Waveguides made of poly-methyl-methacrylate (PMMA) play a major role in the homogeneous distribution of display backlights as a matrix for solid-state dye lasers and polymer optical fibers (POFs). PMMA is favored because of its transparency in the visible spectrum, low price, and well-controlled processability. Nevertheless, technical drawbacks, such as its limited temperature stability, call for new materials. In this work, the copolymerization technique is used to modify the properties of the corresponding homopolymers. The analytical investigation of fourteen copolymers made of methyl-methacrylate (MMA) or ethyl-methacrylate (EMA) as the basis monomer is summarized. Their polymerization behaviors are examined by NMR spectroscopy with subsequent copolymerization parameter evaluation according to Fineman-Ross and Kelen-Tüdös. Therefore, some r-parameter sets are shown to be capable of copolymerizations with very high conversions. The first applications as high-temperature resistant (HT) materials for HT-POFs are presented. Copolymers containing isobornyl-methacrylate (IBMA) as the comonomer are well-suited for this demanding application.