Micellar solubilization of tributylphosphate in aqueous solutions of Pluronic block copolymers. Part I. Effect of the copolymer structure and temperature on the phase behavior.

Solubilization of tributylphosphate (TBP), a polar oil, in various micellar solutions of Pluronic has been investigated by turbidimetry emphasizing the effect of temperature and the role of the PPO and PEO blocks on the phase behavior of the three components systems (Pluronic-TBP-water). [Temperature-composition] diagrams allow monophasic and diphasic domains to be delimited. Two temperatures are shown to have a determining effect on the phase behavior (TBP solubilization); the well known cloud point temperature (CPT, here defined for the three components system) and the solubilization minimum temperature (SMT) which is defined as the lowest temperature allowing solubilization of TBP in the system. Both temperature depend on the copolymer structure and, interestingly, are directly related to the TBP concentration in the medium. Monophasic microemulsions are observed when the temperature ranges between the SMT and the CPT. When T<SMT, the phase separation occurs and is related to the formation of TBP in water emulsion droplets. When T>CPT the system separates in two phase due to the co-precipitation of TBP and Pluronic. Moreover an unexpected evolution of the CPT with the TBP content clearly indicates the occurrence of a structural change of the microemulsions which allows higher quantities of TBP to be solubilized. But the structural change does not allow alone higher quantities of TBP to be solubilized. A well compromise between the SMT and the CPT must be also observed so as to obtain a large extent of monophasic domain after the restructuration. The best compromise is obtained with Pluronics with intermediate hydrophobic character. Reversely, hydrophobic and hydrophilic Pluronics exhibit a very small extent of monophasic domain after the restructuration which does not allow benefit by the structural change.