Nanocomposites of polyethylene with polyhedral oligomeric silsesquioxane: from thermoplastics to vitrimers through silyl ether metathesis. (June 2022)

• Record Type: Journal Article
• Authors: Zhao, B.; Hang, G.; Li, L.; Zheng, S.
• Is Part Of: Materials today chemistry. Volume 24(2022)
• Publication Date: 2022-06
• Subjects: Polyethylene -- POSS -- Vitrimers -- Dynamic covalent bonds -- Shape memory properties -- Reprocessing properties; Chemistry -- Periodicals; Materials -- Research -- Periodicals; Materials science -- Periodicals; Chemistry; Materials -- Research; Electronic journals; Periodicals; 660.282
• DOI: 10.1016/j.mtchem.2021.100759
• Languages: English
• ISSNs: 2468-5194

Abstract

Abstract: In this contribution, we reported the transformation of linear polyethylene-polyhedral oligomeric silsesquioxane (PE-POSS) copolymers into PE vitrimers through silyl ether metathesis. First, the PE-POSS copolymers were synthesized via the ring-opening metathesis polymerisation (ROMP) of cyclooctene with heptaisobutyl POSS-norbornene followed by subsequent hydrogenation reaction. The PE-POSS copolymers were microphase -separated, and the POSS cages were aggregated into the microdomains with the size of 10–20 nm. The thermoplastic PE-POSS nanocomposites were transformed into the PE vitrimers via direct silyl ether metathesis, which was catalyzed with zinc trifluoromethyl sulfonate [Zn(OTf)2 ]. It was found that the cross-linking with the dynamic covalent bonds occurred within the POSS microdomains. The cross-linking significantly influenced the morphologies and thermal and mechanical properties of the materials. More importantly, the cross-linked PE products displayed the self-adaptivity at elevated temperature, that is, the PE-POSS thermoplastics were transformed into PE-polysilsesquioxane vitrimers. Because of the formation of cross-linked networks, the PE vitrimers were endowed with shape memory properties. In the meantime, the permanent shapes of the shape memory PEs can readily be reprogrammed by taking advantage of the self-adaptivity of the vitrimers. Graphical abstract: Image 1 Highlights: Polyhedral oligomeric silsesquioxane–containing polyethylene (PE) was synthesized via ring-opening metathesis polymerisation. The PE hybrids were cross-linked with dynamic silyl ether bonds. The PE networks displayed reprocessing and shape memory properties. The original shape of the shape memory polymers can be reprogrammed.