A series of hybrid thermoplastic polyurethanes (PUs) were synthesized from bi-functional polyhedral oligomeric silsesquioxane (B-POSS) and polycaprolactone (PCL) using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent for the first time. The newly synthesized hybrid materials were fully characterized in terms of structure, morphology, thermal and mechanical performance, as well as their toughening effect toward polyesters. Thermal gravimeter analysis (TGA) and differential scanning calorimetry (DSC) showed enhanced thermal stability by 76 °C higher in decomposition temperature (Td) of the POSS PUs, and 22 °C higher glass transition temperature (Tg) when compared with control PU without POSS. Static contact angle results showed a significant increment of 49.8° and 53.4° for the respective surface hydrophobicity and lipophilicity measurements. More importantly, both storage modulus (G’) and loss modulus (G’’) are improved in the hybrid POSS PUs and these parameters can be further adjusted by varying POSS content in the copolymer. As a biodegradable hybrid filler, the as-synthesized POSS PUs also demonstrated a remarkable effect in toughening commercial polyesters, indicating a simple yet useful strategy in developing high-performance polyester for advanced biomedical applications.
Star-shaped cyclophosphazene (ACP) was employed as covalent crosslinker to form a rigid segment in polyurethanes network, to enhance the mechanical performance and to add extra flame retardant property. The effects of different ACP contents on the shape memory ability and fire resistance performance of polyurethane (PU) were studied. Tensile tests suggested high flexibility of the PUs with the maximum elongation-at-break of 161.59%. Dynamic mechanical analysis (DMA) indicated good shape recovery ratio of 72.58% after more than three repeated cycles. Under thermal treatment, the temporary shape could recover to its original state in 10 s. The peak heat release rate (pHRR), total heat released (THR) and temperature at pHRR (Tp) of flame-retardant shape memory polyurethane (FSPU) by micro-combustion calorimeter (MCC) was as low as 183.2 W/g, 21.4 KJ/g, 330.8 °C respectively, suggesting good inherent fire-resistant performance. As amine-containing crosslinkers are one of the most common building units in thermosetting polymers, we anticipate that our finding will have significant benefits beyond shape memory and fire-resistance.
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