Nanocomposites of Poly(n-Butyl Acrylate) with Fe3O4: Crosslinking with Hindered Urea Bonds, Reprocessing and Related Functional Properties.

In this contribution, we reported the synthesis of the nanocomposites of poly(n-butyl acrylate) with Fe3O4 nanoparticles (NPs) via dynamic crosslinking of poly(n-butyl acrylate)-grafted Fe3O4 NPs with hindered urea bonds (HUBs). Towards this end, the surfaces of Fe3O4 NPs were grafted with poly(n-butyl acrylate-ran-2-(3-tert-butyl-3-ethylureido)ethyl acrylate) chains [denoted as Fe3O4-g-P(BA-r-TBEA)] via living radical polymerization. Thereafter, 1,2-bis(tert-butyl)ethylenediamine was used as a crosslinker to afford the organic-inorganic networks with variable contents of Fe3O4 NPs and crosslinking densities. It was found that the fine dispersion of Fe3O4 NPs in the matrix of poly(n-butyl acrylate) was achieved. The nanocomposites exhibited excellent reprocessing properties, attributed to the introduction of HUBs. Owing to the crosslinking, the nanocomposites displayed excellent shape memory properties. Further, the nanocomposites possessed photo- and magnetic-thermal properties, which were inherited from Fe3O4 NPs. These functional properties allow triggering the shape shifting of the nanocomposites in an uncontacted fashion.

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.