A three-dimensional polyester resin synthesis process and its application

Abstract

The invention relates to the technical field of polyester resins, and discloses a three-dimensional polyester resin synthesis process and its application, wherein nitrogen is introduced into a reaction kettle, polyester diol, neopentyl glycol, trihydroxy flame retardant monomer, isophthalic acid, and antioxidant are added, and the material is cooled and discharged after the reaction to obtain a three-dimensional polyester resin. When preparing the three-dimensional polyester resin, the present invention adds a polyester diol macromolecular monomer and a trihydroxy flame retardant monomer for polymerization reaction, and the molecular chain of the obtained polyester resin contains a phosphate structure and an isocyanuric acid nitrogen-containing heterocycle to form a nitrogen-phosphorus flame retardant system, which gives the polyester resin good flame retardancy. With the three-dimensional polyester resin as the base resin component of the paint, the limiting oxygen index of the paint film is also high, and it has certain flame retardancy. At the same time, the pencil hardness and impact resistance of the paint are higher, and the cross-cut test reaches level 0.

Description

Technical Field

[0001] The invention relates to the technical field of polyester resins, in particular to a three-dimensional polyester resin synthesis process and application thereof. Background Art

[0002] Polyester resin is usually made of diols, dibasic acids, phthalic anhydride, maleic anhydride and other raw materials through polycondensation reaction. It has the advantages of good transparency, high brightness, heat resistance and excellent electrical properties. It is widely used in paints, coatings, adhesives and other applications. By optimizing the synthesis conditions of polyester resin and giving it better mechanical strength, flame retardancy and other properties, polyester resin with higher performance indicators can be obtained, which helps to improve the quality and performance of products and meet the application needs of different fields.

[0003] Adding functional monomers when preparing polyester resin can give the resin unique properties, such as high temperature resistance, flame retardancy, toughness, etc. The patent with announcement number CN105694014B discloses a method for preparing a hyperbranched waterborne polyester resin, using trimethylolpropane, 2,2-dimethylolpropionic acid, neopentyl glycol, isophthalic acid, maleic anhydride, phthalic anhydride, adipic acid, etc. as monomers, and the hyperbranched waterborne polyester resin obtained by polymerization has the advantages of good hydrolysis resistance, high gloss, good wear resistance, strong adhesion, impact resistance, etc. Compared with the hyperbranched waterborne polyester resin of the invention, the present invention adds polyester diol macromolecular monomers and trihydroxy flame retardant monomers when preparing polyester resin, and the obtained three-dimensional polyester resin and paint have better flame retardancy, hardness, impact resistance and other properties. Summary of the invention

[0004] (i) The present invention provides a three-dimensional polyester resin and paint thereof, which solves the problems of low hardness, poor impact resistance and flame retardancy of polyester resin-based paints.

[0005] (II) Technical solution: A three-dimensional polyester resin synthesis process: nitrogen is introduced into a reaction kettle, polyester diol, neopentyl glycol, trihydroxy flame retardant monomer, isophthalic acid, antioxidant diisopropyl alcohol ether diphenyl phosphite are added, heated to 110-120°C, phthalic anhydride and catalyst monobutyl tin triisooctanoate are added, first heated to 165-180°C, reacted for 2-3h, then heated to 195-210°C to react until the acid value is 15-20 KOH / g; the reaction kettle is evacuated until the acid value drops to 8-10KOH / g, cooled and discharged to obtain a three-dimensional polyester resin.

[0006] The polyester diol is one or a combination of poly(1,4-cyclohexanedimethanol adipate) diol and poly(1,4-cyclohexanedicarboxylic acid) hexanediol diol.

[0007] The structural formula of trihydroxy flame retardant monomer is: .

[0008] Preferably, the mass ratio of polyester diol, neopentyl glycol, trihydroxy flame retardant monomer, isophthalic acid, antioxidant, phthalic anhydride, and monobutyl tin triisooctanoate is (910-930): (575-585): (80-200): (460-500): (0.8-1.3): (1180-1210): (5.7-6.4).

[0009] Preferably, the preparation method of the polyester diol is as follows: add a diol, a dibasic acid and an antioxidant in a mass ratio of (623-722): (278-377): (0.9-1.1) into a reaction kettle, heat to 100-120°C, stir for 10-20 minutes, then heat to 140-160°C, react for 4-6 hours, then heat to 210-220°C, react until the acid value is ≦2 KOH / g, and reflux the unreacted diol and dibasic acid until the acid value drops to ≦0.01 KOH / g to obtain the polyester diol.

[0010] Preferably, the diol is 1,4-cyclohexanedimethanol or 1,6-hexanediol, and the dibasic acid is 1,4-cyclohexanedicarboxylic acid or 1,6-hexanediic acid.

[0011] Preferably, the synthesis process of the trihydroxy flame retardant monomer is as follows: add toluene, pentaerythritol phosphate PEPA, triglycidyl isocyanurate and tetrabutylammonium bromide in a mass ratio of (180-220):100:(12-16) into a reaction bottle, heat to 100-110°C, condense and reflux for 12-18h, distill under reduced pressure, wash with methanol, and recrystallize the product in dichloromethane to obtain the trihydroxy flame retardant monomer. The reaction formula is as follows: .

[0012] Preferably, the three-dimensional polyester resin is used in paint: the three-dimensional polyester resin is added to propylene glycol methyl ether acetate solvent, titanium dioxide, dispersant, anti-settling agent are added after stirring, the mixed solution is ground to a fineness of ≦20 μm, and then propylene glycol methyl ether acetate solvent, methyl ether amino resin, butyl acetate cellulose, epoxy resin, organic bentonite, benzenesulfonic acid are added, and mixed evenly to obtain a three-dimensional polyester resin-based paint.

[0013] Preferably, the mass ratio of three-dimensional polyester resin, titanium dioxide, dispersant, anti-settling agent, methyl etherified amino resin, butyl acetate cellulose, epoxy resin, organic bentonite, and benzenesulfonic acid is (160-195): (118-130): (1-1.2): (0.8-1.2): (40-55): (30-38): (26-30): (15-18): (3.4-4.3)

[0014] (III) Technical effect: The present invention uses 1,4-cyclohexanedimethanol or 1,6-hexanediol as diol, 1,4-cyclohexanedicarboxylic acid or 1,6-hexanediol as dibasic acid, and obtains polyester diol through polycondensation reaction. The present invention uses pentaerythritol phosphate PEPA to react with triglycidyl isocyanurate to obtain a novel trihydroxy flame retardant monomer.

[0015] When preparing the three-dimensional polyester resin, the present invention adds a trihydroxy flame retardant monomer for polymerization reaction. The molecular chain of the obtained polyester resin contains a phosphate structure and an isocyanuric acid nitrogen-containing heterocycle to form a nitrogen-phosphorus flame retardant system, which gives the polyester resin good flame retardancy. The three-dimensional polyester resin is used as the base resin component of the paint, and the limiting oxygen index of the paint film is also high, which has certain flame retardancy.

[0016] When preparing the polyester resin, the polyester diol is added as a macromolecular monomer, and the trihydroxy flame retardant monomer added at the same time contains three hydroxyl groups, and undergoes polymerization reaction with monomers such as isophthalic acid and phthalic anhydride to form a three-dimensional polyester resin with a branched network molecular chain structure, which has better mechanical properties. The three-dimensional polyester resin-based paint is used as the base resin of the paint, and the pencil hardness and impact resistance of the obtained three-dimensional polyester resin-based paint are higher, and the cross-cut test reaches level 0.

[0017] The polyester resin and paint synthesis process of the present invention are optimized and designed, and advanced reaction technology and efficient separation and purification technology are used, so that the synthesis reaction time of the three-dimensional polyester resin is short and the production efficiency is high. This helps to reduce production costs and improve market competitiveness. The synthesis process formula of the present invention is flexible, and the formula can be adjusted according to different application requirements to synthesize three-dimensional polyester resins and paints with different properties. At the same time, this patent also provides a variety of reinforcing additives to further optimize the performance of the polyester resin. This diversity makes this patent have a wide range of application prospects in many fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is the hydrogen NMR spectrum of trihydroxy flame retardant monomer. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0020] The CAS registration number of pentaerythritol phosphate PEPA is 5301-78-0, and the CAS registration number of triglycidyl isocyanurate is 2451-62-9.

[0021] Titanium dioxide, model number Fangyuan FR-767.

[0022] Dispersant, model Deqian Disponer912 wetting dispersant.

[0023] Anti-settling agent, model Sanfu K-200 fumed silica.

[0024] Methyl etherified amino resin, model number is Changxin ETERMINO 9603-80 amino resin.

[0025] Butyl acetate cellulose, model: American Eastman CAB-381-2.

[0026] Epoxy resin, model Nan Ya 128 epoxy resin.

[0027] Organic bentonite, model: Hemmingsdeqian BENGEL828.

[0028] Example 1

[0029] (1) Add 400 mL of toluene, 27 g of pentaerythritol phosphate PEPA, 15 g of triglycidyl isocyanurate and 2.1 g of catalyst tetrabutylammonium bromide to the reaction bottle, heat to 110°C, condense and reflux for 12 h, distill under reduced pressure, wash with methanol, and recrystallize the product in dichloromethane to obtain a trihydroxy flame retardant monomer. The yield is 67.5%.

[0030] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the trihydroxy flame retardant monomer shows that 1 H NMR (400MHz, DMSO-d6), δ4.79-4.77(m,3H), 4.30-4.18(m,12H), 4.12-4.07(m,9H), 3.97-3.92(m, 3H), 3.81-3.76(m, 3H), 3.62-3.48(m, 12H).

[0031] (2) Add 72.2 g of 1,4-cyclohexanedimethanol, 27.8 g of 1,6-adipic acid and 0.11 g of antioxidant diisopropyl alcohol ether diphenyl phosphite into a reaction kettle, heat to 100°C, stir for 20 min, then heat to 140°C, react for 6 h, then raise the temperature to 210°C and react until the acid value is ≦2 KOH / g. Use the reflux method to reflux the unreacted diol and dibasic acid until the acid value drops to ≦0.01 KOH / g to obtain poly(1,4-cyclohexanedimethanol adipate) diol.

[0032] (3) Nitrogen was introduced into the reaction kettle, and 922 g of poly(1,4-cyclohexanedimethanol adipate), 579 g of neopentyl glycol, 80 g of trihydroxy flame retardant monomer, 480 g of isophthalic acid, and 1 g of antioxidant diisopropyl ether diphenyl phosphite were added. The reaction kettle was heated to 120°C, and 1192 g of phthalic anhydride and 6 g of catalyst monobutyl tin triisooctanoate were added. The reaction kettle was first heated to 170°C and reacted for 3 h, and then heated to 210°C to react until the acid value was about 20 KOH / g. The reaction kettle was evacuated until the acid value dropped to about 10 KOH / g, and the material was cooled and discharged to obtain a three-dimensional polyester resin.

[0033] (4) Add 1950 g of three-dimensional polyester resin to 250 mL of propylene glycol methyl ether acetate solvent, stir, then add 1300 g of titanium dioxide, 12 g of dispersant, and 11 g of anti-settling agent. Grind the mixture to a fineness of ≦20 μm, then add 750 mL of propylene glycol methyl ether acetate solvent, 400 g of methyl ether amino resin, 300 g of butyl acetate cellulose, 260 g of epoxy resin, 150 g of organic bentonite, and 34 g of benzenesulfonic acid. Mix well to obtain a three-dimensional polyester resin-based paint.

[0034] Example 2

[0035] (1) Add 500 mL of toluene, 33 g of pentaerythritol phosphate PEPA, 15 g of triglycidyl isocyanurate and 2.4 g of catalyst tetrabutylammonium bromide to the reaction bottle, heat to 100 ° C, condense and reflux for 12 hours, distill under reduced pressure, wash with methanol, and recrystallize the product in dichloromethane to obtain a trihydroxy flame retardant monomer. The yield is 73.2%.

[0036] (2) Add 62.3 g of 1,6-hexanediol, 37.7 g of 1,4-cyclohexanedicarboxylic acid and 0.09 g of antioxidant diisopropyl alcohol ether diphenyl phosphite into the reaction kettle, heat to 120°C, stir for 10 min, then heat to 160°C, react for 4 h, then raise the temperature to 220°C and react until the acid value is ≦2 KOH / g. Use the reflux method to reflux the unreacted diol and dibasic acid until the acid value drops to ≦0.01 KOH / g to obtain 1,4-cyclohexanedicarboxylic acid-hexanediol ester diol.

[0037] (3) Nitrogen was introduced into the reaction kettle, and 930 g of 1,4-cyclohexanedicarboxylic acid-hexanediol ester diol, 575 g of neopentyl glycol, 140 g of trihydroxy flame retardant monomer, 500 g of isophthalic acid, and 0.8 g of antioxidant diisopropyl alcohol ether diphenyl phosphite were added. The reaction kettle was heated to 110°C, and 1180 g of phthalic anhydride and 6.4 g of catalyst monobutyl tin triisooctanoate were added. The reaction kettle was first heated to 180°C and reacted for 2 h, and then heated to 195°C to react until the acid value was about 15 KOH / g. The reaction kettle was evacuated until the acid value dropped to about 10 KOH / g, and the material was cooled and discharged to obtain a three-dimensional polyester resin.

[0038] (4) Add 1800 g of three-dimensional polyester resin to 200 mL of propylene glycol methyl ether acetate solvent, stir, add 1250 g of titanium dioxide, 10 g of dispersant, and 10 g of anti-settling agent, grind the mixture to a fineness of ≦20 μm, then add 800 mL of propylene glycol methyl ether acetate solvent, 500 g of methyl etherified amino resin, 325 g of butyl cellulose acetate, 300 g of epoxy resin, 150 g of organic bentonite, and 40 g of benzenesulfonic acid, mix well, and obtain a three-dimensional polyester resin-based paint.

[0039] Example 3

[0040] (1) Add 500 mL of toluene, 30 g of pentaerythritol phosphate PEPA, 15 g of triglycidyl isocyanurate and 1.8 g of catalyst tetrabutylammonium bromide into the reaction bottle, heat to 110°C, condense and reflux for 12 h, distill under reduced pressure, wash with methanol, and recrystallize the product in dichloromethane to obtain a trihydroxy flame retardant monomer. The yield is 69.1%.

[0041] (2) Nitrogen was introduced into the reaction kettle, and 455 g of 1,4-cyclohexanedicarboxylic acid-hexanediol ester diol, 455 g of polyadipate-1,4-cyclohexanedimethanol ester diol, 585 g of neopentyl glycol, 200 g of trihydroxy flame retardant monomer, 460 g of isophthalic acid, and 1.3 g of antioxidant diisopropyl alcohol ether diphenyl phosphite were added. The reaction kettle was heated to 110°C, and 1210 g of phthalic anhydride and 5.7 g of catalyst monobutyl tin triisooctanoate were added. The reaction kettle was first heated to 165°C and reacted for 3 h, and then heated to 210°C for reaction until the acid value was about 15 KOH / g. The reaction kettle was evacuated until the acid value dropped to 8 KOH / g, and the material was cooled and discharged to obtain a three-dimensional polyester resin.

[0042] (3) Add 1600 g of three-dimensional polyester resin to 150 mL of propylene glycol methyl ether acetate solvent, stir and add 1180 g of titanium dioxide, 10 g of dispersant and 8 g of anti-settling agent. Grind the mixture to a fineness of ≦20 μm, then add 850 mL of propylene glycol methyl ether acetate solvent, 550 g of methyl etherified amino resin, 380 g of butyl acetate cellulose, 300 g of epoxy resin, 180 g of organic bentonite and 43 g of benzenesulfonic acid. Mix well to obtain a three-dimensional polyester resin-based paint.

[0043] Comparative Example 1

[0044] (1) Nitrogen was introduced into a reaction kettle, 579 g of neopentyl glycol, 80 g of trihydroxy flame retardant monomer (prepared according to the method of Example 1), 480 g of isophthalic acid, 1 g of antioxidant diisopropyl alcohol ether diphenyl phosphite were added, and the mixture was heated to 120° C. 1192 g of phthalic anhydride and 6 g of catalyst monobutyl tin triisooctanoate were added. The mixture was first heated to 170° C. and reacted for 3 h, and then heated to 210° C. and reacted until the acid value was about 20 KOH / g; the reaction kettle was evacuated until the acid value dropped to about 10 KOH / g, and the mixture was cooled and discharged to obtain a three-dimensional polyester resin.

[0045] (3) Add 1950 g of three-dimensional polyester resin to 250 mL of propylene glycol methyl ether acetate solvent, stir, then add 1300 g of titanium dioxide, 12 g of dispersant, and 11 g of anti-settling agent. Grind the mixture to a fineness of ≦20 μm, then add 750 mL of propylene glycol methyl ether acetate solvent, 400 g of methyl etherified amino resin, 300 g of butyl acetate cellulose, 260 g of epoxy resin, 150 g of organic bentonite, and 34 g of benzenesulfonic acid. Mix well to obtain a three-dimensional polyester resin-based paint.

[0046] Comparative Example 2

[0047] (1) Nitrogen was introduced into a reaction kettle, and 922 g of poly(1,4-cyclohexanedimethanol adipate) diol (prepared according to the method of Example 1), 579 g of neopentyl glycol, 480 g of isophthalic acid, and 1 g of antioxidant diisopropyl alcohol ether diphenyl phosphite were added. The reaction kettle was heated to 120° C., and 1192 g of phthalic anhydride and 6 g of catalyst monobutyl tin triisooctanoate were added. The reaction kettle was first heated to 170° C. and reacted for 3 h, and then heated to 210° C. to react until the acid value was about 20 KOH / g. The reaction kettle was evacuated until the acid value dropped to about 10 KOH / g, and the material was cooled and discharged to obtain a polyester resin.

[0048] (2) Add 1950 g of polyester resin to 250 mL of propylene glycol methyl ether acetate solvent, stir, then add 1300 g of titanium dioxide, 12 g of dispersant, and 11 g of anti-settling agent. Grind the mixture to a fineness of ≦20 μm, then add 750 mL of propylene glycol methyl ether acetate solvent, 400 g of methyl etherified amino resin, 300 g of butyl acetate cellulose, 260 g of epoxy resin, 150 g of organic bentonite, and 34 g of benzenesulfonic acid. Mix well to obtain a polyester resin-based paint.

[0049] Comparative Example 3

[0050] (1) Nitrogen was introduced into a reaction kettle, and 922 g of poly(1,4-cyclohexanedimethanol adipate) diol (prepared according to the method of Example 1), 579 g of neopentyl glycol, 80 g of trimethylolpropane, 480 g of isophthalic acid, and 1 g of antioxidant diisopropyl alcohol ether diphenyl phosphite were added. The reaction kettle was heated to 120° C., and 1192 g of phthalic anhydride and 6 g of catalyst monobutyl tin triisooctanoate were added. The reaction kettle was first heated to 170° C. and reacted for 3 h, and then heated to 210° C. and reacted until the acid value was about 20 KOH / g. The reaction kettle was evacuated until the acid value dropped to about 10 KOH / g, and the material was cooled and discharged to obtain a three-dimensional polyester resin.

[0051] (2) Add 1950 g of three-dimensional polyester resin to 250 mL of propylene glycol methyl ether acetate solvent, stir, then add 1300 g of titanium dioxide, 12 g of dispersant, and 11 g of anti-settling agent. Grind the mixture to a fineness of ≦20 μm, then add 750 mL of propylene glycol methyl ether acetate solvent, 400 g of methyl ether amino resin, 300 g of butyl acetate cellulose, 260 g of epoxy resin, 150 g of organic bentonite, and 34 g of benzenesulfonic acid. Mix well to obtain a three-dimensional polyester resin-based paint.

[0052] The three-dimensional polyester resin (Comparative Example 2 is polyester resin) was poured into a mold, dried at 140° C. for 8 hours, and formed into a film. The limiting oxygen index was tested according to the GB / T 2406.1-2008 method.

[0053] The three-dimensional polyester resin-based paint is sprayed on the tinplate surface and dried at 140°C for 6 hours to form a paint film.

[0054] The limiting oxygen index was tested according to GB / T 2406.1-2008. The mirror gloss of the paint film was tested according to GB / T 9754-2007. The hardness of the paint film was tested according to GB / T 6739-2022. The paint film was subjected to a cross-cut test according to GB / T 9286-2021. The impact resistance was tested according to GB / T 1732-2020.

[0055] As can be seen from Table 1, when preparing the three-dimensional polyester resin in Examples 1-3, a trihydroxy flame retardant monomer is added for polymerization reaction, and the molecular chain of the obtained polyester resin contains a phosphate structure and an isocyanuric acid nitrogen-containing heterocycle to form a nitrogen-phosphorus flame retardant system, which gives the polyester resin good flame retardancy, and the limiting oxygen index reaches 27.7-30.2%. With the three-dimensional polyester resin as the base resin component of the paint, the limiting oxygen index of the paint film is also relatively high, reaching 26.4-27.3%, and has a certain flame retardancy.

[0056] In comparative example 1, trihydroxy flame retardant monomers were also added to prepare the three-dimensional polyester resin. The molecular chain of the obtained polyester resin contained a nitrogen-phosphorus flame retardant system of phosphate and isocyanuric acid nitrogen-containing heterocyclic rings. The three-dimensional polyester resin and its paint had a high limiting oxygen index and good flame retardancy.

[0057] In comparative example 2, no trihydroxy flame retardant monomer was added when preparing the polyester resin. In comparative example 3, conventional trimethylolpropane was used instead of the trihydroxy flame retardant monomer when preparing the three-dimensional polyester resin. Both polyester resins do not contain the nitrogen-phosphorus flame retardant system of phosphate and isocyanuric acid nitrogen-containing heterocyclic rings. The limiting oxygen index of the polyester resin and its paint is very low, and the flame retardancy is poor.

[0058] As can be seen from Table 2, polyester diol is added as a macromonomer when preparing the polyester resin in Examples 1-3, and the trihydroxy flame retardant monomer added at the same time contains three hydroxyl groups, which reacts with isophthalic acid, phthalic anhydride and other monomers to form a three-dimensional polyester resin with a branched network molecular chain structure, which has better mechanical properties. When it is used as the base resin of the paint, the obtained three-dimensional polyester resin-based paint has higher pencil hardness and impact resistance, the cross-cut test reaches level 0, and the mirror gloss is good.

[0059] In Comparative Example 1, polyester diol macromonomer was not added when preparing the three-dimensional polyester resin. The obtained three-dimensional polyester resin and its paint had poor mechanical properties, low pencil hardness and impact resistance, and the cross-cut test was only level 1.

[0060] In Comparative Example 2, no trihydroxy flame retardant monomer was added during the preparation of the polyester resin. The obtained polyester resin had a linear molecular chain structure and did not have a branched network molecular chain structure. The obtained three-dimensional polyester resin and its paint had poor mechanical properties, low pencil hardness and impact resistance, and the cross-cut test was only level 1.

[0061] In comparative example 3, when preparing the three-dimensional polyester resin, polyester diol macromonomer is added, and conventional trimethylolpropane is used instead of trihydroxy flame retardant monomer. The obtained polyester resin has a branched network molecular chain structure. The three-dimensional polyester resin and its paint have good mechanical properties, high pencil hardness and impact resistance, and the cross-cut test reaches level 0.

[0062] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A three-dimensional polyester resin synthesis process, characterized in that: The three-dimensional polyester resin synthesis process comprises: introducing nitrogen into a reaction kettle, adding polyester diol, neopentyl glycol, trihydroxy flame retardant monomer, isophthalic acid, and antioxidant, heating to 110-120° C., adding phthalic anhydride and catalyst monobutyl tin triisooctanoate, first heating to 165-180° C., reacting for 2-3 hours, and then heating to 195-210° C. to react until the acid value is 15-20 KOH / g; evacuating the reaction kettle until the acid value drops to 8-10 KOH / g, cooling and discharging, and obtaining the three-dimensional polyester resin; The polyester diol is one or a combination of poly(1,4-cyclohexanedimethanol adipate) diol and poly(1,4-cyclohexanedicarboxylic acid) hexanediol diol; The structural formula of the trihydroxy flame retardant monomer is: ； The mass ratio of the polyester diol, neopentyl glycol, trihydroxy flame retardant monomer, isophthalic acid, antioxidant, phthalic anhydride, and monobutyl tin triisooctanoate is (910-930): (575-585): (80-200): (460-500): (0.8-1.3): (1180-1210): (5.7-6.4).

2. The three-dimensional polyester resin synthesis process according to claim 1, characterized in that: The preparation method of the polyester diol is as follows: add diol, dibasic acid and antioxidant into a reaction kettle, heat to 100-120°C, stir for 10-20min, then heat to 140-160°C, react for 4-6h, then heat to 210-220°C, react until the acid value is ≦2 KOH / g, reflux unreacted diol and dibasic acid until the acid value drops to ≦0.01 KOH / g, and obtain polyester diol.

3. The three-dimensional polyester resin synthesis process according to claim 2, characterized in that: The mass ratio of the diol, the dibasic acid and the antioxidant is (623-722): (278-377): (0.9-1.1).

4. The three-dimensional polyester resin synthesis process according to claim 2, characterized in that: The diol is 1,4-cyclohexanedimethanol or 1,6-hexanediol, and the dibasic acid is 1,4-cyclohexanedicarboxylic acid or 1,6-hexanediol.

5. The three-dimensional polyester resin synthesis process according to claim 1, characterized in that: The synthesis process of the trihydroxy flame retardant monomer is as follows: toluene, pentaerythritol phosphate PEPA, triglycidyl isocyanurate, and tetrabutylammonium bromide are added into a reaction bottle, heated to 100-110° C., condensed and refluxed for 12-18 hours, distilled under reduced pressure, washed with methanol, and the product was recrystallized in dichloromethane to obtain the trihydroxy flame retardant monomer.

6. The three-dimensional polyester resin synthesis process according to claim 5, characterized in that: The mass ratio of pentaerythritol phosphate PEPA, triglycidyl isocyanurate and tetrabutylammonium bromide is (180-220):100:(12-16).

7. Use of a three-dimensional polyester resin synthesized by the synthesis process according to any one of claims 1 to 6 in paint, characterized in that: The three-dimensional polyester resin is added to the propylene glycol methyl ether acetate solvent, and titanium dioxide, a dispersant, and an anti-settling agent are added after stirring. The mixed liquid is ground to a fineness of ≦20 μm, and then the propylene glycol methyl ether acetate solvent, methyl etherified amino resin, butyl acetate cellulose, epoxy resin, organic bentonite, and benzenesulfonic acid are added and mixed evenly to obtain a three-dimensional polyester resin-based paint.

8. The use of the three-dimensional polyester resin in paint according to claim 7, characterized in that: The mass ratio of the three-dimensional polyester resin, titanium dioxide, dispersant, anti-settling agent, methyl etherified amino resin, butyl acetate cellulose, epoxy resin, organic bentonite and benzenesulfonic acid is (160-195): (118-130): (1-1.2): (0.8-1.2): (40-55): (30-38): (26-30): (15-18): (3.4-4.3).

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