Citation: Wei-cong Mai, Bin Sun, Ding-cai Wu, Ruo-wen Fu. Fabrication and Structural Control of Hollow Nanonetwork-structured Polystyrene and Carbon Materials[J]. Acta Polymerica Sinica, ;2018, 0(7): 930-938. doi: 10.11777/j.issn1000-3304.2018.18044 shu

Fabrication and Structural Control of Hollow Nanonetwork-structured Polystyrene and Carbon Materials

Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, School of Chemistry, Sun Yat-sen University, Guangzhou 510275

Corresponding author: Ruo-wen Fu, cesfrw@mail.sysu.edu.cn
Received Date: 5 February 2018
Revised Date: 10 April 2018
Available Online: 15 May 2018

As an important class of novel porous materials, nanonetwork-structured polymer and carbon materials have an unique three-dimensional (3D) interconnected hierarchical porous structure, and thus hold considerable promise in a spectrum of applications including energy, adsorption, separation, catalysis, medicine, and so on. This study focuses on the innovative structure design, controllable fabrication and structure-property relationship of novel nanonetwork-structured polystyrene and carbon materials. Hollow nanonetwork-structured polystyrene (HNNS-PS), with hollow microporous PS spherical network unit was designed and fabricated on molecular-level by combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and Friedel-Crafts hypercrosslinking reaction. The 3D nanonetwork structure was controlled by precisely tuning the molecular weight of PS. Gel permeation chromatography (GPC), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and nitrogen adsorption were used to characterize the structure and morphology of HNNS-PS, and intelligent gravimetric analyzer (IGA) was used to determine the adsorption capacity of HNNS-PS towards toluene vapor. Additionally, the inheritance of 3D nanonetwork structure during carbonization was realized by tuning the heating rate. It is found that, by utilizing the SI-ATRP technique, one was able to precisely tune the PS molecular weight and to fabricate SiO₂-g-PS building blocks with different PS molecular weight, i.e., SiO₂-g-PS-22.4k, SiO₂-g-PS-46.9k and SiO₂-g-PS-94.4k. As the molecular weight of PS went up from 2.26 × 10⁴ to 4.69 × 10⁴ and 9.44 × 10⁴, the diameter of the nanospheres increased from 196 nm to 223 and 282 nm. After the Friedel-Crafts hypercrosslinking reaction and silica etching, HNNS-PS with different PS molecular weight was obtained. Due to the introduction of the micropores, the diameter of the network units increased to 263, 280 and 332 nm, respectively. As the molecular weight of PS went up, the Brunauer-Emmett-Teller surface area (S_BET) of HNNS-PS increased from 346 m² g⁻¹ to 390 and 450 m² g⁻¹. HNNS-PS had a high adsorption capacity of up to 534 mg g⁻¹ towards toluene vapor at 25 °C. In addition, when the heating rate was low (1 or 2 K min⁻¹) during carbonization, the as-prepared carbon materials could preserve their 3D nanonetwork structure morphologies with S_BET up to 696 m² g⁻¹, which paved the way for the design and fabrication of 3D nanonetwork structured carbon materials, and thus would have important theoretic significance and application value.
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