CN114855302B - 一种持久固定其宏观非中心对称排布的有机非线性光学材料的大面积制备及应用 - Google Patents
一种持久固定其宏观非中心对称排布的有机非线性光学材料的大面积制备及应用 Download PDFInfo
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Abstract
本发明属于光学材料技术领域，涉及非线性有机晶体技术领域，具体涉及一种持久固定其宏观非中心对称排布的有机非线性光学材料的大面积制备及应用。本发明首先采用环状低聚糖化合物包合有机非线性晶体形成主‑客体结构的超分子，然后加入交联剂使超分子包合物交联，再利用静电纺丝技术在高压静电场下以及环状化合物的作用下，持久的固化有机非线性材料的非中心对称排列，进而获得具有非线性活性且高稳定性的大面积纳米纤维。同时，该方法获得非线性纤维材料的尺寸可以根据静电纺丝机接收器的进行调节，且制备工艺简单，成本低廉，且材料非线性性能优异，从而极大拓宽了非线性有机晶体的光学应用，使其还可以应用于生物医疗成像领域。
Description
技术领域
本发明属于光学材料技术领域，涉及非线性有机晶体技术领域，具体涉及一种持久固定其宏观非中心对称排布的有机非线性光学材料的大面积制备及应用。
背景技术
非线性光学晶体是一种重要的光电信息功能材料，是光电子技术特别是激光技术的重要物质基础，是高新技术和现代军事技术中不可缺少的关键材料。非线性光学晶体材料的发展程度与激光技术的发展密切相关，因为其可以用来进行激光频率转换，扩展激光的波长；调制激光的强度、相位，实现激光信号的全息存储、消除波前畴变的自泵浦相位共轭等。随着全球信息化浪潮的迅猛发展和光电子技术的广泛应用，国内外对光电功能晶体尤其是非线性光学晶体的市场需求剧增，各发达国家都将其放在优先发展的位置，并将其作为一项重要战略措施列入各自的高技术发展计划中，给予高度的重视和支持。
目前，对有机非线性光学晶体的研究主要集中在二阶非线性光学有机晶体方面。在设计适用于晶体生长的非线性光学有机材料时，不仅要考虑分子本身的非线性，而且要充分考虑分子的结构是否有利于使其实现非中心对称排列。这主要是因为材料的宏观二阶非线性不仅取决于其组成分子(9生色团)的微观非线性，还与生色团的排列取向有关。研究表明，只有形成宏观的非中心对称结构，有机非线性光学材料才能具备高的非线性系数和极快的响应时间，才可以应用在激光频率转换器、光参量振荡器、扩展激光的波长、光电调制器、集成电子器件、实现激光信号的全息存储和太赫兹器件等领域。虽然高非线性有机晶体由于自身具有非对称性的给电子-受体架构，并具有大的偶极矩，一般易于实现自组装。但是，研究表明，有75％的有机材料即使在晶体中取中心对称排列，也不能体现出宏观的二阶非线性，从而大大增加了有机单晶方面的研究难度。当前，虽然搭建有机金属框架Langmuri-Blodgett、场支持下极化排列等方法都可以实现晶体的宏观非线性，但利用上述方法制备得到的有机纳米非线性晶体具有光子传输弱、强激光照射下不稳定，强极性溶剂中容易失去宏观非线性，且制作成本高等不足，导致其难以实现激光频率转换，也不能耦合在集成光电路中。此外，现有的斜板法(An investigation on the growth andcharacterization of DAST crystals grown by two zone growth technique A.S.HajaHameed,W.C.Yub,et al.Journal of crystal growth.2005.117-124.282.)，降温结晶法(Large-Size Bulk and Thin-Film Stilbazolium-Salt Single Crystals forNonlinear Optics and THz Generation.Advanced function materials.2007,2018-2023,17)等制备周期长，单批次获得晶体数目少，不利于大批量生产。因此，研发一种更为简单可行的高稳定性有机非线性材料的制备方法变得势在必行。
发明内容
为了克服上述现有技术的不足，本发明首先采用环状低聚糖化合物包合有机非线性晶体，形成主-客体结构的超分子，然后加入交联剂使超分子包合物交联，并利用静电纺丝技术在高压静电场下和环状化合物的作用下，实现了有机非线性材料的宏观非中心对称排列，同时获得了高稳定性的具有非线性活性的大面积纳米纤维。
为实现上述目的，本发明是通过以下技术方案来实现的：
本发明提供一种有机非线性光学材料的制备方法，具体为：将环状低聚糖化合物、有机非线性晶体原料和交联剂溶解在有机溶剂中制成纺丝液，以环状低聚糖化合物作为主体分子去包合客体分子有机非线性晶体原料，然后通过静电纺丝技术在高压静电场的诱导作用下以及环状化合物的作用下，将纺丝液制成纤维膜，纤维膜再经高温退火后制备得到有机非线性光学材料。
优选地，所述环状低聚糖化合物在有机溶剂中的质量分数的15-35％。
优选地，所述交联剂的质量为环状低聚糖化合物的1-15％，所述有机非线性晶体原料的质量为环状低聚糖化合物的1-5％。
本发明首先将环状低聚糖化合物、交联剂以及有机非线性晶体原料溶解在有机溶剂中制成纺丝液，然后利用静电纺丝技术将纺丝液制成有机非线性光学材料。即首先采用环状低聚糖化合物包合有机非线性晶体，由于环状低聚糖化合物具有空腔结构，可以通过该化合物包合有机非线性材料形成主-客体结构的超分子。然后加入交联剂使超分子包合物交联，再利用静电纺丝技术在高压静电场下和以及环状化合物的作用下，持久的固化了有机非线性材料的非中心对称排列，从而制备得到高稳定性的具有非线性活性且高稳定性的大面积纳米纤维(即有机非线性光学材料)，这种制备方法在制备上转换发光材料几乎未有报道。制备的纤维面积可以为5-100cm(宽度)×5-100cm(长度)，其纤维面积由转轴直径大小(有5,8,10,15cm等不同规格)以及接收平板尺寸决定，可按需调控(比如实施例1采用直径为5厘米的转轴，这样纺丝出来宽度为15厘米的纤维膜，而轴承直径越大，制备的纤维宽度也就越大)。且主客体所采用的包合技术可以形成单分子包合物、多分子包合物以及大分子包合物。
优选地，所述环状低聚糖化合物包括α-，β-，γ-环糊精、甲基-环糊精，二甲基-环糊精、三甲基-环糊精、支连-环糊精、羟丙基-环糊精(HP-βCD)、羟乙基-环糊精、吡喃糖、氨基环糊精或其他环糊精衍生物。具体地，所述环状低聚糖化合物为HP-βCD。
优选地，所述有机非线性晶体原料为苯乙烯基甲基吡啶盐类。
更优选地，所述苯乙烯基甲基吡啶盐类为二甲氨基苯乙烯基甲基吡啶盐类。
进一步地，所述二甲氨基苯乙烯基甲基吡啶盐类包括4-(4-二甲氨基苯乙烯基)甲基吡啶对甲苯磺酸盐(DAST)、4-(4-二甲氨基苯乙烯基)甲基吡啶2，4，6-三甲基苯磺酸盐(DSTMS)、4-(4-二甲氨基苯乙烯基)甲基吡啶萘磺酸盐(DSNS-1)、4-(4-二甲氨基苯乙烯基)甲基吡啶对乙烯基苯磺酸盐(DSSS)、4-(4-二甲氨基苯乙烯基)甲基吡啶2，4-二甲基苯磺酸盐、4-(4-二甲氨基苯乙烯基)甲基吡啶2-萘磺酸盐(DSNS-2)、4-(4-二甲氨基苯乙烯基)甲基吡啶对苯氨基苯磺酸(DSPAS)、4-(4-二甲氨基苯乙烯基)甲基吡啶4-氨基萘磺酸(DSNAS)、4-(4-二甲氨基苯乙烯基)甲基吡啶4-(4-二甲氨基苯基)偶氮甲基苯磺酸(DSMO)、4-(4-二甲氨基苯乙烯基)甲基吡啶对氯苯磺酸盐(DASC)、2-(4-羟基苯乙烯基) 甲基苯并噻唑对甲苯磺酸盐(OHB-T)。具体地，所述二甲氨基苯乙烯基甲基吡啶盐类为 DAST。
优选地，所述高温退火为180-200℃高温处理4-6个小时。具体地，所述高温退火为190℃高温处理5个小时。
优选地，所述交联剂选自通用塑料、工程塑料、特性塑料和有机酸酐。
更优选地，所述通用塑料包括聚乙烯吡咯烷酮(PVP)、聚苯乙烯(PS)、丙烯腈-丁二烯-苯乙烯共聚合物(ABS)、聚乙烯(PE)、聚丙烯(PP)；所述工程塑料包括聚酰胺 (PA)、聚甲醛(POM)；所述特性塑料包括高温尼龙、聚苯硫醚；所述有机酸酐包括甲酸酐、乙酸酐、丙酸酐、顺丁烯二酸酐、邻苯二甲酸酐、丁烷四羧酸(BTCA)、异丁酸酐。具体地，所述交联剂为BTCA。
优选地，所述有机溶剂包括去离子水、二甲基亚砜(DMSO)、N、N二甲基甲酰胺(DMF)、N、N二甲基乙酰胺(DMAC)、N甲基甲酰胺(NMF-1)、N甲氨吗啉(NMF-2)，丙烯腈、氯仿、环己烷、甲苯、二甲苯、吡啶、2-硝基丙烷、炔烃和N-甲基吡咯烷酮(NMP) 中的一种或多种。具体地，所述有机溶剂为DMF。
优选地，静电纺丝时，转速为150-1000rpm/min、纺丝液的推送速率为0.1-20mL/h，针头与转轴的初始距离为5-20cm，针头孔直径为0.1-1mm，电压为5-30kV，温度为 15-60℃。具体地，转速为600rpm/min、纺丝液的推送速率为1mL/h，针头与转轴的初始距离为10cm，针头孔直径为0.5mm，电压为15kV，温度为25℃。
优选地，静电纺丝利用静电纺丝机进行，纺丝前首先将纺丝液装入注射器中，再将注射器装入推送装置上，并在转轴上或者接受板上贴上一层纤维布或者金属铝箔纸。
进一步地，所述注射器规格为1、2.5、5、10、20、50、100mL等，针头孔直径为 0.1-1mm。
本发明还提供了采用上述的制备方法制备得到的有机非线性光学材料。
本发明还提供了上述的有机非线性光学材料在制备光学材料或医疗成像剂方面的应用。
本发明解决了有机非线性晶体在强极性溶剂中容易失去宏观非线性的难题，而且稳固了非线性晶体的光学活性，同时还极大的提高了非线性材料在强极性溶剂中稳定性，使其可以应用在频率转换和双光子成像方面，即可应用于制备光学材料或医疗成像剂。
与现有技术相比，本发明的有益效果是：
本发明首先采用环状低聚糖化合物包合有机非线性晶体形成主-客体结构的超分子，然后加入交联剂使超分子包合物交联，再利用静电纺丝技术在高压静电场下以及环状化合物的作用下，持久的固化有机非线性材料的非中心对称排列，进而获得具有非线性活性且高稳定性的大面积纳米纤维。同时，该方法获得非线性纤维材料的尺寸可以根据静电纺丝机接收器的进行调节，且制备工艺简单，成本低廉，且材料非线性性能优异，从而极大拓宽了非线性有机晶体的光学应用，使其还可以应用于生物医疗成像领域。本发明解决了有机非线性晶体的在强极性溶剂中失去宏观非线性的难题，不仅稳固了非线性晶体的光学活性，而且极大的提高了非线性材料在强极性溶剂中稳定性，使其可以应用在频率转换和双光子成像方面。
附图说明
图1为DAST纺丝纤维膜的实物图；
图2为DAST纺丝纤维膜的电子扫描显微镜(SEM)图；
图3为DAST纺丝纤维膜的瞬态荧光显微镜图；
图4为DAST纺丝纤维膜的变温单光子荧光光谱；
图5为DAST纺丝纤维膜的双光子荧光强度与功率变化关系图；
图6为DAST纺丝纤维膜的在水中浸泡2个月后在365nm光源照射下的图片；
图7为DAST纺丝纤维膜的细胞成像图(左图为明场下的大肠杆菌成像图；右图为1000nm光源下的肠杆菌成像图)；
图8为DAST有机晶体纳米片的荧光显微镜成像图。
具体实施方式
下面对本发明的具体实施方式作进一步说明。在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。此外，下面所描述的本发明各个实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互组合。
下述实施例中的实验方法，如无特殊说明，均为常规方法，下述实施例中所用的试验材料，如无特殊说明，均为可通过常规的商业途径购买得到。
实施例1一种持久固定其宏观非中心对称排布的有机非线性光学材料的大面积制备方法
本实施例采用静电纺丝的方法制备一种可以持久固定宏观非中心对称排布的有机非线性光学材料，且能够满足大面积制备和有效应用的目的。
本实施例所采用的环状低聚糖化合物为羟丙基环糊精(HP-βCD)，选取的有机非线性材料为二甲氨基苯乙烯基甲基吡啶盐类为4-(4-二甲氨基苯乙烯基)甲基吡啶对甲苯磺酸盐(DAST)。具体制备方法包括以下步骤：
(1)将6g HP-βCD、0.065g DAST和0.6g丁烷四羧酸(BTCA)溶解在15mL DMF 中，60℃加热充分搅拌24小时后，获得纺丝溶液；
(2)取5mL纺丝溶液利用静电纺丝机进行纺丝，首先将纺丝液装入5mL注射器(针头孔直径为0.1-1mm)中，再将注射器装入推送装置上，在转轴上或者接受板上贴上一层纤维布或者金属铝箔纸，纺丝机的转轴直径为5cm，转速为600rpm/min、纺丝液的推送速率为1mL/h，针头与转轴的初始距离为10cm，针头孔直径为0.5mm，电压为15kV，温度为25℃，期间保持通风，经上述纺丝操作后制备得到纺丝纤维膜。最后经过高温退火(190℃上高温处理5个小时)处理后获得不溶于水的DAST纺丝纤维膜(简称DAST 纤维)，即宏观非中心对称排布的有机非线性光学材料。如图1所示，为20cm×15cm的DAST纤维。本发明方法可以根据不同的要求制备不同面积尺寸的发光纤维膜。
从图2和3可以看出，采用上述方法制备的DAST纤维直径分布均匀，在荧光显微镜下呈现黄绿色。通过该纤维的变温单光子瞬态荧光光谱(图4)可以看出，该纤维的耐热性好，在450K的温度下依旧具有较高强度的信号。通过图5的双光子荧光强度和泵浦功率关系(测试采用的激发光源为1540nm的飞秒激光)，可以看出，仅仅需要2mW的激发功率，该DAST纤维就可以发生双光子吸收，从而在680nm左右显示出双光子荧光信号。
同时，相比于传统的有机非线性材料，对该DAST纤维进行高温退火后，可以在水中稳定的发光。如图6所示，将该DAST纤维浸泡在水中2个月后，在365nm的紫外光照射下，依旧可以发出黄绿色的荧光。说明该DAST纤维在强极性溶剂中具有较好的稳定性。
此外，将该DAST纤维研磨后投喂给大肠杆菌，发现其可以对大肠杆菌进行标记，利用双光子荧光共聚焦显微镜，可以看到其活体成像图片，如图7所示。因此，该DAST 纤维不仅具有优异的光电信号，可应用于制备光学材料，还具有较好的成像功能，可以应用在生物医疗成像上。
对比例1DAST有机晶体纳米片的制备方法
具体制备方法包括以下步骤：
(1)将0.001g DAST晶体原料加入到5mL甲醇中，在1200rpm/min下搅拌20小时制成DAST-甲醇混合液；
(1)常温下取0.1mL DAST-甲醇混合液，滴加到玻璃亲水基板(表面清洁的玻璃载玻片在紫外臭氧机中清洗30分钟后)上，150℃下蒸发3小时；
(3)蒸发后冷却到室温，将基板移入培养皿中，加再入0.2mL甲醇培养液，将培养皿置于室温下培养36小时，得到DAST有机晶体纳米片。如图8所示，该晶体片在泵浦光的照射下完全分解，在水中更不能长期稳定的保存，所以不能应用于光电集成以及细胞成像等领域。
以上对本发明的实施方式作了详细说明，但本发明不限于所描述的实施方式。对于本领域的技术人员而言，在不脱离本发明原理和精神的情况下，对这些实施方式进行多种变化、修改、替换和变型，仍落入本发明的保护范围内。
Claims (5)
1.一种有机非线性光学材料的制备方法，其特征在于，将环状低聚糖化合物、有机非线性晶体原料和交联剂溶解在有机溶剂中制成纺丝液，以环状低聚糖化合物作为主体分子去包合客体分子有机非线性晶体原料，然后通过静电纺丝技术在高压静电场的诱导作用下以及环状化合物的作用下，将纺丝液制成纤维膜，纤维膜再经高温退火后制备得到有机非线性光学材料；所述环状低聚糖化合物为α-，β-，γ-环糊精、甲基-环糊精，二甲基-环糊精、三甲基-环糊精、羟丙基-环糊精、羟乙基-环糊精、氨基环糊精或其他环糊精衍生物，所述有机非线性晶体原料为苯乙烯基甲基吡啶盐类，所述交联剂为有机酸酐或丁烷四羧酸，所述高温退火为180-200℃高温处理4-6个小时；静电纺丝时，转速为150-1000rpm/min、纺丝液的推送速率为0.1-20mL/h，针头与转轴的初始距离为5-20cm，针头孔直径为0.1-1mm，电压为5-30kV，温度为15-60℃。
2.根据权利要求1所述的一种有机非线性光学材料的制备方法，其特征在于，所述环状低聚糖化合物在有机溶剂中的质量分数的15-35％。
3.根据权利要求1所述的一种有机非线性光学材料的制备方法，其特征在于，所述交联剂的质量为环状低聚糖化合物的1-15％，所述有机非线性晶体原料的质量为环状低聚糖化合物的1-5％。
4.采用权利要求1-3任一项所述的制备方法制备得到的有机非线性光学材料。
5.权利要求4所述的有机非线性光学材料在制备光学材料或医疗成像剂方面的应用。
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| CN112216787A (zh) * | 2020-09-22 | 2021-01-12 | 电子科技大学 | 一种基于pvdf/dast复合纤维材料的柔性压电发电机及其制备方法 |
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| CN112216787A (zh) * | 2020-09-22 | 2021-01-12 | 电子科技大学 | 一种基于pvdf/dast复合纤维材料的柔性压电发电机及其制备方法 |
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