Photoinitiated Cationic Polymerization: Reactivity and Mechanistic Aspects

Kahveci, Muhammet U.; Yılmaz, Görkem; Yaǧcı, Yusuf

doi:10.1002/9780470594179.ch11

Cited by 35 publications

(22 citation statements)

References 157 publications

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“…This can be attributed to the wide availability of photoinitiators and the high reactivity and availability of monomers. 6,7 Especially methacrylate and acrylate monomers have rendered signicant interest and commercial importance. Due to the wide range of methacrylate and acrylate monomers and difunctional oligomers available on the market, the structural properties of the resulting polymers can be tailored giving access to materials with a variety of properties.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, most free-radical polymerization systems are sensitive to oxygen inhibition and thus require an inert atmosphere for high polymerization rates and full monomer conversion to be reach. 1,[6][7][8] Cationic photopolymerization has been shown to be advantageous compared to free-radical polymerization in several aspects. 7 Oxygen inhibition does not occur for cationic polymerization and furthermore, once initiated, cationically polymerizable monomers, such as epoxides and vinyl ethers, undergo dark polymerization in which they can continue to polymerize without radiation.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization

et al. 2018

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Increased environmental awareness has led to a demand for sustainable, bio-based materials.Consequently, the development of new benign synthesis pathways utilizing a minimum of reaction steps and available bio-based building blocks is needed. In the present study, vinyl ether alcohols and functional carboxylic acids were used to synthesize bifunctional vinyl ether esters using the immobilized enzyme Candida antarctica lipase B as a catalyst. Vinyl ethers are attractive alternatives to (meth) acrylates due to low allergenic hazards, low toxicity, and fast polymerization; however, difficult synthesis limits the monomer availability. The synthesis was performed in one-pot and the described method was successful within a broad temperature range (22-90 C) and in various organic solvents as well as in the bulk. The synthesis of different vinyl ether esters reached high conversions (above 90%) after less than 1 h and products were purified by removing the enzyme by filtration using only small amounts of acetone. This approach is a straightforward route to reach monomers with multiple types of functionalities that can be used as different photo-curable thermoset resins. In this work, this was demonstrated by polymerizing the monomers with cationic and radical UV-polymerization. By changing the functional carboxylic acids, the architecture of the final polymer can be tailored, herein demonstrated by two examples. In the developed versatile method, carboxylic acids can be used directly as acyl donors, constituting a more sustainable alternative to the carboxylic acid derivatives used today.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization

et al. 2018

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“…Over the last decades, there has been a growing interest for the industrial application of photoinitiated cationic polymerization (CP) reactions, which have several advantages over the free radical polymerization (FRP). Epoxides and vinyl ethers that exhibit a low volatility and a negligible toxicity and lead to polymers with good adhesion and mechanical properties are the most classical and widely used cationic monomers.…”

Section: Introductionmentioning

confidence: 99%

“…Onium salts have been extensively studied as photoinitiators (PI) for CP. Among them, diaryliodonium and triarylsulfonium are commercially important.…”

Section: Introductionmentioning

confidence: 99%

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Mokbel

Toufaily

Hamieh

et al. 2015

J of Applied Polymer Sci

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Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one-component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms.

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“…Similarly, cationic photopolymerization has been developed with great success over last decades, although this reaction found less applications than the previous one. Most of the cationic systems use oniums salts as photoacid generators [6][7].…”

Section: Introductionmentioning

confidence: 99%

Photopolymerization using Photolatent Amine Catalysts

Salmi

Allonas

Ley

et al. 2012

J. Photopol. Sci. Technol.

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In this paper, the ability of two photobase generators, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (PBG1) and tetramethylguanidine phenylglyoxylate (PBG2), to polymerize epoxides at room temperature was investigated. The polymerization, which proceeds at room temperature, was found to be speeded up in the presence of thiols. On the basis of the results, and taking into account that both photobases are released during photochemical processes that also generate radicals, interpenetrated epoxy-acrylate polymer networks were also produced. Finally, a polythiourethane polymer was obtained using the strongest photobase generator PBG2.

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Photoinitiated Cationic Polymerization: Reactivity and Mechanistic Aspects

Cited by 35 publications

References 157 publications

Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization

Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Photopolymerization using Photolatent Amine Catalysts

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