Supporting Information Hypercrosslinked Organic Microporous Polymers Based on Alternative Copolymerization of Bismaleimide Hui Gao, Lei Ding, Wenqing Li, Guifeng Ma, Hua Bai and Lei Li *, College of Materials, Xiamen University, Xiamen, 361005, P. R. China Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, Xiamen University, Xiamen 361005, P. R. China E-mail: lilei@xmu.edu.cn Tel: +86-592-2186296 Fax: +86-592-2183937.
Experimental section Materials N,N'-4,4'-diphenylmethane-bismaleimide (BDM), N,N'-(4-Methyl-1, 3-phenylene) bismalemide (BMP) were provided by Institute of Chemistry, Chinese Academy of Sciences. N,N'-1,4-phenylenedimaleimide (p-pdm) was obtained from Tokyo Chemical Industry. N,N'-1,3-phenylenedimaleimide (m-pdm), styrene (St) and divinylbenzene (DVB) were purchased from J&K Scientific Co. Ltd. 2,2'-azobisisobutyronitrile (AIBN) was purchased from Tianjin Guangfu Fine Chemical Research Institute. Magnesium sulfate (MgSO 4 ) and N,N-Dimethylformamide (DMF) were obtained from Sinopharm Chemical Reagent Co. Ltd. DMF was predried with MgSO 4 and subsequently distilled prior to be used as solvent. Preparation of the bismaleimide-based HOMPs Typically, a solution of BDM (0.7167 g, 2 mmol), DVB (0.2604 g, 2 mmol), and AIBN (0.0038 g, 0.02mmol) were dissolved in 10 ml DFM in a 25 ml round-bottom flask equipped with a condenser and a argon gas inlet. The solution was stirred at room temperature and deoxygenated by argon bubbling for 0.5 h, and then kept at 80 o C for 24 h. The resulting solids were separated by filter-suction and extracted in a Soxhlet extractor by THF for 12 h to further remove the unreacted monomer. Finally the
obtained powder was dried under reduced pressure at 80 C for 24 h. Characterization The chain structures of the polymers were characterized by 13 C cross-polarization magic angle spinning (CP/MAS) NMR spectra (WB 400 MHz BRUKER AV III spectrometer). Measurements were made with a 4 mm MAS probe spinning at 12 khz. The incorporation of the DVB/St and bismaleimide comonomers were confirmed by a Fourier transform infrared (FTIR) spectrometer (NICOLET is10). The morphology of samples was observed by scanning electron microscopy (SEM) (SU-70, Hitachi) under an electron beam with an accelerating voltage of 10 kv and a working distance of 15 mm.elemental analysis was performed by an Elementar Vario EL III elemental analyzer. The thermogravimetric analysis (TGA) of the copolymers was conducted by a thermal analyzer (Q500 V6.7 Build 203), under N 2 atmosphere with a heating rate of 10 o C min 1. Nitrogen adsorption/desorption isotherms at 77.3 K were obtained using a Micromeritics TriStar II 3020 static volumetric analyzer. Prior to adsorption measurements, the samples were degassed for 12 h at 100 ºC ensuring that the residual pressure fell below 10 mbar. The Brunauer-Emmett-Teller surface area was calculated within the relative pressure range 0.05 to 0.2. Total volume was calculated at P/P 0 = 0.99. The CO 2 adsorption isotherms were measured at 273 K and 298 K using
Micromeritics TriStar II 3020 static volumetric analyzer. The N 2 adsorption isotherms were measured at 273 K up to 1.0 bar. The H 2 adsorption isotherms were measured using a Micromeritics ASAP 2020 static volumetric analyzer at 77.3 K up to 1.0 bar. Kinetics of hydrogen adsorption for the HOMPs was determined on dosing the first aliquot of hydrogen using a Micromeritics ASAP 2020 M surface areas and porosity analyzer and the standard calculation routines in its software named ROA (rate of adsorption). Kinetics of carbon dioxide adsorption for the HOMPs was determined on dosing the first aliquot of carbon dioxide using a Micromeritics ASAP 2020 M surface areas and porosity analyzer and the standard calculation routines in its software named ROA (rate of adsorption). Measurement of organic vapor adsorption Organic vapor adsorption was measured by a home-made device 1. In a typical adsorption of benzene experiment, a certain amount of HOMPs were weighed and loaded in a small metallic basket, and then the basket was hung by a quartz spring in a stainless steel tube charged with saturated vapor of benzene, and the height of the basket was measured immediately through the telescopic cathetometer. After an hour, height was measured again. Adsorption capacity value was thus calculated (the height difference of the ending number and the original number
multiplies the coefficient of the quartz spring, and then the obtained value divide the weight of HOMPs). The other organic vapor adsorption experiment was done following the same procedure.
Table S1 The amount of raw materials in each experiment. a Samples Bismaleimide BDM/g BMP/g m-pdm/g P-PDM /g St/g DVB/g 1 0.7167 - - - 0.4166-2 0.7167 - - - - 0.2604 3 0.7167 - - - 0.2083 0.1302 4-0.5640 - - 0.4166-5 - 0.5640 - - - 0.2604 6-0.5640 - - 0.2083 0.1320 7 - - 0.5364-0.4166-8 - - 0.5364 - - 0.2604 9 - - 0.5364-0.2083 0.1320 10 - - - 0.2680 0.2083-11 - - - 0.2680-0.1320 12 - - - 0.2680 0.1042 0.0651 a The amount of AIBN is fixed at 1 mol % of biamaleimide in all experiments.
Table S2 Elemental Analysis of Polymers samples Theoretical (wt %) Experimental (wt %) C H N C H N BDM-St 78.35 5.29 4.94 74.78 6.04 5.27 BMI-St 75.87 5.30 5.71 71.00 5.85 5.70 m-pdm-st 75.55 5.04 5.88 72.70 5.85 5.96 p-pdm-st 75.55 5.04 5.88 70.90 5.83 6.11 BDM-DVB 76.14 4.91 5.73 71.78 5.80 4.98 BMI-DVB 72.78 4.85 6.06 66.02 5.71 5.74 m-pdm-dvb 72.29 4.52 7.03 66.34 5.42 6.07 p-pdm-dvb 72.29 4.52 7.03 62.38 5.51 6.25
Figure S1 The SEM micrograph of the BDM-DVB.
Statistics Graph (1 measurem ents) 40 Number (%) 30 20 10 0 1 10 100 1000 10000 Size (d.nm ) Mean with +/-1 Standard Deviation error bar Figure S2. The size distribution of BDM-DVB measured by dynamical light scattering.
Figure S3 The FTIR spectra of BDM, BMP, m-pdm and p-pdm.
Figure S4. Differential (top) and number fraction (bottom) pore size distribution of BDM-DVB (a, b) and m-pdm-dvb (c, d) measured by mercury intrusion porosimetry.
Figure S5 Nitrogen adsorption/desorption isotherms for BDM-DVB before (blue) and after (red) being immersed 1 M HCl (red) for 12 h.
Figure S6 TGA curve of the BDM-DVB, BMP-DVB, m-pdm-dvb and p-pdm-dvb.
1.0 Normalized adsorption amount 0.5 0.0 0 10 20 30 40 50 60 70 80 Time (s) Figure S7 Kinetics of carbon dioxide adsorption for p-pdm-dvb at 273 K/0.133 bar.
Figure S8 Adsorption isotherms of CO 2 and N 2 at 273 K for p-pdm-dvb.
Figure S9 Adsorption selectivity of CO 2 over N 2 for p-pdm-dvb derived from the initial slope method at 273 K.
1.0 Normalized adsorption amount 0.8 0.6 0.4 0.2 0.0 0 10 20 30 40 50 60 70 80 Time (s) Figure S10 Kinetics of hydrogen adsorption for p-pdm-dvb at 77.3 K/0.06 bar.
Figure S11 Nitrogen adsorption/desorption isotherms for activated carbon.
Figure S12 Nitrogen adsorption/desorption isotherms for pure poly(divinylbenzene).
Figure S13 CO 2 adsorption and desorption isotherms at 273 K for pure poly(divinylbenzene).
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