Pyridine derivative as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and relates to a pyridine derivative, a preparation method thereof and an application of the pyridine derivative in improving directional alignment of silver powder of a water-based silver powder coating. The structure of the pyridine derivative is as follows: # imgabs0 #. The molecular weight of the pyridine derivative is small, the relative molecular mass is only about 500-700, the synthesis process is simple, and the synthesis time is shortened. On the basis of the pyridine derivative, the pyridine derivative can be freely combined with any monomer, the proportion of the monomer can be freely adjusted to the maximum extent, and the requirement of the water-based polyester for directional arrangement of the silver powder can be met only by ensuring that the pyridine derivative accounts for 10% or above of the mass of the monomer.

Description

Technical Field

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

[0002] The directional arrangement of water-based silver powder is a major problem facing the global industry. Silver powder flash paint has a special decorative effect and its application is becoming more and more extensive. It not only plays an important role in the color of automotive paint, but can also be used for machine tools, TV shells, VCD shells, mobile phone shells, and even wall decoration. Due to its flaky structure, there are problems with the arrangement of silver powder in the paint. If the arrangement of silver powder is not well controlled, the color will not meet the requirements, it will be difficult to construct, and it will be easy to make flowers, which will eventually affect the decorative effect. Therefore, how to control the arrangement of silver powder and avoid flowers is a problem that every formulator and builder must solve, and the traditional silver powder directional additives are expensive, which limits the use of formulators. Therefore, it is of great significance to explore green new silver powder directional coatings.

[0003] Prior art CN 107760173 A discloses a water-based baking varnish with directional alignment effect and its preparation method. The components include 5-10% water-based acrylic dispersion; 30-40% water-based polyester dispersion; 5-15% water-based amino resin; 0-3% neutralizer; 5-15% water-based silver powder; 5-10% cosolvent; 10-25% pure water; 1-5% modified wax emulsion; 0-10% water-based color paste; 1-3% anti-settling agent; 0.1-1% auxiliary agent. In order to achieve the silver powder alignment effect, a water-based polyester dispersion with a molecular weight greater than 10,000 is used, and a high molecular weight water-based acrylic dispersion and a modified wax emulsion are also added. The high molecular weight molecular structure is relied on to achieve rapid surface drying for effective positioning of silver powder or pearlescent powder.

[0004] Prior art CN 117164727 A discloses a water-based high molecular weight polyether ester polymer, a water-based highly oriented pearlescent silver powder surface material and a preparation method thereof; the water-based highly oriented pearlescent silver powder surface material also includes 15-20 parts of water-based polyester resin; 20-30 parts of water-based pigment and filler slurry; 5-7 parts of water-based silver powder; 0.10.5 parts of leveling agent; 8-12 parts of water-based amino resin; 20-30 parts of deionized water; the amount of the water-based high molecular weight polyether ester polymer added is 7-10 parts. The polyester resin in the invention has excellent mechanical properties, water properties, stability and weather resistance, and good compatibility with additives; the water-based silver powder used in the invention not only has high hiding power and tinting power, but also can form a dense protective layer on the metal surface, which covers the surface of the metal and plays a role in protecting the substrate.

[0005] However, the above-mentioned prior arts have common defects: first, it is difficult to synthesize high molecular weight water-based polyesters or polyether esters, and the viscosity of high molecular weight water-based polyesters or polyether esters is extremely high, and the difficulty of dispersion will also increase exponentially accordingly, and it is easy to disperse unevenly. Secondly, it is necessary to add high molecular weight polymers such as water-based acrylic dispersions and modified wax emulsions or water-based amino resins to help the silver powder orient. There are obvious compatibility problems between these polymers, and it is difficult to adjust them so that these polymers can be perfectly blended. Summary of the invention

[0006] The invention aims to provide a pyridine derivative with a small molecular weight, a preparation method thereof and an application thereof in improving the directional arrangement of silver powder in water-based silver powder coating.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] A pyridine derivative, the structure of which is as follows:

[0009]

[0010] Based on the same inventive concept, the present invention claims a method for preparing the pyridine derivative, comprising the following steps:

[0011] The pyridine dicarboxylic acid, the benzene derivative and the diacid are mixed 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. for 20-40 min in an inert gas atmosphere; the mixture is heated to 170-200° C., and after the reaction is completed, the mixture is cooled and separated to obtain the pyridine derivative; the diacid is one or more of 2-carbonylsuccinic acid, 2-methoxy-2-ene-succinic acid, and 2-ethoxy-2-ene-succinic acid;

[0012] The benzene derivative is one or more of hydroquinone, resorcinol, p-phenylenediamine and m-phenylenediamine.

[0013] The product obtained by reacting pyridine dicarboxylic acid, benzene derivatives and diacids in a molar ratio of 1:1.5-2.5:1.5-2.5 has good purity and high yield; too large or too small a molar ratio of any raw material will affect the effect of obtaining the target product.

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

[0015] In a preferred embodiment, the completion of the reaction means that the reaction is stopped after the acid value reaches the theoretical index.

[0016] In a preferred embodiment, the catalyst is one or more of monobutyltin oxide, dibutyltin oxide, and butyltin acid.

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

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

[0019] In one preferred embodiment, the heating rate to 170-200° C. is 1-2° C. / min. A heating rate that is too fast or too slow will lead to side reactions, such as decarboxylation reaction, etherification reaction, etc.

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

[0021] A water-based polyester resin, the raw materials of which include the pyridine derivative, polyol, polyacid and dihydroxyalkyl acid, wherein the molar ratio of the pyridine derivative, polyol, polyacid and dihydroxyalkyl acid is 1:1:2-3:1.

[0022] In a preferred embodiment, the dihydroxyalkyl acid is dimethylolpropionic acid or dimethylolbutanoic acid.

[0023] In a preferred embodiment, the polyol is a diol or a triol.

[0024] In a preferred embodiment, the diol is one or more of ethylene glycol, hexylene glycol, and neopentyl glycol.

[0025] In a preferred embodiment, the diol is trimethylolpropane.

[0026] In a preferred embodiment, the polyacid is a dibasic acid or a tribasic acid.

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

[0028] In a preferred embodiment, the tribasic acid is trimellitic anhydride.

[0029] Based on the same inventive concept, the present invention claims protection for a method for preparing the water-based polyester resin, comprising the following steps: after mixing the pyridine derivative, polyol, polyacid and dihydroxyalkyl acid, adding a second catalyst, stirring for 20-40 minutes at 120-160°C in an inert gas atmosphere; 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.

[0030] The completion of the reaction is when the theoretical water output and acid value level are reached, and the reaction endpoint is determined.

[0031] In one preferred embodiment, the second catalyst is one or more of monobutyltin oxide, dibutyltin oxide, and butyltin acid.

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

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

[0034] In one preferred embodiment, the heating rate to 170-200° C. is 1-2° C. / min. A 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 a preferred embodiment, the amount of the neutralizer added is the same as the molar amount of the dihydroxyalkyl acid.

[0037] In one preferred embodiment, the solid content of the waterborne polyester resin is 10% to 50%. Based on the same inventive concept, the present invention claims to protect the use of the waterborne polyester resin in improving the directional arrangement of silver powder in waterborne silver powder coatings.

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

[0039] In one preferred embodiment, the water-based silver powder baking varnish comprises the following components by weight: 30-50 parts of the water-based polyester resin, 6-15 parts of the amino resin, 5-15 parts of the silver powder, 5-10 parts of the precipitated barium sulfate, 5-7 parts of the film-forming agent, 0.2-0.5 parts of the wetting and dispersing agent, 0.2-0.5 parts of the leveling agent, 0.2-0.5 parts of the thickener, 2-3 parts of the neutralizer, 5-10 parts of the deionized water, and 0.3-0.67 parts of the 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 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 by the ADA effect, the water-based polyester resin added with the pyridine derivative has a very high adsorption and fixation effect on positively charged metal powders such as silver powder. Silver powder is a flaky structure, and the orderly arrangement of silver powder can bring extremely high gloss and reflectivity, and the appearance of the product will appear bright and beautiful. The disordered arrangement of silver powder will diffusely reflect light, making the surface of the coating dull. When the paint is drying, the flaky silver powder is very easy to swing around, and the pyridine derivative can suppress the swing of the silver powder through electrostatic adsorption, thereby achieving an excellent arrangement of the silver powder.

[0044] 2. Good water and solvent resistance

[0045] The large conjugated structure inside the pyridine derivative leads to an average bond length inside the molecule, an average chemical bond potential energy, and a chemical bond that is less likely to break. It becomes more difficult for hydration to attack the fragile ester chemical bonds in the molecule. In addition, the swelling effect of the organic solvent on the molecule will also be suppressed by the electron cloud enriched on the molecular 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 resins, and the esterification reaction is a reversible reaction. Long-term exposure to excess water will lead to instability of the ester group. Water-based polyester is made by a dispersion method. The resin curls up into small micelles in water, with water-soluble groups exposed to the outside and fat-soluble groups wrapped inside the micelles, which is also called a double-layer structure. The higher the ZETA potential of the double layer, the more stable the micelles are, and it is less likely to precipitate and cause demulsification. 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 derivative can provide a large amount of charge for 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 coagulation 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 need to add additional ingredients such as water-based acrylic dispersion and wax emulsion, no need to consider compatibility issues.

[0051] 3. Based on the pyridine derivative, it can be freely combined with any monomer, and the monomer ratio can be freely adjusted to the greatest extent. It only needs to ensure that the pyridine derivative accounts for more than 10% of the monomer mass to meet the requirements of water-based polyester for directional arrangement of silver powder, and can significantly improve the water resistance, organic reagent resistance and acid and alkali corrosion resistance of the resin.

[0052] 4. The present invention utilizes electrostatic adsorption and chelation, and compared with the simple surface rapid drying method of the prior art, the technical means achieves better stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 Schematic diagram of the synthesis of pyridine derivatives;

[0054] Figure 2 Schematic diagram of achieving complete conjugation of the entire molecule through enol interconversion of pyridine derivatives;

[0055] Figure 3 is the NMR spectrum of intermediate 1;

[0056] Figure 4 is the NMR spectrum of intermediate 2;

[0057] Figure 5 is the NMR spectrum of intermediate 3;

[0058] Figure 6 is the NMR spectrum of intermediate 4;

[0059] Figure 7 is the NMR spectrum of intermediate 5;

[0060] Figure 8 is the NMR spectrum of intermediate 6;

[0061] Fig. 9 is the NMR spectrum of intermediate 7;

[0062] Fig.10 is the NMR spectrum of intermediate 8;

[0063] Fig.11 is the NMR spectrum of intermediate 9;

[0064] Fig.12 is the NMR spectrum of intermediate 10;

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

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

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

[0068] Fig.16 The NMR spectrum of intermediate 14. DETAILED DESCRIPTION

[0069] The present invention is not limited to the following specific embodiments. A person skilled in the art can implement the present invention in various other specific embodiments according to the contents disclosed in the present invention, or any simple changes or modifications made to the design structure and ideas of the present invention fall within the protection scope of the present invention. It should be noted that the embodiments and features in the embodiments of the present invention can be combined with each other without conflict.

[0070] Example 1

[0071] Synthesis of intermediates

[0072] 1. Synthesis of intermediate 1:

[0073] according to Figure 1 As shown in the synthesis schematic 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, and 0.3% of the mass of monobutyltin oxide was added as a catalyst. Nitrogen was introduced for protection, stirring was started, and the temperature was raised to 140°C for 30 minutes. Then the temperature was raised to 180°C at a rate of 1°C / min and the temperature was kept for 3 hours. The reaction end point was determined by the quality of the reaction water and the acid value, and the acid value should drop to 194 mgKOH / g. Intermediate 1 was synthesized and analyzed, and 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 The NMR spectrum of intermediate 1.

[0081] like Figure 2 As shown, the pyridine derivative (intermediate 1) is characterized in that the 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 improve 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 monobutyltin oxide as a catalyst, pass nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by 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, and 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 The NMR spectrum of intermediate 2.

[0092] 3. Synthesis of Comparative Example Intermediate 3:

[0093] Replace pyridine-2,6-dicarboxylic acid with phthalic acid

[0094] Weigh 1 mol of isophthalic acid, 2 mol of hydroquinone, and 2 mol of 2-carbonylsuccinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, pass nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value, and the acid value should drop to 194 mgKOH / g. Intermediate 3 is synthesized and analyzed, and the structure is as follows:

[0095]

[0096] The chemical formula is: 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 The NMR spectrum of intermediate 3.

[0102] 4. Synthesis of Comparative Example Intermediate 4:

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

[0104] Weigh 1 mol of isophthalic acid, 1 mol of hydroquinone, and 1 mol of 2-carbonylsuccinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, pass nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value, and 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 The NMR spectrum of intermediate 4.

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

[0113] Substituting 1,4-succinic 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 monobutyltin oxide as a catalyst, pass nitrogen protection, start stirring, 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 end point is determined by 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 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-succinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, introduce nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value, and the acid value should drop to 313 mgKOH / g. Intermediate 6 is synthesized and analyzed, and 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 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] Weigh 1 mol of isophthalic acid, 2 mol of hydroquinone, and 2 mol of 1,4-succinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, pass nitrogen protection, 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 temperature for 3 hours. The end point of the reaction is determined by the quality of the reaction water and the acid value. The acid value should drop to 204 mgKOH / g. Intermediate 7 is synthesized and analyzed, and the structure is as follows:

[0135]

[0136] The chemical formula is: 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] Fig. 9 The NMR spectrum of intermediate 7.

[0142] 8. Synthesis of Comparative Example Intermediate 8:

[0143] The amount of hydroquinone added is half of that of the comparative example intermediate 7

[0144] Weigh 1 mol of isophthalic acid, 1 mol of hydroquinone, and 1 mol of 1,4-succinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, introduce nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value. The acid value should drop to 313 mgKOH / g. Intermediate 8 is synthesized and analyzed, and the structure is as follows:

[0145]

[0146] The chemical formula is: 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] Fig.10 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 monobutyltin oxide as a catalyst, pass nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value. The acid value should drop to 194 mgKOH / g. Intermediate 9 is 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] Fig.11 The NMR spectrum of intermediate 9.

[0162] 10. Synthesis of Intermediate 10

[0163] Resuscitol instead of hydroquinone

[0164] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of resorcinol, and 2 mol of 2-carbonylsuccinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, pass nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value. The acid value should drop to 194 mgKOH / g. Intermediate 10 is synthesized and analyzed, and the structure is as follows:

[0165]

[0166] The chemical formula is: 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] Fig.12 is the NMR spectrum of intermediate 10.

[0172] 11. Synthesis of Intermediate 11

[0173] Replace hydroquinone with p-phenylenediamine

[0174] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of p-phenylenediamine, and 2 mol of 2-carbonylsuccinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, introduce nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value, and the acid value should drop to 195 mgKOH / g. Intermediate 11 was synthesized and analyzed, and the structure is as follows:

[0175]

[0176] The chemical formula is: 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] Fig.13 is the NMR spectrum of intermediate 11.

[0182] 12. Synthesis of Intermediate 12

[0183] Replace hydroquinone with m-phenylenediamine

[0184] Weigh 1 mol of pyridine-2,6-dicarboxylic acid, 2 mol of m-phenylenediamine, and 2 mol of 2-carbonylsuccinic acid into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, introduce nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value, and the acid value should drop to 195 mgKOH / g. Intermediate 12 is synthesized and analyzed, and the structure is as follows:

[0185]

[0186] The chemical formula is: 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] Fig.14 The NMR spectrum of intermediate 12

[0192] 2-Methoxy-2-ene-butanedioic acid replaces 2-oxosuccinic 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 monobutyltin oxide as a catalyst, introduce nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value, and the acid value should drop to 184 mgKOH / g. Intermediate 13 was synthesized and analyzed, and 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] Fig.15 The NMR spectrum of intermediate 13.

[0202] 14. Synthesis of Intermediate 14

[0203] Replace 2-oxosuccinic acid with 2-ethoxy-2-ene-succinic 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 monobutyltin oxide as a catalyst, introduce nitrogen protection, 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 temperature for 3 hours. The reaction endpoint is determined by the quality of the reaction water and the acid value, and the acid value should drop to 177 mgKOH / g. Intermediate 14 is synthesized and analyzed, and 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] Fig.16 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 56mgKOH / g. Obtain the amphifunctional emulsified polyester 1 with a molecular weight of 995.

[0215] 2.500g of the emulsified polyester 1 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 1 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% by mass of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 53mgKOH / g. A tetrafunctional emulsified polyester 2 with a molecular weight of 1055 is obtained.

[0219] 2.500g of the emulsified polyester 2 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 44g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 2 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 212mgKOH / g.

[0220] Example 4

[0221] (diol, triacid)

[0222] 1. Weigh 1 mol of intermediate 1, 1 mol of dimethylol propionic acid, 1 mol of trimellitic anhydride and 3 mol of neopentyl glycol into a reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 49mgKOH / g. The trifunctional emulsified polyester 3 with a molecular weight of 1145 is obtained.

[0223] 2.500g of the emulsified polyester 3 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 41g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 3 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% of the mass of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 45mgKOH / g. The hexafunctional emulsified polyester 4 with a molecular weight of 1235 is obtained.

[0227] 2.500g of the emulsified polyester 4 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 38g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 3 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 71mgKOH / g. Obtain the amphifunctional emulsified polyester 5 with a molecular weight of 789.

[0230] 2.500g of the emulsified polyester 5 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 60g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 5 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 56mgKOH / g. Obtain the amphifunctional emulsified polyester 6 with a molecular weight of 994.

[0233] 2.500g of the emulsified polyester 6 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 6 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 71mgKOH / g. Obtain the amphifunctional emulsified polyester 7 with a molecular weight of 788.

[0236] 2.500g of the emulsified polyester 7 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 60g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 7 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 58mgKOH / g. Obtain the amphifunctional emulsified polyester 8 with a molecular weight of 967.

[0239] 2.500g of the emulsified polyester 8 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 49g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 8 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 72mgKOH / g. Obtain the amphifunctional emulsified polyester 9 with a molecular weight of 776.

[0242] 2.500g of the emulsified polyester 9 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 60g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 9 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, 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 reaches the end point when the water output reaches 72g, and the acid value is measured to be 58mgKOH / g. Obtain the amphifunctional emulsified polyester 10 with a molecular weight of 966.

[0245] 2.500g of the emulsified polyester 10 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 49g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 10 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 116mgKOH / 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 72mgKOH / g. Obtain the amphifunctional emulsified polyester 11 with a molecular weight of 774.

[0248] 500g of the emulsified polyester 11 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 60g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 11 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 145mgKOH / g.

[0249] Embodiment 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 56mgKOH / g. Obtain the amphifunctional emulsified polyester 12 with a molecular weight of 995.

[0251] 2.500g of the emulsified polyester 12 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 12 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 113mgKOH / g.

[0252] Embodiment 14

[0253] 1. Weigh 1 mol of intermediate 10, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid and 2 mol of neopentyl glycol into a reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 56mgKOH / g. Obtain the amphifunctional emulsified polyester 13 with a molecular weight of 995.

[0254] 2.500g of the emulsified polyester 13 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 13 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 113mgKOH / g.

[0255] Embodiment 15

[0256] 1. Weigh 1 mol of intermediate 11, 1 mol of dimethylolpropionic acid, 1 mol of adipic acid and 2 mol of neopentyl glycol into a reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, 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 reaches the end point when the water output reaches 72g, and the acid value is measured to be 56mgKOH / g. Obtain the amphifunctional emulsified polyester 14 with a molecular weight of 991.

[0257] 2.500g of the emulsified polyester 14 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 14 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 113mgKOH / g.

[0258] Example 16

[0259] 1. Weigh 1 mol of intermediate 12, 1 mol of dimethylol propionic acid, 1 mol of adipic acid and 2 mol of neopentyl glycol into a reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, 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 reaches the end point when the water output reaches 72g, and the acid value is measured to be 56mgKOH / g. Obtain the amphifunctional emulsified polyester 15 with a molecular weight of 991.

[0260] 2.500g of the emulsified polyester 15 was put into the disperser, the temperature was adjusted to 40℃, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 15 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 113mgKOH / g.

[0261] Embodiment 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, 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 reaches the end point when the water output reaches 72g, and the acid value is measured to be 55mgKOH / g. Obtain the amphifunctional emulsified polyester 16 with a molecular weight of 1023.

[0263] 2.500g of the emulsified polyester 16 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 16 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 110mgKOH / g.

[0264] Embodiment 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 reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, 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 reaches the end point when the water output reaches 72g, and the acid value is measured to be 55mgKOH / g. Obtain the amphifunctional emulsified polyester 17 with a molecular weight of 1023.

[0266] 2.500g of the emulsified polyester 17 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 17 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 110mgKOH / g.

[0267] Embodiment 19

[0268] Dicarboxymethylbutyric acid replaces dicarboxymethylpropionic acid

[0269] 3. Weigh 1 mol of intermediate 1, 1 mol of dihydroxymethylbutyric acid, 1 mol of adipic acid and 2 mol of neopentyl glycol into a reactor, add 0.3% by weight of monobutyltin oxide as a catalyst, introduce nitrogen protection, start stirring, heat to 140°C and keep warm for 30 minutes. Then heat to 180°C at a heating rate of 1°C / min and keep warm for 3 hours. The reaction reaches the end point when the water output reaches 72g, and the acid value is measured to be 55mgKOH / g. Obtain the amphifunctional emulsified polyester 18 with a molecular weight of 1009.

[0270] 4.500g of the emulsified polyester 18 was put into the disperser, the temperature was adjusted to 40°C, and the stirring device was turned on to stir thoroughly. At the same time, 47g of N,N-dimethylethanolamine was added for neutralization. 750g of water was weighed and added in three batches, and the mixture was poured out after continuous stirring for 30 minutes, and the product 18 was obtained by filtration. The solid content was 40%, and the hydroxyl value was 111mgKOH / g.

[0271] The above products 1-18 are mixed into water-based silver powder paint, the formula is as follows:

[0272] 40 parts of water-based polyester resin (product 1-18); 10 parts of amino resin; 10 parts of silver powder; 5 parts of precipitated barium sulfate; 7 parts of film-forming agent; 0.4 parts of wetting and dispersing agent; 0.3 parts of leveling agent; 0.2 parts of thickener; 3 parts of neutralizer; 10 parts of deionized water; 0.67 parts of defoaming agent. The specific raw materials are as follows:

[0273]

[0274]

[0275] Add the materials into a 1L paint mixing tank according to the formula amount, disperse at high speed for 30 minutes, add a thickener to adjust the viscosity, and obtain a water-based silver powder paint.

[0276] The performance of the 18 water-based silver powder paints was tested, and the results are as follows:

[0277] Table 1 Performance test results of water-based silver powder 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 baking varnish 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 to 4 compare the waterborne polyesters synthesized from intermediate 1 and acids and alcohols of different functionalities, which have similar properties. This proves that intermediate 1 can be copolymerized with any polyols and acids to bring about significant improvements in resin properties, including but not limited to silver powder arrangement performance, 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 improve 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 not as good as 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 products 8 to 11 without conjugated structure are far weaker than products 1 to 4 in terms of silver powder arrangement, water resistance and solvent resistance. The quality of product performance is closely related to the conjugated effect and electron cloud density of the intermediate. The comparison between product 5 and product 1 proves the superiority of ADA structure. The comparison between product 6 and product 7 and product 1 proves that sufficient electron cloud density cannot be obtained by conjugated structure alone.

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

[0294] It should be noted that the above embodiments are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the embodiments here. Any obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

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, characterized in that ,, including the following steps: The pyridine dicarboxylic acid, the benzene derivative and the diacid are mixed 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. for 20-40 min in an inert gas atmosphere; the mixture is heated to 170-200° C., and after the reaction is completed, the mixture is cooled and separated to obtain the pyridine derivative; the diacid is one or more of 2-carbonylsuccinic acid, 2-methoxy-2-ene-succinic acid, and 2-ethoxy-2-ene-succinic acid; The benzene derivative is one or more of hydroquinone, resorcinol, p-phenylenediamine and m-phenylenediamine.

3. The preparation method according to claim 2, characterized in that: The pyridinedicarboxylic acid is one or both of pyridine-2,6-dicarboxylic acid and pyridine-2,5-dicarboxylic acid.

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

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

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

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

1.

8. The aqueous polyester resin according to claim 7, 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.

9. The method for preparing an aqueous polyester resin according to claim 7, characterized in that: The method comprises the following steps: mixing the pyridine derivative, polyol, polyacid and dihydroxyalkyl acid, adding a second catalyst, stirring for 20-40 minutes at 120-160° C. in an inert gas atmosphere; then heating to 170-200° C., stopping the reaction after the reaction is completed, adding a neutralizer and water, dispersing, and obtaining the water-based polyester resin.

10. A water-based silver powder baking varnish, characterized in that: Comprising the water-based polyester resin according to claim 7.

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