Synthetic approaches for multiblock copolymers

Beyer, Valentin P.; Kim, Jungyeon; Becer, C. Remzi

doi:10.1039/c9py01571j

Cited by 64 publications

(67 citation statements)

References 169 publications

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“…Conventionally, linear polymers (i.e., multi block polymers 118 ) or non‐linear polymers (i.e., star polymers, 119 bottle brush polymers 120 etc.) were prepared either by sequential polymerization of various monomer units using inherently compatible polymer chemistries (i.e., two anionic, ROP etc.)…”

Section: Role Of Initiators and Catalysts In Orthogonal Polymerization Systemsmentioning

confidence: 99%

Orthogonal synthesis and modification of polymer materials

Shahrokhinia

Biswas

Reuther

2021

Journal of Polymer Science

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In this review, we detail the progress throughout the years toward developing truly orthogonal polymerization mechanisms and modification procedures en route to complex macromolecular structures built from synthetic polymer materials. The orthogonal modifications of polymer side‐chains and end‐groups via sequential click reactions is described providing post‐polymerization routes to functional materials and unique polymer topologies. Further, historical and modern orthogonal polymerization methodologies are thoroughly reviewed showing the evolution of the field through the decades long study of selective polymerization mechanisms that provide unique copolymer structures that are typically difficult to achieve. These include the combinations of reversible deactivation radical polymerization mechanisms with a variety of polymerization mechanisms including ring opening polymerizations, ring opening metathesis polymerizations, and cationic polymerizations, to name a few.

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Section: Role Of Initiators and Catalysts In Orthogonal Polymerization Systemsmentioning

confidence: 99%

Orthogonal synthesis and modification of polymer materials

Shahrokhinia

Biswas

Reuther

2021

Journal of Polymer Science

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“…Even a moderate tendency toward blockiness in the monomer unit distribution can result in considerably different properties relative to completely random polymers of the same composition [ 1 , 2 , 3 , 4 , 5 ]. Recent reviews [ 6 , 7 , 8 , 9 , 10 ] discuss a number of well-established techniques nowadays available for the synthesis of multiblock copolymers. Depending on the synthetic conditions, the monomer unit order in copolymer chains varies from fully determined in the so-called sequence-defined polymers [ 11 ] to statistical in the products of macromolecular reactions, such as post-modification, end coupling, or interchain exchange [ 12 ].…”

Section: Introductionmentioning

confidence: 99%

Multiblock Copolymers of Norbornene and Cyclododecene: Chain Structure and Properties

et al. 2021

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We investigate the structure–property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By adjusting the reaction time, catalyst amount, and composition of the initial system, we obtain a set of statistical multiblock copolymers that differ in the composition and average length of norbornene and dodecenylene unit sequences. Structural, thermal, and mechanical characterization of the copolymers with NMR, XRD, DSC (including thermal fractionation by successive self-nucleation and annealing), and rotational rheology allows us to relate the reaction conditions to the average length of crystallizable unit sequences, thicknesses of corresponding lamellas, and temperatures of their melting. We demonstrate that isolated dodecenylene units can be incorporated into crystalline lamellas so that even nearly random copolymers should retain crystallinity. Weak high-temperature endotherms observed in the multiblock copolymers of norbornene with cyclododecene and other cycloolefins could indicate that the corresponding systems are microphase-separated in the melt state.

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“…13,14 Controlled radical polymerization has also made a significant step towards this goal through the synthesis of sequence-controlled multiblock copolymers yielding complex structures with unlimited variations in chain length, composition and encoded information. 3,15 Importantly, the synthesis of sequence-controlled multiblocks is scalable, applicable to higher molecular weight polymers and amenable to non-experts, in particular when combined with simple and one pot processes that do not necessitate the use of any specialized equipment. 3 Such materials have already shown great promise in a range of applications where sequence has been demonstrated to determine fundamental polymer properties and applications (e.g.…”

Section: Introductionmentioning

confidence: 99%

Concurrent Control over Sequence and Dispersity in Multiblock Copolymers

Antonopoulou¹,

Whitfield²,

Truong³

et al. 2020

Preprint

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Controlling monomer sequence in synthetic macromolecules is a major challenge in polymer science and the order of building blocks has already been demonstrated to determine macromolecular folding, self-assembly and fundamental polymer properties. Dispersity is another key parameter in material design, with both low and high dispersity polymers displaying complementary properties and functions. However, synthetic approaches that can simultaneously control both sequence and dispersity remain experimentally unattainable. Here we report a simple, one pot, and rapid synthesis of sequence-controlled multiblocks with on demand control over dispersity while maintaining high livingness, excellent agreement between theoretical and experimental molecular weights and quantitative yields. Key to our approach is the regulation in chain transfer agent activity during controlled radical polymerization that enables the preparation of multiblocks with gradually ascending (Ɖ=1.16 →1.60), descending (Ɖ=1.66 →1.22), alternating low and high dispersity values (Ɖ=1.17 →1.61 →1.24 →1.70 →1.26) or any combination thereof. The enormous potential of our methodology was further demonstrated through the impressive synthesis of highly ordered pentablock, octablock and decablock copolymers yielding the first generation of multiblocks with concurrent control over both sequence and dispersity.

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Synthetic approaches for multiblock copolymers

Abstract: Multiblock copolymers (MBCs) are an emerging class of synthetic polymers that exhibit different macromolecular architectures and behaviours to those of homopolymers or di/triblock copolymers.

Cited by 64 publications

References 169 publications

Orthogonal synthesis and modification of polymer materials

Orthogonal synthesis and modification of polymer materials

Multiblock Copolymers of Norbornene and Cyclododecene: Chain Structure and Properties

Concurrent Control over Sequence and Dispersity in Multiblock Copolymers

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