二苯基金刚烷改性3,6-咔唑共聚物的合成及性能

咔唑类蓝色发光材料固有的低玻璃化转变温度严重限制了实际应用，为了解决这个问题，本文制备了一种高稳定性聚咔唑蓝光材料。以单体3，6-二溴-9-（2-乙基己基）咔唑和N-（2-乙基己基）-3，6-二（4，4，5，5-四甲基-1，3，2-二氧硼戊烷-2-基）咔唑、1，3-二（4-溴苯基）金刚烷为原料，以四（三苯基膦）钯为催化剂，通过调整单体比例，经Suzuki反应合成了数均分子量约3500~6000的3，6-咔唑-二苯基金刚烷共聚物。差热扫描量热测试结果表明，在加入摩尔分数分别为10%、30%和50%的二苯基金刚烷后，共聚物玻璃化转变温度从3，6-咔唑均聚物的66℃分别显著升高至78℃、93℃、106℃，热重测试的失重5%热分解温度同样随着二苯基金刚烷含量的升高而升高。低含量二苯基金刚烷改性共聚物的荧光量子产率较3，6-咔唑均聚物高，显示了优良的荧光传递特性。且共聚物薄膜态时的最大荧光发射波长均处于蓝光最适波长范围内。研究结果表明：二苯基金刚烷的加入显著改善了咔唑聚合物的热稳定性能，还改善了发光性能，制备的共聚物是一种非常有应用前景的新型蓝光材料。

Synthesis and properties of diphenyladamantane modified 3,6-carbazole copolymers

The inherent low glass transition temperature of carbazole blue luminescent materials severely limits its practical applications. To solve this problem, a kind of highly stable polycarbazole blue light material was prepared. By using 3,6-dibromo-9-(2-ethylhexyl)carbazole and N-(2-ethylhexyl) -3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole, 1,3-bis(4-bromophenyl)adamantane as the monomers, several 3,6-carbazole-diphenyladamantane copolymers were synthesized by palladium-catalyzed Suzuki coupling reaction. The number average molecular weight of the copolymer was in the range of 3500-6000. The DSC test results showed that after adding 10%, 30% and 50% molar contents of diphenyladamantane, the glass transition temperature of the copolymer significantly rose from 66℃ of the 3,6-carbazole homopolymer to 78℃, 93℃ and 106℃, respectively. As the content of diphenyladamantane increased, the thermal decomposition temperature (at 5% weight loss) of the copolymer also rose. The low-content diphenyladamantane modified copolymer had higher fluorescence quantum yield than the 3,6-carbazole homopolymer, showing excellent fluorescence transfer ability. The maximum fluorescence emission wavelength in the copolymer film state was within the optimal blue light wavelength range. The results showed that the addition of diphenyladamantane significantly improved the thermal stability of the carbazole polymer and the luminescence properties. The prepared copolymer was a new type of blue light emitting material with promising application.