Ultrafast dynamics of styrene microemulsions, polystyrene nanolatexes, and structural analogues of polystyrene

N T Hunt, A A Jaye, A Hellman, S R Meech

Research output: Contribution to journalArticle

43 Citations (Scopus)

Abstract

The ultrafast optically heterodyne-detected optical-Kerr-effect is used to compare the dynamics of styrene neat and in dodecane solution with those of styrene dispersed as the oil phase in a oil-in-water microemulsion. The dynamics in the microemulsion are similar to those of the neat liquid, both on the ultrafast and picosecond time scales, but there is also evidence for additional inhomogeneous broadening in the microemulsion. The styrene in the microemulsion was photopolymerized to yield isolated latex particles. The effect of polymerization on the ultrafast dynamics is dramatic. The picosecond diffusive response seen for the monomer is suppressed, whereas the ultrafast spectral density shifts to higher frequency in the polymer. Similar dynamics are seen for polystyrene in solution. This behavior is further analyzed through an investigation of the ultrafast dynamics of solutions of toluene, bibenzyl, a polystyrene oligomer, and polystyrene itself. It is concluded that the shift to higher frequency in the spectral density corresponds to the opening of additional intramolecular relaxation pathways in the larger more flexible molecules. It is found that both molecular and intramolecular librational dynamics are sensitive to their environment.
Original languageEnglish
Pages (from-to)100-108
Number of pages9
JournalJournal of Physical Chemistry B
Volume108
Issue number1
DOIs
Publication statusPublished - 8 Jan 2004

Fingerprint

Styrene
Polystyrenes
Microemulsions
styrenes
polystyrene
analogs
Spectral density
Oils
oils
Optical Kerr effect
Latex
Toluene
latex
Kerr effects
Latexes
oligomers
Oligomers
Particles (particulate matter)
toluene
Polymers

Keywords

  • ultrafast dynamics
  • styrene microemulsions
  • polystyrene nanolatexes
  • structural analogues
  • polystyrene
  • nanoscience

Cite this

Hunt, N T ; Jaye, A A ; Hellman, A ; Meech, S R . / Ultrafast dynamics of styrene microemulsions, polystyrene nanolatexes, and structural analogues of polystyrene. In: Journal of Physical Chemistry B. 2004 ; Vol. 108, No. 1. pp. 100-108.
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Ultrafast dynamics of styrene microemulsions, polystyrene nanolatexes, and structural analogues of polystyrene. / Hunt, N T ; Jaye, A A ; Hellman, A ; Meech, S R .

In: Journal of Physical Chemistry B, Vol. 108, No. 1, 08.01.2004, p. 100-108.

Research output: Contribution to journalArticle

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T1 - Ultrafast dynamics of styrene microemulsions, polystyrene nanolatexes, and structural analogues of polystyrene

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AB - The ultrafast optically heterodyne-detected optical-Kerr-effect is used to compare the dynamics of styrene neat and in dodecane solution with those of styrene dispersed as the oil phase in a oil-in-water microemulsion. The dynamics in the microemulsion are similar to those of the neat liquid, both on the ultrafast and picosecond time scales, but there is also evidence for additional inhomogeneous broadening in the microemulsion. The styrene in the microemulsion was photopolymerized to yield isolated latex particles. The effect of polymerization on the ultrafast dynamics is dramatic. The picosecond diffusive response seen for the monomer is suppressed, whereas the ultrafast spectral density shifts to higher frequency in the polymer. Similar dynamics are seen for polystyrene in solution. This behavior is further analyzed through an investigation of the ultrafast dynamics of solutions of toluene, bibenzyl, a polystyrene oligomer, and polystyrene itself. It is concluded that the shift to higher frequency in the spectral density corresponds to the opening of additional intramolecular relaxation pathways in the larger more flexible molecules. It is found that both molecular and intramolecular librational dynamics are sensitive to their environment.

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