苝酰亚胺聚合物染料掺杂聚乙烯醇薄膜滤光片的制备及其激光防护性能研究

Preparation and laser protection performance of perylene imide polymeric dye-doped polyvinyl alcohol film filter

以1,7-二溴-N,N′-二[(2-二甲胺基)乙基]-3,4,9,10-苝酰亚胺为原料,通过Suzuki偶联反应合成了一种苝酰亚胺聚合物染料P(NDME-Ph)n,然后通过季胺化反应得到了一种水溶性的苝酰亚胺聚合物染料MI-P(NDME-Ph)n。将两种聚合物染料P(NDME-Ph)n和MI-P(NDME-Ph)n分别掺杂到聚乙烯醇(PVA)中后得到不同性能的复合薄膜滤光片。紫外吸收光谱研究表明P(NDME-Ph)n和MI-P(NDME-Ph)n两种染料在紫外-可见光范围内均有吸收,同时吸光度随着染料浓度的增加而升高。P(NDME-Ph)n的最大吸收波长位于548nm, MI-P(NDME-Ph)n则表现出吸收峰随着染料浓度增加而出现显著的红移,通过透射电镜表征证实MI-P(NDME-Ph)n在水溶液中存在聚集现象。然而,P(NDME-Ph)n在PVA中因溶解低、分散不均匀而存在的染料颗粒降低了复合薄膜滤光片的激光防护性能。在PVA中,MI-P(NDME-Ph)n受到氢键作用其聚集被抑制,因此复合薄膜同时具有较好的可见光吸收性能和耐热性能。当MI-P(NDME-Ph)n含量为1.25%时,复合薄膜在500~600nm波段的平均光透过率为1.28%,对532nm激光的阻隔大于99%,表现出优异的激光防护效果。

A perylene imide polymer dye P(NDME-Ph)n was synthesized by Suzuki coupling reaction from 1,7-dibromo-N,N′-di[(2-dimethylamine)ethyl]-3,4,9,10-peryleneimide,and then a water-soluble perylene imide polymer dye MI-P(NDME-Ph)n was obtained by quaternary amination reaction.The two polymer dyes P(NDME-Ph)n and MI-P(NDME-Ph)n were separately doped into polyvinyl alcohol(PVA)to obtain composite film filters with different properties.UV-Vis spectroscopy showed that both P(NDME-Ph)n and MI-P(NDME-Ph)n had absorption in the UV-Vis range,and the absorption intensity increased with the increase of dye concentration.The maximum absorption wavelength of P(NDME-Ph)n was at 548nm.The absorption peak of MI-P(NDME-Ph)n showed significantly red shift with the increase of dye concentration.The aggregation of MI-P(NDME-Ph)n in aqueous solution was confirmed by TEM.However,the presence of dye particles of P(NDME-Ph)n in PVA caused by low dissolution and uneven dispersion reduced the laser protection performance of the composite film filter.The composite film had good visible light absorption and thermal stability because the aggregation of MI-P(NDME-Ph)n was suppressed by hydrogen bonding in PVA.When the concentration of MI-P(NDME-Ph)n was 1.25wt%,the average transmittance was 1.28%in the 500~600 nm band,and the blocking of 532nm laser was more than 99%,showing excellent laser protection effect.