Patent GB-982151-A (GB)
Title: New glycidyl ethers and process for their preparation
IPC: C08G59/32
Filed: 1961-11-14
Abstract: The invention comprises glycidyl ethers of the formula: <FORM:0982151/C2/1> where R1, R2 and R3 each represent a hydrogen or halogen atom, a hydroxyl group or a glycidoxy group <FORM:0982151/C2/2> The ethers are prepared by treating an alcohol of the general formula:  Where R11 and R21 each represent a hydrogen or halogen atom or a hydroxy group, with an epihalohydrin or glycerol dihalohydrin in a single stage in the presence of an alkali, preferably sodium hydroxide or potassium hydroxide, or with an epihalohydrin in two stages in the presence first of an acid catalyst (e.g. boron bifluoride), to give the halohydrin ether, which is then dehydrohalogenated to give the glycidyl ether, by using alkali, such sodium hydroxide or potassium hydroxide. Polyhydrine starting materials usually give rise to mixtures.  In the examples:  (1) triglycidylether of 3,4,8-trihydroxy-tetrahydrodicyclopentadiene; (2) diglycidyl ether of 3 (or 4), 8-dihydroxy-tetrahydro-dicyclopentadiene [tricyclo (5.2.1.02.6)-decane-3 (or 4), 8-diol]; (3) diglycidyl ether of 4 (or 3)-chloro-3 (or 4), 8-dihydroxy-tetrahydrodicyclopentadiene [tricyclo (5.2.1.02.6) - 4 (or 3) - chloro - decane-3 (or 4), 8-diol], are prepared, using the second method.  An additional specified alcohol is bromo - dihydroxytetrahydrodicyclopentadiene [tricyclo (5.2.1.02.6)-4 (or 3)-bromo-decane-3 (or 4), 8-diol].  The products may be cured to give epoxy resins (see Division C3).  The following intermediates are prepared in the examples:  (1)  3 : 4-epoxy 8-hydroxytetrahydro-dicyclopentadiene by dry distilling at 120 DEG C. and 0.1 mm. Hg, 8-hydroxy-8 : 9-dihydro-dicyclopentadiene [tricyclo (5.2.1.02.6)-dec-3-ene-8-ol], prepared by hydrolysis of dicyclopentadiene; the epoxy compound is then converted into 3,4,8-trihydroxy-tetrahydro - dicyclopentadiene [tricyclo (5.2.1.02.6)-decane-3,4,8-triol] by mixing with water and boron trifluoride, followed by extraction, and treatment with an ion-exchange resin in the form of a free base; (2) 3 (or 4), 8-dihydroxytetrahydro - dicyclopentadiene [tricyclo - (5.2.1.02.6)-decane-3 (or 4), 8-diol] by treating with hydrogen under 80-120 atmospheres and 100-150 DEG  C., in the presence of Raney Ni catalyst, dicyclopentadiene dioxide [tricyclo (5.2.1.02.6) - 3,4,8,9 - diepoxy - decane], followed by distillation under high vacuum; (3) 4 (or 3)-chloro-3 (or 4), 8-dihydroxy-tetrahydrodicyclopentadiene [tricyclo-(5.2.1.02.6)-4 (or 3)-chlor-decane 3 (or 4) 8 diol] by treating 8 - hydroxy-dihydro - dicyclopentadiene [tricyclo - (5.2.1.02.6) - dec - 3 - ene - 8 - ol] with chlorine at 10-15 DEG  C. in acetone.ALSO:An insoluble and infusible resin is obtained from a curable composition comprising a curing agent for epoxy resins and a glycidyl ether of the general formula <FORM:0982151/C3/1> wherein R1, R2 and R3 each represent a hydrogen or halogen atom, a hydroxy group or a glycidoxy group (see Division C2).  The curing agent may be a basic or acidic compound, e.g. an amine or amide, e.g. an aliphatic or aromatic primary, secondary or tertiary amine, a Mannich's base, piperidine, piperazine, guanidine or guanidine derivative, a formaldehyde resin with urea, melamine or aniline, an aminostyrene polymer, a polyamide, a polymeric polysulphide, an isocyanate or isothiocyanate, phosphoric acid, polybasic carboxylic acid or its anhydride, a polyhydric phenol, a phenol-aldehyde resin which may be oil modified, a reaction product of an aluminium alcoholate or phenolate with a tautomeric compound such as acetoacetic ester, Friedel-Craft's catalysts including BF3 and their complexes with organic compounds, a metal flouborate or a boroxine, e.g. trimethylboroxine. When a monoglycidyl ether of Formula I is used a polycarboxylic acid or its anhydride is generally included to effect cross-linking. Other epoxides may also be present in the curable composition, e.g. mono- or poly-glycidyl ethers of mono- or polyhydric alcohols or phenols or of condensation products of aldehydes with phenols, polyglycidyl esters of polycarboxylic acids, or amino-polyepoxides.  Suitable extenders or fillers may be present, e.g. asphalt, bitumen, glass fibres, mica, quartz meal, cellulose, kaolin, finely dispersed silicic acid or metal powders.  The mixtures of the epoxy compounds and curing agents can be used in solution or emulsion as textile assistants, laminating resins, lacquers, paints, dipping or casting resins, coating compositions, pore fillers, putties or adhesives and the resins are suitable for use as electrical insulators.