CN110591066B - Polyester resin for high-leveling self-curing powder coating and preparation method of two-kettle combined polyester resin - Google Patents
Polyester resin for high-leveling self-curing powder coating and preparation method of two-kettle combined polyester resin Download PDFInfo
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- CN110591066B CN110591066B CN201910969971.XA CN201910969971A CN110591066B CN 110591066 B CN110591066 B CN 110591066B CN 201910969971 A CN201910969971 A CN 201910969971A CN 110591066 B CN110591066 B CN 110591066B
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- 239000004645 polyester resin Substances 0.000 title claims abstract description 65
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 65
- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 58
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 62
- 229920000728 polyester Polymers 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 17
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 claims abstract description 15
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims abstract description 14
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 14
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940035024 thioglycerol Drugs 0.000 claims abstract description 13
- PROQIPRRNZUXQM-UHFFFAOYSA-N (16alpha,17betaOH)-Estra-1,3,5(10)-triene-3,16,17-triol Natural products OC1=CC=C2C3CCC(C)(C(C(O)C4)O)C4C3CCC2=C1 PROQIPRRNZUXQM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940015975 1,2-hexanediol Drugs 0.000 claims abstract description 12
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- PROQIPRRNZUXQM-ZXXIGWHRSA-N estriol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H]([C@H](O)C4)O)[C@@H]4[C@@H]3CCC2=C1 PROQIPRRNZUXQM-ZXXIGWHRSA-N 0.000 claims abstract description 12
- 229960001348 estriol Drugs 0.000 claims abstract description 12
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims abstract description 12
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 106
- 239000002253 acid Substances 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 26
- 238000004321 preservation Methods 0.000 claims description 26
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000010959 steel Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 4
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 11
- 229920000647 polyepoxide Polymers 0.000 abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 6
- 239000003973 paint Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 24
- 238000000034 method Methods 0.000 description 14
- 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 6
- 239000008199 coating composition Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
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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
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy 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
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- 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)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of paint production, and particularly relates to a polyester resin for a high-leveling self-curing powder paint, and a two-kettle combined preparation method of the polyester resin. The polyester resin provided by the invention comprises the following main raw materials: terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol, estriol, 3',4,4' -benzophenone tetracarboxylic dianhydride, biphenyl dicarboxylic acid, ethylenediamine-N, N ' -diacetic acid, 1, 2-hexanediol, neopentyl glycol, and triethanolamine. The polyester resin product obtained by the invention contains hydroxyl and carboxyl at the same time, after the polyester resin product is prepared into powder coating, the hydroxyl in the polyester A material and the carboxyl in the polyester B material are crosslinked and cured under the condition of high temperature (200 ℃/15min), a self-curing coating film can be obtained without additionally using a curing agent or E-12 epoxy resin, and the performance of the coating film can completely meet the application requirement of the conventional powder coating.
Description
Technical Field
The invention belongs to the technical field of paint production, and particularly relates to a polyester resin for a high-leveling self-curing powder paint, and a two-kettle combined preparation method of the polyester resin.
Background
At present, if film formation is to be realized by powder coating, polyester resin is generally cured with curing agent such as TGIC, HAA and the like in the process of powder coating preparation, or carboxyl polyester resin is cured with E-12 epoxy resin, although the application is wide, the following defects still exist:
(1) the prices of the curing agent and the E-12 epoxy resin are higher than those of the polyester resin, so that the cost of the final powder coating is higher;
(2) the mixing of the polyester resin and the curing agent or the E-12 epoxy resin is realized by means of extrusion mixing of a double-screw extruder in the process of preparing the powder coating, and because the polyester resin and the curing agent or the E-12 epoxy resin are in a particle state before mixing, the mixing is not uniform easily, so that the polyester resin and the curing agent or the E-12 epoxy resin in the final powder coating are not uniformly distributed, and the problem of large difference of curing effects of the powder coating in the same batch is often caused;
(3) because of the high reactivity of curing agents such as TGIC, HAA and E-12 epoxy resins, the curing speed is too fast at high temperatures, making it difficult for conventional powder coating formulations to achieve high leveling requirements.
Therefore, there is a need to improve the above-mentioned disadvantages and to invent a polyester resin for a high leveling self-curing powder coating.
Disclosure of Invention
In order to solve the technical problems, the invention provides the polyester resin for the self-curing powder coating, which has high leveling property, low cost and good stability.
The invention provides a polyester resin for a high-leveling self-curing powder coating, which comprises the following main raw materials:
terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol, estriol, 3',4,4' -benzophenone tetracarboxylic dianhydride, biphenyl dicarboxylic acid, ethylenediamine-N, N ' -diacetic acid, 1, 2-hexanediol, neopentyl glycol, and triethanolamine.
The molar parts of the main raw materials are as follows:
10-28 parts of terephthalic acid, 6-16 parts of 3-methyl-1, 5-pentanediol, 4-11 parts of thioglycerol, 2-8 parts of estriol, 5-14 parts of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 7-19 parts of biphenyl dicarboxylic acid, 5-15 parts of ethylenediamine-N, N ' -diacetic acid, 4-13 parts of 1, 2-hexanediol, 6-17 parts of neopentyl glycol and 4-12 parts of triethanolamine.
The polyester resin has an acid value of 15 to 45mgKOH/g, a hydroxyl value of 15 to 45mgKOH/g, and a softening point of 95 to 105 ℃.
The two-kettle combined preparation method of the polyester resin for the high-leveling self-curing powder coating comprises the following steps:
(1) adding terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol and a catalyst A into a reaction kettle A, and heating for esterification reaction;
(2) adding estriol into the esterified material in the step (1), heating to react under the protection of nitrogen, preserving heat, stopping the reaction, cooling, adding a capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride to perform a capping reaction, heating to react under a vacuum condition, cooling after stopping the reaction, and obtaining a polyester A material;
(3) adding biphenyldicarboxylic acid, neopentyl glycol, 1, 2-hexanediol and a catalyst B into a reaction kettle B, heating, carrying out heat preservation reaction, adding ethylenediamine-N, N' -diacetic acid for chain extension reaction, heating, carrying out heat preservation reaction, carrying out vacuum esterification reaction, stopping reaction, removing vacuum, and cooling;
(4) adding a hydroxyl end-capping agent triethanolamine and an antioxidant into the esterified material obtained in the step (3), introducing nitrogen for protection, carrying out heat preservation reaction, stopping the reaction, and cooling to obtain a polyester B material;
(5) and adding the synthesized polyester A material into a reaction kettle B, stirring, mixing, reacting, discharging at high temperature when the reaction is stopped, cooling the polyester resin, and crushing and granulating to obtain the polyester resin for the self-curing powder coating.
The catalyst A is monobutyl tin oxide, and the using amount of the catalyst A is 0.05-0.2% of the total molar amount of the raw materials;
the catalyst B is dibutyltin oxide, and the using amount of the catalyst B is 0.05-0.15% of the total molar amount of the raw materials.
The antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the using amount of the antioxidant is 0.1-0.3% of the total molar amount of the main raw materials.
(5) The cooling of the polyester resin is specifically to cool the polyester resin by using a steel belt with condensed water.
Preferably, the two-kettle combined preparation method of the polyester resin for the high-leveling self-curing powder coating comprises the following steps:
(1) adding terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol and a catalyst A into a reaction kettle A, carrying out heating esterification reaction at 140-190 ℃ for 12-16 h, and stopping the reaction when the acid value is reduced to 20-40 mgKOH/g;
(2) then adding estriol into the esterified material, gradually heating to react to 210-230 ℃ at a speed of 4-6 ℃/h under the protection of nitrogen, carrying out heat preservation reaction for 4-8 h, stopping the reaction when the acid value is reduced to be below 12-20 mgKOH/g, cooling to 180-200 ℃, then adding a capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride to carry out the capping reaction, starting a vacuum system, keeping the vacuum degree at 40-70 mmHg, heating to 220-240 ℃ at a speed of 8-12 ℃/h, keeping the reaction for 2-4 h, stopping the reaction when the acid value reaches 45-75 mgKOH/g, cooling to 120-130 ℃, and carrying out heat preservation to obtain a polyester A material;
(3) adding the biphenyldicarboxylic acid, the neopentyl glycol, the 1, 2-hexanediol and the catalyst B into a reaction kettle B, gradually heating to 160-180 ℃ at a heating rate of 20 ℃/h, carrying out heat preservation reaction for 4-8 h, adding ethylenediamine-N, N' -diacetic acid for chain extension reaction when the acid value is reduced to 8-12 mgKOH/g, simultaneously heating to 210-230 ℃ at a speed of 8-12 ℃/h and carrying out heat preservation reaction for 3-6 h, starting vacuum when the acid value reaches 30-50 mgKOH/g, controlling the vacuum degree to be 50-70 mmHg, carrying out vacuum esterification reaction for 2-5 h at 210-230 ℃, stopping reaction and removing vacuum when the acid value is reduced to 10-25 mgKOH/g, and cooling to 180-200 ℃;
(4) adding a hydroxyl end-capping agent triethanolamine and an antioxidant into the esterified material, introducing nitrogen for protection, reacting at 200-210 ℃ for 1-4 h while keeping the temperature, stopping the reaction when the hydroxyl value reaches 50-80 mgKOH/g, cooling to 120-130 ℃ and keeping the temperature to obtain a polyester B material;
(5) adding the synthesized polyester A material into a reaction kettle B, stirring and mixing the polyester A material and the polyester B material at 120-130 ℃, reacting for 1-3 h, stopping the reaction when the acid value and the hydroxyl value of the reaction mixture are both 15-45mgKOH/g, discharging at high temperature while the reaction mixture is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for the self-curing powder coating.
More preferably, the two-kettle combined preparation method of the polyester resin for the high-leveling self-curing powder coating comprises the following steps:
(1) adding terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol and a catalyst A into a reaction kettle A, heating to 180 ℃, performing esterification reaction for 8 hours, and stopping the reaction when the acid value is reduced to 30 mgKOH/g;
(2) then adding estriol into the esterified material, gradually raising the temperature to react to 220 ℃ at the speed of 5 ℃/h under the protection of nitrogen, preserving the temperature to react for 5h, stopping the reaction and reducing the temperature to 200 ℃ when the acid value is reduced to be below 15mgKOH/g, then adding a capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride to carry out the capping reaction, starting a vacuum system at the same time, keeping the vacuum degree at 70mmHg, raising the temperature to 235 ℃ at the speed of 10 ℃/h, preserving the reaction for 2h, stopping the reaction when the acid value reaches 70mgKOH/g, reducing the temperature to 125 ℃ and preserving the temperature to obtain a polyester A material;
(3) adding biphenyldicarboxylic acid, neopentyl glycol, 1, 2-hexanediol and a catalyst B into a reaction kettle B, gradually heating to 175 ℃ at the rate of 20 ℃/h, carrying out heat preservation reaction for 6h, adding ethylenediamine-N, N' -diacetic acid for chain extension reaction when the acid value is reduced to 10mgKOH/g, heating to 220 ℃ at the rate of 10 ℃/h, carrying out heat preservation reaction for 5h, starting vacuum when the acid value reaches 40mgKOH/g, controlling the vacuum degree to be 60mmHg, carrying out vacuum esterification reaction at 220 ℃ for 2h, stopping reaction and removing vacuum when the acid value is reduced to 20mgKOH/g, and cooling to 180 ℃;
(4) adding a hydroxyl end capping agent triethanolamine and an antioxidant into the esterified material, introducing nitrogen for protection, carrying out heat preservation reaction for 2 hours at 205 ℃, stopping the reaction when the hydroxyl value reaches 70mgKOH/g, cooling to 125 ℃, and carrying out heat preservation to obtain a polyester B material;
(5) adding the synthesized polyester A material into a reaction kettle B, stirring and mixing the polyester A material and the polyester B material at 125 ℃ for reaction for 2 hours, stopping the reaction when the acid value and the hydroxyl value of the reaction mixture are both 30mgKOH/g, discharging at high temperature while the reaction mixture is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for the self-curing powder coating.
Based on the technical defects in the prior art mentioned in the background, the invention simultaneously improves the raw materials and the process to obtain the product which can achieve the aim of the invention. The specific improvement method of the invention is that flexible polyol such as 3-methyl-1, 5-pentanediol, thioglycerol and the like is used in the polyester A material to reduce the softening point and increase the high-temperature leveling ability;
3,3',4,4' -benzophenone tetracarboxylic dianhydride with large steric hindrance is used for end capping to reduce the high-temperature curing rate of the polyester B material component and prolong the leveling time;
in the polyester B material, a linear monomer ethylenediamine-N, N' -diacetic acid is specially used as a chain extender to increase the flexibility and the fluidity of the polyester, and triethanolamine is used as a hydroxyl end-capping agent to reduce the softening point of the polyester B material so as to finally realize the function of high leveling;
the invention also prepares the mixed polyester resin with both carboxyl end capping and hydroxyl end capping by means of a two-kettle combined process, the hydroxyl value and the acid value of the polyester resin are kept in a relatively balanced state, and the polyester resin product finally participating in curing can be ensured to be in a uniform dispersion state by fully mixing in a molten state, so that on one hand, the polyester resin is used for replacing a curing agent or E-12 epoxy resin, the cost is reduced, on the other hand, the same batch of powder coating has better stability, the production difficulty is reduced for powder coating manufacturers, and the coating performance completely meets the conventional requirements of the powder coating.
The polyester resin product obtained by the invention contains hydroxyl and carboxyl at the same time, after the polyester resin product is prepared into powder coating, the hydroxyl in the polyester material A and the carboxyl in the polyester material B are crosslinked and cured under the condition of high temperature (200 ℃/15min), a self-curing coating film can be obtained without additionally using a curing agent or E-12 epoxy resin, and the performance of the coating film can completely meet the application requirement of the conventional powder coating. And because the product of the invention is obtained by melting and mixing two kinds of polyester resin, compared with the existing method of extruding and mixing by adopting double screws, the product has very good miscibility and lower softening point, and is beneficial to obtaining a high leveling coating film.
The finally obtained product is colorless transparent particles, the acid value is 15-45mgKOH/g, the hydroxyl value is 15-45mgKOH/g, and the softening point is 95-105 ℃.
Detailed Description
The present invention will be further described with reference to specific examples so that those skilled in the art may better understand the present invention, but the present invention is not limited thereto.
Example 1
A two-kettle combined preparation method of polyester resin for a high-leveling self-curing powder coating comprises the following steps:
(1) adding terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol and a catalyst A into a reaction kettle A, heating to 180 ℃, carrying out esterification reaction for 8 hours, and stopping the reaction when the acid value is reduced to 30 KOH/g;
(2) then adding estriol into the esterified material, gradually raising the temperature to react to 220 ℃ at the speed of 5 ℃/h under the protection of nitrogen, preserving the temperature to react for 5h, stopping the reaction and reducing the temperature to 200 ℃ when the acid value is reduced to be below 15mgKOH/g, then adding a capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride to carry out the capping reaction, starting a vacuum system at the same time, keeping the vacuum degree at 70mmHg, raising the temperature to 235 ℃ at the speed of 10 ℃/h, preserving the reaction for 2h, stopping the reaction when the acid value reaches 70mgKOH/g, reducing the temperature to 125 ℃ and preserving the temperature to obtain a polyester A material;
(3) adding biphenyldicarboxylic acid, neopentyl glycol, 1, 2-hexanediol and a catalyst B into a reaction kettle B, gradually heating to 175 ℃ at the rate of 20 ℃/h, carrying out heat preservation reaction for 6h, adding ethylenediamine-N, N' -diacetic acid for chain extension reaction when the acid value is reduced to 10mgKOH/g, heating to 220 ℃ at the rate of 10 ℃/h, carrying out heat preservation reaction for 5h, starting vacuum when the acid value reaches 40mgKOH/g, controlling the vacuum degree to be 60mmHg, carrying out vacuum esterification reaction for 2h at 220 ℃, stopping reaction and removing vacuum when the acid value is reduced to 20mgKOH/g, and cooling to 180 ℃;
(4) adding a hydroxyl end capping agent triethanolamine and an antioxidant into the esterified material, introducing nitrogen for protection, carrying out heat preservation reaction for 2 hours at 205 ℃, stopping the reaction when the hydroxyl value reaches 70mgKOH/g, cooling to 125 ℃, and carrying out heat preservation to obtain a polyester B material;
(5) adding the synthesized polyester A material into a reaction kettle B, mixing at 125 ℃, stirring for reaction for 2 hours, stopping the reaction when the acid value and the hydroxyl value of the reaction mixture are both about 30mgKOH/g, discharging at high temperature while the reaction mixture is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for the self-curing powder coating.
The processes and parameters of the embodiments 2 to 4 are the same as those of the embodiment 1, except that the amount of the raw materials is adjusted as follows:
table 1 the amounts of the respective raw materials used in the examples
The catalyst A of the polyester A material is monobutyl tin oxide, and the using amount of the catalyst A is 0.1 percent of the total molar amount of the raw materials.
The catalyst B of the polyester B material is dibutyltin oxide, and the using amount of the catalyst B is 0.1 percent of the total molar amount of the raw materials.
The antioxidant is an antioxidant 1076, namely n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the dosage of the antioxidant is 0.2 percent of the total molar weight of the main raw materials.
Comparative example 1
The procedure is as in example 1, except that the polyester A material does not use 3-methyl-1, 5-pentanediol;
comparative example 2
The procedure was as in example 1 except that the polyester A material was prepared without 3,3',4,4' -benzophenone tetracarboxylic dianhydride;
comparative example 3
The procedure is otherwise the same as in example 1, except that the polyester A material is prepared by replacing the sterically hindered end-capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride with an equimolar amount of the highly reactive end-capping agent adipic acid;
comparative example 4
The procedure is otherwise the same as in example 1, except that the polyester B material is freed from ethylenediamine-N, N' -diacetic acid;
comparative example 5
The procedure is otherwise the same as in example 1, except that the flexible monomer ethylenediamine-N, N' -diacetic acid is replaced with an equimolar amount of the rigid monomer terephthalic acid in the polyester B stream;
comparative example 6
The procedure is as in example 1 except that triethanolamine is not used in the polyester B material;
comparative example 7
General 50/50 polyester-epoxy hybrid powder coating (E-12 epoxy resin was used as the polyester curing component, and plate test was performed according to the powder coating formulation commonly used in the industry) as coating comparative example 7;
comparative example 8
General TGIC polyester powder coating (required to use TGIC as curing agent for polyester, plate test was performed according to TGIC powder coating formulation common in industry) as coating comparative example 8;
comparative example 9
A general-purpose HAA polyester powder coating (plate test was performed according to an HAA powder coating formulation commonly used in the industry, which requires HAA as a curing agent for polyester) was used as comparative coating film example 9.
TABLE 2 comparison of product Properties of examples and comparative examples
| Acid value (mgKOH/g) | Hydroxyl value (mgKOH/g) | Softening Point (. degree. C.) | |
| Example 1 | 35 | 42 | 103 |
| Example 2 | 20 | 26 | 101 |
| Example 3 | 40 | 45 | 96 |
| Example 4 | 32 | 41 | 98 |
| Comparative example 1 | 51 | 38 | 109 |
| Comparative example 2 | 8 | 40 | 92 |
| Comparative example 3 | 18 | 34 | 96 |
| Comparative example 4 | 22 | 45 | 108 |
| Comparative example 5 | 35 | 40 | 112 |
| Comparative example 6 | 52 | 8 | 115 |
Example 5
The following powder coating formulations were used in the examples and comparative examples 1 to 6, and were generally as follows in parts by weight:
preparing a coating layer: the materials are physically and uniformly mixed according to the formula of the powder coating, extruded, tabletted and crushed by a double-screw extruder, and then the tablet materials are crushed and sieved (160 meshes) to prepare the powder coating. And spraying the powder coating on the galvanized iron substrate subjected to surface treatment by using an electrostatic spray gun, and curing at the temperature of 200 ℃/15min to obtain the coating.
The detection of the gel time and the coating index is carried out according to GB/T21776-2008 'Standard guidelines for detection of powder coatings and coatings thereof'. The leveling grade is determined according to JB-T3998-1999 coating leveling scratch determination method, and the higher the leveling grade is, the better the leveling of the coating surface is. The adhesion test is based on GB/T9286-1998 test for marking test of paint films of paints and varnishes.
TABLE 3 coating film Properties of examples and comparative examples
As can be seen from the data or description in the table, the product of the invention can realize full curing without additionally using E-12 epoxy resin or TGIC or HAA as a curing agent, and the leveling grade is generally 7 grades which are higher than those of comparative examples 1-9; the polyester resin has good leveling property after being applied to the coating, and achieves the aim of the invention; and other properties, such as no obvious change after boiling water, excellent indexes such as adhesive force, gloss angle and the like;
the products in comparative examples 1 to 6 have poor impact resistance, poor leveling due to too short gelling time, or no curing of the coating film due to lack of curing groups, and the impact resistance does not meet the requirements; or boiling water resistance, and appearance is inferior to examples 1 to 4.
The products in the comparative examples 7-9 are several common curing systems matched with polyester resin in the current market, the coating performance and boiling water boiling resistance are good, and the application requirements can be completely met, but the curing activity is high, the gelling time is short, the leveling property is general, the leveling grade is about 5, and the leveling grade is not the same as that of the polyester resin product.
Claims (6)
1. The polyester resin for the high-leveling self-curing powder coating is characterized by comprising the following components in parts by weight: the polyester resin comprises the following main raw materials:
terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol, estriol, 3',4,4' -benzophenone tetracarboxylic dianhydride, biphenyl dicarboxylic acid, ethylenediamine-N, N ' -diacetic acid, 1, 2-hexanediol, neopentyl glycol, triethanolamine;
the molar parts of the main raw materials are as follows:
10-28 parts of terephthalic acid, 6-16 parts of 3-methyl-1, 5-pentanediol, 4-11 parts of thioglycerol, 2-8 parts of estriol, 5-14 parts of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 7-19 parts of biphenyl dicarboxylic acid, 5-15 parts of ethylenediamine-N, N ' -diacetic acid, 4-13 parts of 1, 2-hexanediol, 6-17 parts of neopentyl glycol and 4-12 parts of triethanolamine;
the acid value of the polyester resin is 15-45mgKOH/g, the hydroxyl value is 15-45mgKOH/g, and the softening point is 95-105 ℃;
the two-kettle combined preparation method of the polyester resin comprises the following steps:
(1) adding terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol and a catalyst A into a reaction kettle A, heating, and carrying out esterification reaction;
(2) then adding estriol into the esterified material in the step (1), heating to react under the protection of nitrogen, preserving heat, stopping the reaction, cooling, then adding an end-capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride to perform end-capping reaction, heating to react under a vacuum condition, cooling after stopping the reaction, and obtaining a polyester A material;
(3) adding biphenyldicarboxylic acid, neopentyl glycol, 1, 2-hexanediol and a catalyst B into a reaction kettle B, heating for reaction, preserving heat, adding ethylenediamine-N, N' -diacetic acid for chain extension reaction, heating for reaction, preserving heat, carrying out vacuum esterification reaction, stopping reaction, removing vacuum, and cooling;
(4) adding a hydroxyl end-capping agent triethanolamine and an antioxidant into the esterified material obtained in the step (3), introducing nitrogen for protection, carrying out heat preservation reaction, stopping the reaction, and cooling to obtain a polyester B material;
(5) and adding the synthesized polyester A material into a reaction kettle B, stirring and mixing the polyester A material with the polyester B material for reaction, discharging the polyester resin at high temperature after the reaction is stopped, cooling the polyester resin, and crushing and granulating to obtain the polyester resin for the self-curing powder coating.
2. The polyester resin for high leveling self-curing powder coating according to claim 1, wherein:
the catalyst A is monobutyl tin oxide, and the using amount of the catalyst A is 0.05-0.2% of the total molar amount of the raw materials;
the catalyst B is dibutyltin oxide, and the using amount of the catalyst B is 0.05-0.15% of the total molar amount of the raw materials.
3. The polyester resin for high leveling self-curing powder coating according to claim 1, wherein:
the antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and the using amount of the antioxidant is 0.1-0.3% of the total molar amount of the main raw materials.
4. The polyester resin for high leveling self-curing powder coating according to claim 1, wherein:
(5) the cooling of the polyester resin is specifically to cool the polyester resin by using a steel belt with condensed water.
5. The polyester resin for high leveling self-curing powder coating of claim 1, wherein the two-pot combination preparation method of the polyester resin comprises the following steps:
(1) adding terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol and a catalyst A into a reaction kettle A, carrying out heating esterification reaction at 140-190 ℃ for 12-16 h, and stopping the reaction when the acid value is reduced to 20-40 mgKOH/g;
(2) then adding estriol into the esterified material, gradually heating to 210-230 ℃ at a speed of 4-6 ℃/h under the protection of nitrogen, carrying out heat preservation reaction for 4-8 h, stopping the reaction when the acid value is reduced to be below 20mgKOH/g, cooling to 180-200 ℃, then adding a capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride to carry out the capping reaction, starting a vacuum system, keeping the vacuum degree at 40-70 mmHg, heating to 220-240 ℃ at a speed of 8-12 ℃/h, keeping the reaction for 2-4 h, stopping the reaction when the acid value reaches 45-75 mgKOH/g, cooling to 120-130 ℃, and carrying out heat preservation to obtain a polyester A material;
(3) adding biphenyldicarboxylic acid, neopentyl glycol, 1, 2-hexanediol and a catalyst B into a reaction kettle B, gradually heating to 160-180 ℃ at a heating rate of 20 ℃/h, carrying out heat preservation reaction for 4-8 h, adding ethylenediamine-N, N' -diacetic acid for chain extension reaction when the acid value is reduced to 8-12 mgKOH/g, simultaneously heating to 210-230 ℃ at a speed of 8-12 ℃/h, carrying out heat preservation reaction for 3-6 h, starting vacuum when the acid value reaches 30-50 mgKOH/g, controlling the vacuum degree to be 50-70 mmHg, carrying out vacuum esterification reaction for 2-5 h at 210-230 ℃, stopping reaction and removing vacuum when the acid value is reduced to 10-25 mgKOH/g, and cooling to 180-200 ℃;
(4) adding a hydroxyl end-capping agent triethanolamine and an antioxidant into the esterified material, introducing nitrogen for protection, reacting at 200-210 ℃ for 1-4 h while keeping the temperature, stopping the reaction when the hydroxyl value reaches 50-80 mgKOH/g, cooling to 120-130 ℃ and keeping the temperature to obtain a polyester B material;
(5) adding the synthesized polyester A material into a reaction kettle B, stirring and mixing the polyester A material and the polyester B material at 120-130 ℃, reacting for 1-3 h, stopping the reaction when the acid value and the hydroxyl value of the reaction mixture are both 15-45mgKOH/g, discharging at high temperature while the reaction mixture is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for the self-curing powder coating.
6. The polyester resin for high leveling self-curing powder coating of claim 1, wherein the two-pot combination preparation method of the polyester resin comprises the following steps:
(1) adding terephthalic acid, 3-methyl-1, 5-pentanediol, thioglycerol and a catalyst A into a reaction kettle A, heating to 180 ℃, carrying out esterification reaction for 8 hours, and stopping the reaction when the acid value is reduced to 30 KOH/g;
(2) then adding estriol into the esterified material, gradually heating to 220 ℃ at the speed of 5 ℃/h under the protection of nitrogen, carrying out heat preservation reaction for 5h, stopping the reaction and cooling to 200 ℃ when the acid value is reduced to below 15mgKOH/g, then adding a capping agent 3,3',4,4' -benzophenone tetracarboxylic dianhydride to carry out the capping reaction, starting a vacuum system at the same time, keeping the vacuum degree at 70mmHg, heating to 235 ℃ at the speed of 10 ℃/h, keeping the reaction for 2h, stopping the reaction when the acid value reaches 70mgKOH/g, cooling to 125 ℃, and carrying out heat preservation to obtain a polyester A material;
(3) adding biphenyldicarboxylic acid, neopentyl glycol, 1, 2-hexanediol and a catalyst B into a reaction kettle B, gradually heating to 175 ℃ at the rate of 20 ℃/h, carrying out heat preservation reaction for 6h, adding ethylenediamine-N, N' -diacetic acid for chain extension reaction when the acid value is reduced to 10mgKOH/g, heating to 220 ℃ at the rate of 10 ℃/h, carrying out heat preservation reaction for 5h, starting vacuum when the acid value reaches 40mgKOH/g, controlling the vacuum degree to be 60mmHg, carrying out vacuum esterification reaction at 220 ℃ for 2h, stopping reaction and removing vacuum when the acid value is reduced to 20mgKOH/g, and cooling to 180 ℃;
(4) adding a hydroxyl end capping agent triethanolamine and an antioxidant into the esterified material, introducing nitrogen for protection, carrying out heat preservation reaction for 2 hours at 205 ℃, stopping the reaction when the hydroxyl value reaches 70mgKOH/g, cooling to 125 ℃, and carrying out heat preservation to obtain a polyester B material;
(5) adding the synthesized polyester A material into a reaction kettle B, stirring and mixing the polyester A material and the polyester B material at 125 ℃ for reaction for 2 hours, stopping the reaction when the acid value and the hydroxyl value of the reaction mixture are both 30mgKOH/g, discharging at high temperature while the reaction mixture is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin for the self-curing powder coating.
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| DE102009032298A1 (en) * | 2009-07-09 | 2011-01-13 | Bergander, Klaus, Dr. | Enzymatically preparing thiol-functionalized polyester copolymer, useful as e.g. coating, comprises reacting bifunctional alkane dicarboxylic acid and mercaptoalkane diol in presence of lipase under stirring at high temperature in vacuum |
| CN102352042A (en) * | 2011-07-19 | 2012-02-15 | 苏州大学 | Biodegradable amphiphilic polyester with functionally modified side chains |
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| CN109206599A (en) * | 2018-09-07 | 2019-01-15 | 安徽恒隆新材料有限公司 | A kind of high levelling polyester resin for powder coating and the preparation method and application thereof |
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| DE102009032298A1 (en) * | 2009-07-09 | 2011-01-13 | Bergander, Klaus, Dr. | Enzymatically preparing thiol-functionalized polyester copolymer, useful as e.g. coating, comprises reacting bifunctional alkane dicarboxylic acid and mercaptoalkane diol in presence of lipase under stirring at high temperature in vacuum |
| CN103429636A (en) * | 2011-03-10 | 2013-12-04 | 聂克斯姆化学有限公司 | Compositions for improving polyesters |
| CN102352042A (en) * | 2011-07-19 | 2012-02-15 | 苏州大学 | Biodegradable amphiphilic polyester with functionally modified side chains |
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