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BLENDS OF PERFLUOROCARBON END-FUNCTIONALIZED AND TELECHELIC
POLYSTYRENE/POLY n-BUTYL METHACRYLATE. SYNTHESIS AND
MORPHOLOGY STUDIES
by
Victoria Piunova
A Dissertation Presented to the
FACULTY OF THE USC GRADUATE SCHOOL
UNIVERSITY OF SOUTHERN CALIFORNIA
In Partial Fulfillment of the
Requirements for the Degree
DOCTOR OF PHILOSOPHY
(CHEMISTRY)
December 2011
Copyright 2011 Victoria Piunova
Object Description
| Title | Blends of perfluorocarbon end-functionalized and telechelic polystyrene/poly n-butyl methacrylate. Synthesis and morphology studies. |
| Author | Piunova, Victoria |
| Author email | super_dr_chem@yahoo.com;vapiuno@caltech.edu |
| Degree | Doctor of Philosophy |
| Document type | Dissertation |
| Degree program | Chemistry |
| School | College of Letters, Arts And Sciences |
| Date defended/completed | 2011-08-03 |
| Date submitted | 2011-09-28 |
| Date approved | 2011-09-28 |
| Restricted until | 2011-09-28 |
| Date published | 2011-09-28 |
| Advisor (committee chair) | Hogen-Esch, Thieo |
| Advisor (committee member) |
Prakash, Surya Petasis, Nicos Williams, Travis Nutt, Steven |
| Abstract | Structurally well-defined C₄F₉, C₇F₁₅, C₁₀F₂₁ and C₁₃F₂₇ end-functionalized polystyrene (RF-PS) and polybutylmethacrylate (RF-PBMA) were prepared by Atom Transfer Polymerization using the RF–tagged initiators. Blends (1/1 wt/wt) of these polymers were studied by differential scanning calorimetry (DSC), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and optical transmittance (OT). The RF-PS/RF-PBMA blends having molecular weights of 20,000 and C₇F₁₅ or larger end groups, were optically transparent. The AFM micrographs show crater, necklace and other RF mediated morphologies typically at the submicron scale. TEMs of the PS and PBMA blends show the assembly of nm-sized lamellae and lamellar aggregates into domains with sizes in the micron or nanometer scales depending on MW and RF size. A semi-quantitative “phase diagram” the blends shows that lower MWs and longer RF groups improve phase compatibilities. In addition, telechelic C₇F₁₅ and C₁₃F₂₇ functionalized PS and the corresponding PBMA were synthesized by atom transfer polymerization, bromide substitution by sodium azide and click-coupling with propargyl ether. NMR, size exclusion chromatopgraphy and other characterization methods indicated high degrees of end functionalization (≥ 96%) and narrow MW distributions. The miscibility of (1/1 wt/wt) blends of these polymers was studied by TEM, AFM, DSC and optical transmittance. Blends of the telechelic C₇F₁₅ functionalized polymers with molecular weights of 15,000 showed no significant differences with blends of the 15k end- functionalized polymers. However, the AFM and TEM data for the blends of the 30k telechelic polymers showed formation of much smaller and relatively well defined surface and bulk domains. This confirms that beside perfluorocarbon content, the topology of these perfluorocarbon groups plays an important role in blend miscibility. |
| Keyword | polymer blends; polystyrene; poly n-butyl methacrylate; compatibility in polymer blends; phase behavior in polymer blends; perfluorocarbons; perfluorocarbon interactions; phase-separation; ATRP; telechelic polymers; 2-phenyl acrylate; click-chemistry |
| Language | English |
| Part of collection | University of Southern California dissertations and theses |
| Publisher (of the original version) | University of Southern California |
| Place of publication (of the original version) | Los Angeles, California |
| Publisher (of the digital version) | University of Southern California. Libraries |
| Provenance | Electronically uploaded by the author |
| Type | texts |
| Legacy record ID | usctheses-m |
| Rights | Piunova, Victoria |
| Access conditions | The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the author, as the original true and official version of the work, but does not grant the reader permission to use the work if the desired use is covered by copyright. It is the author, as rights holder, who must provide use permission if such use is covered by copyright. The original signature page accompanying the original submission of the work to the USC Libraries is retained by the USC Libraries and a copy of it may be obtained by authorized requesters contacting the repository e-mail address given. |
| Repository name | University of Southern California Digital Library |
| Repository address | USC Digital Library, University of Southern California, University Park Campus MC 7002, 106 University Village, Los Angeles, California 90089-7002, USA |
| Repository email | cisadmin@usc.edu |
| Archival file | uscthesesreloadpub_Volume71/etd-PiunovaVic-300.pdf |
Description
| Title | Page 1 |
| Full text | BLENDS OF PERFLUOROCARBON END-FUNCTIONALIZED AND TELECHELIC POLYSTYRENE/POLY n-BUTYL METHACRYLATE. SYNTHESIS AND MORPHOLOGY STUDIES by Victoria Piunova A Dissertation Presented to the FACULTY OF THE USC GRADUATE SCHOOL UNIVERSITY OF SOUTHERN CALIFORNIA In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY (CHEMISTRY) December 2011 Copyright 2011 Victoria Piunova |
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