Abstract
The dependence of the number of particles Np as a function of the surfactant concentration [S] is investigated for the step polymerization of dithiol-diene emulsions. A sigmoidal curve for log Np vs log [S] is found for a range of monomers regardless of their polarity. Above the critical micellar concentration (6–20 mM), a Np ∝ [S]x relationship is established with an exponent x dependent on the polarity of the two co-monomers. When the two co-monomers are highly water insoluble, x varies typically between 0.6 and 1. With two relatively water soluble co-monomers, x is close to 0. When two co-monomers with contrasting water solubility are involved, the power dependence is more difficult to predict and ranges from 0 to 1, but high x value are generally found when one of the two monomers is highly hydrophobic. This overall trend can be reconciled with the behavior of a conventional emulsion radical chain polymerization.
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Abbreviations
- N p :
-
Number of particle per unit volume (L−1)
- [S]:
-
Surfactant concentration (mol L−1)
- [I]:
-
Initiator concentration (mol L−1)
- CMC:
-
Critical micelle concentration
- SEC:
-
Size exclusion chromatography
- D z :
-
z-Average particle diameter Particle
- D w :
-
Weight-average particle diameter
- D v :
-
Volume-average particle diameter
- D n :
-
Number-average particle diameter
- DLS:
-
Dynamic light scattering
- cryo-TEM:
-
Cryogenic transmission electron microscopy
- \({s}_{\mathrm{diene}}\) :
-
Water-solubility of diene
- \({s}_{\mathrm{dithiol}}\) :
-
Water-solubility of dithiol
- DAP:
-
Diallyl phthalate Diene
- DATP:
-
Diallyl terephthalate
- DAIP:
-
Diallyl isophthalate
- DAA:
-
Diallyl adipate
- DVE:
-
Di(ethylene glycol) divinyl ether
- CHDM:
-
1,4-Bis[(vinyloxy)methyl]cyclohexane
- EDDT:
-
2,2-(Ethylenedioxy)diethanedithiol Dithiol
- DTT:
-
DL-dithiothreitol
- GDMA:
-
Ethylene glycol bismercaptoacetate
- GDMP:
-
Ethylene glycol bis(3-mercaptopropionate)
- DMDS:
-
2,2′-Thioldiethanethiol
- HMDT:
-
1,6-Hexanedithiol
- DBHQ:
-
2,5-Di-tert-butylhydroquinone Radical inhibitor
- SDS:
-
Sodium dodecyl sulfate Surfactant
- TPO-Li:
-
Lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate Water-soluble photoinitator
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Funding
This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Skłodowska-Curie grant agreement n° 765341 (project photo-emulsion, MSCA-ITN-2017).
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Le, C.M.Q., Schmutz, M. & Chemtob, A. Effect of surfactant concentration and monomer polarity on particle nucleation in emulsion step polymerization of dithiol with diene. Colloid Polym Sci 300, 917–925 (2022). https://doi.org/10.1007/s00396-022-04993-z
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DOI: https://doi.org/10.1007/s00396-022-04993-z