Theoretical modeling of associated structures in aqueous solutions of hydrophobically modified telechelic PNIPAM based on a neutron scattering study
テレケリックポリ(N-イソプロピルアクリルアミド)水溶液の中性子小角散乱による研究; 会合構造の理論モデル
古賀 毅*; 田中 文彦*; 元川 竜平
; 小泉 智; Winnik, F. M.*
Koga, Tsuyoshi*; Tanaka, Fumihiko*; Motokawa, Ryuhei; Koizumi, Satoshi; Winnik, F. M.*
ポリ(N-イソプロピルアクリルアミド)(PNIPAM)の両端末を、オクタデシル基で疎水化したテレケリックPNIPAM(HM-PNIPAM)の水溶液は、温度変化に応答してフラワーミセルやメソグロビュール(会合構造)を形成する。この水溶液は、温度とポリマー濃度の変化に応じて、ゾル-ゲル転移や水溶液の白濁等のマクロな状態を変化させる。本論文では、この水溶液に対して中性子小角散乱測定を行い、その結果に対して理論モデルを組み立てることで、マクロな状態変化に伴うメソスケールでの構造変化(ミクロな構造変化)を明らかにした。これにより、マクロな状態変化のメカニズムを明らかにすると同時に、さまざまな温度,ポリマー濃度条件で形成されるフラワーミセルやメゾグロビュールのサイズ,形状を決定した。
On the basis of results from a small-angle neutron scattering (SANS) study of aqueous solutions of a telechelic PNIPAM with octadecyl end groups, we developed a theoretical model of the self-assembly of this polymer in water as a function of temperature and concentration. This model leads us to the following description. In solutions of concentration 10 gL
kept between 10 and 20
C, telechelic PNIPAMs (
) 22 200 gmol
) associate in the form of flower micelles, containing about 12 polymer chains, assembled in a three-layered core-shell morphology with an inner core consisting of the octadecyl units, a dense inner shell consisting of partly collapsed PNIPAM chains, and an outer shell of swollen hydrated chains. Drastic changes in the scattering profile of the solution heated above 31
C are attributed to the formation of mesoglobules (diameter of 40 nm) consisting of about 1000 polymer chains. On further heating, the aggregation number of the mesoglobules increases. It reaches a value of 9000 at 34
C and stays constant upon further heating. In solutions of lower concentration (1 gL
), association of flower micelles and mesoglobules does not occur; however, the structure of individual flower micelles and mesoglobules is not affected by the change in concentration. In solutions of 50 gL
in which flower micelles are expected to be partially connected by bridge chains, a peak attributed to correlation between flower micelles appears in the scattering profiles recorded at low temperature (10-20
C). In spite of the intermicellar bridging connection, the overall temperature dependence of the scattering profile at 50 gL
remains similar to that at 10 gL
. Distinct features of the self-assembled structures formed in aqueous telechelic PNIPAM solutions are discussed in terms of the interactions between water and the polymer main chains.