Patent GB-1017614-A (GB)
Title: Improvements relating to polyester ethers
IPC: C08G63/66
Filed: 1963-04-16
Abstract: A process for the production of a segmented copolymer consisting essentially of a multiplicity of recurring intralinear etherester and ester units represented respectively by <FORM:1017614/C3/1> where G is the radical remaining after removal of the terminal hydroxyl groups from a difunctional polyether glycol of molecular weight 1000 to 5000, R is a divalent aromatic radical remaining after removal of the carboxyl groups from a dicarboxylic aromatic acid and R is the radical remaining after removal of the hydroxyl groups from 1:4-cyclohexanediol or a cyclic diol of formula HO-R11-Q-R11-OH, HO-R11-Q-Q-R11-OH or HO-R11-Q-B-Q-R11-OH, where R11 is -CH2-, -CH2-CH2- or -CH2CH2O-, B is -SO2, -CH2-, -CH2-CH2- or -C(CH3)2- and Q is a phenylene or cyclohexylene radical, with the proviso that all of the radicals Q and R11 in any one diol are alike, the radicals R and R1 being so selected that a polyester in which all the recurring structural units have the formula <FORM:1017614/C3/2> would have, on its fibre forming molecular weight range, a polymer melting temperature (the minimum temperature at which a sample of the polymer leaves a wet molten trail as it is stroked with moderate pressure across a smooth surface of heated block of brass) above 300 DEG C., the ether ester and ester units being interconnected to provide a segmented polymeric structure in which the terminal carbonyl group of one ether ester unit is connected to the terminal oxygen atom of one ester unit to provide an ester linkage, 75% to 95% by weight of the segmented copolymer being provided by the ether ester units and 5 to 25% by weight by the ester units are made by subjecting to melt polymerization a mixture of the polyether glycol, the divalent aromatic acid and an ester-forming derivative thereof and the cyclic diol.  The cyclic glycols which may be used in forming the ester segments include 1:4-cyclohexane-diol, p-xylylene glycol, p:p-bis - (hydroxymethyl) - biphenyl, p - p1 - bis-(hydroxymethylphenyl) - sulphone, 1:4 - bis-(hydroxymethyl) - cyclohexane, 4:41 - bis-(hydroxymethyl) - bicyclohexyl, 4:41 - bis-(hydromethylcyclohexyl)-sulphone and p-bis-(hydroxyethoxy)-benzene. Specified dicarbcyclic acids are terephthalic, tetramethylene terephthalic, tetrachloroterephthalic, dibenzoic, p:p1 - sulphonyl dibenzoic, 1:2 - bis - (p-carboxyphenyl) -ethane and 2:6-naphthalene dicarboxylic acid.  Specified difunctional polyethers are polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polypentamethylene ether glycol, polyhexamethylene ether glycol and polydioxolane and polyformals made by reacting formaldehyde with pentamethylene glycol or a mixture thereof with tetramethylene glycol. The difunctional polyether may be incorporated by using the dicarboxymethyl acids of polyalkylene ethers or esters thereof. In modifications of the process, amide urethane or sulphonamide linkages may be incorporated in the final product.  The examples describe the preparation of polymers from:-(I) polytetramethylene ether glycol, the diethyl ester of p:p1-sulphonyl-dibenzoic acid and 1:4-bis-(hydroxymethyl)-cyclohexane and (II) polytetramethylene ether glycol, p:p-dibenzoic acid and 1:4-bis-(hydroxymethyl) -cyclohexane.