Abstract
The kinetics of photoinduced copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations were assessed as a function of copper(II) amine-based ligands. Copper(II) bromide ligated with 1,1,4,7,10,10-hexamethylenetetramine (HMTETA) exhibited the fastest kinetics in both Norrish type(I) and type(II) photoinitiating systems. A characteristic induction period is observed with these polymerizations and is manipulated by adding an external tertiary amine in Norrish Type(II) photoinitating systems or by changing the anion of the copper(II) salt. Halides, specifically bromide and chloride, exhibit the fastest kinetics with the smallest induction period in comparison with organic anions, such as bistriflimide and triflate. The temporal control of the photo-CuAAC polymerization is affected by pre-ligation of the copper catalyst, by the presence of certain anions such as acetate, and by specific ligands such as tetramethylethylenediamine (TMEDA).