CN112920713B - Allyl modified raw lacquer and preparation method thereof - Google Patents
Allyl modified raw lacquer and preparation method thereof Download PDFInfo
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- CN112920713B CN112920713B CN202110212970.8A CN202110212970A CN112920713B CN 112920713 B CN112920713 B CN 112920713B CN 202110212970 A CN202110212970 A CN 202110212970A CN 112920713 B CN112920713 B CN 112920713B
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- 239000004922 lacquer Substances 0.000 title claims abstract description 155
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 allyl ether ester Chemical class 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 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 abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 102
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 38
- 239000000376 reactant Substances 0.000 claims description 27
- 239000012074 organic phase Substances 0.000 claims description 25
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 24
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 23
- 239000012153 distilled water Substances 0.000 claims description 23
- 239000011630 iodine Substances 0.000 claims description 23
- 229910052740 iodine Inorganic materials 0.000 claims description 23
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001723 curing Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- 239000005028 tinplate Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 3
- NKFIBMOQAPEKNZ-UHFFFAOYSA-N 5-amino-1h-indole-2-carboxylic acid Chemical compound NC1=CC=C2NC(C(O)=O)=CC2=C1 NKFIBMOQAPEKNZ-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 3
- 150000008064 anhydrides Chemical group 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 claims description 3
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 3
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 2
- 239000002184 metal Substances 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 21
- 239000007788 liquid Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 108010029541 Laccase Proteins 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 2
- RMTXUPIIESNLPW-UHFFFAOYSA-N 1,2-dihydroxy-3-(pentadeca-8,11-dienyl)benzene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1O RMTXUPIIESNLPW-UHFFFAOYSA-N 0.000 description 1
- QARRXYBJLBIVAK-UEMSJJPVSA-N 3-[(8e,11e)-pentadeca-8,11-dienyl]benzene-1,2-diol;3-[(8e,11e)-pentadeca-8,11,14-trienyl]benzene-1,2-diol;3-[(8e,11e,13e)-pentadeca-8,11,13-trienyl]benzene-1,2-diol;3-[(e)-pentadec-8-enyl]benzene-1,2-diol;3-pentadecylbenzene-1,2-diol Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O.CCCCCC\C=C\CCCCCCCC1=CC=CC(O)=C1O.CCC\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.C\C=C\C=C\C\C=C\CCCCCCCC1=CC=CC(O)=C1O.OC1=CC=CC(CCCCCCC\C=C\C\C=C\CC=C)=C1O QARRXYBJLBIVAK-UEMSJJPVSA-N 0.000 description 1
- IYROWZYPEIMDDN-UHFFFAOYSA-N 3-n-pentadec-8,11,13-trienyl catechol Natural products CC=CC=CCC=CCCCCCCCC1=CC=CC(O)=C1O IYROWZYPEIMDDN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- DQTMTQZSOJMZSF-UHFFFAOYSA-N urushiol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1O DQTMTQZSOJMZSF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C09D193/00—Coating compositions based on natural resins; Coating compositions based on derivatives thereof
-
- 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
-
- 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
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
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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)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses allyl modified raw lacquer and a preparation method thereof. Under the action of a catalyst, raw lacquer reacts with allyl glycidyl ether to generate allyl ether modified raw lacquer (AGE-L), and then reacts with methacrylic anhydride to obtain allyl ether ester modified raw lacquer (MAA-AGE-L). The allyl modified raw lacquer prepared by the invention has the light/oxygen dual-curing characteristic, the activity of ultraviolet light/oxygen dual-curing reaction of the modified raw lacquer can be controlled by adjusting the content of allyl ether and allyl ester groups in the modified raw lacquer, and a cured product is transparent and light yellow, has excellent mechanical property and chemical medium resistance, and can be applied to coating of woodware, metal, plastics and the like.
Description
Technical Field
The invention relates to allyl modified raw lacquer and a preparation method thereof, in particular to a method for preparing allyl modified raw lacquer by reacting raw lacquer with allyl glycidyl ether and methacrylic anhydride.
Background
The natural raw lacquer is dried to form a film mainly under the action of laccase, and the film forming process is slow and is limited by temperature and humidity (the optimal pH value is 6.5 +/-0.5, the temperature is 25-35 ℃, and the relative humidity is 60-90%). Although the paint film of the natural raw lacquer has good chemical corrosion resistance, the paint film is generally darker in color and large in brittleness, and the popularization and application of the paint film are restricted by the performance defects of the natural raw lacquer.
At present, the quick-drying technology of raw lacquer is mainly realized by physical and chemical methods such as blending, grafting and the like. Patents CN201310714996.8, CN201310715388.9 and CN201310716528.4 disclose methods of photo-curing and film-forming by modifying raw lacquer with organosilicon containing amino, epoxy and olefin groups, respectively. Lu et al (Progress in Organic Coatings,2004,51(3):238-243) modify raw lacquer by amino-containing Organic silicon, and utilize the synergistic catalysis of laccase and Organic silicon, so that the surface drying time of the raw lacquer is shortened from 4.5h to about 1h, and the drying speed of the raw lacquer is effectively improved. A series of self-drying modified raw lacquers are prepared from the polypropylene ring (Chinese raw lacquer, 2000,19(3):1-7) by using metal compound modified urushiol, can be naturally dried to form a film and is not influenced by laccase and temperature and humidity.
Although the above method can increase the drying speed of raw lacquer, the drying time is still long, and usually about 1h is needed. In recent years, ultraviolet curing technology provides a new method for improving the drying speed of raw lacquer. Xiujiangrong (doctor academic thesis, 2011, college of chemistry and materials, university of Fujian province) makes the natural raw lacquer quickly dry and solidify within 2min by ultraviolet light-initiated polymerization without an external photoinitiator. Although the photocuring technology can improve the drying film-forming speed of the natural raw lacquer, the problems of low flexibility, low impact strength, deep color and the like of a paint film still exist.
According to the invention, structural units such as allyl ether and allyl ester are introduced into the urushiol molecular structure of the raw lacquer, so that ultraviolet/oxygen dual-curing reaction activity of the modified raw lacquer is endowed, and the ultraviolet/oxygen curing reaction speed is regulated and controlled by controlling the content of double bonds of different types, so that the controllable curing of the coating is realized. The allyl modified raw lacquer has the characteristics of high ultraviolet curing speed, light color of cured substances, excellent mechanical property and the like, and can be applied to the fields of high-performance special coatings and the like.
Disclosure of Invention
The invention provides allyl modified raw lacquer and a preparation method thereof. The paint film has fast drying speed, light color, excellent mechanical performance and chemical medium resistance.
The technical scheme of the invention is as follows: the allyl modified raw lacquer comprises the following main components in the chemical structural formula:
the preparation method of the allyl modified raw lacquer comprises the following steps:
the first step is as follows: under the action of a catalyst, raw lacquer reacts with allyl glycidyl ether at the temperature of 80-140 ℃ for 2-10 h; after the reaction is finished, washing the reactant to be neutral by water, and distilling an organic phase under reduced pressure to obtain allyl ether modified raw lacquer (AGE-L);
the second step is that: under the action of a catalyst and a polymerization inhibitor, AGE-L and methacrylic anhydride (MAA) react for 2 to 8 hours at the temperature of between 60 and 110 ℃; after the reaction is finished, washing the reactant with saturated sodium bicarbonate water solution, saturated sodium chloride water solution and distilled water to be neutral, and distilling an organic phase under reduced pressure to obtain allyl ether ester modified raw lacquer (MAA-AGE-L);
the chemical reaction formula of the preparation process is as follows:
in the first step, the catalyst is any one or more of potassium hydroxide, sodium hydroxide, benzyltriethylammonium chloride and benzyldimethylamine, and the using amount of the catalyst is 1-5% of the mass of the raw lacquer; the ratio of the phenolic hydroxyl group of the raw lacquer to the allyl glycidyl ether substance is 1: 1-2.5.
In the second step, the catalyst is one or more of sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, 4-dimethylaminopyridine, anhydrous sodium ethoxide and p-toluenesulfonic acid, and the using amount of the catalyst is 0.5-6% of the mass of AGE-L; the polymerization inhibitor is any one or more of hydroquinone, 4-methoxyphenol, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, methyl hydroquinone and tetrachlorobenzoquinone, and the dosage of the polymerization inhibitor is 0.5-5% of the total mass of reactants; the ratio of the hydroxyl group of the allyl ether modified raw lacquer to the amount of the anhydride group substance of methacrylic anhydride is 1: 1-1.5.
In the first step, the optimal preparation reaction conditions of the allyl ether modified raw lacquer are as follows: the catalyst is potassium hydroxide with the usage of 2 wt% of raw lacquer, the ratio of the raw lacquer phenolic hydroxyl group to the allyl glycidyl ether substance is 1:2, the reaction temperature is 100 ℃, and the reaction time is 4 hours; under the reaction condition, the obtained allyl ether modified raw lacquer has an iodine value of 189g I2100g, a hydroxyl number of 193mg KOH/g.
In the second step, the optimal preparation reaction conditions of the allyl ether ester modified raw lacquer are as follows: the catalyst is 4-dimethyl with 1 percent of raw lacquer by weightAminopyridine, wherein the polymerization inhibitor is 4-methoxyphenol with the raw lacquer dosage of 0.5 percent, the ratio of the allyl ether modified raw lacquer hydroxyl to the methacrylic anhydride is 1:1.1, the reaction temperature is 90 ℃, and the reaction time is 2 hours; under the reaction condition, the obtained allyl ether ester modified raw lacquer has an iodine value of 138g I2100g, hydroxyl value of 20mg KOH/g.
The allyl modified raw lacquer is applied to ultraviolet light/oxygen dual-curing film formation.
The allyl modified raw lacquer is dried to form a film under the irradiation of ultraviolet light; mixing allyl modified raw lacquer and photoinitiator uniformly at normal temperature, sampling and coating on a tinplate, wherein the thickness of the coating is 25 μm, an electrodeless lamp (iron) is used as a light source, and the dominant wavelength of ultraviolet light is 365nm, and the light intensity is 216mW/cm2Irradiating for 120s under the condition to form a film; the initiator is any one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzoin dimethyl ether, a photoinitiator 4265, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, diaryl iodonium salt and triaryl sulfonium salt, and the using amount of the initiator is 0.1-10 wt% of the mass of the allyl modified raw lacquer.
The allyl modified raw lacquer is dried to form a film in an oxygen or air environment; the allyl modified raw lacquer and the drier are mixed evenly at normal temperature, sampled and coated on a tinplate, the thickness of the coating is 15 mu m, and the tinplate is dried to form a film in a constant temperature and humidity box with the temperature of 25-35 ℃ and the relative humidity of 40-90 percent within one week.
The drier is any one or more of cobalt iso-octoate, manganese iso-octoate, lead iso-octoate, zinc iso-octoate, calcium iso-octoate, cobalt naphthenate, manganese naphthenate, lead naphthenate, zinc naphthenate and calcium naphthenate, and the using amount of the drier is 0-5 wt% of the mass of the allyl modified raw lacquer.
The invention has the beneficial effects that:
1. synthesizing an allyl modified raw lacquer which has the dual characteristics of being capable of being dried to form a film under the environment of ultraviolet irradiation or oxygen (air);
2. the allyl modified raw lacquer has fast drying and film forming speed, light color of a paint film, excellent mechanical property and excellent chemical corrosion resistance. By adjusting the content of allyl ether and allyl ester groups in the modified raw lacquer, the ultraviolet/oxygen curing reaction activity and the lacquer film property of the modified raw lacquer can be effectively controlled.
Drawings
FIG. 1 film appearance of raw lacquer and allyl-modified raw lacquer.
FIG. 2 is a graph of the infrared spectra (FT-IR) of raw lacquer and allyl modified raw lacquer.
FIG. 3 NMR spectra of raw lacquer and allyl-modified raw lacquer: (1H NMR) graph.
Lacquer: raw lacquer; AGE-L: allyl ether modified raw lacquer; MAA-AGE-L: allyl ether ester modified raw lacquer. Infrared spectrum of allyl modified raw lacquer (fig. 2): 3481cm-1Is located at 3384cm, which is a phenolic hydroxyl group stretching vibration absorption peak-1Is at alcoholic hydroxyl absorption peak of 1718cm-1Is represented by C ═ O absorption peak, 1086cm-1Is at an ether bond absorption peak of 925cm-1Is shown as an absorption peak of the unsaturated double bond of the allyl ether at 814cm-1The absorption peak of unsaturated double bond of allyl ester is shown.
Of allyl-modified raw lacquer1HNMR spectra (fig. 3): raw lacquer: δ 7.99 (. delta.OH) on the side chain ortho-phenolic hydroxyl group,. delta.9.15 (. delta.OH) on the side chain meta-phenolic hydroxyl group; AGE-L: δ 3.37 (OH generated by ring opening of epoxy), δ 4.94 to 4.97, and 3.42 to 3.47 (hydrogen introduced after ring opening of allyl glycidyl ether), δ 5.40 to 5.91, and 5.08 to 5.29 (allyl glycidyl ether-CH ═ CH)2Hydrogen of (d); MAA-AGE-L: delta 6.05 to 6.28, 5.56, 4.17, 3.52 to 3.60 and 1.80 to 1.87 (in allyl ester group, -CH)3And terminal-C ═ CH2Hydrogen).
Detailed Description
An allyl modified raw lacquer and a preparation method thereof. The method is realized by the following steps:
the first step is as follows: under the action of a catalyst, raw lacquer reacts with allyl glycidyl ether at the temperature of 80-140 ℃ for 2-10 h; after the reaction is finished, the reactant is washed to be neutral by water, and the organic phase is distilled under reduced pressure to obtain allyl ether modified raw lacquer (AGE-L).
The second step is that: under the action of a catalyst and a polymerization inhibitor, AGE-L and methacrylic anhydride (MAA) react for 2 to 8 hours at the temperature of between 60 and 110 ℃; after the reaction is finished, the reactant is washed to be neutral by saturated sodium bicarbonate water solution, saturated sodium chloride water solution and distilled water, and the organic phase is distilled under reduced pressure to obtain the allyl ether ester modified raw lacquer (MAA-AGE-L).
In the first step, the amount ratio of the phenolic hydroxyl group of the raw lacquer to the allyl glycidyl ether substance is 1: 1-2.5; the catalyst comprises one or more of potassium hydroxide, sodium hydroxide, benzyltriethylammonium chloride and benzyldimethylamine, and the using amount of the catalyst is 0.5-5% of the mass of the raw lacquer; the optimal reaction temperature is 100 ℃, and the optimal reaction time is 6 h.
In the second step, the ratio of hydroxyl groups of the allyl ether modified raw lacquer (AGE-L) to the amount of methacrylic anhydride to anhydride group substances is 1: 1-1.5; the catalyst comprises one or more of sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, 4-dimethylamino pyridine, anhydrous sodium ethoxide, p-toluenesulfonic acid or tertiary amine, and the amount of the catalyst is 0.5-6% of the weight of the raw paint; the polymerization inhibitor comprises one or more of hydroquinone, 4-methoxyphenol, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, methyl hydroquinone and tetrachlorobenzoquinone, and the amount of the polymerization inhibitor is 0.5-5% of the weight of the raw paint; the optimal reaction temperature is 90 ℃, and the optimal reaction time is 2 h.
The allyl modified raw lacquer has ultraviolet light/oxygen dual-curing characteristics, and can be dried to form a film under ultraviolet light irradiation or an oxygen (air) environment.
The allyl modified raw lacquer can be dried into a film under the irradiation of ultraviolet light, and is characterized in that a certain amount of the allyl modified raw lacquer and a photoinitiator are uniformly mixed at normal temperature, a sample is coated on a tinplate (the thickness of the coating is 25 mu m), an electrodeless lamp (iron) is used as a light source, the dominant wavelength of the ultraviolet light is 365nm, and the light intensity is 216mW/cm2Irradiating under the condition for 120s to dry and form a film.
The initiator is any one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone (photoinitiator 1173), benzoin dimethyl ether (photoinitiator BDK651), photoinitiator 4265 (50% TPO, 50% 1173), phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide (photoinitiator 819), diaryl iodonium salt and triaryl sulfonium salt, and the using amount of the initiator is 0.1-10% of the mass of the allyl modified raw lacquer.
The allyl modified raw lacquer can be dried to form a film in an oxygen (air) environment, and is characterized in that a certain amount of the allyl modified raw lacquer and a drier are uniformly mixed at normal temperature, sampled and coated on a tinplate (the thickness of the coating is 15 mu m), and the tinplate is placed in a constant temperature and humidity cabinet with the temperature of 25-35 ℃ and the relative humidity of 40-90% to be dried to form a film within one week.
The drier is one or more of cobalt iso-octoate, manganese iso-octoate, lead iso-octoate, zinc iso-octoate, calcium iso-octoate, cobalt naphthenate, manganese naphthenate, lead naphthenate, zinc naphthenate and calcium naphthenate, and the using amount of the drier is 0-5% of the mass of the allyl modified raw lacquer.
Example 1
20g of raw lacquer, 32g of allyl glycidyl ether and 0.4g of potassium hydroxide were placed in a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, distilling the organic phase under reduced pressure to obtain a red-brown transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 193mg KOH/g and iodine value of 189g I2100g, viscosity 400 mPas (25 ℃).
20g of AGE-L, 0.2g of 4-dimethylaminopyridine and 0.1g of 4-methoxyphenol were added to a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and the mixture was stirred to raise the temperature to 90 ℃ and then 24g of methacrylic anhydride was slowly added dropwise thereto, followed by reaction for 2 hours. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value of 20mg KOH/g and iodine value of 138gI2100g, viscosity 2000 mPas (25 ℃).
Example 2
20g of raw lacquer, 48g of allyl glycidyl ether and 0.4g of potassium hydroxide were placed in a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and reacted at 100 ℃ for 4 hours. Washing the reaction mixture with distilled water to neutral, and organic phaseDistilling under reduced pressure to obtain a red brown transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 200mg KOH/g and iodine value of 182g I2100g, viscosity 380 mPas (25 ℃).
20g of AGE-L, 0.2g of 4-dimethylaminopyridine and 0.1g of 4-methoxyphenol were added to a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and the mixture was stirred to raise the temperature to 90 ℃ and then 24g of methacrylic anhydride was slowly added dropwise thereto, followed by reaction for 2 hours. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value of 26mg KOH/g and iodine value of 160g I2100g, viscosity 1800 mPas (25 ℃).
Example 3
20g of raw lacquer, 32g of allyl glycidyl ether and 0.6g of potassium hydroxide were placed in a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, vacuum distilling the organic phase to obtain red brown transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 180mg KOH/g and iodine value of 176g I2100g, viscosity 480 mPas (25 ℃).
In a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, 20g of the above AGE-L, 0.2g of 4-dimethylaminopyridine and 0.1g of 4-methoxyphenol were charged, and the mixture was stirred to raise the temperature to 90 ℃ and 22.9g of methacrylic anhydride was slowly added dropwise, followed by reaction for 2 hours after completion of the addition. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value 35mg KOH/g and iodine value 125g I2100g of a polymer and a viscosity of 2200 mPas (25 ℃).
Example 4
20g of raw lacquer, 32g of allyl glycidyl ether and 0.4g of benzyltriethylammonium chloride were placed in a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, respectively, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, vacuum distilling the organic phase to obtain red brown transparent liquid,namely allyl ether modified raw lacquer (AGE-L), the hydroxyl value of which is 173mg KOH/g and the iodine value of which is 168g I2100g, viscosity 300 mPas (25 ℃).
In a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, 20g of the above AGE-L, 0.2g of 4-dimethylaminopyridine and 0.1g of 4-methoxyphenol were charged, and the mixture was stirred to raise the temperature to 90 ℃ and 22.9g of methacrylic anhydride was slowly added dropwise, followed by reaction for 2 hours after completion of the addition. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value of 30mg KOH/g and iodine value of 140g I2100g, viscosity 1800 mPas (25 ℃).
Example 5
20g of raw lacquer, 32g of allyl glycidyl ether and 0.4g of potassium hydroxide were placed in a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, distilling the organic phase under reduced pressure to obtain a red-brown transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 193mg KOH/g and iodine value of 189g I2100g, viscosity 400 mPas (25 ℃).
In a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, 20g of the above AGE-L, 0.2g of 4-dimethylaminopyridine and 0.1g of 4-methoxyphenol were charged, and the mixture was stirred to raise the temperature to 90 ℃ and 22.9g of methacrylic anhydride was slowly added dropwise, followed by reaction for 2 hours after completion of the addition. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value of 25mg KOH/g and iodine value of 145g I2100g, viscosity 2100 mPas (25 ℃).
Example 6
20g of raw lacquer, 32g of allyl glycidyl ether and 0.4g of potassium hydroxide were placed in a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, distilling the organic phase under reduced pressure to obtain brownish red transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 193mgKOH/g, iodine number 189g I2100g, viscosity 400 mPas (25 ℃).
In a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, 20g of the above AGE-L, 0.2g of 4-dimethylaminopyridine and 0.1g of 4-methoxyphenol were charged, and the mixture was stirred to 80 ℃ and slowly added dropwise with 22.9g of methacrylic anhydride, followed by reaction for 2 hours after completion of the dropwise addition. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value 35mg KOH/g and iodine value 120g I2100g, viscosity 1500 mPas (25 ℃).
Example 7
In a 250mL four-necked round bottom flask equipped with a stirrer, a condenser and a thermometer, 20g of raw lacquer, 25.3g of allyl glycidyl ether and 0.4g of sodium hydroxide were charged, respectively, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, distilling the organic phase under reduced pressure to obtain a red-brown transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 208mg KOH/g and iodine value of 193g I2100g, viscosity 450 mPas (25 ℃).
20g of AGE-L, 0.2g of pyridine and 0.1g of hydroquinone were put into a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, stirred and heated to 80 ℃ and 22.9g of methacrylic anhydride was slowly added dropwise, and the reaction was carried out for 2 hours after the addition. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value of 26mg KOH/g and iodine value of 135g I2100g of the polymer, viscosity 1880 mPas (25 ℃).
Example 8
In a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, 20g of raw lacquer, 24.4g of allyl glycidyl ether and 0.6g of benzyldimethylamine were charged, respectively, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, distilling the organic phase under reduced pressure to obtain a brownish red transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 230mg KOH/g and iodine value of 179g I2100g, viscosity 470 mPas (25 ℃).
20g of AGE-L, 0.2g of sulfuric acid, and 0.1g of 2, 6-di-t-butyl-p-cresol were put into a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser, and a thermometer, and the mixture was stirred to 80 ℃ to slowly add 22.9g of methacrylic anhydride dropwise thereto, followed by reaction for 2 hours. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value of 41mg KOH/g and iodine value of 116g I2100g of the polymer, and a viscosity of 1760 mPas (25 ℃).
Example 9
In a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, 20g of raw lacquer, 25.7g of allyl glycidyl ether and 0.6g of benzyldimethylamine were charged, respectively, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, distilling the organic phase under reduced pressure to obtain a red-brown transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), with hydroxyl value of 169mg KOH/g and iodine value of 171g I2100g, viscosity 550 mPas (25 ℃).
20g of AGE-L, 0.2g of p-toluenesulfonic acid and 0.1g of p-benzoquinone were added to a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, and stirred to 80 ℃ to slowly add 22.9g of methacrylic anhydride dropwise, followed by reaction for 2 hours after the dropwise addition. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value 43mg KOH/g and iodine value 117g I2100g, viscosity 2100 mPas (25 ℃).
Example 10
In a 250mL four-necked round-bottomed flask equipped with a stirrer, a condenser and a thermometer, 20g of raw lacquer, 24.4g of allyl glycidyl ether and 0.4g of potassium hydroxide were charged, respectively, and reacted at 100 ℃ for 6 hours. Washing the reactant with distilled water to neutrality, distilling the organic phase under reduced pressure to obtain a red-brown transparent liquid, i.e. allyl ether modified raw lacquer (AGE-L), measuring hydroxyl value of 186mg KOH/g and iodine value of 167g I2100g, viscosity 450 mPas (25 ℃).
In the condenser pipe with a stirrerAnd a thermometer into a 250mL four-necked round-bottomed flask, 20g of the above AGE-L, 0.2g of zinc chloride and 0.1g of 2-t-butylhydroquinone were added, and the mixture was stirred and heated to 80 ℃ to slowly add 22.9g of methacrylic anhydride dropwise, followed by reaction for 2 hours after completion of the addition. Washing the reactant with saturated sodium bicarbonate, saturated sodium chloride water solution and distilled water to neutrality, vacuum distilling the organic phase to obtain orange red transparent liquid, i.e. allyl ether ester modified raw lacquer (MAA-AGE-L), measuring hydroxyl value of 47mg KOH/g and iodine value of 109g I2100g of a polymer and a viscosity of 2200 mPas (25 ℃).
Example 11
And irradiating AGE-L and MAA-AGE-L with ultraviolet light to dry and form a film. Uniformly mixing 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone (photoinitiator 1173) and 100g of allyl ether modified raw lacquer (AGE-L) or allyl ether ester modified raw lacquer (MAA-AGE-L) at normal temperature, sampling and coating on a tinplate (coating thickness is 25 mu m), taking an electrodeless lamp (iron) as a light source, and performing ultraviolet light dominant wavelength of 365nm and light intensity of 216mW/cm2Under the condition of irradiation for 120s, the paint film is dried into a film, the paint film is transparent and light yellow, the pencil hardness of the paint films of AGE-L and MAA-AGE-L respectively reaches H and 2H, the paint film is not abnormal after being soaked in water, absolute ethyl alcohol and 5% NaCl aqueous solution for 7 days, and the paint film is dried into a film by 10% HCl and 10% H2SO4No abnormality is found after 3 days of middle-soaking. Under the same condition, the paint film of the natural raw lacquer is brownish yellow, and the pencil hardness is B grade.
Example 12
AGE-L and MAA-AGE-L are dried in an oxygen (air) atmosphere to form a film. Under the condition of not adding any drier, the allyl modified raw lacquer is very slow in oxidation curing, long in curing time and slow in improvement of film performance, and the curing speed and the film performance can be effectively improved after the drier is added. 3g of cobalt iso-octoate (cobalt iso-octoate content is 12 wt%) and 100g of allyl ether modified raw lacquer (AGE-L) or allyl ether ester modified raw lacquer (MAA-AGE-L) are uniformly mixed at normal temperature, a sample is coated on a tinplate (coating thickness is 15 mu m), the tinplate is placed in a constant temperature and humidity box with the temperature of 30 ℃ and the relative humidity of 80%, the MAA-AGE-L is dried within 50min, and the AGE-L is dried within 2 h. Placing in a constant temperature and humidity box with the temperature of 30 ℃ and the relative humidity of 80 percent for a week, completely curing the paint film, wherein the paint film is transparent and light yellow, the pencil hardness of AGE-L and MAA-AGE-L paint films is 2H, and the paint film is prepared by mixing water, sodium chloride, potassium chloride, sodium chloride,the product is free from abnormal condition after being soaked in absolute ethyl alcohol and 5% NaCl water solution for 7 days, and is soaked in 10% HCl and 10% H2SO4No abnormality is found after 3 days of middle-soaking. Under the same conditions, the paint film of the natural raw lacquer is black, and the pencil hardness is H.
The film properties of the raw lacquer and the allyl-modified raw lacquer are shown in tables 1 and 2.
TABLE 1 mechanical Properties of raw lacquer and allyl-modified raw lacquer cured lacquer film
TABLE 2 resistance of allyl-modified raw lacquer to chemical media
Note: 1) "+" indicates that the paint film is normal and "-" indicates that the paint film is abnormal.
2) Soaking in water, ethanol and 5% NaCl for 7 days, 10% HCl and 10% H2SO4The soaking time is 3 days, and the soaking time is 3 hours by using 10 percent NaOH.
Claims (9)
1. A preparation method of allyl modified raw lacquer is characterized by comprising the following steps:
the first step is as follows: under the action of a catalyst, raw lacquer reacts with allyl glycidyl ether at the temperature of 80-140 ℃ for 2-10 h; after the reaction is finished, washing the reactant to be neutral by water, and carrying out reduced pressure distillation on an organic phase to obtain allyl ether modified raw lacquer AGE-L;
the second step is that: under the action of a catalyst and a polymerization inhibitor, AGE-L and methacrylic anhydride MAA react for 2-8 h at the temperature of 60-110 ℃; after the reaction is finished, washing the reactant with a saturated sodium bicarbonate aqueous solution, a saturated sodium chloride aqueous solution and distilled water to be neutral, and distilling an organic phase under reduced pressure to obtain allyl ether ester modified raw lacquer MAA-AGE-L;
the chemical reaction formula of the preparation process is as follows:
2. the preparation method of the allyl modified raw lacquer as claimed in claim 1, wherein in the first step, the catalyst is any one or more of potassium hydroxide, sodium hydroxide, benzyltriethylammonium chloride and benzyldimethylamine, and the using amount of the catalyst is 1-5% of the mass of the raw lacquer; the ratio of the phenolic hydroxyl group of the raw lacquer to the allyl glycidyl ether substance is 1: 1-2.5.
3. The preparation method of the allyl modified raw lacquer as claimed in claim 1, wherein in the second step, the catalyst is one or more of sulfuric acid, perchloric acid, zinc chloride, ferric trichloride, pyridine, 4-dimethylaminopyridine, anhydrous sodium ethoxide and p-toluenesulphonic acid, and the amount of the catalyst is 0.5-6% of the mass of AGE-L; the polymerization inhibitor is any one or more of hydroquinone, 4-methoxyphenol, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, methyl hydroquinone and tetrachlorobenzoquinone, and the using amount of the polymerization inhibitor is 0.5-5% of the total mass of reactants; the ratio of the hydroxyl group of the allyl ether modified raw lacquer to the amount of the anhydride group substance of methacrylic anhydride is 1: 1-1.5.
4. The method for preparing allyl-modified raw lacquer according to claim 1, wherein in the first step, the optimal reaction conditions for preparing the allyl ether-modified raw lacquer are as follows: the catalyst is potassium hydroxide with the usage of 2 wt% of raw lacquer, the ratio of the raw lacquer phenolic hydroxyl group to the allyl glycidyl ether substance is 1:2, the reaction temperature is 100 ℃, and the reaction time is 4 hours; under the reaction conditions, the obtained alkeneIodine value of propyl ether modified raw lacquer is 189g I2100g, a hydroxyl number of 193mg KOH/g.
5. The method for preparing allyl ether ester modified raw lacquer according to claim 1, wherein in the second step, the optimal reaction conditions for preparing the allyl ether ester modified raw lacquer are as follows: 4-dimethylamino pyridine with the raw lacquer consumption of 1 wt% is used as a catalyst, 4-methoxyphenol with the raw lacquer consumption of 0.5 wt% is used as a polymerization inhibitor, the mass ratio of allyl ether modified raw lacquer hydroxyl to methacrylic anhydride is 1:1.1, the reaction temperature is 90 ℃, and the reaction time is 2 hours; under the reaction condition, the obtained allyl ether ester modified raw lacquer has an iodine value of 138g I2100g, hydroxyl value of 20mg KOH/g.
6. Use of the allyl modified raw lacquer prepared by the method of claim 1 in uv/oxygen dual curing film formation.
7. The use according to claim 6, wherein the allyl-modified raw lacquer is dried to a film under UV irradiation; mixing allyl modified raw lacquer and photoinitiator uniformly at normal temperature, sampling and coating on tinplate, wherein the coating thickness is 25 percentμm, using electrodeless lamp iron as light source, and using ultraviolet light with dominant wavelength of 365nm and light intensity of 216mW/cm2Irradiating for 120s under the condition to form a film; the initiator is any one or more of 2-hydroxy-2-methyl-1-phenyl-1-acetone, benzoin dimethyl ether, a photoinitiator 4265, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, diaryl iodonium salt and triaryl sulfonium salt, and the using amount of the initiator is 0.1-10 wt% of the mass of the allyl modified raw lacquer.
8. The use according to claim 6, wherein the allyl-modified raw lacquer is dried to a film in an atmosphere containing oxygen; mixing allyl modified raw lacquer and drier uniformly at normal temperature, sampling and coating on tinplate with a coating thickness of 15%μAnd m, drying the film in a constant temperature and humidity box with the temperature of 25-35 ℃ and the relative humidity of 40-90% within one week to form the film.
9. The use according to claim 8, wherein the drier is any one or more of cobalt iso-octoate, manganese iso-octoate, lead iso-octoate, zinc iso-octoate, calcium iso-octoate, cobalt naphthenate, manganese naphthenate, lead naphthenate, zinc naphthenate and calcium naphthenate, and the amount of the drier is 0-5% of the mass of the allyl modified raw lacquer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504971A (en) * | 2016-01-21 | 2016-04-20 | 南京林业大学 | Epoxy-resin-modified UV (ultraviolet) raw lacquer ink for digital jet printing and preparation method thereof |
| CN107345087A (en) * | 2016-05-05 | 2017-11-14 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of laccol propenyl ether photocuring film |
| CN107779095A (en) * | 2016-08-30 | 2018-03-09 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of laccol propenoic acid ester photocureable film |
| CN109734588A (en) * | 2019-02-14 | 2019-05-10 | 中国林业科学研究院林产化学工业研究所 | A kind of ether-containing, ester bond allyl anacardol monomer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105504971A (en) * | 2016-01-21 | 2016-04-20 | 南京林业大学 | Epoxy-resin-modified UV (ultraviolet) raw lacquer ink for digital jet printing and preparation method thereof |
| CN107345087A (en) * | 2016-05-05 | 2017-11-14 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of laccol propenyl ether photocuring film |
| CN107779095A (en) * | 2016-08-30 | 2018-03-09 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation method of laccol propenoic acid ester photocureable film |
| CN109734588A (en) * | 2019-02-14 | 2019-05-10 | 中国林业科学研究院林产化学工业研究所 | A kind of ether-containing, ester bond allyl anacardol monomer and preparation method thereof |
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