Study On The Photosensitized Synthesis Of Quadricyclane

Quadricyclane is a kind liquid hydrocarbon with highly strained structure and high density, which makes it an efficient propellant for rocket and position controlling agent of missiles. Meanwhile, quadricyclane has attracted considerable attention in the field of solar energy storage.In this thesis, quadricyclane is produced in the absence of solvent, with 4, 4'-bis(diethylamino)benzophenone as the triplet sensitizer. We study two reaction systems to produce quadricyclane of high purity. Also the kinetics is explored in self-designed reactor.Because of the coke formation in the static photoreactor, it can't obtain quadricyclane of high purity. To overcome the shortcoming, we change the clean reactor during the reaction period. Then the conversion reaches 99% and the selectivity reaches 100%. To restrain the coke formation, the circulation photoreactor is designed. In contrast with the static reactor, the circulation reactor has obvious merits as follows: (1) the restraint of the coke formation (2) the decrease of the sensitizer needed (3) the reduction of time for reaction.For the two kinds of reactors, the invovlement of conversion with the time and sensitizer concentration is studied. Using the circulation reactor, the kinetics of reaction is studied and the activation energy is found as 29.173 kJ/mol.The quadricyclane of high purity is obtained by vacuum distillation. The product is identified by ¹HNMR and ¹³CNMR. It is found that quadricyclane can reverse to norbornadiene under improper keeping condition. To avoid the reverse reaction from quadricyclane to norbornadiene, a little triethylamine is needed to add to the quadricyclane.