Hyperbranched polyimides (HB PIs) have unique mac romolecule structures allowing introduction of large number of functional groups. These polymers are of inter est as polymeric supports,1 active components of gas sep aration2 and proton exchange3 membranes, optical mate rials,4 etc. Earlier, we have described one pot versatile synthesis of HB PIs by high temperature polycondensation of 2,4,6 triaminotoluene sulfate (TAT) with 4,4 ́ [propane 2,2 diylbis(4,1 phenyleneoxy)]diphthalic dianhydride (PBPA) in catalytic media comprising melted benzoic acid (BA) and tertiary amine.5 This method shows significant advantages as compared with a conventional two step polymeric precursor method. The BA melt is a good solvent for a large variety of PIs. Being environmentally friendly, synthesis of PIs in the BA melt6 proceeds with a very high rate (due to catalysis of acylation step) and provides the easiness of isolation of the polymer (due to microphase separation in the reaction mixture upon cooling). In the present work, we describe the synthesis of a novel trifunctional monomer, 2,4,6 tris(4 aminophenoxy)tolu ene (TAPT, 1). Polycondensation of TAPT with PBPA in BA at 140 C following A2+B3 procedure affords a novel HB PI (Scheme 1). In contrast to TAT, which is prone to oxidation and can be used only as salts formed by TAT with strong acids, TAPT is isolable as a free base. The synthetic scheme towards TAPT involves two steps (see Scheme 1): (i) synthesis of 2,4,6 tris(4 nitrophenoxy) toluene (2) by condensation of 2 methylphloroglucinol (3)7 with 1 fluoro 4 nitrobenzene (4) in the presence of K2CO3 and (ii) subsequent reduction of nitro groups with hydrazine hydrate. Structures of the synthesized com pounds were examined by 1H NMR spectroscopy, IR spectroscopy, elemental analysis, and DSC. IR spectrum of the isolated polymeric product con tains absorptions at 1790 and 1720 cm–1 characteristic of imide rings thus confirming its polyimide structure. Poly imide is soluble in DMSO, DMF, DMAA, THF, and

中文翻译：

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2,4,6-三(4-氨基苯氧基)甲苯和由其衍生的超支化聚酰亚胺

超支化聚酰亚胺 (HB PI) 具有独特的大分子结构，可以引入大量官能团。这些聚合物可用作聚合物载体、1 气体分离 2 和质子交换 3 膜的活性成分、光学材料 4 等。 早些时候，我们已经描述了通过 2,4 的高温缩聚一锅多功能合成 HB PI， 6 三氨基甲苯硫酸盐 (TAT) 与 4,4 ́ [丙烷 2,2 二基双(4,1 苯氧基)]二邻苯二甲酸二酐 (PBPA) 在包含熔融苯甲酸 (BA) 和叔胺的催化介质中。5 这种方法显示出显着的优势与传统的两步聚合前体方法相比。BA 熔体是多种 PI 的良好溶剂。由于环保，在 BA 熔体中 PI 的合成以非常高的速率进行（由于酰化步骤的催化作用），并且易于分离聚合物（由于冷却时反应混合物中的微相分离）。在目前的工作中，我们描述了一种新型三官能单体 2,4,6 三（4 氨基苯氧基）甲苯 (TAPT, 1) 的合成。TAPT 与 PBPA 在 BA 中在 140 C 下按照 A2+B3 程序缩聚得到一种新的 HB PI（方案 1）。与 TAT 容易氧化并且只能作为 TAT 与强酸形成的盐使用相比，TAPT 可作为游离碱分离。TAPT 的合成方案包括两个步骤（参见方案 1）：（i）2,4 的合成，6 三(4 硝基苯氧基) 甲苯 (2) 通过 2 甲基间苯三酚 (3)7 与 1 氟 4 硝基苯 (4) 在 K2CO3 存在下缩合和 (ii) 随后用水合肼还原硝基。通过 1 H NMR 光谱、IR 光谱、元素分析和 DSC 检查合成化合物的结构。分离的聚合物产品的 IR 光谱包含在 1790 和 1720 cm-1 处具有酰亚胺环特征的吸收，从而证实了其聚酰亚胺结构。聚酰亚胺可溶于 DMSO、DMF、DMAA、THF 和 分离的聚合物产品的 IR 光谱包含在 1790 和 1720 cm-1 处具有酰亚胺环特征的吸收，从而证实了其聚酰亚胺结构。聚酰亚胺可溶于 DMSO、DMF、DMAA、THF 和 分离的聚合物产品的 IR 光谱包含在 1790 和 1720 cm-1 处具有酰亚胺环特征的吸收，从而证实了其聚酰亚胺结构。聚酰亚胺可溶于 DMSO、DMF、DMAA、THF 和