Photochemical control of rheology

• Author(s): Avó, João Miguel Ribeiro
• Date: 2014
• Persistent ID: http://hdl.handle.net/10362/14065
• Origin: Repositório Institucional da UNL
• Subject(s): Photochemistry; Photopolymerization; Photorheology; Ionic liquids; Coumarins
• Document Type: Doctoral thesis
• Language: English
• Advisor(s): Parola, A. J.; Lima, João
• Contributor(s): RUN

Description

The main objective of the research work developed in the framework of this PhD thesis was the preparation and development of novel photorheological fluids. This was pursued following two distinct strategies. The first one focused on the synthesis of tripodal compounds functionalized with photodimerizable moieties of cinnamic acid, coumarin and anthracene. Two sets of compounds were prepared, varying the central unit as well as spacers resulting in molecules with different solubilities and molecular weight. All compounds were characterized towards their photochemical properties and all exhibited photoreactivity upon irradiation with ultra-violet light. In particular, both coumarin derivatives exhibited the greatest photopolymerization reactivity, resulting in the formation of dendrimeric nanoparticles or in the increase of viscosity of organic solutions. The second strategy was focused on the careful design of photosensitive ionic liquids, based on the results of several quantitative structure-property relationship studies. Thus, photosensitive ionic liquids were synthesized bearing cinnamic acid or coumarin moieties in the organic cation. Upon irradiation, all compounds exhibited reactivity, which resulted in changes in their physical properties, such as melting point or viscosity. In addition, novel coumarin chromophores with different photophysical and photochemical properties were developed. It is expected that these compounds may find application in the preparation of new photosensitive ionic liquids.