Photoinitiator excited triplet

Oxygen has two possible interactions during the polymerization process [94], and these reactions are illustrated in Fig. 2. The first of these is a quenching of the excited triplet state of the initiator. When this quenching occurs the initiator will absorb the light and move to its excited state, but it will not form the radical or radicals that initiate the polymerization. A reduction in the quantum yield of the photoinitiator will be observed. The second interaction is the reaction with carbon based polymerizing radicals to form less reactive peroxy radicals. The rate constant for the formation of peroxy radicals has been found to be of the order of 109 1/mol-s [94], Peroxy radicals are known to have rate constants for reaction with methyl methacrylate of 0.241/mol-s [100], while polymer radicals react with monomeric methyl methacrylate with a rate constant of 5151/mol-s [100], This difference implies that peroxy radicals are nearly 2000 time less reactive. Obviously, this indicates that even a small concentration of oxygen in the system can severely reduce the polymerization rate. 

To overcome quenching, some photoinitiators decay quite rapidly via unim-olecular fragmentation from the excited triplet state and leave little time for the... 

The substitution of l-chloro-2-naphthoxide ion by sulfite ion in water can also be initiated by visible light (436 nm) with the complex [Ru(bipy)2]Cl as the sensitizer and the complex [Co(bipy)3](C104)2 as the intermediate electron carrier3315. Another possibility is a dye photoinitiated reaction. In the latter example, the excited triplet of the dye (fluorescein, eosine or erythrosine) receives an electron from S03 2 whose radical anion (S03) reacts with halonaphthoxides to give finally the substitution product33c. 

The most probable photochemical primary process of the polymerization reaction is shown in the energy level diagramm of Fig. 24. In the photoinitiation reaction an excited adjacent monomer molecule M is added to the reaction center, best represented by the metastable triplet DRi monomer molecule. Owing to the spin conservation rules, we conclude that an excited triplet dimer- diradical DR2 is formed in the chemical reaction. We may, therefore, formulate the reaction as follows ... 

A Study of the benzoyl radicals obtained by irradiation of the ketones (6-11) has shown that the a-cleavage results from the excited triplet state. " endo and cxu-(2-Hydroxy-[2.2.2]bicyclo-5-en-l-yl)-phenylmethanones have been synthesized and studied as potential photoinitiators for radical polymerization. The photoinitiators (12) have been investigated in some detail. ... 

Quantitative photophysical, photochemical and photopolymerisation data are presented on five novel water soluble benzophenone photoinitiators. Phosphorescence quantum yields, triplet lifetimes and transient formation on conventional flash photolysis correlate with the ability of the initiators to photoinduce the polymerisation of 2-hydroxyethylmethacrylate and a commercial monoacrylate resin in aqueous media. The results indicate that the lowest excited triplet state of the initiator is abstracting an electron from the tertiary amine cosynergist probably via a triplet exciplex followed by hydrogen atom abstraction. This is confirmed by a detailed analysis on the effect of oxygen, pH and the ionisation potential of the amine on transient formation and photopolymerisation. Using photocalorimetry a linear correlation is found between the photopolymerisation quantum yields of the initiators and their photoreduction quantum yields in aqueous media. 

The results clearly show that the photoinitiating activity of the water soluble benzophenone in the presence of an amine is mainly associated with the ability of the lowest excited triplet - state to abstract an electron from the amine co-synergist via an intermediate exciplex shown in Scheme I. The radical anion will then induce hydrogen atom abstraction to give a ketyl radical and an alkylamino radical. The latter is mainly responsible for inducing polymerisation of the acrylic monomer and supports earlier work on the benzophenone-triethylamine tetramine-induced photopolymerisation of methylmethacrylate during which terminal amine groups were detected (2 ) ... 

Two types of compounds are employed as photoinitiators of free radical polymerizations, which differ in their mode of action of generating reactive free radicals. Type I initiators undergo a very rapid bond cleavage after absorption of a photon. On the other hand, type II initiators form relatively long-Hved excited triplet states capable of undergoing hydrogen-abstraction or electron-transfer reactions with co-initiator molecules that are deliberately added to the monomer-containing system. 

It is also possible to form graft copolymers on the surface of fibers by coating them with photoinitiators, like benzophenone together with a monomer and then irradiating them with ultraviolet light [414]. Similar to the action of the anthraquinone dyes shown above, benzophenone in the excited triplet state mainly abstracts hydrogens and forms radicals on the surface [415]. 

The photoinduced a-cleavage reaction is not or is only slightly affected by triplet quenchers including styrene, owing to the short lifetime of the excited triplet state [27]. This circumstance makes benzoin photoinitiators particularly useful for industrial applications involving the styrene monomer. 

Initiation of the reaction of l-chloro-2-naphthoxide anion with NajSO, has been proposed to occur by ET between the excited triplet state of the substrate and its ground state. This reaction can be dye-photoinitiated-" or initiated by visible light with a Ru complex as sensitizer and a Co complex as the intermediate electron carrier.- - For the 1-bromo derivative, photohomolytic CBr bond dissociation is proposed. "... 

This reaction is based on a stoichiometric reaction of multifunctional olefins (enes) with thiols. The addition reaction can be initiated thermally, pho-tochemically, and by electron beam and radical or ionic mechanism. Thiyl radicals can be generated by the reaction of an excited carbonyl compound (usually in its triplet state) with a thiol or via radicals, such as benzoyl radicals from a type I photoinitiator, reacting with the thiol. The thiyl radicals add to olefins, and this is the basis of the polymerization process. The addition of a dithiol to a diolefin yields linear polymer, higher-functionality thiols and alkenes form cross-linked systems. 

The primary reaction of Type 2 photoinitiators is a hydrogen abstraction from the tertiary amine by a triplet excited ketone. The amino radical thus formed is sufficiently active to initiate the polymerization of vinyl monomers Scheme 2. 

The insight of photoinitiation is complicated. Even when CT absorption is observed, the initiation process may not start from a charge transferred state or form ion-radicals. An alternative mechanism is triplet excitation via charge transfer absorption. Namely, when the CT excited level is higher than the triplet level, a considerable amount of the CT excitation would be converted to the triplet state. The TMPD+-naphthalene pair fits in this case (20). Conversely, the contribution of CT might be predominant even when the CT interaction in the ground state is not observed. As shown in Eqs. (14) and (16), charge transfer interaction will not take part in photoexcitation but occurs in the excited state. Possible reaction mechanismus may be explained as follows. 

The first reaction in each sequence is the photoinitiated electron transfer, and can in principle occur from either an excited singlet state, or a triplet state. The second reaction is the charge recombination reaction or back reaction , as it is sometimes... 

Such compounds as polynuclear aromatics, heteroaromatics, ketones, quinones and dyes can serve as donors. Both excited singlet and triplet-states of these products can be involved in the PET. Diaryliodonium salts, triarylsulfonium salts, phosphonium salts, ammonium salts, pyrylium and thiapyrylium salts possess enough thermal stability and corresponding reduction potential to function as electron acceptors (R X+). In order to select suitable photoinitiator systems based on compounds discussed, the Weller-Eq. (5) can be employed. 

The first reaction describes the excitation of uranyl ions. The excited sensitizer can lose the energy A by a non-radiative process (12b), by emission (12c) or by energy transfer in monomer excitation to the triplet state (12d). Radicals are formed by reaction (12e). The detailed mechanism of step (12e) is so far unknown. Electron transfer probably occurs, with radical cation and radical anion formation these can recombine by their oppositely charged ends. The products retain their radical character. Step (12g) corresponds to propagation and step (12f) to inactivation of the excited monomer by collision with another molecule. The photosensitized initiation and polymerization of methacrylamide [69] probably proceeds according to scheme (12). Ascorbic acid and /7-carotene act as sensitizers of isoprene photoinitiation in aqueous media [70], and diacetyl (2, 3-butenedione) as sensitizer of viny-lidene chloride photopolymerization in a homogeneous medium (N--methylpyrrolidone was used as solvent) [71]. 

The low activation energy of the thermal addition polymerization reaction confirms the necessity of a (librational) motion of the molecules in the initiation process. The first addition process differs from all the following addition proccesses by the metastable monomer diradical structure, which — in contrast to the DR , AC , and DC structures with n > 2 — has a limited life-time given by the phosphorescence decay of the monomer triplet state. Therefore, the librational excitation must be performed during the life-time of the monomer reaction centre. In the case of the low temperature photopolymerization reaction the librational excitation has to be prepared optically via the decay of the electronic excitation. This is in contrast to the photopolymerization reaction at high temperatures, where numerous molecular motions are thermally and stationary present in the crystals. Due to this difference two photons (2hv) are required in every dimer initiation process at low temperatures and only one photon (hv -i- kT) is required at high temperatures. The two paths of the photoinitiation reaction are illustrated below by the arrows in Fig. 26. The respective pair states are characterized by M M and M M as discussed below. 

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