Hydrophobic and Hydrophilic Control in Polyphosphazene Materials
Open Access
- Author:
- Steely, Lee Brent
- Graduate Program:
- Chemistry
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- July 27, 2007
- Committee Members:
- Harry R Allcock, Committee Chair/Co-Chair
Alan James Benesi, Committee Member
Mary Elizabeth Williams, Committee Member
James Patrick Runt, Committee Member - Keywords:
- hydrophobic
polyphosphazenes
fluorine
surface modification - Abstract:
- This thesis is the culmination of several recent studies focused on the surface characterization of polyphosphazenes specifically the properties of water repellency or hydrophobicity. Chapter 1 is a background account of polyphosphazene chemistry and the hydrophobicity of polyphosphazenes. Chapter 2 provides an examination of the role of surface morphology on hydrophobicity. This study deals in depth with the electrospinning of poly[bis(2,2,2-trifluoroethoxy)phosphazene] in tetrahydrofuran. This process yields fiber mats or bead and fiber mats which exhibit roughness in continuous contact with the water droplet (fiber mats) or discontinuous contact (bead and fiber mats). These surface roughness types are compared to spun cast films using water contact angles to measure the air-water-polymer interface. The influence of aromatic moieties and fluorine content on the air-water-polymer interface is examined in Chapter 3. This study examines the influence of fluorine content and aryloxy groups on the hydrophobicity of a polyphosphazene surface via static water contact angle measurements on a goniometer. Polymer surfaces of spun cast and electrospun mats were probed with advancing, receeding, and static water contact angle and dip coated slides of the same materials were also examined with a Langmuir-Blogett trough. Chapter 4 is a description of the environmental plasma surface treatments of polyphosphazenes as a method of functionalizing solid polymer surfaces. The treatment procedure of functionalizing spun cast and electrospun poly[bis(2,2,2-trifluoroethoxy)phosphazene] surfaces with plasma gases of oxygen, nitrogen, methane, and tetrafluoromethane is detailed. The resulting functionalization of the surface is examined with XPS and water contact angle data. In Chapter 5 fluoroalkoxy polyphosphazenes were processed with liquid carbon dioxide into foams. The foams were then tested for flame retardance and hydrophobicity. Appendixes A-C contain studies on moisture sensitive phosphoranimine monomer storage, micelle formation in water from triblock copolymers, and single ion conductive membranes with increased hydrophobicity respectively. Although the appendixes examine polyphosphazene hydrophobic relationships they are not specific to surface hydrophobicity of solids and were not placed in the main text. Appendix A involves the optimization of storage conditions for a phosphoranimine monomer. Conditions examined include room temperature to -80 ºC and dilution with a variety of organic solvents. The micelle formation of A-B-A triblock copolymer of poly[bis(2,2,2-trifluoroethoxy)phosphazene]-poly(propylene-glycol)-poly[bis(2,2,2-trifluoroethoxy)phosphazene] was explored in appendix B. It was determined with light scattering and TEM that hairpin folding of our triblock copolymer allowed micelle formation with the two hydrophobic poly[bis(2,2,2-trifluoroethoxy)phosphazene] blocks facing the hydrophobic core of the micelle. Appendix C details the lithium ion conductivity of poly[norbornene-pendent-cyclotriphosphazene] with sulfonimide and methoxyethoxyethoxy groups attached. These results are then compared with unbound lithium counter ion systems.