CN111440298A - Aromatic ring and heterocyclic ring modified waterborne alkyd resin and preparation method thereof - Google Patents
Aromatic ring and heterocyclic ring modified waterborne alkyd resin and preparation method thereof Download PDFInfo
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- CN111440298A CN111440298A CN202010509791.6A CN202010509791A CN111440298A CN 111440298 A CN111440298 A CN 111440298A CN 202010509791 A CN202010509791 A CN 202010509791A CN 111440298 A CN111440298 A CN 111440298A
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- alkyd resin
- rosin
- dehydration
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- 229920000180 alkyd Polymers 0.000 title claims abstract description 73
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 43
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 70
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000010992 reflux Methods 0.000 claims abstract description 68
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 66
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 66
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 66
- 230000018044 dehydration Effects 0.000 claims abstract description 64
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 51
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 43
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 43
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000005642 Oleic acid Substances 0.000 claims abstract description 43
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 43
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 43
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 43
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- 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 38
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 35
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 35
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 35
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 35
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001816 cooling Methods 0.000 claims abstract description 26
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 13
- BDLXTDLGTWNUFM-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethanol Chemical compound CC(C)(C)OCCO BDLXTDLGTWNUFM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000007599 discharging Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 11
- 238000005086 pumping Methods 0.000 claims description 11
- 238000005070 sampling Methods 0.000 claims description 11
- 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 8
- 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 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 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 8
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 8
- 239000002023 wood Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract 1
- 238000000605 extraction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- -1 amine salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
- C08G63/21—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (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 an aromatic ring and heterocycle modified waterborne alkyd resin and a preparation method thereof, wherein the raw materials comprise 26-30 parts of oleic acid, 6-8 parts of rosin, 16-18 parts of benzoic acid, 18-22 parts of isophthalic acid, 50-53 parts of phthalic anhydride, 18-22 parts of trimethylolpropane, 6-8 parts of neopentyl glycol, 5-8 parts of dehydration solvent, 0.04-0.06 part of catalyst and 4-6 parts of trimellitic anhydride by weight, the materials are subjected to multistage heating, dehydration reflux, extraction of the dehydration solvent under the condition of a certain acid value, addition of trimellitic anhydride for heat preservation, and finally addition of propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the whole formula amount, stirring, cooling and discharging The water resistance and other physical and chemical properties are greatly improved, and the technology is remarkably improved in the field.
Description
Technical Field
The invention belongs to the field of resin production and processing, and particularly relates to a water-based alkyd resin for an industrial coating and a preparation method thereof.
Background
Among the resins for solvent-based coating, alkyd resin is the backbone resin for coating, and the yield is the largest, but the amount of organic solvent consumed by alkyd resin is the first in the coating industry. In the research field of reducing organic volatiles in alkyd resins, waterborne alkyd resins were the first to gain much attention from researchers. However, the alkyd resin has more ester bonds on the main chain of the molecule, is unstable to hydrolysis in a water medium, so that the resin is easy to degrade, and the activity of the drier is reduced, so that the waterborne alkyd is easy to lose dryness in storage. Although the research on the water-based alkyd paint is earlier than that of other water-based resin paints, the industrialization and commercialization of the water-based alkyd paint are greatly lagged behind that of other varieties.
The development of waterborne alkyds goes through two stages, namely an external emulsification stage and an internal emulsification stage. The external emulsification is to emulsify the conventional alkyd resin by using a method of adding a surfactant to obtain alkyd resin emulsion, and the system obtained by the method has poor storage stability, large particle size and poor paint film gloss. The internal emulsification process is currently used primarily for the synthesis of aqueous alkyd resin dispersions. Generally, alkyd resin is prepared into resin with higher acid value, and is neutralized into salt base by weak base, and the salt base is firstly dissolved in organic solvent such as alcohol ether and then dispersed in water. This is a class of resins known in the past as "water-soluble alkyds", which are essentially solutions of amine salts of the resins in organic solvents diluted with water to form fairly stable dispersions of polymer aggregates, and not alkyds that dissolve in water.
Disclosure of Invention
The problems to be solved by the invention are as follows:
1. the water-based alkyd resin is realized, so that the alkyd resin becomes an environment-friendly and low-pollution product for coating;
2. the drying property, the initial water resistance and other properties of the waterborne alkyd resin are improved through modification;
3. by introducing structures such as aromatic rings, heterocyclic rings and the like into the alkyd resin molecules, the physical and mechanical properties and chemical properties of the resin such as gloss, hardness, wear resistance and the like are improved.
In order to achieve the purpose, the invention researches an aromatic ring and heterocyclic ring modified waterborne alkyd resin, which comprises the following raw materials, by weight, 26-30 parts of oleic acid, 6-8 parts of rosin, 16-18 parts of benzoic acid, 18-22 parts of isophthalic acid, 50-53 parts of phthalic anhydride, 18-22 parts of trimethylolpropane, 6-8 parts of neopentyl glycol, 5-8 parts of a dehydration solvent, 0.04-0.06 part of a catalyst and 4-6 parts of trimellitic anhydride.
Preferably, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 28 parts of oleic acid, 6 parts of rosin, 16 parts of benzoic acid, 20 parts of isophthalic acid, 51 parts of phthalic anhydride, 19 parts of trimethylolpropane, 7 parts of neopentyl glycol, 6 parts of a dehydration solvent, 0.04 part of a catalyst and 4 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Preferably, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 26 parts of oleic acid, 7 parts of rosin, 17 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 20 parts of trimethylolpropane, 8 parts of neopentyl glycol, 5 parts of a dehydration solvent, 0.05 part of a catalyst and 4 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Preferably, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 29 parts of oleic acid, 8 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 21 parts of trimethylolpropane, 8 parts of neopentyl glycol, 8 parts of a dehydration solvent, 0.05 part of a catalyst and 5 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Preferably, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 30 parts of oleic acid, 7 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 52 parts of phthalic anhydride, 18 parts of trimethylolpropane, 6 parts of neopentyl glycol, 7 parts of a dehydration solvent, 0.05 part of a catalyst and 5 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Preferably, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 27 parts of oleic acid, 8 parts of rosin, 18 parts of benzoic acid, 22 parts of isophthalic acid, 50 parts of phthalic anhydride, 21 parts of trimethylolpropane, 6 parts of neopentyl glycol, 8 parts of a dehydration solvent, 0.06 part of a catalyst and 6 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Preferably, the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or two of gum rosin and wood rosin.
Preferably, the preparation method of the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
s1, putting 26-30 parts of oleic acid, 6-8 parts of rosin, 16-18 parts of benzoic acid, 18-22 parts of isophthalic acid, 50-53 parts of phthalic anhydride, 18-22 parts of trimethylolpropane, 6-8 parts of neopentyl glycol, 5-8 parts of a dehydration solvent and 0.04-0.06 part of a catalyst into a reaction kettle in one step, uniformly stirring, heating to 80-100 ℃, and preserving heat for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling and measuring the acid value to be 16-20mgKOH/g, and stopping the reaction;
s2, cooling to 180 ℃, starting a vacuum pump, pumping out the dehydration solvent under negative pressure (about 40 minutes), and stopping the negative pressure when the dehydration solvent in the reflux condenser is pumped out in a drop shape; keeping the temperature at 170-180 ℃, adding 4-6 parts of trimellitic anhydride, and reacting at the temperature for about 45 minutes;
s3, cooling to 120-130 ℃ after the reaction is finished, adding propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula amount, stirring for 20-30 minutes, cooling to 80-90 ℃, and discharging to obtain the modified waterborne alkyd resin.
Preferably, the preparation method of the other aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
s1, putting 26 parts of oleic acid, 7 parts of rosin, 17 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 20 parts of trimethylolpropane, 8 parts of neopentyl glycol, 5 parts of a dehydration solvent, 0.05 part of a catalyst and 4 parts of trimellitic anhydride into a reaction kettle in one step by weight, uniformly stirring, heating to 80-100 ℃, and preserving heat for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling to measure that the acid value is 17mgKOH/g, and stopping the reaction;
s2, cooling to 180 ℃, starting a vacuum pump, pumping out the dehydration solvent under negative pressure (about 40 minutes), and stopping the negative pressure when the dehydration solvent in the reflux condenser is pumped out in a drop shape; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
s3, cooling to 120-130 ℃ after the reaction is finished, adding propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula amount, stirring for 20-30 minutes, cooling to 80-90 ℃, and discharging to obtain the modified waterborne alkyd resin.
Preferably, the preparation method of the other aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
s1, putting 30 parts of oleic acid, 7 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 52 parts of phthalic anhydride, 18 parts of trimethylolpropane, 6 parts of neopentyl glycol, 7 parts of a dehydration solvent, 0.05 part of a catalyst and 5 parts of trimellitic anhydride into a reaction kettle in one step by weight, uniformly stirring, heating to 80-100 ℃, and preserving heat for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling and measuring the acid value to be 16mgKOH/g, and stopping the reaction;
s2, cooling to 180 ℃, starting a vacuum pump, pumping out the dehydration solvent under negative pressure (about 40 minutes), and stopping the negative pressure when the dehydration solvent in the reflux condenser is pumped out in a drop shape; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
s3, cooling to 120-130 ℃ after the reaction is finished, adding propylene glycol methyl ether and ethylene glycol tert-butyl ether solution which accounts for 20-25% of the total formula weight, stirring for 20-30 minutes, cooling to 80-90 ℃, and discharging to obtain the modified waterborne alkyd resin.
The innovation points of the invention are as follows:
(a) hydrophilic monomers are introduced into the alkyd resin molecules by a condensation polymerization method, and the water-based property of the resin is tested. The monomer can provide hydrophilic performance and can be partially crosslinked into a net structure, so that the molecular weight of the waterborne alkyd resin is improved, and the performance is further improved;
(b) various performances of water resistance, machinery and the like of the water-based alkyd resin are improved by introducing aromatic rings, rosin and other heterocycles. The special structure of the aromatic ring can increase the hardness, the wear resistance and other properties of the resin; the characteristics of larger steric resistance in a rosin structure are utilized, the hardness, the drying speed and the glossiness of a resin film are improved, the hydrolysis resistance and the chemical resistance of the water-based resin can also be improved, and the viscosity of a system can be reduced to a certain extent;
(c) the resin water-based treatment can be realized by adopting a one-time feeding method, and the process is simple; the product has low VOC content, is safe and environment-friendly, and meets the environmental protection policy of national and market requirements;
(d) the process of reflux dehydration after multi-stage temperature rise is an innovative point of the invention, and the process has the beneficial effects that: the molecular weight of the resin can be improved, and the crosslinking degree can be increased; the risk of overflowing the pot is small, and the production safety is improved; the molecular weight distribution is more uniform, and the resin performance is improved.
Due to the innovation, the aromatic ring and heterocyclic ring modified waterborne alkyd resin prepared by the invention has great improvement on the aspects of dryness, water resistance and other physical and chemical properties, and has obvious technical progress in the field.
Detailed Description
Example 1
The aromatic ring and heterocyclic ring modified waterborne alkyd resin disclosed by the invention comprises the following raw materials of 28 parts of oleic acid, 6 parts of rosin, 16 parts of benzoic acid, 20 parts of isophthalic acid, 51 parts of phthalic anhydride, 19 parts of trimethylolpropane, 7 parts of neopentyl glycol and 6 parts of a dehydration solvent; 0.04 part of catalyst and 4 parts of trimellitic anhydride, wherein the parts are by weight.
Wherein the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or more of gum rosin, wood rosin and rosin of Songjiang oil.
The preparation method of the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
(1) oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like are put into a reaction kettle at one time, stirred uniformly, heated to 80-100 ℃, and kept warm for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling to measure that the acid value is 18mgKOH/g, and stopping the reaction;
(2) cooling to 180 deg.C, opening vacuum pump, pumping out dewatering solvent under negative pressure (about 40 min), and stopping negative pressure when the dewatering solvent in reflux condenser is pumped out in drop form; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
(3) after the reaction is finished, cooling to 120-130 ℃, adding propylene glycol methyl ether and ethylene glycol tert-butyl ether solution which accounts for 20-25% of the total formula weight, stirring for 20-30 minutes, cooling to 80-90 ℃, and discharging to obtain the aromatic ring and heterocyclic ring modified waterborne alkyd resin.
Example 2
The aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following raw materials of 26 parts of oleic acid, 7 parts of rosin, 17 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 20 parts of trimethylolpropane, 8 parts of neopentyl glycol and 5 parts of a dehydration solvent; 0.05 part of catalyst and 4 parts of trimellitic anhydride, wherein the parts are by weight.
Wherein the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or more of gum rosin, wood rosin and rosin of Songjiang oil.
The preparation method of the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
(1) oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like are put into a reaction kettle at one time, stirred uniformly, heated to 80-100 ℃, and kept warm for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling to measure that the acid value is 17mgKOH/g, and stopping the reaction;
(2) cooling to 180 deg.C, opening vacuum pump, pumping out dewatering solvent under negative pressure (about 40 min), and stopping negative pressure when the dewatering solvent in reflux condenser is pumped out in drop form; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
(3) after the reaction is finished, the temperature is reduced to 120-130 ℃, propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula weight are added, the mixture is stirred for 20-30 minutes and then cooled to 80-90 ℃, and the modified waterborne alkyd resin is obtained after discharging.
Example 3
The aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following raw materials of 29 parts of oleic acid, 8 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 21 parts of trimethylolpropane, 8 parts of neopentyl glycol and 8 parts of a dehydration solvent; 0.05 part of catalyst and 5 parts of trimellitic anhydride, wherein the parts are by weight.
Wherein the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or more of gum rosin, wood rosin and rosin of Songjiang oil.
The preparation method of the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
(1) oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like are put into a reaction kettle at one time, stirred uniformly, heated to 80-100 ℃, and kept warm for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling and measuring the acid value to be 19mgKOH/g, and stopping the reaction;
(2) cooling to 180 deg.C, opening vacuum pump, pumping out dewatering solvent under negative pressure (about 40 min), and stopping negative pressure when the dewatering solvent in reflux condenser is pumped out in drop form; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
(3) after the reaction is finished, the temperature is reduced to 120-130 ℃, propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula weight are added, the mixture is stirred for 20-30 minutes and then cooled to 80-90 ℃, and the modified waterborne alkyd resin is obtained after discharging.
Example 4
The aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following raw materials of 30 parts of oleic acid, 7 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 52 parts of phthalic anhydride, 18 parts of trimethylolpropane, 6 parts of neopentyl glycol and 7 parts of a dehydration solvent; 0.05 part of catalyst and 5 parts of trimellitic anhydride, wherein the parts are by weight.
Wherein the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or more of gum rosin, wood rosin and rosin of Songjiang oil.
The preparation method of the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
(1) oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like are put into a reaction kettle at one time, stirred uniformly, heated to 80-100 ℃, and kept warm for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling and measuring the acid value to be 16mgKOH/g, and stopping the reaction;
(2) cooling to 180 deg.C, opening vacuum pump, pumping out dewatering solvent under negative pressure (about 40 min), and stopping negative pressure when the dewatering solvent in reflux condenser is pumped out in drop form; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
(3) after the reaction is finished, the temperature is reduced to 120-130 ℃, propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula weight are added, the mixture is stirred for 20-30 minutes and then cooled to 80-90 ℃, and the modified waterborne alkyd resin is obtained after discharging.
Example 5
The aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following raw materials of 27 parts of oleic acid, 8 parts of rosin, 18 parts of benzoic acid, 22 parts of isophthalic acid, 50 parts of phthalic anhydride, 21 parts of trimethylolpropane, 6 parts of neopentyl glycol and 8 parts of a dehydration solvent; 0.06 part of catalyst and 6 parts of trimellitic anhydride, wherein the parts are by weight.
Wherein the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or more of gum rosin, wood rosin and rosin of Songjiang oil.
The preparation method of the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises the following steps:
(1) oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like are put into a reaction kettle at one time, stirred uniformly, heated to 80-100 ℃, and kept warm for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling to measure the acid value to be 20mgKOH/g, and stopping the reaction;
(2) cooling to 180 deg.C, opening vacuum pump, pumping out dewatering solvent under negative pressure (about 40 min), and stopping negative pressure when the dewatering solvent in reflux condenser is pumped out in drop form; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
(3) after the reaction is finished, the temperature is reduced to 120-130 ℃, propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula weight are added, the mixture is stirred for 20-30 minutes and then cooled to 80-90 ℃, and the modified waterborne alkyd resin is obtained after discharging.
The resin obtained in the embodiment and a resin product of the same type of an enterprise in the same industry are prepared into a gray finish together, and the test performance is as follows:
TABLE 1 results of performance testing of coatings prepared from the resins of examples 1-5
The data in table 1 show that the invention has excellent performances and is far higher than the index requirements specified by the national standard. Compared with the same type of products, the invention has great advantages in the performances of water resistance, salt spray resistance, flash rust resistance, drying time and the like, wherein the solution described in the example 2 has the minimum volatile matter content, the solution described in the example 4 has the minimum drying time, and the other solutions have the advantages and the disadvantages and can be selected to be adaptive according to the needs.
Example 6
The aromatic ring and heterocyclic ring modified waterborne alkyd resin disclosed by the invention comprises the following raw materials, by weight, 26-30 parts of oleic acid, 6-8 parts of rosin, 16-18 parts of benzoic acid, 18-22 parts of isophthalic acid, 50-53 parts of phthalic anhydride, 18-22 parts of trimethylolpropane, 6-8 parts of neopentyl glycol, 5-8 parts of a dehydration solvent, 0.04-0.06 part of a catalyst and 4-6 parts of trimellitic anhydride.
More specifically, the preparation raw material of the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprises 28 parts of oleic acid, 6 parts of rosin, 16 parts of benzoic acid, 20 parts of isophthalic acid, 51 parts of phthalic anhydride, 19 parts of trimethylolpropane, 7 parts of neopentyl glycol, 6 parts of a dehydration solvent, 0.04 part of a catalyst and 4 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Or more specifically, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 26 parts by weight of oleic acid, 7 parts by weight of rosin, 17 parts by weight of benzoic acid, 19 parts by weight of isophthalic acid, 53 parts by weight of phthalic anhydride, 20 parts by weight of trimethylolpropane, 8 parts by weight of neopentyl glycol, 5 parts by weight of a dehydration solvent, 0.05 part by weight of a catalyst and 4 parts by weight of trimellitic anhydride.
Or more specifically, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 29 parts of oleic acid, 8 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 21 parts of trimethylolpropane, 8 parts of neopentyl glycol, 8 parts of a dehydration solvent, 0.05 part of a catalyst and 5 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Or more specifically, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 30 parts of oleic acid, 7 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 52 parts of phthalic anhydride, 18 parts of trimethylolpropane, 6 parts of neopentyl glycol, 7 parts of a dehydration solvent, 0.05 part of a catalyst and 5 parts of trimellitic anhydride, wherein the parts are calculated by weight.
Or more specifically, the raw materials for preparing the aromatic ring and heterocyclic ring modified waterborne alkyd resin comprise 27 parts of oleic acid, 8 parts of rosin, 18 parts of benzoic acid, 22 parts of isophthalic acid, 50 parts of phthalic anhydride, 21 parts of trimethylolpropane, 6 parts of neopentyl glycol, 8 parts of a dehydration solvent, 0.06 part of a catalyst and 6 parts of trimellitic anhydride, wherein the parts are calculated by weight.
More specifically, the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or two of gum rosin and wood rosin.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. An aromatic ring and heterocyclic ring modified waterborne alkyd resin is characterized in that: the raw materials comprise, by weight, 26-30 parts of oleic acid, 6-8 parts of rosin, 16-18 parts of benzoic acid, 18-22 parts of isophthalic acid, 50-53 parts of phthalic anhydride, 18-22 parts of trimethylolpropane, 6-8 parts of neopentyl glycol, 5-8 parts of a dehydration solvent, 0.04-0.06 part of a catalyst and 4-6 parts of trimellitic anhydride.
2. The aromatic ring and heterocycle modified waterborne alkyd resin of claim 1, wherein: the raw materials comprise 28 parts of oleic acid, 6 parts of rosin, 16 parts of benzoic acid, 20 parts of isophthalic acid, 51 parts of phthalic anhydride, 19 parts of trimethylolpropane, 7 parts of neopentyl glycol, 6 parts of a dehydration solvent, 0.04 part of a catalyst and 4 parts of trimellitic anhydride, wherein the parts are by weight.
3. The aromatic ring and heterocycle modified waterborne alkyd resin of claim 1, wherein: the raw materials comprise 26 parts of oleic acid, 7 parts of rosin, 17 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 20 parts of trimethylolpropane, 8 parts of neopentyl glycol, 5 parts of a dehydration solvent, 0.05 part of a catalyst and 4 parts of trimellitic anhydride, wherein the parts are calculated by weight.
4. The aromatic ring and heterocycle modified waterborne alkyd resin of claim 1, wherein: the raw materials comprise 29 parts of oleic acid, 8 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 53 parts of phthalic anhydride, 21 parts of trimethylolpropane, 8 parts of neopentyl glycol, 8 parts of a dehydration solvent, 0.05 part of a catalyst and 5 parts of trimellitic anhydride, wherein the parts are by weight.
5. The aromatic ring and heterocycle modified waterborne alkyd resin of claim 1, wherein: the raw materials comprise 30 parts of oleic acid, 7 parts of rosin, 16 parts of benzoic acid, 19 parts of isophthalic acid, 52 parts of phthalic anhydride, 18 parts of trimethylolpropane, 6 parts of neopentyl glycol, 7 parts of a dehydration solvent, 0.05 part of a catalyst and 5 parts of trimellitic anhydride, wherein the parts are by weight.
6. The aromatic ring and heterocycle modified waterborne alkyd resin of claim 1, wherein: the raw materials comprise 27 parts of oleic acid, 8 parts of rosin, 18 parts of benzoic acid, 22 parts of isophthalic acid, 50 parts of phthalic anhydride, 21 parts of trimethylolpropane, 6 parts of neopentyl glycol, 8 parts of a dehydration solvent, 0.06 part of a catalyst and 6 parts of trimellitic anhydride, wherein the parts are calculated by weight.
7. The aromatic ring and heterocycle modified waterborne alkyd resin of any of claims 1-6, wherein: the catalyst is one or two of dibutyltin dilaurate and di-n-butyltin oxide in organotin; the oleic acid is one or more of linoleic acid, eleostearic acid and dehydrated ricinoleic acid; the rosin is one or two of gum rosin and wood rosin.
8. A preparation method of aromatic ring and heterocycle modified waterborne alkyd resin is characterized by comprising the following steps: the method comprises the following steps:
s1, putting oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like which are prepared according to any one of the proportions in claims 1 to 6 into a reaction kettle at one time, uniformly stirring, heating to 80-100 ℃, and preserving heat for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling and measuring the acid value to be 16-20mgKOH/g, and stopping the reaction;
s2, cooling to 180 ℃, starting a vacuum pump, pumping out the dehydration solvent under negative pressure (about 40 minutes), and stopping the negative pressure when the dehydration solvent in the reflux condenser is pumped out in a drop shape; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
s3, cooling to 120-130 ℃ after the reaction is finished, adding propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula amount, stirring for 20-30 minutes, cooling to 80-90 ℃, and discharging to obtain the modified waterborne alkyd resin.
9. The process for preparing aromatic ring-and-heterocyclic ring-modified waterborne alkyd resin according to claim 8, wherein: the method comprises the following steps:
s1, putting oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like which are proportioned according to the proportion in claim 3 into a reaction kettle at one time, uniformly stirring, heating to 80-100 ℃, and preserving heat for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling to measure that the acid value is 17mgKOH/g, and stopping the reaction;
s2, cooling to 180 ℃, starting a vacuum pump, pumping out the dehydration solvent under negative pressure (about 40 minutes), and stopping the negative pressure when the dehydration solvent in the reflux condenser is pumped out in a drop shape; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
s3, cooling to 120-130 ℃ after the reaction is finished, adding propylene glycol methyl ether and ethylene glycol tert-butyl ether solution accounting for 20-25% of the total formula amount, stirring for 20-30 minutes, cooling to 80-90 ℃, and discharging to obtain the modified waterborne alkyd resin.
10. The process for preparing aromatic ring-and-heterocyclic ring-modified waterborne alkyd resin according to claim 8, wherein: the method comprises the following steps:
s1, putting oleic acid, rosin, benzoic acid, isophthalic acid, phthalic anhydride, trimethylolpropane, neopentyl glycol, a catalyst and the like which are proportioned according to the proportion in claim 5 into a reaction kettle at one time, uniformly stirring, heating to 80-100 ℃, and preserving heat for 30-40 minutes; continuously raising the temperature to 170-180 ℃ at the speed of 1 ℃ per minute, and performing reflux dehydration for 1 hour; heating to 180 ℃ and 190 ℃, and dehydrating under reflux for 1 hour; heating to 190 ℃ and 200 ℃, and dehydrating under reflux for 1 hour; continuously heating to 200-215 ℃, and refluxing and dehydrating for 1.5-2 hours; then the temperature is increased to 215 ℃ and 230 ℃, and the reflux dehydration is carried out for 1.5 to 2 hours; sampling and measuring the acid value to be 16mgKOH/g, and stopping the reaction;
s2, cooling to 180 ℃, starting a vacuum pump, pumping out the dehydration solvent under negative pressure (about 40 minutes), and stopping the negative pressure when the dehydration solvent in the reflux condenser is pumped out in a drop shape; keeping the temperature at 170-180 ℃, adding trimellitic anhydride, and reacting for about 45 minutes at the temperature;
s3, cooling to 120-130 ℃ after the reaction is finished, adding propylene glycol methyl ether and ethylene glycol tert-butyl ether solution which accounts for 20-25% of the total formula weight, stirring for 20-30 minutes, cooling to 80-90 ℃, and discharging to obtain the modified waterborne alkyd resin.
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