Crivello salts

It was not until the invention of iodonium and sulfonium salts as photo-initiators by Crivello (1975) that cationic photo-polymerization became practical (see Crivello et al., 1977,1990,2000). Upon irradiation of these Crivello salts, acids are generated. Another significant difference between free radical and cationic polymerizations is the latter process is a living polymerization— once the acid species is formed, it remains active even after the irradiation is stopped. In contrast to this behavior free radicals die soon after irradiation is stopped. Also, unhke free radical polymerizations cationic reactions are not inhibited by oxygen. Quite often the dark reaction following irradiation can play an important role in enabhng a cationic system to develop its full properties and this leads manufacturers of commercial cationic photopolymers to often recommend a thermal (dark) postcure after carrying out the photo-irradiation process. 

Crivello, J. V. Cationic Polymerization — Iodonium and Sulfonium Salt Photoinitiators, Vol. 62, pp. 1-48. 

Crivello, J. V., Lockhart, T. P., and Lee, J. L., Diaryl-iodonium salts as thermal initiators of cationic polymerization,... 

A number of reagents derived from nitrate salts and acid anhydrides have been reported for the V-nitration of amides and related compounds. Crivello first reported the use of metal nitrates in trifluoroacetic anhydride (TFAA) for the nitration of aromatic systems. Chapman... 

J. Crivello, in J. P. Fouiassier andj. F. Rabek, eds., Radiation Curing in Polymer Science andTechnology (Vol II) Photoinitiating Systems, Elsevier, New York, 1993, Chapt. 8, for a review on onium salts. 

Crivello (lib) has described a series of diaryliodonium (107) and triarylsulfonium salts (108) which function as initiators for ultraviolet activated cationic polymerization. The... 

Several dyes have been found to sensitize the cationic polymerization of cyclohexene oxide, epichlorohydrin, and 2-chloroethyl vinyl ether initiated by diaryliodonium salts (109,110). Acridinium dyes such as acridine orange and acridine yellow were found to be effective sensitizers. One example of a benzothiazolium dye (setoflavin T) was also reported, but no other class of dye nor any other example of a dye absorbing at longer wavelengths were discovered. Crivello and Lam favored a sensitization mechanism in which direct energy transfer from the dye to the diaryliodonium salt occurred. Pappas (12,106) provided evidence that both energy transfer and electron transfer sensitization were feasible in this system. 

The reactivity of cycloaliphatic epoxy monomers with cations is higher than that of glycidyl ether monomers. For this reason, cycloaliphatic epoxies are used for UV-cure coatings. The most efficient initiators are complex aromatic salts of Lewis acids such as diaryl iodonium, triarylsul-fonium, or arene diazonium (Table 2.23) (Crivello, 1999). 

Photoinitiation of radical polymerization has long been known. Recently, a group of photoinitiators for cationic polymerization hase been discovered and developed by Crivello et al.1J. They include diaryliodonium (7),2) triarylsulfonium (2), 3 5) dialkylphenacylsulfonium (J), 6) and dialkyl-4-hydroxyphenylsulfonium salts (4) 7). 

One very interesting new application of Lewis acids in curing epoxy adhesives has appeared within the last 25 years. The Lewis acid initiator for the cationic polymerization is formed by the heat or ultraviolet light-induced decomposition of Lewis acid Lewis base salts. Several patents by Crivello and coworkers43 47 describe compounds containing... 

Crivello, J. V, Heat Curable Cationically Polymerizable Compositions and Method of Curing Same with Onium Salts and Reducing Agents, U.S. Patent No. 4,216,288, 1980. 

Crivello and Lam [69] have reported that the diaryliodonium salt-ascorbate redox system readily initiates the cationic polymerization of appropriate monomers. N-Alkoxy pyridinium salts were also shown [70] to participate in this redox process. The polymerization mechanism depicted below is quite similar to that described for the iodonium salts (Scheme 17). 

In recent years, the photochemistry and polymerization behaviour of iodonium 12,37,38.39) triphenylsulfonium salts was investigated. Crivello and... 

Besides the most important area of surface coatings, the use of photopolymers as photoresists in the manufacture of printed circuits is well established. Photoimaging with aryldiazonium salt photoinitiators and multifunctional cresol-novolac epoxides was first described by Schlesinger Crivello has mentioned several new photoresists based on the photopolymerization of epoxides with onium initiators Meier and Zweifel have shown that iron arene salts in combination with multifunctional cresol-novolac epoxides yield photoresists with high resolution and contrast. Dual functional epoxides (cf. Sect. 5) containing chalcone groups as light-sensitive units have been described as suitable photoresists especially... 

The method of iodonium salt synthesis using iodonium bromide was similar to that published by Crivello and co-workers [57-59]. Symmetrical iodonium salts... 

As shown in scheme 73, irradiation of the resist results in the decomposition of an added photoactive acid generator (Crivello s salt) thus liberating a Bronsted s acid, which upon heating leads to cleavage of the t-BOC protecting group. The irradiated regions are soluble in basic water... 

Nitric acid salts in the presence of other acids have been previously described (Vol. I, p, 46). It was recently reported by Crivello [125] that metal nitrates in trifluoroacetic anhydride (TFAA) can nitrate aromatic compounds at room temperature in very good yields. Thus ammonium nitrate with TFAA nitrated benzene to nitrobenzene with a yield of 95%. 

The diaryliodonium metal halide complex salts are not commercially available at this writing. Methods for their preparation are reviewed in a paper by Crivello and Lam (4). 

The bulky anion then stabilizes the intermediate adduct from protonation of the epoxy group and then facilitates insertion of epoxide at the cationic propagation site. Rapid polymerization can then occur. Cationic photopolymerization of epoxides often involves the photo-generation of acid from an initiator such as diaryliodonium or triaryl sulfonium salts (Crivello, 1999). The anions are important in controlling the addition at the cationic site and are typically BF4 and PFg. The reactivity of the system depends also on the structure of the epoxide. 

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