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Synthesis of sub-100 nm PMMA nanoparticles initiated by ammonium persulfate/ascorbic acid in acetone-water mixture

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Abstract

The polymer nanoparticles with size less than 100 nm can be prepared by surfactant-free emulsion polymerization (SFEP) with co-solvent, but it needs to be conducted in high temperature at over the azeotropic point of the solution. In the present study, the redox initiator of ammonium persulfate/ascorbic acid (APS/ASA) was applied to reduce the reaction temperature of SFEP with acetone as co-solvent. The effects of temperature, acetone content, monomer concentration, and initiator on the particle size of poly(methyl methacrylate) (PMMA) were investigated to control average diameter of PMMA nanoparticles (PNs) efficiently. The results showed that the PMMA nanoparticles with 45 nm in diameter and uniform size (PDI < 0.05) can be synthesized conveniently through controlling the ratio of APS/ASA.

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References

  1. Wang L, Gao J, An Z, Zhao X, Yao H, Zhang M (2018) Polymer microsphere for water-soluble drug delivery via carbon dot-stabilizing W/O emulsion. J Mater Sci 54:5160–5175

    Google Scholar 

  2. Li X, Wei Y, Lv P, Wu Y, Ogino K, Ma G (2019) Preparation of ropivacaine loaded PLGA microspheres as controlled-release system with narrow size distribution and high loading efficiency. Colloid Surf A 562:237–246

    CAS  Google Scholar 

  3. Huang J, Tian C, Wang J, Liu J, Li Y, Liu Y (2018) Fabrication of selective electroless copper plating on PET sheet: effect of PET surface structure on resolution and adhesion of copper coating. Appl Surf Sci 458:734–742

    CAS  Google Scholar 

  4. Wang X, Yu K, An R, Han L, Zhang Y, Shi L (2019) Self-assembling GO/modified HEC hybrid stabilized pickering emulsions and template polymerization for biomedical hydrogels. Carbohydr Polym 207:694–703

    CAS  PubMed  Google Scholar 

  5. Wang Q, Li Q, Yasir Akram M, Ali S, Nie J, Zhu X (2018) Decomposable PVA-based super-hydrophobic 3D porous material for effective water/oil separation. Langmuir 51:15700–15707

    Google Scholar 

  6. Guo Z, Gu H, Chen Q, He Z, Xu W, Zhang J (2019) Macroporous monoliths with pH-induced switchable wettability for recyclable oil separation and recovery. J Colloid Interface Sci 534:183–194

    CAS  PubMed  Google Scholar 

  7. Cabral H, Matsumoto Y, Mizuno K, Chen Q, Murakami M, Kimura M (2011) Accumulation of sub-100 nm polymeric micelles in poorly permeable tumours depends on size. Nat Nanotechnol 6:815–823

    CAS  PubMed  Google Scholar 

  8. Zeng Q, Wu D, Zou C, Xu F, Fu R, Li Z (2010) Template-free fabrication of hierarchical porous carbon based on intra-/inter-sphere crosslinking of monodisperse styrene-divinylbenzene copolymer nanospheres. Chem Commun 46:5927–5929

    CAS  Google Scholar 

  9. Nandiyanto ABD, Suhendi A, Ogi T, Iwaki T, Okuyama S (2012) Synthesis of additive-free cationic polystyrene particles with controllable size for hollow template applications. Colloid Surf A 396:96–105

    CAS  Google Scholar 

  10. Yang X, Xue X, Luo Y, Lin TY, Zhang H, Lac D (2017) Sub-100nm, long tumor retention SN-38-loaded photonic micelles for tri-modal cancer therapy. J Control Release 261:297–306

    CAS  PubMed  PubMed Central  Google Scholar 

  11. Wang J, Mao W, Lock LL, Tang J, Sui M, Sun W (2015) The role of micelle size in tumor accumulation, penetration, and treatment. ACS Nano 9:7195–7206

    CAS  PubMed  Google Scholar 

  12. Larpent C, Amigoni GS, De SDA (2003) Synthesis of metal-complexing nanoparticles by post-functionalisation of reactive nanolatexes produced by microemulsion polymerisation. C R Chimie 6:1275–1283

    CAS  Google Scholar 

  13. Antonietti M, Basten R, Lohmann S (1995) Polymerization in microemulsions - a new approach to ultrafine, highly functionalized polymer dispersions. Macromol Chem Phys 196:441–466

    CAS  Google Scholar 

  14. Rao JP, Geckeler KE (2011) Polymer nanoparticles: preparation techniques and size-control parameters. Prog Polym Sci 36:887–913

    CAS  Google Scholar 

  15. Arunbabu D, Jana T (2011) Charged polystyrene nanoparticles: role of ionic comonomers structures. J Colloid Interface Sci 361:534–542

    CAS  PubMed  Google Scholar 

  16. Ishii H, Ishii M, Nagao D, Konno M (2014) Advanced synthesis for monodisperse polymer nanoparticles in aqueous media with sub-millimolar surfactants. Polymer 55:2772–2779

    CAS  Google Scholar 

  17. Zhou C, Che R, Zhong L, Xu W, Guo D, Lei J (2011) Effect of particle structure on the peel strength and heat resistance properties of vinyl acetate/acrylate latexes laminating adhesives. J Appl Polym Sci 119:2857–2865

    CAS  Google Scholar 

  18. Aguilar J, Rabelero M, Nuño DSM, Mendizábal E, Martínez RA, López RG (2011) Narrow size-distribution poly(methyl methacrylate) nanoparticles made by semicontinuous heterophase polymerization. J Appl Polym Sci 119:1827–1834

    CAS  Google Scholar 

  19. Jang J, Bae J, Ko S (2005) Synthesis and curing of poly(glycidyl methacrylate) nanoparticles. J Polym Sci A 43:2258–2265

    CAS  Google Scholar 

  20. Deng J, Chen B, Luo X, Yang W (2009) Synthesis of nano-latex particles of optically active helical substituted polyacetylenes via catalytic microemulsion polymerization in aqueous systems. Macromolecules 42:933–938

    CAS  Google Scholar 

  21. Pu G, Dubay MR, Zhang J, Severtson SJ, Houtman CJ (2012) Polyacrylates with high biomass contents for pressure-sensitive adhesives prepared via mini-emulsion polymerization. Ind Eng Chem Res 51:12145–12149

    CAS  Google Scholar 

  22. Roberge S, Dubé MA (2006) The effect of particle size and composition on the performance of styrene/butyl acrylate miniemulsion-based PSAs. Polymer 47:799–807

    CAS  Google Scholar 

  23. Hazra C, Kundu D, Chatterjee A, Chaudhari A, Mishra S (2014) Poly(methyl methacrylate) (core)–biosurfactant (shell) nanoparticles: size controlled sub-100nm synthesis, characterization, antibacterial activity, cytotoxicity and sustained drug release behavior. Colloid Surf A 449:96–113

    CAS  Google Scholar 

  24. Liu B, Fu Z, Meng W, Chen M, Wu G, Zhang M (2018) New insights on in situ charge neutralization governing particle size distribution in macroemulsion polymerization. Colloid Surf A 540:242–250

    CAS  Google Scholar 

  25. Zhenxing H, Xiaowei Y, Junliang L, Yuping Y, Ling W, Yanwei Z (2011) An investigation of the effect of sodium dodecyl sulfate on quasi-emulsifier-free emulsion polymerization for highly monodisperse polystyrene nanospheres. Eur Polym J 47:24–30

    Google Scholar 

  26. Yeong SCMH, Choi KH, Sang OK, Yoon KK, In JC (2001) Synthesis of exfoliated PMMA/Na-MMT nanocomposites via soap-free emulsion polymerization. Macromolecules 34:8978–8985

    Google Scholar 

  27. Zhang Q, Wang WJ, Lu Y, Li BG, Zhu S (2011) Reversibly coagulatable and redispersible polystyrene latex prepared by emulsion polymerization of styrene containing switchable amidine. Macromolecules 44:6539–6345

    CAS  Google Scholar 

  28. Yamamoto T, Yokoyama T (2015) Effect of counter ionic radius in initiator on particle size in soap-free emulsion polymerization of styrene. Chem Lett 44:824–825

    CAS  Google Scholar 

  29. Ruszkay KSWSJ (1998) Oxidation of aldehydes with oxone ® in aqueous acetone. Tetrahedron 54:401–410

    Google Scholar 

  30. Camli ST, Buyukserin F, Balci O, Budak GG (2010) Size controlled synthesis of sub-100 nm monodisperse poly(methylmethacrylate) nanoparticles using surfactant-free emulsion polymerization. J Colloid Interface Sci 344:528–532

    CAS  PubMed  Google Scholar 

  31. An Z, Tang W, Hawker CJ, Stucky GD (2006) One-step microwave preparation of well-defined and functionalized polymeric nanoparticles. J Am Chem Soc 128:15054–15055

    CAS  PubMed  Google Scholar 

  32. Park JG, Forster JD, Dufresne ER (2010) High-yield synthesis of monodisperse dumbbell-shaped polymer nanoparticles. J Am Chem Soc 132:5960–5961

    CAS  PubMed  Google Scholar 

  33. Kim JW, Suh KD (2008) Monodisperse polymer particles synthesized by seeded polymerization techniques. J Ind Eng Chem 14:1–9

    CAS  Google Scholar 

  34. Okubo M, Yamada A, Shibao S, Nakamae K, Matsumoto T (1981) Studies on suspension and emulsion. XLVI Emulsifier-free emulsion polymerization of styrene in acetone–water. J Appl Polym Sci 26:1675–1679

    CAS  Google Scholar 

  35. Kim G, Lim S, Lee BH, Shim SE, Choe S (2010) Effect of homogeneity of methanol/water/monomer mixture on the mode of polymerization of MMA: soap-free emulsion polymerization versus dispersion polymerization. Polymer 51:1197–1205

    CAS  Google Scholar 

  36. Nunes JS, Asua JM (2013) Synthesis of high solids content low surfactant/polymer ratio nanolatexes. Langmuir 29:3895–3902

    CAS  Google Scholar 

  37. Fowler CI, Jessop PG, Cunningham MF (2012) Aryl amidine and tertiary amine switchable surfactants and their application in the emulsion polymerization of methyl methacrylate. Macromolecules 45:2955–2962

    CAS  Google Scholar 

  38. Singh V, Tripathi DN, Malviya T, Sanghi R (2009) Persulfate/ascorbic acid initiated synthesis of poly(acrylonitrile)-grafted tamarind seed gum: a potential commercial gum. J Appl Polym Sci 111:539–554

    CAS  Google Scholar 

  39. Kohut SN, Pirri R, Asua JM, Leiza JR (2009) Redox initiator systems for emulsion polymerization of acrylates. J Polym Sci A 47:2917–2927

    Google Scholar 

  40. Li Z, Cheng H, Han CC (2012) Mechanism of narrowly dispersed latex formation in a surfactant-free emulsion polymerization of styrene in acetone–water mixture. Macromolecules 45:3231–3239

    CAS  Google Scholar 

  41. Tanrisever T, Okay O, Sönmezoğlu IÇ (1996) Kinetics of emulsifier–free emulsion polymerization of methyl methacrylate. J Appl Polym Sci 61:485–493

    CAS  Google Scholar 

  42. Luna XJL, Guyot A, Bourgeat LE (2002) Synthesis and characterization of silica/poly (methyl methacrylate) nanocomposite latex particles through emulsion polymerization using a cationic azo initiator. J Colloid Interface Sci 250:82–92

    Google Scholar 

  43. Fowler CI, Muchemu CM, Miller RE, Phan L, O’Neill C, Jessop PG (2011) Emulsion polymerization of styrene and methyl methacrylate using cationic switchable surfactants. Macromolecules 44:2501–2509

    CAS  Google Scholar 

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Funding

We gratefully acknowledge the National Key R&D Program of China (no. 2016YFC0204901) and National Natural Science Foundation of China (no. 51803132) for the financial support.

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  1. State Key Laboratory of Polymer Materials Engineering of China (Sichuan University), Polymer Research Institute of Sichuan University, Chengdu, 610065, China

    Xia Li, Yun Huang & Yi Dan

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  1. Xia Li
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  2. Yun Huang
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  3. Yi Dan
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Correspondence to Yun Huang or Yi Dan.

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Li, X., Huang, Y. & Dan, Y. Synthesis of sub-100 nm PMMA nanoparticles initiated by ammonium persulfate/ascorbic acid in acetone-water mixture. Colloid Polym Sci 298, 225–232 (2020). https://doi.org/10.1007/s00396-020-04600-z

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  • DOI: https://doi.org/10.1007/s00396-020-04600-z

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