Isomeric Effect Enabled Thermally Driven Self-Assembly of Hydroxystyrene-Based Block Copolymers.

Kanimozhi, C; Kim, M; Larson, SR; Choi, JW; Choo, Y; Sweat, DP; Osuji, CO; Gopalan, P

Isomeric Effect Enabled Thermally Driven Self-Assembly of Hydroxystyrene-Based Block Copolymers.

Kanimozhi, C Kim, M Larson, SR Choi, JW Choo, Y

Sweat, DP Osuji, CO Gopalan, P

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Publisher:: AMER CHEMICAL SOC
Publication Type:: Journal Article
Citation:: ACS Macro Lett, 2016, 5, (7), pp. 833-838
Issue Date:: 2016-07-19

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Field	Value	Language
dc.contributor.author	Kanimozhi, C
dc.contributor.author	Kim, M
dc.contributor.author	Larson, SR
dc.contributor.author	Choi, JW
dc.contributor.author	Choo, Y https://orcid.org/0000-0003-2715-0618
dc.contributor.author	Sweat, DP
dc.contributor.author	Osuji, CO
dc.contributor.author	Gopalan, P
dc.date.accessioned	2022-08-15T19:40:39Z
dc.date.available	2022-08-15T19:40:39Z
dc.date.issued	2016-07-19
dc.identifier.citation	ACS Macro Lett, 2016, 5, (7), pp. 833-838
dc.identifier.issn	2161-1653
dc.identifier.issn	2161-1653
dc.identifier.uri	http://hdl.handle.net/10453/160236
dc.description.abstract	We demonstrate through isomeric effect the modulation of thermal properties of poly(hydroxystyrene) (PHS)-based block copolymers (BCPs). A minimal structural change of substituting 3HS for 4HS in the BCP results in a drastic decrease in Tg, which in turn enables the thin film assembly of the BCP via thermal annealing. We synthesized a series of poly(3-hydroxystyrene-b-tert-butylstyrene) [P(3HS-b-tBuSt)] and poly(4-hydroxystyrene-b-tert-butylstyrene) [P(4HS-b-tBuSt)] BCPs by sequential anionic polymerization of protected 3HS/4HS monomer and tBuSt followed by deprotection. Measured Tg of P(3HS) was ∼20-30 °C lower than P(4HS) of comparable molecular weights. As a result, thermally driven self-assembly of P(3HS-b-tBuSt) BCPs in both bulk and thin film is demonstrated. For P(4HS-b-tBuSt) thermal annealing in thin-film at high temperatures results in poorly developed morphology due to cross-linking reaction of the 4HS block. The smallest periodicity observed for P(3HS-b-tBuSt) was 8.8 nm in lamellar and 11.5 nm in cylindrical morphologies. The functionality of the 3HS block was exploited to incorporate vapor phase metal oxide precursors to generate sub-10 nm alumina nanowires.
dc.format	Print-Electronic
dc.language	eng
dc.publisher	AMER CHEMICAL SOC
dc.relation.ispartof	ACS Macro Lett
dc.relation.isbasedon	10.1021/acsmacrolett.6b00376
dc.rights	info:eu-repo/semantics/closedAccess
dc.subject	0303 Macromolecular and Materials Chemistry, 0306 Physical Chemistry (incl. Structural)
dc.title	Isomeric Effect Enabled Thermally Driven Self-Assembly of Hydroxystyrene-Based Block Copolymers.
dc.type	Journal Article
utslib.citation.volume	5
utslib.location.activity	United States
utslib.for	0303 Macromolecular and Materials Chemistry
utslib.for	0306 Physical Chemistry (incl. Structural)
pubs.organisational-group	/University of Technology Sydney
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology
pubs.organisational-group	/University of Technology Sydney/Faculty of Engineering and Information Technology/School of Civil and Environmental Engineering
utslib.copyright.status	closed_access	*
dc.date.updated	2022-08-15T19:40:36Z
pubs.issue	7
pubs.publication-status	Published
pubs.volume	5
utslib.citation.issue	7

Abstract:

We demonstrate through isomeric effect the modulation of thermal properties of poly(hydroxystyrene) (PHS)-based block copolymers (BCPs). A minimal structural change of substituting 3HS for 4HS in the BCP results in a drastic decrease in Tg, which in turn enables the thin film assembly of the BCP via thermal annealing. We synthesized a series of poly(3-hydroxystyrene-b-tert-butylstyrene) [P(3HS-b-tBuSt)] and poly(4-hydroxystyrene-b-tert-butylstyrene) [P(4HS-b-tBuSt)] BCPs by sequential anionic polymerization of protected 3HS/4HS monomer and tBuSt followed by deprotection. Measured Tg of P(3HS) was ∼20-30 °C lower than P(4HS) of comparable molecular weights. As a result, thermally driven self-assembly of P(3HS-b-tBuSt) BCPs in both bulk and thin film is demonstrated. For P(4HS-b-tBuSt) thermal annealing in thin-film at high temperatures results in poorly developed morphology due to cross-linking reaction of the 4HS block. The smallest periodicity observed for P(3HS-b-tBuSt) was 8.8 nm in lamellar and 11.5 nm in cylindrical morphologies. The functionality of the 3HS block was exploited to incorporate vapor phase metal oxide precursors to generate sub-10 nm alumina nanowires.

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http://hdl.handle.net/10453/160236