CN114181378B - 一种三芳基硼类共轭聚合物多孔材料及其制备方法和用途 - Google Patents

一种三芳基硼类共轭聚合物多孔材料及其制备方法和用途 Download PDF

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CN114181378B
CN114181378B CN202111412131.7A CN202111412131A CN114181378B CN 114181378 B CN114181378 B CN 114181378B CN 202111412131 A CN202111412131 A CN 202111412131A CN 114181378 B CN114181378 B CN 114181378B
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任毅
薛策策
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Abstract

本发明公开了一种三芳基硼类共轭聚合物多孔材料及其制备方法和用途。本发明提出了一种三芳基类共轭聚合物多孔材料的新颖制备方法，即利用硼‑锡交换反应作为聚合手段制备新型三芳基类共轭聚合物多孔材料，克服了采用贵金属催化的碳‑碳偶联反应的制备方法中存在的成本高以及不易纯化等缺陷，更为经济高效。本发明的三芳基类共轭聚合物多孔材料可以实现对有机氨类的荧光检测，其中吡啶对发明的材料P2‑Th、P2‑Th2、P2‑Th3的荧光猝灭比例分别为83.8％、73.5％、41.3％，本发明的三芳基类共轭聚合物多孔材料在荧光检测领域具有良好的应用前景。

Description

一种三芳基硼类共轭聚合物多孔材料及其制备方法和用途
技术领域
本发明涉及一种三芳基硼类共轭聚合物多孔材料及其制备方法和用途，属于 有机多孔材料技术领域。
背景技术
多孔材料在近百年的发展历史中，已经走过了从天然多孔材料到人工合成多 孔材料，从无机多孔材料到无机有机杂化多孔材料再到有机多孔材料的历程。多 孔有机聚合物是一类由碳、氢、氧、氮、磷、硫等元素组成的具有较大比表面积 聚合物多孔材料，其在拥有较高比表面积的同时，由有机小分子通过共价键连接 构筑，赋予多孔有机聚合物质量轻、热化学稳定性好、结构可设计性强以及合成 方法多样的优势，使得多孔有机聚合物成为了一种具有强大发展潜力的多孔材 料。
多孔有机材料的制备如果按照反应类型分类的话，可以分为可逆反应与不可 逆反应。可逆反应可以生成带有晶型的孔材料，其中主要以2005年，Yaghi课题 组[1]报道的共价有机框架(COFs)，以及2008年Arne Thomas课题组[2]报道的共价 三嗪网络(CTFs)为代表。不可逆反应则生成无定形的孔材料，最早可以追溯 1974年Davankov等人[3]报道的交联聚苯乙烯的合成，以及2002年Budd课题组 [4,5]报道的固有微孔聚合物(PIMs)，2007年Copper课题组[6]报道的共轭微孔聚 合物(CMPs)，2009年，朱广山课题组[7]报道的多孔芳香骨架聚合物(PAFs) 为代表。
其中CMPs是一类构筑单元通过π共轭骨架连接的无定形微孔聚合物材料， 具有更加优异的热稳定性和化学稳定性，CMPs由于具有离域的π电子，在光 电、传感方面具有较大的应用前景[8]。Copper课题组最早使用的是Sonogashira 偶联反应，在此之后也发展了多种金属催化偶联反应用于合成CMPs,极大地丰富 了CMPs的合成手段。但由于金属催化剂价格昂贵，目前CMPs仍难以大规模应 用。
在2012年，新加坡国立大学江东林课题组[9]第一次报道了共轭微孔聚合物 材料TCB-CMP用作化学传感器以测试芳香烃蒸汽。TCB-CMP由咔唑衍生物缩 合而成，该聚合物呈现蓝色发光并具有大表面积(比表面积为1280m2/g，孔体 积为0.923cm3/g)。与线性聚合物的类似物CB-LP相比，TCBCMP显示出更高的 检测灵敏度。此外TCB-CMP在富电子芳烃蒸气存在下显示荧光增强，在缺电子 芳烃蒸气存在下剧烈荧光猝灭，并且材料可以重复使用而不会损失灵敏度和响应 性。这篇工作中作者明确指出，CMPs的一些结构特征使其具有优异的检测性能。 具体而言：较大的共轭网络可以促进激子在骨架上的迁移；微孔特性有利于将芳 烃分子吸收到聚合物的密闭空间中；骨架大的表面积加宽了CMPs和芳烃之间的 界面；这些特性使CMPs具有快速响应时间和高灵敏度。
目前基于三芳基硼共轭多孔材料[10,11]的合成通常是以三(4-溴2,3,5,6-四甲基苯基)硼烷作为结构单元，并使用传统的贵金属催化的碳-碳偶联反应(如Suzuki、Sonogashira、炔自聚偶联反应)来制备。除此之外，传统三芳基硼多孔材料通常 具有较大的位阻保护硼原子中心，但这也较低了传统三芳基硼多孔材料与路易斯 碱类物质的作用，其只能用于氟离子的检测。
因此，无论从经济上，还是材料性质的优化方面，传统的三芳基硼多孔材料 及制备方法都存在较大的局限性。
参考文献：
1.Adrien P.Co^te′,A.I.B.,Nathan W.Ockwig,Michael O’Keeffe,Adam J.Matzger,Omar M.Yaghi,Porous,Crystalline,Covalent Organic Frameworks.Science2005,310,1166-1170.
2.Kuhn,P.；Antonietti,M.；Thomas,A.,Porous,covalent triazine-basedframeworks prepared by ionothermal synthesis.Angew.Chem.Int.Ed.Engl.2008,47,3450-3453.
3.V.A.DAVANKOV,S.V.R.,and M.P.TSYURUPA,MACRONET ISOPOROUS GELSTHROUGH CROSSLINKING OF DISSOLVED POLYSTYRENE.Journal of Polymer Science PartC-Polymer Symposium 1974,47, 95-101.
4.McKeown,N.B.；Budd,P.M.,Exploitation of Intrinsic Microporosity inPolymer-Based Materials.Macromolecules 2010,43,5163-5176.
5.McKeown,N.B.；Makhseed,S.；Budd,P.M.,Phthalocyanine-based nanoporousnetwork polymers.Chem.Commun.2002,23,2780-2781.
6.Jiang,J.X.；Su,F.；Trewin,A.；Wood,C.D.；Campbell,N.L.；Niu,H.；Dickinson,C.；Ganin,A.Y.；Rosseinsky,M.J.；Khimyak,Y.Z.；Cooper,A.I., Conjugatedmicroporous poly(aryleneethynylene)networks.Angew.Chem.Int.Ed. Engl.2007,46,8574-8578.
7.Ben,T.；Ren,H.；Ma,S.；Cao,D.；Lan,J.；Jing,X.；Wang,W.；Xu,J.；Deng, F.；Simmons,J.M.；Qiu,S.；Zhu,G.,Targeted synthesis of a porous aromatic frameworkwith high stability and exceptionally high surface area.Angew.Chem.Int.Ed.Engl.2009,48,9457-9460.
8.Lee,J.M.；Cooper,A.I.,Advances in Conjugated Microporous Polymers.Chem.Rev.2020,120,2171-2214.
9.Liu,X.；Xu,Y.；Jiang,D.,Conjugated microporous polymers as molecularsensing devices:microporous architecture enables rapid response and enhancessensitivity in fluorescence-on and fluorescence-offsensing.J.Am.Chem.Soc.2012, 134,8738-8741.
10.Li,Z.；Li,H.；Xia,H.；Ding,X.；Luo,X.；Liu,X.；Mu,Y., Triarylboron-Linked Conjugated Microporous Polymers:Sensing and Removal of FluorideIons.Chemistry 2015,21,17355-17362.
11.Zhao,W.；Zhuang,X.；Wu,D.；Zhang,F.；Gehrig,D.；Laquai,F.；Feng,X.,Boron-π-nitrogen-based conjugated porous polymers with multi-functions.J.Mater. Chem.A,2013,1,13878-13884.
发明内容
本发明解决的技术问题是：传统的三芳基硼类共轭多孔材料存在应用上的局 限以及制备方法不经济等问题。
为了解决上述技术问题，本发明提供了一种三芳基硼类共轭聚合物多孔材 料，其化学结构式为下列式a-式k中的任意一种：
Figure BDA0003374063800000031
其中，n为结构单元重复个数，且n取值为1～1000之间的整数。
本发明还提供了上述的三芳基硼类共轭聚合物多孔材料的制备方法，反应方 程式如下：
Figure BDA0003374063800000041
包括如下步骤：
将BBr3溶于二氯苯中得到三溴化硼的二氯苯溶液，将含双烷基锡基的噻吩 类原料溶于二氯苯后缓慢滴加入三溴化硼的二氯苯溶液，氮气保护下于 160～200℃下搅拌反应，得到固体沉淀，经洗涤、过滤后得到产物。
优选地，所述的含双烷基锡基的噻吩类原料与BBr3的摩尔比为0.5～2:1。
优选地，所述搅拌反应的时间为2～5天。
优选地，所述的洗涤为：在无水无氧条件下采用二氯甲烷进行洗涤；所述二 氯甲烷经除水除氧处理。
优选地，所述的过滤在无水无氧条件下进行。
本发明还提供了上述的三芳基硼类共轭聚合物多孔材料在荧光检测中的应 用。
优选地，所述应用包括在检测有机氨类物质中的应用。
优选地，所述有机氨类物质包括吡啶和三乙胺。
本发明与现有技术相比，具有如下有益效果：
1.本发明提出了一种三芳基硼类共轭聚合物多孔材料的新颖制备方法，即利 用硼-锡交换反应作为聚合手段制备新型三芳基硼类共轭聚合物多孔材料，克服 了采用贵金属催化的碳-碳偶联反应的制备方法中存在的成本高以及后处理复 杂、不易纯化等缺陷，更为经济高效。
2.本发明的三芳基硼类共轭聚合物多孔材料可以实现对有机氨类的荧光检 测，其中吡啶对本发明的材料P2-Th、P2-Th2、P2-Th3的荧光猝灭比例分别为83.8％、 73.5％、41.3％，本发明的三芳硼基类共轭聚合物多孔材料在荧光检测领域具有 良好的应用前景。
附图说明
图1为实施例1制备的三芳基硼类共轭聚合物多孔材料P1-Th的红外光谱 图；
图2为实施例2制备的三芳基硼类共轭聚合物多孔材料P2-Th的红外光谱 图；
图3为实施例3制备的三芳基硼类共轭聚合物多孔材料P1-Th2的红外光谱 图；
图4为实施例4制备的的三芳基硼类共轭聚合物多孔材料P2-Th2的红外光 谱图；
图5为实施例5制备的三芳基硼类共轭聚合物多孔材料P1-Th3的红外光谱 图；
图6为实施例6制备的三芳基硼类共轭聚合物多孔材料P2-Th3的红外光谱 图；
图7为实施例7制备的三芳基硼类共轭聚合物多孔材料P1-BTh的红外光谱 图；
图8为实施例8制备的三芳基硼类共轭聚合物多孔材料P2-BTh的红外光谱 图；
图9为实施例9制备的三芳基硼类共轭聚合物多孔材料P1-BTh2的红外光谱 图；
图10为实施例10制备的三芳基硼类共轭聚合物多孔材料P2-BTh2的红外光 谱图；
图11为P1-Th对吡啶的荧光检测光谱；
图12为P1-Th2对吡啶的荧光检测光谱；
图13为P1-Th3对吡啶的荧光检测光谱；
图14为P1-Th对三乙胺的荧光检测光谱；
图15为P1-Th2对三乙胺的荧光检测光谱；
图16为P1-Th3对三乙胺的荧光检测光谱；
图17为本发明实施例2、4、6、8中所制备的三芳基硼类共轭聚合物多孔材 料的在荧光下的发光图片；
图18为实施例6制备的三芳基硼类共轭聚合物多孔材料P2-Th3对吡啶 (pyridine)的荧光响应(材料在加吡啶前后的荧光颜色变化)。
具体实施方式
为使本发明更明显易懂，兹以优选实施例，并配合附图作详细说明如下。
实施例1
一种三芳基硼类共轭聚合物多孔材料P1-Th的合成路线与步骤如下：
Figure BDA0003374063800000061
先加入BBr3(0.424g，1.69mmol)于100-mL的Schlenk管中，随后补入10mL 二氯苯，将化合物2,5-双(三甲基锡基)噻吩(1.03g，2.51mmol)溶于二氯苯后缓 慢滴加。此时生成大量黄色沉淀增大搅拌，补充溶剂总量至30mL，将Schlenk 管转入油浴，支口用氮气保护于180℃搅拌3天。等反应时间结束后，待Schlenk 管冷却后转移到手套箱内。在手套箱里用经除水除氧处理的二氯甲烷反复洗涤固 体，用砂芯漏斗过滤。最后将固体转移到小瓶内在真空下抽取4小时，得到黄色 固体240.0mg。11B MAS SSNMR(400MHz)δ(iso)47.4ppm；BET area(以BET 法测得的催化剂表面积)：234.1m2/g；其红外光谱图如图1所示。
实施例2
一种三芳基硼类共轭聚合物多孔材料P2-Th的合成路线及步骤如下：
Figure BDA0003374063800000071
化合物P2-Th的合成方法同化合物P1-Th(实施例1)。投料：BBr3(0.371g，1.48mmol)，化合物2,5-双(三正丁基锡基)噻吩(1.47g，2.22mmol)，最后得到 黄色固体204.0mg。11B MAS SSNMR(400MHz)δ(iso)46.1ppm；BET area：648.7 m2/g；其红外光谱如图2所示。
实施例3
一种三芳基硼类共轭聚合物多孔材料P1-Th2的合成路线与步骤如下：
Figure BDA0003374063800000072
化合物P1-Th2的合成方法同实施例1。投料：BBr3(0.374g,1.49mmol)，化合 物5,5'-双(三甲基锡基)-2,2'-联噻吩(1.01g，2.05mmol)，最后得到桔红色固体369.6 mg。11BMAS SSNMR(400MHz)δ(iso)43.6ppm；BET area：164.6m2/g；其红外 光谱图如图3所示。
实施例4
一种三芳基硼类共轭聚合物多孔材料P2-Th2的合成路线与步骤如下：
Figure BDA0003374063800000081
化合物P2-Th2的合成方法同实施例1。投料：BBr3(0.265g,1.06mmol)，化合 物5,5'-双(三正丁基锡基)-2,2'-联噻吩(1.28g，1.72mmol)，最后得到桔红色固体 306.0mg。11BMAS SSNMR(400MHz)δ(iso)44.4ppm；BET area：163.6m2/g； 其红外光谱图如图4所示。
实施例5
一种三芳基硼类共轭聚合物多孔材料P1-Th3的合成路线与步骤如下：
Figure BDA0003374063800000082
化合物P1-Th3的合成方法同实施例1。投料：BBr3(0.297g,1.18mmol)，化合 物5,5”-双(三甲基锡基)-2,2',5',2”-三联噻吩(1.02g，1.78mmol)，最后得到血红色 固体462.0mg。11B MAS SSNMR(400MHz)δ(iso)42.7ppm；BET area：60.7m2/g； 其红外光谱图如图5所示。
实施例6
一种三芳基硼类共轭聚合物多孔材料P2-Th3的合成路线与步骤如下：
Figure BDA0003374063800000083
化合物P2-Th3的合成方法同实施例1。投料：BBr3(0.318g，1.27mmol)，化 合物5,5”-双(三正丁基锡基)-2,2':5',2”-三联噻吩(1.57g，1.90mmol)，最后得到血红 色固体498.8mg。11B MAS SSNMR(400MHz)δ(iso)43.0ppm；BET area：107.3 m2/g；其红外光谱图如图6所示。
实施例7
一种三芳基硼类共轭聚合物多孔材料P1-BTh的合成路线与步骤如下：
Figure BDA0003374063800000091
化合物P1-BTh的合成方法同实施例1。投料：BBr3(0.334g，1.33mmol)，化 合物1,3,5-三(5-(三甲基锡基)噻吩-2-基)苯(1.08g，1.33mmol)，最后得到浅绿色固 体483.7mg。11BMAS SSNMR(400MHz)δ(iso)42.4ppm；BET area：428.4m2/g； 其红外光谱图如图7所示。
实施例8
一种三芳基硼类共轭聚合物多孔材料P2-BTh的合成路线与步骤如下：
Figure BDA0003374063800000092
化合物P2-BTh的合成方法同实施例1。投料：BBr3(0.249g，1.00mmol)，化 合物1,3,5-三(5-(三正丁基锡基)噻吩-2-基)苯(1.18g，0.990mmol)，最后得到浅黄 色固体365.0mg。11B MAS SSNMR(400MHz)δ(iso)42.8ppm；BET area：586.2 m2/g；其红外光谱图如图8所示。
实施例9
一种三芳硼基类共轭聚合物多孔材料P1-BTh2的合成路线与步骤如下：
Figure BDA0003374063800000101
化合物P1-BTh2的合成方法同实施例1。投料：BBr3(0.207g,0..83mmol)，化 合物1,3,5-三(5'-(三甲基锡基)-[2,2'-联噻吩]-5-基)苯(0.88g,0.83mmol)，最后得到 桔红色固体500.0mg。BET area：206.8m2/g；其红外光谱图如图9所示。
实施例10
一种三芳基硼类共轭聚合物多孔材料P2-BTh2的制备方法，包括如下步骤：
Figure BDA0003374063800000102
化合物P2-BTh2的合成方法同实施例1。投料：BBr3(0.305g,1.22mmol)，化 合物1,3,5-三(5'-(三正丁基锡基)-[2,2'-联噻吩]-5-基)苯(1.74g,1.22mmol)，最后得 到桔红色固体664.0mg。BET area：235.9m2/g；其红外光谱图如图8所示。
其中，实施例2、4、6、8制备的三芳基硼有机多孔材料在荧光检测下的发 光情况如图17所示。实施例2制备的三芳基硼有机多孔材料P2-Th产生黄色荧 光，实施例4制备的三芳基硼有机多孔材料P2-Th2产生桔色荧光，实施例6制 备的三芳基硼有机多孔材料P2-Th3产生红色荧光，实施例8制备的三芳基硼有 机多孔材料P2-BTh产生蓝绿色荧光。
应用实施例
将上述实施例中制备所得的三芳基硼类共轭聚合物多孔材料分别用于检测 吡啶和三乙胺，以实施例2、4、6制备的P2-Th、P2-Th2和P2-Th3为例，具体方 法如下：
用氮气排掉整个管路原有的空气，随后将氮气流速始终控制在0.03L/min。 在手套箱内样品装到比色皿后接入整个气路中。首先在氮气下完成第一次采谱， 随后通过三通阀来调整气路，当氮气线在吡啶内鼓泡后，开始采谱。按照上述的 方法，分别使用了P2-Th、P2-Th2、P2-Th3这三类分子来观察吡啶或三乙胺对材 料的荧光响应，结果如图11～16所示。最后测得吡啶对四种材料P2-Th、P2-Th2、 P2-Th3的荧光猝灭比例分别为83.8％、73.5％、41.3％。直接将吡啶加入固体 P2-Th3后，固体荧光颜色由红色转变为橙色，如图18所示。
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的 限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明的前提下， 还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。

Claims (9)

1.一种三芳基硼类共轭聚合物多孔材料，其特征在于，其化学结构式为下列式a-式k中的任意一种：
Figure QLYQS_1
；
其中，n为结构单元重复个数，且n取值为1~1000之间的整数。
2.权利要求1所述的三芳基硼类共轭聚合物多孔材料的制备方法，其特征在于，反应方程式如下：
Figure QLYQS_2
；
包括如下步骤：
将BBr3溶于二氯苯中得到三溴化硼的二氯苯溶液，将含双烷基锡基的噻吩类原料溶于二氯苯后缓慢滴加入三溴化硼的二氯苯溶液，氮气保护下于160~200℃下搅拌反应，得到固体沉淀，经洗涤、过滤后得到产物。
3.如权利要求2所述的三芳基硼类共轭聚合物多孔材料的制备方法，其特征在于，所述的含双烷基锡基的噻吩类原料与BBr3的摩尔比为0.5~2:1。
4.如权利要求2所述的三芳基硼类共轭聚合物多孔材料的制备方法，其特征在于，所述搅拌反应的时间为2~5天。
5.如权利要求2所述的三芳基硼类共轭聚合物多孔材料的制备方法，其特征在于，所述的洗涤为：在无水无氧条件下采用二氯甲烷进行洗涤；所述二氯甲烷经除水除氧处理。
6.如权利要求2所述的三芳基硼类共轭聚合物多孔材料的制备方法，其特征在于，所述的过滤在无水无氧条件下进行。
7.权利要求1所述的三芳基硼类共轭聚合物多孔材料在荧光检测中的应用。
8.如权利要求7所述的应用，其特征在于，包括在检测有机氨类物质中的应用。
9.如权利要求8所述的应用，其特征在于，所述有机氨类物质包括吡啶和三乙胺。
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