Thermal and mechanical properties of semi‐interpenetrating polymer networks composed of diisocyanate‐bridged, four‐armed, star‐shaped ε‐caprolactone oligomers and poly(ε‐caprolactone)

Semi‐interpenetrating polymer networks (S‐IPNs) were prepared by the reactions of hydroxyl‐terminated four‐armed, star‐shaped ε‐caprolactone oligomers with degrees of polymerization per one oligocaprolactone chain ( n s) of 3, 5, and 10 and 2,4‐tolylene diisocyanate (TDI) in the presence of poly(ε‐caprolactone) (PCL). In the dynamic mechanical analysis of the S‐IPN [2,4‐tolylene diisocyanate bridged hydroxyl‐terminated four‐armed, star‐shaped ε‐caprolactone oligomer (TH4CLO)/PCL], only one tan δ peak was observed; its temperature increased with increasing TH4CLO content and with decreasing n value. Differential scanning calorimetric analyses of the TH4CLOs and TH4CLO/PCLs revealed that the TH4CLOs with n s of 3 and 5 were amorphous, whereas TH4CLO with an n of 10 was semicrystalline and that the crystallization of the PCL chain for TH4CLO/PCLs was more strongly disturbed with increasing TH4CLO content and decreasing n value. Although the tensile strength, modulus, and elongation at break of TH4CLO were much lower than those of PCL, those values increased with the n value. Although the tensile strength and modulus of the TH4CLO/PCLs decreased with increasing TH4CLO content, TH4CLO ( n  = 3)/PCL 50/50 showed the highest elongation at break (314%) among the S‐IPNs because of the suppression of crystallization of the polycaprolactone chain. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4229–4236, 2013