Anionic Polymerization of Phenyl Glycidyl Ether in Miniemulsion

Abstract

The anionic polymerization of phenyl glycidyl ether (PGE) in miniemulsion was investigated. Didodecyldimethylammonium hydroxide was used as an inisurf, i.e., exhibiting both surface-active properties and the ability to initiate polymerization by means of its hydroxide counterion. Stable miniemulsions were obtained by ultrasonication, and then polymerization was carried out to produce genuine R,ω-dihydroxylated polyether chains as revealed by 1 H NMR, FTIR, or mass spectroscopic methods. The average molecular weight could be increased by varying the initiator concentration, type and concentration of surfactants or by adding a cosurfactant (typically alcohol). In all attempts, polymer chains increased in size with conversion but remained small, with a critical polymerization degree of DP max ) 8. A mechanism was proposed to account for these results. From these observations, phenyl glycidyl ether could be used as a model monomer to investigate ionic polymerization in miniemulsion.

On the key role of the interface in the cationic polymerisation of p-methoxystyrene in miniemulsion

“…6 shows the conversion versus time plots for all experiments done under these conditions. The polymerisation rate increases with temperature as expected from previous studies [1,2]. Almost similar polymerisation rates are obtained with triflic acid and APTS.…”

“…This trapped compound [12] modifies the osmotic pressure into the particles to counteract the Laplace pressure, and is called an 'osmotically' (or kinetically) stable emulsion or miniemulsion. Ostwald ripening could not be seen in any IPE systems [1][2][3][4][5], since the polymer chains that are generated through interfacial polymerisation act as this specific trapped species.…”

“…This rather polar molecule, compared to pMOS, generated smaller chains simply by increasing the interfacial water content. An opposite effect was seen during the anionic polymerisation of phenyl glycidyl ether [2] because oligomers generated in situ are dihydroxylated and thus more polar. In an attempt to modify the interface polarity, we moved to a more hydrophobic surfactant, the aristonic acid, which contains two alkyl chains on the benzene ring (see structure in Scheme 1 derived from mass spectrometry analyses).…”

“…Termination reaction of course involves water, and this process may be reversible (alkyl cyanoacrylates [3,4] or episulfides [5]) or not (phenyl glycidyl ether [2] and pmethoxystyrene (pMOS) [1]). In all cases, anyway, only low molar mass oligomers are produced.…”

Polymer dispersions from catalytic polymerization in aqueous systems

“…[9][10][11][12][13][14] Polymerization methods other than free radical polymerization, namely polycondensation/polyaddition and ionic polymerizations, have also been studied in aqueous systems as a route to polymer dispersions. [15][16][17] Polyurethane dispersions are prepared commercially as secondary dispersions or by polycondensation or polyaddition of prepolymers in aqueous systems. 2,18 First publ.…”