CN115850674A - Strong-alkali-resistant polyester resin, preparation method thereof and strong-alkali-resistant powder coating - Google Patents
Strong-alkali-resistant polyester resin, preparation method thereof and strong-alkali-resistant powder coating Download PDFInfo
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- CN115850674A CN115850674A CN202211610266.9A CN202211610266A CN115850674A CN 115850674 A CN115850674 A CN 115850674A CN 202211610266 A CN202211610266 A CN 202211610266A CN 115850674 A CN115850674 A CN 115850674A
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- polyester resin
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- alkali
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- 238000000576 coating method Methods 0.000 title claims abstract description 91
- 239000011248 coating agent Substances 0.000 title claims abstract description 86
- 239000004645 polyester resin Substances 0.000 title claims abstract description 67
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 67
- 239000000843 powder Substances 0.000 title claims abstract description 60
- 239000003513 alkali Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 44
- 239000002585 base Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims abstract description 13
- -1 glycidyl ester Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 9
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- 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 5
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 4
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000004814 polyurethane Substances 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000009835 boiling Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000005336 cracking Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000227 grinding Methods 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000007873 sieving Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000002981 blocking agent Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- OZCWUNHGNVXCCO-UHFFFAOYSA-N oxiran-2-ylmethyl hydrogen carbonate Chemical group OC(=O)OCC1CO1 OZCWUNHGNVXCCO-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000010998 test method 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
- 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 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical group C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical group CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000539 dimer Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
A polyester resin resistant to strong alkali, a preparation method thereof and a powder coating resistant to strong alkali, wherein the polyester resin resistant to strong alkali is prepared from the following raw materials; 5.4-6.0 parts of polyol, 5.8-6.3 parts of polybasic acid, 0.05-0.35 part of glycidyl ester, 0.008-0.012 part of esterification catalyst and 0.1-0.3 part of end capping agent. The invention selects the synthetic monomer containing the steric hindrance group, adopts polyfunctional group alcohol to carry out end capping and secondary vacuum process, effectively improves the steric hindrance effect and the curing crosslinking density, reduces the content of residual carboxyl in the polyester resin to be within 1mgKOH/g, and reduces the reaction of carboxyl and strong base. The prepared polyester resin is applied to polyurethane powder coating, and the coating has good leveling property, mechanical property, adhesive force and boiling resistance, and has excellent strong alkali resistance.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a strong-base-resistant polyester resin, a preparation method thereof and a strong-base-resistant powder coating.
Background
The corrosion of metals in nature is mainly electrochemical corrosion. Whether the metal material is stored or used, the metal material always contacts with the surrounding atmosphere or some media, elements such as hydrogen, oxygen, sulfur, chlorine and the like exist in the atmosphere, and certain humidity is contained in the atmosphere, and the elements cause the difference of the pH value of humid gas, so that the metal material is used in the atmosphere, electrochemical conditions are easily formed, and if the metal material is used in an acid-base salt medium, the corrosion is more serious.
The anticorrosion function of the powder coating is to form a layer of compact coating on the surface of the metal, prevent water, oxygen and other electrolytes from contacting the inside of the metal and shield the environment. The alkali resistance of the coating refers to the resistance of the coating film to alkali corrosion, namely, the coating test plate is soaked in alkali liquor with certain concentration under specified conditions, and the phenomena of light loss, foaming, whitening, falling off and the like do not occur within specified time.
Polyester resin contains a large amount of ester bonds, the alkali resistance of the ester bonds is poor, in the existing polyester/TGIC, polyester/HAA, polyester/epoxy and polyurethane powder coating systems, the alkali resistance of the polyurethane system is slightly good, but the mechanical property of the coating and the adhesion force to a base material are poor, the coating is short of durability in a strong alkaline solution, the coating is in a strong alkaline environment for a long time, the physical and chemical structures of the coating are damaged, and the phenomena of light loss, foaming, cracking, pulverization, falling off and the like are serious.
A Chinese patent publication No. CN 111393621A, published on 7, 10 and 2020, "a corrosion-resistant polyester resin and a preparation method thereof" discloses that the corrosion-resistant polyester resin comprises the following raw materials: 15 to 20 portions of polyether glycol, 20 to 25 portions of dihydric alcohol, 10 to 20 portions of polyfunctional acid or polyfunctional anhydride, 35 to 60 portions of dibasic acid or dibasic anhydride, 0.1 to 2 portions of catalyst, 0.1 to 2 portions of antioxidant and 3 to 5 portions of sheet-shaped blocking agent. The corrosion resistance of 5% alkali liquor is tested, and the corrosion resistance requirement of high-concentration strong alkali cannot be met.
Disclosure of Invention
The invention aims to provide a polyester resin with strong alkali resistance and a preparation method thereof; the method comprises the steps of selecting a synthetic monomer containing a steric hindrance group, carrying out end capping by adopting polyfunctional alcohols and carrying out a secondary vacuum process, effectively improving the steric hindrance effect and the curing crosslinking density, reducing the content of residual carboxyl in polyester resin to be within 1mgKOH/g, and reducing the reaction of carboxyl and strong base.
The invention also aims to provide the strong alkali resistant powder coating, which comprises the raw materials of the strong alkali resistant polyester resin, has good coating leveling property, mechanical property, adhesive force and boiling resistance, is soaked in 50 percent by weight of NaOH for 96 hours at the temperature of 30 ℃, has the coating gloss retention rate of more than 75 percent, and has no cracking, pulverization and falling-off phenomena; 50 percent by weight of NaOH is soaked for 22 hours at the temperature of 60 ℃, the gloss retention rate of the coating is more than 60 percent, and the coating has no cracking, chalking and dropping phenomena and has excellent strong alkali resistance.
The specific technical scheme of the invention is as follows:
the strong base resistant polyester resin comprises the following raw materials in parts by mass:
5.4-6.0 parts of polyol, 5.8-6.3 parts of polybasic acid, 0.05-0.35 part of glycidyl ester, 0.008-0.012 part of esterification catalyst and 0.1-0.3 part of end capping agent.
The polyalcohol is neopentyl glycol, 1,4-cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propylene glycol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propylene glycol, 1,6-hexanediol, trimethylolethane or trimethylolpropane, and the polyalcohol at least comprises one of trimethylolethane and trimethylolpropane.
Preferably, the polyhydric alcohol is neopentyl glycol, 1,4-cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane in a mass ratio of 1.5 to 2.0:1.5-2.5:0.7-1.3:0-0.3:0-0.3:0-0.1:0-1.0:0-1.0, and at least one of trimethylolethane and trimethylolpropane.
The polybasic acid is one or a mixture of more of terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride and trimesic acid.
Preferably, in the polybasic acid, the mass ratio of terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride and trimesic acid is 4.5-5.5:0-1.5:0-0.8:0-0.15:0-0.15.
The glycidyl ester is one or more of tertiary carbonic acid glycidyl ester or tertiary carbonic acid glycidyl ester and adipic acid diglycidyl ester, methacrylic acid glycidyl ester and dimer acid diglycidyl ester. As a hydrophobic material, it is possible to reduce the penetration of polar solvents or chemicals into the paint film and to reduce the hydrolysis of ester bonds.
The esterification catalyst is monobutyl tin oxide or stannous oxalate;
the end capping agent is one or two of trimethylolethane and trimethylolpropane.
The polyester resin resistant to strong base has a hydroxyl value of 90-120mgKOH/g, an acid value of 0-1mgKOH/g, a viscosity of 2500-5000mPa & s, and a glass transition temperature of 48-53 ℃.
The invention provides a preparation method of a strong alkali resistant polyester resin, which comprises the following steps:
1) Putting the formula amount of polyalcohol into a reaction kettle, heating to melt, starting stirring, adding the formula amount of polybasic acid, esterification catalyst and glycidyl ester, heating to 230-240 ℃, and maintaining the reaction until the acid value is 5-10mgKOH/g;
2) Cooling to 210-220 deg.C, and vacuumizing to obtain polymer with acid value of 0-2 mgKOH/g;
3) Adding a formula amount of end capping reagent, and keeping the reaction condition for 30-60min; and vacuumizing again to obtain the alkali-resistant polyester resin.
Heating to 100-150 ℃ in the step 1) for melting;
in the step 2), the vacuum pumping is carried out for 2-3h under the condition of-0.09 MPa to-0.1 MPa.
The vacuum pumping reaction in the step 3) refers to: vacuumizing for 1-2h under the conditions of-0.09 MPa to-0.1 MPa and 210-220 ℃.
In the synthetic process, the alcohol and the acid are subjected to esterification reaction (reversible) in the first step to generate a low molecular weight polymer, and the introduction of a material containing steric hindrance groups (tertiary carboxylic acid glycidyl ester and tertiary carboxylic acid glycidyl ester) can improve the effective steric hindrance effect; the second step of vacuum polycondensation is to improve the molecular weight and is beneficial to improving the performances of impact, bending and the like; and thirdly, blocking by using a blocking agent, and then carrying out secondary vacuum polycondensation, so that residual carboxyl at the tail end of a molecular chain is further reduced, the possibility of reaction with strong base is reduced, and the strong base resistance of the powder coating is improved. Moreover, the monomer contains larger groups, has better hydrophobicity, and can reduce the permeation of polar solvents or chemical substances to a paint film and the hydrolysis of ester bonds when being introduced into resin, such as tertiary carbonic acid glycidyl ester and monomers (2-butyl-2-ethyl-1,3-propylene glycol, 2,2,4-trimethyl-1,3-pentanediol and the like) with the side chains containing the larger groups; residual carboxyl at the tail end of the molecular weight of the resin reacts with alkali in a strong alkaline solution, so that the coating is easy to corrode, and secondary vacuum can reduce the residual carboxyl as much as possible; the polyfunctional alcohol can improve the branching degree and the crosslinking density, thereby improving the corrosion resistance of the coating.
The invention provides a strong alkali resistant powder coating, which comprises the raw materials of the strong alkali resistant polyester resin;
the alkali-resistant powder coating comprises the following raw materials in parts by mass: 35-50 parts of strong base resistant polyester resin, 20-30 parts of isocyanate, 20-40 parts of pigment, 1.0-2.0 parts of flatting agent, 0.3-0.8 part of benzoin and 0.3-0.8 part of wetting accelerator.
The isocyanate is selected from caprolactam blocked isocyanate, B1530;
the pigment is one or two of titanium dioxide or carbon black;
the leveling agent is GLP588;
the wetting enhancer is BLC701B wetting enhancer.
The preparation method of the alkali-resistant powder coating comprises the following steps:
fully premixing all the raw materials according to the formula ratio, extruding the mixture by a double-screw extruder, setting the temperature of a zone I to be 95-105 ℃, the temperature of a zone II to be 105-120 ℃, the temperature of a zone III to be 95-110 ℃, the feeding rotating speed frequency to be 25-35Hz and the screw rotating speed frequency to be 35-45Hz, crushing and grinding the extruded sheet materials, and sieving the crushed sheet materials by a 200-mesh sieve to obtain the composite material.
The invention selects the monomer containing steric hindrance group, in the aspect of alkali resistance, the polyester resin contains a large amount of ester bonds, the alkali resistance of the ester bonds is poor, and the effective steric hindrance can reduce the permeation of polar solvent and chemical substances to the paint film and reduce the hydrolysis of the ester bonds. The invention adopts polyfunctional group alcohols to carry out end capping and secondary vacuum process. The end capping agent adopts polyfunctional alcohols, so that the branching degree can be improved, and the improvement of the curing crosslinking density is beneficial to the improvement of strong alkali resistance; the secondary vacuum process can further reduce the residual carboxyl in the molecular chain and reduce the possibility of reaction with strong alkali solution. The hydroxyl content in the polyester resin is 90-120mgKOH/g, the residual carboxyl content is reduced to be within 1mgKOH/g, the prepared polyester resin is applied to powder coating, 50 percent of NaOH by weight is soaked for 96 hours at the temperature of 30 ℃, the gloss retention rate of the coating is more than 75 percent, and the phenomena of cracking, pulverization and falling off do not occur; 50 percent by weight of NaOH is soaked for 22 hours at the temperature of 60 ℃, the gloss retention rate of the coating is more than 60 percent, and the coating has no cracking, chalking and dropping phenomena and has excellent strong alkali resistance.
Detailed Description
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 with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. 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.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
The strong base resistant polyester resin comprises the following raw materials in parts by mass: as shown in table 1.
The preparation method of the alkali-resistant polyester resin in the embodiment 1 specifically comprises the following steps:
according to the table 1, adding the polyol with the formula amount into a reaction kettle, heating to 130 ℃ for melting, starting stirring, adding the polybasic acid, the esterification catalyst and the tertiary carboxylic acid glycidyl ester with the formula amount, heating to 235 ℃ and maintaining the reaction until the acid value is 5.9mgKOH/g; cooling to 215 ℃, and vacuumizing for 2.5h under the condition of-0.1 MPa to obtain a polymer with an acid value of 1.5 mgKOH/g; adding a formula amount of end capping agent, and maintaining for 50min; and (5) secondary vacuum pumping. Vacuumizing for 2h under the conditions of-0.1 MPa and 215 ℃ to obtain the strong base resistant polyester resin with the acid value of 0.3mgKOH/g, the viscosity of 3520mPa & s and the hydroxyl value of 99.6 mgKOH/g.
A strong base resistant powder coating, the raw materials of which comprise the strong base resistant polyester resin of the above example 1; the raw material components and the parts by mass of the specific powder coating are shown in table 2.
The preparation method of the powder coating comprises the following steps: weighing the raw materials according to the formula shown in the table 1, extruding the fully premixed raw materials by a double-screw extruder, setting the parameters as 105 ℃ in a region I, 110 ℃ in a region II, 110 ℃ in a region III, 30Hz in feeding speed frequency and 35Hz in screw speed frequency, crushing and grinding the extruded sheet materials, and sieving the crushed sheet materials by a 200-mesh sieve to obtain the alkali-resistant powder coating.
The prepared powder coating is electrostatically sprayed on an iron plate with a specific specification, and the curing is finished under the condition of 200 ℃/15 min.
Example 2
The strong base resistant polyester resin comprises the following raw materials in parts by mass: as shown in table 1.
The preparation method of the alkali-resistant polyester resin in the embodiment 2 specifically comprises the following steps:
according to the table 1, adding the polyol with the formula amount into a reaction kettle, heating to 120 ℃ for melting, starting stirring, adding the polybasic acid, the esterification catalyst and the tertiary carboxylic acid glycidyl ester with the formula amount, heating to 233 ℃ and maintaining the reaction until the acid value is 7.5mgKOH/g; cooling to 218 ℃, and vacuumizing for 3h under the condition of-0.1 MPa to obtain a polymer with an acid value of 1.6 mgKOH/g; adding a blocking agent, and maintaining for 30min; vacuumizing for 2h under the conditions of-0.1 MPa and 212 ℃ to obtain the strong base resistant polyester resin with the acid value of 0.3mgKOH/g, the viscosity of 3120 mPa.s and the hydroxyl value of 98.3 mgKOH/g;
a strong base resistant powder coating, the raw materials of which comprise the strong base resistant polyester resin of the above example 2; the specific raw material components and the parts by mass of the powder coating are shown in table 2.
The preparation method of the powder coating comprises the following steps: weighing raw materials according to the formula shown in the table 1, extruding the fully premixed raw materials through a double-screw extruder, setting the parameters as 103 ℃ in a region I, 115 ℃ in a region II, 110 ℃ in a region III, 35Hz in feeding speed frequency and 41Hz in screw speed frequency, crushing and grinding the extruded sheet materials, and sieving the crushed sheet materials through a 200-mesh sieve to obtain the alkali-resistant powder coating.
The prepared powder coating is electrostatically sprayed on an iron plate with a specific specification, and the curing is finished under the condition of 200 ℃/15 min.
Example 3
The strong base resistant polyester resin comprises the following raw materials in parts by mass: as shown in table 1.
The preparation method of the alkali-resistant polyester resin in the embodiment 3 specifically comprises the following steps:
according to the table 1, adding the polyol with the formula amount into a reaction kettle, heating to 110 ℃ for melting, starting stirring, adding the polybasic acid, the esterification catalyst and the tertiary carboxylic acid glycidyl ester with the formula amount, heating to 238 ℃ and maintaining the reaction until the acid value is 6.6mgKOH/g; cooling to 210 ℃, and vacuumizing for 2h under the condition of-0.1 MPa to obtain a polymer with an acid value of 1.0 mgKOH/g; adding a blocking agent, and maintaining for 50min; vacuumizing for 1.8h under the conditions of-0.1 MPa and 220 ℃ to obtain the strong base resistant polyester resin with the acid value of 0.6mgKOH/g, the viscosity of 2860 mPa.s and the hydroxyl value of 110.1 mgKOH/g;
a strong base resistant powder coating, the raw materials of which comprise the strong base resistant polyester resin of the above example 3; the specific raw material components and the parts by mass of the powder coating are shown in table 2.
The preparation method of the powder coating comprises the following steps: weighing the raw materials according to the formula shown in the table 1, extruding the fully premixed raw materials by a double-screw extruder, setting the parameters as 100 ℃ in a region I, 108 ℃ in a region II, 105 ℃ in a region III, 33Hz in feeding speed frequency and 45Hz in screw speed frequency, crushing and grinding the extruded sheet materials, and sieving the crushed sheet materials by a 200-mesh sieve to obtain the alkali-resistant powder coating.
The prepared powder coating is electrostatically sprayed on an iron plate with a specific specification, and the curing is finished under the condition of 200 ℃/15 min.
Example 4
The strong base resistant polyester resin comprises the following raw materials in parts by mass: as shown in table 1.
The preparation method of the alkali-resistant polyester resin in the embodiment 4 specifically comprises the following steps:
according to the table 1, adding the polyol with the formula amount into a reaction kettle, heating to 125 ℃ for melting, starting stirring, adding the polybasic acid, the esterification catalyst and the tertiary carboxylic acid glycidyl ester with the formula amount, heating to 237 ℃, and maintaining the reaction until the acid value is 7.3mgKOH/g; cooling to 217 deg.C, and vacuumizing under-0.1 MPa for 2.2h to obtain polymer with acid value of 1.7 mgKOH/g; adding a blocking agent, and maintaining for 45min; vacuumizing for 2h under the conditions of-0.1 MPa and 210 ℃ to obtain the alkali-resistant polyester resin with the acid value of 0.3mgKOH/g, the viscosity of 3380mPa & s and the hydroxyl value of 96.5 mgKOH/g;
a strong base resistant powder coating, the raw materials of which comprise the strong base resistant polyester resin of the above embodiment 4; the specific raw material components and the parts by mass of the powder coating are shown in table 2.
The preparation method of the powder coating comprises the following steps: weighing raw materials according to the formula shown in the table 1, extruding the fully premixed raw materials through a double-screw extruder, setting the parameters as 105 ℃ in a region I, 116 ℃ in a region II, 108 ℃ in a region III, 30Hz in feeding speed and 38Hz in screw speed, crushing and grinding the extruded sheet materials, and sieving the crushed sheet materials through a 200-mesh sieve to obtain the alkali-resistant powder coating.
The prepared powder coating is electrostatically sprayed on an iron plate with a specific specification, and the curing is finished under the condition of 200 ℃/15 min.
Example 5 (for comparison)
The polyester resin comprises the following raw materials in parts by mass: as shown in table 1.
The preparation method of the polyester resin in this embodiment 5 specifically includes:
according to the table 1, putting the polyalcohol into a reaction kettle, heating to 120 ℃ for melting, starting stirring, adding terephthalic acid and an esterification catalyst, heating to 235 ℃ and maintaining the reaction until the acid value is 6.0mgKOH/g; cooling to 215 ℃, and vacuumizing for 1h under the condition of-0.1 MPa to obtain the polyester resin with the acid value of 1.8mgKOH/g, the viscosity of 3850 mPa.s and the hydroxyl value of 100.2 mgKOH/g.
The application of the polyester resin is used for powder coating.
The raw materials for the powder coating included the comparative polyester resin of example 5 above; the specific raw material components and the parts by mass of the powder coating are shown in table 2.
The preparation method of the powder coating comprises the following steps: weighing raw materials according to the formula shown in the table 1, extruding the fully premixed raw materials by a double-screw extruder with the parameters of 98 ℃ in a region I, 116 ℃ in a region II, 105 ℃ in a region III, 33Hz in feeding speed and 44Hz in screw speed, crushing the extruded sheet, grinding, and sieving by a 200-mesh sieve to obtain the powder coating.
The prepared powder coating is electrostatically sprayed on an iron plate with a specific specification, and the curing is finished under the condition of 200 ℃/15 min.
Example 6 (for comparison)
The polyester resin comprises the following raw materials in parts by mass: as shown in table 1.
The preparation method of the polyester resin in this embodiment 6 specifically includes:
according to the table 1, putting the polyalcohol into a reaction kettle, heating to 122 ℃ for melting, starting stirring, adding terephthalic acid, isophthalic acid and an esterification catalyst, heating to 233 ℃ and maintaining the reaction until the acid value is 6.2mgKOH/g; cooling to 211 ℃, and vacuumizing for 1h under the condition of-0.1 MPa to obtain a polymer with an acid value of 1.1 mgKOH/g; adding a blocking agent, and maintaining for 37min; vacuum pumping is carried out for 1.2h under the condition of-0.1 MPa, and the polyester resin with the acid value of 0.8mgKOH/g, the viscosity of 2730 mPa.s and the hydroxyl value of 90.8mgKOH/g is obtained.
The application of the polyester resin is used for powder coating.
The raw materials for the powder coating included the comparative polyester resin of example 6 above; the specific raw material components and the parts by mass of the powder coating are shown in table 2.
The preparation method of the powder coating comprises the following steps: weighing raw materials according to the formula shown in the table 1, extruding the fully premixed raw materials by a double-screw extruder, setting the parameters to be 93 ℃ in a region I, 111 ℃ in a region II, 104 ℃ in a region III, 34Hz in feeding speed frequency and 44Hz in screw speed frequency, crushing and grinding the extruded sheets, and sieving the crushed sheets by a 200-mesh sieve to obtain the powder coating.
The prepared powder coating is electrostatically sprayed on an iron plate with a specific specification, and the curing is finished under the condition of 200 ℃/15 min.
Example 7 (for comparison)
The polyester resin comprises the following raw materials in parts by mass: as shown in table 1.
The preparation method of the polyester resin in this embodiment 7 specifically includes:
according to the table 1, putting polyol into a reaction kettle, heating to 111 ℃ for melting, starting stirring, adding polybasic acid, an esterification catalyst and tertiary carbonic acid glycidyl ester, heating to 236 ℃ and maintaining the reaction until the acid value is 6.4mgKOH/g; cooling to 214 deg.C, and vacuumizing under-0.1 MPa for 1.1h to obtain polyester resin with acid value of 0.9mgKOH/g, viscosity of 3530mPa · s, and hydroxyl value of 91.5 mgKOH/g.
The application of the polyester resin is used for powder coating.
The starting materials for the powder coating included the comparative polyester resin of example 7 above; the specific raw material components and the parts by mass of the powder coating are shown in table 2.
The preparation method of the powder coating comprises the following steps: weighing raw materials according to the formula shown in the table 1, extruding the fully premixed raw materials by a double-screw extruder with the parameters of 94 ℃ in the area I, 114 ℃ in the area II, 101 ℃ in the area III, 39Hz in the feeding speed and 41Hz in the screw speed, crushing and grinding the extruded sheet materials, and sieving the crushed sheet materials by a 200-mesh sieve to obtain the powder coating.
The prepared powder coating is electrostatically sprayed on an iron plate with a specific specification, and the curing is finished under the condition of 200 ℃/15 min.
TABLE 1 raw materials and parts by mass of examples
The underlined data in the table are not satisfactory for the present invention.
The various test criteria are as follows: the acid value test is shown in the standard GB/T6743-2008; the viscosity test is shown in the standard GB/T9751.1-2008; glass transition temperature (Tg) test, see standard GB/T19466.2-2004.
TABLE 2 powder coating materials in parts by weight and Performance index
The powder coating samples obtained in examples 1 to 7 (both-side spray and corner kettle cover powder coatings) were tested according to the relevant test standards, wherein example 5 is a polyester resin for conventional polyurethane powder coatings, examples 6 and 7 are polyester resins synthesized from different raw materials and processes, and the polyester resins were used as reference comparative resins for examples 1 to 4 of the present invention, and were tested simultaneously according to the same test methods, and the specific indexes are shown in table 3. The test criteria are as follows: the adhesion test is shown in the standard GB/T9286-1998; the gloss of the sample plate is directly measured by a gloss meter, see GB/T9754; the impact resistance is tested by adopting an impact tester of a national Tianjin instrument testing machine factory, and is shown in GB/T1732-93; the leveling performance is obtained by testing a BYK leveling instrument; bending test method GBT 6742-2007.
The invention discloses a method for detecting strong alkali resistance of a powder coating, which comprises the following steps: firstly preparing a sodium hydroxide solution with the mass fraction of 50%, pouring the sodium hydroxide solution into a container, immersing half of the cured coating sample plate into a strong alkali solution, then closing the container, and placing the container in a water bath kettle at a specific temperature. And (4) after the sample plate is placed for a certain time, taking out the sample plate, washing the sample plate clean by using distilled water, and detecting the coating light retention rate and the coating state.
TABLE 3 Properties of powder coatings prepared from the polyester resins of the examples
As can be seen from the test results, the coating cured at 200 ℃/15min has good leveling property, and the coating does not change obviously after being boiled for 2 hours. The resin of the present invention is excellent in impact and bending properties in terms of mechanical properties, while those of comparative examples 6 and 7 are not satisfactory. In a strong alkali resistance experiment, the light retention rate of the powder coating in comparative example 5 is 36% after the powder coating is soaked for 96 hours at 30 ℃, the partial area of the coating has cracking and falling phenomena, the light retention rates of the coatings in comparative examples 6 and 7 are 60.5% and 51.2% respectively, the partial area of the coating has cracking phenomena, but the light retention rate of the resin provided by the invention is more than 75%, and the surface of the coating is complete without cracking, powdering and falling phenomena; after being soaked for 22h at 60 ℃, the coating of comparative example 5 is severely matt and has large-area pulverization and shedding phenomena, the gloss retention of comparative examples 6 and 7 is reduced to be within 10%, and the coating part area has cracking and shedding phenomena, but the resin coating of the invention has the gloss retention of more than 60%, has no cracking, pulverization and shedding phenomena, and has excellent strong alkali resistance.
In addition, the sample of the embodiment 1 to the embodiment 4 is unchanged by adopting 5% concentration normal temperature alkali liquor for 500h, and the light retention rate is still more than 80% after the experiment for 45 days.
Claims (10)
1. The strong base resistant polyester resin is characterized by comprising the following raw materials in parts by mass:
5.4-6.0 parts of polyol, 5.8-6.3 parts of polybasic acid, 0.05-0.35 part of glycidyl ester, 0.008-0.012 part of esterification catalyst and 0.1-0.3 part of end capping agent.
2. The alkali-resistant polyester resin as claimed in claim 1, wherein the polyol is one or more selected from the group consisting of neopentyl glycol, 1,4-cyclohexanedimethanol, and 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, and trimethylolpropane, and at least one of trimethylolethane and trimethylolpropane.
3. The alkali-resistant polyester resin according to claim 1 or 2, wherein the polyol is neopentyl glycol, 1,4-cyclohexanedimethanol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane in a mass ratio of 1.5 to 2.0:1.5-2.5:0.7-1.3:0-0.3:0-0.3:0-0.1:0-1.0:0-1.0, and at least one of trimethylolethane and trimethylolpropane.
4. The alkali-resistant polyester resin as claimed in claim 1 or 2, wherein the polybasic acid is a mixture of terephthalic acid and one or more of isophthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride and trimesic acid.
5. The alkali-resistant polyester resin as claimed in claim 1 or 4, wherein the mass ratio of terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, trimellitic anhydride and trimesic acid in the polybasic acid is 4.5-5.5:0-1.5:0-0.8:0-0.15:0-0.15.
6. The polyester resin according to any of claims 1 to 5, wherein the polyester resin has a hydroxyl value of 90 to 120mgKOH/g, an acid value of 0 to 1mgKOH/g, a viscosity of 2500 to 5000 mPa-s, and a glass transition temperature of 48 to 53 ℃.
7. A process for the preparation of a polyester resin resistant to strong bases according to any one of claims 1 to 6, characterized in that it comprises the following steps:
1) Putting the formula amount of polyalcohol into a reaction kettle, heating to melt, starting stirring, adding the formula amount of polybasic acid, esterification catalyst and glycidyl ester, heating to 230-240 ℃, and maintaining the reaction until the acid value is 5-10mgKOH/g;
2) Cooling to 210-220 deg.C, and vacuumizing to obtain polymer with acid value of 0-2 mgKOH/g;
3) Adding a formula amount of end capping agent, and keeping the reaction condition for 30-60min; and vacuumizing again to obtain the alkali-resistant polyester resin.
8. The preparation method of claim 7, wherein the vacuum pumping in the step 2) is performed for 2-3h under-0.1 MPa.
9. The preparation method according to claim 7 or 8, wherein the re-vacuumizing in step 3) is: vacuumizing for 1-2h under the conditions of-0.09 MPa to-0.1 MPa and 210-220 ℃.
10. A powder coating resistant to strong bases, characterized in that it comprises a polyester resin resistant to strong bases according to any one of claims 1 to 6.
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| US6555226B1 (en) * | 2000-10-26 | 2003-04-29 | Bp Corporation North America Inc. | Polyester resin for powder coating |
| CN104311806A (en) * | 2014-10-20 | 2015-01-28 | 浙江天松新材料股份有限公司 | Polyester resin for high-leveling transparent powder coating, and preparation method of polyester resin |
| CN107033755A (en) * | 2016-12-05 | 2017-08-11 | 安徽神剑新材料股份有限公司 | A kind of outdoor type powdery paints hydroxyl telechelic polyester resin and preparation method thereof |
| WO2022032570A1 (en) * | 2020-08-13 | 2022-02-17 | 擎天材料科技有限公司 | Hydroxyl-terminated polyester resin, preparation method therefor and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6555226B1 (en) * | 2000-10-26 | 2003-04-29 | Bp Corporation North America Inc. | Polyester resin for powder coating |
| CN104311806A (en) * | 2014-10-20 | 2015-01-28 | 浙江天松新材料股份有限公司 | Polyester resin for high-leveling transparent powder coating, and preparation method of polyester resin |
| CN107033755A (en) * | 2016-12-05 | 2017-08-11 | 安徽神剑新材料股份有限公司 | A kind of outdoor type powdery paints hydroxyl telechelic polyester resin and preparation method thereof |
| WO2022032570A1 (en) * | 2020-08-13 | 2022-02-17 | 擎天材料科技有限公司 | Hydroxyl-terminated polyester resin, preparation method therefor and use thereof |
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