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Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers
Published on: June 20, 2019
Crystalline Isotactic Polyterpenoid from Citronellal: A Viscous Bottlebrush Polymer with Order-Disorder Transitions
Xinru Zhang1, Jian Hu1, Wenpeng Zhao1
1Key Laboratory of Rubber-Plastics, Ministry of Education/Shandong Province Key Laboratory of High Performance Rubber Materials and Engineering, School of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao, 266045, China.
Abstract:
Most terpene-derived polymers reported to date are amorphous resins, elastomers, or cross-linked networks. Here we report a crystalline isotactic polyterpenoid, poly(4,8-dimethyl-1,7-nonadiene) (PDMND), synthesized from naturally abundant citronellal using a pyridylamido hafnium catalyst. Temperature-dependent WAXD reveals that PDMND adopts an isotactic-polypropylene-like (3/1) helical backbone with an axial repeat of ca. 6.6 Å. Unlike conventional semicrystalline polyolefins, the densely populated, nonlinear terpenoid side groups prohibit chain folding and promote the packing of fully extended bottlebrush-like rigid rods. DSC, WAXD, FTIR, and rheological analyses reveal reversible order-disorder transitions from an ordered cylindrical-rod crystal to a side-chain-disordered phase and further to a nematic-like crystalline state before melting. This work expands terpene-derived polymers from amorphous materials to crystalline stereoregular polyolefins with unusual bottlebrush-rod packing.
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