Hosouk Cho


Pittman, Charles U.

Committee Member

Toghiani, Hossein

Committee Member

Mead, Keith T.

Committee Member

Koscho, Michael E.

Committee Member

Thomas, Gloria

Date of Degree


Document Type

Dissertation - Open Access


Organic Chemistry

Degree Name

Doctor of Philosophy


College of Arts and Sciences


Department of Chemistry


A new class of organic-inorganic hybrid nanocomposites containing well-defined polyhedral oligomeric silsesquioxane (POSS) monomers, which have been copolymerized with organic monomers, were synthesized. Poly(isobutyl methacrylate-co-butanediol dimethacrylate-co-3-methacrylylpropyl-heptaisobutyl(T8)polyhedral oligomeric silsesquioxane) (P(iBMA-co-BDMA-co-MA-POSS)) nanocomposites with different crosslink densities (BDMA loadings of 1, 3 and 5 wt%) and different MA-POSS percentages (5, 10, 15, 20 and 30 wt%) have been synthesized by radical-initiated terpolymerization. Linear P(iBMA-co-MA-POSS) copolymers were also prepared. Viscoelastic properties and morphologies were studied by DMTA (dynamic mechanical thermal analysis) and TEM (transmission electron microscopy). Two types of inorganic-organic hybrid polyhedral oligomeric silsesquioxane (POSS) / vinyl ester (VE) nanocomposites were synthesized. The first type contained a mixture of T8, T10 and T12 cages, each multifunctionalized with 3-methacrylylpropyl groups. The second type contained octa(3-methacrylylpropyldimethylsiloxyl)(T8)POSS. VE/POSS samples with weight ratios of 99/1, 97/3, 95/5, 90/10, 85/15 and 80/20 were prepared of each type. The nanocomposites were characterized by DMTA, TEM, scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (X-EDS), swelling, extraction and FT-IR. Three classes of inorganic-organic hybrid phenolic resin/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were also synthesized via condensation polymerization. The POSS macromers employed included multifunctional dichloromethylsilylethylheptaisobutyl(T8)POSS, trisilanolheptaphenyl-POSS, and poly(phenylsilsesquioxane) uncured POSS. A nonfunctional octaisobutyl(T8)POSS was blended into the uncured phenolic resin followed by curing under the same conditions as those used for the other three nanocomposites classes. Phenolic/POSS samples with weight ratios of 99/1, 97/3, 95/5 and 90/10 were prepared of each type. Octaaminophenyl(T8)POSS and dodecaaminophenyl(T12)POSS were synthesized, characterized and then incorporated into two types of thermoset resins: (1) the bisphenol-F-based cyanate ester resin, PT-15, and (2) epoxy (Epon 828, Shell Chemical Corp.)/ 4,4?-diaminodiphenylmethane (DDM) resin, respectively, to make two series of nanocomposites. The sum of amino groups in both DDM and POSS were held in a 1:1 mole ratio to the epoxy groups. EPON-828/POSS/DDM (78.63/0/21.37, 77.48/5/17.52, 76.34/10/13.66, 74.05/20/5.95 and 72.28/27.72/0 wt/wt/wt compositions for both series) was prepared. PT-15/POSS composites (99/1, 97/3 and 95/5 wt/wt compositions for both types) were also prepared.