CN110627800B - 一种光可逆刺激响应荧光材料及其应用 - Google Patents

一种光可逆刺激响应荧光材料及其应用 Download PDF

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CN110627800B
CN110627800B CN201910902305.4A CN201910902305A CN110627800B CN 110627800 B CN110627800 B CN 110627800B CN 201910902305 A CN201910902305 A CN 201910902305A CN 110627800 B CN110627800 B CN 110627800B
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徐斌
杨闰清
田文晶
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Abstract

一种光可逆刺激响应荧光材料及其在应用，属于光致变色材料技术领域。具体分子结构为以四苯基乙烯、三苯胺和螺吡喃为基本结构单元，通过酯化反应合成的一类不对称光致变色材料。在固体状态下经过365nm的紫外灯照射前后会表现出截然不同的紫外‑可见吸收光谱和(或)荧光发射光谱的双重颜色变化。在经过可见光长时间照射之后，发生变化的材料的紫外‑可见吸收光谱和(或)荧光发射光谱会可逆复原为初始的颜色及状态，具有优良的抗疲劳性、稳定性和可逆性。该材料可以单独溶解在有机溶剂中涂抹使用，可以掺杂进聚合物中通过静电纺丝和铺膜等方式做成复合材料，作为光可逆材料应用在防伪、颜色可逆聚合物薄膜等领域。

Description

一种光可逆刺激响应荧光材料及其应用
技术领域
本发明属于光致变色材料技术领域，具体涉及一种光可逆刺激响应荧光材料及其在防伪、颜色可逆聚合物薄膜等领域中的应用。
背景技术
光致变色材料是指某一特定的材料，在某一特定波长的光的照射下其结构发生转变，并且伴随着紫外-可见吸收或发生光谱的变化；在另一特定波长的光的照射或加热处理时其结构又可以变为原来状态。基于其优秀的性质，光致变色材料在光能记忆、涂料、信息储存和防伪等领域的潜在应用价值受到越来越多的重视。螺吡喃(SP)分子为一经典光致变色分子，其在逻辑门、多重刺激响应等领域均有较大的潜在应用价值。但是该分子只在溶液状态具有光致变色性质，在聚集状态下由于分子堆积紧密导致无法实现光致变色性质，这极大的限制了其实际应用(Adv,Mater.2017,29,1605271)。
聚集诱导发光(AIE)材料的发现解决了荧光材料在聚集状态下荧光淬灭 (ACQ)问题，这类材料本身具有较为扭曲的结构，在单分子状态下由于分子内振转运动导致不发或发出较为微弱的荧光，但在聚集之后分子内振转运动受到限制，因此会发出明亮的荧光，并且分子本身的扭曲结构也同时会为紧密堆积的分子创造一定的空间(Chem.Commun.2009,4332-4353；Chem.Soc.Rev.2011,40,5361- 5388)。
中国专利CN105670389A公布了一种基于螺吡喃和AIE分子的光致变色材料，其在紫外灯和加热两种刺激下具有可逆的光学性质。但是该材料本身为较明显的黄色，无论是掺杂进聚合物中还是实际防伪喷涂中显现出的颜色会进一步遮盖被标记物本身的颜色，并且该材料需要与热源直接接触来实现颜色变化的可逆返回，实际应用较为局限。因此，发明一种无色，并且仅依靠光刺激、无需与刺激媒介直接接触就可实现可逆变化的材料，在光能记忆、信息长距离传输和防伪等领域具有较大潜在的应用价值。
发明内容
本发明提出的一种光可逆刺激响应荧光材料，具体分子结构为以四苯基乙烯(TPE)、三苯胺(TPA)和螺吡喃(SP)为基本结构单元，通过酯化反应合成的一类不对称光致变色材料。研究发现这一类材料在固体状态下经过365nm的紫外灯照射前后会表现出截然不同的紫外-可见吸收光谱和(或)荧光发射光谱的双重颜色变化。在经过可见光长时间照射之后，之前被紫外灯照射所导致发生变化的材料的紫外-可见吸收光谱和(或)荧光发射光谱会可逆复原为初始的颜色及状态，具有优良的抗疲劳性、稳定性和可逆性。
本发明所述的光可逆刺激响应荧光材料，以四苯基乙烯(TPE)、三苯胺(TPA) 和螺吡喃(SP)为基本结构单元，通过酯键将螺吡喃(SP)和四苯基乙烯(TPE) 或三苯胺(TPA)连接，其结构式如下所示：
Figure BDA0002212200410000021
其中R为H、CH3、OCH3或N(CH3)2；
进一步，本发明所述的光可逆刺激响应荧光材料，其结构式如下之一所示：
Figure BDA0002212200410000022
Figure BDA0002212200410000031
具有上述任意一种结构的光可逆刺激响应荧光材料，其固态粉末在经过 365nm紫外灯照射之后，其可见吸收光谱和荧光发射光谱均会发生明显的变化，经过波长大于450nm的灯光不停照射12小时后，其可见吸收光谱和荧光发射光谱均能可逆变为未被紫外灯照射的状态。这种光刺激可逆变化可以重复500次以上。
具有上述任意一种结构的光可逆刺激响应荧光材料，不仅可以单独使用，而且可以通过掺杂搅拌进聚合物(聚甲基丙烯酸甲酯、聚丙烯腈、聚乙烯、聚苯乙烯、酚醛树脂等)中，作为光可逆刺激响应材料，应用在防伪、颜色可逆聚合物薄膜等诸多领域。
附图说明
图1：为实施例1制备的光致变色材料在石英片上经过旋涂方式形成的薄膜在365nm紫外灯照射前后的紫外吸收光谱，插图是薄膜在经过紫外灯和450nm 灯光交替照射5次过程中588nm处吸光度的变化曲线；
图2：为实施例1制备的光致变色材料在石英片上经过旋涂方式形成的薄膜在365nm紫外灯照射前后的荧光发射光谱，插图是其薄膜在经过紫外灯和450nm 灯光交替照射5次过程中荧光发射波长的变化曲线；
图3：为实施例1制备的光致变色材料溶解在二氯甲烷中喷涂在滤纸上在紫外灯照射前后形成的鲤鱼跃龙门图案以及在黑暗环境中图案的荧光颜色变化的照片；
图4：为实施例1制备的光致变色材料掺杂进聚丙烯腈中经过静电纺丝形成白色薄膜在紫外灯照射前后的不同图案的写入和擦除的照片；
图5：为实施例1制备的光致变色材料掺杂进聚甲基丙烯酸甲酯中经过滴涂法形成的透明薄膜在紫外灯照射前后的图案的写入与擦除的照片。
具体实施方法
本发明给出了一类具有光可逆刺激响应荧光材料的合成方法及其在防伪、可逆聚合物薄膜等领域中的应用。
实施例1：
Figure BDA0002212200410000041
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(1,2,2-三苯基乙烯基)苯酚(1mmol，348mg)。将反应装置置于冰水浴中2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺(1.5mmol， 309mg)的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。
后处理：将反应中的不溶物通过抽滤除去，收集滤液倒入分液漏斗中，先用 0.5M的盐酸溶液洗涤两次，然后用饱和的碳酸氢钠溶液洗涤两次。紧接着收集有机相溶液，加入无水硫酸钠干燥，过滤除无水硫酸钠固体，通过减压蒸馏将滤液中的溶剂除去。最后得到的产物经过硅胶柱分离提纯(石油醚/二氯甲烷，1：1 v/v)，得到的产物TPE-SP为淡绿色粉末(378.6mg,52％)。
1H NMR(500MHz,CDCl3)δ8.09–7.93(m,2H),7.22(t,J＝7.6Hz,1H),7.18 –7.07(m,9H),7.02(dd,J＝10.0,6.4Hz,8H),6.93(dd,J＝16.5,9.8Hz,3H),6.80– 6.72(m,3H),6.67(d,J＝7.7Hz,1H),5.89(d,J＝10.3Hz,1H),3.74(dt,J＝14.8,7.4 Hz,1H),3.68–3.50(m,1H),3.04–2.87(m,1H),2.87–2.69(m,1H),1.29(s,3H), 1.17(s,3H).LC-MS(ESI):m/z:计算值:710.83，实验值：711.52[M+H]+。元素分析实验值(计算值):C 79.5(79.42)，H 5.4(5.39)，N 3.9(3.94)。
实施例2：
Figure BDA0002212200410000051
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(1-苯基-2,2-二甲苯基乙烯基)苯酚(1mmol，377mg)。将反应装置置于冰水浴中2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺 (1.5mmol，309mg)的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。后处理的详细步骤同例 1。最后得到的产物b-TPE-SP为淡绿色粉末(363mg,48％)。
LC-MS(ESI):m/z:计算值:738.88，实验值：739.65[M+H]+。元素分析实验值(计算值):C 79.7(79.65)，H 5.8(5.73)，N 3.8(3.79)。
实施例3：
Figure BDA0002212200410000052
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(2,2-二(4-甲氧苯基)-1-苯基乙烯基)苯酚(1mmol，409mg)。将反应装置置于冰水浴中2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺(1.5mmol，309mg)的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。后处理的详细步骤同例 1。最后得到的产物c-TPE-SP为淡绿色粉末(458mg,58％)。
LC-MS(ESI):m/z:计算值:770.88，实验值：771.53[M+H]+。元素分析实验值 (计算值):C 76.3(76.35)，H 5.5(5.49)，N 3.7(3.63)。
实施例4：
Figure BDA0002212200410000061
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(2,2-二(4-二甲氨基)苯基-1-苯基乙烯基)苯酚(1mmol，435mg)。将反应装置置于冰水浴中2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺(1.5mmol，309mg)的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌 10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。后处理的详细步骤同例1。最后得到的产物d-TPE-SP为淡绿色粉末(326mg,40％)。
LC-MS(ESI):m/z:计算值:796.97，实验值：797.88[M+H]+。元素分析实验值(计算值):C 76.9(76.86)，H 6.1(6.07)，N 7.0(7.03)。
实施例5：
Figure BDA0002212200410000062
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(二苯胺基)苯酚(1mmol，261mg)。将反应装置置于冰水浴中2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺(1.5mmol，309mg)的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。后处理的详细步骤同例1。最后得到的产物TPA- SP为淡蓝色粉末(333mg,52％)。
LC-MS(ESI):m/z:计算值:623.71，实验值：624.56[M+H]+。元素分析实验值(计算值):C 75.1(75.10)，H 5.4(5.33)，N 6.8(6.74)。
实施例6：
Figure BDA0002212200410000071
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(二甲苯基氨基)苯酚(1mmol，289mg)。将反应装置置于冰水浴中2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺(1.5mmol，309mg) 的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。后处理的详细步骤同例1。最后得到的产物 b-TPA-SP为淡蓝色粉末(335mg,50％)。
LC-MS(ESI):m/z:计算值:651.76，实验值：652.50[M+H]+。元素分析实验值(计算值):C 75.6(75.56)，H 5.7(5.72)，N 6.5(6.45)。
实施例7：
Figure BDA0002212200410000081
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(二(4-甲氧苯基)氨基)苯酚(1mmol，321mg)。将反应装置置于冰水浴中2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺(1.5mmol， 309mg)的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。后处理的详细步骤同例1。最后得到的产物c-TPA-SP为淡蓝色粉末(386mg,55％)。
LC-MS(ESI):m/z:计算值:683.76，实验值：684.67[M+H]+。元素分析实验值(计算值):C 72.0(72.02)，H 5.5(5.45)，N 6.2(6.15)。
实施例8：
Figure BDA0002212200410000082
合成步骤：在50mL两口圆底烧瓶中加入6mL干燥的无水二氯甲烷溶液，然后依次加入4-二甲基吡啶(1.5mg)、1-羧乙基吲哚啉螺吡喃分子(1mmol，380mg) 和4-(二(4-(二甲氨基)苯基)氨基)苯酚(1mmol，347mg)。将反应装置置于冰水浴中 2分钟，待溶液降温到0℃后向反应体系里缓慢滴加二环己基碳二亚胺(1.5mmol， 309mg)的二氯甲烷溶液(4mL)。之后保持反应处在0℃搅拌10min，最后将冰水浴撤去，待反应在常温环境中搅拌反应12h。后处理的详细步骤同例1。最后得到的产物d-TPA-SP为淡蓝色粉末(519mg,40％)。
LC-MS(ESI):m/z:计算值:709.85，实验值：710.78[M+H]+。元素分析实验值(计算值):C 72.8(72.76)，H 6.1(6.11)，N 9.9(9.87)。
实施例9：
将实施例1制备的光致可逆变色材料按照20mg/mL的浓度溶解在四氢呋喃中，通过旋涂均匀涂在石英片上，溶剂蒸发干后形成60nm厚的薄膜。刚制备的薄膜肉眼可见为无色，黑暗环境中365nm紫外灯照射下初始为青色荧光；在 365nm紫外灯持续照射5分钟后薄膜颜色肉眼可见为深蓝色，在黑暗环境中为红色荧光。图1为薄膜在365nm紫外灯持续照射前后的紫外-可见吸收光谱。初始薄膜在320nm有吸收峰，在经过紫外灯照射后在588nm处出现一个新的吸收峰。图2为薄膜在365nm紫外灯持续照射前后的荧光发射光谱。初始薄膜在456nm有发射峰，在经过紫外灯照射后在672nm处出现一个新的发射峰。在经过450nm 的蓝光灯持续照射12小时之后，薄膜的吸收光谱和荧光发射光谱均恢复为初始峰位。图1和图2中的插图为薄膜在经过紫外灯和蓝光灯交替照射后的可逆性及抗疲劳性测试，显示了材料较好的性质。
实施例10：
将实施例1制备的光致可逆变色材料按照1mg/mL的浓度溶解在二氯甲烷中，喷涂在挡有镂空的带有“鲤鱼跃龙门”图案的铁板的滤纸上。为了对比突出颜色变化，“龙门”图案使用不具有光致变色性质的罗丹明B溶液进行喷涂；“鲤鱼和池塘”图案使用实施例1的二氯甲烷溶液进行喷涂。待溶剂挥发完全，“鲤鱼和池塘”图案在可见光下为无色(图3a)，在黑暗环境中为青色荧光(图3c)，“龙门”图案为粉红色(图3a)，在黑暗环境中为红色荧光(图3a)；经过紫外灯照射5分钟后，“鲤鱼和池塘”图案在可见光下为蓝紫色(图3b)，在黑暗环境中为红色荧光(图3d)，“龙门”图案颜色和荧光没有变化。之后用450nm蓝光灯照射图案12小时，图案颜色和荧光均恢复为初始颜色(图3a)和荧光颜色(图 3c)。
实施例11：
将实施例1制备的光致可逆变色材料(5mg)掺杂进聚丙烯腈(1g)的N,N- 二甲基甲酰胺(9.5mL)溶液中，通过静电纺丝技术制得10厘米*10厘米大小的白色薄膜。该薄膜同样具有光致可逆变色的性质，具体展示如图4所示：初始薄膜为白色(图4a)，紧接着用紫外灯照射上方放置有镂空“小鹿”图案铁板的薄膜，照射部位出现紫色“小鹿”图案(图4b)，接下来用日光灯照射图案部位2小时，图案颜色褪去(图4c)；接着用紫外灯照射上方放置有镂空“枫叶”图案铁板的薄膜，照射部位出现紫色“枫叶”图案(图4 d)，接下来用日光灯照射图案部位2小时，图案颜色褪去；接着更换带有不同图案的铁板重复上述步骤，薄膜出现不同图案(图4e和图4f)；最后用蓝光灯照射带有图案的部位，图案颜色褪去，薄膜颜色恢复为初始白色(图4a)。
实施例12：
将实施例1制备的光致可逆变色材料(10mg)掺杂进的聚甲基丙烯酸甲酯 (1g)的N,N-二甲基甲酰胺(9.5mL)溶液中，通过真空流式法制得10厘米*10 厘米大小的透明薄膜(图5a)。接着用紫外灯照射上方放置有镂空“小鹿”图案铁板的薄膜，只有照射部位出现紫色“小鹿”图案，薄膜其余部位均为无色透明(图 5b)；接下来用日光灯照射图案部位2小时，图案颜色褪去，整个薄膜恢复为初始的无色透明状态(图5a)，具有可逆性。

Claims (3)

1.一种光可逆刺激响应荧光材料，其结构式如下所示：
Figure FDA0003070434910000011
其中R为H、CH3、OCH3或N(CH3)2。
2.如权利要求1所述的一种光可逆刺激响应荧光材料，其特征在于：其结构式如下之一所示，
Figure FDA0003070434910000012
3.权利要求1或2所述的一种光可逆刺激响应荧光材料在防伪或颜色可逆聚合物薄膜领域中的应用。
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