Patent GB-988512-A (GB)
Title: Improvements in and relating to esters of sulphonium salts
Inventor: VALENTINE LESLIE MACKENZIE
IPC: C07C381/12
Filed: 1960-02-23
Abstract: The invention comprises esters, the cations of which have the general formula <FORM:0988512/C2/1> wherein OW is the radical of an acid, with the proviso that when the acid is a monocarboxylic acid, the latter does not contain more than 3 carbon atoms; R1 and R2 are hydrogen, or an alkyl group containing from 1 to 3 carbon atoms and may be the same or different; R3 is (CHR1.CHR2OW) or an alkyl, substituted alkyl where the substituent does not contain -SH or >NH groups or aralkyl radical; and R4 is (CHR1.CHR2OW) or, if OW is the radical of sulphuric acid it may also be an alkyl, substituted alkyl where the substituent does not contain -SH or >NH groups or aralkyl radical, the positive charge on the sulphur atom being balanced either by a separate anion or by the presence of a negative charge in the sulphonium salt molecule.  The radical OW is suitably the radical of an inorganic polybasic acid or a salt thereof.  The preferred esters are the sulphates. Specified salts are the sodium and barium salts. The substituent on the alkyl residue represented by R3 or R4 preferably does not contain -OH groups but may be for example carboxyl, nitrile or halogen.  The esters may be prepared by esterifying the appropriate mono-, bis- or tris-(b -hydroxyalkyl) sulphonium salt with an acid or anhydride. Suitable acids or anhydrides include chlorosulphonic acid, fuming sulphuric acid, acetic anhydride or propionic anhydride. The salts of the acid esters may be prepared by neutralization of the acid esters with a base, such as sodium carbonate or barium hydroxide. Examples are given for the preparation of (1) the sodium and barium salts of tris-(b -sulphaloethyl) sulphonium inner salt, (2) the phosphate ester of bis-(b -hydroxyethyl) ethyl sulphonium bromide, and (3) methyl 2-sulphatoethyl lauryl sulphonium inner salt.  The esters behave as alkylating agents.  They may be used in the treatment of polymeric materials containing at least one reactive -OH, >NH or -SH group as in Specification 988,511.  The esters may also be used in the formation of polymers (see Division C3).  The (b -hydroxyalkyl) sulphonium salts may be prepared by reacting the appropriate sulphide with an alkyl halide or a hydroxyalkyl halide. In an example, lauryl 2-hydroxyethyl sulphide is prepared from lauryl mercaptan and 2-chloroethanol in the presence of sodium methoxide and then refluxed with excess methyl iodide to give methyl 2-hydroxyethyl lauryl sulphonium iodide.ALSO:Polymers of the structure:-<FORM:0988512/C3/1> in which Y- is an anion, n can be any integer greater than 1, R1 may be an alkyl, alicyclic, aralkyl, aromatic or heterocyclic residue and R3 is (CHR1CHR2OW) in which R1 and R2\t are hydrogen or an alkyl group containing from 1 to 3 carbon atoms and may be the same or different; or an alkyl, substituted alkyl where the substituent does not contain -SH or >NH groups, or aralkyl radical and OW is the radical of an acid, with the proviso that when the acid is a mono carboxylic acid the latex does not contain more than 3 carbon atoms; may be obtained by reacting stoichiometric amount of the compound <FORM:0988512/C3/2> (see Division C2) with a diol HO.R1.OH.  The polymers may be linear or crosslinked three-dimensional networks and may be used as anion exchange resins.