CN116535622A - Self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and preparation method thereof - Google Patents
Self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and preparation method thereof Download PDFInfo
- Publication number
- CN116535622A CN116535622A CN202310511120.7A CN202310511120A CN116535622A CN 116535622 A CN116535622 A CN 116535622A CN 202310511120 A CN202310511120 A CN 202310511120A CN 116535622 A CN116535622 A CN 116535622A
- Authority
- CN
- China
- Prior art keywords
- acid
- alkyd resin
- self
- drying
- hydrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000180 alkyd Polymers 0.000 title claims abstract description 89
- 238000001035 drying Methods 0.000 title claims abstract description 39
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 39
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000007787 solid Substances 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 11
- 229930195729 fatty acid Natural products 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 allyl glycerol ether Chemical compound 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000007519 polyprotic acids Polymers 0.000 claims description 5
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 3
- HPQUMJNDQVOTAZ-UHFFFAOYSA-N 2,2-dihydroxypropanoic acid Chemical compound CC(O)(O)C(O)=O HPQUMJNDQVOTAZ-UHFFFAOYSA-N 0.000 claims description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 claims description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- KPKMKACZPZUNDP-UHFFFAOYSA-N 2-methylprop-2-enoic acid;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O KPKMKACZPZUNDP-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- CUXYLFPMQMFGPL-SUTYWZMXSA-N all-trans-octadeca-9,11,13-trienoic acid Chemical compound CCCC\C=C\C=C\C=C\CCCCCCCC(O)=O CUXYLFPMQMFGPL-SUTYWZMXSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000539 dimer Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229960003656 ricinoleic acid Drugs 0.000 claims description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000003784 tall oil Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229920005862 polyol Polymers 0.000 claims 1
- 150000003077 polyols Chemical class 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 21
- 239000002966 varnish Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 20
- 229920005989 resin Polymers 0.000 abstract description 19
- 239000011347 resin Substances 0.000 abstract description 19
- 238000004132 cross linking Methods 0.000 abstract description 10
- 229920003180 amino resin Polymers 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000007605 air drying Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000011343 solid material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000012855 volatile organic compound Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical compound C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940100573 methylpropanediol Drugs 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000008601 oleoresin Substances 0.000 description 1
- MAYUCBCSAVDUKG-UHFFFAOYSA-N orthoacetic acid Chemical compound CC(O)(O)O MAYUCBCSAVDUKG-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6828—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of alkyd resin preparation, and in particular relates to an air-drying/baking dual-purpose hydrolysis-resistant multipurpose alkyd resin and a preparation method thereof, wherein the alkyd resin has a molecular weight of 3000-15000, an acid value of 15-60mgKOH/g, a hydroxyl value of 50-120mgKOH/g, a solid content of 65-80% and a neutralization degree of 50-100%. The resin is pure alkyd resin, so that the gloss under the high humidity condition is improved; the alkyd resin can be self-dried at room temperature and used for alkyd self-drying paint, and has the characteristics of high gloss, high solid-dry hardness and excellent water resistance; the coating can also participate in the crosslinking reaction of amino resin, is used for alkyd baking varnish, has excellent flexibility on the basis of keeping high hardness and high gloss, and can be applied to common water-based metal baking varnish and water-based coiled material baking varnish; the alkyd resin has excellent hydrolysis resistance and excellent storage stability.
Description
Technical Field
The invention belongs to the technical field of alkyd resin preparation, and particularly relates to self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and a preparation method thereof.
Background
The alkyd paint is gradually converted into a water-based product from a solvent type according to environmental protection and industry requirements, the alkyd resin is used as a main body of the paint product, the hydrolysis resistance, the gloss, the surface dry-real dryness, the hardness, the water resistance of a paint film and other comprehensive performances are greatly reduced, in practical application, the resin is expected to be used for self-drying paint and baking paint in the market, and the resin has higher requirements on the resin performance due to different use mechanisms and application standards of the two types of paint.
Most of the alkyd resins with excellent hydrolysis resistance sold in the market are acrylic resin modified alkyd, but certain ungrafted acrylic resin components exist in the reaction, so that the gloss and adhesive force of a paint film are affected, and the gloss of the existing alkyd resin is difficult to reach a gloss with an angle of 20 degrees being more than 90 degrees under the condition of high humidity; whereas pure alkyd (non-modified) resins face the difficult problem of easy hydrolysis on long-term storage.
Disclosure of Invention
Aiming at the technical problems existing at present, the invention provides an air-drying/baking dual-purpose hydrolysis-resistant alkyd resin and a preparation method thereof, wherein the resin is pure alkyd resin, and excellent wettability of the resin can ensure excellent gloss after film formation, and especially the gloss under high humidity condition is improved; the alkyd resin can be self-dried at room temperature and used for alkyd self-drying paint, and has the characteristics of high gloss, high solid-dry hardness and excellent water resistance; the coating can also participate in the crosslinking reaction of amino resin, is used for alkyd baking varnish, has excellent flexibility on the basis of keeping high hardness and high gloss, and can be applied to common water-based metal baking varnish and water-based coiled material baking varnish; the alkyd resin has excellent hydrolysis resistance and excellent storage stability.
According to the invention, a special monomer is introduced, and is branched to a resin main chain in a side chain group mode, so that an umbrella cap structure is formed, easily-hydrolyzed groups on the resin are protected, and the problem of unstable storage of the water-based alkyd resin is solved; by introducing double bonds and hydroxyl groups into the special monomer, the special monomer has the dual functions of self-drying and crosslinking curing, and side chain groups participate in oxidative crosslinking due to the structure of the double bonds, so that the crosslinking density under the self-drying condition is improved, the water resistance of a paint film is improved, and meanwhile, the gloss of the paint film under the high humidity condition is improved due to the reactivity of the side chains, so that the paint film has the self-drying performance of water soaking resistance, quick surface drying and quick upper hardness; meanwhile, the special monomer has a hydroxyl structure, the hydroxyl content of the resin is improved, and the special monomer is matched with amino resin to be applied to baking varnish, is resistant to MEK (methyl ethyl ketone) solvent wiping, has excellent various resistance indexes, and widens the application field of the water-based alkyd resin. The specific technical scheme is as follows:
an air-drying/baking dual-purpose hydrolysis-resistant alkyd resin has a molecular weight of 3000-15000, an acid value of 15-60mgKOH/g, a hydroxyl value of 50-120mgKOH/g, a solid content of 65-80% and a neutralization degree of 50-100%.
Preferably, the alkyd resin has a solids content of 65-75%.
Preferably, the alkyd resin comprises special monomers in preparation raw materials, and the preparation method of the special monomers is as follows: dimethylol propionic acid and allyl glycerol ether are mixed, heated to 120-150 ℃ and reacted for 2-5 hours to obtain a special monomer; the allyl glycidyl ether is one of glycidyl methacrylate, allyl-2, 3-glycidyl ether, o-diallyl bisphenol A diglycidyl ether, cardanol glycidyl ether, allyl fluorine-containing glycidyl ether and ethylene glycol diglycidyl ether dimethacrylate phosphate; the mass ratio of dihydroxypropionic acid to allyl glycerol ether is 1:0.8-1.5.
Further preferably, the alkyd resin comprises the following preparation raw materials in parts by weight: 10-30wt% of polyalcohol, 10-30wt% of polybasic acid, 10-20wt% of fatty acid, 1-15wt% of special monomer, 0.01-1wt% of catalyst, 1-5wt% of neutralizer, 1-5wt% of water-based monomer and the balance of hydrophilic solvent.
Further preferably, the polybasic acid is two or any one of isophthalic acid, phthalic acid, terephthalic acid, succinic acid, glutaric acid, phthalic anhydride, adipic acid, cyclohexanedicarboxylic acid, benzoic acid, dimer acid and maleic anhydride.
Further preferably, the polyalcohol is one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol in any proportion. More preferably, one or more of propylene glycol, glycerol, methylpropanediol, cyclohexanol, trimethylolpropane, butanediol, neopentyl glycol, pentanediol, octanediol, heptanediol, cyclohexanedimethanol, pentaerythritol, and trihydroxyethane are used in any proportion.
Further preferably, the water-based monomer is one or more of phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, dimethylolpropionic acid, sodium metaxylylene sulfonate and polyethylene glycol, which are mixed in any proportion.
Further preferably, the fatty acid is one or more of soybean oil fatty acid, linoleic acid, eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid and tall oil acid.
Further preferably, the catalyst is one of antimony, organotin catalyst and hypophosphorous acid, and the hydrophilic solvent is one or more selected from ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether acetate, ethanol, n-butanol, isopropanol and butanol.
Further preferably, the neutralizing agent is selected from one of ammonia water, N-dimethylethanolamine, diethanolamine, triethanolamine, triethylamine, 1-methyldiethanolamine, and sodium hydroxide.
The preparation method of the self-drying/baking dual-purpose hydrolysis-resistant alkyd resin comprises the following steps:
(1) Mixing dihydroxypropionic acid with allyl glycerol ether, heating and reacting to obtain a special monomer;
(2) Putting polyalcohol, polybasic acid, special monomer and fatty acid into a reactor, slowly heating to 100-120 ℃, putting a catalyst into the reactor, slowly heating to 130-150 ℃, and preserving heat for 1-1.5h;
(3) Continuously heating to 5-10 ℃ per hour until the temperature reaches 210-240 ℃, carrying out heat preservation reaction, observing the water yield of the reaction, starting to measure the acid value when the water yield is 88-93%, and cooling to 150-160 ℃ after the acid value is less than 5-20 mgKOH/g;
(4) Then adding an aqueous monomer, reacting for 0.5-1h, and then cooling to 60-80 ℃;
(5) Adding hydrophilic solvent and neutralizing agent, and stirring completely and uniformly to obtain alkyd resin.
The preparation method is simple, short in time and safe in process, and the alkyd tree synthesized by the method has no abnormality after special monomers are introduced into the alkyd tree and stored in a 50 ℃ incubator for 12 months.
The alkyd resin disclosed by the invention can be self-dried at room temperature and used for alkyd self-drying paint, and has the characteristics of high gloss, high solid-dry hardness and excellent water resistance; the polyurethane can also participate in the crosslinking reaction of amino resin, is used for alkyd baking varnish, has excellent flexibility on the basis of keeping high hardness and high gloss, and can be applied to common water-based metal baking varnish and water-based coiled material baking varnish.
The special monomer is introduced into the invention and grafted on the side chain of the resin, so that the resin has excellent hydrolysis resistance and excellent storage stability, and solves the problems of poor hydrolysis resistance and difficult application commonly existing in water-based pure alkyd resin (non-acrylic acid modified alkyd resin). The special monomer has a double bond structure, so that side chain groups participate in oxidative crosslinking, the crosslinking density under the self-drying condition is improved, the water resistance of a paint film is improved, and meanwhile, the gloss of the paint film under the high humidity condition is improved due to the reactivity of the side chain; meanwhile, the special monomer has a hydroxyl structure, the hydroxyl content of the resin is improved, and the special monomer is matched with amino resin to be applied to baking varnish, so that various resistance indexes are excellent, and the application field of the water-based alkyd resin is widened. The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin provided by the invention is used as a water-based alkyd resin, so that the solvent usage amount in the paint is effectively reduced, the VOC emission is reduced, and the alkyd resin is safe and environment-friendly.
The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and the preparation method thereof provided by the invention are pure alkyd resins, so that the gloss under the high humidity condition is improved, the hydrolysis resistance is excellent, and the storage stability is excellent. The alkyd resin can be self-dried at room temperature and used for alkyd self-drying paint, and has the characteristics of high gloss, high solid-dry hardness and excellent water resistance; the alkyd resin can also participate in the crosslinking reaction of amino resin, is used for alkyd baking varnish, has excellent flexibility on the basis of keeping high hardness and high gloss, can be applied to general water-based metal baking varnish and water-based coiled material baking varnish, has excellent various resistance indexes, widens the application field of the water-based alkyd resin, effectively reduces the use amount of solvents in the paint, reduces VOC (volatile organic compound) emission, and is safe and environment-friendly.
Detailed Description
The above-described aspects of the present invention will be described in further detail by way of the following embodiments, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples. All techniques realized based on the above description of the present invention are within the scope of the present invention, and the following examples are accomplished by conventional techniques unless otherwise specified.
Example 1
Self-drying/baking dual-purpose hydrolysis-resistant multipurpose alkyd resin:
synthesis of special monomers: mixing dimethylol propionic acid with allyl-2, 3-epoxypropyl ether and other substances, heating to 130 ℃, reacting for 5 hours to obtain a special monomer, and filtering for later use;
86g of neopentyl glycol, 250g of soybean oil fatty acid, 43g of special monomer, 120g of trimethylolpropane, 10g of adipic acid, 190g of isophthalic acid and 6g of maleic anhydride are added into a four-neck flask provided with a thermometer, a stirring device and a condensation water-dividing device, and the mixture is heated and slowly heated to completely melt solid materials, and stirring is started; adding 0.3g of tin oxide serving as a catalyst under the material melting condition of 120 ℃, adjusting the material temperature to 150 ℃ within 2 hours, preserving heat for reaction for 1 hour, controlling the heating rate to 10 ℃/hour, gradually heating to 220 ℃, preserving heat for reaction at the temperature, continuously observing the water yield in the reaction process, starting to measure the acid value when the water yield reaches 90% of the theoretical water yield, cooling the material to 160 ℃, adding 30g of trimellitic anhydride, reacting for 0.5 hour, measuring the acid value to be less than 50mgKOH/g, and cooling to 60 ℃;
cooling to 60 ℃, adding 25g of neutralizing agent, namely N, N-dimethylethanolamine, stirring and reacting for 0.5 hour, adding 200g of hydrophilic solvent, namely ethylene glycol monobutyl ether, and adjusting the solid content of the product to 75wt%, thus obtaining the self-drying/baking dual-purpose hydrolysis-resistant alkyd resin with 8000 molecular weight, 75% of neutralization degree and 18mgKOH/g acid value.
After special monomers are introduced into the alkyd tree synthesized by the invention, the alkyd resin is stored for 12 months in a 50 ℃ incubator without abnormality, and the alkyd resin without the special monomers is stored for 15 days in the 50 ℃ incubator with turbidity and layering.
Example 2
Self-drying/baking dual-purpose hydrolysis-resistant multipurpose alkyd resin:
synthesis of special monomers: dimethylolpropionic acid and glycidyl methacrylate and other substances are mixed, the temperature is raised to 130 ℃, the special monomer is obtained after reaction for 5 hours, and the mixture is filtered for standby;
80g of pentaerythritol, 260g of soybean oil fatty acid, 43g of special monomer, 110g of trimethylolpropane, 200g of phthalic anhydride and 4g of maleic anhydride are added into a four-neck flask provided with a thermometer, a stirring device and a condensation water diversion device, and the mixture is heated and slowly heated to completely melt solid materials, and stirring is started; adding 0.3g of hypophosphorous acid serving as a catalyst under the material melting condition of 120 ℃, adjusting the material temperature to 150 ℃ within 2 hours, preserving heat for reaction for 1 hour, controlling the heating rate to 10 ℃/hour, gradually heating to 220 ℃, preserving heat for reaction at the temperature, continuously observing the water yield in the reaction process, when the water yield reaches 90% of the theoretical water yield, starting to measure the acid value, when the theoretical acid value is less than 5mgKOH/g, cooling the material to 160 ℃, adding 35g of trimellitic anhydride, reacting for 0.5 hour, measuring the acid value to be less than 50mgKOH/g, and cooling to 60 ℃;
cooling to 60 ℃, adding 20g of neutralizing agent, namely N, N-dimethylethanolamine, stirring and reacting for 0.5 hour, adding 200g of hydrophilic solvent, namely ethylene glycol monobutyl ether, and adjusting the solid content of the product to 75wt%, thus obtaining the self-drying/baking dual-purpose hydrolysis-resistant alkyd resin with the molecular weight of 7000, the neutralization degree of 70% and the acid value of 15mgKOH/g.
Example 3
Self-drying/baking dual-purpose hydrolysis-resistant multipurpose alkyd resin:
synthesis of special monomers: mixing dimethylolpropionic acid with the amount of substances such as o-diallyl bisphenol A diglycidyl ether, heating to 130 ℃, reacting for 5 hours to obtain a special monomer, and filtering for later use;
80g of trimethylolpropane, 260g of soybean oil fatty acid, 40g of special monomer, 110g of glycerol, 200g of phthalic anhydride and 4.5g of maleic anhydride are added into a four-neck flask provided with a thermometer, a stirring device and a condensation water-dividing device, and the mixture is heated and slowly heated to completely melt solid materials, and stirring is started; adding 0.3g of hypophosphorous acid serving as a catalyst under the material melting condition of 120 ℃, adjusting the material temperature to 150 ℃ within 2 hours, preserving heat for reaction for 1 hour, controlling the heating rate to 10 ℃/hour, gradually heating to 220 ℃, preserving heat for reaction at the temperature, continuously observing the water yield in the reaction process, when the water yield reaches 90% of the theoretical water yield, starting to measure the acid value, when the theoretical acid value is less than 5mgKOH/g, cooling the material to 160 ℃, adding 35g of trimellitic anhydride, reacting for 0.5 hour, measuring the acid value to be less than 50mgKOH/g, and cooling to 60 ℃;
cooling to 60 ℃, adding 30g of N, N dimethylethanolamine as a neutralizing agent, stirring for reacting for 0.5 hour, adding 200g of ethylene glycol monobutyl ether as a hydrophilic solvent, and adjusting the solid content to 75wt% to obtain the self-drying/baking dual-purpose hydrolysis-resistant alkyd resin, wherein the molecular weight of the resin is 7500, the neutralization degree is 80%, and the acid value is 20mgKOH/g.
Example 4
Self-drying/baking dual-purpose hydrolysis-resistant multipurpose alkyd resin:
synthesis of special monomers: mixing dimethylolpropionic acid with cardanol glycidyl ether and other substances, heating to 130 ℃, reacting for 5 hours to obtain a special monomer, and filtering for later use;
80g of trimethylolpropane, 260g of linoleic acid, 40g of special monomer, 110g of glycerol, 200g of phthalic acid and 4.5g of maleic anhydride are added into a four-neck flask provided with a thermometer, a stirring device and a condensation water diversion device, and the mixture is heated and slowly heated to completely melt the solid materials, and stirring is started; adding 0.3g of hypophosphorous acid serving as a catalyst under the material melting condition of 120 ℃, adjusting the material temperature to 150 ℃ within 2 hours, preserving heat for reaction for 1 hour, controlling the heating rate to 10 ℃/hour, gradually heating to 220 ℃, preserving heat for reaction at the temperature, continuously observing the water yield in the reaction process, when the water yield reaches 90% of the theoretical water yield, starting to measure the acid value, when the theoretical acid value is less than 5mgKOH/g, cooling the material to 160 ℃, adding 35g of trimellitic anhydride, reacting for 0.5 hour, measuring the acid value to be less than 50mgKOH/g, and cooling to 60 ℃;
cooling to 60 ℃, adding 18g of neutralizing agent, namely N, N-dimethylethanolamine, stirring and reacting for 0.5 hour, adding 200g of hydrophilic solvent, namely propylene glycol methyl ether, and adjusting the solid content of the product to 75wt%, thus obtaining the self-drying/bakeable dual-purpose hydrolysis-resistant alkyd resin, wherein the molecular weight of the resin is 9000, the neutralization degree is 65%, and the acid value is 15mgKOH/g.
Example 5
Self-drying/baking dual-purpose hydrolysis-resistant multipurpose alkyd resin:
synthesis of special monomers: dimethylol propionic acid and allyl fluorine-containing glycidyl ether and other substances are mixed, the temperature is raised to 130 ℃, the special monomer is obtained after reaction for 5 hours, and the mixture is filtered for standby;
80g of trimethylolpropane, 260g of dehydrated ricinoleic acid, 40g of special monomer, 110g of pentaerythritol, 215g of phthalic anhydride and 4.5g of maleic anhydride are added into a four-neck flask provided with a thermometer, a stirring device and a condensation water-dividing device, and the mixture is heated and slowly heated to completely melt solid materials, and stirring is started; adding 0.3g of hypophosphorous acid serving as a catalyst under the material melting condition of 120 ℃, adjusting the material temperature to 150 ℃ within 2 hours, preserving heat for reaction for 1 hour, controlling the heating rate to 10 ℃/hour, gradually heating to 220 ℃, preserving heat for reaction at the temperature, continuously observing the water yield in the reaction process, when the water yield reaches 90% of the theoretical water yield, starting to measure the acid value, when the theoretical acid value is less than 5mgKOH/g, cooling the material to 160 ℃, adding 35g of trimellitic anhydride, reacting for 0.5 hour, measuring the acid value to be less than 50mgKOH/g, and cooling to 60 ℃;
cooling to 60 ℃, adding 30g of neutralizing agent N, N dimethylethanolamine, stirring for reacting for 0.5 hour, adding 200g of hydrophilic solvent propylene glycol methyl ether, and adjusting the solid content to 75wt% to obtain the self-drying/bakeable dual-purpose hydrolysis-resistant alkyd resin, wherein the molecular weight of the resin is 10000, the neutralization degree is 85%, and the acid value is 20mgKOH/g.
The alkyd resin disclosed by the invention is not modified by acrylic resin, and the comprehensive performance of the alkyd resin exceeds that of acrylic modified alkyd resins sold in the market.
As self-drying resin, the following excellent properties were obtained
As a baking varnish type resin (amino resin) having the following excellent properties
| Gloss of the product | Excellent wettability, high glossiness of 20 DEG angle > 90, 60 DEG angle > 95 |
| MEK wiping | More than or equal to 150 times |
| Hardness of | The hardness of the pencil is more than or equal to 2H |
| Storage stability | Stored at 50℃for 14 days |
| T-bend | ≤3T |
| Adhesion force | Level 0 |
| Storage stability | 50 ℃ storageStored for 14 days |
Test examples
The product in example 1 was selected, and a normal temperature air-dried top coat was formulated according to the following formulation, and the performance evaluation results were as follows:
table 1 air-drying top-coat formulation
| Raw material name | Proportioning, wt% |
| Alkyd resins | 35 |
| Ethylene glycol monobutyl ether | 5 |
| NN dimethylethanolamine | 0.8 |
| Defoaming agent 810 | 0.2 |
| Leveling agent 450 | 0.1 |
| Substrate wetting agent 4100 | 0.1 |
| Titanium white powder | 15 |
| Red powder | 8 |
| Deionized water | 35.8 |
| Totals to | 100 |
Table 2 results of testing the Performance of the Normal temperature air-dried topcoat
The product of example 1 was selected and the baking varnish was formulated according to the following formulation, with the following performance evaluation results:
table 3 baking varnish formulation
| Raw material name | Proportioning, wt% |
| Alkyd resins | 35 |
| Ethylene glycol monobutyl ether | 5 |
| NN dimethylethanolamine | 0.8 |
| Defoaming agent A10 | 0.2 |
| Leveling agent 450 | 0.1 |
| Substrate wetting agent 4100 | 0.1 |
| Titanium white powder | 15 |
| 325 amino resin | 7 |
| Deionized water | 36.8 |
| Totals to | 100 |
TABLE 4 stoving varnish performance test results
Through color paint performance evaluation, the performance of the water-based resin reaches the application standard of the oleoresin, and the performance is excellent.
The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and the preparation method thereof provided by the invention are pure alkyd resins, so that the gloss under the high humidity condition is improved, the hydrolysis resistance is excellent, and the storage stability is excellent. The alkyd resin can be self-dried at room temperature and used for alkyd self-drying paint, and has the characteristics of high gloss, high solid-dry hardness and excellent water resistance; the alkyd resin can also participate in the crosslinking reaction of amino resin, is used for alkyd baking varnish, has excellent flexibility on the basis of keeping high hardness and high gloss, can be applied to general water-based metal baking varnish and water-based coiled material baking varnish, has excellent various resistance indexes, widens the application field of the water-based alkyd resin, effectively reduces the use amount of solvents in the paint, reduces VOC (volatile organic compound) emission, and is safe and environment-friendly.
Claims (10)
1. The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin is characterized in that the molecular weight of the alkyd resin is 3000-15000, the acid value is 15-60mgKOH/g, the hydroxyl value is 50-120mgKOH/g, the solid content is 65-80%, and the neutralization degree is 50-100%.
2. The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin as claimed in claim 1, wherein the alkyd resin comprises special monomers as raw materials, and the preparation method of the special monomers is as follows: dimethylol propionic acid and allyl glycerol ether are mixed, heated to 120-150 ℃ and reacted for 2-5 hours to obtain a special monomer; the allyl glycidyl ether is one of glycidyl methacrylate, allyl-2, 3-glycidyl ether, o-diallyl bisphenol A diglycidyl ether, cardanol glycidyl ether, allyl fluorine-containing glycidyl ether and ethylene glycol diglycidyl ether dimethacrylate phosphate;
the mass ratio of the dihydroxypropionic acid to the allyl glycerol ether is 1:0.8-1.5.
3. The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin as claimed in claim 2, wherein the alkyd resin comprises the following raw materials in parts by weight: 10-30wt% of polyalcohol, 10-30wt% of polybasic acid, 10-20wt% of fatty acid, 1-15wt% of special monomer, 0.01-1wt% of catalyst, 1-5wt% of neutralizer, 1-5wt% of water-based monomer and the balance of hydrophilic solvent.
4. A self-drying/bakeable dual-purpose hydrolysis-resistant alkyd resin according to claim 3, wherein the polyacids are two or more of isophthalic acid, phthalic acid, terephthalic acid, succinic acid, glutaric acid, phthalic anhydride, adipic acid, cyclohexanedicarboxylic acid, dimer acid and maleic anhydride.
5. The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin as recited in claim 3, wherein the polyol is one or more of dihydric alcohol, trihydric alcohol and tetrahydric alcohol in any proportion.
6. The self-drying/baking dual-purpose hydrolysis-resistant alkyd resin as claimed in claim 3, wherein the water-based monomer is one or more of phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, dimethylolpropionic acid, sodium metaxylylene sulfonate and polyethylene glycol.
7. A self-drying/bakeable dual-purpose hydrolysis-resistant alkyd resin as recited in claim 3, wherein the fatty acid is one or more of soybean oil fatty acid, linoleic acid, eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid, tall oil acid, or any ratio thereof.
8. A self-drying/bakeable dual-purpose hydrolysis-resistant alkyd resin according to claim 3, wherein the catalyst is one of antimony-based, organotin-based, hypophosphorous acid; the hydrophilic solvent is selected from one or more of ethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether acetate, ethanol, n-butanol, isopropanol and butanol.
9. A self-drying/bakeable dual-purpose hydrolysis-resistant alkyd resin according to claim 3, wherein the neutralizing agent is selected from one of ammonia, N dimethylethanolamine, diethanolamine, triethanolamine, triethylamine, 1-methyldiethanolamine, sodium hydroxide.
10. A method for preparing the self-drying/baking dual-purpose hydrolysis-resistant alkyd resin as claimed in any one of claims 1 to 9, which comprises the following steps:
(1) Mixing dimethylol propionic acid and allyl glycerol ether, heating and reacting to obtain a special monomer;
(2) Putting polyalcohol, polybasic acid, special monomer and fatty acid into a reactor, slowly heating to 100-120 ℃, putting a catalyst into the reactor, slowly heating to 130-150 ℃, and preserving heat for 1-1.5h;
(3) Continuously heating to 5-10 ℃ per hour until the temperature reaches 210-240 ℃, carrying out heat preservation reaction, observing the water yield of the reaction, starting to measure the acid value when the water yield is 88-93%, and cooling to 150-160 ℃ after the acid value is less than 5-20 mgKOH/g;
(4) Then adding an aqueous monomer, reacting for 0.5-1h, and then cooling to 60-80 ℃;
(5) Adding hydrophilic solvent and neutralizing agent, and stirring completely and uniformly to obtain alkyd resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310511120.7A CN116535622A (en) | 2023-05-05 | 2023-05-05 | Self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310511120.7A CN116535622A (en) | 2023-05-05 | 2023-05-05 | Self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116535622A true CN116535622A (en) | 2023-08-04 |
Family
ID=87453793
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310511120.7A Pending CN116535622A (en) | 2023-05-05 | 2023-05-05 | Self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116535622A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117186369A (en) * | 2023-10-13 | 2023-12-08 | 山西天宁新材料有限公司 | Hyperbranched nonionic water-based alkyd resin and preparation method thereof |
-
2023
- 2023-05-05 CN CN202310511120.7A patent/CN116535622A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117186369A (en) * | 2023-10-13 | 2023-12-08 | 山西天宁新材料有限公司 | Hyperbranched nonionic water-based alkyd resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4273690A (en) | Coating compositions of an alkyd-acrylic graft copolymer | |
| US4242243A (en) | High solids ambient temperature curing coatings of acrylic-fatty acid drying oil resins | |
| US4517322A (en) | Acrylated alkyd and polyester resins | |
| JP2599938B2 (en) | Method for producing water-dilutable air-dried lacquer-binder | |
| CN110183678B (en) | Water-based hyperbranched polyester resin and preparation method and application thereof | |
| CA1101576A (en) | Aqueous coating composition of an acrylic-vinyl oxazoline ester polymer | |
| US2653141A (en) | Partial esters of polyhydroxyl polyethers | |
| CN116535622A (en) | Self-drying/baking dual-purpose hydrolysis-resistant alkyd resin and preparation method thereof | |
| USRE31309E (en) | High solids ambient temperature curing coatings of acrylic-fatty acid drying oil resins | |
| US4322324A (en) | Ampho-ionic group-containing alkyd resins | |
| EP0330887B1 (en) | Coatings based on polycondensation and/or polyaddition products containing carboxylic and amino groups, and their use | |
| US4740566A (en) | High gloss color keyed guide coat | |
| US11673986B2 (en) | Acrylic modified polyester resin and preparation method thereof | |
| EP1765945B1 (en) | Metal packaging coating containing 1,3,5-triazine carbamate crosslinker | |
| CN113278139B (en) | Hydrolysis-resistant polyester resin for water-based coil primer coating and preparation method thereof | |
| CN113388093B (en) | Hydrolysis-resistant polyester resin for water-based coil finish paint and preparation method thereof | |
| CN111205444B (en) | Modified waterborne polyester resin with high dicyclopentadiene content as well as preparation method and application thereof | |
| JP2814504B2 (en) | Resin composition | |
| CA1096530A (en) | Graft polymer compositions of terminated epoxy resin, processes for making and using same, and substrates coated therewith | |
| US4120835A (en) | Thermosetting acrylic enamel containing iron pyrophosphate | |
| DE4416281C1 (en) | Low temp.-curing binder compsn. for coating materials | |
| US4810758A (en) | Resinous composition for coating use, which is excellent in weather resistance and in low temperature curing properties, its preparation and coating composition containing the same | |
| CN112390916B (en) | Acrylic acid modified polyester resin and preparation method thereof | |
| JPH0157707B2 (en) | ||
| CN116874751A (en) | Hydrolysis-resistant non-grafted modified water-based alkyd resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |