寻找具有预定物理化学和化学性质的新发光团。十四。聚(3 -氨基丙烯)的n -芳基亚甲基和n -己基亚甲基衍生物

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引用次数: 0

摘要

研究了用Leykart-Wallach反应与芳香族或杂环醛烷基化聚(3-氨基丙烯)(PAP)衍生物与自身荧光合成聚合物的可能性。采用丙烯酰胺→PAA (Mν = 100 kDa)→PAP→烷基化PAP的顺序转化法制备n -烷基化PAP衍生物。由于PAA在非水(乙醚、四氢呋喃等)溶剂中溶解度低,无法用LiAlH4将聚丙烯酰胺的酰胺基还原为胺,因此优化了其他还原剂对PAA的还原。结果表明,以胺-乙酸-二恶烷为溶剂,以NaBH4(悬浮在无水的1,4-二恶烷中)为还原剂还原PAA酰胺基的最佳条件。通过红外光谱分析,得到的产物为3-氨基丙烯(基本单元的主要量)、丙烯酰胺和丙烯酸的共聚物。为了修饰所得聚合物的结构,使用Leuckart-Wallach反应,其中选择以下具有发光的醛:pyrene3 -aldehyde, 2-羟基-1-naphthaldehyde,蒽-9-carbaldehyde和3.5 phenyl-1-(4-甲酰基苯基)-2-pyrazoline。为了得到N-Ar/ het -亚甲基衍生物,PAP、醛和98%甲酸的混合物在恶劣条件下(甘油浴6小时)加热,分离纯化。所获得的改性聚合物样品在固态和溶液形式下都具有强烈的荧光,这表明Leykart-Wallach反应成功通过。得到了混合溶剂-乙酸乙酯-甲酸溶液的光谱特征。1).对于原始醛类和共聚物,光谱荧光曲线都失去了振荡结构,这可能是由于混合溶剂对荧光粉分子(用于原始醛类)和处于基态和激发态的甲基氨基- n -芳基亚甲基-[…СН2-СН(СН2-NH-CH2-Ar)-…]和甲基氨基- n -基亚甲基[…-СН2-СН(СН2-NH-CH2-Het)-…]基团的特定作用。对于介质不均匀的聚合物具有局部极性区。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Search for new luminophores with predetermined physicochemical and chemical properties. XIV.N-Arylmethylene- and N-hetarylmethylene derivatives of poly (3‒aminopropene)
The possibility of creating polymers with fluorescence, derivatives of poly (3-aminopropene) (PAP) by alkylation of amino groups with aromatic or heterocyclic aldehydes by Leykart-Wallach reaction with own fluorescence was investigated. Synthesis of N-alkylated PAP derivatives was performed by sequential conversion: acrylamide → PAA (Mν = 100 kDa) → PAP → alkylated PAP. Due to the impossibility of using LiAlH4 to reduce the amide groups of polyacrylamide to amine due to the low solubility of PAA in the non-aqueous (diethyl ether, tetrahydrofuran, etc.) solvents, the reduction of PAA by other reducing agents was optimized. It was found that the best conditions for the reduction of amide groups of PAA to amine - acetic acid - dioxane as a solvent and NaBH4 (suspended in anhydrous 1,4-dioxane) as a reducing agent. According to IR spectroscopy, the products obtained are copolymers of 3-aminopropene (the main amount of elementary units), acrylamide and acrylic acid. To modify the structure of the obtained polymer, the Leuckart-Wallach reaction was used, where the following aldehydes having luminescence were selected: pyrene-3-aldehyde, 2-hydroxy-1-naphthaldehyde, anthracene-9-carbaldehyde, and 3.5 phenyl-1-(4-formylphenyl)-2-pyrazoline. To obtain N-Ar/Het-methylene derivatives, a mixture of PAP, aldehyde and 98% formic acid was heated under harsh conditions (6 hours, glycerol bath), isolated and purified. The obtained modified samples of polymers are intensely fluorescent both in the solid state and in the form of solutions, which indicates the successful passage of the Leykart-Wallach reaction. Spectral characteristics were obtained for solutions in a mixed solvent – ethyl acetate – formic acid (9 : 1). For both the original aldehydes and the copolymers in the mixed solvent used, the spectral fluorescence curves lose their oscillatory structure, probably due to the specific effect of the mixed solvent on the phosphor molecules (for the original aldehydes) and the side methylamino-N-arylmethylene - […СН2-СН(СН2-NH-CH2-Ar)- …] and methylamino-N-getarylmethylene […-СН2-СН(СН2-NH-CH2-Het)-…] groups both in the ground and in the excited state, and for polymers of inhomogeneity of the medium with local polarity zones.
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