Patent GB-672935-A (GB)
Title: Improvements in or relating to epoxy ethers
IPC: C07D303/24
Filed: 1949-06-17
Abstract: a -Glycol diglycidyl ethers of the formula <FORM:0672935/IV (a)/1> R and R1 being substituents selected from the group consisting of hydrogen, saturated aliphatic radicals, aromatic, alicyclic and heterocyclic radicals, which are prepared by the dehydrohalogenation of a -glycol diallyl ether dichlorohydrins (see Group IV (b)) may be polymerized in the presence of polymerization catalysts such as boron trifluoride and perchloric acid.  They may also be reacted with alcoholic or phenolic compounds, acids, amines and generally with compounds containing active hydrogen.ALSO:In a process for preparing an a -glycol diglycidyl ether of the formula <FORM:0672935/IV (b)/1> R and R1 being substituents selected from the group consisting of hydrogen, saturated aliphatic radicals, aromatic, alicyclic and heterocyclic radicals, an a -glycol diallyl ether dichlorohydrin is dehydrohalogenated by treatment with a base. The starting material may be prepared by (1) heating allyl alcohol and an oxide <FORM:0672935/IV (b)/2> p  wherein R and R1 are defined as above; (2) heating the resultant a -glycol monoallyl ether with epichlorohydrin in the presence of an acidic catalyst to form the a -glycol diallyl ether mono-chlorohydrin; (3) adding hypochlorous acid to the a -glycol diallyl ether monochlorohydrin to form the a -glycol diallyl ether dichlorohydrins.  Acidic catalysts which may be employed in the first two steps include boron trifluoride, perchloric acid, stannic halides, antimony trihalides, antimony pentahalides, zinc halides and ferric halides.  The acidic catalyst is neutralized on completion of the first step, excess allyl alcohol is stripped off, the a -glycol monoallyl ether is distilled under reduced pressure and heated with epichlorohydrin.  The reaction products are neutralized, the a -glycol diallyl ether monochlorohydrin is distilled off under reduced pressure and treated with hypochlorous acid.  The a -glycol diallyl ether dichlorohydrin formed is treated with a hydroxide or carbonate of an alkali metal or alkaline earth metal, sodium hydroxide being preferred.  The hypochlorous acid in the second step may be generated in situ by reacting a hypochlorite and dilute mineral acid or may be employed as an aqueous solution.  Sodium hypochlorite may be used or other hypochlorites preferably not containing a metal yielding an insoluble hydroxide in the last stage of the process.  In examples: (I) allyl alcohol is heated with ethylene oxide in the presence of boron trifluoride.  The catalyst is neutralized with concentrated ammonium hydroxide solution, excess allyl alcohol is distilled off, followed by the ethylene glycol monoallyl ether. The latter is heated with epichlorohydrin, boron trifluoride being added, the catalyst is neutralized and ethylene glycol diallyl ether monochlorohydrin is distilled off and mixed with sodium hypochlorite, sulphuric acid then being added until excess hypochlorous acid is present.  The mixture is neutralized and extracted with carbon tetrachloride.  The latter is removed from the extract and the ethylene glycol diglycidyl ether is obtained by distillation under reduced pressure.  The process is repeated with stronger hypochlorite solutions.  (II) Propylene glycol diglycidyl ether, (III) butylene glycol diglycidyl ether, and (IV) phenyl ethylene glycol diglycidyl ether are obtained similarly using 1,2-epoxypropane, 2,3-epoxy-butane and styrene oxide respectively, instead of ethylene oxide as starting materials.  In examples (II) and (III) boron trifluoride dissolved in acetic acid is used as catalyst.  The a -glycol diglycidyl ethers may be reacted with alcoholic or phenolic compounds, acids, amines and generally with compounds containing active hydrogen or they may be polymerized in the presence of suitable polymerization catalysts.