Direct through anionic, cationic, and radical active species: Terminal carbon–halogen bond for “controlled”/living polymerizations of styrene

Satoh, Kotaro; Mori, Yoshiko; Kamigaito, Masami

doi:10.1002/pola.29261

Cited by 6 publications

(6 citation statements)

References 52 publications

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“…Three parallel simulation runs are performed to eliminate the statistical error, and the error bars shown in Figure c are smaller than the symbols. The obtained k ave (∞) = 9.60 × 10 –16 ns –1 are numerically close to the experimental measurements of the kinetics of living free radical polymerization of PS, and k ave (∞) is further used in the numerical integration of the kinetic equation of chain growth, d[ M ]/d t = − k ave [ M ]. The integrated kinetic behavior is compared to experimental data in Figure d.…”

Section: Resultssupporting

confidence: 73%

“…The kinetics behavior of the PS chain growth is linearly dependent on the conversion ratio p , and the reaction conversion reaches 99.8% at 370 K for a 10 ns MD run. The average number molecular weight of the product is 5187, and the polydispersity index ( M w / M n ) converges into 1.04 (1.06 and 1.13 in experiments), showing a narrow distribution of the molecular weight of the PS product (Figure b). The chain length statistics at different stages presented in Figure c follow the normal distribution.…”

Section: Resultsmentioning

confidence: 99%

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Reactive Molecular Simulation with Size Extrapolation to Bridge the Polymerization Mechanism and Kinetics

Chen,

Wu,

et al. 2024

Macromolecules

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Reactive molecular dynamics (MD) is performed to simulate polymerization and bridge the microscopic reaction behavior with kinetics. The reaction rate constant computed by MD simulations shows size dependence and can be extrapolated to estimate the corresponding rate constant at the macroscopic scale. Polymerization of Lennard-Jones monomers with a free radical mechanism is simulated to demonstrate that the reactive simulation with size extrapolation is capable of the qualitative modeling reaction kinetics of chain growth and chain transfer reactions. The approach is extended to the polymerization of polystyrene (PS) by a living free radical polymerization mechanism, in which ethylbenzene is represented by all-atom and coarse-grained molecular representations. The kinetics behavior of PS chain growth agrees favorably with experiments, and the yielded PS product displays a narrow distribution with a polydispersity index of 1.04 for >90% conversion of styrene monomers. The comparisons of simulation results between all-atom and coarse-grained models show that the kinetics and reaction dynamics of the polymerization of PS are consistent at both levels. The method demonstrates the possibility of using reactive MD with size extrapolation to model the polymerization kinetics of real systems, which paves the way toward large-scale modeling of polymerization bridging the reaction mechanism and kinetics and further provides new insights into reaction kinetics from a computational perspective.

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Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Reactive Molecular Simulation with Size Extrapolation to Bridge the Polymerization Mechanism and Kinetics

Chen,

Wu,

et al. 2024

Macromolecules

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“…A mechanistic transformation study was conducted by Satoh et al, 360 in which PS done from living anionic polymerization is transformed to a macroinitiator capable of undergoing either controlled radical polymerization or living cationic polymerization by direct halogenation of PS. The living anionic polymerization was conducted with typical conditions, inert environment, and sec-BuLi as initiator, however, the resulting polymer in this case was involved in direct halogenation by CCl 4 .…”

Section: Living Anionic Polymerizationmentioning

confidence: 99%

Linear Block Copolymer Synthesis

et al. 2022

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Block copolymers form the basis of the most ubiquitous materials such as thermoplastic elastomers, bridge interphases in polymer blends, and are fundamental for the development of high-performance materials. The driving force to further advance these materials is the accessibility of block copolymers, which have a wide variety in composition, functional group content, and precision of their structure. To advance and broaden the application of block copolymers will depend on the nature of combined segmented blocks, guided through the combination of polymerization techniques to reach a high versatility in block copolymer architecture and function. This review provides the most comprehensive overview of techniques to prepare linear block copolymers and is intended to serve as a guideline on how polymerization techniques can work together to result in desired block combinations. As the review will give an account of the relevant procedures and access areas, the sections will include orthogonal approaches or sequentially combined polymerization techniques, which increases the synthetic options for these materials.

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“…The hybridizations can be diverse for various combinations, such as chain/step‐growth polymerizations, addition/ring‐opening polymerizations, radical/ionic polymerizations, and stereoselective/nonstereoselective polymerizations. [ 8–35 ] The polymers obtained are composed of different types of monomer enchainments, such as alternating, random, tapered, gradient, block, and multiblock structures, which can be varied by the combinations and conditions used. Since polymer properties are highly dependent on monomer enchainment, controlled hybrid polymerizations are new emerging research areas in precision polymerizations enabling the design and synthesis of novel polymeric materials.…”

Section: Introductionmentioning

confidence: 99%

Hybridization of Step‐/Chain‐Growth and Radical/Cationic Polymerizations Using Thioacetals as Key Components for Triblock, Periodic and Random Multiblock Copolymers with Thermoresponsiveness

Uchiyama

Osumi

Satoh

et al. 2021

Macromol. Rapid Commun.

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A novel strategy for synthesizing a series of multiblock copolymers is developed by combining radical/cationic step‐growth polymerizations of dithiols and divinyl ethers and chain‐growth cationic degenerative chain‐transfer (DT) polymerizations of vinyl ethers using thioacetals as key components. The combination of radical step‐growth polymerization and a cationic thiol‐ene reaction or cationic step‐growth polymerization enables the synthesis of a series of macro chain‐transfer agents (CTAs) composed of poly(thioether) and thioacetal groups at different positions. The resulting products are 1) bifunctional macro CTAs with thioacetal groups at both chain ends, 2) periodic macro CTAs periodically having thioacetal groups in the main chain, and 3) random macro CTAs randomly having thioacetal groups in the main chain. Subsequently, the obtained macro CTAs are used for chain‐growth cationic DT polymerization of methoxyethyl vinyl ether (MOVE) to result in 1) triblock, 2) periodic, and 3) random multiblock copolymers consisting of poly(thioether) and poly(MOVE) segments. All these triblock and multiblock copolymers composed of hydrophobic poly(thioether) and hydrophilic poly(MOVE) segments show an amphiphilic tendency to form characteristic micelles in aqueous solutions. In addition, due to the thermoresponsive poly(MOVE) segments, the obtained copolymers exhibit lower critical solution temperatures that depend on the segment sequences and lengths.

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Direct through anionic, cationic, and radical active species: Terminal carbon–halogen bond for “controlled”/living polymerizations of styrene

Cited by 6 publications

References 52 publications

Reactive Molecular Simulation with Size Extrapolation to Bridge the Polymerization Mechanism and Kinetics

Reactive Molecular Simulation with Size Extrapolation to Bridge the Polymerization Mechanism and Kinetics

Linear Block Copolymer Synthesis

Hybridization of Step‐/Chain‐Growth and Radical/Cationic Polymerizations Using Thioacetals as Key Components for Triblock, Periodic and Random Multiblock Copolymers with Thermoresponsiveness

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