2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

Feng, Hongbo; Changez, Mohammad; Hong, Kunlun; Mays, Jimmy W.; Kang, Nam-Goo

doi:10.1021/acs.macromol.6b02084

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

Journal Article · Thu Dec 22 23:00:00 EST 2016 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.6b02084· OSTI ID:1339400

^[1]; Changez, Mohammad ^[2]; ^[3]; Mays, Jimmy W. ^[4]; ^[1]

Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
A'Sharqiyah Univ., Ibra (Oman). Dept. of Basic Sciences
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

Poly(2-isopropenyl-2-oxazoline) (PIPOx) has drawn significant attention for numerous applications. However, the successful living anionic polymerization of 2-isopropenyl-2-oxazoline has not been reported previously. In this paper, we describe how well-defined PIPOx with quantitative yields, controlled molecular weights from 6800 to over 100 000 g/mol and low polydispersity indices (PDI ≤ 1.17) were synthesized successfully via living anionic polymerization using diphenylmethylpotassium/diethylzinc (DPM-K/Et₂Zn) in tetrahydrofuran (THF) at 0 °C. In particular, we report the precise synthesis of well-defined PIPOx with the highest molecular weight ever reported (over 100 000 g/mol) and low PDI of 1.17. The resulting polymers were characterized by ¹H and ¹³C nuclear magnetic resonance spectroscopy (NMR) along with size exclusion chromatography (SEC). Additionally, the reactivity of living PIPOx was investigated by crossover block copolymerization with styrene (St), 2-vinylpyridine (2VP), and methyl methacrylate (MMA). It was found that the nucleophilicity of living PIPOx is of this order: living PS > living P2VP > living PMMA > living PIPOx. The self-assembly behavior in bulk of PIPOx-b-PS-b-PIPOx triblock copolymers having different block ratios of 10:80:10 and 25:50:25 was studied using transmission electron microscopy (TEM). Finally, the formation of spherical and lamellar nanostructures, respectively, was observed.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

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

Contributing Organization:: A'Sharqiyah Univ., Ibra (Oman)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1339400

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 1 Vol. 50; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Block Copolymers: Synthesis, Self-Assembly, and Applications Feng, Hongbo; Lu, Xinyi; Wang, Weiyu Polymers, Vol. 9, Issue 12 https://doi.org/10.3390/polym9100494	journal	October 2017
Poly(2-isopropenyl-2-oxazoline) as a versatile platform towards thermoresponsive copolymers Jerca, Florica Adriana; Jerca, Valentin Victor; Anghelache, Alina Maria Polymer Chemistry, Vol. 9, Issue 25 https://doi.org/10.1039/c8py00612a	journal	January 2018

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2-isopropenyl-2-oxazoline
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Living anionic polymerization
block copolymer
water-soluble polymer

2-Isopropenyl-2-oxazoline: Well-Defined Homopolymers and Block Copolymers via Living Anionic Polymerization

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