CN113698812A - Plant oil-based reactive film-forming additive and preparation method thereof - Google Patents
Plant oil-based reactive film-forming additive and preparation method thereof Download PDFInfo
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- CN113698812A CN113698812A CN202110817961.1A CN202110817961A CN113698812A CN 113698812 A CN113698812 A CN 113698812A CN 202110817961 A CN202110817961 A CN 202110817961A CN 113698812 A CN113698812 A CN 113698812A
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- linoleic acid
- film
- acid diethanolamide
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- based reactive
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- 239000010773 plant oil Substances 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000000654 additive Substances 0.000 title claims description 6
- 230000000996 additive effect Effects 0.000 title claims description 6
- CKNOIIXFUKKRIC-HZJYTTRNSA-N (9z,12z)-n,n-bis(2-hydroxyethyl)octadeca-9,12-dienamide Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)N(CCO)CCO CKNOIIXFUKKRIC-HZJYTTRNSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 8
- 239000008158 vegetable oil Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims description 7
- 235000020778 linoleic acid Nutrition 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 239000003444 phase transfer catalyst Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 230000009435 amidation Effects 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000003209 petroleum derivative Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 9
- 239000012855 volatile organic compound Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- -1 alcohol ethers Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JMIZWXDKTUGEES-UHFFFAOYSA-N 2,2-di(cyclopenten-1-yloxy)ethyl 2-methylprop-2-enoate Chemical compound C=1CCCC=1OC(COC(=O)C(=C)C)OC1=CCCC1 JMIZWXDKTUGEES-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000018783 Dacrycarpus dacrydioides Nutrition 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 240000007320 Pinus strobus Species 0.000 description 1
- 235000008578 Pinus strobus Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- RSVDRWTUCMTKBV-UHFFFAOYSA-N sbb057044 Chemical compound C12CC=CC2C2CC(OCCOC(=O)C=C)C1C2 RSVDRWTUCMTKBV-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/14—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof
- C07D301/16—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic peracids, or salts, anhydrides or esters thereof formed in situ, e.g. from carboxylic acids and hydrogen peroxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
- C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
-
- 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
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a vegetable oil-based reactive film-forming aid, which is epoxy linoleic acid diethanolamide glycidyl ether. The invention also relates to a preparation method of the plant oil-based reactive film-forming assistant, and the film-forming assistant can reduce the lowest film-forming temperature, participates in the reaction and has the advantage of no generation of VOC.
Description
Technical Field
The invention relates to a plant oil-based reactive film-forming aid and a preparation method thereof.
Background
The film forming assistant of the water paint is a solvent of polymer, during the drying process of a coating film, the residual film forming assistant after water evaporation enables polymer microdrops to be dissolved and fused into a continuous film, although some regulations consider that substances with the boiling point higher than 250 ℃ can not fall into the VOC range, after the film is formed, the currently common alcohol ether film forming assistant gradually volatilizes and escapes along with the time, thereby polluting the environment. The reactive coalescent not only lowers the film forming temperature, but also chemically reacts with the polymer to form part of the coating.
CN1177782C Rohm and Haas company discloses a compound containing a double bond as a reactive coalescent and a method of improving the stability of a reactive coalescent. US4,141,868 discloses reactive film-forming aids containing vinyl groups. Common species are dicyclopentenyloxyethyl methacrylate ("DCPOEMA"), dicyclopentenyloxyethyl acrylate ("DCPOEA"), dicyclopentenyloxyacrylate ("DCPOA") and dicyclopentenyloxymethacrylate ("DCPOMA"). CN201710478377.1 discloses a method for using a film-forming assistant for reactive coatings, wherein the addition amount of the film-forming assistant in a coating formula is more than 6 percent (wt), the formula contains a photoinitiator, and the coating is water-based paint with unsaturated double bonds.
However, there is still a need for film-forming aids with better performance than those disclosed in the prior art. Accordingly, the present invention is intended to disclose a reactive film-forming aid derived from vegetable oil, which has not been disclosed before, a composition comprising an aqueous coating agent containing the film-forming aid, which is capable of effectively forming a film having smoothness, resistance to hydrolysis reaction, no pungent odor, and high efficiency even when used in a small amount.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a vegetable oil-based reactive film-forming aid, wherein the film-forming aid is epoxy linoleic acid diethanolamide glycidyl ether, and the structural formula is as follows:
the film-forming assistant is added in the production process of the water-based paint.
The mass fraction of the film-forming aid is 1-30% relative to the solid content of the polymer emulsion in the water-based paint.
The mass fraction of the film-forming aid is 1-12% relative to the solid content of the polymer emulsion in the water-based paint.
The polymer in the water-based paint is selected from one or a mixture of two of acrylic acid copolymer and styrene-acrylic acid copolymer.
The amount of polymer in the aqueous coating is in the range of 10% to 80% by weight.
The amount of polymer in the aqueous coating is in the range of 35% to 55% by weight.
The film-forming aid also comprises a solvent, wherein the solvent is one or more selected from water, alcohol, petroleum fractions, esters and alcohol ethers.
A preparation method of a vegetable oil-based reactive film-forming aid comprises the following steps:
step 1, Synthesis of linoleic acid diethanolamide
Firstly carrying out amidation and esterification reactions on linoleic acid and diethanolamine, wherein the molar ratio of the linoleic acid to the diethanolamine is 3: 0.8-1.5; the dosage of the water-carrying agent is 2 times of that of the linoleic acid, the reaction temperature is 80-150, the reaction time is 3-8 hours, the reaction is carried out until no water is generated, then the temperature is reduced to 50-80, and diethanolamine is added for ester exchange reaction, wherein the molar ratio of the linoleic acid to the diethanolamine is 3: 1.6-3.0; the reaction time is 60-360 min.
Step 2, synthesis of linoleic acid diethanolamide diglycidyl ether
The raw material proportion of the reaction is that n (linoleic acid diethanolamide), n (epichlorohydrin), n (sodium hydroxide) and 1 (1-4) and (1-5), the reaction temperature is 50-80 ℃; the phase transfer catalyst is 0.1-1% of linoleic acid diethanolamide. The water-carrying agent is 1-5 times of the weight of the linoleic acid diethanolamide; the reaction time is (1.0-4.0) h.
The phase transfer catalyst can be benzyl trimethyl ammonium chloride, benzyl triethyl ammonium chloride (TEBA), tetrabutyl ammonium bromide (TBAB), tetrabutyl ammonium chloride, tetrabutyl ammonium hydrogen sulfate, trioctylmethyl ammonium chloride, dodecyl trimethyl ammonium chloride, and tetradecyl trimethyl ammonium chloride.
Petroleum ether, benzene toluene, cyclohexane, chloroform and carbon tetrachloride as water carrying agents.
And 3, synthesizing epoxy linoleic acid diethanolamide glycidyl ether.
The double bonds on the linoleic acid diethanolamide glycidyl ether are oxidized into epoxy groups by using hydrogen peroxide and glacial acetic acid as oxidants under the process conditions that n (linoleic acid diethanolamide glycidyl ether), n (formic acid), n (hydrogen peroxide) is 1, (2-5), (2-6), m (linoleic acid diethanolamide glycidyl ether) and m (solvent): m (catalyst) ═ 1, (1-3) (0.05-0.1) (mass ratio), reaction temperature 50-80 deg.C and reaction time 3-7 h.
The solvent can be selected from toluene, xylene, petroleum ether, and cyclohexane.
The catalyst is selected from phosphoric acid, sulfuric acid, trifluoroacetic acid, titanium dioxide and ammonium molybdate.
An aqueous coating composition comprising the aforementioned coalescent.
The film-forming additive disclosed by the invention can reduce the lowest film-forming temperature, participates in reaction and has the advantage of not generating VOC (volatile organic compounds).
The above-described and other features, aspects, and advantages of the present application will become more apparent with reference to the following detailed description.
Drawings
FIG. 1 is a nuclear magnetic spectrum of epoxy linoleic acid diethanolamide glycidyl ether.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs. The use of "first," "second," and similar terms in the description and claims of the present application do not denote any order, quantity, or importance, but rather the terms are used to distinguish one element from another. Also, the use of the terms "a" or "an" and the like do not denote a limitation of quantity, but rather denote the presence of at least one.
The plant oil-based reactive film-forming aid is epoxy linoleic acid diethanolamide glycidyl ether, and has the following structural formula:
the film-forming assistant is added in the production process of the water-based paint.
The mass fraction of the film-forming aid is 1-30% relative to the solid content of the polymer emulsion in the water-based paint.
The mass fraction of the film-forming aid is 1-12% relative to the solid content of the polymer emulsion in the water-based paint.
The polymer in the water-based paint is selected from one or a mixture of two of acrylic acid copolymer and styrene-acrylic acid copolymer.
The amount of polymer in the aqueous coating is in the range of 10% to 80% by weight
The amount of polymer in the aqueous coating is in the range of 45% to 75% by weight.
The film-forming aid also comprises a solvent, wherein the solvent is one or more selected from water, alcohol, petroleum fractions, esters and alcohol ethers.
The synthesis of epoxy linoleic acid diethanol amide glycidyl Ether (ELDG) comprises the following three steps: first step, synthesis of linoleic acid diethanolamide
84g (0.3mol) of linoleic acid is firstly added into a three-neck flask provided with an electric stirrer, a water separator and a thermometer, oleic acid is heated to 70 ℃, 10.5g of diethanolamine (0.1mol) is then added, 80mL of cyclohexane is used for refluxing and water separation, and no water is generated after reaction for 4 hours at a certain temperature. Then 21g (0.2mol) of diethanolamine is added for reaction for 6h, and the obtained product is distilled by a rotary evaporator to obtain yellow viscous liquid, namely the intermediate oleic acid diethanolamide.
The second step is that: synthesis of linoleic acid diethanolamide diglycidyl ether
A250 mL four-neck flask equipped with an electric stirrer, a thermometer, a reflux condenser and a constant pressure dropping funnel was heated by a constant temperature oil bath, 36.7g (0.1mol) of oleic acid diethanolamide, 0.3g of benzyltriethylammonium chloride and 50g of benzene were sequentially added, 7.2g (0.18mol) of solid sodium hydroxide was added to the flask in portions, and the mixture was stirred while controlling the temperature at a constant temperature. Then, 14.8g (0.16mol) of epichlorohydrin was added to the dropping funnel having a constant pressure, and slowly dropped into the flask to carry out the reaction. After the reaction is finished, removing the sodium hydroxide and the phase transfer catalyst by suction filtration, and reserving filtrate, and then washing and drying. And distilling under normal pressure to remove excessive epichlorohydrin and solvent to obtain light yellow transparent liquid, namely the intermediate linoleic acid diethanolamide diglycidyl ether.
The third step: synthesis of epoxy linoleic acid diethanol amide glycidyl ether
47.9g (0.1mol) of linoleic acid diethanolamide glycidyl ether, 6.9g (0.1mol) of formic acid, 50mL of toluene and 0.15g of p-toluenesulfonic acid are added into a 250mL three-neck flask with mechanical stirring, a reflux condenser and temperature control, the temperature is raised to 50 ℃, 28.0g (30%) of hydrogen peroxide (0.25mol) is added dropwise, and after the dropwise addition is finished, the mixed reactant is heated to 60 ℃ and the reaction is continued for 3 hours. After the reaction is finished, the crude product is subjected to NaHCO with the concentration of 2%3The solution is washed and adjusted to be neutral, then washed by saturated saline, and the organic phase is distilled and dried under reduced pressure to obtain the target product. The map is shown in figure 1.
Epoxy linoleic acid diethanolamide glycidyl ether performance test
Rate of volatilization
The rate of volatilization is related to the rate at which the coating dries. The rate of evaporation is very important to be slower than that of water, and after the water is evaporated, the polymerization agent softens the latex particles and causes them to fuse into a continuous film.
The volatilization rate of n-butyl acetate is 1.0
The evaporation rate of the film-forming aid ELDG of the present invention is much lower than TEXNOL, which allows them to remain in the emulsion for a sufficient time to participate in the reaction of the emulsion.
Drying Property
With a commercial film-forming aid TexanolTMIn contrast, the drying performance of the coalescent can be determined according to the following procedure.
(1) 20g of a binder selected from an acrylic copolymer or a styrene-acrylic copolymer and an amount of a film-forming aid capable of producing an optimum film are added to the test beaker, the mixture is mixed and stirred until uniformly mixed.
(2) The prepared coalescent and binder from step 1 was stretched on a support paper using a wire coater until a 100 micron thick film layer was obtained. Then, the resulting film was dried at room temperature.
(3) Touch the prepared film with a finger, record the time when the fingerprint is no longer displayed on the film.
Odor test
With a commercial film-forming aid TexanolTMIn contrast, the coalescent odor test can be performed according to the following procedure.
(1) 10g of the film-forming assistant TexanolTMAnd the ELDG added to each test beaker.
(2) Please five evaluators smell and record the odor intensity as 1 to 6, (1, no odor, 2, slightly odor, 3, tasted but not pungent, 4, pungent odor, 5, strong pungent odor, 6, intolerable taste.)
Volatile Organic Compound (VOC) testing
VOC testing of the coalescents can be performed according to ISO11890-2 standard, in contrast to the commercial coalescent, Texanol.
Minimum Film Forming Temperature (MFFT) test
The MFFT test was carried out by decreasing the film formation temperature as follows:
the Scotch Tape biaxially oriented polypropylene was placed on an ICI SheenMFTBarsS-3300. The sample was drawn down on the tape using a 1 inch cube Sheen film applicator with a gap size of 75 microns. The point at which the film became continuous and did not crack, i.e., the MFFT value, was read after 60-90 minutes.
Cracking degree test
The samples were applied to a white pine board with a brush. The coating was applied in stripes perpendicular to the length of the panel. Each sample was weighed to reach 41.8m2Coating amount of/L. The coated panels were dried for 24 hours at 40 ℃/70% relative humidity. The degree of cracking of the coating film was determined with a magnifying glass.
The degree of cracking is reported in the following scale: no. 10, trace/small amount 8, small amount 7, small amount 6, small amount/medium, medium amount 5, medium/heavy amount 4, heavy amount 3, heavy amount 2, heavy/heavy, and heavy amount 1.
It can be seen that the film-forming additive of the invention not only can reduce the minimum film-forming temperature, but also participates in the reaction, and has the advantage of no VOC.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and the description is given here only for clarity, and those skilled in the art should integrate the description, and the embodiments may be combined appropriately to form other embodiments understood by those skilled in the art.
Claims (6)
1. The plant oil-based reactive film-forming additive is characterized in that the film-forming additive is epoxy linoleic acid diethanolamide glycidyl ether, and the structural formula is as follows:
the film-forming assistant is added in the production process of the water-based paint.
2. The vegetable oil-based reactive coalescent of claim 1, wherein the mass fraction of coalescent is 1-30% relative to the solids content of the polymer emulsion in the aqueous coating.
3. The vegetable oil-based reactive coalescent of claim 1, wherein the polymer of said aqueous coating is selected from the group consisting of acrylic acid copolymer, styrene-acrylic acid copolymer, and mixtures thereof.
4. The vegetable oil-based reactive coalescent of claim 1, wherein the amount of polymer in the aqueous coating material is in the range of 10 wt.% to 80 wt.%.
5. The vegetable oil-based reactive coalescent of claim 1, further comprising a solvent selected from one or more of water, alcohol, petroleum distillate, ester, alcohol ether.
6. A preparation method of a plant oil-based reactive film-forming aid is characterized by comprising the following steps:
step 1, Synthesis of linoleic acid diethanolamide
Firstly carrying out amidation and esterification reactions on linoleic acid and diethanolamine, wherein the molar ratio of the linoleic acid to the diethanolamine is 3: 0.8-1.5; the dosage of the water-carrying agent is 2 times of that of the linoleic acid, the reaction temperature is 80-150, the reaction time is 3-8 hours, the reaction is carried out until no water is generated, then the temperature is reduced to 50-80, and diethanolamine is added for ester exchange reaction, wherein the molar ratio of the linoleic acid to the diethanolamine is 3: 1.6-3.0; the reaction time is 60-360 min;
step 2, synthesis of linoleic acid diethanolamide diglycidyl ether
The raw material proportion of the reaction is that n (linoleic acid diethanolamide), n (epichlorohydrin), n (sodium hydroxide) and 1 (1-4) and (1-5), the reaction temperature is 50-80 ℃; the phase transfer catalyst is 0.1-1% of linoleic acid diethanolamide. The water-carrying agent is 1-5 times of the weight of the linoleic acid diethanolamide; the reaction time is 1-4 h;
step 3, synthesizing epoxy linoleic acid diethanolamide glycidyl ether;
the double bonds on the linoleic acid diethanolamide glycidyl ether are oxidized into epoxy groups by using hydrogen peroxide and glacial acetic acid as oxidants under the process conditions that n (linoleic acid diethanolamide glycidyl ether), n (formic acid), n (hydrogen peroxide) is 1, (2-5), (2-6), m (linoleic acid diethanolamide glycidyl ether) and m (solvent): m (catalyst) is 1, (1-3) and (0.05-0.1) (mass ratio), the reaction temperature is 50-80 ℃, and the reaction time is 3-7 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344300A (en) * | 1999-01-18 | 2002-04-10 | 戴尔尼化学品公司 | paint composition |
| CN104789030A (en) * | 2015-04-29 | 2015-07-22 | 福建省创益建材科技有限公司 | Film-forming assistant for environment-friendly latex paints and preparation method thereof |
| CN112358456A (en) * | 2020-07-24 | 2021-02-12 | 润泰化学（泰兴）有限公司 | Preparation method of film forming aid, film forming aid and coating containing film forming aid |
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- 2021-07-20 CN CN202110817961.1A patent/CN113698812A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344300A (en) * | 1999-01-18 | 2002-04-10 | 戴尔尼化学品公司 | paint composition |
| CN104789030A (en) * | 2015-04-29 | 2015-07-22 | 福建省创益建材科技有限公司 | Film-forming assistant for environment-friendly latex paints and preparation method thereof |
| CN112358456A (en) * | 2020-07-24 | 2021-02-12 | 润泰化学（泰兴）有限公司 | Preparation method of film forming aid, film forming aid and coating containing film forming aid |
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