【摘要】：共價有機(jī)多孔聚合物(COPs)一般包括共軛微孔聚合物(CMPs)、自具微孔聚合物(PIMs)、超交聯(lián)聚合物(HCPs)等。與其它聚合物相比,COPs具有密度小,比表面積高,孔隙率大,吸附性強(qiáng),不易分解等優(yōu)點(diǎn)�？紤]到三苯基咪唑類化合物具有剛性的分子結(jié)構(gòu),同時咪唑環(huán)還可以與金屬離子絡(luò)合以及與鹵代烴反應(yīng),故有利于拓寬COPs材料的應(yīng)用范圍。本論文以三苯基咪唑類化合物作為COPs的構(gòu)筑單元,合成了兩類COPs材料。主要工作包括以下兩方面:(1)采用Yamamoto偶聯(lián)合成共價有機(jī)多孔聚合物PTBPIs。我們先設(shè)計并合成了三種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(其中烷基分別為-CH3,-CH2CH3和-(CH2)3CH3;標(biāo)記為TBPI-Me,TBPI-Et和TBPI-Bu)。隨后分別以TBPI-Me、TBPI-Et和TBPI-Bu為構(gòu)筑單元,雙1,5-環(huán)辛二烯(0)鎳為催化劑,采用Yamamoto偶合反應(yīng)合成了PTBPI-Me、PTBPI-Et和PTBPI-Bu三種COPs。研究結(jié)果表明PTBPI-Me和PTBPI-Et的比表面積較為接近,分別為512.20 m~2 g~(-1)和477.30 m~2 g~(-1),其孔容分別為0.35 cm3 g~(-1)和0.36 cm3 g~(-1)。而對于PTBPI-Bu,其比表面積降為34.09 m~2 g~(-1),孔容降為0.13 cm3 g~(-1)。在273 K條件下,PTBPI-Me、PTBPI-Et和PTBPI-Bu的CO_2吸附容量分別為1.99 mmol g~(-1)、1.80 mmol g~(-1)和0.96 mmol g~(-1)。此外,我們將PTBPI-Me用CH3I處理,得到了離子鹽型PTBPI-[Mmim][I]。和PTBPI-Me相比,PTBPI-[Mmim][I]的表面積降至22.39 m~2 g~(-1),孔容降低為0.09 cm3g~(-1)。上述研究結(jié)果表明,咪唑環(huán)上取代基的大小對PTBPIs的比表面積、孔容以及吸附能力具有一定的調(diào)控作用。(2)采用氰基三聚反應(yīng)合成共價有機(jī)多孔聚合物PTCPIs。設(shè)計并合成了2,4,5-三(4-氰基苯基)~(-1)H-咪唑(標(biāo)記為TCPI-H)及其N-烷基取代的咪唑衍生物(其中烷基為-CH3,-CH2CH3,-(CH2)3CH3;標(biāo)記為TCPI-Me,TCPI-Et和TCPI-Bu)。以TCPIs為構(gòu)筑單元,在500℃下以氯化鋅為催化劑,采用氰基三聚反應(yīng)合成了四種PTCPIs。研究結(jié)果表明PTCPI-H比表面積最高,為1462.94 m~2 g~(-1);PTCPI-Me與PTCPI-Et的比表面積比較接近,分別為1366.40 m~2 g~(-1)和1347.83 m~2 g~(-1);PTCPI-Bu比表面積為1080.86 m~2 g~(-1)。298 K下PTCPI-Me的CO_2吸附容量可達(dá)到2.02 mmol g~(-1)。此外,我們采用硝化反應(yīng)后修飾PTCPIs,得到了部分苯環(huán)硝基取代的有機(jī)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的比表面積分別下降為1074.27 m~2 g~(-1),1138.95 m~2 g~(-1),1085.11 m~2 g~(-1),824.39 m~2 g~(-1)。而常溫下PTCPI-Me-NO_2的CO_2吸附數(shù)據(jù)上升至2.20 mmol g~(-1)。上述研究結(jié)果表明,后修飾聚合物對PTCPIs的比表面積以及吸附能力具有一定的調(diào)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，

本文編號：2206546