Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers

Bernd Oschmann; Jimmy Lawrence; Morgan W. Schulze; Jing M. Ren; Athina Anastasaki; Yingdong Luo; Mitchell D. Nothling; Christian W. Pester; Kris T. Delaney; Luke A. Connal; Alaina J. McGrath; Paul G. Clark; Christopher M. Bates; Craig J. Hawker

doi:10.1021/acsmacrolett.7b00262

Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers

Bernd Oschmann, Jimmy Lawrence, Morgan W. Schulze, Jing M. Ren, Athina Anastasaki, Yingdong Luo, Mitchell D. Nothling, Christian W. Pester, Kris T. Delaney, Luke A. Connal, Alaina J. McGrath, Paul G. Clark, Christopher M. Bates^*, Craig J. Hawker

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

77 Citations (Scopus)

Abstract

The effect of dispersity on block polymer self-assembly was studied in the monodisperse limit using a combination of synthetic chemistry, matrix-assisted laser desorption ionization spectroscopy, and small-angle X-ray scattering. Oligo(methyl methacrylate) (oligoMMA) and oligo(dimethylsiloxane) (oligoDMS) homopolymers were synthesized by conventional polymerization techniques and purified to generate an array of discrete, semidiscrete, and disperse building blocks. Coupling reactions afforded oligo(DMS-MMA) block polymers with precisely tailored molar mass distributions spanning single molecular systems (D= 1.0) to low-dispersity mixtures (d ≈ 1.05). Discrete materials exhibit a pronounced decrease in domain spacing and sharper scattering reflections relative to disperse analogues. The order-disorder transition temperature (T_ODT) also decreases with increasing dispersity, suggesting stabilization of the disordered phase, presumably due to the strengthening of composition fluctuations at the low molar masses investigated.

Original language	English
Pages (from-to)	668-673
Number of pages	6
Journal	ACS Macro Letters
Volume	6
Issue number	7
DOIs	https://doi.org/10.1021/acsmacrolett.7b00262
Publication status	Published - 18 Jul 2017
Externally published	Yes

Access to Document

10.1021/acsmacrolett.7b00262

Cite this

Oschmann, B., Lawrence, J., Schulze, M. W., Ren, J. M., Anastasaki, A., Luo, Y., Nothling, M. D., Pester, C. W., Delaney, K. T., Connal, L. A., McGrath, A. J., Clark, P. G., Bates, C. M., & Hawker, C. J. (2017). Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers. ACS Macro Letters, 6(7), 668-673. https://doi.org/10.1021/acsmacrolett.7b00262

@article{5ad89ff3f4964ae3a592d554669d301b,

title = "Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers",

abstract = "The effect of dispersity on block polymer self-assembly was studied in the monodisperse limit using a combination of synthetic chemistry, matrix-assisted laser desorption ionization spectroscopy, and small-angle X-ray scattering. Oligo(methyl methacrylate) (oligoMMA) and oligo(dimethylsiloxane) (oligoDMS) homopolymers were synthesized by conventional polymerization techniques and purified to generate an array of discrete, semidiscrete, and disperse building blocks. Coupling reactions afforded oligo(DMS-MMA) block polymers with precisely tailored molar mass distributions spanning single molecular systems (D= 1.0) to low-dispersity mixtures (d ≈ 1.05). Discrete materials exhibit a pronounced decrease in domain spacing and sharper scattering reflections relative to disperse analogues. The order-disorder transition temperature (TODT) also decreases with increasing dispersity, suggesting stabilization of the disordered phase, presumably due to the strengthening of composition fluctuations at the low molar masses investigated.",

author = "Bernd Oschmann and Jimmy Lawrence and Schulze, {Morgan W.} and Ren, {Jing M.} and Athina Anastasaki and Yingdong Luo and Nothling, {Mitchell D.} and Pester, {Christian W.} and Delaney, {Kris T.} and Connal, {Luke A.} and McGrath, {Alaina J.} and Clark, {Paul G.} and Bates, {Christopher M.} and Hawker, {Craig J.}",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = jul,

day = "18",

doi = "10.1021/acsmacrolett.7b00262",

language = "English",

volume = "6",

pages = "668--673",

journal = "ACS Macro Letters",

issn = "2161-1653",

publisher = "American Chemical Society",

number = "7",

}

Oschmann, B, Lawrence, J, Schulze, MW, Ren, JM, Anastasaki, A, Luo, Y, Nothling, MD, Pester, CW, Delaney, KT, Connal, LA, McGrath, AJ, Clark, PG, Bates, CM & Hawker, CJ 2017, 'Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers', ACS Macro Letters, vol. 6, no. 7, pp. 668-673. https://doi.org/10.1021/acsmacrolett.7b00262

TY - JOUR

T1 - Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers

AU - Oschmann, Bernd

AU - Lawrence, Jimmy

AU - Schulze, Morgan W.

AU - Ren, Jing M.

AU - Anastasaki, Athina

AU - Luo, Yingdong

AU - Nothling, Mitchell D.

AU - Pester, Christian W.

AU - Delaney, Kris T.

AU - Connal, Luke A.

AU - McGrath, Alaina J.

AU - Clark, Paul G.

AU - Bates, Christopher M.

AU - Hawker, Craig J.

PY - 2017/7/18

Y1 - 2017/7/18

N2 - The effect of dispersity on block polymer self-assembly was studied in the monodisperse limit using a combination of synthetic chemistry, matrix-assisted laser desorption ionization spectroscopy, and small-angle X-ray scattering. Oligo(methyl methacrylate) (oligoMMA) and oligo(dimethylsiloxane) (oligoDMS) homopolymers were synthesized by conventional polymerization techniques and purified to generate an array of discrete, semidiscrete, and disperse building blocks. Coupling reactions afforded oligo(DMS-MMA) block polymers with precisely tailored molar mass distributions spanning single molecular systems (D= 1.0) to low-dispersity mixtures (d ≈ 1.05). Discrete materials exhibit a pronounced decrease in domain spacing and sharper scattering reflections relative to disperse analogues. The order-disorder transition temperature (TODT) also decreases with increasing dispersity, suggesting stabilization of the disordered phase, presumably due to the strengthening of composition fluctuations at the low molar masses investigated.

AB - The effect of dispersity on block polymer self-assembly was studied in the monodisperse limit using a combination of synthetic chemistry, matrix-assisted laser desorption ionization spectroscopy, and small-angle X-ray scattering. Oligo(methyl methacrylate) (oligoMMA) and oligo(dimethylsiloxane) (oligoDMS) homopolymers were synthesized by conventional polymerization techniques and purified to generate an array of discrete, semidiscrete, and disperse building blocks. Coupling reactions afforded oligo(DMS-MMA) block polymers with precisely tailored molar mass distributions spanning single molecular systems (D= 1.0) to low-dispersity mixtures (d ≈ 1.05). Discrete materials exhibit a pronounced decrease in domain spacing and sharper scattering reflections relative to disperse analogues. The order-disorder transition temperature (TODT) also decreases with increasing dispersity, suggesting stabilization of the disordered phase, presumably due to the strengthening of composition fluctuations at the low molar masses investigated.

UR - http://www.scopus.com/inward/record.url?scp=85024910397&partnerID=8YFLogxK

U2 - 10.1021/acsmacrolett.7b00262

DO - 10.1021/acsmacrolett.7b00262

M3 - Article

SN - 2161-1653

VL - 6

SP - 668

EP - 673

JO - ACS Macro Letters

JF - ACS Macro Letters

IS - 7

ER -

Effects of Tailored Dispersity on the Self-Assembly of Dimethylsiloxane-Methyl Methacrylate Block Co-Oligomers

Abstract

Access to Document

Other files and links

Fingerprint

Cite this