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Associating behavior of star-like amphiphilic polymers consisting of two or three poly(ethylene oxide) (PEO) chains and one stearyl chain (C18) was investigated. Although the aggregation number ( N agg  ) of linear analogue of amphiphilic polymers monotonically decreased with increasing number-average molecular weight of PEO ( M n   ,PEO ), the N agg  of micelles of star-like amphiphilic polymers with M n   ,PEO = 550 g/mol was smaller than that with M n   ,PEO = 750 g/mol, whereas that with M n   ,PEO ≥ 750 g/mol showed general M n   ,PEO dependence. Small-angle X-ray scattering analyses revealed that the occupied area of one PEO chain on the interface between hydrophobic core and corona layer in the micelles of star-like polymers was much narrower than that in the linear amphiphilic polymers. This result indica ted the PEO chains of star-like polymers partially took unfavorable conformation near the core-corona interface in polymer micelles. The effect of local conformation of PEO chains near the interface on the associating behavior became significant as M n   ,PEO decreased. Therefore, in polymer micelles of star-like amphiphilic polymers containing PEO with M n   ,PEO = 550 g/mol, the enlargement of occupied area of PEO on the core-corona interface should be caused to avoid the formation of unfavorable conformations of partial PEO chains, resulting in a decrease in N agg  s.

polymers

Effect of Molecular Architecture on Associating Behavior of Star-Like Amphiphilic Polymers Consisting of Plural Poly(ethylene oxide) and One Alkyl Chain