CN111876058B - Polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and preparation method thereof - Google Patents
Polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and preparation method thereof Download PDFInfo
- Publication number
- CN111876058B CN111876058B CN202010690416.6A CN202010690416A CN111876058B CN 111876058 B CN111876058 B CN 111876058B CN 202010690416 A CN202010690416 A CN 202010690416A CN 111876058 B CN111876058 B CN 111876058B
- Authority
- CN
- China
- Prior art keywords
- polyester resin
- acid
- powder coating
- mgkoh
- resistant powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 72
- 239000011248 coating agent Substances 0.000 title claims abstract description 69
- 239000000843 powder Substances 0.000 title claims abstract description 57
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 52
- 239000004645 polyester resin Substances 0.000 title claims abstract description 52
- 238000013035 low temperature curing Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 18
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000006085 branching agent Substances 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- WYHYNUWZLKTEEY-UHFFFAOYSA-N cyclobutane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C1 WYHYNUWZLKTEEY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 21
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 18
- 238000012360 testing method Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000005070 sampling Methods 0.000 claims description 14
- 229920001897 terpolymer Polymers 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 4
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 2
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000005903 acid hydrolysis reaction Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
- -1 3, 5-di-tert-butyl-4-hydroxyphenyl Chemical group 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and a preparation method thereof, wherein the acid value of the polyester resin is 30-38 mgKOH/g, the glass transition temperature is 55-65 ℃, the melt viscosity at 200 ℃ is 2500-6000 mPa & s, and the polyester resin is prepared from the following raw materials: 28-43% of polyol, 0.1-1.8% of branching agent, 39-63% of polybasic acid, 1-10% of epoxy group ternary ethylene copolymer, 3-12% of acidolysis agent, 0.5-6% of 1, 3-cyclobutane dicarboxylic acid, 0.06-0.23% of esterification catalyst and 0.5-1.0% of antioxidant. The polyester resin can be used for preparing super-weather-resistant powder coating with a beta-hydroxyalkylamide compound, the prepared powder coating has good storage stability, the curing at 140-160 ℃ can be realized, and the cured coating has excellent ageing resistance and impact resistance.
Description
Technical Field
The invention relates to the technical field of polyester resin, in particular to polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and a preparation method thereof.
Background
The powder coating is a solid powder coating composed of solid resin, pigment, filler, auxiliary agent and the like, has the advantages of no solvent, zero VOC, recyclability, easy spraying (the thickness of one-time coating can reach 30-500 microns), excellent comprehensive performance, low cost and the like, and is widely applied to the fields of household appliances, mechanical equipment, anticorrosive pipelines, building materials and the like. Powder coatings exposed to the open air are subject to degradation by aging due to a variety of factors including exposure to sunlight, moisture, pollutants (e.g., acid rain), and temperature changes. As the degradation process progresses, the powder coating can have appearance changes such as reduced gloss, yellowing, chalking and the like, the decorative performance of the powder coating is influenced, and the product failure caused by the aging of the coating can cause billions of capital loss every year. The weather resistance of the coating is improved, and the application of the super weather-resistant powder coating is an important way for prolonging the service life of the product and reducing the aging loss of the coating.
The traditional super weather-resistant powder coating needs more than 180 ℃ for curing, and has higher energy consumption, and researches show that the curing temperature is reduced by 10 ℃ every time, and the coating energy can be saved by about 10 percent. With the trend of environmental protection and the enhancement of social environmental protection consciousness, the coating of the super-weather-resistant powder coating is developing rapidly towards the field of low-temperature curing (160 ℃), and the low-temperature curing powder coating becomes the inevitable development trend of the powder coating industry.
CN104530408B discloses a polyester resin for super-weather-resistant powder coating, which is prepared by using fluorinated organic alcohol and fluorinated organic acid as raw materials to carry out polyester synthesis, and the prepared product has extremely strong water resistance and light resistance and can meet the super-weather-resistant requirement of special fields; CN106750222A discloses carboxyl-terminated fluorine-containing polyester resin for super-weather-resistant powder coating and a preparation method thereof, wherein the fluorine content is 5% of a Primid system with the content of 1%, and the prepared powder coating has the advantages of super-weather resistance, high glossiness, excellent leveling property, excellent impact property and the like. The technology of using fluorine modified polyester in the patent can realize the ultra-weather resistance of the coating, and the prepared polyester is suitable for curing at the temperature of more than 180 ℃.
CN109280468A discloses an organic silicon modified polyester resin for super weather-proof powder coating and a preparation method thereof, wherein the resin is mainly prepared from dihydric alcohol, polyhydric alcohol, organic silicon, dibasic acid, a silanol catalyst, an esterification catalyst and an acidolysis agent; CN110527073A discloses a high-temperature-resistant and super-weather-resistant silicon-containing polyester resin for powder coating, and the prepared powder coating has high gloss, excellent mechanical properties, and excellent leveling property and heat resistance. The coating is endowed with super-weather resistance by the way of modifying polyester by silicon, and the curing temperature of the prepared polyester is 200 ℃.
CN102504219B discloses a preparation method of polyester resin for super weather-proof outdoor powder coating, wherein polyhydric alcohol and polybasic acid are subjected to polycondensation to prepare high-molecular polyester resin, and the product has high gloss and excellent weather resistance; CN107189045A discloses a low-temperature super-weather-resistant bending-resistant saturated polyester resin for TGIC system powder coating and a preparation method thereof, wherein super-weather-resistant polyester suitable for being cured at 170 ℃ for 15min by TGIC is synthesized by adjusting the proportion of trimethylolpropane, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid; CN103131308B discloses a high-low acid value two-component carboxyl-terminated polyester resin composition for an ultra-weather-resistant dry-mixed extinction powder coating, wherein the ultraviolet light-resistant accelerated aging time of the polyester is more than 2 times of that of a conventional weather-resistant extinction powder coating. The super-weather-resistant performance of the polyester coating is realized by adjusting the proportion of the polyhydric alcohol and the polybasic acid in the formula, and the curing temperature of the polyester is higher than 170 ℃.
The existing super-weather-resistant powder coating is generally problematic in certain curing process at a lower temperature (160 ℃): (1) the ultra-weather resistance of polyester resin is generally realized by high IPA content in the formula, but the defect of deterioration of the mechanical property of the resin is caused, or the weather resistance is improved by using alicyclic polybasic acid to replace aromatic polybasic acid, introducing organosilicon modification and the like, but the glass transition temperature of the resin is easy to be lowered, and the storage stability of the powder is reduced; (2) in order to ensure the leveling appearance and mechanical properties of the ultraweatherable polyester coating at low curing temperatures, the glass transition temperature of the polyester resin is generally designed to be low so that the coating has low melt viscosity at a low curing temperature and better flexibility is imparted to the coating, but this causes the prepared powder coating to be prone to caking during storage.
Disclosure of Invention
The invention aims to provide polyester resin for Primid system low-temperature curing powder coating and a preparation method thereof, the powder coating prepared from the polyester can be cured at the temperature of 140-160 ℃, and the cured coating has outstanding ultra-weather resistance and impact resistance and good storage stability.
The applicant finds that by introducing an epoxy group terpolymer unit into a polyester structure, the storage stability of the powder coating can be ensured, and simultaneously the impact resistance and the weather resistance of the super weather-resistant powder coating under the condition of low-temperature curing can be improved; the 1, 3-cyclobutane dicarboxylic acid is used for polyester end capping through a specific acidolysis process, the aliphatic ring structure can provide better ultraviolet aging resistance for the coating, the glass transition temperature of the polyester is not greatly reduced, and the polyester powder coating can be prepared and cured at the low temperature of below 160 ℃.
Specifically, the technical scheme adopted by the invention is as follows:
the invention provides polyester resin for a Primid system low-temperature curing super-weather-resistant powder coating, which has an acid value of 30-38 mgKOH/g, a glass transition temperature of 55-65 ℃ and a melt viscosity of 2500-6000 mPa & s at 200 ℃, and is prepared from the following raw materials in percentage by mass: 28-43% of polyol, 0.1-1.8% of branching agent, 39-63% of polybasic acid, 1-10% of epoxy group ternary ethylene copolymer, 3-12% of acidolysis agent, 0.5-6% of 1, 3-cyclobutane dicarboxylic acid, 0.06-0.23% of esterification catalyst and 0.5-1.0% of antioxidant.
Preferably, the polyester resin is prepared from the following raw materials in percentage by mass: 28-40% of polyol, 0.1-1.5% of branching agent, 40-60% of polyacid, 3-10% of epoxy-based terpolymer, 3-12% of acidolysis agent, 1-5% of 1, 3-cyclobutane dicarboxylic acid, 0.08-0.2% of esterification catalyst and 0.5-1.0% of antioxidant.
Preferably, the polyol is at least one selected from the group consisting of neopentyl glycol, 2-butyl-2-ethyl-1, 3-propanediol, and 1, 4-cyclohexanedimethanol.
Preferably, the branching agent is at least one selected from trimethylolpropane, trimethylolethane, glycerol, and pentaerythritol.
Preferably, the polybasic acid is at least one selected from isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, adipic acid, succinic acid, and dodecanedioic acid.
Preferably, the epoxy-based terpolymer is selected from ethylene-butyl acrylate-glycidyl methacrylate terpolymer (PTW) from dupont.
Preferably, the acid hydrolysis agent is selected from at least one of isophthalic acid, trimellitic anhydride, pyromellitic anhydride, adipic acid and succinic acid, wherein the molar percentage of the isophthalic acid is not less than 60% of the acid hydrolysis agent; more preferably, the acid hydrolysis agent is at least one selected from isophthalic acid, pyromellitic anhydride and succinic acid, wherein the molar percentage of the isophthalic acid is not less than 70% of the acid hydrolysis agent.
Preferably, the esterification catalyst is at least one selected from the group consisting of monobutyl tin oxide, monobutyl triisooctanoic acid tin and stannous oxalate.
Preferably, the antioxidant is at least one selected from hindered phenol antioxidants and phosphite antioxidants; more preferably, the antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010), tetrakis (2, 4-di-tert-butylphenyl-4, 4' -biphenyl) bisphosphonite (P-EPQ).
Another object of the present invention is to provide a method for preparing the above polyester resin, comprising the steps of:
adding polyol, a branching agent and an esterification catalyst into a reaction vessel according to a ratio, heating to 160 ℃ under the protection of nitrogen, adding a ratio of polybasic acid, introducing nitrogen, continuously heating for reaction, gradually heating to 248 ℃, reacting for 2-5 hours until the material is clear, and sampling to test the acid value to be 4-15 mgKOH/g; cooling to 220 ℃, adding the acidolysis agent and the epoxy group terpolymer into the reaction kettle according to the proportion, reacting for 1-3 hours, sampling and testing the acid value, wherein the acid value reaches 40-45 mgKOH/g; adding 1, 3-cyclobutane dicarboxylic acid in a proportion into a reaction kettle, continuously reacting for 2-4 hours until the acid value reaches 45-50 mgKOH/g, performing vacuum polycondensation for 1-3 hours at a vacuum degree of-0.097 MPa, the acid value reaches 30-38 mgKOH/g, the melt viscosity reaches 2500-6000 mPa & s (200 ℃), stopping vacuum-pumping, adding an antioxidant, uniformly stirring and dispersing, and discharging to obtain the polyester resin for the Primid system low-temperature curing super-weather-resistant powder coating.
Detailed Description
The present invention will be described in further detail with reference to examples. It will also be understood that the following examples are included merely for purposes of further illustrating the invention and are not to be construed as limiting the scope of the invention, as the invention extends to insubstantial modifications and adaptations of the invention following in the light of the principles set forth herein. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples.
The present invention will be described in detail below with reference to examples and comparative examples, in which the components of the polyester resins of the examples and comparative examples are shown in Table 1 below (unless the following components are specifically noted in units of g):
TABLE 1
The properties of the polyester resins of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 2 below:
TABLE 2
Note: the acid value was tested according to GB/T6743-; viscosity was tested according to astm d 4287; the glass transition temperature was tested according to GB/T19466.2.
The preparation method of the polyester resin of examples 1 to 4 is as follows:
adding polyol, a branching agent and an esterification catalyst into a reaction vessel according to a ratio, heating to 160 ℃ under the protection of nitrogen, adding a ratio of polybasic acid, introducing nitrogen, continuously heating for reaction, gradually heating to 248 ℃, reacting for 2-5 hours until the material is clear, and sampling to test the acid value to be 4-15 mgKOH/g; cooling to 220 ℃, adding the acidolysis agent and the epoxy group terpolymer into the reaction kettle according to the proportion, reacting for 1-3 hours, sampling and testing the acid value, wherein the acid value reaches 40-45 mgKOH/g; adding 1, 3-cyclobutane dicarboxylic acid in a ratio into a reaction kettle, continuously reacting for 2-4 hours until the acid value reaches 45-50 mgKOH/g, performing vacuum polycondensation for 1-3 hours, keeping the vacuum degree at-0.097 MPa, keeping the acid value at 30-38 mgKOH/g, and the melt viscosity reaches 2500-6000 mPa & s (200 ℃), stopping vacuum-pumping, adding an antioxidant, uniformly stirring and dispersing, and discharging to obtain the polyester resin for the low-temperature curing super-weather-resistant powder coating.
The polyester resin of comparative example 1 was prepared as follows:
adding polyol, a branching agent and an esterification catalyst into a reaction vessel according to a ratio, heating to 160 ℃ under the protection of nitrogen, adding a ratio of polybasic acid, introducing nitrogen, continuously heating for reaction, gradually heating to 248 ℃, reacting for 2-5 hours until the material is clear, and sampling to test the acid value to be 4-15 mgKOH/g; cooling to 220 ℃, adding the acidolysis agent, the epoxy group ternary ethylene copolymer and the 1, 3-cyclobutane dicarboxylic acid in proportion into a reaction kettle, reacting for 2-4 hours, sampling, testing the acid value, wherein the acid value reaches 45-50 mgKOH/g, vacuumizing, polycondensing for 1-3 hours, the vacuum degree is-0.097 MPa, the acid value reaches 30-38 mgKOH/g, the melt viscosity reaches 2500-6000 mPa.s (200 ℃), stopping vacuumizing, adding the antioxidant, stirring uniformly, and discharging to obtain the polyester resin.
The polyester resin of comparative example 2 was prepared as follows:
adding polyol, a branching agent and an esterification catalyst into a reaction vessel according to a ratio, heating to 160 ℃ under the protection of nitrogen, adding a ratio of polybasic acid, introducing nitrogen, continuously heating for reaction, gradually heating to 248 ℃, reacting for 2-5 hours until the material is clear, and sampling to test the acid value to be 4-15 mgKOH/g; and cooling to 220 ℃, adding the acidolysis agent and the epoxy group ternary ethylene copolymer in proportion into a reaction kettle, reacting for 2-4 hours, sampling, testing the acid value, wherein the acid value reaches 45-50 mgKOH/g, vacuumizing, polycondensing for 1-3 hours, the vacuum degree is-0.097 MPa, the acid value reaches 30-38 mgKOH/g, the melt viscosity reaches 2500-6000 mPa.s (200 ℃), stopping vacuumizing, adding the antioxidant, stirring, dispersing uniformly, and discharging to obtain the polyester resin.
The polyester resin of comparative example 3 was prepared as follows:
adding polyol, a branching agent and an esterification catalyst into a reaction vessel according to a ratio, heating to 160 ℃ under the protection of nitrogen, adding a ratio of polybasic acid, introducing nitrogen, continuously heating for reaction, gradually heating to 248 ℃, reacting for 2-5 hours until the material is clear, and sampling to test the acid value to be 4-15 mgKOH/g; cooling to 220 ℃, adding the acidolysis agent in a proportion into the reaction kettle, reacting for 1-3 hours, sampling and testing the acid value, wherein the acid value reaches 40-45 mgKOH/g; adding 1, 3-cyclobutane dicarboxylic acid in a proportional amount into a reaction kettle, continuously reacting for 2-4 hours until the acid value reaches 45-50 mgKOH/g, carrying out vacuum polycondensation for 1-3 hours, keeping the vacuum degree at-0.097 MPa, keeping the acid value at 30-38 mgKOH/g, and keeping the melt viscosity at 2500-6000 mPa.s (200 ℃), stopping vacuum-pumping, adding an antioxidant, stirring uniformly, dispersing, and discharging to obtain the polyester resin.
Performance testing of powder coatings made from the polyester resins of examples 1-4 and comparative examples 1-3:
1. respectively weighing the polyester resins of the examples 1-4 and the comparative examples 1-3, the beta-hydroxyalkylamide curing agent T-105, the flatting agent GLP588, the titanium dioxide, the barium sulfate and the benzoin according to the proportion shown in the following table 3, uniformly mixing (note: if no special description is provided, the component units in the table 3 are g), performing melt extrusion, tabletting and crushing by using a screw extruder, and then crushing and sieving the tablets to obtain a powder coating;
TABLE 3
2. Powder coatings prepared from the polyester resins of examples 1-4 and comparative examples 1-3 of the invention are electrostatically sprayed on an iron plate, cured at 150 ℃ for 15min to obtain an ultra-weather-resistant powder coating with the thickness of 60-70 mu m, and then subjected to performance tests, wherein the test results are shown in Table 4:
(1) gloss was tested according to GB/T9754-2007;
(2) impact was tested according to GB/T1732-1993;
(3) UVB aging was tested according to GB/T14522-2008;
(4) the powder storage stability was tested according to GB/T21782.8-2008.
TABLE 4
Remarking: the higher the level of powder agglomeration, the more severe the agglomeration tendency.
As can be seen from Table 4: the low-temperature curing super-weather-resistant powder coating prepared from the polyester resin in the embodiments 1-4 can be cured at the temperature below 160 ℃, the coating has excellent ageing resistance and impact resistance, the prepared powder coating has good storage stability, and the powder coating prepared from the conventional polyester resin (comparative examples 1-3) has the problems of incomplete curing of the coating, poor impact resistance and ageing resistance of the coating, easy agglomeration of the powder coating and the like when cured at a low temperature (the temperature is lower than 160 ℃).
Claims (9)
1. A polyester resin for Primid system low-temperature curing super-weather-resistant powder coating is characterized in that: the acid value of the polyester resin is 30-38 mgKOH/g, the glass transition temperature is 55-65 ℃, the melt viscosity at 200 ℃ is 2500-6000 mPa & s, and the polyester resin is prepared from the following raw materials in percentage by mass: 28 to 43 percent of polyol, 0.1 to 1.8 percent of branching agent, 39 to 63 percent of polybasic acid, 1 to 10 percent of epoxy group ternary ethylene copolymer, 3 to 12 percent of acidolysis agent, 0.5 to 6 percent of 1, 3-cyclobutane dicarboxylic acid, 0.06 to 0.23 percent of esterification catalyst and 0.5 to 1.0 percent of antioxidant;
the preparation method of the polyester resin comprises the following preparation steps: adding polyol, a branching agent and an esterification catalyst into a reaction vessel according to a ratio, heating to 160 ℃ under the protection of nitrogen, adding a ratio of polybasic acid, introducing nitrogen, continuously heating for reaction, gradually heating to 248 ℃, reacting for 2-5 hours until the material is clear, and sampling to test the acid value to be 4-15 mgKOH/g; cooling to 220 ℃, adding the acidolysis agent and the epoxy group terpolymer into the reaction kettle according to the proportion, reacting for 1-3 hours, sampling and testing the acid value, wherein the acid value reaches 40-45 mgKOH/g; adding 1, 3-cyclobutane dicarboxylic acid in a ratio into a reaction kettle, continuously reacting for 2-4 hours until the acid value reaches 45-50 mgKOH/g, performing vacuum polycondensation for 1-3 hours at a vacuum degree of-0.097 MPa, the acid value reaches 30-38 mgKOH/g, the melt viscosity reaches 2500-6000 mPa & s at 200 ℃, stopping vacuum-pumping, adding an antioxidant, uniformly stirring and dispersing, and discharging to obtain the polyester resin.
2. The Primid system polyester resin for low temperature curing super weather resistant powder coating according to claim 1, characterized in that: the polyol is at least one of neopentyl glycol, 2-butyl-2-ethyl-1, 3-propanediol and 1, 4-cyclohexanedimethanol.
3. The Primid system polyester resin for low temperature curing super weather resistant powder coating according to claim 1, characterized in that: the branching agent is at least one selected from trimethylolpropane, trimethylolethane, glycerol and pentaerythritol.
4. The Primid system polyester resin for low temperature curing super weather resistant powder coating according to claim 1, characterized in that: the polybasic acid is selected from at least one of isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, adipic acid, succinic acid and dodecanedioic acid.
5. The Primid system polyester resin for low temperature curing super weather resistant powder coating according to claim 1, characterized in that: the epoxy-based terpolymer is selected from ethylene-butyl acrylate-glycidyl methacrylate terpolymer.
6. The Primid system polyester resin for low temperature curing super weather resistant powder coating according to claim 1, characterized in that: the acidolysis agent is at least one of isophthalic acid, trimellitic anhydride, pyromellitic anhydride, adipic acid and succinic acid, wherein the mole percentage of the isophthalic acid is not lower than 60% of the acidolysis agent.
7. The Primid system polyester resin for low temperature curing super weather resistant powder coating according to claim 1, characterized in that: the esterification catalyst is at least one of monobutyl tin oxide, monobutyl triisooctanoic acid tin and stannous oxalate.
8. The Primid system polyester resin for low temperature curing super weather resistant powder coating according to claim 1, characterized in that: the antioxidant is at least one selected from hindered phenol antioxidants and phosphite antioxidants.
9. The method for preparing the polyester resin for Primid system low-temperature curing super-weather-resistant powder coating according to any one of claims 1 to 8, comprising the steps of: the preparation method comprises the following preparation steps: adding polyol, a branching agent and an esterification catalyst into a reaction vessel according to a ratio, heating to 160 ℃ under the protection of nitrogen, adding a ratio of polybasic acid, introducing nitrogen, continuously heating for reaction, gradually heating to 248 ℃, reacting for 2-5 hours until the material is clear, and sampling to test the acid value to be 4-15 mgKOH/g; cooling to 220 ℃, adding the acidolysis agent and the epoxy group terpolymer into the reaction kettle according to the proportion, reacting for 1-3 hours, sampling and testing the acid value, wherein the acid value reaches 40-45 mgKOH/g; adding 1, 3-cyclobutane dicarboxylic acid in a ratio amount into a reaction kettle, continuously reacting for 2-4 hours until the acid value reaches 45-50 mgKOH/g, performing vacuum polycondensation for 1-3 hours, keeping the vacuum degree at-0.097 MPa, keeping the acid value at 30-38 mgKOH/g, and obtaining the polyester resin for the Primid system low-temperature curing super-weather-resistant powder coating after the melt viscosity reaches 2500-6000 mPa & s at 200 ℃ and stopping vacuum pumping, adding an antioxidant, stirring and dispersing uniformly, and discharging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010690416.6A CN111876058B (en) | 2020-07-17 | 2020-07-17 | Polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010690416.6A CN111876058B (en) | 2020-07-17 | 2020-07-17 | Polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111876058A CN111876058A (en) | 2020-11-03 |
| CN111876058B true CN111876058B (en) | 2022-02-18 |
Family
ID=73155716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010690416.6A Active CN111876058B (en) | 2020-07-17 | 2020-07-17 | Polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111876058B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960342A (en) * | 2022-12-29 | 2023-04-14 | 江苏百思德新材料有限公司 | Low-acid polyester resin for super weather-resistant bi-component powder coating and application thereof |
| CN115895010B (en) * | 2023-01-06 | 2023-05-02 | 河南华佳新材料技术有限公司 | Flame-retardant high-temperature-resistant metallized film for capacitor and preparation method thereof |
| CN116948157B (en) * | 2023-07-25 | 2025-09-30 | 擎天材料科技有限公司 | A low-temperature curing high-leveling polyester resin and its preparation method and application |
| CN116813891B (en) * | 2023-07-26 | 2024-04-16 | 惠州市华泓新材料股份有限公司 | Fatty acid modified polyester, preparation method and offset printing compound |
| CN117285854B (en) * | 2023-10-10 | 2025-10-28 | 廊坊市泰铭金属涂装材料有限公司 | A super weather-resistant powder coating for heavy machinery |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080048025A (en) * | 2005-09-14 | 2008-05-30 | 도요 보세키 가부시키가이샤 | Polyester, polyester manufacturing method, and polyester molding |
| KR20100112610A (en) * | 2008-01-09 | 2010-10-19 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Polyester composition resistant to hydrolysis |
| CN102311618B (en) * | 2010-06-29 | 2013-12-04 | 金发科技股份有限公司 | Hydrolysis-resistant aliphatic-aromatic copolyester and preparation method thereof |
| CN102010501B (en) * | 2010-10-27 | 2013-03-13 | 中国电器科学研究院 | Polyester resin for beta-hydroxyalkylamide low-temperature curing weather-resistant powder coating and preparation method thereof |
| CN103772921B (en) * | 2012-10-22 | 2016-06-29 | 黑龙江鑫达企业集团有限公司 | A kind of fiberglass reinforced polyethyleneterephthalate/polycarbonate alloy |
| CN102977346B (en) * | 2012-11-20 | 2014-12-10 | 广州擎天材料科技有限公司 | Polyester resin for triglycidyl isocyanurate (TGIC)-cured weather-resistant heat transfer printing powdery paint and preparation method thereof |
| CN103483565B (en) * | 2013-07-31 | 2015-12-23 | 广州擎天材料科技有限公司 | A kind of semi-crystalline polyester resin for TGIC curing high leveling powder coating and its synthetic method |
| CN103740068A (en) * | 2013-12-30 | 2014-04-23 | 安徽科聚新材料有限公司 | Low-warpage high glow wire flame-retardant glass fiber-reinforced composite material and preparation method thereof |
| CN104845221A (en) * | 2014-12-17 | 2015-08-19 | 王妮娜 | Flame retardant modified PTT polyester |
-
2020
- 2020-07-17 CN CN202010690416.6A patent/CN111876058B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111876058A (en) | 2020-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111876058B (en) | Polyester resin for Primid system low-temperature curing super-weather-resistant powder coating and preparation method thereof | |
| EP3835379B1 (en) | Polyester resin composition, powder coating and workpiece | |
| CN101735431B (en) | Weather-resistant polyester resin with excellent water boiling resistance and preparation method thereof | |
| CN109280468B (en) | Silicone-modified polyester resin for ultra-weather-resistant powder coating and preparation method thereof | |
| TWI454503B (en) | Branched polyester for powder coatings | |
| CN111533892B (en) | Polyester resin for high-weather-resistance low-temperature TGIC (triglycidyl isocyanurate) curing powder coating and preparation method thereof | |
| CN103739830A (en) | A kind of polyester resin for TGIC curing high-toughness powder coating and preparation method thereof | |
| CN108641561B (en) | Polyester resin for extinction type powder coating, preparation method and extinction type powder coating | |
| CN111205446A (en) | A kind of high temperature resistant organic amine modified polyester resin and its preparation method and application | |
| CN113604136B (en) | Sand grain powder coating with super-delayed mechanical properties and preparation method thereof | |
| CN114316232B (en) | Polyester resin for high-hardness high-transparency powder coating and preparation method thereof | |
| CN112079998B (en) | Polyester resin with excellent mechanical properties and weather resistance for powder coating and preparation method thereof | |
| CN112625223B (en) | Solvent-free saturated polyester resin for coil steel finish paint and preparation method thereof | |
| CN119371645B (en) | High-transparency weather-resistant polyester resin and preparation method thereof | |
| CN112521838B (en) | Extinction transparent polyester resin composition and preparation method and application thereof | |
| CN114106304A (en) | Low-temperature curing weather-resistant polyester resin, low-temperature curing weather-resistant powder coating and preparation method | |
| US4379895A (en) | Acid-capped polyester resins | |
| CN112011257A (en) | Polyester resin for special vehicle powder coating and preparation method and application thereof | |
| CN115403752A (en) | Polyester resin and preparation method and application thereof | |
| CN108165170A (en) | High-weatherability powdery paints terminal carboxyl polyester resin and preparation method thereof | |
| CN113603872A (en) | Polyester resin with super-delayed mechanical property and preparation method and application thereof | |
| CN113999376A (en) | high-Tg high-impact-resistance polyester resin for dual-curable powder coating and preparation method and application thereof | |
| CN115466379B (en) | Super weather-resistant polyester resin composition and preparation method and application thereof | |
| CN113248694A (en) | Super-weather-resistant flexible polyester resin and preparation method thereof | |
| CN117659832B (en) | A polyester resin composition for matte powder coatings, its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |