CN115651173B - Bio-based water-based alkyd resin and preparation method and application thereof - Google Patents
Bio-based water-based alkyd resin and preparation method and application thereof Download PDFInfo
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- CN115651173B CN115651173B CN202211428535.XA CN202211428535A CN115651173B CN 115651173 B CN115651173 B CN 115651173B CN 202211428535 A CN202211428535 A CN 202211428535A CN 115651173 B CN115651173 B CN 115651173B
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- 229920000180 alkyd Polymers 0.000 title claims abstract description 163
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 239000002994 raw material Substances 0.000 claims abstract description 46
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 33
- 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 26
- 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 26
- 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 26
- 229920005862 polyol Polymers 0.000 claims abstract description 25
- 235000019486 Sunflower oil Nutrition 0.000 claims abstract description 18
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 18
- 239000001361 adipic acid Substances 0.000 claims abstract description 18
- 239000002600 sunflower oil Substances 0.000 claims abstract description 18
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 small molecule polyol Chemical class 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 69
- 238000006136 alcoholysis reaction Methods 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 25
- 238000000576 coating method Methods 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 238000005886 esterification reaction Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000006184 cosolvent Substances 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 239000002562 thickening agent Substances 0.000 claims description 8
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 239000000976 ink Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000013556 antirust agent Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 47
- 238000003860 storage Methods 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 238000013461 design Methods 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 21
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 20
- 235000011187 glycerol Nutrition 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 238000001816 cooling Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 230000032798 delamination Effects 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000036571 hydration Effects 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QMYDVDBERNLWKB-UHFFFAOYSA-N propane-1,2-diol;hydrate Chemical compound O.CC(O)CO QMYDVDBERNLWKB-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000015784 hyperosmotic salinity response Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008199 coating composition Substances 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 group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Paints Or Removers (AREA)
Abstract
The invention provides a bio-based water-based alkyd resin, and a preparation method and application thereof, wherein the preparation raw materials of the bio-based water-based alkyd resin comprise the following components in parts by weight: 20-30 parts of sunflower oil, 10-15 parts of small molecular polyalcohol, 0.01-0.1 part of catalyst, 10-20 parts of bio-based oligomer and 4-6 parts of N, N-dimethylethanolamine; the preparation raw materials of the bio-based oligomer comprise a combination of bio-based small molecule polyol, bio-based adipic acid and rosin. Through the design and mutual compounding of the preparation raw materials and the process, the bio-based water-based alkyd resin is more environment-friendly, remarkably improves the stability, has excellent water resistance, corrosion resistance, toughness and strength, and has excellent comprehensive performance. The water-based paint containing the bio-based water-based alkyd resin has excellent storage stability and workability, and a paint film has excellent adhesive force, water resistance and corrosion resistance, and is wide in application range.
Description
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a bio-based water-based alkyd resin, and a preparation method and application thereof.
Background
Petroleum belongs to non-renewable resources, and with the shortage of petroleum resources and the continuous rise of prices thereof, the market is increasingly calling for the use of renewable resources instead of traditional petroleum-based resources. In addition, paints/coatings and inks using petroleum as a raw material consume precious petroleum resources and emit a large amount of Volatile Organic Compounds (VOCs) into the air, thereby causing environmental pollution. Therefore, the development of environmentally friendly coatings, especially aqueous coatings, is becoming a major development direction for coatings.
Alkyd resin occupies a relatively large proportion in the paint, has the advantages of low-cost and easily available raw materials, good glossiness and fullness of a paint film, good adhesive force, good pigment wettability and the like, and is widely applied to the fields of wood paint, industrial paint, building paint and the like. With the rapid development of aqueous coatings, the waterborne nature of alkyd resins is also imperative.
One of the methods for the aqueous modification of alkyd resins is to emulsify the alkyd resin with a surfactant to obtain a water-dispersed alkyd resin. For example, CN104774544a discloses a water-based alkyd emulsion, a water-based alkyd varnish and a water-based alkyd color paint, wherein the water-based alkyd emulsion comprises the following raw materials in percentage by mass: 40-60% of alkyd base resin, 2-5% of alkaline compound, 2-5% of YX-001 nonionic emulsifier, 2-5% of YX-002 anionic emulsifier and 25-54% of deionized water; the alkyd base resin is prepared by esterification and polycondensation of soybean oleic acid, hyperbranched polyol, trimethylolpropane, pentaerythritol, benzoic acid, rosin, phthalic anhydride and isophthalic acid. The aqueous alkyd emulsion has uniform particle size distribution and higher cost performance, and has good application in the aspects of varnish and colored paint. However, the addition of a large amount of emulsifier in the emulsion affects the film forming performance of the paint, and the water resistance and the decoration of the paint film are poor, so that the original performance advantage of the alkyd resin is lost.
Another method for the waterborne treatment of alkyd resins is to prepare alkyd resins from monomers containing hydrophilic groups, which in turn form water-dilutable alkyd resins under the action of a cosolvent. For example, CN101942077a discloses a self-drying sulfonate group-containing water-dilutable alkyd resin, the synthetic formulation comprising, in weight percent: 20-30% of vegetable oil fatty acid, 2-5% of monocarboxylic acid, 20-30% of dihydric alcohol or polyhydric alcohol, 20-30% of polybasic carboxylic acid or polybasic anhydride, 2-5% of sulfonate group-containing functional monomer, 2-5% of glycidyl ester compound, 0.01-0.2% of catalyst and 20-30% of cosolvent. The water-dilutable alkyd resin does not need to use a large amount of emulsifier, but the emulsion viscosity is high, the workability is affected, and the water resistance of a paint film is poor.
The current common method for the water-based alkyd resin is a salification method, excessive carboxyl is introduced into alkyd molecules, and then a neutralizing agent is utilized to neutralize the carboxyl for salification, so that the water-soluble alkyd resin is obtained. For example CN102604517a discloses a high performance waterborne alkyd coating, which is prepared by the following steps: (a) Vegetable oil fatty acid and polybasic acid and polyalcohol react to obtain oily alkyd resin; (b) The oily alkyd resin reacts with trimellitic anhydride to obtain oily alkyd resin with excessive carboxyl; (c) Neutralizing the oily alkyd resin with excessive carboxyl by using a neutralizing agent to obtain water-based alkyd resin; (d) And mixing the water-based alkyd resin, the water-based amino resin and water, and adjusting the pH to obtain the water-based alkyd resin coating. The aqueous alkyd resin and the paint obtained by the salifying method have good film forming property, but have poor storage stability, so that the paint is extremely easy to have the problem of sedimentation and caking, great construction difficulty is brought, and the paint film has obvious insufficient resistance.
At present, the water-based alkyd resin has certain environmental protection problems besides the defects of the performance. The water-based alkyd and the water-based paint still use the synthetic emulsion taking the petroleum monomer as the raw material, so that the search for other resources for replacing petroleum as the raw material source for synthesizing the high polymer material becomes more and more important, and the obtained product for replacing the traditional petroleum product has important significance for environmental protection and saving of petroleum resources. In addition, certain solvent is needed in the common water-based paint, and the waste paint film cannot be biodegraded, so that the risks of environmental pollution and damage to human health are brought. Therefore, developing a resin and coating with excellent comprehensive performance and meeting the environmental protection requirement is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the bio-based water-based alkyd resin, and the preparation method and application thereof, and the design and the compounding of the preparation raw materials enable the bio-based water-based alkyd resin to be environment-friendly, reduce environmental pollution, have excellent stability and comprehensive performance, and serve as a film forming substance of the water-based paint, so that a paint film has excellent adhesive force, water resistance and corrosion resistance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a bio-based waterborne alkyd resin, which comprises the following raw materials in parts by weight:
the preparation raw materials of the bio-based oligomer comprise a combination of bio-based small molecule polyol, bio-based adipic acid and rosin.
In the bio-based water-based alkyd resin provided by the invention, firstly, bio-based micromolecular polyol, bio-based adipic acid and rosin are used as preparation raw materials to obtain a bio-based oligomer; then reacting the bio-based oligomer with sunflower oil and small-molecule polyol to obtain a prepolymer; and then neutralizing with N, N-dimethylethanolamine to obtain the bio-based waterborne alkyd resin. According to the invention, through the design of the preparation raw materials and the mutual compounding thereof, the compatibility of the specific bio-based oligomer and other components is particularly introduced, so that the dependence on petroleum resources is reduced, the significance on environmental protection is realized, the product stability of the bio-based water-based alkyd resin is obviously improved, the requirement of long-term stable storage can be met, and the bio-based water-based alkyd resin has excellent comprehensive performance. The bio-based water-based alkyd resin is used in water paint, has excellent storage stability and workability, forms a paint film, has good adhesive force, excellent corrosion resistance and excellent toughness and strength, can play a good role in alkali resistance and corrosion resistance, and is suitable for different substrates such as steel, walls, floors and the like.
In the preparation raw materials of the bio-based waterborne alkyd resin, the sunflower oil is 20-30 parts, for example, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts or 29 parts, and specific point values among the above point values are limited in space and in the interest of brevity, and the specific point values included in the range are not exhaustive.
The small molecule polyol is 10-15 parts, for example, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts or 14.5 parts, and specific point values between the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
The catalyst may be present in an amount of 0.01 to 0.1 parts, for example, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, or 0.09 parts, and specific point values between the above point values, are limited in length and for brevity, the present invention is not intended to be exhaustive list of the specific point values included in the range.
The biobased oligomer is 10-20 parts, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, or 19 parts, and specific point values between the above point values, are for brevity and for brevity, the invention is not intended to be exhaustive of the specific point values encompassed by the scope of the invention.
The N, N-dimethylethanolamine may be 4-6 parts, for example, 4.1 parts, 4.3 parts, 4.5 parts, 4.7 parts, 4.9 parts, 5 parts, 5.1 parts, 5.3 parts, 5.5 parts, 5.7 parts, or 5.9 parts, and specific point values between the above point values, and is not intended to be exhaustive or to limit the invention to the specific point values included in the range.
Preferably, the sunflower oil has an iodine value of 120-140g/100g, for example 122g/100g, 125g/100g, 126g/100g, 128g/100g, 130g/100g, 131g/100g, 133g/100g, 135g/100g, 137g/100g or 139g/100g, and specific point values between the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive list of the specific point values included in the range.
Preferably, the small molecule polyol comprises any one or a combination of at least two of glycerol, trimethylolpropane, propylene glycol, neopentyl glycol or diethylene glycol, more preferably glycerol, still more preferably bio-based glycerol.
Preferably, the catalyst comprises a metal hydroxide, further preferably lithium hydroxide.
Preferably, the preparation raw materials of the bio-based oligomer comprise the following components in parts by weight:
20-25 parts of bio-based micromolecular polyol
60-70 parts of bio-based adipic acid
10-15 parts of rosin.
In the preparation raw materials of the bio-based oligomer, the bio-based small molecule polyol is 20-25 parts, for example, 20.5 parts, 21 parts, 21.5 parts, 22 parts, 22.5 parts, 23 parts, 23.5 parts, 24 parts or 24.5 parts, and specific point values among the above point values are limited in length and for simplicity, and the present invention does not exhaustively list the specific point values included in the range.
The bio-based adipic acid is 60-70 parts, for example, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts or 69 parts, and specific point values between the above point values, are for brevity and for brevity, the present invention is not intended to be exhaustive of the specific point values included in the ranges.
The rosin may be 10-15 parts, for example, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts or 14.5 parts, and specific point values between the above point values, are limited in space and for brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
Preferably, the bio-based small molecule polyol comprises bio-based glycerol and/or bio-based propylene glycol, further preferably bio-based glycerol.
As a preferable technical scheme of the invention, the preparation raw materials of the bio-based oligomer comprise bio-based glycerin, bio-based adipic acid and rosin, and the bio-based glycerin, the bio-based adipic acid and the rosin are all bio-based substances, so that the preparation method is environment-friendly. Meanwhile, due to the design of the bio-based oligomer, the control difficulty of the preparation process of the bio-based water-based alkyd resin can be reduced, side reactions are reduced, the stability of the bio-based water-based alkyd resin is improved, the bio-based water-based alkyd resin is used as a film forming substance of a water-based paint, the paint is endowed with excellent storage stability and workability, and a paint film is endowed with excellent adhesive force, water resistance, salt resistance and corrosion resistance, and has good performance in toughness and strength.
Preferably, the rosin has an acid number of 160-180mg KOH/g, which may be, for example, 162mg KOH/g, 165mg KOH/g, 168mg KOH/g, 170mg KOH/g, 172mg KOH/g, 175mg KOH/g or 178mg KOH/g, and specific point values between the above point values, are limited in scope and for the sake of brevity the invention is not exhaustive list of the specific point values included in the range.
Preferably, the softening point of the rosin is 74-80 ℃, for example, 75 ℃, 76 ℃, 77 ℃, 78 ℃ or 79 ℃, and specific point values between the above point values, are not exhaustive of the specific point values included in the range for reasons of space and for reasons of simplicity.
Preferably, the acid value of the biobased oligomer is not more than 90mg KOH/g, and may be, for example, 85mg KOH/g, 80mg KOH/g, 75mg KOH/g, 70mg KOH/g, 65mg KOH/g, 60mg KOH/g, 55mg KOH/g, 50mg KOH/g, 45mg KOH/g, 40mg KOH/g, or the like.
Preferably, the biobased oligomer is prepared using a process comprising: and mixing the bio-based micromolecular polyol, bio-based adipic acid and rosin, and then reacting to obtain the bio-based oligomer.
Preferably, the reaction is carried out in the presence of an organic solvent.
Preferably, the organic solvent comprises an aromatic solvent, further preferably xylene.
Preferably, the bio-based oligomer is prepared from 10-20 parts by weight of an organic solvent, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts of an organic solvent, and specific point values between the above point values, are limited in space and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the temperature of the reaction is 160-200 ℃, for example 165 ℃, 170 ℃, 172 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃, 188 ℃, 190 ℃ or 195 ℃, and specific point values between the above point values, limited in space and for reasons of simplicity, the invention is not exhaustive of the specific point values comprised in the range, more preferably 175-185 ℃.
Preferably, the reaction time is 1-5h, for example, 1.25h, 1.5h, 1.75h, 2h, 2.25h, 2.5h, 2.75h, 3h, 3.25h, 3.5h, 3.75h, 4h, 4.25h, 4.5h or 4.75h, and specific point values between the above point values, are limited in length and for brevity, the invention is not exhaustive list of specific point values included in the range.
Preferably, the acid value of the system is monitored during the reaction, and the reaction is stopped when the acid value is less than or equal to 90mg KOH/g, so as to obtain the bio-based oligomer.
Preferably, the preparation raw materials further comprise 5-10 parts of a cosolvent in parts by weight, for example, the cosolvent may be 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts or 9.5 parts, and specific point values between the above point values are limited in length and for brevity, the present invention is not exhaustive to list the specific point values included in the range.
Preferably, the cosolvent comprises any one or a combination of at least two of propylene glycol butyl ether, ethylene glycol butyl ether or propylene glycol methyl ether, and further preferably propylene glycol butyl ether.
Preferably, the preparation raw materials further comprise 25-40 parts by weight of water, for example, the water may be 26 parts, 28 parts, 30 parts, 31 parts, 33 parts, 35 parts, 37 parts or 39 parts, and specific point values among the above point values, which are limited in space and for the sake of brevity, the present invention is not exhaustive.
As a preferable technical scheme of the invention, the preparation raw materials of the bio-based water-based alkyd resin comprise the following components in parts by weight:
in a second aspect, the present invention provides a method of preparing a bio-based waterborne alkyd according to the first aspect, the method comprising: carrying out alcoholysis reaction on the sunflower oil and the micromolecular polyol in the presence of a catalyst to obtain an alcoholysis product; the alcoholysis product and the bio-based oligomer are subjected to esterification reaction to obtain a prepolymer; and mixing the prepolymer with N, N-dimethylethanolamine to obtain the bio-based waterborne alkyd resin.
The bio-based water-based alkyd resin is prepared by a process of a step method, a bio-based low polymer is prepared by bio-based small molecular polyol, bio-based adipic acid and rosin, then, the sunflower oil and the small molecular polyol are subjected to alcoholysis reaction in the presence of a catalyst, and the alcoholysis product and the bio-based low polymer are subjected to esterification reaction to obtain a prepolymer; and neutralizing and hydrating with N, N-dimethyl ethanolamine to obtain the bio-based water-based alkyd resin. The invention reduces the control difficulty of the reaction process, improves the stability of the reaction product, further improves the stability of the final product and improves the comprehensive performance of the bio-based water-based alkyd resin through the design of the preparation raw materials and the synthesis process.
Preferably, the alcoholysis reaction is carried out at a temperature of 200-250 ℃, such as 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃, and specific values between the above values, are limited in space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the alcoholysis reaction is carried out for a period of time ranging from 0.5 to 3 hours, for example, from 0.75 hours, 1 hour, 1.25 hours, 1.5 hours, 1.75 hours, 2 hours, 2.25 hours, 2.5 hours or 2.75 hours, and specific point values between the above point values, are limited in length and for brevity, the invention is not intended to be exhaustive of the specific point values included in the range.
Preferably, the end point of the alcoholysis reaction is judged by adopting a method for testing ethanol tolerance, and when the solution in the reaction system is mixed with ethanol in a volume ratio of 1:5, the mixture is clear and transparent, which represents that the alcoholysis reaction is completed.
Preferably, the temperature of the esterification reaction is 200-240 ℃, and may be 205 ℃, 210 ℃, 215 ℃, 218 ℃, 220 ℃, 222 ℃, 225 ℃, 228 ℃, 230 ℃, 232 ℃ or 235 ℃, and specific point values between the above point values, for reasons of space and for reasons of simplicity, the present invention is not exhaustive of the specific point values included in the range, and further preferably 215-225 ℃.
Preferably, the time for the esterification reaction is 0.5 to 3 hours, for example, may be 0.75 hours, 1 hour, 1.25 hours, 1.5 hours, 1.75 hours, 2 hours, 2.25 hours, 2.5 hours or 2.75 hours, and specific point values between the above point values, are limited in length and for brevity, the present invention is not exhaustive of the specific point values included in the range.
Preferably, the acid value of the prepolymer is 50mg KOH/g or less, for example, the acid value may be 48mg KOH/g, 45mg KOH/g, 42mg KOH/g, 40mg KOH/g, 38mg KOH/g, 35mg KOH/g, 32mg KOH/g, 30mg KOH/g, 28mg KOH/g, 25mg KOH/g, 22mg KOH/g, 20mg KOH/g or the like.
Preferably, the acid value of the system is tested in the esterification reaction process until the acid value is less than or equal to 50mg KOH/g, and the prepolymer is obtained.
Preferably, the esterification reaction further comprises a step of removing an organic solvent (aromatic solvent) after completion.
Since the preparation process of the bio-based oligomer is performed in the presence of an organic solvent, the resulting bio-based oligomer includes the organic solvent; after the esterification reaction is finished, the residual organic solvent in the system needs to be removed. Preferably, the method of removal is distillation under reduced pressure.
Preferably, the temperature of the reduced pressure distillation is 170-190 ℃, e.g., 172 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃, 188 ℃, or the like.
Preferably, after the prepolymer and the N, N-dimethylethanolamine are uniformly mixed, a cosolvent and water are added, and the mixture is uniformly dispersed, so that the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid, is obtained.
Preferably, the preparation method specifically comprises the following steps:
mixing bio-based micromolecule polyalcohol, bio-based adipic acid, rosin and an organic solvent, and reacting at 160-200 ℃ until the acid value of a system is less than or equal to 90mg KOH/g to obtain the bio-based oligomer;
carrying out alcoholysis reaction on sunflower oil and small-molecule polyol for 0.5-3h at 200-250 ℃ in the presence of a catalyst to obtain an alcoholysis product;
the alcoholysis product and the bio-based oligomer are subjected to esterification reaction for 0.5-3h at the temperature of 200-240 ℃ until the acid value of the system is less than or equal to 50mg KOH/g, so as to obtain a prepolymer;
and removing the organic solvent in the prepolymer, uniformly mixing the prepolymer with N, N-dimethylethanolamine, adding a cosolvent and water, and uniformly dispersing to obtain the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid.
In a third aspect, the present invention provides the use of a bio-based waterborne alkyd as described in the first aspect in a coating, ink or adhesive.
In a fourth aspect, the present invention provides a waterborne alkyd coating comprising a biobased waterborne alkyd as described in the first aspect.
Preferably, the aqueous alkyd paint further comprises any one or a combination of at least two of drier, pigment, filler, dispersing agent, flash rust inhibitor or thickener.
Preferably, the drier is an aqueous drier.
Preferably, the water-based alkyd paint is an air-drying primer and comprises the following components in parts by weight:
the bio-based aqueous alkyd resin is 50-60 parts, and for example, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts or 59 parts and the like can be used.
The dispersant is 0.1 to 1 part, and for example, may be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or the like.
The pigment is 5-20 parts, and for example, 6 parts, 8 parts, 10 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts or the like can be used.
The filler is 5-30 parts, and for example, 6 parts, 8 parts, 10 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, 22 parts, 25 parts or 28 parts, etc.
The aqueous drier is 0.1-1 part, for example, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part or 0.9 part, etc.
The flash rust inhibitor is 0.1-1 part, for example, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part or 0.9 part, etc.
The thickener is 0.1-1 part, and for example, may be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, or 0.9 part, etc.
Preferably, the filler comprises barium sulphate and/or talc.
Preferably, the water-based alkyd paint (self-drying primer) also comprises water, so that the viscosity of the water-based alkyd paint meets the construction requirements.
Compared with the prior art, the invention has the following beneficial effects:
(1) In the bio-based water-based alkyd resin, through the design of the preparation raw materials and the mutual compounding of the preparation raw materials, the specific bio-based oligomer and the sunflower oil and other components are particularly compatible, so that the bio-based water-based alkyd resin not only has the advantages of reproducibility, reduced dependence on petroleum resources, more environment friendliness, but also remarkably improves the stability of the bio-based water-based alkyd resin, so that the bio-based water-based alkyd resin can meet the requirement of long-term stable storage, and has excellent water resistance, corrosion resistance, toughness and strength, and excellent comprehensive performance.
(2) The bio-based water-based alkyd resin is prepared by adopting a step method process, the control difficulty of a reaction process is low, side reactions are reduced, the operability is good, and the stability and the comprehensive performance of the product are obviously improved.
(3) The water-based paint containing the bio-based water-based alkyd resin has excellent storage stability, does not generate layering, sedimentation, caking or skinning phenomenon after long-term storage, is excellent in construction performance, has good paint film adhesive force, can reach 0 level, has salt water resistance of not less than 96 hours, has water resistance of not less than 120 hours, has excellent water resistance, salt resistance and corrosion resistance, has good toughness and strength, has the drying time of not more than 2.5 hours as a self-drying primer, has high drying speed, can play a good role in resisting salt, alkali and corrosion, has a wide application range, and has the advantages of no toxicity, low VOC and no heavy metal.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In the following embodiments of the present invention, all of the materials involved are commercially available products. For example, rosin is a commercially available product with a softening point of 74-80 ℃ and an acid value of 160-180mg KOH/g; the sunflower oil is a commercial product, and the iodine value is 120-140g/100g; the foregoing data is a product specification provided by the supplier.
Preparation example 1
The bio-based oligomer A1 comprises the following preparation raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A1 comprises the following steps: adding dimethylbenzene, bio-based glycerol, bio-based adipic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; continuously heating to 180 ℃ and preserving heat for 2 hours, and cooling when the acid value is smaller than 90mg KOH/g, thereby obtaining the bio-based oligomer A1.
Preparation example 2
The bio-based oligomer A2 comprises the following preparation raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A2 comprises the following steps: adding dimethylbenzene, bio-based glycerol, bio-based adipic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; continuously heating to 185 ℃ and preserving heat for 2 hours, and cooling when the acid value is smaller than 90mg KOH/g, thus obtaining the bio-based oligomer A3.
Preparation example 3
The bio-based oligomer A3 comprises the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A3 comprises the following steps: adding dimethylbenzene, bio-based glycerol, phthalic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; continuously heating to 180 ℃ and preserving heat for 2 hours, and cooling when the acid value is smaller than 90mg KOH/g, thereby obtaining the bio-based oligomer A3.
Preparation example 4
The bio-based oligomer A4 is prepared from the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A4 comprises the following steps: adding dimethylbenzene, bio-based glycerol, bio-based adipic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; continuously heating to 175 ℃ and preserving heat for 2 hours, and cooling when the acid value is smaller than 90mg KOH/g, thereby obtaining the bio-based oligomer A4.
Preparation example 5
The bio-based oligomer A5 comprises the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A5 comprises the following steps: adding dimethylbenzene, bio-based glycerol, bio-based adipic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; continuously heating to 180 ℃ and preserving heat for 2 hours, and cooling when the acid value is smaller than 90mg KOH/g, thereby obtaining the bio-based oligomer A5.
Preparation of comparative example 1
The bio-based oligomer B1 comprises the following preparation raw materials in parts by weight:
the specific preparation method of the bio-based oligomer B1 comprises the following steps: adding dimethylbenzene, bio-based glycerol, phthalic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; continuously heating to 230 ℃ and preserving heat for 2 hours, and cooling when the acid value is smaller than 90mg KOH/g, thereby obtaining the bio-based oligomer B1.
Example 1
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based water-based alkyd resin comprises the following steps:
(1) Simultaneously adding sunflower oil and glycerin into a reaction kettle according to the formula amount, starting heating, starting stirring, adding lithium hydroxide when the temperature is raised to 120 ℃, raising the temperature to 240 ℃ for alcoholysis reaction for 1.5 hours, clarifying and transparentizing after mixing the solution in the reaction system with ethanol in a volume ratio of 1:5, and ending alcoholysis to obtain an alcoholysis product;
(2) Cooling the reaction system to 120 ℃, adding the biobased oligomer A1 (preparation example 1), continuously heating to 220 ℃ and preserving heat for 1h until the acid value of the system is less than 50mg KOH/g, and obtaining the oligomer; cooling the reaction system to 180 ℃, and removing dimethylbenzene by reduced pressure distillation;
(3) And cooling the system to 70 ℃, adding N, N-dimethylethanolamine, stirring uniformly, then adding propylene glycol butyl ether and water, and dispersing uniformly to obtain the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid.
Example 2
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based water-based alkyd resin comprises the following steps:
(1) Simultaneously adding sunflower oil and glycerin into a reaction kettle according to the formula amount, starting heating, starting stirring, adding lithium hydroxide when the temperature is raised to 120 ℃, raising the temperature to 240 ℃ for alcoholysis reaction for 1.5 hours, clarifying and transparentizing after mixing the solution in the reaction system with ethanol in a volume ratio of 1:5, and ending alcoholysis to obtain an alcoholysis product;
(2) Cooling the reaction system to 120 ℃, adding the biobased oligomer A1 (preparation example 1), continuously heating to 220 ℃ and preserving heat for 1h until the acid value of the system is less than 50mg KOH/g, and obtaining the oligomer; cooling the reaction system to 180 ℃, and removing dimethylbenzene by reduced pressure distillation;
(3) And cooling the system to 70 ℃, adding N, N-dimethylethanolamine, stirring uniformly, then adding propylene glycol butyl ether and water, and dispersing uniformly to obtain the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid.
Example 3
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin is the same as that of the example 1.
Example 4
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin is the same as that of the example 1.
Examples 5 to 6
A biobased waterborne alkyd differing from example 1 only in that the biobased oligomer A1 therein was replaced with equal mass of biobased oligomer A4, biobased oligomer A5, respectively; other materials, proportions and preparation methods were the same as in example 1.
Comparative example 1
A bio-based waterborne alkyd resin differs from example 1 only in that N, N-dimethylethanolamine is replaced with an equivalent amount of diethylethanolamine, and the other materials, amounts and preparation methods are the same as in example 1.
Comparative example 2
A bio-based waterborne alkyd resin differs from example 1 only in that N, N-dimethylethanolamine is replaced with an equivalent amount of triethylamine, and other raw materials, amounts and preparation methods are the same as in example 1.
Comparative example 3
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin is the same as that of the example 1.
Comparative example 4
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin is the same as that of the example 1.
Comparative example 5
A biobased waterborne alkyd differing from example 1 only in that the biobased oligomer A1 therein was replaced with an equal mass of biobased oligomer B1; other materials, proportions and preparation methods were the same as in example 1.
Comparative example 6
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based water-based alkyd resin comprises the following steps:
(1) Adding the formula amount of sunflower oil and 12 parts of glycerol into a reaction kettle, heating and stirring, adding lithium hydroxide when the temperature is raised to 120 ℃, raising the temperature to 240 ℃ for alcoholysis reaction for 1.5 hours, and after the solution in the reaction system is mixed with ethanol in a volume ratio of 1:5, clarifying and transparentizing, ending alcoholysis, thus obtaining an alcoholysis product;
(2) Cooling the reaction system to 120 ℃, adding 10 parts of glycerin, adipic acid, rosin and xylene according to the formula, continuously heating to 220 ℃, and preserving heat for 1h until the acid value of the system is less than 50mg KOH/g, thus obtaining an oligomer; cooling the reaction system to 180 ℃, and removing dimethylbenzene by reduced pressure distillation;
(3) And cooling the system to 70 ℃, adding N, N-dimethylethanolamine, stirring uniformly, then adding propylene glycol butyl ether and water, and dispersing uniformly to obtain the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid.
Comparative example 7
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin is the same as that of the example 1.
Comparative example 8
The bio-based water-based alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin is the same as that of the example 1.
The biobased waterborne alkyd resins provided in examples 1-6, comparative examples 1-8 were subjected to the following performance tests:
(1) Appearance and uniformity: visually observing whether the sample is clear and transparent or has layering phenomenon;
(2) Fineness: testing was performed according to the method in the determination of the fineness of grind of GB/T1724-2019 paints, varnishes and printing inks;
(3) Degree of hydration: testing the uniformity degree of the bio-based water-based alkyd resin mixed with water in equal mass ratio; and (3) good: can be uniformly mixed after stirring; generally: after stirring, the materials are not uniformly mixed, but no obvious layering phenomenon exists; the difference is: obvious delamination appears after stirring;
(4) Smell: whether there is a pungent odor or the odor is of a magnitude;
the test results are shown in table 1:
TABLE 1
According to the performance test combined with Table 1, the preparation raw materials and the process design and the mutual compounding of the preparation raw materials enable the bio-based aqueous alkyd resin to have high degree of hydration, good stability, fineness less than or equal to 25 mu m, good uniformity, low fineness and no obvious irritant air temperature, and the bio-based aqueous alkyd resin dispersion is environment-friendly. In addition, by combining the test results of example 1 and examples 5-6, it is known that the bio-based waterborne alkyd resin with more excellent performance can be obtained by optimizing the component formula of the bio-based oligomer; if the alcohol content in the biobased oligomer is outside the preferred range (examples 5-6), it will affect the molecular weight and molecular weight distribution of the polymer and thus the homogeneity and degree of hydration of the biobased waterborne alkyd. Comparative examples 1-2 used diethylethanolamine and triethylamine as neutralizing agents, respectively, so that the obtained bio-based waterborne alkyd resin had a general degree of waterborne and had a pungent odor; the amount of biobased oligomer used in comparative examples 3-4 was outside the range defined by the present invention, and the resulting waterborne alkyd had poor reaction and delamination; the use of the bio-based oligomer B1 prepared from phthalic acid in comparative example 5 resulted in a reduced stability and degree of hydration of the waterborne alkyd; the bio-based oligomer is not adopted in the preparation of comparative example 6, but the bio-based aqueous alkyd resin is prepared by a conventional process, so that the bio-based aqueous alkyd resin has poor stability, low water-based degree and layering phenomenon after standing; the amount of glycerin used in comparative example 7 was outside the range defined in the present invention, and the amount of sunflower oil used in comparative example 8 was outside the range defined in the present invention, affecting the degree of reaction of the aqueous alkyd resin, thus resulting in delamination.
Application example
The water-based alkyd paint specifically comprises the following components in parts by weight:
wherein the bio-based aqueous alkyd resins are respectively provided in examples 1-5 and comparative examples 1-4, and the amounts are calculated by mass thereof; the dispersant is a commercially available anionic acrylate polymer (hyperdispersant 303); the pigment is titanium dioxide; the water-based drier is cobalt drier (HLD-061 drier); the flash rust inhibitor is SC2190Z type flash rust inhibitor; the thickener is a commercially available polyurethane thickener (PUR 80 thickener).
The preparation method of the water-based alkyd paint comprises the following steps: mixing bio-based water-based alkyd resin, a dispersing agent, pigment, talcum powder and barium sulfate according to the formula amount, and dispersing at the rotating speed of 700r/min for 10min until the mixture is uniform; then adding a water-based drier and an anti-flash rust agent, dispersing for 35min at 1500r/min, and grinding until the fineness is less than 50 mu m; and finally adding water and a thickening agent, stirring for 15min at 1100r/min until the water and the thickening agent are completely and uniformly mixed to obtain the water-based alkyd paint.
The performance test was carried out on the aforementioned aqueous alkyd coating by the method in Standard GB/T25251-2010 alkyd coating, the aqueous alkyd coating to be tested was applied to a substrate to form a paint film having a thickness of 150. Mu.m, and the following tests were carried out on the coating (before application) and the paint film (after film formation):
(1) State in the container: visually observing whether hard lumps exist in the coating, and judging whether the coating is in a uniform state after stirring, wherein the coating is uniform without hard lumps;
(2) And (3) construction: brushing whether there is an obstacle;
(3) Storage stability: whether layering, skinning and sedimentation occur or not in 48 hours;
(4) Drying time: the drying time is less than or equal to 5 hours, and the product is qualified;
(5) Salt water resistance: soaking a paint film to be tested in a 3% NaCl aqueous solution, and recording the time of foaming or rusting; if the test result is more than or equal to 96 hours, the phenomenon of foaming or rusting still does not occur after soaking for 96 hours;
(6) Adhesion force: testing by using a cross-hatch method;
(7) Water resistance: soaking a paint film to be tested in water, and recording the time of foaming or rusting; if the test result is more than or equal to 120 hours, the phenomenon of foaming or rusting still does not appear after soaking for 120 hours;
the test results are shown in tables 2 and 3:
TABLE 2
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| State in container | Qualified product | Qualified product | Qualified product | Qualified product | Slight delamination | Slight delamination |
| Workability of construction | Qualified product | Qualified product | Qualified product | Qualified product | Qualified product | Qualified product |
| Storage stability | Qualified product | Qualified product | Qualified product | Qualified product | Slight delamination | Slight delamination |
| Drying time (h) | 2 | 2.5 | 2.5 | 2 | 3.5 | 2.5 |
| Salt tolerance (h) | ≥96 | ≥96 | ≥96 | ≥96 | 96 | 72 |
| Adhesion force | Level 0 | Level 0 | Level 0 | Level 0 | Level 1 | Level 1 |
| Water resistance (h) | ≥120 | ≥120 | ≥120 | ≥120 | 96 | 96 |
TABLE 3 Table 3
As shown by the combination of the performance test results of Table 2, the bio-based water-based alkyd resin provided by the invention is used for preparing water-based paint, so that the paint has excellent storage stability, does not generate sedimentation, caking or skinning phenomenon after long-term storage, has excellent construction property, has good adhesion with a base material, can reach 0 level, has salt water resistance of more than or equal to 96 hours, has water resistance of more than or equal to 120 hours, has excellent water resistance, salt resistance and corrosion resistance, has the drying time of less than or equal to 2.5 hours as self-drying primer, has high drying speed, can play a good role in salt resistance, alkali resistance and corrosion resistance, and has the advantages of no toxicity, low VOC and no heavy metal. From the test results of example 1 and examples 5-6, it is known that bio-based aqueous alkyd resins and coatings with more excellent properties can be obtained by optimizing the component formulation of the bio-based oligomer; if the alcohol content in the biobased oligomer is outside the preferred range (examples 5-6), it will affect the molecular weight and molecular weight distribution of the polymer and thus the properties of the coating and paint film.
As is clear from the test results of tables 2 and 3, the bio-based aqueous alkyd resins of comparative examples 1-2 have a slightly lower degree of hydration and a slightly lower stability, so that the aqueous coating compositions containing them have poor storage stability, have delamination, and have reduced salt tolerance and adhesion. The proportions of the bio-based oligomer, the glycerol and the sunflower oil are adjusted in the comparative examples 3-4 and 7-8, so that the reaction degree of the bio-based water-based alkyd resin is not expected, and various performances of the water-based paint are poor; the biobased oligomer B1 used in the comparative example 5 is prepared from phthalic acid and glycerol, so that the stability and the degree of waterborne alkyd resin are reduced, the stability of the prepared waterborne coating is poor, and the paint film performance is poor; comparative example 6 is a bio-based waterborne alkyd prepared by a conventional process, and the bio-based oligomer disclosed by the invention is not adopted, so that the stability of the bio-based waterborne alkyd is poor, the storage stability of a water-based paint containing the bio-based waterborne alkyd is poor, the corrosion resistance (salt water resistance) and the adhesive force of a paint film are obviously insufficient, and the protection requirement of a primer cannot be met.
The applicant states that the present invention is illustrated by the above examples as a bio-based waterborne alkyd resin, and a method of making and using the same, but the present invention is not limited to, i.e., it is not meant that the present invention must be practiced in dependence upon, the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (32)
1. The bio-based aqueous alkyd resin is characterized by comprising the following raw materials in parts by weight:
the preparation raw materials of the bio-based oligomer comprise the following components in parts by weight:
20-25 parts of bio-based micromolecular polyol
60-70 parts of bio-based adipic acid
10-15 parts of rosin;
the bio-based waterborne alkyd resin is prepared by a method comprising the following steps: carrying out alcoholysis reaction on the sunflower oil and the micromolecular polyol in the presence of a catalyst to obtain an alcoholysis product; the alcoholysis product and the bio-based oligomer are subjected to esterification reaction to obtain a prepolymer; and mixing the prepolymer with N, N-dimethylethanolamine to obtain the bio-based waterborne alkyd resin.
2. The biobased waterborne alkyd of claim 1, wherein the sunflower oil has an iodine value of 120-140g/100g.
3. The biobased waterborne alkyd of claim 1, wherein the small molecule polyol comprises any one or a combination of at least two of glycerol, trimethylolpropane, propylene glycol, neopentyl glycol, or diethylene glycol.
4. The biobased waterborne alkyd of claim 1, wherein the small molecule polyol is glycerol.
5. The biobased waterborne alkyd of claim 1, wherein the small molecule polyol is biobased glycerol.
6. The biobased waterborne alkyd of claim 1, wherein the catalyst comprises a metal hydroxide.
7. The biobased waterborne alkyd according to claim 1, wherein the catalyst is lithium hydroxide.
8. The biobased waterborne alkyd of claim 1, wherein the biobased small molecule polyol comprises biobased glycerol and/or biobased propylene glycol.
9. The biobased waterborne alkyd of claim 1, wherein the biobased small molecule polyol is biobased glycerol.
10. The biobased waterborne alkyd resin of claim 1, wherein the rosin has an acid number of 160-180mg KOH/g.
11. The biobased waterborne alkyd resin of claim 1, wherein the softening point of the rosin is 74-80 ℃.
12. The biobased waterborne alkyd according to claim 1, wherein the biobased oligomer has an acid number of 90mg KOH/g or less.
13. The biobased waterborne alkyd of claim 1, wherein the biobased oligomer is prepared by a process comprising: and mixing the bio-based micromolecular polyol, bio-based adipic acid and rosin, and then reacting to obtain the bio-based oligomer.
14. The biobased waterborne alkyd according to claim 13, wherein the reaction is performed in the presence of an organic solvent.
15. The biobased waterborne alkyd of claim 14, wherein the organic solvent comprises an aromatic solvent.
16. The biobased waterborne alkyd according to claim 13, wherein the temperature of the reaction is 160-200 ℃.
17. The biobased waterborne alkyd according to claim 13, wherein the temperature of the reaction is 175-185 ℃.
18. The biobased waterborne alkyd according to claim 13, wherein the reaction time is 1-5 hours.
19. The biobased waterborne alkyd resin of claim 1, wherein the preparation raw material further comprises 5-10 parts by weight of a cosolvent.
20. The biobased waterborne alkyd of claim 19, wherein the co-solvent comprises any one or a combination of at least two of propylene glycol butyl ether, ethylene glycol butyl ether, or propylene glycol methyl ether.
21. The biobased waterborne alkyd resin of claim 1, wherein the preparation raw materials further comprise 25-40 parts by weight of water.
22. A method of preparing a biobased waterborne alkyd according to any of claims 1-21, wherein the method of preparing comprises: carrying out alcoholysis reaction on the sunflower oil and the micromolecular polyol in the presence of a catalyst to obtain an alcoholysis product; the alcoholysis product and the bio-based oligomer are subjected to esterification reaction to obtain a prepolymer; and mixing the prepolymer with N, N-dimethylethanolamine to obtain the bio-based waterborne alkyd resin.
23. The method of claim 22, wherein the alcoholysis reaction temperature is 200-250 ℃.
24. The method of claim 22, wherein the alcoholysis reaction is carried out for a period of time ranging from 0.5 to 3 hours.
25. The process of claim 22, wherein the temperature of the esterification reaction is 200-240 ℃.
26. The process of claim 22, wherein the esterification reaction is carried out for a period of time ranging from 0.5 to 3 hours.
27. The method of claim 22, wherein the prepolymer has an acid number of 50mg KOH/g or less.
28. The method of claim 22, wherein the bio-based waterborne alkyd is obtained by uniformly mixing the prepolymer with N, N-dimethylethanolamine, adding a cosolvent and water, and uniformly dispersing.
29. The preparation method according to claim 22, characterized in that it comprises in particular:
mixing bio-based micromolecule polyalcohol, bio-based adipic acid, rosin and an organic solvent, and reacting at 160-200 ℃ until the acid value of a system is less than or equal to 90mg KOH/g to obtain the bio-based oligomer;
carrying out alcoholysis reaction on sunflower oil and small-molecule polyol for 0.5-3h at 200-250 ℃ in the presence of a catalyst to obtain an alcoholysis product;
the alcoholysis product and the bio-based oligomer are subjected to esterification reaction for 0.5-3h at the temperature of 200-240 ℃ until the acid value of the system is less than or equal to 50mg KOH/g, so as to obtain a prepolymer;
and removing the organic solvent in the prepolymer, uniformly mixing the prepolymer with N, N-dimethylethanolamine, adding a cosolvent and water, and uniformly dispersing to obtain the bio-based waterborne alkyd resin.
30. Use of a bio-based waterborne alkyd according to any of claims 1-21 in a coating, ink or adhesive.
31. A waterborne alkyd coating comprising the biobased waterborne alkyd of any of claims 1-21.
32. The waterborne alkyd coating of claim 31, further comprising any one or a combination of at least two of a drier, pigment, filler, dispersant, anti-rust agent, or thickener.
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