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Title: High Surface Area Poly(3-hexylthiophenes) Thin Films from Cleavable Graft Copolymers

Abstract

A strategy for the fabrication of high surface area poly(3-hexylthiophene) thin films by removal of nanoscale domains formed from graft copolymers is presented. This approach relies on the synthesis and characterization of cleavable graft copolymers based on regioregular poly(3-hexylthiophene) (rr-P3HT) main chain and sacrificial poly(styrene) side chains. An alkoxyamine initiator based on 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) was incorporated at the 3-position of the functionalized thienyl repeat unit, 2, via a cleavable trityl ether linker. Grignard metathesis (GRIM) copolymerization of 2 and 2,5-dibromo-3-hexylthiophene afforded regioregular P3HT with randomly incorporated alkoxyamine groups. Polymerization of styrene from the P3HT backbone for different time periods afforded graft copolymers with controllable sacrificial chain lengths. These materials were characterized using an array of techniques such as {sup 1}H and {sup 13}C NMR spectroscopy and size exclusion chromatography (SEC). An approach to obtain nanoporous P3HT thin films by cleavage of the trityl ether linker followed by complete removal of poly(styrene) is reported with the as-cast graft copolymer thin films displaying an irregular microphase-separated structure with an average domain size {approx}30 nm as determined by grazing incidence small-angle X-ray scattering (GISAXS) measurements. Significantly, this length scale was conserved after removal of the sacrificial component which allows this strategy to havemore » potential application in diverse fields such as organic photovoltaics.« less

Authors:
; ; ; ;  [1]
  1. UCSB
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE
OSTI Identifier:
1002318
Resource Type:
Journal Article
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 43; Journal Issue: (1) ; 01, 2010
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; POLYCYCLIC SULFUR HETEROCYCLES; SYNTHESIS; SURFACE AREA; COPOLYMERS; NANOSTRUCTURES; PORE STRUCTURE; COPOLYMERIZATION

Citation Formats

Sivanandan, Kulandaivelu, Chatterjee, Tirtha, Treat, Neil, Kramer, Edward J, and Hawker, Craig J. High Surface Area Poly(3-hexylthiophenes) Thin Films from Cleavable Graft Copolymers. United States: N. p., 2010. Web. doi:10.1021/ma902009q.
Sivanandan, Kulandaivelu, Chatterjee, Tirtha, Treat, Neil, Kramer, Edward J, & Hawker, Craig J. High Surface Area Poly(3-hexylthiophenes) Thin Films from Cleavable Graft Copolymers. United States. doi:10.1021/ma902009q.
Sivanandan, Kulandaivelu, Chatterjee, Tirtha, Treat, Neil, Kramer, Edward J, and Hawker, Craig J. Tue . "High Surface Area Poly(3-hexylthiophenes) Thin Films from Cleavable Graft Copolymers". United States. doi:10.1021/ma902009q.
@article{osti_1002318,
title = {High Surface Area Poly(3-hexylthiophenes) Thin Films from Cleavable Graft Copolymers},
author = {Sivanandan, Kulandaivelu and Chatterjee, Tirtha and Treat, Neil and Kramer, Edward J and Hawker, Craig J},
abstractNote = {A strategy for the fabrication of high surface area poly(3-hexylthiophene) thin films by removal of nanoscale domains formed from graft copolymers is presented. This approach relies on the synthesis and characterization of cleavable graft copolymers based on regioregular poly(3-hexylthiophene) (rr-P3HT) main chain and sacrificial poly(styrene) side chains. An alkoxyamine initiator based on 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) was incorporated at the 3-position of the functionalized thienyl repeat unit, 2, via a cleavable trityl ether linker. Grignard metathesis (GRIM) copolymerization of 2 and 2,5-dibromo-3-hexylthiophene afforded regioregular P3HT with randomly incorporated alkoxyamine groups. Polymerization of styrene from the P3HT backbone for different time periods afforded graft copolymers with controllable sacrificial chain lengths. These materials were characterized using an array of techniques such as {sup 1}H and {sup 13}C NMR spectroscopy and size exclusion chromatography (SEC). An approach to obtain nanoporous P3HT thin films by cleavage of the trityl ether linker followed by complete removal of poly(styrene) is reported with the as-cast graft copolymer thin films displaying an irregular microphase-separated structure with an average domain size {approx}30 nm as determined by grazing incidence small-angle X-ray scattering (GISAXS) measurements. Significantly, this length scale was conserved after removal of the sacrificial component which allows this strategy to have potential application in diverse fields such as organic photovoltaics.},
doi = {10.1021/ma902009q},
journal = {Macromolecules},
number = (1) ; 01, 2010,
volume = 43,
place = {United States},
year = {2010},
month = {3}
}