CN116096777A - Polyester resin for metal powder coating and preparation method and application thereof - Google Patents
Polyester resin for metal powder coating and preparation method and application thereof Download PDFInfo
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- CN116096777A CN116096777A CN202280004573.4A CN202280004573A CN116096777A CN 116096777 A CN116096777 A CN 116096777A CN 202280004573 A CN202280004573 A CN 202280004573A CN 116096777 A CN116096777 A CN 116096777A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 98
- 239000002184 metal Substances 0.000 title claims abstract description 98
- 238000000576 coating method Methods 0.000 title claims abstract description 96
- 239000000843 powder Substances 0.000 title claims abstract description 92
- 239000011248 coating agent Substances 0.000 title claims abstract description 89
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 59
- 239000004645 polyester resin Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 20
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 41
- 238000001816 cooling Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 23
- 230000032050 esterification Effects 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 19
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- -1 glycidyl ester Chemical group 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000009477 glass transition Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 14
- 239000000049 pigment Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000005484 gravity Effects 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- IPNPIHIZVLFAFP-UHFFFAOYSA-N phosphorus tribromide Chemical compound BrP(Br)Br IPNPIHIZVLFAFP-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or 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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- 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
- C08G63/81—Preparation processes using solvents
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (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)
Abstract
The invention provides a polyester resin for a metal powder coating, and a preparation method and application thereof, wherein the polyester resin for the metal powder coating comprises the following raw materials: polyhydric alcohol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent and tertiary glycidyl carbonate. The polyester resin for the metal powder coating has the advantages that the polarity of the polyester resin is enhanced due to the introduction of the halogenated bisphenol A with the halogen side group, and the enhancement of the polarity is beneficial to the improvement of the surface tension of the resin. In the high-temperature curing process of the metal powder coating, the metal pigment can lighten the influence of gravity sedimentation under the tensile force of the resin surface tension, and the metal pigment is firmly fixed on the surface of the coating, so that the coating shows better metal effect.
Description
Technical Field
The invention belongs to the technical field of powder coatings, and particularly relates to a polyester resin for a metal powder coating, and a preparation method and application thereof.
Background
With the importance of environmental protection, as an environment-friendly, high-efficiency and economical powder coating, the variety is continuously increased and the application field is gradually expanded with the rapid development of technology in recent years. In the aspect of decoration, besides the common powder coating varieties with different gloss and flat surfaces, the varieties and the amounts of orange lines, wrinkles, sand lines, patterns, hammers and metal powder coatings are also increased, and the powder coatings gradually penetrate into various fields of solvent type coating application. Among the above-mentioned varieties, metal powder coating materials are known by industry as a high-grade product in the field of powder coating materials, and the product can be further subdivided into metal powder coating materials such as metal sparkling, metal plating, metal pattern, hammer tone, metal luster texture and the like.
At present, a high-performance metal powder coating in the market is mostly prepared by a thermal bonding method, and because the bonding method is high in requirements on bonding equipment and technology, more researches are conducted on the bonding equipment and technology. The research reports on metal powder coating are basically concentrated on bonding equipment and technology, and the research on matched polyester is basically not reported. Because of the lack of matched polyester resin in the market at present, the advanced powder manufacturer utilizes stronger formulation research and development design capability, and simultaneously prepares the metal powder coating by matching with advanced bonding equipment and strict process control, but the problem of unstable product batch is still difficult to solve. For most small and medium enterprises with weak capital and technical capability, the research and development production of related metal powder are difficult. In order to promote the development of metal powder coating, research on the aspects of strengthening manufacturing equipment, process, raw materials and the like by linking up the upstream and downstream is needed. In terms of matched resin, the research on special polyester for metal powder coating is relatively lacking at present, and in order to meet the demand of the market on rapid increase of the dosage of the metal powder coating, it is necessary to provide a polyester resin suitable for the metal powder coating, so as to reduce the dependence on equipment and process control, thereby promoting rapid development of the metal powder coating.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the first aspect of the invention provides a polyester resin for metal powder coating, and bonding metal powder coating prepared by using the polyester resin has outstanding metal effect and beautiful appearance.
The second aspect of the invention provides a preparation method of the polyester resin for the metal powder coating.
In a third aspect, the present invention provides a metal powder coating comprising the polyester resin for a metal powder coating.
According to a first aspect of the present invention, there is provided a polyester resin for a metal powder coating material, the raw materials for the preparation comprising: polyhydric alcohol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent and tertiary glycidyl carbonate.
In some embodiments of the present invention, the polyester resin for metal powder coating is prepared from the following raw materials in mass fraction: 20 to 35 weight percent of polyalcohol, 3 to 20 weight percent of halogenated bisphenol A, 30 to 55 weight percent of terephthalic acid, 2 to 10 weight percent of phthalic anhydride, 5 to 15 weight percent of acidolysis agent and 1 to 5 weight percent of tertiary glycidyl ester.
In some preferred embodiments of the present invention, the halogenated bisphenol a has the structural formula of formula I:
wherein each R is independently selected from H and/or halogen, and at least one R is H and at least one R is halogen.
Preferably, the halogenated bisphenol a comprises a dihalo bisphenol a having the structural formula Ia:
wherein R is 1 Is halogen;
further preferred, the halogenated bisphenol a has the structural formula Ib:
in some preferred embodiments of the present invention, the halogenated bisphenol A is used in an amount of 5wt% to 20wt% in mass fraction; preferably 5wt% to 15wt%.
In some more preferred embodiments of the present invention, the polyol comprises at least one of neopentyl glycol, ethylene glycol, 2-methyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol, or trimethylolpropane; preferably a combination of neopentyl glycol and other polyols. Further preferably, the ratio of neopentyl glycol and other polyols is greater than 5:1, a step of; still more preferably, the ratio of neopentyl glycol and other polyols is greater than 6:1.
in some more preferred embodiments of the present invention, the polyol is used in an amount of 25wt% to 35wt% in mass fraction; preferably 28wt% to 33wt%.
In some more preferred embodiments of the present invention, the terephthalic acid is used in an amount of 30wt% to 50wt% in terms of mass fraction; preferably 35wt% to 50wt%; more preferably 35 to 45wt%.
In some more preferred embodiments of the present invention, the phthalic anhydride acid is used in an amount of 3wt% to 10wt% in mass fraction; preferably 4 to 10wt%; more preferably 5 to 10wt%.
In some more preferred embodiments of the present invention, the acidolysis agent comprises at least one of isophthalic acid, succinic acid, adipic acid, or 1, 4-cyclohexanedicarboxylic acid; preferably, the acidolysis agent is used in an amount of 7 to 15 weight percent in terms of mass fraction; preferably 7 to 12wt%.
In some more preferred embodiments of the present invention, the amount of the glycidyl versatate is 1.5wt% to 5wt% in mass fraction; preferably 2 to 5wt%; more preferably 3 to 5wt%.
In some more preferred embodiments of the present invention, the raw materials for preparing the polyester resin for the metal powder coating further include an esterification catalyst, a curing accelerator, and an antioxidant. In the preparation raw materials of the polyester resin for the metal powder coating, polyhydric alcohol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent and tertiary glycidyl ester are components of a skeleton structure of the polyester resin, wherein the tertiary glycidyl ester is used as a blocking agent; the esterification catalyst is used for adjusting the esterification polycondensation reaction rate and the reaction degree, and the curing accelerator and the antioxidant are respectively used for improving certain properties of the polyester resin.
In some more preferred embodiments of the present invention, the esterification catalyst comprises at least one of monobutyl tin oxide, dibutyl tin oxide, or stannous oxalate. Preferably, the dosage of the esterification catalyst is 0.05-0.15% of the total mass of the materials.
In some more preferred embodiments of the present invention, the curing accelerator comprises benzyl triethylammonium chloride, triphenyl, and at least one of phosphorus bromide, triphenylphosphine, or t-butylamine; the dosage of the curing accelerator is 0.01-0.1% of the total mass of the materials.
In some more preferred embodiments of the invention, the antioxidants include a primary antioxidant and a secondary antioxidant, the primary antioxidant including antioxidant 1076 and/or antioxidant 1010; the secondary antioxidants include antioxidant 168 and/or antioxidant 626. Preferably, the mass ratio of the primary antioxidant to the secondary antioxidant is 1: 2-2: 1, a step of; further preferably 1:1.
in some more preferred embodiments of the present invention, the polyester resin for metal powder coating has an acid value of 30mgKOH/g to 35mgKOH/g, a melt viscosity of 200℃of 350 mp.s to 9000mp.s, a glass transition temperature Tg of 60℃to 70℃and a reactivity of 180℃of 120s to 360s. Preferably, the polyester resin for metal powder coating has a melt viscosity of 4000mp.s to 800 mp.s at 200 ℃, a glass transition temperature Tg of 62 ℃ to 70 ℃ and a reactivity of 180 ℃ of 180s to 360s. Further preferably, the polyester resin for metal powder coating has a melt viscosity of 5000mp.s to 7000mp.s at 200 ℃, a glass transition temperature Tg of 62 ℃ to 68 ℃ and a reactivity of 240s to 330s at 180 ℃.
According to a second aspect of the present invention, there is provided a method for producing a polyester resin for a metal powder coating, comprising the steps of:
s1: heating and melting polyalcohol and halogenated bisphenol A in an inert atmosphere, and adding terephthalic acid to perform esterification polycondensation reaction until the material is clear and transparent;
s2: after cooling, adding phthalic anhydride to react until the material is clear and transparent; continuously cooling, adding an acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45mgKOH/g to 52mgKOH/g;
s3: cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the material is 35mgKOH/g to 42 mgKOH/g;
s4: continuously cooling, adding tertiary glycidyl ester to carry out end capping reaction, and obtaining the polyester resin for the metal powder coating.
In some embodiments of the invention, in S1, the temperature of the esterification polycondensation reaction is 240 ℃ to 245 ℃.
In some preferred embodiments of the invention, in S2, the temperature is reduced to 230-236 ℃, and phthalic anhydride is added for reaction until the material is clear and transparent; continuously cooling to 228-233 ℃, adding acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45-52 mgKOH/g.
In some more preferred embodiments of the present invention, in S3, the temperature of the vacuum polycondensation reaction is 225 ℃ to 230 ℃ and the vacuum degree is-0.085 MPa to-0.1 MPa; preferably-0.095 MPa.
The preparation method of the polyester resin for the metal powder coating comprises the following steps:
s1: heating and melting polyol, halogenated bisphenol A and an esterification catalyst in an inert atmosphere, and adding terephthalic acid to perform esterification polycondensation reaction until the materials are clear and transparent;
s2: after cooling, adding phthalic anhydride to react until the material is clear and transparent; continuously cooling, adding an acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45mgKOH/g to 52mgKOH/g;
s3: cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the material is 35mgKOH/g to 42 mgKOH/g;
s4: continuously cooling, adding tertiary glycidyl ester for end capping reaction, cooling, adding a curing agent and an antioxidant when the acid value of the material is 30mgKOH/g to 35mgKOH/g, and stirring to obtain the polyester resin for the metal powder coating.
According to a third aspect of the present invention, there is provided a metal powder coating comprising the polyester resin for a metal powder coating.
The beneficial effects of the invention are as follows:
1. the polyester resin for the metal powder coating has the advantages that the polarity of the polyester resin is enhanced due to the introduction of the halogenated bisphenol A with the halogen side group, and the enhancement of the polarity is beneficial to the improvement of the surface tension of the resin. In the high-temperature curing process of the metal powder coating, the metal pigment can lighten the influence of gravity sedimentation under the tensile force of the resin surface tension, and the metal pigment is firmly fixed on the surface of the coating, so that the coating shows better metal effect.
2. According to the invention, the tertiary glycidyl ester is introduced into the main chain of the polyester resin as the end-capping agent, and the tertiary carbon group suspended in the tertiary glycidyl ester structure can increase the wettability to the metal pigment, so that the metal pigment is better coated in the resin, and the peeling risk of the metal pigment after bonding and bonding the resin is reduced.
3. The preparation method of the polyester resin for the metal powder coating enables all raw materials to be fully polymerized into a main chain, brings further optimization performance to the resin, and is characterized in that: (a) The phthalic anhydride has obviously higher reactivity than terephthalic acid, and the addition of the phthalic anhydride in the second step can not only avoid incomplete reaction of terephthalic acid caused by the competing polymerization reaction with terephthalic acid, but also ensure complete reaction of halogenated bisphenol A; (b) The tertiary glycidyl ester is taken as a monofunctional group, the polymerization degree of the main chain can be influenced by the addition of the tertiary glycidyl ester in the early stage of synthesis, meanwhile, the Tg of the polyester can be obviously reduced by a larger side group in the structure.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a graph showing the distribution of silver powder in a metal powder coating of a polyester resin according to example 1 of the present invention.
FIG. 2 is a graph showing the distribution of silver powder in the metal powder paint coating of the polyester resin of comparative example 1 of the present invention.
FIG. 3 is a graph showing the distribution of silver powder in the metal powder paint coating of the polyester resin of comparative example 2 of the present invention.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Examples 1 to 5
S1: heating the polyalcohol, the halogenated bisphenol A and the esterification catalyst to be melted under the protection of inert gas according to the formula composition of the table 1, then adding terephthalic acid, gradually heating to 240-245 ℃ for esterification polycondensation reaction until the materials are clear and transparent;
s2: cooling to below 236 ℃, adding phthalic anhydride, and continuing to react until the materials are clear and transparent;
s3: cooling to below 233 ℃, adding acidolysis agent to continue the reaction until the material is clear and transparent, and controlling the acid value within the range of 45mgKOH/g to 52mgKOH/g;
s4: and cooling to below 228 ℃ for vacuum polycondensation reaction, and releasing vacuum when the acid value of the reaction material is 35mgKOH/g to 42 mgKOH/g.
S5: cooling to 210 ℃ below, adding tertiary glycidyl ester to carry out end capping reaction, and when the acid value of the detected material reaches 30-35 mgKOH/g, cooling, adding a curing accelerator and an antioxidant, stirring and dispersing uniformly, and discharging to obtain the polyester resin for the metal powder coating.
Comparative example 1
This comparative example produced a polyester resin, which differs from example 5 in that the tertiary glycidyl ester was adjusted to the first charge, in the following steps:
s1: heating polyol, halogenated bisphenol A, tertiary glycidyl ester and an esterification catalyst to be melted under the protection of inert gas according to the formula composition of the table 1, then adding terephthalic acid, gradually heating to a heat preservation temperature for esterification polycondensation reaction until the materials are clear and transparent;
s2: cooling to below 236 ℃, adding phthalic anhydride, and continuing to react until the materials are clear and transparent;
s3: cooling to below 233 ℃, adding acidolysis agent to continue the reaction until the material is clear and transparent, and controlling the acid value within the range of 42mgKOH/g to 46 mgKOH/g;
s4: cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the reaction material is 30mgKOH/g to 35 mgKOH/g.
S5: cooling to 210 deg.c, adding curing accelerator and antioxidant, stirring to disperse homogeneously, and discharging to obtain the polyester resin.
Comparative example 2
The comparative example prepared a polyester resin, which was prepared by the following steps:
1) Heating the polyalcohol and the esterification catalyst to be melted under the protection of inert gas according to the formula composition of the table 1, then adding terephthalic acid, gradually heating to the heat preservation temperature for esterification polycondensation reaction until the materials are clear and transparent;
2) Cooling to below 235 ℃, adding acidolysis agent to continue the reaction until the material is clear and transparent, and controlling the acid value within the range of 42mgKOH/g to 46 mgKOH/g;
3) Cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the reaction material is 30mgKOH/g to 35 mgKOH/g.
4) Cooling, adding a curing accelerator and an antioxidant, stirring, dispersing uniformly, and discharging to obtain the polyester resin.
TABLE 1 polyester resin formulation
Test examples
The polyester resins produced in examples 1 to 5 and comparative examples 1 to 2 were subjected to performance tests in which:
acid number was tested according to GB/T6743-2008;
melt viscosity: ICI cone viscosity at 200 ℃ as determined according to ASTM D4287-88;
glass transition temperature (Tg): testing was performed according to GB/T19466.2;
surface tension: testing was performed according to GB/T22237-2008;
reactivity refers to the time required for the resin to react with the curing agent to gel, measured at 180℃according to GB/T16995-1997.
The test results are shown in table 2:
TABLE 2 Properties of polyester resin
Further, the polyester resins prepared according to the methods of examples 1 to 5 and comparative examples 1 to 2 were prepared on metal powder coatings, respectively, and the preparation of the metal powder coatings was divided into two stages of powder coating base powder preparation and bonding processing according to the process flow: 1) Preparing powder coating base powder: weighing the components according to the formula of the powder base in the table 3, and obtaining the required powder coating base powder after premixing, melt extrusion, cooling tabletting, crushing and sieving; 2) Bonding processing: the powder base powder, silver powder and bonding auxiliary agent are put into a bonding pot according to the formula of the metal powder coating in table 3, and are stirred and heated at high speed, and bonded. After bonding, rapidly placing the materials into a cold mixing pot for low-speed stirring and cooling, and sieving to obtain the metal powder coating. The bonded metal powder coating was electrostatically sprayed on the pretreated cold-rolled steel sheet, cured at 200 ℃ for 10min to obtain a coating template, and the coating properties and metal effects were measured, and the test results were as shown in table 4 below.
TABLE 3 composition of metallic powder coatings
The effect of the metal powder is mainly to meet the apparent metal effect, and the judging method is basically a visual method, which is also a commonly adopted method in the industry. The leveling property is mainly to observe the evenness of a coating film and see whether orange peel and other phenomena exist or not, and the leveling property is generally compared with a PCI standard board, wherein 1-9 shows that the evenness is poor to good. The uniformity of the metal powder is mainly to see whether the metal powder is uniformly distributed on the surface of the sample plate, and whether the metal powder is excessive in some areas and less in some areas is known as bloom in the industry. If the bonding effect is poor, the free metal pigment is easily adsorbed on the periphery of the template due to electrostatic adsorption, so that four sides are shiny, namely the frame effect in the industry. If the metal pigment is settled in the curing process, the metal effect of the coating can be directly affected, the coating with the metal effect can be obtained only if the metal pigment floats on the surface of the coating, and the distribution of the metal pigment on the surface of the coating can be observed microscopically through a scanning electron microscope. The scanning patterns of the coating electron microscope of example 1, comparative example 1 and comparative example 2 correspond to those shown in fig. 1, fig. 2 and fig. 3, respectively.
TABLE 4 Properties of Metal powder coating
| Appearance leveling | Uniformity of metal powder | Silver powder floating condition | Frame effect | |
| Example 1 | 5-6 | Uniformity of | Float upwards | Without any means for |
| Example 2 | 7-8 | Uniformity of | Float upwards | Without any means for |
| Example 3 | 4-5 | Uniformity of | Float upwards | Without any means for |
| Example 4 | 6-7 | Uniformity of | Float upwards | Without any means for |
| Example 5 | 6-7 | Uniformity of | Float upwards | Without any means for |
| Comparative example 1 | 6-7 | Uniformity of | Slightly sink down | Without any means for |
| Comparative example 2 | 6-7 | Hair waving | Obvious sinking | Obvious and obvious |
As can be seen from the comparison results of Table 4, when the polyester prepared by the formulation and the process of the invention is used for preparing metal powder coating, the metal pigment and the base powder are fully bonded together, the metal pigment and the base powder basically have no peeling phenomenon, and the coating has no bloom and frame effect. As can be seen from the observation of the distribution of the silver powder in the coating by a scanning electron microscope (figures 1-3), the silver powder in the coating prepared by the polyester provided by the invention floats upwards and is uniformly distributed on the surface of the coating, the silver powder in the coating of the comparative example 1 prepared by the formula provided by the invention and the conventional process only slightly sinks, and the silver powder in the coating of the comparative example 2 prepared by the conventional formula obviously sinks. In addition, the polyester of the invention can meet the preparation of metal powder coatings with different levels of level.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. A polyester resin for metal powder coating is characterized in that: the preparation raw materials comprise: polyhydric alcohol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent and tertiary glycidyl carbonate.
2. The polyester resin for metal powder coating according to claim 1, wherein: the polyester resin for the metal powder coating is prepared from the following raw materials in percentage by mass: 20 to 35 weight percent of polyalcohol, 3 to 20 weight percent of halogenated bisphenol A, 30 to 55 weight percent of terephthalic acid, 2 to 10 weight percent of phthalic anhydride, 5 to 15 weight percent of acidolysis agent and 1 to 5 weight percent of tertiary glycidyl ester.
3. The polyester resin for metal powder coating according to claim 1, wherein: the halogenated bisphenol A has the structural formula of formula I:
wherein each R is independently selected from H and/or halogen, and at least one R is H and at least one R is halogen.
4. The polyester resin for metal powder coating according to claim 1, wherein: the polyol comprises at least one of neopentyl glycol, ethylene glycol, 2-methyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol or trimethylolpropane.
5. The polyester resin for metal powder coating according to claim 1, wherein: the raw materials for preparing the polyester resin for the metal powder coating also comprise an esterification catalyst, a curing accelerator and an antioxidant.
6. The polyester resin for metal powder coating according to claim 1, wherein: the acid value of the polyester resin for the metal powder coating is 30 mgKOH/g-35 mgKOH/g, the melt viscosity at 200 ℃ is 350 mg P.s-9000 mg P.s, the glass transition temperature Tg is 60 ℃ to 70 ℃, and the reactivity at 180 ℃ is 120 s-360 s.
7. A preparation method of polyester resin for metal powder coating is characterized in that: the method comprises the following steps:
s1: heating and melting polyalcohol and halogenated bisphenol A in an inert atmosphere, and adding terephthalic acid to perform esterification polycondensation reaction until the material is clear and transparent;
s2: after cooling, adding phthalic anhydride to react until the material is clear and transparent; continuously cooling, adding acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45 mgKOH/g-52 mgKOH/g;
s3: cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the material is 35 mgKOH/g-42 mgKOH/g;
s4: continuing to cool, adding tertiary glycidyl ester to carry out end capping reaction, and obtaining the polyester resin for the metal powder coating according to any one of claims 1-6.
8. The method for producing a polyester resin for metal powder coating according to claim 7, wherein: s2, cooling to 230-236 ℃, and adding phthalic anhydride to react until the materials are clear and transparent; continuously cooling to 228-233 ℃, adding acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45-52 mgKOH/g.
9. The method for producing a polyester resin for metal powder coating according to claim 7, wherein: the preparation method of the polyester resin for the metal powder coating comprises the following steps:
s1: heating and melting polyol, halogenated bisphenol A and an esterification catalyst in an inert atmosphere, and adding terephthalic acid to perform esterification polycondensation reaction until the materials are clear and transparent;
s2: after cooling, adding phthalic anhydride to react until the material is clear and transparent; continuously cooling, adding acidolysis agent to react until the material is clear and transparent, and controlling the acid value to be 45 mgKOH/g-52 mgKOH/g;
s3: cooling to perform vacuum polycondensation reaction, and releasing vacuum when the acid value of the material is 35 mgKOH/g-42 mgKOH/g;
s4: continuously cooling, adding tertiary glycidyl ester for end capping reaction, cooling, adding a curing agent and an antioxidant when the acid value of the material is 30 mgKOH/g-35 mgKOH/g, and stirring to obtain the polyester resin for the metal powder coating according to any one of claims 1-6.
10. A metal powder coating comprising the polyester resin for metal powder coating according to any one of claims 1 to 6.
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| Application Number | Priority Date | Filing Date | Title |
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| PCT/CN2022/126222 WO2024082179A1 (en) | 2022-10-19 | 2022-10-19 | Polyester resin for metal powder coating, preparation method therefor, and application thereof |
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| DE60206669T2 (en) * | 2001-02-06 | 2006-07-06 | Dainippon Ink And Chemicals, Inc. | Resin composition for powder coating, powder coating and coated articles |
| CN104311806B (en) * | 2014-10-20 | 2016-05-11 | 浙江天松新材料股份有限公司 | A kind of mylar and preparation method thereof for high levelling transparent powder paint |
| CN104558559B (en) * | 2014-12-04 | 2016-01-27 | 佛山市高明同德化工有限公司 | Saturated polyester resin that the wide pigment-dispersing of a kind of intermiscibility is good and preparation method thereof |
| CN107254240B (en) * | 2017-04-20 | 2019-05-28 | 浙江传化天松新材料有限公司 | A kind of high decorative surface of curable epoxide, enhanced water resistance polyester resin for powder coating and preparation method thereof |
| CN107540826A (en) * | 2017-07-31 | 2018-01-05 | 安徽优科新材料科技有限公司 | Novel high-grade bicycle use saturated polyester and preparation method thereof |
| EP3835379A4 (en) * | 2019-08-02 | 2021-11-03 | Kinte Materials Science and Technology Co., Ltd. | Polyester resin composition, powder coating and workpiece |
| CN110408013A (en) * | 2019-08-30 | 2019-11-05 | 广东工业大学 | A kind of polyester resin for powder coating and preparation method thereof |
| CN112625224A (en) * | 2020-12-28 | 2021-04-09 | 常州市碳索新材料科技有限公司 | Polyester resin for heat dissipation powder coating and preparation method thereof |
| CN113999376B (en) * | 2021-11-24 | 2023-06-13 | 新中法高分子材料股份有限公司 | High Tg high impact resistance polyester resin for dual-curable powder coating and preparation method and application thereof |
| CN115124701B (en) * | 2022-08-10 | 2023-12-22 | 浙江超浪新材料有限公司 | Difunctional polyester resin, powder coating and application |
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