Synthesis, Characterization and Gas Adsorption Properties of Hypercrosslinked Polymers Based on Carbazoles Containing Aldehyde or Ketone Groups†

doi:10.7503/cjcu20170823

Abstract

Abstract:

Three novel carbazoles CM-2, CM-3 and CM-4 were designed and synthesized by ketone- or aldehyde-functionalization of carbazole. Then a series of hypercrosslinked porous polycarbazoles(HPP-2, HPP-3 and HPP-4) was prepared using CM-2, CM-3 and CM-4 as monomers under the catalysis of FeCl₃. The structures of the novel carbazoles and the hypercrosslinked porous polycarbazoles(HPPs) were characterized by nuclear magnetic resonance(¹H NMR, ¹³C NMR), magic angle spinning nuclear magnetic resonance(MAS NMR), infrared(IR) and mass spectrometry(MS). The thermal stability and the gas(nitrogen, carbon dioxide and methane) adsorption properties of the obtained HPPs were also investigated. The results show that the structures of the novel carbazoles and the polymers are consistent with the molecular design. Three kinds of HPPs begin to degrade around 400 ℃ and render a mass loss less than 25% at 800 ℃, denoting that these materials have a good thermal stability. HPP-2, HPP-3 and HPP-4 present BET specific surface areas of 330, 420 and 660 m²/g, with pore sizes mainly distributed at 0.98, 0.96 and 1.07 nm, respectively. The adsorption capacities of CO₂ on HPP-2, HPP-3 and HPP-4 are 6.90%, 8.30% and 9.80%, while those of CH₄ on HPP-2, HPP-3 and HPP-4 are 1.10%, 1.30% and 1.60%, respectively. The results show that the obtained polymers possess mainly micropores and present high adsorption capacity for CO₂ and CH₄. This work provides a new approach for the synthesis of hypercrosslinked porous polycarbazoles.

Key words: Aldehyde-modified carbazole, Ketone-modified carbazole, Hypercrosslinked polymer, Porosity, Gas adsorption

CLC Number:

O631
O626

TrendMD:

ZHANG Rongrong,YUAN Guangming,LUO Weihua. Synthesis, Characterization and Gas Adsorption Properties of Hypercrosslinked Polymers Based on Carbazoles Containing Aldehyde or Ketone Groups^†[J]. Chem. J. Chinese Universities, 2018, 39(9): 2105.

Figures/Tables 11

Scheme 1 Synthesis of aldehyde- or ketone-modified carbazoles CM-2, CM-3 and CM-4

Scheme 2 Synthesis of hypercrosslinked polymers HPP-2 and HPP-4

Scheme 3 Synthesis of hypercrosslinked polymer HPP-3

Fig.1 1H NMR spectrum of CM-3

Fig.2 13C CP/MAS NMR spectra of HPP-2(a), HPP-3(b) and HPP-4(c)

Fig.3 FTIR spectra of HPP-2 and corresponding monomer CM-2(A), HPP-3 and CM-3(B), and HPP-4 and CM-4(C)

Fig.4 TG curves of HPP-2(a), HPP-3(b) and HPP-4(c)

Fig.5 SEM images of polymers HPP-2(A), HPP-3(B) and HPP-4(C)

Fig.6 Nitrogen adsorption-desorption isotherms of HPP-2(a), HPP-3(b) and HPP-4(c) measured at 77 K(A) and the PSD profiles of HPP-2(a), HPP-3(b) and HPP-4(c) calculated by NLDFT(B)The adsorption and desorption branches are labeled with solid and open symbols, respectively.

Fig.7 Gravimetric CO2(A) and CH4(B) adsorption-desorption isotherms for HPP-2(a), HPP-3(b) and HPP-4(c) at 273 K

Table 1 Porosity properties and gas uptake capacities of polymers HPP-2—HPP-4

Polymer	$S BET a$ /(m²·g^-1)	$S micro b$ /(m²·g^-1)	$V total c$ /(cm³·g^-1)	$D pore d$ /nm	CO₂ uptake^e(%)	CH₄ uptake^e(%)
HPP-2	330	200	0.21	0.98	6.90	1.10
HPP-3	420	250	0.39	0.96	8.30	1.30
HPP-4	660	470	0.68	1.07	9.80	1.60

Table 1 Porosity properties and gas uptake capacities of polymers HPP-2—HPP-4

Polymer	$S BET a$ /(m²·g^-1)	$S micro b$ /(m²·g^-1)	$V total c$ /(cm³·g^-1)	$D pore d$ /nm	CO₂ uptake^e(%)	CH₄ uptake^e(%)
HPP-2	330	200	0.21	0.98	6.90	1.10
HPP-3	420	250	0.39	0.96	8.30	1.30
HPP-4	660	470	0.68	1.07	9.80	1.60

References 33

[1]	Zhou Y. M., Kong X. Z., Han H., Jiang X. B., Zhu X. L., Chem. J. Chinese Universities, 2017, 38(3), 495—502
	(周亚梅, 孔祥正, 韩慧, 姜绪宝, 朱晓丽. 高等学校化学学报, 2017, 38(3), 495—502)
[2]	Xu S., Luo Y., Tan B., Macromol. Rapid Commun., 2013, 34(6), 471—484
[3]	Guan Y. W., Ben T., Zhang D. L., Xu J., Pei C. Y., Zhu L. K., Lu C. J., Meng F. X., Deng F., Qiu S. L., Chem. J. Chinese Universities, 2012, 33(10), 2152—2157
	(关有为, 贲腾, 张大梁, 徐君, 裴翠颖, 朱良奎, 逯春晶, 孟凡星, 邓风, 裘式纶. 高等学校化学学报, 2012, 33(10), 2152—2157)
[4]	Wood C. D., Tan B., Trewin A., Niu H., Bradshaw D., Rosseinsky M. J., Khimyak Y. Z., Campbell N. L., Kirk R., Stöckel E., Cooper A. I., Chem. Mater., 2007, 19(8), 2034—2048
[5]	Tsyurupa M. P., Davankov V. A., React. Funct. Polym., 2006, 66(7), 768—779
[6]	Sidorov S. N., Bronstein L. M., Davankov V. A., Tsyurupa M. P., Solodovnikov S. P., Valetsky P. M., Chem. Mater., 1999, 11(11), 3210—3215
[7]	Molla R. A., Bhanja P., Ghosh K., Islam S. S., Bhaumik A., Islam S. M., Chem. Cat. Chem., 2017, 9(11), 1939—1946
[8]	Mane S., Ponrathnam S., Chavan N., Ind. Eng. Chem.Res., 2015, 54(27), 6893—6901
[9]	Geetanjali, Singh R., Chauhan S. M. S., J. Braz. Chem. Soc., 2006, 17(2), 421—425
[10]	Fan S. H., Yang J., Wei T., Zhang J., Zhang N., Chai M. Q., Jin X. Y., Wu H., Talanta, 2016, 160, 713—720
[11]	Luo Y., Li B., Wang W., Wu K., Tan B., Adv. Mater., 2012, 24(42), 5703—5707
[12]	Zhi Y. F., Li K., Xia H., Xue M., Mu Y., Liu X. M., J. Mater. Chem. A, 2017, 5(18), 8697—8704
[13]	Wang W. J., Zhou M., Yuan D. Q., J. Mater. Chem. A, 2017, 5(4), 1334—1347
[14]	Zhu J. H., Chen Q., Sui Z. Y., Pan L., Yu J., Han B. H., J. Mater. Chem. A, 2014, 2(38), 16181—16189
[15]	Li Z.P., Li H., Xia H., Chem. Eur. J., 2015, 21(48), 17355—17362
[16]	Zhu X., Ding S., Abney C. W., Browning K. L., Sacci R. L., Veith G. M., Tian C. C., Dai S., Chem. Commun., 2017, 53(54), 7645—7648
[17]	Tan L. X., Tan B. E., Chem. Soc. Rev., 2017, 46(11), 3322—3356
[18]	Das S., Heasman P., Ben T., Qiu S.L., Chem. Rev., 2017, 117(3), 1515—1563
[19]	Luo Y., Zhang S., Ma Y., Wang W., Tan B., Polym. Chem., 2013, 4(4), 1126—1131
[20]	Pan L., Chen Q., Zhu J. H., Yu J. G., He Y. J., Han B. H., Polym. Chem., 2015, 6(13), 2478—2487
[21]	Liu H., Li S., Yang H. Y., Liu S. H., Chen L. Y., Tang Z. W., Fu R. W., Wu D. C., Adv. Mater., 2017, 29(27), 1700723
[22]	Chen Q., Luo M., Hammershoj P., Zhou D., Han Y., Laursen B. W., Yan C. G., Han B. H., J. Am. Chem. Soc., 2012, 134(14), 6084—6087
[23]	Cao Q., Chen Q., Han B. H., Acta Chim. Sinica, 2015, 73(6), 541—556
[24]	Chen Q., Liu D. P., Luo M., Feng L. J., Zhao Y. C., Han B. H., Small, 2014, 10(2), 308—315
[25]	Chen Q., Liu D. P., Zhu J. H., Han B. H., Macromolecules, 2014, 47(17), 5926—5931
[26]	Luo J., Zhang X., Zhang J., ACS Catal., 2015, 5(4), 2250—2254
[27]	Pan L., Xu M. Y., Feng L. J., Chen Q., He Y. J., Han B. H., Polym. Chem., 2016, 7(12), 2299—2307
[28]	Feng L. J., Chen Q., Zhu J. H., Liu D. P., Zhao Y. C., Han B. H., Polym. Chem., 2014, 5(8), 3081—3088
[29]	Liu J., Chen Q., Sun Y. N., Xu M. Y., Liu W., Han B. H., RSC Adv., 2016, 6(54), 48543—48549
[30]	Su C. L., Tandiana R., Tian B. B., Sengupta A., Tang W., Su J., Loh K. P., ACS Catal., 2016, 6(6), 3594—3599
[31]	Bheemireddy S. R., Hautzinger M. P., Li T., Lee B., Plunkett K. N., J. Am. Chem. Soc., 2017, 139(16), 5801—5807
[32]	Liu J., Liu Y. F., Jiang X. W., Luo Y. L., Lyu Y. O., Micropor. Mesopor. Mat., 2017, 250, 203—209
[33]	Yang X., Yu M., Zhao Y., Zhang C., Wang X., Jiang J.X., RSC Advance, 2014, 4(105), 61051—61055