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Synthesis, characterization and thin film morphology of poly(styrene-block-methyl methacrylate) containing UV photolabile junction points

James T Goldbach, University of Massachusetts Amherst


Diblock copolymers are a class of polymers where two dissimilar polymer blocks are joined together at a common end. The dissimilarity of the blocks causes a phase separation to take place, however the connectivity of the blocks keeps the length scale of this phase separation on the order of the radius of gyration of each of the blocks. Throughout this thesis, the synthesis and morphology of diblock copolymers that have a specific, UV cleavable chemical moiety located at the junction point between the two blocks is investigated. The two junction points targeted to this end are the [4π + 4π] photodimer of anthracene and the 2-nitrobenzyl ester. The diblock copolymer containing the [4π + 4π] photodimer of anthracene exhibits thermal as well as UV lability upon heating above ∼130°C, or UV irradiation at 280 nm. Thin films of this polymer on neutrally-interacting substrates were annealed at 80°C under the presence of supercritical carbon dioxide to avoid thermal degradation that would occur if films were annealed above the glass transition temperature of both blocks (>110°C). The transition from microphase-separated to macrophase-separated morphology is thoroughly investigated by AFM upon thermal and UV cleavage to create blends of diblock and homopolymer in situ. In addition, the selective removal of each polymer block after cleavage by washing with selective solvents is demonstrated. The diblock copolymer containing the 2-nirobenzyl ester moiety is also synthesized and its morphology in thin films is investigated. This diblock, upon cleavage, leaves behind more useful functionality than the diblock with the [4π + 4π] photodimer of anthracene as junction point, as well as being thermally stable at temperatures that allows thermal annealing of thin films. The UV cleavage characteristics of this copolymer in solution are investigated by SEC. Also, irradiation of thin films at a wavelength that does not degrade or cross-link either polymer block causes selective junction point cleavage, as expected. The morphology of UV cleaved thin films on neutrally-interacting substrates is investigated by AFM.

Subject Area


Recommended Citation

Goldbach, James T, "Synthesis, characterization and thin film morphology of poly(styrene-block-methyl methacrylate) containing UV photolabile junction points" (2003). Doctoral Dissertations Available from Proquest. AAI3110491.