Free radical initiators benzophenone

The chemistry involved in LfV-curable resin systems has been extensively investigated and thoroughly surveyed [88-94]. LfV-radiation polymerization, is in principle, completely analogous to the conventional addition polymerization. A photoinitiator is used in UV polymerization. Its function is the same as the free-radical initiator. A conventional initiator possesses a thermally labile bond which is cleaved to form free-radical species, but the photoinitiator has a bond which breaks upon absorption of radiant energy. Benzoin ethers, benzyldialkyl ketals, benzophenone, and acetophenone derivatives are the important LfV-photoinitiators [95-99]. 

As already shown, it is technically possible to incorporate additive functional groups within the structure of a polymer itself, thus dispensing with easily extractable small-molecular additives. However, the various attempts of incorporation of additive functionalities into the polymer chain, by copolymerisation or free radical initiated grafting, have not yet led to widespread practical use, mainly for economical reasons. Many macromolecular stabiliser-functionalised systems and reactive stabiliser-functionalised monomers have been described (cf. ref. [576]). Examples are bound-in chromophores, e.g. the benzotriazole moiety incorporated into polymers [577,578], but also copolymerisation with special monomers containing an inhibitor structural unit, leading to the incorporation of the antioxidant into the polymer chain. Copolymers of styrene and benzophenone-type UV stabilisers have been described [579]. Chemical combination of an antioxidant with the polymer leads to a high degree of resistance to (oil) extraction. 

UV light induced grafting onto wood cellulose is reported for several vinyl monomers. The reaction is initiated by free radical initiators such as phenylace-tophenone and benzophenone derivatives. Percent grafting-time conversion curves are determined as a function of the initiators, monomers, pulps and additives. Additional typical results obtained in IR spectroscopy, GPC and thermal analysis are reported. A discussion about the use of a photochemical procedure in obtaining cellulose graft copolymers is presented. 

Among the UV sensitizers, some of which may accelerate the crosslinking rate by 100-200 times that of ordinary free-radical initiated processes, are ethers of benzoin, benzophenones, anthrone, benzil, and Michler s ketone [81]. 

Cheiv. Descrip. Benzophenone CAS 119-61-9 EINECS/ELINCS 204-337-6 Uses Free radical initiator for UV curing used in adhesives, chem. intermediates, coatings (metal, paper, wood), electronics (conformal, encapsulants, photoresists, solder masks), inks (flexo and gravure, litho, offset, screen) intermediate for mfg. of antihistamines, hypnotics, insecticides... 

Gosh and Mukherjee reported that monochloroacetic, dichloroacetic and trichloroacetic acids readily initiate photopolymerization of methyl methacrylate at 40 °C in visible light when used in the presence of dimethylaniline. The inhibition period decreases with an increase in the number of chlorine substitution of acetic acid. Addition of benzophenone decreases the induction period. They believe that free-radical initiation is a result of a collapse of the exiplex (acid-dimethylaniline) and an electron transfer from the nitrogen to the carbonyl oxygen of the acid. ... 

Physical entrapment or chemical coupling is a well-established procedure for MIP preparation. First, a complex is formed between a functional monomer and template in an appropriate solvent solution. Then the complex is immobilized by polymerization in excess of a cross-linker. Predominantly, free-radical polymerization thermally launched with a 2,2-azobis(isobutyronitrile) (AIBN) initiator, is performed. In the case of photo-radical polymerization, a benzophenone or acetopho-none derivative is also used as the initiator [101]. Next, the template is extracted by rinsing the resulting MIP block with a suitably selected solvent solution. The bulk... 

The addition of thiols to olefins (thiolene reaction), to form thioethers, is a well-known reaction. The process can occur by either free-radical or ionic mechanisms. The free-radical reaction can be initiated thermally via a peroxide or by UV irradiation with benzophenone. The initiation step involves the formation of a thiyl radical by hydrogen atom abstraction. Both of these species are capable of starting polymer chains (Table 2.30). 

Photopolymerization is traditionally initiated by direct photolysis of a precursor to provide free radicals via bond homolysis. Examples of such initiators include benzoin, and benzoin ethers, disulfides, and azoalkanes or dialkylperoxides. Hydrogen abstraction chemistry, typified by benzophenone photochemistry, is also recognized as extremely useful. However, a number of viable commercial photopolymer imaging systems are based upon ionic (especially cationic) polymerization. These systems will be discussed next. 

It should be pointed out that o-phthalaldehyde is a suitable free radical source, without requirement of an additional hydrogen donor, for the reduction of pyridinium ions, although the initiation mechanism is quite similar to that described for benzophenone. 

In the second group of systems diarylhalonium salts, failing to initiate polymerization generate the carbenium salts by decomposition induced by free radicals formed photochemk Benzophenone, benzil or maleic anhydride were used as sources of free radicals ... 

It is also well established [2,6-8] that in the photoinduced vinyl polymerization promoted by benzophenone, the free radical deriving from the hydrogen donor is active in the initiation step, whereas the semipinacol radical mainly undergoes self-coupling and combination with the growing polymer chains. It is pointed out, however, that this termination reaction may involve both hydrogen transfer and direct combination (Scheme 2). 

Gosh and Gosh [105] studied photoinitiated polymerization of methyl methacrylate initiated by the BP-TV,A-dimethylaniline couple, and Clarke and Shanks [106] tested the influence of a variety of amines on benzophenone-initiated polymerization. That amino radicals resulted during the initiation the polymerization by benzophenone-tertiary aromatic amines was shown by Li through the use of ESR and spin-trapping methods [107]. It was shown that the rate of photoinitiated polymerization depends on the structure of the amine. More recently [108] benzophenone-tertiary aromatic amines were studied as initiators of the free-radical polymerization of polyol acrylates. Illustrative kinetic curves recorded during photoinitiated polymerization of TMPTA are shown in Figure 23. 

Aliphatic sulfides can be efficient co-initiators for the photoinduced polymerization induced by benzophenone [185, 186]. An exceptionally strong effect was observed for 2,4,6-trimethyl-1,3,5-trithiane (TMT). A model reaction for free-radical formation during photoreduction of an initiator triplet state by a sulfide is the photoreduction of benzophenone by dimethyl sulfide [171, 187-189]. In this process it was established that electron transfer from the sulfur atom to the triplet state of the benzophenone is a primary photochemical step. In this step, radical ions are formed. The overall quantum yields of photoproducts (ketyl radicals and radical anions) are low (Ed) 0.26) in aqueous solution, in the range 0.16-0.20 in mixed water-acetonitrile solution and less then 0.01 in pure acetonitrile. These results suggest that, in organic solvents, back electron transfer within the radical-ion pair to regenerate the reactants is the dominant process. 

Polymerization of butane-1,4-diol dimethacrylate, sensitized by benzophenone in the presence of three different sulfides, has been described by Andrzejewska et al. [190]. The measurements show that in the absence and in the presence of propyl sulfide and 2,2 -thiobisethanol no polymer was formed. This can be explained by the effective back electron transfer process that occurs in the radical-ion pair in organic solvents. Effective polymerization was observed only in the presence of TMT. Laser flash photolysis studies performed for the benzophenone-TMT pair allow one to construct a scheme (Scheme 23) explaining characteristic features of the mechanism of polymerization initiated by the system. The results prompted the authors to study other symmetrically substituted 1,3,5-trithianes as electron donors for benzophenone-sensitized free-radical polymerization (Figure 38 Table 12) [191]. 

It was not suggested how the aryldiazomethane was initially formed but the minimum reaction temperature was lowered by 150° C on introduction of a phenyldi-azomethane catalyst. In contrast, pyrolysis of benzophenone azine gave no tetra-phenylethylene and only a trace of nitrogen . Benzophenone azine decomposes by a free radical process at 375-500 °C to afford principally benzhydrylideneimine, benzonitrile and 6-phenylphenanthridine accompanied by lesser quantities of benzene, biphenyl, diphenylmethane and benzhydrylideneaniline by the following pathways... 

The triplet excited benzophenone abstracts a hydrogen atom from THF producing benzhydryl and THF free radicals. Both radicals are easily oxidized by J0 I AsF resulting in the formation of possible initiating species for cationic polymerization. Hydrogen abstraction by phenyl radicals propagates the chain. 

Figure 8, Chain reaction photoinitiation. The efficiency of photoinitiation can be increased by chain reactions. Hydrogen abstraction by triplet excited benzophenone forms a THF free radical. Subsequent oxidation by the aryliodonium salt produces the THF cation capable of initiating polymerization, and a phenyl radical. Hydrogen abstraction by the phenyl radical produces the THF free radical completing the...

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