Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Focus Review
  • Published:

Synthesis of functional polymers by the Pd-mediated polymerization of diazoacetates and polycondensation of bis(diazocarbonyl) compounds

Polymer Journal volume 52, pages 269–277 (2020)Cite this article

Subjects

Abstract

Our recent studies on the polymerization of diazocarbonyl compounds to afford functional polymers are reviewed. In the first part of this article, the Pd-mediated polymerization of diazoacetates is described. Various functionalized diazoacetates with ester substituents were prepared and polymerized with Pd-based initiating systems to yield poly(substituted methylene)s (PSMs) with functional groups on each carbon atom in the main chain. The physical and chemical properties of the resulting functionalized PSMs were examined relative to those of their vinyl polymer counterparts [poly(substituted ethylene)s] possessing the same functional groups on every other carbon atom, and enhanced properties due to the effects of the dense packing of the functional groups in the PSMs were observed in some examples. The second part of this report summarizes our recent results on the polycondensation of bifunctional diazocarbonyl compounds as monomers. Three successful examples, namely, (1) the synthesis of well-defined unsaturated polyesters by the transition metal-catalyzed, single-component polycondensation of bis(diazoacetate)s, (2) the preparation of a new type of aromatic polyamine by the polycondensation of bis(diazoacetate)s with aromatic diamines, and (3) the multicomponent polycondensation of bis(diazocarbonyl) compounds affording an unprecedented acid-degradable polymer, poly(β-keto enol ether), are described.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References and notes

  1. Doyle MP, Mckervey MA, Ye T. Modern catalytic methods for organic synthesis with diazo compounds. New York: John Wiley & Sons; 1998.

    Google Scholar 

  2. Zhang Z, Wang J. Recent studies on the reactions of α-diazocarbonyl compounds. Tetrahedron. 2008;64:6577–605.

    Article  CAS  Google Scholar 

  3. Ihara E. Poly(substituted Methylene) synthesis: construction of C−C main chain from one carbon unit. Adv Polym Sci. 2010;231:191–231.

    Article  CAS  Google Scholar 

  4. Ihara E, Shimomoto H. Polymerization of diazoacetates: new synthetic strategy for C-C main chain polymers. Polymer. 2019;174:234–58.

    Article  CAS  Google Scholar 

  5. Jellema E, Jongerius AL, Reek JNH, de Bruin B. C1 polymerization and related C−C bond forming ‘carbene insertion’ reactions. Chem Soc Rev. 2010;39:1706–23.

    Article  CAS  Google Scholar 

  6. Franssen NMG, Walters AJC, Reek JNH, de Bruin B. Carbene insertion into transition metal–carbon bonds: a new tool for catalytic C–C bond formation. Catal Sci Technol. 2011;1:153–65.

    Article  CAS  Google Scholar 

  7. Cahoon CR, Bielawski CW. Metal-promoted C1 polymerizations. Coord Chem Rev. 2018;374:261–78.

    Article  CAS  Google Scholar 

  8. Ihara E, Takahashi H, Akazawa M, Itoh T, Inoue K. Polymerization of various alkyl diazoacetates initiated with (N-Heterocyclic Carbene)Pd/borate systems. Macromolecules. 2011;44:3287–92.

    Article  CAS  Google Scholar 

  9. Ihara E, Akazawa M, Itoh T, Fujii M, Yamashita K, Inoue K, et al. π‑AllylPdCl-Based initiating systems for polymerization of alkyl diazoacetates: initiation and termination mechanism based on analysis of polymer chain end structures. Macromolecules. 2012;45:6869–77.

    Article  CAS  Google Scholar 

  10. Ihara E, Okada R, Sogai T, Asano T, Kida M, Inoue K, et al. Pd-mediated polymerization of diazoacetates with aromatic ester group: synthesis and photophysical property of poly(1-pyrenylmethoxycarbonylmethylene). J Polym Sci Part A. 2013;51:1020–3.

    Article  CAS  Google Scholar 

  11. Shimomoto H, Itoh E, Itoh T, Ihara E, Hoshikawa N, Hasegawa N. Polymerization of hydroxy-containing diazoacetates: synthesis of hydroxy-containing “Poly(substituted methylene)s” by palladium-mediated polymerization and poly(ester−ether)s by polycondensation through O−H insertion reaction. Macromolecules. 2014;47:4169–77.

    Article  CAS  Google Scholar 

  12. Shimomoto H, Shimizu K, Takeda C, Kikuchi M, Kudo T, Mukai H, et al. Synthesis of polymers with densely-grafted oligo(ethylene glycol)s by Pd-initiated polymerization of oxyethylene-containing diazoacetates. Polym Chem. 2015;6:8124–31.

    Article  CAS  Google Scholar 

  13. Shimomoto H, Asano H, Itoh T, Ihara E. Pd-initiated controlled polymerization of diazoacetates with a bulky substituent: synthesis of well-defined homopolymers and block copolymers with narrow molecular weight distribution from cyclophosphazene-containing diazoacetates. Polym Chem. 2015;6:4709–14.

    Article  CAS  Google Scholar 

  14. Shimomoto H, Oda A, Kanayama M, Sako T, Itoh T, Ihara E, et al. Pd-initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid-containing products. J Polym Sci Part A. 2016;4:1742–51.

    Article  Google Scholar 

  15. Shimomoto H, Kikuchi M, Aoyama J, Sakayoshi D, Itoh T, Ihara E. Cyclopolymerization of Bis(diazocarbonyl) compounds leading to well-defined polymers essentially consisting of cyclic constitutional units. Macromolecules. 2016;49:8459–65.

    Article  CAS  Google Scholar 

  16. Kato F, Chandra A, Tokita M, Asano H, Shimomoto H, Ihara E, et al. Self-assembly of hierarchical structures using cyclotriphosphazene-containing Poly(substituted methylene) block copolymers. ACS Macro Lett. 2018;7:37–41.

    Article  CAS  Google Scholar 

  17. Shimomoto H, Kudo T, Tsunematsu S, Itoh T, Ihara E. Fluorinated poly(substituted methylene)s prepared by pd-initiated polymerization of fluorine-containing alkyl and phenyl diazoacetates: their unique solubility and postpolymerization modification. Macromolecules. 2018;51:328–35.

    Article  CAS  Google Scholar 

  18. Takaya T, Oda T, Shibazaki Y, Hayashi Y, Shimomoto H, Ihara E, et al. Excited-state dynamics of pyrene incorporated into poly(substituted methylene)s: effects of dense packing of pyrenes on excimer formation. Macromolecules. 2018;51:5430–9.

    Article  CAS  Google Scholar 

  19. Imoto M, Nakaya T. Polymerization by carbenoids, carbenes, and nitrenes. J Macromol Sci Polym Rev. 1972;7:1–48.

    Article  CAS  Google Scholar 

  20. Ihara E, Saiki K, Goto Y, Itoh T, Inoue K. Polycondensation of Bis(diazocarbonyl) compounds with aromatic diols and cyclic ethers: synthesis of new type of polyetherketones. Macromolecules. 2010;43:4589–98.

    Article  CAS  Google Scholar 

  21. Ihara E, Hara Y, Itoh T, Inoue K. Three-component polycondensation of bis(diazoketone) with dicarboxylic acids and cyclic ethers: synthesis of new types of poly(ester ether ketone)s. Macromolecules. 2011;44:5955–60.

    Article  CAS  Google Scholar 

  22. Shimomoto H, Hara Y, Itoh T, Ihara E. Synthesis of well-defined unsaturated polyesters by transition-metal-catalyzed polycondensation of Bis(diazoacetate)s. Macromolecules. 2013;46:5483–7.

    Article  CAS  Google Scholar 

  23. Xiao L, Li Y, Liao L, Liu L. Denitrogen alkene polymerization of bisdiazo compounds by copper(II) catalysts. New J Chem. 2013;37:1874–7.

    Article  CAS  Google Scholar 

  24. Shimomoto H, Mukai H, Bekku H, Itoh T, Ihara E. Ru-catalyzed polycondensation of dialkyl 1,4-phenylenebis(diazoacetate) with Dianiline: synthesis of well-defined aromatic polyamines bearing an alkoxycarbonyl group at the adjacent carbon of each nitrogen in the main chain framework. Macromolecules. 2017;50:9233–8.

    Article  CAS  Google Scholar 

  25. Shimomoto H, Mori T, Itoh T, Ihara E. Poly(β-keto enol ether) prepared by three-component polycondensation of Bis(diazoketone), Bis(1,3-diketone), and tetrahydrofuran: mild acid-degradable polymers to afford well-defined low molecular weight components. macromolecules. Macromolecules. 2019;52:5761–68.

    Article  CAS  Google Scholar 

  26. Taylor LD, Cerankowski LD. Preparation of films exhibiting a balanced temperature dependence to permeation by aqueous solutions—a study of lower consolute behavior. J Polym Sci Polym Chem Ed. 1975;13:2551–70.

    Article  CAS  Google Scholar 

  27. Sugihara S, Hashimoto K, Matsumoto Y, Kanaoka S, Aoshima S. Thermosensitive polyalcohols: synthesis via living cationic polymerization of vinyl ethers with a silyloxy group. J Polym Sci Part A. 2003;41:3300–12.

    Article  CAS  Google Scholar 

  28. Weaver JVM, Bannister I, Robinson KL, Bories-Azeau X, Armes SP, Smallridge M, et al. Stimulus-responsive water-soluble polymers based on 2-hydroxyethyl methacrylate. Macromolecules. 2004;37:2395–403.

    Article  CAS  Google Scholar 

  29. Lutz J-F. Polymerization of oligo(Ethylene Glycol) (Meth)acrylates: toward new generations of smart biocompatible materials. J Polym Sci Part A. 2008;46:3459–70.

    Article  CAS  Google Scholar 

  30. Lutz J-F. Thermo-switchable materials prepared using the OEGMA-platform. Adv Mater. 2011;23:2237–43.

    Article  CAS  Google Scholar 

  31. Shimomoto H, Yamada T, Itoh T, Ihara E. Carbon-carbon main chain polymer with accumulated oligo(ethylene glycol)-substituted cyclotriphosphazenes: study on the LCST-type phase separation of organic-inorganic poly(substituted methylene)s. Polym J. 2019. in press.

  32. Unpublished results.

  33. Deng Q-H, Xu H-W, Yuen AW-H, Xu Z-J, Che C-M. Ruthenium-catalyzed one-pot carbenoid N−H insertion reactions and diastereoselective synthesis of prolines. Org Lett. 2008;10:1529–32.

    Article  CAS  Google Scholar 

  34. Kreye O, T Tόth, MAR Meier. Introducing multicomponent reactions to polymer science: passerini reactions of renewable monomers. J Am Chem Soc. 2011;128:1790–2.

    Article  Google Scholar 

  35. Yang B, Zhao Y, Wang S, Zhang Y, Fu C, Wei Y, et al. Synthesis of multifunctional polymers through the Ugi reaction for protein conjugation. Macromolecules. 2014;47:5607–12.

    Article  CAS  Google Scholar 

  36. Shimomoto H, Kawamata J, Murakami H, Yamashita K, Itoh T, Ihara E. Polymerization of alkyl diazoacetates initiated by the amidinate/Pd system: efficient synthesis of high molecular weight poly(alkoxycarbonylmethylene)s with moderate stereoregularity. Polym Chem. 2017;8:4030–7.

    Article  CAS  Google Scholar 

  37. Shimomoto H, Ichihara S, Hayashi H, Itoh T, Ihara E. Polymerization of alkyl diazoacetates initiated by Pd(naphthoquinone)/borate systems: dual role of naphthoquinones as oxidant and anionic ligand for generating active Pd(II) species. Macromolecules. 2019;52:6976–87.

    Article  CAS  Google Scholar 

  38. Chu J-H, Xu X-H, Kang S-M, Liu N, Wu Z-Q. Fast living polymerization and helix-sense-selective polymerization of diazoacetates using air-stable palladium(II) catalysts. J Am Chem Soc. 2018;140:17773–81.

    Article  CAS  Google Scholar 

  39. Zhukhovitskiy AV, Kobylianskii IJ, Thomas AA, Evans AM, Delaney CP, Flanders NC, et al. A dinuclear mechanism implicated in controlled carbene polymerization. J Am Chem Soc. 2019;141:6473–8.

    Article  CAS  Google Scholar 

  40. Hetterscheid DGH, Hendriksen C, Dzik WI, Smits JMM, van Eck ERH, Rowan AE, et al. Rhodium-mediated stereoselective polymerization of “Carbenes”. J Am Chem Soc. 2006;128:9746–52.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

I deeply thank Prof. Eiji Ihara (Ehime University) for his assistance and helpful discussion and all my coworkers and collaborators for sharing their experimental data. This research was partially supported by Grants-in-Aid for Young Scientists (B) (JSPS KAKENHI grant numbers: 26810071 and 16K17916) and a Grant-in-Aid for Scientific Research (C) (JSPS KAKENHI grant number: 19K05586).

Author information

Authors and Affiliations

  1. Department of Materials Science and Biotechnology, Graduate School of Science and Engineering, Ehime University, 3 Bunkyo-cho, Matsuyama, 790-8577, Japan

    Hiroaki Shimomoto

Authors
  1. Hiroaki Shimomoto
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Hiroaki Shimomoto.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shimomoto, H. Synthesis of functional polymers by the Pd-mediated polymerization of diazoacetates and polycondensation of bis(diazocarbonyl) compounds. Polym J 52, 269–277 (2020). https://doi.org/10.1038/s41428-019-0271-7

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-019-0271-7

This article is cited by

Search

Advanced search

Quick links