CN1252145C - 连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷及其制法和用途 - Google Patents
连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷及其制法和用途 Download PDFInfo
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Abstract
本发明涉及连有偶氮吲哚发色团的二阶非线性光学聚硅氧烷,具有以下通式:式中x=0.05~0.60,n=30-100,R为吲哚基团或咔唑基团。将侧链连有吲哚基团的聚硅氧烷高分子与对硝基苯基重氮氟硼酸盐反应得该类高分子化合物。该类高分子具有较高的二阶非线性光学性能和良好的综合性能,可以在远程通讯、数据存储、相位共轭等方面得到实际应用。
Description
技术领域
本发明涉及连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷高分子材料及其制备方法和用途。
背景技术
非线性光学(NLO)材料是激光技术的重要物质基础之一,是高技术研究的一个组成部分。三十多年来,非线性光学已经逐步发展成一门独立的光学分支,非线性光学材料则在激光的倍频、混频、参量放大与振荡、集成光学、光学通讯等各个方面有着不可缺少的重要作用,它们可以用来控制光束的相位、偏振态或频率,还可用来存储和恢复信息或使光束偏转,使之在光纤信道之间传输光信息。常见的非线性光学材料主要有无机晶体材料、半导体材料、有机晶体材料、金属有机晶体材料、有机高分子材料等。其中,二阶非线性光学高分子材料(包括电光材料和光折变材料)由于其良好的溶解加工性能、结构可调性和高的非线性光学性能等优点,从而吸引了众多科学家的研究兴趣和研究热情。而结构明确、性能稳定的键合型高分子材料更是备受瞩目。虽然这方面的研究已有不短的历史,但设计、合成键合型的二阶非线性光学高分子材料仍然具有较大的挑战性。这方面的报道参见相关文献(如Moerner W.E.,Jepsen A.G.,Thompson C.L.,Anna Rev Mater Sci[J],1997,27:585-623.Moerner W.E.,Silence S.M.,Chem Rev,1994,94:127.)。
吲哚是一种苯并杂环,在结构上与咔唑相似,但体积却小许多,已有的研究表明连有以吲哚基团取代咔唑基团作为电荷给予体部分的发色团作为侧链的高分子可以体现出很大的二阶非线性光学效应,其二阶非线性光学系数d33值可以达到49pm/V。(Moon H.,Hwang J.,Kim N.,Park S.Y.,Macromolecules,2000,33:5116-5123.)可是,文献报道的合成路线比较长,小分子的分离不太容易。
发明内容
本发明的目的就在于提供一种连有偶氮吲哚发色团的二阶非线性光学聚硅氧烷及其制法和用途。该类高分子不仅合成方便,而且纯化简单,可作为新型光学材料在远程通讯、数据存储、相位共轭等方面的得到实际应用。
本发明提供的技术方案是:连有偶氮吲哚发色团的二阶非线性光学聚硅氧烷,具有以下通式:
式中x=0.05~0.60,n=30-100,R为吲哚基团或咔唑基团。
本发明还提供了上述二阶非线性聚硅氧烷的制备方法,将1摩尔连有吲哚基团和R基团的聚硅氧烷高分子溶于N-甲基吡咯烷酮中(质量百分比浓度为8~15%),加入0.05~0.60摩尔对硝基苯基重氮氟硼酸盐,然后在0~5℃反应6~10小时;加入0.05~0.60摩尔的无水碳酸钾,在0~5℃反应1~2小时,分离、纯化即得所需连有偶氮吲哚发色团的二阶非线性聚硅氧烷;上述R基团为吲哚基团或咔唑基团。
本发明的连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷高分子可以作为新型光学材料在远程通讯、数据存储、相位共轭等方面的实际应用。
本发明的优点集中在以下几个方面:
1.本发明连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷高分子的合成简单,纯化方便,反应条件较为温和。
2.本发明介绍的连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷高分子具有很高的二阶非线性光学性能(实施例1和2中高分子的d33分别为25和27pm/V)。
3.本发明描述了一种崭新的连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷高分子的制备,丰富了二阶非线性光学材料化学研究的内容,从一定程度上拓展了二阶非线性光学高分子合成化学的方法。
具体实施方式
实施例1:
R为吲哚基团,x为0.40时,合成路线如下:
合成方法为:在装有搅拌磁子的Schlenk管中,加入含氢硅油、N-烯丙基吲哚、少许二氯二聚环戊二烯合铂催化剂、无水甲苯,在氩气保护条件下于60℃搅拌反应48小时,冷却至室温,减压蒸去大量溶剂。再加入适量甲醇,放入冰箱冷冻两小时后,倒出上层清液,将沉淀溶于少量三氯甲烷,再用甲醇重沉淀,如此数次,得浅绿色粘稠固体聚硅氧烷1,40℃真空干燥。其中含氢硅油与N-烯丙基吲哚的摩尔数比为1∶2。
称取上述200毫克聚硅氧烷高分子1,放入一30ml试管中,加入N-甲基吡咯烷酮(使得到的溶液质量百分比浓度为8~15%),室温搅拌至高分子完全溶解,冰浴,待溶液温度降至0℃后,加入87毫克新制的对硝基苯基重氮氟硼酸盐,冰浴条件下反应8小时,然后加入0.2克无水K2CO3,保持冰浴条件,继续搅拌1小时,过滤,用四氢呋喃清洗反应试管,收集滤液,减压抽去四氢呋喃,加入30ml甲醇,得到红色的沉淀,过滤,收集红色固体,用甲醇洗涤数次,真空干燥,即得所需连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷(聚(吲哚基)(偶氮吲哚基)硅氧烷)2。
实施例2:
R为咔唑基团,x为0.37时,合成路线如下:
合成方法为:在装有搅拌磁子的Schlenk管中,加入含氢硅油、N-烯丙基吲哚、少许二氯二聚环戊二烯合铂催化剂、无水甲苯,在氩气保护条件下于60℃搅拌反应48小时,冷却至室温,然后加入N-烯丙基咔唑,在氩气保护条件下于60℃继续搅拌反应60小时,减压蒸去大量溶剂。再加入适量甲醇,放入冰箱冷冻两小时后,倒出上层清液,将沉淀溶于少量三氯甲烷,再用甲醇重沉淀,如此数次,得浅白色固体聚硅氧烷P1,40℃真空干燥。其中上述所用含氢硅油与N-烯丙基吲哚、N-烯丙基咔唑的摩尔数比为1∶0.4∶1.5。
称取上述260毫克聚硅氧烷高分子P1,放入一30ml试管中,加入N-甲基吡咯烷酮(使得到的溶液质量百分比浓度为8~15%),室温搅拌至高分子完全溶解,冰浴,待溶液温度降至0℃后,加入102毫克新制的对硝基苯基重氮氟硼酸盐,冰浴条件下反应8小时,然后加入0.25克无水K2CO3,保持冰浴条件,继续搅拌1小时,过滤,用四氢呋喃清洗反应试管,收集滤液,减压抽去四氢呋喃,加入30ml甲醇,得到红色的沉淀,过滤,收集红色固体,用甲醇洗涤数次,真空干燥,即得所需连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷(聚(咔唑基)(偶氮吲哚基)硅氧烷)P2。
Claims (3)
2权利要求1所述的二阶非线性光学聚硅氧烷的制法,其特征在于:将1摩尔连有吲哚基团和R基团的聚硅氧烷高分子溶于质量百分比浓度为8~15%的N-甲基吡咯烷酮中,加入0.05~0.60摩尔的对硝基苯基重氮氟硼酸盐,然后在0~5℃反应6~10小时;加入0.05~0.60摩尔的无水碳酸钾,反应1~2小时,分离、纯化即得所需连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷;上述R基团为吲哚基团或咔唑基团。
3权利要求1所述连有偶氮吲哚发色团侧基的二阶非线性光学聚硅氧烷用作为远程通讯、数据存储、相位共轭方面的光学材料。
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