Patent GB-604075-A (GB)
Title: Manufacture of new highly polymeric linear esters and the production of filaments, fibres and the like therefrom
IPC: C08G63/82
Filed: 1945-11-23
Abstract: Alkyd resins are prepared by heating, preferably in the absence of oxygen (e.g. in a stream of nitrogen), acids of the formula <FORM:0604075/IV(a)/1> where R is -S- or -S(CH2)nS- (n being an integer not greater than 6) or ester-forming derivatives thereof with ethylene or tri-, tetra-, penta-, or hexa-methylene glycol under conditions such that during the later stages of the reaction volatile by-products and excess of glycol are removed and continuing the heating until filaments extruded or spun from the molten or re-melted resin can be permanently extended by cold-drawing to form fibres. Suitable derivatives are esters and half-esters such as low alkyl (e.g. methyl, ethyl, propyl, butyl, amyl, hexyl, and heptyl), cycloalkyl, and aryl (e.g. phenyl) esters; acid halides; and ammonium and amine salts.  When the acid itself is used a large excess (e.g. 4 to 5 molar proportions) and when an ester is used about 1 1/2 molar proportions of glycol are preferably used.  When a dihalide is used a diluent such as an inert organic liquid and a base such as a tertiary organic base (e.g. pyridine, N-methylpiperidine, N - dimethylaniline, N - diethylaniline) are preferably present.  Specified ester interchange catalysts which may be present are lithium, sodium, and potassium, or their carbonates or their borates, calcium, magnesium or its oxide, the alcoholates (e.g. methylates and ethylates) or glycolates of the foregoing, beryllium, zinc, cadmium, aluminium, chromium, molybdenum, manganese, iron, cobalt, nickel, copper, silver, mercury, tin, lead, bismuth, antimony, platinum, and palladium. Filaments extruded or spun from the molten or re-melted resin may be cold-drawn to form fibres and the resin may also be used for films, mouldings, hot melt coatings, adhesives, e.g. for bonding laminated fabrics such as doubled fabric collars, plasticizers, and binders for coating compositions.  In examples: ethylene glycol is heated in nitrogen with: (1) methyl a  : b  - bis - (phenylthio) - ethane - 4 : 41 - dicarboxylate; (2) methyl diphenylthioether-4 : 41-dicarboxylate; (3) diphenylthioether-4 : 41-dicarboxylic acid, in the presence of lithium and magnesium.  The products may be formed into filaments which may be colddrawn to give fibres.  Methyl a  : b - bis - (phenylthio) - ethane-4 : 41-dicarboxylate is prepared by reacting the sodium salt of p-nitrophenylmercaptan with ethylene dibromide to give a  : b -bis-(p - nitrophenylthio)-ethane, reducing the nitro groups to amino, converting the amino groups to nitrile, hydrolyzing, and methylating.  Methyl diphenylthioether - 4 : 41 - dicarboxylate is made by converting the amine groups of thioaniline into nitrile, hydrolyzing, and methylating.ALSO:Methyl a ,b  - bis - (phenylthio) - ethane-4 : 41-dicarboxylate is prepared by reacting the sodium salt of p-nitrophenylmercaptan with ethylene dibromide to give p-bis-(p-nitrophenylthio)-ethane, reducing the nitro groups to amino, converting the amino groups to nitrile, hydrolysing, and methylating.  Methyl diphenylthioether - 4 : 41 - dicarboxylate is made by converting the amine groups of thioaniline into nitrile, hydrolysing, and methylating.