Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

Neve, Jeroen De; Haven, Joris J.; Harrisson, Simon; Junkers, Thomas

doi:10.1002/ange.201906842

Cited by 14 publications

(7 citation statements)

References 36 publications

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“…For these reasons, some researchers have gone to great lengths to produce monodisperse samples of conjugated polymers. These include constructing them in a discrete manner through stepwise synthesis, − single couplings between Fibonacci numbers, manual separation of chain lengths, , and polymerizing from a template . The high degree of effort required and rapidly diminishing returns at higher weights limit wider applications.…”

mentioning

confidence: 99%

Homogenous Synthesis of Monodisperse High Oligomers of 3-Hexylthiophene by Temperature Cycling

McKeown

Cheng

et al. 2019

J. Am. Chem. Soc.

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Whereas monodisperse polymers are ubiquitous in Nature, they remain elusive to synthetic chemists. Absolute control over polymer length and structure is essential to imparting chemical functionality, reproducible properties, and specific solid-state behavior. Precise polymer length has proven to be extremely difficult to control. The most successful examples are generally similar to solid-phase oligo nucleotide or peptide synthesis, wherein the polymer is built up one unit at a time with each sequential monomer addition requiring purification and deprotection (or other functional group activation) step. We have discovered a stepwise homogeneous catalyst-transfer polymerization to prepare monodisperse oligo(3-hexylthiophene) using temperature to limit additions to one unit per chain per cycle. This is the first reported example of a one-pot synthesis of monodisperse oligomers that requires no additional purification or intermediate steps. It is our hope that the strategy of temperature cycling to "freeze" intermediates will be generalizable to other living polymerization techniques, such as other catalyst-transfer polymerization systems, and those where a resting state involves an association between the catalyst and growing chain.

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confidence: 99%

Homogenous Synthesis of Monodisperse High Oligomers of 3-Hexylthiophene by Temperature Cycling

McKeown

Cheng

et al. 2019

J. Am. Chem. Soc.

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“…De Neve et al used for example monodisperse oligomers made from RAFT polymerization and mixed those in specific quantities, showcasing how designer MWDs can be elegantly created. [30] On the other hand, however, they also highlighted that the creation of really broad distributions is challenging. Achieving any designer distribution that is significantly broader than Ð = 2 is also here a problem.…”

Section: Blending Of Polymer Distributionsmentioning

confidence: 99%

Polymers in the Blender

Junkers

2020

Macro Chemistry & Physics

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Ever since the birth of controlled polymerizations, polymer synthesis always strived toward distributions that are as narrowly dispersed as possible. Yet, such polymers are not always advantageous, and only recently methods have started to develop that allow to create polymers with controllable molecular weight and dispersity. Stretching beyond that, there are also now tools to create distributions of any shape. This level of control, even if this is just the start of these endeavors, has tremendous potential for developing materials with superior and more precise physical properties. The principles for the synthesis of different molecular weight distributions shapes are introduced and discussed.

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“…[2][3][4] To tune the Tg of linear polymers, synthetic and practical strategies have been developed to tailor chain length, backbone-and side-chain chemistry, and blend composition. [5][6][7][8][9] Despite such advances, [10][11][12] elucidating the effect of structural parameters on Tg has remained a continuing grand challenge for linear polymers 13,14 and a greater one for non-linear architectures due to a combination of sidechain and backbone dispersities. 12,13,[15][16][17][18] Controlling dispersity, the inherent structural heterogeneity of synthetic polymers, is paramount for elucidating their structure-property relationships.…”

Section: Introductionmentioning

confidence: 99%

“…[5][6][7][8][9] Despite such advances, [10][11][12] elucidating the effect of structural parameters on Tg has remained a continuing grand challenge for linear polymers 13,14 and a greater one for non-linear architectures due to a combination of sidechain and backbone dispersities. 12,13,[15][16][17][18] Controlling dispersity, the inherent structural heterogeneity of synthetic polymers, is paramount for elucidating their structure-property relationships. A small variation in dispersity has a significant impact on the optoelectronic, 19,20 NMR dynamics, 21 and self-assembly behaviors of linear oligomers and polymers.…”

Section: Introductionmentioning

confidence: 99%

Elucidating the Impact of Structural Parameters on the Glass Transition Temperatures of Bottlebrush Polymers

Dearman

Ogbonna

Amofa

et al. 2022

Preprint

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The glass transition of branched polymers is determined by multiple structural parameters that dictate their inter- and intramolecular interactions, and ultimately, their molecular packing in the amorphous phase. Here we examined the impact of side chain length, backbone length, molecular weight composition, and topology on the glass transition behavior of bottlebrush polymers. Through examining precision bottlebrush polymer libraries (PBP, ĐSC = 1.0), we find the infinite molecular weight Tg is reached at a specific brush length after which the effect of the side-chain length dominates. Being a factor more dominant than the backbone, side-chain length affects the Tg of bottlebrush polymers across all sizes and topology variations. To demonstrate the versatility of side chain engineering strategies, a broad range of Tg and glass transition behavior was targeted through judicious choice of side chain length, blend ratios, and brush topology.

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Deconstructing Oligomer Distributions: Discrete Species and Artificial Distributions

Cited by 14 publications

References 36 publications

Homogenous Synthesis of Monodisperse High Oligomers of 3-Hexylthiophene by Temperature Cycling

Homogenous Synthesis of Monodisperse High Oligomers of 3-Hexylthiophene by Temperature Cycling

Polymers in the Blender

Elucidating the Impact of Structural Parameters on the Glass Transition Temperatures of Bottlebrush Polymers

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