CN115819226B - Method for synthesizing o-phenylphenoxyethyl acrylate - Google Patents
Method for synthesizing o-phenylphenoxyethyl acrylate Download PDFInfo
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- CN115819226B CN115819226B CN202211574849.0A CN202211574849A CN115819226B CN 115819226 B CN115819226 B CN 115819226B CN 202211574849 A CN202211574849 A CN 202211574849A CN 115819226 B CN115819226 B CN 115819226B
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- phenylphenoxyethanol
- phenylphenoxyethyl acrylate
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- VAZQKPWSBFZARZ-UHFFFAOYSA-N 2-(2-phenylphenoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1C1=CC=CC=C1 VAZQKPWSBFZARZ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- GSOBKKBOWPKAMP-UHFFFAOYSA-N 1-(2-phenylphenoxy)ethanol Chemical compound CC(O)OC1=CC=CC=C1C1=CC=CC=C1 GSOBKKBOWPKAMP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000010292 orthophenyl phenol Nutrition 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000011973 solid acid Substances 0.000 claims description 10
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 9
- 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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012788 optical film Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 2
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 o-phenylphenoxyethyl alcohol Chemical compound 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of organic synthesis, and provides a method for synthesizing o-phenylphenoxyethyl acrylate, which comprises the following steps: s1, mixing and stirring o-phenylphenol, a first catalyst and a first solvent until the o-phenylphenol, the first catalyst and the first solvent are dissolved, introducing ethylene oxide for reaction, and performing reduced pressure distillation after the reaction is finished to obtain o-phenylphenoxyethanol; s2, mixing and stirring the o-phenylphenoxyethanol, a polymerization inhibitor, an antioxidant, a second catalyst and a second solvent, heating, adding acrylic acid, heating to reflux, filtering after the reaction is finished, and collecting filtrate; s3, washing the filtrate to be neutral, and adding a polymerization inhibitor again to perform reduced pressure distillation to obtain the o-phenylphenoxyethyl acrylate. By the technical scheme, the problems of low yield and purity and poor chromaticity of the o-phenylphenoxyethyl acrylate in the prior art are solved.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing o-phenylphenoxyethyl acrylate.
Background
Currently, optical film materials are attracting attention of a large number of researchers due to their excellent light transmittance, refractive index, chemical resistance and optical corrosion properties, and optical films are a type of optical medium materials that transmit light beams through interfaces, and are widely used in technical fields such as optics and optoelectronics, and commonly used types include brightness enhancement films, diffusion films, and the like. Raw materials of the optical film include acrylic esters, and domestic common photo-curing acrylic esters include trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), neopentyl glycol diacrylate (NPGDA), and l, 6-hexanediol diacrylate (HDDA).
Ortho-phenylphenoxyethyl acrylate is a representative compound of acrylate polymers or copolymers containing an aromatic ring structure, which has excellent transparency and high refractive index, and is widely used in the industries of optical materials such as optical resins (diluents for optical resin UV adhesives, high refractive index optical film resin components, diluents, and the like), optical coatings, optical adhesives, optical lenses, and eyeglass manufacturing.
The industrial preparation method of the o-phenylphenoxyethyl acrylate generally adopts an esterification method, namely a method for removing water generated in the esterification reaction process by utilizing an aromatic solvent such as benzene, toluene, xylene and the like in the presence of an acid catalyst and a polymerization inhibitor. In the past, inorganic acid such as concentrated sulfuric acid, concentrated phosphoric acid and the like is generally used as a catalyst, but the concentrated sulfuric acid has high corrosiveness to equipment and high oxidizing property, and the final product is quite dark in color and even brownish black. At present, organic acids such as p-toluenesulfonic acid, methanesulfonic acid and the like, solid acids or catalysts such as strong acid ion exchange resins and the like are adopted, but products with very low chromaticity are difficult to obtain, and the yield and purity of the products are also not ideal, so that the improvement of the yield, purity and chromaticity of the o-phenylphenoxyethyl acrylate is a technical problem which needs to be solved by a person skilled in the art.
Disclosure of Invention
The invention provides a method for synthesizing o-phenylphenoxyethyl acrylate, which solves the problems of low yield and purity and poor chromaticity of the o-phenylphenoxyethyl acrylate in the related technology.
The technical scheme of the invention is as follows:
a method for synthesizing o-phenylphenoxyethyl acrylate, comprising the steps of:
s1, mixing and stirring o-phenylphenol, a first catalyst and a first solvent until the o-phenylphenol, the first catalyst and the first solvent are dissolved, introducing ethylene oxide for reaction, and performing reduced pressure distillation after the reaction is finished to obtain o-phenylphenoxyethanol;
s2, mixing and stirring the o-phenylphenoxyethanol, a polymerization inhibitor, an antioxidant, a second catalyst and a second solvent, heating, adding acrylic acid, heating to reflux, filtering after the reaction is finished, and collecting filtrate;
s3, washing the filtrate to be neutral, and adding a polymerization inhibitor again to perform reduced pressure distillation to obtain the o-phenylphenoxyethyl acrylate.
As a further technical scheme, the mass ratio of the o-phenylphenol in the S1 to the first catalyst is 1 (0.01-0.2).
As a further technical scheme, the first catalyst comprises one or more of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate and potassium bicarbonate.
As a further technical scheme, the mass ratio of the o-phenylphenol in the S1 to the first solvent is 1 (0.3-2).
As a further technical scheme, the first solvent comprises one or more of ethylene glycol dimethyl ether, methanol and ethanol.
As a further technical scheme, the flow rate of ethylene oxide introduced into the S1 is 0.1mL/min.
As a further technical scheme, the molar ratio of the o-phenylphenol to the ethylene oxide in the S1 is 1 (0.95-1.7).
As a further technical scheme, the temperature is 80-160 ℃, the pressure is 0.3-1.5 MPa, and the time is 0.1-2 h during the reaction in the S1.
As a further technical scheme, the S1 reaction device is a continuous micro-reaction pipeline device, and is preferably a continuous reactor of a mixing micro-reaction channel of HY19-052-1A and HY19-052-2A of corning.
As a further technical scheme, the mass of the polymerization inhibitor in the S2 is (0.01-0.1)% of the mass of the o-phenylphenoxyethanol.
As a further technical scheme, the polymerization inhibitor comprises one or more of p-methoxyphenol, hydroquinone, cupric chloride, cupric sulfate and 2, 6-di-tert-butyl-4-methylphenol.
As a further technical scheme, the mass of the antioxidant in the S2 is (0.1-1)% of the mass of the o-phenylphenoxyethanol.
As a further technical scheme, the antioxidant comprises one or two of hypophosphorous acid and sodium hypophosphite.
As a further technical scheme, the mass ratio of the o-phenylphenoxyethanol to the second catalyst in the S2 is 1 (0.02-0.1).
As a further technical scheme, the second catalyst comprises a solid acid and an oxide.
As a further technical scheme, the mass ratio of the solid acid to the oxide is 1 (0.1-0.9).
As a further technical scheme, the solid acid comprises one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, p-toluenesulfonic acid and methanesulfonic acid.
As a further technical scheme, the oxide comprises one or two of silicon oxide and aluminum oxide.
As a further technical scheme, the mass ratio of the o-phenylphenoxyethanol to the second solvent in the S2 is 1 (0.6-5).
As a further technical scheme, the second solvent comprises one or more of cyclohexane, toluene, benzene and n-hexane.
As a further technical scheme, the temperature when the acrylic acid is added into the S2 is 70 ℃.
As a further technical scheme, the molar ratio of the o-phenylphenoxyethanol to the acrylic acid in the S2 is 1 (1.03-1.7).
As a further technical scheme, the temperature of the reflux in the step S2 is 78-93 ℃ and the time is 4-14 h.
As a further technical scheme, the mass of the polymerization inhibitor added in the S3 is 0.01% of the mass of the o-phenylphenoxyethanol.
As a further technical scheme, the vacuum degree is-0.03 to-0.1 MPa, the time is 4-10 h, and the temperature is 40-65 ℃ during reduced pressure distillation in the step S3.
The working principle and the beneficial effects of the invention are as follows:
1. the invention uses a continuous synthesis reaction system, improves the synthesis reaction efficiency of the o-phenylphenoxyethyl acrylate, shortens the reaction period, and solves the problems of poor stability and long production period of the o-phenylphenoxyethyl acrylate obtained by using kettle reaction at present.
2. According to the invention, o-phenylphenoxyethyl alcohol and acrylic acid are used as raw materials, solid acid and oxide are used as catalysts, and esterification reaction is carried out in the presence of a polymerization inhibitor and an antioxidant, so that the obtained o-phenylphenoxyethyl acrylate has high purity, high yield and high refractive index. Meanwhile, the recyclable solid acid and oxide are used as the catalyst, so that the waste of the catalyst is reduced, the production cost is further reduced, and the environmental pollution is reduced.
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 one of ordinary skill 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
S1, adding 100g of o-phenylphenol and 2g of potassium hydroxide into a round bottom flask, adding 50g of absolute ethyl alcohol, stirring at 55 ℃ until the mixture is completely dissolved, adjusting the temperature of a corning micro-reaction channel mixer to 140 ℃, adjusting the pressure of the regulated ethylene oxide to 0.8MPa after the constant temperature, controlling the flow rate of 0.1mL/min to enter the corning micro-reaction channel mixer, controlling the molar ratio of the ethylene oxide to the o-phenylphenol to be 1:1, reacting for 0.5h, and directly performing reduced pressure distillation to obtain solid o-phenylphenoxyethanol (125.8 g);
s2, directly adding 3.774g of catalyst, 0.025g of p-methoxyphenol, 0.629g of hypophosphorous acid and 125g of cyclohexane into the solid obtained in the step S1, stirring and heating to 70 ℃, rapidly adding 50.8g of acrylic acid, continuously stirring and heating to 83 ℃ to reflux and divide water, starting timing, reacting for 8 hours, cooling the reaction solution to room temperature, filtering, collecting filtrate, and enabling the catalyst to consist of silicon oxide and phosphotungstic acid with the mass ratio of 0.4:1;
s3, washing the filtrate obtained in the step S2 to be neutral, refluxing and separating water, adding 0.015g of p-methoxyphenol, carrying out reduced pressure distillation, controlling the highest temperature to 65 ℃, and controlling the vacuum degree to be minus 0.098MPa, thereby obtaining 151.2g of product (yield 96.0%), wherein the purity of liquid chromatography is 94.0%, the color number is 10Haze (standard color comparison of platinum and cobalt), and the refractive index is 25℃:1.5777.
example 2
S1, adding 100g of o-phenylphenol and 1g of sodium carbonate into a round bottom flask, adding 30g of anhydrous methanol, stirring at 55 ℃ until the mixture is completely dissolved, adjusting the temperature of a corning micro-reaction channel mixer to be 80 ℃, adjusting the pressure of ethylene oxide to be 0.3MPa after the constant temperature, controlling the flow rate of 0.1mL/min into the corning micro-reaction channel mixer, controlling the molar ratio of the ethylene oxide to the o-phenylphenol to be 0.95:1, and directly performing reduced pressure distillation after reacting for 2 hours to obtain solid o-phenylphenoxyethanol (119.6 g);
s2, directly adding 2.392g of catalyst, 0.012g of hydroquinone, 0.12g of sodium hypophosphite and 71.8g of n-hexane into the solid obtained in the step S1, stirring and heating to 70 ℃, rapidly adding 41.5g of acrylic acid, continuously stirring and heating to 78 ℃ to reflux and divide water, starting timing, reacting for 14 hours, cooling the reaction solution to room temperature, filtering, collecting filtrate, and enabling the catalyst to consist of alumina and phosphomolybdic acid with the mass ratio of 0.1:1;
s3, washing the filtrate obtained in the step S2 to be neutral, refluxing and separating water, adding 0.012g of hydroquinone, carrying out reduced pressure distillation, controlling the highest temperature to be 55 ℃, and the highest vacuum degree to be-0.05 MPa to obtain 143g of product (the yield is 95.5%), wherein the purity of liquid chromatography is 93.5%, the color number is 10Haze (standard color comparison of platinum and cobalt), and the refractive index is 25℃:1.5772.
example 3
S1, adding 100g of o-phenylphenol and 20g of sodium bicarbonate into a round bottom flask, adding 200g of ethylene glycol dimethyl ether, stirring at 55 ℃ until the mixture is completely dissolved, adjusting the temperature of a corning micro-reaction channel mixer to 160 ℃, adjusting the pressure of ethylene oxide to 1.5MPa after constant temperature, controlling the flow rate of 0.1mL/min into the corning micro-reaction channel mixer, controlling the molar ratio of the ethylene oxide to the o-phenylphenol to be 1.7:1, reacting for 0.1h, and directly performing reduced pressure distillation to obtain the solid o-phenylphenoxyethanol (125.8 g);
s2, directly adding 12.58g of catalyst, 0.126g of copper sulfate, 1.258g of hypophosphorous acid and 629g of toluene into the solid obtained in the step S1, stirring and heating to 70 ℃, rapidly adding 71.9g of acrylic acid, continuously stirring and heating to 93 ℃ to reflux and divide water, starting timing, reacting for 4 hours, cooling the reaction solution to room temperature, filtering, collecting filtrate, and enabling the catalyst to consist of silicon oxide and p-toluenesulfonic acid with the mass ratio of 0.9:1;
s3, washing the filtrate obtained in the step S2 to be neutral, refluxing and separating water, adding 0.013g of copper sulfate, carrying out reduced pressure distillation, controlling the highest temperature to be 40 ℃, and the highest vacuum degree to be-0.03 MPa to obtain 149.8g of a product (the yield is 95.1%), wherein the liquid chromatography purity is 93.9%, the color number is 15Haze (standard color comparison of platinum and cobalt), and the refractive index is 25℃:1.5773.
example 4
The difference from example 1 is only that the addition of p-methoxyphenol in S3 is 0.035g, giving 149g of the product (yield 94.6%), the liquid chromatography purity is 93.2%, the color number is 15Haze (standard colorimetric for platinum cobalt), the refractive index is 25 ℃ C.): 1.5770.
example 5
The difference from example 1 was only that the amount of p-methoxyphenol added in S3 was 0.0065g, giving 148.5g of product (yield 94.3%), liquid chromatography purity 93.3%, colour number 15Haze (platinum cobalt standard colorimetric) and refractive index 25 ℃ C: 1.5771.
example 6
The difference from example 1 is only that the catalyst in S2 consists of silica and phosphotungstic acid in a mass ratio of 0.05:1, giving 148g of product (yield 94.0%), a liquid chromatographic purity of 93.2%, a colour number of 15Haze (standard colour comparison of platinum and cobalt), a refractive index of 25 ℃ C: 1.5770.
example 7
The difference from example 1 is only that the catalyst in S2 consists of silica and phosphotungstic acid in a mass ratio of 0.15:1, giving 148.4g of product (yield 94.2%), a liquid chromatographic purity of 93.3%, a colour number of 15Haze (standard colour comparison of platinum and cobalt), a refractive index of 25 ℃ C: 1.5771.
comparative example 1
The difference from example 1 is only that the silica in the S2 catalyst is calcined activated silica, giving 140.7g of product (89.3% yield), a liquid chromatography purity of 88.7%, a colour number of 30Haze (platinum cobalt standard colorimetric) and a refractive index of 25 ℃ C.): 1.5768.
the synthesis method of the o-phenylphenoxyethyl acrylate provided by the embodiments 1-3 of the invention has the advantages of high synthesis efficiency and short reaction period, and the obtained o-phenylphenoxyethyl acrylate has high yield and purity and high refractive index; examples 4 to 5 are different from example 1 only in that the addition amount of p-methoxyphenol in S3 is different, and the yield, purity and refractive index of the finally obtained o-phenylphenoxyethyl acrylate are lower than those of examples 1 to 3; the catalyst in the step S2 of the example 6 is composed of silicon oxide and phosphotungstic acid in a mass ratio of 0.05:1, the catalyst in the step S2 of the example 7 is composed of silicon oxide and phosphotungstic acid in a mass ratio of 0.15:1, and the yield, purity and refractive index of the obtained o-phenylphenoxyethyl acrylate are lower than those of the examples 1 to 3, so that the yield, purity and refractive index of the obtained o-phenylphenoxyethyl acrylate are optimal only when the mass ratio of solid acid to oxide in the catalyst is 1 (0.1 to 0.9).
Comparative example 1 differs from example 1 only in that the silica in the S2 catalyst is a calcined activated silica, which is used as a carrier of a phosphotungstic acid catalyst in the reaction system, whereas the silica and phosphotungstic acid in example 1 are used together as a catalyst for the reaction, resulting in lower yield, purity and refractive index of the o-phenylphenoxyethyl acrylate finally obtained in comparative example 1 than in example 1.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A method for synthesizing o-phenylphenoxyethyl acrylate, comprising the steps of:
s1, mixing and stirring o-phenylphenol, a first catalyst and a first solvent until the o-phenylphenol, the first catalyst and the first solvent are dissolved, introducing ethylene oxide for reaction, and performing reduced pressure distillation after the reaction is finished to obtain o-phenylphenoxyethanol;
s2, mixing and stirring the o-phenylphenoxyethanol, a polymerization inhibitor, an antioxidant, a second catalyst and a second solvent, heating, adding acrylic acid, heating to reflux, filtering after the reaction is finished, and collecting filtrate;
s3, washing the filtrate to be neutral, and adding a polymerization inhibitor again to perform reduced pressure distillation to obtain o-phenylphenoxyethyl acrylate;
the second catalyst consists of a solid acid and an oxide;
the mass ratio of the solid acid to the oxide is 1 (0.1-0.9);
the solid acid is one or more of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, paratoluenesulfonic acid and methanesulfonic acid;
the oxide is one or two of silicon oxide and aluminum oxide.
2. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the mass ratio of o-phenylphenol to the first catalyst to the first solvent in S1 is 1 (0.01-0.2): 0.3-2.
3. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the molar ratio of o-phenylphenol to ethylene oxide in S1 is 1 (0.95-1.7).
4. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the reaction temperature in the step S1 is 80-160 ℃, the pressure is 0.3-1.5 MPa, and the time is 0.1-2 h.
5. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the molar ratio of o-phenylphenoxyethanol to acrylic acid in S2 is 1 (1.03-1.7).
6. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the mass of the polymerization inhibitor in S2 is (0.01-0.1)% of the mass of o-phenylphenoxyethanol; the mass of the antioxidant is (0.1-1)% of the mass of the o-phenylphenoxyethanol.
7. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the mass ratio of the o-phenylphenoxyethanol to the second catalyst in S2 is 1 (0.02-0.1).
8. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the mass of the polymerization inhibitor added again in the step S3 is 0.01% of the mass of the o-phenylphenoxyethanol.
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