Visible light induced step-growth polymerization by electrophilic aromatic substitution reactions

Kılıçlar, Hüseyin Cem; Altınkök, Çağatay; Yılmaz, Görkem; Yaǧcı, Yusuf

doi:10.1039/d1cc01444g

Cited by 22 publications

(13 citation statements)

References 50 publications

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“…Compared to thermal polymerization methods, photopolymerization has a number of benefits, including better adaptability, higher reaction rates and spatiotemporal control, and a lower energy requirement, offering greener, safer, and more environmentally friendly reaction conditions [ 19 , 20 , 21 , 22 , 23 ]. In recent years, photoinitiated cationic ROP has been vastly studied and successfully applied to several industrially important monomers, including lactides, [ 24 ] ε-caprolactone, [ 25 ] cyclic ethers [ 26 ], and epoxides [ 27 ]. Obtained polymers in particular have deserved attention because of their influence on commercial applications, including adhesives, coatings, the encapsulation of electronic components, and 3D printing [ 28 , 29 , 30 , 31 , 32 , 33 , 34 ].…”

Section: Introductionmentioning

confidence: 99%

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

2023

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Photochemical techniques have recently been revitalized as they can readily be adapted to different polymerization modes to yield a wide range of complex macromolecular structures. However, the implementation of the photoinduced cationic methods in the polymerization of cyclic siloxane monomers has scarcely been investigated. Octamethylcyclotetrasiloxane (D4) is an important monomer for the synthesis of polydimethylsiloxane (PDMS) and its copolymers. In this study, the cationic ring-opening polymerization (ROP) of D4, initiated by diphenyl iodonium hexafluorophosphate (DPI), has been studied. Both direct and indirect initiating systems acting at broad wavelength using benzophenone and pyrene were investigated. In both systems, photochemically generated protonic acids and silylium cations are responsible for the polymerization. The kinetics of the polymerization are followed by viscosimetry and GPC analyses. The reported approach may overcome the problems associated with conventional methods and therefore represents industrial importance for the fabrication of polysiloxanes.

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Section: Introductionmentioning

confidence: 99%

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

2023

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“…[23,24] There are three main types of 3D printing technology that utilize photopolymerization: stereolithography, digital light processing (DLP), and direct laser write. [25][26][27][28] Benefiting from the high reaction rate and spatio-temporal control of dimanganese decacarbonyl chemistry, [29][30][31] a novel visible light induced polymerization method as a highresolution and swift 3D DLP printing system was offered. Previously, (Mn 2 (CO) 10 ) methodology was successfully applied to radical, [32,33] cationic, [34][35][36] and atom transfer radical [37,38] polymerization systems by our group.…”

Section: Introductionmentioning

confidence: 99%

Visible Light Induced High Resolution and Swift 3D Printing System by Halogen Atom Transfer

Tomal

Kılıçlar

Fiedor

et al. 2022

Macromol. Rapid Commun.

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3D printing technology offers solutions for numerous needs in industry and the daily life of individuals. In recent years, most research efforts have focused on this technology as the market share has grown and requirements have become specified in their related fields. In this work, a novel visible light induced 3D printing system with high resolution and short printing time using dimanganese decacarbonyl (Mn 2 (CO) 10 ) in combination with organic halides is reported. The radicals formed through halogen abstraction by photochemically generated manganese pentacarbonyl from organic halides with high quantum efficiency initiate the polymerization of acrylic resins. The kinetics of the process using various halide-containing molecules in the photoinitiaiting system are investigated with real-time fourrier transform infrared spectroscopy and photo-differential scanning calorimetry analyses, and the characteristics of 3D printouts are presented and compared with that of the commercial photoinitiator, 2,4,6-trimethylbenzoyl)phosphine oxide without Mn 2 (CO) 10 . The results obtained confirm that the combination of Mn 2 (CO) 10 and structurally diverse organic halides is a class of promising 3D system for various applications.

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“…[26,27] These methods may include cationic, anionic, or cycloaddition reactions. [28][29][30] The extraordinarily successful developments of photoinduced approaches to cationic, anionic, and cycloaddition reactions raised interest in photochemistry. [31] Even though cationic methods on polymerization and postmodifications are well studied, the corresponding anionic methods require complex setups.…”

Section: Introductionmentioning

confidence: 99%

Photoinduced Side‐Chain Functionalization, Grafting, Cross‐Linking, and Chain Extension by Thiol‐Epoxide Click Reaction Using Photo Base Generator

Kılıçlar

Yılmaz

et al. 2022

Macro Chemistry & Physics

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In this work, photoinduced thiol-epoxy click reaction for side-chain functionalization, chain-extension, grafting, and cross-linking of polymers prepared by atom transfer radical polymerization by using 1,5-diazabicyclo[5.4.0]undec-5-ene thioxanthone acetate (Tx-DBU) as a photo base generator (PBG) is described. Irradiation of Tx-DBU at 365 nm leads to the generation of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in neutral form as a super base. DBU is capable of abstracting protons from thiols and thus formed thiolates are excellent nucleophiles that exhibit high affinity toward electrophiles such as epoxide rings. Appropriately selected thiols are successfully used for the desired reactions. The precursors and resulting polymers are characterized using 1 H-NMR, Fourier transform infrared, gel permeation chromatography, and differential scanning calorimetry measurements. This study shows that the use PBGs can further be extended to the synthesis of various complex macromolecular structures by the described post modification processes.

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Visible light induced step-growth polymerization by electrophilic aromatic substitution reactions

Abstract: A novel visible light induced step-growth polymerization to form poly(phenylene methylene) by electrophilic aromatic substitution reactions is described.

Cited by 22 publications

References 50 publications

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

Photoinitiated Cationic Ring-Opening Polymerization of Octamethylcyclotetrasiloxane

Visible Light Induced High Resolution and Swift 3D Printing System by Halogen Atom Transfer

Photoinduced Side‐Chain Functionalization, Grafting, Cross‐Linking, and Chain Extension by Thiol‐Epoxide Click Reaction Using Photo Base Generator

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