CN110183626B - 一种共轭聚合物及其制备方法与应用 - Google Patents
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Abstract
本公开提供了一种共轭聚合物及其制备方法与应用，该共轭聚合物为线性共轭聚合物或超支化共轭聚合物，所述线性共轭聚合物结构如式Ⅰ所示：
所述超支化共轭聚合物具有式Ⅱ所示化学结构：
本公开制备的共轭聚合物均可用于硝基芳香族化合物的微痕量检测。通过实验表明，本公开提供的超支化共轭聚合物较高的光稳定性和热稳定性，且对NACs的检测效果更好。
Description
技术领域
本公开属于荧光检测技术领域，涉及一种共轭聚合物及其制备方法与应用。
背景技术
这里的陈述仅提供与本公开有关的背景信息，而不必然构成现有技术。
硝基芳香族化合物(NACs)，如2,4,6-三硝基甲苯(TNT)、2,4,6-三硝基苯酚(PA)等，是爆炸物的主要成分。众所周知，爆炸物对人类生命危害很大，对生态系统和环境也造成了严重的损害。随着爆炸物在建筑业和军工业中的广泛应用，迫切需要开发灵敏的非接触式传感方法来实现硝基芳烃爆炸物高效检测。迄今为止，荧光传感器因其检出限低，灵敏度高，选择性好等特点而备受关注。其中一维(1D)的共轭聚合物在检测NACs中报道最多，据本公开发明人研究了解，现有一维的共轭聚合物具有光稳定性较低、热稳定性较低、检测效果较差等缺陷。
发明内容
为了解决现有技术的不足，本公开的目的是提供一种共轭聚合物及其制备方法与应用。该共轭聚合物具有较高的光稳定性和热稳定性，且对NACs的检测效果更好。
为了实现上述目的，本公开的技术方案为：
一方面，一种共轭聚合物，为线性共轭聚合物或超支化共轭聚合物；
所述线性共轭聚合物结构如式Ⅰ所示：
所述超支化共轭聚合物具有式Ⅱ所示化学结构：
其中，线性共轭聚合物的重均分子量为5×104～8×104g mol-1；超支化共轭聚合物的重均分子量为1×104～2×104g mol-1。
另一方面，一种上述共轭聚合物的制备方法，包括以甲基吡嗪类化合物和N-己基-3,6-二醛咔唑为原料通过以下路线进行反应，甲基吡嗪类化合物为2,5-二甲基吡嗪或2,3,5,6-四甲基吡嗪；
第三方面，一种上述共轭聚合物在检测硝基芳香族化合物中的应用。
第四方面，一种硝基芳香族化合物检测传感器，采用的传感材料包括上述共轭聚合物。
第五方面，一种检测硝基芳香族化合物的方法，将待测溶液加入至上述共轭聚合物的溶液中，进行荧光检测。
本公开的有益效果为：
通过实验表明，本公开制备的共轭聚合物均可用于硝基芳香族化合物的微痕量检测。实验结果表明与线性共轭聚合物相比，超支化共轭聚合物对硝基芳香族化合物的灵敏感性更高。超支化共轭聚合物(1.25×104M-1)的Stern-Volmer常数(Ksv)比线性共轭聚合物(1.67×103M-1)高7.5倍，而超支化共轭聚合物(8μM)对硝基芳香族化合物的检测限却比线性共轭聚合物(65μM)低8.1倍。
2.本公开制备的共轭聚合物具有较高的热稳定性，其中，超支化共轭聚合物在分子内具有更大的空间位阻，从而使得超支化共轭聚合物具有更高的热稳定性。
3.本公开制备的共轭聚合物在光照射下均显示出良好的稳定性。
附图说明
构成本公开的一部分的说明书附图用来提供对本公开的进一步理解，本公开的示意性实施例及其说明用于解释本公开，并不构成对本公开的不当限定。
图1为本公开实施例1和实施例2制备的P1和P2的光谱图，a为吸收光谱，b为荧光光谱，P1激发波长为300nm，P2激发波长为310nm；
图2为热重分析曲线，a本公开实施例1和实施例2制备的P1和P2，b为对比化合物；
图3为本公开实施例1和实施例2制备的P1和P2的荧光猝灭表征图，a为不同浓度PA(CPA＝0,0.2,0.4,0.6,…4×10-4M)加入到P1溶液中P1的荧光变化曲线，b为不同浓度PA(CPA＝0,0.2,0.4,0.6,…4×10-4M)加入到P2溶液中P2的荧光变化曲线，c为P1的荧光猝灭效率曲线，d为P2的荧光猝灭效率曲线；
图4为本公开实施例1和实施例2制备的P1和P2的Stern-Volmer图；
图5为本公开实施例1和实施例2制备的P1和P2的猝灭效应示意图；
图6为本公开实施例1和实施例2制备的P1和P2对不同分析物的猝灭效率表征图；
图7为本公开实施例1和实施例2制备的P1和P2的HOMO和LUMO能量表征图；
图8为本公开实施例1和实施例2制备的P1和P2的荧光稳定性曲线，P1的激发波长为300nm，P2的激发波长为310nm，狭缝宽度：5nm，电压：700V。
具体实施方式
应该指出，以下详细说明都是示例性的，旨在对本公开提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本公开所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本公开的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
鉴于现有一维的共轭聚合物存在热稳定性较低、检测效果较差等不足，为了解决如上的技术问题，本公开提出了一种共轭聚合物及其制备方法与应用。
本公开的一种典型实施方式，提供了一种共轭聚合物，为线性共轭聚合物或超支化共轭聚合物；
所述线性共轭聚合物结构如式Ⅰ所示：
所述超支化共轭聚合物具有式Ⅱ所示化学结构：
其中，线性共轭聚合物的重均分子量(Mw)为5×104～8×104g mol-1；超支化共轭聚合物的重均分子量(Mw)为1×104～2×104g mol-1。
该实施方式的一种或多种实施例中，线性共轭聚合物的多分散系数(PDI)为1.30～1.31。
该实施方式的一种或多种实施例中，超支化共轭聚合物的多分散系数(PDI)为1.63～1.64。
该实施方式的一种或多种实施例中，为超支化共轭聚合物。
本公开的另一种实施方式，提供了一种上述共轭聚合物的制备方法，包括以甲基吡嗪类化合物和9-己基-9H-咔唑-3,6-二甲醛为原料通过以下路线进行反应，甲基吡嗪类化合物为2,5-二甲基吡嗪或2,3,5,6-四甲基吡嗪；
该实施方式的一种或多种实施例中，所述方法包括以下步骤：甲基吡嗪类化合物的甲基与9-己基-9H-咔唑-3,6-二甲醛的醛基进行缩合反应获得线性共轭聚合物或超支化共轭聚合物。
该实施方式的一种或多种实施例中，甲基吡嗪类化合物与9-己基-9H-咔唑-3,6-二甲醛的摩尔比为1:1.05～1.35。
该实施方式的一种或多种实施例中，反应条件为：碱性条件下加热至75～80℃进行回流。
该系列实施例中，回流时间为20～26h。
该实施方式的一种或多种实施例中，溶剂为二甲基亚砜(DMSO)。能够增加原料溶解度。
该系列实施例中，反应体系中添加十六烷基三甲基溴化铵(CTMAB)。
为了获得更为纯净的共轭聚合物，该实施方式的一种或多种实施例中，将反应后的物料倒入冰水中，采用二氯甲烷进行萃取，将萃取后的二氯甲烷相去除溶剂，加入甲醇进行沉淀，采用乙酸乙酯将沉淀物进行索式提取。
该系列实施例中，采用二氯甲烷进行萃取5～7次。
该系列实施例中，索式提取的时间为24～36h。
本公开中提供了N-己基-3,6-二醛咔唑的制备方法，其反应路线如下：
本公开的第三种实施方式，提供了一种上述共轭聚合物在检测硝基芳香族化合物中的应用。
该实施方式的一种或多种实施例中，所述硝基芳香族化合物为2,4,6-三硝基苯酚。经过实验表明本公开提供的共轭聚合物对2,4,6-三硝基苯酚的猝灭效率更高。
本公开的第四种实施方式，提供了一种硝基芳香族化合物检测传感器，采用的传感材料包括上述共轭聚合物。
本公开的第五种实施方式，提供了一种检测硝基芳香族化合物的方法，将待测溶液加入至上述共轭聚合物的溶液中，进行荧光检测。
该实施方式的一种或多种实施例中，荧光检测是激发波长为300～310nm。
为了使得本领域技术人员能够更加清楚地了解本公开的技术方案，以下将结合具体的实施例详细说明本公开的技术方案。
实施例中制备线性共轭聚合物(P1)和超支化共轭聚合物(P2)的路线如下：
实施例1
化合物a的合成：
将咔唑(3.25g,0.02mmol)溶于放有40mL二甲基甲酰胺(DMF)的100mL单孔烧瓶中，然后将KOH(1.6g,,0.032mmol)加入混合溶剂中搅拌大约半小时后将1-溴己烷(4g,0.024mmol)一滴一滴的加入到混合溶液中。浆混合溶液在80℃下搅拌回流24h。反应停止后将混合液冷却至室温，然后缓慢倒入200mL冰水中，得到黄色固体，过滤固体，将粗产品用二氯甲烷萃取三次，出去二氯甲烷后用乙醇重结晶，置于冰箱中缓慢析出得到白色固体结晶。干燥后直接用于下一步反应。
化合物b的合成：
在氮气氛围下，在冰水浴中奖化合物a(2g,7.3mmol)溶于干燥的DMF(21.8mL)溶于的100mL三口烧瓶中，然后将POCl3(15.7mL)缓慢滴入到混合液中，在冰水浴中保持30min，然后在90℃下回流48h。冷却至室温后，将反应混合物缓慢倒入冰水中，用适量的NaOH中和产生的酸和多余的三氯氧磷。将溶液用二氯甲烷萃取三次，收集合并二氯甲烷萃取液，并通过硅胶色谱柱(硅氧烷，石油醚/乙酸乙酯)进一步纯化，然后获得化合物b，为黄色固体，产率50％。1H-NMR(400MHz,CDCl3),δ(ppm):10.11(s,2H),8.67(s,2H),8.08(d,J＝8.5Hz,2H),7.86(d,J＝8.5Hz,2H),4.38(dt,J＝7.2Hz,2H),1.92(hept,J＝7.1Hz,2H),1.48-1.18(6H),0.9(t,J＝7.1Hz,3H).
P1的合成：
将2,5-二甲基吡嗪(0.1g，0.925mmol)9-己基-9H-咔唑-3,6-二甲醛(0.3g，0.98mmol)溶于含有DMSO(5mL)的100mL单孔烧瓶中。然后向混合物中加入KOH(0.3g，5.35mmol)和少量十六烷基三甲基溴化铵(CTMAB)，将混合物在75℃的温度下搅拌并回流24小时。冷却至室温后，将混合物倒入冰水(200mL)中，用二氯甲烷萃取6次，蒸发二氯甲烷，得到粗产物。然后通过甲醇沉淀粗产物，最后用乙酸乙酯进一步纯化索氏提取24小时以除去过量的单体，得到0.26g红色固体，产率62％。1H-NMR(400MHz，DMSO-d6),δ(ppm):7.81(dd,J＝51.2Hz,14H),7.32-6.78(m,4H),4.37(s,4H),1.75(s,4H),1.31(d,J＝61.2Hz,12H),0.8(d,J＝9.4Hz,6H).FT-IR:3057cm-1,2925cm-1,2856cm-1,1597cm-1,1515cm-1,1452cm-1,1221cm-1,1152cm-1,914cm-1.
实施例2
P2的合成：
将2,3,5,6-四甲基吡嗪(0.1g，0.735mmol)，9-己基-9H-咔唑-3,6-二甲醛(0.3g，0.98mmol)溶于含有DMSO(5mL)的100mL单孔烧瓶中。然后向混合物中加入KOH(0.3g，5.35mmol)和少量十六烷基三甲基溴化铵(CTMAB)，将混合物在75℃的温度下搅拌并回流24小时。冷却至室温后，将混合物倒入到冰水(200mL)中，用二氯甲烷萃取6次，蒸发二氯甲烷，得到粗产物。然后通过甲醇沉淀粗产物，最后用乙酸乙酯进一步纯化索氏提取24小时以除去过量的单体，得到0.31g红色固体，产率53％。1H-NMR(400MHz,DMSOd6),δ(ppm):9.11-7.83(m,12H),7.84-7.08(m,16H),7.08-6.67(m,4H),4.28(d,J＝28.8Hz,8H),1.70(s,8H),1.10(s,24H),0.73(d,J＝22.5Hz,12H).FT-IR:3057cm-1,2919cm-1,2856cm-1,1628cm-1,1597cm-1,1522cm-1,1452cm-1,1221cm-1,1146cm-1,908cm-1.
对实施例1制备的P1和实施例2制备的P2进行性能表征如下：
1、溶解性
两种聚合物在常用溶剂中表现出良好的溶解性，例如四氢呋喃、N,N-二甲基甲酰胺、二甲基亚砜、二氯甲烷等(表1)。良好的溶解性可能是由于聚合物中烷基链的大的空间位阻使得难以紧密包装，同时它有助于溶剂分子渗透到聚合物内部，从而增加溶解度。
表1室温下聚合物P1和P2在常用有机溶剂中的溶解性
++:易溶；+:能溶或超声可溶；-:不溶
Tol:甲苯；EA:乙酸乙酯
2、光学性质
通过紫外吸收光谱和荧光发射光谱研究了两种聚合物的光学性质。如图1所示，P1和P2在CH2Cl2溶液中表现出非常相似的吸收光谱。在230nm处的吸收峰归因于咔唑单元的π-π电子跃迁，300nm附近的最大吸收峰(λmax(a))归因于从咔唑部分到吡嗪单元的分子内电荷转移。作为超支化共轭聚合物，P2具有较大的空间位阻效应，这限制了聚合物P2中的分子扭转，并导致P2的更好的平面性，因此，P2(303nm)的λmax(a)显示比P1(297nm)的λmax长6nm。P1和P2的荧光光谱也彼此相似。如图2所示，P1和P2的荧光发射峰(λmax(f))几乎彼此相同。P2的荧光强度仍然大于P1的荧光强度，这是由于P2的较大的空间位阻限制了聚合物P2中的振动和旋转，导致更高的荧光量子效率。
3、热稳定性
通过TGA热分析研究了P1和P2的热稳定性。如图2a所示，TGA曲线显示两种聚合物损失5wt％时的分解温度P1为318℃，P2为288℃。然而，当Tm>403℃时，P2显示出更高的热稳定性。超支化结构赋予P2在分子内具有更大的空间位阻。这使得P2比P1更硬，从而使P2具有更高热稳定性。本实验室之前合成的化合物(如图2b中已给出结构)5％热失重温度为257℃，明显低于本实验P2的5％热失重温度(288℃)，并且当失重达到40％的时候，本实验中P1失重温度为488℃，P2为586℃，P2的热稳定性明显比之前本实验室合成的以吡嗪和二乙烯基苯构筑的超支化聚合物的热稳定性(501℃,图2b)要高的多(Ma et al,Sensors andActuators B 238(2017)48–57)，说明聚合物P2具有优越的热稳定性。
4、PA在溶液中对荧光猝灭的性能
2,4,6-三硝基苯酚(PA)对聚合物P1和P2均有荧光猝灭效应。加入PA后测量这两种聚合物的荧光光谱。如图3所示，在低浓度PA下，P1和P2的发射强度均显着降低，然后在高PA浓度下缓慢下降，表明这两种聚合物在低浓度下对PA很灵敏。当CPA＝4×10-4M时，P1和P2的猝灭效率分别为71％和93％(图3c，3d)。可以看出，P2的猝灭效率远高于P1。
Stern-Volmer猝灭常数(KSV)是衡量光学传感器性能的重要参数。猝灭过程可以通过Stern-Volmer关系进行分析
I0/I＝1+KSV[Q] (1)
其中I0是初始荧光强度，I是任何给定分析物浓度的溶液的荧光强度，[Q]是分析物的浓度。相对PL强度(I0/I)与CH2Cl2溶液中PA浓度的Stern-Volmer曲线如图4所示.P1的线性Stern-Volumer关系与PA浓度(CPA)相关，CPA范围为0～3.0×10-4M。P1和P2的KSV值分别为1.67×103M-1和1.72×104M-1。显然，P2的KSV比P1的KSV高10.3倍，这意味着在超支化聚合物P2中发生显着增强的超猝灭效应。
PA中两种传感材料的检测限(LOD)可以从CL＝3S/Ksv的公式中获得，其中CL是LOD的值，S表示空白样品被测了15次的荧光强度的标准偏差。聚合物P1和P2的检测限分别为65μM和P2的8μM，表明P2的LOD比P1的LOD低8.1倍。该结果进一步证实了P2中的超级猝灭效应增强。
检测爆炸物的大多数荧光猝灭通常归因于光诱导电子转移(PET)机制。在激发态，激子从聚合物的LUMO转移到硝基芳族化合物，导致荧光猝灭。
P2的增强的超猝灭效应可能与其2D共轭结构有关。如图5所示，一旦PA分子与受激发的聚合物P1接触，激子扩散长度(EDL)范围内的激子就可以迁移到PA，从而通过PET机制产生荧光猝灭。因此，一旦PA分子与聚合物接触，就可以猝灭EDL内的一段聚合物。这就是所谓的超级猝灭效应。相比之下，一旦PA分子与受激发的聚合物P2接触，激子就可以通过四个通道迁移到PA。这意味着，一旦PA分析物与聚合物P2接触，聚合物的圆形区域可以被猝灭，半径不长于EDL。1D聚合物P1中的超级猝灭效应可定义为“线性猝灭”，而2D聚合物P2中的超级猝灭效应可定义为“区域猝灭”。因此，容易理解的是，超支化聚合物P2表现出比线性聚合物P1强得多的超级猝灭效果。
5、共轭聚合物对不同分析物的选择性
选择性对于评估传感材料的性能很重要。测量了P1和P2对几种分析物的猝灭效率。如图6所示，可以发现这两种聚合物对分析物如PA、DNT和NB等响应性能较好，但对其他无硝基化合物如氯苯和BQ等几乎没有或没有反应响应。
硝基芳香族爆炸物是缺电子化合物，通常比非硝基化合物具有更低的LUMO能级，它们更容易与富电子荧光化合物进行电荷转移。在含硝基炸药中，PA具有最低的LUMO水平，并且从荧光传感器的LUMO能量到PA工艺的PA的LUMO能量的驱动力相对高于DNT和NB。对于其他无硝基分析物，例如氯苯和BQ等，它们都没有显着的电子有效能力，这是相对低的猝灭效率的原因。结果表明，与其他无硝基芳烃相比，P1和P2可以选择性地检测硝基芳香炸药。图7显示了分析物的HOMO和LUMO水平以及P1和P2的相应单体。与实验中获得的猝灭效率一致，具有较低LUMO水平的爆炸物容易从聚合物获得电子，这是较高荧光猝灭行为的原因。
6、共轭聚合物在1800s内的光稳定性研究
光稳定性是荧光传感材料最重要的因素之一。在这项工作中，测量了P1和P2在1800s内的荧光稳定性。如图8所示，两种聚合物在光照射下均显示出良好的稳定性，曝光时间在1800s内。与P1相比，P2具有更好的荧光稳定性，并且在1800秒内荧光强度几乎没有降低，而P1显示约10％的荧光强度降低。
结论
超支化共轭聚合物P2和线性共轭聚合物P1均能够对硝基芳香族化合物进行检测，超支化共轭聚合物P2表现出比线性共轭聚合物P1大得多的增强的荧光超级猝灭。P2的2D共轭性质为激子提供了多迁移通道，因此导致“区域猝灭”，而1D聚合物P1仅允许“线性猝灭”。
以上所述仅为本公开的优选实施例而已，并不用于限制本公开，对于本领域的技术人员来说，本公开可以有各种更改和变化。凡在本公开的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。
Claims (16)
1.一种共轭聚合物在检测硝基芳香族化合物中的应用，其特征是，所述共轭聚合物为线性共轭聚合物；
所述线性共轭聚合物结构如式Ⅰ所示：
线性共轭聚合物的重均分子量为5×104～8×104g mol-1。
2.一种共轭聚合物在检测硝基芳香族化合物中的应用，其特征是，所述共轭聚合物为超支化共轭聚合物；
所述超支化共轭聚合物具有式Ⅱ所示化学结构：
超支化共轭聚合物的重均分子量为1×104～2×104g mol-1。
3.如权利要求1-2任一项所述的应用，其特征是，所述共轭聚合物的制备方法包括以甲基吡嗪类化合物和N-己基-3,6-二醛咔唑为原料通过以下路线进行反应，甲基吡嗪类化合物为2,5-二甲基吡嗪或2,3,5,6-四甲基吡嗪；
或，
4.如权利要求3所述的应用，其特征是，所述方法包括以下步骤：甲基吡嗪类化合物的甲基与9-己基-9H-咔唑-3,6-二甲醛的醛基进行缩合反应获得线性共轭聚合物或超支化共轭聚合物。
5.如权利要求4所述的应用，其特征是，甲基吡嗪类化合物与9-己基-9H-咔唑-3,6-二甲醛的摩尔比为1:1.05～1.35。
6.如权利要求4所述的应用，其特征是，反应条件为：碱性条件下加热至75～80℃进行回流。
7.如权利要求6所述的应用，其特征是，回流时间为20～26h。
8.如权利要求4所述的应用，其特征是，反应所使用的溶剂为二甲基亚砜。
9.如权利要求4所述的应用，其特征是，反应体系中添加十六烷基三甲基溴化铵。
10.如权利要求3所述的应用，其特征是，将反应后的物料倒入冰水中，采用二氯甲烷进行萃取，将萃取后的二氯甲烷相去除溶剂，加入甲醇进行沉淀，采用乙酸乙酯将沉淀物进行索式提取。
11.如权利要求10所述的应用，其特征是，采用二氯甲烷进行萃取5～7次。
12.如权利要求3所述的应用，其特征是，索式提取的时间为24～36h。
13.如权利要求6所述的应用，其特征是，所述硝基芳香族化合物为2,4,6-三硝基苯酚。
14.一种硝基芳香族化合物检测传感器，其特征是，采用的传感材料包括权利要求1-2中任一项所述的共轭聚合物。
15.一种检测硝基芳香族化合物的方法，其特征是，将待测溶液加入至权利要求1-2任一项中所述的共轭聚合物的溶液中，进行荧光检测。
16.如权利要求15所述的方法，其特征是，荧光检测的激发波长为300～310nm。
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