Photoinitiated polymerization of ethyl cyanoacrylate by phosphonium salts

Önen, Aysęn; Arsu, Nergis; Yaǧcı, Yusuf

doi:10.1002/(sici)1522-9505(19990201)264:1<56::aid-apmc56>3.0.co;2-5

Cited by 41 publications

(32 citation statements)

References 12 publications

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“…Photoinitiated polymerizations have led to significant advances in various technologically important fields including coatings, inks, adhesives, varnishes, microelectronics, 3D printing, and microlithography. In these applications, polymers were synthesized by various photochemical reactions involving free radical, cationic, anionic, and step‐growth polymerizations as well as copper catalyzed click processes, which provides formation of films with different physical and chemical properties. Recently, light‐induced reactions have also become important methodology for controlled/living radical polymerizations, nanocomposites, and hyperbranched polymers, which were useful materials for drug delivery applications .…”

Section: Methodsmentioning

confidence: 99%

Near‐Infrared‐Induced Cationic Polymerization Initiated by Using Upconverting Nanoparticles and Titanocene

Zhu

Guan

et al. 2019

Macromol. Rapid Commun.

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Although most of the technologically applied photochemical processes are based on free radical polymerization, after the discovery of onium salt photochemistry by Crivello, [11] photoinitiated cationic polymerization has gained interest due to their thermal stability, solubility in most of the cationically polymerizable monomers, insensitivity to oxygen and high quantum efficiency to generate reactive species. [3] The existing onium salt-based photoinitiating systems for cationic polymerization include iodonium, [11] sulfonium, [12] alkoxy pyridinium, [13] and phosphonium [14] salts. However, unless additional chromophores are incorporated [15] into the salt structure the absorption of these salts at above 300 nm is rather low. In order to match with the wavelength requirements for certain practical applications, the sensitivity range of onium salts was extended to higher wavelengths by using free radical photoinitiators, [16] charge transfer complexes, [17] and singlet and triplet photosensitizers. [18] It was also shown that nanoparticles [19] and highly conjugated molecules [20] can also sensitize cationic polymerization by photoinduced electron transfer reactions. Among all these strategies, so-called free radical promoted cationic polymerization outlined in Scheme 1 is most widely used methodology as many free radical photointiators acting at broad wavelength range are readily available.In this process, photochemically formed electron donor radicals are oxidized by onium salts. The cations thus generated are used as initiating species for cationic polymerizations. As a consequence of the redox reaction, aryl radicals are also generated that can undergo various subsequent reactions resulting in the chemical amplification of the photons absorbed by the system. Free radical photoinitiators including aromatic carbonyl compounds, [21] acyl phosphine oxides, [22] acyl germanes, [23] organotellurium, [24] manganese carbonyl compounds, [25] and silanes [26] were successfully used to promote cationic polymerizations Despite the fact that the above-mentioned indirect systems can successfully initiate cationic polymerization at the near UV and visible range, [3] it is highly desirable to extend the spectral sensitivity to lower energy irradiation, such as nonharmful near-infrared (NIR) region which also limits side reactions resulting in self-initiation of monomers and degradation of already-formed polymers and oligomers. However, until recently, reports describing NIR sensitized photopolymerizations are exceedingly scarce. Several examples reported in the literature are mostly based on cyanine dyes and polymethines. [27] Besides their use in conventional photopolymerization formulations, polymethines with zwitter ionic structure Photopolymerization A new near-infrared (NIR)-sensitized photoinitiating system for free-radicalpromoted cationic polymerization of oxirane and vinyl monomers such as cyclohexene oxide, and n-butyl vinyl ether (BVE), and N-vinyl carbazole (NVC) is described. A three-component photoinitiating ...

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Section: Methodsmentioning

confidence: 99%

Near‐Infrared‐Induced Cationic Polymerization Initiated by Using Upconverting Nanoparticles and Titanocene

Zhu

Guan

et al. 2019

Macromol. Rapid Commun.

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“…Photoassisted anionic polymerization has long been examined but remains less studied than the free radical polymerization or the cationic polymerization due to the longer reaction time this polymerization technique requires compared to the two others. [194] Recently, alternatives to the conventional light-curing strategies based on photobase generations has been proposed in the literature, [195][196][197][198][199][200] notably based on photoinduced electron transfer (PET) processes. [201][202][203] Typically, these strategies are based on the photooxidation of a metal complex when opposed to the appropriate electron-deficient partner.…”

Section: Ferrocene and Alkyl-substituted Ferrocenesmentioning

confidence: 99%

Recent advances on ferrocene-based photoinitiating systems

Dumur

2021

European Polymer Journal

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Photoinitiators of polymerization with reversible electrochemical properties are actively researched as these molecules can advantageously be used in photocatalytic systems, enabling to reduce the photoinitiators content within the photocurable resins. In this field, ferrocene which is extensively used by electrochemists as a reference compound for cyclic voltammetry also exhibits a significant absorption in the visible range as well as a low oxidation potential so that this metallocene was used as a potential candidate for the design of photoinitiators of polymerization. Over the years, ferrocene has been examined in numerous polymerization processes going from anionic to cationic polymerizations, but also for the freeradical polymerization of acrylates or as a sacrificial electron donor in free radical polymerization processes. Parallel to this, the development of cheap, compact and energysaving irradiation setups based on light-emitting diodes (LEDs) have clearly favored the development of visible light photoinitiators and this technology has nowadays the potential to replace the well-established UV photopolymerization. In this review, an overview of the recent development of the ferrocene-based photoinitiating systems is provided. To evidence the interest of the ferrocene derivatives recently developed, comparisons with benchmark photoinitiators will be provided.

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“…Moreover, the more powerful monomer ethyl cyanoacrylate (ECA) was polymerized by NCS − ions generated by photoinduced ligand exchange reactions 42,43. We have demonstrated that, besides these organometallic complexes, specially designed organic compounds such as alkoxy pyridinium44 and phosphonium45 salts can also act as photoinitiators for anionic polymerization of ECA.…”

Section: Polymerizationmentioning

confidence: 99%

Phenacyl onium salt photoinitiators: synthesis, photolysis, and applications

Yaǧcı

Durmaz

Aydoğan

2007

The Chemical Record

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Onium salts, namely sulfonium, phosphonium, ammonium, and pyridinium salts containing phenacyl group are photoinitiators appropriate for the polymerization of monomers such as oxiranes and vinyl ethers, which are not polymerizable by a free-radical mechanism. The initiation is accomplished by direct or indirect (sensitized) photolysis of the salts. Depending on the type of the salt, the direct photoinitiation of cationic polymerization involves reversible or irreversible processes. The photolysis of phenacylsulfonium compounds proceeds by a reversible process, while the other types undergo irreversible photolysis leading to complete fragmentation of the photoinitiator. An additionally useful tool, namely photosensitized generation of initiating species enlarges the versatility of these salts as photoinitiators. Photoinitiated free-radical and zwitterionic polymerizations by using phenacyl-type salts are also addressed. Keto-enol tautomerization of phenacyl pyridinium salts is discussed. Moreover, an interesting application concerning in situ synthesis of clay-poly(methyl methacrylate) nanocomposites with the aid of the phenacyl anilinium salt-based photopolymerization technique is noted.

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Photoinitiated polymerization of ethyl cyanoacrylate by phosphonium salts

Cited by 41 publications

References 12 publications

Near‐Infrared‐Induced Cationic Polymerization Initiated by Using Upconverting Nanoparticles and Titanocene

Near‐Infrared‐Induced Cationic Polymerization Initiated by Using Upconverting Nanoparticles and Titanocene

Recent advances on ferrocene-based photoinitiating systems

Phenacyl onium salt photoinitiators: synthesis, photolysis, and applications

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