WO2024082179A1 - Polyester resin for metal powder coating, preparation method therefor, and application thereof - Google Patents
Polyester resin for metal powder coating, preparation method therefor, and application thereof Download PDFInfo
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- WO2024082179A1 WO2024082179A1 PCT/CN2022/126222 CN2022126222W WO2024082179A1 WO 2024082179 A1 WO2024082179 A1 WO 2024082179A1 CN 2022126222 W CN2022126222 W CN 2022126222W WO 2024082179 A1 WO2024082179 A1 WO 2024082179A1
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- metal powder
- polyester resin
- powder coating
- mgkoh
- transparent
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 102
- 239000002184 metal Substances 0.000 title claims abstract description 102
- 238000000576 coating method Methods 0.000 title claims abstract description 97
- 239000000843 powder Substances 0.000 title claims abstract description 93
- 239000011248 coating agent Substances 0.000 title claims abstract description 71
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 58
- 239000004645 polyester resin Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 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 21
- 229920005862 polyol Polymers 0.000 claims abstract description 19
- 150000003077 polyols Chemical class 0.000 claims abstract description 19
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 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
- 239000000463 material Substances 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 21
- 230000032050 esterification Effects 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000006068 polycondensation reaction Methods 0.000 claims description 17
- NRBQOOIIBPCJEC-UHFFFAOYSA-N tert-butyl oxiran-2-ylmethyl carbonate Chemical compound CC(C)(C)OC(=O)OCC1CO1 NRBQOOIIBPCJEC-UHFFFAOYSA-N 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 6
- 230000009477 glass transition Effects 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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 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
- 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
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 239000000049 pigment Substances 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000005484 gravity Effects 0.000 abstract description 2
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004062 sedimentation Methods 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 235000013350 formula milk Nutrition 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 8
- 238000007667 floating Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 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 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 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
- 239000008199 coating composition Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000009413 insulation Methods 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
- 238000004886 process control Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000007873 sieving Methods 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
- 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
- 206010040844 Skin exfoliation Diseases 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
- 230000015572 biosynthetic process Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 230000002860 competitive effect Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 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
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 235000020610 powder formula Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 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
- 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
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- 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
Definitions
- the invention belongs to the technical field of powder coatings, and in particular relates to a polyester resin for metal powder coatings and a preparation method and application thereof.
- the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art.
- the first aspect of the present invention provides a polyester resin for metal powder coating, and the bonding metal powder coating prepared by using the polyester has a prominent metal effect and a beautiful appearance.
- the second aspect of the present invention provides a method for preparing the polyester resin for metal powder coating.
- a third aspect of the present invention provides a metal powder coating comprising the polyester resin for metal powder coating.
- a polyester resin for metal powder coating is provided.
- the raw materials for preparing the polyester resin include: polyol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, an acidolysis agent and tert-butyl glycidyl carbonate.
- the polyester resin for metal powder coating is prepared from raw materials including, by mass fraction, 20wt% to 35wt% of polyol, 3wt% to 20wt% of halogenated bisphenol A, 30wt% to 55wt% of terephthalic acid, 2wt% to 10wt% of phthalic anhydride, 5wt% to 15wt% of acidolysis agent and 1wt% to 5wt% of tert-butyl glycidyl carbonate.
- the halogenated bisphenol A has a structural formula of Formula I:
- each R is independently selected from H and/or halogen, and at least one R is H and at least one R is halogen.
- the halogenated bisphenol A comprises dihalogenated bisphenol A having the structural formula Ia:
- R 1 is halogen
- the halogenated bisphenol A has a structural formula of Formula Ib:
- the amount of the halogenated bisphenol A is 5 wt% to 20 wt% by mass, preferably 5 wt% to 15 wt%.
- the polyol includes at least one of neopentyl glycol, ethylene glycol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-propanediol, 1,6-hexanediol, 1,4-cyclohexanediol or trimethylolpropane; preferably, it is a combination of neopentyl glycol and other polyols. Further preferably, the ratio of neopentyl glycol to other polyols is greater than 5:1; further preferably, the ratio of neopentyl glycol to other polyols is greater than 6:1.
- the amount of the polyol is 25 wt% to 35 wt% by mass, preferably 28 wt% to 33 wt%.
- the amount of terephthalic acid is 30 wt% to 50 wt% by mass; preferably 35 wt% to 50 wt%; and more preferably 35 wt% to 45 wt%.
- the amount of the phthalic anhydride acid is 3 wt% to 10 wt% by mass; preferably 4 wt% to 10 wt%; and more preferably 5 wt% to 10 wt%.
- the acidolysis agent includes at least one of isophthalic acid, succinic acid, adipic acid or 1,4-cyclohexanedicarboxylic acid; preferably, the amount of the acidolysis agent is 7wt% to 15wt% by mass; preferably 7wt% to 12wt%.
- the amount of versatile glycidyl carbonate is 1.5 wt% to 5 wt% by mass; preferably 2 wt% to 5 wt%; and more preferably 3 wt% to 5 wt%.
- the raw materials for preparing the polyester resin for metal powder coatings further include an esterification catalyst, a curing accelerator, and an antioxidant.
- an esterification catalyst for preparing the polyester resin for metal powder coatings of the present invention
- polyols, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent, and tert-butyl glycidyl carbonate are components of the skeleton structure of the polyester resin, wherein tert-butyl glycidyl carbonate is used as a capping agent;
- the esterification catalyst is used to adjust the esterification polycondensation reaction rate and reaction degree, and the curing accelerator and antioxidant are used to improve certain properties of the polyester resin, respectively.
- the esterification catalyst includes at least one of monobutyltin oxide, dibutyltin oxide or stannous oxalate.
- the amount of the esterification catalyst is 0.05% to 0.15% by mass of the total material.
- the curing accelerator includes at least one of benzyltriethylammonium chloride, triphenylphosphine, phosphine bromide, triphenylphosphine or tert-butylamine; the amount of the curing accelerator is 0.01% to 0.1% by mass of the total material.
- the antioxidant includes a primary antioxidant and a secondary antioxidant
- the primary antioxidant includes antioxidant 1076 and/or antioxidant 1010
- the secondary antioxidant includes antioxidant 168 and/or antioxidant 626.
- the mass ratio of the primary antioxidant to the secondary antioxidant is 1:2 to 2:1, and more preferably 1:1.
- the acid value of the polyester resin for metal powder coating is 30 mgKOH/g to 35 mgKOH/g
- the melt viscosity at 200°C is 3500 mp.s to 9000 mp.s
- the glass transition temperature Tg is 60°C to 70°C
- the reactivity at 180°C is 120s to 360s.
- the melt viscosity at 200°C of the polyester resin for metal powder coating is 4000 mp.s to 8000 mp.s
- the glass transition temperature Tg is 62°C to 70°C
- the reactivity at 180°C is 180s to 360s.
- the melt viscosity at 200°C of the polyester resin for metal powder coating is 5000 mp.s to 7000 mp.s
- the glass transition temperature Tg is 62°C to 68°C
- the reactivity at 180°C is 240s to 330s.
- a method for preparing a polyester resin for metal powder coating comprising the following steps:
- the temperature of the esterification polycondensation reaction is 240°C to 245°C.
- the temperature is lowered to 230°C to 236°C, phthalic anhydride is added to react until the material becomes clear and transparent; the temperature is further lowered to 228°C to 233°C, an acidolysis agent is added to react until the material becomes clear and transparent, and the acid value is controlled to be between 45 mgKOH/g and 52 mgKOH/g.
- the temperature of the vacuum polycondensation reaction is 225°C to 230°C, and the vacuum degree is -0.085 MPa to -0.1 MPa; preferably -0.095 MPa.
- the method for preparing the polyester resin for metal powder coating comprises the following steps:
- a metal powder coating comprising the polyester resin for metal powder coating.
- the polyester resin for metal powder coating of the present invention has enhanced polarity of polyester resin due to the introduction of halogenated bisphenol A with halogen side groups, and the enhancement of polarity is conducive to improving the surface tension of the resin.
- the metal pigment can reduce the influence of gravity sedimentation under the pulling force of the resin surface tension, stabilize the metal pigment on the coating surface, and make the coating show better metal effect.
- tert-butyl glycidyl carbonate is introduced into the main chain of the polyester resin as a capping agent.
- the tert-carbon group suspended in the structure of tert-butyl glycidyl carbonate can increase the wettability of the metal pigment, so that the metal pigment is better coated in the resin, thereby reducing the risk of peeling after the metal pigment is bonded to the resin.
- the preparation method of the polyester resin for metal powder coating of the present invention allows all raw materials to be fully polymerized into the main chain, bringing further optimized performance to the resin, which is reflected in: (a) the reaction activity of phthalic anhydride is significantly higher than that of terephthalic acid. Its addition in the second step can not only avoid the competitive polymerization with terephthalic acid resulting in incomplete reaction of terephthalic acid, but also ensure the complete reaction of halogenated bisphenol A; (b) tert-butyl glycidyl carbonate is a monofunctional group. Its addition in the early stage of synthesis will affect the polymerization degree of the main chain. At the same time, the larger side groups in its structure will significantly reduce the Tg of the polyester.
- the present invention utilizes the high reactivity of the epoxy group in tert-butyl glycidyl carbonate, uses it as a capping agent and introduces it into the main chain by reacting with the carboxyl group at a relatively low temperature, which will not affect the polymerization degree of the main chain. At the same time, placing the tertiary carbon group at the end of the main chain has a limited effect on the Tg of the polyester.
- FIG. 1 shows the distribution of silver powder in a metal powder coating of a polyester resin in Example 1 of the present invention.
- FIG. 2 shows the distribution of silver powder in the metal powder coating of the polyester resin in Comparative Example 1 of the present invention.
- FIG. 3 shows the distribution of silver powder in the metal powder coating of the polyester resin in Comparative Example 2 of the present invention.
- This comparative example prepares a polyester resin, which is different from Example 5 in that tert-butyl glycidyl carbonate is adjusted to the first step of feeding, and the specific process is as follows:
- This comparative example prepared a polyester resin, and the specific process was as follows:
- the polyol and the esterification catalyst are heated under the protection of inert gas until they are melted, and then terephthalic acid is added, and the temperature is gradually increased to the insulation temperature to carry out esterification polycondensation reaction until the material is clear and transparent;
- polyester resins obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were tested for performance, wherein:
- Reactivity refers to the time required for the resin and curing agent to react into gel, and is measured at 180°C according to GB/T 16995-1997.
- polyester resins prepared according to the methods of Examples 1-5 and Comparative Examples 1-2 are respectively used to prepare metal powder coatings.
- the preparation of metal powder coatings can be divided into two stages according to the process flow: powder coating base powder preparation and bonding processing: 1) Preparation of powder coating base powder: weigh each component according to the base powder formula in Table 3, and obtain the required powder coating base powder after premixing, melt extrusion, cooling and tableting, crushing and pulverizing and sieving; 2) Bonding processing: put powder base powder, silver powder and bonding aid into a bonding pot according to the metal powder coating formula in Table 3, stir and heat at high speed, and bond. After bonding, quickly put the material into a cold mixing pot for low-speed stirring and cooling, and obtain metal powder coating after sieving. The bonded metal powder coating is electrostatically sprayed on a pre-treated cold-rolled steel plate, cured at 200°C for 10 minutes to obtain a coating sample, and its coating performance and metal effect are tested. The test results are shown in Table 4 below.
- the effect of metal powder is mainly to meet the apparent metal effect, and the judgment method is basically a visual method, which is also a commonly used method in the industry. Leveling mainly observes the flatness of the coating to see if there are orange peel and other phenomena. It is generally compared with the standard board of PCI, and 1-9 indicates that the flatness is from poor to good.
- the uniformity of metal powder mainly depends on whether the metal powder is evenly distributed on the surface of the sample. Some areas have too much metal powder and some areas have less, which is called flower in the industry. As a metal powder, if the bonding effect is not good, the free metal pigment will be easily adsorbed around the sample due to electrostatic adsorption, so that the four sides are shiny, which is what the industry calls the frame effect.
- Example 1 If the metal pigment settles during the curing process, it will directly affect the metal effect of the coating. Only when the metal pigment floats on the surface of the coating can a coating with a metal effect be obtained. The distribution of the metal pigment on the surface of the coating can be observed microscopically by scanning electron microscopy.
- the coating electron microscope scanning images of Example 1, Comparative Example 1 and Comparative Example 2 correspond to Figures 1, 2 and 3 respectively.
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- Polymers & Plastics (AREA)
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Abstract
The present invention provides a polyester resin for a metal powder coating, and a preparation method therefor and an application thereof. The polyester resin for the metal powder coating is prepared from the following raw materials: polyol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, an acidolysis agent, and tertiary glycidyl carbonate. The polyester resin for the metal powder coating of the present invention, by introducing a halogenated bisphenol A with a halogen side group, enhances the polarity of the polyester resin, the polarity enhancement being beneficial in increasing the surface tension of the resin. In the process of the high-temperature curing of the metal powder coating, the metal pigment can, under the pulling force of the surface tension of the resin, reduce the influence of gravity sedimentation, thereby stabilizing the metal pigment is stabilized on the surface of the coating, so that the coating shows a better metal effect.
Description
本发明属于粉末涂料技术领域，尤其涉及一种金属粉末涂料用聚酯树脂及其制备方法和应用。The invention belongs to the technical field of powder coatings, and in particular relates to a polyester resin for metal powder coatings and a preparation method and application thereof.
随着人们对环境保护的重视，作为环保、高效能、高效率和经济型的粉末涂料，近年来随着技术的快速发展，品种不断增加，应用领域逐步扩大。在装饰性方面，除了普通的不同光泽，平整表面的粉末涂料品种外，桔纹、皱纹、砂纹、花纹、锤纹、金属粉末涂料品种和用量也在增多，逐步参透到溶剂型涂料应用的各个领域。在上述品种中，金属粉末涂料被行业公认为粉末涂料领域中的一种高档产品，其产品可以进一步细分为金属闪光、金属镀层、金属花纹、锤纹和金属光泽纹理型等金属粉末涂料，这种粉末涂料的特点是都含有金属颜填料，通过改变金属颜填料种类及规格，涂料配方和制造工艺，可以得到不同性能和涂膜外观的粉末涂料。As people pay more attention to environmental protection, as environmentally friendly, high-performance, high-efficiency and economical powder coatings, with the rapid development of technology in recent years, the varieties are increasing and the application fields are gradually expanding. In terms of decoration, in addition to the ordinary powder coating varieties with different gloss and flat surface, the varieties and usage of orange grain, wrinkle, sand grain, pattern, hammer grain and metal powder coatings are also increasing, and gradually penetrate into various fields of solvent-based coatings. Among the above varieties, metal powder coatings are recognized by the industry as a high-end product in the field of powder coatings. Its products can be further subdivided into metal powder coatings such as metal flash, metal plating, metal pattern, hammer grain and metal gloss texture. The characteristic of this powder coating is that it contains metal pigments and fillers. By changing the type and specification of metal pigments and fillers, the coating formula and the manufacturing process, powder coatings with different performance and coating appearance can be obtained.
目前市场上高性能金属粉末涂料大多采用热粘结邦定法制备，由于邦定法制备金属粉末涂料对邦定设备和工艺要求较高，因此针对邦定设备和工艺开展了较多的研究。有关金属粉末涂料的研究报道基本集中在邦定设备和工艺，对于配套聚酯的研究基本未见报道。由于目前市面上缺乏相配套的聚酯树脂，技术先进的粉末厂商凭借较强的配方研发设计能力，同时搭配先进的邦定设备和严格的工艺控制来制备金属粉末涂料，但依旧难以解决产品批次间不稳定的问题。对于大部分资金实力不强、技术能力不足的中小企业，则难以进行相关金属粉的研发生产。为了促进金属粉末涂料的发展，亟需上下游联动起来加强制造设备、工艺及原材料等方面的研究。在配套树脂方面，目前对于金属粉末涂料专用聚酯的研究还比较缺乏，为了满足市场对金属粉末涂料用量快速上涨的需求，有必要提供一款适用于金属粉末涂料用的聚酯树脂，以此来降低对设备和工艺控制的依赖性，从而推动金属粉末涂料的快速发展。At present, most high-performance metal powder coatings on the market are prepared by thermal bonding. Since the bonding method has high requirements for bonding equipment and processes for preparing metal powder coatings, more research has been carried out on bonding equipment and processes. Research reports on metal powder coatings are basically concentrated on bonding equipment and processes, and there are basically no reports on the research of supporting polyesters. Due to the lack of matching polyester resins on the market, technologically advanced powder manufacturers rely on strong formula research and development design capabilities, and use advanced bonding equipment and strict process control to prepare metal powder coatings, but it is still difficult to solve the problem of instability between product batches. For most small and medium-sized enterprises with weak financial strength and insufficient technical capabilities, it is difficult to carry out the research and development and production of related metal powders. In order to promote the development of metal powder coatings, it is urgent to link up upstream and downstream to strengthen research on manufacturing equipment, processes and raw materials. In terms of supporting resins, there is currently a lack of research on polyesters specifically for metal powder coatings. In order to meet the market's demand for the rapid increase in the use of metal powder coatings, it is necessary to provide a polyester resin suitable for metal powder coatings to reduce dependence on equipment and process control, thereby promoting the rapid development of metal powder coatings.
发明内容Summary of the invention
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明第一个方面提出一种金属粉末涂料用聚酯树脂，利用该聚酯制备的邦定金属粉末涂料具有突出的金属效果和靓丽的外观。The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the first aspect of the present invention provides a polyester resin for metal powder coating, and the bonding metal powder coating prepared by using the polyester has a prominent metal effect and a beautiful appearance.
本发明的第二个方面提出了一种所述金属粉末涂料用聚酯树脂的制备方法。The second aspect of the present invention provides a method for preparing the polyester resin for metal powder coating.
本发明的第三个方面提出了一种包含所述金属粉末涂料用聚酯树脂的金属粉末涂料。A third aspect of the present invention provides a metal powder coating comprising the polyester resin for metal powder coating.
根据本发明的第一个方面，提出了一种金属粉末涂料用聚酯树脂，制备原料包括：多元醇、卤代双酚A、对苯二甲酸、苯酐、酸解剂和叔碳酸缩水甘油酯。According to a first aspect of the present invention, a polyester resin for metal powder coating is provided. The raw materials for preparing the polyester resin include: polyol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, an acidolysis agent and tert-butyl glycidyl carbonate.
在本发明的一些实施方式中，以质量分数计，所述金属粉末涂料用聚酯树脂，制备原料包括：20wt％～35wt％多元醇、3wt％～20wt％卤代双酚A、30wt％～55wt％对苯二甲酸、2wt％～10wt％苯酐、5wt％～15wt％酸解剂和1wt％～5wt％叔碳酸缩水甘油酯。In some embodiments of the present invention, the polyester resin for metal powder coating is prepared from raw materials including, by mass fraction, 20wt% to 35wt% of polyol, 3wt% to 20wt% of halogenated bisphenol A, 30wt% to 55wt% of terephthalic acid, 2wt% to 10wt% of phthalic anhydride, 5wt% to 15wt% of acidolysis agent and 1wt% to 5wt% of tert-butyl glycidyl carbonate.
在本发明的一些优选的实施方式中，所述卤代双酚A具有式I的结构式：In some preferred embodiments of the present invention, the halogenated bisphenol A has a structural formula of Formula I:
其中，每个R独立选自H和/或卤素，且至少有一个R为H和至少有一个R为卤素。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.
优选地，所述卤代双酚A包括二卤代双酚A，具有式Ia的结构式：Preferably, the halogenated bisphenol A comprises dihalogenated bisphenol A having the structural formula Ia:
其中，R
1为卤素；
Wherein, R 1 is halogen;
进一步优选地，所述卤代双酚A具有式Ib的结构式：Further preferably, the halogenated bisphenol A has a structural formula of Formula Ib:
在本发明的一些优选的实施方式中，以质量分数计，所述卤代双酚A的用量为5wt％～20wt％；优选为5wt％～15wt％。In some preferred embodiments of the present invention, the amount of the halogenated bisphenol A is 5 wt% to 20 wt% by mass, preferably 5 wt% to 15 wt%.
在本发明的一些更优选的实施方式中，所述多元醇包括新戊二醇、乙二醇、2-甲基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、1,3-丙二醇、1,6–己二醇、1,4-环己烷二醇或三羟甲基丙烷中的至少一种；优选为新戊二醇和其他多元醇的组合物。进一步优选地，新戊二醇和其他 多元醇的比例大于5：1；更进一步优选地，新戊二醇和其他多元醇的比例大于6：1。In some more preferred embodiments of the present invention, the polyol includes at least one of neopentyl glycol, ethylene glycol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-propanediol, 1,6-hexanediol, 1,4-cyclohexanediol or trimethylolpropane; preferably, it is a combination of neopentyl glycol and other polyols. Further preferably, the ratio of neopentyl glycol to other polyols is greater than 5:1; further preferably, the ratio of neopentyl glycol to other polyols is greater than 6:1.
在本发明的一些更优选的实施方式中，以质量分数计，所述多元醇的用量为25wt％～35wt％；优选为28wt％～33wt％。In some more preferred embodiments of the present invention, the amount of the polyol is 25 wt% to 35 wt% by mass, preferably 28 wt% to 33 wt%.
在本发明的一些更优选的实施方式中，以质量分数计，所述对苯二甲酸的用量为30wt％～50wt％；优选为35wt％～50wt％；进一步优选为35wt％～45wt％。In some more preferred embodiments of the present invention, the amount of terephthalic acid is 30 wt% to 50 wt% by mass; preferably 35 wt% to 50 wt%; and more preferably 35 wt% to 45 wt%.
在本发明的一些更优选的实施方式中，以质量分数计，所述苯酐酸的用量为3wt％～10wt％；优选为4wt％～10wt％；进一步优选为5wt％～10wt％。In some more preferred embodiments of the present invention, the amount of the phthalic anhydride acid is 3 wt% to 10 wt% by mass; preferably 4 wt% to 10 wt%; and more preferably 5 wt% to 10 wt%.
在本发明的一些更优选的实施方式中，所述酸解剂包括间苯二甲酸、丁二酸、己二酸或1,4-环己烷二甲酸中的至少一种；优选的，以质量分数计，所述酸解剂的用量为7wt％～15wt％；优选为7wt％～12wt％。In some more preferred embodiments of the present invention, the acidolysis agent includes at least one of isophthalic acid, succinic acid, adipic acid or 1,4-cyclohexanedicarboxylic acid; preferably, the amount of the acidolysis agent is 7wt% to 15wt% by mass; preferably 7wt% to 12wt%.
在本发明的一些更优选的实施方式中，以质量分数计，所述叔碳酸缩水甘油酯的用量为1.5wt％～5wt％；优选为2wt％～5wt％；进一步优选为3wt％～5wt％。In some more preferred embodiments of the present invention, the amount of versatile glycidyl carbonate is 1.5 wt% to 5 wt% by mass; preferably 2 wt% to 5 wt%; and more preferably 3 wt% to 5 wt%.
在本发明的一些更优选的实施方式中，所述金属粉末涂料用聚酯树脂的制备原料还包括酯化催化剂、固化促进剂、抗氧剂。本发明所述金属粉末涂料用聚酯树脂的制备原料中多元醇、卤代双酚A、对苯二甲酸、苯酐、酸解剂、叔碳酸缩水甘油酯为聚酯树脂的骨架结构组成部分，其中叔碳酸缩水甘油酯作为封端剂；所述酯化催化剂用于调节酯化缩聚反应速率和反应程度，所述固化促进剂和抗氧剂分别用于改善聚酯树脂的某些性能。In some more preferred embodiments of the present invention, the raw materials for preparing the polyester resin for metal powder coatings further include an esterification catalyst, a curing accelerator, and an antioxidant. In the raw materials for preparing the polyester resin for metal powder coatings of the present invention, polyols, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent, and tert-butyl glycidyl carbonate are components of the skeleton structure of the polyester resin, wherein tert-butyl glycidyl carbonate is used as a capping agent; the esterification catalyst is used to adjust the esterification polycondensation reaction rate and reaction degree, and the curing accelerator and antioxidant are used to improve certain properties of the polyester resin, respectively.
在本发明的一些更优选的实施方式中，所述酯化催化剂包括单丁氧化锡、二丁基氧化锡或草酸亚锡中的至少一种。优选的，所述酯化催化剂的用量为总物料质量数的0.05％～0.15％。In some more preferred embodiments of the present invention, the esterification catalyst includes at least one of monobutyltin oxide, dibutyltin oxide or stannous oxalate. Preferably, the amount of the esterification catalyst is 0.05% to 0.15% by mass of the total material.
在本发明的一些更优选的实施方式中，所述固化促进剂包括苄基三乙基氯化铵、三苯基以及溴化磷、三苯基膦或叔丁基胺中的至少一种；所述固化促进剂的用量为总物料质量数的0.01％～0.1％。In some more preferred embodiments of the present invention, the curing accelerator includes at least one of benzyltriethylammonium chloride, triphenylphosphine, phosphine bromide, triphenylphosphine or tert-butylamine; the amount of the curing accelerator is 0.01% to 0.1% by mass of the total material.
在本发明的一些更优选的实施方式中，所述抗氧剂包括主抗氧剂和辅抗氧剂，所述主抗氧剂包括抗氧剂1076和/或抗氧剂1010；所述辅抗氧剂包括抗氧剂168和/或抗氧剂626。优选的，所述主抗氧剂与所述辅抗氧剂的质量比为1：2～2：1；进一步优选为1：1。In some more preferred embodiments of the present invention, the antioxidant includes a primary antioxidant and a secondary antioxidant, the primary antioxidant includes antioxidant 1076 and/or antioxidant 1010; the secondary antioxidant includes antioxidant 168 and/or antioxidant 626. Preferably, the mass ratio of the primary antioxidant to the secondary antioxidant is 1:2 to 2:1, and more preferably 1:1.
在本发明的一些更优选的实施方式中，所述金属粉末涂料用聚酯树脂的酸值为30mgKOH/g～35mgKOH/g，200℃熔体粘度为3500mp.s～9000mp.s，玻璃化转变温度Tg为60℃～70℃，180℃的反应性为120s～360s。优选地，所述金属粉末涂料用聚酯树脂200℃熔体粘度为4000mp.s～8000mp.s，玻璃化转变温度Tg为62℃～70℃，180℃的反应性为180s～360s。进一步优选地，所述金属粉末涂料用聚酯树脂200℃熔体粘度为5000mp.s～7000mp.s，玻璃化 转变温度Tg为62℃～68℃，180℃的反应性为240s～330s。In some more preferred embodiments of the present invention, the acid value of the polyester resin for metal powder coating is 30 mgKOH/g to 35 mgKOH/g, the melt viscosity at 200°C is 3500 mp.s to 9000 mp.s, the glass transition temperature Tg is 60°C to 70°C, and the reactivity at 180°C is 120s to 360s. Preferably, the melt viscosity at 200°C of the polyester resin for metal powder coating is 4000 mp.s to 8000 mp.s, the glass transition temperature Tg is 62°C to 70°C, and the reactivity at 180°C is 180s to 360s. Further preferably, the melt viscosity at 200°C of the polyester resin for metal powder coating is 5000 mp.s to 7000 mp.s, the glass transition temperature Tg is 62°C to 68°C, and the reactivity at 180°C is 240s to 330s.
根据本发明的第二个方面，提出了一种金属粉末涂料用聚酯树脂的制备方法，包括以下步骤：According to a second aspect of the present invention, a method for preparing a polyester resin for metal powder coating is provided, comprising the following steps:
S1：惰性氛围下，将多元醇、卤代双酚A加热融化，再加入对苯二甲酸进行酯化缩聚反应至物料澄清透明；S1: In an inert atmosphere, heat and melt the polyol and halogenated bisphenol A, then add terephthalic acid to carry out esterification and polycondensation reaction until the material becomes clear and transparent;
S2：降温后，加入苯酐反应至物料澄清透明；继续降温，加入酸解剂反应至物料澄清透明，控制酸值为在45mgKOH/g至52mgKOH/g；S2: After cooling, add phthalic anhydride to react until the material is clear and transparent; continue cooling, add acidolysis agent to react until the material is clear and transparent, and control the acid value to be between 45 mgKOH/g and 52 mgKOH/g;
S3：降温进行真空缩聚反应，待物料酸值为35mgKOH/g至42mgKOH/g时解除真空；S3: Cooling down to carry out vacuum polycondensation reaction, and releasing the vacuum when the acid value of the material is 35 mgKOH/g to 42 mgKOH/g;
S4：继续降温，加入叔碳酸缩水甘油酯进行封端反应，制得所述金属粉末涂料用聚酯树脂。S4: Continue to cool down, add tert-butyl glycidyl carbonate to carry out end-capping reaction, and obtain the polyester resin for metal powder coating.
在本发明的一些实施方式中，S1中，所述酯化缩聚反应的温度为240℃～245℃。In some embodiments of the present invention, in S1, the temperature of the esterification polycondensation reaction is 240°C to 245°C.
在本发明的一些优选的实施方式中，S2中，降温至230℃～236℃，加入苯酐反应至物料澄清透明；继续降温至228℃～233℃，加入酸解剂反应至物料澄清透明，控制酸值为在45mgKOH/g至52mgKOH/g。In some preferred embodiments of the present invention, in S2, the temperature is lowered to 230°C to 236°C, phthalic anhydride is added to react until the material becomes clear and transparent; the temperature is further lowered to 228°C to 233°C, an acidolysis agent is added to react until the material becomes clear and transparent, and the acid value is controlled to be between 45 mgKOH/g and 52 mgKOH/g.
在本发明的一些更优选的实施方式中，S3中，所述真空缩聚反应的温度为225℃～230℃，真空度为-0.085MPa至-0.1MPa；优选为-0.095MPa。In some more preferred embodiments of the present invention, in S3, the temperature of the vacuum polycondensation reaction is 225°C to 230°C, and the vacuum degree is -0.085 MPa to -0.1 MPa; preferably -0.095 MPa.
所述金属粉末涂料用聚酯树脂的制备方法，包括以下步骤：The method for preparing the polyester resin for metal powder coating comprises the following steps:
S1：惰性氛围下，将多元醇、卤代双酚A、酯化催化剂加热融化，再加入对苯二甲酸进行酯化缩聚反应至物料澄清透明；S1: In an inert atmosphere, heat and melt the polyol, halogenated bisphenol A, and esterification catalyst, and then add terephthalic acid to carry out esterification polycondensation reaction until the material becomes clear and transparent;
S2：降温后，加入苯酐反应至物料澄清透明；继续降温，加入酸解剂反应至物料澄清透明，控制酸值为在45mgKOH/g至52mgKOH/g；S2: After cooling, add phthalic anhydride to react until the material is clear and transparent; continue cooling, add acidolysis agent to react until the material is clear and transparent, and control the acid value to be between 45 mgKOH/g and 52 mgKOH/g;
S3：降温进行真空缩聚反应，待物料酸值为35mgKOH/g至42mgKOH/g时解除真空；S3: Cooling down to carry out vacuum polycondensation reaction, and releasing the vacuum when the acid value of the material is 35 mgKOH/g to 42 mgKOH/g;
S4：继续降温，加入叔碳酸缩水甘油酯进行封端反应，待物料酸值为30mgKOH/g至35mgKOH/g时，降温加入固化剂和抗氧剂，搅拌后制得所述金属粉末涂料用聚酯树脂。S4: Continue to cool down, add tert-butyl glycidyl carbonate to perform end-capping reaction, and when the acid value of the material is 30 mgKOH/g to 35 mgKOH/g, cool down, add curing agent and antioxidant, and stir to obtain the polyester resin for metal powder coating.
根据本发明的第三个方面，提出了一种金属粉末涂料，包括所述的金属粉末涂料用聚酯树脂。According to a third aspect of the present invention, a metal powder coating is provided, comprising the polyester resin for metal powder coating.
本发明的有益效果为：The beneficial effects of the present invention are:
1.本发明的金属粉末涂料用聚酯树脂由于引入了具有卤素侧基的卤代双酚A而增强了聚酯树脂的极性，极性的增强有利于提高树脂的表面张力。金属粉末涂料在高温固化过程中，金属颜料在树脂表面张力的拉动力下可以减轻重力沉降的影响，将金属颜料稳固在涂层表面， 使涂层表现出更佳的金属效果。1. The polyester resin for metal powder coating of the present invention has enhanced polarity of polyester resin due to the introduction of halogenated bisphenol A with halogen side groups, and the enhancement of polarity is conducive to improving the surface tension of the resin. During the high-temperature curing process of metal powder coating, the metal pigment can reduce the influence of gravity sedimentation under the pulling force of the resin surface tension, stabilize the metal pigment on the coating surface, and make the coating show better metal effect.
2.本发明中叔碳酸缩水甘油酯作为封端剂引入到聚酯树脂主链，叔碳酸缩水甘油酯结构中悬挂的叔碳基团可以增加对金属颜料的润湿性，使得金属颜料更好的包覆于树脂中，从而降低了金属颜料与树脂邦定粘结后的剥离风险。2. In the present invention, tert-butyl glycidyl carbonate is introduced into the main chain of the polyester resin as a capping agent. The tert-carbon group suspended in the structure of tert-butyl glycidyl carbonate can increase the wettability of the metal pigment, so that the metal pigment is better coated in the resin, thereby reducing the risk of peeling after the metal pigment is bonded to the resin.
3.本发明的金属粉末涂料用聚酯树脂的制备方法使得各原材料均可以很充分的聚合到主链中，为树脂带来进一步的优化性能，体现在：(a)苯酐反应活性明显高于对苯二甲酸，其放在第二步投料加入既可以避免与对苯二甲酸发生竞聚反应导致对苯二甲酸反应不完全，又可以确保卤代双酚A反应完全；(b)叔碳酸缩水甘油酯作为一种单官能团其在合成前期加入会影响主链的聚合度，同时其结构中较大的侧基会明显降低聚酯的Tg，本发明利用叔碳酸缩水甘油酯中环氧基的高反应性，将其作为封端剂并在较低温度下与羧基反应引入到主链中，既不会影响主链的聚合度，同时将叔碳基团放在主链末端对聚酯Tg的影响也有限。3. The preparation method of the polyester resin for metal powder coating of the present invention allows all raw materials to be fully polymerized into the main chain, bringing further optimized performance to the resin, which is reflected in: (a) the reaction activity of phthalic anhydride is significantly higher than that of terephthalic acid. Its addition in the second step can not only avoid the competitive polymerization with terephthalic acid resulting in incomplete reaction of terephthalic acid, but also ensure the complete reaction of halogenated bisphenol A; (b) tert-butyl glycidyl carbonate is a monofunctional group. Its addition in the early stage of synthesis will affect the polymerization degree of the main chain. At the same time, the larger side groups in its structure will significantly reduce the Tg of the polyester. The present invention utilizes the high reactivity of the epoxy group in tert-butyl glycidyl carbonate, uses it as a capping agent and introduces it into the main chain by reacting with the carboxyl group at a relatively low temperature, which will not affect the polymerization degree of the main chain. At the same time, placing the tertiary carbon group at the end of the main chain has a limited effect on the Tg of the polyester.
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below with reference to the accompanying drawings and embodiments, wherein:
图1为本发明实施例1中聚酯树脂的金属粉末涂料涂层中银粉分布情况。FIG. 1 shows the distribution of silver powder in a metal powder coating of a polyester resin in Example 1 of the present invention.
图2为本发明对比例1中聚酯树脂的金属粉末涂料涂层中银粉分布情况。FIG. 2 shows the distribution of silver powder in the metal powder coating of the polyester resin in Comparative Example 1 of the present invention.
图3为本发明对比例2中聚酯树脂的金属粉末涂料涂层中银粉分布情况。FIG. 3 shows the distribution of silver powder in the metal powder coating of the polyester resin in Comparative Example 2 of the present invention.
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The following will be combined with the embodiments to clearly and completely describe the concept of the present invention and the technical effects produced, so as to fully understand the purpose, characteristics and effects of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative work are all within the scope of protection of the present invention.
实施例1～5Embodiments 1 to 5
S1：按照表1的配方组成将多元醇、卤代双酚A和酯化催化剂在惰性气体保护下加热至融化，然后加入对苯二甲酸，逐步升温至240℃～245℃进行酯化缩聚反应直至物料澄清透明；S1: According to the formula composition in Table 1, the polyol, halogenated bisphenol A and esterification catalyst are heated under the protection of inert gas until they are melted, and then terephthalic acid is added, and the temperature is gradually increased to 240° C. to 245° C. to carry out esterification polycondensation reaction until the material is clear and transparent;
S2：降温至236℃以下，加入苯酐，继续反应直至物料澄清透明；S2: Cool down to below 236°C, add phthalic anhydride, and continue the reaction until the material is clear and transparent;
S3：降温至233℃以下，加入酸解剂继续反应直至物料澄清透明，控制酸值在45mgKOH/g至52mgKOH/g的范围；S3: Cool down to below 233°C, add acidolysis agent and continue the reaction until the material is clear and transparent, and control the acid value in the range of 45mgKOH/g to 52mgKOH/g;
S4：降温至228℃以下进行真空缩聚反应，待反应物料酸值35mgKOH/g至42mgKOH/g即解除真空。S4: Cooling to below 228°C for vacuum polycondensation reaction, and releasing the vacuum when the acid value of the reaction material reaches 35 mgKOH/g to 42 mgKOH/g.
S5：降温至210℃以下，加入叔碳酸缩水甘油酯进行封端反应，检测物料酸值达到30至 35mgKOH/g时，降温加入固化促进剂和抗氧剂搅拌分散均匀后出料，制得金属粉末涂料用聚酯树脂。S5: Cooling down to below 210°C, adding tert-butyl glycidyl carbonate to perform end-capping reaction, and when the acid value of the material reaches 30 to 35 mgKOH/g, cooling down, adding a curing accelerator and an antioxidant, stirring and dispersing the mixture evenly, and then discharging the material to obtain a polyester resin for metal powder coating.
对比例1Comparative Example 1
本对比例制备了一种聚酯树脂，与实施例5的区别在于叔碳酸缩水甘油酯调整为第一步投料，具体过程为：This comparative example prepares a polyester resin, which is different from Example 5 in that tert-butyl glycidyl carbonate is adjusted to the first step of feeding, and the specific process is as follows:
S1：按表1配方组成将多元醇、卤代双酚A、叔碳酸缩水甘油酯和酯化催化剂在惰性气体保护下加热至融化，然后加入对苯二甲酸，逐步升温至保温温度进行酯化缩聚反应直至物料澄清透明；S1: Heat the polyol, halogenated bisphenol A, tert-butyl glycidyl carbonate and esterification catalyst under the protection of inert gas until they are melted according to the formulation in Table 1, then add terephthalic acid, gradually raise the temperature to the insulation temperature to carry out esterification polycondensation reaction until the material is clear and transparent;
S2：降温至236℃以下，加入苯酐，继续反应直至物料澄清透明；S2: Cool down to below 236°C, add phthalic anhydride, and continue the reaction until the material is clear and transparent;
S3：降温至233℃以下，加入酸解剂继续反应直至物料澄清透明，控制酸值在42mgKOH/g至46mgKOH/g的范围；S3: Cool down to below 233°C, add acidolysis agent and continue the reaction until the material is clear and transparent, and control the acid value in the range of 42mgKOH/g to 46mgKOH/g;
S4：降温进行真空缩聚反应，待反应物料酸值30mgKOH/g至35mgKOH/g即解除真空。S4: Cooling down to carry out vacuum polycondensation reaction, and releasing the vacuum when the acid value of the reaction material reaches 30 mgKOH/g to 35 mgKOH/g.
S5：降温至210℃以下加入固化促进剂和抗氧剂搅拌分散均匀后出料，制得聚酯树脂。S5: Cooling the mixture to below 210°C, adding a curing accelerator and an antioxidant, stirring and dispersing the mixture evenly, and then discharging the mixture to obtain a polyester resin.
对比例2Comparative Example 2
本对比例制备了一种聚酯树脂，具体过程为：This comparative example prepared a polyester resin, and the specific process was as follows:
1)按表1配方组成将多元醇和酯化催化剂在惰性气体保护下加热至融化，然后加入对苯二甲酸，逐步升温至保温温度进行酯化缩聚反应直至物料澄清透明；1) According to the formulation in Table 1, the polyol and the esterification catalyst are heated under the protection of inert gas until they are melted, and then terephthalic acid is added, and the temperature is gradually increased to the insulation temperature to carry out esterification polycondensation reaction until the material is clear and transparent;
2)降温至235℃以下，加入酸解剂继续反应直至物料澄清透明，控制酸值在42mgKOH/g至46mgKOH/g的范围；2) Cooling to below 235°C, adding an acidolysis agent to continue the reaction until the material is clear and transparent, and controlling the acid value in the range of 42 mgKOH/g to 46 mgKOH/g;
3)降温进行真空缩聚反应，待反应物料酸值30mgKOH/g至35mgKOH/g即解除真空。3) The temperature is lowered to carry out vacuum polycondensation reaction, and the vacuum is released when the acid value of the reaction material reaches 30 mgKOH/g to 35 mgKOH/g.
4)降温加入固化促进剂和抗氧剂搅拌分散均匀后出料，制得聚酯树脂。4) Cooling, adding curing accelerator and antioxidant, stirring and dispersing evenly, and then discharging the material to obtain polyester resin.
表1聚酯树脂配方组成Table 1 Polyester resin formula composition
试验例Test example
对实施例1～5和对比例1～2制得的聚酯树脂进行性能测试，其中：The polyester resins obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were tested for performance, wherein:
酸值按照GB/T6743-2008进行测试；The acid value is tested according to GB/T6743-2008;
熔融粘度：200℃下根据ASTM D4287-88测定的ICI锥板粘度；Melt viscosity: ICI cone and plate viscosity at 200°C measured according to ASTM D4287-88;
玻璃化转变温度(Tg)：按照GB/T 19466.2进行测试；Glass transition temperature (Tg): tested in accordance with GB/T 19466.2;
表面张力：按照GB/T22237—2008进行测试；Surface tension: Tested in accordance with GB/T22237-2008;
反应性是指树脂与固化剂反应至凝胶所需的时间，根据GB/T 16995-1997在180℃下测定。Reactivity refers to the time required for the resin and curing agent to react into gel, and is measured at 180°C according to GB/T 16995-1997.
测试结果如表2所示：The test results are shown in Table 2:
表2聚酯树脂的性能Table 2 Properties of polyester resin
进一步，将按照实施例1-5和对比例1-2方法制得的聚酯树脂分别制备金属粉末涂料上，金属粉末涂料的制备按工艺流程可以分为粉末涂料底粉制备和邦定加工两段：1)粉末涂料底粉的制备：按表3底粉配方称量各组分，经过预混合、熔融挤出、冷却压片、破碎和粉碎过筛后得到所需的粉末涂料底粉；2)邦定加工：按表3金属粉末涂料配方将粉末底粉、银粉及邦定助剂投入邦定锅，进行高速搅拌升温，邦定粘结。粘结完成后，迅速将物料放入冷混锅 中进行低速搅拌冷却，过筛后得到金属粉末涂料。将邦定好的金属粉末涂料通过静电喷涂于经过前处理的冷轧钢板上，在200℃下固化10min得到涂层样板，并检测其涂层性能和金属效果，测试结果如下表4。Further, the polyester resins prepared according to the methods of Examples 1-5 and Comparative Examples 1-2 are respectively used to prepare metal powder coatings. The preparation of metal powder coatings can be divided into two stages according to the process flow: powder coating base powder preparation and bonding processing: 1) Preparation of powder coating base powder: weigh each component according to the base powder formula in Table 3, and obtain the required powder coating base powder after premixing, melt extrusion, cooling and tableting, crushing and pulverizing and sieving; 2) Bonding processing: put powder base powder, silver powder and bonding aid into a bonding pot according to the metal powder coating formula in Table 3, stir and heat at high speed, and bond. After bonding, quickly put the material into a cold mixing pot for low-speed stirring and cooling, and obtain metal powder coating after sieving. The bonded metal powder coating is electrostatically sprayed on a pre-treated cold-rolled steel plate, cured at 200°C for 10 minutes to obtain a coating sample, and its coating performance and metal effect are tested. The test results are shown in Table 4 below.
表3金属粉末涂料的组成Table 3 Composition of metal powder coatings
金属粉的效果主要是为了满足表观的金属效果，判断的方法基本上为目视的方法，这也是行业内普遍采用的方法。流平性主要是观察涂膜的平整度，看是否有橘皮等现象，一般是和PCI的标准板进行对比，1-9表示平整度从差到好。金属粉的均匀性主要是看金属粉在样板表面分布是否均匀，是否有的区域金属粉过多，有的区域少，业内称为发花。作为金属粉，如果邦定效果不好，游离的金属颜料会因为静电吸附的原因，容易被吸附在样板的四周，从而使得四边发亮，即业内所说的边框效应。如果金属颜料在固化过程发生沉降，则会直接影响涂层的金属效果，只有金属颜料浮在涂层表面，才能获得金属效果的涂层，通过扫描电镜可以在微观上观察金属颜料在涂层表面的分布。实施例1、对比例1和对比例2的涂层电镜扫描图分别对应如图1、图2和图3所示。The effect of metal powder is mainly to meet the apparent metal effect, and the judgment method is basically a visual method, which is also a commonly used method in the industry. Leveling mainly observes the flatness of the coating to see if there are orange peel and other phenomena. It is generally compared with the standard board of PCI, and 1-9 indicates that the flatness is from poor to good. The uniformity of metal powder mainly depends on whether the metal powder is evenly distributed on the surface of the sample. Some areas have too much metal powder and some areas have less, which is called flower in the industry. As a metal powder, if the bonding effect is not good, the free metal pigment will be easily adsorbed around the sample due to electrostatic adsorption, so that the four sides are shiny, which is what the industry calls the frame effect. If the metal pigment settles during the curing process, it will directly affect the metal effect of the coating. Only when the metal pigment floats on the surface of the coating can a coating with a metal effect be obtained. The distribution of the metal pigment on the surface of the coating can be observed microscopically by scanning electron microscopy. The coating electron microscope scanning images of Example 1, Comparative Example 1 and Comparative Example 2 correspond to Figures 1, 2 and 3 respectively.
表4金属粉末涂料的性能Table 4 Properties of metal powder coatings
| The | 外观流平Appearance leveling | 金属粉均一性Metal powder uniformity | 银粉上浮情况Silver powder floating situation | 边框效应Border effect |
| 实施例1Example 1 | 5-65-6 | 均匀Uniform | 上浮Floating | 无none |
| 实施例2Example 2 | 7-87-8 | 均匀Uniform | 上浮Floating | 无none |
| 实施例3Example 3 | 4-54-5 | 均匀Uniform | 上浮Floating | 无none |
| 实施例4Example 4 | 6-76-7 | 均匀Uniform | 上浮Floating | 无none |
| 实施例5Example 5 | 6-76-7 | 均匀Uniform | 上浮Floating | 无none |
| 对比例1Comparative Example 1 | 6-76-7 | 均匀Uniform | 轻微下沉Slight sinking | 无none |
| 对比例2Comparative Example 2 | 6-76-7 | 发花Flowering | 下沉明显Sinking is obvious | 明显obvious |
从表4的对比结果可知，采用本发明的配方和工艺制备的聚酯用于金属粉末涂料制备时，金属颜料与底粉充分粘结在一起，金属颜料与底粉基本没有剥离现象，涂层不存在发花和边框效应。通过扫描电镜观察涂层中银粉分布(图1-图3)可知，采用本发明的聚酯制备的涂层中银粉均上浮并均匀分布在涂层表面，采用本发明提供的配方搭配常规工艺制备的对比例 1涂层中银粉只出现轻微的下沉，常规配方制备的对比例2涂层中银粉出现明显的下沉。此外，本发明的聚酯可以满足不同流平等级金属粉末涂料的制备。From the comparison results in Table 4, it can be seen that when the polyester prepared by the formula and process of the present invention is used for the preparation of metal powder coatings, the metal pigment and the base powder are fully bonded together, the metal pigment and the base powder are basically not peeled off, and the coating does not have flowery and frame effects. The distribution of silver powder in the coating is observed by scanning electron microscopy (Figures 1-3). It can be seen that the silver powder in the coating prepared by the polyester of the present invention is all floating and evenly distributed on the surface of the coating. The silver powder in the coating of Comparative Example 1 prepared by the formula provided by the present invention and the conventional process only slightly sinks, and the silver powder in the coating of Comparative Example 2 prepared by the conventional formula obviously sinks. In addition, the polyester of the present invention can meet the preparation of metal powder coatings with different leveling grades.
上面对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The above is a detailed description of the embodiments of the present invention, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge of ordinary technicians in the relevant technical field without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.
Claims (10)
- 一种金属粉末涂料用聚酯树脂，其特征在于：制备原料包括：多元醇、卤代双酚A、对苯二甲酸、苯酐、酸解剂和叔碳酸缩水甘油酯。A polyester resin for metal powder coating, characterized in that the raw materials for preparation include: polyol, halogenated bisphenol A, terephthalic acid, phthalic anhydride, acidolysis agent and tert-butyl glycidyl carbonate.
- 根据权利要求1所述的金属粉末涂料用聚酯树脂，其特征在于：以质量分数计，所述金属粉末涂料用聚酯树脂，制备原料包括：20wt％～35wt％多元醇、3wt％～20wt％卤代双酚A、30wt％～55wt％对苯二甲酸、2wt％～10wt％苯酐、5wt％～15wt％酸解剂和1wt％～5wt％叔碳酸缩水甘油酯。The polyester resin for metal powder coating according to claim 1 is characterized in that: the raw materials for preparing the polyester resin for metal powder coating include, by mass fraction, 20wt% to 35wt% of polyol, 3wt% to 20wt% of halogenated bisphenol A, 30wt% to 55wt% of terephthalic acid, 2wt% to 10wt% of phthalic anhydride, 5wt% to 15wt% of acidolysis agent and 1wt% to 5wt% of tert-butyl glycidyl carbonate.
- 根据权利要求1所述的金属粉末涂料用聚酯树脂，其特征在于：所述卤代双酚A具有式I的结构式：The polyester resin for metal powder coating according to claim 1, characterized in that the halogenated bisphenol A has a structural formula of Formula I:
其中，每个R独立选自H和/或卤素，且至少有一个R为H和至少有一个R为卤素。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. - 根据权利要求1所述的金属粉末涂料用聚酯树脂，其特征在于：所述多元醇包括新戊二醇、乙二醇、2-甲基-1,3-丙二醇、2-乙基-2-丁基-1,3-丙二醇、1,3-丙二醇、1,6–己二醇、1,4-环己烷二醇或三羟甲基丙烷中的至少一种。The polyester resin for metal powder coating according to claim 1 is characterized in that the polyol includes at least one of neopentyl glycol, ethylene glycol, 2-methyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1,3-propanediol, 1,6-hexanediol, 1,4-cyclohexanediol or trimethylolpropane.
- 根据权利要求1所述的金属粉末涂料用聚酯树脂，其特征在于：所述金属粉末涂料用聚酯树脂的制备原料还包括酯化催化剂、固化促进剂、抗氧剂。The polyester resin for metal powder coating according to claim 1 is characterized in that the raw materials for preparing the polyester resin for metal powder coating also include an esterification catalyst, a curing accelerator, and an antioxidant.
- 根据权利要求1所述的金属粉末涂料用聚酯树脂，其特征在于：所述金属粉末涂料用聚酯树脂的酸值为30mgKOH/g～35mgKOH/g，200℃熔体粘度为3500mp.s～9000mp.s，玻璃化转变温度Tg为60℃～70℃，180℃的反应性为120s～360s。The polyester resin for metal powder coating according to claim 1 is characterized in that the acid value of the polyester resin for metal powder coating is 30 mgKOH/g to 35 mgKOH/g, the melt viscosity at 200°C is 3500 mp.s to 9000 mp.s, the glass transition temperature Tg is 60°C to 70°C, and the reactivity at 180°C is 120s to 360s.
- 一种金属粉末涂料用聚酯树脂的制备方法，其特征在于：包括以下步骤：A method for preparing a polyester resin for metal powder coating, characterized in that it comprises the following steps:S1：惰性氛围下，将多元醇、卤代双酚A加热融化，再加入对苯二甲酸进行酯化缩聚反应至物料澄清透明；S1: In an inert atmosphere, heat and melt the polyol and halogenated bisphenol A, then add terephthalic acid to carry out esterification and polycondensation reaction until the material becomes clear and transparent;S2：降温后，加入苯酐反应至物料澄清透明；继续降温，加入酸解剂反应至物料澄清透明，控制酸值为在45mgKOH/g至52mgKOH/g；S2: After cooling, add phthalic anhydride to react until the material is clear and transparent; continue cooling, add acidolysis agent to react until the material is clear and transparent, and control the acid value to be between 45 mgKOH/g and 52 mgKOH/g;S3：降温进行真空缩聚反应，待物料酸值为35mgKOH/g至42mgKOH/g时解除真空；S3: Cooling down to carry out vacuum polycondensation reaction, and releasing the vacuum when the acid value of the material is 35 mgKOH/g to 42 mgKOH/g;S4：继续降温，加入叔碳酸缩水甘油酯进行封端反应，制得如权利要求1～6任一项所述 的金属粉末涂料用聚酯树脂。S4: Continue to cool down, add tert-butyl glycidyl carbonate to carry out end-capping reaction, and obtain the polyester resin for metal powder coating as claimed in any one of claims 1 to 6.
- 根据权利要求7所述的金属粉末涂料用聚酯树脂的制备方法，其特征在于：S2中，降温至230℃～236℃，加入苯酐反应至物料澄清透明；继续降温至228℃～233℃，加入酸解剂反应至物料澄清透明，控制酸值为在45mgKOH/g至52mgKOH/g。The method for preparing a polyester resin for metal powder coating according to claim 7 is characterized in that: in S2, the temperature is lowered to 230°C to 236°C, phthalic anhydride is added to react until the material becomes clear and transparent; the temperature is further lowered to 228°C to 233°C, an acidolysis agent is added to react until the material becomes clear and transparent, and the acid value is controlled to be between 45 mgKOH/g and 52 mgKOH/g.
- 根据权利要求7所述的金属粉末涂料用聚酯树脂的制备方法，其特征在于：所述金属粉末涂料用聚酯树脂的制备方法，包括以下步骤：The method for preparing a polyester resin for metal powder coating according to claim 7 is characterized in that the method for preparing a polyester resin for metal powder coating comprises the following steps:S1：惰性氛围下，将多元醇、卤代双酚A、酯化催化剂加热融化，再加入对苯二甲酸进行酯化缩聚反应至物料澄清透明；S1: In an inert atmosphere, heat and melt the polyol, halogenated bisphenol A, and esterification catalyst, and then add terephthalic acid to carry out esterification polycondensation reaction until the material becomes clear and transparent;S2：降温后，加入苯酐反应至物料澄清透明；继续降温，加入酸解剂反应至物料澄清透明，控制酸值为在45mgKOH/g至52mgKOH/g；S2: After cooling, add phthalic anhydride to react until the material is clear and transparent; continue cooling, add acidolysis agent to react until the material is clear and transparent, and control the acid value to be between 45 mgKOH/g and 52 mgKOH/g;S3：降温进行真空缩聚反应，待物料酸值为35mgKOH/g至42mgKOH/g时解除真空；S3: Cooling down to carry out vacuum polycondensation reaction, and releasing the vacuum when the acid value of the material is 35 mgKOH/g to 42 mgKOH/g;S4：继续降温，加入叔碳酸缩水甘油酯进行封端反应，待物料酸值为30mgKOH/g至35mgKOH/g时，降温加入固化剂和抗氧剂，搅拌后制得如权利要求1～6任一项所述的金属粉末涂料用聚酯树脂。S4: Continue to cool down, add tert-butyl glycidyl carbonate to perform end-capping reaction, and when the acid value of the material is 30 mgKOH/g to 35 mgKOH/g, cool down, add curing agent and antioxidant, and stir to obtain the polyester resin for metal powder coating as claimed in any one of claims 1 to 6.
- 一种金属粉末涂料，包括如权利要求1～6任一项所述的金属粉末涂料用聚酯树脂。A metal powder coating, comprising the polyester resin for metal powder coating as claimed in any one of claims 1 to 6.
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| CN202280004573.4A CN116096777A (en) | 2022-10-19 | 2022-10-19 | Polyester resin for metal powder coating and preparation method and application thereof |
| 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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