CN116103035A - 一种基于罗丹明染料的室温磷光材料及其应用 - Google Patents
一种基于罗丹明染料的室温磷光材料及其应用 Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 53
- 239000001022 rhodamine dye Substances 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 55
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000010453 quartz Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 12
- 229940043267 rhodamine b Drugs 0.000 claims description 11
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 6
- MYIOYATURDILJN-UHFFFAOYSA-N rhodamine 110 Chemical compound [Cl-].C=12C=CC(N)=CC2=[O+]C2=CC(N)=CC=C2C=1C1=CC=CC=C1C(O)=O MYIOYATURDILJN-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 5
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 5
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- -1 sulfonyl rhodamine B Chemical compound 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000009194 climbing Effects 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
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- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 4
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- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 4
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- 238000001228 spectrum Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000001301 oxygen Substances 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
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- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
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Abstract
本发明公开了一种基于罗丹明染料的室温磷光材料及其应用,该磷光材料为由罗丹明染料和聚膦酸酯类聚合物组成的余辉体系;采用如下制备方法获得:首先将聚膦酸酯类聚合物溶解于二甲亚砜中;然后加入罗丹明染料,搅拌均匀后,将所得溶液滴涂在石英基底上烘干成膜,得到室温磷光材料。所得室温磷光材料用于信息加密和防伪技术领域。本发明聚膦酸酯类聚合物的刚性网络环境抑制了染料的分子运动,降低了三重态激子的非辐射失活,实现了基于罗丹明染料的室温磷光发射。本发明成本较低,具有较好的普适性,为荧光染料的室温磷光发射提供了一种简便的策略,同时在信息防伪领域具有较好的应用前景。
Description
技术领域
本发明属于磷光材料技术领域,具体涉及一种基于罗丹明衍生物的长寿命聚合物室温磷光材料及其制备和应用。
背景技术
室温磷光材料由于其独特的发光特性,在防伪、生物成像、有机发光二极管(OLED)和信息加密领域具有广泛的应用前景。传统的磷光材料主要集中在含稀土的无机材料上,但由于制备方法复杂,成本高,因而进展缓慢。与无机磷光材料相比,纯有机室温磷光材料生物毒性低、加工性能好、可塑性强。因此开发纯有机室温磷光材料是至关重要的。众所周知,从单重态到三重态的系间窜越(ISC)过程是自旋禁阻的,三重态激子受到自由运动和氧猝灭的影响,从而导致非辐射失活。因此,实现室温磷光发射仍然是一个巨大的挑战。近年来,许多杰出的策略被设计来促进ISC过程和抑制非辐射衰减速率,包括重原子效应、晶体工程、主客体相互作用、碳点和聚合物基质掺杂。
目前已经有许多方法致力于实现高量子产率和长发射寿命的室温磷光材料。报道的主要方法是晶体形式,因为晶体可以压缩分子的振动并保护分子隔绝氧气。但是晶体工程存在柔性较小、加工难度大等缺点,且由于晶体易受温度和溶剂的影响,不容易大规模应用。而共聚和主客体相互作用往往涉及到复杂的分子设计,不利于体系的构建。这些困难阻碍了研究者们利用大量的荧光染料库来开发磷光材料。
发明内容
针对现有技术存在的上述不足,本发明目的在于提供一种普适性强,成本较低的基于罗丹明染料的室温磷光材料,解决现有室温磷光材料成份复杂、普适性不强,并且加工难度大,不利于大规模应用等问题。
进一步,本发明还提供了上述室温磷光材料在实现信息防伪上的应用。
为了解决上述技术问题,本发明采用了如下的技术方案:
一种基于罗丹明染料的室温磷光材料,其特征在于,由聚膦酸酯类聚合物和罗丹明染料组成余光体系;所述聚膦酸酯类聚合物具有如下结构:
所述基于罗丹明染料的室温磷光材料采用如下方法制备而成:
1)将聚膦酸酯类聚合物溶解于二甲亚砜中,配置成浓度为20-22g/L的溶液,然后向该溶液中加入罗丹明染料,搅拌均匀;所述聚膦酸酯类聚合物和罗丹明染料的质量比为98-102:1;
2)将所得溶液滴涂在石英基底上烘干成膜,得到室温磷光材料。
其中,所述步骤2)为于真空烘箱中,温度为58-62℃干燥时间为22-24h。
进一步,所述罗丹明染料为罗丹明(RhB)、磺酰罗丹明B(SRB)、罗丹明6G(Rh6G)或罗丹明110(Rh110)中的任一种:
进一步,所述聚膦酸酯类聚合物的制备方法包括:
S11、制备聚膦酸酯类聚合物中间体
(1)将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、对苯醌和乙二醇乙醚加入到装有磁石,氩气进出口的三口烧瓶中;140-145℃下反应4-4.2h,并将所得产物冷却至室温后过滤,洗涤,得聚膦酸酯类聚合物中间体的粗产品;其中,所述9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和对苯醌的摩尔比相同;
(2)将聚膦酸酯类聚合物中间体的粗产品重结晶,冷却过滤后,放入真空烘箱中干燥,得到白色的粉末状固体,即为聚膦酸酯类聚合物中间体;
S12、制备聚膦酸酯类聚合物:
(1)将步骤S11所得聚膦酸酯类聚合物中间体、苯膦酰二氯和氯化锌,加入配有机械搅拌装置和氩气进出口的四口烧瓶中,在160-165℃的温度下加热反应一段时间,直到体系变得粘稠出现爬杆现象;再升温到230-235℃继续反应5-5.5h,抽真空除去氯化氢气体,所得产物冷却后即得到聚膦酸酯类聚合物粗产品;所述聚膦酸酯类聚合物中间体和苯膦酰二氯的摩尔比相同;
(2)所步骤(1)所得聚膦酸酯类聚合物粗产品用三氯甲烷溶解,然后用无水乙醚沉淀;最后用丙酮作为索氏提取器的溶剂在85-95℃回流8-9h,烘干得到聚膦酸酯类聚合物。
本发明还提供一种基于罗丹明染料的室温磷光材料室温磷光材料的应用,应用于信息加密及防伪技术领域。
相比现有技术,本发明具有如下有益效果:
1、本发明创造性地采用罗丹明染料和聚膦酸酯类聚合物组成余辉体系,发光时间长达2s以上;并且本发明磷光材料发光颜色为红色,丰富了磷光材料的发光颜色,解决目前室温磷光材料的发光颜色大多为蓝色、绿色,而红色的磷光发射比较少的问题。
2、本发明采用普通的小分子为原料制备聚膦酸酯类聚合物,成分简单,制备方便;并且,所制备的聚膦酸酯类聚合物具有良好的刚性结构,其刚性网络环境抑制了染料的分子运动,降低了三重态激子的非辐射失活,实现了基于罗丹明染料的室温磷光发射。
3、本发明为简捷、高效的荧光染料型室温磷光材料的制备提供了新的研究方向及技术支持,也丰富了赐予染料以磷光发射材料的应用;不但制备方法简单,成本较低;且选择商用罗丹明染料,多种类型的罗丹明染料都适用,具有很强的普适性,生产成本低,利于大规模应用。
4、本发明基于染料的室温磷光材料的制备方法具有很强的普适性,对于多种类型的罗丹明染料都适用。在365nm的紫外灯源关闭后可以得到余辉颜色为橙红色、橙色和橙黄色的室温磷光材料,可用于信息加密及发防伪等应用领域。
5、本发明聚合物的室温磷光材料相比于小分子体系有更好的生物相容性,具有柔性较大,可大面积制备等优点。
附图说明
图1为本发明实施例1制得的室温磷光薄膜在365nm紫外灯下的磷光发射图;
图2为本发明实施例1制得的室温磷光薄膜在大气环境下365nm激发时所测得的相关光物理性质谱图;
图3为本发明实施例2-4制得的室温磷光薄膜在365nm紫外灯下磷光发射现象;
图4为本发明实施例2-4制得的室温磷光薄膜在365nm激发时的荧光发射光谱;
图5为本发明实施例2-4制得的室温磷光薄膜在365nm激发后的磷光发射光谱;
图6为本发明实施例2-4制得的室温磷光薄膜在365nm激发时不同发射波长下的磷光寿命谱图。
具体实施方式
下面结合实施例对本发明作进一步的详细说明。
一、一种基于罗丹明染料的室温磷光材料
由聚膦酸酯类聚合物和罗丹明染料组成余光体系;
其中,所述聚膦酸酯类聚合物具有如下结构:
进一步,所述罗丹明染料为罗丹明(RhB)、磺酰罗丹明B(SRB)、罗丹明6G(Rh6G)或罗丹明110(Rh110),具体结构如下:
二、所述聚膦酸酯类聚合物的制备
(1)制备聚膦酸酯类聚合物中间体
将17g的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物,7g对苯醌和34ml乙二醇乙醚加入到装有磁石,氩气进出口的三口烧瓶中。在140℃下反应4h,将得到的产物冷却至室温过滤,然后用乙二醇乙醚和甲醇洗涤。将得到的粗产品用乙二醇乙醚重结晶,冷却后过滤,在60℃的真空烘箱中干燥24h,得到白色的粉末状固体产品。
(2)制备聚膦酸酯类聚合物
称取3.4125g步骤(1)得到的固体粉末,2.05g苯膦酰二氯和0.014g氯化锌于100ml的配有机械搅拌装置和氩气进出口的四口烧瓶中,在160℃的温度下,在氩气的保护环境中,加热瓶内的反应物呈现液态,维持该温度一段时间直到体系变得粘稠出现爬杆现象。然后将温度升高到230℃继续反应5h,后期抽真空以除去体系中残留的氯化氢气体。反应物冷却后即为聚膦酸酯类聚合物的粗产品,将所得粗产品用三氯甲烷溶解,然后用无水乙醚沉淀,再用丙酮作为索氏提取器的溶剂将粗产品在90℃回流8h,烘干得到聚膦酸酯类聚合物。
经红外光谱和核磁共振氢谱检测,所述聚膦酸酯类聚合物具有如下结构:
三、基于罗丹明染料的室温磷光材料的制备
实施例1
称取所得到的聚膦酸酯类聚合物20mg溶解于1ml的二甲亚砜溶液当中,配置成20g/L的溶液。然后,称量0.2mg罗丹明B(RhB)加入到上述溶液中,将配好的溶液滴涂在石英片上,在95℃下烘干成膜,即得基于罗丹明染料的室温磷光材料。
实施例2-4
实施例2-4与实施例1的方法相同,不同点在于,将罗丹明B分别换成了磺酰罗丹明B(SRB),罗丹明6G(Rh6G)或罗丹明110(Rh110)。由此可见,该方法对于罗丹明染料具有普适性。
本发明中,罗丹明(RhB)、磺酰罗丹明B(SRB)、罗丹明6G(Rh6G)或罗丹明110(Rh110)和聚膦酸酯类聚合物的结构式如下:
所用溶剂(二甲亚砜)结构式如下:
四、验证磷光材料发光特性
验证方法:
在大气环境下用365nm、30W紫外灯对得到的薄膜进行激发,即可观察到不同染料聚合物体系的室温磷光现象。
如图1所示,在大气环境下用365nm紫外灯对实施例1所得到的薄膜进行激发,可以明显观察到磷光从强到弱最后消失的现象(顺序为从左到右,从上到下)。
如图2所示,图2为实施例1所得薄膜对应的相关光物理性质的谱图,由图2(a、b、c)可知薄膜在365nm激发下在596nm处具有较强的荧光强度(图2a)和磷光强度(图2b)以及在596nm的最佳发射下具有285.14ms(图2c)的磷光寿命。
如图3所示,在大气环境下用365nm紫外灯对实施例2-4得到的薄膜进行激发,可以明显观察到磷光的不同颜色的发射现象,其磷光发射时间为2s,具有发光时间长的优点,应用于信息加密和防伪技术邻域时,更有利于使用者观察。
图4为本发明实施例2-4制得的室温磷光薄膜在365nm激发时的荧光发射光谱;由图4(a、b、c)可知,具有较强的荧光发射,其颜色分别为橙红色,橙色以及橙黄色。
图5为本发明实施例2-4制得的室温磷光薄膜在365nm激发后的磷光发射光谱;由图5可知,磷光发射较强,最佳发射分别位于602nm,582nm以及568nm左右。
图6为本发明实施例2-4制得的室温磷光薄膜在365nm激发时不同发射波长下的磷光寿命谱图。由图6可知,三种薄膜在最佳发射下的磷光寿命分别为247.62ms,101.60ms,94.16ms。具有较长的磷光寿命。
由此可见,本发明提供了一种普适性强,成本较低的基于罗丹明染料的室温磷光材料,解决现有室温磷光材料成份复杂、普适性不强,并且加工难度大,不利于大规模应用等问题。创造性地采用罗丹明染料和聚膦酸酯类聚合物组成余辉体系,发光时间长达2s以上;并且本发明磷光材料发光颜色为红色,丰富了磷光材料的发光颜色,解决目前室温磷光材料的发光颜色大多为蓝色、绿色,而红色的磷光发射比较少的问题。
本发明为简捷、高效的荧光染料型室温磷光材料的制备提供了新的研究方向及技术支持,也丰富了赐予染料以磷光发射材料的应用。特别适用于信息加密及发防伪等应用领域。
最后需要说明的是,以上实施例仅用以说明本发明的技术方案而非限制技术方案,本领域的普通技术人员应当理解,那些对本发明的技术方案进行修改或者等同替换,而不脱离本技术方案的宗旨和范围,均应涵盖在本发明的权利要求范围当中。
Claims (8)
3.根据权利要求1或2所述基于罗丹明染料的室温磷光材料,其特征在于,所述聚膦酸酯类聚合物和罗丹明染料的质量比为98-102:1。
5.根据权利要求4所述基于罗丹明染料的室温磷光材料,其特征在于,所述S11制备聚膦酸酯类聚合物中间体的方法包括:
(1)将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、对苯醌和乙二醇乙醚加入到装有磁石,氩气进出口的三口烧瓶中;140-145℃下反应4-4.2h,并将所得产物冷却至室温后过滤,洗涤,得聚膦酸酯类聚合物中间体的粗产品;其中,所述9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物和对苯醌的摩尔比相同;
(2)将聚膦酸酯类聚合物中间体的粗产品重结晶,冷却过滤后,放入真空烘箱中干燥,得到白色的粉末状固体,即为聚膦酸酯类聚合物中间体;
所述S12制备聚膦酸酯类聚合物的方法包括:
(1)将步骤S11所得聚膦酸酯类聚合物中间体、苯膦酰二氯和氯化锌,加入配有机械搅拌装置和氩气进出口的四口烧瓶中,在160-165℃的温度下加热反应一段时间,直到体系变得粘稠出现爬杆现象;再升温到230-235℃继续反应5-5.5h,抽真空除去氯化氢气体,所得产物冷却后即得到聚膦酸酯类聚合物粗产品;所述聚膦酸酯类聚合物中间体和苯膦酰二氯的摩尔比相同;
(2)所步骤(1)所得聚膦酸酯类聚合物粗产品用三氯甲烷溶解,然后用无水乙醚沉淀;最后用丙酮作为索氏提取器的溶剂在85-95℃回流8-9h,烘干得到聚膦酸酯类聚合物。
6.根据权利要求3所述基于罗丹明染料的室温磷光材料,其特征在于,其制备方法包括:
S21、将权利要求4或5所得聚膦酸酯类聚合物溶解于二甲亚砜中,配置成浓度为20-22g/L的溶液,然后向该溶液中加入罗丹明染料,搅拌均匀;所述聚膦酸酯类聚合物和罗丹明染料的质量比为98-102:1;
S22、将S21所得溶液滴涂在石英基底上烘干成膜,得到室温磷光材料。
7.根据权利要求6所述基于罗丹明染料的室温磷光材料,其特征在于,所述步骤S22为于真空烘箱中,温度为58-62℃干燥时间为22-24h。
8.一种基于罗丹明染料的室温磷光材料室温磷光材料的应用,其特征在于,采用权利要求1-7任一所述室温磷光材料应用于信息加密及防伪技术领域。
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