CN112480905A - 多重刺激响应材料及其制备方法与应用 - Google Patents
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Abstract
Description
技术领域
本申请属于智能响应荧光材料技术领域,尤其涉及一种多重刺激响应材料及其制备方法与应用。
背景技术
圆偏振光是指由传播方向相同、振动方向相互垂直的两平面偏振光叠加后所合成的旋转电矢量端点描出圆轨迹的光。能发射出圆偏振光的材料称为圆偏振发光(Circularly Polarized Luminescence,CPL)材料,其在数据存储、识别传感、量子计算、3D显示等领域均具有重要的潜在应用。
激响应变色材料是一类能够对外界刺激例如光、机械力、溶剂、剪切力和温度等产生相应的单重或多重信号的智能材料。近年来,许多新型智能响应荧光材料被开发出来,并广泛应用于防伪、传感器、荧光探针、发光材料、3D显示器件和信息加密等方面。
然而,现有的有机光致变色材料普遍为单一作用单重响应,例如仅对光或热产生相应的响应信号,难以满足智能化的应用需求。此外,现有绝大多数的有机光致变色材料往往在稀溶液中都具有很好的发光性能,但是,在浓溶液或者呈固态时,发光强度减弱甚至消失,极大地限制了发光材料的应用。
发明内容
本申请的目的在于提供一种多重刺激响应材料及其制备方法与应用,旨在解决现有响应变色材料为单一响应,且在聚集态下荧光易淬灭的问题。
为实现上述申请目的,本申请采用的技术方案如下:
第一方面,所述多重刺激响应材料包括如下分子结构通式I的组分:
第二方面,本申请提供一种多重刺激响应材料的制备方法,包括如下步骤:
将所述第一化合物和所述第二化合物于有机溶剂中混合得到第一混合物,
第三方面,本申请提供的多重刺激响应材料或由制备方法制备得到的多重刺激响应材料在多重防伪、生物检测、智能传感、发光材料、3D智能显示、信息加密中的应用。
本申请第一方面提供的多重刺激响应变色材料,其以四苯乙烯基单取代羧酸和含芳香基团脂肪胺盐作为分子骨架,通过有机物羧基与氨基之间相互作用成盐进而在有机溶液中析出微晶的独特方式制备,该多重刺激响应变色材料结构简单,制备新颖,响应快速,灵敏度高。经实验测试,该多重刺激响应变色材料可对光、研磨、溶剂熏蒸外界刺激产生相应的响应信号,使得发光强度或发光颜色发生明显改变,其具有明显的力致荧光变色、力致发光性质和光致变色的性质,同时还具有圆偏振发光的特性,满足了当前多元化的应用需求,并可广泛应用。
本申请第二方面提供的制备方法,将第一化合物和第二化合物化合物的取代羧基和取代氨基在有机溶液中相互作用成盐进而析出微晶的独特制备方式,合成了上述多重刺激响应变色材料,合成方式简单,产率高,反应条件可控,易于实现多重刺激响应变色材料的规模化制备。
本申请第三方面提供的多重刺激响应变色材料集多重刺激响应变色性能和圆偏振发光性能于一体,将该多重刺激相应变色材料应用于制备防伪标签或者是信息加密技术上,响应速度快,灵敏度高,有利于极大地拓宽多刺激智能响应材料的应用场景。
附图说明
为了更清楚地说明本申请实施例中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本申请的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是实施例1制备的化合物在固态下的发光情况,A为化合物在固态条件下的日光表现,B为化合物在固态条件下的荧光表现。
图2是实施例1的化合物粉末经研磨、溶剂熏蒸等操作前后的颜色变化。
图3是实施例1的化合物粉末和单晶经紫外光照射前后的颜色变化。
图4是实施例1的化合物单晶经紫外光照射前后的颜色变化。
图5是实施例1的化合物外力刺激发出的力致发光现象。
图6是实施例1和例2的化合物圆偏振发光光谱图。
图7是制备防伪标签的示意图。
图8是实施例1的化合物制备的防伪标签在不同处理条件下的颜色变化。
图9是实施例3的化合物制备的防伪标签在不同处理条件下的颜色变化。
具体实施方式
为了使本申请要解决的技术问题、技术方案及有益效果更加清楚明白,以下结合实施例,对本申请进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本申请,并不用于限定本申请。
本申请中,“至少一个”是指一个或者多个,“多个”是指两个或两个以上。“以下至少一项(个)”或其类似表达,是指的这些项中的任意组合,包括单项(个)或复数项(个)的任意组合。例如,“a,b,或c中的至少一项(个)”,或,“a,b,和c中的至少一项(个)”,均可以表示:a,b,c,a-b(即a和b),a-c,b-c,或a-b-c,其中a,b,c分别可以是单个,也可以是多个。
应理解,在本申请的各种实施例中,上述各过程的序号的大小并不意味着执行顺序的先后,部分或全部步骤可以并行执行或先后执行,各过程的执行顺序应以其功能和内在逻辑确定,而不应对本申请实施例的实施过程构成任何限定。
在本申请实施例中使用的术语是仅仅出于描述特定实施例的目的,而非旨在限制本申请。在本申请实施例和所附权利要求书中所使用的单数形式的“一种”、“所述”和“该”也旨在包括多数形式,除非上下文清楚地表示其他含义。
术语“第一“、“第二”仅用于描述目的,用来将目的如物质彼此区分开,而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。例如,在不脱离本申请实施例范围的情况下,第一XX也可以被称为第二XX,类似地,第二XX也可以被称为第一XX。由此,限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。
本申请实施例第一方面提供一种多重刺激响应材料,多重刺激响应材料包括如下分子结构通式I的组分:
本申请第一方面提供的多重刺激响应变色材料,其以四苯乙烯基单取代羧酸和含芳香基团脂肪胺盐作为分子骨架,通过有机物羧基与氨基之间相互作用成盐进而在有机溶液中析出微晶的独特方式制备,该多重刺激响应变色材料结构简单,制备新颖,响应快速,灵敏度高。经实验测试,该多重刺激响应变色材料可对光、研磨、溶剂熏蒸外界刺激产生相应的响应信号,使得发光强度或发光颜色发生明显改变,其具有明显的力致荧光变色、力致发光性质和光致变色的性质,同时还具有圆偏振发光的特性。满足了当前多元化的应用需求,并可广泛应用。
具体的,通式I中,R1,R2选自相同或不相同的H、烷基、苯基中的任意一种。优选的,烷基选自C1~C3的烷基。
在一些实施例中,通式I中,R选自优选的,当R选自分子结构通式I为如下结构通式:其中,R1,R2选自相同或不相同的H、烷基、苯基中的任意一种,R3选自H、非芳香取代基中的任意一种,且烷基选自C1~C3的烷基。
优选的,Ar选自芳杂环基、萘基中的任意一种,选择芳杂环基或萘基有利于形成多重刺激响应材料进行反应。
进一步优选的,Ar选自以下结构中的任意一种:
其中,*表示结合位点。
进一步优选的,通式I中,R选自Ar,分子结构通式I为如下结构通式:
其中,*表示含有手性碳原子,可代表具有R,S手性方向的两种化合物。在式1~式93中,含有手性碳原子的结构式得到的多重刺激响应材料具有更好的圆偏振发光性质。
本申请提供的多重刺激响应变色材料包括式1~式93中至少一种结构式,得到的材料具有光致变色、力致变色和力致发光特性,且具有圆偏振发光特性。该类化合物响应于光、外力和蒸汽等多种外界刺激,满足了当前多元化的应用需求,并具有圆偏振发光特性,可广泛应用于各领域。
本申请实施例第二方面提供一种多重刺激响应材料的制备方法,包括如下步骤:
S02.将第一化合物和第二化合物于有机溶剂中混合得到第一混合物,
本申请第二方面提供的制备方法,将第一化合物和第二化合物化合物的取代羧基和取代氨基在有机溶液中相互作用成盐进而析出微晶的独特制备方式,合成了上述多重刺激响应变色材料,合成方式简单,产率高,反应条件可控,易于实现多重刺激响应变色材料的规模化制备。
进一步的,提供第二化合物其中,R选自Ar中的任意一种,R1,R2选自相同或不相同的H、烷基、苯基中的任意一种,R3选自H、非芳香取代基中的任意一种。优选的,Ar选自芳杂环基、萘基中的任意一种;烷基选自C1~C3的烷基。
在一些实施例中,第二化合物选自其中,R1,R2选自H、烷基、苯基中的任意一种,R3选自H、非芳香取代基中的任意一种。优选的,烷基选自C1~C3的烷基。在本发明优选实施例中,第二化合物选自其中,R1和R2选自非相同取代基,R3选自氢原子,得到的第二化合物为含芳香基团手性脂肪胺,当第二化合物为手性化合物的情况下使反应得到的刺激响应材料具有圆偏振发光性质。
优选的,第一化合物和第二化合物的摩尔比为1:(1~1.2)。在本发明优选实施例中,第一化合物和第二化合物的摩尔比为1:1,控制第一化合物和第二化合物B之间绝对等物质量相互作用,以获得较为纯净的产物。
在步骤S02中,将第一化合物和第二化合物于有机溶剂中混合得到第一混合物。
优选的,有机溶剂选自二氯甲烷、正己烷、乙酸乙酯、丙酮、甲醇中的至少一种。具体的可根据实际工艺条件进行灵活选择,以不影响化合物A和化合物B之间的相互作用结果为前提。
进一步优选的,有机溶解的添加量选自30~50mL。
优选的,将第一混合物于室温静置、析晶并抽滤处理的步骤中,将将第一混合物于室温静置1~3小时进行有机溶剂挥发,析出微晶并抽滤取固体。
本申请实施例第三方面提供一种多重刺激响应材料或由制备方法制备得到的多重刺激响应材料在多重防伪、生物检测、智能传感、发光材料、3D智能显示、信息加密中的应用。
本申请第三方面提供的多重刺激响应变色材料集多重刺激响应变色性能和圆偏振发光性能于一体,将该多重刺激相应变色材料应用于制备防伪标签或者是信息加密技术上,响应速度快,灵敏度高,有利于极大地拓宽多刺激智能响应材料的应用场景。
下面结合具体实施例进行说明。
实施例1
实施例1制备如下化合物:
该化合物的具体合成方法包括:
将4-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)置于50mL规格的圆底烧瓶内,注入30mL二氯甲烷(DCM)、再将S-1-苯乙胺(121mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.43g,产率为86.5%。
其中,实施例1所涉及的合成路线如下:
实施例2
实施例2合成了以下化合物:
该化合物的具体合成方法包括:
将4-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)止于50mL规格的圆底烧瓶内,注入30mL二氯甲烷(DCM)、再将R-1-苯乙胺(121mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.42g,产率为84.5%。
其中,实施例2所涉及的合成路线如下:
实施例3
实施例3合成了以下化合物:
该化合物的具体合成方法包括:
将4-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)止于50mL规格的圆底烧瓶内,注入30mL二氯甲烷(Meoh)、再将苄胺(107mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.40g,产率为82.8%。
其中,实施例3所涉及的合成路线如下:
实施例4
实施例4合成了以下化合物:
该化合物的具体合成方法包括:
将3-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)置于50mL规格的圆底烧瓶内,注入30mL30mL乙酸乙酯(EtoAc)和15ml正己烷(n-Hexane)、再将S-1-苯乙胺(121mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.44g,产率为88.5%。
其中,实施例4所涉及的合成路线如下:
实施例5
实施例5合成了以下化合物:
该化合物的具体合成方法包括:
将3-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)置于50mL规格的圆底烧瓶内,注入30mL乙酸乙酯(EtoAc)和15ml正己烷(n-Hexane)、再将R-1-苯乙胺(121mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.45g,产率为90.5%。
其中,实施例5所涉及的合成路线如下:
实施例6
实施例6合成了以下化合物:
该化合物的具体合成方法包括:
将3-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)置于50mL规格的圆底烧瓶内,注入30mL甲醇(Meoh)、再将苄胺(107mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.44g,产率为90.9%。
其中,实施例6所涉及的合成路线如下:
实施例7
实施例7合成了以下化合物:
该化合物的具体合成方法包括:
将4-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)置于50mL规格的圆底烧瓶内,注入30mL二氯甲烷(DCM)、再将二苯甲胺胺(183mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.47g,产率为84.1%。
其中,实施例7所涉及的合成路线如下:
实施例8
实施例8合成了以下化合物:
该化合物的具体合成方法包括:
将4-(1,2,2-三苯基乙烯基)苯甲酸(376mg,1.00mmol)置于50mL规格的圆底烧瓶内,注入30mL乙酸乙酯(EtoAc)、再将4-甲氧基吡啶(108mg,1.00mmol)注入上述体系,静置沉积微晶,抽滤,最终得到呈白色粉末状的目标化合物0.44g,产率为90.8%。
其中,实施例8所涉及的合成路线如下:
性能测试:
将实施例制备得到的化合物分别进行以下四个性能测试试验,具体如下:
(1)检测实施例1合成的化合物的光致发光效应,测试方法包括:将化合物置于紫外光照射下观察化合物的发光情况。
(2)检测实施例1合成的化合物的力致变色、和光致变色和力致发光性能,检测化合物的力致变色性能的方法包括:将实施例1合成的化合物的固态粉末进行研磨、溶剂熏蒸等操作后进行紫外光照射;检测化合物的光致变色性能的方法包括:将化合物的固态粉末进行紫外光照射,观察紫外光照射前后样品的颜色变化;检测化合物力致发光的方法包括:将化合物的固粉末用刮勺等硬质物摩擦,可观察到化合物具有力致发光的性质。
(3)检测实施例1和实施例2合成的化合物的圆偏振发光性质,检测圆偏振发光性质的方法包括:使用可测试圆偏振发光性质的仪器进行测试,观察圆偏振发光信号。
(4)将实施例1和实施例3合成的化合物在二氯甲烷溶剂中的沉积物分别抽滤成膜,制成一张具有防伪功能的标签,贴上透明胶带保护,再检测实施例1和实施例3合成的化合物在制备防伪标签上的应用。
结果分析:
测试试验(1)中,将实施例1合成的化合物置于紫外光照射下观察化合物的发光情况,结果如附图1所示,图1为实施例1制备的化合物固态下的发光情况,其中,图1A为化合物在日光下的状态,图1B为化合物在固态条件下的荧光表现。如结果所示,化合物在在固态条件下具有较强的深蓝色荧光,这表明实施例1提供的化合物在固态下同样具有光致发光的性质。
测试试验(2)中,将实施例1合成的化合物分别进行力致变色、和光致变色和力致发光性能性能的测试。
化合物的力致变色性能测试结果如附图2所示,化合物的发光性能发生了变化,其发射的荧光由深蓝色变为黄绿色荧光,表明本实施例制备的化合物具有力致变色性能。具体地,初始样品在紫外光下发射深蓝色荧光,经研磨后,由深蓝色变为黄绿色荧光;另外,经研磨的样品进行二氯甲烷,其在紫外光下由黄绿色荧光转变为深蓝色荧光。
化合物的光致变色性能测试结果如附图3和图4所示,经紫外光照射处理,化合物粉末(图3)和单晶(图4)的颜色由白色晶体变为橙红色粉末,表明本实施例制备的化合物具有光致变色性能。
化合物的力致发光性能性能测试结果如附图5所示,瓶内的粉末经刮勺划过之后观察到蓝色发光,表明其具有力致发光的性质。
测试试验(3)中,检测实施例1和实施例2合成的化合物的圆偏振发光性质,结果如附图6所示,改变手性取代基的手性方向可以使得目标产物的呈现完全相反的圆偏振发光信号,表明本实施例制备的化合物具有圆偏振发光性质,同时可以通过改变手性取代基的方向调控圆偏振发光的信号。
可见,测试了该类多重刺激响应变色材料的圆偏振发光信号和多重刺激响应性能。圆偏振发光测试表明了该类多重刺激响应材料的圆偏振发光性能,结果显示其具有左右手方向的圆偏振发光信号,具有明显的圆偏振发光性质。同时多重刺激响应性能的测试结果显示,该类材料对光、研磨和溶剂熏蒸等外界刺激均产生相应的响应信号,不同的外界刺激下可呈现不同类型的颜色变化或发光强度变化,且具有明显的力致变色性能和力致发光性质。
测试试验(4)中,将实施例1和实施例3合成的化合物在二氯甲烷溶剂中的沉积物分别抽滤成膜,制成一张具有防伪功能的标签,贴上透明胶带保护,其结构如附图7所示,形成的材料结构依次包括一玻璃片,设置在玻璃瓶任一一面的刺激材料薄膜,设置在刺激材料薄膜背离玻璃片的一面的滤纸片,设置在滤纸片背离刺激材料薄膜的一面的透明胶带,得到具有防伪功能的标签。
如附图8所示,将化合物1所制备的标签在日光下照射,呈白色,而在紫外光照射下显示为蓝色荧光,当施加外力于标签内,其在日光下颜色没有什么变化,而在紫外光照射下,力刺激的地方呈现绿色荧光,形成对比;同时在暗室中,力的刺激也会有力致发光的现象;紫外灯照射之后撤去,未经力刺激的地方呈现橙红色的变色现象,经力刺激的地方没有明显现象。由此,表明该化合物可用于制备多重防伪标签。
如附图9所示,作为对比,将化合物3所制备的标签在日光下呈白色,而在紫外光照射下显示为蓝色荧光,当外力在标签中间划一道,在日光下颜色没有什么变化,而在紫外光照射下,力刺激的地方呈现蓝绿色荧光,形成对比;同时在暗室中,力的刺激也会有力致发光的现象。但在紫外灯照射之后没有明显现象,化合物1形成对比。
可见,多种防伪技术均显示了该类材料具有良好的防伪效果,具体的表现为在抽滤的材料微晶膜上可以实现力致变色,光致变色,力致发光等系列防伪手段,表明本申请实施例提供的多重刺激响应变色材料可用于制备防伪标签并且应用于防伪领域。
综上,本申请提的多重刺激响应变色材料结构简单,制备新颖,响应快速,灵敏度高。经实验测试,该多重刺激响应变色材料可对光、研磨、溶剂熏蒸外界刺激产生相应的响应信号,使得发光强度或发光颜色发生明显改变,其具有明显的力致荧光变色、力致发光性质和光致变色的性质,同时还具有圆偏振发光的特性。满足了当前多元化的应用需求,并可广泛应用。
以上所述仅为本申请的较佳实施例而已,并不用以限制本申请,凡在本申请的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本申请的保护范围之内。
Claims (10)
2.根据权利要求1所述的多重刺激响应材料,其特征在于,所述Ar选自芳杂环基、萘基中的任意一种;和/或,
所述烷基选自C1~C3的烷基。
7.根据权利要求6所述的多重刺激响应材料的制备方法,其特征在于,所述第一化合物和所述第二化合物的摩尔比为1:(1~1.2)。
8.根据权利要求7所述的多重刺激响应材料的制备方法,其特征在于,所述第一化合物和所述第二化合物的摩尔比为1:1。
9.根据权利要求6所述的多重刺激响应材料的制备方法,其特征在于,所述有机溶剂选自二氯甲烷、正己烷、乙酸乙酯、丙酮、甲醇中的至少一种。
10.权利要求1~5任一所述的多重刺激响应材料或由权利要求6~9任一所述的制备方法制备得到的多重刺激响应材料在多重防伪、生物检测、智能传感、发光材料、3D智能显示、信息加密中的应用。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050040366A1 (en) * | 2002-03-28 | 2005-02-24 | Yasuhiro Yagi | Fluorescent substance and fluorescent composition containing the same |
WO2016090062A1 (en) * | 2014-12-02 | 2016-06-09 | Massachusetts Institute Of Technology | Multistimuli-responsive white luminescent materials including metal elements |
CN106397450A (zh) * | 2016-09-06 | 2017-02-15 | 北京化工大学 | 一种基于双荧光发色团的力和光双重响应型自组装体及其制备方法 |
US20170174983A1 (en) * | 2014-03-25 | 2017-06-22 | Sabic Global Technologies B.V. | Color changing material |
CN110117235A (zh) * | 2019-05-21 | 2019-08-13 | 江苏萨瑞斯医疗科技有限公司 | 具有聚集诱导发光和力致变色特性的化合物及其制备方法和应用 |
CN110878031A (zh) * | 2019-11-25 | 2020-03-13 | 深圳大学 | 发光材料、发光材料的合成方法及应用 |
CN111072439A (zh) * | 2019-11-25 | 2020-04-28 | 深圳大学 | 一种发光材料及其合成方法及应用 |
-
2020
- 2020-11-10 CN CN202011247757.2A patent/CN112480905B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050040366A1 (en) * | 2002-03-28 | 2005-02-24 | Yasuhiro Yagi | Fluorescent substance and fluorescent composition containing the same |
US20170174983A1 (en) * | 2014-03-25 | 2017-06-22 | Sabic Global Technologies B.V. | Color changing material |
WO2016090062A1 (en) * | 2014-12-02 | 2016-06-09 | Massachusetts Institute Of Technology | Multistimuli-responsive white luminescent materials including metal elements |
CN106397450A (zh) * | 2016-09-06 | 2017-02-15 | 北京化工大学 | 一种基于双荧光发色团的力和光双重响应型自组装体及其制备方法 |
CN110117235A (zh) * | 2019-05-21 | 2019-08-13 | 江苏萨瑞斯医疗科技有限公司 | 具有聚集诱导发光和力致变色特性的化合物及其制备方法和应用 |
CN110878031A (zh) * | 2019-11-25 | 2020-03-13 | 深圳大学 | 发光材料、发光材料的合成方法及应用 |
CN111072439A (zh) * | 2019-11-25 | 2020-04-28 | 深圳大学 | 一种发光材料及其合成方法及应用 |
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