Periodic organic–organometallic microdomain structures in poly(styrene‐block‐ferrocenyldimethylsilane) copolymers and blends with corresponding homopolymers

Abstract

A series of poly(styrene-block-ferrocenyldimethylsilane) copolymers (SF) with different relative molar masses of the blocks were prepared by sequential anionic polymerization. The bulk morphology of these polymers, studied by TEM and SAXS, showed well-ordered lamellar and cylindrical domains as well as disordered micellar structures. Temperature-dependent rheological measurements exhibited an order-disorder transition for SF 17/8 (the numbers refer to the relative molar masses in 10 3 g/mol) between 170 and 180°C, and an order-order transition for SF 9/19 between 190 and 200°C. The morphologies of binary blends of the diblocks with homopolymer were also investigated. In the blends the molar mass of the homopolymer was always less than the molar mass of the matching block. Ordered spheres on a bcc lattice and double-gyroid morphology were observed for the blends. The double-gyroid morphology was found only in F-rich diblock/homopolymer systems.

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.…”

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

“…Then, an equal volume of tetrahydrofurane (THF) was added in order to promote the FS propagation from the ferrocenyllithium-based macroanions. [8][9][10][11] After stirring for a further 2 h, the reaction was terminated with degassed methanol. The raw product was isolated by precipitation in hexane.…”

“…Also, it influences neither the PFDMS crystallization nor the sample's morphology. [9,45] The resulting diblock copolymer has an overall molar mass (M n ) of 24.3 kg Á mol À1 (PDI ¼ 1.05), with a PS block of M n ¼ 12.0 kg Á mol À1 and a PFDMS block of M n ¼ 12.3 kg Á mol À1 . At room temperature, the volume fraction of PS in the amorphous and crystalline sample is 0.586 and 0.614, respectively, taking a density of 1.05 g Á cm À3 for the amorphous PS and densities of 1.294 and 1.455 g Á cm À3 for the amorphous and crystalline PFDMS, respectively.…”

“…[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.…”

Triply Periodic Bicontinuous Structures as Templates for Photonic Crystals: A Pinch‐off Problem

“…[1][2][3] To fabricate these 3D microstructures, various methods, including microphase separation by block copolymers [4,5] , multi-beam interference lithography [6][7][8] , and phase-mask lithography [9] have been studied. The low refractive index of the patterned materials, however, has limited their application as photonic crystals with complete PBGs.…”