Aperiodic Copolymers

Lutz, Jean‐François

doi:10.1021/mz5004823

Cited by 62 publications

(58 citation statements)

References 50 publications

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“…While early approaches in the field of sequence control usually employed controlled radical polymerizations to synthesize controlled polymers, more recent approaches are often based on stepwise iterative synthesis methods, because only in the latter case can monodisperse and sequence‐defined macromolecules be obtained. However, nomenclature in the field of sequence control is not strictly defined yet and the terms sequence controlled and sequence defined are not used consistently . Throughout this review, we describe monodisperse macromolecules with perfectly defined monomer sequences, where the position of every monomer unit within the macromolecule is exactly known and monodisperse macromolecules are obtained.…”

Section: Introductionmentioning

confidence: 99%

“…

and sequence defined are not used consistently. [3][4][5] Throughout this review, we describe monodisperse macro molecules with perfectly defined monomer sequences, where the position of every monomer unit within the macromolecule is exactly known and monodisperse macromolecules are obtained. Due to the multitude of syn thetic approaches yielding monodisperse macromolecules, with different levels of control (control over sequence, side chains, backbone, and stereochemistry) as well as different reaction scales and molecular structures, these approaches are thoroughly summarized and compared to one another herein.

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confidence: 99%

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Recent Progress in the Design of Monodisperse, Sequence-Defined Macromolecules

Solleder

Schneider

Wetzel

et al. 2017

Macromol. Rapid Commun.

181

173

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This review describes different synthetic strategies towards sequence-defined, monodisperse macromolecules, which are built up by iterative approaches and lead to linear non-natural polymer structures. The review is divided in three parts: solution phase-, solid phase-, and fluorous- and polymer-tethered approaches. Moreover, synthesis procedures leading to conjugated and non-conjugated macromolecules are considered and discussed in the respective sections. A major focus in the evaluation is the applicability of the different approaches in polymer chemistry. In this context, simple procedures for monomer and oligomer synthesis, overall yields, scalability, purity of the oligomers, and the achievable level of control (side-chains, backbone, stereochemistry) are important benchmarks.

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Section: Introductionmentioning

confidence: 99%

“…

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mentioning

confidence: 99%

Recent Progress in the Design of Monodisperse, Sequence-Defined Macromolecules

Solleder

Schneider

Wetzel

et al. 2017

Macromol. Rapid Commun.

181

173

View full text Add to dashboard Cite

show abstract

“…In particular, very interesting progress has been made using controlled radical polymerization methods . However, the sequence‐controlled polymers obtained via these methods are still polydisperse and contain sequence defects . Some new applications of polymers, for example, in the field of data storage, may require macromolecules with perfectly controlled chain lengths and primary structures.…”

Section: Introductionmentioning

confidence: 99%

“…[39][40][41][42][43] However, the sequence-controlled polymers obtained via these methods are still polydisperse and contain sequence defects. [ 44,45 ] Some new applications of polymers, for example, in the fi eld of data storage, [ 31,46 ] may require macro molecules with perfectly controlled chain lengths and primary structures. In order to synthesize monodisperse sequence-defi ned polymers, new synthetic methods have to be identifi ed.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Monodisperse Sequence‐Defined Polymers Using Protecting‐Group‐Free Iterative Strategies

Trinh

Laure

Lutz

2015

Macro Chemistry & Physics

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The synthesis of “precision” polymers with finely controlled molecular structures is an important new development in synthetic polymer chemistry. This trend is the logical outcome of the continuing evolution of the field of polymer synthesis. Indeed, during the last few decades, synthetic tools, such as living ionic polymerizations, controlled radical polymerizations, and click chemistry, have revolutionized the synthesis of polymers with controlled architectures such as block, graft, star, brush, hyperbranched or cyclic polymers. These aspects being solved, it is now time for polymer chemists to address more challenging questions such as the design of monodisperse polymers and the control of primary (i.e., comonomer sequences), secondary (i.e., single‐chain folding), and tertiary (i.e., single‐chain compartmentalization) structures. Here, new synthetic tools have to be developed or imported from other disciplines such as organic chemistry and biochemistry. For instance, solid‐phase iterative chemistry, which was initially introduced for the synthesis of oligopeptides and oligonucleotides, is an interesting methodology for preparing monodisperse sequence‐defined polymers. However, such approaches are usually time‐consuming and request demanding coupling/capping/deprotection steps. Yet, interesting protecting‐group‐free methodologies have been described in recent years for simplifying and accelerating these processes. These promising new approaches are briefly listed and explained in this article.

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“…There also exists more specialized types of randomness such as gradient, tapered, and inverse‐tapered sequences. Indeed, the variability of classes of nondeterministic polymeric sequences available within current technical capabilities is stretching the limits of the usual nomenclature …”

Section: Introductionmentioning

confidence: 99%

Effects of Blockiness and Polydispersity on the Phase Behavior of Random Block Copolymers

Vanderwoude

Shi

2016

Macro Theory & Simulations

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The effects of blockiness and compositional/sequential polydispersity on the order–disorder transition of random block copolymers are studied using a segment model of random block copolymers. Specifically, the copolymers are randomly assembled from a collection of equal‐length “segments,” while the characteristics of the segments are chosen according to the nature of the polydispersity. The phase behavior of the model system is examined using the random phase approximation. The critical points of the system are calculated over a range of blockiness and polydispersity for a variety of segment models. It is observed that the critical value of the Flory–Huggins parameter χ, above which the homogeneous phase becomes unstable, is inversely proportional to the blockiness. Furthermore, it is found that sequential and compositional dispersity decreases the critical value of χ, but that the effect of sequential dispersity is much weaker. At sufficiently large compositional dispersity, the random block copolymers can undergo macrophase separation. In this region of phase space, the critical point is entirely determined by the compositional polydispersity.

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Aperiodic Copolymers

Cited by 62 publications

References 50 publications

Recent Progress in the Design of Monodisperse, Sequence-Defined Macromolecules

Recent Progress in the Design of Monodisperse, Sequence-Defined Macromolecules

Synthesis of Monodisperse Sequence‐Defined Polymers Using Protecting‐Group‐Free Iterative Strategies

Effects of Blockiness and Polydispersity on the Phase Behavior of Random Block Copolymers

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