide, 20 phthalic anhydride, 8 dimethylolpropionic acid, 5 benzoic acid, 30 butyl ether, 15 n-butanol.

According to one embodiment of the invention, the dimethylolpropionic acid-modified, water-dilutable phenolic resin by weight comprises 80 linseed oil, 20 maleic anhydride, 33 tung oil, 13 glycerol, 0.008 potassium hydroxide, 25 phthalic anhydride, 12 dimethylolpropionic acid, 7 benzoic acid, 40 butyl ether, 10 n-butanol.

According to one embodiment of the invention, the dimethylolpropionic acid-modified, water-dilutable phenolic resin comprises by weight 90 linseed oil, 30 maleic anhydride, 40 tung oil, 20 glycerol, 0.001 potassium hydroxide, 30 phthalic anhydride, 15 dimethylolpropionic acid, 10 benzoic acid, 50 butyl ether, 5 n-butanol.

According to one embodiment of the invention, the dimethylolpropionic acid-modified, water-dilutable phenolic resin is prepared by the following process:

Step 1: Mixing linseed oil and maleic anhydride at room temperature, heating to 240-250 ° C and keeping warm for 7-9 h to obtain a first product;

Step 2: Mixing tung oil, polyol and potassium hydroxide, heating to 240-250 ° C and keeping warm for 1-1.5 hours;

Step 3: Cool the product obtained in Step 2 to 170-190 ° C, add phthalic anhydride, dimethylolpropionic acid and benzoic acid, reflux xylene while heating to 170-190 ° C and keep warm for 0.5-1.5 h, heating at 200-210 ° C and keeping warm for 6-8 h to obtain a second product.

Step 4: Mixing butyl ether, n-butanol with the first product, adding the second product, adding an amine neutralizer when the temperature has dropped to 95-105 ° C such that the pH of the mixture is 8.5- 9 is to obtain water-dilutable phenolic resin.

The water reducible phenolic resin of the present invention is benzene free, reduces VOC emissions and has a high safety factor during transportation and application; It not only meets the technical requirements of oleoresin, but also has greatly improved safety and environmental friendliness, so that it truly embodies safety and environmental friendliness.

BRIEF DESCRIPTION OF THE DRAWINGS

A variety of other features and advantages of the present invention will be apparent to those skilled in the art from a study of the detailed description of the following preferred embodiments. The attached figures represent only preferred embodiments, but are not to be understood as limiting

1 Fig. 3 shows a flow chart of the production process of the dimethylolpropionic acid-modified, water-dilutable phenolic resin of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The present invention provides a variety of applicable and combinable concepts encompassed within the context of the present invention. The following specific exemplary embodiments describe exemplary and illustrative embodiments, but are not intended to be limiting.

In the following, the invention will be described in detail by reference to the enclosed figures and exemplary embodiments:
According to a first aspect, a dimethylolpropionic acid-modified, water-dilutable phenolic resin is provided, comprising by weight:
70-90 linseed oil
10-30 maleic anhydride
30-40 tung oil
10-20 polyol
0.005-0.01 potassium hydroxide
20-30 phthalic anhydride
8-15 dimethylolpropionic acid
5-10 benzoic acid
30-50 butyl ether
5-15 n-butanol.

In this case, the polyol used in the context of this invention may be triol and / or tetraol, such as pentaerythritol, glycerol or a mixture thereof.

According to a second aspect of the invention, a process for the preparation of the water-dilutable phenolic resin is provided, 1 Fig. 10 shows a flow chart of the production process of the water-dilutable phenolic resin of this invention. As in 1 the production process comprises:

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

Step 2: Mixing 30-40 parts by weight of tung oil, 10-20 parts by weight of polyol and 0.005-0.01 parts by weight of potassium hydroxide, heating to 240-250 ° C and keeping warm for 1-1.5 hours;

Step 3: cooling the product obtained in step 2 to 170-190 ° C, adding 20-30 parts by weight of phthalic anhydride, 8-15 parts by weight of dimethylolpropionic acid and 5-10 parts by weight of benzoic acid, refluxing xylene with simultaneous heating to 170-190 ° C and Keeping warm for 0.5-1.5 h, heating to 200-210 ° C and keeping warm for 6-8 h to obtain a second product;

Step 4: Mixing 30-50 parts by weight of butyl ether, 5-15 parts by weight of n-butanol with the first product, adding the second product, adding an amine neutralizing agent when the temperature has dropped to 95-105 ° C such that the pH Value is 8.5-9 to obtain water-dilutable phenolic resin.

In the second step, the alcoholysis reaction takes place at 240-250 ° C. A method of measuring ethanol tolerance may be used to determine the end point of the alcoholysis reaction. The detailed procedure comprises: The reaction product from step 2 is mixed with 95% ethanol in a volume ratio of 1: 5 at 25 ° C and the end point of the alcoholysis reaction can be determined as soon as the mixture is transparent.

In the fourth step, amine neutralizer is added to adjust the pH of the resin such that the pH of the final product is 8.5-9. The amine neutralizing agent used may be a product such as triethylamine or MPA-95, the weight parts of the amine neutralizing agent to be added are 5-10. The chemical name of AMP-95 is 2-amino-2-methyl-1-propanol, a multifunctional amine additive that can adjust the pH of the emulsion adhesive to remain stable, which has a humidifying and dispersing effect and at any stage of the entire paint process, including manufacture, storage, transportation, application, and final coating.

Further, the production method according to the present invention also includes step 5: adding water to dilute the water-reducible phenolic resin. The exact method involves adding water to dilute the water-reducible phenolic resin, wherein the amount of water added can be regulated depending on the solids content of the resin required for production. Thinning allows for easier storage and subsequently easier application of the prepared water reducible phenolic resin.

Based on the water-dilutable phenolic resin and the production method thereof in the present invention, various factors can be optionally selected and a variety of embodiments can be designed. Therefore, the specific embodiments described herein are merely exemplary, but not limiting. For a more detailed description of the invention, the following exemplary embodiments are selected for illustration.

Embodiment 1

The water-dilutable phenolic resin comprises in this example by weight: 70 linseed oil, 10 maleic anhydride, 30 tung oil, 10 pentaerythritol, 0.005 potassium hydroxide, 20 phthalic anhydride, 8 dimethylolpropionic acid, 5 benzoic acid, 30 butyl ether, 15 n-butanol.

The process for producing the phenolic resin in this example comprises:

Step 1: mixing linseed oil and maleic anhydride at room temperature, heating to 240 ° C and keeping warm for 7 h to obtain a first product;

Step 2: Mixing tung oil, pentaerythritol and potassium hydroxide, heating to 240 ° C and keeping warm for 1 h to produce an alcoholysis reaction;

Step 3: Cool the alcoholysis product obtained in step 2 to 170 ° C, add phthalic anhydride, dimethylolpropionic acid and benzoic acid, reflux xylene with simultaneous heating to 170 ° C and heat for 0.5 h, heat to 200 ° C and keep warm for 6 h, to obtain a second product;

Step 4: Mixing butyl ether, n-butanol with the first product, adding the second product, adding 8 parts by weight of triethylamine when the temperature has dropped to 95 ° C such that the pH of the mixture is 8.5-9 to obtain water-dilutable phenolic resin;

Step 5: Add a reasonable amount of tap water to the water reducible phenolic resin to achieve the resin solids required for production, and fill.

Embodiment 2

The phenolic resin in this example comprises by weight: 90 linseed oil, 30 maleic anhydride, 40 tung oil, 20 pentaerythritol, 0.01 potassium hydroxide, 30 phthalic anhydride, 15 dimethylolpropionic acid, 10 benzoic acid, 50 butyl ether, 5 n-butanol.

The production method of the phenol resin in this example is the same as in Embodiment 1.

Embodiment 3

The phenolic resin comprises by weight in this example: 80 linseed oil, 20 maleic anhydride, 33 tung oil, 13 pentaerythritol, 0.008 potassium hydroxide, 25 phthalic anhydride, 12 dimethylolpropionic acid, 7 benzoic acid, 40 butyl ether, 10 n-butanol.

The production method of the phenol resin in this example is the same as in Embodiment 1.

Embodiment 4

The phenolic resin in this example comprises by weight: 70 linseed oil, 10 maleic anhydride, 30 tung oil, 10 glycerin, 0.005 potassium hydroxide, 20 phthalic anhydride, 8 dimethylolpropionic acid, 5 benzoic acid, 30 butyl ether, 15 n-butanol.

The production process of the phenolic resin in this example comprises:

Step 1: mixing linseed oil and maleic anhydride at room temperature, heating to 250 ° C and keeping warm for 8 h to obtain a first product;

Step 2: Mixing tung oil, glycerine and potassium hydroxide, heating to 245 ° C and keeping warm for 1.5 h to produce an alcoholysis reaction;

Step 3: cooling the alcoholysis product obtained in step 2 to 180 ° C, adding phthalic anhydride, dimethylolpropionic acid and benzoic acid, refluxing xylene with simultaneous heating to 180 ° C and keeping warm for 1 h, heating to 210 ° C and keeping warm for 7 h, to get a second product;

Step 4: Mixing butyl ether, n-butanol with the first product, adding the second product, adding 10 parts by weight of triethylamine when the temperature has dropped to 100 ° C such that the pH of the mixture is 8.5-9 to obtain water-dilutable phenolic resin;

Step 5: Add a reasonable amount of tap water to the water reducible phenolic resin to achieve the resin solids required for production, and fill.

Embodiment 5

The phenolic resin in this example comprises by weight: 80 linseed oil, 20 maleic anhydride, 33 tung oil, 13 glycerin, 0.008 potassium hydroxide, 25 phthalic anhydride, 12 dimethylolpropionic acid, 7 benzoic acid, 40 butyl ether, 10 n-butanol.

The production method of the phenol resin in this example is the same as in Embodiment 4.

Embodiment 6

The phenolic resin in this example comprises by weight: 90 linseed oil, 30 maleic anhydride, 40 tung oil, 20 glycerin, 0.01 potassium hydroxide, 30 phthalic anhydride, 15 dimethylolpropionic acid, 10 benzoic acid, 50 butyl ether, 5 n-butanol.

The production method of the phenol resin in this example is the same as in Embodiment 4.

Embodiment 7

The phenolic resin in this example comprises by weight: 80 linseed oil, 20 maleic anhydride, 33 tung oil, 13 parts by weight of a mixture of glycerol and pentaerythritol, 0.008 potassium hydroxide, 25 phthalic anhydride, 12 dimethylolpropionic acid, 7 benzoic acid, 40 butyl ether, 10 n-butanol.

The production process of the phenolic resin in this example comprises:

Step 1: mixing linseed oil and maleic anhydride at room temperature, heating to 245 ° C and keeping warm for 9 h to obtain a first product;

Step 2: Mixing tung oil, the mixture of glycerin and pentaerythritol and potassium hydroxide, heating to 245 ° C and keeping warm for 1 h to cause an alcoholysis reaction;

Step 3: Cool the alcoholysis product obtained in step 2 to 190 ° C, add phthalic anhydride, dimethylolpropionic acid and benzoic acid, reflux xylene with simultaneous heating to 190 ° C and hold for 1.5 h, heat to 205 ° C and keep warm for 8 h, to obtain a second product;

Step 4: Mixing butyl ether, n-butanol with the first product, adding the second product, adding 5 parts by weight of triethylamine when the temperature has dropped to 105 ° C such that the pH of the mixture is 8.5-9 to obtain water-dilutable phenolic resin;

Step 5: Add a reasonable amount of tap water to the water reducible phenolic resin to achieve the resin solids required for production, and fill.

Embodiment 8

The phenolic resin in this example comprises by weight: 90 linseed oil, 30 maleic anhydride, 40 tung oil, 20 parts by weight of a mixture of glycerol and pentaerythritol, 0.01 potassium hydroxide, 30 phthalic anhydride, 15 dimethylolpropionic acid, 10 benzoic acid, 50 butyl ether, 5 n-butanol.

The production method of the phenol resin in this example is the same as in Embodiment 7.

Embodiment 9

The phenolic resin in this example comprises by weight: 70 linseed oil, 10 maleic anhydride, 30 tung oil, 10 a mixture of glycerol and pentaerythritol, 0.05 potassium hydroxide, 20 phthalic anhydride, 8 dimethylolpropionic acid, 5 benzoic acid, 30 butyl ether, 15 n-butanol.

The production method of the phenol resin in this example is the same as in Embodiment 7.

The user recognizes the appearance, the color and the gloss as well as the acid value indicators of the water-dilutable phenolic resin prepared in Example 1. The specific indicators and actual detection values are shown in Table 1: Table 1 distinguishing Technical indicators Actual detection values Appearance water-colored white, transparent red-brown Color and gloss (Fe-Co method) / value ≤ 9 ≤ 13 Acid value / mg KOH / g ≤ 20 ≤ 20

From the detection data, it can be seen that the water-reducible phenolic resin of the present invention has a good quality and a performance exceeding that of oleoresin. The detection results of other embodiments are similar to those shown in Table 1 and are not listed here.

Claims (7)

Dimethylolpropionic acid-modified, water-dilutable phenolic resin comprising by weight: 70-90 linseed oil 10-30 maleic anhydride 30-40 tung oil 10-20 polyol 0.005-0.01 potassium hydroxide 20-30 phthalic anhydride 8-15 dimethylolpropionic acid 5-10 benzoic acid 30-50 butyl ether 5-15 n-butanol. Dimethylolpropionic acid-modified, water-dilutable phenolic resin according to claim 1, characterized in that the polyol consists of pentaerythritol and / or glycerol. Dimethylolpropionic acid-modified, water-dilutable phenolic resin according to claim 1, comprising by weight: 80 linseed oil, 20 maleic anhydride, 33 tung oil, 13 pentaerythritol, 0.008 potassium hydroxide, 25 phthalic anhydride, 12 dimethylolpropionic acid, 7 benzoic acid, 40 butyl ether, 10 n-butanol. Dimethylolpropionic acid-modified, water-dilutable phenolic resin according to claim 1, comprising by weight: 70 linseed oil, 10 maleic anhydride, 30 tung oil, 10 glycerin, 0.005 potassium hydroxide, 20 phthalic anhydride, 8 dimethylolpropionic acid, 5 benzoic acid, 30 butyl ether, 15 n-butanol. Dimethylolpropionic acid-modified, water-dilutable phenolic resin according to claim 1, comprising by weight: 80 linseed oil, 20 maleic anhydride, 33 tung oil, 13 glycerol, 0.008 potassium hydroxide, 25 phthalic anhydride, 12 dimethylolpropionic acid, 7 benzoic acid, 40 butyl ether, 10 n-butanol. Dimethylolpropionic acid-modified, water-dilutable phenolic resin according to claim 1, comprising by weight: 90 linseed oil, 30 maleic anhydride, 40 tung oil, 20 glycerol, 0.001 potassium hydroxide, 30 phthalic anhydride, 15 dimethylolpropionic acid, 10 benzoic acid, 50 butyl ether, 5 n-butanol. A dimethylolpropionic acid-modified, water-dilutable phenolic resin according to any one of claims 1 to 6 prepared by the following process: Step 1: mixing linseed oil and maleic anhydride at room temperature, heating to 240-250 ° C and keeping warm for 7-9 hours to obtain a first product to obtain; Step 2: Mixing tung oil, polyol and potassium hydroxide, heating to 240-250 ° C and keeping warm for 1-1.5 hours; Step 3: Cool the product obtained in Step 2 to 170-190 ° C, add phthalic anhydride, dimethylolpropionic acid and benzoic acid, reflux xylene while heating to 170-190 ° C and keep warm for 0.5-1.5 hours, heating at 200-210 ° C and keeping warm for 6-8 h to obtain a second product. Step 4: Mixing butyl ether, n-butanol with the first product, adding the second product, adding an amine neutralizer when the temperature has dropped to 95-105 ° C such that the pH of the mixture is 8.5- 9 is to obtain water-dilutable phenolic resin.

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