CN117586688A - Polyester resin for transparent powder coating with low curing temperature and high leveling property, and preparation method and application thereof - Google Patents
Polyester resin for transparent powder coating with low curing temperature and high leveling property, and preparation method and application thereof Download PDFInfo
- Publication number
- CN117586688A CN117586688A CN202311707565.9A CN202311707565A CN117586688A CN 117586688 A CN117586688 A CN 117586688A CN 202311707565 A CN202311707565 A CN 202311707565A CN 117586688 A CN117586688 A CN 117586688A
- Authority
- CN
- China
- Prior art keywords
- powder coating
- polyester resin
- transparent powder
- temperature
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 78
- 239000000843 powder Substances 0.000 title claims abstract description 57
- 239000004645 polyester resin Substances 0.000 title claims abstract description 55
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 aliphatic polyols Chemical class 0.000 claims abstract description 47
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 36
- 229920005862 polyol Polymers 0.000 claims abstract description 35
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 27
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000001723 curing Methods 0.000 claims description 46
- 239000000463 material Substances 0.000 claims description 25
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical class OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical group C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 239000002981 blocking agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 2
- JVZZUPJFERSVRN-UHFFFAOYSA-N 2-methyl-2-propylpropane-1,3-diol Chemical compound CCCC(C)(CO)CO JVZZUPJFERSVRN-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
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 2
- 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 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
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000005452 bending Methods 0.000 description 10
- 239000003973 paint Substances 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000006085 branching agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 238000002834 transmittance 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
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- KRFFWELOYNJROH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 KRFFWELOYNJROH-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- WTKWFNIIIXNTDO-UHFFFAOYSA-N 3-isocyanato-5-methyl-2-(trifluoromethyl)furan Chemical compound CC1=CC(N=C=O)=C(C(F)(F)F)O1 WTKWFNIIIXNTDO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- LIXPMKNZESBUKY-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(O)(C(CO)(CO)CO)C1=CC(=C(C(=C1)C(C)(C)C)C)C(C)(C)C)C(C)(C)C)C LIXPMKNZESBUKY-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- RZWDOHOQSSGFOR-UHFFFAOYSA-N bromo-ethyl-triphenyl-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(Br)(C=1C=CC=CC=1)(CC)C1=CC=CC=C1 RZWDOHOQSSGFOR-UHFFFAOYSA-N 0.000 description 1
- IKWKJIWDLVYZIY-UHFFFAOYSA-M butyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCC)C1=CC=CC=C1 IKWKJIWDLVYZIY-UHFFFAOYSA-M 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZXQYGBMAQZUVMI-GCMPRSNUSA-N gamma-cyhalothrin Chemical compound CC1(C)[C@@H](\C=C(/Cl)C(F)(F)F)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 ZXQYGBMAQZUVMI-GCMPRSNUSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The application discloses a polyester resin for a transparent powder coating with low curing temperature and high leveling property, a preparation method and application thereof, wherein the polyester resin for the transparent powder coating comprises the following raw materials in percentage by weight: 20-35%; aliphatic polyols having a cyclic structure: 3.0 to 10 percent; asymmetric aliphatic polyols having side chain groups: 2.5 to 5.0 percent; straight chain aliphatic polyol without pendant groups: 0.5 to 2.0 percent; aromatic polyacids: 35-45%; aliphatic polybasic acid having a cyclic structure: 5-15%; aliphatic polybasic acids of linear structure: 0 to 2.0 percent; end capping agent: 5-8%; esterification catalyst: 0.05 to 0.15 percent; curing accelerator: 0.075-0.2%; an antioxidant: 0.3 to 0.5 percent. When the transparent powder coating prepared from the polyester resin is sprayed on a mirror plate, the curing temperature is lower than 200, and the lowest temperature can reach 150. The coating film after being cured at the temperature has higher transparency, excellent leveling property and excellent flexibility, and can be processed later.
Description
Technical Field
The application relates to the technical field of polyester resin, in particular to polyester resin for transparent powder coating with low curing temperature and high leveling property, and a preparation method and application thereof.
Background
As green environment-friendly industrial paint products, the powder paint has the characteristics of no pollution, zero VOCs emission, high recycling rate, simple coating process, high automation degree and the like because of no organic solvent in the components, has been widely accepted by the market, is rapidly developed and gradually replaces the market share of solvent-based paint, and becomes the preferable industrial paint products in the 'double carbon' background. In some applications, it is desirable to further form a clear coat over the primer coat, so clear powder coatings are the preferred choice for environmental-friendly clear coats.
The transparent powder coating system mainly comprises: acrylic and polyacid curing systems, hydroxyl polyester and blocked isocyanate curing systems, polyester and TGIC curing systems, and the like. The transparent powder coating prepared by the acrylic resin and the polyacid curing system is mainly applied to the surface finishing effect of high-end products such as automobile aluminum wheels, hardware metals, bathroom and the like. However, the acrylic resin has poor dispersion performance and high requirements on extrusion mixing effect, namely equipment and process. The powder of the acrylic resin and the polybasic acid curing system has low glass transition temperature (about 35 ℃) and poor storage stability; meanwhile, the low surface tension characteristic of the paint is easy to cause the defect of the surface of a paint film, so that the paint film is required to be produced in a dust-free workshop and transported by refrigeration, and the application and popularization of the paint film are greatly limited.
The transparent powder coating of the hydroxyl value polyester and blocked isocyanate curing system is prepared by taking polyester resin as matrix resin and blocked isocyanate as curing agent, and releases deblocking of the curing agent during curing, and needs a recovery device; and the compatibility with the common polyester system is poor, the brittleness is large, and the large-scale application is limited. And the polyurethane curing temperature is mostly 200 ℃, and the curing agent is not more selectable.
The transparent powder coating of the polyester and TGIC curing system is generally prepared by taking polyester resin as matrix resin and triglycidyl isocyanurate as curing agent, and when the transparent powder coating is used as finishing paint, the coating film compatibility with a bottom layer is good, the production process is mature, and the transparent powder coating is a variety which develops faster in recent years, but the transparency of common polyester is slightly poorer than that of an acrylic acid system, the leveling performance cannot reach the level of the acrylic acid transparent powder coating, so that the flatness after finishing is poorer, and the finishing coating is accompanied with slight pinhole-shaped defects, and the finishing effect on the bottom coating is obviously influenced.
Disclosure of Invention
In order to solve the problems, the application provides a polyester resin for transparent powder coating, which has high transparency, good leveling property and curing temperature lower than 200 ℃ and higher than 150 ℃.
The application discloses a polyester resin for transparent powder coating with low curing temperature and high leveling property, which comprises the following raw materials in percentage by weight:
neopentyl glycol: 20-35%;
aliphatic polyols having a cyclic structure: 3.0 to 10 percent;
asymmetric aliphatic polyols having side chain groups: 2.5 to 5.0 percent;
straight chain aliphatic polyol without pendant groups: 0.5 to 2.0 percent;
aromatic polyacids: 35-45%;
aliphatic polybasic acid having a cyclic structure: 5-15%;
aliphatic polybasic acids of linear structure: 0 to 2.0 percent;
end capping agent: 5-8%;
esterification catalyst: 0.05 to 0.15 percent;
curing accelerator: 0.075-0.2%;
an antioxidant: 0.3 to 0.5 percent.
The application introduces the aliphatic polyol with the cyclic structure into the raw material component of the polyester resin, and ensures that the synthetic polyester resin still has the glass transition temperature of about 60 ℃ when the polyester has flexible chains (the straight-chain aliphatic polyol without side groups and the aliphatic polybasic acid with the straight-chain structure) by utilizing the rigid structure of the aliphatic polyol with the cyclic structure. The higher glass transition temperature endows the polyester resin to prepare powder coating with good crushing, grinding and other processing performances and good storage stability.
Meanwhile, the asymmetric aliphatic polyhydric alcohol with side chain groups is introduced, and the side chain and the asymmetric structure endow the polyester product with non-crystallinity, so that the viscosity of the polyester is reduced, and the transparency of the polyester is improved. The polyester resin has the advantages that the linear aliphatic polyol without side groups and the aliphatic polybasic acid with a linear structure are matched, so that the main chain structure and the side chain structure of the polyester molecule have strong bending resistance under the action of external force, the molecular structure is stable, and the polyester resin is endowed with excellent flexibility.
The usage amount of the aromatic polybasic acid is controlled, the aliphatic polybasic acid with a cyclic structure and the aliphatic polybasic acid with a linear structure are introduced, compared with the aromatic polybasic acid, the aliphatic polybasic acid with the cyclic structure and the aliphatic polybasic acid with the linear structure have higher reactivity, the esterification reaction can be carried out at a relatively low temperature, the high-temperature side reaction and yellowing of the polyester resin in the synthesis process are reduced, the obtained polyester resin has light chromaticity, the absorbance of visible light is less compared with that of the polyester resin with a yellow phase, and the transparency of the prepared transparent powder coating film is higher.
The method skillfully adds no branching agent into the polyester raw material component, and ensures that the resin is always in a linear structure in the esterification and polycondensation stage to control the molecular weight to be increased too fast.
The following provides several alternatives, but not as additional limitations to the above-described overall scheme, and only further additions or preferences, each of which may be individually combined for the above-described overall scheme, or may be combined among multiple alternatives, without technical or logical contradictions.
Alternatively, the aliphatic polyhydric alcohol with a cyclic structure is tricyclodecanedimethanol or a combination of tricyclodecanedimethanol and at least one of 1, 4-cyclohexane diol and hydrogenated bisphenol A.
Optionally, the tricyclodecane dimethanol accounts for 3.0-5.0% of the raw material components by mass percent. Compared with polyol and polybasic acid with regular structures, the synthesized polyester has the characteristics of difficult formation of a crystallization area, lower viscosity, high transparency and the like.
Optionally, the asymmetric aliphatic polyol with side chain groups is selected from one or a combination of a plurality of 2-methyl-2-propyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol and 2, 4-trimethyl-1, 3-pentanediol.
Optionally, the straight-chain aliphatic polyol without side groups is selected from one or a combination of a plurality of 1, 6-hexanediol, 1, 4-butanediol and 1, 5-pentanediol.
Optionally, the aliphatic polybasic acid with a cyclic structure is selected from one or a combination of more of 1, 4-cyclohexane dicarboxylic acid, hexahydrophthalic anhydride, 1, 2-cyclo-succinic acid and furan dicarboxylic acid.
Optionally, the aromatic polyacid is terephthalic acid or isophthalic acid.
Optionally, the aliphatic polybasic acid with a linear structure is selected from one or a combination of more than one of 1, 6-adipic acid, 1, 10-sebacic acid, 1, 8-suberic acid, 1, 12-dodecanedioic acid, 1, 9-azelaic acid and 1, 7-pimelic acid; preferably one or a combination of several of 1, 6-adipic acid, 1, 10-sebacic acid and 1, 8-suberic acid.
Alternatively, the capping agent is a combination of a glycidyl versatate EP-10 with hydrogenated trimellitic anhydride and/or trimellitic anhydride.
The end-capping agent adopts the combination of tertiary glycidyl ester EP-10 and hydrogenated trimellitic anhydride or trimellitic anhydride: firstly, the end capping agent can be ensured to be subjected to end capping at a lower temperature after polycondensation, and the chromaticity of the resin is shallower; secondly, trimellitic anhydride or hydrogenated trimellitic anhydride has high functional group characteristics, and even if one molecule of a polyester molecule segment reacts with tertiary glycidyl ester EP-10, three active carboxyl functional groups still remain.
The esterification catalyst is one or the combination of a plurality of stannous oxalate, n-butyl titanate and tetraisopropyl titanate.
The antioxidant is a combination of hindered phenol antioxidants and phosphite antioxidants.
The hindered phenol antioxidant is one or a combination of more of pentaerythritol tetra- [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-stearyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5- (3, 5-di-tert-butyl-4-hydroxyphenyl) s-triazine-2, 4,6 (1H, 3H, 5H) trione or N, N' -bis- [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hexamethylenediamine.
The phosphite antioxidant is one or a combination of more of tri (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite or bis (2, 6-di-tert-butyl-4-tolyl) pentaerythritol diphosphite.
The curing accelerator is selected from one or a combination of more of triphenyl ethyl phosphorus bromide, triphenyl butyl phosphonium bromide, tetrabutyl ammonium chloride, tetraethyl ammonium chloride, tetrapropyl ammonium bromide, methyl triethyl ammonium chloride, benzyl trimethyl ammonium chloride and benzyl triethyl ammonium chloride.
The application also provides a preparation method of the polyester resin for the transparent powder coating, which has low curing temperature and high leveling property, and comprises the following steps:
s1, uniformly mixing neopentyl glycol, aliphatic polyol with a cyclic structure, asymmetric aliphatic polyol with side chain groups, linear aliphatic polyol without side groups and an esterification catalyst, and heating to 110-130 ℃ under normal pressure to melt;
s2, adding aromatic polybasic acid, aliphatic polybasic acid with a cyclic structure and aliphatic polybasic acid with a linear structure, heating to 170-180 ℃ within 0.5-2 h under the protection of protective gas, and distilling out esterified water; heating to 193-195 ℃ within 2-6 h; heating to 230-235 deg.c in 3-5 hr to react in heat preservation for 1-1.5 hr; until the reaction degree reaches 95%, and the heat preservation is finished;
s3, continuously reacting under reduced pressure for 60-150 min;
s4, reducing the temperature of the materials, adding a blocking agent, and reacting for 90-120 min;
s5, keeping the temperature of the materials at 210-215 ℃, adding a curing accelerator and an antioxidant, and stirring and reacting for 20-60 min to obtain the polyester resin for the transparent powder coating.
The preparation method disclosed by the application is concise in procedure, environment-friendly and high in production efficiency.
Optionally, in the step S4, when the temperature of the material is reduced to 220-225 ℃, adding trimellitic anhydride and/or hydrogenated trimellitic anhydride in the end capping agent, controlling the temperature to 213-217 ℃ and reacting for 60-80 min; and adding tertiary glycidyl ester EP-10 in the end capping agent, controlling the temperature at 210-215 ℃ and reacting for 30-40 min.
The polyester molecular chain segment has high-activity carboxyl functional groups, the acid value of the polyester is controlled to be 38-42 mgKOH/g, and the polyester molecular chain segment is matched with a curing accelerator, so that the activation energy of a reaction system is reduced, the low-temperature curing is realized, and the density of the prepared powder coating film is ensured due to the higher carboxylic acid concentration. The low-temperature curing performance is expected to be used for coating films of heat-sensitive substrates, and the application prospect of the transparent polyester powder coating is further expanded.
The application skillfully adds no branching agent into the polyester component, ensures that the resin is always in a linear structure in the esterification and polycondensation stages, controls the molecular weight to increase too fast, and reduces the viscosity of the synthesized polyester resin by matching with a low-temperature polycondensation process (230-235 ℃ C., conventional polyester: 240-245 ℃ C.).
The active epoxy group in the tertiary glycidyl ester EP-10 is utilized to react with carboxyl in the polyester resin to generate hydroxyl. The molecular formula of the tertiary glycidyl ester EP-10 has large side groups, so that the fluidity of the polyester resin can be increased, and the prepared powder coating film is ensured to have a mirror surface leveling effect; when the powder coating is used as a finishing paint, it contributes to its compatibility with the base film. The small amount of hydroxyl groups formed by reaction in the end capping process improves the adhesive force of the coating film and the metal substrate, and is favorable for the coating film to show more excellent impact performance when subjected to secondary processing by external force.
The application also provides a preparation method of the transparent powder coating with low curing temperature and high leveling property, which comprises the steps of uniformly mixing the polyester resin for the transparent powder coating, the curing agent, the leveling agent and the degassing agent, dispersing by an extruder, grinding and screening to prepare the transparent powder coating. Preferably the curing agent is TGIC.
The coating film has excellent flexibility, good crushing, grinding and other processing performances and good storage stability.
According to the preparation method, through the design innovation of the main chain structure and the end-capped structure of the polyester resin, the prepared polyester resin has the properties of light chromaticity, higher glass transition temperature than that of the acrylic resin, low viscosity, high reactivity and the like, when the transparent powder coating prepared from the polyester resin for the transparent powder coating with low curing temperature and high leveling property disclosed by the application is sprayed on a mirror plate, the transparent powder coating can be cured below 200 ℃, the minimum can be cured at 150 ℃, the cured coating film has higher transparency and excellent leveling property, and meanwhile, the coating film has excellent flexibility and can be subjected to secondary processing such as bending, stamping and the like. If sprayed on the patterned primer, the primer pattern can be rendered realistic.
Detailed Description
The following examples are presented to illustrate the present application in more detail, but are not intended to be limiting, and therefore any changes that come within the meaning and range of equivalency of the claims of the application are to be embraced therein.
Reagents, methods and apparatus employed in the present application are those conventional in the art. Reagents and materials used in this application are commercially available unless otherwise indicated.
Table 1 shows the raw material formulations for the synthesis of polyesters in examples 1 to 3 and comparative examples 1 to 7, and the performance indexes of the synthetic polyesters. The acid value of the polyester resin is detected according to the GB/T6743-2008 standard; viscosity was measured according to GB/T9751.1-2008; the glass transition temperature was measured according to the GB/T19466.2-2004 standard.
Preparation of polyester resin:
examples 1 to 3 and comparative examples 1 to 5 were each synthesized by the following procedure:
step S1, adding neopentyl glycol, aliphatic polyol with a cyclic structure, asymmetric aliphatic polyol with side chain groups, linear aliphatic polyol without side groups and an esterification catalyst into a reaction kettle provided with a heating device, a stirrer and a distillation column according to the materials and the amounts shown in the table 1, uniformly mixing, and heating to 110-130 ℃ under normal pressure to melt;
step S2, adding aromatic polybasic acid, aliphatic polybasic acid with a cyclic structure and aliphatic polybasic acid with a linear structure according to the materials and the amounts shown in the table 1, stirring under the protection of nitrogen, and heating at a speed of 2-3 ℃ per minute; when the temperature of the materials is raised to 170-180 ℃, esterified water starts to be generated and is distilled out through a distillation column; at the moment, the temperature rising rate is regulated and controlled to rise 2-3 ℃ every 30 minutes; when the temperature of the material rises to 195+/-2 ℃, the temperature rising rate is regulated and controlled to be 4-6 ℃ every 30 minutes, and when the temperature of the material rises to 230-235 ℃, the heat preservation reaction is carried out for 1-1.5 hours; when the gas temperature at the top of the distillation column is reduced to be less than 70 ℃, the water yield of the esterified water reaches 95% or more of the theoretical water yield, and the heat preservation is finished;
step S3, gradually vacuumizing to-0.098 to-0.095 MPa at the temperature of 230-235 ℃ and continuously reacting for 60-150 minutes;
s4, the temperature of the materials is reduced to 220-225 ℃, trimellitic anhydride and/or hydrogenated trimellitic anhydride in the formula amount of the end capping agent is added, the temperature is controlled at 215+/-2 ℃, and the reaction is carried out for 60-80 minutes; then controlling the temperature of the materials at 215+/-2 ℃, adding tertiary glycidyl ester EP-10 in the formula amount of the end capping agent, controlling the temperature at 210-215 ℃ and reacting for 30-40 minutes;
and S5, keeping the temperature of the materials at 210-215 ℃, adding a curing accelerator and an antioxidant, stirring and reacting for 40 minutes, and discharging to obtain the polyester resins of examples 1-3 and comparative examples 1-5.
Comparative example 6 synthesis of polyester resin:
comparative example 6 the step S4 of adding the tertiary glycidyl ester EP-10 and reacting the tertiary glycidyl ester EP-10 in the non-end-capping agent is omitted according to the above process to synthesize the polyester resin.
Comparative example 7 synthesis of polyester resin:
the formula system of the comparative example 7 has no trimellitic anhydride or hydrogenated trimellitic anhydride end capping agent, and if the process is adopted, the reaction is incomplete, and the quality index of the synthesized polyester resin is affected.
Comparative example 7 was synthesized according to the following procedure:
step 1: adding neopentyl glycol, aliphatic polyol with a cyclic structure, asymmetric aliphatic polyol with side chain groups, straight-chain aliphatic polyol without side groups and an esterification catalyst into a reaction kettle provided with a heating device, a stirrer and a distillation column according to the materials and the amounts shown in the table 1, uniformly mixing, and heating to 110-130 ℃ under normal pressure to melt;
step 2: adding aromatic polybasic acid, aliphatic polybasic acid with cyclic structure and aliphatic polybasic acid with linear structure according to the materials and the amounts shown in table 1, stirring under the protection of nitrogen, and heating at a speed of 2-3 ℃ per minute; when the temperature of the materials is raised to 170-180 ℃, esterified water starts to be generated and is distilled out through a distillation column; at the moment, the temperature rising rate is regulated and controlled to rise 2-3 ℃ every 30 minutes; when the temperature of the material rises to 195+/-2 ℃, the temperature rising rate is regulated and controlled to be 4-6 ℃ every 30 minutes, and when the temperature of the material rises to 235+/-2 ℃, the heat preservation reaction is carried out for 1-1.5 hours; when the gas temperature at the top of the distillation column is reduced to be less than 70 ℃, the water yield of the esterified water reaches 95% or more of the theoretical water yield, and the heat preservation is finished;
step 3, when the temperature of the material is reduced to 220-225 ℃, the corresponding amount of isophthalic acid and adipic acid in the end capping agent is increased to 240 ℃ according to the description of the table 1, and the reaction is carried out for 60-90 minutes at 240 ℃;
step 4: gradually vacuumizing to-0.098 to-0.095 MPa at 230-235 ℃ and continuing to react for 60-150 minutes;
step 5, controlling the temperature of the materials at 215+/-2 ℃, adding tertiary glycidyl ester EP-10 in the formula amount of the end capping agent, controlling the temperature at 210-215 ℃ and reacting for 30-40 minutes;
and 6, keeping the temperature of the materials at 210-215 ℃, adding a curing accelerator and an antioxidant, stirring and reacting for 40 minutes, and discharging to obtain the polyester resin.
Preparing transparent powder coating:
TABLE 2 transparent powder coating composition (unit: g)
| Name of the name | Polyester resin | Curing agent | Leveling agent | Degassing agent |
| Quality of | 454 | 39.5 | 4 | 2.5 |
In Table 2, the curing agent used was Huntsman PT810 triglycidyl isocyanurate; the leveling agent adopts a Trojan Powderite 486CFL; deaerating agent: BENZOIN (BENZOIN) is MIWON BENZOIN
3 polyester resins synthesized in examples 1 to 3 and 7 polyester resins synthesized in comparative examples 1 to 7 were added with a curing agent (TGIC), a leveling agent, a degassing agent, etc. in the proportions shown in Table 2, and the mixture was uniformly mixed and dispersed by an extruder, milled and sieved; and then, after electrostatic spraying, curing the coating film under the curing condition of 150 ℃/15-20 min, and testing the performance of the coating film.
Performance test of clear powder coating:
transparency and appearance of the coating film: the prepared powder coating is sprayed on a mirror surface stainless steel plate, and after solidification, clarity is evaluated by comparing the clarity of mirror surface imaging and pure mirror surface imaging after spraying the powder coating through naked eyes.
The film thickness, gloss, leveling grade, impact property, adhesive force, bending resistance and other properties of the coating are all tested by spraying the coating onto a common steel plate.
The leveling grade of the coating adopts PCI grade, specifically, the leveling grade corresponding to the coating to be measured is judged by visual comparison of the coating to be measured and a PCI leveling grade comparison board (grade 0-10), and the method belongs to a general leveling grade judging method in industry.
The thickness test of the coating film is detected according to the GB/T13452.2-2008 standard;
gloss test of the coating film was measured according to GB/T1743-1979;
impact properties of the coating film were measured according to GB-T1732-1993;
the adhesion test of the coating film was measured according to the standard of GB/T9286-1998;
the bending resistance test of the coating film is detected according to the GB/T30791-2014 standard;
gel time test of powder coatings was measured according to GB/T16995-1997;
the test results are shown in Table 3.
TABLE 3 results of Performance test of clear powder coatings
As can be seen from table 3: the transparent powder coatings prepared in examples 1-3 are cured at 150 ℃ for 15-20 min, so that low-temperature curing is realized; the prepared coating film has the advantages of smooth and fine surface, good transparency, and a leveling grade of 9-10, and has a mirror effect; the bending performance can reach 0T, the impact performance can pass through the bending device at the front and back of 50kg.cm, and the bending device has excellent flexibility and can be applied to workpieces needing post-processing.
Compared with comparative example 1, the transparent powder coating has more excellent processability, better transparency and higher leveling grade, which shows that the influence of the aliphatic polyol with a cyclic structure on the glass transition temperature of the polyester resin is larger; meanwhile, the viscosity of the system is reduced, and the transparent coating achieves higher leveling grade and transparency.
Example 1 compared with comparative example 2, the coating film had better transparency and higher leveling grade. In combination with comparative example 1, it is demonstrated that the aliphatic polyol having a cyclic structure plays an important role in the glass transition temperature, viscosity and transparency of the polyester resin system, and that the tricyclodecane dimethanol must be ensured in the aliphatic polyol having a cyclic structure and a certain amount of tricyclodecane dimethanol must be achieved, so that the viscosity and transparency of the system are low.
Example 2 is compared with comparative example 3, and the system of comparative example 3 has high viscosity, poor leveling (leveling grade is less than or equal to 6 grade), poor impact (recoil difference), poor bending property (1T) and poor transparency (gloss 128%), which shows that the asymmetric aliphatic polyol with side chain groups plays a positive role in obtaining a transparent powder coating film with high leveling, post-processing and high transparency.
Comparative example 4 shows poorer bending performance (2T) compared with example 2 and comparative example 3, and the transparency is equivalent to that of example 2, which shows that the straight-chain aliphatic polyol without side groups plays a key role in the flexibility of the coating film in the system.
Comparative example 5 compared with example 1, the viscosity of the polyester resin was remarkably increased and the chromaticity was yellowish without adding the aliphatic polybasic acid having a cyclic structure and increasing the amount of the aromatic polybasic acid. The coating film of comparative example 5 has significantly reduced transmittance, and has a certain orange peel phenomenon on the surface, and has significantly reduced transmittance and reduced impact and bending properties. It is described that the amount of aromatic polybasic acid to be used is controlled in the synthesis of a polyester resin for transparent powder which has high leveling property, post-processability and high transparency, and a certain amount of aliphatic polybasic acid must be used on the premise of ensuring processability (high glass transition temperature).
Example 3 in comparison with comparative example 6, it was found that the tertiary glycidyl ester EP-10 in the end-capping agent plays a very important role in controlling the viscosity and transparency of the polyester resin, ensuring the transparency of the coating film. Example 3 is compared with comparative example 7 and shows that the powder coating cannot be cured at low temperature without using trimellitic anhydride, hydrogenated trimellitic anhydride in the capping agent.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be appreciated by persons skilled in the art that the above embodiments are not intended to limit the invention in any way, and that all technical solutions obtained by means of equivalent substitutions or equivalent transformations fall within the scope of the invention.
Claims (10)
1. The polyester resin for the transparent powder coating with low curing temperature and high leveling property is characterized by comprising the following raw materials in percentage by weight:
neopentyl glycol: 20-35%;
aliphatic polyols having a cyclic structure: 3.0 to 10 percent;
asymmetric aliphatic polyols having side chain groups: 2.5 to 5.0 percent;
straight chain aliphatic polyol without pendant groups: 0.5 to 2.0 percent;
aromatic polyacids: 35.0 to 45 percent;
aliphatic polybasic acid having a cyclic structure: 5-15%;
aliphatic polybasic acids of linear structure: 0 to 2.0 percent;
end capping agent: 5-8%;
esterification catalyst: 0.05 to 0.15 percent;
curing accelerator: 0.075-0.2%;
an antioxidant: 0.3 to 0.5 percent.
2. The polyester resin for transparent powder coating material having a low curing temperature and high leveling property according to claim 1, wherein the aliphatic polyol having a cyclic structure is tricyclodecanedimethanol or a combination of tricyclodecanedimethanol and at least one of 1, 4-cyclohexane diol and hydrogenated bisphenol A.
3. The polyester resin for transparent powder coating having a low curing temperature and high leveling property according to claim 2, wherein the tricyclodecane dimethanol is contained in an amount of 3.0 to 5.0% by mass based on the raw material composition.
4. The polyester resin for transparent powder coating with low curing temperature and high leveling property according to claim 1, wherein the asymmetric aliphatic polyol with side chain groups is selected from one or a combination of several of 2-methyl-2-propyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol.
5. The polyester resin for transparent powder coating with low curing temperature and high leveling property according to claim 1, wherein the aliphatic polybasic acid with a cyclic structure is selected from one or a combination of more of 1, 4-cyclohexane dicarboxylic acid, hexahydrophthalic anhydride, 1, 2-cyclo-succinic acid and furan dicarboxylic acid.
6. The polyester resin for transparent powder coating material having a low curing temperature and high leveling property according to claim 1, wherein the aromatic polybasic acid is terephthalic acid or isophthalic acid.
7. The polyester resin for transparent powder coating with low curing temperature and high leveling property according to claim 1, wherein the end-capping agent is a combination of tertiary glycidyl ester EP-10 and hydrogenated trimellitic anhydride and/or trimellitic anhydride.
8. The preparation method of the polyester resin for the transparent powder coating with low curing temperature and high leveling property is characterized by comprising the following steps of:
s1, uniformly mixing neopentyl glycol, aliphatic polyol with a cyclic structure, asymmetric aliphatic polyol with side chain groups, linear aliphatic polyol without side groups and an esterification catalyst, and heating to 110-130 ℃ at normal pressure to melt;
s2, adding aromatic polybasic acid, aliphatic polybasic acid with a cyclic structure and aliphatic polybasic acid with a linear structure, heating to 170-180 ℃ within 0.5-2 h under the protection of protective gas, and distilling out esterified water; heating to 193-195 in 2-6 h; heating to 230-235 deg.c in 3-5 hr to react in heat preservation for 1-1.5 hr; until the reaction degree reaches 95%, and the heat preservation is finished;
s3, continuously reacting under reduced pressure for 60-150 min;
s4, reducing the temperature of the materials, adding a blocking agent, and reacting for 90-120 min;
s5, keeping the temperature of the materials between 210 and 215, adding a curing accelerator and an antioxidant at the temperature, and stirring and reacting for 20 to 60 minutes to obtain the polyester resin for the transparent powder coating according to any one of claims 1 to 8.
9. The method for preparing a polyester resin for a transparent powder coating with low curing temperature and high leveling property according to claim 8, wherein in the step S4, when the material temperature is reduced to 220-225 ℃, trimellitic anhydride and/or hydrogenated trimellitic anhydride in a blocking agent is added, the temperature is controlled to 213-217 ℃, and the reaction is carried out for 60-80 min; adding tertiary glycidyl ester EP-10 in the end capping agent, controlling the temperature between 210 and 215, and reacting for 30 to 40 minutes.
10. The preparation method of the transparent powder coating with low curing temperature and high leveling property is characterized by comprising the following steps: the polyester resin for transparent powder coating, as claimed in any one of claims 8 to 9, a curing agent, a leveling agent and a degassing agent are uniformly mixed and dispersed by an extruder, milled and sieved to prepare a transparent powder coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311707565.9A CN117586688A (en) | 2023-12-13 | 2023-12-13 | Polyester resin for transparent powder coating with low curing temperature and high leveling property, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311707565.9A CN117586688A (en) | 2023-12-13 | 2023-12-13 | Polyester resin for transparent powder coating with low curing temperature and high leveling property, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117586688A true CN117586688A (en) | 2024-02-23 |
Family
ID=89921914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311707565.9A Pending CN117586688A (en) | 2023-12-13 | 2023-12-13 | Polyester resin for transparent powder coating with low curing temperature and high leveling property, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117586688A (en) |
-
2023
- 2023-12-13 CN CN202311707565.9A patent/CN117586688A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104311806B (en) | A kind of mylar and preparation method thereof for high levelling transparent powder paint | |
| WO2012005647A1 (en) | Branched polyester | |
| CN106634476B (en) | A kind of curable epoxide high-flexibility polyester resin for powder coating and preparation method thereof | |
| CN111533892B (en) | Polyester resin for high-weather-resistance low-temperature TGIC (triglycidyl isocyanurate) curing powder coating and preparation method thereof | |
| CN107254034A (en) | One kind has good anti-stoning transparent powder paint polyester resin and preparation method thereof | |
| CN112646150A (en) | Boiling-resistant high-leveling polyester resin for HAA (haha) cured powder coating and preparation method thereof | |
| CN113861398A (en) | Polyester resin containing diphenyl ether structure, powder coating and preparation method thereof | |
| CN113121802B (en) | Polyester resin for fast-curing, flexible and high-hardness super-weather-resistant and low-light powder coating and preparation method thereof | |
| CN116199870B (en) | Polyester resin containing isobutyl side group structure, powder coating and preparation method thereof | |
| CN112384549A (en) | Hydroxyl-terminated polyester resin and preparation method and application thereof | |
| CN117586688A (en) | Polyester resin for transparent powder coating with low curing temperature and high leveling property, and preparation method and application thereof | |
| CN112752808A (en) | Low bake powder coating resins | |
| CN114181384B (en) | Polyester resin for low-cost, pinhole-resistant and high-hardness HAA system and preparation method thereof | |
| CN116285636A (en) | Low-gloss polyurethane powder coating and preparation method thereof | |
| CN112521838B (en) | Extinction transparent polyester resin composition and preparation method and application thereof | |
| WO2002024823A2 (en) | Polyester triglycidyl isocyanurate resin powder coatings based on 1, 3-propanediol | |
| CN112062942B (en) | Ultralow temperature curing polyester resin and preparation method and application thereof | |
| CN113045738B (en) | Indoor polyester resin capable of reducing consumption of epoxy resin and preparation method thereof | |
| CN111621007B (en) | Polyester resin for high-weather-resistance low-temperature HAA curing powder coating and preparation method thereof | |
| CN110790909B (en) | Polyester resin and preparation method thereof | |
| US4365046A (en) | Process to control the curing reaction between a copolyester resin and an epoxide compound, and a composition formed for that process | |
| EP2520601A1 (en) | Process for producing polyesters | |
| KR100987188B1 (en) | Isocyanate modified carboxy-polyester resin, and chipping-resistant powder coating composition for automobile containing thereof | |
| CN115403752B (en) | Polyester resin and preparation method and application thereof | |
| CN114196000B (en) | High-coating Tg scratch-resistant TMA-free polyester resin, preparation method thereof and powder coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |