Precise synthesis of poly(1-adamantyl methacrylate) by atom transfer radical polymerization

Abstract

1-Adamantyl methacrylate (AdMA) was polymerized using the atom transfer radical polymerization (ATRP) method with methyl α-bromoisobutyrate (MBiB), copper(I) bromide (CuBr), copper(II) bromide (CuBr₂ ) and 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA) in toluene at 60 °C, producing well-defined poly(1-adamantyl methacrylate) (PAdMA). Simultaneous control of the molecular weight and tacticity of PAdMA was successfully achieved by the ATRP method using the MBiB/CuBr/CuBr₂ /tris[2-(dimethylamino)ethyl]amine-initiating system in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) at -20 °C. Block copolymerization of AdMA and methyl methacrylate (MMA) was successfully achieved by the poly(methyl methacrylate) macroinitiator/CuBr₂ /HMTETA/tin(II) 2-ethylhexanoate-initiating system based on activators generated by electron transfer (AGET) ATRP method. Differential scanning calorimetry revealed the relationship between the glass transition temperature, molecular weight and tacticity of the obtained PAdMA.