Patent GB-808301-A (GB)
Title: Hydroxy-substituted polyethers and a process for their preparation
IPC: C07C43/178
Filed: 1956-12-12
Abstract: Hydroxy substituted polyethers of the formula <FORM:0808301/IV (a)/1> wherein Y is a monovalent hydrocarbon radical, X is a bivalent organic radical and the OH groups are alcoholic, R is hydrogen or alkyl, n = 3 or 4 and m is 0 or any integer up to 50, are prepared by reacting with heat a di-(halohydrocarbon) tri- or tetra-(hydrocarbon) substituted benzene and/or a di-(hydroxyhydrocarbon) tri- or tetra-(hydrocarbon) substituted benzene with a compound having at least two alcoholic hydroxyl groups.  Suitable halogen-containing starting materials are 1,4-bis-(chloromethyl) tetramethyl benzene; 1,4-bis-(chloroethyl) tetraethyl benzene; 1,3-bis-(1-bromopentyl) dihexyl didecyl benzene.  Suitable hydroxyl-containing starting materials are 1,4-bis-(hydroxymethyl) tetramethyl benzene; 1,3-bis-(hydroxymethyl) tetrabutyl benzene; 1,2-bis-(1-hydroxyethyl) tetraoctyl benzene.  Suitable compounds with at least two alcoholic hydroxyl groups are ethylene glycol; triethylene glycol; 1,5-pentanediol; glycerol allyl ether; glycerol monolinoleate; sulphonyldipropanol; glycerol monoacetate; glycerol; pentaerythritol; polyallyl alcohol; 3-cyclohexenediol-1,5; polyol formed from bis phenols and epichlorohydrin as described in Specification 681,001; and products obtained by hydrolysis of butadiene dioxide, diglycidyl ether, epoxidized triglycerides, or diglycidyl ether of bisphenol or resorcinol.  Catalysts, e.g. p-toluenesulphonic or sulphamic acid and solvents or diluents, e.g. tetrachloroethane, hexachloropropane, carbon tetrachloride, benzene, toluene or dioxane may be used.  When HCl is evolved it may be removed by bubbling air or nitrogen through the reaction mixture or by adding Na2CO3, K2CO3 or epox materials, e.g. epichlorhydrin.  The products may be used for coating or impregnating or for making films.  Products with extra hydroxyl groups or with unsaturated linkages may be cured with heat or with crosslinking agents such as methylol melamine, methylol phenol and urea, or they may be reacted with drying oil fatty acids, or rosin acids for air-drying coating compositions.  The products may also be reacted with polyiarboxylic acids or anhydrides and fatty acids to form modified alkyd resins or with polyisocyanates to form polyurethanes, or where they contain ethylenic unsaturation may be polymerized alone or with other monomers by means of a peroxide catalyst.  They may also be etherified, esterified, hydrogenated or halogenated if desired.  Polyethers with long hydrocarbon side chains are oil soluble and useful e.g. as pour point depressants with lubricating oils or with fuel oils, or as surface-active agents or detergents.  The Specification contains many examples most of which are concerned with the reaction of 1,4-bis-(chloromethyl) or 1,4-bis-(hydroxymethyl tetramethyl benzene with various diols or triols in differing proportions to produce products of varying molecular weights.  In Example XX: 1,4-bis-(b -hydroxyethoxymethyl) tetramethylbenzene prepared as in Example XV was heated with dimethyldiacetoxysilane to yield a liquid polymer of mol. wt. 1497. In Example XXIII a polyether from glycerol and 1,4-bis-(hydroxymethyl) tetramethylbenzene was esterified with soya oil fatty acids.  Addition of cobalt drier to a xylene solution of the product gave a film-forming composition. In Example XXIV a polyether from glycerol and 1,4 - bis - (hydroxymethyl) tetramethylbenzene was dissolved in cyclohexanone and mixed with a urea-melamine-formaldehyde resin to give a composition which on baking yielded hard, flexible, resistant films.  Esters of polyethers of lower molecular weight (Examples 16, 18, 22) are useful as plasticizers for polyvinyl chloride.ALSO:Hydroxy polyethers of the formula <FORM:0808301/IV (b)/1> wherein Y is a monovalent hydrocarbon radical, R is H or an alkyl radical, X is a bivalent organic radical and n is 3 or 4, are prepared by reacting with heat 1 mol. of a di-(halohydrocarbon) tri- or tetra-(hydrocarbon) substituted benzene and/or a di-(hydroxyhydrocarbon) tri- or tetra-(hydrocarbon) substituted with at least 2 mols. of a substance having at least two alcoholic hydroxyl groups.  Suitable aromatic starting materials are 1,4-bis-(chloromethyl)-tetramethyl benzene; 1,4-bis-(1-chloroethyl)-tetraethyl benzene; 1,3-bis-(1-bromopentyl) - dihexyl didecyl benzene; 1,4 - bis (hydroxymethyl) - tetramethylbenzene; 1,3-bis - (hydroxymethyl) - tetrabutyl benzene; 1,2-bis - (1 - hydroxyethyl) - tetraoctyl benzene.  The halogenated starting materials may be prepared by reacting the poly-(hydrocarbon) substituted benzene, e.g. durene with formaldehyde and hydrogen chloride.  Hydrolysis of these substances, e.g. with caustic soda yields the corresponding hydroxyl - substituted starting materials. Suitable alcoholic starting materials are ethylene glycol; triethylene glycol; 1,5-pentandiol; glycerol allyl ether; glycerol monolinoleate; sulphonyldipropanol; glycerol monoacetate; glycerol; pentaerythritol; polyallyl alcohol; 3-cyclohexanediol-1,5; and materials obtained by hydrolysis of polyepoxides such as butadiene dioxide, diglycidyl ether or epoxidized triglycerides.  Products may be etherified with monohydric alcohols, esterified with monocarboxylic acids to yield esters or ethers suitable as plasticisers for rubbers or vinyl resins.  Example XV describes the heating of ethylene glycol, in presence of benzene and p-toluenesulphonic acid with 1,4-bis-(hydroxymethyl) tetramethylbenzene.  The catalyst was neutralized with sodium bicarbonate, water, benzene and excess ethylene glycol removed by distillation under reduced pressure and the solid residue extracted with water and crystallized from toluene.  The product was <FORM:0808301/IV (b)/2> (M.Pt. 97-100 DEG  C.).  Example XVI describes esterification of the above product with butyric anhydride, Example XVII with 2-ethylhexanoic acid, Example XVIII with pelargonic acid and Example XIX with stearic acid.  Example XXI describes the production of 1,4-bis-(beta, gamma-dihydroxypropoxymethyl)-tetramethyl benzene and Example XXII of esters thereof with butyric acid, pelargonic acid and caproic acid.