Patent GB-828364-A (GB)
Title: Improvements in and relating to the preparation of ethers of epoxy-substituted phenols and the resulting ethers and their polymers
IPC: C07D303/24
Filed: 1957-04-10
Abstract: The invention comprises ethers of (i) an epoxy-substituted alcohol or a dihydric alcohol with (ii) a monohydric or polyhydric phenol, the phenol ring or rings of which contain at least one epoxyalkyl or epoxycycloalkyl substituent.  Preferred ethers have the formulae <FORM:0828364/IV (b)/1> <FORM:0828364/IV (b)/2> where Z is an aromatic hydrocarbon radical, R is a radical derived from a dihydric aliphatic, cycloaliphatic or heterocyclic alcohol by the removal of one-OH group, or an epoxy-substituted aliphatic, cycloaliphatic or heterocyclic radical containing not more than 12 carbon atoms, R1 is a bivalent radical derived from a dihydric alcohol, X is epoxyalkyl or epoxycycloalkyl, m and n are integers.  Also preferred are ethers having the formula <FORM:0828364/IV (b)/3> where W is a hydrocarbon radical of valency "A," b is an integer, and A is at least 2.  The compounds of the invention may be prepared by treating an ether derived from (i) an epoxy-substituted alcohol or a dihydric alcohol, and (ii) a monohydric or polyhydric phenol, the phenol ring or rings of which contain at least one ethylenically unsaturated alkyl or cycloalkyl groups, with a perorganic acid.  Inert solvents may be used.  The intermediate unsaturated ethers may be prepared by etherifying, e.g. with a halo-epoxy-substituted alkane or an alkane having the grouping <FORM:0828364/IV (b)/4> the corresponding unsaturated phenol.  The compounds of the invention may be polymerized (see Group IV (a)).ALSO:Polymers are derived from ethers of (i) an epoxy substituted alcohol or a dihydric alcohol with (ii) a monohydric or polyhydric phenol, the phenol ring or rings of which contain at least one epoxy alkyl or epoxycycloalkyl substituent. Three main types of polymer are disclosed: (A) ethers containing one epoxy group from linear polymers in the presence of Friedel Crafts catalysts, e.g. AlCl3, AlBr3, BiCl3, ZnCl2 and BF3 complexes.  Both the liquid and solid polymers prepared in this way are useful as additives for lubricating compositions-both as pour point depressants and as viscosity index improvers-and as plasticizers.  (B) Ethers containing more than one epoxy group may be reacted with polyhydric compounds (e.g. resorcinol, bis-phenol A and catechol) to produce higher molecular weight compounds, which may have their epoxy content increased by reaction with epichlorhydrin.  (C) Polymers may be derived directly from ethers containing more than one epoxy group. The higher M.W. ethers (B) and the polyepoxy ethers (C) may be polymerized alone or with other polyepoxides, e.g. glycidyl polyethers of polyhydric phenols or alcohols (such as epichlorhydrin/bisphenol A condensates), in the presence of conventional epoxy resin curing catalysts.  The following curing catalysts are disclosed: phthalic or hexahydrophthalic anhydrides, BF3 or ether or amine complexes thereof (e.g. BF3/ethylamine), phosphoric acid and partial esters thereof, ethylene diamine, diethylene triamine, m-phenylene diamine, diamino pyridine, Zn or Ni fluoroborates, K persulphate, Mg perchlorate, polyisocyanates, drying oil fatty acids, and methylol urea or melamines.  In Examples (1)-(7) and (10)-(14) various ethers containing more than one epoxy group are cured (i.e. type (C)).  In Examples (1) and (9) similar ethers are cured with di- and poly-glycidyl ethers of bisphenol A.  In Example (8) a mono-epoxy ether of type (A) is stated to be polymerizable.  No examples are given of type (B), but in Example (15) a similar type of compound is prepared by reacting 2,2-bis(4 - hydroxy - 3 - allylphenyl) propane with the diglycidyl ether of bisphenol A; the resultant polymer is then epoxidized in the peracetic acid in the presence of chloroform, and finally cured with m-phenylene diamine. Uses of polymers.-Apart from the uses discussed under type (A) above, the polymers are said to be useful for casting, potting, surface coating, impregnating, adhesives and (Example (1)) glass cloth laminates.  Uses of monomers.-As diluents for more viscous polyepoxides.  Uses of monomers and polymers.-As plasticizers and stabilizers for vinyl polymers, especially polyvinyl halides, either alone or in combination with ureas or cadmium salts.