CN108976485B - 一种凝胶多糖与稀土复合的柔性发光薄膜及其制备方法 - Google Patents
一种凝胶多糖与稀土复合的柔性发光薄膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种凝胶多糖与稀土复合的柔性发光薄膜及其制备方法,包括稀土发光材料和离子液体改性的凝胶多糖衍生物,该薄膜在水条件下合成,不仅发光性能得到明显提高,而且通透性非常好。其中稀土发光材料与离子液体改性凝胶多糖衍生物的质量比为:1:50,稀土发光材料中包括有机配体和粘土,其中,粘土中稀土离子的交换量约为:0.3~1.1/单元,稀土元素具体为L n系元素:N d、S m、E u、G d、D y、Ho、E r、Tm和Y b中的一种或多种,有机配体为TTA(α‑噻吩甲酰三氟丙酮),离子液体改性的凝胶多糖衍生物中包括凝胶多糖和羧基官能化咪唑离子液体,其摩尔比为:1:5。本发明还公开了上述包含凝胶多糖衍生物的改性方法、发光材料的制备方法以及稀土的柔性凝胶多糖发光薄膜的制备方法。本发明的产品性能优异,制备工艺绿色环保,中心离子的稳定性和发光性能好,荧光寿命长。
Description
技术领域
本发明属于稀土发光材料领域,涉及一种柔性透明发光薄膜及其制备方法,具体为一种基于改性天然多糖、纳米粘土和稀土配合物的柔性稀土透明发光薄膜及其制备方法。
背景技术
稀土配合物其独特的发光性质如大的斯托克斯位移,尖锐的发射分布和长寿命的激发态而具有荧光寿命长、发光单色性好、吸光能力强、发射谱线丰富、发光覆盖范围广等优异的性能,它们在照明、显示、生物荧光标记等领域具有潜在的应用价值,然而纯复合物本身的缺陷限制了它们在实际中的应用,如光、热稳定性及机械性差、成膜性不好及易团聚等,众多研究者,将稀土嵌入和功能化而产生纳米级别的有序组装,形成纳米粘土基质与有机化合物如吡啶羧酸,卟啉,氨基醇,多元醇,聚合物等原位复合,以产生有机-无机杂化物,该新型发光材料不但具有稀土离子优异的发光性能,而且还具有较高的光稳定性,热稳定性和机械稳定性且水溶性好,绿色环保。
锂皂石为白色粉末,因其单独片层带负电荷,对阳离子及中性分子具有极强的离子交换能力和吸附能力,在锂皂石的片层上可以原位形成稀土配合物,因而可以锂皂石为基质制备稀土杂化发光材料,以锂皂石为基质,掺杂稀土元素的β-二酮的配合物,并利用水溶性的离子液体对疏水性的凝胶多糖进行修饰,将二者复合,它们的发光性能具有出异乎寻常的优越性,荧光强度提高了几百倍,荧光效率和荧光寿命也有很大的提高,同时,由于其在水中具有很好的膨胀性能,为在水溶液中制备稀土发光薄膜奠定了一个很好的基础。
发光材料的薄膜化是实现其器件化的重要前提,将发光材料与高分子材料结合制备成透明薄膜,可以拓宽发光材料在柔性、可折叠发光器件等方面的应用。然而,传统发光薄膜制备中用到的高分子材料为PVA、PMMA、PAS等石油裂解产物,由于以传统的石油工业和煤炭工业为基础的原料的不可再生性,人们迫切需要通过绿色过程从可再生资源中发展新材料,以满足社会的需求,因此,寻求天然高分子材料替代石油化工产业链中的合成高分子材料引起了人们的极大关注,凝胶多糖是β-1,3-葡聚糖家族中最具特色的一种,其主链上含有支链,是一种新型微生物胞外多糖,化学和酶学分析已确定,该多糖是由葡萄糖在C1和C3位上以β-1,3-糖苷键连接而成的无分支的多糖聚合物,这种大分子的β-1,3-葡聚糖大约由300-500个葡萄糖残基组成,其平均聚合度为450,相对分子量大约为74000,主要以长链状结构存在,但由于其分子内部的相互作用与分子间的氢键结合,可以形成更为复杂的三维结构,其在自然状态下,是以圆环状的小颗粒形式存在的,与淀粉的结构相类似,凝胶多糖不溶于水,这限制了它的广泛应用。但凝胶多糖分子中存在大量羟基,通过化学改性可在重复单元上引入不同的基团。这些基团的引入一方面可以改善其溶解性,近年来,许多科研工作者对其进行了改性,使其水溶性大大提升,为接下来的工作奠定了很好的基础。
综上所述,传统发光薄膜的制备工艺环保性不强。凝胶多糖可作为传统合成高分子材料的替代物,提升薄膜制备工艺的环保性,但其难溶于水和常规有机溶剂,限制了它的应用,因此,需要寻找一种有效溶剂,促进其溶解的同时又不对薄膜发光性能产生影响。
发明内容
本发明为解决公知技术中存在的技术问题而提供一种绿色环保的含稀土的柔性凝胶多糖发光薄膜及其制备方法。
本发明公开了一种稀土与高分子复合的柔性凝胶多糖发光薄膜的制备方法,包括稀土发光材料和离子液体改性的凝胶多糖衍生物,该薄膜在水环境下合成,不仅发光性能得到明显提高,而且通透性(透光性)非常好,其中稀土发光材料与离子液体改性凝胶多糖衍生物的质量比为:1:50,稀土发光材料中包括有机配体和纳米粘土,其中,纳米粘土中稀土离子的交换量约为:0.3~1.1/单元,稀土元素具体为Ln系元素:N d、S m、E u、G d、D y、Ho、E r、Tm和Y b中的一种或多种,有机配体为TTA(α-噻吩甲酰三氟丙酮),离子液体改性的凝胶多糖衍生物中包括凝胶多糖和羧基官能化咪唑离子液体,其摩尔比为:1:5,本发明还公开了上述包含凝胶多糖衍生物的改性方法、发光材料的制备方法。
稀土与高分子复合的柔性凝胶多糖发光薄膜的制备方法,其特征在于,采用以下步骤:
羧基官能化咪唑离子液体的结构式如下:
羧基官能化咪唑离子液体改性的凝胶多糖和稀土发光材料的结构式如下:
附图说明
图1为本发明中柔性发光薄膜制备过程中Cur(a)、Cur-N3(b)、Cur- NH2(c)、Cur-NH-I(d)四种物质的傅里叶红外变换图;
图2为本发明中柔性发光薄膜中Cur-NH-IL的核磁共振图;
图3为本发明中柔性发光薄膜Lap@Eu3+(TTA)n Cur-NH-IL的荧光激发光谱图(λ1=612nm, λ2=379nm);
图4为本发明中柔性发光薄膜Lap@Eu3+(TTA)n Cur-NH-IL的荧光发射光谱图(λ1=612nm, λ2=379nm);
图5为本发明中柔性发光薄膜Lap@Eu3+(TTA)n Cur-NH-IL的荧光寿命光谱图(λ1=612nm, λ2=379nm);
图6为本发明中离子液体IL质谱图;
图7为本发明中离子液体IL核磁共振H谱图;
图8为本发明中荧光薄膜Lap@Eu3+(TTA)n Cur-NH-IL日光灯照射图;
图9为本发明中荧光薄膜Lap@Eu3+(TTA)n Cur-NH-IL紫外灯照射图;
具体实施方式
为能进一步了解本发明的发明内容、特点及功效,列举以下实施例,并配合附图详细说明如下:
实施例1:
一种含稀土的柔性凝胶多糖发光薄膜的制备方法,采用以下步骤:
(1)取锂皂石1g于反应器中,加入双蒸水溶解,超声处理,使其充分膨胀,直至溶液呈透明凝胶态,再加入0.1mol/L的LnCl3·6H2O溶液于恒温油浴中搅拌,然后离心分离,再进行超声洗涤,干燥后,得到离子交换后的水溶性凝胶态纳米粘土,其中,每1g纳米粘土加15ml双蒸水和10ml0.1mol/L的LnCl3·6H2O溶液,记作Lap@Eu3+;
(2)取TTA(α-噻吩甲酰三氟丙酮)于反应器中,加入无水乙醇溶解,然后将步骤(1)得到凝胶状态的纳米粘土加入其中,超声均匀后,再加入无水乙醇,反应后,离心洗涤,干燥,得到水溶性凝胶态稀土发光材料,其中,每1g纳米粘土加TTA(α-噻吩甲酰三氟丙酮)0.15g, 记作Lap@Eu3+(TTA)n;
(3)分别称取1-甲基咪唑和β-溴丙酸,将二者混合放入圆底烧瓶中,再加入无水乙醇作为溶剂,在80℃油浴中回流反应24h,反应停止后,除去无水乙醇溶剂,然后用无水乙醚洗涤,用丙酮除水提纯,得粘稠状液体甲基咪唑羧酸离子液体记为IL;
(4)称取凝胶多糖(真空干燥过夜),充氮气条件下加热混匀搅拌,加入NaN3,继续在加热下搅拌冷却至室温,取出在磁力搅拌器上,加入三苯基磷和四溴化碳,室温下反应,反应完成后用甲醇将改性胶多糖沉淀,再多次洗涤,置于真空干燥箱中干燥,记为Cur-N3;
(5)将步骤(4)得到的产物用硼氢化钠还原得到氨基官能化凝胶多糖,记为Cur-NH2;
(6)用EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺)和NHS(N-羟基琥珀酰亚胺)将步骤(3)制得的IL(离子液体)充分活化后,将其加入到步骤(5)中得到的凝胶多糖衍生物氨基官能化凝胶多糖中其中Cur-NH2: EDC: NHS: IL:DIPEA=1:6:6:5:7.5(摩尔比),待反应完成后,将杂质透析干净,将样品冻干备用,记为Cur-NH-IL;
(7)取水溶性的离子液体改性凝胶多糖和稀土发光材料分散到水中,加入适量PVA溶液辅助成膜,均匀后,超声,采用滴加法滴加到玻璃片上,放入60℃烘箱中,慢慢干燥,得到一张轻薄、均匀,透明的发光薄膜,Lap@Eu3+(TTA)n Cur-NH-IL;
(8)请参见图8、图9,图8是柔性凝胶多糖发光薄膜的日光灯图片,从图中可以看出,发光薄膜的表面很平整,很均匀,说明离子液体可以很好的将凝胶多糖充分溶解,同时由于离子液体与发光材料颗粒的静电吸附作用,使其可以均匀分散。发光薄膜均匀的形貌使其具有很好的透明度。图9是柔性凝胶多糖发光薄膜的紫外灯照射图,说明薄膜的发光性良好。请参见图1、图2分别是Cur-NH-IL的核磁共振和傅里叶红外变换图,其中傅里叶红外变换图在1716cm-1的羰基伸缩振动峰1662 cm-1的N-H伸缩振动峰,1405 cm-1的C-N的伸缩振动峰以及核磁共振碳谱图中位移为175ppm处为羰基碳的峰,证明成功合成了离子液体改性的凝胶多糖衍生物。请参见图3、图4、图5分别为柔性凝胶多糖发光薄膜的荧光激发、发射和寿命谱图。图3是在室温下612nm作为监测波长得到的荧光激发光谱图,在250~400nm出现一宽峰,并且最大激发波长中心为379nm,说明配体的“天线效应”可以将能量传递给稀土离子。图4是在室温下作为监测波长得到的发射光谱图,在560-720nm范围内出现了5个特征发射峰,分别是579nm、592nm、612nm、652nm和698nm,代表了Eu3+的5D0→7FJ(J=0,1,2,3,4)能级跃迁,并且以5D0→7F2跃迁(612nm)的发射强度最高,因此材料在紫外灯下呈现了鲜艳的红色,图5是发光薄膜的荧光寿命图,如图可知,柔性凝胶多糖发光薄膜的寿命为2.7ms,因此,薄膜具有良好的荧光强度以及良好的透明度,使其在可光学器件上有很大的潜在应用价值。
实施例2:
一种含稀土的柔性凝胶多糖发光薄膜的制备方法,采用以下步骤:
(1)与实施例1的步骤(1)相同;
(2)与实施例1的步骤(2)相同;
(3)与实施例1的步骤(3)相同;
(4)与实施例1的步骤(4)相同;
(5)与实施例1的步骤(5)相同;
(6)用EDC(1-(3-二甲氨基丙基)-3-乙基碳二亚胺)和NHS(N-羟基琥珀亚胺)将步骤(3)制得的IL(离子液体)充分活化后,将其加入到步骤(5)中得到的凝胶多糖衍生物氨基官能化凝胶多糖中其中Cur-NH2: EDC: NHS: IL:DIPEA=1:6:6:6:7.5(摩尔比),待反应完成后,将杂质透析干净,将样品冻干备用,记为Cur-NH-IL。
(7)与实施例1的步骤(7)相同;
(8)上述发光薄膜Ⅱ与实施案例1中的发光薄膜Ⅰ一样,具有轻薄、均匀、透明的性质,在紫外灯下,该发光薄膜Ⅱ也呈现明显的亮红色,最大发射波长在612nm。
实施例3:
一种含稀土的柔性凝胶多糖发光薄膜的制备方法,采用以下步骤:
(1)与实施例1的步骤(1)相同;
(2)与实施例1的步骤(2)相同;
(3)与实施例1的步骤(3)相同;
(4)与实施例1的步骤(4)相同;
(5)与实施例1的步骤(5)相同;
(6)与实施例1的步骤(6)相同;
(7)取水溶性的离子液体改性凝胶多糖和稀土发光材料分散到水中,加入适量PVA溶液辅助成膜,均匀后,超声,采用滴加法滴加到玻璃片上,放入50℃烘箱中,慢慢干燥,得到一张轻薄、均匀,透明的发光薄膜,Lap@Eu3+(TTA)n Cur-NH-IL。
(8)上述发光薄膜Ⅲ与实施案例1中的发光薄膜Ⅰ一样,具有轻薄、均匀、透明的性质,在紫外灯下,该发光薄膜Ⅲ也呈现明显的亮红色,最大发射波长在612nm。
实施例4:
一种含稀土的柔性凝胶多糖发光薄膜的制备方法,采用以下步骤:
(1)与实施例1的步骤(1)相同;
(2)与实施例1的步骤(2)相同;
(3)与实施例1的步骤(3)相同;
(4)与实施例1的步骤(4)相同;
(5)与实施例1的步骤(5)相同;
(6)与实施例1的步骤(6)相同;
(7)取水溶性的离子液体改性凝胶多糖和稀土发光材料分散到水中,加入适量PVA溶液辅助成膜,均匀后,超声,采用滴加法滴加到玻璃片上,放入40℃烘箱中,慢慢干燥,得到一张轻薄、均匀,透明的发光薄膜,Lap@Eu3+(TTA)n Cur-NH-IL。
(8)上述发光薄膜Ⅳ与实施案例1中的发光薄膜Ⅰ一样,具有轻薄、均匀、透明的性质,在紫外灯下,该发光薄膜Ⅳ也呈现明显的亮红色,最大发射波长在612nm。
实施例5:
一种含稀土的柔性凝胶多糖发光薄膜的制备方法,采用以下步骤:
(1)与实施例1的步骤(1)相同;
(2)与实施例1的步骤(2)相同;
(3)与实施例1的步骤(3)相同;
(4)与实施例1的步骤(4)相同;
(5)与实施例1的步骤(5)相同;
(6)与实施例1的步骤(6)相同;
(7)取水溶性的离子液体改性凝胶多糖和稀土发光材料分散到水中,加入适量PVA溶液辅助成膜,均匀后,超声,采用滴加法滴加到玻璃片上,放入30℃烘箱中,慢慢干燥,得到一张轻薄、均匀,透明的发光薄膜,Lap@Eu3+(TTA)n Cur-NH-IL。
(8)上述发光薄膜Ⅴ与实施案例1中的发光薄膜Ⅰ一样,具有轻薄、均匀、透明的性质,在紫外灯下,该发光薄膜Ⅴ也呈现明显的亮红色,最大发射波长在612nm。
实施例6:
一种含稀土的柔性凝胶多糖发光薄膜的制备方法,采用以下步骤:
(1)与实施例1的步骤(1)相同;
(2)与实施例1的步骤(2)相同;
(3)与实施例1的步骤(3)相同;
(4)与实施例1的步骤(4)相同;
(5)与实施例1的步骤(5)相同;
(6)与实施例1的步骤(6)相同;
(7)取水溶性的离子液体改性凝胶多糖和稀土发光材料分散到水中,加入适量PVA溶液辅助成膜,均匀后,超声,采用滴加法滴加到玻璃片上,放入室温中,慢慢干燥,得到一张轻薄、均匀,透明的发光薄膜,Lap@Eu3+(TTA)n Cur-NH-IL。
(8)上述发光薄膜Ⅵ与实施案例1中的发光薄膜Ⅰ一样,具有轻薄、均匀、透明的性质,在紫外灯下,该发光薄膜Ⅵ也呈现明显的亮红色,最大发射波长在612nm。
Claims (2)
2.根据权利要求1所述的凝胶多糖与稀土复合的柔性发光薄膜,其制备方法的特征在于采用以下步骤:
(1)称取干燥后的凝胶多糖,充氮气条件下加热混匀搅拌,加入NaN3,继续在加热下加热搅拌冷却至室温,取出在磁力搅拌器上,加入三苯基膦和四溴化碳,室温下反应,重结晶,烘干得叠氮化凝胶多糖;
(2)将步骤(1)得到的产物用硼氢化钠还原得到氨基官能化凝胶多糖;
(3)用1-(3-二甲氨基丙基)-3-乙基碳二亚胺和N-羟基琥珀酰亚胺将IL羧酸功能化离子液体充分活化后,将其加入到步骤(2)中得到的凝胶多糖衍生物氨基官能化凝胶多糖中,待反应完成后,将杂质透析干净,将样品冻干备用;
(4)取步骤(3)中得到的含咪唑基离子液体改性凝胶多糖和稀土发光材料分散到水中,加入适量PVA辅助成膜,搅拌均匀后,超声,滴加到玻璃片上流延成膜,放入烘箱中,缓慢干燥,得到均匀、透明的发光薄膜。
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