Redox initiated cationic polymerization: Silane<i>‐N‐</i>aryl heteroaromatic onium salt redox couples

Crivello, James V.; Lee, Julia L.

doi:10.1002/pola.24239

Cited by 14 publications

(19 citation statements)

References 24 publications

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“…Acylsulfonium salts are also highly efficient compared to iodonium salts as shown by Molleo et al [190] In that study, an interesting tuning of the gel time can be performed through the adjustment of the ppm level of metallic catalyst (e.g. 30 s gel time to 110 s when changing the Pt catalyst level from 8 to 2 ppm).N-Arylheteroaromaticonium salts can also be proposed though a difficult RCP of oxetanes was observed [191] when highly successful for activated epoxides and vinylethers.…”

Section: Other Catalystsmentioning

confidence: 92%

Redox two-component initiated free radical and cationic polymerizations: Concepts, reactions and applications

Garra

Dietlin

Morlet‐Savary

et al. 2019

Progress in Polymer Science

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Redox polymerizations are of huge importance throughout academic and industrial polymer science. Many authors propose the reaction of reducing (Red) and oxidizing (Ox) agents to accelerate/initiate radical or cationic polymerizations. As a result of activation energies typically below 80 kJ/mol, such reactions can occur under mild conditions, e.g., at room temperature, with reduced energy consumptions and robust in applications, such as the fabrication of composites. However, a clear definition of redox polymerization can only be found in reviews dealing with redox free radical polymerizations (FRP) published twenty years ago (or more). Therefore, a fresh and broader update is provided here for more recent work. The concepts involved when the "Red" and "Ox" agents constituting the redox initiating system are mixed under mild conditions are presented, followed by a discussion of the redox FRP initiating systems in bulk. Initiating systems dealing with the redox cationic polymerization (CP) are reviewed, and parallels between conventional FRP/CP and controlled polymerizations, in which redox systems are used, is provided. Many redox agents are useful in both modes. Finally, dual-cure (redox/photochemical; redox dual FRP/CP) systems is presented and selected applications are reviewed. Altogether, the state of the art for redox two-component polymerizations is provided, along with some perspectives.

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Section: Other Catalystsmentioning

confidence: 92%

Redox two-component initiated free radical and cationic polymerizations: Concepts, reactions and applications

Garra

Dietlin

Morlet‐Savary

et al. 2019

Progress in Polymer Science

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“…Such a property is highly researched in industries as it allows to produce colorless coatings. [231][232][233][234][235][236][237][238][239][240][241][242][243][244][245][246] Photolysis experiments realized with the D12/EDB and D12/Iod systems proved the photobleaching to be extremely fast compared to that observed for the other dyes. It can be thus concluded that the superiority of D12 over the other dyes relies in its fast interaction with the two co-initiators, speeding up the polymerization process so that the oxidative and the reductive cycles could concomitantly contribute to the formation of initiating radicals (See Figure 14).…”

Section: Push-pull Dyes Based On Indane-13-dionementioning

confidence: 99%

“…It has to be noticed that, in-situ generation of strong acids in resins is already reported in the literature, except that these strong acids have only been obtained by mean of redox reactions involving the use of transition metals. Thus, the generation of strong acids by reaction of a copper-catalyzed reduction of iodonium salts with benzoins, [242,243] or the platinum-catalyzed reduction of iodonium salts with boranes or silanes [244][245][246][247] have previously been reported in the literature. Besides, traces of residual metals can constitute a major impediment for further use of polymers.…”

Section: 3-bis(dicyanomethylidene)indanementioning

confidence: 99%

Recent advances on visible light photoinitiators of polymerization based on Indane-1,3-dione and related derivatives

Dumur

2021

European Polymer Journal

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Photoinitiators that can operate under visible light and low light intensity are actively researched as this last generation of photoinitiators can address different issues raised by the traditional UV photoinitiators. Notably, the safety concern related to the use of UV light, the high energy consumption resulting from the use of UV irradiation setups, the low light penetration of UV light within the photocurable resins are three major concerns that visible light photoinitiators successfully address. Besides, the photoinitiating ability and the polymerization kinetic should remain high in order these new generations of photoinitiators to be capable to replace the traditional UV photoinitiators. Among the different scaffolds examined for the design of efficient visible light photoinitiators, indane-1,3-dione has been identified as a promising scaffold for the design of various structures. By the presence of the activated methylene group standing between the two ketone groups, this electron acceptor is an ideal candidate for the design of push-pull dyes by one of the simplest reactions, namely the Knoevenagel reaction. This group is also a good electron acceptor as the two ketone groups can be advantageously used in the electronic delocalization by mesomerism. If this electron acceptor has been extensively studied for the design of push-pull dyes, its scope of application was not only limited to the design of push-pull dyes and products issued from cyclization reactions, the design of compounds with extended aromaticities, improvement of the electronwithdrawing ability by substitution of the ketone groups by appropriate groups were examined as possible chemical modifications enabling to improve the photoinitiating ability of photoinitiators based on indane-1,3-dione and its related derivatives. In this review, an overview of the different visible light photoinitiators based on indane-1,3-dione and derivatives is provided. To evidence the performance of the different photoinitiators, comparisons with reference compounds will be provided.

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“…Several groups have developed several onium salt series as photo-cationic initiators for the cationic polymerization of cyclic ethers, alkyl vinyl ethers, and epoxides [ 10 , 11 , 12 , 13 , 14 , 15 ]. The sulfonium and iodonium salts were indefinitely stable without photo-irradiation, but under photo-irradiation, initiating species were generated, which polymerized rapidly without inhibition or retardation, indicating the presence of a latent initiator.…”

Section: Introductionmentioning

confidence: 99%

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

Kim

Lee

2014

Materials

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In order to study the capability of pyrazinium salt derivatives to act as photo-initiators of epoxide monomers, benzyl pyrazinium hexafluoroantimonate (BPH), benzyl 3,5-dimethyl pyrazine hexafluoroantimonate (BDH) and benzyl quinoxalinium hexafluoroantimonate (BQH) were synthesized by the Menschutkin reaction of benzyl bromide with pyrazine, 2,6-dimethyl pyrazine, and quinoxaline, followed by exchanging with hexafluoroantimonate (SbF6). BPH, BDH, and BQH exhibited characteristic ultraviolet (UV) absorbance as well as exothermic peaks as a function of irradiation time in a differential photo-calorimeter (DPC). In the absence of photo-irradiation, cyclohexene oxide (CHO) underwent slow polymerization at 25 °C using BPH derivatives, but quantitative conversion was achieved even after a 5-min photo-irradiation. In addition, photo-irradiation was required for the photo-polymerization of CHO and styrene oxide (STO), which was characterized by a short induction period followed by a very rapid and exothermic polymerization. While glycidyl methyl ether (GME) required long induction periods, glycidyl phenyl ether (GPE) underwent rather slow and/or no photo-polymerization. The reactivity order of the monomers was CHO > STO >> GME >>> GPE, and the reactivity order for the photo-polymerization of CHO was BPH > BQH > BDH. It was found that BPH, BDH, and BQH could serve as photo-latent initiators for CHO, STO and GME, respectively.

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Redox initiated cationic polymerization: Silane‐N‐aryl heteroaromatic onium salt redox couples

Cited by 14 publications

References 24 publications

Redox two-component initiated free radical and cationic polymerizations: Concepts, reactions and applications

Redox two-component initiated free radical and cationic polymerizations: Concepts, reactions and applications

Recent advances on visible light photoinitiators of polymerization based on Indane-1,3-dione and related derivatives

Benzylpyrazinium Salts as Photo-Initiators in the Polymerization of Epoxide Monomers

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