Polyhydroxyurethane and Poly(ethylene oxide) Multiblock Copolymer Networks: Crosslinking with Polysilsesquioxane, Reprocessing and Solid Polyelectrolyte Properties.

This contribution reports the synthesis of polyhydroxyurethane (PHU)-poly(ethylene oxide) (PEO) multiblock copolymer networks crosslinked with polysilsesquioxane (PSSQ). First, the linear PHU-PEO multiblock copolymers were synthesized via the step-growth polymerization of bis(6-membered cyclic carbonate) (B6CC) with α,ω-diamino-terminated PEOs with variable molecular weights. Thereafter, the PHU-PEO copolymers were allowed to react with 3-isocyanatopropyltriethoxysilane (IPTS) to afford the derivatives bearing triethoxysilane moieties, the hydrolysis and condensation of which afforded the PHU-PEO networks crosslinked with PSSQ. It was found that the PHU-PEO networks displayed excellent reprocessing properties in the presence of trifluoromethanesulfonate [Zn(OTf)2]. Compared to the PHU networks crosslinked via the reaction of difunctional cyclic carbonate with multifunctional amines, the organic-inorganic PHU networks displayed the decreased reprocessing temperature. The metathesis of silyl ether bonds is responsible for the improved reprocessing behavior. By adding lithium trifluoromethanesulfonate (LiOTf), the PHU-PEO networks were further transformed into the solid polymer electrolytes. It was found that the crystallization of PEO chains in the crosslinked networks was significantly suppressed. The solid polymer electrolytes had the ionic conductivity as high as 7.64 × 10-5 S × cm-1 at 300 K. More importantly, the solid polymer electrolytes were recyclable; the reprocessing did not affect the ionic conductivity.

Nanocomposites of Polyhydroxyurethane with POSS Microdomains: Synthesis via Non-Isocyanate Approach, Morphologies and Reprocessing Properties.

In this contribution, we reported the synthesis of a novel trifunctional POSS cyclic carbonate [POSS-3(5CC)]. With a difunctional five-member cyclic carbonate and a trifunctional polyetheramine as the precursor, the nanocomposites of polyhydroxyurethane (PHU) with POSS were synthesized. Transmission electron microscopy (TEM) showed that the nanocomposites of PHUs with POSS were microphase-separated; the spherical POSS microdomains via POSS-POSS interactions were generated with the size of 20~40 nm in diameter. After the introduction of POSS microdomains, the nanocomposites displayed improved thermal and mechanical properties. More importantly, the nanocomposites still displayed the reprocessing properties of vitrimers.