Radical polymerization of trifluoromethyl-substituted methyl methacrylates and their application for use in pressure-sensitive paint

Abstract

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.

Effect of polymer matrix on the performance of pressure‐sensitive paint comprising 5,10,15,20‐tetrakis(pentafluorophenyl)porphinato platinum(II) and poly(1,1,1,3,3,3‐hexafluoroisopropyl‐co‐tert‐butyl methacrylates)

“…reported the Q and e values of 0.78 and 0.17, respectively, for TBM in conventional bulk radical copolymerization with styrene at 60°C . In our previous paper, we determined the Q and e values of HFIPM as 1.21 and 1.19, respectively, in conventional radical copolymerization with styrene in ethyl acetate at 60°C. Subsequently, we calculated the r HFIPM and r TBM as 0.46 and 0.77, respectively, under Alfrey and Price's Q – e framework.…”

“…Recently, we reported the systematic study of PMMA and three derivatives with trifluoromethyl groups, namely poly(2,2,2‐trifluoroethyl methacrylate) (PTFEM), poly(1,1,1,3,3,3‐hexafluoroisopropyl methacrylate) (PHFIPM), and poly(nonafluoro‐ tert ‐butyl methacrylate) (PNFTBM), as binders and PtTFPP as the luminescent dye in a PSP (Chart ) . In a detailed temperature sensitivity analysis of PSP coating comprising PtTFPP and these polymers, we identified two structural features that are crucial for reducing the temperature sensitivity.…”

“…Because the analyte of PSP is the oxygen molecule, the permeability of oxygen molecules in the polymer matrix is essential for successful measurement. Typical oxygen‐permeable polymers in PSP applications are polydimethylsiloxane, fluorinated polymethacrylates and poly(3‐trimethylsilyl‐1‐propyne) …”

Fabrication of asymmetrically superhydrophobic cotton fabrics via mist copolymerization of 2,2,2‐trifluoroethyl methacrylate

“…We designed a novel functional copolymer as shown in Scheme . By comparing with other highly fluorinated monomers often used for fabricating superhydrophobic surfaces, monomer of 2,2,2‐trifluoroethyl methacrylate (TFMA) is inexpensive and environmentally friendly . Meanwhile, 2‐isocyanatoethyl methacrylate (IEM) could covalently link the copolymer chains onto the cotton surface through the reaction between the isocyanate group and the hydroxyl groups in cellulose.…”

“…inexpensive and environmentally friendly. [37][38][39][40] Meanwhile, 2isocyanatoethyl methacrylate (IEM) could covalently link the copolymer chains onto the cotton surface through the reaction between the isocyanate group and the hydroxyl groups in cellulose. Monomer of divinylbenzene (DVB) was expected to increase nanoscale roughness by forming cross-linkages between the copolymer chains.…”