基于三苯基咪唑的共价有机多孔聚合物的合成与应用
发布时间：2018-08-27 07:27
【摘要】：共价有机多孔聚合物(COPs)一般包括共轭微孔聚合物(CMPs)、自具微孔聚合物(PIMs)、超交联聚合物(HCPs)等。与其它聚合物相比,COPs具有密度小,比表面积高,孔隙率大,吸附性强,不易分解等优点。考虑到三苯基咪唑类化合物具有刚性的分子结构,同时咪唑环还可以与金属离子络合以及与卤代烃反应,故有利于拓宽COPs材料的应用范围。本论文以三苯基咪唑类化合物作为COPs的构筑单元,合成了两类COPs材料。主要工作包括以下两方面:(1)采用Yamamoto偶联合成共价有机多孔聚合物PTBPIs。我们先设计并合成了三种N-烷基取代的咪唑衍生物2,4,5-三(4-溴苯基)~(-1)-烷基~(-1)H-咪唑(其中烷基分别为-CH3,-CH2CH3和-(CH2)3CH3;标记为TBPI-Me,TBPI-Et和TBPI-Bu)。随后分别以TBPI-Me、TBPI-Et和TBPI-Bu为构筑单元,双1,5-环辛二烯(0)镍为催化剂,采用Yamamoto偶合反应合成了PTBPI-Me、PTBPI-Et和PTBPI-Bu三种COPs。研究结果表明PTBPI-Me和PTBPI-Et的比表面积较为接近,分别为512.20 m~2 g~(-1)和477.30 m~2 g~(-1),其孔容分别为0.35 cm3 g~(-1)和0.36 cm3 g~(-1)。而对于PTBPI-Bu,其比表面积降为34.09 m~2 g~(-1),孔容降为0.13 cm3 g~(-1)。在273 K条件下,PTBPI-Me、PTBPI-Et和PTBPI-Bu的CO_2吸附容量分别为1.99 mmol g~(-1)、1.80 mmol g~(-1)和0.96 mmol g~(-1)。此外,我们将PTBPI-Me用CH3I处理,得到了离子盐型PTBPI-[Mmim][I]。和PTBPI-Me相比,PTBPI-[Mmim][I]的表面积降至22.39 m~2 g~(-1),孔容降低为0.09 cm3g~(-1)。上述研究结果表明,咪唑环上取代基的大小对PTBPIs的比表面积、孔容以及吸附能力具有一定的调控作用。(2)采用氰基三聚反应合成共价有机多孔聚合物PTCPIs。设计并合成了2,4,5-三(4-氰基苯基)~(-1)H-咪唑(标记为TCPI-H)及其N-烷基取代的咪唑衍生物(其中烷基为-CH3,-CH2CH3,-(CH2)3CH3;标记为TCPI-Me,TCPI-Et和TCPI-Bu)。以TCPIs为构筑单元,在500℃下以氯化锌为催化剂,采用氰基三聚反应合成了四种PTCPIs。研究结果表明PTCPI-H比表面积最高,为1462.94 m~2 g~(-1);PTCPI-Me与PTCPI-Et的比表面积比较接近,分别为1366.40 m~2 g~(-1)和1347.83 m~2 g~(-1);PTCPI-Bu比表面积为1080.86 m~2 g~(-1)。298 K下PTCPI-Me的CO_2吸附容量可达到2.02 mmol g~(-1)。此外,我们采用硝化反应后修饰PTCPIs,得到了部分苯环硝基取代的有机多孔聚合物(PTCPIs-NO_2)。PTCPI-H-NO_2、PTCPI-Me-NO_2、PTCPI-Et-NO_2和PTCPI-Bu-NO_2的比表面积分别下降为1074.27 m~2 g~(-1),1138.95 m~2 g~(-1),1085.11 m~2 g~(-1),824.39 m~2 g~(-1)。而常温下PTCPI-Me-NO_2的CO_2吸附数据上升至2.20 mmol g~(-1)。上述研究结果表明,后修饰聚合物对PTCPIs的比表面积以及吸附能力具有一定的调控作用。
[Abstract]:Covalent organic porous polymer (COPs) includes conjugated microporous polymer (CMPs), self-contained microporous polymer (PIMs), supercrosslinked polymer (HCPs), and so on. Compared with other polymers, Cops has the advantages of low density, high specific surface area, large porosity, strong adsorbability, and difficult to decompose. Considering the rigid molecular structure of triphenyl imidazole compounds, the imidazole ring can also complexate with metal ions and react with halogenated hydrocarbons, so it is beneficial to broaden the application of COPs materials. In this paper, two kinds of COPs materials were synthesized by using triphenyl imidazole compounds as building units of COPs. The main work includes the following two aspects: (1) Synthesis of covalent organic porous polymer PTBPIs. by Yamamoto coupling We first designed and synthesized three N-alkyl substituted imidazole derivatives, 2tr (4-bromophenyl) ~ (-1) -alkyl ~ (-1) H-imidazole (where the alkyl groups are -Ch _ 3- Ch _ 2CH _ 3 and-(CH2) _ 3CH _ 3; labeled as TBPI-Me,TBPI-Et and TBPI-Bu). Three kinds of COPs., PTBPI-Me,PTBPI-Et and PTBPI-Bu, were synthesized by Yamamoto coupling reaction with TBPI-Me,TBPI-Et and TBPI-Bu as building units and Bis (1) 5-cyclooctene (0) nickel as catalyst, respectively. The results show that the specific surface area of PTBPI-Me and PTBPI-Et is close to 512.20 mG-1 and 477.30 mg-1, respectively, and the pore volume is 0.35 cm3 g-1 and 0.36 cm3 g-1, respectively. For PTBPI-Bu, the specific surface area decreased to 34.09 mg ~ (-1) and the pore volume decreased to 0.13 cm3 g ~ (-1). At 273 K, the CO_2 adsorption capacities of PTBPI-Et and PTBPI-Bu were 1.99 mmol g ~ (-1) and 1.80 mmol g ~ (-1) and 0.96 mmol g ~ (-1), respectively. In addition, the ion salt type PTBPI- [Mmim] [I] was obtained by treating PTBPI-Me with CH3I. Compared with PTBPI-Me, the surface area of PTBPI- [Mmim] [I] decreased to 22.39 mg-1 and the pore volume decreased to 0.09 cm3g~ (-1). The results show that the size of substituents on imidazole ring has a certain effect on the specific surface area, pore volume and adsorption ability of PTBPIs. (2) PTCPIs. is synthesized by cyano-trimerization. In this paper, we have designed and synthesized 2o 4N 5- tris (4-cyanophenyl) ~ (-1) H-imidazole (labeled TCPI-H) and its N-alkyl substituted imidazole derivatives (where alkyl is -Ch _ 3H _ 3H _ 2CH _ 3- (CH2) _ 3CH _ 3; labeled as TCPI-Me,TCPI-Et and TCPI-Bu). Four kinds of PTCPIs. were synthesized by cyanotrimerization with zinc chloride as catalyst and TCPIs as building unit at 500 鈩，
本文编号：2206546
[Abstract]:Covalent organic porous polymer (COPs) includes conjugated microporous polymer (CMPs), self-contained microporous polymer (PIMs), supercrosslinked polymer (HCPs), and so on. Compared with other polymers, Cops has the advantages of low density, high specific surface area, large porosity, strong adsorbability, and difficult to decompose. Considering the rigid molecular structure of triphenyl imidazole compounds, the imidazole ring can also complexate with metal ions and react with halogenated hydrocarbons, so it is beneficial to broaden the application of COPs materials. In this paper, two kinds of COPs materials were synthesized by using triphenyl imidazole compounds as building units of COPs. The main work includes the following two aspects: (1) Synthesis of covalent organic porous polymer PTBPIs. by Yamamoto coupling We first designed and synthesized three N-alkyl substituted imidazole derivatives, 2tr (4-bromophenyl) ~ (-1) -alkyl ~ (-1) H-imidazole (where the alkyl groups are -Ch _ 3- Ch _ 2CH _ 3 and-(CH2) _ 3CH _ 3; labeled as TBPI-Me,TBPI-Et and TBPI-Bu). Three kinds of COPs., PTBPI-Me,PTBPI-Et and PTBPI-Bu, were synthesized by Yamamoto coupling reaction with TBPI-Me,TBPI-Et and TBPI-Bu as building units and Bis (1) 5-cyclooctene (0) nickel as catalyst, respectively. The results show that the specific surface area of PTBPI-Me and PTBPI-Et is close to 512.20 mG-1 and 477.30 mg-1, respectively, and the pore volume is 0.35 cm3 g-1 and 0.36 cm3 g-1, respectively. For PTBPI-Bu, the specific surface area decreased to 34.09 mg ~ (-1) and the pore volume decreased to 0.13 cm3 g ~ (-1). At 273 K, the CO_2 adsorption capacities of PTBPI-Et and PTBPI-Bu were 1.99 mmol g ~ (-1) and 1.80 mmol g ~ (-1) and 0.96 mmol g ~ (-1), respectively. In addition, the ion salt type PTBPI- [Mmim] [I] was obtained by treating PTBPI-Me with CH3I. Compared with PTBPI-Me, the surface area of PTBPI- [Mmim] [I] decreased to 22.39 mg-1 and the pore volume decreased to 0.09 cm3g~ (-1). The results show that the size of substituents on imidazole ring has a certain effect on the specific surface area, pore volume and adsorption ability of PTBPIs. (2) PTCPIs. is synthesized by cyano-trimerization. In this paper, we have designed and synthesized 2o 4N 5- tris (4-cyanophenyl) ~ (-1) H-imidazole (labeled TCPI-H) and its N-alkyl substituted imidazole derivatives (where alkyl is -Ch _ 3H _ 3H _ 2CH _ 3- (CH2) _ 3CH _ 3; labeled as TCPI-Me,TCPI-Et and TCPI-Bu). Four kinds of PTCPIs. were synthesized by cyanotrimerization with zinc chloride as catalyst and TCPIs as building unit at 500 鈩，
本文编号：2206546
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