Patent GB-1019130-A (GB)
Title: New tris phenols and epoxide resins prepared therefrom
IPC: C08G59/08
Filed: 1964-11-12
Abstract: As reagents in the manufacture of epoxide resins by reaction with epichlorohydrin in the presence of an alkali, use is made of trisphenols of the formula <FORM:1019130/C3/1> in which R1 and R2, which may be the same or different, denote hydrogen atoms or methyl or ethyl groups, R1 denotes a chlorine atom or an alkyl group of 1-5 carbon atoms and n is 0, 1 or 2 (see Division C2).  A typical trisphenol is a ,a 1,a 11 - tris(4 - hydroxyphenyl - 1,3,5 - triisopropylbenzene. The molcular ratio of epichlorohydrin to trisphenol may be 1-50:1 and the molecular ratio of alkali to trisphenol may be 0.5-4:1.  The reaction is preferably effected in the presence of water, the proportion of which may be 0.1-75% of the total weight of the reactants.  A monohydric aliphatic alcohol of 1-4 carbon atoms may also be included in the reaction mixture, suitably in a proportion of 20-80% of the total weight of the reactants. The epoxide resins may be cured with conventional curing agents, which may be (1) amines, (2) organic polyacids and anhydrides, (3) amides having reactive amino groups, (4) Friedel-Crafts metal halides, (5) phosphoric acid and partial esters thereof, or (6) salts of inorganic acids.  Specific examples of all these classes are given.  Coating formulations may be obtained by modifying the epoxide resins with urea - formaldehyde, phenol - formaldehyde or melamine-formaldehyde resin or by esterifying the epoxide resins with the fatty acids of linseed oil, coconut oil or dehydrated castor oil.  Examples 12-18 describe the manufacture of epoxy resins, and Examples 19-21 describe curing processes.ALSO:The invention comprises trisphenols of the formula <FORM:1019130/C2/1> in which R1 and R2, which may be the same or different, denote hydrogen atoms or methyl or ethyl groups, R1 denotes a chlorine atom or an alkyl group of 1-5 carbon atoms and n is 0, 1 or 2.  The trisphenols may be prepared by reacting a compound of the formula <FORM:1019130/C2/2> or a compound of the formula <FORM:1019130/C2/3> in which R3 denotes a = CH2 or = CHCH3 group, with phenol or an appropriately substituted phenol in the presence of an acidic condensation catalyst.  Specified compounds of Formula II include a ,a 1,a 11-trihydroxy-1,3,5-triethylbenzene, a ,a 1,a 11 - trihydroxy - 1,3,5 - triisopropylbenzene and a ,a 1,a 11 - trihydroxy - 1 - methyl - 3 - ethyl - 5 - isopropylbenzene. Specified compounds of Formula III are 1,3,5-trivinylbenzene, 1,3,5 - tris - (isopropenyl) benzene and 1,3,5 - tris - (2 - sec. - butenyl) - benzene. A number of suitable phenols are specified.  The specified catalysts include mineral acids and Friedel-Crafts catalysts, examples of both of which are given, and also acid-activated clays and acidic ion exchange resins. The reaction may be effected in a solvent, a number of which are specified.  The products may be chlorinated so as to introduce one or two chlorine atoms into each phenol residue. Chlorination may be effected with sodium or potassium hypochlorite or with chlorine gas. Typical examples describe the manufacture of products from phenol and a ,a 1,a 11-trihydroxy-1,3,5 - triisopropylbenzene, a ,a 1,a 11-trihydroxy-1,3,5 - triethylbenzene and 1,3,5-triisopropenylbenzene, the catalysts used including gaseous hydrogen chloride, aqueous hydrochloric acid, hydrofluoric acid and an acid-activated bentonite clay.  An example is given also of the chlorination of a ,a 1,a 11-tris -(hydroxyphenyl)-1,3,5-triisopropylbenzene with sodium hypochlorite so as to introduce two chlorine atoms into each phenol residue.  The products are useful in the manufacture of epoxide resins (see Division C3).