可溶性近红外吸收剂氨基酞菁的合成及应用

Synthesis and application of soluble near-infrared absorption amino phthalocyanine dyes

通过先合成脂肪氨基邻苯二腈再合成酞菁的工艺制备了一系列可溶性近红外吸收氨基酞菁。采用核磁共振氢谱(1H NMR)、红外光谱(FT-IR)、溶解性实验、紫外吸收光谱(UV-Vis)、热重分析法(TGA)对氨基酞菁的结构和性能进行了表征。结果表明成功合成了不同结构的氨基酞菁。在酞菁外围-位取代脂肪族氨基以及采用Mn2+配位,可以得到较高溶解性的氨基酞菁。脂肪族氨基的供电子性能,尤其是-位取代,配合Mn2+,可使酞菁Q带出现较大红移,3,3′,3″,3--四正丁氨基锰酞菁(α-Tn BAMn Pc)在三氯甲烷溶液中的最大吸收波长可达870 nm。研究了α-Tn BAMn Pc在聚甲基丙烯酸甲酯(PMMA)和水性聚氨酯(WPU)中的近红外吸收性能,在PMMA膜片中,α-Tn BAMn Pc的添加量超过0.60%(质量分数)时,在862 nm波长处透过率为0;在WPU涂层中,α-Tn BAMn Pc含量超过0.40%(质量分数)时,在866 nm波长处透过率为0。

A series of soluble near-infrared absorption amino phthalocyanine dyes were synthesized with preparation of amino phthalonitriles firstly. The structure and performance of phthalocyanines were characterized by 1H NMR, Fourier transform infrared spectroscopy（FT-IR）, solution test, UV-visible absorption spectroscopy（UV-Vis）, thermal gravimetric analysis（TGA）. The results showed that amino phthalocyanines were successfully synthesized. The solubility of amino phthalocyanines was greatly influenced by substituents, position of the substituents and metal ions. When aliphatic amine was used as the peripheral substituent at α position and Mn2＋was used as the central substituent of phthalocyanine, solubility could greatly be increased. A red-shift of the Q-band was observed when aliphatic amine and Mn2＋ were introduced into phthalocyanine, mainly due to the electron-donating ability of aliphatic amine. The 3, 3′, 3″, 3α-tetra-n-butyl amine manganese（Ⅱ） phthalocyanine（α-Tn BAMn Pc） showed Q-band peak at 870 nm in chloroform. The near-infrared absorption performance of α-Tn BAMn Pc in poly（methyl methacrylate）（PMMA） and waterborne polyurethane（WPU） films was investigated. For PMMA-（α-Tn BAMn Pc） films, the transmission at 862 nm was near 0 when the content of α-Tn BAMn Pc was more than 0.60%（mass）. The transmission at 866 nm approached 0 with the content of α-Tn BAMn Pc beyond 0.40%（mass） for WPU-（ α-Tn BAMn Pc） films.