A Novel Crystallization Scheme in Poly[styrene‐<i>block</i>‐(ferrocenyl dimethylsilane)] Diblock Copolymers

Xu, Jianjun; Bellas, Vasilios; Jungnickel, B.‐J.; Stühn, Bernd; Rehahn, Matthias

doi:10.1002/macp.201000220

Cited by 8 publications

(5 citation statements)

References 78 publications

(84 reference statements)

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“…These data display a series of Bragg reflections indicating crystalline order. The obtained reflections are in accordance with the monoclinic structure of PFS as reported in the literature. , The diffraction pattern of the block copolymer PS 727 - b -(PI 658 - g -PFS) varies smoothly with scattering angle and shows no indication of crystalline order. These results give a hint for a suppressed crystallization of PFS attached to the block copolymer backbone.…”

Section: Resultssupporting

confidence: 88%

Structure Formation of Metallopolymer-Grafted Block Copolymers

et al. 2016

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Microphase separation drives the structure formation in block copolymers. Here, functional metallopolymer-grafted diblock copolymers consisting of polystyrene-block-polyisoprene (PS-b-PI) as polymer backbone featuring low molar mass polyferrocenyldimethylsilane (PFS) and polyvinylferrocene (PVFc) are synthesized via an iterative anionic grafting-to polymerization strategy. PS-b-PI block copolymers having about 30 mol % 1,2-polyisoprene moieties are subjected to platinum-catalyzed hydrosilylation reaction for the introduction of chlorosilane groups. The Si–Cl moieties are shown to efficiently react with the active metallopolymers yielding block-selective metallopolymer-grafted copolymers with 34 vol % PVFc and 43 vol % PFS as evidenced by 1H NMR spectroscopy as well as size exclusion chromatography. The microphase separation of the functional metallopolymer-grafted block copolymers is evidenced via TEM measurements revealing fascinating morphologies. The structure formation of the PVFc-grafted block copolymers is studied in more detail by TEM, small-angle X-ray scattering, wide-angle X-ray scattering, and atomic force microscopy measurements evidencing a lamellar morphology featuring a spherical substructure for the PVFc segments inside the polyisoprene lamellae.

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Section: Resultssupporting

confidence: 88%

Structure Formation of Metallopolymer-Grafted Block Copolymers

et al. 2016

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“…At first, the researchers' imagination was just limited to crystalline BCP systems similar to PFS, which requires that the crystalline block can be grown at room temperature by epitaxial growth to obtain a core with high crystallinity, that is, the crystallization process must be slow, and the crystal growth should be carried out in a state close to thermodynamic equilibrium. [ 141 ] At the same time, the corona‐forming block must have a relatively high solubility in the solvent so that the whole polymer chain can exist as individual free chains in solution to achieve controllable epitaxial growth. [ 20 ] In addition, when defects appear in the seed during growth, the crystalline block should preferably have sufficient mobility, i.e ., a relatively low glass transition temperature, to eliminate these defects.…”

Section: Discussionmentioning

confidence: 99%

Precise and Controllable Assembly of Block Copolymers^†

et al. 2022

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Bixin Jin received his PhD degree in Material Science and Engineering from Beijing Institute of Technology under the supervision of Prof. Xiaoyu Li in 2020. Currently, he works as a postdoctoral fellow in the same group. His research is focused on the precise self-assembly of liquid crystalline block copolymers. Yiqi Chen has been a MS student in Materials and Chemical Engineering at Beijing Institute of Technology under the supervision of Prof. Xiaoyu Li since 2021. Her research interest is precise self-assembly of liquid crystalline block copolymers. Yunjun Luo has been a professor in the school of Material Science and Engineering at Beijing Institute of Technology since 1999, and the director of the Key Laboratory of High Energy Density Materials of the Ministry of Education. His research interests are energetic materials and polymer materials. Xiaoyu Li has been a professor in the school of Material Science and Engineering at Beijing Institute of Technology since 2017. His current research interests mainly include the precise assembly of crystalline/liquid crystalline block copolymers and supramolecular motifs, and synthesis and applications of novel energetic polymers.Contents 1. Introduction 94 2. Extension of Precise Self-Assembly Methodology 95 2.1. "Seeded-Growth" method 95 2.2. "Self-Seeding" method 97 2.3. "In-Situ Nucleation-Growth" method 98 2.4. Comparison of the three different growth modes 99 3. Precise Controllable Self-Assembly of 2D Structures 99 3.1. Crystalline BCP systems 99 3.2. Liquid crystalline BCP systems 101 3.3. Other systems 101 4. Multilevel Self-Assembled Structures 102 4.1. Multilevel self-assembly via non-covalent interactions 102 4.2. Multilevel self-assembly at interfaces 103 5. Application of Functionalized Precise Self-assembled Structures 104 6. Conclusions and Perspectives 105 © 2022 SIOC, CAS, Shanghai, & WILEY-VCH GmbH www.cjc.wiley-vch.de 95

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“…PFS BCPs phase-separate on the nanoscale due to the immiscibility of the PFS block with a wide range of organic or inorganic coblocks. 264 The effect of crystallisation can be avoided by using unsymmetrically substituted PFSs (e.g. 256 Following initial reports in the mid 1990s, 46 bulk and thin film self-assembly has been studied in detail for a variety of PFS-containing BCPs including PFDMS-b-PMMA, 53,257 PI-b-PFDMS, 258 49,219 BCPs have been reported previously.…”

Section: Pfs Bcps: Properties and Applicationsmentioning

confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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This in-depth review covers progress in the area of polyferrocenylsilanes (PFS), a well-established, readily accessible class of main chain organosilicon metallopolymer consisting of alternating ferrocene and organosilane units. Soluble, high molar mass samples of these materials were first prepared in the early 1990s by ring-opening polymerisation (ROP) of silicon-bridged [1]ferrocenophanes (sila[1]ferrocenophanes). Thermal, transition metal-catalysed, and also two different living anionic ROP methodologies have been developed: the latter permit access to controlled polymer architectures, such as monodisperse PFS homopolymers and block copolymers. Depending on the substituents, PFS homopolymers can be amorphous or crystalline, and soluble in organic solvents or aqueous media. PFS materials have attracted widespread attention as high refractive index materials, electroactuated redox-active gels, fibres, films, and nanoporous membranes, as precursors to nanostructured magnetic ceramics, and as etch resists to plasmas and other radiation. PFS block copolymers form phase-separated iron-rich, redox-active and preceramic nanodomains in the solid state with applications in nanolithography, nanotemplating, and nanocatalysis. In selective solvents functional micelles with core-shell structures are formed. Block copolymers with a crystallisable PFS core-forming block were the first to be found to undergo "living crystallisation-driven self-assembly" in solution, a controlled method of assembling block copolymers into 1D or 2D structures that resembles a living covalent polymerisation, but on a longer length scale of 10 nm-10 μm.

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A Novel Crystallization Scheme in Poly[styrene‐block‐(ferrocenyl dimethylsilane)] Diblock Copolymers

Cited by 8 publications

References 78 publications

Structure Formation of Metallopolymer-Grafted Block Copolymers

Structure Formation of Metallopolymer-Grafted Block Copolymers

Precise and Controllable Assembly of Block Copolymers^†

Polyferrocenylsilanes: synthesis, properties, and applications

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A Novel Crystallization Scheme in Poly[styrene‐block‐(ferrocenyl dimethylsilane)] Diblock Copolymers

Cited by 8 publications

References 78 publications

Structure Formation of Metallopolymer-Grafted Block Copolymers

Structure Formation of Metallopolymer-Grafted Block Copolymers

Precise and Controllable Assembly of Block Copolymers†

Polyferrocenylsilanes: synthesis, properties, and applications

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Product

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Precise and Controllable Assembly of Block Copolymers^†