Association Behavior of Poly (ethylene oxide) -Poly (propylene oxide) Alternating Multiblock Copolymers in Water toward Thermally Induced Phase Separation

Horiuchi, T.; Sakai, T.; Sanada, Y.; Watanabe, K.; Aida, M.; Katsumoto, Y.

Langmuir 33(51): 14649-14656


ISSN/ISBN: 0743-7463
PMID: 29236506
DOI: 10.1021/acs.langmuir.7b02810
Accession: 050563001

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Thermal changes in the association behavior of poly(ethylene oxide)-poly(propylene oxide) alternating multiblock (PEO-PPO AMB) copolymers in water are investigated by the use of transmittance and light scattering measurements. Two PEO-PPO AMB copolymers with a different weight fraction of PEO, (EO220PO33)8 and (EO68PO33)9, are prepared. The weight-average molecular weights of (EO220PO33)8 and (EO68PO33)9 estimated by static light scattering measurements are 1.3 × 105 and 4.1 × 104 g mol-1, respectively. The number of PEO-PPO repeating pairs is over 8. It is found that the aqueous solution of (EO220PO33)8 undergoes phase separation with a lower critical solution temperature (LCST) of around 58 °C at 0.3 wt %. For the aqueous (EO68PO33)9 solution, the LCST is estimated to be ca. 42 °C. The critical solution concentration for (EO68PO33)9 is not clear because of a small concentration dependence of Tc at a higher concentration range. Dynamic light scattering measurements indicate that a micellelike aggregate is formed below the LCST. From the Debye plot, it is elucidated that the second virial coefficient, A2, starts going down at around 32 °C for (EO220PO33)8 and below 15 °C for (EO68PO33)9. The A2 value of (EO220PO33)8 approaches 0 near 50 °C, whereas that of (EO68PO33)9 approaches 0 at around 35 °C. At a high temperature, the attractive interaction among the copolymers becomes dominant, thereby inducing the formation of micellelike aggregates.