Oxygen-Sensing Properties of 5,10,15,20-Tetraphenylporphinato Platinum(II) and Palladium(II) Covalently Bound on Poly(isobutyl-co-2,2,2-trifluoroethyl methacrylate)
Oxygen-Sensing Properties of 5,10,15,20-Tetraphenylporphinato Platinum(II) and Palladium(II) Covalently Bound on Poly(isobutyl-co-2,2,2-trifluoroethyl methacrylate)
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DOI：
10.1002/pola.23818
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发表时间：
2010-02-01
影响因子：
--
通讯作者：
Yano, Shigenobu
中科院分区：
文献类型：
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作者：
Obata, Makoto;Matsuura, Noriko;Yano, Shigenobu
合成了一种含有5,10,15,20-四苯基卟啉钯（PdTPP）（单体1a）的新型甲基丙烯酸酯单体，并与甲基丙烯酸异丁酯（IBM）和2,2,2-三氟甲基丙烯酸乙酯（TFEM）共聚，得到了含有PdTPP（共聚物2a）的聚（IBM-co-TFEM），作为一种用于压敏涂料的染料共轭透氧聚合物。通过紫外-可见光谱和扩展x射线吸收精细结构分析证实了PdTPP在共聚物2a中的引入。共聚物2a和PdTPP与poly的混合物（IBM-co-TFEM）的Stern-Volmer图都显示向下弯曲，这与先前报道的铂配合物类似物（共聚物2b）不同。利用二元模型拟合得到两个不同的Stern-Volmer常数（K-SV1和K-SV2）和分割比f(1)。有趣的是，共聚物2a的f(1)值几乎恒定在0.98左右，而PdTPP和poly的混合物（IBM-co-TFEM）的f(1)值随着温度的升高从0.889增加到0.967。这一发现表明，在PdTPP和poly（IBM-co-TFEM）的混合物中存在两种不同的微非均质性，一种与温度相关，另一种与温度无关。染料共轭方法有效地消除了温度相关的微非均质性，但不能消除与温度无关的微非均质性。在无氧条件下，共聚物2a和2b及其混合物的发光衰减表明，温度依赖的微观非均质性涉及氧扩散过程，而温度无关的微观非均质性似乎是PdTPP的固有性质。(C) 2009 Wiley期刊公司高分子材料学报，2010,31 (2):663- 667
A novel methacrylate monomer bearing 5,10,15,20-tetraphenyl porphyrinato palladium(II) (PdTPP) (monomer 1a) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2-trifluoroethyl methacrylate (TFEM) to give poly (IBM-co-TFEM) bearing PdTPP (copolymer 2a) as a dye-conjugated oxygen-permeable polymer for pressure-sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV-vis spectroscopy and extended X-ray absorption fine structure analysis. The Stern-Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM-co-TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b) previously reported. The plots were successfully fitted with a two-site model to give two distinct Stern-Volmer constants (K-SV1 and K-SV2) and the partition ratio f(1). Interestingly, the f(1) values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM-co-TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature-dependent and the other temperature-independent, in the mixture of PdTPP and poly(IBM-co-TFEM). The dye-conjugation approach effectively eliminates the temperature-dependent, but not the temperature-independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature-dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature-independent one appears to be inherent nature in PdTPP. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 663-670, 2010