One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites
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| Language: | English |
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University of Toledo / OhioLINK
2017
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| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=toledo151114123960565 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-toledo151114123960565 |
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oai_dc |
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NDLTD |
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English |
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NDLTD |
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Chemistry |
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Chemistry Gadient, Jennifer N. One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites |
| author |
Gadient, Jennifer N. |
| author_facet |
Gadient, Jennifer N. |
| author_sort |
Gadient, Jennifer N. |
| title |
One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites |
| title_short |
One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites |
| title_full |
One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites |
| title_fullStr |
One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites |
| title_full_unstemmed |
One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites |
| title_sort |
one-pot in-situ synthesis of poly(3-hexylthiophene)/metal oxide composites |
| publisher |
University of Toledo / OhioLINK |
| publishDate |
2017 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=toledo151114123960565 |
| work_keys_str_mv |
AT gadientjennifern onepotinsitusynthesisofpoly3hexylthiophenemetaloxidecomposites |
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1719453176480923648 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-toledo1511141239605652021-08-03T07:04:34Z One-Pot In-Situ Synthesis of Poly(3-hexylthiophene)/Metal Oxide Composites Gadient, Jennifer N. Chemistry Development of composite materials is integral to the advancement of modern technology with current applications in fields such as solar cells, fuel cells, biotechnology, and automobile parts. These composites offer advantages over pure materials by allowing for selection of and tuning of specific properties such as hardness, processibility, electrical conductivity, or ionic conductivity by selection of matrix and filler and careful control of the ratio of matrix to filler. This allows for a broad range of possible applications for the final product. The matrix and filler in the composite can be any type of material, including biomass, inorganic particles, organic small molecules, nanomaterials, ceramics or polymers. The composite is defined by which materials are used as the major and minor components, which are referred to as the composite matrix and the filler. The focus of this research will be on the synthesis of polymer-metal oxide composites. Synthesis of polymer-inorganic composites can be achieved through a variety of methods including ex-situ synthesis, in-situ formation of one phase in the presence of the fully formed second phase, or in-situ formation of both phases in the same reaction vessel. For a one pot method to be possible, both reactions must occur under compatible conditions. Initial studies in targeted systems thus often focus on formation of each phase separately before attempting composite synthesis. Poly(3-hexylthiophene) (P3HT) is a widely studied conducting polymer with applications in polymer based electronics and organic photovoltaics (OPVs). P3HT is often used as a benchmark material to investigate the effects of new fillers, synthesis or fabrication methods, or bonding between layers on the efficiency of OPVs. In this work a one-pot in-situ synthesis of poly(3-hexylthiophene) (P3HT)/metal oxide composites has been explored. Exploration of P3HT polymerization as a function of time, temperature, and Fe<sup>3+</sup>:3HT ratio was carried out with the intent of determining conditions that would allow for synthesis of P3HT with high yields and acceptable Mws while still being compatible with the desired conditions for NHSG reactions to eventually allow composite synthesis. In the process, a thorough investigation of solvent effects on the polymerization of 3-hexylthiophene with FeCl<sub>3</sub> was carried out. It was observed that no commonly used pure solvent could give highly reproducible high Mw polymer with quantitative yield. However, a solvent mixture of dichloromethane with nitrobenzene gave reproducibly high Mw polymer as well as high yields. Changes in solvents did not significantly change the ordering of the polymer. Two metal oxide systems, ZnO and V<sub>2</sub>O<sub>5</sub>, were investigated using the non-hydrolytic sol-gel method. This method allows crystallization of metal oxides at lower temperatures than traditional solid state methods as well as many other low temperature routes, making it a promising pathway for in situ synthesis of inorganic fillers in a polymer system. ZnO and V<sub>2</sub>O<sub>5</sub> were successfully synthesized. However, crystallization of ZnO required heating temperatures higher than the stability limit of P3HT. In contrast, V<sub>2</sub>O<sub>5</sub> was successfully crystallized after heating powders recovered from room temperature reactions to 250 <sup>o</sup>C. Two vanadium precursors, VCl<sub>3</sub> and VOCl<sub>3</sub>, as well as two oxygen sources, diisopropyl ether and diethyl ether, were explored, and reaction conditions were optimized with respect to vanadium to oxygen ratios and reaction times.Based on the results on the separate synthesis of P3HT and V<sub>2</sub>O<sub>5</sub>, initial conditions for the one-pot in-situ synthesis of P3HT/V<sub>2</sub>O<sub>5</sub> composites were chosen. However, it was found that the presence of an ether has a detrimental effect on the polymerization of P3HT and reduces both Mw and yield. A separate study was carried out to determine the effects of ether type, ether concentration and reaction time on the polymerization. Based on these results, diisopropyl ether was chosen as the most suitable oxygen source. A series of P3HT/V<sub>2</sub>O<sub>5</sub> samples were prepared by reacting VCl<sub>3</sub> or VOCl<sub>3</sub> with iPr<sub>2</sub>O while carrying out the oxidative polymerization of 3HT. Chloroform and a mixture of dichloromethane/nitrobenzene were chosen as solvent systems. Composites consisting of P3HT and VO<sub>x</sub> were successfully synthesized by this one pot in-situ method. Homogeneous dispersion of vanadium throughout the polymer matrix was confirmed by EDS, although the amount of vanadium incorporated into the polymer was in all cases significantly lower than the amount added to the reaction vessel. Most composites showed improved conductivities and thermal stabilities when compared to pristine polymer 2017 English text University of Toledo / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=toledo151114123960565 http://rave.ohiolink.edu/etdc/view?acc_num=toledo151114123960565 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |