In this contribution, we reported a novel synthesis of block copolymer networks composed of poly(ε-caprolactone)(PCL) and polyethylene(PE) via the co-hydrolysis and condensation of α,ω-ditriethoxylsilane-terminated PCL and PE telechelics. First, α,ω-dihydroxylterminated PCL and PE telechelics were synthesized via the ring-opening polymerization of ε-caprolactone and the ring-opening metathesis polymerization of cyclooctene followed by hydrogenation of polycyclooctene. Both α,ω-ditriethoxylsilane-terminated PCL and PE telechelics were obtained via in situ reaction of α,ω-dihydroxyl-terminated PCL and PE telechelics with 3-isocyanatopropyltriethoxysilane. The formation of networks was evidenced by the solubility and rheological tests. It was found that the block copolymer networks were microphase-separated. The PCL and PE blocks still preserved the crystallinity. Owing to the formation of crosslinked networks, the materials displayed shape memory properties. More importantly, the combination of PCL with PE resulted that the block copolymer networks had the triple shape memory properties, which can be triggered with the melting and crystallization of PCL and PE blocks. The results reported in this work demonstrated that triple shape memory polymers could be prepared via the formation of block copolymer networks.
In this contribution,we reported the preparation of vitrimers by using commodity thermoplastics via post crosslinking with hindered urea bonds(HUBs).First,three hindered urea diisocyanates(HUDIs)were synthesized via the reactions of N,N'-di-tert-butylethylenediamine,N,N'-diethylethylenediamine,and piperazine with isophorone diisocyanate(IPDI).Thereafter,these HUDIs were used as the crosslinking agents to crosslink poly(hydroxyether of bisphenol A)(PH),a commodity thermoplastics.Fourier transform infrared(FTIR)spectroscopy and dynamic mechanical thermal analyses(DMTA)indicated that the PH thermosets were successfully obtained.It was found that the thermosets displayed the behavior of vitrimers.The PH thermosets can be reprocessed at elevated temperature without using catalyst and the mechanical strengths of vitrimers were recovered as high as 95%.The reprocessing properties are attributable to dynamic exchange reaction of hindered urea bonds,contingent on types of hindered urea bonds.
