Skip to main content
SpringerLink
Log in

Visible light induced synthesis of PMMA microspheres

  • Original Contribution
  • Published:
Colloid and Polymer Science Aims and scope Submit manuscript

Abstract

Poly(methyl methacrylate) microspheres with narrow particle size distribution were synthesized successfully under visible light (LED@420 nm) in this study, and no RAFT agent was involved. A novel acylphosphine oxide, (2,4-dimethylphenyl) phenylphosphine oxide (2,4-DMTPO), was used as the photoinitiator. Uniform microspheres with the weight-average diameter (Dw) of 1.03 μm and polydispersity index (PDI) of 1.06 were obtained upon irradiation for 30 min, when the ratio of methyl methacrylate (MMA) to solvent was 1:10, the amount of polyvinylpyrrolidone (PVP) and 2,4-DMTPO was 30 wt% and 2 wt% of MMA, respectively. However, no microspheres could be detected instead of large blocks when (2,4,6-trimethylbenzoyl) diphenylphosphine oxide (TPO) was the photoinitiator under the same condition. It could be due to the higher light absorption ability and quantum yield of 2,4-DMTPO at 420 nm than TPO. A possible formation mechanism of PMMA microspheres was proposed and the effects of photoinitiator, MMA, irradiation time, and PVP were discussed. Results shown that regular microspheres were formed when the irradiation time exceeded 30 min, and the amount of PVP was in the range of 25 to 40 wt% of MMA. Lowering the amount of photoinitiator to 0.5 wt% resulted in ca. 66% and 4% decrease of Dw and PDI, respectively. This study may provide a rapid and energy saving way of synthesizing monodispersed PMMA microsphere, which would be benefit for the fields of coating, template, and so on.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Scheme1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Scheme 2
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Peng B, van der Wee E, Imhof A, van Blaaderen A (2012) Synthesis of monodisperse, highly cross-linked, fluorescent PMMA particles by dispersion polymerization. Langmuir 28:6776–6785. https://doi.org/10.1021/la301288r

    Article  CAS  PubMed  Google Scholar 

  2. Kawaguchi S, Ito K (2005) Dispersion polymerization. In :Okubo M (ed) Polymer Particles: -/-. Berlin, Heidelberg, pp299–328

  3. Tan J, Zhao G, Lu Y, Zeng Z, Winnik MA (2014) Synthesis of PMMA microparticles with a narrow size distribution by photoinitiated RAFT dispersion polymerization with a macromonomer as the stabilizer. Macromolecules 47:6856–6866. https://doi.org/10.1021/ma501432s

    Article  CAS  Google Scholar 

  4. Cho YS, Shin CH, Han S (2016) Dispersion polymerization of polystyrene particles using alcohol as reaction medium. Nanoscale Res Lett 11:46. https://doi.org/10.1186/s11671-016-1261-8

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Huo F, Wang X, Zhang Y, Zhang X, Xu J, Zhang W (2013) RAFT dispersion polymerization of styrene in water/alcohol: the solvent effect on polymer particle growth during polymer chain propagation. Macromol Chem Phys 214:902–911. https://doi.org/10.1002/macp.201200640

    Article  CAS  Google Scholar 

  6. Ma Z, Lacroix-Desmazes P (2004) Dispersion polymerization of 2-hydroxyethyl methacrylate stabilized by a hydrophilic/CO2-philic poly(ethylene oxide)-b-poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) (PEO-b-PFDA) diblock copolymer in supercritical carbon dioxide. Polymer 45:6789–6797. https://doi.org/10.1016/j.polymer.2004.07.065

    Article  CAS  Google Scholar 

  7. McAllister TD, Farrand LD, Howdle SM (2016) Improved particle size control for the dispersion polymerization of methyl methacrylate in supercritical carbon dioxide. Macromol Chem Phys 217:2294–2301. https://doi.org/10.1002/macp.201600131

    Article  CAS  Google Scholar 

  8. Woods HM, Nouvel C, Licence P, Irvine DJ, Howdle SM (2005) Dispersion polymerization of methyl methacrylate in supercritical carbon dioxide: an investigation into stabilizer anchor group. Macromolecules 38:3271–3282. https://doi.org/10.1021/ma048406+

    Article  CAS  Google Scholar 

  9. Ki B, Yu YC, Jeon HJ, Yu W-R, Ryu HW, Youk JH (2012) Dispersion polymerization of styrene using poly(4-vinylpyridine) macro-RAFT agent under UV radiation. Fibers Polym 13:135–138. https://doi.org/10.1007/s12221-012-0135-7

    Article  CAS  Google Scholar 

  10. Tan J, Wu B, Yang J, Zhu Y, Zeng Z (2010) Photoinitiated dispersion polymerization using polyurethane based macrophotoinitiator as stabilizer and photoinitiator. Polymer 51:3394–3401. https://doi.org/10.1016/j.polymer.2010.05.052

    Article  CAS  Google Scholar 

  11. Shen S, Sudol ED, El-Aasser MS (1993) Control of particle size in dispersion polymerization of methyl methacrylate. J Polym Sci Part A: Polym Chem 31:1393–1402. https://doi.org/10.1002/pola.1993.080310606

  12. Ye Q, Zhang Z, Ge X, Ni Y, Wang M (2002) Formation of monodisperse poly(methyl methacrylate) particles by radiation-induced dispersion polymerization. II. Particle size and size distribution. Colloid Polym Sci 280:1091–1096. https://doi.org/10.1007/s00396-002-0652-9

    Article  CAS  Google Scholar 

  13. Dai Q, Wu D, Zhang Z, Ye Q (2003) Preparation of monodisperse poly(methyl methacrylate) particles by radiation-induced dispersion polymerization using vinyl terminus polysiloxane macromonomer as a polymerizable stabilizer. Polymer 44:73–77. https://doi.org/10.1016/S0032-3861(02)00728-0

  14. Pachfule P, Acharjya A, Roeser J, Sivasankaran RP, Ye MY, Bruckner A, Schmidt J, Thomas A (2019) Donor-acceptor covalent organic frameworks for visible light induced free radical polymerization. Chem Sci 10:8316–8322. https://doi.org/10.1039/c9sc02601k

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  15. Chen J, Zeng Z, Yang J, Chen Y (2008) Photoinitiated dispersion polymerization of methyl methacrylate: a quick approach to prepare polymer microspheres with narrow size distribution. J. Polym. Sci. Part A: Polym Chem 46:1329–1338. https://doi.org/10.1002/pola.22473

    Article  CAS  Google Scholar 

  16. Tan J, Rao X, Wu X, Deng H, Yang J, Zeng Z (2012) Photoinitiated RAFT dispersion polymerization: a straightforward approach toward highly monodisperse functional microspheres. Macromolecules 45:8790–8795. https://doi.org/10.1021/ma301799r

    Article  CAS  Google Scholar 

  17. Tan J, Rao X, Yang J, Zeng Z (2015) Monodisperse highly cross-linked “living” microspheres prepared via photoinitiated RAFT dispersion polymerization. RSC Adv 5:18922–18931. https://doi.org/10.1039/c4ra15224g

    Article  CAS  Google Scholar 

  18. Tan J, Zhao G, Zeng Z, Winnik MA (2015) PMMA microspheres with embedded lanthanide nanoparticles by photoinitiated dispersion polymerization with a carboxy-functional macro-RAFT agent. Macromolecules 48:3629–3640. https://doi.org/10.1021/acs.macromol.5b00688

    Article  CAS  Google Scholar 

  19. Xie C, Wang Z, Liu Y, Song L, Liu L, Wang Z, Yu Q (2019) A novel acyl phosphine compound as difunctional photoinitiator for free radical polymerization. Prog Org Coat 135:34–40. https://doi.org/10.1016/j.porgcoat.2019.05.021

    Article  CAS  Google Scholar 

  20. Mahmod R, Yahya MZ, Abdullah N (2017) Photoinitiated dispersion polymerization of crosslinked polymer in polar solvents: effect of reaction parameter on morphology, size and size distribution and yield. Indian J Sci Technol 10. https://doi.org/10.17485/ijst/2017/v10i2/110372

  21. Xie C, Leng K, Sheng J, Wang X, Li Q, Song L, Liu L, Sun H, Huang X, Wang Z, Yu Q (2020) Preparation of poly(methyl methacrylate) microspheres via photopolymerization initiated by LED light source. Colloid Polym Sci 298:1285–1291. https://doi.org/10.1007/s00396-020-04694-5

    Article  CAS  Google Scholar 

  22. Gao Y, Zhang J, Liang J, Yuan D, Zhao W (2022) Research progress of poly(methyl methacrylate) microspheres: Preparation, functionalization and application. Eur Poly J 175:111379. https://doi.org/10.1016/j.eurpolymj.2022.111379

  23. Duan H, Leng K, Xu X, Li Q, Liu D, Han Y, Gao J, Yu Q, Wang Z (2021) Monoacylphosphine oxides with substituents in the phosphonyl moiety as Norrish I photoinitiators: Synthesis, photoinitiation properties and mechanism. J Photochem Photobiol A 421:113517. https://doi.org/10.1016/j.jphotochem.2021.113517

  24. Paine AJ, Luymes W, McNulty J (1990) Dispersion polymerization of styrene in polar solvents. 6. Influence of reaction parameters on particle size and molecular weight in poly(N-vinylpyrrolidone)-stabilized reactions. Macromolecules 23:3104–3109. https://doi.org/10.1021/ma00214a012

    Article  CAS  Google Scholar 

Download references

Funding

This work was supported by the Natural Science Foundation of Shandong Province (ZR2020LFG002, ZR2020QB023), the Foundation of 2019 Science and Technology Projects of Qingdao West Coast New District [grant number: 2019–18], and the Research Foundation of Qingdao Fusilin Chemical Science &Technology Co., Ltd. (FSL-RF 2019).

Author information

Authors and Affiliations

  1. College of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao, China

    Zhen Wang, Kangwei Leng, Jiuhong Liu, Yueqiu Li, Shucheng Liu, Zhongwei Wang, Qing Yu & Yuxi Han

  2. Qingdao Technical College, Qingdao, China

    Yan Li

Authors
  1. Zhen Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kangwei Leng
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jiuhong Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yueqiu Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shucheng Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Yan Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhongwei Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Qing Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Yuxi Han
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

This work was performed by Zhen Wang and Kangwei Leng under the guidance of Qing Yu. Data collection and analysis were performed by Jiuhong Liu, Yueqiu Li, and Shucheng Liu. Zhen Wang prepared the original manuscript. The manuscript was revised by Yan Li, Qing Yu, Zhongwei Wang, and Yuxi Han.

Corresponding authors

Correspondence to Qing Yu or Yuxi Han.

Ethics declarations

Conflict of interest

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.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wang, Z., Leng, K., Liu, J. et al. Visible light induced synthesis of PMMA microspheres. Colloid Polym Sci 301, 655–663 (2023). https://doi.org/10.1007/s00396-023-05102-4

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00396-023-05102-4

Keywords

Search

Navigation