阅读说明：本技术 一种醇酸树脂及其制备方法 (Alkyd resin and preparation method thereof ) 是由 张华� 徐从青 谢宠 阮晓亮 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种醇酸树脂,按质量百分比计,包括如下组份：5～25％的环己烷1,2-二甲酸二异壬基酯副产物；20～30％的多元醇；20～35％的多元酸；5～20％的一元酸；0.01～1％的减色剂；0.01～5％的回流溶剂；10～25％的稀释溶剂；环己烷1,2-二甲酸二异壬基酯副产物按质量百分比计包括5～15％的壬醇,5～15％的壬酸,25～35％的壬酸壬酯,25～35％的羟甲基二壬酯,5～15％由壬醛而来的醇醛缩合物,5～15％由壬酸而来的高碳酯。本发明的醇酸树脂能有效利用DINCH的副产物,免去后续的副产物处理成本,降低对环境污染,能制备出施工固含高、光泽高、鲜映性高的涂料。(The invention discloses alkyd resin which comprises the following components in percentage by mass: 5-25% of cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product; 20-30% of a polyol; 20-35% of polybasic acid; 5-20% of monoacid; 0.01-1% of color reducing agent; 0.01-5% of a reflux solvent; 10-25% of a diluent solvent; the cyclohexane 1, 2-dicarboxylic acid diisononyl ester byproduct comprises, by mass, 5-15% of nonanol, 5-15% of nonanoic acid, 25-35% of nonyl nonanoate, 25-35% of hydroxymethyl dinonyl ester, 5-15% of an aldol condensation product derived from nonanal, and 5-15% of a high-carbon ester derived from nonanoic acid. The alkyd resin can effectively utilize the by-product of DINCH, thereby avoiding the subsequent by-product treatment cost, reducing the environmental pollution and preparing the coating with high construction solid content, high gloss and high distinctness of image.)

1. The alkyd resin is characterized by comprising the following components in percentage by mass:

5-25% of cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product;

20-30% of a polyol;

20-35% of polybasic acid;

5-20% of monoacid;

0.01-1% of color reducing agent;

0.01-5% of a reflux solvent;

10-25% of a diluent solvent;

the cyclohexane 1, 2-dicarboxylic acid diisononyl ester byproduct comprises, by mass, 5-15% of nonanol, 5-15% of pelargonic acid, 25-35% of nonyl pelargonate, 25-35% of hydroxymethyl dinonyl ester, 5-15% of an aldol condensation product derived from nonanal, and 5-15% of a high-carbon ester derived from nonanoic acid.

2. The alkyd resin of claim 1, comprising, in mass percent:

18% cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product;

27.8% of a polyol;

26% of a polybasic acid;

16% of a monobasic acid;

0.2% of a color reducing agent;

2% of a reflux solvent;

10% of a diluting solvent.

3. The alkyd resin of claim 1, wherein said cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product is available from the registered petrochemical BASF corporation;

and/or the polyalcohol is one or more of ethylene glycol, glycerol, pentaerythritol, 1, 6-hexanediol, trimethylolpropane and neopentyl glycol.

4. The alkyd resin of claim 1, wherein said polybasic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, hexahydrophthalic anhydride, and trimellitic anhydride;

and/or the monobasic acid is one or more of isooctanoic acid, isononanoic acid, lauric acid, stearic acid and benzoic acid.

5. The alkyd resin of claim 1, wherein the color reducing agent is one or more of phosphoric acid, hypophosphorous acid, and triphenyl phosphite.

6. The alkyd resin of claim 1, wherein said refluxing solvent is xylene and/or D40 mineral spirits.

7. The alkyd resin of claim 1, wherein said diluent solvent is one or more of xylene, butyl acetate, propylene glycol methyl ether acetate, Solvesso 100 mineral spirits, and n-butanol.

8. A process for the preparation of an alkyd resin according to any of claims 1 to 7, comprising the steps of:

s1, adding cyclohexane 1, 2-diisononyl phthalate byproduct, polyol, polybasic acid, monobasic acid and color reducing agent into a reactor, introducing nitrogen, wherein the flow rate is 0.1-15 m³And/h, stirring, heating until water is discharged, keeping the temperature for 0.1-3 h at the water discharge temperature, then heating for 0.1-10 h to the highest reaction temperature of 200-250 ℃, adding a reflux solvent, keeping the temperature at the highest reaction temperature until the solid acid value is less than 15mgKOH/g, and the Gauss viscosity is 25 ℃: Z1-Z7;

s2, cooling to 120-170 ℃, adding a diluting solvent, and uniformly stirring.

9. The process according to claim 8, wherein the nitrogen flow in S1 is 5m³And h, preserving the temperature of effluent for 1h, heating to 230 ℃ in 5h, adding a reflux solvent, preserving the temperature at 230 ℃ until the solid acid value is less than 15mgKOH/g and the Grignard viscosity is 25 ℃: Z4-Z6.

10. The process for preparing an alkyd resin according to claim 8, wherein in S2, the temperature is reduced to 140 ℃, and the diluent solvent is added and stirred uniformly.

Technical Field

The invention relates to the field of polymer synthesis, in particular to alkyd resin and a preparation method thereof.

Background

DINCH (cyclohexane 1, 2-diisononyl phthalate) is a common chemical raw material, a large amount of byproducts are generated in the production of DINCH, and the environment is damaged, and a common treatment method is to add a subsequent treatment process to treat the byproducts, so that various treatment costs are generated; meanwhile, the coating prepared by the existing resin has one or more defects of insufficient solid content, low gloss, poor distinctness of image and the like.

There is a need for an alkyd resin which can effectively utilize DINCH byproducts, eliminate the subsequent byproduct treatment cost, reduce environmental pollution, and prepare a coating with high construction solid content, high gloss and high distinctness of image, and a preparation method thereof to solve the above technical problems.

Disclosure of Invention

In order to solve the technical problems, the invention provides the alkyd resin and the preparation method thereof, the alkyd resin can effectively utilize the by-product of DINCH, the subsequent by-product treatment cost is avoided, the environmental pollution is reduced, and the paint with high construction solid content, high gloss and high distinctness of image can be prepared.

The invention solves the technical problems by the following technical scheme:

the invention provides alkyd resin which comprises the following components in percentage by mass:

5-25% of cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product;

20-30% of a polyol;

20-35% of polybasic acid;

5-20% of monoacid;

0.01-1% of color reducing agent;

0.01-5% of a reflux solvent;

10-25% of a diluent solvent;

the cyclohexane 1, 2-dicarboxylic acid diisononyl ester byproduct comprises, by mass, 5-15% of nonanol, 5-15% of pelargonic acid, 25-35% of nonyl pelargonate, 25-35% of hydroxymethyl dinonyl ester, 5-15% of an aldol condensation product derived from nonanal, and 5-15% of a high-carbon ester derived from nonanoic acid.

Preferably, the alkyd resin comprises the following components in percentage by mass:

18% cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product;

27.8% of a polyol;

26% of a polybasic acid;

16% of a monobasic acid;

0.2% of a color reducing agent;

2% of a reflux solvent;

10% of a diluting solvent.

In the present invention, the cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product is conventional in the art;

preferably, the cyclohexane 1, 2-dicarboxylic acid diisononyl ester by-product is available from the Nondestine petrochemical BASF corporation.

In the present invention, the polyols are conventional in the art;

preferably, the polyol is one or more of ethylene glycol, glycerol, pentaerythritol, 1, 6-hexanediol, trimethylolpropane and neopentyl glycol.

In the present invention, the polybasic acid is conventional in the art;

preferably, the polybasic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, hexahydrophthalic anhydride and trimellitic anhydride.

In the present invention, the monoacids are conventional in the art;

preferably, the monobasic acid is one or more of isooctanoic acid, isononanoic acid, lauric acid, stearic acid and benzoic acid.

In the present invention, the color reducing agent is conventional in the art;

preferably, the color reducing agent is one or more of phosphoric acid, hypophosphorous acid and triphenyl phosphite.

In the present invention, the refluxing solvent is conventional in the art;

preferably, the refluxing solvent is xylene and/or D40 solvent oil.

In the present invention, the diluting solvent is conventional in the art;

preferably, the diluting solvent is one or more of xylene, butyl acetate, propylene glycol methyl ether acetate, Solvesso 100 solvent oil and n-butanol.

The invention also provides a preparation method of the alkyd resin, which comprises the following steps:

s1, adding cyclohexane 1, 2-diisononyl phthalate byproduct, polyol, polybasic acid, monobasic acid and color reducing agent into a reactor, introducing nitrogen, wherein the flow rate is 0.1-15 m³And/h, stirring, heating until water is discharged, keeping the temperature for 0.1-3 h at the water discharge temperature, then heating for 0.1-10 h to the highest reaction temperature of 200-250 ℃, adding a reflux solvent, keeping the temperature at the highest reaction temperature until the solid acid value is less than 15mgKOH/g, and the Gauss viscosity is 25 ℃: Z1-Z7;

s2, cooling to 120-170 ℃, adding a diluting solvent, and uniformly stirring.

Preferably, in S1, the flow rate of nitrogen is 5m³And h, preserving the temperature of effluent for 1h, heating to 230 ℃ in 5h, adding a reflux solvent, preserving the temperature at 230 ℃ until the solid acid value is less than 15mgKOH/g and the Grignard viscosity is 25 ℃: Z4-Z6;

preferably, in S2, the temperature is reduced to 140 ℃, and the diluting solvent is added and stirred uniformly.

The starting materials of the present invention are all commercially available.

The invention has the advantages and beneficial effects that: the alkyd resin can effectively utilize the by-product of DINCH, the subsequent by-product treatment cost is saved, the environmental pollution is reduced, and the paint with high construction solid content, high gloss and high distinctness of image can be prepared.

Detailed Description

The following further describes embodiments of the present invention with reference to examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.

The starting materials used in the following examples and comparative examples are commercially available.

Example 1

This example provides an alkyd resin comprising 180kg of DINCH byproduct; 38kg of glycerol; 240kg of trimethylolpropane; 260kg of phthalic anhydride; 160kg of isononanoic acid; 1kg of hypophosphorous acid; 1kg of triphenyl phosphite; 120kg of xylene.

The preparation method of the alkyd resin of this example is as follows:

s1, putting DINCH byproduct, glycerol, trimethylolpropane, phthalic anhydride, 160kg of isononanoic acid and triphenyl phosphite into a reactor, introducing nitrogen, and introducing nitrogen at the flow rate of 5m³And/h, starting stirring, heating to effluent, keeping the temperature for 1h at the effluent temperature, then heating to 230 ℃ for 5h, adding 20kg of dimethylbenzene, and keeping the temperature at 230 ℃ until the solid acid value is less than 15mgKOH/g and the Grignard viscosity is 25 ℃: Z4-Z6;

s2, cooling to 120-170 ℃, adding the rest dimethylbenzene, and uniformly stirring.

Comparative example 1

This comparative example provides a resin having a designation of ESC-3180 produced by Dongsheng chemical company Limited, which comprises, in mass percent: 26.5 percent of isononanoic acid, 4.5 percent of neopentyl glycol, 15 percent of trimethylolpropane, 9.3 percent of pentaerythritol, 27 percent of hexahydrophthalic anhydride, 0.1 percent of hypophosphorous acid, 0.1 percent of triphenyl phosphite and 17.5 percent of dimethylbenzene.

The solid content is 79-81%; gaster viscosity 25 ℃: Z4-Z6, and the solid acid value is less than 12 mgKOH/g.

Comparative example 2

This comparative example provides a resin having a designation of ESC-2414, manufactured by Dongsheng chemical (Shanghai) Co., Ltd, which comprises, in mass percent: 15% of lauric acid, 8% of benzoic acid, 31.0% of trimethylolpropane, 26.8% of phthalic anhydride, 0.1% of hypophosphorous acid, 0.1% of triphenyl phosphite, 5% of xylene and 14% of propylene glycol monomethyl ether acetate.

The solid content is 79-81%; gaster viscosity 25 ℃: Z6-Z7, and the solid acid value is less than 12 mgKOH/g.

The resins of example 1, comparative example 1 and comparative example 2 are prepared into coatings, and the coating has the following formula in percentage by mass: 50% of resin (products of example 1, comparative example 1 and comparative example 2), 13824.5% of amino resin, 4% of DBE solvent, 8% of n-butanol, 21.3% of xylene and a leveling agent BYK 3150.2%.

The properties of the coatings prepared from the products of example 1, comparative example 2 were examined as shown in table 1 below:

TABLE 1 coating Properties prepared from the resins of example 1, comparative examples 1-2

Numbering	Example 1	Comparative example 1	Comparative example 2
				Construction viscosity (paint 4 cup)	14 seconds	14 seconds	14 seconds
Construction anchor	52.9％	50.1％	49.5％
				Film thickness (micron)	23	23	25
Hardness of	96	105	95
				Impact (positive impact)	50	50	50
Impact (recoil)	20	5	20
				Solvent resistance (xylene)	1 minute 35 seconds	3 minutes	1 minute and 20 seconds
Gloss (60 degree angle)	100	95	99
				Distinctness of image	Optimization of	Slightly better	A little bit worse

As can be seen from the above effects, the alkyd resin of the invention has the characteristics of high construction solid content, high gloss, high distinctness of image and the like. In this process, the use of the DINCH byproduct can reduce the damage of the DINCH byproduct to the environment and reduce various costs generated by processing the DINCH byproduct.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.