The Effect of the Heteroatom Moiety of Allylic Salts on the Addition Fragmentation Initiation of Cationic Polymerization

Önen, Aysęn; Yaǧcı, Yusuf

doi:10.1002/1521-3935(20010601)202:9<1950::aid-macp1950>3.0.co;2-u

Cited by 17 publications

(7 citation statements)

References 14 publications

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“…The overall process is depicted in Scheme . A variety of mono- or biallyl sulfonium, phosphonium, and pyridinium salts have been investigated for the initiation of cationic polymerization using the addition–fragmentation technique. ,− …”

Section: Photoinitiation Of Chain Polymerization By Photoinduced Elec...mentioning

confidence: 99%

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

2016

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Photochemical reactions, particularly those involving photoinduced electron transfer processes, establish a substantial contribution to the modern synthetic chemistry, and the polymer community has been increasingly interested in exploiting and developing novel photochemical strategies. These reactions are efficiently utilized in almost every aspect of macromolecular architecture synthesis, involving initiation, control of the reaction kinetics and molecular structures, functionalization, and decoration, etc. Merging with polymerization techniques, photochemistry has opened up new intriguing and powerful avenues for macromolecular synthesis. Construction of various polymers with incredibly complex structures and specific control over the chain topology, as well as providing the opportunity to manipulate the reaction course through spatiotemporal control, are one of the unique abilities of such photochemical reactions. This review paper provides a comprehensive account of the fundamentals and applications of photoinduced electron transfer reactions in polymer synthesis. Besides traditional photopolymerization methods, namely free radical and cationic polymerizations, step-growth polymerizations involving electron transfer processes are included. In addition, controlled radical polymerization and "Click Chemistry" methods have significantly evolved over the last few decades allowing access to narrow molecular weight distributions, efficient regulation of the molecular weight and the monomer sequence and incredibly complex architectures, and polymer modifications and surface patterning are covered. Potential applications including synthesis of block and graft copolymers, polymer-metal nanocomposites, various hybrid materials and bioconjugates, and sequence defined polymers through photoinduced electron transfer reactions are also investigated in detail.

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Section: Photoinitiation Of Chain Polymerization By Photoinduced Elec...mentioning

confidence: 99%

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

2016

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“…Allylic sulfonium salts with various substituents at the allylic moiety can effectively convert radicals into radical cations that can initiate cationic polymerization of CHO 21, 22. The synthesis of allylic sulfonium salts involves the reaction of bromoallylic precursors with tetrahydrothiophene (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…To investigate the substituent and counter ion effects on polymerization rate, a serious of allylic sulfonium salts ( 1a–d ) having different substituents at the allylic moiety and counter ions was prepared. They were synthesized according to the reported procedures 13, 14, 16, 20–22. The salts were obtained as white crystals.…”

Section: Methodsmentioning

confidence: 99%

Allyl sulfonium salt as a novel initiator for active cationic polymerization of epoxide by shooting with radicals species

Yılmaz

Sudo

Endō

2010

J. Polym. Sci. A Polym. Chem.

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A rapid cationic polymerization of cyclohexene oxide that completed within a few minutes was achieved by a new initiation system that involves (1) a copper-catalyzed reduction of benzoyl peroxide by an ascorbic acid derivative that generates free radicals and (2) capture of the radicals by allyl sulfonium salt having hexafluoroantimonate (SbF À 6 ) as a counter anion, followed by fragmentation of sulfonium radical cation, from which a super acid HSbF 6 was produced to initiate the rapid polymerization. The key factor in designing an efficient allyl sulfonium salt was attachment of an electron withdrawing ester group at the allyl group, of which ability to stabilize the formed radical can enhance the efficiency in trapping radicals by the allylic salt. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: [4178][4179][4180][4181][4182][4183] 2010

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“…Similarly to photolatent onium initiators that may be activated through the use of free radical coinitiator upon visible light, they suggested to activate thermolatent cationic initiators by using free radical sources that are released at lower temperature than the normal onium salt's temperature threshold [349][350][351][352]. To this end, they developed a series of specially designed allyl onium salts.…”

Section: Page 31 Of 163mentioning

confidence: 99%

Control of reactions and network structures of epoxy thermosets

Vidil¹,

Tournilhac²,

Musso

et al. 2016

Progress in Polymer Science

293

252

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Recent advances in macromolecular chemistry have revolutionized the way we perceive the synthesis of polymers. Polymerization, to be modern, must be "controlled", which usually means capable of producing macromolecules of well-defined structure. The purpose of this review is to examine how the chemistry of epoxy resins, an almost century-old chemistry, is also involved in this movement. Epoxy resins are characterized by both the flexibility of implementation and the qualities of the polymers obtained. Key materials in health-, mobility-and energy related technologies, these resins are heavily present in high-performance composites, electronic boards, adhesives and coatings. Currently, a large number of resins and hardeners are available on the market or described in the literature and an interesting point is that almost any combination of the two is possible. Common to all these recipes and processes is that a liquid (or soluble) resin at some point becomes insoluble and solid. It is very important to know how to manage this transition, physically known as the gel point, as it is the point after which the shape of the object is irreversibly set. Taking into account the variety of epoxy polymerization processespolyaddition, anionic or cationic polymerization-we detail a number of methods to program the occurrence of the gel point and how this type of control affects the structure of the growing network.

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The Effect of the Heteroatom Moiety of Allylic Salts on the Addition Fragmentation Initiation of Cationic Polymerization

Cited by 17 publications

References 14 publications

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

Photoinduced Electron Transfer Reactions for Macromolecular Syntheses

Allyl sulfonium salt as a novel initiator for active cationic polymerization of epoxide by shooting with radicals species

Control of reactions and network structures of epoxy thermosets

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