Block copolymers containing stable radical and fluorinated blocks with long-range ordered morphologies prepared by anionic polymerization

Cintora, Alicia; Takano, Hiroki; Khurana, Mohit; Chandra, Alvin; Hayakawa, Teruaki; Ober, Christopher K.

doi:10.1039/c9py00416e

Block copolymers containing stable radical and fluorinated blocks with long-range ordered morphologies prepared by anionic polymerization

Journal Article · Tue Aug 20 00:00:00 UTC 2019 · Polymer Chemistry

DOI:https://doi.org/10.1039/c9py00416e· OSTI ID:1802610

Cintora, Alicia ^[1]; Takano, Hiroki ^[2]; Khurana, Mohit ^[3]; ^[2]; ^[2]; ^[3]

Cornell Univ., Ithaca, NY (United States). Dept. of Materials Science and Engineering; OSTI
Tokyo Inst. of Technology (Japan). Dept. of Materials Science and Engineering. School of Materials and Chemical Technology
Cornell Univ., Ithaca, NY (United States). Dept. of Materials Science and Engineering

We report a facile synthetic approach to create stable radical block copolymers containing a secondary fluorinated block via anionic polymerization using a bulky, sterically hindered countercation composed of a sodium ion and di-benzo-18-crown-6 complex. The synthetic conditions described in this report allowed for controlled molecular weights and dispersity (<1.3) of both homopolymers: poly(2,2,6,6-tetramethyl-1-piperidinyloxy-methacrylate) (PTMA) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) as well as their block copolymers (PTMA-b-PTFEMA). The stable radical concentration of the polymers was determined by electron spin resonance (ESR) and showed radical content above 70%. An analysis of the microphase morphologies in PTMA-b-PTFEMA thin films via atomic force microscopy (AFM) and grazing incidence small angle X-ray scattering (GISAXS) showed clear evidence of long-range ordering of lamellar and cylindrical morphologies with 32 and 36 nm spacing, respectively. The long-range ordering of the morphologies was developed with the aid of two separate neutral layers: PTMA-ran-PTFEMA-ran-poly(hydroxyl ethyl methacrylate) (PHEMA) and poly(isobutyl methacrylate) (PiBMA)-ran-PTFEMA-ran-PHEMA, which helped us corroborate, along with the Zisman method, the surface energy estimation of PTMA to be 30.1 mJ m^-2.

View Accepted Manuscript (DOE)

Research Organization:: Cornell Univ., Ithaca, NY (United States)

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

Grant/Contract Number:: SC0014336

OSTI ID:: 1802610

Alternate ID(s):: OSTI ID: 1559095

Journal Information:: Polymer Chemistry, Journal Name: Polymer Chemistry Journal Issue: 37 Vol. 10; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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