CN117417661B - Preparation method and application of high-flash-point low-VOC diluent - Google Patents
Preparation method and application of high-flash-point low-VOC diluent Download PDFInfo
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- CN117417661B CN117417661B CN202311538502.5A CN202311538502A CN117417661B CN 117417661 B CN117417661 B CN 117417661B CN 202311538502 A CN202311538502 A CN 202311538502A CN 117417661 B CN117417661 B CN 117417661B
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- 239000003085 diluting agent Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003094 microcapsule Substances 0.000 claims abstract description 54
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 53
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 22
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229960000583 acetic acid Drugs 0.000 claims abstract description 11
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 11
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 claims abstract description 11
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006334 epoxy coating Polymers 0.000 claims abstract description 9
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 6
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002262 Schiff base Substances 0.000 claims description 10
- 150000004753 Schiff bases Chemical class 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 229920002545 silicone oil Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- AMVXVPUHCLLJRE-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)hexane-1,6-diamine Chemical compound CO[Si](OC)(OC)CCCNCCCCCCN AMVXVPUHCLLJRE-UHFFFAOYSA-N 0.000 claims description 7
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- DJBRKGZFUXKLKO-UHFFFAOYSA-N 3-(pyridin-2-yldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSC1=CC=CC=N1 DJBRKGZFUXKLKO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 238000006459 hydrosilylation reaction Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 24
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- -1 phenyl glycidyl Chemical group 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000012855 volatile organic compound Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 5
- 238000005576 amination reaction Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000005028 tinplate 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a preparation method and application of a high-flash-point low-VOC diluent, which belong to the technical field of paint diluents and comprise the following raw materials in parts by weight: 16-18 parts of syringaldehyde, 30-35 parts of modified microcapsule, 75-95 parts of N, N-dimethylformamide, 0.9-1.1 parts of glacial acetic acid, 24-28 parts of epichlorohydrin, 0.46-0.54 part of benzyl triethyl ammonium chloride and 22-26 parts of base catalyst; according to the invention, a phenyl glycidyl aldehyde structure and a modified microcapsule structure are introduced in the preparation process of the diluent, the outer layer of the modified microcapsule is a chemically crosslinked structure of aminated silicon dioxide and 3- (2-pyridine dithio) propionic acid, the inner core contains the modifier, and through the mutual synergistic effect of the functional groups, the prepared diluent is safe and environment-friendly, has a high flash point, and can dilute and reduce viscosity and remarkably improve the corrosion resistance and mechanical property of the epoxy coating.
Description
Technical Field
The invention relates to the technical field of paint diluents, in particular to a preparation method and application of a high-flash-point low-VOC diluent.
Background
The epoxy coating has excellent adhesion, chemical resistance and corrosion resistance, and is widely applied to industries such as pipeline containers, automobiles, ships, terraces and the like. However, the viscosity of the pure epoxy paint is too high, and problems such as leveling property and the like can occur in the construction process, namely that a thinner is required to be added to reduce the viscosity and improve the fluidity in order to meet the process requirements. In the traditional epoxy paint, toluene, n-butyl alcohol and phthalate are taken as main materials, although the diluent can improve the volatility of the paint, enhance the cohesiveness and the adhesiveness, the emission of a large amount of volatile organic compounds can cause serious pollution to the environment, and in the curing process, the volatilization of the solvent can cause the paint film to generate pores, so that the performance of the paint film is reduced.
Chinese patent CN103146243B provides a benzene-free diluent for paint, which comprises dimethyl carbonate, DBE high boiling point solvent, propylene glycol methyl ether acetate, butyl acetate and high boiling point aromatic hydrocarbon S-150 solvent, and the diluent prepared from the raw materials has wide application range and strong dilution capability, but the flash point of the raw materials is very low, potential safety hazard exists in the transportation and storage processes, and the application of the paint diluent as a market commodity is limited.
Therefore, it is a technical problem to be solved at present to provide a low VOC diluent suitable for epoxy coatings with high flash point and enhanced mechanical properties and corrosion resistance properties of the coating.
Disclosure of Invention
The invention aims to provide a preparation method and application of a high-flash-point low-VOC diluent, which are used for solving the problems in the background technology.
In order to achieve the above object, the present invention provides the following technical solutions:
a method of preparing a high flash point low VOC diluent comprising the steps of:
step S1, preparing the following raw materials in parts by weight: 16-18 parts of syringaldehyde, 30-35 parts of modified microcapsule, 75-95 parts of N, N-dimethylformamide, 0.9-1.1 parts of glacial acetic acid, 24-28 parts of epichlorohydrin, 0.46-0.54 part of benzyl triethyl ammonium chloride and 22-26 parts of base catalyst;
s2, adding syringaldehyde and the modified microcapsule into N, N-dimethylformamide, adding glacial acetic acid while stirring, and carrying out heating reflux reaction for 4-5h to obtain a Schiff base monomer;
and S3, mixing the Schiff base monomer prepared in the step S2 with epoxy chloropropane, heating to 90-95 ℃ while stirring, adding benzyl triethyl ammonium chloride, stirring under the protection of nitrogen, reacting for 5-6 hours, cooling to 65 ℃ after the reaction is finished, dropwise adding 30% sodium hydroxide aqueous solution while stirring, controlling the dropwise adding within 30 minutes, continuing to stir and react for 4-5 hours after the dropwise adding, filtering, precipitating and washing the filtrate with hot deionized water for 3-5 times, dissolving in absolute methanol, cooling to-20 ℃, recrystallizing, and vacuum drying at 30 ℃ for 8-12 hours to obtain the high-flash-point low-VOC diluent.
Further, the base catalyst is a 30% by mass aqueous sodium hydroxide solution.
Further, the preparation method of the modified microcapsule comprises the following steps:
under ice bath, dissolving sodium laurylsulfate and an emulsifier OP-10 in deionized water, adding a modifier, tetraethoxysilane and octadecyltrimethoxysilane, stirring at 1300-1500rpm for 15-25min, and placing in a cell pulverizer for ultrasonic fine emulsification for 20-30min to obtain a pre-emulsion, wherein the dosage ratio of sodium laurylsulfate to the emulsifier OP-10 to deionized water to the modifier to tetraethoxysilane to octadecyltrimethoxysilane is 0.25-0.75g:0.25-0.75g:10g:9.5-10.5g:1.5-2.5g;
a2, adjusting the pH of the pre-emulsion prepared in the step B1 to 7.5 by using an ammonia water solution with the mass fraction of 25% at room temperature, stirring for 24 hours at room temperature, and vacuum drying for 12-16 hours at 60 ℃ to obtain microcapsules;
in the reaction process, tetraethoxysilane and octadecyltrimethoxysilane form a silicon dioxide shell layer through the co-hydrolysis and co-condensation reaction at an oil-water interface, the modifier is coated, and the solvent is removed through vacuum drying to obtain the microcapsule;
step A3, after ultrasonically mixing the microcapsule, deionized water, anhydrous ethanol and N- (6-aminohexyl) -3-aminopropyl trimethoxy silane for 30min, stirring at room temperature for reaction for 6-8h, centrifuging, precipitating, washing and drying to obtain an aminated microcapsule, ultrasonically dispersing the aminated microcapsule and DMF, dropwise adding a mixed solution a of 4-dimethylaminopyridine, N-dicyclohexylcarbodiimide, 3- (2-pyridyldithio) propionic acid and DMF, heating to 110 ℃ after the dropwise adding is finished, stirring for 2-3h, centrifuging after the reaction is finished, washing the precipitate with 40% ethanol solution for 3-5 times by mass fraction, and drying to obtain a modified microcapsule;
wherein, the dosage ratio of the microcapsule, deionized water, absolute ethyl alcohol and N- (6-amino hexyl) -3-amino propyl trimethoxy silane is 5g:10mL:25-35mL:0.3-0.5mL, the dosage ratio of the amination microcapsule, DMF and the mixed liquor a is 3g:50-60mL:10mL of the mixture a, wherein the dosage ratio of the 4-dimethylaminopyridine, the N, N-dicyclohexylcarbodiimide, the 3- (2-pyridyldithio) propionic acid and the DMF is 0.52-0.82g:0.63-1.03mL:0.8-1.2g:10mL, firstly, treating the microcapsule by using N- (6-aminohexyl) -3-aminopropyl trimethoxy silane to obtain an amination microcapsule, and then, carrying out amidation reaction on carboxyl of 3- (2-pyridine dithio) propionic acid and amino on the amination microcapsule by using 4-dimethylaminopyridine as a catalyst and N, N-dicyclohexylcarbodiimide as a dehydrating agent to obtain a modified microcapsule;
in the reaction process, the amount of 3- (2-pyridine dithio) propionic acid is controlled to be slightly lower than that of the amination microcapsule, so that the prepared modified microcapsule has residual amino groups in the reaction process which can participate in.
Further, the preparation method of the modifier comprises the following steps:
adding allyl glycidyl ether and hydrogen-containing silicone oil into isopropanol, heating to 65-75 ℃, adding an isopropanol solution of chloroplatinic acid, continuously stirring for 18-20h, and removing isopropanol under reduced pressure to obtain a modifier, wherein the dosage ratio of the allyl glycidyl ether, the hydrogen-containing silicone oil, the isopropanol solution of chloroplatinic acid and the isopropanol is 3-9mL:100mL: 40. Mu.L: 300mL, hydrogen content of hydrogen-containing silicone oil is 0.5-1.4%, and platinum content in isopropanol solution of chloroplatinic acid is 1%.
In another aspect, the present invention provides the use of a high flash point low VOC diluent as described above in an epoxy coating.
Compared with the prior art, the invention has the following beneficial effects:
(1) In order to improve the dilution viscosity reduction and synergy of the prepared diluent, the invention introduces a phenyl glycidyl aldehyde structure and a modified microcapsule structure in the preparation process of the diluent, the phenyl glycidyl aldehyde structure can endow the diluent with good compatibility with epoxy paint, the outer layer of the modified microcapsule is a chemically crosslinked structure of aminated silicon dioxide and 3- (2-pyridine dithio) propionic acid, the inner core contains the modifier, the aminated silicon dioxide is provided with fatty chains, siloxane structures and silicon dioxide structures, the low-polarity organic silicon structure formed by the fatty chains and the siloxane structures can endow the diluent with low-viscosity property, simultaneously, the epoxy paint can effectively reduce the chain entanglement degree between long-chain resins and intermolecular interaction, effectively reduce the viscosity of epoxy paint, the silicon dioxide structure contains a plurality of active hydroxyl groups, the active hydroxyl groups are easy to form hydrogen bonds with the resins in the epoxy paint, the hydrogen bonds between the resins and the resin molecules are avoided, the 3- (2-pyridine dithio) propionic acid contains pyridine rings and dynamic disulfide bonds, the pyridine rings not only have rigidity, but also can serve as hydrogen bonds, the epoxy paint can be further improved, the epoxy paint can be further reduced by the hydrogen bonds, the epoxy paint has good corrosion resistance and the epoxy paint can be further improved by the epoxy paint with the epoxy paint, and the epoxy paint has good self-viscosity and corrosion resistance, and the epoxy paint has good corrosion resistance and corrosion resistance, the flexibility and corrosion resistance of the coating can be further improved.
(2) In the technical scheme of the invention, the diluent contains high-boiling-point structures such as silicon dioxide, polysiloxane, phenyl glycidyl ether and the like, has high flash point, is healthy, safe and harmless, and meets the requirements of environmental protection.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preferably, the present embodiment provides a preparation method of a modifier, including the following steps:
6mL of allyl glycidyl ether and 100mL of hydrogen-containing silicone oil are added into 300mL of isopropanol, the temperature is raised to 65-75 ℃, 40 mu L of isopropanol solution of chloroplatinic acid is added, stirring is continued for 19h, isopropanol is removed under reduced pressure, and the modifier is obtained, wherein the hydrogen content of the hydrogen-containing silicone oil is 1.0%, and the platinum content of the isopropanol solution of chloroplatinic acid is 1%.
Example 2
Preferably, the embodiment provides a preparation method of the modified microcapsule, which comprises the following steps:
under ice bath, dissolving 0.5g sodium lauryl sulfate and 0.5g emulsifier OP-10 in deionized water, adding 10g modifier prepared in example 1, 10g tetraethoxysilane and 2g octadecyltrimethoxysilane, stirring at 1400rpm for 20min, placing in a cell pulverizer, and carrying out ultrasonic fine emulsification for 25min to obtain a pre-emulsion;
a2, adjusting the pH of the pre-emulsion prepared in the step B1 to 7.5 by using an ammonia water solution with the mass fraction of 25% at room temperature, stirring for 24 hours at room temperature, and drying in vacuum for 14 hours at 60 ℃ to obtain microcapsules;
step A3, after 5g of microcapsules, 10mL of deionized water, 0.4mL of absolute ethyl alcohol and N- (6-aminohexyl) -3-aminopropyl trimethoxy silane are ultrasonically mixed for 30min, stirring and reacting for 7h at room temperature, centrifuging, washing and drying the precipitate to obtain the aminated microcapsules, dispersing 3g of the aminated microcapsules and 55mL of DMF ultrasonically, dropwise adding 0.67g of 4-dimethylaminopyridine, 0.83mL of N, N-dicyclohexylcarbodiimide, 1.0g of 3- (2-pyridyldithio) propionic acid and 10mL of DMF mixed solution a, heating to 110 ℃ after the dropwise adding is finished, stirring for 2.5h, centrifuging, washing the precipitate with 40% ethanol solution for 4 times after the reaction is finished, and drying to obtain the modified microcapsules.
Example 3
The embodiment provides a preparation method of a high-flash-point low-VOC diluent, which comprises the following steps:
step S1, preparing the following raw materials in parts by weight: the material comprises the following raw materials in parts by weight: 16 parts of syringaldehyde, 30 parts of the modified microcapsule prepared in the example 2, 75 parts of N, N-dimethylformamide, 0.9 part of glacial acetic acid, 24 parts of epichlorohydrin, 0.46 part of benzyl triethyl ammonium chloride and 22 parts of base catalyst, wherein the base catalyst is a sodium hydroxide aqueous solution with the mass fraction of 30%;
s2, adding syringaldehyde and the modified microcapsule into N, N-dimethylformamide, adding glacial acetic acid while stirring, and carrying out heating reflux reaction for 4 hours to obtain a Schiff base monomer;
and S3, mixing the Schiff base monomer prepared in the step S2 with epoxy chloropropane, heating to 90 ℃ while stirring, adding benzyl triethyl ammonium chloride, stirring for reacting for 5 hours under the protection of nitrogen, cooling to 65 ℃ after the reaction is finished, dropwise adding 30% sodium hydroxide aqueous solution while stirring, controlling the dropwise adding within 30 minutes, continuing stirring for reacting for 4 hours after the dropwise adding, filtering, precipitating and washing filtrate with hot deionized water for 3 times, dissolving in anhydrous methanol, cooling to-20 ℃, recrystallizing, and placing in vacuum at 30 ℃ for 8 hours to obtain the high-flash-point low-VOC diluent.
Example 4
The embodiment provides a preparation method of a high-flash-point low-VOC diluent, which comprises the following steps:
step S1, preparing the following raw materials in parts by weight: 17 parts of syringaldehyde, 32.5 parts of modified microcapsule prepared in example 2, 85 parts of N, N-dimethylformamide, 1.0 part of glacial acetic acid, 26 parts of epichlorohydrin, 0.50 part of benzyl triethyl ammonium chloride and 24 parts of base catalyst, wherein the base catalyst is a sodium hydroxide aqueous solution with the mass fraction of 30%;
s2, adding syringaldehyde and the modified microcapsule into N, N-dimethylformamide, adding glacial acetic acid while stirring, and carrying out heating reflux reaction for 4.5 hours to obtain a Schiff base monomer;
and S3, mixing the Schiff base monomer prepared in the step S2 with epoxy chloropropane, heating to 92.5 ℃ while stirring, adding benzyl triethyl ammonium chloride, stirring under the protection of nitrogen, reacting for 5.5 hours, cooling to 65 ℃ after the reaction is finished, dropwise adding 30% sodium hydroxide aqueous solution while stirring, controlling the dropwise adding within 30 minutes, continuing to stir and react for 4.5 hours after the dropwise adding, filtering, precipitating and washing the filtrate with hot deionized water for 4 times, dissolving in absolute methanol, cooling to-20 ℃, recrystallizing, and then placing in vacuum drying at 30 ℃ for 10 hours to obtain the high-flash-point low-VOC diluent.
Example 5
The embodiment provides a preparation method of a high-flash-point low-VOC diluent, which comprises the following steps:
step S1, preparing the following raw materials in parts by weight: 18 parts of syringaldehyde, 35 parts of modified microcapsule prepared in example 2, 95 parts of N, N-dimethylformamide, 1.1 parts of glacial acetic acid, 28 parts of epichlorohydrin, 0.54 part of benzyl triethyl ammonium chloride and 26 parts of base catalyst, wherein the base catalyst is a sodium hydroxide aqueous solution with the mass fraction of 30%;
s2, adding syringaldehyde and the modified microcapsule into N, N-dimethylformamide, adding glacial acetic acid while stirring, and carrying out heating reflux reaction for 4-5h to obtain a Schiff base monomer;
and S3, mixing the Schiff base monomer prepared in the step S2 with epoxy chloropropane, heating to 95 ℃ while stirring, adding benzyl triethyl ammonium chloride, stirring for reaction for 6 hours under the protection of nitrogen, cooling to 65 ℃ after the reaction is finished, dropwise adding 30% sodium hydroxide aqueous solution while stirring, controlling the dropwise adding within 30 minutes, continuing stirring for reaction for 5 hours after the dropwise adding, filtering, precipitating and washing filtrate with hot deionized water for 5 times, dissolving in anhydrous methanol, cooling to-20 ℃, recrystallizing, and placing in vacuum at 30 ℃ for 12 hours to obtain the high-flash-point low-VOC diluent.
Comparative example 1
The allyl glycidyl ether in example 1 was removed, the remaining raw materials and preparation process were kept unchanged, the prepared material was replaced with the modifier in example 2, the remaining raw materials and preparation process were kept unchanged, and the prepared material was replaced with the modified microcapsule in example 4, the remaining raw materials and preparation process were kept unchanged.
Comparative example 2
The modifier in example 2 was removed, the remaining materials and preparation were kept unchanged, and the prepared material was replaced with the modified microcapsule in example 4, and the remaining materials and preparation were kept unchanged.
Comparative example 3
The microcapsules of example 2 were removed, the remaining materials and preparation were kept unchanged, and the prepared material was replaced with the modified microcapsules of example 4, the remaining materials and preparation were kept unchanged.
Comparative example 4
The 3- (2-pyridyldithio) propionic acid of example 2 was removed, the remaining materials and preparation were kept unchanged, and the prepared material was replaced with the modified microcapsule of example 4, and the remaining materials and preparation were kept unchanged.
Comparative example 5
This comparative example provides a commercially available absolute ethanol.
Performance detection
The high flash point low VOC diluents prepared in examples 4-6 and comparative examples 1-4 of the present invention were tested for flash point (closed) according to ISO 2719-2016 and the results are shown in Table 1;
TABLE 1
| Detecting items | Lightning (closed) DEG C |
| Example 4 | ＞100 |
| Example 5 | ＞100 |
| Example 6 | ＞100 |
| Comparative example 1 | ＞100 |
| Comparative example 2 | ＞100 |
| Comparative example 3 | ＞100 |
| Comparative example 4 | ＞100 |
| Comparative example 5 | 12 |
As can be seen from Table 1, the diluents prepared in examples 4-6 and comparative examples 1-4 have high flash points of the prepared diluents up to 100℃or more, and the risk of deflagration does not occur during storage and transportation or construction, whereas the flash point of absolute ethanol, which is a common non-reactive diluent for epoxy paint, is low, and there is a serious safety hazard during use and storage.
Application example
The epoxy resin E51 was diluted with the diluents prepared in examples 4 to 6 and comparative examples 1 to 5 of the present invention, the amount of the above-mentioned diluents was 12% by mass of the coating, the amount of the curing agent 4,4' -diaminodicyclohexylmethane was 28% by mass of the coating, and the epoxy coating was obtained by dispersing for 5 minutes at 1700rpm in a high-speed dispersing machine, uniformly mixing, coating the epoxy coating on tin plate with a 60 μm bar, curing for 7d at room temperature, and then the following properties of the epoxy coating were respectively examined:
non-volatile content was tested according to GB/T1725-2007;
viscosity test is carried out by using Discovery DHR-2 rotary rheometer of America TA instruments company at 25deg.C with shear rate of 0.01-300s -1 ；
Testing the hardness of the coating by adopting a pencil hardness tester;
impact resistance of the coating: according to GB/T1732-1993, a BGD 304 paint film impact instrument of Guangzhou Bidada is adopted for testing;
coating flexibility: according to GB/T30791-2014, a T bending machine is adopted for testing, and the test board is repeatedly folded around and the bending stage number is recorded;
corrosion resistance: immersing 2/3 of the coating in 3% sodium chloride solution, 10% sulfuric acid solution and 5% sodium hydroxide solution respectively according to GB/T1763-1979 to observe the time corresponding to the phenomena of paint film spots, flaking, foaming and the like;
TABLE 2
As can be seen from Table 2, compared with comparative examples 1 to 5, the epoxy coating added with the diluents prepared in examples 4 to 6 has a higher nonvolatile content, and thus is more environment-friendly, and at the same time, has more excellent corrosion resistance, viscosity reduction effect and mechanical properties, and therefore, the diluents prepared in the application have more excellent dilution effect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. A method of preparing a high flash point low VOC diluent comprising the steps of:
step S1, preparing the following raw materials in parts by weight: 16-18 parts of syringaldehyde, 30-35 parts of modified microcapsule, 75-95 parts of N, N-dimethylformamide, 0.9-1.1 parts of glacial acetic acid, 24-28 parts of epichlorohydrin, 0.46-0.54 part of benzyl triethyl ammonium chloride and 22-26 parts of base catalyst;
s2, adding syringaldehyde and the modified microcapsule into N, N-dimethylformamide, adding glacial acetic acid while stirring, and carrying out heating reflux reaction for 4-5h to obtain a Schiff base monomer;
step S3, mixing the Schiff base monomer prepared in the step S2 with epoxy chloropropane, heating to 90-95 ℃ while stirring, adding benzyl triethyl ammonium chloride, stirring under the protection of nitrogen, reacting for 5-6 hours, cooling to 65 ℃ after the reaction is finished, dropwise adding a base catalyst while stirring, controlling the dropwise adding within 30 minutes, continuing stirring for 4-5 hours after the dropwise adding, filtering, precipitating and washing filtrate with hot deionized water for 3-5 times, dissolving in anhydrous methanol, cooling to-20 ℃, recrystallizing, and then placing in vacuum at 30 ℃ for 8-12 hours to obtain the high-flash-point environment-friendly diluent;
the modified microcapsule is prepared by carrying out hydrolytic condensation on a modifier, tetraethoxysilane and octadecyl trimethoxysilane, drying to obtain a microcapsule, modifying the microcapsule by N- (6-aminohexyl) -3-aminopropyl trimethoxysilane to obtain an aminated microcapsule, and carrying out amidation reaction on the aminated microcapsule and 3- (2-pyridyldithio) propionic acid;
the modifier is prepared by the hydrosilylation reaction of allyl glycidyl ether and hydrogen-containing silicone oil;
specifically, the preparation method of the modified microcapsule comprises the following steps:
under ice bath, sodium laurylsulfate and an emulsifier OP-10 are dissolved in deionized water, a modifier, tetraethoxysilane and octadecyltrimethoxysilane are added, stirring is carried out for 15-25min at 1300-1500rpm, and then the mixture is placed in a cell pulverizer for ultrasonic fine emulsification for 20-30min, thus obtaining a pre-emulsion;
and (A2) at room temperature, regulating the pH value of the pre-emulsion prepared in the step (B1) to 7.5 by using an ammonia water solution with the mass fraction of 25%, stirring for 24 hours at room temperature, and vacuum drying for 12-16 hours at 60 ℃ to obtain microcapsules, wherein the dosage ratio of the microcapsules to deionized water to absolute ethyl alcohol to N- (6-amino hexyl) -3-amino propyl trimethoxysilane is 5g:10mL:25-35mL:0.3-0.5mL;
step A3, after ultrasonically mixing microcapsules, deionized water, absolute ethyl alcohol and N- (6-aminohexyl) -3-aminopropyl trimethoxy silane for 30min, stirring at room temperature for reacting for 6-8h, centrifuging, precipitating, washing and drying to obtain aminated microcapsules, ultrasonically dispersing the aminated microcapsules and DMF, dropwise adding a mixed solution a of 4-dimethylaminopyridine, N-dicyclohexylcarbodiimide, 3- (2-pyridyldithio) propionic acid and DMF, heating to 110 ℃ after the dropwise adding is finished, stirring for 2-3h, centrifuging after the reaction is finished, washing the precipitate with 40% ethanol solution for 3-5 times by mass fraction, and drying to obtain modified microcapsules, wherein the dosage ratio of the aminated microcapsules to the DMF to the mixed solution a is 3g:50-60mL:10mL.
2. The method of preparing a high flash point low VOC diluent according to claim 1, characterized by: the preparation method of the modifier comprises the following steps:
adding allyl glycidyl ether and hydrogen-containing silicone oil into isopropanol, heating to 65-75 ℃, adding an isopropanol solution of chloroplatinic acid, continuously stirring for 18-20h, and removing isopropanol under reduced pressure to obtain the modifier.
3. The method of preparing a high flash point low VOC diluent according to claim 1, characterized by: in the step A1, the dosage ratio of sodium lauryl sulfate, emulsifier OP-10, deionized water, modifier, tetraethoxysilane and octadecyltrimethoxysilane is 0.25-0.75g:0.25-0.75g:10g:9.5-10.5g:1.5-2.5g.
4. The method of preparing a high flash point low VOC diluent according to claim 1, characterized by: the dosage ratio of 4-dimethylamino pyridine, N-dicyclohexylcarbodiimide, 3- (2-pyridine dithio) propionic acid and DMF in the mixed solution a is 0.52-0.82g:0.63-1.03mL:0.8-1.2g:10mL.
5. A method of preparing a high flash point low VOC diluent according to claim 2, characterized by: the dosage ratio of the allyl glycidyl ether, hydrogen-containing silicone oil, isopropyl alcohol solution of chloroplatinic acid and isopropyl alcohol is 3-9mL:100mL: 40. Mu.L: 300mL, hydrogen content of hydrogen-containing silicone oil is 0.5-1.4%, and platinum content in isopropanol solution of chloroplatinic acid is 1%.
6. The method of preparing a high flash point low VOC diluent according to claim 1, characterized by: the alkali catalyst is a sodium hydroxide aqueous solution with the mass fraction of 30%.
7. Use of the method for the preparation of a high flash point low VOC diluent according to any of claims 1-6 in epoxy coatings.
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| CN106432735A (en) * | 2016-09-18 | 2017-02-22 | 安徽科光新材料有限公司 | Double-terminated epoxy silicone oil and preparation method thereof |
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