Salt-Induced Switching of Microdomain Morphology of Ionically Functionalized Diblock Copolymers

Schöps, M.; Leist, Heike; DuChesne, and Alexander; Wiesner, Ulrich

doi:10.1021/ma9818578

Cited by 31 publications

(35 citation statements)

References 18 publications

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“…The partial structures of BCPs, such as the junction points between blocks and polymer-chain ends, have been found to significantly affect self-assembly behavior. − Recently, Park demonstrated a simple way of tuning the microphase-separated structures generated from polystyrene- block -poly(ethylene oxide) (PS- b -PEO) through modification of the PEO chain-end structure . For example, PS- b -PEO bearing sulfonic acid groups at the PEO chain ends formed a lamellar nanostructure, while the unmodified PS- b -PEO with terminal hydroxyl groups was less ordered, demonstrating that block incompatibility can be controlled by the end groups.…”

Section: Introductionmentioning

confidence: 99%

Chain-End Functionalization with a Saccharide for 10 nm Microphase Separation: “Classical” PS-b-PMMA versus PS-b-PMMA-Saccharide

et al. 2018

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Microphase-separated structures of block copolymers (BCPs) have attracted much attention as template materials for bottom-up nanofabrication. At the same time, chain-end modification has become a leading facile and efficient technique for fine-tuning the morphologies of microphase-separated structures generated from BCPs. Herein, we describe the preparation of well-defined polystyrene-block-poly(methyl methacrylate)s (PS-b-PMMAs) bearing highly hydrophilic mono/oligosaccharide moieties at their PMMA chain ends (SM-mono/oligosaccharides) as well as the impact of the mono/oligosaccharide on microphase separation behavior. PS-b-PMMAs were terminal-selectively transesterified using the titanium alkoxide of 6-azido-1-hexanol to introduce azido groups into the side chains of the terminal MMA units. The azido-functionalized PS-b-PMMAs were subsequently click reacted with ethynyl-functionalized mono/oligosaccharides to yield SM-mono/oligosaccharides. Small-angle X-ray scattering and microscopy experiments reveal that PS-b-PMMAs bearing maltotrioses at their chain ends (SM-MTs), and with total molecular weights of ∼10 kg mol–1, successfully form microphase-separated structures, although the unmodified PS-b-PMMAs exist in miscible states. Interestingly, the SM-MT with equivalent PS- and PMMA-MT-block volume fractions microphase separated to form a hexagonally close-packed cylinder with a domain spacing of 11.5 nm, rather than a lamellar structure, implying that the phase diagram for microphase separation is significantly affected by strong maltotriose aggregation. Hence, the results presented herein demonstrate that the incorporation of oligosaccharide moieties at chain ends is an efficient means of fine-tuning the size features as well as the morphologies of BCP microphase-separated structures.

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Section: Introductionmentioning

confidence: 99%

Chain-End Functionalization with a Saccharide for 10 nm Microphase Separation: “Classical” PS-b-PMMA versus PS-b-PMMA-Saccharide

et al. 2018

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“…Block copolymers have attracted widespread attention due to their intriguing ability to self‐assemble into different sophisticated structures, which are primarily governed by crystallization process and microphase separation . The complicated nanoscale block copolymer assemblies have promising applications in numerous fields, such as waveguides, electronic and optoelectronic devices, and biomineralization mimics . Thus, to fabricate functional nanostructures with various morphologies, it is required to further understand the crystallization mechanism of block copolymers and also interplay between crystallization and microphase separation.…”

Section: Introductionmentioning

confidence: 99%

Competition Between Interfacial Interaction and Microphase Separation in Crystallization of Filled Block Copolymers

Liu

Zhou

Liu

et al. 2019

J Polym Sci B Polym Phys

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Understanding the effect of repulsive interaction between blocks on crystallization in block copolymers is beneficial for the design and development of sophisticated nanostructures. Dynamic Monte Carlo simulations were performed to reveal the crystallization mechanism of block copolymers containing onedimensional nanofiller under different repulsive interaction strengths between crystallizable and noncrystallizable blocks. During crystallization, crystalline morphology is determined by the competition between segmental orientation perpendicular to microphase interfaces dominated by microphase separation and that along the direction of the long axis of the nanofiller controlled by interfacial interaction. As the repulsive interaction between different blocks is strengthened, the competition between microphase separation and interfacial interaction is intensified, eventually leading to an increase in crystallization rate and a degradation in crystalline morphology.

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“…[1] The presence of functional groups along the chains could lead to significant changes in their behavior in the solid state and in solution. [2] A particular challenge is the preparation of primary amino-functionalized polymers. [3] Primary amines undergo a variety of reactions and are usually used to initiate the ring-opening polymerization of N-carboxyanhydrides of a-amino acids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Poly(ethylene oxide)s Bearing Functional Groups along the Chain

Dimitrov

Berlinova

2003

Macromol. Rapid Commun.

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Well‐defined poly(ethylene oxide)s (PEOs) bearing reactive sites regularly distributed along the chain have been synthesized by the polycondensation of PEO containing a central tertiary amino group with dichloromethane, followed by quaternization with suitable reagents to obtain polyzwitterionic or cationic PEOs with alkyl, allyl, or fluorocarbon pendant groups. The pendant allyl groups have been converted into primary amino groups by reaction with 2‐aminoethanethiol hydrochloride to obtain polyamino‐functionalized PEO.Polyfunctional PEOs bearing different pendant groups.magnified imagePolyfunctional PEOs bearing different pendant groups.

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Salt-Induced Switching of Microdomain Morphology of Ionically Functionalized Diblock Copolymers

Cited by 31 publications

References 18 publications

Chain-End Functionalization with a Saccharide for 10 nm Microphase Separation: “Classical” PS-b-PMMA versus PS-b-PMMA-Saccharide

Chain-End Functionalization with a Saccharide for 10 nm Microphase Separation: “Classical” PS-b-PMMA versus PS-b-PMMA-Saccharide

Competition Between Interfacial Interaction and Microphase Separation in Crystallization of Filled Block Copolymers

Synthesis of Poly(ethylene oxide)s Bearing Functional Groups along the Chain

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