S-(α, α′-disubstituted-α″-acetic acid)—substituted dithiocarbonate derivatives for controlled radical polymerizations, process and polymers made therefrom

A method for forming a S-(α,α′-disubstituted-α″-acetic acid) or bis S-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compound of the formula:

• comprising the steps of:
• reacting a metal salt of a dithiocarbamate, a haloform, and a ketone in the presence of a base in the optional presence of a phase transfer catalyst selected from a polyether, an onium salt, and combinations thereof to form a reaction product;
• and
• acidifying said reaction product to form said S-(α,α′-disubstituted-α″-acetic acid) or bis S-(α,α′-disubstituted-α″-acetic acid) dithiocarbamate compound;
• wherein j is 1 or 2;
• R12 and R13, independently, are the same or different, are optionally substituted, and represent a linear or branched alkyl having from 1 to 12 carbon atoms, and an aryl group having from 6 to 18 carbon atoms:
• R12 and R13 can form and be part of a substituted or unsubstituted cyclic ring having from 3 to 12 carbon atoms;
• when substituted, said R12 and R13 substituents are selected from an alkyl group having 1 to 6 carbon atoms, aryl, halogen, cyano, nitro, and an ether residue having 2 to 20 carbon atoms;
• with the proviso that when j is 1, T is (—NR15R16), and when i is 2, T is a divalent radical haying a nitrogen' atom directly connected to each carbon atom of the two thiocarbonyl groups;
• wherein R15 and R16, independently, are the same or different, optionally substituted, and represent hydrogen, linear or branched alkyl having from 1 to 18 carbons, aryl having from 6 to 18 carbon atoms, arylalkyl having from 7 to 18 carbons, alkenealkyl having from 3 to 18 carbon atoms, a polyalkylene glycol ether residue;
• R15 and R16 taken together with the nitrogen atom to which they are attached form a substituted or unsubstituted cyclic ring having a total of 4 to 12 carbon atoms, optionally having heteroatoms selected from N, O, NH C(O), and S;
• when substituted said R15 and R16 substituents are selected from alkyl having from 1 to 6 carbon atoms, aryl, halogen, cyano, amino, an alkene group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, an acyloxy group, a carbamoyl group, an alkylcarbonyl group, an alkylarylcarbonyl group, an arylcarbonyl group, an arylalkylcarbonyl group, a phthalimido group, a maleimido group, a succinimido group, amidino group, a guanidimo group, an allylgroup, an epoxy group, an alkoxy group, a hydroxyl group, an ether residue having a total of 2 to 20 carbon atoms, nitro, a carboalkoxy group, a heterocyclic group having one or more hetero atoms selected from S, O, and N;
• and an alkali metal salt and quaternary ammonium salt thereof.