Patent GB-1004465-A (GB)
Title: Improvements in and relating to sulfophenoxyalkoxy-substituted aromatic monocarboxylic acids and derivatives thereof
IPC: C07C69/92
Filed: 1962-10-30
Abstract: Linear polyesters are the condensation product of an aromatic dicarboxylic acid, e.g. terephthalic acid, or a dialkyl ester thereof, a diol, e.g. an acyclic or alicyclic aliphatic glycol such as ethylene glycol or 1,4-cyclohexanedimethanol, or a diester thereof, and from 0.1-5 mole per cent, based on the total amount of dicarboxylic acid compound or compounds present, of a sulphonated compound of the general formula <FORM:1004465/C3/1> wherein M is an alkali metal, e.g. Na, K, Li, Rb or Cs, n is an integer from 1 to 12, Ar is a divalent arylene radical, e.g. phenylene or naphthylene, and R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The polyesters are produced by heating the dicarboxylic acid compound, diol and sulphonated compound at 150 DEG  C. to 270 DEG  C. in an inert atmosphere, subsequently removing the excess diol from the reaction mixture by heating to 300 DEG  C. under reduced pressure and finally heating the reaction mixture to 225 DEG  to 325 DEG  C. at 0.1 mm. to 20 mm. of mercury in an inert atmosphere. 0.1 to 5 mole per cent of the dicarboxylic acid compound or diol may be replaced by one or more different co-monomers of similar difunctionality such as a hydroxy carboxylic acid or ester thereof, or a compound of the formulae <FORM:1004465/C3/2> wherein Y is an SO3H or SO3M radical and M, n and R are as above defined and p is an integer from 1-12.  In Example (4) dimethyl terephthalate, methyl 3-2-[4-((sodiumsulpho))phenoxy]ethoxy) benzoate, ethylene glycol, zinc acetate and antimony oxide are heated in a reactor to effect ester exchange and then at a high temperature whilst passing nitrogen through the mixture to effect polycondensation to a white crystalline polyester. Other examples show the reaction of dimethyl terephthalate, ethylene glycol and methyl 3-(2-[4 - ((sodiumsulpho)) phenoxy] ethoxy) benzoate with or without dimethyl sebacate, or isophthalate; dimethyl terephthalate, ethylene glycol and nickel 2 - (2 - [4 - ((sodium- or potassium-sulpho)) phenoxy]ethoxy) benzoates, or methyl - 2 - (2 - [4 - ((sodiumsulpho))phenoxy]ethoxy)benzoate and dimethyl isophthalate; dimethyl terephthalate and sebacate, ethylene glycol and methyl-4-(5-[4-((sodiumsulpho))phenoxy]pentox benzoate; dimethyl terephthalate and isophthalate ethylene glycol and methyl 4-(5-[4-((lithiumsulpho))phenoxy] pentoxy) benzoate; dimethyl terephthalate, ethylene glycol, dimethyl 2-(potassiumsulpho)-fluorene - 9,9 - dipropionate and methyl-4-(5-[4 - ((lithiumsulpho))phenoxy]pentoxy) - benzoate; dimethyl terephthalate and sebacate, 1,4-cyclohexanedimethanol in methanol and methyl - 4 - (5 - [4 - ((sodiumsulpho))phenoxy] pentoxy)benzoate; and dimethyl terephthalate, methyl - 2 - (2 - [4 - ((potassiumsulpho)) pentoxy]ethoxy)benzoate and dimethyl-5-(2-[4 - ((sodiumsulpho))phenoxy]ethoxy) - isophthalate and ethylene glycol.ALSO:The invention relates to compounds of the general formula <FORM:1004465/C2/1> wherein X is an SO3H or -SO3M radical in which M is an alkali metal, e.g. lithium, sodium, potassium, rubidium or cesium, n is an integer from 1 to 12, Ar is a divalent arylene e.g. phenylene or naphthalene radical and R is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.  The compounds claimed per se are methyl 2- and 3-(2-[4-((sodiumsulpho))phenoxy] ethoxy) - benzoates, methyl 2 - (2 - [4 -((lithium - and potassiumsulpho))phenoxy] ethoxy) - benzoates, methyl 4 - (5 - [4-((lithium - and sodiumsulpho))phenoxy]pentoxy)-benzoates, and 2 - (4 - [sulphophenoxy]ethoxy) benzoic acid.  Among other specified compounds are 2 - (2 - [4 - ((lithiumsulpho))phenoxy] ethoxy)benzoic acid, 4 - (2 - [4 - sulphophenoxy] ethoxy)napthhoic acid, 2 - ethylhexyl 3-(2 - [4 - ((potassiumsulpho)) phenoxy]ethoxy) benzoate and methyl 4-(2-[4-((potassiumsulpho)) phenoxy]ethoxy)naphthoate.  The compounds are produced by sulphonating a compound of the general formula <FORM:1004465/C2/2> wherein n, Ar and R have the same meanings as given above, with a mixture of sulphuric acid and acetic anhydride followed by neutralisation, if an alkali metal salt is desired.  In an example methyl 3-(sodiumoxy) benzoate is reacted with phenoxyethyl bromide to produce methyl 3-(2-phenoxy ethoxy) benzoate which is separated and sulphonated with acetic anhydride and sulphuric acid to produce methyl 3-(2[4 sulpho phenoxy] ethoxy benzoate. Other examples of preparations are given.ALSO:Linear polyesters formed by condensing an aromatic dicarboxylic acid or dialkyl ester thereof, a diol or diester thereof, and from 0.1-5 moles per cent, based on the total amount of dicarboxylic acid compounds present, of a sulphonated compound of the general formula <FORM:1004465/D1-D2/1> wherein M is an alkali metal, n is an integer from 1 to 12, Ar is a divalent arylene radical e.g. pehnylene or naphthylene, and R p  is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, are dyed with basic or disperse dyes.  Improved dyeability can be obtained when 0.1 to 5 mole per cent of either the dicarboxylic acid, or dial, is replaced by one or more different comonomers of similar difunctionality.  The comonomers may serve as dye assistants and have the formulae <FORM:1004465/D1-D2/2> and <FORM:1004465/D1-D2/3> where Y is H or MSO3, M, n and R being as defined above and p is 1 to 12, preferably 2 to 8.  Dye carriers may be present. Many examples are given.