Investigations Into Chain-Length-Dependent Termination in Bulk Radical Polymerization of 1H, 1H, 2H, 2H-Tridecafluorooctyl Methacrylate

✍ Scribed by Johannes Barth; Rebekka Siegmann; Sabine Beuermann; Gregory T. Russell; Michael Buback

• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 693 KB
• Volume: 213
• Category: Article
• ISSN: 1022-1352
• DOI: 10.1002/macp.201100479

✦ Synopsis

Abstract

The SP‐PLP‐EPR technique is used to carry out a detailed investigation of the radical termination kinetics of 1__H__, 1__H__, 2__H__, 2__H__‐tridecafluorooctyl methacrylate (TDFOMA) in bulk at relatively low conversion. Composite‐model behavior for chain‐length‐dependent termination rate coefficients, k~t~^i,i^, is observed. It is found that for TDFOMA, i~c~ ≈ 60 independent of temperature, and α~s~ ≈ 0.65 and α~l~ ≈ 0.2 at 80 °C and above. However, at lower temperatures the situation is strikingly different, with the significantly higher average values of α~s~ = 0.89 ± 0.15 and α~l~ = 0.32 ± 0.10 being obtained at 50 °C and below. This makes TDFOMA the first monomer to be found that exhibits clearly different exponent values, α~s~ and α~l~, at lower and higher temperature, and that has both a high α~s~, like an acrylate, and a high i~c~, like a methacrylate.