Patent GB-1023716-A (GB)
Title: Hydrophobic vinyl sulphones and related sulphone compounds and the treatment of textiles therewith
IPC: D06M13/278
Filed: 1964-04-30
Abstract: The invention comprises vinyl ethyl sulphones of the formula <FORM:1023716/C2/1> <FORM:1023716/C2/2> and the corresponding related sulphone compounds of the formula <FORM:1023716/C2/3> in which R0 represents hydrogen or methyl, R represents a straight-chain C10-C18 alkyl group, a branched-chain C10-C16 alkyl group or an alkaryl group in which the alkyl group has 9-12 carbon atoms, R1 represents a straight-chain C10-C18 alkyl group, R2 represents a straight chain C1-C18 alkyl group X represents oxygen or sulphur, and A is a good leaving group for E2 elimination.  Suitable groups are (1) X is O and A is the cation of weak N bases, i.e., (a) <FORM:1023716/C2/4> where R3, R4 and R5 are alkyl, aryl or alkaryl groups of a tertiary amine having an ionization constant less than 10-3, and Z is an anion, or (b) A=+N­Y Z-, where Y is part of a heterocyclic ring containing the N atom, such as pyridine or alkyl pyrrolidine, and Z is an anion; (2) X=O or S and A is the anion of an acid having the formula -SSO3M, M is an alkali metal such as Na, K or Li; (3) X=O and A is a sulphonium salt, i.e. <FORM:1023716/C2/5> where R6 and R7 are saturated or unsaturated alkyl groups such as methyl, ethyl or allyl and Z is an anion as in (1) (a).  The vinyl ethyl sulphones may be obtained by reacting divinyl sulphone with the appropriate alcohol or mercaptan in the presence of a condensation catalyst, or by reacting divinyl sulphone with a secondary amine at room or elevated temperature, preferably at from 25 DEG  to 200 DEG  C. and under anhydrous conditions. Suitable catalysts are alkaline materials such as alkali metals and their alkoxides.  The reaction is preferably carried out under an inert gas.  Related sulphone compounds of class 1(a) may be obtained by treating a b -substituted ethyl vinyl sulphone of Formula I with a secondary amine R3R4NH to form a b 1-amino ethyl derivative of Formula III, where A is NR3R4, followed by quaternization of the tertiary amine with alkylating agent R5Z such as alkyl halides or sulphates.  Sulphonyl compounds of class 1(b) may be obtained as above or by treating a b -substituted ethyl vinyl sulphone derivative of Formula I with a mixture of an appropriate heterocyclic tertiary amine and an acid salt of the said tertiary amine. Related sulphone compounds of class (2) may be prepared for example by treating a b -substituted ethyl vinyl sulphone derivative of Formula I with an alkali metal thiosulphate, e.g. sodium thiosulphate.  Related sulphone compounds of class (3) may be prepared by treating a b -substituted ethyl vinyl sulphone derivative of Formula I with an alkyl mercaptan R6SH and an alkaline condensation catalyst to form a b 1-thioether derivative of Formula III, where A is SR6, followed by alkylation of the S atom with alkylating agents such as alkyl halides or alkyl sulphates to form the sulphonium salt.  The compounds may be used for treating cellulosic textiles to render them permanently water-repellent and resistant to water-borne stains (see Division D1).ALSO:A cellulosic textile is treated with a vinyl sulphone of the formula:-  <FORM:1023716/D1-D2/1> or <FORM:1023716/D1-D2/2> or with a related sulphone compound of the formula:-  <FORM:1023716/D1-D2/3> where R0 represents hydrogen or methyl, R represents a straight-chain C10-C18 alkyl group, a branched-chain C10-C16 alkyl group or an alkaryl group in which the alkyl group has 9-12 carbon atoms, R1 represents a straight-chain C10-C18 alkyl group, R2 represents a straight-chain C1-C18 alkyl group, X represents oxygen or sulphur, and A represents a good leaving group for E2 elimination.  Suitable groups are (1) X is 0 and A is the cation of weak N bases i.e. <FORM:1023716/D1-D2/4> where R3, R4 and R5 are alkyl, aryl or aralkyl groups of a tertiary amine having an ionization constant less than 10-3 and Z is an anion, or (b) A = +N­Y Z-, where Y is part of a heterocyclic ring containing the N atom such as pyridine or alkyl pyrrolidine, and Z is an anion.  (2) X = O or S and A is the anion of an acid having the formula -SSO3M.  M is an alkali metal such as Na, K or Li.  (3) X = O and A is a sulphonium salt i.e. <FORM:1023716/D1-D2/5> where R6 and R7 are alkyl or alkenyl groups such as methyl, ethyl or alkyl and Z is an anion as in (1)a (see Division C2), by heating the textile in contact with said vinyl sulphone in the presence of an acid binding agent to render the textile permanently water repellant and resistant to waterborne stains. Suitable cellulosic textiles include cotton, rayon, linen and mixtures thereof, either with each other or with non-cellulosic textiles such as polyhexamethylene adipamide, polycaproamide, polyethyleneterephthalate or polyacrylonitrile.  The sulphones or related sulphones may be dispersed or emulsified in an aqueous medium and the textile immersed in it, or, the treating agent may be dissolved in an organic solvent.  An acid-binding agent may be dissolved in the same aqueous medium or it may be applied by immersing the textile in a separate aqueous solution containing it before or after applying the sulphone treating agent. Preferably, when the organic solvent is used, the acid binding agent is in a separate solution in water, and the textile is dried between soaking with the sulphone treating agent and with the acid binding agent. Suitable acid binding agents are carbonates, hydroxides and bicarbonates of most metals such as alkali metals and alkaline earth metals.  The curing step is carried out at an elevated temperature, usually after the fabric has dried, of about 30 to 200 DEG C. for about 30 seconds to 24 hours.  Natural and synthetic waxes may be incorporated in the treating bath in which the vinyl sulphone is applied to the textile.