Cationic Polymerization of p-Methoxystyrene in Miniemulsion

Cationic Polymerization of p-Methoxystyrene in Miniemulsion

The cationic polymerization of p-methoxystyrene (pMOS) in miniemulsion in the presence of dodecylbenzenesulfonic acid (DBSA) was studied. DBSA acts as both protonic initiator and surfactant (INISURF). The recipe was first optimized to generate stable latexes from a miniemulsion, i.e., droplets/parti...

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Bibliographic Details
Published in:Macromolecules Vol. 35; no. 21; pp. 7919 - 7927
Main Authors: Cauvin, Séverine, Sadoun, Amel, Dos Santos, Rosalina, Belleney, Joël, Ganachaud, François, Hemery, Patrick
Format: Journal Article
Language:English
Published: Washington, DC American Chemical Society 08-10-2002
Subjects:
Applied sciences
Exact sciences and technology
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
Anionic surfactant
Emulsion polymerization
Cationic polymerization
Kinetics
Experimental study
Sulfonic acid
Styrene derivative polymer
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Summary:The cationic polymerization of p-methoxystyrene (pMOS) in miniemulsion in the presence of dodecylbenzenesulfonic acid (DBSA) was studied. DBSA acts as both protonic initiator and surfactant (INISURF). The recipe was first optimized to generate stable latexes from a miniemulsion, i.e., droplets/particles of constant size throughout the polymerization. The miniemulsion polymerization process was highly reproducible, quite fast at high temperatures (100% conversion in 8 h at 60 °C) and applicable even at high monomer content (typically 40 wt %). Poly(pMOS) of small average molar masses (≈1000 g mol-1) and controlled functionality were synthesized. The sharp increase in molar masses at low conversion was indebted to a decrease of water content at the interface through a cosurfactant effect. Above 20% conversion, the chain length limitation, also observed in previous ionic polymerizations in emulsion studies and referred to as critical DP, was confirmed by modeling simple kinetics. At final conversion, polymer degradation occurred as revealed by SEC, MALDI−TOF, and 1H NMR. The particles quickly coalesced in the absence of a cosurfactant.
Bibliography:ark:/67375/TPS-NRM2GNZ9-5
istex:AF3C0D0B80714E5A2A34536DC4E890AFD79E29C4
ISSN:0024-9297
1520-5835
DOI:10.1021/ma0202890