Patent GB-1007819-A (GB)
Title: Improvements in and relating to sulfophenoxy, sulfophenylthio and sulfophenyl-sulfonyl-substituted alkanoic acids, salts and esters and their use in dyeable polyesters
IPC: C07C309/42
Filed: 1962-10-30
Abstract: A dyeable linear polyester is made from an aromatic dicarboxylic acid or dialkyl ester thereof, a diol or a diester thereof, and 0.1-5 mole per cent of a compound of formula <FORM:1007819/C3/1> in which M is an alkali metal, Y is an oxygen or sulphur atom or a sulphonyl group, n is an integer of from 1 to 12, and R is a hydrogen or alkyl radical containing from 1 to 8 carbon atoms. Suitable dicarboxylic acid compounds are monocyclic aromatic dicarboxylic acids and their di-alkyl esters containing 1-8 carbon atoms in each alkyl group. Aromatic diacids specified include phthalic and terephthalic acids. Suitable diols are acyclic and alicyclic aliphatic glycols containing 2-10 carbon atoms, aliphatic/aromatic diols and aromatic diols. Diols specified include ethylene glycol, 1,4-bis-(hydroxymethyl) cyclohexane, ethylene oxide and 2,2,4,4-tetra-methyl-cyclobutane-1,3-diol. Up to 10 moles of diol may be used per mole of acid.  Sulphonated compounds specified include methyl (4 - [sodium sulpho]phenoxy) acetate, methyl 6 - (4 - [sodium sulpho]phenoxy) hexanoate, methyl 6-(4-[sodium sulpho]phenyl thio) hexanoate, methyl 8 - (4 - [potassium sulpho]phenyl thio] octanoate, butyl (4 - [lithium sulpho]phenyl thio) acetate, butyl (4-[potassium sulpho]phenoxy) acetate, ethyl 8-(4-[lithium sulpho]phenoxy) octanoate, methyl (4 - [lithium sulpho]phenyl sulphonyl) octanoate, methyl 6 - (4 - [sodium sulpho]phenyl sulphonyl) hexanoate, methyl 8 - (4 - [lithium sulpho] sulphonyl) octanoate, butyl 6 - (4-[potassium sulpho] phenyl sulphonyl) hexanoate, ethyl (4 - [potassium sulpho] phenyl sulphonyl) acetate, ethyl (4 - [potassium sulpho] phenyl thio) acetate.  Up to 10 mole per cent of the dicarboxylic acid or diol may be replaced by another monomer of similar difunctionality or by a hydroxycarboxylic acid. Copolymerizable acids specified include: azelaic, sebacic and 3,6-dimethyl sebacic.  As comonomers there can also be used compounds of formula:  <FORM:1007819/C3/2> where p = 1-12 and Y1 is H or MSO3, e.g. dimethyl 2-(potassium sulpho) fluorene-9,9-dipropionate or dimethyl 2,7-di-(lithium sulpho) fluorene-9,9-dipropionate.  Another class of comonomer is represented by the formula: <FORM:1007819/C3/3> where Ar1 is aromatic, e.g. dimethyl 5-(4-[sodium sulpho] phenoxy ethoxy) iso-phthalate. 0.001-1% of a catalyst, e.g. zinc acetate sodium hexabutyl titanate or Sb2O3, may be present during the reaction.  Other additives may be colour inhibitors, pigments, delustrants, and viscosity stabilizers.  The polyester may be made either by heating the reactants in an inert atmospher (a) at 150-270 DEG  C., (b) at 300 DEG  C. under reduced pressure to remove the excess diol and (c) at 225-325 DEG  C./0.1-5 mm. Hg to polymerize or by carrying out all three stages at atmospheric pressure in an inert gas stream.  The products may be made into fibres, films, textile and moulded articles. Specifications 1,006,578 and 1,007,820 are referred to.ALSO:The invention comprises compounds of the formula <FORM:1007819/C2/1> wherein X is an -SO3H or an -SO3M radical, M being an alkali metal atom, Y is an oxygen atom, sulphur atom or a sulphonyl radical, n is an integer from 1 to 12, and R is a hydrogen atom or an alkyl radical of 1 to 8 carbon atoms. The novel compounds may be made by reacting a compound of the general formula <FORM:1007819/C2/2> with a sulphonating agent comprised of a mixture of sulphuric acid and acetic anhydride, preferably in the ratio of from 0.1 : 1 to 1 : 1. The ratio of sulphuric acid to starting material is preferably from 0.5 : 1 to 5 : 1.  Suitable temperatures are in the range from -15 DEG  to 50 DEG  C.  An inert solvent such as methylene dichloride, ethylene dichloride or ethyl acetate may be used.  The compound in which Y is -SO2- can also be made by oxidizing the corresponding sulphonated phenylthioalkanoic acid or ester, e.g. with peracetic acid or hydrogen peroxide, preferably in dimethylformamide, acetone or ethyl acetate, at temperatures from 30 DEG  to 100 DEG  C.  The metallosulpho derivatives may be obtained by reacting the sulphonated compounds with an alkali metal hydroxide or alkoxide, or an alkali metal salt of an acid weaker than sulphonic acid to form the corresponding alkali metal salt, for example at 5-110 DEG  C. in alcoholic or aqueous solution. The phenylthioalkanoic acids and esters can be obtained by the reaction of an alkali metal thiophenolate with a haloalkanoic acid or ester. Specifications 1,006,578 and 1,007,820 are referred to.