Abstract
Polymeric peroxide is an equimolar alternating copolymer formed by the reaction of a monomer with molecular oxygen (O2). Various polyperoxides have been successfully synthesized using different techniques, such as free radical polymerization, condensation polymerization, and insertion polymerization in the solid state. A wide variety of physical and chemical characteristics are displayed by these polyperoxides, making them attractive candidates for various applications. Due to their high exothermal degrading behavior and autocombustibility, polyperoxides are a viable alternative to fuels derived from petroleum. Additionally, polyperoxides have a wide range of applications, such as free radical initiators, curatives, biocompatible drug carriers, coating materials, dismantlable adhesives, and molding precursors. In this focused review, we report on recent efforts in developing vinyl homo- and copolyperoxides, their physicochemical behaviors, and various applications. Finally, the existing opportunities, possible challenges, and some viewpoints on future directions in vinyl polyperoxide research are highlighted.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Buy this article
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Brodie BC. Ueber die bildung der hyperoxyde organischer säureradicale. Justus Liebigs Ann Chem. 1858;108:79–83. https://doi.org/10.1002/jlac.18581080117
Staudinger H. Erfahrungen über einige explosionen. Angew Chem. 1922;35:657–9. https://doi.org/10.1002/ange.19220359302
Samanta P, Mete S, Pal S, De P. Polymeric peroxides: synthesis, characterization, degradation and applications. J Macromol Sci Part A. 2022;59:711–30.
Kishore K, Mukundan T. Poly(styrene peroxide): an auto-combustible polymer fuel. Nature. 1986;324:130–1.
Sato E, Tamura H, Matsumoto A. Cohesive force change induced by polyperoxide degradation for application to dismantlable adhesion. ACS Appl Mater Interfaces. 2010;2:2594–601.
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.
Subramanian K, Kishore K. Application of polystyrene peroxide as a curative in coating and molding compositions. Eur Polym J. 1997;33:1365–7.
Fujioka T, Taketani S, Nagasaki T, Matsumoto A. Self-assembly and cellular uptake of degradable and water-soluble polyperoxides. Bioconjugate Chem. 2009;20:1879–87.
Murthy KS, Kishore K, Mohan VK. Vinyl monomer based polyperoxides as potential initiators for radical polymerization: an exploratory investigation with poly(α-methylstyrene peroxide). Macromolecules. 1994;27:7109–14.
Nanda AK, Kishore K. Autocatalytic oxidative polymerization of indene by cobalt porphyrin complex and kinetic investigation of the polymerization of styrene. Macromolecules. 2001;34:1600–5.
Pal S, Ghorai PK, De P. Oxidative polymerization of para-substituted styrene derivatives: synthesis, characterization and kinetics study. Polymer. 2012;53:3687–94.
Pal S, Ghorai PK, De P. Kinetic and thermochemical study of the oxidative polymerizations of α-substituted styrenes. Polym Bull. 2012;69:149–61.
De P, Sathyanarayana DN. Para-substituted poly(styrene peroxide)s: synthesis, characterization, thermal reactivities and chain dynamics studies in solution. Macromol Chem Phys. 2002;203:420–6.
De P, Sathyanarayana DN, Sadasivamurthy P. Sridhar S. Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy. Polymer. 2001;42:8587–93.
De P. Comparative study of the chain dynamics of polymers containing peroxy linkages in the backbone. Polym Prepr. 2005;46:852–3.
Pal S, Dhawan A, De P. Ortho- and meta-substituted polystyrene polyperoxides: synthesis, characterization and thermal decomposition studies. Polym Int. 2014;63:746–51.
Mete S, Choudhury N, De P. Degradable alternating polyperoxides from poly(ethylene glycol) substituted styrenic monomers with water solubility and thermoresponsiveness. J Polym Sci Part A Polym Chem. 2018;56:2030–8.
Pal S, De P. Poly(9-vinyl anthracene peroxide): synthesis, characterization, degradation and application as macroinitiator for the polymerization of methyl methacrylate. Polymer. 2013;54:2652–7.
Mete S, Mukherjee P, Maiti B, Pal S, Ghorai PK, De P. Degradable crystalline polyperoxides from fatty acid containing styrenic monomers. Macromolecules. 2018;51:8912–21.
De P, Sathyanarayana DN. Synthesis of poly(1,3-diisopropenylbenzene peroxide). Indian J Chem. 2001;40A:1009–11.
Razuvaev GA, Boguslavskaya LS, Barabashina RA. Synthesis and properties of polymeric peroxides of acrylic acid phenyl esters. Zh Organicheskoi Khimii. 1972;8:1601–8.
De P, Sathyanarayana DN, Sadasivamurthy P. Sridhar S. Synthesis, spectral characterization and thermochemical studies on poly(phenyl methacrylate peroxide). J Appl Polym Sci. 2003;88:2364–8.
Pal S, De P. Water soluble polyperoxides from 2-(2-methoxyethoxy)ethyl methacrylate: influence of molecular oxygen on thermoresponsive properties and thermal degradation. Chem Commun. 2012;48:4229–31.
Pal S, Das A, Maiti S, De P. Synthesis and characterization of a biodegradable polymer prepared via radical copolymerization of 2-(acetoacetoxy)ethyl methacrylate and molecular oxygen. Polym Chem. 2012;3:182–9.
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.
Mete S, Mukherjee P, Goswami KG, Ghorai PK, De P. Polyperoxides from cyclic monomers: synthesis, characterization and high pressure kinetics study. ACS Appl Polym Mater. 2020;2:4109–17.
Khan EH, Pal S, De P. N-Hydroxyphthalimide-mediated oxidation of styrene by molecular oxygen. Macromol Chem Phys. 2013;214:2181–8.
Mayo FR, Miller AA, Russell GA. The oxidation of unsaturated compounds. IX. The effects of structure on the rates and products of oxidation of unsaturated compounds. J Am Chem Soc. 1958;80:2500–7.
Jayanthi S, Kishore K. Oxidative copolymerization: microstructure analysis of the terpolymer of styrene, methyl methacrylate, and oxygen. Macromolecules. 1993;26:1985–9.
De P, Sathyanarayana DN. Polymerization of vinyl acetate with styrene and α-methylstyrene under high oxygen pressure. Indian J Chem. 2001;40A:1282–7.
De P, Sathyanarayana DN. Reactivity ratios for the terpolymerization of methyl methacrylate, vinyl acetate and molecular oxygen. J Polym Sci Part A Polym Chem. 2002;40:564–72.
De P, Sathyanarayana DN. High-pressure kinetics of oxidative copolymerization of styrene with α-methylstyrene. Macromol Chem Phys. 2002;203:2218–24.
Pal S, Vaish A, De P. The effect of different catalysts on the monomer reactivity ratios in oxidative copolymerization of styrene and α-methylstyrene. Polym Int. 2015;64:541–6.
De P, Sathyanarayana DN. Synthesis and characterization of copolyperoxides of indene with styrene, α-methylstyrene and α-phenylstyrene. J Polym Sci Part B Polym Phys. 2002;40:2004–17.
De P, Sathyanarayana DN, Sadasivamurthy P, Sridhar S. Reactivity ratios for the oxidative copolymerizations of indene with methyl methacrylate and methacrylonitrile. Eur Polym J. 2002;38:847–55.
De P, Sathyanarayana DN. Determination of the reactivity ratios for the oxidative copolymerizations of indene with methyl, ethyl and butyl acrylates. Macromol Chem Phys. 2002;203:573–9.
De P, Sathyanarayana DN. Oxidative copolymerization of indene with p-tert-butylstyrene: synthesis, characterization, thermal analysis and reactivity ratios. J Polym Sci Part A Polym Chem. 2002;40:9–18.
De P, Sathyanarayana DN. Free-radical oxidative copolymerization of indene with vinyl acetate and isopropenyl acetate: synthesis and characterization. J Appl Polym Sci. 2002;86:639–46.
Mete S, Goswami KG, De P. Composition dependent crystallization behaviour of copolyperoxides from methyl methacrylate and 4-vinylbenzyl stearate. J Polym Sci. 2020;58:766–78.
Subramanian K. Formation, degradation, and applications of polyperoxides. J Macromol Sci Part C Polym Rev. 2003;43:323–83.
Nanda AK, Ganesh K, Kishore K, Surianarayan M. End-group analysis of vinyl polyperoxides by MALDI-TOF-MS, FT-IR technique and thermochemical calculations. Polymer. 2000;41:9063–72.
Cais RE, Bovey FA. Carbon-13 nuclear magnetic resonance study of the microstructure and molecular dynamics of poly(styrene peroxide). Macromolecules. 1977;10:169–78.
Sato E, Matsumoto A. Facile synthesis of functional polyperoxides by radical alternating copolymerization of 1,3-dienes with oxygen. Chem Rec. 2009;9:247–57.
Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29:1702–6.
De P, Chattopadhyay S, Giridhar M, Sathyanarayana DN. Kinetics of thermal degradation of vinyl polyperoxides in solution. Polym Degrad Stab. 2002;76:161–70.
Sivalingam G, De P, Karthik R, Giridhar M. Thermal degradation kinetics of vinyl polyperoxide copolymers. Polym Degrad Stab. 2004;84:173–9.
De P, Chattopadhyay S, Giridhar M, Sathyanarayana DN. Thermal degradation studies of para-substituted poly(styrene peroxide)s. Polym. Degrad Stab. 2002;76:511–4.
De P, Chattopadhyay S, Giridhar M, Sathyanarayana DN. Thermal degradation kinetics of para-substituted poly(styrene peroxide)s in solution. J Appl Polym Sci. 2002;86:957–61.
Jose NR-L, David JL, Josefa H-R, Alexander NPH, Francisco G-C, Roger NFT. Mechanism of reaction of hydrogen peroxide with horseradish peroxidase: identification of intermediates in the catalytic cycle. J Am Chem Soc. 2001;123:11838–47.
Pal S, Das A, Maiti S, De P. Biodegradation and in vitro biocompatibility of polyperoxides: alternating copolymers of vinyl monomers and molecular oxygen. J Biomat Sci Polym Ed. 2012;23:2105–17.
Silant’ev MA, Perepelitsina EO, Grachev VP, Kurochkin SA. Irregular polystyrene peroxides – a promising macroinitiators synthesized by radical polymerization under oxygen inflow. Eur Polym J. 2017;89:67–77.
Sato E, Hagihara T, Matsumoto A. Facile synthesis of main-chain degradable block copolymers for performance enhanced dismantlable adhesion. ACS Appl Mater Interfaces. 2012;4:2057–64.
Mukundan T, Annakutty KS, Kishore K. A novel solid fuel system based on an auto-pyrolysable polymer. Fuel. 1993;72:688–9.
Sato E, Omori C, Yuri M, Koda Y, Horibe H. Thermal latent reductants for controlled degradation of polyperoxides and their application to high performance dismantlable adhesives. ACS Appl Polym Mater. 2019;1:2140–8.
Acknowledgements
The authors are grateful to Ms. Pampa Chawdhury for helpful discussions.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interests
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Samanta, P., Mete, S., Pal, S. et al. Synthesis, characterization, degradation and applications of vinyl polyperoxides. Polym J 56, 283–296 (2024). https://doi.org/10.1038/s41428-023-00860-y
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41428-023-00860-y