Spontaneous polymerization of amphiphilic vinyl monomers, 2 spontaneous polymerization of sodium alkyl 2-hydroxy-3-methacryloyloxypropyl phosphates in micellar and inverse micellar systems

The spontaneous polymerization of sodium alkyl 2‐hydroxy‐3‐methacryloyloxypropyl phosphates (Cn‐AHMP) was investigated in the temperature range from 35°C to 80°C in water and in benzene. The polymerization activity in both solvents changed with the alkyl chain length in the order: C12 > C8 > C14 ≫ C16. Similarly to the C12 monomer, C14‐AHMP only polymerizes above the critical micelle concentration (cmc), proving that micelle‐formation is essential for the spontaneous polymerization. The polymerization of the C8 analogue occurs even a little below the cmc, in contrast to C12 ‐ and C14‐AHMP. This behaviour suggests the existence of smaller aggregates than the micelle below the cmc in water. The polymerization of C16‐AHMP did not take place spontaneously in both solvents, in spite of the formation of micellar aggregates in water. The lack of polymerization ability is related to the inactivity to generate initiating radical species in the micellar system.