A Simple Way for Synthesis of Alkyne‐Telechelic Poly(methyl methacrylate) via Single Electron Transfer Radical Coupling Reaction

Abstract

The telechelic α,ω-alkyne-poly(methyl methacrylate) (alkyne-PMMA-alkyne) was synthesized by single electron transfer radical coupling (SETRC) reaction of α-alkyne, ω-bromine-poly(methyl methacrylate) (alkyne-PMMA-Br). The propargyl 2-bomoisobutyrate (PgBiB) was first prepared to initiate atom transfer radical polymerization (ATRP) of methyl methacrylate at 45 ℃ using CuCl/1,1,4,7,10,10-hexamethyl triethylenetetramine (HMTETA) as homogeneous catalytic system. Then the SETRC reaction was conducted at room temperature in the presence of nascent Cu(0) and N,N,N',N",. The precursor alkyne-PMMA-Br and coupled product alkyne-PMMA-alkyne were characterized by GPC and 1 H NMR in detail.

Versatility of radical coupling in construction of topological polymers

“…This SETRC was carried out at room temperature using alkyne-PMMA-Br as precursor and nanosize Cu(0)/ PMDETA as catalytic system, and the coupling efficiency could exceed 90% in 24 h (Scheme 16). 144 The lower temperature would largely depress the possible disproportionation termination and increase the expected bimolecular combination. Thus, this work also provides a promising strategy for preparing well dened a,u-telechelic polymers with various functional groups, especially for poly(methyl)acrylate based structures.…”