Patent GB-712588-A (GB)
Title: Improvements in and relating to trimethylol phenol compounds
Filed: 1950-09-28
Abstract: Phenol-aldehyde resins.  Ethers of 2 : 4 : 6-tris-(hydroxymethyl)-phenol, of the general formula <FORM:0712588/IV (a)/1> (wherein R represents an aliphatic, cycloaliphatic or aryl-substituted aliphatic group, including their halogen-substituted derivatives), can be cured by the action of catalysts such as acids or acid engendering reagents, e.g. hydrochloric, maleic, oxalic or especially phosphoric acid, or preferably ammonium or amine (e.g. morpholine, urea or ethanolamine) salts of sulphuric acid or of sulphonic acids (e.g. benzene-, p-toluene- or o- or p-phenol-sulphonic acid).  When the group R is unsaturated, sulphur and rubber accelerators or metallic driers may alternatively be used.  In an example, the morpholine or urea salt of p-and/or o-phenolsulphonic acid is added to a paint based on the allyl ether and pigmented with titanium oxide.  Replacement of these catalysts by phosphoric acid yields a coating of interior gloss.  The ethers may also be compounded with fillers and used as casting resins, e.g. the allyl ether may be compounded with carbon black and then cured.  Polyvinyl resin compositions.  The ethers formulated above are also useful as plasticizers for vinyl type synthetic resins, for which purpose the presence of minor proportions of the corresponding 2- and 4-mono- and 2 : 4-and 2 : 6-bis-(hydroxymethyl) compounds is not detrimental.  In examples using pure tris-(hydroxymethyl) compounds: (1) the allyl ether is milled with polyvinyl alcohol and water on heated rolls; (2) the benzyl ether is similarly milled with polyvinyl butyral and acetone.  In further examples, the allyl ether of the mixed tris-, bis- and mono-(hydroxymethyl) compounds is mixed with: (3) polyvinyl butyral, n-butanol, toluene, a little phosphoric acid, and aluminium flake, to produce a varnish; (4) polyvinyl formal, furfural, isopropanol and diacetone alcohol; (5) a solution of polyvinyl formal, to produce an insulating coating for electrical wires.  Specification 712,525, [Group IV (b)], is referred to.ALSO:The invention comprises compounds of the general formula <FORM:0712588/IV (b)/1> wherein R represents an aliphatic, cycloaliphatic or aryl-substituted aliphatic group, including their halogen-substituted derivatives, and n is 3, or mixtures of a major amount thereof with compounds in which n is 1 or 2, and the preparation of the compound in which n is 3 by reacting previously isolated sodium 2 : 4 : 6-tris(hydroxymethyl)-phenate with a halide RX, wherein X represents chlorine, bromine or iodine, at a temperature not exceeding 65 DEG  C.  In examples: (1)-(9) sodium 2 : 4 : 6-tris-(hydroxymethyl)-phenate is reacted with methyl iodide, allyl bromide (under two different sets of conditions), benzyl chloride, 2-methallyl chloride, 2 : 3- and 1 : 3-dichloropropene-1(yielding the b - and g -chloroallyl ethers respectively), isoamyl iodide and n-butyl bromide; (10) phenol is warmed with 3 molecular proportions of formaldehyde in aqueous caustic soda and the reaction mixture is heated with allyl chloride; (11) and (12) the proportions of phenol and formaldehyde in (10) are varied.  Specification 712,525 is referred to.ALSO:Ethers of methylolphenols, of the general formula <FORM:0712588/V/1> wherein R represents an aliphatic, cycloaliphatic or aryl-substituted aliphatic group, including their halogen-substituted derivatives, and n is 3, or mixtures of a major amount thereof with compounds in which n is 1 or 2, are useful as mild curing agents for synthetic rubbers, e.g. butadiene rubbers.  Specification 712,525, [Group IV (b)], is referred to.