Patent GB-650117-A (GB)
Title: A process for preparing mixed ethers of bis-phenols and polymers thereof
Filed: 1948-03-18
Abstract: Mixed di-ethers of a bis-(4-hydroxyphenyl) alkane having the hydroxyphenyl groups linked to the same carbon atom of the alkane, and the hydrogen atom of one hydroxy group replaced by a b  : g -mono-olefinic radical and the hydrogen atom of the other hydroxy group replaced by the group directly linked to the hydroxy group of a monohydroxy epoxyalkane having the hydroxy group linked to a carbon atom other than that to which the epoxy oxygen atom is linked, are employed in the preparation of resinous products by first polymerizing either all the epoxide groups (e.g. with Friedel Craft catalysts such as aluminium chloride), or all the b  : g -olefinic groups (with a peroxide polymerization catalyst) to give soluble fuzible polymers, and then polymerizing the remaining unpolymerized epoxide or olefinic groups to give the final insoluble, infusible polymer.  A typical di-ether of the invention is the allyl, glycidyl diether of bis-(4 - hydroxyphenyl) - 2 : 2 - propane, but many others are specified. Alternatively the epoxide and olefinic groups may be polymerized simultaneously, e.g. by heat alone, or the bis-ethers may be copolymerized with other epoxides, e.g. ethylene or isobutylene oxide, or epichlorohydrin, or with compounds containing a vinylidene group, e.g. styrene, acrylonitrile, vinyl chloride, vinyl acetate, methyl methacrylate or diallyl phthalate.  The Specifications open to inspection under Sect. 91 comprises also the use of bis-ethers in which the olefinic group is not restricted to a b  : g  group, and of bis-ethers of bis-(4-hydroxyaryl) alkanes in general.  This subject-matter does not appear in the Specification as accepted.ALSO:A mixed di-ether of a bis-(4-hydroxyphenyl)-alkane having the hydroxyphenyl groups linked to the same carbon atom of the alkane, the hydrogen atom of one hydroxy group replaced by a b  : g -mono-olefinic radical and the hydrogen atom of the second hydroxy group replaced by the group directly linked to the hydroxy group of a mono-hydroxy epoxy-alkane having the hydroxy group linked to a carbon atom other than the carbon atom to which the epoxy oxygen atom is linked, is prepared by treating the bis-(4-hydroxyphenyl)-alkane with a b  : g -mono-olefinic chloride or bromide in presence of about 1/2 mol. of an alkali to give the mono-ether, which is then further reacted in the presence of alkali with a monohydroxy epoxyalkane in which the OH group is replaced by chlorine or bromine.  Many suitable starting materials are specified, including bis - (4 - hydroxyphenyl) - 1 : 1 - ethane, 1 : 1 - propane, 2 : 2-butane, 2 : 2-hexane, and 1 : 1-isopentane, and similar compounds with the phenyl radical containing one or two methyl, propyl and butyl groups.  These bis-(4-hydroxyphenyl)-alkanes are prepared by condensing the phenol or derivative with aldehydes or ketones.  The b  : g -mono-olefinic chloride or bromide may be, for example, methallyl, crotyl, tiglyl, 2-hexenyl or methylvinyl carbinyl chloride, or crotyl, angelyl or 2-octenyl bromide.  The usual epoxy compound used is epichlorohydrin, but others mentioned include 1-chloro-2 : 3-epoxybutane, 1 - chloro - 2 - methyl - 2 : 3 - epoxypropane, 1 - bromo - 2 : 3 - epoxypentane, 1 - bromo - 4 - ethyl - 2 : 3 - epoxypentane, and 1-chloro-2 : 3-epoxydecane. The usual reaction temperature is 60-150 DEG  C.; the base may be used in aqueous solution.  In an example, bis-(4-hydroxyphenyl)-2 : 2-propane is treated with allyl chloride in presence of ethanolic sodium hydroxide to give the mono-ether, which is treated with epichlorohydrin and aqueous sodium hydroxide to give an allyl, glycidyl ether of the bis-phenol.  Many other bis-ethers are specified.  The Specification as open to inspection under Sect. 91 comprises also the preparation of the bis-ethers by etherification of the hydroxy groups of the bis-phenol in any order, and it is also stated that bis-(4-hydroxyaryl)-alkanes and mono-olefinic halides in general may be employed in the reaction.  This subject-matter does not appear in the Specification as accepted.