CN105445210A - 一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法 - Google Patents
一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法 Download PDFInfo
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Abstract
酸致变色是近几年来发展较快的一种变色形式。虽然聚合物酸致变色性能方面的研究较多,酸致变色性能与溶剂之间的关系和酸致变色性能与酸强度之间的关系已有报道,但是酸致变色跟聚合物结构之间的关系尚未报道。因此在本发明,我们以2-氨基取代基的嘧啶单体作为共聚物缺电子基团,以苯环作为富电子基团,利用Suzuki反应成功合成了新型共轭聚合物,对聚合物进行结构表征和性能研究并讨论了嘧啶单元取代基对嘧啶和苯交替共聚物酸致变色性能的影响,同时进一步着重讨论了交替单元(苯单元)对嘧啶类共聚物酸致变色性能的影响,提供了新的一种具有酸致变色性能的聚合物并确定了其酸致变色范围和最低响应酸浓度,酸掺杂后代表性聚合物的结构式如摘要图所示。
Description
技术领域
本发明涉及一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法,属于信息存储、电极材料与新型酸碱敏感的传感材料等技术领域并有着潜在的应用前景。
背景技术
酸致变色是近几年来发展较快的一种变色形式,是指由于pH值的不同或接触酸性或碱性气体而造成的可逆的颜色变化,具有酸致变色性能的材料称之为酸致变色材料,具有其性能的聚合物为pH或者传感器等领域的应用提供借鉴。2008年Jeong-HoKim,JaeYunJaung研究了卟啉-喹屋啉衍生物的酸致变色性能并发现不断添加三氟乙酸溶液导致化合物的紫外峰发生红移并且Q带出现了一个新峰,甲磺酸的添加导致聚合物荧光光谱发生淬灭现象,PrachiSingh,AbhishekBaheti等研究了Amine-SubstitutedBenzophenazines(氨基取代苯并吩嗪)发现虽然燃料的吸收光谱没有收到各种酸本身的影响,但是三氟乙酸的添加使喹屋啉单元发生质子化,本发明研究了以2-氨基-4,6-二氯嘧啶和2,5-二己基-1,4-苯基二硼酸乙二醇酯单体为原料合成了一种共轭程度较大的嘧啶单元和苯单元组成的共轭聚合物,并对其结构和酸致变色性能进行了探讨.
与噻吩、吡咯等富电子基团相反,由缺电子芳香环构成的聚合物一般具有还原掺杂(n-doping)以后导电率显著提高,荧光性能增强等特点。另外,设计主链上含有缺电子芳香环的,具有还原掺杂性的聚合物在聚合物电池电极材料、电化学电容器等方面具有较大的应用前景,在缺电子化合物当中,2-氨基嘧啶是一种典型的缺电子芳香杂环化合物,具有广泛的生理活性并在有机发光,光伏电池等领域有一定的应用,虽然含有嘧啶环聚合物的研究一直没有间断过,但是由嘧啶单元和苯单元组成的共轭聚合物的研究尚鲜见报道,作电极材料是含嘧啶杂环类共轭聚合物主要的应用之一,在发达国家以全聚合物材料作电池的应用研究取得了一定的进展,由缺电子基团构成的聚合物能够进行n型掺杂,可以作聚合物电池负极材料,n型电池的电解液用量少,容易精密化,由缺电子芳香环与富电子芳香环组成的电荷移动型共轭聚合物同时具有p、n两型的掺杂性能,而且通过选择性的改变各聚合单元可设计出具有不同特性的功能聚合物。因此在π-共轭聚合物的研究中,电荷转移型(CT-Type)聚合物及其电极行为的研究成为重要发展方向,电荷转移型共聚物是指由缺电子单元和富电子单元组成的一类共轭聚合物,在电荷转移力的作用下,富电子单元的电子云偏向于缺电子单元、共聚物分子内的电荷发生转移,使单元之间相互作用增加,提高共聚物的共轭程度,这样就可以得到基态和激发态能量差较低的窄带能隙(lowbandgap)共轭聚合物.
本发明通过化学方法,利用卤化物与金属钯催化的有机硼化合物之间的Suzuki偶联反应成功合成了具有良好的导电性能和较好的溶解性能的主链含2-甲基嘧啶与苯的新型共轭聚合物并着重讨论了聚合物的嘧啶单元取代基和苯交替单元对聚合物酸致变色性能的影响.
与其他嘧啶类聚合物相比,此类聚合物在常用有机溶剂中具有一定的溶解性。聚合物光学性能测试结果表明:该聚合物在氯仿溶液中的紫外可见吸收光谱在319nm处出现最大吸收峰,聚合物的氯仿溶液存在酸致变色现象,随着三氟乙酸浓度的增加,共聚物原来的吸收峰的强度不断降低,并且出现了一个新的吸收峰,UV—Vis吸收峰发生红移;在酸性介质中,聚合物荧光强度随着酸浓度的增加逐渐减低,表明聚合物在酸性溶剂中具有荧光淬灭现象。
发明内容
本发明用2-氨基-4,6-二氯嘧啶和2,5-二己基-1,4-苯基二硼酸乙二醇酯单体,以Pd(PPh3)4为催化剂,采用1H-NMR、13CNMR、红外光谱、紫外光谱、荧光光谱等测试手段,成功的实现了此聚合物的合成并对其结构进行表征,探讨其独特的酸致变色性能并确认最低响应酸浓度.
结果表明本发明中制备的主链分含2-氨基嘧啶与聚[2-氨基-4,6-嘧啶2,5-二己基-1,4-苯]是溶解性较好的共轭聚合物,它在常用有机溶剂中具有一定的溶解性并具有酸致变色现象,在它的氯仿溶液中添加CF3C00H后,聚合物原来的吸收峰强度不断降低,并且出现了一个新的吸收峰,UV—Vis吸收峰发生红移。荧光强度随着酸浓度的增加逐渐降低,表明聚合物在酸性溶剂中具有荧光淬灭现象。通过荧光可以算出,聚合物对三氟乙酸的检出下线分别为2.17×10-8mol/L。主链含嘧啶类共轭聚合物的酸致变色性能研究表明,与其他含嘧啶-苯交替单元和嘧啶-芴交替单元组成的共聚物相比,由2-氨基嘧啶合成的共聚物响应酸浓度最低,可检测浓度范围从4.573×10-8mol/L~2.541×10-3mol/l。
本发明的目的之一是提供一种可溶性聚合物合成方法并利用缺电子基团与富电子基团之间的电荷转移,提高聚合物的共轭程度,从而达到改善聚合物加工性能.
本发明的目的之二是提供一种具有酸致变色性能的新型聚合物信息。虽然聚合物酸致变色性能方面的研究较多,但聚合物分子结构对酸致变色性能的影响尚未研究报道。所以此聚合物酸致变色性能方面的研究有着潜在的应用前景.
本发明的目的之三是提供此聚合物酸致变色灵敏范围、最低响应酸浓度和对三氟乙酸的荧光检出下线.
本发明的目的之四是提供具有很好的酸致变色性能的聚合物材料作为信息存储与传感等领域的应用前景。
与现有其他方法和技术相比较,本发明具有如下优点
(1)本发明提到的制备方法简单,合成出来的聚合物溶解性好并具有良好的导电性能粉末状产物,适宜于大批量工业生产,因此具有工业使用价值.
(2)本发明利用的Suzuki聚合反应具有巨大空间、反应条件不太苛刻、反应毒性较小及可获得结构规整的交替共聚物.
(3)具有还原掺杂(n-doping)以后导电率显著提高,荧光性能增强等特点的2-氨基嘧啶是一种典型的缺电子芳香杂环化合物,具有广泛的生理活性并在有机发光,光伏电池等领域有一定的应用.
(4)本发明着重研究了尚鲜见报道的嘧啶单元和苯单元组成的共轭聚合物结构对其酸致变色性能的影响,揭开了新的研究方向。
附图说明
图1:聚合物合成路线;
图2:聚合物的氢谱(a)和碳谱图(b);
图3:单体和聚合物的红外光谱图;
图4:聚合物在不同浓度的氯仿--CF3COOH混合液中的紫外吸收峰变化;
图5:聚合物在不同浓度的氯仿--CF3COOH混合液中的荧光光谱变化(a)和CF3COOH浓度与I0/I之间的关系图(b);
图6:红外光谱图:(a)纯聚合物;(b)聚合物暴露在CF3COOH中;(c)纯CF3COOH溶液。
具体实施方式
实施例
合成聚合物:在100ml聚合瓶中通入氩气,电磁搅拌下依次加入2-氨基-4,6-二氯嘧啶(0.296mmol,48.5mg),2,5-二己基-1,4-苯基二硼酸乙二醇酯单体(0.296mmol,114.3mg),碳酸铯Cs2CO3(1.48mmol,481.2mg,),再加14.8mlDME和7.4ml去离子水,电磁搅拌下通入氩气15min,加钯催化Pd(PPh3)4(0.0148mmol,17.2mg),氩气保护下,将反应体系回流48h,反应物冷却到室温,生成物用乙醇洗涤,氯仿/乙醇重结晶2次,用水洗涤后50℃真空干燥24h,可得68mg黄色粉末物,收率为68%,通过图2、图3,确定聚合物成功合成。1H-NMR(CHCl3,δ):δ=6.72~7.90ppm(m,3H,-CH),δ=5.17ppm(broads,2H,-NH2),δ=2.79ppm(t,4H,-CH2),δ=1.23~1.90ppm(m,16H,-CH2),δ=0.782ppm(t,6H,-CH3)。13CNMR(75MHz,CDCl3):δ=13.67,21.85,28.46,30.80,39.40,130.25,137.47,138.78,138.76,163.19,165.46,167.41.
制备聚合物溶液:通过不断改变聚合物-氯仿-三氟乙酸混合液中的三氟乙酸浓度,成功的制备具有不同浓度的聚合物溶液,得到的各混合液浓度如下:(1)0,(2)4.573×10-8,(3)2.058×10-7,(4)8.918×10-7,(5)2.493×10-6,(6)9.353×10-6,(7)2.307×10-5,(8)1.397×10-4,(9)4.827×10-4,(10)1.397×10-3,(11)2.541×10-3;
聚合物溶液进行测试:通过紫外吸收光谱、荧光光谱和红外光谱等测试手段,对聚合物-氯仿-三氟乙酸混合液进行测试,确定聚合物酸致变色范围和最低响应酸浓度。图4所示随着三氟乙酸浓度的增加,聚合物的紫外吸收峰强度快速降低,同时在长波处出现了一个新的紫外吸收峰并不同浓度的聚合物氯仿--CF3COOH混合液荧光光谱发生明显的红移(424nm到464nm),与紫外吸收光谱相比,显得受到更强的影响。与此同时,CF3COOH的浓度从零增加到1.829×10-7时,荧光强度迅速降低直到荧光峰完全消失。图5(b)所示通过对低浓度三氟乙酸存在下聚合物在424nm处荧光强度的变化曲线进行线性拟合,通过标准曲线可知聚合物对三氟乙酸的荧光检出下线约为2.17×10-8mol/L。拟合直线方程为Y=(0.0156±0.341)+(4.5734±0.411)X,相关系数R2=0.9685.
推测酸致变色后的聚合物结构式:通过红外光谱,以其为基础推测了聚合物酸致变色后的结构式。在图6曲线(a)中~3288cm-1和3497cm-1处出现的–NH2对应的峰,在曲线(b)中在~3240cm-1和3481cm-1处出现并且–NH2的特征峰变宽。嘧啶环中C=N的特征峰在曲线(a)中出现在1630cm-1and1562cm-1处,在曲线(b)中出现在1680cm-1和1603cm-1处。烷基链典型的伸缩振动峰在曲线(a)、(b)中2852cm-1和2953cm-1处出现。根据红外光谱数据,氨基、嘧啶环的特征峰向低波数移动,但是烷基链典型的伸缩振动峰没有发生明显的变化。在曲线(b)中–NH2特征峰的变宽说明在CF3COOH的作用下产生了新的N-H键并且它新的吸收峰与原吸收峰重叠。由于芳环上的N原子被质子化、产生了两个氢,在1580cm-1~1400cm-1范围内有所变化。从曲线(b)可以观察到CH3COOH中C=O的特征吸收峰在1786cm-1处出现(与曲线(c)中~1786cm-1基本相同)。以红外光谱图为基础推测了聚合物酸致变色后的结构式。酸掺杂后代表性聚合物的结构式如摘要图所示。
Claims (6)
1.本发明是一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法,包括如下具体步骤:
(1)合成聚合物:在100ml聚合瓶中通入氩气,电磁搅拌下依次加入2-氨基-4,6-二氯嘧啶(0.296mmol,48.5mg),2,5-二己基-1,4-苯基二硼酸乙二醇酯单体(0.296mmol,114.3mg),碳酸铯Cs2CO3(1.48mmol,481.2mg,),再加14.8mlDME和7.4ml去离子水,电磁搅拌下通入氩气15min,加钯催化Pd(PPh3)4(0.0148mmol,17.2mg),氩气保护下,将反应体系回流48h,反应物冷却到室温,生成物用乙醇洗涤,氯仿/乙醇重结晶2次,用水洗涤后50℃真空干燥24h,可得68mg黄色粉末,收率为68%,聚合物合成路线见附图1,通过红外光谱、氢谱、碳谱确定聚合物成功合成部分见附图2(a)、(b)和附图3.
(2)制备聚合物溶液:通过不断改变聚合物-氯仿-三氟乙酸混合液中的三氟乙酸浓度,成功的制备具有不同浓度的聚合物溶液.
(3)聚合物溶液进行测试:通过紫外吸收光谱、荧光光谱和红外光谱等测试手段,对聚合物-氯仿-三氟乙酸混合液进行测试,确定聚合物酸致变色范围和最低响应酸浓度.
(4)推测酸致变色后的聚合物结构式:通过红外光谱,以其为基础推测了聚合物酸致变色后的结构式。
2.根据权利要求书1所述的一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法,其典型特征在于:通过多次合成聚合物,本发明合成出了具有溶解性很好的聚合物并确定了聚合反应的最佳温度范围(85~95℃),如果超过该温度,虽然反应产率高,但是随之聚合物的分子量增大导致聚合物的溶解性降低。
3.根据权利要求书1所述的一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法,其典型特征在于:本聚合物的氯仿溶液存在酸致变色现象并在酸性溶剂中具有荧光淬灭现象。
4.根据权利要求书1所述的一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法,其典型特征在于:本发明研究了聚合物结构对聚合物质子化作用的影响,对聚合物在氯仿-三氟乙酸混合液进行了紫外吸收光谱和荧光光谱测试,成功的确定了聚合物的酸致变色灵敏范围和最低响应酸浓度。
5.根据权利要求书1所述的一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法,其典型特征在于:本发明用的聚合物嘧啶环上的氨基可以明显降低聚合物的最低响应酸浓度,因为是由于嘧啶环上的取代基有利于氢键的形成,由于-NH2为弱碱性基团,聚合物在被质子化的同时容易受到酸性环境的影响有可能形成氢键,因此与嘧啶环上含氢基或甲基的聚合物相比,此聚合物中更容易发生酸致变色现象并其紫外光谱响应酸浓度最低(4.573×10-8mol/L),荧光检测下限高达2.17×10-8mol/L。
6.根据权利要求书1所述的一种具有酸致变色性能的聚合物检测三氟乙酸浓度的方法,其典型特征在于:本发明进一步讨论交替单元对嘧啶类聚合物酸致变色性能的影响,与已有报道的主链含芴交替单元的聚合物相比(最低响应酸浓度为4.80×10-6mol/L),主链含苯的聚合物响应酸浓度更低(最低响应酸浓度为4.573×10-8mol/L)。
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CN109916850A (zh) * | 2019-04-04 | 2019-06-21 | 新疆大学 | 基于近红外光谱显著性分析检测样品理化性质的方法 |
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