Patent GB-859643-A (GB)
Title: Process for the preparation of lactone adducts and polyesters
IPC: C08G59/64
Filed: 1957-04-15
Abstract: A polyester or a lactone adduct (see Group IV (b)), is made by heating a lactone having at least six carbon atoms in the ring with an initiator which is an organic compound containing at least one alcoholic hydroxyl group or a primary or secondary amino group attached directly to carbon in the presence of an inorganic acidic compound as a catalyst.  Preferred lactone and initiator are as specified in Specification 859,642.  The catalyst may be sulphuric acid, phoshporic acid, a Friedel-Crafts compound or a complex thereof.  The polyesters may be reacted with polyisocyanate to form polyurethanes and, particularly if their terminal hydroxyl groups are acylated, are suitable for use as plasticizers, e.g. for vinyl chloride-vinyl acetate copolymers. Examples describe the polycondensation of epsilon-caprolactone, various methyl substituted epsiloncaprolactones and mixtures thereof using ethylene glycol or hexamethylene diamine as initiator.  Specifications 859,639, 859,640, 859,641, 859,644 and 859,645 also are referred to.ALSO:A lactone adduct or a polyester (see Group IV (a)) is made by reacting a lactone having at least six carbon atoms in the ring with an organic compound containing at least one alcoholic hydroxyl group or a primary or secondary amino group attached directly to carbon in the presence of an inorganic acidic compound as catalyst.  The lactones preferably have the formula:  <FORM:0859643/IV(b)/1> where n is at least four, at least n + 2 R's are hydrogen, the remainder of the R's are hydrogen, alkyl, cycloalkyl, alkoxy or single ring aromatic radicals, none of the substituents contain more than about twelve carbon atoms, and the total number of carbon atoms in the substituents on a lactone ring does not exceed about twelve.  The hydroxyl or amino compounds preferably have the formula:  R1 (YH)y in which R1 is an aliphatic, cycloaliphatic, aromatic or heterocyclic radical, y is at least 1, and Y is -O-, -NH- or -N R11-, R11 being alkyl, aryl, aralkyl or cyclo alkyl.  The Specification lists a very large number of such compounds including conventional aliphatic, cycloaliphatic, aromatic and heterocyclic mono-, di- and higher poly-amines; mono hydric, dihydric and higher polyhydric aliphatic, cycloaliphatic, aromatic and heterocyclic alcohols; reaction products of monoepoxides (e.g. ethylene, propylene, 1-butylene, isobutylene, butadiene and styrene oxides) with di- or higher-functional compounds having reactive hydrogen atoms in the form of primary or secondary hydroxyls, phenolic hydroxyls, primary or secondary amino, amido, hydrazino, guanido, ureido, mercapto, sulphino, sulphonamide or carboxyl groups or phosphorous oxyacid, and aliphatic, cycloaliphatic or aromatic amino alcohols.  The inorganic acidic catalyst may be hydrochloric, sulphuric or phosphoric acid, a Friedel-Crafts compound or a complex thereof. The reaction between methanol and epsilon-capro lactone produces initially mainly the compound <FORM:0859643/IV(b)/2> but a side reaction may produce the compound CH3O (CH2)5 COOH The reaction between a mono-amine of formula R1NH2 and epsilon-caprolactone produces initially the compound <FORM:0859643/IV(b)/3> The reaction between a dirl of formula OH R1OH and epsilon-caprolactone produces initially the compound <FORM:0859643/IV(b)/4> These initial products may then react with further lactone to produce polyesters, polyamides, &c.  In Examples (1) -(7) and (10) Polyesters are made (see Group IV (a)) (8) Epsilon-caprolactone and methanol are refluxed in presence of sulphuric acid and after neutralisation with sodium methoxide, excess methanol is removed by distillation and the product then distilled to yield as distillate methyl 6- hydroxycaproate (9) A mixture of 3, 5, 5-trimethyl- and 3, 3, 5-trimethyl-epsilon-caprolactone is refluxed with methanol in the presence of sulphuric acid and after removal of the catalyst with an anion-exchange resin, excess methanol is removed by distillation and the product distilled to give an adduct containing on average 1,7 mols of lactone per mol of methanol. Specifications 859,639, 859,640, 859,641, 859,642, 859,644 and 859,645 are referred to.