Title page for ETD etd-03282012-211802

Type of Document Dissertation
URN etd-03282012-211802
Title Synthesis and Properties of Ion-Containing Block and Segmented Copolymers and Their Composites
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Long, Timothy E. Committee Chair
Madsen, Louis A. Committee Member
Moore, Robert Bowen III Committee Member
Turner, S. Richard Committee Member
Vlachos, Pavlos P. Committee Member
  • step-growth polymerization
  • multi-walled carbon nanotubes
  • sulfonated block copolymers
  • sulfonated polyurethane
  • nanocomposites
  • ionic liquids
  • electroactive actuator
Date of Defense 2012-03-16
Availability unrestricted
Ion-containing segmented polyurethanes exhibit unique morphology and physical properties due to synergistic interactions of electrostatic, hydrogen bonding, and hydrophobic interactions. A fundamental investigation on a series of well-defined ion-containing polyurethanes elucidated the influence of charge placement, charge density, and soft segment structure on physical properties, hydrogen bonding, and morphologies. An unprecedented comparison of poly(ethylene oxide)(PEO)-based sulfonated polyurethanes containing sulfonate anions either in the soft segments or hard segments revealed that sulfonate charge placement dramatically influenced microphase separation and physical properties of segmented polyurethanes, due to altered hydrogen bonding and thermodynamic immiscibility between soft and hard segments. Moreover, studies on sulfonated polyurethanes with identical sulfonated hard segments but different soft segment structures indicated that soft segment structure tailored sulfonated polyurethanes for a wide range of mechanical properties.

Sulfonated polyurethanes incorporated with ammonium-functionalized multi-walled carbon nanotubes (MWCNTs) generated novel polyurethane nanocomposites with significantly enhanced mechanical performance. Modification of MWCNTs followed a dendritic strategy, which doubled the functionality by incorporating two ammonium cations per acid site. Complementary characterization demonstrated successful covalent functionalization and formation of surface-bound ammonium salts. Upon comparison with pristine MWCNTs, ammonium-functionalized MWCNTs exhibited significantly enhanced dispersibility in both

DMF and sulfonated polyurethane matrices due to good solvation of ammonium cations and intermolecular ionic interactions between anionic polyurethanes and cationic MWCNTs.

Segmented polyurethanes containing sulfonated PEO-based soft segments and nonionic hard segments were incorporated with various contents of room temperature ionic liquid, 1-ethyl-3-methylimidazolium ethylsulfate (EMIm ES), to investigate the influence of ionic liquid on physical properties, morphologies, and ionic conductivity. Results indicated that EMIm ES preferentially located in the sulfonated PEO soft phase, leading to significantly enhanced ionic conductivity and well-maintained mechanical properties. These properties are highly desirable for electromechanical transducer applications. Electromechanical actuators fabricated with sulfonated polyurethane/IL composite membranes exhibited effective response under a low applied voltage (4 V). However, in the case of an imidazolium-containing segmented polyurethane with imidazolium ionic hard segments and hydrophobic poly(tetramethylene oxide) (PTMO) soft segments, EMIm ES selectively located into the imidazolium ionic hard domains, as evidenced with a constant PTMO soft segment glass transition temperature (Tg) and systematically reduced imidazolium hard segment Tg. Dielectric relaxation spectroscopy demonstrated that ionic conductivity of imidazolium-containing segmented polyurethanes increased by five orders of magnitude upon incorporation of 30 wt% EMIm ES.

Imidazolium-containing sulfonated pentablock copolymers were also investigated to elucidate the influence of imidazolium counter cation structures on solution rheology, morphology, and thermal and mechanical properties. Combination of living anionic polymerization and post functionalization strategies provided well-defined sulfonated pentablock copolymers containing structured imidazolium cations in sulfonated polystyrene middle block. Varying alkyl substitute length on imidazolium cations tailored physical properties and morphologies of sulfonated pentablock copolymers. Results indicated that long alkyl substitutes (octyl and dodecyl) on imidazolium cations significantly influenced solution rheological behavior, morphology, and water uptake properties of sulfonated pentablock copolymers due to the altered characteristic of imidazolium cations. Imidazolium-containing sulfonated pentablock copolymers exhibited systematically tailored mechanical properties due to the plasticizing effect of alkyl substitutes. In addition, incorporation of ionic liquids into sulfonated pentablock copolymers further tailored their mechanical properties and ionic conductivity, which made these materials suitable for electromechanical transducer applications. All sulfonated pentablock copolymers were successfully fabricated into actuator devices, which exhibited effective actuation under a low applied voltage (4 V).

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