Poly[bis(triphenylamine) ether]s with low glass transition temperatures as photoconductors in fast photorefractive systems
作者:Ostrauskaite, Jolita、Karickal, Haridas R.、Leopold, Andre、Haarer, Dietrich、Thelakkat, Mukundan
DOI:10.1039/b105930k
日期:2002.12.10
A series of photoconducting poly(tetraphenyldiaminobiphenylene alkyl ether)s in which tetraphenyldiaminobiphenyl (TPD) units are covalently linked through flexible oligomethylene glycol spacers in the main chain were synthesized and the thermal, optical and electrochemical properties were studied. Due to the introduction of flexible spacers, the polymers are highly soluble and could be obtained as film-forming materials with appreciably high molecular weights. The polymers exhibit glass transition temperatures between 92 °C and 128 °C which is about 100 °C less than those main chain polymeric bis(triphenylamine)s without such spacers. The HOMO value as determined from cyclic voltammetry is about −5.1 eV. The glass transition temperature of the photorefractive composites prepared by mixing the different polymers with an electro-optic chromophore, 1-(2-ethylhexyloxy)-2,5-dimethyl-4-(4-nitrophenylazo)benzene,
EHDNPB, could be tuned over a wide range about room temperature by just changing the photoconductor and without the need of any additional amount of plasticizer. Degenerate four-wave mixing and two-beam coupling in composites with the composition, photoconductor ∶ EHDNPB ∶ C60
(60 ∶ 39 ∶ 1 by wt/wt%) results in refractive index modulations of 10−3 with corresponding response time ∼10 ms and a photorefractive gain of Γ = 13 cm−1 for a writing beam intensity of 1 W cm−2
(645 nm) under an external electric field of 60 V µm−1.
一系列在主链上通过柔性低聚亚甲基二醇间隔基共价连接四苯基二氨基联苯(TPD)单元的光导聚(四苯基二氨基联苯烷基醚)被合成,并研究了其热学、光学和电化学性质。由于引入了柔性间隔基,这些聚合物具有高溶解性,并可获得具有相当高分子量的成膜材料。这些聚合物表现出92至128°C的玻璃化转变温度,比没有此类间隔基的主链聚双(三苯胺)低约100°C。从循环伏安法测得的HOMO值约为-5.1 eV。通过将不同聚合物与电光染料1-(2-乙基己氧基)-2,5-二甲基-4-(4-硝基苯偶氮)苯,EHDNPB混合制备的光折变复合材料的玻璃化转变温度,可以通过仅改变光导体而不需要任何额外增塑剂的量,在室温附近广泛范围内调节。具有组成光导体∶EHDNPB∶C60(重量比60∶39∶1%)的复合材料中退化四波混频和双光束耦合导致折射率调制为10-3,相应的响应时间约为10毫秒,并且在60 V μm-1的外加电场下,对于1 W cm-2(645 nm)的写入光束强度,光折变增益为Γ=13 cm-1。