CN112646150A - Boiling-resistant high-leveling polyester resin for HAA (haha) cured powder coating and preparation method thereof - Google Patents
Boiling-resistant high-leveling polyester resin for HAA (haha) cured powder coating and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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Abstract
The invention discloses a boiling-resistant high-leveling polyester resin for HAA curing powder coating and a preparation method thereof, wherein the resin is prepared by copolymerization of 2,3,5, 6-tetrafluoroterephthalic acid, tetrahydrophthalic anhydride, isophthalic acid, isosorbide, 2,5-2 (N-dodecyl formamide) -terephthalic acid, neopentyl glycol, 2,3, 3-tetrafluoro-1, 4-butanediol and 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol. The prepared polyester resin has an acid value of 33-37mgKOH/g, a viscosity of 2000-5000mPa.s and a hydroxyl value of less than 2.5 mgKOH/g. The reaction speed of the terminal carboxyl and the HAA hydroxyl can be greatly reduced, so that the powder coating has excellent leveling property and surface fineness, and simultaneously, the storage stability of the system is ensured due to the rigid structure of the powder coating.
Description
Technical Field
The invention belongs to the field of polyester resin for powder coating, and particularly relates to a boiling-resistant high-leveling polyester resin for HAA (heat-resistant acrylic) cured powder coating and a synthesis method thereof.
Background
Outdoor powder coating systems are divided into triglycidyl isocyanurate (TGIC) and Hydroxyalkylamide (HAA) groups according to their curing systems. The TGIC has a triazine ring epoxy structure, the prepared powder coating has high film hardness, clear and bright plate surface, no pinhole in thick coating, good weather resistance, yellowing resistance and adjustable curing speed; but has biological sensitization and potential carcinogenicity, and is clearly specified by the European Union, so that the powder coating cannot be used as a curing agent of powder coating; in addition, because of good compatibility with polyester, small molecular TGIC can generate strong plasticizing effect after being added into polyester, so that the Tg of the powder can be greatly reduced by the TGIC, and the storage stability of the powder is further influenced. HAA has a high-activity amide hydroxyl structure, has the advantages of energy conservation, no toxicity and mechanical properties, and has poor compatibility with polyester, and the Tg of the powder is not reduced basically, so that the storage stability of the powder is not influenced; meanwhile, due to the inherent chemical structure, the curing speed is still fast even under the condition of no catalyst, and the leveling of the obtained coating cannot achieve a satisfactory effect; in addition, the HAA has a four-methylene structure in the middle, so that the glass transition temperature of a coating film is low, and the water boiling resistance is poor. Therefore, a polyester resin of an HAA curing system with good water boiling resistance and excellent leveling property needs to be synthesized.
Chinese patent CN107254035A discloses a polyester resin for beta hydroxyalkylamide cured powder coating with good water resistance and a preparation method thereof, the invention adopts conventional polyalcohol, polybasic acid and hydrogenated dimer acid to synthesize the polyester resin by a two-step method under the action of tin catalysts, and the obtained powder coating has excellent boiling, leveling and fullness. The invention mainly relies on hydrogenated dimer acid to obtain boiling-resistant polyester, the acid value of the resin is lower, the late-stage and HAA curing crosslinking density is low, and the boiling-resistant polyester is possibly unfavorable for water boiling; furthermore, the low Tg of the polyesters may influence the storage stability, and no mention is made of the residual hydroxyl number. Chinese patent CN101735431A discloses a weather-resistant polyester resin with excellent water boiling resistance and a preparation method thereof, the invention adopts general dibasic acid and polyhydric alcohol to synthesize the polyester resin by a two-step method under the action of a catalyst, the resin has high Tg and proper viscosity, and the obtained TGIC powder coating has excellent water boiling, leveling and mechanical properties. The polyester is mainly used for TGIC curing, is environmentally unfavorable, and does not mention the boiling resistance and leveling property of a coating obtained after HAA curing.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a boiling-resistant high-leveling polyester resin for HAA curing powder coating, and the obtained polyester resin product has good boiling resistance, excellent leveling property and surface fineness.
In order to obtain the polyester, the following technical scheme is adopted:
the boiling-resistant high-leveling polyester resin for the HAA curing powder coating is characterized by being prepared by polycondensation of main raw materials, namely 2,3,5, 6-tetrafluoroterephthalic acid, tetrahydrophthalic anhydride, isophthalic acid, isosorbide, 2,5-2 (N-dodecylformamide) -terephthalic acid, neopentyl glycol, 2,3, 3-tetrafluoro-1, 4-butanediol and 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol.
The raw materials comprise the following components:
in order to realize good boiling resistance, the invention copolymerizes fluorine-containing hydrophobic monomers and conventional monomers with good water resistance to obtain oligomers, and simultaneously adds synthesized 2,5-2 (N-dodecyl formamide) -terephthalic acid containing long side chains into the oligomers to be terminated, and then carries out vacuum polycondensation to obtain polyester with good boiling resistance; and finally, the polyester powder coating is more resistant to boiling through the auxiliary collocation of the silane coupling agent. In addition, the long-carbon alkane-based structure of the 2,5-2 (N-dodecyl formamide) -terephthalic acid has great steric hindrance effect on two carboxyl groups, so that the reaction speed of the terminal carboxyl group and the HAA hydroxyl group can be greatly reduced, the powder coating has excellent leveling property and surface fineness, and the storage stability of the system is ensured due to the rigid structure.
Preferably, the amount of the catalyst added in the polyester synthesis is 0.05 to 0.3 percent of the total mole number of the materials;
preferably, the catalyst in the polyester synthesis is tetra-n-propyl zirconate;
preferably, in order to prevent the materials from yellowing in the synthesis process, 0.05 to 0.15 percent of antioxidant based on the total molar number of the materials is also added;
preferably, the antioxidant is DSTP.
2,5-2 (N-dodecylformamide) -terephthalic acid
The formic acid has the following structural formula:
preferably, 2,5-2 (N-dodecylformamide) -terephthalic acid is prepared as follows: slowly dripping the pyromellitic dianhydride solution into the dodecane primary amine solution for amidation dehydration reaction, and then separating and purifying to obtain the 2,5-2 (N-dodecyl formamide) -terephthalic acid.
Preferably, the molar ratio of pyromellitic anhydride to dodecane primary amine is 1: 2;
preferably, the solvent for dissolving pyromellitic anhydride and dodecane primary amine is acetone or tetrahydrofuran;
preferably, the temperature of the amidation reaction is 25-35 ℃ and the automatic liquid-adding device dropping speed is 40-60 drops/min.
The invention also aims to provide a preparation method of the boiling-resistant high-leveling polyester resin for HAA cured powder coating, which comprises the following steps:
(1) adding neopentyl glycol, 2,3, 3-tetrafluoro-1, 4-butanediol and 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol into a four-neck flask according to the formula amount, stirring, heating and melting;
(2) adding 2,3,5, 6-tetrafluoroterephthalic acid and tetra-n-propyl zirconate into the mixture obtained in the step (1), introducing protective gas, and heating for esterification until the material is clear and transparent;
(3) adding isophthalic acid, tetrahydrophthalic anhydride and isosorbide into the oligomer obtained in the step (2), and continuing esterification until no distillate is discharged from a reaction system;
(4) adding an antioxidant DSTP, carrying out vacuum polycondensation, and stopping when the acid value of the reaction material is less than 8 mgKOH/g;
(5) adding 2,5-2 (N-dodecyl formamide) -terephthalic acid, slowly carrying out esterification reaction with polyester, detecting the acid value of the material to be 43-49mgKOH/g when the system has no distillate, and further carrying out vacuum until the acid value of the material is 33-37 mgKOH/g;
(6) cooling, adding auxiliary agent and discharging.
Preferably, the stirring speed in step (1) is 100-180 rpm, preferably 150 rpm.
Preferably, the protective gas in step (2) is nitrogen or argon, preferably nitrogen.
Preferably, the overall process esterification temperature is 235-245 ℃.
Preferably, the esterification and copolymerization process, the stirring speed is 200-300 r/min, preferably 250 r/min.
Preferably, the vacuum process is carried out, and the vacuum degree is controlled to be-0.09- (-0.1), and is preferably-0.097.
Preferably, the auxiliary agent is a silane coupling agent, and the addition amount of the silane coupling agent is 0.2% of the total moles of the formula.
Preferably, the polyester resin has an acid value of 33-37mgKOH/g, a viscosity of 2000-5000mpa.s/200 ℃, and a hydroxyl value of less than 2.5 mgKOH/g.
The HAA curing powder coating containing the polyester resin is prepared from the following raw materials in percentage by mass: 3% of beta hydroxyalkyl amide, 57% of polyester resin as claimed in claim 1, 20% of titanium dioxide, 18.5% of 5HB, 1% of leveling agent, 0.3% of benzoin and 0.2% of CB, and the beta hydroxyalkyl amide is obtained by mixing, melt extrusion, tabletting, crushing and sieving.
The polyester resin finally obtained by the invention has more hydrophobic fluorine elements in molecular chain segments, and can obviously improve the boiling resistance of the HAA system coating; in addition, 2,5-2 (N-dodecyl formamide) -terephthalic acid is used as an end-capping reagent, so that a long side chain structure is arranged beside a carboxyl group at the end position of a polyester molecule, and the corrosion of water molecules to resin and HAA crosslinking parts is further shielded; more importantly, the dibasic acid with the special structure can obviously slow down the reaction speed with HAA, the obtained coating has more excellent leveling property, boiling resistance and surface fineness, and simultaneously, the storage stability of the system is improved due to the rigid structure of the coating.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the examples.
Example 1
The preparation method of the boiling-resistant high-leveling polyester resin for the HAA cured powder coating comprises the following steps:
(1) adding neopentyl glycol, 2,3, 3-tetrafluoro-1, 4-butanediol and 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol into a four-neck flask according to the formula amount and shown in Table 1, opening the flask to stir at the rotating speed of 150 revolutions per minute, and heating and melting;
(2) adding 2,3,5, 6-tetrafluoroterephthalic acid and tetra-n-propyl zirconate into the mixture obtained in the step (1), introducing protective gas, stirring at a rotating speed of 250 r/min, and continuously heating for esterification until the material is clear and transparent, wherein the esterification heat preservation temperature is 240 ℃;
(3) adding isophthalic acid, tetrahydrophthalic anhydride and isosorbide into the oligomer obtained in the step (2), and continuing esterification until no distillate comes out from the reaction system, wherein the esterification temperature is 239 ℃;
(4) adding antioxidant DSTP, and carrying out vacuum polycondensation, wherein the vacuum degree is less than-0.097, and the reaction is stopped when the acid value of the reaction material is 7.82 mgKOH/g;
(5) adding 2,5-2 (N-dodecyl formamide) -terephthalic acid, slowly carrying out esterification reaction with polyester, detecting the acid value of the material to be 43-49mgKOH/g when the system has no distillate, and further carrying out vacuum until the acid value of the material is 33-37 mgKOH/g;
(6) cooling, adding 0.2% of silane coupling agent, and discharging.
The raw material composition of each formulation in examples 1-4 is shown in table 1:
TABLE 1 amount (moles) of each raw material used in examples 1 to 4
Comparative example 1: the procedure is as in example 1 except that 2,2,3, 3-tetrafluoro-1, 4-butanediol is not used.
Comparative example 2: the procedure is as in example 1 except that 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol is not used.
Comparative example 3: the procedure is as in example 1 except that 2,5-2 (N-dodecylformamide) -terephthalic acid is not used.
Comparative example 4: the procedure of example 1 was repeated, except that 2,3,5, 6-tetrafluoroterephthalic acid was not used.
Comparative example 5: the procedure of example 1 was repeated, except that 2,3,5, 6-tetrafluoroterephthalic acid was changed to terephthalic acid.
Comparative example 6: the polyester resin in example A of Chinese patent CN107254035A is adopted.
TABLE 2 relevant technical indices corresponding to the polyester resins of the examples and comparative examples
| Acid value (mgKOH/g) | Hydroxyl value (mgKOH/g) | Viscosity (mpa.s/200 ℃ C.) | |
| Example 1 | 33.15 | 1.92 | 3510 |
| Example 2 | 35.64 | 2.34 | 2930 |
| Example 3 | 36.87 | 2.11 | 4560 |
| Example 4 | 34.97 | 1.89 | 4230 |
| Comparative example 1 | 33.59 | 2.24 | 3980 |
| Comparative example 2 | 36.14 | 2.35 | 4800 |
| Comparative example 3 | 36.55 | 2.44 | 4620 |
| Comparative example 4 | 34.99 | 2.01 | 4020 |
| Comparative example 5 | 33.32 | 2.47 | 3860 |
| Comparative example 6 | 26.54 | 5.71 | 6850 |
HAA curing powder system formula: 30g of beta hydroxyalkyl amide, 570g of polyester resin of examples and comparative examples, 200g of titanium dioxide, 5HB185g, 10g of flatting agent, 3g of benzoin and CB2g, and the materials are subjected to mixing, melt extrusion, tabletting, crushing and sieving to obtain powder with a certain particle size, electrostatic spraying, and curing in an oven at 180 ℃ for 20min to obtain a coating, wherein the detection results are shown in the following table 3.
| Gel time (s/180 ℃ C.) | Levelling out (PCI) | Impact (kg. cm) | Gloss (%) | |
| Example 1 | 267 | 7+ | 50/50 | 96.3 |
| Example 2 | 308 | 8 | 50/50 | 97.5 |
| Example 3 | 321 | 8 | 50/50 | 97.8 |
| Example 4 | 275 | 7+ | 50/50 | 96.8 |
| Comparative example 1 | 245 | 7 | 50/50 | 94.1 |
| Comparative example 2 | 236 | 7 | 50/50 | 93.5 |
| Comparative example 3 | 165 | 6- | 50/45 | 89.3 |
| Comparative example 4 | 261 | 6+ | 15/0 | 93.6 |
| Comparative example 5 | 255 | 6+ | 50/40 | 94.3 |
| Comparative example 6 | 198 | 6 | 50/45 | 93.4 |
Boiling resistance test conditions of the HAA cured powder coating: 100 ℃ results are given in Table 4 below
As can be seen from Table 3, after 2,5-2 (N-dodecylformamide) -terephthalic acid is added, the gelation time of the HAA curing system is obviously longer than that of an unadditized system, which shows that the monomer can obviously slow down the reaction speed of terminal carboxyl and HAA, improve the leveling of the coating, improve the wettability of polyester to pigments and fillers by the long-carbon-chain alkyl structure and fluorine element, and further improve the leveling, gloss and surface fineness of the coating. As can be seen from Table 4, compared with the comparative example, the polyester resin obtained by the invention has hydrophobic fluorine element and high steric hindrance structure, so that the resin coating has very good boiling resistance and adhesion after boiling.
Claims (11)
1. The boiling-resistant high-leveling polyester resin for the HAA curing powder coating is characterized by being prepared by polycondensation of main raw materials, namely 2,3,5, 6-tetrafluoroterephthalic acid, tetrahydrophthalic anhydride, isophthalic acid, isosorbide, 2,5-2 (N-dodecylformamide) -terephthalic acid, neopentyl glycol, 2,3, 3-tetrafluoro-1, 4-butanediol and 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol.
2. The polyester resin according to claim 1, wherein the composition of the raw materials is as follows:
3. the boiling-resistant high-leveling polyester resin for the HAA curing powder coating according to claim 1 or 2, wherein the amount of the catalyst added in the polyester synthesis is 0.05-0.3% of the total mole number of the materials;
preferably, the catalyst in the polyester synthesis is tetra-n-propyl zirconate;
preferably, in order to prevent the materials from yellowing in the synthesis process, 0.05 to 0.15 percent of antioxidant based on the total molar number of the materials is also added;
preferably, the antioxidant is DSTP.
4. The polyester resin according to any of claims 1 to 3, wherein 2,5-2 (N-dodecylformamide) -terephthalic acid has the following structural formula:
preferably, 2,5-2 (N-dodecylformamide) -terephthalic acid is prepared as follows: slowly dripping the pyromellitic dianhydride solution into the dodecane primary amine solution for amidation dehydration reaction, and then separating and purifying to obtain the 2,5-2 (N-dodecyl formamide) -terephthalic acid.
5. The polyester resin according to claim 4, wherein the molar ratio of pyromellitic anhydride to dodecylprimary amine is 1: 2;
preferably, the solvent for dissolving pyromellitic anhydride and dodecane primary amine is acetone or tetrahydrofuran;
preferably, the temperature of the amidation reaction is 25-35 ℃ and the dropping speed of the liquid adding device is 40-60 drops/min.
6. The method for preparing polyester resin according to any one of claims 1 to 5, comprising the steps of:
(1) adding neopentyl glycol, 2,3, 3-tetrafluoro-1, 4-butanediol and 2,2,3,3,4, 4-hexafluoro-1, 5-pentanediol into a four-neck flask according to the formula amount, stirring, heating and melting;
(2) adding 2,3,5, 6-tetrafluoroterephthalic acid and tetra-n-propyl zirconate into the mixture obtained in the step (1), introducing protective gas, and heating for esterification until the material is clear and transparent;
(3) adding isophthalic acid, tetrahydrophthalic anhydride and isosorbide into the oligomer obtained in the step (2), and continuing esterification until no distillate is discharged from a reaction system;
(4) adding an antioxidant DSTP, carrying out vacuum polycondensation, and stopping when the acid value of the reaction material is less than 8 mgKOH/g;
(5) adding 2,5-2 (N-dodecyl formamide) -terephthalic acid, slowly carrying out esterification reaction with polyester, detecting the acid value of the material to be 43-49mgKOH/g when the system has no distillate, and further carrying out vacuum until the acid value of the material is 33-37 mgKOH/g;
(6) cooling, adding auxiliary agent and discharging.
7. The polyester resin according to claim 6, wherein the stirring speed in step (1) is 100-180 rpm, preferably 150 rpm.
8. The polyester resin according to claims 6 to 7, wherein the protective gas in step (2) is nitrogen or argon, preferably nitrogen;
preferably, the whole process esterification temperature is 235-245 ℃;
preferably, in the esterification copolymerization process, the stirring speed is 200-300 r/min, preferably 250 r/min;
preferably, the vacuum process is controlled to a vacuum degree of-0.09 to-0.1, preferably-0.097.
9. The polyester resin according to any one of claims 6 to 8, wherein the auxiliary agent is a silane coupling agent added in an amount of 0.2% based on the total moles of the formulation.
10. The polyester resin as claimed in any one of claims 6 to 9, wherein the polyester resin has an acid value of 33 to 37mgKOH/g, a viscosity of 2000 and 5000mpa.s/200 ℃, and a hydroxyl value of less than 2.5 mgKOH/g.
11. HAA-curable powder coating comprising the polyester resin according to claim 1, wherein the coating is prepared from the following raw materials in parts by mass: 3% of beta hydroxyalkyl amide, 57% of polyester resin as claimed in claim 1, 20% of titanium dioxide, 18.5% of 5HB, 1% of leveling agent, 0.3% of benzoin and 0.2% of CB, and the beta hydroxyalkyl amide is obtained by mixing, melt extrusion, tabletting, crushing and sieving.
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Cited By (3)
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| CN112961334A (en) * | 2021-04-25 | 2021-06-15 | 山东尚核电力科技有限公司 | Polyester resin for corrosion-resistant weather-resistant high-storage-performance powder coating |
| CN114163620A (en) * | 2021-12-23 | 2022-03-11 | 安徽神剑新材料股份有限公司 | Water-stain-resistant whitening-resistant polyester resin and preparation method and application thereof |
| CN115403752A (en) * | 2022-09-20 | 2022-11-29 | 擎天材料科技有限公司 | Polyester resin and preparation method and application thereof |
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| CN112961334A (en) * | 2021-04-25 | 2021-06-15 | 山东尚核电力科技有限公司 | Polyester resin for corrosion-resistant weather-resistant high-storage-performance powder coating |
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| CN115403752A (en) * | 2022-09-20 | 2022-11-29 | 擎天材料科技有限公司 | Polyester resin and preparation method and application thereof |
| CN115403752B (en) * | 2022-09-20 | 2024-05-14 | 擎天材料科技有限公司 | Polyester resin and preparation method and application thereof |
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