CN116102834B - 一种光致变色可复写薄膜及制备方法和应用 - Google Patents

一种光致变色可复写薄膜及制备方法和应用 Download PDF

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CN116102834B
CN116102834B CN202211463764.5A CN202211463764A CN116102834B CN 116102834 B CN116102834 B CN 116102834B CN 202211463764 A CN202211463764 A CN 202211463764A CN 116102834 B CN116102834 B CN 116102834B
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罗洋辉
刘敏
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Abstract

本发明公开了一种光致变色可复写薄膜及制备方法和应用,所述的可复写薄膜材料包括PVDF、PEG、近红外光致变色配合物,所述的近红外光致变色配合物为[Co(NCS)2(pyz)2]n,所述的[Co(NCS)2(pyz)2]n占PVDF的质量百分比为0.47~10%;所述的PEG与PVDF的质量比为0.2~1.2:1~6。该可复写薄膜可在近红外触发下发生光致变色行为,着色速度快,在空气中可恢复初始颜色,在颜色切换速率和可逆性方面具有良好的性能。在创建动态颜色变化的信息、无墨印刷、可重写颜色显示和光信息加密等方面具有很大的应用前景。

Description

一种光致变色可复写薄膜及制备方法和应用
技术领域
本发明涉及一种光致变色材料,特别涉及一种光致变色可复写薄膜及制备和应用。
背景技术
近年来,光致变色材料作为一种智能材料,一直以来都是研究和关注的热点之一。它能够在紫外光、可见光等光刺激下,激活发色团分子结构发生变化,从而改变其颜色,而光源撤去或经过另一种波长的光照射后,又能恢复到原来的颜色。光致变色材料对于光的可逆性响应,使其在色彩显示、光致变色镀膜玻璃、数据存储、光电器件、安防系统等实际应用中具有广阔前景。
层状金属有机框架由于层状结构和层间弱相互作用力,使其具有独特的化学和光学性质,广泛应用于载流子传输、传感器、锂离子导电性、吸附和分离等方面,特别是可作为光致变色材料应用于光致变色眼镜、透镜和滤光片、可擦除和无墨打印、3D数据存储等方面。然而,层状金属有机框架作为光致变色分子的选择、设计、合成困难等问题都极大地限制了其在该领域的进一步应用。
传统上,光致变色材料主要分为两大类:有机和无机光致变色材料。如:偶氮苯、二苯乙烯衍生物、螺吡喃和数百种有机光致变色分子和二氧化钛、二氧化锡、半导体等无机光致变色分子。这类材料合成工艺复杂、反应前体毒性高、生产成本高、热稳定性差,均制约了其进一步的开发和应用。同时,大部分已经报道的光致变色材料依赖于紫外线和高能可见光来驱动颜色变化,这通常会带来:光致发光分子有机成分分解、循环稳定性差、环境污染、安全问题等问题。
发明内容
发明目的:本发明旨在提供一种光致变色可复写薄膜,该可复写薄膜可在近红外触发下发生光致变色行为,着色速度快,在空气中可恢复初始颜色,在颜色切换速率和可逆性方面具有良好的性能;本发明的另一目的在于提供一种所述光致变色可复写薄膜的制备方法;本发明的另一目的在于提供一种所述光致变色可复写薄膜在无墨光可逆印刷、可复写制备中的应用。
技术方案:本发明所述的可复写薄膜材料包括PVDF、PEG、近红外光致变色配合物,所述的近红外光致变色配合物为[Co(NCS)2(pyz)2]n,(pyz=吡嗪),所述的[Co(NCS)2(pyz)2]n占PVDF的质量百分比为0.47~10%;所述PEG与PVDF的质量比为(0.2~1.2):(1~6)。
优选地,[Co(NCS)2(pyz)2]n占PVDF的质量百分比为0.67%,PEG与PVDF的质量比为(0.8~1): 2.25。
优选地,所述的PEG为PEG-6000,所述的PVDF为PVDF-50000。
本发明所述的光致变色可复写薄膜的制备方法,包括以下步骤:
(1)PEG溶于有机溶剂中,搅拌至完全溶解呈透明色,再向其中加入PVDF,搅拌至PVDF完全溶解且呈现透明状,其中PEG和PVDF的质量比为(0.2~1.2):(1~6);
(2)将3D [Co(NCS)2(pyz)2]n粉末加入步骤(1)得到的PVDF/PEG凝胶中,搅拌至粉末在凝胶中均匀分散,搅拌加热,趁热将掺杂凝胶转移至模具中成型。所述的[Co(NCS)2(pyz)2]n占PVDF的质量百分比为0.47~10%。
进一步地,步骤(1)中溶剂为N,N-二甲基甲酰胺;所述PEG与溶剂的质量体积比为(0.2~1.2 g):(10~50 mL)。
进一步地,步骤(1)中PEG的溶解条件为:在30~70 ℃,100~400 rpm下搅拌20-50min至PEG完全溶解;PVDF的溶解条件为:在300~600 rpm下搅拌2~5 h至完全溶解。
进一步地,步骤(2)中,所述搅拌加热温度为80-90 ℃,加热时间为6~10 h。
进一步地,步骤(2)中,成型的条件为:将凝胶倒入器皿中静置3~6天。
本发明所述的光致变色可复写薄膜或上述方法制备的光致变色可复写薄膜可应用于无墨光可逆印刷、可复写制备中。
有益效果:与现有技术相比,本发明具有如下显著优点:(1)所述光致变色可复写薄膜结合了近红外光致变色配合物的特性,能够在近红外光刺激下短时间内着色,光源撤去后在空气中一段时间后脱色,具有良好的光致变色可逆性和循环稳定性;(2)所述光致变色可复写薄膜的制备方法简单、颜色均匀且无任何毒性;(3)本发明提供的光致变色可复写薄膜在实现无油墨光可逆打印、创建动态颜色变化的信息、可重写颜色显示和光信息加密等方面具有广阔的应用前景。
附图说明
图1为实施例1可复写薄膜在着色(120 s)/脱色(120 s)循环过程中的紫外吸收强度变化(650 nm)图;
图2为实施例2可复写薄膜在近红外光源下的书写效果图。
具体实施方式
下面结合附图对本发明的技术方案作进一步说明。
实施例1
(1)将1.2 g PEG倒入三颈烧瓶中,加入50 mL N,N-二甲基甲酰胺(DMF),在70 ℃、400 rpm条件下搅拌50 min至完全溶解,在继续搅拌的条件下向其中加入6 g PVDF,600rpm下搅拌5 h至PVDF完全溶解,得到无色透明的混合溶液1;
(2)将3D [Co(NCS)2(pyz)2]n粉末0.6 g加入溶液1中,搅拌至粉末在溶胶中均匀分散,在90 ℃的油浴锅中搅拌加热10 h,得到溶液2。趁热将溶液2倒入直径为75 mm的半圆形器皿中静止6天,即可获得[Co(NCS)2(pyz)2]n掺杂的光致变色可复写薄膜。该可复写薄膜在着色(120 s)/脱色(120 s)循环过程中的紫外吸收强度变化(650 nm)图如图1所示。
本实施例中得到的[Co(NCS)2(pyz)2]n与PVDF的质量百分比为10 %,PVDF与PEG的质量比为1.2 : 6。
实施例2
(1)将0.2 g PEG倒入三颈烧瓶中,加入10 mL N,N-二甲基甲酰胺(DMF),在30 ℃、100 rpm条件下搅拌至完全溶解,在继续搅拌的条件下向其中加入1 g PVDF,300 rpm下搅拌2 h至PVDF完全溶解,得到无色透明的混合溶液1;
(2)将3D [Co(NCS)2(pyz)2]n粉末4.7 mg加入溶液1中,搅拌至粉末在溶胶中均匀分散,在80 ℃的油浴锅中搅拌加热6 h,得到溶液2。趁热将溶液2倒入直径为75 mm的半圆形器皿中静止3天,即可获得[Co(NCS)2(pyz)2]n掺杂的光致变色可复写薄膜。该可复写薄膜在近红外光源下的书写效果图如图2所示。
本实施例中得到的[Co(NCS)2(pyz)2]n与PVDF的质量百分比为0.47%,PVDF与PEG的质量比为0.2 : 1。
实施例3
(1)将0.6 g PEG倒入三颈烧瓶中,加入30 mL N,N-二甲基甲酰胺(DMF),在50 ℃、200 rpm条件下搅拌至完全溶解,在搅拌的条件下再向其中加入1.35 g PVDF,600 rpm下搅拌3 h至PVDF完全溶解,得到无色透明的混合溶液1;
(2)将3D [Co(NCS)2(pyz)2]n9 mg粉末加入溶液1中,搅拌至粉末在溶胶中均匀分散,在90 ℃的油浴锅中搅拌加热8 h,得到溶液2。趁热将溶液2倒入直径为75 mm的半圆形器皿中静止4天,即可获得[Co(NCS)2(pyz)2]n掺杂的光致变色可复写薄膜。
本实施例中得到的[Co(NCS)2(pyz)2]n与PVDF的质量百分比为0.67%,PVDF与PEG的质量比为1 : 2.25。
对比例1
步骤(1)和实施例1相同。步骤(2)将3D [Co(NCS)2(pyz)2]n粉末3 mg加入溶液1中,搅拌至粉末在溶胶中均匀分散,在80 ℃的油浴锅中搅拌加热6 h,得到溶液2。趁热将溶液2倒入直径为75 mm的半圆形器皿中静止3天,即可获得[Co(NCS)2(pyz)2]n掺杂的光致变色可复写薄膜。
所得的光致变色可复写薄膜中,[Co(NCS)2(pyz)2]n与PVDF的质量百分比为0.3%,对比例1的结果显示,当近红外光致变色配体掺杂量过低时,在低能量近红外照射,颜色变化微弱,以至肉眼无法观察到。
对比例2
步骤(1)和实施例2相同。步骤(2)中将3D [Co(NCS)2(pyz)2]n粉末1 g加入溶液1中,搅拌至粉末在溶胶中均匀分散,在90 ℃的油浴锅中搅拌加热10 h,得到溶液2。趁热将溶液2倒入直径为75 mm的半圆形器皿中静止5天,即可获得[Co(NCS)2(pyz)2]n掺杂的光致变色可复写薄膜。
所得的光致变色可复写薄膜中,[Co(NCS)2(pyz)2]n与PVDF的质量百分比为16.7%,对比例2的结果显示,当近红外光致变色配体掺杂量过高时,薄膜的稳定性差,且颜色薄膜过深,近红外照射下颜色对比变化不明显。

Claims (9)

1.一种光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,所述薄膜材料包括PVDF、PEG和近红外光致变色配合物,所述的近红外光致变色配合物为[Co(NCS)2(pyz)2]n,所述的[Co(NCS)2(pyz)2]n占PVDF的质量百分比为0.47~10%,所述PEG与PVDF的质量比为0.2~1.2 : 1~6。
2.根据权利要求1所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,所述PEG与PVDF的质量比为0.8~1: 2.25。
3.根据权利要求1所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,光致变色薄膜的制备方法包括以下步骤:
(1)PEG溶于有机溶剂中,搅拌至完全溶解呈透明色,再加入PVDF,搅拌至完全溶解得到PVDF/PEG凝胶;
(2)将3D [Co(NCS)2(pyz)2]n粉末加入上述PVDF/PEG凝胶中,搅拌至粉末在凝胶中均匀分散,搅拌加热,趁热将掺杂凝胶转移至模具中成型。
4.根据权利要求3所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,步骤(1)中所述有机溶剂为N,N-二甲基甲酰胺。
5.根据权利要求3所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,步骤(1)中所述PEG与溶剂的质量体积比为0.2~1.2 g : 10~50 mL。
6.根据权利要求3所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,步骤(1)中所述PEG的溶解条件为:在30~70 ℃,100~400 rpm下搅拌20-50 min至PEG完全溶解。
7.根据权利要求3所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,所述PVDF的溶解条件为:在300~600 rpm下搅拌2~5 h至完全溶解。
8.根据权利要求3所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,步骤(2)中,搅拌加热温度为80-90 ℃,加热时间为6~10 h。
9.根据权利要求3所述的光致变色可复写薄膜在无墨光可逆印刷制备中的应用,其特征在于,步骤(2)中,所述成型的条件为:将凝胶倒入器皿中静置3~6天。
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