CN115651173A - Bio-based waterborne alkyd resin and preparation method and application thereof - Google Patents
Bio-based waterborne alkyd resin and preparation method and application thereof Download PDFInfo
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- CN115651173A CN115651173A CN202211428535.XA CN202211428535A CN115651173A CN 115651173 A CN115651173 A CN 115651173A CN 202211428535 A CN202211428535 A CN 202211428535A CN 115651173 A CN115651173 A CN 115651173A
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- alkyd resin
- waterborne alkyd
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- 229920000180 alkyd Polymers 0.000 title claims abstract description 147
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 77
- 239000003973 paint Substances 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 50
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 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
- 238000000034 method Methods 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 24
- 239000001361 adipic acid Substances 0.000 claims abstract description 18
- 235000011037 adipic acid Nutrition 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- 235000019486 Sunflower oil Nutrition 0.000 claims abstract description 17
- 239000002600 sunflower oil Substances 0.000 claims abstract description 17
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 6
- 230000001070 adhesive effect Effects 0.000 claims abstract description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000000576 coating method Methods 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 26
- 238000006136 alcoholysis reaction Methods 0.000 claims description 22
- 239000011248 coating agent Substances 0.000 claims description 21
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 238000005886 esterification reaction Methods 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
- 238000002156 mixing Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- -1 small molecule polyol Chemical class 0.000 claims description 7
- 239000002562 thickening agent Substances 0.000 claims description 7
- 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 239000000203 mixture 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
- 230000035484 reaction time Effects 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
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 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
- 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
- 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
- 238000010438 heat treatment Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- 230000032798 delamination Effects 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000243 solution 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
- 238000010276 construction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000006185 dispersion Substances 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
- 238000004062 sedimentation Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 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
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000013065 commercial product Substances 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
- 238000005187 foaming Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000227 grinding 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
- 239000000463 material Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007086 side reaction Methods 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
- 239000005711 Benzoic acid Substances 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 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
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229920003180 amino resin Polymers 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
- 230000015572 biosynthetic process 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
- 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 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
- 230000032050 esterification Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 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
- 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 waterborne alkyd resin as well as a preparation method and application thereof, wherein the bio-based waterborne alkyd resin comprises the following raw materials in parts by weight: 20-30 parts of sunflower oil, 10-15 parts of small molecular polyol, 0.01-0.1 part of catalyst, 10-20 parts of bio-based oligomer and 4-6 parts of N, N-dimethylethanolamine; the raw materials for preparing the bio-based oligomer comprise a combination of bio-based small molecular polyol, bio-based adipic acid and rosin. Through the design of the preparation raw materials and processes and the mutual compounding of the raw materials and the processes, the bio-based waterborne alkyd resin is more environment-friendly, the stability is obviously improved, and the bio-based waterborne alkyd resin has excellent water resistance, corrosion resistance, toughness and strength and 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 waterborne alkyd resin as well as 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 the price of petroleum resources, the market calls for using renewable resources to replace traditional petroleum-based resources more and more. In addition, the paint/coating and ink using petroleum as raw material not only consumes valuable petroleum resources, but also discharges a large amount of Volatile Organic Compounds (VOC) into the air, thereby bringing about the problem of environmental pollution. Therefore, the development of environment-friendly coatings is becoming a serious issue, and especially water-based coatings are becoming the main development direction of coatings.
The alkyd resin occupies a large proportion in the paint, has the advantages of cheap and easily-obtained 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 water-based paint, the water-based alkyd resin is also imperative.
One of the methods for making an alkyd resin aqueous is to emulsify the alkyd resin with a surfactant to obtain a water-dispersible alkyd resin. For example, CN104774544A discloses a water-based alkyd emulsion, a water-based alkyd varnish and a water-based alkyd paint, wherein the water-based alkyd emulsion is composed of the following raw materials by mass percent: 40-60% alkyd base resin, 2-5% alkaline compound, 2-5% YX-001 nonionic emulsifier, 2-5% YX-002 anionic emulsifier, 25-54% deionized water; wherein the alkyd base resin is prepared by esterification and polycondensation of soya-bean oil acid, hyperbranched polyol, trimethylolpropane, pentaerythritol, benzoic acid, rosin, phthalic anhydride and isophthalic acid. The waterborne alkyd emulsion has the advantages of uniform particle size distribution and high cost performance, and has good application in varnish and colored paint. However, the addition of a large amount of emulsifier in the emulsion can affect the film-forming property of the paint, and the water resistance and the decoration of the paint film are not good, so that the original performance advantages of the alkyd resin are lost.
Another method for the aquosity of the alkyd resin is to prepare the alkyd resin by using a monomer containing a hydrophilic group, and then form the water-dilutable alkyd resin under the action of a cosolvent. For example, CN101942077A discloses a self-drying water-dilutable alkyd resin containing sulfonate groups, 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 acid 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 has high viscosity, which affects the workability, and the water resistance of a paint film is poor.
The existing method for water-based curing of alkyd resin is a salt-forming method, wherein excessive carboxyl is introduced into alkyd molecules, and then neutralization is carried out on the carboxyl by using a neutralizing agent to form salt, so as to obtain the water-soluble alkyd resin. For example, CN102604517A discloses a high-performance water-based alkyd resin coating, which is prepared by the following steps: (a) Vegetable oil fatty acid, polybasic acid and polyalcohol react to obtain oily alkyd resin; (b) Reacting the oily alkyd resin 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 a water-based alkyd resin; (d) And (3) mixing the water-based alkyd resin with the water-based amino resin and water, and adjusting the pH value to obtain the water-based alkyd resin coating. The water-based alkyd resin and paint obtained by a salt forming method have good film forming property, but the water-based alkyd resin and paint have poor storage stability, so that the paint is easy to settle and agglomerate, great construction difficulty is brought, and the resistance of a paint film is obviously insufficient.
At present, the waterborne alkyd resin has certain environmental protection problems besides the defects in performance. The water-based alkyd and the water-based paint still use the synthetic emulsion taking petroleum monomers as raw materials, and the search of other resources for replacing petroleum as raw material sources for synthesizing high polymer materials becomes more and more important, so that the obtained product has important significance for environmental protection and petroleum resource saving by replacing the traditional petroleum product. In addition, a certain amount of solvent is needed in the common water-based paint, and the waste paint film cannot be biodegraded, thereby bringing the risks of environmental pollution and damage to human health. Therefore, the development of a resin and a coating which have excellent comprehensive performance and meet 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 waterborne alkyd resin and the preparation method and the application thereof, through the design and compounding of the preparation raw materials, the bio-based waterborne alkyd resin is green and environment-friendly, reduces the environmental pollution, has excellent stability and comprehensive performance, and can be used as a film forming substance of a waterborne coating to ensure that a paint film has excellent adhesive force, water resistance and corrosion resistance.
In order 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 is prepared from the following raw materials in parts by weight:
the raw materials for preparing the bio-based oligomer comprise a combination of bio-based small molecular polyol, bio-based adipic acid and rosin.
In the bio-based waterborne 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 bio-based oligomer; then reacting the bio-based oligomer with sunflower oil and micromolecular polyol to obtain a prepolymer; and neutralizing with N, N-dimethylethanolamine to obtain the bio-based waterborne alkyd resin. According to the invention, through the design and mutual compounding of the preparation raw materials, especially the introduction of specific bio-based oligomer for compatibility with other components, not only is the dependence on petroleum resources reduced and the important significance on environmental protection is achieved, but also the product stability of the bio-based waterborne alkyd resin is obviously improved, the requirement of long-term stable storage can be met, and the bio-based waterborne alkyd resin has excellent comprehensive performance. The bio-based water-based alkyd resin is used in water-based paint, has excellent storage stability and workability, good adhesion of a formed paint film, excellent corrosion resistance, excellent toughness and strength, can play a good alkali resistance and corrosion resistance role, and is suitable for different substrates such as steel, wall surfaces, ground surfaces and the like.
In the raw materials for preparing 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 points between the above points are limited by space and for simplicity, and the invention is 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 the specific values therebetween are not exhaustive and are not included for brevity.
The catalyst is present in an amount of 0.01 to 0.1 parts, and may be, 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 the specific values therebetween are not exhaustive, and for the sake of brevity and clarity, the invention is not intended to be limited to the specific values encompassed by the scope disclosed herein.
The bio-based oligomer is present in 10-20 parts, for example 11, 12, 13, 14, 15, 16, 17, 18 or 19 parts, and the specific points between the above are not exhaustive for the invention and are not intended to limit the scope of the invention to the specific points included in the recited range for brevity and clarity.
The N, N-dimethylethanolamine is present in 4 to 6 parts, and may for example be 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 values therebetween are not exhaustive and the invention is not intended to include specific values within the stated range for the sake of brevity and conciseness.
Preferably, the iodine value of the sunflower oil is 120-140g/100g, such as 122g/100g, 125g/100g, 126g/100g, 128g/100g, 130g/100g, 131g/100g, 133g/100g, 135g/100g, 137g/100g or 139g/100g, and the specific values therebetween are limited in space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the small molecule polyol comprises any one of glycerol, trimethylolpropane, propylene glycol, neopentyl glycol or diethylene glycol or a combination of at least two of glycerol, glycerol is further preferred, and bio-based glycerol is further preferred.
Preferably, the catalyst comprises a metal hydroxide, further preferably lithium hydroxide.
Preferably, the raw materials for preparing the bio-based oligomer comprise the following components in parts by weight:
20-25 parts of bio-based small molecular polyol
60-70 parts of bio-based adipic acid
10-15 parts of rosin.
The bio-based small molecule polyol is 20-25 parts, such as 20.5 parts, 21 parts, 21.5 parts, 22 parts, 22.5 parts, 23 parts, 23.5 parts, 24 parts or 24.5 parts, in the raw material for preparing the bio-based oligomer, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not intended to be limited to the specific values included in the range.
The bio-based adipic acid is 60 to 70 parts, for example 61, 62, 63, 64, 65, 66, 67, 68 or 69 parts, and specific values therebetween, not exhaustive of the included ranges for purposes of brevity and clarity.
The rosin is 10 to 15 parts, for example 10.5, 11, 11.5, 12, 12.5, 13, 13.5, 14 or 14.5 parts, and specific values therebetween, not to be exhaustive of the specific values included in the range for brevity and conciseness.
Preferably, the bio-based small molecule polyol comprises bio-based glycerol and/or bio-based propylene glycol, further preferably bio-based glycerol.
As the preferable technical scheme of the invention, the preparation raw material of the bio-based oligomer comprises the combination of bio-based glycerol, bio-based adipic acid and rosin, and the three are all bio-based substances, so that the bio-based oligomer is green and environment-friendly. Meanwhile, the design of the bio-based oligomer can reduce the control difficulty of the preparation process of the bio-based waterborne alkyd resin, reduce the occurrence of side reactions, improve the stability of the bio-based waterborne alkyd resin, enable the bio-based waterborne alkyd resin to be used as a film forming substance of a waterborne coating, endow the coating with excellent storage stability and construction property, enable a paint film to have excellent adhesive force, water resistance, salt resistance and corrosion resistance, and have good performances in the aspects of 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 the specific values therebetween, are not intended to be exhaustive and for the sake of brevity.
Preferably, the softening point of the rosin is from 74 to 80 ℃, for example 75 ℃, 76 ℃, 77 ℃, 78 ℃ or 79 ℃, and specific values therebetween, are not exhaustive for the invention and for the sake of brevity.
Preferably, the acid value of the bio-based oligomer is 90mg KOH/g or less, 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, or 40mg KOH/g, or the like.
Preferably, the bio-based oligomer is prepared using a method comprising: mixing bio-based micromolecular polyalcohol, 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 raw material for preparing the bio-based oligomer comprises 10-20 parts by weight of the organic solvent, for example, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts or 19 parts by weight of the organic solvent, and specific points between the above points are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction temperature is 160-200 ℃, for example, 165 ℃, 170 ℃, 172 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃, 188 ℃, 190 ℃ or 195 ℃, and the specific values therebetween, and the invention is not exhaustive and for the sake of brevity only, and the specific values included in the range are further preferably 175-185 ℃.
Preferably, the reaction time is 1 to 5 hours, for example, 1.25 hours, 1.5 hours, 1.75 hours, 2 hours, 2.25 hours, 2.5 hours, 2.75 hours, 3 hours, 3.25 hours, 3.5 hours, 3.75 hours, 4 hours, 4.25 hours, 4.5 hours or 4.75 hours, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the acid value of the system is monitored during the reaction process, 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 raw materials for preparation further comprise 5-10 parts by weight of cosolvent, for example, the cosolvent can 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 values between the above values are limited by space and for conciseness, and the invention is not exhaustive to list the specific 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 is further preferably propylene glycol butyl ether.
Preferably, the preparation raw material further comprises 25-40 parts by weight of water, for example, the water can be 26 parts, 28 parts, 30 parts, 31 parts, 33 parts, 35 parts, 37 parts or 39 parts, and specific points between the above points are limited by space and for conciseness, and the invention is not exhaustive enumeration of specific points included in the range.
As a preferable technical scheme of the invention, the preparation raw materials of the bio-based waterborne 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 resin as described in the first aspect, the method comprising: carrying out alcoholysis reaction on sunflower oil and small molecular polyol in the presence of a catalyst to obtain an alcoholysis product; carrying out esterification reaction on the alcoholysis product and a bio-based oligomer to obtain a prepolymer; and mixing the prepolymer with N, N-dimethylethanolamine for water-based hydration to obtain the bio-based water-based alkyd resin.
The bio-based waterborne alkyd resin provided by the invention is prepared by a step-by-step process, firstly, bio-based micromolecular polyol, bio-based adipic acid and rosin are used for preparing bio-based oligomer, and then, after alcoholysis reaction of sunflower oil and micromolecular polyol in the presence of a catalyst, esterification reaction is carried out on the alcoholysis product and the bio-based oligomer to obtain a prepolymer; and then neutralizing and hydrating by 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 synthesis process, the control difficulty of the reaction process is reduced, the stability of the reaction product is improved, the stability of the final product is further improved, and the comprehensive performance of the bio-based waterborne alkyd resin is improved.
Preferably, the alcoholysis reaction is carried out at a temperature of 200 to 250 ℃ and may be, for example, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ or 245 ℃, and the specific values therebetween are not intended to be exhaustive and for the sake of brevity.
Preferably, the alcoholysis reaction is carried out for a period of time of 0.5 to 3 hours, for example, 0.75 hour, 1 hour, 1.25 hour, 1.5 hour, 1.75 hour, 2 hours, 2.25 hours, 2.5 hours or 2.75 hours, and the specific values therebetween are not exhaustive, and the invention is not intended to limit the scope to the specific values included in the range for brevity and conciseness.
Preferably, the end point of the alcoholysis reaction is judged by a method for testing ethanol tolerance, and when the solution in the reaction system is mixed with ethanol in a volume ratio of 1.
Preferably, the temperature of the esterification reaction is 200 to 240 ℃, for example, 205 ℃, 210 ℃, 215 ℃, 218 ℃, 220 ℃, 222 ℃, 225 ℃, 228 ℃, 230 ℃, 232 ℃ or 235 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range, and further preferably 215 to 225 ℃.
Preferably, the esterification reaction time is 0.5 to 3 hours, for example, 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 values therebetween, which are not exhaustive and included in the range for reasons of brevity and clarity.
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, or 20mg KOH/g, and the like.
Preferably, the acid value of the system is tested in the esterification reaction process, and the esterification reaction is completed when the acid value is less than or equal to 50mg KOH/g, so as to obtain the prepolymer.
Preferably, the esterification reaction further comprises a step of removing the organic solvent (aromatic solvent) after completion.
Because the preparation process of the bio-based oligomer is carried out in the presence of an organic solvent, the obtained bio-based oligomer comprises the organic solvent; after the esterification reaction is finished, the residual organic solvent in the system needs to be removed. Preferably, the removal method is distillation under reduced pressure.
Preferably, the temperature of the reduced pressure distillation is 170-190 ℃, such as 172 ℃, 175 ℃, 178 ℃, 180 ℃, 182 ℃, 185 ℃ or 188 ℃, etc.
Preferably, the prepolymer and N, N-dimethylethanolamine are uniformly mixed, then a cosolvent and water are added, and uniform dispersion is performed, so that the bio-based waterborne alkyd resin is obtained, namely the bio-based waterborne alkyd resin dispersion.
Preferably, the preparation method specifically comprises:
mixing bio-based micromolecular polyol, bio-based adipic acid, rosin and an organic solvent, and reacting at 160-200 ℃ until the acid value of the system is less than or equal to 90mg KOH/g to obtain a bio-based oligomer;
carrying out alcoholysis reaction on sunflower oil and small molecular polyol at 200-250 ℃ for 0.5-3h in the presence of a catalyst to obtain an alcoholysis product;
carrying out esterification reaction on the alcoholysis product and a bio-based oligomer at 200-240 ℃ for 0.5-3h until the acid value of a system is less than or equal to 50mg KOH/g 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 a use of a bio-based waterborne alkyd resin according to the first aspect in a coating, ink or adhesive.
In a fourth aspect, the present invention provides a waterborne alkyd coating comprising a bio-based waterborne alkyd resin according to the first aspect.
Preferably, the water-based alkyd paint also comprises any one of a drier, a pigment, a filler, a dispersant, an anti-flash rust agent or a thickening agent or the combination of at least two of the two.
Preferably, the drier is an aqueous drier.
Preferably, the water-based alkyd paint is a self-drying primer, and comprises the following components in parts by weight:
wherein, the bio-based waterborne alkyd resin is 50-60 parts, for example, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts or 59 parts, etc.
The dispersant may be present in an amount of 0.1 to 1 part, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 parts.
The pigment is 5-20 parts, for example, 6 parts, 8 parts, 10 parts, 11 parts, 13 parts, 15 parts, 17 parts or 19 parts.
The filler is 5 to 30 parts, and may be, for example, 6 parts, 8 parts, 10 parts, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, 20 parts, 22 parts, 25 parts, 28 parts, or the like.
The aqueous drier is 0.1 to 1 part, and may be, 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.
The flash rust inhibitor is 0.1 to 1 part, and may be, 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.
The thickener is 0.1 to 1 part, and may be, 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.
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) According to the bio-based waterborne alkyd resin provided by the invention, through the design and mutual compounding of the preparation raw materials, especially the specific bio-based oligomer is compatible with sunflower oil and other components, so that the bio-based waterborne alkyd resin has the advantages of reproducibility, reduction of dependence on petroleum resources, greenness and environmental protection, and remarkable improvement of the stability of the bio-based waterborne 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 waterborne alkyd resin is prepared by adopting a step-by-step process, the control difficulty of the reaction process is low, the occurrence of side reactions is 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, can not generate the phenomena of layering, sedimentation, caking or skinning after long-term storage, has excellent application property, good paint film adhesion which can reach 0 grade, has the salt water resistance of more than or equal to 96 hours and the water resistance of more than or equal to 120 hours, has excellent water resistance, salt tolerance and corrosion resistance, has good toughness and strength, has the drying time of less than or equal to 2.5 hours when being used as an air-drying primer, has high drying speed, can play good roles of salt resistance, alkali resistance and corrosion resistance, has wide application range, and has the advantages of no toxicity, low VOC and no heavy metal.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
In the following embodiments of the present invention, the raw materials are all commercially available products. For example, rosin is a commercial product, the softening point is 74-80 ℃, and the acid value is 160-180mg KOH/g; the sunflower oil is a commercial product, and the iodine value is 120-140g/100g; the aforementioned data is the product specification provided by the supplier.
Preparation example 1
The bio-based oligomer A1 is prepared from the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A1 is as follows: 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; and continuously heating to 180 ℃, preserving the temperature for 2h, and cooling when the reaction is carried out until the acid value is less than 90mg KOH/g to obtain the bio-based oligomer A1.
Preparation example 2
The bio-based oligomer A2 is prepared from the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A2 is as follows: 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; and continuously heating to 185 ℃, preserving the heat for 2 hours, and cooling when the reaction is carried out until the acid value is less than 90mg KOH/g, thereby obtaining the bio-based oligomer A3.
Preparation example 3
The bio-based oligomer A3 is prepared from the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A3 is as follows: adding dimethylbenzene, bio-based glycerol, phthalic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; and continuously heating to 180 ℃, preserving the temperature for 2h, and cooling when the reaction is carried out until the acid value is less than 90mg KOH/g, thus 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; and continuously heating to 175 ℃, preserving the temperature for 2h, and cooling when the reaction is carried out until the acid value is less than 90mg KOH/g, thereby obtaining the bio-based oligomer A4.
Preparation example 5
The bio-based oligomer A5 is prepared from the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer A5 is as follows: 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; and continuously heating to 180 ℃, preserving the temperature for 2h, and cooling when the reaction is carried out until the acid value is less than 90mg KOH/g, thereby obtaining the bio-based oligomer A5.
Preparation of comparative example 1
The bio-based oligomer B1 is prepared from the following raw materials in parts by weight:
the specific preparation method of the bio-based oligomer B1 is as follows: adding dimethylbenzene, bio-based glycerol, phthalic acid and rosin into a reaction kettle according to the formula amount, heating to 150 ℃, and starting stirring; and continuously heating to 230 ℃, preserving the temperature for 2h, and cooling when the reaction is carried out until the acid value is less than 90mg KOH/g, thereby obtaining the bio-based oligomer B1.
Example 1
The bio-based waterborne alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin comprises the following steps:
(1) Simultaneously putting the sunflower oil and the glycerol into a reaction kettle according to the formula amount, starting to heat, starting stirring, adding lithium hydroxide when the temperature is raised to 120 ℃, raising the temperature to 240 ℃ to perform alcoholysis reaction for 1.5 hours until the solution in the reaction system is mixed with ethanol in a volume ratio of 1;
(2) Cooling the reaction system to 120 ℃, adding the bio-based oligomer A1 (preparation example 1), continuously heating to 220 ℃, and keeping the temperature for 1h until the acid value of the system is less than 50mg KOH/g, thus 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, uniformly stirring, then adding propylene glycol butyl ether and water, and uniformly dispersing to obtain the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid.
Example 2
The bio-based waterborne alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin comprises the following steps:
(1) Simultaneously putting the sunflower oil and the glycerol into a reaction kettle according to the formula amount, starting to heat, starting stirring, adding lithium hydroxide when the temperature is raised to 120 ℃, raising the temperature to 240 ℃ to perform alcoholysis reaction for 1.5 hours until the solution in the reaction system is mixed with ethanol in a volume ratio of 1;
(2) Cooling the reaction system to 120 ℃, adding the bio-based oligomer A1 (preparation example 1), continuously heating to 220 ℃, and keeping the temperature for 1h until the acid value of the system is less than 50mg KOH/g, thereby 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, uniformly stirring, then adding propylene glycol butyl ether and water, and uniformly dispersing to obtain the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid.
Example 3
The bio-based waterborne 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 example 1.
Example 4
The bio-based waterborne 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 example 1.
Examples 5 to 6
A bio-based waterborne alkyd resin, which is different from the alkyd resin in example 1 only in that bio-based oligomer A1 is replaced by equal mass of bio-based oligomer A4 and equal mass of bio-based oligomer A5; other materials, ratios and preparation methods were the same as in example 1.
Comparative example 1
A bio-based waterborne alkyd resin, which differs from example 1 only in that N, N-dimethylethanolamine is replaced by an equal amount of diethylethanolamine, and the other raw materials, amounts, and preparation methods are the same as those of example 1.
Comparative example 2
A bio-based waterborne alkyd resin differs from example 1 only in that N, N-dimethylethanolamine is replaced by an equal amount of triethylamine, and other raw materials, amounts and preparation methods are the same as those in example 1.
Comparative example 3
The bio-based waterborne 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 example 1.
Comparative example 4
The bio-based waterborne 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 example 1.
Comparative example 5
A bio-based waterborne alkyd resin differing from example 1 only in that bio-based oligomer A1 therein is replaced with an equal mass of bio-based oligomer B1; other materials, ratios and preparation methods were the same as in example 1.
Comparative example 6
The bio-based waterborne alkyd resin comprises the following raw materials in parts by weight:
the preparation method of the bio-based waterborne alkyd resin comprises the following steps:
(1) Adding sunflower oil and 12 parts of glycerol according to the formula ratio into a reaction kettle, heating and stirring, adding lithium hydroxide when the temperature is raised to 120 ℃, heating to 240 ℃ to perform alcoholysis reaction for 1.5h, mixing the solution in the reaction system and ethanol according to a volume ratio of 1;
(2) Cooling the reaction system to 120 ℃, adding 10 parts of glycerol, adipic acid, rosin and xylene according to the formula amount, continuously heating to 220 ℃, and keeping the temperature for 1h until the acid value of the system is less than 50mg KOH/g, thereby 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, uniformly stirring, then adding propylene glycol butyl ether and water, and uniformly dispersing to obtain the bio-based waterborne alkyd resin, namely the bio-based waterborne alkyd resin dispersoid.
Comparative example 7
The bio-based waterborne 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 example 1.
Comparative example 8
The bio-based waterborne 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 example 1.
The following performance tests were performed on the bio-based waterborne alkyd resins provided in examples 1-6 and comparative examples 1-8:
(1) Appearance and uniformity: visually observing whether the sample is clear and transparent or not and whether the layering phenomenon exists or not;
(2) Fineness: testing according to the method for determining the grinding fineness of the GB/T1724-2019 colored paint, varnish and printing ink;
(3) Degree of hydration: testing the uniformity of the bio-based waterborne alkyd resin mixed with water in equal mass proportion; well: after stirring, the components can be uniformly mixed; in general: the mixture is not mixed evenly after being stirred, but no obvious layering phenomenon exists; difference: obvious layering appears after stirring;
(4) Odor: whether or not there is pungent smell and the size of the smell;
the test results are shown in table 1:
TABLE 1
According to the performance test in the table 1, the invention has the advantages that through the design of the preparation raw materials and the preparation process and the mutual compounding of the raw materials and the process, the bio-based waterborne alkyd resin has high waterborne degree, good stability, fineness of less than or equal to 25 mu m, good uniformity, low fineness and no obvious pungent temperature, and is a green and environment-friendly bio-based waterborne alkyd resin dispersion. In addition, the test results of the example 1 and the examples 5-6 are combined to show that the invention can obtain the bio-based waterborne alkyd resin with more excellent performance by optimizing the component formula of the bio-based oligomer; if the alcohol content of the bio-based 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 the degree of hydrogamy of the bio-based waterborne alkyd resin. In comparative examples 1-2, diethylethanolamine and triethylamine are respectively used as neutralizing agents, so that the obtained bio-based water-based alkyd resin has a general water-based degree and has pungent odor; in comparative examples 3 to 4, the amount of the bio-based oligomer was outside the range defined in the present invention, and the resulting waterborne alkyd resin had poor reaction degree and had delamination; the use of bio-based oligomer B1 prepared with phthalic acid in comparative example 5 resulted in a reduction in the stability and the degree of waterborne alkyd resin; in the preparation of comparative example 6, the bio-based oligomer is not adopted, but the bio-based waterborne alkyd resin is prepared by a conventional process, so that the bio-based waterborne alkyd resin has poor stability, low waterborne degree and layering phenomenon after standing; the amount of glycerol in comparative example 7 is outside the range defined by the present invention, and the amount of sunflower oil in comparative example 8 is outside the range defined by the present invention, affecting the degree of reaction of the waterborne alkyd resin, thus resulting in delamination.
Application example
A water-based alkyd paint is specifically a self-drying primer, and comprises the following components in parts by weight:
wherein, the bio-based waterborne alkyd resins are respectively provided in examples 1-5 and comparative examples 1-4, and the dosage is calculated by the mass; 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 anti-flash rust agent is SC2190Z type anti-flash rust agent; 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 waterborne alkyd resin, a dispersant, pigment, talcum powder and barium sulfate according to the formula amount, and dispersing at the rotating speed of 700r/min for 10min to be uniform; then adding a water-based drier and an anti-flash rust agent, dispersing for 35min at 1500r/min, and grinding to a fineness of less than 50 μm; and finally, adding water and a thickening agent, and stirring at 1100r/min for 15min until the mixture is completely and uniformly mixed to obtain the water-based alkyd paint.
The performance test of the waterborne alkyd paint is carried out by a method in GB/T25251-2010 alkyd resin paint, the waterborne alkyd paint to be tested is coated on a substrate to form a paint film with the thickness of 150 mu m, and the following tests are carried out on the paint (before coating) and the paint film (after film forming):
(1) State in the container: visually observing whether hard blocks exist in the coating, and whether the coating is in a uniform state after stirring, wherein the coating is qualified if no hard blocks exist and the coating is uniform;
(2) Construction property: whether the brush coating has obstacles or not;
(3) Storage stability: whether the phenomena of layering, skinning and sedimentation appear in 48 hours or not;
(4) Drying time: the drying time is less than or equal to 5 hours, namely 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 bubbling or rusting still does not occur after the soaking for 96 hours;
(6) Adhesion force: testing by adopting a grid cutting 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 120h, the phenomenon of bubbling or rusting still does not occur after the glass is soaked for 120 h;
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 the vessel | Qualified | Qualified | Qualified | Qualified | Slight delamination | Slight delamination |
| Workability | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified |
| Storage stability | Qualified | Qualified | Qualified | Qualified | Slight delamination | Slight delamination |
| Drying time (h) | 2 | 2.5 | 2.5 | 2 | 3.5 | 2.5 |
| Salt water resistance (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
The performance test results in the table 2 show that the bio-based waterborne alkyd resin provided by the invention is used for preparing waterborne coatings, so that the coatings have excellent storage stability, can not generate the phenomena of sedimentation, agglomeration or skinning after long-term storage, have excellent application property, have good adhesion with substrates, can reach the level 0, have the salt water resistance of not less than 96 hours and the water resistance of not less than 120 hours, have excellent water resistance, salt tolerance and corrosion resistance, have the drying time of not more than 2.5 hours when being used as self-drying primer, have high drying speed, can play good roles of salt resistance, alkali resistance and corrosion resistance, and have the advantages of no toxicity, low VOC and no heavy metal. Combining the test results of example 1 and examples 5-6, it can be seen that by optimizing the formulation of the components of the bio-based oligomer, more excellent performance of bio-based waterborne alkyd resin and paint can be obtained; if the alcohol content of the bio-based 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.
Comparing the test results in tables 2 and 3, it can be seen that the bio-based waterborne alkyd resins of comparative examples 1-2 have slightly lower degree of waterborne property and slightly lower stability, so that the waterborne coatings containing the bio-based waterborne alkyd resins have poor storage stability, delamination phenomenon, and reduced salt resistance and adhesion of the paint films. In comparative examples 3-4 and 7-8, the reaction degree of the bio-based waterborne alkyd resin is not expected by adjusting the proportion of the bio-based oligomer, the glycerol and the sunflower oil, so that the performances of the waterborne coating are poor; the bio-based oligomer B1 used in the comparative example 5 is prepared from phthalic acid and glycerol, so that the stability and the water-based degree of the water-based alkyd resin are reduced, and the prepared water-based paint has poor stability and poor paint film performance; comparative example 6 a bio-based waterborne alkyd resin was prepared by a conventional process without the bio-based oligomer of the present invention, resulting in poor stability of the bio-based waterborne alkyd resin, poor storage stability of the waterborne coating containing the same, significant deficiencies in both corrosion resistance (salt water resistance) and adhesion of the paint film, and failure to meet the protection requirements of the primer.
The applicant states that the invention is illustrated by the above examples, but the invention is not limited to the above examples, i.e. the invention must not be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The bio-based waterborne alkyd resin is characterized by comprising the following raw materials in parts by weight:
the raw materials for preparing the bio-based oligomer comprise a combination of bio-based small molecular polyol, bio-based adipic acid and rosin.
2. The biobased waterborne alkyd resin of claim 1, wherein the sunflower oil has an iodine value of 120-140g/100g;
preferably, the small molecule polyol comprises any one of glycerol, trimethylolpropane, propylene glycol, neopentyl glycol or diethylene glycol or a combination of at least two thereof, preferably glycerol, further preferably bio-based glycerol;
preferably, the catalyst comprises a metal hydroxide, further preferably lithium hydroxide.
3. The bio-based waterborne alkyd resin according to claim 1 or 2, wherein the raw materials for preparing the bio-based oligomer comprise the following components in parts by weight:
20-25 parts of bio-based small molecular polyol
60-70 parts of bio-based adipic acid
10-15 parts of rosin;
preferably, the bio-based small molecule polyol comprises bio-based glycerol and/or bio-based propylene glycol, further preferably bio-based glycerol;
preferably, the acid value of the rosin is 160-180mg KOH/g;
preferably, the softening point of the rosin is 74-80 ℃;
preferably, the acid value of the bio-based oligomer is 90mg KOH/g or less.
4. The biobased waterborne alkyd resin of any of claims 1-3, wherein the biobased oligomer is prepared using a process comprising: mixing bio-based small molecular polyol, bio-based adipic acid and rosin, and then reacting to obtain a bio-based oligomer;
preferably, the reaction is carried out in the presence of an organic solvent;
preferably, the organic solvent comprises an aromatic solvent;
preferably, the temperature of the reaction is 160 to 200 ℃, further preferably 175 to 185 ℃;
preferably, the reaction time is 1-5h.
5. The bio-based waterborne alkyd resin of any of claims 1-4, wherein the raw materials further comprise, in parts by weight, 5-10 parts of a co-solvent;
preferably, the cosolvent comprises any one of propylene glycol butyl ether, ethylene glycol butyl ether or propylene glycol methyl ether or a combination of at least two of the two;
preferably, the preparation raw material also comprises 25-40 parts of water by weight.
6. A method of preparing a bio-based waterborne alkyd resin according to any of claims 1-5, wherein the method comprises: carrying out alcoholysis reaction on sunflower oil and small molecular polyol in the presence of a catalyst to obtain an alcoholysis product; carrying out esterification reaction on the alcoholysis product and a bio-based oligomer to obtain a prepolymer; and mixing the prepolymer with N, N-dimethylethanolamine for water-based hydration to obtain the bio-based water-based alkyd resin.
7. The method of claim 6, wherein the alcoholysis reaction is carried out at a temperature of from 200 to 250 ℃;
preferably, the alcoholysis reaction is carried out for 0.5 to 3 hours;
preferably, the temperature of the esterification reaction is 200-240 ℃;
preferably, the esterification reaction time is 0.5-3h;
preferably, the acid value of the prepolymer is less than or equal to 50mg KOH/g;
preferably, the prepolymer and N, N-dimethylethanolamine are uniformly mixed, then a cosolvent and water are added, and the mixture is uniformly dispersed, so that the bio-based waterborne alkyd resin is obtained.
8. The preparation method according to claim 6 or 7, characterized in that the preparation method specifically comprises:
mixing bio-based micromolecular polyol, bio-based adipic acid, rosin and an organic solvent, and reacting at 160-200 ℃ until the acid value of the system is less than or equal to 90mg KOH/g to obtain a bio-based oligomer;
carrying out alcoholysis reaction on sunflower oil and small molecular polyol at 200-250 ℃ for 0.5-3h in the presence of a catalyst to obtain an alcoholysis product;
carrying out esterification reaction on the alcoholysis product and a bio-based oligomer at 200-240 ℃ for 0.5-3h until the acid value of a system is less than or equal to 50mg KOH/g to obtain a prepolymer;
and removing the organic solvent in the prepolymer, uniformly mixing the organic solvent with N, N-dimethylethanolamine, adding a cosolvent and water, and uniformly dispersing to obtain the bio-based waterborne alkyd resin.
9. Use of a bio-based waterborne alkyd resin according to any of claims 1-5 in a coating, ink or adhesive.
10. A waterborne alkyd coating, characterized in that the waterborne alkyd coating comprises a bio-based waterborne alkyd resin according to any of claims 1-5;
preferably, the water-based alkyd paint also comprises any one or a combination of at least two of a drier, a pigment, a filler, a dispersant, an anti-flash rust agent or a thickener.
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