阅读说明：本技术 一种配合物及其制备方法、应用 (Complex and preparation method and application thereof ) 是由 高启超 罗懿 黄小娟 陈月 夏建荣 高仁金 于 2020-11-27 设计创作，主要内容包括：本申请公开了一种配合物及其制备方法和应用,所述配合物选自具有式Ⅰ所示结构式的物质的任一种。本申请提供的配合物可用于催干天然生漆,利用该配合物来克服传统天然生漆的干燥速度慢的缺点,有效的缩短了天然生漆的干燥时间。(The application discloses a complex and a preparation method and application thereof, wherein the complex is selected from any one of substances with a structural formula shown in a formula I. The complex provided by the application can be used for drying natural raw lacquer, the defect of low drying speed of the traditional natural raw lacquer is overcome by using the complex, and the drying time of the natural raw lacquer is effectively shortened.)

1. A complex, which is characterized in that the complex is selected from any one of substances with a structural formula shown as a formula I;

in formula I, n has a value range of: n is more than or equal to 2 and less than or equal to 20.

2. A process for preparing the complex of claim 1, comprising:

(1) reacting a mixture I containing indole, pyridine-2-formaldehyde and potassium bisulfate to obtain an intermediate product A1;

(2) reacting a mixture II containing the intermediate product A1, iodine and pyridine-2-formaldehyde to obtain an intermediate product A2;

(3) and reacting the mixture III containing the intermediate product A2 and the cupric salt to obtain the complex.

3. The method according to claim 2, wherein the conditions of reaction I are: methanol is used as a solvent, and the reaction temperature is 60-70 ℃; the reaction time is 20-48 hours;

the conditions of the reaction II are as follows: 1, 2-dichlorobenzene is used as a solvent, and the reaction temperature is 160-190 ℃; the reaction time is 4-10 hours;

the conditions of the reaction III are as follows: dimethyl formamide is used as a solvent, and the reaction temperature is 50-100 ℃; the reaction time is 2-8 hours;

preferably, the cupric salt is selected from at least one of cupric chloride, cupric nitrate and cupric acetate;

preferably, in the step (1), the mass ratio of the indole to the pyridine-2-formaldehyde to the potassium bisulfate is 4.0-8.0 g: 3.0-6.0 g: 4.0-10.0 g;

in the step (2), the mass ratio of the intermediate product A1 to iodine to pyridine-2-formaldehyde is 1.0-4.0 g: 0.02-0.5 g: 0.2-2.0 g;

in the step (3), the mass ratio of the intermediate product A2 to the cupric salt is 2.0-4.0 g: 0.01 to 2.0 g.

4. A quick-drying natural raw lacquer, characterized in that the quick-drying natural raw lacquer comprises a complex and a natural raw lacquer;

the complex is selected from at least one of the complex described in claim 1 and the complex prepared by the method described in claim 2 or 3.

5. The quick-drying raw lacquer according to claim 4, wherein the quick-drying raw lacquer comprises the following components in percentage by weight:

0.1-4 parts by weight of a complex;

96-99.9 parts of natural raw lacquer;

preferably, in the quick-drying raw lacquer, the content of each component is as follows:

0.5-2 parts by weight of a complex;

98-99.5 parts of natural raw lacquer;

preferably, the natural raw lacquer is at least one selected from Ankang lacquer, plain lacquer, city lacquer, Mao dam lacquer and Qinling lacquer.

6. A process for the preparation of a quick-drying raw lacquer according to claim 4 or 5, characterized in that it comprises:

and mixing the complex with the natural raw lacquer to obtain the quick-drying natural raw lacquer.

7. A quick-drying natural raw paint film comprising any one of the quick-drying natural raw paint according to claim 4 or 5 and the quick-drying natural raw paint produced by the method according to claim 6.

8. The quick-drying natural varnish film of claim 7, wherein the quick-drying natural varnish film has a thickness of 50 to 100 microns.

9. A method of producing a quick-drying natural varnish film according to claim 7 or 8, characterised in that the method comprises: and coating the mixture containing the complex and the natural raw lacquer to obtain the quick-drying natural raw lacquer film.

10. The method of manufacturing according to claim 9, comprising: and (3) coating and drying a mixture containing 0.1-4 parts by weight of the complex and 96-99.9 parts by weight of the natural raw lacquer to obtain the quick-drying natural raw lacquer film.

Technical Field

The application relates to a complex and a preparation method and application thereof, belonging to the technical field of coatings.

Background

Natural raw lacquer is commonly called as "earth lacquer", also called as "Chinese lacquer" or "Chinese lacquer", which is a special product in China and is a name of "king of coating". The natural raw lacquer is a pure natural milky white paint secreted by lacquer trees, the color of the natural raw lacquer gradually becomes dark and finally becomes brown after contacting with oxygen, the time for hardening and film forming on the surface is greatly influenced by temperature and humidity, generally for several hours, the oxidation film forming process is completed by continuously absorbing oxygen for oxidation under the catalysis of laccase and cross-linking and polymerizing at normal temperature. The paint film has beautiful appearance, excellent corrosion resistance, abrasion resistance, durability and other properties, and is the earliest natural resin used by human beings. Many unearthed cultural relics, such as Western Han coffin and lacquerware heaped out of the Han dynasty horse Wang of Hunan Changsha in 1972, have been 2000 years ago, the lacquer film of the lacquerware is bright and new, the long history of using natural raw lacquer as coating in China and the super-strong durability of the natural raw lacquer are fully proved, and the durability of any synthetic coating exceeds that of the natural raw lacquer so far. It also has some disadvantages such as slow drying time, limited temperature and humidity. The disadvantages of natural raw lacquer limit its application scope. There is currently a report of a copper-containing catalyst polymer for use in the drying of raw lacquer.

However, to date no solution or at least satisfactory solution to the problem of how to improve the quick drying cure of natural raw paint films has been provided in the field of natural raw paint film preparation.

Disclosure of Invention

According to one aspect of the application, a complex is provided, wherein the complex is selected from any one of substances with a structural formula shown in a formula I, the complex can be used for drying raw lacquer, the complex is used for overcoming the defect of slow drying speed of the traditional raw lacquer, and the drying time of the raw lacquer is effectively shortened.

According to a first aspect of the present application, there is provided a complex selected from any one of the substances having the formula shown in formula i;

in formula I, n has a value range of: n is more than or equal to 2 and less than or equal to 20.

Specifically, inIn the formula I, Cu²⁺Form coordination relationship with nitrogen element of A2, and counter ion (anion) can be NO₃ ^-、Cl^-、CH₃COO^-。

According to a second aspect of the present application, there is provided a process for the preparation of the above complex, the process comprising:

(1) reacting a mixture I containing indole, pyridine-2-formaldehyde and potassium bisulfate to obtain an intermediate product A1;

(2) reacting a mixture II containing the intermediate product A1, iodine and pyridine-2-formaldehyde to obtain an intermediate product A2;

(3) and reacting the mixture III containing the intermediate product A2 and the cupric salt to obtain the complex.

Optionally, the complex is prepared by the following method:

(1) indole, pyridine-2-carbaldehyde and potassium bisulfate were refluxed in methanol overnight. Cooling to room temperature, adding water to obtain a brown orange intermediate product A1;

(2) dissolving the intermediate product A1 obtained in the step (1) in 1, 2-dichlorobenzene, adding iodine and pyridine-2-formaldehyde, and carrying out reflux reaction to obtain an intermediate product A2;

(3) and (3) dissolving the intermediate product A2 obtained in the step (2) and a cupric salt in dimethylformamide, and reacting at room temperature to obtain the complex with the structure shown in the formula I.

Alternatively, the complex is prepared by adopting the following method:

(1) refluxing 4.0-8.0 g indole, 3.0-6.0 g pyridine-2-carbaldehyde and 4.0-10.0 g potassium bisulfate in 50mL methanol overnight. Cooling to room temperature, adding 80mL of water to obtain a brown-orange intermediate product A1;

(2) dissolving 1.0-4.0 g A1 of the intermediate product obtained in the step (1) in 20mL of 1, 2-dichlorobenzene, adding 0.02-0.5 g of iodine and 0.2-2.0 g of pyridine-2-formaldehyde, and carrying out reflux reaction for 6-14 hours to obtain an intermediate product A2;

(3) and (3) dissolving 2.0-4.0 g of the intermediate product A2 obtained in the step (2) and 0.0-2.0 g of cupric salt in dimethylformamide, and reacting at room temperature to obtain the complex with the structure shown in the formula I.

Specifically, the complex is prepared by the following method:

(1) 5.0g of indole, 4.57g of pyridine-2-carbaldehyde and 5.13g of potassium hydrogensulfate are refluxed overnight in 50mL of methanol. Cooling to room temperature, adding 80mL of water to obtain a brown-orange intermediate product A1; the preparation route is shown as a reaction formula II:

(2) dissolving the intermediate product 2.0g A1 obtained in the step (1) in 20mL of 1, 2-dichlorobenzene, adding 0.08g of iodine and 0.5g of pyridine-2-formaldehyde, and carrying out reflux reaction for 8 hours to obtain an intermediate product A2; the preparation route is shown as a reaction formula III:

(3) and (3) dissolving 3.0g of the intermediate product A2 obtained in the step (2) and 1.0g of cupric salt in dimethylformamide, and reacting at room temperature to obtain the complex with the structure shown in the formula I. The preparation route is shown as a reaction formula IV:

optionally, the conditions of reaction I are: methanol is used as a solvent, and the reaction temperature is 60-70 ℃; the reaction time is 20-48 hours;

the conditions of the reaction II are as follows: 1, 2-dichlorobenzene is used as a solvent, and the reaction temperature is 160-190 ℃; the reaction time is 4-10 hours;

the conditions of the reaction III are as follows: dimethyl formamide is used as a solvent, and the reaction temperature is 50-100 ℃; the reaction time is 2-8 hours.

Optionally, the cupric salt is selected from at least one of cupric chloride, cupric nitrate and cupric acetate.

Optionally, in the step (1), the mass ratio of the indole to the pyridine-2-formaldehyde to the potassium bisulfate is 4.0-8.0 g: 3.0-6.0 g: 4.0-10.0 g;

in the step (2), the mass ratio of the intermediate product A1 to iodine to pyridine-2-formaldehyde is 1.0-4.0 g: 0.02-0.5 g: 0.2-2.0 g;

in the step (3), the mass ratio of the intermediate product A2 to the cupric salt is 2.0-4.0 g: 0.0 to 2.0 g.

According to a third aspect of the present application, there is provided a quick-drying raw lacquer comprising a complex and a raw lacquer;

the complex is selected from at least one of the complexes and the complexes prepared by the method.

In the application, the complex with the structure as shown in formula I in the natural raw lacquer can improve the drying speed of the natural raw lacquer.

Optionally, in the quick-drying raw lacquer, the content of each component is as follows:

0.1-4 parts by weight of a complex;

96-99.9 parts of natural raw lacquer.

Optionally, in the quick-drying raw lacquer, the content of each component is as follows:

0.5-2 parts by weight of a complex;

98-99.5 parts of natural raw lacquer.

In the quick-drying natural raw lacquer, the upper limit of the content of the complex with the structure shown in the formula I is selected from 0.5 part by weight, 1 part by weight, 2 parts by weight and 4 parts by weight; the lower limit of the content of the complex with the structure shown in the formula I is selected from 0.1 part by weight, 0.5 part by weight, 1 part by weight and 2 parts by weight.

The upper limit of the content of the natural raw lacquer is selected from 98 parts by weight, 99 parts by weight, 99.5 parts by weight and 99.9 parts by weight; the lower limit of the content of the raw lacquer is selected from 96 parts by weight, 98 parts by weight, 99 parts by weight, 99.5 parts by weight.

Optionally, the natural raw lacquer is selected from at least one of Ankang lacquer, plain lacquer, city lacquer, Mao dam lacquer and Qinling lacquer.

According to a fourth aspect of the present application, there is provided a method of preparing the above quick-drying raw lacquer, the method comprising:

and mixing the complex with the natural raw lacquer to obtain the quick-drying natural raw lacquer.

According to a fifth aspect of the present application there is provided a quick-drying natural raw paint film comprising any one of the quick-drying natural raw paints according to any one of claims 6 to 9, the quick-drying natural raw paint prepared according to the method of claim 10.

Optionally, the thickness of the quick-drying natural raw paint film is 50-100 micrometers.

Optionally, the quick-drying natural raw paint film is prepared by the following method:

placing 0.1-4 parts by weight of the complex with the structure as shown in the formula I and 96-99.9 parts by weight of natural raw lacquer in a reactor, and stirring and mixing uniformly at room temperature; and (5) coating, and drying at normal temperature to obtain the quick-drying natural raw paint film.

Optionally, the upper limit of the film thickness of the quick-drying raw natural paint film is selected from 60 microns, 70 microns, 90 microns, 100 microns; the lower limit of the film thickness of the quick-drying raw natural paint film is selected from the group consisting of 50 microns, 60 microns, 70 microns, 90 microns.

As a preferred embodiment, the method for preparing the natural raw paint film described above comprises at least the following steps:

placing 0.5 part by weight of the complex with the structure as shown in the formula I and 99.5 parts by weight of the natural raw lacquer into a reactor, and stirring and mixing uniformly at normal temperature;

and (5) coating, and drying at normal temperature to obtain the quick-drying natural raw paint film.

According to a sixth aspect of the present application there is provided a method of preparing a quick-drying natural varnish film as described above, the method comprising: and coating the mixture containing the complex and the natural raw lacquer to obtain the quick-drying natural raw lacquer film.

Optionally, the method comprises: and (3) coating and drying a mixture containing 0.1-4 parts by weight of the complex and 96-99.9 parts by weight of the natural raw lacquer to obtain the quick-drying natural raw lacquer film.

The beneficial effects that this application can produce include:

1) according to the quick-drying natural raw lacquer, the complex with the structure shown in the formula I is introduced into the natural raw lacquer, so that the curing speed of the natural raw lacquer can be greatly increased;

2) the preparation method of the quick-drying raw lacquer is simple to operate and wide in raw material source; by introducing the complex with the structure shown as the formula I into the natural raw lacquer through the method, the curing speed of the natural raw lacquer can be greatly accelerated.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.

The analysis method in the examples of the present application is as follows:

NMR spectroscopy was performed using AVANCE III HD (Bruker-BioSpin).

The drying performance of the paint film is tested according to the method for measuring the drying time of the paint film and the putty film of GB 1728-1979.

Indole, pyridine-2-carbaldehyde, potassium bisulfate, methanol, 1, 2-dichlorobenzene, iodine, copper chloride, copper nitrate, and copper acetate were purchased from Shanghai Allantin Biotech Co., Ltd;

the natural raw lacquer is Mao-Ba lacquer, purchased from Delong raw lacquer science and technology Limited liability company of Lichuan city.

The film thickness of the obtained quick-drying natural raw paint film is 50-100 micrometers.

EXAMPLE 1 preparation of the Complex

(1) 5.0g of indole, 4.57g of pyridine-2-carbaldehyde and 5.13g of potassium hydrogensulfate are refluxed overnight in 50mL of methanol. Cooling to room temperature, adding 80mL of water to obtain a brown-orange intermediate product A1; the preparation route is shown as a reaction formula II:

nuclear magnetic data:¹H-NMR:(300MHz,DMSO-d₆)；δ(ppm):6.14(1H),6.89(2H),7.00-7.01(2H),7.06(2H),7.31(2H),7.37(2H),7.56-7.52(1H),7.65(1H),8.09-8.04(1H),8.64(1H),11.01(2H).

(2) dissolving the intermediate product 2.0g A1 obtained in the step (1) in 20mL of 1, 2-dichlorobenzene, adding 0.08g of iodine and 0.5g of pyridine-2-formaldehyde, and carrying out reflux reaction for 8 hours to obtain an intermediate product A2; the preparation route is shown as a reaction formula III:

nuclear magnetic data:¹H-NMR:(300MHz,DMSO-d₆)；δ(ppm):6.87(2H),7.16(2H),7.29(2H),7.48(2H),7.65-7.61(2H),7.90(2H),8.09-8.19(2H),8.96-9.00(2H),10.71(2H)。

(3) dissolving 3.0g of the intermediate product A2 obtained in the step (2) and 1.0g of cupric salt in dimethylformamide, and reacting at room temperature to obtain the complex with the structure shown in the formula I, wherein the value of n is 15. The preparation route is shown as a reaction formula IV:

EXAMPLE 2 preparation of quick-drying Natural varnish film D1

Adding 0.1 g of the complex prepared in the example 1 into 99.9 g of the natural raw lacquer, placing the mixture into a reactor, and stirring and mixing the mixture evenly at normal temperature;

and (3) coating, wherein the thickness of the coating is 100 microns, and placing the coating in a constant temperature box with the temperature of 30 ℃ and the humidity of 80% to obtain a quick-drying natural raw paint film which is marked as D1.

EXAMPLE 3 preparation of quick-drying Natural varnish film D2

Adding 1 g of the complex prepared in the example 2 into 99 g of the natural raw lacquer, placing the mixture into a reactor, and stirring and mixing the mixture evenly at normal temperature;

and (3) coating, wherein the thickness of the coating is 70 microns, and placing the coating in a constant temperature box with the temperature of 30 ℃ and the humidity of 80% to obtain a quick-drying natural raw paint film which is marked as D2.

EXAMPLE 4 preparation of quick-drying Natural varnish film D3

2 g of the complex prepared in the example 1 is added with 98 g of natural raw lacquer and placed in a reactor, and the mixture is stirred and mixed evenly at normal temperature;

and (3) coating, wherein the thickness of the coating is 60 microns, and placing the coating in a constant temperature box with the temperature of 30 ℃ and the humidity of 80% to obtain a quick-drying natural raw paint film which is marked as D3.

EXAMPLE 5 preparation of quick-drying Natural varnish film D4

Adding 4 g of the complex prepared in the example 2 into 96 g of natural raw lacquer, placing the mixture into a reactor, and stirring and mixing the mixture evenly at normal temperature;

and (3) coating, wherein the thickness of the coating is 90 microns, and placing the coating in a constant temperature box with the temperature of 30 ℃ and the humidity of 80% to obtain a quick-drying natural raw paint film which is marked as D4.

Comparative example 1 preparation of a Natural raw lacquer film D0

The natural raw lacquer is directly coated with a film with the thickness of 50 microns, and is placed in a constant temperature oven with the temperature of 30 ℃ and the humidity of 80 percent to obtain a natural raw lacquer film which is marked as D0.

Comparing the drying properties of the quick-drying natural lacquer films D1-D4 with that of the comparative example D0, it can be seen that the drying speed of the lacquer film containing the complex is significantly increased.

Example 6 Performance testing

The drying time of the paint film was tested according to the determination method of GB1728-1979 paint film and putty film drying time. The results are shown in Table 1.

TABLE 1

Sample numbering	Surface drying time/minute	Actual drying time/hour
			D0	180	12
D1	150	9
			D2	100	6
D3	60	3
			D4	50	1.5

As can be seen from Table 1, the quick-drying natural lacquer films D1-D4 produced have a shorter drying time.

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.