A pyridine derivative, a method for preparing the same and use thereof

Abstract

The application belongs to the technical field of organic synthesis, and relates to a pyridine derivative, a preparation method thereof and application of the pyridine derivative in improving directional arrangement of silver powder of water-based silver powder paint. The structure of the pyridine derivative is as follows: the pyridine derivative has small molecular weight, the relative molecular mass is only about 500-700, the synthesis process is simple, and the synthesis time is reduced. On the basis of the pyridine derivative, the pyridine derivative can be combined with any monomer freely, the proportion of the monomer can be adjusted freely to the maximum extent, and only the pyridine derivative needs to account for more than 10% of the mass of the monomer, so that the requirement of water-based polyester for directional arrangement of silver powder can be met.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic synthesis, and relates to a pyridine derivative, a preparation method thereof and application of the pyridine derivative in improving directional arrangement of silver powder in water-based silver powder paint. BACKGROUND

[0002] The directional arrangement of water-based silver powder is a big problem faced by the global industry. Silver powder flash paint has special decorative effects, and its application is becoming more and more widespread. It not only plays an important role in the color of automobile paint, but also can be used for machine tools, television housings, VCD housings, mobile phone housings, and even wall decorations. Due to its flaky structure, the arrangement of silver powder in paint is problematic. If the arrangement of silver powder is not well controlled, the color will not meet the requirements, it is not easy to work, and it is easy to do flowers, which will ultimately affect the decorative effect. Therefore, how to control the arrangement of silver powder and avoid mottling is a problem that every formula designer and builder must solve, and the traditional silver powder directional additive is expensive, which limits the use of formula designers. Therefore, it is of great significance to explore green new silver powder directional paint.

[0003] The prior art CN 107760173 A discloses a water-based baking paint with directional arrangement effect and a preparation method thereof. The components include water-based acrylic dispersion 5-10%; water-based polyester dispersion 30-40%; water-based amino resin 5-15%; neutralizing agent 0-3%; water-based silver powder 5-15%; cosolvent 5-10%; pure water 10-25%; modified wax emulsion 1-5%; water-based color paste 0-10%; anti-settling agent 1-3%; and auxiliary agent 0.1-1%. In order to meet the silver powder arrangement effect, a water-based polyester dispersion with a molecular weight greater than 10000 is used, and a water-based acrylic dispersion with a large molecular weight and a modified wax emulsion are also added. The effective positioning of silver powder or pearl powder is realized by relying on the molecular structure of the large molecular weight to achieve rapid drying on the surface.

[0004] The prior art CN 117164727 A discloses a water-based high molecular polyether ester polymer, a water-based high directional pearl silver powder topcoat material and a preparation method thereof; the water-based high directional pearl silver powder topcoat material further includes water-based polyester resin 15-20 parts; water-based pigment and filler paste 20-30 parts; water-based silver powder 5-7 parts; leveling agent 0.10.5 parts; water-based amino resin 8-12 parts; 20-30 parts of deionized water; and the addition amount of the water-based high molecular polyether ester polymer is 7-10 parts. The polyester resin in the present application has excellent mechanical properties, water resistance, stability and weather resistance, and good compatibility with auxiliary agents; the water-based silver powder used in the present application not only has high hiding power and coloring power, but also can form a dense protective layer on the surface of the metal, which covers the surface of the metal and plays a protective role for the substrate

[0005] But the prior art has the common defects: first, the synthesis of the high molecular weight water-based polyester or polyether ester is difficult, and the viscosity of the high molecular weight water-based polyester or polyether ester is extremely large, and the dispersion difficulty will also be multiplied, and it is easy to disperse unevenly. Secondly, it is necessary to add high molecular weight polymers such as water-based acrylic dispersion and modified wax emulsion or water-based amino resin to help the silver powder orientation, and there is a clear compatibility problem between these polymers. It is difficult to adjust these polymers to perfectly blend. SUMMARY

[0006] The purpose of the present application is to provide a pyridine derivative with small molecular weight, a preparation method thereof, and an application thereof in improving the silver powder orientation arrangement of water-based silver powder paint.

[0007] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0008] A pyridine derivative has the following structure:

[0009]

[0010] Based on the same inventive concept, the present application claims a preparation method of the pyridine derivative, comprising the following steps:

[0011] The pyridine dicarboxylic acid, the benzene derivative and the diacid are mixed according to a molar ratio of 1:1.5-2.5:1.5-2.5, a catalyst is added, and stirring is carried out under an inert gas atmosphere at 120-160℃ for 20-40min; then the temperature is raised to 170-200℃, after the reaction is completed, cooling and separation are carried out, and the pyridine derivative is obtained; the diacid is one or several of 2-carbonyl butanedioic acid, 2-methoxy-2-alkenyl butanedioic acid and 2-ethoxy-2-alkenyl butanedioic acid.

[0012] The benzene derivative is one or several of p-benzenediol, m-benzenediol, p-phenylenediamine and m-phenylenediamine.

[0013] The purity of the product obtained after the pyridine dicarboxylic acid, the benzene derivative and the diacid are reacted according to a molar ratio of 1:1.5-2.5:1.5-2.5 is good, and the yield is high; too large or too small molar ratio of any raw material will affect the effect of obtaining the target product.

[0014] In one preferred embodiment, the pyridine dicarboxylic acid is one or both of pyridine-2,6-dicarboxylic acid and pyridine-2,5-dicarboxylic acid.

[0015] In one preferred embodiment, the reaction completion refers to stopping the reaction after the acid value reaches the theoretical index.

[0016] In one preferred embodiment, the catalyst is one or more of monobutyl tin oxide, dibutyl tin oxide, and butyl tin acid.

[0017] In one preferred embodiment, the catalyst is added in an amount of 0.01%-0.5% of the total mass of the reaction material.

[0018] In one preferred embodiment, the inert gas is nitrogen or argon.

[0019] In one preferred embodiment, the temperature is raised to 170-200°C at a rate of 1-2°C / min. Too fast or too slow a rate of temperature increase will result in side reactions, such as decarboxylation and etherification.

[0020] Based on the same inventive concept, the present application claims the use of the pyridine derivative in improving the directional arrangement of silver powder in water-based silver powder paint.

[0021] A water-based polyester resin, the raw materials of which include the pyridine derivative, polyhydric alcohol, polybasic acid, and dihydroxy alkyl acid, the molar ratio of the pyridine derivative, polyhydric alcohol, polybasic acid, and dihydroxy alkyl acid being 1:1:2-3:1.

[0022] In one preferred embodiment, the dihydroxy alkyl acid is dimethylol propanoic acid or dimethylol butanoic acid.

[0023] In one preferred embodiment, the polyhydric alcohol is dihydric alcohol or trihydric alcohol.

[0024] In one preferred embodiment, the dihydric alcohol is one or more of ethylene glycol, hexanediol, and neopentyl glycol.

[0025] In one preferred embodiment, the dihydric alcohol is trimethylol propane.

[0026] In one preferred embodiment, the polybasic acid is dihydric acid or trihydric acid.

[0027] In one preferred embodiment, the dihydric acid is one or both of hexahydrophthalic anhydride and adipic acid.

[0028] In one preferred embodiment, the trihydric acid is trimellitic anhydride.

[0029] Based on the same inventive concept, the present application claims the preparation method of the water-based polyester resin, comprising the following steps: mixing the pyridine derivative, polyhydric alcohol, polybasic acid and dihydroxy alkyl acid, then adding the second catalyst, stirring under the inert gas atmosphere at 120-160℃ for 20-40min; then heating to 170-200℃, stopping the reaction after the reaction is completed, adding the neutralizing agent and water, and dispersing to obtain the water-based polyester resin.

[0030] The reaction completion is judged by reaching the theoretical water output and acid value level.

[0031] In one preferred embodiment, the second catalyst is one or more of monobutyl tin oxide, dibutyl tin oxide and butyl tin acid.

[0032] In one preferred embodiment, the catalyst is added in an amount of 0.01-0.5% of the total mass of the reaction material.

[0033] In one preferred embodiment, the inert gas is nitrogen or argon.

[0034] In one preferred embodiment, the heating rate to 170-200℃ is 1-2℃ / min. The suitable heating rate can effectively reduce the occurrence of side reactions and improve the application performance of the resin.

[0035] In one preferred embodiment, the neutralizing agent is one or more of N,N-dimethylethanolamine, triethylamine and ethylenediamine, preferably N,N-dimethylethanolamine. N,N-dimethylethanolamine has a relatively high boiling point and is safer.

[0036] In one preferred embodiment, the amount of the neutralizing agent added is the same as the molar amount of the dihydroxy alkyl acid.

[0037] In one preferred embodiment, the solid content of the water-based polyester resin is 10%-50%. Based on the same inventive concept, the present application claims the application of the water-based polyester resin in improving the directional arrangement of the silver powder in the water-based silver powder coating.

[0038] A water-based silver powder baking paint comprising the water-based polyester resin as described above.

[0039] In one preferred embodiment, the water-based silver powder baking paint comprises the following components by weight parts: 30-50 parts of the water-based polyester resin, 6-15 parts of amino resin, 5-15 parts of silver powder, 5-10 parts of precipitated barium sulfate, 5-7 parts of film-forming agent, 0.2-0.5 parts of wetting dispersant, 0.2-0.5 parts of leveling agent, 0.2-0.5 parts of thickening agent, 2-3 parts of neutralizing agent, 5-10 parts of deionized water and 0.3-0.67 parts of defoaming agent.

[0040] Add the materials into the paint mixing tank according to the formula, disperse at high speed for 30-60 minutes, adjust the viscosity, and you will get the water-based silver powder baking paint.

[0041] The water-based silver powder baking varnish prepared by the present invention has the following advantages:

[0042] 1. Excellent arrangement of silver powder

[0043] Benefiting from the large conjugated system of the pyridine derivative and the high electron cloud density brought about by the ADA effect, the water-based polyester resin containing the pyridine derivative has a very strong adsorption and fixation effect on positively charged metal powders such as silver powder. Silver powder has a flaky structure. The orderly arrangement of the silver powder can bring extremely high gloss and reflectivity, resulting in a bright and beautiful product appearance. Disordered silver powder arrangement will diffusely reflect light, resulting in a dull and matte coating surface. As the coating dries, the flaky silver powder tends to move around. The pyridine derivative can suppress this movement through electrostatic adsorption, thus achieving excellent silver powder arrangement.

[0044] 2. Good water and solvent resistance

[0045] The large conjugated structure within the pyridine derivatives results in average bond lengths and bond potentials within the molecule, making them less susceptible to breakage. This makes it more difficult for hydration to attack the fragile ester bonds within the molecule. Furthermore, the swelling effect of organic solvents on the molecule is suppressed by the electron cloud enriched on the molecule's surface.

[0046] 3. High stability

[0047] The shelf life of water-based coatings generally does not exceed 3 months because water is more polar than organic solvents and is more likely to corrode the resin, and the esterification reaction is a reversible reaction. Long-term exposure to excess water will cause the ester group to become unstable. Water-based polyesters are made using a dispersion method. The resin curls up into small micelles in water, with the water-soluble groups exposed to the outside and the fat-soluble groups wrapped inside the micelles. This is also called a double-layer structure. The higher the zeta potential of the double layer, the more stable the micelles are, and the less likely they are to aggregate and break the emulsion. The higher the zeta potential of the double layer, the more difficult it is for water molecules to approach the micelles, the more stable the ester groups are, and the less likely they are to hydrolyze. The pyridine derivatives can provide a large amount of charge to the double layer structure, which can make the micelle surface carry a large amount of charge, increase the zeta potential of the micelle surface, inhibit the aggregation and hydrolysis of the latex particles, and improve stability.

[0048] Therefore, compared with the prior art, the advantages of the present invention are:

[0049] 1. The pyridine derivative has a small molecular weight, with a relative molecular mass of only about 500-700, which greatly reduces the difficulty of synthesis and reduces the synthesis time.

[0050] 2. No additional water-based acrylic ester dispersion and wax emulsion needs to be added, and no compatibility problem needs to be considered.

[0051] 3. On the basis of the pyridine derivative, any monomer can be combined freely, and the monomer ratio can be adjusted freely to the maximum extent. Only the pyridine derivative accounts for more than 10% of the mass of the monomer, the water-based polyester can meet the requirements of silver powder directional arrangement, and the water resistance, organic reagent resistance and acid and alkali corrosion resistance of the resin can be significantly improved.

[0052] 4. The present application utilizes electrostatic adsorption and chelation, and compared with the existing technology of simple surface rapid drying means, the stability realized by the technical means is better. BRIEF DESCRIPTION OF DRAWINGS

[0053] Figure 1 is a synthesis diagram of the pyridine derivative;

[0054] Figure 2 is a diagram of the pyridine derivative realizing complete conjugation of the whole molecule through enol tautomerism;

[0055] Figure 3 is a nuclear magnetic resonance spectrum of intermediate 1;

[0056] Figure 4 is a nuclear magnetic resonance spectrum of intermediate 2;

[0057] Figure 5 is a nuclear magnetic resonance spectrum of intermediate 3;

[0058] Figure 6 is a nuclear magnetic resonance spectrum of intermediate 4;

[0059] Figure 7 is a nuclear magnetic resonance spectrum of intermediate 5;

[0060] Figure 8 is a nuclear magnetic resonance spectrum of intermediate 6;

[0061] Figure 9 is a nuclear magnetic resonance spectrum of intermediate 7;

[0062] Figure 10 is a nuclear magnetic resonance spectrum of intermediate 8;

[0063] Figure 11 is a nuclear magnetic resonance spectrum of intermediate 9;

[0064] Figure 12 is a nuclear magnetic resonance spectrum of intermediate 10;

[0065] Figure 13 is the NMR spectrum of intermediate 11;

[0066] Figure 14 is the NMR spectrum of intermediate 12;

[0067] Figure 15 is the NMR spectrum of intermediate 13;

[0068] Figure 16 is the NMR spectrum of intermediate 14. DETAILED DESCRIPTION

[0069] The present invention is not limited to the following specific embodiments. Based on the disclosure of the present invention, a person skilled in the art may adopt a variety of other specific embodiments to implement the present invention. Any simple changes or modifications made to the design structure and concept of the present invention fall within the scope of protection of the present invention. It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other unless they conflict.

[0070] Example 1

[0071] Synthesis of intermediates

[0072] 1. Synthesis of intermediate 1:

[0073] according to Figure 1 As shown in the synthesis diagram, 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of hydroquinone, and 2 mol of 2-carbonylsuccinic acid were weighed and put into the reactor. 0.3% of the mass of the reaction materials was added as a catalyst of monobutyltin oxide. Nitrogen was introduced for protection. Stirring was started and the temperature was raised to 140°C and kept warm for 30 minutes. Then the temperature was raised to 180°C at a rate of 1°C / min and kept warm for 3 hours. The reaction end point was determined by measuring the quality of the reaction water and the acid value. The acid value should drop to 194 mgKOH / g. Intermediate 1 was synthesized and analyzed. The structure is as follows:

[0074]

[0075] The chemical formula is: C 27 H 17 NO 14 ;

[0076] Exact mass: 579.1;

[0077] Molecular weight: 579.4;

[0078] m / z:579.1(100.0%),580.1(30.3%),581.1(7.3%),582.1(1.3%)

[0079] Elemental analysis: C, 55.97; H, 2.96; N, 2.42; O, 38.66.

[0080] Figure 3 is the NMR spectrum of intermediate 1.

[0081] like Figure 2 As shown, the pyridine derivative (intermediate 1) is characterized in that complete conjugation of the entire molecule can be achieved through enol interconversion, which greatly increases the electron cloud density of the intermediate. The pyridine ring on pyridine-2,6-dicarboxylic acid is enriched with a large number of electron clouds, which acts as an electron donor (Electron donor / ED) in this system. 2-Carbonylsuccinic acid is also enriched with a large number of electron clouds after enol interconversion, and the electron cloud density is slightly weaker, which acts as an electron cloud acceptor (Electron acceptor / EA) in this system. Because of the conjugated relationship, the pyridine-2,6-dicarboxylic acid group and 2-carbonylsuccinic acid form a pair of electron donor-acceptor complexes (EDA) under the matchmaking of hydroquinone. This system can greatly improve the electron transfer efficiency within the molecule and significantly increase the electron cloud density of both ED and EA. Benefiting from the increase in electron cloud density, the pyridine derivative has a strong adsorption and fixation effect on particles with positive charges on the surface, such as metal powders.

[0082] 2. Synthesis of Comparative Example Intermediate 2

[0083] The amount of hydroquinone added is half of the theoretical value

[0084] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 1 mol of hydroquinone, and 1 mol of 2-carbonylsuccinic acid into a reactor, add 0.3% of the mass of the reaction materials as a catalyst, introduce nitrogen protection, start stirring, and heat to 140°C and keep warm for 30 minutes. Then, heat to 180°C at a rate of 1°C / min and keep warm for 3 hours. The reaction endpoint is determined by measuring the quality of the reaction water and the acid value. The acid value should drop to 301 mgKOH / g. Intermediate 2 is synthesized and analyzed. The structure is as follows:

[0085]

[0086] The chemical formula is: C 17 H 11 NO9

[0087] Exact mass: 373.0

[0088] Molecular weight: 373.3

[0089] m / z: 373.0 (100.0%), 374.0 (19.2%), 375.0 (1.9%), 375.1 (1.7%)

[0090] Elemental analysis: C, 54.70; H, 2.97; N, 3.75; O, 38.58

[0091] Figure 4 NMR spectrum of intermediate 2.

[0092] 3. Synthesis of intermediate 3 of the comparative example:

[0093] Substitution of phthalic acid for pyridine-2,6-dicarboxylic acid

[0094] 1 mol of isophthalic acid, 2 mol of hydroquinone, and 2 mol of 2-carboxybutanedioic acid were weighed into a reaction kettle, 0.3% of monobutyl tin oxide based on the mass of the reaction material was added as a catalyst, nitrogen was introduced for protection, stirring was started, and the temperature was raised to 140°C for 30 min. Then the temperature was raised to 180°C at a rate of 1°C / min, and the reaction was maintained for 3 h. The reaction endpoint was determined by measuring the mass of water produced and the acid value, which should be reduced to 194 mgKOH / g. Intermediate 3 was synthesized and analyzed, and the structure is as follows:

[0095]

[0096] Chemical formula: C 28 H 18 O 14

[0097] Exact mass: 578.1

[0098] Molecular weight: 578.4

[0099] m / z: 578.1 (100.0%), 579.1 (31.0%), 580.1 (7.5%), 581.1 (1.3%)

[0100] Elemental analysis: C, 58.14; H, 3.14; O, 38.72

[0101] Figure 5 NMR spectrum of intermediate 3.

[0102] 4. Synthesis of intermediate 4 of the comparative example:

[0103] The addition of hydroquinone is half of that of intermediate 3 of the comparative example

[0104] Weigh 1 mol of isophthalic acid, 1 mol of hydroquinone, and 1 mol of 2-carbonylsuccinic acid into a reactor. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, heat to 180°C at a rate of 1°C / min and keep the reaction for 3 hours. The reaction endpoint is determined by measuring the quality of the reaction water and the acid value; the acid value should drop to 302 mgKOH / g. Intermediate 4 is synthesized and analyzed, and the structure is as follows:

[0105]

[0106] The chemical formula is: C 18 H 12 O9

[0107] Exact mass: 372.0

[0108] Molecular weight: 372.3

[0109] m / z:372.0(100.0%),373.1(19.9%),374.1(3.7%)

[0110] Elemental analysis: C, 58.07; H, 3.25; O, 38.68.

[0111] Figure 6 is the NMR spectrum of intermediate 4.

[0112] 5. Synthesis of Comparative Example Intermediate 5:

[0113] Substituting 1,4-butanedioic acid for 2-oxosuccinic acid

[0114] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of hydroquinone, and 2 mol of 1,4-butanedioic acid into a reactor, add 0.3% of the mass of the reaction materials as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, heat to 180°C at a rate of 1°C / min and keep the reaction for 3 hours. The reaction endpoint is determined by measuring the quality of the reaction water and the acid value. The acid value should drop to 204 mgKOH / g. Intermediate 5 is synthesized and analyzed, and the structure is as follows:

[0115]

[0116] The chemical formula is: C 27 H 21 NO 12

[0117] Exact mass: 551.1

[0118] Molecular weight: 551.5

[0119] m / z:551.1(100.0%),552.1(30.3%),553.1(6.9%),554.1(1.2%)

[0120] Elemental analysis: C, 58.81; H, 3.84; N, 2.54; O, 34.81

[0121] Figure 7 is the NMR spectrum of intermediate 5.

[0122] 6. Synthesis of Comparative Example Intermediate 6

[0123] The amount of hydroquinone added is half of that of the comparative example intermediate 5

[0124] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 1 mol of hydroquinone, and 1 mol of 1,4-butanedioic acid into a reactor, add 0.3% of the mass of the reaction materials as a catalyst, pass nitrogen protection, start stirring, and heat to 140°C and keep warm for 30 minutes. Then increase the temperature to 180°C at a rate of 1°C / min and keep the reaction for 3 hours. The reaction endpoint is determined by measuring the quality of the reaction water and the acid value. The acid value should drop to 313 mgKOH / g. Intermediate 6 is synthesized and analyzed. The structure is as follows:

[0125]

[0126] The chemical formula is: C 17 H 13 NO8

[0127] Exact mass: 359.1

[0128] Molecular weight: 359.3

[0129] m / z:359.1(100.0%),360.1(19.2%),361.1(3.4%)

[0130] Elemental analysis: C, 56.83; H, 3.65; N, 3.90; O, 35.62

[0131] Figure 8 is the NMR spectrum of intermediate 6.

[0132] 7. Synthesis of Comparative Example Intermediate 7

[0133] Replace 2-oxosuccinic acid with 1,4-succinic acid

[0134] Take 1 mol of isophthalic acid, 2 mol of hydroquinone, 2 mol of 1,4-butanedioic acid into the reaction kettle, add 0.3% of the mass of monobutyl tin oxide as catalyst, protect by nitrogen, start stirring, and heat to 140°C for 30 min. Then heat to 180°C at a rate of 1°C / min, and keep for 3 h. Determine the reaction endpoint by measuring the water mass and acid value, and the acid value should be reduced to 204 mgKOH / g. Synthesize intermediate 7, analyze its structure as follows:

[0135]

[0136] Chemical formula: C 28 H 22 O 12

[0137] Exact mass: 550.1

[0138] Molecular weight: 550.5

[0139] m / z: 550.1 (100.0%), 551.1 (31.0%), 552.1 (7.1%), 553.1 (1.2%)

[0140] Elemental analysis: C, 61.09; H, 4.03; O, 34.88

[0141] Figure 9 The nuclear magnetic resonance spectrum of intermediate 7.

[0142] 8, Synthesis of intermediate 8 in the comparative example:

[0143] The addition of hydroquinone is half of intermediate 7 in the comparative example

[0144] Take 1 mol of isophthalic acid, 1 mol of hydroquinone, and 1 mol of 1,4-butanedioic acid into the reaction kettle, add 0.3% of the mass of monobutyl tin oxide as catalyst, protect by nitrogen, start stirring, and heat to 140°C for 30 min. Then heat to 180°C at a rate of 1°C / min, and keep for 3 h. Determine the reaction endpoint by measuring the water mass and acid value, and the acid value should be reduced to 313 mgKOH / g. Synthesize intermediate 8, analyze its structure as follows:

[0145]

[0146] Chemical formula: C 18 H 14 O8

[0147] Exact mass: 358.1

[0148] Molecular weight: 358.3

[0149] m / z:358.1(100.0%),359.1(19.9%),360.1(3.5%)

[0150] Elemental analysis: C, 60.34; H, 3.94; O, 35.72.

[0151] Figure 10 is the NMR spectrum of intermediate 8.

[0152] 9. Synthesis of Intermediate 9

[0153] Pyridine-2,5-dicarboxylic acid replaces pyridine-2,6-dicarboxylic acid

[0154] Weigh 1 mol of pyridine-2,5-dicarboxylic acid, 2 mol of hydroquinone, and 2 mol of 2-carbonylsuccinic acid into a reactor, add 0.3% of the mass of the reaction materials as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, heat to 180°C at a rate of 1°C / min and keep the reaction for 3 hours. The reaction endpoint is determined by measuring the quality of the reaction water and the acid value. The acid value should drop to 194 mgKOH / g. Intermediate 9 was synthesized and analyzed, and the structure is as follows:

[0155]

[0156] The chemical formula is: C 27 H 17 NO 14

[0157] Exact mass: 579.1

[0158] Molecular weight: 579.4

[0159] m / z:579.1(100.0%),580.1(30.3%),581.1(7.3%),582.1(1.3%)

[0160] Elemental analysis: C, 55.97; H, 2.96; N, 2.42; O, 38.66.

[0161] Figure 11 is the NMR spectrum of intermediate 9.

[0162] 10. Synthesis of Intermediate 10

[0163] Replacing hydroquinone with resorcinol

[0164] Take 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of resorcinol, and 2 mol of 2-carbonyl succinic acid into the reaction kettle, add 0.3% of monobutyl tin oxide as a catalyst, protect with nitrogen, start stirring, and heat to 140°C for 30 min. Then heat to 180°C at a rate of 1°C / min, and keep the temperature for 3 h. Determine the reaction endpoint by measuring the water produced and the acid value, which should be reduced to 194 mgKOH / g. Synthesize intermediate 10, analyze its structure, as follows:

[0165]

[0166] Chemical formula: C 27 H 17 NO 14

[0167] Exact mass: 579.1

[0168] Molecular weight: 579.4

[0169] m / z: 579.1 (100.0%), 580.1 (30.3%), 581.1 (7.3%), 582.1 (1.3%)

[0170] Elemental analysis: C, 55.97; H, 2.96; N, 2.42; O, 38.66;

[0171] Figure 12 NMR spectrum of intermediate 10.

[0172] 11. Synthesis of intermediate 11

[0173] Replace resorcinol with p-phenylenediamine

[0174] Take 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of p-phenylenediamine, and 2 mol of 2-carbonyl succinic acid into the reaction kettle, add 0.3% of monobutyl tin oxide as a catalyst, protect with nitrogen, start stirring, and heat to 140°C for 30 min. Then heat to 180°C at a rate of 1°C / min, and keep the temperature for 3 h. Determine the reaction endpoint by measuring the water produced and the acid value, which should be reduced to 195 mgKOH / g. Synthesize intermediate 11, analyze its structure, as follows:

[0175]

[0176] Chemical formula: C 27 H 21 N5O 10

[0177] Exact mass: 575.1

[0178] Molecular Weight: 575.5

[0179] m / z: 575.1 (100.0%), 576.1 (31.7%), 577.1 (6.9%), 578.1 (1.1%)

[0180] Elemental Analysis: C, 56.35; H, 3.68; N, 12.17; O, 27.80;

[0181] Figure 13 NMR Spectrum of Intermediate 11

[0182] 12. Synthesis of Intermediate 12

[0183] Replacing hydroquinone with m-phenylenediamine

[0184] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of m-phenylenediamine, and 2 mol of 2-carboxybutanedioic acid into a reaction kettle, add 0.3% of monobutyl tin oxide by mass of the reaction material as a catalyst, protect with nitrogen, start stirring, and heat to 140°C for 30 min. Then heat to 180°C at a rate of 1°C / min, and heat for 3 h. Determine the reaction endpoint by measuring the reaction water mass and acid value, and the acid value should be reduced to 195 mgKOH / g. Synthesize intermediate 12, and analyze its structure as follows:

[0185]

[0186] Chemical formula: C 27 H 21 N5O 10

[0187] Exact mass: 575.1

[0188] Molecular Weight: 575.5

[0189] m / z: 575.1 (100.0%), 576.1 (31.7%), 577.1 (6.9%), 578.1 (1.1%)

[0190] Elemental Analysis: C, 56.35; H, 3.68; N, 12.17; O, 27.80

[0191] Figure 14 NMR Spectrum of Intermediate 12

[0192] Replacing 2-carboxybutanedioic acid with 2-methoxy-2-ene-butanedioic acid

[0193] 13. Synthesis of Intermediate 13

[0194] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of m-phenylenediamine, and 2 mol of 2-methoxy-2-ene-butanedioic acid into a reactor, add 0.3% of the mass of the reaction materials as a catalyst, pass nitrogen protection, start stirring, and heat to 140°C and keep warm for 30 minutes. Then, heat to 180°C at a rate of 1°C / min and keep the reaction for 3 hours. The reaction endpoint is determined by measuring the quality of the reaction water and the acid value. The acid value should drop to 184 mgKOH / g. Intermediate 13 is synthesized and analyzed. The structure is as follows:

[0195]

[0196] The chemical formula is: C 29 H 21 NO 14

[0197] Exact mass: 607.1

[0198] Molecular weight: 607.5

[0199] m / z: 607.1 (100.0%), 608.1 (32.5%), 609.1 (8.0%), 610.1 (1.5%)

[0200] Elemental analysis: C, 57.34; H, 3.48; N, 2.31; O, 36.87

[0201] Figure 15 is the NMR spectrum of intermediate 13.

[0202] 14. Synthesis of Intermediate 14

[0203] Replace 2-oxosuccinic acid with 2-ethoxy-2-ene-butanedioic acid

[0204] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of m-phenylenediamine, and 2 mol of 2-ethoxy-2-ene-butanedioic acid into a reactor, add 0.3% of the mass of the reaction materials as a catalyst, pass nitrogen protection, start stirring, and heat to 140°C and keep warm for 30 minutes. Then, heat to 180°C at a rate of 1°C / min and keep the reaction for 3 hours. The reaction endpoint is determined by measuring the quality of the reaction water and the acid value. The acid value should drop to 177 mgKOH / g. Intermediate 14 is synthesized and analyzed. The structure is as follows:

[0205]

[0206] The chemical formula is: C 31 H 25 NO 14

[0207] Exact mass: 635.1

[0208] Molecular weight: 635.5

[0209] m / z: 635.1 (100.0%), 636.1 (34.7%), 637.1 (8.7%), 638.1 (1.6%)

[0210] Elemental analysis: C, 58.59; H, 3.97; N, 2.20; O, 35.24

[0211] Figure 16 is the NMR spectrum of intermediate 14.

[0212] Example 2

[0213] (diol, dibasic acid)

[0214] 1. Weigh 1 mol of intermediate 1, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 56 mgKOH / g. This yields amphifunctional emulsified polyester 1 with a molecular weight of 995.

[0215] Place 2,500g of emulsified polyester 1 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 47g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain Product 1. Solids content: 40%, hydroxyl value: 113mgKOH / g.

[0216] Example 3

[0217] (Triol, dibasic acid)

[0218] 1. Weigh 1 mol of intermediate 1, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of trimethylolpropane into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst. Purge with nitrogen and start stirring. Raise the temperature to 140°C and hold for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and hold for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 53 mgKOH / g. A tetrafunctional emulsified polyester 2 with a molecular weight of 1055 is obtained.

[0219] Place 2,500g of emulsified polyester 2 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 44g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain Product 2. The solids content is 40%, and the hydroxyl value is 212mgKOH / g.

[0220] Example 4

[0221] (diol, tribasic acid)

[0222] 1. Weigh 1 mol of intermediate 1, 1 mol of dimethylolpropionic acid, 1 mol of trimellitic anhydride, and 3 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst. Purge with nitrogen and start stirring. Raise the temperature to 140°C and hold for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and hold for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 49 mgKOH / g. A trifunctional emulsified polyester 3 with a molecular weight of 1145 is obtained.

[0223] Place 2,500g of emulsified polyester 3 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 41g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain Product 3. The solids content is 40%, and the hydroxyl value is 147mgKOH / g.

[0224] Example 5

[0225] (Triol, triacid)

[0226] 1. Weigh 1 mol of intermediate 1, 1 mol of dimethylolpropionic acid, 1 mol of trimellitic anhydride, and 3 mol of trimethylolpropane into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 45 mgKOH / g. This yields hexafunctional emulsified polyester 4 with a molecular weight of 1235.

[0227] Place 2,500g of emulsified polyester 4 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 38g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 3. The solids content is 40%, and the hydroxyl value is 272mgKOH / g.

[0228] Comparative Example 6

[0229] 1. Weigh 1 mol of intermediate 2, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst. Purge with nitrogen and start stirring. Raise the temperature to 140°C and hold for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and hold for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 71 mgKOH / g. This yields amphifunctional emulsified polyester 5 with a molecular weight of 789.

[0230] Place 2,500g of emulsified polyester 5 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 60g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 5. Solids content: 40%, hydroxyl value: 142mgKOH / g.

[0231] Comparative Example 7

[0232] 1. Weigh 1 mol of intermediate 3, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 56 mgKOH / g. This yields amphifunctional emulsified polyester 6 with a molecular weight of 994.

[0233] Place 2,500g of emulsified polyester 6 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 47g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 6. The solids content is 40%, and the hydroxyl value is 113mgKOH / g.

[0234] Comparative Example 8

[0235] 1. Weigh 1 mol of intermediate 4, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 71 mgKOH / g. This yields amphifunctional emulsified polyester 7 with a molecular weight of 788.

[0236] Place 2,500g of emulsified polyester 7 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 60g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 7. Solids content: 40%, hydroxyl value: 142mgKOH / g.

[0237] Comparative Example 9

[0238] 1. Weigh 1 mol of intermediate 5, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 58 mgKOH / g. This yields amphifunctional emulsified polyester 8 with a molecular weight of 967.

[0239] Place 2,500g of emulsified polyester 8 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 49g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 8. The solids content is 40%, and the hydroxyl value is 116mgKOH / g.

[0240] Comparative Example 10

[0241] 1. Weigh 1 mol of intermediate 6, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 72 mgKOH / g. This yields amphifunctional emulsified polyester 9 with a molecular weight of 776.

[0242] Place 2,500g of the emulsified polyester 9 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 60g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 9. The solids content is 40%, and the hydroxyl value is 145mgKOH / g.

[0243] Comparative Example 11

[0244] 1. Weigh 1 mol of intermediate 7, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst. Purge with nitrogen and start stirring. Raise the temperature to 140°C and hold for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and hold for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 58 mgKOH / g. This yields an amphifunctional emulsified polyester 10 with a molecular weight of 966.

[0245] Place 2,500 g of the emulsified polyester 10 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 49 g of N,N-dimethylethanolamine for neutralization. Add 750 g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 10. Solids content: 40%, hydroxyl value: 116 mgKOH / g.

[0246] Comparative Example 12

[0247] 1. Weigh 1 mol of intermediate 8, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, initiate stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 72 mgKOH / g. This yields an amphifunctional emulsified polyester 11 with a molecular weight of 774.

[0248] Place 500g of emulsified polyester 11 in a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 60g of N,N-dimethylethanolamine for neutralization. Add 750g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 11. The solids content is 40% and the hydroxyl value is 145mgKOH / g.

[0249] Example 13

[0250] 1. Weigh 1 mol of intermediate 9, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst. Purge with nitrogen and start stirring. Raise the temperature to 140°C and hold for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and hold for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 56 mgKOH / g. This yields an amphifunctional emulsified polyester 12 with a molecular weight of 995.

[0251] 2.500g of the polyester to be emulsified 12 is put into a disperser, the temperature is adjusted to 40°C, the stirring device is turned on for sufficient stirring. At the same time, 47g of N,N-dimethyl ethanolamine is added for neutralization. 750g of water is weighed and added in three batches, and after 30min of continuous stirring, it is poured out and filtered to obtain product 12. Solid content 40%, hydroxyl value 113mgKOH / g.

[0252] Example 14

[0253] 1. 1 mol of intermediate 10, 1 mol of dimethylol propionic acid, 1 mol of adipic acid and 2 mol of neopentyl glycol are put into a reaction kettle, 0.3% of monobutyl tin oxide by mass of the reaction material is added as a catalyst, nitrogen is introduced for protection, stirring is turned on, and the temperature is raised to 140°C for 30min. Then it is raised to 180°C at a rate of 1°C / min, and the reaction is kept for 3h. When the water output reaches 72g, the reaction reaches the end point, and the acid value is measured to be 56mgKOH / g. A polyester to be emulsified 13 with a molecular weight of 995 is obtained.

[0254] 2. 500g of the polyester to be emulsified 13 is put into a disperser, the temperature is adjusted to 40°C, the stirring device is turned on for sufficient stirring. At the same time, 47g of N,N-dimethyl ethanolamine is added for neutralization. 750g of water is weighed and added in three batches, and after 30min of continuous stirring, it is poured out and filtered to obtain product 13. Solid content 40%, hydroxyl value 113mgKOH / g.

[0255] Example 15

[0256] 1. 1 mol of intermediate 11, 1 mol of dimethylol propionic acid, 1 mol of adipic acid and 2 mol of neopentyl glycol are put into a reaction kettle, 0.3% of monobutyl tin oxide by mass of the reaction material is added as a catalyst, nitrogen is introduced for protection, stirring is turned on, and the temperature is raised to 140°C for 30min. Then it is raised to 180°C at a rate of 1°C / min, and the reaction is kept for 3h. When the water output reaches 72g, the reaction reaches the end point, and the acid value is measured to be 56mgKOH / g. A polyester to be emulsified 14 with a molecular weight of 991 is obtained.

[0257] 2. 500g of the polyester to be emulsified 14 is put into a disperser, the temperature is adjusted to 40°C, the stirring device is turned on for sufficient stirring. At the same time, 47g of N,N-dimethyl ethanolamine is added for neutralization. 750g of water is weighed and added in three batches, and after 30min of continuous stirring, it is poured out and filtered to obtain product 14. Solid content 40%, hydroxyl value 113mgKOH / g.

[0258] Example 16

[0259] 1. Weigh 1 mol of intermediate 12, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 56 mgKOH / g. This yields an amphifunctional emulsified polyester 15 with a molecular weight of 991.

[0260] Place 2,500 g of the emulsified polyester 15 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 47 g of N,N-dimethylethanolamine for neutralization. Add 750 g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 15. The solids content is 40%, and the hydroxyl value is 113 mgKOH / g.

[0261] Example 17

[0262] 1. Weigh 1 mol of intermediate 13, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 55 mgKOH / g. This yields amphifunctional emulsified polyester 16 with a molecular weight of 1023.

[0263] Place 2,500 g of emulsified polyester 16 into a disperser, adjust the temperature to 40°C, and stir thoroughly. Simultaneously, add 47 g of N,N-dimethylethanolamine for neutralization. Add 750 g of water in three batches. Stir continuously for 30 minutes, then pour out and filter to obtain product 16. Solids content: 40%, hydroxyl value: 110 mgKOH / g.

[0264] Example 18

[0265] 1. Weigh 1 mol of intermediate 14, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid, and 2 mol of neopentyl glycol into a reaction kettle. Add 0.3% by weight of monobutyltin oxide as a catalyst, purge with nitrogen, start stirring, and heat to 140°C for 30 minutes. Then, increase the temperature to 180°C at a rate of 1°C / min and maintain the reaction for 3 hours. The reaction reaches endpoint when the water output reaches 72 g. The acid value is measured to be 55 mgKOH / g. This yields an amphifunctional emulsified polyester 17 with a molecular weight of 1023.

[0266] 2.500g of the polyester to be emulsified 17 was put into a disperser, the temperature was adjusted to 40°C, and the stirring device was turned on for sufficient stirring. At the same time, 47g of N,N-dimethyl ethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and after 30min of continuous stirring, it was poured out and filtered to obtain product 17. Solid content 40%, hydroxyl value 110mgKOH / g.

[0267] Example 19

[0268] Dicarboxymethyl butyric acid replaces dicarboxymethyl propionic acid

[0269] 3. 1mol of intermediate 1, 1mol of dimethylol butyric acid, 1mol of adipic acid and 2mol of neopentyl glycol were weighed into a reaction kettle, 0.3% of monobutyl tin oxide of the mass of the reaction material was added as a catalyst, nitrogen was introduced for protection, stirring was turned on, and the temperature was raised to 140°C for 30min. Then it was raised to 180°C at a rate of 1°C / min, and the reaction was kept for 3h. When the water output reached 72g, the reaction reached the end point, and the acid value was measured to be 55mgKOH / g. A polyester to be emulsified 18 with a molecular weight of 1009 was obtained.

[0270] 4. 500g of the polyester to be emulsified 18 was put into a disperser, the temperature was adjusted to 40°C, and the stirring device was turned on for sufficient stirring. At the same time, 47g of N,N-dimethyl ethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and after 30min of continuous stirring, it was poured out and filtered to obtain product 18. Solid content 40%, hydroxyl value 111mgKOH / g.

[0271] The above products 1-18 were formulated into water-based silver powder baking paint, with the following formula:

[0272] Water-based polyester resin (products 1-18) 40 parts; amino resin 10 parts; silver powder 10 parts; precipitated barium sulfate 5 parts; film forming agent 7 parts; wetting dispersant 0.4 parts; leveling agent 0.3 parts; thickening agent 0.2 parts; neutralizing agent 3 parts; deionized water 10 parts; defoaming agent 0.67 parts. Among them, the specific of raw materials are as follows:

[0273]

[0274]

[0275] The materials were added to a 1L paint mixing tank according to the formula amount, high-speed dispersion for 30min, and the thickening agent was added to adjust the viscosity, to obtain a water-based silver powder baking paint.

[0276] The performance of the 18 water-based silver powder baking paints configured was tested, and the results are shown below:

[0277] Table 1 Performance test results of water-based silver powder baking paint prepared in examples 1-4

[0278]

[0279]

[0280] Table 2 Performance test results of water-based silver powder paint prepared in comparative examples 5-11

[0281]

[0282]

[0283] Table 3 Performance test results of water-based silver powder paint prepared in Examples 12-18

[0284]

[0285]

[0286]

[0287] The test standards or test methods for each performance in the above table are as follows:

[0288]

[0289]

[0290] Examples 1-4 compare waterborne polyesters synthesized from Intermediate 1 with acids and alcohols of varying functionalities, demonstrating similar properties. This demonstrates that Intermediate 1 can be copolymerized with any polyol or acid, resulting in significant improvements in resin properties, including but not limited to silver powder alignment, water resistance, acid and alkali resistance, and organic solvent resistance.

[0291] In order to clarify the performance differences among Examples 1 to 11, we must first analyze the differences among intermediates 1 to 8. Intermediate 1, as a large conjugated structure, has an ADA electron enrichment effect (two electron acceptors and one electron donor), which greatly improves the electron cloud density of intermediate 1, which is beneficial to the electrostatic adsorption of silver powder. Intermediate 2 has a smaller conjugated structure, but has electron donors and electron acceptors, which can also increase the electron cloud density of intermediate 2. The conjugated structure of intermediate 3 is similar to that of intermediate 1, but there are no electron donors and electron acceptors, and the electron cloud density is lower than that of intermediate 1. Intermediate 4 has a smaller conjugated structure and has no electron donor, so the electron cloud density is lower. Intermediates 5 to 8 do not have a conjugated structure.

[0292] By comparing the product performance, it can be found that the products 8-11 without conjugated structure are far weaker than the products 1-4 in silver powder arrangement, water resistance and solvent resistance. The product performance is closely related to the conjugated effect and electron cloud density of the intermediate. The comparison between the product 5 and the product 1 proves the superiority of the ADA structure. The comparison between the product 6, the product 7 and the product 1 proves that the conjugated structure alone cannot obtain sufficient electron cloud density.

[0293] Examples 12-18 prove the feasibility of replacing the monomers within a certain range.

[0294] It should be noted that the above examples are merely examples for clearly illustrating the present application, and are not intended to limit the implementation manners of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, all the implementation manners cannot be exhausted. Any obvious changes or variations derived from the technical scheme of the present application are still within the protection scope of the present application.

Claims

1. A pyridine derivative, characterized in that Its structure is as follows:

2. The method for preparing a pyridine derivative according to claim 1, wherein The following steps are involved: After mixing pyridinedicarboxylic acid, a benzene derivative, and a diacid in a molar ratio of 1:1.5-2.5:1.5-2.5, a catalyst is added, and the mixture is stirred at 120-160°C under an inert gas atmosphere for 20-40 minutes; the mixture is then heated to 170-200°C. After the reaction is complete, the mixture is cooled and separated to obtain the pyridine derivative; the diacid is 2-carbonylsuccinic acid; The benzene derivative is hydroquinone; and the pyridinedicarboxylic acid is pyridine-2,6-dicarboxylic acid.

3. The preparation method according to claim 2, characterized in that The catalyst is one or more of monobutyltin oxide, dibutyltin oxide and butylstannoic acid; the added amount of the catalyst is 0.01%-0.5% of the total mass of the reaction materials.

4. The preparation method according to claim 2, characterized in that The heating rate to 170-200°C is 1-2°C / min.

5. Use of the pyridine derivative according to claim 1 in improving the directional arrangement of silver powder in water-based silver powder coatings.

6. A water-based polyester resin, characterized in that The raw materials include the pyridine derivative according to claim 1, polyol, polyacid and dihydroxyalkyl acid, and the molar ratio of the pyridine derivative, polyol, polyacid and dihydroxyalkyl acid is 1:1:2-3:

1.

7. The water-based polyester resin according to claim 6, characterized in that The dihydroxyalkyl acid is dimethylol propionic acid or dimethylol butyric acid; the polyol is diol or triol; and the polyacid is dibasic acid or tribasic acid.

8. The method for preparing the water-based polyester resin according to claim 6, wherein: The method comprises the following steps: mixing the pyridine derivative, polyol, polyacid and dihydroxyalkyl acid, adding a second catalyst, stirring at 120-160° C. in an inert gas atmosphere for 20-40 minutes; then heating to 170-200° C., stopping the reaction after the reaction is completed, adding a neutralizer and water, and dispersing to obtain the water-based polyester resin.

9. A water-based silver powder baking varnish, characterized in that: Comprising the water-based polyester resin according to claim 6.

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