Title page for ETD etd-09052003-105648

Type of Document Dissertation
Author O'Brien, Kristen Wilson
URN etd-09052003-105648
Title Synthesis of Functionalized Poly(dimethylsiloxane)s and the Preparation of Magnetite Nanoparticle Complexes and Dispersions
Degree PhD
Department Chemistry
Advisory Committee
Advisor Name Title
Riffle, Judy S. Committee Chair
Esker, Alan R. Committee Member
Lesko, John Jack Committee Member
Long, Timothy E. Committee Member
McGrath, James E. Committee Member
  • polymers
  • steric stabilization
  • magnetic fluids
  • iron oxides
Date of Defense 2003-08-21
Availability unrestricted
Poly(dimethylsiloxane) (PDMS) fluids containing magnetite nanoparticles stabilized with carboxylic acid-functionalized PDMS were prepared. PDMS-magnetite complexes were characterized using transmission electron microscopy, elemental analysis, and vibrating sample magnetometry. PDMS-magnetite complexes containing up to 67 wt% magnetite with magnetizations of ~52 emu gram-1 were prepared. The magnetite particles were 7.4 ± 1.7 nm in diameter. Calculations suggested that the complexes prepared using mercaptosuccinic acid-functionalized PDMS (PDMS-6COOH) complexes contained unbound acid groups whereas the mercaptoacetic acid-functionalized PDMS (PDMS-3COOH) complexes did not. Calculations showed that the PDMS-3COOH and PDMS-6COOH covered the same surface area on magnetite. Calculations were supported by molecular models and FTIR analyses. The complexes were dispersed into PDMS carrier fluids by ultrasonication, resulting in magnetic PDMS fluids with potential biomedical applications.

Magnetite particles (100 nm to 1 mm in diameter) were prepared by crystallization from goethite/glycol/water solutions under pressure. Two methods for particle growth were investigated in which the crystallization medium was varied by adjusting the amount of water or by adding itaconic acid. Particle surfaces were analyzed by x-ray photoelectron spectroscopy (XPS). Particles with clean surfaces were coated with carboxylic acid-functionalized poly(e-caprolactone) stabilizers. Adding itaconic acid to the reactions afforded particles ~100 nm in diameter. The magnetite particles displayed magnetic hysteresis. The particles were dispersed into vinyl ester resins by ultrasonication and it was demonstrated that the ~100 nm particles remained dispersed for three days without agitation. These dispersions have applications in magnetic induction heating for composite repair.

Living polymerizations of hexamethylcyclotrisiloxane were terminated with dimethylchlorosilane, phenylmethylchlorosilane, or diisopropylchlorosilane (DIPCS). Platinum-catalyzed hydrosilation of the hydrosilane-terminated PDMS with allyloxyethanol afforded a systematic series of hydroxyalkyl-terminated PDMS. The reactions were successful except for the hydrosilation of the sterically-hindered DIPCS-functionalized PDMS where no reaction was observed. Hydroxyalkyl-terminated PDMS oligomers were successful in initiating the stannous octoate-catalyzed copolymerization of e-caprolactone, which afforded PDMS-b-PCL diblock copolymers of controlled composition.

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