Study on the Molecular Design of Photoconductive Compounds for the Irradiation Systems with Visible or Ultraviolet Light and Their Photophysical Chemistry Properties
|School||Dalian University of Technology|
|Keywords||Anthraquinone Spiropyran Photochromic Photobleaching Photopolymerizable|
With the development of information technology, holographic data storage as an alternative to traditional magnetic storage technology has been more widely appreciated. Photopolymerizable materials with high sensitivity, high resolution, high diffraction efficiency, wide spectral response, easy processing, latitude, storage stability, etc., as an ideal holographic recording materials, become a research hotspot. In the photopolymerizable material system, photoinitiator play a pivotal role, directly determines the efficiency and impact of light-induced polymerization, the development of efficient, superior performance photoinitiators utmost importance. This paper synthesized amino anthraquinone and spiropyran two sensitive to visible light and ultraviolet photoinitiator, the synthesized also investigated photoinitiator photoexcitation intramolecular electron transfer properties, and its in the visible, or ultraviolet polymerization initiator system performance testing. First, the molecular design, synthesis of amino-anthraquinone photoinitiator sensitive to visible light. From 1,5 - diamino-anthraquinone and 1,5 - dichloro-anthraquinone departure, after alkylation, condensation, esterification reaction of a secondary amine synthesized anthraquinone, anthraquinone and a tertiary amino group containing acrylate anthraquinone group of seven sensitive to visible light function compounds. By IR, MS, 1H-NMR of these initiators were characterized. Secondly, the design and synthesis of spiropyran class UV sensitive photoinitiators. Salicylaldehyde used as a starting material, after nitration, condensation, Friedel-Crafts, synthesized by esterification reaction of two five-step containing a cationic group and a cinnamate group containing spiropyran photochromic optical functional compounds. By MS, 1H-NMR, 13C-NMR, g-COSY, g-HSQC and other methods were characterized. Again, photobleaching experiments using amino anthraquinone compound of the visible light function primary photoreaction tested molecule to introduce a photopolymerizable acrylate functional groups of the light compound / o-hexaaryl bisimidazole (HABI) system photobleaching rate is relatively fast, highly efficient photoinitiator performance. By UV - visible spectroscopy, tested three spiropyran compound light function photochromic properties, was found to contain a cationic group trimethylamine spiropyran compounds, with reversible photochromic properties, it also showed acid photochromic properties. Tertiary amine-containing cationic group eighteen spiropyran compounds, tertiary amines as eighteen long carbon chain effect, just showing normal photochromic properties. Cinnamate functional groups containing spiropyran initiator in addition to a photochromic properties, it can also produce light-induced polymerization. Finally, each type of optical functional amino anthraquinone compounds and spiropyran compounds like optical functional visible or ultraviolet light induced polymerization initiator system in the performance of the test results show that the amino-anthraquinone compounds in the polymerization system in the visible light induced monomers can be effectively photopolymerization initiator, a double bond conversion of about 68% can be achieved. And as a reference without initiator system, double bond conversion rate was about 8%. For the cationic group-containing light function spiropyran compounds can be used as effective UV initiator photopolymerization initiator, double conversion rate up to 70%, and no optical functional spiropyran compound initiator system, a double bond about 10% conversion rate. Also found that amines can effectively prevent light-induced free radicals generated by oxygen quenching, serve to shift the role of free radicals in the whole polymerization system plays a key role. Which contains a cinnamate group spiropyran light absorbing agent is used as initiator and initiator added to the polymerization, the amine compound is added to the polymerization reaction does not promote, but reduced the polymerization rate.