Porous Polymers Derived from Octavinylsilsesquioxane by Cationic Polymerization

Abstract

A new rapid and efficient approach is developed for the preparation of porous materials via cationic polymerization of octavinylsilsesquioxane (OVS). The reaction proceeds rapidly and efficiently at room temperature, forming a predominantly covalent porous network polymer. A series of experiments are conducted to clarify the effects of reaction time, temperature, and solvent on the polymerization process. The results show that all the products possess a nanoporous structure with surface areas of approximately 300 – 620 m2 g−1 and a pore volume of 0.15 – 0.54 cm3 g−1. The porosity of these polymers can be readily tailored by changing the reaction conditions. The post functionalization of the materials is further investigated by epoxidation and the application of these polymers as carbon dioxide adsorbents (up to 0.98 mmol g−1) is also explored. The work has general implications in understanding the reactive nature of the cationic polymerization of OVS and is very promising for promoting the application of porous materials.

Rapid Polymerization of Aromatic Vinyl Monomers to Porous Organic Polymers via Acid Catalysis at Mild Condition

“…It is shown that the PTVPP holds a carbon dioxide adsorption capability as high as 13.3 wt% at 273 K and 8.2 wt% at 298 K. These values are slightly higher than that of PTVP‐1 which are 12.3 and 6.8 wt% at 273 and 298 K, respectively (Figure a). These performances are also superior to the recent reports . The higher results can be attributed to the existence of nitrogen element in PTVPP backbone which shows better affinity of carbon dioxide .…”

“…It would be more ideal to develop new synthetic methods of POPs with higher surface areas and much milder conditions. Liu and co‐workers have reported an interesting cationic polymerization of porous polymers based on non‐aromatic vinyl monomers, which successfully achieved a series of porous polymers with moderate surface area for gas adsorption . However, it is still challenging to synthesize POPs with high surface areas under very mild conditions.…”

“…These performances are also superior to the recent reports. [56] The higher results can be attributed to the existence of nitrogen element in PTVPP backbone which shows better affinity of carbon dioxide. [2] However, the PTVP-1 exhibit higher H 2 uptake than the PTVPP due to the higher BET surface area (Figure 3b).…”

“…Liu and co-workers have reported an interesting cationic polymerization of porous polymers based on nonaromatic vinyl monomers, which successfully achieved a series of porous polymers with moderate surface area for gas adsorption. [56] However, it is still challenging to synthesize POPs with high surface areas under very mild conditions.Here, we report the synthesis of a series of POPs with high surface areas based on aromatic vinyl monomers by one-step acid catalysis method in an open system at room temperature. In this work, two aromatic vinyl monomers, namely 1,3,6,8-tetrakis(4vinylphenyl) pyrene (TVP) and 5,10,15,20-tetra(4-vinylphenyl)porphyrin (TVPP), are chosen as the building blocks, and the cheap Lewis acids (AlCl 3 , FeCl 3 , SnCl 4 , ZnCl 2 ) and protonic acid (H 2 SO 4 ) are adopted as the catalysts (Scheme 1).…”

Reassessing the Physicochemical Properties of Ordered Mesoporous Polymer and Copolymer Nanocasts

“…However, only a high cross-linking degree was suitable to generate a porous polymer. Currently, the synthesis and application of nanoporous organic polymers and their composites remain areas of intense research activity [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23]. Nevertheless, hard templating strategies appeared to be a suitable pathway to generate nanostructured polymeric materials and soft materials in general [24].…”