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)

Abstract

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.

Polymerizable Oxygen Probe Derived from Platinum-Based Porphyrins for Oxygen Sensing and Pressure-Sensitive Paints

“…Obata et al. reported that the temperature sensitivity of poly­( tert -butyl methacrylate) ( T g ∼ 126 °C) was −1.01%/°C . In this work, S T of F1a ( T g ∼ 149 °C) was −0.63%/°C.…”

“…S T s of F1a , F2 , and F3 were −0.63, −0.61, and −0.92%/°C, respectively. Compared with F3 ( T g ∼ 103 °C), the high glass transition temperature ( T g ) could decrease the temperature dependence, ,, so that luminescent intensities of F1a and F2 were less affected by temperature. Obata et al.…”

“…For demonstrating the applicability, the monomer was copolymerized with t -butyl styrene (tBs) to obtain copolymers of poly­(tBs- co -( PtTFPP-1MA )) ( P1a–c , Scheme ) by tuning the molar/weight ratios of the probe in the poly­( t -butyl styrene) [poly­(tBs)] matrix. Poly­(tBs) has been demonstrated as a good matrix for PSP because the steric hindrance of the tertiary butyl group can help the permeation of oxygen molecules in the polymer matrix. , Also, the high glass transition temperature of poly­(tBs) ( T g ∼ 149 °C) as compared with poly­( tert -butyl methacrylate) ( T g ∼ 126 °C) or poly­(isobutyl methacrylate) ( T g ∼ 53 °C) could minimize temperature influence on PSP . For comparison of the chemical linking and physical doping of the probes on sensing, a homopolymer of poly­(tBs) ( P2 ) was synthesized and used as a matrix for physically doping PtTFPP .…”

“…Poly(tBs) has been demonstrated as a good matrix for PSP because the steric hindrance of the tertiary butyl group can help the permeation of oxygen molecules in the polymer matrix. 26,27 Also, the high glass transition temperature of poly(tBs) (T g ∼ 149 °C) 28 as compared with poly(tert-butyl methacrylate) (T g ∼ 126 °C) 29 or poly(isobutyl methacrylate) (T g ∼ 53 °C) 30 could minimize temperature influence on PSP. 29 For comparison of the chemical linking and physical doping of the probes on sensing, a homopolymer of poly(tBs) (P2) was synthesized and used as a matrix for physically doping PtTFPP.…”

“…26,27 Also, the high glass transition temperature of poly(tBs) (T g ∼ 149 °C) 28 as compared with poly(tert-butyl methacrylate) (T g ∼ 126 °C) 29 or poly(isobutyl methacrylate) (T g ∼ 53 °C) 30 could minimize temperature influence on PSP. 29 For comparison of the chemical linking and physical doping of the probes on sensing, a homopolymer of poly(tBs) (P2) was synthesized and used as a matrix for physically doping PtTFPP. Furthermore, for understanding whether the steric hindrance play critical roles in the new polymers, poly(St-co-(PtTFPP-1MA)) (P3) was synthesized.…”