The influence of thiocarbonylthio compounds on the B(C6F5)3 catalyzed cationic polymerization of styrene

Destephen, Aurélie; Román, Estíbaliz González de San; Ballard, Nicholas

doi:10.1039/d2py00016d

Cited by 5 publications

(6 citation statements)

References 76 publications

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“…It is worth noting that the xanthate-type cationic RAFT agent, which may be partially formed by radical copolymerization of MA and IBVE as well as the photoaddition reaction between EXEP and IBVE, would also mediate the cationic RAFT polymerization. EXEP may also stabilize the propagating cation through a degenerative transfer mechanism although it is not an efficient cationic RAFT agent . In contrast, EXEP is more efficient than DTCB owing to the higher reactivity for the radical RAFT polymerization.…”

Section: Resultsmentioning

confidence: 99%

“…EXEP may also stabilize the propagating cation through a degenerative transfer mechanism although it is not an efficient cationic RAFT agent. 59 In contrast, EXEP is more efficient than DTCB owing to the higher reactivity for the radical RAFT polymerization. Hence, EXEP is more competitive for the radical copolymerization of MA and IBVE.…”

Section: Design Of Polymerization Systems For 3d Printingmentioning

confidence: 99%

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Photoinduced 3D Printing through a Combination of Cationic and Radical RAFT Polymerization

Zhao

et al. 2022

Macromolecules

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Photopolymerization-based three-dimensional (3D) printing techniques have been widely utilized to fabricate polymeric materials with complex architectures. The application of reversible deactivation radical polymerization (RDRP) in 3D printing is emerging as a powerful tool to introduce various postprinting abilities but is still at an early stage. Here, a photoinduced free radical-promoted cationic reversible addition−fragmentation chain transfer (RAFT) polymerization method was developed, utilizing the direct photolysis of the RAFT agent as a radical source, which was further combined with photo-iniferter RAFT polymerization to prepare polymer networks. The polymerization mechanism was studied by model polymerization using monofunctional monomers. The effects of each component on the properties of the final materials and polymerization behavior of the cross-linking systems were studied in detail. This method was successfully applied in a digital light processing (DLP) techniquebased commercial 3D printer. Finally, polymer welding of the printed objects through both cationic and radical RAFT chain extension was realized, expanding avenues of postprinting and future applications in various fields.

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Section: Resultsmentioning

confidence: 99%

Section: Design Of Polymerization Systems For 3d Printingmentioning

confidence: 99%

Photoinduced 3D Printing through a Combination of Cationic and Radical RAFT Polymerization

Zhao

et al. 2022

Macromolecules

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“…172 With the advancements in reactive cationic and lightcontrolled polymerization, cationic RAFT polymerization has gained considerable attention in conventional systems, drawing inspiration from photoinitiated cationic RAFT polymerization. [173][174][175][176][177][178] The control degree during polymerization has significantly improved, especially in photoinitiated polymerization where chain growth is directly regulated by light. This emerging research area is expected to expand the range of applications for cationic polymerization, including UV curing, 3D printing, synthesis of highly complex structures, and patterns for electronic devices in biomedicine.…”

Section: Photocontrolled Cationic Polymerizationmentioning

confidence: 99%

Recent advances in green cationic polymerization

Zhu,

Yu,

Liu

et al. 2024

Journal of Polymer Science

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Traditional living/controlled cationic polymerization provides a simple synthetic route for the preparation of various polymers with set molecular weight, narrow molecular weight distribution, and clear structure. Nowadays, under the requirements of sustainable development, it is very important to explore the green chemical technology in depth. This review offers an overview of initiation systems, reaction media, polymerization techniques, and monomers, with the aim of summarizing environmentally friendly methods utilized in the field of cationic polymerization over the past 15 years. It covers a variety of directions from traditional initiation systems to green initiators, from corrosive solvents to environmentally friendly solvents, from drop initiation to external stimulation initiation, from petroleum fractionated monomers to bio‐based monomers. These methods and Techniques aim to develop advanced high‐quality polymer products using cationic polymerization, and achieving efficient energy savings and reducing emissions. The ongoing exploration of green‐controlled cationic polymerization holds promise for opening up new avenues and novel technology for high‐performance polyolefin materials.

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“…[59,60] Thus, cationic RAFT polymerizations of these less reactive monomers are still challenging. [11,57,61] We thus first synthesized a series of exo-olefin compounds ((CH 3 ) 2 C(PhY)À CH 2 C(=CH 2 )PhY) by developing selective cationic dimerizations of αMS and its derivatives (CH 2 =CHPhY) with protonic oxo acids at relatively high temperature. In addition to these exo-olefin compounds with "homodimer" structures, we prepared those with "heterodimer" structures (RÀ CH 2 C(=CH 2 )PhY; R ¼ 6 (CH 3 ) 2 C(PhY)) via different synthetic routes to examine the effects of substituents (R) on the subsequent cationic RAFT polymerizations.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, there have been no cationic RAFT polymerizations of these hydrocarbon monomers thus far reported except for the case with thioether as degenerative chain‐transfer (DT) agents for αMS [59,60] . Thus, cationic RAFT polymerizations of these less reactive monomers are still challenging [11,57,61] …”

Section: Introductionmentioning

confidence: 99%

Cationic β‐Scission of C−H and C−C Bonds for Selective Dimerization and Subsequent Sulfur‐Free RAFT Polymerization of α‐Methylstyrene and Isobutylene

Tanimoto,

Uchiyama,

Kamigaito

2023

Angew Chem Int Ed

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A series of exo‐olefin compounds ((CH3)2C(PhY)–CH2C(=CH2)PhY) were prepared by selective cationic dimerization of α‐methylstyrene (αMS) derivatives (CH2=C(CH3)PhY) with p‐toluenesulfonic acid (TsOH) via β‐C–H scision. They were subsequently used as reversible chain transfer agents for sulfur‐free cationic RAFT polymerization of αMS via β‐C–C scission in the presence of Lewis acid catalysts such as SnCl4. In particular, exo‐olefin compounds with electron‐donating substituents, such as a 4‐MeO group (Y) on the aromatic ring, worked as efficient cationic RAFT agents for αMS to produce poly(αMS) with controlled molecular weights and exo‐olefin terminals. Other exo‐olefin compounds (R–CH2C(=CH2)(4‐MeOPh)) with various R groups were prepared by different methods to examine the effects of R groups on the cationic RAFT polymerization. A sulfur‐free cationic RAFT polymerization also proceeded for isobutylene (IB) with the exo‐olefin αMS dimer ((CH3)2C(Ph)–CH2C(=CH2)Ph). Furthermore, telechelic poly(IB) with exo‐olefins at both terminals was obtained with a bifunctional RAFT agent containing two exo‐olefins. Finally, block copolymers of αMS and MMA were prepared via mechanistic transformation from cationic to radical RAFT polymerization using exo‐olefin terminals containing 4‐MeOPh groups as common sulfur‐free RAFT groups for both cationic and radical polymerizations.

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The influence of thiocarbonylthio compounds on the B(C₆F₅)₃ catalyzed cationic polymerization of styrene

Abstract: When applied to the cationic polymerization of styrene, thiocarbonylthio compounds can lead to a dual control mechanism, where degenerative chain transfer occurs concurrent with a reversible addition mechanism.

Cited by 5 publications

References 76 publications

Photoinduced 3D Printing through a Combination of Cationic and Radical RAFT Polymerization

Photoinduced 3D Printing through a Combination of Cationic and Radical RAFT Polymerization

Recent advances in green cationic polymerization

Cationic β‐Scission of C−H and C−C Bonds for Selective Dimerization and Subsequent Sulfur‐Free RAFT Polymerization of α‐Methylstyrene and Isobutylene

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