Photoinitiators-primary processes

Primary processes occurring in the excited state of a UV radical photoinitiator. (Adapted from Jablonski, A., Z. Physik, 94, p. 38 (1935).)... 

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 ... 

Section 4.4) on the photoinitiation process, one can anticipate that under certain conditions (identical free radicals formed), the rules regulating the primary processes can also be applied for the secondary processes. The results presented in Figure 8 confirm this expectation. It is clear from the data (Figure 8) that the rate of polymerization as initiated by the series of cyanine borates in Table 2 increases as the driving force of the electron transfer increases. This behavior is predicted by the classical theory of photoinduced electron transfer. 

Some particular ketones usable as multiphoton photoinitiators have been synthesized. For example, a compound containing two-electron donating groups linked by a conjugated chain (10.55) is sensitive in the range 800-1000 nm the initiation mechanism is not fully understood an electron transfer with the monomer might be the primary process [189]. Newly developed cross-conjugated photoinitiators with bathochromic shifts exhibit one and two photon activity [190]. 

A chain reaction polymerization of vinyl monomer, which is usually carried out by a photoinitiator to produce a primary radical (R ), which can interact with a monomer molecule (M) in a propagating process to form a polymer chain composed of a large number of monomer units (see Eq. [2] and reaction Scheme [3]. 

The initiating radicals are assumed to be SCN, ONO or N3 free radicals. Tris oxalate-ferrate-amine anion salt complexes have been studied as photoinitiators (A = 436 nm) of acrylamide polymer [48]. In this initiating system it is proposed that the CO2 radical anion found in the primary photolytic process reacts with iodonium salt (usually diphenyl iodonium chloride salt) by an electron transfer mechanism to give photoactive initiating phenyl radicals by the following reaction machanism ... 

Many reviews have been written on the photochemistry of aromatic carbonyl compounds269 and on the use of these compounds as photoinitiators.270 272 Primary radicals are generated by one of the following processes ... 

The S-S linkage of disulfides and the C-S linkage of certain sulfides can undergo photoinduced homolysis. The low reactivity of the sulfur-centered radicals in addition or abstraction processes means that primary radical termination can be a complication. The disulfides may also be extremely susceptible to transfer to initiator (Ci for 88 is ca 0.5, Sections 6.2.2.2 and 9.3.2). However, these features are used to advantage when the disulfides are used as initiators in the synthesis of tel ec he lies295 or in living radical polymerizations. 96 The most common initiators in this context are the dithiuram disulfides (88) which are both thermal and photochemical initiators. The corresponding monosulfides [e.g. (89)J are thermally stable but can be used as photoinitiators. The chemistry of these initiators is discussed in more detail in Section 9.3.2. 

Similar to the above discussed processes, the photoinitiation of the copolymerization between cyclohexene and AN in the presence of pyromellitic dianhydride or phthalic anhydride is based on the sequence of PET and proton transfer [30]. Consequently, the copolymerization rate with the former acceptor (Rp = 1.6x 10-4moll-1 s-1) is higher than this of the latter (Rp = 1.4x 10-4moll-1 s-1 [AN] = 4.5 mol l-1, 30°C). Interestingly, the average-molar weights of the alternating copolymers lie between 1000-2000 g mol- The reason for this very small value is possibly an efficient primary radical termination due to the formation of the two radicals IV and V see Eq. (4). Exact polymer characterization data are not available, so far. 

In the present ehapter we consider the inter- or intramolecular photoinduced electron transfer phenomenon. We mainly focus on photoinduced electron transfer processes that lead to the photoinitiation of polymerization, and on processes initiated by photoredueed or photooxidized excited states. We concentrate especially on a description of the kinetic schemes, a description of the reactions that follow the primary proeess of eleetron transfer, and the characteristics of intermediates formed after electron transfer. Understanding the complexity of the processes of photo-initiated polymerization requires a thorough analysis of the examples illustrating the meehanistie aspects of the formation of free radicals with the ability to start polymerization. 

In each system, the primary photo-event is dissociation of the cationic photoinitiator to produce an acid. This reaction proceeds with a quantum efficiency that is characteristic of the particular initiator. The photogenerated acid then interacts with a carefully chosen polymer matrix to initiate a chain reaction, or acts as a catalyst, such that a single molecule of photogenerated acid serves to initiate a cascade of bond making or breaking reactions. The effective quantum efficiency of the overall process is the product of the photolysis reaction efficiency times the length of the chain reaction (or the catalytic chain length). This multiplicative response constitutes... 

Given that the rate of generation of primary radicals, at a given light flux, is a function of the concentration of photoinitiator, the induction period depends also on initiator concentration. In order to eliminate this induction period of polymerization in industrial scale applications, many photocuring processes are carried... 

In spite of the numerous studies reported on photooxidation of polyolefins, the detailed mechanism of the complete process remains unresolved. The relative contribution by species involved in photoinitiation, the origins of the oxidative scission reaction, and the role played by morphology in the case of photoreactions in solid state are not completely understood. Primary initiator species in polyethylenes [123] and polypropylenes [124] are believed to be mainly ketones and hydroperoxides. During early oxidation hydroperoxides are the dominant initiator, particularly in polypropylene, and can be photolyzed by wavelengths in solar radiation [125]. Macro-oxy radicals from photolysis of polyethylene hydroperoxides undergo rapid conversion to nonradical oxy products as evidenced by ESR studies [126]. Some of the products formed are ketones susceptible to Norrish I and II reactions leading to chain scission [127,128]. Norrish II reactions predominate under ambient conditions [129]. Concurrent with chain scission, crosslinking, for instance via alkoxy macroradical combination [126], can take place with consequent gel formation [130,131]. 

Table 1 Common examples of photoinitiators that undergo primary photofragmentation processes...

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