Date of Award


Degree Name

MS in Polymers and Coatings


Chemistry & Biochemistry


Philip Costanzo


Polymer matrices are commonly used as guest-host systems for organic chromophores for use in non-linear optical materials. The chromophores must be aligned or poled in an electric field in order to impart anisotropy and non-linear activity to the material. This poling process raises several issues, the two largest being the eventual relaxation of the chromophores back into random orientations due to brownian motion, and high molecular weight polymer matrices limiting chromophore mobility during poling. The prevention of this relaxation process is an area of significant interest, especially in applications that require long term coating stability and activity. In this study, a polymer matrix is synthesized that seeks to solve both of these problems with one system. The ideal system would be one that allows for chromophore mobility during processing, but once chromophores have reached the desired orientation, limits mobility and relaxation during in-service usage. A copolymer of methyl methacrylate and a Diels-Alder adduct cross-linking monomer was synthesized in order to meet these challenges. This polymer was blended with commercially available acrylic polymer and organic chromophore molecules in order to test the viability of the solution. It was found that at the percent composition of cross-linker being utilized in the study, the Diels-Alder linkages were not reforming in any measurable amount due to the low amount of Diels-Alder active monomer units. This led to the development of a new system based on mixing polyfuran based polymers with polymaleimide based polymers during processing. This method allows for high amounts of cross-linking after processing ceases, which achieves both initial goals of the project, as well as allowing facile synthesis of the desired polymer components.

Another attempt to address these issues in polymer matrix formation led to the use of a novel inimer system. The cross-linking agent was also the polymerization initiator, and these functionalities were separated by a Diels-Alder linkage that would fall apart upon exposure to thermal stimulus. These polymers were synthesized and isolated easily, although in some cases gelation occurred. In order to observe the extent of the cross-linking inimer being incorporated into the matrix, cleavage experiments were performed to induce the breaking of the Diels-Alder adduct. Analyzing the Diels-Alder cleaved polymer led to an interesting result: all polymers showed an increase in apparent molecular weight when analyzed by gel permeation chromatography. The increase in molecular weight occurring upon cleavage of main chain bonds has never before been observed in literature. The explanation proposed was that the polymer adopted a "ropeball" like topology consisting of tightly coiled loops and knots. Upon cleavage of the cross-links, the ropeball was able to unwind into a much more linear topology, occupying a much larger hydrodynamic volume. This increase in hydrodynamic volume would cause the gel permeation chromatography results to show an apparent increase in molecular weight.