CN115466220A - 一种具有三阶非线性光学性能的双偶氮五元唑环单体及其聚合物和制备方法 - Google Patents

一种具有三阶非线性光学性能的双偶氮五元唑环单体及其聚合物和制备方法 Download PDF

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CN115466220A
CN115466220A CN202210958899.2A CN202210958899A CN115466220A CN 115466220 A CN115466220 A CN 115466220A CN 202210958899 A CN202210958899 A CN 202210958899A CN 115466220 A CN115466220 A CN 115466220A
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张良
钱宗钰
黄壮
季亚楠
薛梦娜
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Yancheng Institute of Technology
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Abstract

本发明公开了一种具有三阶非线性光学性能的双偶氮五元唑环单体及其聚合物和制备方法。该聚合物的单体由含五元唑环偶氮结构中间体与N‑(2‑羟乙基)‑N‑乙基苯胺通过重氮偶合反应得到双偶氮中间体，再与甲基丙烯酰氯反应得到，再通过原子转移自由基聚合方法得到该侧链型功能聚合物。本发明制得的单体和聚合物，其三阶非线性光学性能得到大幅提高，且具有较好的加工性能。

Description

一种具有三阶非线性光学性能的双偶氮五元唑环单体及其聚 合物和制备方法
技术领域
本发明属于光学材料技术领域，具体涉及一种具有三阶非线性光学性能的双偶氮五元唑环单体及其聚合物和制备方法。
背景技术
随着激光技术的发展和广泛应用，光电子技术已经成为重要的高新技术，包括光通讯、光信息处理、全息技术、光计算机等。但是，激光本身只能提供有限波长的高强度相干光源，如果要对激光束进行调频、调幅、调相、调偏等调制操作，就必须依靠一些材料的非线性光学效应来完成。在这些材料中，聚合物类非线性光学材料受到格外的关注，因为与无机和有机非线性光学材料相比，聚合物有其得天独厚的优势，它除了继承了有机小分子非线性光学材料的非线性光学系数大、响应速度快、直流介电常数低等优点外，由于其分子链以共价键连接，因此材料的机械强度高、化学稳定性好、加工性能优良，可以根据使用要求制成各种形状，如膜、片、纤维等。
原子转移自由基聚合(ATRP)方法是1995年由Matyjaszewski和Sawamoto 课题组几乎同时发现的，这种聚合方法是以可逆的卤原子转移为基础，通过氧化还原反应，卤原子从有活性的烷基卤化物(R-X)上转移到低价的过渡金属化合物上，形成烷基自由基(R·)和高价态的金属络合物(X-Mn+1t-Y/Ligand 盐)。烷基自由基与单体发生加成反应，生成中间体(R-M·)，再从高价态的金属络合物中夺取卤素，如此往复循环，伴随着自由基活性种与大分子有机卤化物休眠种之间的可逆动态平衡，实现对聚合反应的有效控制(见ATRP反应机理)。原子转移自由基聚合兼具自由基聚合和活性聚合的优点，适用单体范围广，在较温和的条件下经过简单的合成路线就可以合成结构规整的聚合物，得到的聚合物分子量分布指数比较窄，就尽可能的排除了由于分布指数的不同造成对聚合物三阶非线性光学性能的影响。此外，聚合物在聚合过程中数均分子量随反应时间而线性增长，因此从理论上可以得到任意分子量的聚合物。
Figure BDA0003790958930000021
ATRP反应机理
在申请号200610155971.9的专利中已报道了具有三阶非线性光学性能的偶氮单体及其聚合物，聚合物具有良好的三阶非线性光学性能，且成膜性较好，但聚合物三阶非线性极化率系数离实际应用仍有一定距离，因此需要一种能够大幅提高极化率系数的材料，使其更具应用价值。
发明内容
解决的技术问题：针对上述技术问题，本发明提供了一种具有三阶非线性光学性能的双偶氮五元唑环单体及其聚合物和制备方法，通过在结构体系中引入杂环替代苯环可以有效降低离域能，增加偶氮结构则可以提高共轭性，从而大幅提高三阶非线性极化率系数，使聚合物的三阶非线性光学性能大幅提高，且具有较好的加工性能。
技术方案：一种具有三阶非线性光学性能的双偶氮五元唑环单体，由下述通式(I)表示：
Figure BDA0003790958930000022
式中，R1表示氮、氧或硫原子；
R2表示氢、硝基、氰基、氯、溴或甲氧基。
一种具有三阶非线性光学性能的含双偶氮五元唑环结构的聚合物，由下述通式(II)表示：
Figure BDA0003790958930000023
式中，R1表示氮、氧或硫原子；
R2表示氢、硝基、氰基、氯、溴或甲氧基；
n表示20～100的整数。
其中，通式(I)表示的单体的制备方法，包括以下步骤：
a.制备含五元唑环偶氮结构中间体的盐溶液，所述含五元唑环偶氮结构中间体为通式(III)的一种；
Figure BDA0003790958930000031
式中，R1表示氮、氧或硫原子；
R2表示氢、硝基、氰基、氯、溴或甲氧基；
b.以N-(2-羟乙基)-N-乙基苯胺为偶合试剂，在pH＝1～3进行重氮偶合反应，将含有亚硝酸钠、N-(2-羟乙基)-N-乙基苯胺的氢氧化钠水溶液冷却至2℃以下，搅拌下将其滴入含五元唑环偶氮结构中间体的盐溶液，保持反应温度低于2℃，滴加完毕在5℃以下继续搅拌5小时，将反应液抽滤并用水洗涤得到含五元唑环双偶氮结构的中间体；
c.以摩尔质量份计，取1份干燥后的含五元唑环双偶氮结构的中间体溶入四氢呋喃中，加1～2份的附酸剂，滴加2～3份的甲基丙烯酰氯，在冰浴下反应 1～3小时，再在常温下反应4～6小时，倒入水中析出所需化合物。
优选的，步骤a中所述盐溶液为硫酸盐溶液。
优选的，步骤b中N-(2-羟乙基)-N-乙基苯胺的摩尔质量与含五元唑环偶氮结构中间体的摩尔质量相等。
优选的，步骤c中所述附酸剂为三乙胺。
通式(II)表示的聚合物的制备方法，步骤如下：采用通式(I)表示的化合物作为单体，加入单体摩尔用量的0.5～5％的引发剂、0.5～5％的催化剂和0.5～ 10％的配体，加溶剂搅拌后除尽聚合管中氧气，封管，置油浴中进行原子转移自由基聚合反应，油浴温度为60～120℃，反应时间1～5天，用乙酸乙酯析出聚合物，再用乙酸乙酯洗涤除去残余单体，即得所需聚合物。
优选的，所述引发剂为α-溴代异丁酸乙酯、苄氯、苄溴或1-氯甲烷。
优选的，所述催化剂为氯化亚铁或溴化亚铜；所述配体为五甲基二乙烯三胺或三苯基膦。
优选的，所述溶剂为环己酮、甲苯、苯甲醚、四氢呋喃或对二甲苯。
上述制备方法可以表示如下：
Figure BDA0003790958930000041
式中，R1表示氮、氧或硫原子；
R2表示氢、硝基、氰基、氯、溴或甲氧基。
有益效果：1.本发明获得了一种可用于自由基聚合的烯类单体，从而，由功能性单体聚合得到聚合物，所得聚合物有优异的宏观的三阶非线性极化率系数；
2.本发明获得的聚合物主链为甲基丙烯酸酯，侧链含有烷基结构，聚合物表现出良好的溶解性和成膜性，制成膜后表现出优异的三阶非线性极化率系数，在光学器件上具有更高的应用价值；
3.通过引入五元唑环和增加共轭偶氮结构数量，大幅提高材料三阶非线性极化率系数；
4.通过改变五元唑环上取代基可以产生不同的电子效应，从而能调节聚合物的三阶非线性光学性能；
5.通过原子转移自由基聚合方法实现聚合，所得聚合物可调节分子量，并且减少由于链的长短不一造成的对三阶非线性光学性能的影响。
具体实施方式
下面结合具体实施例对本发明作进一步描述。
实施例1
取0.5-3g含咪唑环偶氮结构的中间体制成硫酸盐溶液，置于冰浴中冷却。
取N-(2-羟乙基)-N-乙基苯胺1-4g，亚硝酸钠0.5-2g，加入氢氧化钠水溶液配成溶液，并用冰浴冷却至2℃以下。在搅拌下将N-(2-羟乙基)-N-乙基苯胺溶液慢慢滴加到硫酸盐溶液中，同时保持温度低于2℃。滴加完毕继续在5℃以下搅拌5小时，将反应液抽滤并用大量去离子水洗涤得到含咪唑环双偶氮结构的中间体。
取含咪唑环双偶氮结构的中间体1-4g，溶于40mL四氢呋喃，加1～3mL 三乙胺，在冰浴下搅拌均匀。取1-3g甲基丙烯酰氯慢慢滴加到上述溶液中，在冰浴下反应1～3小时，再在常温下反应4～6小时。反应液倒入水中析出并重结晶得到含咪唑环双偶氮结构的单体。用Z-扫描方法测得该单体的一个试样的三阶非线性极化率系数为9.41×10-11esu。
在聚合管中加入含咪唑环双偶氮结构的单体400-550mg，按照单体/α-溴代异丁酸乙酯/氯化亚铁/三苯基膦＝80-120/1/1/1的摩尔配比称取其它的配料，加入环己酮2-6mL，搅匀后除尽管中氧气并充氮气保护，封管后置于80-110℃油浴中反应三天。聚合液用乙酸乙酯沉析并洗涤，抽滤烘干得到聚合产物。由凝胶渗透色谱测得该聚合物的一个试样的数均分子量为14600，分子量分布指数为 1.22；由Z-扫描方法测得其三阶非线性极化率系数为9.12×10-10esu。
实施例2
取0.5-3g含5-甲氧基噁唑环偶氮结构的中间体制成硫酸盐溶液，置于冰浴中冷却。
取N-(2-羟乙基)-N-乙基苯胺1-4g，亚硝酸钠0.5-2g，加入氢氧化钠水溶液配成溶液，并用冰浴冷却至2℃以下。在搅拌下将N-(2-羟乙基)-N-乙基苯胺溶液慢慢滴加到硫酸盐溶液中，同时保持温度低于2℃。滴加完毕继续在5℃以下搅拌5小时，将反应液抽滤并用大量去离子水洗涤得到含5-甲氧基噁唑环双偶氮结构的中间体。
取含5-甲氧基噁唑环双偶氮结构的中间体1-4g，溶于40mL四氢呋喃，加1～3mL三乙胺，在冰浴下搅拌均匀。取1-3g甲基丙烯酰氯慢慢滴加到上述溶液中，在冰浴下反应1～3小时，再在常温下反应4～6小时。反应液倒入水中析出并重结晶得到含5-甲氧基噁唑环双偶氮结构的单体。用Z-扫描方法测得该单体的一个试样的三阶非线性极化率系数为6.64×10-11esu。
在聚合管中加入含5-甲氧基噁唑环双偶氮结构的单体400-550mg，按照单体 /α-溴代异丁酸乙酯/氯化亚铁/三苯基膦＝80-120/1/1/1的摩尔配比称取其它的配料，加入环己酮2-6mL，搅匀后除尽管中氧气并充氮气保护，封管后置 80-110℃油浴中反应三天。聚合液用乙酸乙酯沉析并洗涤，抽滤烘干得到聚合产物。由凝胶渗透色谱测得该聚合物的一个试样的数均分子量为15700，分子量分布指数为1.20；由Z-扫描方法测得其三阶非线性极化率系数为1.21×10-10esu。
实施例3
取0.5-3g含5-硝基噻唑环偶氮结构的中间体制成硫酸盐溶液，置于冰浴中冷却。
取N-(2-羟乙基)-N-乙基苯胺1-4g，亚硝酸钠0.5-2g，加入氢氧化钠水溶液配成溶液，并用冰浴冷却至2℃以下。在搅拌下将N-(2-羟乙基)-N-乙基苯胺溶液慢慢滴加到硫酸盐溶液中，同时保持温度低于2℃。滴加完毕继续在5℃以下搅拌5小时，将反应液抽滤并用大量去离子水洗涤得到含5-硝基噻唑环双偶氮结构的中间体。
取含5-硝基噻唑环双偶氮结构的中间体1-4g，溶于40mL四氢呋喃，加 1～3mL三乙胺，在冰浴下搅拌均匀。取1-3g甲基丙烯酰氯慢慢滴加到上述溶液中，在冰浴下反应1～3小时，再在常温下反应4～6小时。反应液倒入水中析出并重结晶得到含5-硝基噻唑环双偶氮结构的单体。用Z-扫描方法测得该单体的一个试样的三阶非线性极化率系数为5.97×10- 10esu。
在聚合管中加入含5-硝基噻唑环双偶氮结构的单体400-550mg，按照单体/ α-溴代异丁酸乙酯/氯化亚铁/三苯基膦＝80-120/1/1/1的摩尔配比称取其它的配料，加入环己酮2-6mL，搅匀后除尽管中氧气并充氮气保护，封管后置80-110℃油浴中反应三天。聚合液用乙酸乙酯沉析并洗涤，抽滤烘干得到聚合产物。由凝胶渗透色谱测得该聚合物的一个试样的数均分子量为11300，分子量分布指数为1.35；由Z-扫描方法测得其三阶非线性极化率系数为1.27×10-9esu。

Claims (10)

1.一种具有三阶非线性光学性能的双偶氮五元唑环单体，其特征在于，由下述通式(I)表示：
Figure FDA0003790958920000011
式中，R1表示氮、氧或硫原子；
R2表示氢、硝基、氰基、氯、溴或甲氧基。
2.由权利要求1所述单体制得的聚合物，其特征在于，由下述通式(II)表示：
Figure FDA0003790958920000012
式中，R1表示氮、氧或硫原子；
R2表示氢、硝基、氰基、氯、溴或甲氧基；
n表示20～100的整数。
3.权利要求1所述单体的制备方法，其特征在于，包括以下步骤：
a.制备含五元唑环偶氮结构中间体的盐溶液，所述含五元唑环偶氮结构中间体为通式(III)的一种；
Figure FDA0003790958920000013
式中，R1表示氮、氧或硫原子；
R2表示氢、硝基、氰基、氯、溴或甲氧基；
b.以N-(2-羟乙基)-N-乙基苯胺为偶合试剂，在pH＝1～3进行重氮偶合反应，将含有亚硝酸钠、N-(2-羟乙基)-N-乙基苯胺的氢氧化钠水溶液冷却至2℃以下，搅拌下将其滴入含五元唑环偶氮结构中间体的盐溶液，保持反应温度低于2℃，滴加完毕在5℃以下继续搅拌5小时，将反应液抽滤并用水洗涤得到含五元唑环双偶氮结构的中间体；
c.以摩尔质量份计，取1份干燥后的含五元唑环双偶氮结构的中间体溶入四氢呋喃中，加1～2份的附酸剂，滴加2～3份的甲基丙烯酰氯，在冰浴下反应1～3小时，再在常温下反应4～6小时，倒入水中析出所需化合物。
4.根据权利要求3所述的单体的制备方法，其特征在于，步骤a中所述盐溶液为硫酸盐溶液。
5.根据权利要求3所述的单体的制备方法，其特征在于，步骤b中N-(2-羟乙基)-N-乙基苯胺的摩尔质量与含五元唑环偶氮结构中间体的摩尔质量相等。
6.根据权利要求3所述的单体的制备方法，其特征在于，步骤c中所述附酸剂为三乙胺。
7.权利要求2所述的聚合物的制备方法，其特征在于，步骤如下：采用通式(I)表示的化合物作为单体，加入单体摩尔用量的0.5～5％的引发剂、0.5～5％的催化剂和0.5～10％的配体，加溶剂搅拌后除尽聚合管中氧气，封管，置油浴中进行原子转移自由基聚合反应，油浴温度为60～120℃，反应时间1～5天，用乙酸乙酯析出聚合物，再用乙酸乙酯洗涤除去残余单体，即得所需聚合物。
8.根据权利要求7所述的聚合物的制备方法，其特征在于，所述引发剂为α-溴代异丁酸乙酯、苄氯、苄溴或1-氯甲烷。
9.根据权利要求7所述的聚合物的制备方法，其特征在于，所述催化剂为氯化亚铁或溴化亚铜；所述配体为五甲基二乙烯三胺或三苯基膦。
10.根据权利要求7所述的聚合物的制备方法，其特征在于，所述溶剂为环己酮、甲苯、苯甲醚、四氢呋喃或对二甲苯。
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