Oxygen/Sulfur Atom Exchange Copolymerization of Carbon Disulfide and Propylene Oxide by a Highly Effective Heterogeneous Berlin Green Catalyst

Abstract

In this study, we report that Berlin Green (FeFe-BG) framework exhibits superior performance in the catalytic coupling of carbon disulfide (CS₂) and propylene oxide (PO) to generate a random copolymer containing thioether, propylene monothiocarbonate and ether units. Oxygen and sulfur atom exchange was detected in polymeric and cyclic thiocarbonate byproducts and utilized to modulate the copolymerization of CS₂ and propylene oxide. The coupling of PO and CS₂ was selective for copolymer formation under various reaction conditions. ¹H and ¹³C NMR spectroscopy determined two distinct polymer linkages and two cyclic byproducts. Copolymer number average molecular weights ranged from 6.4 kg/mol to 10.5 kg/mol, with a comparatively low polydispersity of 1.3–1.7. The CS₂/PO molar feed ratio had a significant impact on the O/S exchange process; the ratio of cyclic thiocarbonate byproducts could be efficiently regulated by tuning the CS₂ molar feed ratio.

Keywords

Carbon disulfide / Copolymerization / Prussian Blue analogue / Heterogeneous catalysis / Berlin Green

References

[1] Wang J, He Y S, Yang J. Adv. Mater., 2015, 27(3): 569.

[2] He L, Zhao H, Theato P. Angew. Chem. Int. Ed., 2018, 57(40): 13012.

[3] Kloxin C J, Scott T F, Park H Y, Bowman C N. Adv. Mater., 2011, 23(17): 1977.

[4] Bruce P G, Freunberger S A, Hardwick L J, Tarascon J-M. Nat. Mater., 2012, 11(1): 19.

[5] Luo M, Zhang X H, Du B Y, Wang Q, Fan Z Q. Polym. Chem., 2015, 6(27): 4978.

[6] Zhang X H, Theato P. Sulfur-containing Polymers: from Synthesis to Functional Materials, 2021, Weinheim: John Wiley & Sons

[7] Luo M, Zhang X H, Darensbourg D J. Acc. Chem. Res., 201, 49(10): 2209.

[8] Ochiai B, Yoshii K, Nagai D, Endo T. J. Polym. Sci. Pol. Chem., 2005, 43(5): 1014.

[9] Nakano K, Tatsumi G, Nozaki K. J. Am. Chem. Soc., 2007, 129(49): 15116.

[10] Zhang X H, Liu F, Sun X K, Chen S, Du B Y, Qi G R, Wan K M. Macromolecules, 2008, 41(5): 1587.

[11] Luo M, Zhang X H, Darensbourg D J. Macromolecules, 2015, 48(16): 5526.

[12] Luo M, Zhang X H, Du B Y, Wang Q, Fan Z Q. Macromolecules, 2013, 46(15): 5899.

[13] Cao X H, Wang H L, Yang J L, Wang R Y, Hong X, Zhang X H, Xu J T, Wang H. Chin. Chem. Lett., 2022, 33(2): 1021.

[14] Sarapas J M, Tew G N. Angew. Chem. Int. Ed., 201, 55(51): 15860.

[15] Tian T, Hu R, Tang B Z. J. Am. Chem. Soc., 2018, 140(19): 6156.

[16] Yuan J, Xiong W, Zhou X, Zhang Y, Shi D, Li Z, Lu H. J. Am. Chem. Soc., 2019, 141(12): 4928.

[17] Smith R A, Fu G, McAteer O, Xu M, Gutekunst W R. J. Am. Chem. Soc., 2019, 141(4): 1446.

[18] Xia Y, Zhang X, Yang S. Angew. Chem. Int. Ed., 2018, 57(20): 5665.

[19] Zhang C J, Zhang X H. Macromolecules, 2020, 53(1): 233.

[20] Jiang X F, Huang H, Chai Y F, Lohr T L, Yu S Y, Lai W, Pan Y J, Delferro M, Marks T J. Nat. Chem., 2017, 9(2): 188.

[21] DeMartino A W, Zigler D F, Fukuto J M, Ford P C. Chem. Soc. Rev., 2017, 46(1): 21.

[22] Sze N D, Ko M K W. Nature, 1979, 280(5720): 308.

[23] Sze N D, K W Ko M. Nature, 1979, 278(5706): 731.

[24] Yang J L, Hu L F, Cao X H, Wang Y, Zhang X H. Chin. J. Chem., 2020, 38(3): 269.

[25] Darensbourg D. J., Andreatta J. R., Jungman M. J., Reibenspies J. H., Dalton Trans., 2009, (41), 8891

[26] Darensbourg D J, Wilson S J, Yeung A D. Macromolecules, 2013, 46(20): 8102.

[27] Diebler J, Komber H, Haussler L, Lederer A, Werner T. Macromolecules, 201, 49(13): 4723.

[28] Simonov A, De Baerdemaeker T, Bostrom H L B, Rios Gomez M L, Gray H J, Chernyshov D, Bosak A, Burgi H B, Goodwin A L. Nature, 2020, 578(7794): 256.

[29] Margadonna S, Prassides K, Fitch A N. Angew. Chem. Int. Ed., 2004, 43(46): 6316.

[30] Qian J F, Wu C, Cao Y L, Ma Z F, Huang Y H, Ai X P, Yang H X. Adv. Energy Mater., 2018, 8(17): 1702619.

[31] Lu Y, Wang L, Cheng J, Goodenough J B. Chem. Commun., 2012, 48(52): 6544.

[32] Hu L, Zhang P, Chen Q W, Mei J Y, Yan N. RSC Adv., 2011, 1(8): 1574.

[33] Kaye S S, Long J R. J. Am. Chem. Soc., 2005, 127(18): 6506.

[34] Yi H, Qin R, Ding S, Wang Y, Li S, Zhao Q, Pan F. Adv. Funct. Mater., 2021, 31(6): 2006970.

[35] Deng L, Yang Z, Tan L, Zeng L, Zhu Y, Guo L. Adv. Mater., 2018, 30(31): 1802510.

[36] Tang P Y, Han L J, Hegner F S, Paciok P, Biset-Peiro M, Du H C, Wei X K, Jin L, Xie H B, Shi Q, Andreu T, Lira-Cantu M, Heggen M, Dunin-Borkowski R E, Lopez N, Galan-Mascaros J R, Morante J R, Arbiol J. Adv. Energy Mater., 2019, 9(34): 1901836.

[37] Yan L, Liu Y, Zha K, Li H, Shi L, Zhang D. ACS Appl. Mater. Interfaces, 2017, 9(3): 2581.

[38] Khan M U, Khan S U, Kiriatnikom J, Zareen S, Zhang X H. Polyhedron, 2022, 214: 115640.

[39] Wei R J, Zhang X H, Du B Y, Fan Z Q, Qi G R. J. Mol. Catal. A Chem., 2013, 379: 38.

[40] Zhang X H, Chen S, Wu X M, Sun X K, Liu F, Qi G R. Chin. Chem. Lett., 2007, 18(7): 887.

[41] Khan M U, Khan S U, Kiriratnikom J, Zareen S, Zhang X H. Chin. Chem. Lett., 2022, 33(2): 1081.

[42] Khan M U, Khan S U, Cao X, Usman M, Yue X, Ghaffar A, Hassan M, Zhang C, Zhang X H. Chem. Asian J., 2023, 18(1): e202201050.

[43] Wu H L, Yang J L, Luo M, Wang R Y, Xu J T, Du B Y, Zhang X H, Darensbourg D J. Macromolecules, 201, 49(23): 8863.

[44] Yue T J, Ren W M, Liu Y, Wan Z Q, Lu X B. Macromolecules, 201, 49(8): 2971.

[45] Luo M, Zhang X H, Darensbourg D J. Polym. Chem., 2015, 6(39): 6955.

[46] Zhang C J, Wu H L, Li Y, Yang J L, Zhang X H. Nat. Commun., 2018, 9(1): 2137.

[47] Yang J L, Wu H L, Li Y, Zhang X H, Darensbourg D J. Angew. Chem. Int. Ed., 2017, 56(21): 5774.

[48] Ren W M, Yue T J, Li M R, Wan Z Q, Lu X B. Macromolecules, 2017, 50(1): 63.

[49] Yue T J, Ren W M, Chen L, Gu G G, Liu Y, Lu X B. Angew. Chem. Int. Ed., 2018, 57(39): 12670.

[50] Yue T J, Bhat G A, Zhang W J, Ren W M, Lu X B, Darensbourg D J. Angew. Chem. Int. Ed., 2020, 59(32): 13633.

[51] Zhang C J, Zhang X H. Chin. J. Polym. Sci., 2019, 37(10): 951.

[52] Wu X Y, Xu Y K, Jiang H, Wei Z X, Hong J J, Hernandez A S, Du F, Ji X L. Acs. Appl. Energ. Mater., 2018, 1(7): 3077.

[53] Kulesza P J, Malik M A, Denca A, Strojek J. Anal. Chem., 199, 68(14): 2442.

[54] Shen L, Wang Z, Chen L. Chem. Eur. J., 2014, 20(39): 12559.

[55] Panov G I, Starokon E V, Pirutko L V, Paukshtis E A, Parmon V N. J. Catal., 2008, 254(1): 110.

[56] Hadjiivanov K. Adv. Catal., 2014, 57: 99.