CN115819226A - Method for synthesizing o-phenyl phenoxyethyl acrylate - Google Patents
Method for synthesizing o-phenyl phenoxyethyl acrylate Download PDFInfo
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- CN115819226A CN115819226A CN202211574849.0A CN202211574849A CN115819226A CN 115819226 A CN115819226 A CN 115819226A CN 202211574849 A CN202211574849 A CN 202211574849A CN 115819226 A CN115819226 A CN 115819226A
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- synthesizing
- phenylphenoxyethyl acrylate
- phenylphenoxyethanol
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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 31
- 238000000034 method Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 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 21
- 235000010292 orthophenyl phenol Nutrition 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 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
- 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 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 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
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000002156 mixing 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
- 239000011973 solid acid Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 8
- 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 description 8
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 7
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004811 liquid chromatography Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 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
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 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
- 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
- 229910000029 sodium carbonate Inorganic materials 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
- 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
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 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
- 229940098779 methanesulfonic acid Drugs 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
- 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 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 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
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 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
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 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
- 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 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
- 238000009776 industrial production Methods 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 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
- 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 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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 is dissolved, introducing ethylene oxide to react, and after the reaction is finished, carrying out reduced pressure distillation to obtain o-phenylphenoxyethanol; s2, mixing and stirring the o-phenylphenoxyethanol, the polymerization inhibitor, the antioxidant, the second catalyst and the second solvent, heating, adding acrylic acid, heating to reflux, filtering after the reaction is finished, and collecting filtrate; and S3, washing the filtrate to be neutral, adding the polymerization inhibitor again, and carrying out reduced pressure distillation to obtain the o-phenylphenoxyethyl acrylate. Through 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 receiving attention of a great number of researchers due to excellent light transmittance, refractive index, chemical resistance and optical corrosion resistance, and optical films are a class of optical medium materials for transmitting light beams through an interface, and are widely used in the technical fields of optics, photoelectrons and the like, and common types include brightness enhancement films, diffusion films and the like. The raw materials of the optical film comprise acrylic esters, and the domestic common light-cured acrylic esters comprise trimethylolpropane triacrylate (TMPTA), tripropylene glycol diacrylate (TPGDA), dipropylene glycol diacrylate (DPGDA), neopentyl glycol diacrylate (NPGDA), l, 6-hexanediol diacrylate (HDDA) and the like.
The o-phenylphenoxyethyl acrylate is a representative compound of an acrylate polymer or copolymer containing an aromatic ring molecular structure, has excellent transparency and high refractive index, and is widely used in industries of optical materials such as optical resins (diluents of optical resin UV adhesives, high refractive index optical film resin components, diluents and the like), optical coatings, optical adhesives, optical lenses, spectacle manufacturing and the like.
The industrial production of o-phenylphenoxyethyl acrylate is generally carried out by esterification, i.e. by removing water produced during esterification reaction between alcohol and acrylic acid in the presence of an acidic catalyst and a polymerization inhibitor using an aromatic solvent such as benzene, toluene, xylene, etc. In the past, inorganic acids such as concentrated sulfuric acid and concentrated phosphoric acid are generally used as catalysts, but the concentrated sulfuric acid and the concentrated phosphoric acid have high corrosion to equipment and strong oxidizability, so that the final product is often very dark in color, even brownish black. At present, organic acids such as p-toluenesulfonic acid and methanesulfonic acid, solid acid or strong acid ion exchange resin and other catalysts are adopted, but obtaining products with low chromaticity is difficult, and the yield and purity of the products are not ideal, so that the improvement of the yield, purity and chromaticity of o-phenylphenoxyethyl acrylate is a technical problem urgently needed to be solved by technical personnel in the field.
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 comprises the following steps:
s1, mixing and stirring o-phenylphenol, a first catalyst and a first solvent until the o-phenylphenol is dissolved, introducing ethylene oxide to react, and after the reaction is finished, carrying out reduced pressure distillation to obtain o-phenylphenoxyethanol;
s2, mixing and stirring the o-phenylphenoxyethanol, the polymerization inhibitor, the antioxidant, the second catalyst and the second solvent, heating, adding acrylic acid, heating to reflux, filtering after the reaction is finished, and collecting filtrate;
and S3, washing the filtrate to be neutral, adding the polymerization inhibitor again, and carrying out reduced pressure distillation to obtain the o-phenylphenoxyethyl acrylate.
As a further technical scheme, the mass ratio of the o-phenylphenol to the first catalyst in the S1 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 to the first solvent in the S1 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 introducing the ethylene oxide 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 reaction temperature in the S1 is 80-160 ℃, the pressure is 0.3-1.5 MPa, and the reaction time is 0.1-2 h.
As a further technical scheme, the S1 reaction device is a continuous micro-reaction pipeline device, and preferably a Corning mixed micro-reaction channel continuous reactor of HY19-052-1A and HY 19-052-2A.
As a further technical scheme, the mass of the polymerization inhibitor in 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, copper chloride, copper sulfate and 2,6-di-tert-butyl-4-methylphenol.
As a further technical scheme, the mass of the antioxidant in 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 solution, the second catalyst includes 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 proposal, the temperature of the S2 when adding the acrylic acid 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 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 percent of that of the o-phenylphenoxyethanol.
As a further technical scheme, the vacuum degree is-0.03 to-0.1 MPa, the time is 4 to 10 hours, and the temperature is 40 to 65 ℃ during the reduced pressure distillation in the S3.
The working principle and the beneficial effects of the invention are as follows:
1. the method 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 the kettle type reaction at present.
2. The o-phenylphenoxyethyl acrylate prepared by using the o-phenylphenoxyethanol and the acrylic acid as raw materials and using the solid acid and the oxide as catalysts through an esterification reaction in the presence of a polymerization inhibitor and an antioxidant has high purity, high yield and high refractive index. Meanwhile, recyclable solid acid and oxide are used as the catalyst, so that the waste of the catalyst is reduced, the production cost is reduced, and the environmental pollution is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present 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 o-phenylphenol and the potassium hydroxide are completely dissolved, keeping the temperature of a corning micro-reaction channel mixer at 140 ℃, keeping the temperature constant, adjusting the pressure of ethylene oxide to be 0.8MPa, 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 carrying out reduced pressure distillation to obtain a solid of o-phenylphenoxy ethanol (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 S1, stirring and heating to 70 ℃, quickly adding 50.8g of acrylic acid, continuously stirring and heating to 83 ℃, refluxing and dividing water, starting timing, reacting for 8 hours, cooling the reaction liquid to room temperature, filtering, and collecting filtrate, wherein the catalyst consists of silicon oxide and phosphotungstic acid with the mass ratio of 0.4;
and S3, washing the filtrate obtained in the step S2 to be neutral, refluxing and dividing water, adding 0.015g of p-methoxyphenol, carrying out reduced pressure distillation, controlling the highest temperature to be 65 ℃ and the highest vacuum degree to be-0.098 MPa, and obtaining 151.2g of a product (yield is 96.0%), the liquid chromatographic purity is 94.0%, the color number is 10Haze (platinum-cobalt standard color comparison), 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, then adding 30g of anhydrous methanol, stirring at 55 ℃ until the o-phenylphenol and the sodium carbonate are completely dissolved, keeping the temperature of a corning micro-reaction channel mixer at 80 ℃, keeping the temperature constant, adjusting the pressure of ethylene oxide to be 0.3MPa, 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 0.95, reacting for 2 hours, and directly carrying out reduced pressure distillation to obtain a solid of 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 S1, stirring and heating to 70 ℃, quickly adding 41.5g of acrylic acid, continuously stirring and heating to 78 ℃, refluxing and dividing water, starting timing, reacting for 14 hours, cooling the reaction liquid to room temperature, filtering, and collecting filtrate, wherein the catalyst consists of alumina and phosphomolybdic acid with the mass ratio of 0.1;
and S3, washing the filtrate obtained in the step S2 to be neutral, refluxing and dividing 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, and obtaining 143g of a product (the yield is 95.5%), the liquid chromatography purity is 93.5%, the color number is 10Haze (platinum-cobalt standard color comparison), 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, then adding 200g of ethylene glycol dimethyl ether, stirring at 55 ℃ until the o-phenylphenol and the sodium bicarbonate are completely dissolved, keeping the temperature of a corning micro-reaction channel mixer at 160 ℃, keeping the temperature constant, adjusting the pressure of ethylene oxide to be 1.5MPa, 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 1.7, reacting for 0.1h, and directly carrying out reduced pressure distillation to obtain a 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 S1, stirring and heating to 70 ℃, quickly adding 71.9g of acrylic acid, continuously stirring and heating to 93 ℃, refluxing and dividing water, starting timing, reacting for 4 hours, cooling the reaction liquid to room temperature, filtering, and collecting filtrate, wherein the catalyst consists of silicon oxide and p-toluenesulfonic acid in a mass ratio of 0.9;
and S3, washing the filtrate obtained in the S2 to be neutral, refluxing and dividing 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, and obtaining 149.8g of a product (the yield is 95.1%), the liquid chromatography purity is 93.9%, the color number is 15Haze (platinum-cobalt standard color comparison), and the refractive index is 25 ℃:1.5773.
example 4
The only difference from example 1 was that p-methoxyphenol was added in an amount of 0.035g in S3 to yield 149g of product (94.6% yield), 93.2% liquid chromatography purity, 15Haze (platinum-cobalt standard colorimetric) color number, 25 ℃ refractive index: 1.5770.
example 5
Except that the amount of p-methoxyphenol added in S3 was 0.0065g, as compared to example 1, to give 148.5g of the product (yield 94.3%), a liquid chromatography purity of 93.3%, a colour number of 15Haze (platinum-cobalt standard colour), a refractive index of 25 ℃:1.5771.
example 6
The only difference from example 1 is that the catalyst in S2 consists of silica and phosphotungstic acid in a mass ratio of 0.05: 1.5770.
example 7
The only difference from example 1 is that the catalyst in S2 consists of silica and phosphotungstic acid in a mass ratio of 0.15 to 1, giving 148.4g of product (yield 94.2%), a liquid chromatographic purity of 93.3%, a colour number of 15Haze (platinum-cobalt standard colorimetric), a refractive index of 25 ℃:1.5771.
comparative example 1
The only difference from example 1 is that the silica in the S2 catalyst was calcined activated silica to give 140.7g of product (89.3% yield), 88.7% purity by liquid chromatography, 30Haze (platinum-cobalt standard colorimetric) colour number, refractive index 25 ℃:1.5768.
the synthesis method of o-phenylphenoxyethyl acrylate provided by embodiments 1-3 of the invention has 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; in example 6, the catalyst in step S2 consists of silicon oxide and phosphotungstic acid in a mass ratio of 0.05, in example 7, the catalyst in step S2 consists of silicon oxide and phosphotungstic acid in a mass ratio of 0.15.
Comparative example 1 differs from example 1 only in that the silica in the S2 catalyst is calcined activated silica and serves as a support for a phosphotungstic acid catalyst in the reaction system, while the silica and phosphotungstic acid together serve as a catalyst for the reaction in example 1, resulting in the yield, purity and refractive index of the o-phenylphenoxyethyl acrylate finally obtained in comparative example 1 being lower than those in example 1.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing o-phenylphenoxyethyl acrylate is characterized by comprising the following steps:
s1, mixing and stirring o-phenylphenol, a first catalyst and a first solvent until the o-phenylphenol is dissolved, introducing ethylene oxide for reaction, and after the reaction is finished, carrying out reduced pressure distillation to obtain o-phenylphenoxyethanol;
s2, mixing and stirring the o-phenylphenoxyethanol, the polymerization inhibitor, the antioxidant, the second catalyst and the second solvent, heating, adding acrylic acid, heating to reflux, filtering after the reaction is finished, and collecting filtrate;
and S3, washing the filtrate to be neutral, adding the polymerization inhibitor again, and carrying out reduced pressure distillation to obtain the o-phenylphenoxyethyl acrylate.
2. The method for synthesizing o-phenylphenoxyethyl acrylate as claimed in claim 1, wherein the mass ratio of the o-phenylphenol to the first catalyst to the first solvent in S1 is 1 (0.01-0.2) to 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 S1 is 80-160 ℃, the pressure is 0.3-1.5 MPa, and the reaction 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 that 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 7, wherein the second catalyst comprises a solid acid and an oxide.
9. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 8, wherein the mass ratio of the solid acid to the oxide is 1 (0.1-0.9).
10. The method for synthesizing o-phenylphenoxyethyl acrylate according to claim 1, wherein the mass of the polymerization inhibitor added in S3 is 0.01% of the mass of o-phenylphenoxyethanol.
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