CN116574448A - Plant oil-based self-repairing water-based photo-curing coating with stable nanocellulose and preparation method thereof - Google Patents
Plant oil-based self-repairing water-based photo-curing coating with stable nanocellulose and preparation method thereof Download PDFInfo
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- CN116574448A CN116574448A CN202310362700.4A CN202310362700A CN116574448A CN 116574448 A CN116574448 A CN 116574448A CN 202310362700 A CN202310362700 A CN 202310362700A CN 116574448 A CN116574448 A CN 116574448A
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- vegetable oil
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- 238000000576 coating method Methods 0.000 title claims abstract description 37
- 229920001046 Nanocellulose Polymers 0.000 title claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011248 coating agent Substances 0.000 title claims abstract description 34
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 11
- 239000010773 plant oil Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 79
- 239000008158 vegetable oil Substances 0.000 claims abstract description 79
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 125000000129 anionic group Chemical group 0.000 claims abstract description 15
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- -1 acrylic ester Chemical class 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000002383 tung oil Substances 0.000 claims description 13
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007900 aqueous suspension Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 2
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 229920000263 Rubber seed oil Polymers 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 239000002159 nanocrystal Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000000725 suspension Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000001723 curing Methods 0.000 abstract description 4
- 150000008064 anhydrides Chemical group 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- 230000006378 damage Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229920002334 Spandex Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/005—Drying oils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F7/00—Chemical modification of drying oils
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A plant oil-based self-repairing water-based photo-curing coating with stable nanocellulose and a preparation method thereof. Firstly, vegetable oil reacts with maleic anhydride to generate maleic anhydride vegetable oil; then, carrying out anhydride ring opening modification on the generated maleic anhydride vegetable oil by utilizing hydroxyethyl acrylate to obtain a vegetable oil-based unsaturated polyester resin prepolymer; then neutralizing carboxyl in the vegetable oil-based unsaturated polyester resin prepolymer by using an alkaline neutralizer to obtain anionic aqueous vegetable oil-based unsaturated polyester resin, and adding a photoinitiator to obtain photosensitive resin; finally, mixing the resin with the nano cellulose suspension, and obtaining a final product after high-speed dispersion. The prepared water-based light-cured resin has good thermal property, mechanical property, coating property and self-repairing property after light curing, and can be used in the field of light-cured coatings. Most of the raw materials used in the invention are from renewable resources, and the material preparation process is simple and environment-friendly.
Description
Technical Field
The invention belongs to the field of photo-curing materials, and particularly relates to a plant oil-based self-repairing water-based photo-curing coating with stable nanocellulose and a preparation method thereof.
Background
As petroleum resources are increasingly exhausted, environmental problems are continuously exacerbated, and it is necessary to develop biomass resources to replace petroleum resources. The vegetable oil yield is rich, but the processing means of the product is comparatively backward, and the comprehensive utilization degree is low. Therefore, the molecular structure characteristics of the vegetable oil can be utilized to carry out chemical modification so as to develop products with high added value, and the vegetable oil can be applied to the fields of printing ink, plasticizer, 3D printing, paint and the like. The water-based paint uses water to replace an organic solvent as a diluent, and has the advantages of low emission of Volatile Organic Compounds (VOC), low toxicity and safety compared with the traditional paint which usually uses organic compounds as the diluent. The ultraviolet curing technology has the characteristics of high efficiency, energy conservation, wide adaptability, economy, environmental protection and the like. The ultraviolet light curing coating is also an environment-friendly coating, and has the advantages of high crosslinking rate and low curing temperature. The photo-curing technology is applied to the water-based paint, so that the advantages of the water-based paint and the photo-curing technology can be combined. However, the water-based paint also has the problems of poor mechanical properties, poor water resistance, low stability and the like, and further researches on improving various properties of the water-based paint are still needed.
Pickering emulsions are emulsions that utilize solid particles in place of surfactants to stabilize water-oil systems. The solid particles are provided with hydrophilic or lipophilic groups, can be wetted by water or oil and adsorbed at the interface of two phases, so that the stability of emulsion is effectively improved, the harm of the surfactant to human bodies and the environment can be reduced, and the emulsion can be widely applied to the fields of foods, medicines, chemical industry, coatings and the like. The Pickering emulsion is prepared from biomass solid particles such as nanocellulose, nano chitosan, protein and the like, and has the characteristics of greenness, environmental protection, no toxicity and safety. In addition, the application of the nano-sized particles in the aqueous coating increases the mechanical properties and the film coating properties of the coating to some extent. Thus, the preparation of Pickering emulsions using biomass particles for application in aqueous paints is of great importance.
Aiming at the problem that the paint is easy to damage, the self-repairing performance is introduced into the paint, and the paint is an effective solution. Since 2011, researchers have first proposed the concept of "Vitrimer", and materials based on dynamic covalent bonds, which achieve self-repairing properties by reversible exchange through chemical bonds, have been gradually developed. The dynamic covalent bond has stronger stability and higher bond energy, and the material is endowed with good self-repairing performance. At present, dynamic covalent bonds such as dynamic ester bonds, disulfide bonds, hindered urea bonds and the like are applied to materials so as to realize the self-repairing performance of the materials.
Disclosure of Invention
The technical problems to be solved are as follows: the invention provides a plant oil-based self-repairing type water-based photo-curing coating with stable nanocellulose and a preparation method thereof, which solve the problems of high VOC emission, serious environmental pollution, influence on body health and the like of the traditional coating, and improve the problems of short storage period, low film-forming mechanical property, need of a large amount of surfactants and the like of the water-based coating.
The technical scheme is as follows: a preparation method of a plant oil-based self-repairing water-based light-cured coating with stable nanocellulose comprises the following steps: (1) Adding vegetable oil and maleic anhydride into a reactor, wherein the molar ratio of the vegetable oil to the maleic anhydride is 1 (0.5-5), heating to 110-180 ℃ for reaction for 1-5 h after uniformly stirring, and then heating to 110-120 ℃ for reaction for 1-3 h in a glass drying furnace to obtain maleated vegetable oil; (2) 1, adding acrylic ester, polymerization inhibitor and catalyst into the reactor, wherein the molar ratio of acrylic ester to maleic anhydride is (0.5-2), the polymerization inhibitor is 0.5-2% of the total mass of maleic anhydride vegetable oil and acrylic ester, the catalyst is 0.5-3% of the total mass of maleic anhydride vegetable oil and acrylic ester, heating to 80-150 ℃ for reaction for 1-5 h, dissolving the product in dichloromethane, washing with 10wt.% NaCl aqueous solution at 30-50 ℃, drying, and removing solvent by rotary evaporation to obtain the vegetable oil-based unsaturated polyester resin prepolymer; (3) Adding an alkaline neutralizer into the vegetable oil-based unsaturated polyester resin prepolymer to neutralize carboxyl, wherein the molar ratio of the alkaline neutralizer to the carboxyl in the vegetable oil-based unsaturated polyester resin prepolymer is (1-1.5): 1, heating to 30-80 ℃ to react for 0.5-3 hours, and obtaining the anionic aqueous vegetable oil-based unsaturated polyester resin; (4) Adding 1-3% of photoinitiator into the anionic water-based vegetable oil-based unsaturated polyester resin, and uniformly stirring to obtain photosensitive resin; (5) Mixing photosensitive resin with nano cellulose aqueous suspension, and then performing high-speed dispersion, wherein the mass ratio of the nano cellulose in the nano cellulose aqueous suspension to the photosensitive resin is 1% -4%, and the mass ratio of the photosensitive resin to the nano cellulose aqueous suspension is (0.5-3): 10, so as to obtain the plant oil-based self-repairing water-based light-cured coating with stable nano cellulose.
The vegetable oil in the step (1) is at least one of tung oil, rubber seed oil, dehydrated castor oil, linseed oil, soybean oil and rapeseed oil, and the molar ratio of the vegetable oil to maleic anhydride is 1:3.
The acrylic ester in the step (2) is at least one of hydroxyethyl acrylate and hydroxyethyl methacrylate; the molar ratio of the acrylic ester to the maleic anhydride is 1:1; the catalyst is at least one of 4-dimethylaminopyridine and triphenylphosphine, and the dosage of the catalyst is 1% of the total mass of the maleinized vegetable oil and the acrylic ester; the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, p-methoxyphenol and 2, 6-di-tert-butyl-p-methylphenol, and the amount of the polymerization inhibitor is 0.5% of the total mass of maleated vegetable oil and acrylic ester.
The alkaline neutralizer in the step (3) is at least one of triethylamine, triethanolamine, diethylamine and diethanolamine; the molar ratio of the alkaline neutralizer to carboxyl in the vegetable oil-based unsaturated polyester resin prepolymer is 1:1.
The photoinitiator in the step (4) is at least one of Darocur 1173, irgacure 184, irgacure 651 and Irgacure 369, and the dosage of the photoinitiator is 2% of the total mass of the obtained anionic water-based vegetable oil-based unsaturated polyester resin.
The nanocellulose in step (5) is at least one of nanofibrillar cellulose and cellulose nanocrystals.
The speed range of the high-speed dispersion is 25000-30000rpm.
The plant oil-based self-repairing water-based light-cured coating with stable nanocellulose prepared by the method.
The beneficial effects are that: (1) The vegetable oil-based water-based light-cured resin synthesized by the invention has higher stability, and the cured material has excellent tensile property, thermal property, coating property and self-repairing property, and can be used as a water-based light-cured coating.
(2) The synthetic method comprises the steps of modifying vegetable oil through maleic anhydride, opening an anhydride ring of the synthesized maleic anhydride vegetable oil through acrylic ester, neutralizing carboxyl by using an alkaline neutralizer, adding a photoinitiator, and finally preparing the water-based photocuring paint by using nanocellulose as a stabilizer; the raw materials used in the method are mostly derived from biomass, so that the method is environment-friendly and simple in preparation process.
Drawings
FIG. 1 is an FT-IR spectrum of a tung oil-based hydroxyethyl acrylate prepolymer;
FIG. 2 is a drawing of a tung oil based hydroxyethyl acrylate prepolymer 1 H NMR spectroscopy;
FIG. 3 is a synthetic route to tung oil based acrylate prepolymers.
Detailed Description
The following examples of the present invention are merely further illustrative of the present invention and are not intended to limit the scope or spirit of the present invention. The invention is further described in detail below with reference to examples.
Example 1
(1) Adding tung oil and maleic anhydride in a molar ratio of 1:3 into a reactor, reacting for 3.5 hours at 150 ℃, and then heating to 110 ℃ in a glass drying furnace for reacting for 3 hours to obtain maleated tung oil.
(2) Adding hydroxyethyl acrylate (the molar ratio of the hydroxyethyl acrylate to the maleic anhydride is 1:1), a polymerization inhibitor 4-methoxyphenol (the polymerization inhibitor is 0.5 percent of the total mass of the maleated vegetable oil and the acrylic ester) and a catalyst 4-dimethylaminopyridine (the catalyst is 1 percent of the total mass of the maleated vegetable oil and the acrylic ester) into the reactor, heating to 110 ℃ to react for 5 hours, dissolving the product in dichloromethane, washing with a 10wt% NaCl aqueous solution at 40 ℃, drying, and removing the solvent by rotary evaporation to obtain the vegetable oil-based unsaturated polyester resin prepolymer.
(3) Adding triethylamine into the vegetable oil-based unsaturated polyester resin prepolymer, and heating to 60 ℃ to react for 30min to obtain the anionic aqueous vegetable oil-based unsaturated polyester resin.
(4) Adding 2% of photoinitiator Darocur 1173 into the generated anionic water-based vegetable oil-based unsaturated polyester resin, and uniformly stirring to obtain the photosensitive resin.
(5) And adding photosensitive resin into the nano cellulose suspension, wherein the mass ratio of the nano cellulose suspension to the resin is 10:1, and the nano cellulose accounts for 1% of the mass of the photosensitive resin, and uniformly dispersing at 30000rpm to obtain the vegetable oil-based self-repairing water-based light-cured coating.
Example 2
(1) Adding tung oil and maleic anhydride in a molar ratio of 1:3 into a reactor, reacting for 3.5 hours at 150 ℃, and then heating to 110 ℃ in a glass drying furnace for reacting for 3 hours to obtain maleated tung oil.
(2) Adding hydroxyethyl acrylate (the molar ratio of the hydroxyethyl acrylate to the maleic anhydride is 1:1), a polymerization inhibitor 4-methoxyphenol (the polymerization inhibitor is 0.5 percent of the total mass of the maleated vegetable oil and the acrylic ester) and a catalyst 4-dimethylaminopyridine (the catalyst is 1 percent of the total mass of the maleated vegetable oil and the acrylic ester) into the reactor, heating to 110 ℃ to react for 5 hours, dissolving the product in dichloromethane, washing with a 10wt% NaCl aqueous solution at 40 ℃, drying, and removing the solvent by rotary evaporation to obtain the vegetable oil-based unsaturated polyester resin prepolymer.
(3) Adding triethylamine into the vegetable oil-based unsaturated polyester resin prepolymer, and heating to 60 ℃ to react for 30min to obtain the anionic aqueous vegetable oil-based unsaturated polyester resin.
(4) Adding 2% of photoinitiator Darocur 1173 into the generated anionic water-based vegetable oil-based unsaturated polyester resin, and uniformly stirring to obtain the photosensitive resin.
(5) And adding photosensitive resin into the nano cellulose suspension, wherein the mass ratio of the nano cellulose suspension to the resin is 10:1, the nano cellulose accounts for 2% of the mass of the photosensitive resin, and uniformly dispersing at 30000rpm to obtain the vegetable oil-based self-repairing water-based light-cured coating.
Example 3
(1) Adding tung oil and maleic anhydride in a molar ratio of 1:3 into a reactor, reacting for 3.5 hours at 150 ℃, and then heating to 110 ℃ in a glass drying furnace for reacting for 3 hours to obtain maleated tung oil.
(2) Adding hydroxyethyl acrylate (the molar ratio of the hydroxyethyl acrylate to the maleic anhydride is 1:1), a polymerization inhibitor 4-methoxyphenol (the polymerization inhibitor is 0.5 percent of the total mass of the maleated vegetable oil and the acrylic ester) and a catalyst 4-dimethylaminopyridine (the catalyst is 1 percent of the total mass of the maleated vegetable oil and the acrylic ester) into the reactor, heating to 110 ℃ to react for 5 hours, dissolving the product in dichloromethane, washing with a 10wt% NaCl aqueous solution at 40 ℃, drying, and removing the solvent by rotary evaporation to obtain the vegetable oil-based unsaturated polyester resin prepolymer.
(3) Adding triethylamine into the vegetable oil-based unsaturated polyester resin prepolymer, and heating to 60 ℃ to react for 30min to obtain the anionic aqueous vegetable oil-based unsaturated polyester resin.
(4) Adding 2% of photoinitiator Darocur 1173 into the generated anionic water-based vegetable oil-based unsaturated polyester resin, and uniformly stirring to obtain the photosensitive resin.
(5) And adding photosensitive resin into the nano cellulose suspension, wherein the mass ratio of the nano cellulose suspension to the resin is 10:1, the nano cellulose accounts for 3% of the mass of the photosensitive resin, and uniformly dispersing at 30000rpm to obtain the vegetable oil-based self-repairing water-based light-cured coating.
Example 4
(1) Adding tung oil and maleic anhydride in a molar ratio of 1:3 into a reactor, reacting for 3.5 hours at 150 ℃, and then heating to 110 ℃ in a glass drying furnace for reacting for 3 hours to obtain maleated tung oil.
(2) Adding hydroxyethyl acrylate (the molar ratio of the hydroxyethyl acrylate to the maleic anhydride is 1:1), a polymerization inhibitor 4-methoxyphenol (the polymerization inhibitor is 0.5 percent of the total mass of the maleated vegetable oil and the acrylic ester) and a catalyst 4-dimethylaminopyridine (the catalyst is 1 percent of the total mass of the maleated vegetable oil and the acrylic ester) into the reactor, heating to 110 ℃ to react for 5 hours, dissolving the product in dichloromethane, washing with a 10wt% NaCl aqueous solution at 40 ℃, drying, and removing the solvent by rotary evaporation to obtain the vegetable oil-based unsaturated polyester resin prepolymer.
(3) Adding triethylamine into the vegetable oil-based unsaturated polyester resin prepolymer, and heating to 60 ℃ to react for 30min to obtain the anionic aqueous vegetable oil-based unsaturated polyester resin.
(4) Adding 2% of photoinitiator Darocur 1173 into the generated anionic water-based vegetable oil-based unsaturated polyester resin, and uniformly stirring to obtain the photosensitive resin.
(5) And adding photosensitive resin into the nano cellulose suspension, wherein the mass ratio of the nano cellulose suspension to the resin is 10:1, the nano cellulose accounts for 4% of the mass of the photosensitive resin, and uniformly dispersing at 30000rpm to obtain the vegetable oil-based self-repairing water-based light-cured coating.
Example 5
The aqueous coatings of examples 1 to 4 were poured into a self-made polytetrafluoroethylene mold or coated on tin plates, respectively, and after complete evaporation of the water at room temperature, the films were formed by UV curing. Tensile properties: the mechanical properties of the photocurable film were measured according to ASTM D638-2008 using a SANS7CMT-4304 type Universal tester (Shenzhen Santa Classification Instrument Co., ltd.) with a gauge length of 30mm and a stretching rate of 5.0mm/min. Glass transition temperature: the glass transition temperature was measured by DSC8000 differential scanning calorimeter (American PE company). Thermogravimetric analysis: the thermodynamic stability of the photocurable film was measured using an STA 409PC thermogravimetric analyzer (Netzsch company, germany). The heating interval is 40-800 ℃, and the heating rate is 15 ℃/min. Film coating properties: the adhesion of the coating film was tested according to the method of GB/T9286-1998, with the best grade 1 and worst grade 7; the flexibility of the coating film is tested according to the method of GB/T1731-93, the minimum diameter of the shaft rod is 2mm, and the smaller the diameter of the shaft rod is, the better the toughness is; the hardness of the paint film was determined according to GB/T6739-2006, 6H,5H,4H,3H,2H, HB, B,2B,3B,4B,5B,6B, with 6H being the hardest and 6B being the softest. Self-repair rate: and (3) observing the ratio of the reduction of the scratch width before and after repair by using an ICC50W lycra optical microscope to calculate the self-repair rate. The test results of each example are shown in Table 1.
TABLE 1 Main film Performance index for resin samples of examples 1-4
As can be seen from the data in the table, the plant oil-based water-based light-cured coating prepared by the invention has better coating tensile property and film coating property, and can be used as a protective coating for surfaces of metals, wood and the like.
Claims (8)
1. The preparation method of the plant oil-based self-repairing water-based light-cured coating with stable nanocellulose is characterized by comprising the following steps of: (1) Adding vegetable oil and maleic anhydride into a reactor, wherein the molar ratio of the vegetable oil to the maleic anhydride is 1 (0.5-5), heating to 110-180 ℃ for reaction for 1-5 h after uniformly stirring, and then heating to 110-120 ℃ for reaction for 1-3 h in a glass drying furnace to obtain maleated vegetable oil; (2) 1, adding acrylic ester, polymerization inhibitor and catalyst into the reactor, wherein the molar ratio of the acrylic ester to the maleic anhydride is (0.5-2), the polymerization inhibitor is 0.5-2% of the total mass of the maleated vegetable oil and the acrylic ester, the catalyst is 0.5-3% of the total mass of the maleated vegetable oil and the acrylic ester, heating to 80-150 ℃ for reaction for 1-5 h, dissolving the product in dichloromethane, washing with 10wt.% NaCl aqueous solution at 30-50 ℃, drying, and removing the solvent by rotary evaporation to obtain the vegetable oil-based unsaturated polyester resin prepolymer; (3) Adding an alkaline neutralizer into the vegetable oil-based unsaturated polyester resin prepolymer to neutralize carboxyl, wherein the molar ratio of the alkaline neutralizer to the carboxyl in the vegetable oil-based unsaturated polyester resin prepolymer is (1-1.5): 1, and heating to 30-80 ℃ to react for 0.5-3 hours to obtain anionic aqueous vegetable oil-based unsaturated polyester resin; (4) Adding 1% -3% of photoinitiator into the anionic water-based vegetable oil-based unsaturated polyester resin, and uniformly stirring to obtain photosensitive resin; (5) Mixing photosensitive resin with a nano cellulose aqueous suspension, and then performing high-speed dispersion, wherein the mass ratio of the nano cellulose in the nano cellulose aqueous suspension to the photosensitive resin is 1% -4%, and the mass ratio of the photosensitive resin to the nano cellulose aqueous suspension is (0.5-3): 10, so as to obtain the plant oil-based self-repairing water-based photo-curing coating with stable nano cellulose.
2. The method for preparing the nanocellulose-stabilized vegetable oil-based self-repairing aqueous photocurable coating according to claim 1, wherein the vegetable oil in the step (1) is at least one of tung oil, rubber seed oil, dehydrated castor oil, linseed oil, soybean oil and rapeseed oil, and the molar ratio of the vegetable oil to maleic anhydride is 1:3.
3. The method for preparing the nanocellulose-stabilized vegetable oil-based self-repairing aqueous photocurable coating according to claim 1, wherein the acrylate in the step (2) is at least one of hydroxyethyl acrylate and hydroxyethyl methacrylate; the molar ratio of the acrylic ester to the maleic anhydride is 1:1; the catalyst is at least one of 4-dimethylaminopyridine and triphenylphosphine, and the dosage of the catalyst is 1% of the total mass of the maleinized vegetable oil and the acrylic ester; the polymerization inhibitor is at least one of hydroquinone, p-benzoquinone, p-methoxyphenol and 2, 6-di-tert-butyl-p-methylphenol, and the amount of the polymerization inhibitor is 0.5% of the total mass of maleated vegetable oil and acrylic ester.
4. The method for preparing the nanocellulose-stabilized vegetable oil-based self-repairing aqueous photocurable coating according to claim 1, wherein said alkaline neutralizing agent in step (3) is at least one of triethylamine, triethanolamine, diethylamine and diethanolamine; the molar ratio of the alkaline neutralizer to carboxyl in the vegetable oil-based unsaturated polyester resin prepolymer is 1:1.
5. The method for preparing the nanocellulose-stabilized vegetable oil-based self-repairing aqueous photo-curing coating according to claim 1, wherein the photo-initiator in the step (4) is at least one of Darocur 1173, irgacure 184, irgacure 651 and Irgacure 369, and the amount of the photo-initiator is 2% of the total mass of the obtained anionic aqueous vegetable oil-based unsaturated polyester resin.
6. The method for preparing a nanocellulose-stabilized vegetable oil-based self-healing aqueous photocurable coating according to claim 1, wherein said nanocellulose in step (5) is at least one of nanofibrillar cellulose and cellulose nanocrystals.
7. The method for preparing a nanocellulose stable vegetable oil-based self-healing aqueous photocurable coating according to claim 1, wherein the high speed dispersion speed ranges from 25000 rpm to 30000rpm.
8. The nanocellulose-stabilized vegetable oil-based self-healing aqueous photocurable coating prepared by the method of any one of claims 1-7.
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