Chemoselective RAFT Polymerization of a Trivinyl Monomer Derived from Carbon Dioxide and 1,3-Butadiene: From Linear to Hyperbranched

• DOI: 10.1021/acs.macromol.7b02238
• Publication Date: 2017-12-08T20:30:12Z
• Authors: Lifeng Chen; Yao Li; Sicong Yue; Jun Ling; Xufeng Ni; Zhiquan Shen
• Keywords: Raft; Dispersity; Chain transfer; Telomerization; Branching (polymer chemistry)

3-Ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVL), a substituent δ-lactone synthesized through telomerization of CO2 with 1,3-butadiene, is highly functionalized containing six-membered ring and two vinyl groups. It can hardly be polymerized directly common methods due to its poor polymerizability. In this paper, we report the controlled polymerization reactive trivinyl monomer derived from EVL, i.e. methyl-2-ethylidene-5-hydroxyhept-6-enoate methacrylate (MEDMA), which cleavage EVL subsequent esterification methacryloyl chloride. Chemoselective RAFT polymerizations MEDMA mediated by 2-cyanoprop-2-yl-dithiobenzoate (CPDB) are achieved well-defined polymers linear hyperbranched topologies obtained under optimized conditions. show good control in producing PMEDMAs predetermined molecular weights (4000 g/mol) moderate polydispersity indices (below 1.22). The resultant fully characterized 1H NMR, 13C 1H–13C HMQC, DEPT, DLS, TEM. incorporations group allylic ester into polymer chains lead topology. Both ready for introduction amino carboxy groups thiol–ene click chemistry, products self-assemble micelles different morphologies. This protocol develops utilization synthetic significant carbon dioxide transformation.