A process for the preparation of a polyunsaturated thiol comprising: (1) reacting a polyunsaturated alcohol in the presence of a compound of formula R.sub.2SO.sub.2Hal wherein R.sub.2 is a C.sub.1-20 hydrocarbyl group, such an C.sub.1-10 alkyl group, to form a polyunsaturated sulphonyl ester; (2) converting the polyunsaturated sulphonyl ester to a polyunsaturated thioester by reacting with an anion of formula .sup.SC(O)R.sub.4 wherein R.sub.4 is a C.sub.1-20 hydrocarbyl group; (3) converting the polyunsaturated thioester to form a polyunsaturated thiol optionally in the presence of an antioxidant, e.g. using a metal carbonate. (4) reacting said polyunsaturated thiol with a compound (LG)R.sup.3COX wherein X is an electron withdrawing A group and R.sup.3 is an alkylene group carrying a leaving group (LG), such as LG-CH.sub.2 forming (I) where X is an electron withdrawing group and LG is a leaving group; optionally in the presence of an antioxidant, so as to form a polyunsaturated ketone compound.

##STR00001##

The present invention discloses processes for producing methyl ethyl sulfide by contacting dimethyl sulfide and diethyl sulfide in the presence of a suitable catalyst. Methyl ethyl sulfide can be used as an odorant in natural gas. Integrated mercaptan and sulfide manufacturing systems and integrated methods for making mercaptans and sulfides also are disclosed.

Polythioether polymers, sealants containing polythioether polymers, and compounds useful as stabilizing monomers in the manufacture of polythioether polymers are provided. In many embodiments the polymers and sealants demonstrate reduced risk of spoilage that may be caused by low temperature storage of the polymer or uncured sealant. Compounds useful as stabilizing monomers include compounds according to formula I:

CH.sub.2CR.sup.1CHR.sup.2SR.sup.3SCHR.sup.4CR.sup.5CH.sub.2[I]

wherein R.sup.1, R.sup.2, R.sup.4 and R.sup.5 are independently selected from H, CH.sub.3 or C.sub.2H.sub.5, and wherein R.sup.3 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

Polythioether polymers, sealants containing polythioether polymers, and compounds useful as stabilizing monomers in the manufacture of polythioether polymers are provided. In many embodiments the polymers and sealants demonstrate reduced risk of spoilage that may be caused by low temperature storage of the polymer or uncured sealant. Compounds useful as stabilizing monomers include compounds according to formula I:

CH.sub.2CR.sup.1CHR.sup.2SR.sup.3SCHR.sup.4CR.sup.5CH.sub.2[I]

wherein R.sup.1, R.sup.2, R.sup.4 and R.sup.5 are independently selected from H, CH.sub.3 or C.sub.2H.sub.5, and wherein R.sup.3 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

Unsaturated compounds of formula (I): ##STR00001##
wherein: R.sup.1, R.sup.2, and R.sup.3 are each independently H or CH.sub.3; R.sup.4 is a linear or branched C.sub.1-C.sub.30-alkylene; R.sup.5 and R.sup.6 are each independently H, C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.15-cycloalkyl, aryl, CH.sub.2OC.sub.1-C.sub.20-alkyl, or CH.sub.2OC.sub.2-C.sub.20-alkenyl, where R.sup.5 and R.sup.6 may together form a C.sub.3-C.sub.6-alkylene; R.sup.7 is independently H,C.sub.1-C.sub.4-alkyl, or ##STR00002##
where R.sup.8 is C.sub.1-C.sub.22-alkyl or C.sub.2-C.sub.22-alkenyl; and n is an integer from 2 to 200. Mixtures and polymers including the unsaturated compounds of formula (I). A method for preparing polymers by free-radical polymerization of monomers including the unsaturated compounds of formula (I). A process for preparing polymers including polymer-analogous reactions. And polymers including compounds (I) as cement additives, grinding aids, hydraulic binder additives, concrete plasticizers, reactive plasticizers for preparing plastics, rubber, or latex, associative thickeners and antioxidants, or for preparing polyether siloxanes.

Unsaturated compounds of formula (I): ##STR00001##
wherein: R.sup.1, R.sup.2, and R.sup.3 are each independently H or CH.sub.3; R.sup.4 is a linear or branched C.sub.1-C.sub.30-alkylene; R.sup.5 and R.sup.6 are each independently H, C.sub.1-C.sub.20-alkyl, C.sub.3-C.sub.15-cycloalkyl, aryl, CH.sub.2OC.sub.1-C.sub.20-alkyl, or CH.sub.2OC.sub.2-C.sub.20-alkenyl, where R.sup.5 and R.sup.6 may together form a C.sub.3-C.sub.6-alkylene; R.sup.7 is independently H,C.sub.1-C.sub.4-alkyl, or ##STR00002##
where R.sup.8 is C.sub.1-C.sub.22-alkyl or C.sub.2-C.sub.22-alkenyl; and n is an integer from 2 to 200. Mixtures and polymers including the unsaturated compounds of formula (I). A method for preparing polymers by free-radical polymerization of monomers including the unsaturated compounds of formula (I). A process for preparing polymers including polymer-analogous reactions. And polymers including compounds (I) as cement additives, grinding aids, hydraulic binder additives, concrete plasticizers, reactive plasticizers for preparing plastics, rubber, or latex, associative thickeners and antioxidants, or for preparing polyether siloxanes.

Polythioether polymers, sealants containing polythioether polymers, and compounds useful as stabilizing monomers in the manufacture of polythioether polymers are provided. In many embodiments the polymers and sealants demonstrate reduced risk of spoilage that may be caused by low temperature storage of the polymer or uncured sealant. Compounds useful as stabilizing monomers include compounds according to formula I: CH.sub.2CR.sup.1CHR.sup.2SR.sup.3SCHR.sup.4CR.sup.5CH.sub.2 [I] wherein R.sup.1, R.sup.2, R.sup.4 and R.sup.5 are independently selected from H, CH.sub.3 or C.sub.2H.sub.5, and wherein R.sup.3 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

Polythioether polymers, sealants containing polythioether polymers, and compounds useful as stabilizing monomers in the manufacture of polythioether polymers are provided. In many embodiments the polymers and sealants demonstrate reduced risk of spoilage that may be caused by low temperature storage of the polymer or uncured sealant. Compounds useful as stabilizing monomers include compounds according to formula I: CH.sub.2CR.sup.1CHR.sup.2SR.sup.3SCHR.sup.4CR.sup.5CH.sub.2 [I] wherein R.sup.1, R.sup.2, R.sup.4 and R.sup.5 are independently selected from H, CH.sub.3 or C.sub.2H.sub.5, and wherein R.sup.3 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

A process for the preparation of a polyunsaturated thiol comprising: (1) reacting a polyunsaturated alcohol in the presence of a compound of formula R.sub.2SO.sub.2Hal wherein R.sub.2 is a C.sub.1-20 hydrocarbyl group, such an C.sub.1-10 alkyl group, to form a polyunsaturated sulphonyl ester; (2) converting the polyunsaturated sulphonyl ester to a polyunsaturated thioester by reacting with an anion of formula .sup.SC(O)R.sub.4 wherein R.sub.4 is a C.sub.1-20 hydrocarbyl group; (3) converting the polyunsaturated thioester to form a polyunsaturated thiol optionally in the presence of an antioxidant, e.g. using a metal carbonate. (4) reacting said polyunsaturated thiol with a compound (LG)R.sup.3COX wherein X is an electron withdrawing group and R.sup.3 is an alkylene group carrying a leaving group (LG), such as LG-CH.sub.2 forming ##STR00001## where X is an electron withdrawing group and LG is a leaving group; optionally in the presence of an antioxidant, so as to form a polyunsaturated ketone compound.

A process for the preparation of a polyunsaturated thiol comprising: (1) reacting a polyunsaturated alcohol in the presence of a compound of formula R.sub.2SO.sub.2Hal wherein R.sub.2 is a C.sub.1-20 hydrocarbyl group, such an C.sub.1-10 alkyl group, to form a polyunsaturated sulphonyl ester; (2) converting the polyunsaturated sulphonyl ester to a polyunsaturated thioester by reacting with an anion of formula .sup.SC(O)R.sub.4 wherein R.sub.4 is a C.sub.1-20 hydrocarbyl group; (3) converting the polyunsaturated thioester to form a polyunsaturated thiol optionally in the presence of an antioxidant, e.g. using a metal carbonate. (4) reacting said polyunsaturated thiol with a compound (LG)R.sup.3COX wherein X is an electron withdrawing group and R.sup.3 is an alkylene group carrying a leaving group (LG), such as LG-CH.sub.2 forming ##STR00001## where X is an electron withdrawing group and LG is a leaving group; optionally in the presence of an antioxidant, so as to form a polyunsaturated ketone compound.