GB788887A - Improvements in or relating to the production of glycidyl ethers of polyhydric phenols - Google Patents

Improvements in or relating to the production of glycidyl ethers of polyhydric phenols

Info

Publication number
GB788887A
GB788887A GB2913/56A GB291356A GB788887A GB 788887 A GB788887 A GB 788887A GB 2913/56 A GB2913/56 A GB 2913/56A GB 291356 A GB291356 A GB 291356A GB 788887 A GB788887 A GB 788887A
Authority
GB
United Kingdom
Prior art keywords
per cent
epichlorhydrin
phenol
ether
per
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB2913/56A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bataafsche Petroleum Maatschappij NV
Original Assignee
Bataafsche Petroleum Maatschappij NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bataafsche Petroleum Maatschappij NV filed Critical Bataafsche Petroleum Maatschappij NV
Publication of GB788887A publication Critical patent/GB788887A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/02Preparation of ethers from oxiranes
    • C07C41/03Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Epoxy Resins (AREA)

Abstract

In the production of glycidyl ethers of di-, or polyhydric phenols, which on further reaction with additional phenol are converted to epoxy resins, the di-, or polyhydric phenol is reacted with at least 1.5 mols. epihalohydrin per phenolic hydroxyl equivalent in the presence of at least 90-98 per cent of the alkali metal hydroxide per phenolic hydroxyl equivalent, after which the unreacted epihalohydrin is separated from the reaction mixture and the polyglycidyl ether is contacted with additional alkali metal hydroxide in excess of that required to remove the halogen in the glycidyl ethers. Preferably 3-6 mols. epichlorhydrin are reacted per phenolic hydroxyl group. Water formed during the reaction is azeotropically distilled off with the epichlorhydrin, the distilled vapours are condensed, the condensate separated into aqueous and epichlorhydrin layers which latter is recycled to the reaction mixture; flash distillation followed by vacuum distillation may be employed. The glycidyl ether may be purified by adding a solvent, e.g. ketones and aromatic hydrocarbons and water, and separating the brine layer from the solution of the ether in the solvent. A table shows that the further reaction of the ether and a dihydric phenol is affected by the amount of halogen in the ether, the conversion being reduced from 100 per cent at up to 3 per cent chlorine content to 84 per cent with 2.7 per cent Cl content. A table also shows that when the amount of NaOH present is reduced below 90 per cent, the percentage of molecules containing phenolic groups increases rapidly, while if the percentage is increased above 98 per cent the percentage of epichlorhydrin polymers produced increases. Suitable polyhydric phenols for the reaction are resorcinol, phloroglucinol, 1,5 - dihydroxy naphthalene. bis-phenol, novolac resin obtained by acid condensation of phenol or cresol with aldehydes; condensates of phenol with cardanol aliphatic diols or unsaturated fatty oil. The epichlorhydrin acts as a solvent as well as a reactant and suppresses the formation of gelled products with dihydroic phenols. The process may be effected in batch or continuous operation. Epichlorhydrin and bis-phenol in mol. ratio 10/1 were heated to 100 DEG C. in a flask provided with distilling head and separator and 1.90 mols. NaOH added as a 40 per cent aqueous solution; water and epichlorhydrin distilled off to maintain the water in the reaction mixture at about 1.5 per cent; unreacted epichlorhydrin was flashed off and vacuum distilled; the residue was cooled, mixed with an equal weight of isobutyl ketone and 3 times as much water, the brine phase was separated and the organic phase containing 1 per cent chlorine was further reacted with an equal weight of 5 per cent NaOH solution at 80 DEG C.; the brine phase was separated and the product treated with sodium dihydrogen phosphate. The resulting ether was found to contain 0.25 per cent Cl. It had an epoxy equivalent of 0.521 and a molecular weight 355. When heated with 35.6 per cent by weight of bisphenol a 100 per cent conversion was obtained. U.S.A. Specification 2,467,171 is referred to.ALSO:In the production of glycidyl ethers of dihydric phenols which on further reaction with additional phenol are converted to epoxy resins, the dihydric phenol is reacted with at least 1.5 mols. epihalohydrin per phenolic hydroxyl equivalent in the presence of at least 90-98 per cent of the equivalent of alkali metal hydroxide per phenolic hydroxyl equivalent, after which the unreacted epihalohydrin is separated from the reaction mixture and the polyglycidyl ether is contacted with additional alkali metal hydroxide in excess of that required to remove the halogen therein. Preferably 3-6 mols. epichlorhydrin are reacted per phenolic hydroxyl group. Water formed during the reaction is azeotropically distilled off with the epichlorhydrin, the distilled vapours are condensed, and the condensate separated into aqueous and epichlorhydrin layers which latter is recycled to the reaction mixture; flash distillation followed by vacuum distillation may be employed. The glycidyl ether may be purified by adding a solvent, e.g. ketones and aromatic hydrocarbons and water and separating the brine layer from the solution of the ether in the solvent. A table shows that the further reaction of the ether and a dihydric phenol is affected by the amount of halogen in the ether, the conversion being reduced from 100 per cent at up to 3 per cent chlorine content to 84 per cent with 2.7 per cent Cl content. A table also shows that when the amount of NaOH present is reduced below 90 per cent, the percentage of molecules containing phenolic groups increases rapidly while if the percentage is increased above 98 per cent the percentage of epichlorhydrin polymers produced increases. Suitable polyhydric phenols for the reaction are resorcinol, phloroglucinol 1,5-dihydroxy naphthalane bis-phenol, novolac resins obtained by acid condensation of phenol, cresol, &c., with aldehydes; condensates of phenol with cardanol, aliphatic diols or unsaturated fatty oils. The epichlorhydrin acts as a solvent as well as a reactant and suppresses the formation of gelled products with dihydric phenols. The process may be effected in batch or continuous operation. Epichlorhydrin and bis-phenol in mol ratio 10/1 were heated to 100 DEG C. in a flask provided with distilling head and separator and 1.90 mols. NaOH added as a 40 per cent aqueous solution; water and epichlorhydrin were distilled off to maintain the water in the reaction mixture at about 1.5 per cent; unreacted epichlorhydrin was flashed off and vacuum distilled; the residue was cooled, mixed with an equal weight of isobutyl ketone and 3 times as much water, the brine phase was separated and the organic phase containing 1 per cent chlorine was further reacted with an equal weight of 5 per cent NaOH solution at 80 DEG C.; the brine phase was separated and the product treated with sodium dihydrogen phosphate; the resulting ether was found to contain 0.25 per cent Cl, had an epoxy equivalent of 0.521 and a molecular weight of 355. When heated with 35.6 per cent by weight of bis-phenol a 100 per cent conversion was obtained. U.S.A. Specification 2,467,171 is referred to.
GB2913/56A 1955-01-31 1956-01-30 Improvements in or relating to the production of glycidyl ethers of polyhydric phenols Expired GB788887A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US788887XA 1955-01-31 1955-01-31

Publications (1)

Publication Number Publication Date
GB788887A true GB788887A (en) 1958-01-08

Family

ID=22146817

Family Applications (1)

Application Number Title Priority Date Filing Date
GB2913/56A Expired GB788887A (en) 1955-01-31 1956-01-30 Improvements in or relating to the production of glycidyl ethers of polyhydric phenols

Country Status (1)

Country Link
GB (1) GB788887A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0303901A2 (en) * 1987-08-13 1989-02-22 The Dow Chemical Company Method for reducing the aliphatic halide content of epoxy resins
US8461286B2 (en) 2008-03-25 2013-06-11 Dow Global Technologies Llc Process for manufacturing liquid epoxy resins
TWI399390B (en) * 2006-02-28 2013-06-21 Dainippon Ink & Chemicals Method of producing phenol resin and method of producing epoxy resin
CN116063248A (en) * 2022-12-07 2023-05-05 山东尚正新材料科技股份有限公司 Method for continuously producing biomass glycidyl ether

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0303901A2 (en) * 1987-08-13 1989-02-22 The Dow Chemical Company Method for reducing the aliphatic halide content of epoxy resins
EP0303901A3 (en) * 1987-08-13 1989-09-13 The Dow Chemical Company Method for reducing the aliphatic halide content of epoxy resins
TWI399390B (en) * 2006-02-28 2013-06-21 Dainippon Ink & Chemicals Method of producing phenol resin and method of producing epoxy resin
US8461286B2 (en) 2008-03-25 2013-06-11 Dow Global Technologies Llc Process for manufacturing liquid epoxy resins
CN116063248A (en) * 2022-12-07 2023-05-05 山东尚正新材料科技股份有限公司 Method for continuously producing biomass glycidyl ether

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