Photoinitiated cationic polymerization onium salts

Virtually all known types of cationically polymerizable monomers are polymerized using onium salt photoinitiators. Included among these monomers are epoxides, cyclic ethers, mono and polyfunc-tional vinyl compounds, spiroesters, spirocarbonates and cyclic... 

Over the past several years, there have been developed several new classes of onium salt photoinitiators capable of initiating cationic polymerization. The most significant of these are aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and dialkylphenacyl-sulfonium salts. The mechanisms involved in the photolysis of these compounds have been elucidated and will be discussed. In general, on irradiation acidic species are generated which interact with the monomer to initiate polymerization. Using photosensitive onium salts, it is possible to carryout the polymerization of virtually all known cationically polymerizable monomers. A discussion of the various structurally related and experimental parameters will be presented and illustrated with several monomer systems. Lastly, some new developments which make possible the combined radical and cationic polymerization to generate interpenetrating networks will be described. 

Over the past ten years the development of onium salt and other cationic photoinitiators has moved from the realm of speculative investigation to the point today at which they are being employed in numerous commercial applications. Much work still needs to be done in this fields particularly to improve our understanding of the relationship between the structure and the photosensitivity of these photoinitiators. As the field advances, one can expect still other new classes of onium salt photoinitiators to be developed as well as continued improvements to be made in the efficiency of the present systems. An understanding of the mechanism of photosensitization should lead to discovery of more efficient photosensitizers and a further broadening of their spectral response in photoinitiated cationic polymerization. 

Lastly, the process and polymers produced by onium salt photoinitiated cationic polymerizations are eminently useful. Like the corresponding photoinitiated radical polymerizations which they complement, these cationic systems will find a wide range of applications where polymerization speed and economy of energy utilization are of prime concern. 

The mechanism shown above involves a three-step radieal chain process where aryl radicals are converted to oxidizable radicals (R ) that interact with the onium salt. Subsequently, the cations generated by this process initiate polymerizations, while the reduced onium salts that undergo irreversible decomposition to regenerate aryl radicals. The overall consequence is an acceleration of the initiation process due to an increase in the number of initiating cationic species. In addition, Sangermano and Crivello reported that certain onium salt photoinitiators can be reduced by free radicals produced... 

There are three t)q)es of eompositions that eure by eationie meehanism. One of them uses aryldiazonium salts to initiate the reaetion. The seeond one utilizes onium salts and the third one organometallie eomplexes. The most prominent ones are those that eure with the aid of onium salt photoinitiators. Many cationic curable compositions consist of mixtures of compounds with oxirane rings. They may also be mixtures of vinyl ether. In addition, some compositions contain both, epoxides and vinyl ethers. More recent compositions might also include silicone based monomers with epoxide groups. Thus, Crivello and Lee described a synthesis of a series of silicon-epoxy monomers that undergo rapid and efficient photoinitiated cationic polymerizations. Such compounds can be prepared by direct hydrosilylation of olefmic epoxides. 

AYD 08] Aydogan B., Gundogan A.S., Ozturk T. et al, A dithienothiophene derivative as a long-wavelength photosensitizer for onium salt photoinitiated cationic polymerization , Macromolecules, vol. 41, no. 10, pp. 3468-3471, 2008. 

Onium salt cationic photoinitiators present many unique and interesting opportunities for basic studies of cationic ring-opening polymerizations. Since they are latent photochemical sources of strong Bronsted adds, they can be dissolved in the subject monomers and then precisely tri ered on demand by the application of light. Mixing problems and the use of complex stopped-flow devices and other apparatuses required to overcome them are thus avoided. Only the rate of initiation is different in a photoinitiated cationic polymerization as compared to a conventional thermally initiated polymerization. The rate of initiation for an onium salt-photoinitiated cationic potymerization (eqn [68]) is... 

The major portion of the article will be devoted to a discussion of the synthesis and mechanistic aspects of photoinitiation by individual photoinitiator systems. Cationic polymerizations induced by these photoinitiators are dark, i.e., non-photo-chemical, processes which are governed by the same parameters which must be taken into account in polymerizations which occur in the presence of conventional initiators such as Lewis and Bronsted acids. Accordingly, cationic polymerizations induced by halogen and sulfur based onium salt photoinitiators will be discussed only from the context in which they are influenced by factors which have their origin in the photoinitiator. Since the photochemistry of diaryliodonium and triarylsulfonium salts is similar, these two types of photoinitiators will be discussed together. The photolysis of dialkylphenacylsulfonium and dialkyl-4-hydroxyphenylsulfonium salts proceeds by a different mechanism, and they will be discussed separately. 

During the past few years there has been considerable activity by various research groups directed toward the development of new types of onium salt photoinitiators for cationic polymerization. Although much of this work has appeared in fragmentary fashion in the literature, an effort will be made here to briefly report on the most significant developments in this area. 

Lastly, in the past few years, efforts have been progressing in several laboratories to use onium salt photoinitiators as thermal initiators of cationic polymerization. 

Two other patents have also appeared describing the use of alternate free radical sources as reducing agents for diaryliodonium and triarylsulfonium salts Crivello and his coworkers have discovered several other types of reactions which can be used to thermally induce cationic polymerization using onium salt photoinitiators. Diaryliodonium salts are thermally decomposed in the presence of catalytic amounts of copper compounds An organocopper compound is proposed as an intermediate which undergoes electrophilic arylation of cationally polymerizable monomers as shown in Scheme 14 to initiate polymerization. 

Fig. 2 Various types of photoinitiators (1) peroxides, (2) azo compounds based on AIBN, (3) benzoin ethers, (4) triplet photosensitizers, (5) onium salts for cationic polymerization, and (6) controlled free radical polymerization with photoiniferters...

The recent development of several new classes of practical photoinitiators for cationic polymerization has now made it possible to utilize this chemistry in a number of ways to produce highly sensitive photoresists (142-144). The facile synthesis of onium salts (I-III)... 

As outlined in Scheme 2, for cationic photopolymerization a photoinduced formation of species X+ or Lewis acids is required [162]. Such species are formed both by PET between neutral donors and acceptors (see Scheme 3), between neutral donors and positive charged acceptors (see Schemes 9 and 11), respectively, and by an indirect PET between nucleophilic radicals and onium salts or halogen compounds (see Eq. (16) and Scheme 12). Therefore, combinations of compounds, whose light-induced reactions are based on the pathways given above, are usable as photoinitiators for cationic polymerizations, too. Prerequisites for the use of cations... 

It was demonstrated that the P-centered radical of BAPO and its derivatives is oxidized by cationic photoinitiators (onium salts in their ground state). Phosphonium ion, a BAPO fragment, can efficiently initiate cationic polymerization. Thus, under certain conditions, PI used mfree radical polymerization can initiate a cationic polymerization as well. ... 

Initiators based on halonium and sulfonium salts are used commercially in various microlithographic processes and in the coating industry. Onium salts were developed commercially as photoinitiators due to the lower sensitivity of cationic polymerizations to oxygen compared to radical polymerizations. Aromatic halonium and sulfonium salts with complex anions such as SbF6, AsF6 and BF4- do not initiate cationic polymerizations spontaneously, but must be activated by UV irradiation. 

It must also be noted here that not all photoinitiators initiate free-radical polymerization, for example, the use of onium salts as photoinitiators is based on their ability to initiate cationic polymerization processes. 

The results of these photochemical studies form guidelines for the choice of sensitizers, onium salts and other additives potentially useful in the cationic curing of coatings. The sensitized photochemistry of diphenyliodonium hexafluoroarsenate and triphenylsulfonium hexaflurorarsenate was investigated at 366 nm. Product quantum yields are compared to relative rates of photoinitiated cationic polymerization of an epoxy resin. 

---