Three CF 3 -substituted methyl methacrylates (MMAs), 2,2,2-trifluoroethyl methacrylate (TFEMA), 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPMA) and nonafluoro-tert-butyl methacrylate (NFTBMA), were polymerized by conventional radical polymerization to give oxygen-permeable polymers for application in pressure-sensitive paint (PSP). The radical copolymerizations of styrene with TFEMA, HFIPMA, or NFTBMA were carried out to examine the effect of CF 3 groups on the polymerizability. The e values increased in the order of MMA (0.40) < TFEMA (0.76) < HFIPMA (1.19) < NFTBMA (1.31). The homopolymers of TFEMA, HFIPMA and NFTBMA (PTFEMA, PHFIPMA, and PNFTBM, respectively) were examined as polymers for use in PSP using 5,10,15,20tetrakis(pentafluorophenyl)porphinato platinum(II) (PtTFPP). The PSP consisting of PNFTBMA and PtTFPP exerted very high pres-sure sensitivity and very low temperature sensitivity. In the absence of oxygen, the temperature sensitivity decreased in the order of PTFEMA > PHFIPMA > PNFTBMA 5 PMMA, which corresponds to the order of glass transition temperatures (T g ). However, the activation energies of the overall process of the luminescence quenching by oxygen were found to be 16.8 (PMMA), 13.0 (PTFEMA), 6.8 (PHFIPMA), and 4.3 kJ mol 21 (PNFTBMA). Therefore, the low temperature sensitivity of PNFTBMA was attributed to its high degree of substitution with CF 3 groups and to its relatively high T g value.

Copolymers of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate (HFIPM) and tert-butyl methacrylate (TBM) were prepared by conventional radical copolymerization as a novel binders for pressure-sensitive paints (PSP). The monomer reactivity ratios r HFIPM and r TBM were determined as 0.45 and 0.67, respectively. The glass transition temperature of the copolymers increased from 77 to 1268C with increasing mole fraction of TBM units in the copolymer. The PSP were formed by combining the resulting copolymers and 5,10,15,20-tetrakis(pentafluorophenyl)porphinato platinum(II). The pressure and temperature sensitivities of the PSPs were measured at air pressures ranging from 5 to 120 kPa and at temperatures ranging from 0 to 608C. Modified Stern-Volmer plots indicated slight increases in the pressure sensitivity, but significant decrease in the temperature sensitivity as the mole fraction of HFIPM units increased in the copolymer. Applying a theoretical model to our calibration data, we inferred that luminescence quenching is primarily responsible for increasing the temperature sensitivity in the resulting copolymers.