CN114907552A - Hyperbranched alkyd resin and preparation method and application thereof - Google Patents
Hyperbranched alkyd resin and preparation method and application thereof Download PDFInfo
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- CN114907552A CN114907552A CN202210576918.5A CN202210576918A CN114907552A CN 114907552 A CN114907552 A CN 114907552A CN 202210576918 A CN202210576918 A CN 202210576918A CN 114907552 A CN114907552 A CN 114907552A
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- China
- Prior art keywords
- alkyd resin
- hyperbranched
- acid
- anhydride
- hyperbranched alkyd
- Prior art date
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- 229920000180 alkyd Polymers 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003973 paint Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229920005862 polyol Polymers 0.000 claims abstract description 23
- 150000003077 polyols Chemical class 0.000 claims abstract description 23
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 18
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000010790 dilution Methods 0.000 claims abstract description 3
- 239000012895 dilution Substances 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 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 4
- 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 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 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
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 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 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 235000021319 Palmitoleic acid Nutrition 0.000 claims description 2
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 claims description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 238000001035 drying Methods 0.000 abstract description 12
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 25
- 238000001816 cooling Methods 0.000 description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000004821 distillation Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 8
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000008096 xylene Substances 0.000 description 8
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- 241000489492 Arisaema Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002023 wood Substances 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses hyperbranched alkyd resin and a preparation method and application thereof. The preparation method of the hyperbranched alkyd resin comprises the following steps: 1) mixing organic acid anhydride and polyhydric alcohol for prepolymerization, adding a catalyst and then polymerizing to obtain hyperbranched polyester polyol; 2) mixing hyperbranched polyester polyol with unsaturated monoacid or unsaturated monoacid-saturated monoacid compound for reaction to obtain a hyperbranched alkyd resin pre-product; 3) mixing the hyperbranched alkyd resin pre-product with trimellitic anhydride for reaction, adding a solvent for dilution, and adding alkali for neutralization to obtain the hyperbranched alkyd resin. The hyperbranched alkyd resin disclosed by the invention can be diluted by water, has the advantages of high drying speed, simplicity in preparation, low price and the like, is high in hardness, high in glossiness, good in water resistance and excellent in comprehensive performance after film forming, and is suitable for being used for water-based industrial paint.
Description
Technical Field
The invention relates to the technical field of coating resin, in particular to hyperbranched alkyd resin and a preparation method and application thereof.
Background
The alkyd resin is prepared by polycondensing and esterifying polyalcohol, polybasic acid and vegetable oil or vegetable oleic acid, a paint film formed by the alkyd resin is high in glossiness, fullness and distinctness of image, and the alkyd resin also has the advantages of easily available preparation raw materials, low price and the like, and is a preferred film forming material of the solvent-based bi-component wood paint. In recent years, the trend of waterborne coating resins has been, and the application and popularization of waterborne alkyd resins in the market are not very successful, especially, the one-component waterborne alkyd resins can hardly be applied in the industrial field, mainly because: 1) the water-based alkyd resin belongs to an air-drying system, the drying speed is low, even if a drier is added, the water-based alkyd resin can be dried at room temperature for 48-240 hours, and the construction efficiency is seriously influenced; 2) after the water-based alkyd resin is formed into a film, the water resistance of the paint film is poor, particularly the initial water resistance is poor, the paint film cannot be suitable for coating large devices needing outdoor construction, and the application is greatly limited.
Therefore, the development of the water-based alkyd resin which has the advantages of high drying speed, simple preparation, low price, good water resistance of a film formed by the alkyd resin and excellent comprehensive performance is of great significance.
The above statements are merely provided to provide background information related to the present disclosure and may not necessarily constitute prior art.
Disclosure of Invention
One of the purposes of the invention is to provide the water-dilutable hyperbranched alkyd resin which has the advantages of high drying speed, simple preparation, low price, high hardness/high glossiness/good water resistance of a film formed by the film and excellent comprehensive performance.
The second purpose of the invention is to provide a preparation method of the hyperbranched alkyd resin.
The invention also aims to provide the application of the hyperbranched alkyd resin in the water-based industrial paint.
The technical scheme adopted by the invention is as follows:
the preparation method of the hyperbranched alkyd resin comprises the following steps:
1) mixing organic acid anhydride and polyhydric alcohol for prepolymerization, adding a catalyst and then polymerizing to obtain hyperbranched polyester polyol;
2) mixing hyperbranched polyester polyol with unsaturated monoacid or unsaturated monoacid-saturated monoacid compound for reaction to obtain a hyperbranched alkyd resin pre-product;
3) mixing the hyperbranched alkyd resin pre-product with trimellitic anhydride for reaction, adding a solvent for dilution, and adding alkali for neutralization to obtain the hyperbranched alkyd resin.
Preferably, the organic acid anhydride in step 1) is at least one of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, maleic anhydride and fumaric anhydride.
More preferably, the organic acid anhydride in step 1) is at least one of phthalic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
Preferably, the polyol in step 1) is at least one of glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and sorbitol.
More preferably, the polyhydric alcohol in step 1) is at least one of trimethylolpropane, pentaerythritol, ditrimethylol propane and dipentaerythritol.
Preferably, the molar ratio of the organic acid anhydride to the polyol in the step 1) is 1: 1.01-1.15.
More preferably, the molar ratio of the organic acid anhydride to the polyol in the step 1) is 1: 1.03-1.10.
Preferably, the catalyst in the step 1) is at least one of monobutyl tin oxide, dibutyltin dilaurate, stannous octoate, n-butyl titanate and isopropyl titanate.
Further preferably, the catalyst in the step 1) is at least one of monobutyl tin oxide and dibutyltin dilaurate.
Preferably, the amount of the catalyst used in the step 1) is 0.005-0.05% of the mass of a prepolymerization product formed by the prepolymerization of the organic acid anhydride and the polyol.
Preferably, the prepolymerization in the step 1) is carried out at the temperature of between 80 and 140 ℃, and the reaction time is between 1 and 4 hours.
Further preferably, the prepolymerization in the step 1) is carried out at 100-120 ℃, and the reaction time is 2-3 h.
Preferably, the prepolymerization in step 1) is carried out in a protective atmosphere.
Preferably, the protective atmosphere is a nitrogen atmosphere.
Preferably, the polymerization in the step 1) is carried out at 160-220 ℃, and the reaction time is 4-30 h.
More preferably, the polymerization in the step 1) is carried out at 190-210 ℃, and the reaction time is 8-14 h.
Preferably, the polymerization in step 1) is carried out in a protective atmosphere.
Preferably, the protective atmosphere is a nitrogen atmosphere.
Preferably, the unsaturated monobasic acid in the step 2) is at least one of linoleic acid, eleostearic acid, dehydrated ricinoleic acid, high-iodine oleic acid, coconut oleic acid and palmitoleic acid.
More preferably, the unsaturated monobasic acid in the step 2) is at least one of linoleic acid, eleostearic acid, dehydrated ricinoleic acid and high-iodine oleic acid.
Preferably, the saturated monoacid in the step 2) is at least one of benzoic acid, p-tert-butyl benzoic acid, isooctanoic acid, n-decanoic acid and stearic acid.
More preferably, the saturated monoacid in the step 2) is at least one of benzoic acid, isooctanoic acid and stearic acid.
Preferably, the molar ratio of the hydroxyl in the hyperbranched polyester polyol obtained in the step 2) to the carboxyl in the unsaturated monoacid is 1.05-5.00: 1.
Further preferably, the molar ratio of the hydroxyl in the hyperbranched polyester polyol in the step 2) to the carboxyl in the unsaturated monoacid is 1.20-3.00: 1.
Preferably, the molar ratio of hydroxyl in the hyperbranched polyester polyol obtained in the step 2) to carboxyl in the unsaturated monoacid-saturated monoacid compound is 1.05-5.00: 1.
Further preferably, the molar ratio of the hydroxyl in the hyperbranched polyester polyol obtained in the step 2) to the carboxyl in the unsaturated monoacid-saturated monoacid compound is 1.20-3.00: 1.
Preferably, the reaction in the step 2) is carried out at 160-220 ℃, and the reaction time is 4-24 h.
Preferably, the mass ratio of the hyperbranched alkyd resin pre-product in the step 3) to trimellitic anhydride is 1: 0.01-0.08.
Further preferably, the mass ratio of the hyperbranched alkyd resin pre-product in the step 3) to the trimellitic anhydride is 1: 0.01-0.05.
Preferably, the reaction in the step 3) is carried out at 120-160 ℃, and the reaction time is 0.5-2 h.
Preferably, the solvent in step 3) is at least one of acetone, butanone, ethylene glycol monobutyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol butyl ether and propylene glycol methyl ether acetate.
Further preferably, the solvent in step 3) is at least one of butanone, ethylene glycol monobutyl ether and propylene glycol methyl ether.
Preferably, the amount of the solvent in the step 3) is 10-50% of the mass of the hyperbranched alkyd resin pre-product.
Further preferably, the amount of the solvent used in the step 3) is 10-30% of the mass of the hyperbranched alkyd resin pre-product.
Preferably, the base in step 3) is at least one of triethylamine, N-dimethylethanolamine, triethanolamine and N, N-dimethylcyclohexylamine.
Further preferably, the base in step 3) is at least one of triethylamine and N, N-dimethylethanolamine.
Preferably, the molar ratio of the alkali in the step 3) to the carboxyl in the hyperbranched alkyd resin pre-product is 0.65-1.20: 1.
Further preferably, the molar ratio of the alkali in the step 3) to the carboxyl in the hyperbranched alkyd resin pre-product is 0.80-1.00: 1.
A hyperbranched alkyd resin is prepared by the preparation method.
The water-based industrial paint comprises the hyperbranched alkyd resin.
The beneficial effects of the invention are: the hyperbranched alkyd resin disclosed by the invention can be diluted by water, has the advantages of high drying speed, simplicity in preparation, low price and the like, is high in hardness, high in glossiness, good in water resistance and excellent in comprehensive performance after film forming, and is suitable for being used for water-based industrial paint.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of the hyperbranched alkyd resin comprises the following steps:
1) adding 269g of phthalic anhydride and 248g of trimethylolpropane into a four-neck flask, introducing nitrogen, slowly heating to 110 ℃, keeping the temperature at 120 +/-2 ℃ for 2 hours (the reaction can automatically release heat, and the reaction temperature is kept in the range), adding 0.2g of monobutyl tin oxide, changing a rectifying column, slowly heating, controlling the temperature of a distillation head to be less than 98 ℃, and carrying out polycondensation reaction at 190-210 ℃ until the acid value is 20-25 mgKOH/g, thereby obtaining the hyperbranched polyester polyol;
2) reducing the temperature of a reaction system to 180 ℃, adding 420g of dehydrated ricinoleic acid, gradually raising the temperature, controlling the temperature of a distillation head to be less than 103 ℃, raising the temperature to 210 ℃, keeping the temperature for 2h, then reducing the temperature to 180 ℃, adding 15g of xylene, raising the temperature, refluxing and dehydrating for about 5h until the acid value is less than 15mgKOH/g, and then vacuumizing to remove the xylene to obtain a hyperbranched alkyd resin pre-product;
3) and (3) cooling the temperature of the reaction system to 150 ℃, adding 25.5g of trimellitic anhydride, keeping the temperature for 30min after the trimellitic anhydride is completely dissolved, cooling to 130 ℃, adding 225g of ethylene glycol monobutyl ether, keeping the temperature to 75 ℃, adding 25g of N, N-dimethylethanolamine, stirring for 30min, and filtering to obtain the hyperbranched alkyd resin.
The hyperbranched alkyd resin prepared in this example was tested to have a hydroxyl content of 0.8% and an oil content of 46%.
Example 2:
a preparation method of the hyperbranched alkyd resin comprises the following steps:
1) adding 269g of phthalic anhydride and 248g of trimethylolpropane into a four-neck flask, introducing nitrogen, slowly heating to 110 ℃, keeping the temperature at 120 +/-2 ℃ for 2 hours (the reaction can automatically release heat, and the reaction temperature is kept in the range), adding 0.2g of monobutyl tin oxide, changing a rectifying column, slowly heating, controlling the temperature of a distillation head to be less than 98 ℃, and carrying out polycondensation reaction at 190-210 ℃ until the acid value is 20-25 mgKOH/g, thereby obtaining the hyperbranched polyester polyol;
2) reducing the temperature of a reaction system to 180 ℃, adding 300g of dehydrated ricinoleic acid, gradually raising the temperature, controlling the temperature of a distillation head to be less than 103 ℃, raising the temperature to 210 ℃, keeping the temperature for 2h, then reducing the temperature to 180 ℃, adding 15g of xylene, raising the temperature, refluxing and dehydrating for about 4h until the acid value is less than 15mgKOH/g, and then vacuumizing to remove the xylene to obtain a hyperbranched alkyd resin pre-product;
3) and (2) cooling the temperature of the reaction system to 150 ℃, adding 17.8g of trimellitic anhydride, keeping the temperature for 30min after the trimellitic anhydride is completely dissolved, cooling to 130 ℃, adding 225g of ethylene glycol monobutyl ether, keeping the temperature to 75 ℃, adding 21g of N, N-dimethylethanolamine, stirring for 30min, and filtering to obtain the hyperbranched alkyd resin.
The hyperbranched alkyd resin prepared in this example was tested to have a hydroxyl content of 2.0% and an oil content of 38%.
Example 3:
a preparation method of the hyperbranched alkyd resin comprises the following steps:
1) adding 257g of phthalic anhydride and 248g of trimethylolpropane into a four-neck flask, introducing nitrogen, slowly heating to 110 ℃, preserving heat at 120 +/-2 ℃ for 2 hours (the reaction can automatically release heat, and the reaction temperature is maintained in the range), adding 0.2g of monobutyl tin oxide, changing a rectifying column, slowly heating, controlling the temperature of a distillation head to be less than 98 ℃, and carrying out polycondensation reaction at 190-210 ℃ until the acid value is 20-25 mgKOH/g, thereby obtaining the hyperbranched polyester polyol;
2) reducing the temperature of a reaction system to 180 ℃, adding 300g of high-iodine oleic acid, gradually heating, controlling the temperature of a distillation head to be less than 103 ℃, heating to 210 ℃, keeping the temperature for 2h, then cooling to 180 ℃, adding 15g of dimethylbenzene, heating, refluxing and dehydrating for about 4h until the acid value is less than 15mgKOH/g, and then vacuumizing to remove the dimethylbenzene to obtain a hyperbranched alkyd resin pre-product;
3) and (2) cooling the temperature of the reaction system to 150 ℃, adding 22.3g of trimellitic anhydride, keeping the temperature for 30min after the trimellitic anhydride is completely dissolved, cooling to 130 ℃, adding 225g of ethylene glycol monobutyl ether, keeping the temperature to 75 ℃, adding 25g of N, N-dimethylethanolamine, stirring for 30min, and filtering to obtain the hyperbranched alkyd resin.
The hyperbranched alkyd resin prepared in this example was tested to have a hydroxyl content of 2.0% and an oil content of 38%.
Example 4:
a preparation method of the hyperbranched alkyd resin comprises the following steps:
1) adding 260g of phthalic anhydride and 248g of trimethylolpropane into a four-neck flask, introducing nitrogen, slowly heating to 110 ℃, preserving heat at 120 +/-2 ℃ for 2 hours (the reaction can automatically release heat, and the reaction temperature is maintained in the range), adding 0.2g of monobutyl tin oxide, changing a rectifying column, slowly heating, controlling the temperature of a distillation head to be less than 98 ℃, and carrying out polycondensation reaction at 190-210 ℃ until the acid value is 20-25 mgKOH/g, thereby obtaining the hyperbranched polyester polyol;
2) reducing the temperature of a reaction system to 180 ℃, adding 150g of high-iodine oleic acid and 61g of benzoic acid, gradually heating, controlling the temperature of a distillation head to be less than 103 ℃, heating to 210 ℃, keeping the temperature for 2 hours, cooling to 180 ℃, adding 15g of xylene, heating, refluxing and dehydrating for about 3 hours until the acid value is less than 20mgKOH/g, and vacuumizing to remove the xylene to obtain a hyperbranched alkyd resin pre-product;
3) and (2) cooling the temperature of the reaction system to 150 ℃, adding 17.8g of trimellitic anhydride, keeping the temperature for 30min after the trimellitic anhydride is completely dissolved, cooling to 130 ℃, adding 175g of ethylene glycol monobutyl ether, keeping the temperature to 75 ℃, adding 21g of N, N-dimethylethanolamine, stirring for 30min, and filtering to obtain the hyperbranched alkyd resin.
The hyperbranched alkyd resin prepared in this example was tested to have a hydroxyl content of 2.4% and an oil content of 21.5%.
Example 5:
a preparation method of the hyperbranched alkyd resin comprises the following steps:
1) adding 265g of hexahydrophthalic anhydride and 248g of trimethylolpropane into a four-neck flask, introducing nitrogen, slowly heating to 110 ℃, keeping the temperature of 120 +/-2 ℃ for 2 hours (the reaction can automatically release heat, and the reaction temperature is kept in the range), adding 0.2g of monobutyl tin oxide, changing a rectifying column, slowly heating, controlling the temperature of a distillation head to be less than 98 ℃, and carrying out polycondensation reaction at 190-210 ℃ until the acid value is 20-25 mgKOH/g to obtain hyperbranched polyester polyol;
2) reducing the temperature of a reaction system to 180 ℃, adding 150g of high-iodine oleic acid and 72g of isooctanoic acid, gradually heating, controlling the temperature of a distillation head to be less than 103 ℃, heating to 210 ℃, keeping the temperature for 2 hours, cooling to 180 ℃, adding 15g of dimethylbenzene, heating, refluxing and dehydrating for about 12 hours until the acid value is less than 25mgKOH/g, and vacuumizing to remove the dimethylbenzene to obtain a hyperbranched alkyd resin pre-product;
3) and (2) cooling the temperature of the reaction system to 150 ℃, adding 17.8g of trimellitic anhydride, keeping the temperature for 30min after the trimellitic anhydride is completely dissolved, cooling to 130 ℃, adding 185g of ethylene glycol monobutyl ether, keeping the temperature to 75 ℃, adding 21g of N, N-dimethylethanolamine, stirring for 30min, and filtering to obtain the hyperbranched alkyd resin.
The hyperbranched alkyd resin prepared in this example was tested to have a hydroxyl content of 2.6% and an oil content of 21.5%.
Example 6:
1) adding 260g of tetrahydrophthalic anhydride and 268g of pentaerythritol (the purity is 95%) into a four-neck flask, introducing nitrogen, slowly heating to 110 ℃, keeping the temperature at 120 +/-2 ℃ for 2 hours (the reaction can automatically release heat, and the reaction temperature is maintained in the range), adding 0.2g of dibutyltin dilaurate, changing a rectifying column, slowly heating, controlling the temperature of a distillation head to be less than 98 ℃, and carrying out polycondensation reaction at 190-210 ℃ until the acid value is 20-25 mgKOH/g, so as to obtain hyperbranched polyester polyol;
2) reducing the temperature of a reaction system to 180 ℃, adding 380g of linoleic acid and 104g of benzoic acid, gradually heating, controlling the temperature of a distillation head to be less than 103 ℃, heating to 210 ℃, keeping the temperature for 2 hours, then cooling to 180 ℃, adding 20g of xylene, heating, refluxing and dehydrating for about 8 hours until the acid value is less than 25mgKOH/g, and then vacuumizing to remove the xylene to obtain a hyperbranched alkyd resin pre-product;
3) and (3) cooling the temperature of the reaction system to 150 ℃, adding 28.5g of trimellitic anhydride, continuously preserving the temperature for 30min after the trimellitic anhydride is completely dissolved, cooling to 110 ℃, adding 320g of propylene glycol methyl ether, continuously cooling to 70 ℃, adding 31g of triethylamine, stirring for 30min, and filtering to obtain the hyperbranched alkyd resin.
The hyperbranched alkyd resin prepared in this example was tested to have a hydroxyl content of 3.0% and an oil content of 40.0%.
Comparative example:
a preparation method of the hyperbranched alkyd resin comprises the following steps:
adding 255g of phthalic anhydride, 150g of neopentyl glycol, 45g of trimethylolpropane, 150g of dehydrated ricinoleic acid and 0.2g of monobutyl tin oxide into a four-neck flask, introducing nitrogen, slowly heating to 160 ℃, controlling the temperature of a distillation head to be less than 98 ℃, carrying out polycondensation reaction at 160-210 ℃ until the acid value is 15mgKOH/g, cooling to 150 ℃, adding 25g of trimellitic anhydride, continuously preserving the temperature for 30min after all the trimellitic anhydride is dissolved, cooling to 130 ℃, adding 178g of ethylene glycol monobutyl ether, continuously cooling to 75 ℃, adding 25g of N, N-dimethylethanolamine, stirring for 30min, and filtering to obtain the hyperbranched alkyd resin.
Through tests, the hydroxyl content of the hyperbranched alkyd resin prepared by the comparative example is 1.9%, and the oil content is 27.6%.
And (3) performance testing:
100g of hyperbranched alkyd resin (hyperbranched alkyd resin of examples 1 to 6 and comparative example) and 0.5g of cobalt drier (produced by Guangdong Runchang Arisaema New Material Co., Ltd.)
ACMD420) is stirred uniformly, 200g of water is added, the mixture is stirred uniformly and putAfter observation, no delamination and no insoluble substances are observed, a film is scraped on a clean glass plate by using a film coater, the thickness of the scraped film is controlled to be 100 micrometers, the scraped film is placed in a constant temperature (the temperature is 25 ℃) and constant humidity (the relative humidity is 50%) environment to be tested, and the performance test data of the hyperbranched alkyd resins of the examples 1-6 and the comparative example obtained by the test are shown in the following table:
TABLE 1 Performance test data for hyperbranched alkyds of examples 1-6 and comparative examples
Note:
surface drying time: the test is carried out by referring to a cotton blowing ball method in a method for measuring the drying time of paint films and putty films of GB/T1728-1979 (1989);
the actual drying time is as follows: the test is carried out by referring to a filter-press paper method in GB/T1728-1979 (1989) determination methods of drying time of paint films and putty films;
initial water resistance: standing the paint film for 2h in a constant temperature (the temperature is 25 ℃) and constant humidity (the relative humidity is 50%), then flowing water with the temperature of 20-25 ℃ from the upper end of the paint film to the bottom end of the paint film at a certain flow rate for 5min, observing the surface state of the paint film, and observing the surface state after the paint film is dried again;
24h water resistance: standing the paint film for 72h in a constant temperature (the temperature is 25 ℃) and constant humidity (the relative humidity is 50%) environment, observing the state of the paint film, testing the gloss of the paint film, soaking the glass plate with the paint film in deionized water, placing the glass plate in the constant temperature and constant humidity environment for 24h, taking out the glass plate to observe the surface state of the paint film, observing the surface state after the paint film is dried, and testing the gloss of the paint film after water soaking;
pencil hardness/scratch: standing the paint film for 72h in a constant temperature (the temperature is 25 ℃) and constant humidity (the relative humidity is 50%), and testing the surface hardness of the paint film by referring to GB/T6739-2006 color paint and varnish pencil method;
gloss/60 ° before water resistance test and gloss/60 ° after water resistance test: the paint film is firstly kept stand for 72 hours in a constant temperature (the temperature is 25 ℃) and humidity (the relative humidity is 50 percent), then the 60-degree gloss of the paint film is tested according to GB/T1743-1979 paint film gloss determination method, then the glass plate attached with the paint film is soaked in deionized water and is placed in a constant temperature and humidity environment for 24 hours, and then the 60-degree gloss of the paint film after the soaking of the paint film is tested after the surface of the paint film is taken out to be dry;
the paint film of the comparative example still did not reach full dryness due to the test at room temperature for 48h, and no continuous observation was subsequently made to test the full dry time of the comparative example.
As can be seen from Table 1:
a) the hyperbranched alkyd resins prepared in examples 1-6 all show excellent surface drying and actual drying speed, have excellent initial water resistance and 24h water resistance, and simultaneously have higher hardness, and the performances of the hyperbranched alkyd resins are remarkably superior to those of the hyperbranched alkyd resins prepared by adopting a conventional method in a comparative example, because: the hyperbranched alkyd resin prepared in the embodiments 1-6 has very high functionality, has a large number of double bonds at the tail end of polymer molecules, can be quickly dried through air catalytic crosslinking, and forms a compact paint film, so that the hyperbranched alkyd resin has very excellent physical properties;
b) the hyperbranched alkyd resins prepared in examples 1-6 contain a certain number of hydroxyl groups, and the hydroxyl group content is adjustable within the range of 0.5% -3.5%, so that the hyperbranched alkyd resins can be used in a two-component self-drying system.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of hyperbranched alkyd resin is characterized by comprising the following steps:
1) mixing organic acid anhydride and polyol to carry out prepolymerization, adding a catalyst, and carrying out polymerization reaction to obtain hyperbranched polyester polyol;
2) mixing hyperbranched polyester polyol with unsaturated monoacid or unsaturated monoacid-saturated monoacid compound for reaction to obtain a hyperbranched alkyd resin pre-product;
3) mixing the hyperbranched alkyd resin pre-product with trimellitic anhydride for reaction, adding a solvent for dilution, and adding alkali for neutralization to obtain the hyperbranched alkyd resin.
2. A method of preparing a hyperbranched alkyd resin according to claim 1, wherein: the organic acid anhydride in the step 1) is at least one of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, maleic anhydride and fumaric anhydride; the polyalcohol in the step 1) is at least one of glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol and sorbitol.
3. A method of preparing a hyperbranched alkyd resin according to claim 1 or 2, wherein: the molar ratio of the organic acid anhydride to the polyhydric alcohol in the step 1) is 1: 1.01-1.15.
4. A method of preparing a hyperbranched alkyd resin according to claim 1 or 2, wherein: the prepolymerization in the step 1) is carried out at the temperature of 80-140 ℃, and the reaction time is 1-4 h; the polymerization in the step 1) is carried out at 160-220 ℃, and the reaction time is 4-30 h.
5. A method of preparing a hyperbranched alkyd resin according to claim 1, wherein: the unsaturated monobasic acid in the step 2) is at least one of linoleic acid, eleostearic acid, dehydrated ricinoleic acid, high-iodine oleic acid, coconut oleic acid and palmitoleic acid; the saturated monoacid in the step 2) is at least one of benzoic acid, p-tert-butyl benzoic acid, isooctanoic acid, n-decanoic acid and stearic acid.
6. A method of preparing a hyperbranched alkyd resin according to claim 1 or 5, wherein: the molar ratio of hydroxyl in the hyperbranched polyester polyol to carboxyl in the unsaturated monoacid in the step 2) is 1.05-5.00: 1; the molar ratio of hydroxyl in the hyperbranched polyester polyol in the step 2) to carboxyl in the unsaturated monoacid-saturated monoacid compound is 1.05-5.00: 1.
7. A method of preparing a hyperbranched alkyd resin according to claim 1 or 5, wherein: the reaction in the step 2) is carried out at 160-220 ℃, and the reaction time is 4-24 h; the reaction in the step 3) is carried out at the temperature of 120-160 ℃, and the reaction time is 0.5-2 h.
8. A method of preparing a hyperbranched alkyd resin according to claim 1 or 5, wherein: and 3) the mass ratio of the hyperbranched alkyd resin pre-product to trimellitic anhydride in the step 3) is 1: 0.01-0.08.
9. A hyperbranched alkyd resin prepared by the method of any one of claims 1 to 8.
10. An aqueous industrial paint, characterized in that the composition comprises the hyperbranched alkyd resin according to claim 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678412A (en) * | 2022-11-10 | 2023-02-03 | 重庆三峡油漆股份有限公司 | Hyperbranched anticorrosive paint and preparation method thereof |
| 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 |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652501A (en) * | 1970-05-28 | 1972-03-28 | Eastman Kodak Co | Water soluble alkyd resins |
| US20030191236A1 (en) * | 2000-10-14 | 2003-10-09 | Buckmann Alfred Jean Paul | Polymeric aqueous coating compositions |
| CN101029123A (en) * | 2006-03-03 | 2007-09-05 | 同济大学 | Production of aqueous-dispersing alkyd resin |
| CN101148497A (en) * | 2007-10-22 | 2008-03-26 | 苏州巨峰绝缘材料有限公司 | Self-drying type water-solubility alkyd resin and preparation method thereof |
| CN101717564A (en) * | 2009-11-03 | 2010-06-02 | 上海大学 | Preparation method of aqueous hyperbranched polyester resin for paint |
| US20100267886A1 (en) * | 2007-11-19 | 2010-10-21 | Basf Se | Use of highly branched polymers in polymer dispersions for gloss colours |
| CN104086762A (en) * | 2013-08-16 | 2014-10-08 | 立邦工业涂料(上海)有限公司 | Hyperbranched polyester resin pigment dispersant as well as preparation method thereof, color paste and application of color paste |
| CN105669961A (en) * | 2016-02-02 | 2016-06-15 | 成都杰晟蜀邦新材料科技有限公司 | Highly branched alkyd resin with high solid content and low viscosity and preparation method of alkyd resin |
| CN106811034A (en) * | 2016-12-15 | 2017-06-09 | 芜湖浩权建筑工程有限公司 | A kind of water-based insulating paint material and preparation method thereof |
| CN106854277A (en) * | 2016-12-07 | 2017-06-16 | 陕西宝塔山油漆股份有限公司 | A kind of super quick-drying alkide resin and preparation method thereof |
| CN106947068A (en) * | 2017-02-20 | 2017-07-14 | 河北晨阳工贸集团有限公司 | Hyperbranched alkyd emulsion and preparation method thereof |
| CN106978049A (en) * | 2017-05-17 | 2017-07-25 | 河北晨阳工贸集团有限公司 | It is a kind of for aqueous benzoic acid modified alkyd resin of self-drying paint and preparation method thereof |
| CN109749069A (en) * | 2019-01-17 | 2019-05-14 | 广州致辉精化股份有限公司 | A kind of preparation method and applications of hyperbranched modified alkyd resin |
| US20210071029A1 (en) * | 2017-12-20 | 2021-03-11 | Akzo Nobel Coatings International B.V. | Alkyd for pigment paste |
-
2022
- 2022-05-25 CN CN202210576918.5A patent/CN114907552A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652501A (en) * | 1970-05-28 | 1972-03-28 | Eastman Kodak Co | Water soluble alkyd resins |
| GB1361546A (en) * | 1970-05-28 | 1974-07-24 | Eastman Kodak Co | Alkyd resins |
| US20030191236A1 (en) * | 2000-10-14 | 2003-10-09 | Buckmann Alfred Jean Paul | Polymeric aqueous coating compositions |
| CN101029123A (en) * | 2006-03-03 | 2007-09-05 | 同济大学 | Production of aqueous-dispersing alkyd resin |
| CN101148497A (en) * | 2007-10-22 | 2008-03-26 | 苏州巨峰绝缘材料有限公司 | Self-drying type water-solubility alkyd resin and preparation method thereof |
| US20100267886A1 (en) * | 2007-11-19 | 2010-10-21 | Basf Se | Use of highly branched polymers in polymer dispersions for gloss colours |
| CN101717564A (en) * | 2009-11-03 | 2010-06-02 | 上海大学 | Preparation method of aqueous hyperbranched polyester resin for paint |
| CN104086762A (en) * | 2013-08-16 | 2014-10-08 | 立邦工业涂料(上海)有限公司 | Hyperbranched polyester resin pigment dispersant as well as preparation method thereof, color paste and application of color paste |
| CN105669961A (en) * | 2016-02-02 | 2016-06-15 | 成都杰晟蜀邦新材料科技有限公司 | Highly branched alkyd resin with high solid content and low viscosity and preparation method of alkyd resin |
| CN106854277A (en) * | 2016-12-07 | 2017-06-16 | 陕西宝塔山油漆股份有限公司 | A kind of super quick-drying alkide resin and preparation method thereof |
| CN106811034A (en) * | 2016-12-15 | 2017-06-09 | 芜湖浩权建筑工程有限公司 | A kind of water-based insulating paint material and preparation method thereof |
| CN106947068A (en) * | 2017-02-20 | 2017-07-14 | 河北晨阳工贸集团有限公司 | Hyperbranched alkyd emulsion and preparation method thereof |
| CN106978049A (en) * | 2017-05-17 | 2017-07-25 | 河北晨阳工贸集团有限公司 | It is a kind of for aqueous benzoic acid modified alkyd resin of self-drying paint and preparation method thereof |
| US20210071029A1 (en) * | 2017-12-20 | 2021-03-11 | Akzo Nobel Coatings International B.V. | Alkyd for pigment paste |
| CN109749069A (en) * | 2019-01-17 | 2019-05-14 | 广州致辉精化股份有限公司 | A kind of preparation method and applications of hyperbranched modified alkyd resin |
Non-Patent Citations (2)
| Title |
|---|
| 刘国杰: "超支化水稀释性气干醇酸树脂涂料的制备与性能", 《中国涂料》 * |
| 张新荔: "脂肪族超支化聚酯在涂料中的应用研究进展", 《涂料工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115678412A (en) * | 2022-11-10 | 2023-02-03 | 重庆三峡油漆股份有限公司 | Hyperbranched anticorrosive paint and preparation method thereof |
| 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 |
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