Patent GB-867111-A (GB)
Title: Acylated lactone adducts and polyesters
IPC: C08G63/08
Filed: 1957-04-15
Abstract: An acylated lactone adduct or polyester is made by reacting (a) a mono- or poly-carboxylic acid or anhydride thereof with (b) a lactone adduct or polyester formed by heating 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 organic acid or anhydride as a catalyst (i.e. the products of Specification 839,645.) Specified carboxylic acids are acetic, 2-ethylhexanoic, benzoic, methacrylic, oxalic, succinic, maleic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, phthalic, isophthalic and terephthalic acids.  Acylalation may be effected in the presence of a mixture of methane-, ethane- and propane-sulphonic acids as a catalyst.  If greater than an equivalent amount of carboxylic acid is used, the terminal carboxyl groups may be reacted with an alkyl alcohol or an alkyl amine.  The acylated products are suitable plasticizers for polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral, GRS rubber, butadiene-acrylonitrile copolymers and natural rubber.  In Examples (1)-(8), (10), (13) and (14) p Epsilon-caprolactone was heated with 2-ethyl-1, 3- hexanediol, trimethylol propane, glycerol, ethylene glycol, propylene glycol, 2-ethylhexanol, n-hexanol or the butyl ether of ethylene glycol and the product acylated with acetic anhydride, 2-ethyl hexanoic acid, pimelic acid, azelaic acid, adipic acid, or phthalic anhydride; (9) A mixture of epsilon-caprolactone and methyl-epsilon-caprolactone was heated with diethylene triamine and the product acylated with acetic anhydride; (11) and (12) Epsiloncaprolactone was heated with 2-ethylhexanol or cyclohexanol, the products acylated with phthalic anhydride and the acylated products esterified with 2-ethylhexanol; (15) Epsilon-caprolactone was heated with oxo-decanol and the product acylated with methacrylic acid to provide an ester suitable for copolymerizing with vinyl chloride or polyglycol dimethacrylate to provide a "built-in" plasticizer.  Specification 859,642 also is referred to.ALSO:An acylated lactone adduct or polyester is made by reacting (a) a mono- or polycarboxylic acid or anhydride thereof with (b) a lactone adduct or polyester formed by heating 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 organic acid or anhydride as catalyst (i.e. the products of Specification 839,645).  Specified carboxylic acids are acetic, 2-ethylhexanoic, benzoic, methacrylic, oxalic, succinic, maleic, glutaric, adipic, pimelic, suberic, azelaic, sebasic, phthalic, isophthalic and terephthalic acids.  Acylation may be effected in the presence of a mixture of methane-, ethane-, and propene-sulphonic acids as catalyst.  If greater than an equivalent amount of carboxylic acids is used, the terminal carboxyl group may be reacted with an alkyl alcohol or an alkyl amine.  The products may have the general formula:  <FORM:0867111/IV (b)/1> where the Ls are groups of formula:  <FORM:0867111/IV (b)/2> in which n is at least four, at least n +2Rs are hydrogen, the remaining Rs are hydrogen, alkyl, cycloalkyl, alkoxy or single ring aromatic hydrocarbon radicals, and the total number of carbon atoms in the substituents on a given group does not exceed about twelve; the R1s are aliphatic, cycloaliphatic, aromatic or heterocyclic radicals; Y is -O-, -NH- or -NR11-; R11 is an alkyl, aryl, aralkyl or cycloalkyl radical; Z is acyl; Ac is the acyl radical of a dicarboxylic acid; Ac1 is the acyl radical of a mono- or poly-carboxylic acid; m is a number equal to the number of carboxylic acid groups in the acid corresponding to Ac1; Alk stands for alkyl; the Xs average at least one; and y and z are each at least one.  In Examples (1)-(3) Epsilon-capro lactone was heated with 2-ethyl-1,3-hexanediol, trimethylol propane or glycerol, and the products acylated with acetic anhydride; (4), (5), (6), (7) and (8) Epsiloncaprolactone was heated with 2-ethyl-1,3-hexanediol, ethylene glycol, propylene glycol or 2-ethyl-1,3-hexanediol and the products esterified respectively with 2-ethylhexanoic or azelaic acid, pimelic acid, azelaic acid and adipic acid; (9) a mixture of epsilon-caprolactone and methyl-epsilon-caprolactone was heated with diethylene triamine and the product acylated with acetic anhydride; (10) Epsilon-caprolactone was heated with 2-ethyl hexanol and the product acylated with acetic anhydride; (11) Epsilon-caprolactone was heated with 2-ethylhexanol, the product acylated with phthalic acid and the acylated product esterified with 2-ethyl hexanol to yield a product of formula:  <FORM:0867111/IV (b)/3> (12) Epsilon-caprolactone was heated with cyclohexanol, the product acylated with phthalic anhydride and the acylated product esterified with 2-ethylhexanol; (13) Epsiloncaprolactone was heated with n-hexanol and the resulting n-hexyl 6-hydroxyhexanoate was acylated with pimelic acid to yield a product of formula:  <FORM:0867111/IV (b)/4> (14) Epsilon-caprolactone was heated with the butyl ether of ethylene glycol and the product acylated with phthalic anhydride to yield:  <FORM:0867111/IV (b)/5> (15) Epsilon-caprolactone was heated with oxodecanol and the product acylated with methacrylic acid in the presence of hydroquinone and copper sponge (to prevent polymerisation) and a sulphonic acid catalyst.  Specification 859,642 also is referred to.