Styrene (S)-isoprene (I) star-shaped block copolymers of the (SI)4 and (SI)l 2 types were prepared by an anionic polymerization technique. Linear SI arm molecules were prepared with sec-butyilithium as an initiator in benzene, followed by a coupling reaction with the 4-functional linking agent 1,2-bis(methyldichlorosilyl) ethane and the 12-functional 1,1,2,2-tetrakis(2-(trichlorosilyl)ethyl)silane, respectively, under vacuum. The star-shaped block copolymers were isolated by precipitational fractionation from aspolymerized crude products using benzene-methanol mixtures. They were confirmed to have the designed molecular structures by careful characterization. Using a transmission electron microscope it was observed that the microphase-separated structures of solvent-cast films of the samples are polystyrene (PS) cylinders in a polyisoprene (PI) matrix, alternating lametlar structures and PI cylinders in a PS matrix for 4-armed star-shaped block copolymers when the values of the volume fraction of PS, q~s, are 0.23, 0.47 and 0.78, respectively, and lamellar structures for the 12-armed star-shaped block copolymers when the q~s values are ~0.5. Small-angle X-ray scattering studies revealed that lamellar domain spacings of the star-shaped block copolymers are essentially the same as those of the arm molecules, that is, linear diblock copolymers, irrespective of the number of arms.
Посилання на статтю:
Preparation and morphologies of 4- and 12-armed styrene-isoprene star-shaped block copolymers / Y. Matsushita*, T. Takasut, K. Yagi~, K. Tomioka§ and I. Noda // Polymer. – 1994. – Vol 35. – P. 2862-2866.
