Part I of this dissertation deals with the surface modification of poly(tetrafluoroethylene-co-hexafluoro-propylene) (FEP). The reduction of FEP using sodium naphthalide was studied with regard to the kinetics of reaction and the product structure. The thickness of the resulting modified surface layer could be controlled, using reaction time and temperature, in the ranges of 45-90 and 250-800 A. The air-sensitive reduction product contained carbon-carbon double and triple bonds, aliphatic C-H bonds, alcohols, carbonyls and very little fluorine. Hydroboration/oxidation introduced hydroxyl groups in high yield to the surface. The alcohols exhibited low reactivity in esterification reactions in the absence acylation catalysts. Treatment of this surface with ethylene oxide in the presence of LDA rendered a more reactive, primary alcohol-containing, surface. Reaction of the hydroxyl surface produced by hydroboration and oxidation with 1,4-toluene diisocyanate or isophorone diisocyanate resulted in surface-bound isocyanate groups. The reactivity of these surfaces towards nucleophiles was investigated. Part II deals with graft polymerization from surface-confined initiator species. Halogenated surfaces were prepared by treating reduced FEP with chlorine or bromine. Treatment of these surfaces with silver trifluoromethane-sulfonate in the presence of tetrahydrofuran (THF) resulted in the polymerization of THF from the surface. Initiation at temperatures less than $-$10$\sp\circ$C, followed by polymerization at $-$10$\sp\circ$C, resulted in a relatively thick, homogeneous overlayer of the graft polymer. Neopentyl and n-propyl alcohol groups were introduced to the surface of poly(chlorotrifluoroethylene) (PCTFE) by reaction with the appropriate protected alcohol-containing lithium reagent. The corresponding tosylate surfaces were prepared and the reaction of these surfaces with 2-methyloxazoline was studied. Acrylamide monomers were polymerized from hydroxyl surfaces derived from FEP using ceric ion redox initiation. The introduction of trimethylsilyl ketene acetal groups to polymer surfaces was also investigated. Part III deals with the surface chemistry of fibrillar carbon. Oxidation and reactions with carbenes were studied as a means of introducing functional groups to the surface. X-ray photoelectron spectroscopy was used to characterize the products; chemical derivatization was used to determine the functional group composition of the oxidized surface.
| Identifer | oai:union.ndltd.org:UMASS/oai:scholarworks.umass.edu:dissertations-7895 |
| Date | 01 January 1990 |
| Creators | Bening, Robert Charles |
| Publisher | ScholarWorks@UMass Amherst |
| Source Sets | University of Massachusetts, Amherst |
| Language | English |
| Detected Language | English |
| Type | text |
| Source | Doctoral Dissertations Available from Proquest |
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