Poly(ε-caprolactone)-Poly(oxyethylene) Multiblock Copolymers Bearing Along the Chain Regularly Spaced Pendant Amino Groups

Poly(ε‐caprolactone) (PCL) macromers ($\overline M _{\rm n} $ = 1.7–3.8 kDa) which contain one Z‐protected NH2 group per chain were synthesized by ring‐opening polymerization of ε‐caprolactone in the presence of Sn(oct)2 using as initiator a diamine prepared by condensation of N‐Boc‐1,6‐hexanediamine and Nα‐Boc‐Nε‐Z‐L‐Lysine. The coupling of these macromers with COCl end‐capped poly(oxyethylene) (PEO), $\overline M _{\rm n} $ = 1.0 kDa, afforded amphiphilic multiblock poly(ether ester)s (PEEs) which have, along the chain, regularly spaced pendant protected amino groups. Deprotection, accomplished without chain degradation, yielded NH2 groups available for further reactions. The molecular structure of macromers and PEEs was investigated by 1H NMR and SEC. DSC and WAXS analyses showed that macromers and copolymers were semicrystalline and their Tm increased with increase in the molecular weight of PCL segments. The inherent viscosity values (0.25–0.30 dL · g−1), together with SEC analysis results, indicated moderate polymerization degrees.