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

Chemical Engineering

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87 Scopus citations

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 (US)
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
State	Published - Jul 18 2017

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/acsmacrolett.7b00262

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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{a1103ebf44eb41f993c897f16c544899,

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,

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doi = "10.1021/acsmacrolett.7b00262",

language = "English (US)",

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pages = "668--673",

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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

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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.

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

Abstract

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