Search

A series of poly(e-caprolactone) (PCL)-based multiblock poly(ether-ester)s (PEE)s and poly(ether-ester-amide)s (PEEA)s were obtained from α,ω-dihydroxy-PCL (Mα=2-4 kDa) and -COCl di-terminated poly(ethylene oxide) (PEO) macromers (MAC) of different length (Mn = 150, 300, 600, 1 000 Da). 4,7,10-Trioxa-1,13-tridecanediamine was used in the synthesis of PEEAs. Bulk polycondensation processes were accomplished by one step (PEE) and two step (PEEA) procedures. PEEAs with PCL/ MAC/Trioxy molar ratios 1:2:1 and 1:3:2 were investigated. The multiblock copolymer architecture was proved by 1 H NMR and size exclusion chromatography (SEC) techniques. Unimodal molecular weight (MW) distributions and M n values int the range of 13.3-21.0 kDa (PEE) and 8.1 12.8 kDa (PEEA) were found. Crystalline PCL-type phases were identified for both PEEAs and PEEs by X-ray diffraction. The thermal transiotions were investigated by differential scanning calorimetry (DSC), The T m values (49.9-53.4°C) reflect those of the PCL component while the T g of PEEAs (-45 to 52 °C) are higher than those of the PEEs (-58 to -61°C) or the macromers. The equilibrium water uptakes range from 1.0 to 18.4 wt.-% (PEE) and from 4.4 to 8.8 wt.-% (PEEA) depending on both the composition and length of the ethylene oxide sequences. A dependence of surface homogeneity on copolymer composition was found for PEEs by dynamic contact angle measurements.

Segmented poly(ether-ester-amide)s, (PEEA)s, of controlled hydrophilicity degree, based on poly(e-caprolactone) (PCL), were synthesized according to a facile two-step procedure using α,ω-dihydroxy oligomeric PCL, 4,7, 10-trioxa-1,13-tridecanediamine and macromes prepared from poly(ethylene glycol)s and adipoyl chloride. The PEEAs showed M n values in the range 5-11.5 kDa. A PCL-type crystallinity was found by WAXS. DSC indicated T m values (49-51°C) close to that of PCL macromer. Single glass transitions were observed both by DSC and DMTA techniques and the T g values (-58--50°C by DSC) were slightly higher than that of PCL. The water uptake was in the range 4.8-26.0 wt.-% depending on the length of the poly(ethylene glycol) segment.