Spontaneous polymerization of amphiphilic vinyl monomers, 1. Spontaneous polymerization of sodium dodecyl 2‐hydroxy‐3‐methacryloypropyl phosphate

Abstract

Sodium dodecyl2-hydroxy-3-methacryloyloxypropyl phosphate as an amphiphilic vinyl monomer was found to polymerize spontaneously without initiator in water. The polymerization takes place at a monomer concentration higher than the critical micelle concentration via a free-radical mechanism, and complete conversion is achieved even at a very low initial monomer concentration (3 mmol/L) and arather low temperature (35 "C). In benzene, capable of forming inverse micelles, the polymerization also occurs spontaneously. In methanol, which gives an isotropic solution, the spontaneous polymerization proceeds only at high concentration (near 300 mmol/L). The 'H spin-spin relaxation time (T2r) of the monomer changes discontinuously in a range of monomer concentration from 250 to 300 mmol/L in CD,OD, suggesting that some kind of monomer mutual interaction takes place in methanol too. Thus, it can be concluded that the micellar aggregation of monomer molecules triggers the polymerization.

Polymerization of the new double‐charged monomer bis‐1,3(N,N,N‐trimethylammonium dicyanamide)‐2‐propylmethacrylate and ionic conductivity of the novel polyelectrolytes

“…Thus, it was not possible to obtain pure monomer M2 and to carry out its bulk polymerization. Similar spontaneous solution polymerization of ionic vinyl monomers (vinylpyridinium salts in particular [44,45] ) and of some ionic methacrylates [46] has been observed previously. Upon detailed investigation it was observed that the polymerization started spontaneously at a monomer concentration higher than 90 wt% (23.9 mol/L).…”

Controlled polymerizations with constrained geometries

“…In some cases, surfactant monomers in micelles spontaneously undergo radical polymerization without externally added initiators. 8,9 For example, the polymerization of sodium dodecyl 2-hydroxy-3-methacryloyloxypropyl phosphate 1 in water at a concentration above the c.m.c (ca. 10 23 mol L 21 ) takes place even at room temperature (35 °C) without initiator, to attain 100% monomer conversion.…”

“…10 23 mol L 21 ) takes place even at room temperature (35 °C) without initiator, to attain 100% monomer conversion. 8 In contrast, in methanol where 1 does not aggregate to form micelles, no polymerization occurs unless radical initiators are added. The spontaneous polymerization may also be accounted for by 'condensation effect of monomer'.…”

“…Free radical polymerization of lipid monomers in bilayer membranes shows significantly different kinetics from those in the bulk phase. [18][19][20] For example, in the polymerization of a vesicle consisting of a phosphatidylcholine derivative having an acryloyl (7), methacryloyl (8), or sorbyl group (9) at the hydrophobic chain end, the degree of polymerization (D p ) is proportional to [M] 2 and [I] 21 at a high monomer conversion ([M] and [I] are concentrations of monomer and initiator, respectively). In contrast, in bulk under otherwise identical conditions to the above, D p is proportional to [M] and [I] 20.5 .…”

Separated Organized Polymerization of an Amphiphilic Monomer and Acrylamide in One-Pot Reaction

“…Although organized polymerization reactions of amphiphilic monomers have been extensively studied so far, − these works deal with the immobilization of vesicle structures, − the characteristic polymerization of amphiphilic monomers in solid LB fims, − and the spontaneous polymerization of a polymerizable surfactant in micellar form, , etc. Separated organized polymerization to form a homopolymer in one-pot radical reaction has not yet been reported, and the finding in this work is quite new and interesting to note from the viewpoint of polymer chemistry.…”