Synthesis of the Poly(ε‐Caprolactone‐b‐Methyl Methacrylate‐b‐ε‐Caprolactone) ABA Type Block Copolymer by Reverse Atom Transfer Radical Polymerization and “Click” Chemistry

ABSTRACT In this study, the synthesis of poly(ε‐caprolactone‐b‐methyl methacrylate‐b‐ε‐caprolactone) [PCL‐b‐PMMA‐b‐PCL] ABA type block copolymer was carried out. For this purpose, polyε‐caprolactone (PCL) was synthesized by the ring‐opening polymerization technique using ε‐caprolactone. Propargyl‐terminated polyε‐caprolactone (PCL‐propargyl) was prepared by reacting PCL with propargyl chloride. Then, double chlorine‐ended polyazoester‐methyl methacrylate (Cl‐PMMA‐Cl) was obtained from the reaction of 4,4'‐azobis(4‐cyanopentanoyl chloride) and methyl methacrylate using the reverse atom transfer radical polymerization method. Synthesis of double azido‐ended polyazoester‐methyl methacrylate (N 3 –PMMA–N 3 ) was carried out by reacting Cl–PMMA–Cl with NaN 3 . Finally, PCL‐b‐PMMA‐b‐PCL block copolymer was synthesized using PCL‐propargyl and N 3 –PMMA–N 3 via the “click” chemistry method. The synthesized products were characterized using Fourier transform infrared spectroscopy, proton‐nuclear magnetic resonance spectroscopy, scanning electron microscopy, thermogravimetric analysis, gel permeation chromatography, elemental analysis, and fractional precipitation techniques.