Kinetics of In situ Robust Chain-Ends Crosslinked Polymeric Networks Formed Using Catalyst- and Solvent-Free Huisgen Cycloaddition Reaction

Byoung Sun Min; Sang Youl Kim

Macromolecular Research, Vol.25, No.3, 249-254, March, 2017

DOI10.1007/s13233-017-5038-4 Export Citation

Kinetics of In situ Robust Chain-Ends Crosslinked Polymeric Networks Formed Using Catalyst- and Solvent-Free Huisgen Cycloaddition Reaction

Byoung Sun Min, and Sang Youl Kim^{1, †}

4-R&D Institute, Rocket Prouplsion Directorate, Agency for Defense Development, Yuseong, P.O. Box 35-5, Daejeon 34188, Korea
¹Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), 373-1, Guseong-dong,Yuseong-gu, Daejeon 34141, Korea

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At various temperatures, real time FTIR analysis was introduced to monitor the kinetics of the uncatalyzed Huisgen 1,3-dipolar azide-alkyne cycloaddition (AAC) without media, resulting in in situ robust polymeric networks crosslinked with triazoles at chain-ends. Second-order kinetic analysis was used to determine the rate constants for uncatalyzed AAC reaction. Electron-deficient alkynes carrying an α-carbonyl undergo a fast Huisgen reaction within a few hours without any catalysts, proportional to the temperature. Less electron-deficient alkynes led to the decrease of AAC reaction rate significantly, revealing that the AAC reaction rate depends on the molecular structure of alkynes center.

Keywords:electron-deficient dipolarophiles;azide-alkyne cycloaddition;real-time FTIR

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[Referenced By]

[1] Binder WH, Sachsenhofer R, Macromol. Rapid Commun., 28(1), 15 (2007)

[2] Kolb HC, Finn MG, Sharpless B, Angew. Chem.-Int. Edit., 113, 2056 (2001)

[3] Kolb HC, Finn MG, Sharpless B, Angew. Chem.-Int. Edit., 40, 2004 (2001)

[4] Hawker CJ, Wooley KL, Science, 309, 1200 (2005)

[5] Fournier D, Hoogenboom R, Schubert US, Chem. Soc. Rev., 36, 1369 (2007)

[6] Bock VD, Hiemstra H, van Maarseveen JH, Eur. J. Org. Chem., 1, 51 (2006)

[7] Kolb HC, Sharpless KB, Drug Deliv. Today, 8, 1128 (2003)

[8] Alvarez R, Velazquez S, San-Felix A, Aquaro S, De Clereg E, Perno CF, Karlsson A, Balzarini J, Camarasa MJ, J. Med. Chem., 37, 4185 (1994)

[9] Malkoch M, Vestberg R, Gupta N, Mespouille L, Dubois P, Mason AF, Hedrick JL, Liao Q, Frank CW, Kingbury K, Hawker CJ, Chem. Commun., 2774 (2006)

[10] Wang Q, Chan TR, Hilgraf R, Fokin VV, Sharpless KB, Finn MG, J. Am. Chem. Soc., 125(11), 3192 (2003)

[11] Gierlich J, Burley GA, Gramlich PME, Hammond DM, Carell T, Org. Lett., 8, 3639 (2006)

[12] Laughlin ST, Baskin JM, Amacher SL, Bertozzi CR, Science, 320, 664 (2008)

[13] Johnson JA, Baskin JM, Bertozzi CR, Koberstein JF, Turro NJ, Chem. Commun., 3064 (2008)

[14] Codelli JA, Baskin JM, Agard NJ, Berozzi CR, J. Am. Chem. Soc., 130(34), 11486 (2008)

[15] Sletten EM, Bertozzi CR, Org. Lett., 10, 3097 (2008)

[16] Baskin JM, Bertozzi CR, QSAR Comb. Sci., 26, 1211 (2007)

[17] Vuluga D, Legros J, Crousse B, Delpon DB, Green Chem., 11, 156 (2009)

[18] Mcgrath NA, Raines RT, Chem. Sci., 3, 3237 (2012)

[19] Borukhova S, Noёl T, Metten B, de Vos E, Hessel V, ChemSusChem, 6, 2220 (2013)

[20] Becer CR, Hoogenboom R, Schubert US, Angew. Chem.-Int. Edit., 48, 2 (2009)

[21] Sawoo S, Dutta P, Chakraborty A, Mukhopadhyay R, Bouloussa O, Sarkar A, Chem. Commun., 5957 (2008)

[22] van Berkel SS, Dirks AJ, Meeuwissen SA, Pingen DLL, Boerman OC, Laverman P, van Delft FL, Cornelissen JJL, Rutjes FPJ, Chembiochem, 9, 1805 (2008)

[23] Shi F, Waldo JP, Chen Y, Larock RC, Org. Lett., 10, 2409 (2008)

[24] Hong JA, Luo QA, Shah BK, Biomacromolecules, 11(11), 2960 (2010)

[25] Wang D, Li N, Zhao M, Shi W, Ma C, Chen B, Green Chem., 12, 2120 (2010)

[26] Kang H, Lee HJ, Park JC, Song H, Park KH, Top. Catal., 53, 523 (2010)

[27] Thorwirth R, Stolle A, Ondruschka B, Wild A, Schubert US, Chem. Commun., 47, 4370 (2011)

[28] Banerjee R, Maiti S, Dhara D, Green Chem., 16, 1365 (2014)

[29] Keicher T, Kuglstatter W, Eisele S, Wetzel T, Krause H, PROPELLANT-EXPLOS-PYROTECH, 34(3), 210 (2009)

[30] Min BS, Park YC, Yoo JC, PROPELLANT-EXPLOS-PYROTECH, 37(1), 59 (2012)

[31] Reshmi SK, Vijayalakshmi KP, Thomas D, Arunan E, Nair CPR, PROPELLANT-EXPLOS-PYROTECH, 38(4), 525 (2013)

[32] Min BS, Park YC, Yoo JC, Macromol. Res., 20(4), 429 (2012)

[33] Lee DH, Kim KT, Jang Y, Lee S, Jeon HB, Paik H, Min BS, Kim W, J. Appl. Polym. Sci., 15, 131 (2014)

[34] Omrani A, Simon LC, Rostami AA, Ghaemy M, Int. J. Chem. Kinet., 40, 663 (2008)

[35] Min BS, Jeon HB, Jeong TW, Kim SY, Polym. Compos., 6, 7914 (2015)

[36] Huisgen R, J. Org. Chem., 33, 2291 (1968)

[37] Houk KN, Sims J, Duke RE, Strozier RW, George JK, J. Am. Chem. Soc., 95, 7287 (1973)