Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

Lu, Wei; Huang, Caili; Hong, Kunlun; Kang, Nam-Goo; Mays, Jimmy W.

doi:10.1021/acs.macromol.6b01732

Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties

Journal Article · Mon Dec 05 23:00:00 EST 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b01732· OSTI ID:1338533

Lu, Wei ^[1]; Huang, Caili ^[2]; ^[2]; ^[1]; Mays, Jimmy W. ^[1]

Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)

Living anionic polymerization of acrylates is challenging due to intrinsic side reactions including backbiting reactions of propagating enolate anions and aggregation of active chain ends. In this study, the controlled synthesis of poly(1-adamatyl acrylate) (PAdA) was performed successfully for the first time via living anionic polymerization through investigation of the initiation systems of sec-butyllithium/diphenylethylene/lithium chloride (sec-BuLi/DPE/LiCl), diphenylmethylpotassium/diethylzinc (DPMK/Et₂Zn), and sodium naphthalenide/dipenylethylene/diethylzinc (Na-Naph/DPE/Et2Zn) in tetrahydrofuran at -78 °C using custom glass-blowing and high-vacuum techniques. PAdA synthesized via anionic polymerization using DPMK with a large excess (more than 40-fold to DPMK) of Et₂Zn as the ligand exhibited predicted molecular weights from 4.3 to 71.8 kg/mol and polydispersity indices of around 1.10. In addition, the produced PAdAs exhibit a low level of isotactic content (mm triads of 2.1%). The block copolymers of AdA and methyl methacrylate (MMA) were obtained by sequential anionic polymerization, and the distinct living property of PAdA over other acrylates was demonstrated based on the observation that the resulting PAdA-b-PMMA block copolymers were formed with no residual PAdA homopolymer. The PAdA homopolymers exhibit a very high glass transition temperature (133 °C) and outstanding thermal stability (T_d: 376 °C) as compared to other acrylic polymers such as poly(tert-butyl acrylate) and poly(methyl acrylate). These merits make PAdA a promising candidate for acrylic-based thermoplastic elastomers with high upper service temperature and enhanced mechanical strength.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1338533

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 24 Vol. 49; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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