阅读说明：本技术 一种三聚茚酮衍生物改性水性醇酸树脂及其制备方法 (Tripolyindenone derivative modified waterborne alkyd resin and preparation method thereof ) 是由 张武 康伦国 姚东生 于 2020-12-18 设计创作，主要内容包括：本发明涉及一种三聚茚酮衍生物改性水性醇酸树脂及其制备方法,按重量份计,其组成为：植物油酸20.0～45.0份、三聚茚酮衍生物1.0～4.0份、环己二醇单丙烯酸酯3.0～6.0份、多元酸18.0～35.0份、多元醇15.0～40.0份、二甲苯10.0～20.0份、三(4-羧基联苯基)胺2.0～6.0份、混合液8.0～15.0份、苯甲酸2.0～5.0份、二羟甲基丙酸2.5～6.0份、中和剂3.0～10.0份、去离子水100.0～200.0份；本发明制得的三聚茚酮衍生物改性水性醇酸树脂在醇酸树脂结构上通过化学键与三聚茚酮衍生物相连,性能稳定；其不仅具有三聚茚酮的特性,还具有席夫碱的特性,具有良好的抗菌、杀菌功能；制备成涂料时无需外加杀菌剂,可用于水性建筑涂料、水性木器涂料、水性特种涂料等,其应用潜力非常巨大。(The invention relates to a modified waterborne alkyd resin of a trimeric indanone derivative and a preparation method thereof, wherein the modified waterborne alkyd resin comprises the following components in parts by weight: 20.0-45.0 parts of vegetable oil acid, 1.0-4.0 parts of a trimeric indanone derivative, 3.0-6.0 parts of cyclohexanediol monoacrylate, 18.0-35.0 parts of polybasic acid, 15.0-40.0 parts of polyol, 10.0-20.0 parts of xylene, 2.0-6.0 parts of tri (4-carboxyl biphenyl) amine, 8.0-15.0 parts of mixed solution, 2.0-5.0 parts of benzoic acid, 2.5-6.0 parts of dimethylolpropionic acid, 3.0-10.0 parts of a neutralizing agent and 100.0-200.0 parts of deionized water; the modified waterborne alkyd resin of the indenone derivative is connected with the indenone derivative through chemical bonds on the structure of the alkyd resin, so that the performance is stable; the compound has the characteristics of both the indenone trimer and the Schiff base, and has good antibacterial and bactericidal functions; the coating is prepared without adding a bactericide, can be used for water-based building coatings, water-based wood coatings, water-based special coatings and the like, and has great application potential.)

1. A modified waterborne alkyd resin of a trimeric indanone derivative is characterized in that: the composition comprises the following components in parts by weight: 20.0-45.0 parts of vegetable oil acid, 1.0-4.0 parts of a trimeric indanone derivative, 3.0-6.0 parts of cyclohexanediol monoacrylate, 18.0-35.0 parts of polybasic acid, 15.0-40.0 parts of polyol, 10.0-20.0 parts of xylene, 2.0-6.0 parts of tri (4-carboxyl biphenyl) amine, 8.0-15.0 parts of mixed solution, 2.0-5.0 parts of benzoic acid, 2.5-6.0 parts of dimethylolpropionic acid, 3.0-10.0 parts of a neutralizing agent and 100.0-200.0 parts of deionized water.

2. The modified waterborne alkyd resin of claim 1, wherein the modified waterborne alkyd resin comprises: the vegetable oil acid is one or a combination of more of refined castor oil, soybean oil, coconut oil, cottonseed oil, tall oil and palm oil.

3. The modified waterborne alkyd resin of claim 1, wherein the modified waterborne alkyd resin comprises: the polybasic acid is one or a combination of more of phthalic anhydride, hexahydrophthalic anhydride, acetic anhydride, maleic anhydride, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, cyclopentane-1, 2-dicarboxylic acid, adipic acid and azelaic acid.

4. The modified waterborne alkyd resin of claim 1, wherein the modified waterborne alkyd resin comprises: the polyhydric alcohol is one or a combination of more of butanediol, neopentyl glycol, cyclohexanediol, diethylene glycol, trimethylolpropane, trimethylolethane, glycerol and pentaerythritol.

5. The modified waterborne alkyd resin of claim 1, wherein the modified waterborne alkyd resin comprises: the mixed solution is one or a combination of more of dipropylene glycol butyl ether, diethylene glycol butyl ether, alcohol ester twelve, propylene glycol butyl ether and propylene glycol methyl ether acetate; the mass ratio of the propylene glycol butyl ether to the propylene glycol methyl ether acetate is preferably 1: 1.

6. The modified waterborne alkyd resin of claim 1, wherein the modified waterborne alkyd resin comprises: the neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.

7. The modified waterborne alkyd resin of claim 1, wherein the modified waterborne alkyd resin comprises: the preparation process of the modified waterborne alkyd resin containing the indenone derivatives comprises the following steps:

a) adding vegetable oleic acid and polyalcohol into a reactor according to the weight part of the formula, heating and vacuum dehydrating;

b) adding polybasic acid, dimethylolpropionic acid, tri (4-carboxyl biphenyl) amine, a trimeric indanone derivative and xylene, heating, stirring at a low speed, introducing nitrogen for protection, and removing free water and oxygen in the reactor;

c) then heating to 160-170 ℃, carrying out heat preservation stirring reaction for 1.5h, adding benzoic acid for carrying out partial end capping and controlling molecular weight, then heating to 180 ℃, and carrying out heat preservation reaction for 1.5 h;

d) then adding cyclohexanediol monoacrylate, heating to 220-230 ℃ at the speed of 20 ℃/h, carrying out heat preservation reaction for 1.5h, and measuring the acid value every 15min until the acid value reaches the design value;

e) stopping reaction, cooling, removing dimethylbenzene in vacuum, adding the mixed solution, uniformly stirring and dispersing, reducing viscosity, cooling, adding a neutralizing agent, uniformly dispersing, adding deionized water with the formula amount, continuously stirring and dispersing, and filtering to obtain the modified waterborne alkyd resin containing the indenone derivative.

8. The modified waterborne alkyd resin of claim 1, wherein the modified waterborne alkyd resin comprises: the preparation process of the indenone derivative comprises the following steps:

adding the indenone and a proper amount of ethanol into a multifunctional reaction kettle according to the formula amount (the molar ratio of the indenone to the 2-hydroxyethylamine is preferably 1:3), heating to 80-82 ℃, and uniformly stirring; and weighing 2-hydroxyethylamine according to the formula ratio, adding the 2-hydroxyethylamine into a reaction kettle, adding a small amount of glacial acetic acid, continuously performing reflux reaction for 12.0-14.0 h, cooling, recrystallizing, filtering, and performing vacuum drying to obtain the indenone derivative.

Technical Field

The invention relates to a modified alkyd resin, in particular to a modified waterborne alkyd resin of a trimeric indanone derivative and a preparation method thereof, belonging to the technical field of waterborne functional resin synthesis.

Background

The alkyd resin is an important resin for paint, and has the advantages of abundant monomer sources, low price, multiple varieties, large formula change, convenience for chemical modification and good performance; the alkyd paint has the characteristics of good construction performance, high film fullness, good flexibility and the like, and is widely applied to decoration and protection of steel structures. The characteristics of easy construction and cross-linking with oxygen make it self-dry and universal and widely used. Therefore, since the development of alkyd resins, alkyd resins have been an important position in the coating industry, but traditional alkyd resins have certain limitations in certain specific fields.

The truxene has a planar seven-membered ring structure, and its derivatives are mainly used as a liquid crystal material or an organic semiconductor material, etc. as is known from the chemical formula of truxene, it can be regarded as a compound having 3-CH groups₂In recent years, some branched truxene derivatives with extended pi system are synthesized, and truxene has applications in more than ten fields, mainly including photoluminescence, fluorescent probes, electroluminescence, organic solar cells, perovskite solar cells, dye-sensitized solar cells, self-assembly, two-photon absorption, catalysis, field effect transistors, photoresists, nonlinear optics, organic lasers, and the like.

At present, no researcher in China applies the indenone to the development of the alkyd resin, and the combination of the characteristics of the alkyd resin and the indenone has important significance in connecting the indenone to the structure of the alkyd resin.

Disclosure of Invention

In order to solve the technical problems at present, the first object of the invention is to provide a trimeric indanone derivative modified waterborne alkyd resin.

The second purpose of the invention is to provide a preparation method of the trimeric indanone derivative modified waterborne alkyd resin.

The indenone can react with many substances because of the high activity carbonyl group, and is C₃The symmetric structure has certain advantages in the construction of star-shaped materials, dumbbell-shaped materials, hyperbranched materials and porous materials. The indenone is a co-planar nucleus and C₃The symmetrical characteristic enables a wide range of dendrimers, star-shaped molecules, dumbbell-shaped molecules to be designed and synthesized. The indenone serving as a functional unit is applied to various fields and achieves remarkable results, the development of the indenone material plays an important promoting role in the development of the fields, and the indenone is applied to more than ten fields in the organic photoelectric field.

The method prepares the indenone derivative by preparing the indenone, and then connects the indenone derivative with the alkyd resin structure through a chemical bond, so that the stability is good.

In order to realize the first purpose of the invention, the invention adopts the following technical scheme: the invention relates to a modified waterborne alkyd resin of a trimeric indanone derivative, which comprises the following components in parts by weight: 20.0-45.0 parts of vegetable oil acid, 1.0-4.0 parts of a trimeric indanone derivative, 3.0-6.0 parts of cyclohexanediol monoacrylate, 18.0-35.0 parts of polybasic acid, 15.0-40.0 parts of polyol, 10.0-20.0 parts of xylene, 2.0-6.0 parts of tri (4-carboxyl biphenyl) amine, 8.0-15.0 parts of mixed solution, 2.0-5.0 parts of benzoic acid, 2.5-6.0 parts of dimethylolpropionic acid, 3.0-10.0 parts of a neutralizing agent and 100.0-200.0 parts of deionized water.

The vegetable oil acid is one or a combination of more of refined castor oil, soybean oil, coconut oil, cottonseed oil, tall oil and palm oil.

The polybasic acid is one or a combination of more of phthalic anhydride, hexahydrophthalic anhydride, acetic anhydride, maleic anhydride, sebacic acid, terephthalic acid, isophthalic acid, succinic acid, cyclopentane-1, 2-dicarboxylic acid, adipic acid and azelaic acid.

The polyhydric alcohol is one or a combination of more of butanediol, neopentyl glycol, cyclohexanediol, diethylene glycol, trimethylolpropane, trimethylolethane, glycerol and pentaerythritol.

The mixed solution is one or a combination of more of dipropylene glycol butyl ether, diethylene glycol butyl ether, alcohol ester twelve, propylene glycol butyl ether and propylene glycol methyl ether acetate; the mass ratio of the propylene glycol butyl ether to the propylene glycol methyl ether acetate is preferably 1: 1.

The neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.

In order to achieve the second object of the invention, the following method is adopted, and the invention provides a preparation method of the modified waterborne alkyd resin of the indenone derivative, which comprises the following steps:

a) adding vegetable oleic acid and polyalcohol into a reactor according to the weight part of the formula, heating and vacuum dehydrating;

b) adding polybasic acid, dimethylolpropionic acid, tri (4-carboxyl biphenyl) amine, a trimeric indanone derivative and xylene, heating, stirring at a low speed, introducing nitrogen for protection, and removing free water and oxygen in the reactor;

c) then heating to 160-170 ℃, carrying out heat preservation stirring reaction for 1.5h, adding benzoic acid for carrying out partial end capping and controlling molecular weight, then heating to 180 ℃, and carrying out heat preservation reaction for 1.5 h;

d) then adding cyclohexanediol monoacrylate, heating to 220-230 ℃ at the speed of 20 ℃/h, carrying out heat preservation reaction for 1.5h, and measuring the acid value every 15min until the acid value reaches the design value;

e) stopping reaction, cooling, removing dimethylbenzene in vacuum, adding the mixed solution, uniformly stirring and dispersing, reducing viscosity, cooling, adding a neutralizing agent, uniformly dispersing, adding deionized water with the formula amount, continuously stirring and dispersing, and filtering to obtain the modified waterborne alkyd resin containing the indenone derivative.

The preparation method of the trimeric indanone derivative comprises the following steps:

adding the indenone and a proper amount of ethanol into a multifunctional reaction kettle according to the formula amount (the molar ratio of the indenone to the 2-hydroxyethylamine is preferably 1:3), heating to 80-82 ℃, and uniformly stirring; and weighing 2-hydroxyethylamine according to the formula ratio, adding the 2-hydroxyethylamine into a reaction kettle, adding a small amount of glacial acetic acid, continuously performing reflux reaction for 12.0-14.0 h, cooling, recrystallizing, filtering, and performing vacuum drying to obtain the indenone derivative.

The modified waterborne alkyd resin of the indenone derivative prepared by the invention has the following advantages:

1) the modified waterborne alkyd resin of the indenone derivative prepared by the invention is connected with the indenone derivative through chemical bonds on the structure of the alkyd resin, so that the performance is stable;

2) the modified waterborne alkyd resin of the indenone derivative prepared by the invention not only has the characteristics of the indenone, but also has the characteristics of Schiff base, and has good antibacterial and bactericidal functions;

3) the modified waterborne alkyd resin of the indenone derivative prepared by the invention has good adhesive force, good water resistance, good fullness, good fluorescence and good antibacterial and bactericidal functions, does not need an additional bactericide when being prepared into a coating, can be used for waterborne architectural coatings, waterborne wood coatings, waterborne special coatings and the like, and has great application potential.

Detailed Description

The present invention is further described with reference to the following examples to prepare modified waterborne alkyds of the indenone derivatives. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.

Example 1

The modified waterborne alkyd resin of the indenone derivative comprises the following components in parts by weight: 35.0 parts of refined castor oil, 2.2 parts of a trimeric indanone derivative, 4.0 parts of cyclohexanediol monoacrylate, 15.5 parts of phthalic anhydride, 12.0 parts of azelaic acid, 15.0 parts of neopentyl glycol, 15.0 parts of trimethylolpropane, 6.0 parts of xylene, 4.0 parts of tri (4-carboxyl biphenyl) amine, 5.5 parts of propylene glycol butyl ether, 5.5 parts of propylene glycol methyl ether acetate, 3.5 parts of benzoic acid, 4.0 parts of dimethylolpropionic acid, 3.8 parts of triethylamine and 160.0 parts of deionized water.

The preparation method of the modified waterborne alkyd resin containing the indenone derivative comprises the following steps:

a) adding refined castor oil, neopentyl glycol and trimethylolpropane in a reactor according to the weight part of the formula, heating and vacuum dehydrating;

b) adding phthalic anhydride, azelaic acid, dimethylolpropionic acid, tri (4-carboxyl biphenyl) amine, a trimeric indanone derivative and xylene, heating, stirring at a low speed, introducing nitrogen for protection, and removing free water and oxygen in the reactor;

c) then heating to 160-170 ℃, carrying out heat preservation stirring reaction for 1.5h, adding benzoic acid for carrying out partial end capping and controlling molecular weight, then heating to 180 ℃, and carrying out heat preservation reaction for 1.5 h;

d) then adding cyclohexanediol monoacrylate, heating to 220-230 ℃ at the speed of 20 ℃/h, carrying out heat preservation reaction for 1.5h, and measuring the acid value every 15min until the acid value reaches the design value;

e) stopping reaction, cooling, removing dimethylbenzene in vacuum, then adding propylene glycol butyl ether and propylene glycol methyl ether acetate, stirring and dispersing uniformly, reducing viscosity, cooling, adding triethylamine, dispersing uniformly, adding deionized water with the formula amount, continuing stirring and dispersing, and filtering to obtain the modified waterborne alkyd resin of the indenone derivative, wherein the modified waterborne alkyd resin is marked as a sample 1.

Example 2

The modified waterborne alkyd resin of the indenone derivative comprises the following components in parts by weight: 30.0 parts of soybean oil, 1.8 parts of a trimeric indanone derivative, 3.8 parts of cyclohexanediol monoacrylate, 20.0 parts of hexahydrophthalic anhydride, 10.0 parts of cyclopentane-1, 2-dicarboxylic acid, 10.0 parts of pentaerythritol, 20.0 parts of cyclohexanediol, 15.0 parts of xylene, 5.0 parts of tri (4-carboxyl biphenyl) amine, 12.0 parts of dipropylene glycol butyl ether, 3.0 parts of benzoic acid, 3.5 parts of dimethylolpropionic acid, 3.0 parts of ammonia water and 150.0 parts of deionized water.

The preparation method of the modified waterborne alkyd resin containing the indenone derivative comprises the following steps:

a) adding soybean oil, pentaerythritol and cyclohexanediol into a reactor according to the weight part of the formula, heating and vacuum dehydrating;

b) adding hexahydrophthalic anhydride, cyclopentane-1, 2-dicarboxylic acid, dimethylolpropionic acid, tri (4-carboxyl biphenyl) amine, a trimeric indanone derivative and xylene, heating, stirring at a low speed, introducing nitrogen for protection, and removing free water and oxygen in the reactor;

c) then heating to 160-170 ℃, carrying out heat preservation stirring reaction for 1.5h, adding benzoic acid for carrying out partial end capping and controlling molecular weight, then heating to 180 ℃, and carrying out heat preservation reaction for 1.5 h;

d) then adding cyclohexanediol monoacrylate, heating to 220-230 ℃ at the speed of 20 ℃/h, carrying out heat preservation reaction for 1.5h, and measuring the acid value every 15min until the acid value reaches the design value;

e) stopping the reaction, cooling, removing xylene in vacuum, adding dipropylene glycol butyl ether, stirring and dispersing uniformly, reducing viscosity, cooling, adding ammonia water, dispersing uniformly, adding deionized water with the formula amount, continuing stirring and dispersing, and filtering to obtain the modified waterborne alkyd resin containing the indenone derivative, wherein the modified waterborne alkyd resin is marked as sample 2.

Example 3

The modified waterborne alkyd resin of the indenone derivative comprises the following components in parts by weight: 28.0 parts of coconut oil, 1.5 parts of truxene derivative, 3.0 parts of cyclohexanediol monoacrylate, 25.0 parts of acetic anhydride, 5.0 parts of terephthalic acid, 18.0 parts of butanediol, 15.0 parts of trimethylolethane, 15.0 parts of xylene, 4.5 parts of tri (4-carboxyl biphenyl) amine, 9.0 parts of alcohol ester, 4.0 parts of benzoic acid, 4.0 parts of dimethylolpropionic acid, 3.6 parts of triethylamine and 165.0 parts of deionized water.

The preparation method of the modified waterborne alkyd resin containing the indenone derivative comprises the following steps:

a) adding coconut oil, butanediol and trimethylolethane in a reactor according to the weight part of the formula, heating and vacuum dehydrating;

b) adding acetic anhydride, terephthalic acid, dimethylolpropionic acid, tri (4-carboxyl biphenyl) amine, a trimeric indanone derivative and xylene, heating, stirring at a low speed, introducing nitrogen for protection, and removing free water and oxygen in the reactor;

c) then heating to 160-170 ℃, carrying out heat preservation stirring reaction for 1.5h, adding benzoic acid for carrying out partial end capping and controlling molecular weight, then heating to 180 ℃, and carrying out heat preservation reaction for 1.5 h;

d) then adding cyclohexanediol monoacrylate, heating to 220-230 ℃ at the speed of 20 ℃/h, carrying out heat preservation reaction for 1.5h, and measuring the acid value every 15min until the acid value reaches the design value;

e) stopping reaction, cooling, removing xylene in vacuum, adding alcohol ester twelve, stirring and dispersing uniformly, reducing viscosity, cooling, adding triethylamine, dispersing uniformly, adding deionized water with the formula amount, continuing stirring and dispersing, and filtering to obtain the modified waterborne alkyd resin of the indenone derivative, wherein the modified waterborne alkyd resin is marked as a sample 3.

And (3) testing performance indexes: samples 1, 2 and 3 of the above examples were mixed with a conventional waterborne alkyd resin 4 (comparative example 1) to prepare coatings according to the raw material formulation shown in Table 1, and the corresponding coating samples were respectively designated as coating 1, coating 2, coating 3 and coating 4, and the properties thereof were respectively tested.

Table 1: coating formulation

Name of raw materials	Specification of	Amount/% of
			Water (W)	Deionized water	9.0
pH regulator	Sodium bicarbonate	0.3
			Aqueous resin	Sample resins	90.0
Thickening and leveling agent	SN-612	0.3
			Defoaming agent	NXZ	0.2
Wetting agent	Pe100	0.2

The prepared coating is tested for performance indexes according to relevant standards, and the test results are shown in table 2.

Wherein, filiform corrosion: detecting according to the regulation of (GB/T13452.4-92);

adhesion force: the test was carried out using the cross-cut method, as specified in GB/T1720-1988;

pencil hardness: detecting according to the regulation of GB/T6739-2006;

water resistance: detecting according to the regulation of GB/T1733-93;

salt spray resistance: detecting according to the regulation of GB/T1771-1991;

and (3) antibacterial property: the detection is carried out according to the regulation of HG/T3950-2007 antimicrobial paint.

Table 2: performance specification of coating

It can be seen from table 2 that the adhesion, salt spray resistance, filiform corrosion resistance, water resistance, and luminescence performance of the samples of examples 1, 2, and 3 are much better than those of the conventional waterborne alkyd resin, and the antibacterial property of the coating of the samples of examples of the invention is greater than 99.5%, while that of the conventional waterborne alkyd resin is only 48.52%, which shows that the modified waterborne alkyd resin of the invention has good antibacterial performance.

The foregoing description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed; it will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.