Adv Polym Sci (2013) 262: 295–328
DOI: 10.1007/12_2013_238
© Springer-Verlag Berlin Heidelberg 2013
Published online: 27 September 2013
Synthesis of Cyclic Polymers via Ring
Closure
Zhongfan Jia and Michael J. Monteiro
Abstract Cyclic polymers have intrigued scientists for many years and their
diffusion process may have important implications for polymer physics. In this
contribution, we focus on the ring-closure method for synthesis of linear polymers
made by “living” radical polymerization. In the first part, the probability of two
chain ends being in a capture volume to undergo ring closure will be described
using the well-known Gaussian chain end-to-end distance. The probability for knot
or catenane structures will also be discussed. We then describe the thermodynamic
Jacobson–Stockmayer theory for monocyclic ring closure, and an empirical equation based on kinetics. Finally, we give examples of ring closure for many different
polymer systems, including the formation of many complex cyclic topologies.
Keywords Cyclic polymers Á Jacobson–Stockmayer equation Á “Living” radical
polymerization Á Ring-closure
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
1.1 Chain Conformation for Ring Closure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
1.2 Model for Ring Closure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2 Synthetic Methodologies for Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
2.1 Ring Closure Through Homodifunctional Linear Polymers . . . . . . . . . . . . . . . . . . . . . . . . . 304
2.2 Ring Closure Through Hetrodifunctional Linear Polymers . . . . . . . . . . . . . . . . . . . . . . . . . 315
3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Z. Jia and M.J. Monteiro (*)
Australian Institute for Bioengineering and Nanotechnology, The University of Queensland,
Brisbane, QLD 4072, Australia
e-mail: m.monteiro@uq.edu.au
DOI: 10.1007/12_2013_238
© Springer-Verlag Berlin Heidelberg 2013
Published online: 27 September 2013
Synthesis of Cyclic Polymers via Ring
Closure
Zhongfan Jia and Michael J. Monteiro
Abstract Cyclic polymers have intrigued scientists for many years and their
diffusion process may have important implications for polymer physics. In this
contribution, we focus on the ring-closure method for synthesis of linear polymers
made by “living” radical polymerization. In the first part, the probability of two
chain ends being in a capture volume to undergo ring closure will be described
using the well-known Gaussian chain end-to-end distance. The probability for knot
or catenane structures will also be discussed. We then describe the thermodynamic
Jacobson–Stockmayer theory for monocyclic ring closure, and an empirical equation based on kinetics. Finally, we give examples of ring closure for many different
polymer systems, including the formation of many complex cyclic topologies.
Keywords Cyclic polymers Á Jacobson–Stockmayer equation Á “Living” radical
polymerization Á Ring-closure
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
1.1 Chain Conformation for Ring Closure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
1.2 Model for Ring Closure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301
2 Synthetic Methodologies for Ring-Closure Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
2.1 Ring Closure Through Homodifunctional Linear Polymers . . . . . . . . . . . . . . . . . . . . . . . . . 304
2.2 Ring Closure Through Hetrodifunctional Linear Polymers . . . . . . . . . . . . . . . . . . . . . . . . . 315
3 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Z. Jia and M.J. Monteiro (*)
Australian Institute for Bioengineering and Nanotechnology, The University of Queensland,
Brisbane, QLD 4072, Australia
e-mail: m.monteiro@uq.edu.au