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Oxidatively degradable polystyrene: general strategy for the introduction of functional groups into the main chains of vinyl polymers

Abstract

Degradable polymers have degradable functional groups in the main chains. To introduce functional groups into the main chains of polystyrene—a typical vinyl polymer whose main chain consists only of carbon—radical copolymerization of styrene with a bifunctional monomer bearing diacylhydrazine as the functional group was carried out in the presence of a chain-transfer agent or excess initiator to avoid gelation. Soluble polystyrene whose main chain was functionalized by diacylhydrazine in an internally connected manner was obtained by controlling the concentration of the chain transfer agent or the initiator. The oxidation of the obtained polystyrene yielded an oligomer via oxidative degradation of the diacylhydrazine moiety in the main chain.

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References

  1. Scott G. Degradable polymers: principle and applications. 2nd ed. Dordrecht: Kluwer; 2002.

  2. Khemani K, Scholz C. Degradable polymers and materials: principles and practice. 2nd ed. Washington: ACS; 2012.

  3. Kurochkin SA, Silant’ev MA, Perepelitsyna EO, Grachev VP. Molecular oxygen as a regulator of primary chain length of branched polymers formed in 3D radical polymerization. Oxidative polymerization of styrene. Polymer. 2013;54:31–42. https://doi.org/10.1016/j.polymer.2012.11.026.

    Article  CAS  Google Scholar 

  4. Pal S, Banoth B, Rahithya G, Dhawan A, De P. Copolyperoxides of 2-(acetoacetoxy)ethyl methacrylate with methyl methacrylate and styrene; synthesis, characterization, thermal analysis, and reactivity ratios. Polymer. 2012;53:2583–90. https://doi.org/10.1016/j.polymer.2012.04.013.

    Article  CAS  Google Scholar 

  5. Singh RP, Desai SM, Sivaram DS, Kishore K. A novel synthesis of poly(styrene peroxide) with controlled peroxy linkages at room temperature. Chem Phys. 2002;203:2163–9.

    CAS  Google Scholar 

  6. Kishore K, Ravindran K. Thermal reactivity of poly(styrene peroxide): a thermodynamic approach. Macromolecules. 1982;15:1638–9. https://doi.org/10.1021/ma00234a038.

    Article  CAS  Google Scholar 

  7. Nukui M, Yoshino K, Ohkatsu Y, Tsuruta T. Asymmetric copolymerization of styrene with oxygen. Makromol Chem. 1979;180:523–6. https://doi.org/10.1002/macp.1979.021800227.

    Article  CAS  Google Scholar 

  8. Robert K, Volker S. Determination of the rate constants of propagation and termination in the copolymerization of styrene, α-methylstyrene, and methyl methacrylate with molecular oxygen. Macromol Chem. 1970;140:1–19.

    Google Scholar 

  9. Sato E, Taketani S, Omori C, Horibe H, Matsumoto A. Regiospecificity of alternating copolymerization of cyclic conjugated dienes and oxygen. Chem Lett. 2019;48:445–8. https://doi.org/10.1246/cl.181047.

    Article  CAS  Google Scholar 

  10. Yan P, Zhao B, Zhang B, Jiang L, Petcher S, Smith JA, et al. Inverse vulcanized polymers with shape memory, enhanced mechanical properties, and vitrimer behavior. Angew Chem Int Ed. 2020;59:13371–8. https://doi.org/10.1002/anie.202004311.

    Article  CAS  Google Scholar 

  11. Blight LB, Currell BR, Nash BJ, Scott RTM, Stillo C. Chemistry of the modification of sulfur by the use of dicyclopentadiene and of styrene. Brit Polym J. 1980;12:5–11. https://doi.org/10.1002/pi.4980120103.

    Article  CAS  Google Scholar 

  12. Albanese KR, Read de Alaniz J, Hawker CJ, Bates CM. From health supplement to versatile monomer: radical ring-opening polymerization and depolymerization of α-lipoic acid. Polymer. 2004;304:127167. https://doi.org/10.1016/j.polymer.2024.127167.

    Article  CAS  Google Scholar 

  13. Watanabe H, Kamigaito M. Direct radical copolymerizations of thioamides to generate vinyl polymers with degradable thioether bonds in the backbones. J Am Chem Soc. 2023;145:10948–53. https://doi.org/10.1021/jacs.3c01796.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  14. Ivanchenko O, Destarac M. 1’-Thiocarbonyldiimidazole radical copolymerization for the preparation of degradable vinyl polymers. ACS Macro Lett. 2024;13(1):47–51. https://doi.org/10.1021/acsmacrolett.3c00676.

    Article  CAS  PubMed  Google Scholar 

  15. Tardy A, Nicolas J, Gigmes D, Lefay C, Guillaneuf Y. Radical ring-opening polymerization: scope, limitations, and application to (bio)degradable materials. Chem Rev. 2017;117:1319–406. https://doi.org/10.1021/acs.chemrev.6b00319.

    Article  CAS  PubMed  Google Scholar 

  16. Pesenti T, Nicolas J. 100th anniversary of macromolecular science viewpoint: degradable polymers from radical ring-opening polymerization: latest advances, new directions, and ongoing challenges. ACS Macro Lett. 2020;9:1812–35. https://doi.org/10.1021/acsmacrolett.0c00676.

    Article  CAS  PubMed  Google Scholar 

  17. Agarwal S. Chemistry, chances and limitations of the radical ring-opening polymerization of cyclic keteneacetals for the synthesis of degradable polyesters. Polym Chem. 2010;1:953–64. https://doi.org/10.1039/C0PY00040J.

    Article  CAS  Google Scholar 

  18. Sanda F, Endo T. Radical ring-opening polymerization. J Polym Sci Part A Polym Chem. 2000;39:265–76.

    Article  Google Scholar 

  19. Endo T, Tanaka T, Yokozawa T, Kihara N, Koizumi T, Tomita I. Recent advance in radical ring-opening polymerization directed toward new functional materials. In: Tsuruta T, Doyama M, Seno M, editors. New functional materials, vol. C. Elsevier; 1993.

  20. Bailey WJ, Chen PY, Chen SC, Chiao WB, Endo T, Gapud B, et al. Free radical ring-opening polymerization and its use to make biodegradable polymers and functionally terminated oligomers. Makromol Chem Macromol Symp. 1986;6:81–100. https://doi.org/10.1002/masy.19860060111.

    Article  CAS  Google Scholar 

  21. Bailey WJ, Chen PY, Chen SC, Chiao WB, Endo T, Gapud B, et al. Free-radical ring-opening polymerization. J Macromol Sci Chem. 1984;A21:1611–39. https://doi.org/10.1080/00222338408082081.

    Article  CAS  Google Scholar 

  22. Mizukami S, Kihara N, Endo T. Novel poly(silyl enol ether)s via radical ring-opening polymerization and their conversion to polyketones. J Am Chem Soc. 1994;116:6453–4. https://doi.org/10.1021/ja00093a063.

    Article  CAS  Google Scholar 

  23. Baudry R, Sherrington DC. Facile synthesis of branched poly(vinyl alcohol)s. Macromolecules. 2006;39:5230–7. https://doi.org/10.1021/ma061221d.

    Article  CAS  Google Scholar 

  24. Cao Y, Kumar R, Tsarevsky NV. Employing heterocyclic hypervalent iodine compounds with I-Cl bonds as initiators and chain transfer agents in the synthesis of branched polymers. Macromol Chem Phys. 2019;220:1800471. https://doi.org/10.1002/macp.201800471.

    Article  CAS  Google Scholar 

  25. Wang Z, Segar S, Tsarevsky NV. Impact of branching unit structure on the cloud point of highly branched polymers with lower critical solution temperature behavior. Eur Polym J. 2019;111:63–8. https://doi.org/10.1016/j.eurpolymj.2018.12.007.

    Article  CAS  Google Scholar 

  26. Vijayaumar CT, Fink JK. Kinetics of crosslinking copolymerization of styrene with ethylene glycol dimethacrylate in the presence of transfer agent and diluent. Polym Commun. 1988;29:276–7.

    Google Scholar 

  27. Tian C, Yu J, Wang H, Liu F. Synthesis and characterization of soluble branched polymer via free radical copolymerization of styrene and divinylbenzene. Polym Prepr. 2007;48:365–6.

    CAS  Google Scholar 

  28. Yong H, Miao Y, Sigen A, Quan D, Ivankovic A, Singh K, et al. Branched polystyrenes from suspension “Strathclyde” polymerization using a vulcanization accelerator as a chain transfer agent. Polym Chem. 2019;10:885–90. https://doi.org/10.1039/C8PY01639A.

    Article  CAS  Google Scholar 

  29. Kurochkin SA, Makhonina LI, Vasil’ev SG, Perepelitsina EO, Zabrodin VA, Bubnova ML, et al. Hydrodynamic characteristics of branched polystyrenes with varying content of a highly branched fraction. Polym Sci Ser A. 2017;59:613–23. https://doi.org/10.1134/s0965545x17050078.

    Article  CAS  Google Scholar 

  30. Kurochkin SA, Silant’ev MA, Perepelitsyna EO, Grachev VP. Synthesis of branched polymers via radical copolymerization under oxygen inflow. Eur Polym J. 2014;57:202–12. https://doi.org/10.1016/j.eurpolymj.2014.05.022.

    Article  CAS  Google Scholar 

  31. Ren Q, Gong F, Liu C, Zhai G, Jiang B, Liu C, et al. Synthesis of branched polystyrene by ATRP exploiting divinylbenzene as branching comonomer. Eur Polym J. 2006;42:2573–80. https://doi.org/10.1016/j.eurpolymj.2006.06.026.

    Article  CAS  Google Scholar 

  32. Sato T, Sato N, Seno M, Hirano T. Initiator-fragment incorporation radical polymerization of divinylbenzene in the presence of glyoxylic oxime ether: formation of soluble hyperbranched polymer. J Polym Sci Part A Polym Chem. 2003;41:3038–47. https://doi.org/10.1002/pola.10824.

    Article  CAS  Google Scholar 

  33. Eckersley ST, Plumtree A, Rudin A. High speed tensile performance and fractography of acrylic latex films. J Appl Polym Sci. 1993;48:1689–700. https://doi.org/10.1002/app.1993.070481001.

    Article  CAS  Google Scholar 

  34. Eckersley ST, Rudin A. The film formation of acrylic latexes: a comprehensive model of film coalescence. J Appl Polym Sci. 1994;53:1139–47. https://doi.org/10.1002/app.1994.070530902.

    Article  CAS  Google Scholar 

  35. Plessis C, Arzamendi G, Agnely M, Leiza JR, Asua JM. Seeded semibatch emulsion polymerization of n-butyl acrylate: effect of the seed properties. J Polym Sci Part A Polym Chem. 2002;40:2878–83. https://doi.org/10.1002/pola.10375.

    Article  CAS  Google Scholar 

  36. Krishnan S, Klein A, El-Asser MS, Sudol ED. Influence of chain transfer agent on the cross-linking of poly (n-butyl methacrylate-co-N-methylol acrylamide) latex particles and films. Macromolecules. 2003;36:3511–8. https://doi.org/10.1021/ma021121h.

    Article  CAS  Google Scholar 

  37. Xue W, Huglin MB, Jones TGJ. Parameters affecting the lower critical solution temperature of linear and crosslinked poly(N-ethylacrylamide) in aqueous media. Macromol Chem Phys. 2003;42:2192–201. https://doi.org/10.1002/macp.200300008.

    Article  CAS  Google Scholar 

  38. Doura M, Aota H, Matsumoto A. Novel amphiphilic network polymers consisting of nonpolar, short primary polymer chains and polar, long crosslink units: influence of characteristic dangling chains on swelling behavior of resulting amphiphilic gels. J Polym Sci Part A Polym Chem. 2004;42:2192–201. https://doi.org/10.1002/pola.20054.

    Article  CAS  Google Scholar 

  39. Baudis S, Steyrer B, Pulka T, Wilhelm H, Weigel G, Bergmeister H, et al. Photopolymerizable elastomers for vascular tissue regeneration. Macromol Symp. 2010;296:121–6. https://doi.org/10.1002/masy.201051018.

    Article  CAS  Google Scholar 

  40. Agirre A, Nase J, Degrandi E, Creton C, Asua JM. Miniemulsion polymerization of 2-ethylhexyl acrylate. Polymer architecture control and adhesion properties. Macromolecules. 2010;43:8924–32. https://doi.org/10.1021/ma100265f.

    Article  CAS  Google Scholar 

  41. Popescu DL, Tsarevsky NV. Synthesis, functionalization and reductive degradation of multibrominated disulfide-containing hyperbranched polymers. Aust J Chem. 2012;65:28–34. https://doi.org/10.1071/ch11376.

    Article  CAS  Google Scholar 

  42. Han H, Kumar R, Tsarevsky NV. Responsible and degradable highly branched polymers with hypervalent iodine(III) groups at the branching points. Macromol Rapid Commun. 2019;40:1900073. https://doi.org/10.1002/marc.201900073.

    Article  CAS  Google Scholar 

  43. Li Y, Armes S. Synthesis and chemical degradation of branched vinyl polymers prepared via ATRP: use of a cleavable disulfide-based branching agent. Macromolecules. 2005;38:8155–62. https://doi.org/10.1021/ma051121s.

    Article  CAS  Google Scholar 

  44. Kihara N, Iino Y, Misawa T. Oxidative degradation of poly(isophthaloylhydrazine-1,2-diyl)s. J Polym Sci Part A Polym Chem. 2008;46:6255–62. https://doi.org/10.1002/pola.22935.

    Article  CAS  Google Scholar 

  45. Kihara N, Ii R, Ogawa A. Synthesis and properties of nylon-0,2 - oxidatively degradable polymer that is stable in air. J Polym Sci Part A Polym Chem. 2007;45:963–7. https://doi.org/10.1002/pola.21824.

    Article  CAS  Google Scholar 

  46. Kihara N, Yanaze K, Yokoyama S, Kaneko M. Dissolution of a transparent cross-linked polymer monolith in water by oxidative de-crosslinking. Polym J. 2019;51:1007–13. https://doi.org/10.1038/s41428-019-0220-5.

    Article  CAS  Google Scholar 

  47. Immergut EH, Brandrup J, Grulke EA. Polymer Handbook. 4th ed. New York: Wiley; 2003.

  48. Flory PJ. Principle of polymer chemistry. New York: Wiley; 1953.

  49. Oguri T, Kawahara A, Kihara N. Epoxy resin bearing diacylhydrazine moiety as a degradable adhesive for traceless oxidative removal. Polymer. 2016;99:83–9. https://doi.org/10.1016/j.polymer.2016.06.066.

    Article  CAS  Google Scholar 

  50. Nagashima K, Kihara N, Iino Y. Oxidative coupling polymerization of bishydrazide for the synthesis of poly(diacylhydrazine): oxidative preparation of oxidatively degradable polymer. J Polym Sci Part A Polym Chem. 2012;50:4230–8. https://doi.org/10.1002/pola.26225.

    Article  CAS  Google Scholar 

  51. Yanaze K, Kihara N. Superabsorbent polymer solubilized instantly by decrosslinking with sodium hypochlorite. Polym J. 2021;53:1153–5. https://doi.org/10.1038/s41428-021-00499-7.

    Article  CAS  Google Scholar 

  52. Podlech J. Trimethylsilyldiazomethane (TMS-CHN2) and lithiated trimethylsilyldiazomethane - versatile substitutes for diazomethane. J Pr Chem. 1998;340:679–82. https://doi.org/10.1002/prac.19983400714.

    Article  CAS  Google Scholar 

  53. Shioiri T, Aoyama T. Trimethylsilyldiazomethane: a versatile synthon for organic synthesis. In Dondoni A, editor. Advances in the use of synthons in organic chemistry. London: JAI; 1993. p. 51-101. https://doi.org/10.1016/B978-1-4831-0094-4.50007-4.

  54. Presser A, Hüfner A. Trimethylsilyldiazomethane—a mild and efficient reagent for the methylation of carboxylic acids and alcohols in natural products. Monatsh Chem. 2004;135:1015–22. https://doi.org/10.1007/s00706-004-0188-4.

    Article  CAS  Google Scholar 

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Acknowledgements

This work was supported by JSPS KAKENHI Grant Number 20H04372.

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Correspondence to Nobuhiro Kihara.

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Kajiwara, K., Kihara, N. Oxidatively degradable polystyrene: general strategy for the introduction of functional groups into the main chains of vinyl polymers. Polym J (2026). https://doi.org/10.1038/s41428-026-01143-y

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