Synthesis of Blue Emitting Alicyclic Polyimides using One-pot Alternating Copolymerization Method
Synthesis of Blue Emitting Alicyclic Polyimides using One-pot Alternating Copolymerization Method
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DOI：
10.1177/0954008306068252
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发表时间：
2006-10
影响因子：
2.1
通讯作者：
K. Kudo;Takahiro Imai;T. Hamada;S. Sakamoto
中科院分区：
文献类型：
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作者：
K. Kudo;Takahiro Imai;T. Hamada;S. Sakamoto
合成了一系列具有高蓝光9，10-二苯基菲单元的交替共聚酰亚胺(AltPI)，并对其光致发光进行了研究。基于rel[1R，5S，6R]-3-oxabicyclo[3.2.1]octane-2，4-dione-6-spiro-3--(tetrahydrofuran-2-，5--dione)对芳香胺独特的区域选择性开环反应，将两个二胺依次加到螺脂环四元酸二酸酐(DAN)的溶液中，制备了ALT-PI。通过与相应的无规化合物的~1H核磁共振比较，证实了聚酰亚胺的交替结构。λ的玻璃化转变温度高于240℃，5%的失重温度范围为335~376℃。聚酰亚胺在二甲基亚砜溶液中呈现蓝色荧光(AltPI max=435~436 nm)，荧光量子产率为0.64~0.77。在薄膜状态下，虽然与溶液状态相比观察到了较小的红移，但AltPI发出了蓝光(λmax=437-447 nm)。
A series of alternating copolyimides (altPIs) having highly blue fluorescing 9,10-diphenyl-anthracene units were synthesized and the photoluminescence of the altPIs were investigated. The alt-PIs were prepared by sequential addition of two diamines to a solution of spiroalicyclic tetracarboxylic dianhydride, rel[1R,5S,6R]-3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3--(tetrahydrofuran-2-,5--dione) (DAn), on the basis of the unique regioselective ring opening reactivity of DAn to the aromatic amines. The alternating structure of the polyimides was confirmed by comparison of its 1H NMR with that of the corresponding random counterparts. The altPIs showed glass transition temperature higher than 240°C. A 5% weight loss temperature was in a range of 335 to 376°C. The polyimides showed blue fluorescence (λmax = 435 to 436 nm) in DMSO solution with a fluorescence quantum yield of 0.64 to 0.77. In the film state, although small red shift was observed compared to the solution state, the altPIs gave blue emission (λmax = 437 to 447 nm).