Modeling of Living Cationic Ring-Opening Polymerization of Cyclic Ethers: Active Chain End versus Activated Monomer Mechanism

Document Type : Research Article

Authors

1 Nanotechnology Research Center, Urmia University, Urmia, I.R. IRAN

2 Institute of Chemical Research and Technology, Tehran, I.R. IRAN

3 Nanochemistry Department, Institute of Nanotechnology, Urmia University, Urmia, I.R. IRAN

4 Department of Chemistry, Payame Noor University (PNU), Tehran, I.R. IRAN

Abstract

Living cationic ring-opening polymerization of cyclic ethers in the presence of diol was modeled using the method of moments. A widespread kinetic model was developed based on previous experimental studies. Then, the moment and population balance of reactants were obtained. Modeling results were employed to study the influence of initiator and water amounts (as the impurity) as well as feeding policy in polymerization kinetics and final properties of the polymer. In addition, the sensitivity of modeling results to initiation, backbiting, and finally propagation via activated monomer reactions were investigated. Results showed the population of chains is the function of their precursors. In a typical polymerization, chains with diol functionality are the majority. Therefore, most of the polymerized monomers are incorporated into those chains. This makes the chains with diol functionality the determining group in Molecular Weight Distribution (MWD). The kinetics of polymerization and properties of the reactor’s product are highly dependent on the ratio of the rate of propagation via the Activated Monomer (AM) mechanism to the rate of propagation via active chain end (ACE). An increase in this ratio decreases the probability of occurrence of backbiting reaction. Therefore, cyclic dimers are less formed and MWD narrows. On the other hand, decreasing this ratio results in less diol reacted with protonated monomers. Consequently, the rate of regeneration of the initiator and hence the rate of polymerization is decreased. These findings give complete facts about the ring-opening syntheses of polyethers and are valuable for evolving new grades as well as optimization current processes.

Keywords

Main Subjects

References

[1] Tasdelen M.A., Kreutzer J., Yagci Y., In Situ Synthesis of Polymer/Clay Nanocomposites by Living and Controlled/Living Polymerization, Macromol. Chem. Phys,. 211(3): 279–285(2010).
[2]  Aydin M., Tasdelen M.A., Uyar T., Yagci Y., In Situ Synthesis of A(3)-Type Star Polymer/Clay Nanocomposites by Atom Transfer Radical Polymerization, J. Polym. Sci. Part A – Polym. Chem., 51(24): 5257–5262(2013).
[3] Konn C., Morel F., Beyou E., Chaumont P., Bourgeat-Lami E., Nitroxide-Mediated Polymerization of Styrene Initiated from the Surface of Laponite Clay Platelets, Macromolecules, 40(21): 7464–7472 (2007).
[4]  Dizman C., Ates S., Uyar T., Tasdelen M.A., Torun L., Yagci Y., Polysulfone/Clay Nanocomposites
by in Situ Photoinduced Crosslinking Polymerization, Macromol. Mater. Eng., 296(12): 1101–1106(2011).
[5]  Altinkok C., Uyar T., Tasdelen M.A., Yagci Y., In Situ Synthesis of Polymer/Clay Nanocomposites by
Type II Photoinitiated Free Radical Polymerization, J. Polym. Sci. Part A – Polym. Chem., 49(16): 3658–3663 (2011).
[6]  Aydin M., Tasdelen M.A., Uyar T., Jockusch S., Turro N.J., Yagci Y., Polystyrene/Clay Nanocomposites by Atom Transfer Radical Nitroxide Coupling Chemistry, J. Polym. Sci. Part A – Polym. Chem., 51(5): 1024–1028(2013).
[7] Yenice Z., Tasdelen M.A., Oral A., Guler C., Yagci Y., Poly(styrene-b-tetrahydrofuran)/Clay Nanocomposites by Mechanistic Transformation,  J. Polym. Sci. Part A - Polym. Chem., 47(8): 2190–2197 (2009).
[8]  Barlas F.B., Seleci D.A., Ozkan M., Demir B., Seleci M., Aydin M., Folic Acid Modified Clay/Polymer Nanocomposites for Selective Cell Adhesion, J. Mater. Chem., B 2(37): 6412–6421(2014).
[9] Lian R. Hutchings, Paul P. Brooks, Peter Shaw, Paul Ross‐Gardner, One‐Shot Synthesis and Characterization of Block‐Like Statistical Terpolymers via Living Anionic Polymerization, J. Polym. Sci. Part A – Polym. Chem.,57:382-394 (2018).
[10] Tan N.M., Mori R., Tanaka T., Motoyanagi J., Minoda M., Living Cationic Polymerization of a Vinyl Ether with an Unprotected Pendant Alkynyl Group and Their Use for the Protecting Group‐Free Synthesis of Macromonomer‐Type Glycopolymers via CuAAC with Maltosyl Azides, J. Polym. Sci. Part A – Polym. Chem., 57:681-688.
[11] Tasdelen M.A., Poly(epsilon-caprolactone)/Clay Nanocomposites via Click Chemistry, Eur. Polym. J., 47(5): 937–941(2011).
[12]  Arslan M., Tasdelen M.A., Uyar T., Yagci Y., Poly(epsilon caprolactone)/Clay Nanocomposites via Host-Guest Chemistry, Eur. Polym. J., 71: 259–267 (2015).
[13]  Aydin M., Uyar T., Tasdelen M.A., Yagci Y., Polymer/Clay Nanocomposites Through Multiple Hydrogen-Bonding Interactions, J. Polym. Sci. Part A – Polym.Chem,. 53(5): 650–658(2015).
[14] Odian G., “Principles of Polymerization”, 4th ed., John Wiley & Sons, Inc., 555-556 (2004).
[15] Zhao Q., Jerry Qi H., Xie T., Recent Progress in Shape Memory Polymer: New Behavior, Enabling Materials, and Mechanistic Understanding, Prog. Polym. Sc., 49–50: 79–120(2015).
[16] Penczek S., Kubisa P., Szymanski R., Activated Monomer Propagation in Cationic Polymerizations, Makromolekulare Chemie. Macromolecular Symposia, 3(1): 203–220 (1986).
[17] Wojtania M, Kubisa P, Penczek S., Polymerization of Propylene Oxide by Activated Monomer Mechanism. Suppression of Macrocyclics Formation, Makromolekulare Chemie. Macromolecular Symposia, 6(1): 201–206 (1986).
[18] Kubisa P., Activated Monomer Mechanism in the Cationic Polymerization of Cyclic Ethers, Makromolekulare Chemie. Macromolecular Symposia, 13-14(1): 203–210 (1988).
[19] Biedron T, Szymanski R, Kubisa P, and Penczek S., Kinetics of Polymerization by Activated Monomer Mechanism, Makromolekulare Chemie. Macromolecular Symposia, 32(1):155–168 (1990).
[20] Biedron T, Kubisa P, Penczek S., Polyepichlorohydrin Diols Free of Cyclics: Synthesis and Characterization, J Polym. Sci. Part A: Polym. Chem., 29(5): 619–628 (1991).
[21] Steinkoenig J., Jongh P.A.J.M.de, Haddleton D.M., Goldmann A.S., Kowollik C.B., Kempe K., Unraveling the Spontaneous Zwitterionic Copolymerization Mechanism of Cyclic Imino Ethers and Acrylic Acid, Macromolecules, 51(2): 318–327(2018).
[22] Tran J., Pesenti T., Cressonnier J., Lefay C., Gigmes D., Guillaneuf Y., Nicolas J., Degradable Copolymer Nanoparticles from Radical Ring-Opening Copolymerization between Cyclic Ketene Acetals and Vinyl Ethers. Biomacromolecules, 20(1): 305–317(2019).
[23] Ochs J., Veloso A., Tong D.E.M., Alegria A.,  Bujans F.B., An Insight into the Anionic Ring-Opening Polymerization with Tetrabutylammonium Azide for the Generation of Pure Cyclic Poly(glycidyl phenyl ether), Macromolecules, 51(7): 2447–2455(2018).
[24] Royappa AT, Vashi M, Russo C, and Blackwell A., A Comparison of the Cationic Ring-Opening Polymerizations of 3-Oxetanol and Glycidol, Macromolecular Research 21(10):1069–1074(2013).
[25] Vidil T., and Tournilhac F., Supramolecular Control of Propagation in Cationic Polymerization of Room Temperature Curable Epoxy Compositions, Macromolecules 46(23):9240–9248(2013).
[26] Barner-Kowollik C., Modeling for Polymer Design, Macromolecular Theory and Simulations,18(7–8): 384–386 (2009).
[27] Penczek S, Cypryk M, Duda A, Kubisa P, Słomkowski S., Living Ring-Opening Polymerization of Heterocyclic Monomers, Progress in Polym. Sci., 32(2): 247–282(2007).
[28]  Agrawa A., Satapathy A., Mathematical Model for Evaluating Effective Thermal Conductivity of Polymer Composites with Hybrid Fillers, Int. J. Thermal Sci., 89: 203–209 (2015).
[29] Francis A.U., Venkatachalam S., Kanakavel M., Ravindran P.V., Ninan K.N., Structural Characterization of Hydroxyl Terminated Polyepichlorohydrin Obtained Using Boron Trifluoride Etherate and Stannic Chloride as Initiators, Europ. Polym. J., 39(4): 831–841(2003).
[30] Odian G. Principles of Polymerization, 4th ed., John Wiley & Sons, Inc., pp. 557–559 (2004).
[31] Guanaes D., Bittencourt E., Eberlin M.N., Sabino A.A., Influence of Polymerization Conditions on the Molecular Weight and Polydispersity of Polyepichlorohydrin, Europ. Polym. J., 43(5): 2141–2148 (2007).
Iranian Journal of Chemistry and Chemical Engineering
Volume 39, Issue 5 - Serial Number 103
September and October 2020
Pages 95-110

Files

Share

How to cite

Statistics