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Investigation of a Novel Catalyst KOH/K2CO3@γ-Al2O3 Toward Polycarbonate Diol Synthesis

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Abstract

Polycarbonate diols (PCDLs) are intermediates used in the synthesis of polyurethanes (PU), and therefore their efficient and green synthesis is a necessity. In this work, KOH/K2CO3@γ-Al2O3 catalysts were prepared and employed in the synthesis of PCDLs. A 4 wt% KOH/40 wt% K2CO3@γ-Al2O3 catalyst and a DMC: 1,4-BDO molar ratio of 1.25:1 exhibited the best activity for the reaction and gave a PCDL yield of 95% with a molecular weight of 4527 g·mol−1. Moreover, the catalyst could be reused 4 times without a significant loss of the catalytic activity in transesterification. The effects of the catalyst composition and reaction conditions on the synthesis of PCDLs were investigated. The results indicate that the catalyst amount and the molar ratio of DMC: 1,4-BDO can influence the purity of PCDLs.

Graphic Abstract

The reaction equation

Catalyst preparation

The synthesis of PCDLs using DMC and 1,4-BDO

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References

  1. Liu J, Liu Q, Zheng X et al (2016) Synthesis of UV-curable polycarbonate diols (PCDL)-based polyurethane acrylate for negative photoresist. J Polym Bull 73:647–659

    Article  CAS  Google Scholar 

  2. Zhu L, Xue W, Zeng Z (2018) Synthesis of polycarbonate diols catalyzed by calcined hydrotalcites doped with the transition metal Ni2+. New J Chem 42:1–8

    Article  Google Scholar 

  3. Menglu S, Xiangui Y, Gongying W (2018) Synthesis of Polycarbonate Diols(PCDLs) via Two-step Process Using CH3COONa as an Effective Catalyst. J Chem Res Chin Univ 34:578–583

    Article  Google Scholar 

  4. Kim S, Liu S (2018) Smart and biostable polyurethanes for long-term implants. J ACS Biomater Sci Eng 4:1–52

    Article  Google Scholar 

  5. Heath DE (2017) Promoting endothelialization of polymeric cardiovascular biomaterials. J Macromol Chem Phys 218:1–10

    Google Scholar 

  6. Chatti S, Kricheldorf HR, Schwarz G (2006) Copolycarbonates of isosorbide and various diols. J Polym Sci, Part A: Polym Chem 44(11):3616–3628

    Article  CAS  Google Scholar 

  7. Park JH, Jeon JY, Lee JJ et al (2013) Preparation of high-molecular-weight aliphatic polycarbonates by condensation polymerization of diols and dimethyl carbonate. J Macromol 46(9):3301–3308

    Article  CAS  Google Scholar 

  8. Pawłowski P, Rokicki G (2004) Synthesis of oligocarbonate diols from ethylene carbonate and aliphatic diols catalyzed by alkali metal salts. J Polym 45(10):3125–3137

    Article  Google Scholar 

  9. Wang Z, Yang X, Li J et al (2016) Synthesis of high-molecular-weight aliphatic polycarbonates from diphenyl carbonate and aliphatic diols by solid base. J Mol Catal A: Chem 424:77–84

    Article  CAS  Google Scholar 

  10. Wang Z, Bai Y, Jiang W et al (2017) Structure-activity correlations of calcined Mg-Al hydrocalcites for aliphatic polycarbonate synthesis via transesterification process. Chin J Polym Sci 01:138–148

    Google Scholar 

  11. Wang Y, Yang L, Peng X et al (2017) High catalytic activity over novel Mg-Fe/Ti layered double hydroxides (LDHs) for polycarbonate diols (PCDLs): synthesis, mechanism and application. RSC Adv 7:35181–35190

    Article  CAS  Google Scholar 

  12. Song M, Yang X, Wang G (2018) Preparation of polycarbonate diols (PCDLs) from dimethyl carbonate (DMC) and diols catalyzed by KNO3/γ-Al2O3. RSC Adv 8:35014–35022

    Article  CAS  Google Scholar 

  13. Platzek J, Trentmann W (2012) Process for the preparation of polycarbonate polyols. Patent 20120309962 A1, USA

  14. Haba O, Tomizuka H, Endo T (2005) Anionic ring-opening polymerization of methyl 4,6-O-Benzylidene-2,3-O-carbonyl-α-d-glucopyranoside: a firstexample of anionic ring-opening polymerization of five-membered cyclic carbonate without elimination of CO2. J Macromol 38:3562–3563

    Article  CAS  Google Scholar 

  15. Ana PP, Grijpma DW, Feijen J (2003) Enhanced mechanical properties of 1,3-trimethylene carbonate polymers and networks. J Polym 44:6495–6504

    Article  Google Scholar 

  16. Wu GP, Darensbourg DJ (2016) Mechanistic insights into water-mediated tandem catalysis of metal-coordination CO2/epoxide copolymerization and organocatalytic ring-opening polymerization: one-pot, two steps, and three catalysis cycles for triblock copolymers synthesis. J Macromol 49:807–814

    Article  CAS  Google Scholar 

  17. Darensbourg DJ, Moncada AI (2010) Tuning the selectivity of the oxetane and CO2, coupling process catalyzed by (Salen)CrCl/n-Bu4NX: cyclic carbonate formation vs aliphatic polycarbonate production. J Macromol 43:5996–6003

    Article  CAS  Google Scholar 

  18. Tomczyk K, Parzuchowski M et al (2010) Synthesis of oligocarbonate diols from a, ‘green monomer’- dimethyl carbonate-as soft segments for poly (urethane-urea) elastomers. J Polimery 55:366–372

    Article  CAS  Google Scholar 

  19. Aouissi A, Al-Deyab SS (2012) Comparative study between gas phase and liquid phase for the production of DMC from methanol and CO2. J Nat Gas Chem 21(2):189–193

    Article  CAS  Google Scholar 

  20. Kumar P, Srivastava VC, Glaser R et al (2017) Active ceria-calcium oxide catalysts for dimethyl carbonate synthesis by conversion of CO2. J Powder Technol 309:13–21

    Article  CAS  Google Scholar 

  21. Zhou R, Niu Z, Jia L et al (2018) CH3ONa-initiated two-step-transesterification of DMC (dimethyl carbonate) and α, ω-alkanediol for poly(alkylene carbonate). J Inorg Chem Commun 90:82–85

    Article  CAS  Google Scholar 

  22. Wang LP, Xiao B, Wang GY et al (2011) Synthesis of polycarbonate diol catalyzed by metal-organic framework Zn4O[CO2-C6H4-CO2]3. J Sci China Chem 54:1468–1473

    Article  CAS  Google Scholar 

  23. Zhu W, Huang X, Li C et al (2011) High-molecular weight aliphatic polycarbonates by melt polycondensation of dimethyl carbonate and aliphatic diols: synthesis and characterization. J Polym Int 60:1060–1067

    Article  CAS  Google Scholar 

  24. Gong P, Wang Z, Li Z et al (2013) Photochemical synthesis of fluorinated graphene via a simultaneous fluorination and reduction route. J RSC Adv 3:6327–6330

    Article  CAS  Google Scholar 

  25. Wang Y, Yi J, Peng X et al (2018) Structure-property relationships of novel fluorinated polycarbonate polyurethane films with high transparency and thermal stability. J Res Chem Intermed 1157:52–60

    Google Scholar 

  26. Noiroj K, Intarapong P, Luengnaruemitchai A et al (2009) A comparative study of KOH/Al2O3 and KOH/NaY catalysts for biodiesel production via transesterification from palm oil. J Renew Energy 34:1145–1150

    Article  CAS  Google Scholar 

  27. Sengupta S, Reddy SA, Dongara R et al (2014) Improvement in regeneration properties and multicycle stability for K2CO3/Al2O3 adsorbents for CO2 removal from flue gas. J Energy Fuels 28(8):5354–5362

    Article  CAS  Google Scholar 

  28. Tang Y, Chang F, Zhou R et al (2016) No-Glycerol rapid heterogeneous biodiesel production on K2CO3/Al2O3 catalyst by coupling process. Russ J Appl Chem 89(12):2066–2071

    Article  CAS  Google Scholar 

  29. Xie W, Peng H, Chen L (2006) Transesterification of soybean oil catalyzed by potassium loaded on alumina as a solid-base catalyst. J Appl Catal A 300(1):67–74

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by the Six Talent Peaks Project in Jiangsu Province (Grant No. 2014-XCL-016).

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Authors and Affiliations

  1. State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing, 210009, China

    Xun-Qiang Wang, He Li, Qi-Yue Yuan, Xiao-Qin Liu & Ding-Hua Liu

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  1. Xun-Qiang Wang
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  2. He Li
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  3. Qi-Yue Yuan
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  4. Xiao-Qin Liu
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  5. Ding-Hua Liu
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Correspondence to Xiao-Qin Liu or Ding-Hua Liu.

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Wang, XQ., Li, H., Yuan, QY. et al. Investigation of a Novel Catalyst KOH/K2CO3@γ-Al2O3 Toward Polycarbonate Diol Synthesis. Catal Lett 150, 3174–3183 (2020). https://doi.org/10.1007/s10562-020-03207-x

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  • DOI: https://doi.org/10.1007/s10562-020-03207-x

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