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

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/Et 2Zn), 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 Et 2Zn 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-butylmore » 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.« less
Authors:
 [1] ;  [2] ; ORCiD logo [2] ; ORCiD logo [1] ;  [1]
  1. Univ. of Tennessee, Knoxville, TN (United States). Department of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 49; Journal Issue: 24; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Research Org:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1338533

Lu, Wei, Huang, Caili, Hong, Kunlun, Kang, Nam-Goo, and Mays, Jimmy W. Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties. United States: N. p., Web. doi:10.1021/acs.macromol.6b01732.
Lu, Wei, Huang, Caili, Hong, Kunlun, Kang, Nam-Goo, & Mays, Jimmy W. Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties. United States. doi:10.1021/acs.macromol.6b01732.
Lu, Wei, Huang, Caili, Hong, Kunlun, Kang, Nam-Goo, and Mays, Jimmy W. 2016. "Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties". United States. doi:10.1021/acs.macromol.6b01732. https://www.osti.gov/servlets/purl/1338533.
@article{osti_1338533,
title = {Poly(1-adamantyl acrylate): Living Anionic Polymerization, Block Copolymerization, and Thermal Properties},
author = {Lu, Wei and Huang, Caili and Hong, Kunlun and Kang, Nam-Goo and Mays, Jimmy W.},
abstractNote = {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 (Td: 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.},
doi = {10.1021/acs.macromol.6b01732},
journal = {Macromolecules},
number = 24,
volume = 49,
place = {United States},
year = {2016},
month = {12}
}