CN108676150B - 利用次级结构基块构筑的多孔芳香骨架材料 - Google Patents
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Abstract
一种利用次级结构基块构筑的多孔芳香骨架材料PAF‑100和PAF‑101,属于多孔芳香骨架材料制备技术领域。在催化剂作用下,1,4‑双((三(4‑溴苯基)硅基)苯或者4,4’‑双((三(4‑溴苯基)硅基)联苯作为反应物自身发生聚合反应,得到PAF‑100和PAF‑101。热重分析表明PAF‑100和PAF‑101的热分解温度超过500℃,它们具有高的热稳定性。通过N2吸附‑脱附表征,PAF‑100的BET比表面积达到4990m2/g;PAF‑101的BET比表面积达到5114m2/g。合成的聚合物具有显著的多孔性和良好的稳定性,具有广阔的应用前景,本发明为有机多孔材料的合成提供了一种新颖的思路。
Description
技术领域
本发明属于多孔芳香骨架材料制备技术领域,具体涉及一种利用次级结构基块构筑的多孔芳香骨架材料PAF-100和PAF-101。
技术背景
多孔材料在吸附、储存、分离、光电、催化、主客体等领域具有广泛地应用。多孔材料包括无机组成的分子筛、无机-有机组成的金属有机框架材料(metal organicframeworks,MOFs)和有机组成的有机多孔材料。多孔材料的形成过程可以看作一步一步的“组装”过程,(1)传统分子筛,首先原子形成TO4四面体(初级结构单元,例如硅氧四面体[SiO4]4-和铝氧四面体[AlO4]5-),四面体共享氧原子连接成多元环和笼(次级结构单元),最后连接形成多维结构;(2)MOFs,首先有机配体与金属簇或者金属原子通过共价键连接形成初级结构,进一步连接得到网络结构;(3)有机多孔材料,有机基块之间通过不同聚合反应连接形成共价键连接的聚合物。有机多孔材料的制备,需要考虑(1)单体,也就是构筑基块;(2)聚合反应。在分子筛形成过程的启发下,我们提出利用二聚体形成的次级结构基块构筑有机多孔材料,这为多孔芳香骨架化合物(Porous aromatic framework,PAFs)的合成提供了一种新思路。
发明内容
本发明的目的在于提供一种利用次级结构基块构筑的多孔芳香骨架材料PAF-100和PAF-101。本发明从二聚体形式的次级结构基块出发,构筑PAF材料,选择具有四面体结构的“1,4-双((三(4-溴苯基)硅基)苯或者4,4’-双((三(4-溴苯基)硅基)联苯”作为反应单体,制备的PAF-100和PAF-101具有高稳定性;制备的PAF-100其BET比表面积达到4990m2/g,制备的PAF-101其BET比表面积达到5114m2/g。两种材料在氮气吸附方面具体重要应用。
为了实现上述目标,本发明提供两种PAF材料,反应时实验过程可以用以下反应方程式表示,(a)为制备PAF-100;(b)为制备PAF-101:
反应时采用的聚合反应为Yamamoto Type Ullmann偶联反应,具体使用的催化剂为双-(1,5-环辛二烯)镍、2,2-联吡啶、1,5-环辛二烯体系。其中,n表示聚合度,为大于或等于1的整数。
本发明所述制备PAF-100和PAF-101,其步骤如下:
(1)将等物质量的双-(1,5-环辛二烯)镍、2,2-联吡啶及1,5-环辛二烯加入到N,N-二甲基甲酰胺和四氢呋喃(体积比1:2)中,使催化剂老化0.5~2小时;
(2)向步骤(1)得到的反应体系中加入1,4-双((三(4-溴苯基)硅基)苯或者4,4’-双((三(4-溴苯基)硅基)联苯的N,N-二甲基甲酰胺和四氢呋喃溶液(N,N-二甲基甲酰胺和四氢呋喃的体积比1:2),N,N-二甲基甲酰胺和四氢呋喃溶液中1,4-双((三(4-溴苯基)硅基)苯或者4,4’-双((三(4-溴苯基)硅基)联苯的浓度为0.001M~2M之间,双-(1,5-环辛二烯)镍与溴原子的摩尔比例为0.6~1.5:1;
(4)将步骤(3)得到溶液在20℃~100℃下反应10分钟~3天;
(5)向步骤(4)得到的反应体系中加入质量分数30~35%的浓盐酸破坏剩余的双-(1,5-环辛二烯)镍,终止反应,过滤得到淡白色固体;
(6)分别用水、四氢呋喃和丙酮洗涤步骤(5)产物,除去无机盐和可溶性有机物,最后将产物在80~200℃真空干燥4~40小时,得到本发明所述的多孔芳香骨架材料PAF-100或PAF-101。
本方法以二聚体形式的次级结构基块,利用Yamamoto Type Ullmann偶联反应,制备PAF-100和PAF-101,它们具有良好的稳定性和多孔性质(附图7和8),材料可以稳定在500℃以上。PAF-100的BET比表面积达到4990m2/g;PAF-101的BET比表面积达到5114m2/g。
附图说明
图1:本发明反应单体(1)和合成的PAF-100(2)的红外谱图;
图2:本发明反应单体(1)和合成的PAF-101(2)的红外谱图;
图3:本发明合成的PAF-100的热重谱图;
图4:本发明合成的PAF-101的热重谱图;
图5:本发明合成的PAF-100的扫描电镜图;
图6:本发明合成的PAF-101的扫描电镜图;
图7:本发明合成的PAF-100的N2吸附-脱附等温线(实心线代表吸附曲线,空心线代表脱附曲线);
图8:本发明合成的PAF-101的N2吸附-脱附等温线(实心线代表吸附曲线,空心线代表脱附曲线)。
图1所示,为采用本发明所述方法由1,4-双((三(4-溴苯基)硅基)苯通过YamamotoType Ullmann偶联反应得到的PAF-100与反应单体的红外对比谱图(曲线(1)是反应单体的红外对比谱,曲线(2)是PAF-100的红外对比谱。),对应实施例1,1067cm-1的C-Br特征吸收峰,聚合反应后对应位置的C-Br特征吸收峰明显消失,证明聚合反应非常彻底。
图2所示,为采用本发明所述方法由4,4’-双((三(4-溴苯基)硅基)联苯通过Yamamoto Type Ullmann偶联反应得到的PAF-101与反应单体的红外对比谱图(曲线(1)是反应单体的红外对比谱,曲线(2)是PAF-101的红外对比谱。),对应实施例2,1067cm-1的C-Br特征吸收峰,聚合反应后对应位置的C-Br特征吸收峰明显消失,证明聚合反应非常彻底。
图3所示,为采用本发明所述方法由1,4-双((三(4-溴苯基)硅基)苯通过YamamotoType Ulmann偶联反应得到的PAF-100的热重图,对应实施例1,通过热重研究,PAF-100的热分解温度超过500℃,表明其具有高稳定性。
图4所示,为采用本发明所述方法由4,4’-双((三(4-溴苯基)硅基)联苯通过Yamamoto Type Ulmann偶联反应得到的PAF-101的热重图,对应实施例2,通过热重研究,PAF-101的热分解温度超过510℃,表明其具有高稳定性。
图5所示,为采用本发明所述方法由1,4-双((三(4-溴苯基)硅基)苯通过YamamotoType Ullmann偶联反应得到的PAF-100的扫描电镜图,对应实施例1,PAF-100的大小不均匀。
图6所示,为采用本发明所述方法由4,4’-双((三(4-溴苯基)硅基)联苯通过Yamamoto Type Ullmann偶联反应得到的PAF-101的扫描电镜图,对应实施例2,PAF-101的大小不均匀。
图7所示,为采用本发明所述方法由1,4-双((三(4-溴苯基)硅基)苯通过YamamotoType Ullmann偶联反应得到的PAF-100的N2吸附-脱附图,对应实施例1,通过N2吸附-脱附等温线,PAF-100的BET比表面积达到4990m2/g。
图8所示,为采用本发明所述方法由4,4’-双((三(4-溴苯基)硅基)联苯通过Yamamoto Type Ullmann偶联反应得到的PAF-101的N2吸附-脱附图,对应实施例2,通过N2吸附-脱附等温线,PAF-101的BET比表面积达到5114m2/g。
具体实施方式
实施例1:
(1)将1.000g双-(1,5-环辛二烯)镍,0.568g 2,2-联吡啶和0.4mL 1,5-环辛二烯加入到5mL的N,N-二甲基甲酰胺和四氢呋喃中,N,N-二甲基甲酰胺和四氢呋喃的体积比为1:2,使催化剂老化2小时。随后将5mL、0.1M的1,4-双((三(4-溴苯基)硅基)苯的N,N-二甲基甲酰胺和四氢呋喃(体积比1:2)混合溶液加入到上述反应体系中,在60℃下反应24小时。
(2)向步骤(1)的反应体系中加入质量分数30%的浓盐酸破坏剩余的双-(1,5-环辛二烯)镍,终止反应,过滤得到淡白色固体。
(3)分别用100mL水、100mL四氢呋喃和100mL丙酮洗涤步骤(2)产物去除无机盐和可溶性有机物。
(4)最终产物在120℃真空干燥24小时,得到聚合物PAF-100,产率为89%。
(5)将步骤(4)中得到的产物在77K,0~1atm下测得氮气吸附等温线为I-型等温线,如图7所示。
实施例2:
将实施例1步骤(1)中的反应单体改换为4,4’-双((三(4-溴苯基)硅基)联苯,其它条件不变,得到PAF-101,产率为92%。
综上所述,本发明利用二聚体形式的次级构筑基块,制备了具有高比表面积的PAF-100和PAF-101,它们具有良好的热稳定性(热分解温度达到500℃),优异的多孔性质。这为有机多孔材料的合成提供一种新颖的思路。
以上所述,对于本领域的技术人员来说,可以根据本发明的技术方案和技术构思作出其它各种相应的改变和变形,而所有这些改变和变形都应属于本发明后附的权利要求的保护范围。
Claims (2)
1.一种利用次级结构基块构筑的多孔芳香骨架材料,其结构式如下所示:
n表示聚合度,为大于1的整数;且该多孔芳香骨架材料由如下步骤制备得到,
(1)将等物质量的双-(1,5-环辛二烯)镍、2,2-联吡啶及1,5-环辛二烯加入到有机溶剂中,使催化剂老化0.5~2小时;
(2)向步骤(1)得到的反应体系中加入1,4-双((三(4-溴苯基)硅基)苯的有机溶剂溶液,有机溶剂溶液中1,4-双((三(4-溴苯基)硅基)苯的浓度为0.001M~2M,双-(1,5-环辛二烯)镍与溴原子的摩尔比例为0.6~1.5:1;
(4)将步骤(3)得到溶液在20℃~100℃下反应10分钟~3天;
(5)向步骤(4)得到的反应体系中加入质量分数30~35%的浓盐酸破坏剩余的双-(1,5-环辛二烯)镍,终止反应,过滤得到淡白色固体;
(6)分别用水、四氢呋喃和丙酮洗涤步骤(5)产物,除去无机盐和可溶性有机物,最后将产物在80~200℃真空干燥4~40小时,得到多孔芳香骨架材料。
2.如权利要求1所述的利用次级结构基块构筑的多孔芳香骨架材料,其特征在于:有机溶剂为N,N-二甲基甲酰胺和四氢呋喃,两者的体积比为1:2。
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