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Designing unusual polymer topologies with novel telechelics

A novel process has been devised for designing unusual polymer topologies by making use of an electrostatic self-assembly of polymer precursors (telechelics). The key of this challenge is uniform-size telechelic polymers having moderately-strained, cyclic onium salt groups having polycarboxylates as counter anions. The subsequent selective ring-opening reaction at an elevated temperature under "self-assemly" condition of ionic polymer precursors, can convert the ion-pair end groups to the covalently-linked groups to provide a variety of non-linear (branched or cyclic) polymer topologies(Fig.1) in high efficiency. Our polymers are now shown as typical examples in IUPAC Nomenclature for Cyclic Polymers.

Fig.1a; non-linear (branched or cyclic) polymer topologies, Part-1

Fig.1b; non-linear (branched or cyclic) polymer topologies, Part-2

　References

• Synthesis of Orientationally Isomeric Cyclic Stereoblock Polylactides with Head-to-Head and Head-to-Tail Linkages of the Enantiomeric Segments
  N. Sugai, T. Yamamoto, Y. Tezuka, ACS Macro Lett. 1(7), 902-906 (2012).[PDF]
• Surface Modification by Electrostatic Self-Assembly Followed by Covalent Fixation
  M. Foston, C. Hubbell, D.-Y. Park, F. Cook, Y. Tezuka, H. W. Beckham, Angew. Chem. Int. Ed., 51(8), 1849-1852 (2012).[PDF]
• ATRP-RCM Polymer Cyclization: Synthesis of Amphiphilic Cyclic Poystyrene-b-Poly(ethylene oxide) Copolymers
  E. Baba, S. Honda, T. Yamamoto, Y. Tezuka, Polym. Chem., 3(7), 1903-1909 (2012). [PDF]
• A Programmed Polymer Folding: Click and Clip Construction of Doubly Fused Tricyclic and Triply Fused Tetracyclic Polymer Topologies
  N. Sugai, H. Heguri, T. Yamamoto, Y. Tezuka, J. Am. Chem. Soc., 133(49), 19694-19697 (2011).[PDF]
• Topological Polymer Chemistry: A cyclic approach toward novel polymer properties and functions (Review)
  T. Yamamoto, Y. Tezuka, Polym. Chem., 2(9), 1930-1941 (2011).
• Topological Polymer Chemistry by Programmed Self-Assembly and Effective Linking Chemistry (Review)
  T. Yamamoto, Y. Tezuka, Eur. Polym. J., 47, 535-541 (2011).
  
• Effective Click Construction of Bridged- and Spiro-Multicyclic Polymer Topologies with Tailored Cyclic Prepolymers (kyklo-Telechelics)
  N. Sugai, H. Heguri, K. Ohta, Q. Meng, T. Yamamoto, Y. Tezuka, J. Am. Chem. Soc., 132, 14790-14802 (2010). [PDF]
• Topology-Directed Control of Thermal Stability: Micelles Formed from Linear and Cyclized Amphiphilic Block Copolymers
  S. Honda, T. Yamamoto, Y. Tezuka, J. Am. Chem. Soc., 132, 10251-10253 (2010). [PDF]
• Synthesis and Topological Conversion of an 8-shaped Poly(THF) Having a Metathesis-Cleavable Unit at the Focal Position
  K. Ishikawa, T. Yamamoto, H. Harada, Y. Tezuka, Macromolecules, 43, 7062-7067 (2010). [PDF]
• Multimode Diffusion of Ring Polymer Molecules Revealed by a Single-Molecule Study
  S. Habuchi, N. Satoh, T. Yamamoto, Y. Tezuka, M. Vacha, Angew. Chem., Int. Ed., 49, 1460-1463 (2010). [PDF]
• Effective Synthesis of Polymer Catenanes by Cooperative Electrostatic/Hydrogen-bonding Self-assembly and Covalent Fixation
  K. Ishikawa, T. Yamamoto, M. Asakawa, Y. Tezuka, Macromolecules, 43, 168-176 (2010). [PDF]
• Topological Polymer Chemistry in Pursuit of Elusive Polymer Ring Constructions (Review)
  K. Adachi, Y. Tezuka, J. Synth. Org. Chem. Jpn. , 67, 1136-1143 (2009). [PDF]
• Synthesis of Macrocyclised Dimetric Compounds and Their Liquid Crystal Transition Behaviors
  M. Itoh, M. Tokita, K. Adachi, T. Hayakawa, S. Kang, Y. Tezuka, Liq. Cryt., 36(12), 1443-1450 (2009). [PDF]
• Topological Effect on Polymer Crystallization of Linear and Ring Polymers
  N. Okui, N. Ohno, S. Umemoto, Y. Tezuka, Bussei Kenkyu, 92(1), 51-55 (2009). [PDF]
• ATRP-RCM Synthesis of Cyclic Diblock Copolymers
  K. Adachi, S. Honda, S. Hayashi, Y. Tezuka, Macromolecules, 41, 7898-7903 (2008). [PDF]
• Liquid Chromatography of Theta-Shaped and Three-Armed Star Poly(THF)s: Theory and Experimental Evidence of Topological Separation
  A. Vakhrushev, A. Gorbunov, Y. Tezuka, A. Tsuchitani, H. Oike, Anal. Chem., 80, 8153 (2008). [PDF]
• A Defect-Free Ring Polymer: Size-Controlled Cyclic Poly(tetrahydrofuran) Consisting Exclusively of the Monomer Unit
  Y. Tezuka, T. Ohtsuka, K. Adachi, R. Komiya, N. Ohno, N. Okui, Macromol Rapid Commun., 29, 1237-1241 (2008). [PDF]
• ATRP-RCM Synthesis of 8-shaped Poly(methyl acrylate) Using a 4-Armed Star Telechelics
  S. Hayashi, K. Adachi, Y. Tezuka, Polym. J., 40, 572-576 (2008).[PDF]
  

• Synthesis of Polymeric Topological Isomers Having Theta- and Manacle-Constructions with Olefinic Groups at Designated Positions
  Y. Tezuka, N. Takahashi, T. Satoh, K. Adachi, Macromolecules, 40, 7910-7918 (2007). [PDF]
• Synthesis and Palladium-mediated Cross-coupling Reaction of Cyclic (kyklo-) and Open-chain (kentro-) Telechelic Precursors
  Y. Tezuka, R. Komiya, Y. Ido, K. Adachi, React. Funct. Polym., 67, 1233-1242 (2007). [PDF]
• An Efficient Route to Cyclic Polymers by ATRP-RCM Process
  S. Hayashi, K. Adachi, Y. Tezuka, Chem. Lett., 36, 982-983 (2007). [PDF]
• Telechelics Having Unstrained Cyclic Ammonium Salt Groups for Electrostatic Polymer Self-Assembly and Ring-Emitting Covalent Fixation
  K. Adachi, H. Takasugi, Y. Tezuka, Macromolecules, 39, 5585-5588 (2006).[PDF]
• Construction of Polymeric delta-Graph: A Doubly-Fused Tricyclic Topology
  Y. Tezuka, K. Fujiyama, J. Am. Chem. Soc., 127, 6266-6270 (2005). [PDF]
  
• Electrostatic Self-Assembly and Covalent Fixation with Cationic and Anionic Telechelic Precursors for New Loop and Branch Polymer Topologies
  K. Adachi, H. Irie, T. Sato, A. Uchibori, M. Shiozawa, Y. Tezuka, Macromolecules, 38, 10210-10219 (2005). [PDF]
• Synthesis of Polymeric Topological Isomers through Double Metathesis Condensation with H-Shaped Telechelic Precursors
  Y. Tezuka, F. Ohashi, Macromol Rapid Commun., 26, 608-612 (2005). [PDF]
  
• Topological Polymer Chemistry by Dynamic Selection from Electrostatic Polymer Self-Assembly (Review)
  Y. Tezuka, Chem. Rec., 5, 17-26 (2005). [PDF]
  
• Designing Loop and Branch Polymer Topology with Cationic Star Telechelics through Effective Selection of Mono- and Difunctional Counter Anions
  H. Oike, A. Uchibori, A. Tsuchitani, H.-K. Kim, Y. Tezuka, Macromolecules, 37, 7595-7601 (2004).[PDF]
• Synthesis of Polymeric Topological Isomers through Electrostatic Self-Assembly and Covalent Fixation with Star Telechelic Precursors
  Y. Tezuka, A. Tsuchitani, H. Oike, Macromol. Rapid Commun., 25, 1531-1535 (2004).[PDF](Click for Cover Picture)
• Topological Polymer Chemistry by Electrostatic Self-Assembly (Highlight)
  Y. Tezuka, J. Polym. Sci., Part-A: Polym. Chem., 41, 2905-2917 (2003)[PDF](Click for Cover Picture)
  
• Topological Polymer Chemistry: classification and construction of non-linear polymer architectures
  Y. Tezuka, Macromol. Symp., 192, 217-226 (2003) [PDF]
• Designing 8-Shaped Polymer Topology by Metathesis Condensation with Cyclic Poly(THF) Precursors Having Allyl Groups
  Y. Tezuka, R. Komiya, M. Washizuka, Macromolecules, 36, 12-17 (2003) [PDF]
  
• Synthesis of theta-Shaped Poly(THF) by Electrostatic Self-Assembly and Covalent Fixation with Three-armed Star Telechelics Having Cyclic Ammonium Salt Groups
  Y. Tezuka, A. Tsuchitani, Y. Yoshioka, H. Oike, Macromolecules, 36, 65-70 (2003) [PDF]
  
• Synthesis of Polymeric Topological Isomers through Electrostatic Self-Assembly and Covalent Fixation with Telechelic Poly(THF) Having Cyclic Ammonium Salt Groups
  Y. Tezuka, A. Tsuchitani, H. Oike, Polym. Int., 52, 1579-1583 (2003). [PDF]
• Topological Polymer Chemistry
  Y. Tezuka, H. Oike, Prog. Polym. Sci., 27, 1069-1122 (2002) [PDF]
  
• Metathesis Polymer Cyclization with Telechelic Poly(THF) Having Allyl Groups
  Y. Tezuka, R. Komiya, Macromolecules, 35, 8667-8669 (2002) [PDF]
  
• Efficient Synthesis of Cyclic Poly(oxymethylene) by Electrostatic Self-Assembly and Covalent Fixation with Telechelic Precursor Having Cyclic Ammonium Salt Groups
  Y. Tezuka, K. Mori, H. Oike, Macromolecules, 35, 5707-5711 (2002) [PDF]
  
• Topological Polymer Chemistry: Systematic Classification of Nonlinear Polymer Topologies
  Y. Tezuka, H. Oike, J. Am. Chem. Soc., 123, 11570-11576 (2001) [PDF][Supporting Info]
  
• Electrostatic Self-Assembly and Covalent Fixation for Topological Polymer Chemistry (Feature Article)
  Y. Tezuka, H. Oike, , Macromol. Rapid Commun., 22, 1017 (2001) [PDF]
  
• Designing an "A-Ring-with-Branches" Polymer Topology by Electrostatic Self-Assembly and Covalent Fixation with Interiorly-Functionalized Telechelics Having Cyclic Ammonium Salt Groups
  H. Oike, M. Washizuka, Y. Tezuka, Macromol. Rapid Commun., 22, 1128 (2001) [PDF]
  
• Efficient Polymer Cyclization by Electrostatic Self-Assembly and Covalent Fixation with Telechelic Poly(tetrahydrofuran) Having Cyclic Ammonium Salt Groups
  H. Oike, T. Mouri, Y. Tezuka, Macromolecules, 34, 6592 (2001) [PDF]
  
• A Cyclic Macromonomer Designed for a Novel Polymer Network Architecture Having Both Covalent and Physical Linkages
  H. Oike, T. Mouri, Y. Tezuka, Macromolecules, 34, 6229 (2001) [PDF]
  
• Novel Synthesis of Single and Double Cyclic Polystyrenes by Electrostatic Self-Assembly and Covalent fixation with Telechelics Having Cyclic Ammonium Salt Groups
  H. Oike, M. Hamada, S. Eguchi, Y. Danda, Y. Tezuka, Macromolecules, 34, 2776 (2001) [PDF]
  
• Kyklo-Telechelics: Tailored Synthesis of Cyclic Poly(tetrahydrofuran)s Having Two Functional Groups at Opposite Positions
  H. Oike, S. Kobayashi, T. Mouri, Y. Tezuka, Macromolecules, 34, 2742 (2001) [PDF]
  
• Designing Unusual Polymer Topologies by Electrostatic Self-Assembly and Covalent Fixation
  H. Oike, H. Imaizumi, T. Mouri, Y. Yshioka, A. Uchibori and Y. Tezuka,
  J. Am. Chem. Soc., 122, 9592 (2000) [PDF]
  
• Bis(triflate ester)s Having an Additional Functional Group: Initiators for the Preparation of alpha, omega, kentro-Telechelic Poly(THF)s
  H. Oike, S. Kobayashi, Y. Tezuka, E.J. Goethals, Macromolecules, 33, 8898 (2000) [PDF]
  
• Tailored Synthesis of Branched and Network Polymer Structures by Electrostatic Self-Assembly and Covalent Fixation with Telechelic Poly(THF) Having N-Phenyl Pyrrolidinium Salt Groups,
  H. Oike, H. Imamura, H. Imaizumi and Y. Tezuka, Macromolecules, 32, 4819 (1999) [PDF]
  
• Control in Both Backbone and Branch Segment Length of Poly(tetrahydrofuran) Polymacromonomers by Electrostatic Self-Assembly and Covalent Fixation,
  H. Oike, H. Imamura and Y. Tezuka, Macromolecules, 32, 8666 (1999) [PDF]
  
• Synthesis of Poly(tetrahydrofuran) Polymacromonomers Having Mixed Branch Segments through Reshuffling in Electrostatic Self-Assembly and Subsequent Covalent Fixation,
  H. Oike, H. Imamura and Y. Tezuka, Macromolecules, 32, 8816 (1999) [PDF]