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

Asan N., Öztürk T., Hazer B.

ChemistrySelect, vol.11, no.3, 2026 (SCI-Expanded, Scopus) identifier

  • Publication Type: Article / Article
  • Volume: 11 Issue: 3
  • Publication Date: 2026
  • Doi Number: 10.1002/slct.202507237
  • Journal Name: ChemistrySelect
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Chemical Abstracts Core
  • Keywords: ABA type block copolymer, polymethyl methacrylate, reverse atom transfer radical polymerization, ring-opening polymerization, “click” chemistry
  • Karadeniz Technical University Affiliated: Yes

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 (N3–PMMA–N3) was carried out by reacting Cl–PMMA–Cl with NaN3. Finally, PCL-b-PMMA-b-PCL block copolymer was synthesized using PCL-propargyl and N3–PMMA–N3 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.