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通过Suzuki偶联聚合反应合成了3种具有较高相对分子质量的主链含金刚烷共聚单体的聚芴P1~3,聚合产率均在90%以上。热重分析表明,P1~3的分解温度分别达到412、420和430℃。紫外和光致发光(PL)光谱表明,改性后的聚芴比均聚物聚(9,9-二己基芴)(PF6)具有抑制的链簇集行为。所有共聚物的PL主峰均位于423 nm左右,且P2的薄膜态荧光量子效率达到0.56。热退火PL光谱研究表明,共聚物的绿光发射强度随金刚烷摩尔分数的增加而降低,在200℃处理1 h后,P1、P2和P3在520 nm处的与绿光发射相关的荧光相对强度仅为0.084、0.083和0.065,均远远低于PF6的0.225。
Three kinds of polyfluorenes P1 ~ 3 with main chain adamantane comonomers with higher relative molecular mass were synthesized by Suzuki coupling polymerization. The polymerization yields were above 90%. Thermogravimetric analysis showed that the decomposition temperatures of P1 ~ 3 reached 412, 420 and 430 ℃ respectively. Ultraviolet and photoluminescence (PL) spectroscopy showed that the modified polyfluorene had a suppressed cluster behavior than the homopolymer poly (9,9-dihexylfluorene) (PF6). The PL peaks of all the copolymers are all around 423 nm, and the fluorescence quantum efficiency of P2 in the film state reaches 0.56. The results of thermal annealing PL spectra showed that the green emission intensity of the copolymer decreased with the increase of the molar fraction of adamantane. The fluorescence related to green emission of P1, P2 and P3 at 520 nm after treatment at 200 ℃ for 1 h was The intensities are only 0.084, 0.083 and 0.065, which are much lower than 0.225 of PF6.