Relation of auto-acceleration in radical polymerization of methyl methacrylate in bulk with structural changes of the polymerizing system

Lachinov, M. B.; Korolev, B. A.; Dreval, V.Ye.; Cherep, Ye.I; Zubov, V.P.; Vinogradov, G. V.; Kabanov, V.A.

doi:10.1016/0032-3950(82)90129-0

Cited by 9 publications

(4 citation statements)

References 17 publications

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“…Furthermore, the auto‐acceleration is found in DES at a specific conversion (approximately 20%), as shown in Figure 6A. This is attributed to the diffusion‐controlled chain‐termination reaction as the system's viscosity rises 71 . In addition, the results of the model predicted M n and Đ match well with the experiment data ( Figure 6B ) .…”

Section: Resultssupporting

confidence: 61%

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Quantum chemical calculation driven insights into deep eutectic solvent‐accelerated photoinduced reversible complexation‐mediated polymerization

Li,

Fu,

Zhou

et al. 2024

AIChE Journal

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Deep eutectic solvent (DES) is used as both photocatalyst and solvent for photoinduced reversible complexation‐mediated polymerization (photo‐RCMP), which enables a rapid polymerization to produce polymers with predictable molar mass and low molar mass dispersity (Đ). This work illustrates a comprehensive understanding of DES‐accelerated RCMP's mechanism and kinetic features through quantum chemical calculations and kinetic modeling. According to the results, electrons transferring from hydrogen bond in DES to iodine atom in alkyl iodide (RI) initiator under light irradiation lowers the decomposition free energy of complex RI‐DES. This procedure facilitates the generation of primary radicals, thus contributing to the DES‐accelerated phenomenon. In the meantime, the reaction paths are identified by computation as (i) decomposition of RI‐DES under light irradiation generates active radicals and ·I‐DES complex and (ii) combination of two ·I‐DES releases iodine (I2) and regenerates DES. In addition, kinetic modeling based on the method of moments successfully identifies kinetic features of polymerization in the presence and absence of DES, respectively. Kinetic modeling shows a fast increase in primary radicals concentration and rapid build‐up of the photo‐RCMP activation‐deactivation equilibrium, demonstrating that DES is a beneficial photocatalyst and solvent to enable the rapid generation of primary radicals and accelerate the completion of catalytic cycle. This research provides an in‐depth understanding of DES‐involved photo‐RCMP and lays a theoretical foundation for expanding the application of DES to other polymerization systems.

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Section: Resultssupporting

confidence: 61%

“…This is attributed to the diffusion-controlled chain-termination reaction as the system's viscosity rises. 71 In addition, the results of the model predicted M n and Đ match well with the experiment data (Figure 6B).…”

Section: Kinetic Understanding Of Photo-rcmp In Dessupporting

confidence: 76%

Quantum chemical calculation driven insights into deep eutectic solvent‐accelerated photoinduced reversible complexation‐mediated polymerization

Li,

Fu,

Zhou

et al. 2024

AIChE Journal

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“…The effect of CTC most clearly has been illustrated in radical terpolymerization of MA and its derivatives with various donor and acceptor monomers 9–15. Radical polymerization of various monomer systems in the high conversion conditions was also investigated 16–25…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Poly[((maleic anhydride)‐alt‐styrene)‐co‐(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)]

Devrim

Rzaev

Pi̇şki̇n

2005

Macro Chemistry & Physics

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Summary: Novel polyfunctional sulfone‐ and anhydride‐containing reactive terpolymers with different compositions have been synthesized by complex‐radical polymerization of the ternary MA‐St‐APMS acceptor‐donor‐acceptor monomer system. This method allows preparing terpolymers with a sufficiently high content of APMS which essentially increased polyelectrolyte, swelling, IEC and thermal stability of terpolymer films. The terpolymer structure‐composition‐properties (polyelectrolyte, thermal, swelling and cation exchange behavior) relationships were studied by FTIR and 1H{13C} NMR (DEPT‐135) spectroscopy, viscometry, DSC‐TGA methods, and by means of swelling and exchange capacity. The observed H‐bonding between sulfonic acid, amide and anhydride fragments played an important role in the formation of the physically crosslinked and self‐assembled architectures with controllable hydrophilic‐hydrophobic balance. These reactive terpolymers can be used as synthons for exchange membrane preparation and fuel cell applications.

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“…8 -14 Radical polymerization of various monomer systems in the high conversion conditions was also investigated. [15][16][17][18][19][20][21][22][23] The kinetics of these reactions were interpreted by taking into consideration diffusion difficulties, variability of kinetic parameters of elementary reactions and increased role of macromolecules in the high conversion conditions. 18 -23 In this article, the results of the complex-radical terpolymerizations of two acceptor-donor-acceptor systems such as maleic anhydride (MA)-styrene (St)-acrylonitrile (AN) and n-butyl methacrylate (BMA)-St-AN in low and high conversion conditions are described.…”

Section: Introductionmentioning

confidence: 99%

Complex-radical terpolymerization of acceptor-donor-acceptor systems: Maleic anhydride (n-butyl methacrylate)-styrene-acrylonitrile

Medyakova

Rzaev

Güner

et al. 2000

J. Polym. Sci. A Polym. Chem.

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Relation of auto-acceleration in radical polymerization of methyl methacrylate in bulk with structural changes of the polymerizing system

Cited by 9 publications

References 17 publications

Quantum chemical calculation driven insights into deep eutectic solvent‐accelerated photoinduced reversible complexation‐mediated polymerization

Quantum chemical calculation driven insights into deep eutectic solvent‐accelerated photoinduced reversible complexation‐mediated polymerization

Synthesis and Characterization of Poly[((maleic anhydride)‐alt‐styrene)‐co‐(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)]

Complex-radical terpolymerization of acceptor-donor-acceptor systems: Maleic anhydride (n-butyl methacrylate)-styrene-acrylonitrile

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