Abstract
To elucidate the correlation between the oil-water interfacial property and emulsifying performance of polymeric micelles, the polymeric particulate emulsifiers based on the self-assembled micelles of amphiphilic poly(2-(dimethylamino)ethyl methacrylate-co-styrene-co-7-(4-vinylbenzyloxyl)-4-methylcoumarin) (PDSV) had been successfully prepared. The micelle size, morphology, self-assembly behavior, and photo-cross-linking were investigated with a combination of dynamic light scattering (DLS), transmission electron microscopy (TEM), and ultraviolet-visible spectrophotometer. Further systematic investigation on PDSV19 micelles was focused on both emulsifying performance and oil-water interfacial behavior. The larger degree of photo-cross-linking, the poorer emulsifying performance. The DMAEMA unit of PDSV underwent the inversion from protonation to deprotonation with the increasing pH, causing the observed o/w to w/o phase inversion, allowing for direct control over the emulsion stability. Styrene with 1.0 mol% initiator as oil phase and PDSV19 micelles as emulsifiers were employed to prepare solidified polymerized beads. PDSV19 nanoparticles could maintain a good spherical morphology, with most of them adsorbing at the interface or embedding into the solidified polymerized beads whether in acidic, neutral, or alkaline conditions. Moreover, great stacking of PDSV19 nanoparticles was observed at pH 10.3, indicating better emulsifying performance and stability. This paper may be helpful in understanding stimuli-responsive Pickering emulsions stabilized by random terpolymer micelle-based particulate emulsifiers.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
Tang J, Quinlan PJ, Tam KC (2015) Stimuli-responsive Pickering emulsions: recent advances and potential applications. Soft Matter 11(18):3512–3529. https://doi.org/10.1039/C5SM00247H
Kaiser A, Liu T, Richtering W, Schmidt AM (2009) Magnetic capsules and Pickering emulsions stabilized by core−shell particles. Langmuir 25(13):7335–7341. https://doi.org/10.1021/la900401f
Brugger B, Rosen BA, Richtering W (2008) Microgels as stimuli-responsive stabilizers for emulsions. Langmuir 24(21):12202–12208. https://doi.org/10.1021/la8015854
Luo J, Zhou Q, Sun J, Liu R, Liu X (2014) Micelle-assisted synthesis of PANI nanoparticles and application as particulate emulsifier. Colloid Polym Sci 292(3):653–660. https://doi.org/10.1007/s00396-013-3108-5
Liu X, Yi C, Zhu Y, Yang Y, Jiang J, Cui Z, Jiang M (2010) Pickering emulsions stabilized by self-assembled colloidal particles of copolymers of P(St-alt-MAn)-co-P(VM-alt-MAn). J Colloid Interface Sci 351(2):315–322. https://doi.org/10.1016/j.jcis.2010.04.056
Chevalier Y, Bolzinger M-A (2013) Emulsions stabilized with solid nanoparticles: Pickering emulsions. Colloids Surf A Physicochem Eng Asp 439:23–34. https://doi.org/10.1016/j.colsurfa.2013.02.054
Binks BP (2002) Particles as surfactants—similarities and differences. Curr Opin Colloid Interface Sci 7(1-2):21–41. https://doi.org/10.1016/S1359-0294(02)00008-0
Wei W, Wang T, Yi C, Liu J, Liu X (2015) Self-assembled micelles based on branched poly(styrene-alt-maleic anhydride) as particulate emulsifiers. RSC Adv 5(2):1564–1570. https://doi.org/10.1039/C4RA12100G
Zhu Y, Sun J, Yi C, Wei W, Liu X (2016) One-step formation of multiple Pickering emulsions stabilized by self-assembled poly(dodecyl acrylate-co-acrylic acid) nanoparticles. Soft Matter 12(36):7577–7584. https://doi.org/10.1039/C6SM01263A
Yang H, Zhou T, Zhang W (2013) A strategy for separating and recycling solid catalysts based on the pH-triggered Pickering-emulsion inversion. Angew Chem Int Ed 52(29):7455–7459. https://doi.org/10.1002/anie.201300534
Dickinson E (2010) Food emulsions and foams: stabilization by particles. Curr Opin Colloid Interface Sci 15(1-2):40–49. https://doi.org/10.1016/j.cocis.2009.11.001
Hougeir FG, Kircik L (2012) A review of delivery systems in cosmetics. Dermatol Ther 25(3):234–237. https://doi.org/10.1111/j.1529-8019.2012.01501.x
Schrade A, Landfester K, Ziener U (2013) Pickering-type stabilized nanoparticles by heterophase polymerization. Chem Soc Rev 42(16):6823–6839. https://doi.org/10.1039/c3cs60100e
Chen Y, Bai Y, Chen S, Ju J, Li Y, Wang T, Wang Q (2014) Stimuli-responsive composite particles as solid-stabilizers for effective oil harvesting. ACS Appl Mater Interfaces 6(16):13334–13338. https://doi.org/10.1021/am504124a
He X, Ge XW, Wang M, Zhang Z (2005) Polystyrene/melamine-formaldehyde hollow microsphere composite by self-assembling of latex particles at emulsion droplet interface. Polymer 46(18):7598–7604. https://doi.org/10.1016/j.polymer.2005.06.015
Nonomura Y, Kobayashi N (2009) Phase inversion of the Pickering emulsions stabilized by plate-shaped clay particles. J Colloid Interface Sci 330(2):463–466. https://doi.org/10.1016/j.jcis.2008.10.063
Zhou J, Wang L, Qiao X, Binks BP, Sun K (2012) Pickering emulsions stabilized by surface-modified Fe3O4 nanoparticles. J Colloid Interface Sci 367(1):213–224. https://doi.org/10.1016/j.jcis.2011.11.001
Fujii S, Cai Y, Weaver JVM, Armes SP (2005) Syntheses of shell cross-linked micelles using acidic ABC triblock copolymers and their application as pH-responsive particulate emulsifiers. J Am Chem Soc 127(20):7304–7305. https://doi.org/10.1021/ja050049a
Wang F, Yang X, Zhang L, Xu W, Liu H (2017) Novel macromolecular emulsifiers as coatings with water-tolerant antifogging properties based on coumarin-containing copolymeric micelles. Macromol Mater Eng 302:11. https://doi.org/10.1002/mame.201700173
Yi C, Sun J, Zhao D, Hu Q, Liu X, Jiang M (2014) Influence of photo-cross-linking on emulsifying performance of the self-assemblies of poly (7-(4-vinylbenzyloxyl)-4-methylcoumarin-co-acrylic acid). Langmuir 30(23):6669–6677. https://doi.org/10.1021/la500326u
Tian F, Yu Y, Wang C, Yang S (2008) Consecutive morphological transitions in nanoaggregates assembled from amphiphilic random copolymer via water-driven micellization and light-triggered dissociation. Macromolecules 41(10):3385–3388. https://doi.org/10.1021/ma800142j
Zhou QH, Lin J, Li LD, Shang L (2015) Biodegradable micelles self-assembled from miktoarm star block copolymers for MTX delivery. Colloid Polym Sci 293(8):2291–2300. https://doi.org/10.1007/s00396-015-3610-z
Liu X, Kim JS, Wu J, Eisenberg A (2005) Bowl-shaped aggregates from the self-assembly of an amphiphilic random copolymer of poly(styrene-co-methacrylic acid). Macromolecules 38(16):6749–6751. https://doi.org/10.1021/ma050665r
Wang J, Jiang M (2006) Polymeric self-assembly into micelles and hollow spheres with multiscale cavities driven by inclusion complexation. J Am Chem Soc 128(11):3703–3708. https://doi.org/10.1021/ja056775v
Zhu X, Liu M (2011) Self-assembly and morphology control of new l-glutamic acid-based amphiphilic random copolymers: giant vesicles, vesicles, spheres, and honeycomb film. Langmuir 27(21):12844–12850. https://doi.org/10.1021/la202680j
Kalashnikova I, Bizot H, Cathala B, Capron I (2011) New Pickering emulsions stabilized by bacterial cellulose nanocrystals. Langmuir 27(12):7471–7479. https://doi.org/10.1021/la200971f
Yi C, Yang Y, Zhu Y, Liu N, Liu X, Luo J, Jiang M (2012) Self-assembly and emulsification of poly{[styrene-alt-maleic acid]-co-[styrene-alt-(N-3,4- dihydroxyphenylethyl-maleamic acid)]}. Langmuir 28:9211–9222
Piao SH, Kwon SH, Zhang WL, Choi HJ (2015) Celebrating Soft Matter’s 10th anniversary: stimuli-responsive Pickering emulsion polymerized smart fluids. Soft Matter 11(4):646–654. https://doi.org/10.1039/C4SM02393E
Allen C, Eisenberg A, Maysinger D (1999) Copolymer drug carriers: conjugates, micelles and microspheres. S T P Pharma Sci 9:139–151
Allen C, Han J, Yu Y, Maysinger D, Eisenberg D (2000) Polycaprolactone-b- poly(ethylene oxide) copolymer micelles as a delivery vehicle for dihydrotestosterone. J Control Release 63(3):275–286. https://doi.org/10.1016/S0168-3659(99)00200-X
Zhang L, Shen H, Eisenberg A (1997) Phase separation behavior and crew-cut micelle formation of polystyrene-b-poly(acrylic acid) copolymers in solutions. Macromolecules 30(4):1001–1011. https://doi.org/10.1021/ma961413g
Jiang M, Duan H, Chen D (2003) Macromolecular assembly: from irregular aggregates to regular nanostructures. Macromol Symp 195(1):165–170. https://doi.org/10.1002/masy.200390117
Deng Y, Li Y, Wang X (2006) Colloidal sphere formation, H-aggregation, and photoresponsive properties of an amphiphilic random copolymer bearing branched azo side chains. Macromolecules 39(19):6590–6598. https://doi.org/10.1021/ma061335p
Wang F, Ouyang Y, Zou H, Yang Z, Liu H (2017) Self-assembling behavior and stimuli-responsive emulsifying performance of coumarin-containing amphiphilic terpolymer. Colloids Surf A Physicochem Eng Asp 535:274–282. https://doi.org/10.1016/j.colsurfa.2017.09.036
Aveyard R, Binks BP, Clint JH (2003) Emulsions stabilised solely by colloidal particles. Adv Colloid Interf Sci 100(102):503–546
Haase MF, Grigoriev DO, Möhwald H, Shchukin DG (2012) Development of nanoparticle stabilized polymer nanocontainers with high content of the encapsulated active agent and their application in water-borne anticorrosive coatings. Adv Mater 24(18):2429–2435. https://doi.org/10.1002/adma.201104687
Liu H, Chen S, Cui H, Hu J, Cai H, Deng W (2015) Fabrication of triple responsive polymer brushes and their catalytic performance after loading palladium. RSC Adv 5(89):72444–72452. https://doi.org/10.1039/C5RA13245B
Chen S, Liu H, Cui H, Hu J, Cai H (2015) Synthesis of spiropyran-containing random copolymer by atom transfer radical polymerization and its complexation with metal ions. Des Monomers Polym 18(6):574–582. https://doi.org/10.1080/15685551.2015.1045226
Joo M, Shin J, Kim J, You JB, Yoo Y, Kwak MJ, MS O, Im SG (2017) One-step synthesis of cross-linked ionic polymer thin films in vapor phase and its application to an oil/water separation membrane. J Am Chem Soc 139(6):2329–2337. https://doi.org/10.1021/jacs.6b11349
Shen J, Xu J, Hu Y, Li J, Kan C (2017) Fabrication of amino-containing hollow polymer latex and its composite with inorganic nanoparticles. Colloid Polym Sci 295(4):679–688. https://doi.org/10.1007/s00396-017-4059-z
Funding
This work was financially supported by Natural Science Foundation of China (Grant No. 21376271), the Fundamental Research Funds for the Central Universities of Central South University (2017zzts783), and Open-End Fund for the Valuable and Precision Instruments of Central South University.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
ESM 1
(DOCX 587 kb)
Rights and permissions
About this article
Cite this article
Wang, F., Yu, X. & Liu, H. Pickering emulsions stabilized by self-assembled polymeric micelles of coumarin-containing cross-linkable amphiphilic terpolymer. Colloid Polym Sci 296, 385–392 (2018). https://doi.org/10.1007/s00396-017-4259-6
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00396-017-4259-6