Rapid one-pot synthesis of tapered star copolymers <i>via</i> ultra-fast coupling of polystyryllithium chain ends

Tiedemann, P.; Maciol, Kamil; Preis, Jasmin; Frey, Holger

doi:10.1039/c8py01656a

Cited by 8 publications

(18 citation statements)

References 47 publications

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“…This block sequence does not generate any dangling ends from unanchored PI blocks, which are known to reduce the elasticity of the polymer network. 34,88−91 Instead of a conventional five-step sequential synthesis procedure, three steps (Scheme 1) were followed: ( 13 The same quantity of styrene was used in the first and second monomer charges.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…This CA possesses maximized reactivity with respect to living anionic polymer chain ends because of the monochlorosilane moieties and partially alleviates steric constraints because of the propyl spacers. 13 To further accelerate the coupling reaction, the CA was added as a solution in THF. The fading of the orange color of the solution (resulting from PSLi living chain ends, see Figure S2 in the Supporting Information) indicates coupling conversion and therefore was utilized to qualitatively assess the necessary reaction times.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Whereas 1 H NMR spectroscopy is convenient to analyze the degree of PI hydrogenation, the possibility of partial hydrogenation of PS to poly(vinylcyclohexane), PVCH, cannot be assessed because of signal overlap. 13 C NMR analysis was used to ensure no hydrogenation of styrene units occurred. Figure S5 in the Supporting Information displays the 13 C NMR spectrum of (SEP/S) 4 -60-240.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…10−12 We recently introduced tetra[3-(chloro-dimethylsilyl)propyl]silane (TCDMSPS) as a new CA, with maximized reactivity toward living polymer chains and less-dense cores to improve the coupling efficiency. 13 The addition of tetrahydrofuran (THF) is known to increase the coupling rate of polybutadienyl-and polyisoprenyllithium with chlorosilanes, as first observed by Mays and co-workers 14,15 and quantified by Burns and Register. 16 Combining these two principles, the rapid synthesis of low-dispersity tapered star copolymers with arms of the type poly(isoprene-grad-styrene) was achieved without the need for further purification beyond precipitation.…”

Section: ■ Introductionmentioning

confidence: 94%

“…16 Combining these two principles, the rapid synthesis of low-dispersity tapered star copolymers with arms of the type poly(isoprene-grad-styrene) was achieved without the need for further purification beyond precipitation. 13 The formation of such "tapered" copolymers in a more general sense dates back to 1969 with the work of Kraus et al 7,17 and Worsfold. 18 Diene monomers are known to form block-like structures with styrene or alkylstyrenes during statistical copolymerization in apolar media.…”

Section: ■ Introductionmentioning

confidence: 99%

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Tapered Multiblock Star Copolymers: Synthesis, Selective Hydrogenation, and Properties

et al. 2020

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Two series of well-defined multiblock four-arm tapered star copolymers with "arms" of the type poly(styrene)block-poly(isoprene-grad-styrene), (SI/S) 4 , were synthesized on a multigram scale with short reaction times. Targeted molecular weight (M) values ranged from 80 to 240 kg mol −1 with polystyrene (PS) compositions of 40 and 60 wt %. Narrowly distributed (Đ = 1.04−1.12) copolymers were obtained regardless of M and without additional purification beyond precipitation. At sufficiently high M, members of the 40 wt % PS series possessed either a cylindrical or bicontinuous morphology, whereas the 60 wt % PS series yielded lamellae. The star copolymers outperformed their corresponding linear analogues with respect to ultimate toughness and elongation at break. Young's moduli of up to 304 ± 11 MPa were reached, and the overall toughest (83 ± 2 MJ/m 3 ) star copolymer exhibited the highest strain at break (1198 ± 34%). Catalytic hydrogenation of the PI segments was achieved selectively without saturation of styrene units at conversions of ≥98%. More pronounced strain hardening occurred upon hydrogenation. Modulus, toughness, and ultimate strength of the linear tapered copolymer increased substantially upon hydrogenation to poly(styrene)-block-poly((ethylene-alt-propylene)-grad-styrene), SEP/S. However, these mechanical properties for the star copolymer were found to decrease upon hydrogenation to (SEP/S) 4 . These materials, particularly the unsaturated multiblock stars of the highest M, are promising candidates for future advanced materials that require extremely tough elastomers.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 94%

Section: ■ Introductionmentioning

confidence: 99%

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Tapered Multiblock Star Copolymers: Synthesis, Selective Hydrogenation, and Properties

et al. 2020

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Fast and Scalable Synthetic Route to Densely Grafted, Branched Polystyrenes and Polydienes via Anionic Polymerization Utilizing P2VP as Branching Point

Schußmann,

Kreutzer,

Hirschberg

2024

Macromol. Rapid Commun.

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Defined, branched polymer architectures with low dispersity and architectural purity are of great interest to polymer science but are challenging to synthesize. Besides star and comb, especially the pom‐pom topology is of interest as it is the simplest topology with exactly two branching points. Most synthetic approaches to a pom‐pom topology reported lack full control and variability over one of the three topological parameters, the backbone or arm molecular weight and arm number. A new, elegant, fast, and scalable synthetic route without the need of post polymerization modification (PPM) or purification steps during the synthesis to a pom‐pom and a broad variety of topologies made from styrene and dienes is reported, with potential application to barbwire, bottlebrush, mikto‐arm star, Janus type polymers, or multi‐graft copolymers. The key is to inset short Poly(2‐vinyl‐pyridine) blocks (< 2 mol% in the branched product) into the backbone as branching points. Carb anions can react at the C6 carbon of the pyridine ring, grafting the arms onto the backbone. Since the synthetic route to PS pom‐poms has only two steps and is free of PPM or purification, large amounts of up to 300 g of defined pom‐pom structures could be synthesized in one batch.This article is protected by copyright. All rights reserved

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Synthesis and microphase separation of dendrimer-like block copolymers by anionic polymerization strategies

Hartmann

Niebuur

Koch

et al. 2023

European Polymer Journal

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Rapid one-pot synthesis of tapered star copolymers via ultra-fast coupling of polystyryllithium chain ends

Abstract: Efficient coupling of sterically demanding polystyryllithium (PS-Li) chain ends is achieved using tetra[3-(chloro-dimethylsilyl)propyl]silane (TCDMSPS) as a linking agent. This general approach is employed for the rapid synthesis of tapered star copolymers.

Cited by 8 publications

References 47 publications

Tapered Multiblock Star Copolymers: Synthesis, Selective Hydrogenation, and Properties

Tapered Multiblock Star Copolymers: Synthesis, Selective Hydrogenation, and Properties

Fast and Scalable Synthetic Route to Densely Grafted, Branched Polystyrenes and Polydienes via Anionic Polymerization Utilizing P2VP as Branching Point

Synthesis and microphase separation of dendrimer-like block copolymers by anionic polymerization strategies

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