Patent GB-700957-A (GB)
Title: Improvements in or relating to photographic film
IPC: G03C1/93
Filed: 1951-12-24
Abstract: Highly polymeric polyesters of a glycol and terephthalic acid, which have a molecular weight of at least 5000 and which are soluble to the extent of at least 1/2 per cent by weight in trichlorethylene, are prepared (a) by condensing a mixture of a polymethylene glycol having 2 to 10 methylene groups and a polyethylene glycol containing from 1 to 5 oxyethylene radicals with terephthalic acid, an acid chloride or bromide thereof, or a diester thereof with an alcohol of 1 to 6 carbon atoms, the mol. per cent. of polyethylene glycolin in the glycol mixture varying from 20 to 100 per cent., with a preferred range of 25 to 75 per cent., or (b) by condensing a polymethylene glycol having 2 to 10 methylene groups with a mixture of (i) terephthalic acid, an acid chloride or bromide, or a diester thereof with an alcohol of 1 to 6 carbon atoms and (ii) a saturated aliphatic dicarboxylic acid of 4 to 16 carbon atoms, an acid chloride or bromide, or a diester thereof with an alcohol of 1 to 6 carbon atoms, the terephthalic acid compound constituting at least 25 per cent. of the total acid compound, the aliphatic dicarboxylic acid compound constituting from 10 to 75 per cent. of the total acid compound, and a further dicarboxylic acid compound, which may optionally be present and may be bibenzoic, phthalic or isophthalic acid or a dimethyl or diethyl ester thereof, constituting, if present, from 1 to 25 per cent. of the total acid compound.  In both cases, the glycol should be in excess and the esterification may be effected at about the boiling point of the glycols.  The temperature is then increased and the glycols removed by distillation, usually at reduced pressure.  In example 1, dimethyl terephthalate was heated with an excess of a mixture of ethylene glycol and diethylene glycol in equimolar amounts at 170 - 220 DEG C. in the presence of 0.03 per cent. by weight (based on the dimethyl terephthalate) of litharge until evolution of methanol ceased.  The temperature was increased to 250-280 DEG C. and the pressure reduced to 0.1 to 0.5 mm. of mercury.  In examples 6 and 7, polyesters were similarly prepared by reacting diethylene glycol and dimethyl terephthalate, and mixture of diethylene glycol and ethylene glycol (75 and 25 mol. per cent., respectively) and dimethyl terephthalate.  In example 8, a polyester was prepared by reacting ethylene glycol with a mixture of the methyl esters of terephthalic, bibenzoic, and azelaic acids (40, 20, and 40 mol. per cent., respectively). In example 9, a polyester was prepared by reacting ethylene glycol with a mixture of the methyl esters of terephthalic, isophthalic, and sebacic acids (50, 25, and 25 mol. per cent., respectively). In examples 10 and 11, polyesters were prepared by reacting ethylene glycol with an equimolar mixture of the methyl esters of terephthalic and sebacic acids and with a 30, 70 mol. per cent. mixture.  In example 12, ethylene glycol was reacted with an equimolar mixture of dimethyl terephthalate and adipic acid in the presence of Zn3B4O9 catalyst.  Specifications 535,341, 578,079, 627,125 and 718,422 are referred to.