Skip to main content
Log in

Photoinduced atom transfer radical polymerization of methyl methacrylate with conducting polymer nanostructures as photocatalyst

  • Original Research
  • Published:
Iranian Polymer Journal Aims and scope Submit manuscript

Abstract

Light-mediated control/living radical polymerization (CLRP) provides a convenient method to synthesize polymers with controlled molecular weight and narrow molecular weight distribution. However, high-energy wavelengths (such as UV light) and blue light are needed to initiate the polymerization, leading to unwanted side reactions. To overcome these defects, the use of long-wavelength light for light-mediated CLRP is highly desirable. In this work, photoinduced atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was successfully carried out for the synthesis of polyMMA (PMMA) with predictable molecular weights (Mn,GPC) and narrow molecular weight distribution (Mw/Mn). This was achieved using one-dimensional nanopoly(diphenyl butadiyne) (nanoPDPB) as photocatalyst, which activated the dormant alkyl bromides initiator to reversibly produce propagating radicals at ambient temperature. Initiation and termination of polymerization were regulated by periods of light. The polymerization of MMA was accomplished by the radicals generated in the redox reaction of nanoPDPB with EBP. Both 1H nuclear magnetic resonance (1H NMR) spectroscopy and chain-end extension polymerization show highly preserved bromine chain-end functionality in the synthesized PMMA. nanoPDPB displays remarkable photophysical properties in the visible light region. The polymerization of MMA followed the first-order kinetics and the evolution of the Mn,GPC versus monomer conversion and Mw/Mn demonstrated the well-controlled polymerization process. The living character of heterogeneous photomediated ATRP with nanoPDPB as photocatalyst was successfully confirmed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Scheme 1

Similar content being viewed by others

References

  1. Liu B, Yang D, Chen H, Xu H, Wang W, Bai L (2017) Synthesis of novel polymer brushes of poly(acrylonitrile-g-N,N′-dimethylaminoethyl methacrylate) by nitrile modification. Iran Polym J 26:355–364

    Article  CAS  Google Scholar 

  2. Bai L, Zhang L, Pan J, Zhu J, Cheng Z, Zhu X (2013) Developing a synthetic approach with thermoregulated phase-transfer catalysis: facile access to metal-mediated living radical polymerization of methyl methacrylate in aqueous/organic biphasic system. Macromolecules 46:2060–2066

    Article  CAS  Google Scholar 

  3. Liu B, Yang D, Man H, Liu Y, Chen H, Xu H, Wang W, Bai L (2018) A green pickering emulsion stabilized by cellulose nanocrystals via RAFT polymerization. Cellulose 25:77–85

    Article  CAS  Google Scholar 

  4. Braunecker WA, Matyjaszewski K (2007) Controlled/living radical polymerization: features, developments, and perspectives. Prog Polym Sci 32:93–146

    Article  CAS  Google Scholar 

  5. Wang JS, Matyjaszewski K (1995) Controlled/“living” radical polymerization: atom transfer radical polymerization in the presence of transition-metal complexes. J Am ChemSoc 117:5614–5615

    Article  CAS  Google Scholar 

  6. Kato M, Kamigaito M, Sawamoto M, Higashimura T (1995) Polymerization of methyl methacrylate with the carbon tetrachloride/dichlorotris-(triphenylphosphine) ruthenium (II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possibility of living radical polymerization. Macromolecules 28:1721–1723

    Article  CAS  Google Scholar 

  7. Ma A, Zhang J, Wang N, Bai L, Chen H, Wang W, Yang H, Yang L, Niu Y, Wei D (2018) Surface-initiated metal-free photoinduced ATRP of 4-vinylpyridine from SiO2 via visible light photocatalysis for self-healing hydrogels. Ind Eng Chem Res 57:17417–17429

    Article  CAS  Google Scholar 

  8. Chen M, Fan D, Liu S, Rao Z, Dong Y, Wang W, Chen H, Bai L, Cheng Z (2018) Fabrication of self-healing hydrogels with surface functionalized microcapsules from stellate mesoporous silica. Polym Chem. https://doi.org/10.1039/C8PY01402G

    Article  PubMed  PubMed Central  Google Scholar 

  9. Chen H, Liang Y, Wang M, Lv P, XuanY (2009) Reverse ATRP of ethyl acrylate with ionic liquids as reaction medium. Chem Eng J 147:297–301

    Article  CAS  Google Scholar 

  10. Zong G, Chen H, Qu R, Wang C, Ji N (2011) Synthesis of polyacrylonitrile-grafted cross-linked N-chlorosulfonamidated polystyrene via surface-initiated ARGET ATRP, and use of the resin in mercury removal after modification. J Hazard Mater 186:614–621

    Article  CAS  PubMed  Google Scholar 

  11. Wang G, Wu H (2011) Microwave-assisted controlled copolymerization of styrene and acrylonitrile catalyzed by FeCl3/isophthalic acid. Polym Bull 67:1809–1821

    Article  CAS  Google Scholar 

  12. Wang Z, Wang Z, Pan X, Fu L, Lathwal S, Olszewski M, Yan J, Enciso AE, Wang Z, Xia H, Matyjaszewski K (2018) Ultrasonication-induced aqueous atom transfer radical polymerization. ACS Macro Lett 7:275–280

    Article  CAS  Google Scholar 

  13. Theriot JC, Lim C-H, Yang H, Ryan MD, Musgrave CB, Miyake GM (2016) Organocatalyzed atom transfer radical polymerization driven by visible light. Science 352:1082–1092

    Article  CAS  PubMed  Google Scholar 

  14. Chmielarz P, Fantin M, Park S, Isse AA, Gennaro A, Magenau AJD, Sobkowiak A, Matyjaszewski K (2017) Electrochemically mediated atom transfer radical polymerization (eATRP). Prog Polym Sci 69:47–48

    Article  CAS  Google Scholar 

  15. Huang Y, Zhu Y, Egap E (2018) Semiconductor quantum dots as photocatalysts for controlled light-mediated radical polymerization. ACS Macro Lett 7:184–189

    Article  CAS  Google Scholar 

  16. Kaastrup K, Sikes HD (2015) Using photo-initiated polymerization reactions to detect molecular recognition. Chem Soc Rev 45:532–545

    Article  Google Scholar 

  17. Dadashi-Silab S, Tasdelen MA, Kiskan B, Wang X, Antonietti M, Yagci Y (2014) Photochemically mediated atom transfer radical polymerization using polymeric semiconductor mesoporous graphitic carbon nitride. Macromol Chem Phys 215:675–681

    Article  CAS  Google Scholar 

  18. Wang GX, Lu M, Hou ZH, Yang CA, Liang EX, Liu LC, Wu H, Li XL, Xu YX (2015) Photo-induced atom transfer radical polymerization in ionic liquid. J Polym Res 22:60

    Article  CAS  Google Scholar 

  19. Liu LC, Lu M, Hou ZH, Wang GX, Yang CA, Liang EX, Wu H, Li XL, Xu YX (2015) Photo-induced atom transfer radical polymerization with nanosized α-Fe2O3 as photoinitiator. J Appl Polym Sci 132:42389

    Google Scholar 

  20. Dadashi-Silab S, Tasdelen MA, Asiri MA, Khan SB, Yagci Y (2014) Photoinduced atom transfer radical polymerization using semiconductor nanoparticles. Macromol Rapid Commun 35:454–459

    Article  CAS  PubMed  Google Scholar 

  21. Ni X, Ye J, Dong C (2006) Kinetics studies of methyl methacrylate photopolymerization initiated by titanium dioxide semiconductor nanoparticles. J Photochem Photobiol A 181:19–27

    Article  CAS  Google Scholar 

  22. Wang X, Lu Q, Wang X, Joo J, Dahl M, Liu B, Cao C, Yin Y (2016) Photocatalytic surface-initiated polymerization on TiO2 toward well-defined composite nanostructures. ACS Appl Mater Interfaces 8:538–546

    Article  CAS  PubMed  Google Scholar 

  23. Ghosh S, Kouamé NA, Ramos L, Remita S, Dazzi A, Deniset-Besseau A, Beaunier P, Goubard F, Aubert P-H, Remita H (2015) Conducting polymer nanostructures for photocatalysis under visible light. Nature Mater 14:505–511

    Article  CAS  Google Scholar 

  24. Caputo JA, Frenette LC, Zhao N, Sowers KL, Krauss TD, Weix DJ (2017) General and efficient C–C bond forming photoredox catalysis with semiconductor quantum dots. J Am Chem Soc 139:4250–4253

    Article  CAS  PubMed  Google Scholar 

  25. Dadashi-Silab S, Pan X, Matyjaszewski K (2017) Photoinduced iron-catalyzed atom transfer radical polymerization with ppm levels of iron catalyst under blue light irradiation. Macromolecules 50:7967–7977

    Article  CAS  Google Scholar 

  26. Magenau AJD, Strandwitz NC, Gennaro A, Matyjaszewski K (2011) Electrochemically mediated atom transfer radical polymerization. Science 332:81–84

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

This work was jointly funded by the Jiangxi Provincial Natural Science Foundation of China (no. 20171BAB203023), the Science & Technology Plan Projects of Education Department of Jiangxi Province (no. GJJ181074), and the Research Initiation Funds for the Ph.D. of Nanchang Normal University (no. NSBSJJ2018017).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Mang Lu.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lu, M. Photoinduced atom transfer radical polymerization of methyl methacrylate with conducting polymer nanostructures as photocatalyst. Iran Polym J 28, 167–172 (2019). https://doi.org/10.1007/s13726-019-00687-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13726-019-00687-6

Keywords

Navigation