CN115197406A - Polyester resin, powder coating and preparation method thereof - Google Patents
Polyester resin, powder coating and preparation method thereof Download PDFInfo
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- CN115197406A CN115197406A CN202211011146.7A CN202211011146A CN115197406A CN 115197406 A CN115197406 A CN 115197406A CN 202211011146 A CN202211011146 A CN 202211011146A CN 115197406 A CN115197406 A CN 115197406A
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- polyester resin
- powder coating
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- polymer
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- 238000000576 coating method Methods 0.000 title claims abstract description 94
- 239000011248 coating agent Substances 0.000 title claims abstract description 88
- 239000004645 polyester resin Substances 0.000 title claims abstract description 69
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 69
- 239000000843 powder Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 48
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 48
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 claims abstract description 17
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 17
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 16
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 claims abstract description 14
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 239000012974 tin catalyst Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000013538 functional additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000049 pigment Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 52
- 238000001125 extrusion Methods 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 30
- 238000004321 preservation Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000003672 processing method Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 46
- 239000000758 substrate Substances 0.000 description 15
- 239000000976 ink Substances 0.000 description 13
- 239000000155 melt Substances 0.000 description 10
- 229920006267 polyester film Polymers 0.000 description 10
- 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 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 4
- 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 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- ZLVLNNCBGQYRAB-UHFFFAOYSA-N 3,3,4,4-tetrafluorooxolane-2,5-dione Chemical compound FC1(F)C(=O)OC(=O)C1(F)F ZLVLNNCBGQYRAB-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920006397 acrylic thermoplastic Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- NVJMGQMXNBBZIU-UHFFFAOYSA-N dibutyltin;1-dodecylsulfanyldodecane Chemical compound CCCC[Sn]CCCC.CCCCCCCCCCCCSCCCCCCCCCCCC NVJMGQMXNBBZIU-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 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
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000000528 statistical test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses polyester resin, powder coating and a preparation method thereof, relates to the technical field of polyester powder coating, and solves the problems that the surface tension of the existing powder coating is low, and the preparation method cannot adjust the surface tension of the coating to adapt to different production requirements, wherein the polyester resin comprises the following raw materials: 5-8 parts of neopentyl glycol, 1-3 parts of diethylene glycol, 6-11 parts of ethylene glycol, 1-7 parts of isophthalic acid, 9-18 parts of diglycidyl terephthalate, 8-11 parts of tetrabutyl titanate, 6-13 parts of diglycidyl cyclohexane-1, 2-dicarboxylate, 1-2 parts of an organic tin catalyst and 1-2 parts of an antioxidant; the powder coating includes a first component and a second component, the first component including: 50-60 parts of polyester resin and 1-5 parts of curing agent; the second component comprises: 1-20 parts of pigment, 1-30 parts of barium sulfate, 1-3 parts of polytetrafluoroethylene additive, 1-5 parts of functional additive and 5-10 parts of talcum powder.
Description
Technical Field
The invention relates to the technical field of preparation of polyester powder coatings, in particular to a high-surface-tension polyester resin, a high-surface-tension polyester powder coating and a preparation method thereof.
Background
The powder coating does not contain organic solvent, 100 percent of the powder coating is solid, compared with the conventional coating, the powder coating has the advantages of no pollution, energy and resource saving, high mechanical strength of the coating film, complete recovery of the excessive coating and the like, and is more and more widely applied to coating of building shells of household appliances, automobile industry, outdoor bridges, highway guardrails and the like, and the powder coating is coated on a base material to form a polyester film.
In practical applications, in some fields, good wettability and adhesiveness of the polyester film are required, for example, in order to make printing ink and composite adhesive adhere to the surface of the polyester film better, the surface tension of the polyester film should meet a certain standard, otherwise, the adhesion and adhesiveness of the printing ink and the adhesive on the surface of the polyester film are affected, and when the surface tension of the polyester film is below 37mN/m, a plurality of white pages (without printing content) are caused, thereby affecting the quality of printed products and composite products.
However, the surface tension of the conventional powder coating is not particularly limited, and the surface tension of the prepared coating film is not considered in the preparation method of the conventional powder coating, so that the surface tension of the polyester film coated on the housing of the electric appliance is low when the electric appliance with special requirements is manufactured, and the manufactured electric appliance is not qualified. Therefore, there is a strong need for a powder coating with high surface tension and a method for preparing the same, which can be applied to various fields.
Disclosure of Invention
The invention aims to: the invention provides polyester resin, powder coating and a preparation method thereof, aiming at solving the problems that the surface tension of the existing powder coating is low and the preparation method can not adjust the surface tension of the coating to adapt to different production requirements.
The invention specifically adopts the following technical scheme for realizing the purpose:
a polyester resin, the raw materials of which comprise: 5-8 parts of neopentyl glycol, 1-3 parts of diethylene glycol, 6-11 parts of ethylene glycol, 1-7 parts of isophthalic acid, 9-18 parts of diglycidyl terephthalate, 8-11 parts of tetrabutyl titanate, 6-13 parts of diglycidyl cyclohexane-1, 2-dicarboxylate, 1-2 parts of an organic tin catalyst and 1-2 parts of an antioxidant.
A preparation method of a polyester resin is used for preparing the polyester resin, and comprises the following steps:
(1) Melting neopentyl glycol, ethylene glycol and diethylene glycol, adding an organic tin catalyst and tetrabutyl titanate, and performing first treatment to obtain a first polymer; adding isophthalic acid, diglycidyl terephthalate and diglycidyl cyclohexane-1, 2-dicarboxylate into the first polymer, and performing second treatment to obtain a second polymer;
(2) And (3) cooling the second polymer, heating to 205 ℃ at the rate of 18 ℃/h when the acid value of the second polymer is less than or equal to 40mgKOH/g, adding an antioxidant, starting a preset vacuum system to continue polymerization, stopping vacuumizing when the acid value of the second polymer is less than or equal to 15mgKOH/g, adding isophthalic acid to perform carboxyl end capping reaction, performing third treatment, stopping reaction when the acid value reaches 18-60 mgKOH/g, cooling and crushing to obtain the polyester resin.
Optionally, the first processing method includes the specific steps of: gradually heating to 180 ℃ at the speed of 10-12 ℃/h, and carrying out heat preservation treatment for 1-3h.
Optionally, the second processing method specifically includes the steps of: heating to 220 ℃ at the speed of 6-8 ℃/h, and carrying out heat preservation treatment for 4-5h.
Optionally, the third processing method specifically includes the steps of: heating to 228 ℃ at the speed of 9-10 ℃/h, and carrying out heat preservation treatment for 3-4h.
A powder coating comprising a first component and a second component, the first component comprising, in parts by weight: 50-60 parts of the polyester resin as claimed in claim 1, 1-5 parts of a curing agent; the second component includes: 1-20 parts of pigment, 1-30 parts of barium sulfate, 1-3 parts of polytetrafluoroethylene additive, 1-5 parts of functional additive and 5-10 parts of talcum powder.
A method for preparing a powder coating, comprising the steps of:
s1: mixing the first component at high speed for a first preset time to obtain a mixture;
s2: performing first extrusion on the mixture and crushing to obtain a first extrusion material;
s3: adding the first extrusion material and the second component into a mixing device, and mixing at a high speed for a second preset time to obtain a prefabricated object;
s4: performing secondary extrusion on the prefabricated object, and performing cooling, tabletting and coarse crushing treatment to obtain a sheet material to be ground;
s5: and grinding the flakes to be ground, screening target particles, and collecting to obtain the finished powder coating.
Optionally, the first extrusion in S2 is specifically performed by introducing the mixture into an extruder for melt extrusion, wherein the temperature of an extrusion section is 100 to 120 ℃, and the rotation speed of a screw is 500 to 650rpm.
Optionally, the first preset time is 15-25min; the second preset time is 10-30min. Optionally, the second extrusion in S4 is specifically performed by introducing the preformed object into an extruder for melt extrusion, wherein the temperature of an extrusion section is 110 to 130 ℃, and the screw rotation speed is 700 to 850rpm.
Compared with the prior art, the invention has the advantages that:
1. the invention relates to a polyester resin, which is prepared by taking neopentyl glycol, diethylene glycol, ethylene glycol, isophthalic acid, diglycidyl terephthalate, tetrabutyl titanate and diglycidyl cyclohexane-1, 2-dicarboxylate as raw materials to synthesize a linear macromolecular polyester resin with an acid value of 18-45mgKOH/g, a softening point of 90-120 ℃, a glass transition temperature of above 63 ℃ and a viscosity of 175 ℃ of 3500-4500; polymerization of various esters of neopentyl glycol, diethylene glycol, ethylene glycol, diglycidyl terephthalate, tetrabutyl titanate and cyclohexane-1, 2-diglycidyl dicarboxylate enables the molecular weight of the polyester to be larger, and ester groups of partial polyester molecular chains are hydrolyzed by adding isophthalic acid to form terminal carboxyl groups, so that the concentration of polar groups in chain segments is improved, the surface resistance is reduced, and the surface tension is improved; the introduction of the cyclohexane-1, 2-dicarboxylic acid diglycidyl ester enables the finished product polyester resin to have flexible molecular chain segments such as benzene rings and the like, so that the prepared polyester resin is low in curing crosslinking density, low in softening point and high in viscosity, further improves the surface tension of the base material after the base material is coated by the coating after the polyester resin is prepared into the powder coating, and solves the problem of low surface tension of the existing polyester resin.
2. According to the powder coating, barium sulfate is added into the raw materials of the powder coating and can be used as an anti-caking agent, so that a certain roughness can be formed on the surface of a film in the polyester film forming process, the apparent roughness of a coated substrate is improved, and the surface tension of the substrate after the powder coating is coated on the substrate is further improved; meanwhile, more curing agents and functional additives are added into the coating, the coating is firstly subjected to primary melt extrusion with polyester resin to obtain a uniform primary cross-linked mixture, and then subjected to secondary melt extrusion with various additives to obtain a coating film capable of being cured at a low temperature, and the polar group increases the hydrophilicity of the polyester resin, so that the adhesive force of the coating and a base material is greatly improved, and the coating effect of the powder coating on the base material is obviously improved; in addition, the surface tension of the prepared coating can be adjusted by adjusting the formula amount of the coating and the polyester resin, the acid value of the polyester resin and the parameter values in the preparation process, and the defects that the surface tension of the existing powder coating is low and the surface tension of the coating cannot be adjusted by the preparation method to adapt to different production requirements are overcome.
Drawings
Fig. 1 shows the results of the surface property test of treatment group 1.
Fig. 2 shows the results of the surface property test of treatment group 2.
Fig. 3 shows the results of the surface property test of treatment group 3.
Fig. 4 shows the results of the surface property test of treatment group 4.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are some, but not all embodiments of the present invention.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Detailed Description
Referring to fig. 1, the present invention provides a polyester resin, the raw materials of which include: 5-8 parts of neopentyl glycol, 1-3 parts of diethylene glycol, 6-11 parts of ethylene glycol, 1-7 parts of isophthalic acid, 9-18 parts of diglycidyl terephthalate, 8-11 parts of tetrabutyl titanate, 6-13 parts of diglycidyl cyclohexane-1, 2-dicarboxylate, 1-2 parts of an organic tin catalyst and 1-2 parts of an antioxidant. The structural formula of the polyester resin can be shown as follows, and the two ends of the polyester resin are carboxyl groups, so that the concentration of polar groups in chain segments is improved, the surface resistance is reduced, and the surface tension is improved; benzene rings are introduced into the chain segments, so that the flexibility of polyester is enhanced, the curing crosslinking density of polyester resin is reduced, the softening point is low, and the viscosity is high.
Neopentyl glycol, ethylene glycol and diethylene glycol are polymerized with tetrabutyl titanate into a first polymer under the catalysis of an organotin catalyst, and the first polymer reacts with isophthalic acid, diglycidyl terephthalate and diglycidyl cyclohexane-1, 2-dicarboxylate to generate finished polyester resin.
The organotin catalyst of the invention can be selected from monobutyl triisooctoate tin, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate or dibutyltin didodecyl sulfide. Specifically, it is preferable to use monobutyl triisooctanoic acid tin. The monobutyl triisooctanoic acid tin has higher catalytic activity, high catalytic efficiency, longer working life, neutral catalyst and no corrosion to equipment, and does not need to be separated out after the reaction is finished, thereby not influencing the quality of the final product.
It is understood that the polytetrafluoroethylene auxiliary agent is a binary copolymer or a ternary copolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene, a copolymer of vinylidene fluoride, tetrafluoroethylene and hexafluoropropylene and ethylene or propylene, and other polymers, such as polyethylene oxide, inorganic substances and the like, so as to form a compound of polymers with more various components. Tetrafluorosuccinic anhydride is preferred.
The polytetrafluoroethylene auxiliary agent has extremely low surface tension, and the polytetrafluoroethylene auxiliary agent is added into the raw materials, so that the internal friction in resin molecules in the polyester preparation process can be reduced, the melting rate and the deformability of a melt are increased, the apparent viscosity of the melt is reduced, and the overall plasticizing effect is improved. Meanwhile, the melt has low solubility and is incompatible in processing resin, and the melt seeps out of the melt to the surface of the melt in the processing process to form an isolation layer on the surface of metal, so that the adhesive force between the melt and the surfaces of a machine body and a die orifice metal is reduced, the friction between the melt and a machine wall in the movement process is reduced, the non-uniform movement state of the melt in the processing process is improved, and the product quality is improved.
The antioxidant of the present invention may be selected from the group consisting of antioxidant 168, antioxidant 1010, antioxidant 1076, and antioxidant 3114.
Specifically, the antioxidant 168 is preferred, and the antioxidant 168 is a phosphite antioxidant with excellent performance, has strong extraction resistance, is stable to hydrolysis, and can remarkably improve the light stability of the product.
The invention also provides a preparation method of the polyester resin, which is used for preparing the polyester resin, and the preparation method of the polyester resin comprises the following steps:
(1) Melting neopentyl glycol, ethylene glycol and diethylene glycol, adding an organic tin catalyst and tetrabutyl titanate, and performing first treatment to obtain a first polymer; adding isophthalic acid, diglycidyl terephthalate and diglycidyl cyclohexane-1, 2-dicarboxylate into the first polymer, and performing second treatment to obtain a second polymer;
(2) And (3) cooling the second polymer, heating to 205 ℃ at the rate of 18 ℃/h when the acid value of the second polymer is less than or equal to 40mgKOH/g, adding an antioxidant, starting a preset vacuum system to continue polymerization, stopping vacuumizing when the acid value of the second polymer is less than or equal to 15mgKOH/g, adding isophthalic acid to perform carboxyl end-capping reaction, performing third treatment, stopping the reaction when the acid value reaches 18-60 mgKOH/g, cooling and crushing to obtain the polyester resin.
The first processing method comprises the following specific steps: gradually heating to 180 ℃ at the speed of 10-12 ℃/h, and carrying out heat preservation treatment for 1-3h. Specifically, the temperature is gradually increased to 180 ℃ at the speed of 10 ℃/h, and the heat preservation treatment is carried out for 2h.
The second processing method comprises the following specific steps: heating to 220 ℃ at the speed of 6-8 ℃/h, and carrying out heat preservation treatment for 4-5h. Specifically, the temperature is raised to 220 ℃ at the speed of 7 ℃/h, and the heat preservation treatment is carried out for 4.5h.
The third processing method comprises the following specific steps: heating to 228 ℃ at the speed of 9-10 ℃/h, and carrying out heat preservation treatment for 3-4h. Specifically, the temperature is raised to 228 ℃ at the speed of 10 ℃/h, and the heat preservation treatment is carried out for 4h.
In some embodiments of the present invention, the specific operation of (1) is: adding neopentyl glycol, ethylene glycol and diethylene glycol in a formula ratio into a reaction kettle, heating to 135 ℃ for sufficient melting, adding organic tin and tetrabutyl titanate in a formula ratio, carrying out polymerization reaction, gradually heating to 180 ℃ at a speed of 10-12 ℃/h, and then carrying out heat preservation reaction for 1-3h; adding the m-phthalic acid, the terephthalic acid diglycidyl ester and the cyclohexane-1, 2-dicarboxylic acid diglycidyl ester according to the formula ratio, continuing the polymerization reaction, heating to 220 ℃ at the speed of about 6 ℃/h, and keeping the temperature for reaction for 4h to obtain a second polymer.
In some embodiments of the present invention, the specific operation of (2) is: and (2) cooling the second polymer to 185 ℃, heating to about 205 ℃ at the rate of 18 ℃/h when the acid value of the polymer is less than or equal to 40mgKOH/g, adding the antioxidant in a formula amount, starting a preset vacuum system to keep the vacuum degree at about-0.096 MPa, and carrying out vacuum reaction for 2h at the temperature of about 203 ℃ to promote the formation of linear macromolecular polyester. When the acid value of the polymer is less than or equal to 15mgKOH/g, stopping vacuumizing, then adding a capping agent isophthalic acid with the formula amount to perform carboxyl capping reaction, heating to 228 ℃ at the speed of 9 ℃/h, performing heat preservation reaction for 3h, and stopping reaction at three points with acid values of 18, 33 and 45mgKOH/g respectively to obtain three resins with different acid values. Discharging at high temperature while the polyester resin is hot, cooling the polyester resin by using a steel belt with condensed water, and then crushing and granulating to obtain the polyester resin which is colorless and transparent granules.
The surface tension of the coating can be adjusted by adjusting the formula amount and the acid value of the polyester resin, so as to adapt to different production requirements.
In some embodiments of the present invention, the vacuum degree of the predetermined vacuum system in the step (2) is maintained at-0.095 to 0.098Mpa.
The invention also provides a powder coating which is prepared based on the polyester resin, and the powder coating comprises a first component and a second component, wherein the first component comprises 50-60 parts of the polyester resin and 1-5 parts of a curing agent in parts by weight; the second component includes: 1-20 parts of pigment, 1-30 parts of barium sulfate, 1-3 parts of polytetrafluoroethylene additive, 1-5 parts of functional additive and 5-10 parts of talcum powder.
In some embodiments of the present invention, it is preferred that the curing agent used is a TGIC curing agent. Triglycidyl isocyanurate serving as a TGIC curing agent is a curing agent with three functional groups, is mixed with diglycidyl terephthalate with high curing activity, is firstly subjected to primary melt extrusion with polyester resin to obtain a uniform primary cross-linked mixture, and is then subjected to secondary melt extrusion under the combined action of various auxiliaries to obtain a coating with low curing cross-linking density and high viscosity, so that the surface tension of the coating is improved.
In some embodiments of the present invention, the selected functional assistant is one or a combination of a leveling agent and a brightener.
Specifically, the leveling agent used includes, but is not limited to, isophorone, diacetone alcohol, solvesso150, acrylics, silicones, or fluorocarbons. Acrylic leveling agents are preferably used.
Specifically, the brightener can reduce the melt viscosity of the powder coating, increase the fluidity of the coating in a molten state, make the surface tension of the coating more uniform, and avoid the defects of pinholes, shrinkage cavities and the like. The gloss enhancers used include, but are not limited to, acrylate copolymers, modified acrylate copolymers, and methacrylate copolymers. Preferably, modified acrylate copolymers are used as the gloss enhancer of the invention.
The polyester resin is synthesized by taking neopentyl glycol, diethylene glycol, ethylene glycol, isophthalic acid, diglycidyl terephthalate, tetrabutyl titanate and diglycidyl cyclohexane-1, 2-dicarboxylate as raw materials, wherein the acid value of the synthesized linear macromolecular polyester resin is 18-45mgKOH/g, the softening point is 90-120 ℃, the glass transition temperature is above 63 ℃, and the viscosity of 175 ℃ is 3500-4500; polymerization of various esters of neopentyl glycol, diethylene glycol, ethylene glycol, diglycidyl terephthalate, tetrabutyl titanate and cyclohexane-1, 2-diglycidyl dicarboxylate enables the molecular weight of the polyester to be larger, and ester groups of partial polyester molecular chains are hydrolyzed by adding isophthalic acid to form terminal carboxyl groups or salt and hydroxyl groups, so that the concentration of polar groups in chain segments is improved, the surface resistance is reduced, and the surface tension is improved; the flexible molecular chain segments such as tetrabutyl titanate and the like are introduced, so that the prepared polyester resin is low in curing crosslinking density, low in softening point and high in viscosity, the surface tension of the base material after the base material is coated with the coating after the polyester resin is prepared into the powder coating is further improved, and the problem of low surface tension of the existing powder coating is solved.
The invention also provides a preparation method of the powder coating, which comprises the following steps:
s1: mixing the first component at high speed for a first predetermined time to obtain a mixture;
s2: performing first extrusion on the mixture and crushing to obtain a first extrusion material;
s3: adding the first extrusion material and the second component into a mixing device, and mixing at a high speed for a second preset time to obtain a prefabricated object;
s4: performing second extrusion on the prefabricated object, and performing cooling, tabletting and coarse crushing treatment to obtain a sheet material to be ground;
s5: and grinding the flakes to be ground, screening target particles and collecting to obtain the finished powder coating.
In some embodiments of the present invention, according to the procedure for synthesizing polyester, different materials are added into a reaction kettle, heated and stirred to mix and react. Discharging while the material is hot, cooling and crushing the material into sheet materials to obtain the polyester resin. In the above S1, the polyester resin and the curing agent are mixed at a high speed, the mixing device used is a high-speed mixer, the first preset time is 15-25min, and the second preset time is 10-30min.
Preferably, the first preset time is 20min, and the second preset time is 25min.
In the S2, the mixed material of the S1 is introduced into an extruder for melt extrusion, the temperature of an extrusion section is 100-120 ℃, and the rotating speed of a screw is 500-650rpm.
Specifically, in the above S2, the extrusion zone temperature is preferably 110 ℃ and the screw rotation speed is preferably 600rpm.
In the above S1 and S3, the mixing device is a high-speed mixer, and the rotation speed is 750-850r/min. The preferred rotation speed is 800r/min.
In the S4, the mixed material of the S3 is introduced into an extruder for melt extrusion, the temperature of an extrusion section is 110-130 ℃, and the rotating speed of a screw is 700-850rpm.
In some embodiments of the invention, the specific operations of S3 and S4 are that the materials mixed by S1 are poured into an extruder for melt extrusion after being uniformly mixed, the temperature of an extrusion section is 110-130 ℃, and the rotating speed of a screw is 700-850rpm; then cooling and crushing into 1-5mm granules to obtain an extruded material for later use.
Specifically, in the above S4, the extrusion zone temperature is preferably 110 ℃, and the screw rotation speed is preferably 800rpm; then cooling and crushing into 1-5mm granules, preferably 3mm in diameter, to obtain an extruded material for later use.
In the above S5, the particle diameter of the target particle is 165 to 200 mesh. Specifically, the particle size of the target particles is 180 mesh.
In some embodiments of the present invention, the device used for grinding the flakes to be ground in S5 is a mill, and an air inducing system is provided in the mill, and the air inducing system can screen the particles according to different particle sizes.
It can be understood that barium sulfate is added into the coating and can be used as an anti-bonding agent to ensure that a certain roughness can be formed on the surface of the film in the polyester film forming process, so that the apparent roughness of the base material after film coating is improved, and the surface tension of the base material after the powder coating is coated on the base material is further improved; meanwhile, more curing agents and functional additives are added into the coating, the coating and polyester resin are firstly subjected to primary melting extrusion to obtain an even primary cross-linking mixture, and then are subjected to secondary melting extrusion with various additives to obtain a coating film capable of being cured at a low temperature, and the hydrophilicity of the polyester resin is increased due to the polar groups, so that the adhesive force of the coating and a base material is greatly improved, and the coating effect of the powder coating on the base material is obviously improved. In addition, the surface tension of the prepared coating can be adjusted by adjusting the formula amount of the coating and the polyester resin, the acid value of the polyester resin and parameter values in the preparation process, and the defects that the surface tension of the existing powder coating is low and the surface tension of the coating cannot be adjusted by the preparation method to adapt to different production requirements are overcome.
Example 1
1.1 preparation of polyester resin 1
(1) Adding neopentyl glycol, ethylene glycol and diethylene glycol in a formula amount into a reaction kettle, heating to 135 ℃ for sufficient melting, adding stannous octoate and tetrabutyl titanate in the formula amount, carrying out polymerization reaction, gradually heating to 180 ℃ at the speed of 10-12 ℃/h, then carrying out heat preservation reaction for 2h, adding isophthalic acid, diglycidyl terephthalate and diglycidyl cyclohexane-1, 2-dicarboxylate in the formula amount, continuing polymerization reaction, heating to 220 ℃ at the speed of about 6 ℃/h, and carrying out heat preservation reaction for 4h to obtain a second polymer;
(2) Cooling the second polymer to 185 ℃, heating to 205 ℃ at the rate of 18 ℃/h when the acid value of the polymer is less than or equal to 40mgKOH/g, adding antioxidant 168 with the formula amount, starting a vacuum system to keep the vacuum degree between-0.095 MPa and-0.098 MPa, and carrying out vacuum reaction for 2h at the temperature of about 203 ℃ to promote the formation of linear macromolecular polyester; when the acid value of the polymer is less than or equal to 15mgKOH/g, stopping vacuumizing, then adding a capping agent isophthalic acid with the formula amount to perform carboxyl capping reaction, heating to 228 ℃ at the speed of 9 ℃/h, performing heat preservation reaction for 3h, and stopping reaction when the acid value is 45mgKOH/g respectively to obtain the polyester resin 1.
1.2 preparation of powder coating 1
S1: mixing the polyester resin and the curing agent in a formula amount at a high speed for 20min;
s2: melting, extruding and crushing the mixed material obtained in the step S1 to obtain a first extruded material, wherein the temperature of an extrusion section is 100 ℃, and the rotating speed of a screw is 550rpm;
s3: adding the first extrusion material obtained in the step (2) and other raw materials of the coating into a mixing device according to parts by weight, and mixing at a high speed for 10min;
s4: melting, extruding, cooling, tabletting and roughly crushing the mixed material obtained in the step S3 into particles of 3mm to obtain a to-be-ground sheet material, wherein the extrusion section temperature is 110 ℃, and the screw rotation speed is 750rpm;
s5: the flakes to be ground were ground and collected by sieving through 170 mesh particles to obtain the finished powder coating 1.
Example 2
2.1 preparation of polyester resin 2
(1) Adding neopentyl glycol, ethylene glycol and diethylene glycol in a formula amount into a reaction kettle, heating to 135 ℃ for full melting, adding stannous octoate and tetrabutyl titanate in a formula amount, carrying out polymerization reaction, gradually heating to 180 ℃ at a speed of 10-12 ℃/h, and then carrying out heat preservation reaction for 3h; adding m-phthalic acid and terephthalic acid diglycidyl ester according to the formula ratio, continuing polymerization, heating to 220 ℃ at the speed of about 6 ℃/h, and carrying out heat preservation reaction for 4h to obtain a second polymer;
(2) And (2) cooling the second polymer to 185 ℃, heating to 205 ℃ at the rate of 18 ℃/h when the acid value of the polymer is less than or equal to 40mgKOH/g, adding antioxidant 168 with the formula amount, starting a vacuum system to keep the vacuum degree between-0.095 Mpa and-0.098 Mpa, carrying out vacuum reaction for 2h at the temperature of 203 ℃ to promote the formation of linear macromolecular polyester, stopping vacuumizing when the acid value of the polymer is less than or equal to 15mgKOH/g, then adding end-capping reagent isophthalic acid with the formula amount to carry out carboxyl end-capping reaction, heating to 228 ℃ at the rate of 9 ℃/h, carrying out heat preservation reaction for 3h, and stopping the reaction when the acid value is 33mgKOH/g respectively to obtain polyester resin 2.
2.2 preparation of powder coating 2
S1: mixing the polyester resin and the curing agent in a formula ratio at a high speed for 20min;
s2: melting, extruding and crushing the mixed material of the S1 to obtain a first extruded material, wherein the temperature of an extrusion section is 100 ℃, and the rotating speed of a screw is 550rpm;
s3: adding the first extrusion material obtained in the step S2 and other raw materials of the coating into a mixing device according to parts by weight, and carrying out high-speed mixing for 10min;
s4: melting, extruding, cooling, tabletting and roughly crushing the mixed material obtained in the step S3 into particles of 4mm to obtain a to-be-ground sheet material, wherein the temperature of an extrusion section is about 110 ℃, and the rotation speed of a screw is 750rpm;
s5: the flakes to be ground were ground and collected by sieving 180 mesh to obtain the finished powder coating 2.
Example 3
3.1 preparation of polyester resin 3
(1) Adding neopentyl glycol, ethylene glycol and diethylene glycol in a formula amount into a reaction kettle, heating to 135 ℃ for full melting, adding stannous octoate and tetrabutyl titanate in the formula amount, performing polymerization reaction, gradually heating to 180 ℃ at the speed of 10-12 ℃/h, and then performing heat preservation reaction for 1h; adding m-phthalic acid, diglycidyl terephthalate and diglycidyl cyclohexane-1, 2-dicarboxylate in a formula ratio, continuing polymerization, heating to 220 ℃ at a rate of about 6 ℃/h, and carrying out heat preservation reaction for 4h to obtain a second polymer;
(2) Cooling the second polymer to 185 ℃, heating to about 205 ℃ at the rate of 18 ℃/h when the acid value of the polymer is less than or equal to 40mgKOH/g, adding antioxidant 168 with the formula amount, starting a vacuum system to keep the vacuum degree between-0.095 MPa and-0.098 MPa, and carrying out vacuum reaction for 2h at the temperature of about 203 ℃ to promote the formation of linear macromolecular polyester; when the acid value of the polymer is less than or equal to 15mgKOH/g, stopping vacuumizing, then adding a capping agent isophthalic acid with the formula amount to perform carboxyl capping reaction, heating to 228 ℃ at the speed of 9 ℃/h, performing heat preservation reaction for 3h, and stopping reaction when the acid value is 18mgKOH/g respectively to obtain the polyester resin 3.
3.2 preparation of powder coating 3
S1: mixing the polyester resin and the curing agent in a formula ratio at a high speed for 20min;
s2: melting, extruding and crushing the mixed material obtained in the step S1 to obtain a first extruded material, wherein the temperature of an extrusion section is 105 ℃, and the rotating speed of a screw is 600rpm;
s3: adding the first extrusion material obtained in the step S2 and other raw materials of the coating into a mixing device according to parts by weight, and carrying out high-speed mixing for 10min;
s4: melting and extruding the mixed material obtained in the step S3, cooling, tabletting, and coarsely crushing into 5mm particles to obtain a sheet material to be ground, wherein the temperature of an extrusion section is about 125 ℃, and the rotating speed of a screw is 850rpm;
s5: the flakes to be ground were ground and the 190 mesh granules were screened and collected to obtain the finished powder coating 3.
Test example 1 the powder coatings of examples 1-3 were tested for surface properties using a surface tension test pen
By applying the surface tension test pen, the micro changes of the surface tension, the hydrophilicity, the wettability and the like of different solids can be easily analyzed. The analysis method is simple and effective, and accurate results can be quickly known only by scratching one trace on the surface of the substrate. When the test is carried out, an intermediate value is selected as a starting point, for example, 38mN/m, and when the test pen wets the surface of the substrate within 2 seconds, the surface tension of the substrate is greater than or equal to the selected value, a test pen with a larger value needs to be selected for carrying out the second test, and so on, until the test result is condensed into a water bead (spherical shape) within 2 seconds, the value before the test is regarded as the surface tension of the substrate. And then the comparison analysis is carried out. If the nth test shrinks into a bead (sphere), the test pen with a smaller value is replaced to perform the second test until the surface is wet. The method can accurately measure the surface tension and the surface humidity of the base material and judge whether the surface factors of the base material meet the requirements before work so as to adjust the surface factors to the requirements of the work.
The surface tension of the polyester film is determined by applying test inks according to DIN ISO 8296, with ink sticks of approximately 100mm length to the film to be tested, with the inks having known different surface tensions, and observing whether more than 90% of the ink sticks shrink within 2 seconds and form ink drops, and if so, applying the ink sticks again with the ink having the lower surface tension, and carrying out the same observation until no shrinkage and the presence of ink drops, the surface tension of the test ink corresponding to the surface tension of the film. The method can accurately measure the surface tension and the surface humidity of the substrate and judge whether the surface factors of the substrate meet the requirements before work so as to adjust the ink, the coating and the viscosity to the requirements of work.
1.1 design of the experiment
The powder coatings prepared in examples 1 to 3 were selected and coated on a substrate to obtain treatment group 1, treatment group 2 and treatment group 3. And respectively coating the conventional powder coating on the base material to obtain a treatment group 4. Then, each treatment group was tested by using a surface tension test pen 34, a surface tension test pen 36, and a surface tension test pen 38, respectively.
A surface tension test pen 34, a surface tension test pen 36 and a surface tension test pen 38 are respectively used, the pen point and the test surface form an angle of 90 degrees vertically, 3-5N force is applied, and a straight line of 2-3cm is drawn within two seconds. And observing the handwriting shrinkage condition within 5 seconds after the complete line is drawn. Each group of three test straight lines is one straight line drawn by three surface tension test pens, and the condition of each group is shown in figures 1-4.
1.2 analysis of results
The passing criteria were: no shrinkage at all and clear handwriting. A non-passing state: the ink has discontinuous state, shrinks into small water drops or becomes light, and has handwriting disappearance phenomenon. The test results are shown in FIGS. 1-4, and the statistical test results are shown in Table 1.
TABLE 1 surface Performance test results for coatings
| Surface tension test pen 34 | Surface tension test pen 36 | Surface tension test pen 38 | |
| Treatment group 1 | By passing | Do not pass through | Do not pass through |
| |
By passing | By passing | Do not pass through |
| Treatment group 3 | By passing | By passing | By passing |
| Treatment group 4 | Do not pass through | Do not pass through | Do not pass through |
Referring to fig. 1-4, it can be seen that:
(1) The three lines of treatment set 1, line 1, did not shrink at all, had clear handwriting, and lines 2 and 3 were light, unclear, discontinuous, and had small water droplets, so the substrate of treatment set 1 passed the test with the 34 surface tension test pen, but failed the test with the 36, 38 surface tension test pens.
(2) The three straight lines of treatment group 2, straight line 1 and straight line 2, were completely non-shrinking, the handwriting was clear, and straight line 3 was lighter in color, unclear, discontinuous, lacking in color patches, and had small water droplets, so the substrate of treatment group 2 passed the test with surface tension test pens 34 and 36, but not under the test with surface tension test pen 38.
(3) Three straight lines of the treatment group 3, namely the straight line 1, the straight line 2 and the straight line 3, are not contracted at all, the handwriting is clear, and color blocks are not lacked, so that the base material passes the test of three surface tension test pens.
(4) The three straight lines of the substrate of treatment set 4 were not continuous, missing color patches, and had small water droplets, so the substrate did not pass the three surface tension test pens.
It can be seen that the treatment groups 1 to 3 according to the invention have better surface properties than conventional powder coatings. Particularly, the treatment group 3, which is a polyester resin with an acid value of 18, performed the most well, and the three surface tension test pens passed the test.
As described above, the powder coatings prepared in examples 1 to 3 of the present invention coated the substrate surface with a higher surface tension according to the test of the surface tension test pen. The molecular weight of the polyester is larger through the polymerization of various esters, and ester groups of partial polyester molecular chains are hydrolyzed by adding isophthalic acid to form carboxyl end groups, so that the concentration of polar groups in chain segments is improved, the surface resistance is reduced, and the surface tension is improved. The prepared polyester resin has low curing crosslinking density and low softening point, so that the viscosity is high; the introduction of the hydrophilic group greatly improves the adhesive force between the coating and the base material, has good coating effect, further improves the surface tension of the base material after the base material is coated after the polyester resin is prepared into the powder coating, and solves the problems that the surface tension of the existing powder coating is low, and the preparation method can not adjust the surface tension of the coating to adapt to different production requirements.
The above embodiment is only one embodiment of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A polyester resin characterized by: the polyester resin comprises the following raw materials: 5-8 parts of neopentyl glycol, 1-3 parts of diethylene glycol, 6-11 parts of ethylene glycol, 1-7 parts of isophthalic acid, 9-18 parts of diglycidyl terephthalate, 8-11 parts of tetrabutyl titanate, 6-13 parts of diglycidyl cyclohexane-1, 2-dicarboxylate, 1-2 parts of an organic tin catalyst and 1-2 parts of an antioxidant.
2. A method for preparing polyester resin is characterized in that: the method for preparing the polyester resin as claimed in claim 1, comprising the steps of:
(1) Melting neopentyl glycol, ethylene glycol and diethylene glycol, adding an organic tin catalyst and tetrabutyl titanate, and performing first treatment to obtain a first polymer; adding isophthalic acid, diglycidyl terephthalate and diglycidyl cyclohexane-1, 2-dicarboxylate into the first polymer, and performing second treatment to obtain a second polymer;
(2) And (3) cooling the second polymer, heating to 205 ℃ at the rate of 18 ℃/h when the acid value of the second polymer is less than or equal to 40mgKOH/g, adding an antioxidant, starting a preset vacuum system to continue polymerization, stopping vacuumizing when the acid value of the second polymer is less than or equal to 15mgKOH/g, adding isophthalic acid to perform carboxyl end-capping reaction, performing third treatment, stopping the reaction when the acid value reaches 18-60 mgKOH/g, cooling and crushing to obtain the polyester resin.
3. The method for preparing a polyester resin according to claim 2, wherein: the first processing method comprises the following specific steps: gradually heating to 180 ℃ at the speed of 10-12 ℃/h, and carrying out heat preservation treatment for 1-3h.
4. The method for preparing polyester resin according to claim 2, wherein: the second processing method comprises the following specific steps: heating to 220 ℃ at the speed of 6-8 ℃/h, and carrying out heat preservation treatment for 4-5h.
5. The method for preparing polyester resin according to claim 2, wherein: the third processing method comprises the following specific steps: heating to 228 ℃ at the speed of 9-10 ℃/h, and carrying out heat preservation treatment for 3-4h.
6. A powder coating comprising a first component and a second component, characterized in that: the first component comprises the following components in parts by weight: 50-60 parts of the polyester resin as claimed in claim 1, 1-5 parts of a curing agent; the second component includes: 1-20 parts of pigment, 1-30 parts of barium sulfate, 1-3 parts of polytetrafluoroethylene additive, 1-5 parts of functional additive and 5-10 parts of talcum powder.
7. The method of claim 6, comprising:
s1: mixing the first component at high speed for a first predetermined time to obtain a mixture;
s2: performing first extrusion on the mixture and crushing to obtain a first extrusion material;
s3: adding the first extrusion material and the second component into a mixing device, and mixing at a high speed for a second preset time to obtain a prefabricated object;
s4: performing secondary extrusion on the prefabricated object, and performing cooling, tabletting and coarse crushing treatment to obtain a sheet material to be ground;
s5: and grinding the flakes to be ground, screening target particles and collecting to obtain the finished powder coating.
8. The method of claim 7, wherein the powder coating is prepared by: the first extrusion in S2 is specifically carried out by introducing the mixture into an extruder for melt extrusion, wherein the temperature of an extrusion section is 100-120 ℃, and the rotating speed of a screw is 500-650rpm.
9. The method of claim 7, wherein the step of preparing the powder coating comprises: the first preset time is 15-25min; the second preset time is 10-30min.
10. The method of claim 7, wherein the step of preparing the powder coating comprises: the second extrusion in S4 is specifically carried out by introducing the preformed objects into an extruder for melt extrusion, wherein the temperature of an extrusion section is 110-130 ℃, and the rotating speed of a screw is 700-850rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211011146.7A CN115197406B (en) | 2022-08-23 | 2022-08-23 | Polyester resin, powder coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211011146.7A CN115197406B (en) | 2022-08-23 | 2022-08-23 | Polyester resin, powder coating and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104129185A (en) * | 2014-07-22 | 2014-11-05 | 隆昌羽玺新材料科技有限公司 | Polyester film used for bar code printing, and making method thereof |
| CN106893086A (en) * | 2017-03-09 | 2017-06-27 | 江苏欣宝科技股份有限公司 | A kind of thermal transfer polyester resin for powder coating and preparation method thereof |
| CN112048235A (en) * | 2020-09-11 | 2020-12-08 | 安徽鑫友高分子新材料科技有限公司 | Long-acting weather-resistant chlorine salt corrosion-resistant polyester powder coating and preparation method thereof |
| CN112384548A (en) * | 2019-09-18 | 2021-02-19 | 擎天材料科技有限公司 | Polyester resin, preparation method thereof, powder coating and workpiece |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP7388140B2 (en) * | 2018-11-13 | 2023-11-29 | 東洋製罐グループホールディングス株式会社 | Coating composition and coated metal substrate having a coating film made of the coating composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104129185A (en) * | 2014-07-22 | 2014-11-05 | 隆昌羽玺新材料科技有限公司 | Polyester film used for bar code printing, and making method thereof |
| CN106893086A (en) * | 2017-03-09 | 2017-06-27 | 江苏欣宝科技股份有限公司 | A kind of thermal transfer polyester resin for powder coating and preparation method thereof |
| CN112384548A (en) * | 2019-09-18 | 2021-02-19 | 擎天材料科技有限公司 | Polyester resin, preparation method thereof, powder coating and workpiece |
| CN112048235A (en) * | 2020-09-11 | 2020-12-08 | 安徽鑫友高分子新材料科技有限公司 | Long-acting weather-resistant chlorine salt corrosion-resistant polyester powder coating and preparation method thereof |
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| CN115197406B (en) | 2024-03-26 |
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Denomination of invention: A polyester resin, powder coating and its preparation method Granted publication date: 20240326 Pledgee: Chengdu financial holding Financing Guarantee Co.,Ltd. Pledgor: CHENGDU XINDA POLYMER MATERIALS CO.,LTD. Registration number: Y2024510000153 |