Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides

Bradley Seurer, Vandana Vij, Timothy Haddad, Joseph M. Mabry, Andre Lee

Research output: Contribution to journalArticle

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Abstract

Thermal transitions and reaction kinetics of polyhedral oligomeric silsesquioxane (POSS) with phenylethynylphthalimide (PEPI) moieties were investigated. Specifically, this study was designed to probe the influence of the POSS peripheries, types of spacer group in between the PEPI and the SiO 1.5 core, the architecture of the PEPI arrangement with respect to the SiO1.5 core, and the number of PEPI groups per cage on the thermal transitions and the cross-linking reaction of phenylethynyl. PEPI-POSS compounds with isobutyl peripheries exhibited lower melting temperatures as compared to those with phenyl periphery, consequently these isobutyl PEPI-POSS derivatives have a higher phenylethynyl reaction rate, although the onset of reaction temperature was not significantly affected. Changing the spacer group from propyl to phenyl causes an increase in the melting transition temperature along with a higher heat of fusion at melting; however, the more rigid phenyl spacer enables the PEPI-POSS to form a higher degree of crystallinity upon cooling. The more rigid phenyl spacer also initiates the polyene reactions at lower temperatures. For POSS with PEPI attached to either side of the cage, there are two isomers with respect to the SiO1.5 core. This mixture of two isomers inhibits the formation of crystallinity as compared with the "pendent" derivative where both PEPI groups come off from the same corner of POSS cage. Finally, it was found that these PEPI-POSS molecules have reaction kinetics and onset temperatures on par with organic hexafluorophenylethynyl oligoimides, which make these PEPI-POSS molecules excellent candidates as nanocomposite additives in high performance composite applications.

LanguageEnglish (US)
Pages9337-9347
Number of pages11
JournalMacromolecules
Volume43
Issue number22
DOIs
StatePublished - Nov 23 2010

Profile

Reaction kinetics
Isomers
Melting point
Derivatives
Polyenes
Molecules
Temperature
Superconducting transition temperature
Reaction rates
Nanocomposites
Melting
Fusion reactions
Cooling
Composite materials
Hot Temperature

ASJC Scopus subject areas

  • Organic Chemistry
  • Materials Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry

Cite this

Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides. / Seurer, Bradley; Vij, Vandana; Haddad, Timothy; Mabry, Joseph M.; Lee, Andre.

In: Macromolecules, Vol. 43, No. 22, 23.11.2010, p. 9337-9347.

Research output: Contribution to journalArticle

Seurer, Bradley ; Vij, Vandana ; Haddad, Timothy ; Mabry, Joseph M. ; Lee, Andre. / Thermal transitions and reaction kinetics of polyhederal silsesquioxane containing phenylethynylphthalimides. In: Macromolecules. 2010 ; Vol. 43, No. 22. pp. 9337-9347
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