Kenji Ishitake, K. Satoh, M. Kamigaito
Nov 16, 2011
Citations
0
Influential Citations
32
Citations
Journal
Macromolecules
Abstract
A series of silyl methacrylates [CH2═C(CH3)CO2SiR3] with varying silyl group bulkiness [R3Si: Me3Si, Et3Si, Me2tBuSi, iPr3Si, Ph2tBuSi, Ph3Si, and (Me3Si)3Si] were synthesized and radically polymerized to efficiently give soluble polymers with the exception of the highly bulky tris(trimethylsilyl)silyl methacrylate (TTMSSMA), which resulted in insoluble polymers. All the polymers can easily be converted into poly(methacrylic acid) (PMAA) via acid- or fluoride-induced deprotection of the silyl groups and further into poly(methyl methacrylate) (PMMA) via methylation with trimethylsilyldiazomethane for the analysis of molecular weight and tacticity. The tacticity was dependent on the bulkiness of the silyl substituents; the isotacticity increased with increasing bulkiness. Thus, a series of PMAAs and PMMAs with various tacticities ranging from syndiotactic-rich (rr = 74%; Me2tBuSi) to atactic (mr = 50%; iPr3Si) and highly isotactic [mm = 93%; (Me3Si)3Si] enchainment were obtained by conventional radical poly...