Stochastic Simulation of Controlled Radical Polymerization Forming Dendritic Hyperbranched Polymers

Tosaka, Masatoshi; Takeuchi, Hinako; Kibune, Masato; Tong, Tianxiang; Zhu, Nanyi; Yamago, Shigeru

doi:10.1002/anie.202305127

Cited by 7 publications

(10 citation statements)

References 32 publications

(7 reference statements)

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“…BA [b] (%) The larger Ð value compared to that usually observed in linear polymer synthesis is due to the distribution of the number of branches. [16] All these results support the successful synthesis of HBPBA with a controlled structure. The polymer particle determined by dynamic light scattering (DLS) was reasonably controlled with an average diameter (d) of 143 nm and with a polydispersity index (PDI) of 0.14.…”

Section: Tablesupporting

confidence: 59%

“…While the dispersity of the resulting 3 was usually moderate (Ð = 1.5-2), our recent stochastic simulation of the formation process of 3 revealed that the moderate Ðs come from the distribution of the number of branches and that all the polymers have a wellcontrolled branched structure. [16] Furthermore, the (pseudo) generation (G) can be defined like dendrimers. Therefore, this type of HBPs can be named dendritic HBPs.…”

Section: Introductionmentioning

confidence: 99%

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Practical Synthesis of Dendritic Hyperbranched Polyacrylates and Their Topological Block Polymers by Organotellurium‐Mediated Emulsion Polymerization in Water**

et al. 2023

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The practical synthesis of structurally controlled hyperbranched polymers (HBPs) by organotellurium‐mediated radical polymerization (TERP) in water under emulsion conditions is reported. Copolymerization of vinyltelluride named evolmer, which induces controlled branch structure, and acrylates with TERP chain transfer agent (CTA) in water afforded HBPs having dendron structure. The molecular weight, dispersity, branch number, and branch length of the HBPs were controlled by changing the amount of CTA, evolmer, and acrylate monomers. HB‐poly(butyl acrylate)s (HBPBAs) with up to the 8th generation having an average of 255 branches were successfully synthesized. As the monomer conversion reached nearly quantitative and the obtained polymer particles were well dispersed in water, the method is highly suitable for synthesizing topological block polymers, block polymers consisting of different topologies. Thus, linear‐block‐HB, HB‐block‐linear, and HB‐block‐HB‐PBAs with the controlled structure were successfully synthesized by adding the second monomer(s) to the macro‐CTA. The intrinsic viscosity of the resulting homo‐ and topological block PBAs was systematically controlled by the degree of the branch, the branch length, and the topology. Therefore, the method opens the possibility of obtaining various HBPs with diverse branch structures and tuning the polymer properties by the polymer topology.

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Section: Tablesupporting

confidence: 59%

Section: Introductionmentioning

confidence: 99%

Practical Synthesis of Dendritic Hyperbranched Polyacrylates and Their Topological Block Polymers by Organotellurium‐Mediated Emulsion Polymerization in Water**

et al. 2023

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“…Furthermore, the bioconjugates exhibited a slightly broader molecular weight distribution, arising from the distribution of branching junctions during the copolymerization, a characteristic feature for copolymers with inibramers. 48,49 The copolymerization kinetics were studied to determine the relative rate of incorporation of the inibramer into the branched copolymer grafts. The EY/Cu-catalyzed CRBP was performed using molar ratios of [CBMA]/[SBA]/[CT-iBBr 12 ]/[EYH 2 ]/[CuBr 2 ]/[TPMA] = 200/12/0.08/0.01/0.2/ 0.6.…”

Section: Ct-branched Polymer Conjugatesmentioning

confidence: 99%

“…This inaccuracy in measurement was ascribed to gel formation observed during the synthesis of protein bioconjugates due to excessive radical generation. Furthermore, the bioconjugates exhibited a slightly broader molecular weight distribution, arising from the distribution of branching junctions during the copolymerization, a characteristic feature for copolymers with inibramers. , …”

Section: Synthesis and Characterization Of Ct-branched Polymer Conjug...mentioning

confidence: 99%

Tailored Branched Polymer–Protein Bioconjugates for Tunable Sieving Performance

Kapil,

Murata,

Szczepaniak

et al. 2024

ACS Macro Lett.

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Protein−polymer conjugates combine the unique properties of both proteins and synthetic polymers, making them important materials for biomedical applications. In this work, we synthesized and characterized protein-branched polymer bioconjugates that were precisely designed to retain protein functionality while preventing unwanted interactions. Using chymotrypsin as a model protein, we employed a controlled radical branching polymerization (CRBP) technique utilizing a water-soluble inibramer, sodium 2bromoacrylate. The green-light-induced atom transfer radical polymerization (ATRP) enabled the grafting of branched polymers directly from the protein surface in the open air. The resulting bioconjugates exhibited a predetermined molecular weight, well-defined architecture, and high branching density. Conformational analysis by SEC-MALS validated the controlled grafting of branched polymers. Furthermore, enzymatic assays revealed that densely grafted polymers prevented protein inhibitor penetration, and the resulting conjugates retained up to 90% of their enzymatic activity. This study demonstrates a promising strategy for designing protein−polymer bioconjugates with tunable sieving behavior, opening avenues for applications in drug delivery and biotechnology.

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“…Alternatively, computer simulations can be conducted, which have been already recognized as an effective tool to probe the reaction kinetics of traditional (nonexchangeable; static) cross-linked systems. − Specifically, stochastic kinetic Monte Carlo ( k MC) simulations are capable of simulating the cross-linking process with abundant structural information storage. − Such simulations can quantitatively predict the changes of microscopic properties with the extent of reaction under different reaction conditions but can also record the compositional evolution of individual species in an sufficiently large polymer ensemble during cross-linking. , For example, utilizing coupled matrix based Monte Carlo (CMMC), De Smit et al highlighted that reaction conditions for (epoxy-amine-acetoacetate)-based vitrimers need to be optimized to enable a maximization of the number of dynamic groups in a given molecule.…”

Section: Introductionmentioning

confidence: 99%

The Dynamic Interplay of Cross-Linking and Exchange Reaction Probabilities during Vitrimer Synthesis: A Monte Carlo Approach

Liu,

Jin,

Conka

et al. 2024

Macromolecules

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Covalent adaptable networks (CANs) are based on an associative exchange mechanism, and hence, vitrimers have been shown to be an attractive candidate for the synthesis of sustainable cross-linked materials due to synergetic structural stability and reprocessability. Herein, matrix-based kinetic Monte Carlo (kMC) simulations are performed to increase our mechanistic understanding of vitrimer synthesis, selecting step-growth vinylogous carbamothioate (VC)-based CANs as dynamic chemistry. Novelties are (i) the consideration of 8 elementary reaction categories differentiating between cross-linking and exchange reactions as well as inter- and intramolecular reactions (22 in total); and (ii) a dedicated tuning strategy of both intrinsic and diffusion parameters, employing experimental data from Fourier transform infrared spectroscopy and rheological measurements. Upon a model validation at different temperatures (30–60 °C), revealing a key role for mobility constraints due to viscosity increases, emphasis is on the evolution of molecular properties such as the branching density, the reduced mass-average degree of polymerization, the mass-average molar mass, and the mass fraction of the sol, to understand the relationship of kinetics, reaction probabilities, and molecular network properties. The simulation results demonstrate that increasing the temperature to, e.g., 60 °C, sufficiently promotes the exchange rate, leading to a gel point realization at higher conversion enabling the production of more uniform cross-linked structures. They also show that at higher yield, more intramolecular reactions come in to play, complicating the network structural arrangement. It is further shown that the traditional Flory and Macosko–Miller theories are no longer applicable to predicting gel points and molecular properties in dynamic network systems with higher exchange rates. Moreover, the generation of branched and cross-linked structures can be delayed with the increase of the molar ratio of primary amine groups to acetoacetate groups. The current study provides an in-depth understanding of the reaction kinetics for the synthesis of VC-based CANs, and it is an important step toward a generalized elementary reaction step driven kinetic model as well as chemistry design for vitrimer synthesis.

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Stochastic Simulation of Controlled Radical Polymerization Forming Dendritic Hyperbranched Polymers

Cited by 7 publications

References 32 publications

Practical Synthesis of Dendritic Hyperbranched Polyacrylates and Their Topological Block Polymers by Organotellurium‐Mediated Emulsion Polymerization in Water**

Practical Synthesis of Dendritic Hyperbranched Polyacrylates and Their Topological Block Polymers by Organotellurium‐Mediated Emulsion Polymerization in Water**

Tailored Branched Polymer–Protein Bioconjugates for Tunable Sieving Performance

The Dynamic Interplay of Cross-Linking and Exchange Reaction Probabilities during Vitrimer Synthesis: A Monte Carlo Approach

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