Synthesis and Self‐Assembly of Styrene–[1]Dimethylsilaferrocenophane–Methyl Methacrylate Pentablock Copolymers

Abstract

Summary: Well‐defined pentablock copolymers of styrene–[1]dimethylsilaferrocenophane–methyl methacrylate (PMMA‐b‐PFS‐b‐PS‐b‐PFS‐b‐PMMA) are synthesized using lithium naphthalide as initiator and a 1,1‐dimethylsilacyclobutane‐mediated 1,1‐diphenylethylene (DPE) end‐capping technique. Annealing under various conditions followed by analysis by transmission electron microscopy revealed good phase separation by the copolymers and the presence of ordered microstructures, such as spheres‐on/in‐spheres, and spheres‐on/in‐lamellae micromorphologies.Structure of the styrene–[1]dimethylsilaferrocenophane–methyl methacrylate pentablock copolymers.magnified imageStructure of the styrene–[1]dimethylsilaferrocenophane–methyl methacrylate pentablock copolymers.

Polyferrocenylsilane‐Based Polymer Systems

“…Pentablock terpolymers PMMA-b-PFS-b-PS-b-PFS-b-PMMA were synthesized by using the same strategy and lithium naphthalide as a difunctional initiator. [120] Linear dendritic diblock copolymers were synthesized by grafting living PFS onto the benzyl chloride group of first-or second-generation poly(benzyl ether) dendrons. [121] Polyferrocenylphenylphosphine (PFP) block copolymers (PFP-b-PDMS, PFP-b-PFS, PS-b-PFP, and PI-b-PFP) were also prepared by sequential living anionic polymerization.…”

Equilibrium Melting Temperature of Poly(ferrocenyl dimethylsilane) in Homopolymers and Lamellar Diblock Copolymers with Polystyrene

“…[1][2][3][4][5][6][7] Moreover, it counts among the very few metallopolymers accessible by living chain-growth protocols which give access not only to products of defined molar mass and narrow polydispersity but also to a broad variety of copolymer architectures: plenty of PFDMS block copolymers with, e.g., polystyrene (PS), [8][9][10][11] polyisoprene (PI), [12] poly(dimethyl siloxane) (PDMS), [8,12,13] poly(ethylene oxide) (PEO), [14] poly(methyl methacrylate) (PMMA), [15][16][17][18][19][20][21] and poly(2-vinylpyridine) [22] have been synthesized, and they have been shown to develop fascinating morphologies at the nanometer to micrometer scale. [2,7,23] Another important feature of PFDMS is its ability to crystallize.…”

Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock

“…255 Following initial reports in the mid 1990s, 45 Figure 22. 230 Phase diagrams for both PS-b-PFDMS 258 and PS-b-PFEMS 48,218 BCPs have been reported previously. In the bulk, microtomed sections of these materials can be observed by TEM without the need of staining due to the increased scattering ability of the electron-rich PFS domains compared to those of organic polymers.…”