Characterization of Iodonium Salts Differing in the Anion

Gu, Haiyan; Ren, Kun; Grinevich, Oleg; Malpert, John H.; Neckers, Douglas C.

doi:10.1021/jo0015725

Cited by 29 publications

(29 citation statements)

References 20 publications

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“…Therefore, these results show that the SiMo 12 moiety enhances the usual reactivity of the iodonium/TH salt. It is well known that the nucleophilicity of the anions correlates with the cationic photoinitiating ability of the iodonium salts; (a,b) remarkably, our work shows that the polyoxomolybdate anion improves the CP. Two initiating species are likely involved: (i) Ph‐I• + (Reaction 2c) for CP and (ii) the monomer cation M + formed in Reactions 3a and 3b, the monomer/phenyl radical hydrogen abstraction leading to a free‐radical‐promoted CP process; the phenyl radicals appear both in Reaction 2c (direct cleavage of the iodonium moiety) and Reactions 1, 2a; 2b (intramolecular polyoxomolybdate/iodonium electron transfer).…”

Section: Resultssupporting

confidence: 62%

“…(a,b) Diaryliodonium, triarylsulfonium salts (and their corresponding substituted derivatives), and, more recently, thioxanthenium and arylthianthrenium (TH) salts are well‐known cationic PIs for the polymerization of epoxides. They consist of a cationic moiety (where the positively charged iodine or sulfur atom is linked to aromatic groups) and a counter anion . (a,b) The nucleophilicity of the anion strongly affects the efficiency of the polymerization because a high nucleophilic anion may terminate the cationic chain reaction.…”

Section: Introductionmentioning

confidence: 99%

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Iodonium‐polyoxometalate and thianthrenium‐polyoxometalate as new one‐component UV photoinitiators for radical and cationic polymerization

Mokbel

Xiao

Simonnet‐Jégat

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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International audienceFour novel onium salts (onium-polyoxometalate) have been synthesized and characterized. They contain a diphenyliodonium or a thianthrenium (TH) moiety and a polyoxomolybdate or a polyoxotungstate as new counter anions. Outstandingly, these counter anions are photochemically active and can sensitize the decomposition of the iodonium or TH moiety through an intramolecular electron transfer. The phenyl radicals generated upon UV light irradiation (Xe–Hg lamp) are very efficient to initiate the radical polymerization of acrylates. Cations are also generated for the cationic polymerization of epoxides. Remarkably, these novel iodonium and TH salts are characterized by a higher reactivity compared with that of the diphenyliodonium hexafluorophosphate and the commercial TH salt, respectively. Interpenetrating polymer networks can also be obtained under air through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend (monomer conversions > 65%). The photochemical mechanisms are studied by steady-state photolysis, cyclic voltammetry, and electron spin resonance techniques

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Section: Resultssupporting

confidence: 62%

Section: Introductionmentioning

confidence: 99%

Iodonium‐polyoxometalate and thianthrenium‐polyoxometalate as new one‐component UV photoinitiators for radical and cationic polymerization

Mokbel

Xiao

Simonnet‐Jégat

et al. 2015

J. Polym. Sci. Part A: Polym. Chem.

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“…The most effective in our hands is the system quinaldine red in acetonitrile or ethanol (Scheme 1). 18 We observe that the photobleaching rate of QR in acetonitrile correlates well with the basicity of the anions, while that in ethanol correlates well with the photosensitivity of the iodonium cations.…”

Section: Resultsmentioning

confidence: 66%

“…2 Herein, we successfully apply fluorescence probe techniques to evaluate these gallate salts in a typical epoxy silicone oligomers (I) and two other typical resins (II, III) (Figure 3), combining this with the evaluation of the rate of their photoacid release by using a fast analysis technique in solution previously developed in our group. [17][18][19] The results indicate that the larger sized and less nucleophilic tetrakis(pentafluorophenyl)gallate anion renders the iodonium salt more photosensitive. These novel salts show excellent polymerization characteristics.…”

Section: Introductionmentioning

confidence: 98%

Relative Photoactivities of Iodonium Tetrakis(pentafluorophenyl)gallates Measured by Fluorescence Probe Techniques

Ren

Serguievski

et al. 2001

Macromolecules

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A series of iodonium tetrakis(pentafluorophenyl)gallate photoinitiators were employed to catalyze the photopolymerization of three typical epoxy resins. Rates of photoacid release were compared using Quinaldine Red as acid indicator in either acetonitrile or ethanol. A new fluorescence probe technique was successfully employed to follow the cross-linking kinetics of the epoxysilicone oligomer in real time.The results show that these new salts are the most soluble, most reactive photoinitiators with the desirable stability in monomer formulations in this family.

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“…[362,363]. Once the Brønsted acid is released, either by photolysis or thermolysis of an onium salt but also by the thermolysis or hydrolysis of a BF 3 -amine complex (see section 3.3.1.2), epoxy monomers are rapidly activated and polymerization proceeds very quickly according to the ring opening polymerization mechanism (Fig.…”

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

298

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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Characterization of Iodonium Salts Differing in the Anion

Cited by 29 publications

References 20 publications

Iodonium‐polyoxometalate and thianthrenium‐polyoxometalate as new one‐component UV photoinitiators for radical and cationic polymerization

Iodonium‐polyoxometalate and thianthrenium‐polyoxometalate as new one‐component UV photoinitiators for radical and cationic polymerization

Relative Photoactivities of Iodonium Tetrakis(pentafluorophenyl)gallates Measured by Fluorescence Probe Techniques

Control of reactions and network structures of epoxy thermosets

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