Patent GB-1024487-A (GB)
Title: A new bicyclic glycol and polyesters made therefrom
Inventor: HAGSED MILTON JONES
IPC: D01F6/62
Filed: 1963-11-06
Abstract: As component groups of polyesters, use is made of esters of 1,4-bicyclo-(2,2,2) octanedimethanol of the formula <FORM:1024487/C3/1> in which R and R1 represent acyl groups. Suitable esters may be prepared by esterifying the glycol or an ester-forming derivative thereof with a dicarboxylic acid or an ester-forming derivative thereof and then continuing the esterification, optionally in the presence of a catalyst, e.g. antimony trioxide, litharge, zinc acetate, sodium hexabutoxytitanate or an alkyl titanate.  Specified dicarboxylic acids from which polyesters may be prepared are oxalic, succinic, adipic, sebasic and terephthalic acids, methylterephthalic acid, 2,5-and 2,6 - dimethylterephthalic acids, chloroterephthalic acid, 2,5-dichloroterephthalic acid, fluoroterephthalic acid, isophthalic acid, 1,4-, 1,5-, 2,6- and 2,7-naphthalene-dicarboxylic acids, carbonic acid, phenylenediacetic acid, 4-carboxyphenoxy-acetic acid, m- and p-terphenyl - 4,411 - dicarboxylic acids, dodecahydrodibenzoic acid, hexahydroterephthalic acid, 4,41 - dibenzoic acid, 2,21 - and 3,31-dimethyl - 4,41 - bibenzoic acids, 2,21 - dibromo - 4,41 - bibenzoic acid, bis - (4 - carboxyphenyl)methane, 1,1- and 1,2-bis-(4-carboxyphenyl)ethanes, 2,2 - bis - (4 - carboxyphenyl)-propane, 1,2 - bis - (4 - carboxyphenoxy)-ethane, bis - 4 - carboxyphenyl ether, bis-4 - carboxyphenyl sulphide, bis - 4 - carboxyphenyl ketone, bis - 4 - carboxyphenyl sulphoxide, bis - 4 - carboxyphenyl sulphone, 2,8 - dibenzofurandicarboxylic acid, 4,41-stilbenedicarboxylic acid and octadecahydrom - terphenyl - 4,41 - dicarboxylic acid.  The invention extends also to polyester resins containing residues of the glycol formulated above and residues of other hydroxy compounds. Hydroxy compounds specified in this context are ethylene glycol, propylene glycol, butylene glycol, 2,2 - dimethyl - propylene glycol, 2-methyl - 2 - ethylpropylene glycol.  2 - Methyl-2 - propylpropylene glycol, 2,2,3,3,4,4 - hexafluoro - 1,5 - pentanediol, hexamethylene glycol, decamethylene glycol, diethylene glycol, ethylene thiodiglycol, cis- or trans-hexahydro-p-xylylene glycol, cis- or trans-quinitol, bis-(4 - hydroxymethylcyclohexyl), bis - (4-hydroxymethylcyclohexyl)ethane, decahydro-1,4- -1,5-, -2,6- or -2,7-bis-(hydroxymethyl) naphthalene, 1,1 - bis - (hydroxymethyl)-cyclohexane, 1,4 - bis - (2 - hydroxyethyl) benzene, 1,4 - bis - (2 - hydroxyethoxy)benzene, 4 - (2 - hydroxyethyl)benzoic acid, 4 - (2-hydroxyethoxy) benzoic acid, hydroquinone, resorcinol, 4,41 - dihydroxybiphenyl, 3,31 - dibromo - 4,41 - dihydroxybiphenyl, bis - (4-hydroxyphenyl) methane, 2,2 - bis - (4 - hydroxyphenyl) propane, 2,2 - bis - (3,5 - dichloro - 4 - hydroxyphenyl)propane, bis - (4- hydroxyphenyl) ether, bis - (4 - hydroxyphenyl sulphone, bis - (4 - hydroxyphenyl)ketone and bis - (4 - hydroxyphenyl)sulphoxide. Such polyesters may be prepared by esterifying mixtures of the components or by mixing appropriate polyesters.  Examples are given.ALSO:The invention relates in part to 1,4-bicyclo-[2,2,3]-octane-dimethanol and esters thereof of the formula <FORM:1024487/C2/1> in which R and R1 represent hydrogen atoms or acyl groups. The glycol in which R and R1 are both hydrogen atoms may be prepared by reducing the known compound 1,4-bicyclo-[2,2,2]-octanedicarboxylic acid, suitably by treatment with lithium aluminium hydride or by catalytic hydrogenation. Esters of the glycol may be prepared by esterifying the glycol or an ester-forming derivative thereof with a dicarboxylic acid or an ester-forming derivative thereof, suitably by an ester-interchange reaction which may be effected in the presence of a catalyst, e.g. manganous acetate, calcium acetate, litharge, sodium methoxide, sodium hydrogen hexabutoxytitanate or an alkyl titanate.  The esters are useful in the manufacture of fibre-forming polyester resins (see Divisions B5 and C3).