Vinyl ethers, photoinitiator-free polymerization

Photoinitiator Free Polymerization of Maleimides and Vinyl Ethers... 

Thus, a mixture of simple carbonyls Me(CO)n and halides should behave as a photoinitiator of free radical polymerization. Many such systems have been found to function in this way. Complexes formed by irradiation of Fe(CO)5 in the presence of a vinyl monomer (M) (such as MMA, styrene, vinyl acetate, propylene, and vinyl ether) have been studied by Koerner Von Grustrof and colleagues [12,13] and shown to have the chemical struc-... 

Difunctional vinvl ether/difunctional N-maleimide. Up until this point, our results have centered on the reactivity of monofunctional maleimide divinyl ether mixtures. From Kloosterboer s26 work for acrylate polymerization, it is known that the rate of polymerization of a free-radical process is increased dramatically as the functionality of the acrylate is increased. In order to enhance the polymerization rates of maleimide divinyl ether systems, it was decided to synthesize difimctional maleimides for copolymerization with difunctional vinyl ethers. The results in Table V indicate that the photoinitiated TTDBM [bismaleimide made from maleic anhydride and 4,7,10-... 

Vinyl ethers can also be formulated with acrylic and unsaturated polyesters containing maleate or fumarate functionality. Because of their ability to form alternating copolymers by a free-radical polymerization mechanism, such formulations can be cured using free-radical photoinitiators. With acrylic monomers and oligomers, a hybrid approach has been taken using both simultaneous cationic and free-radical initiation. A summary of these approaches can be found in Table 9. 

Free radical promoted, cationic polymerization also occurs upon irradiation of pyridinium salts in the presence of acylphosphine oxides. But phosphonyl radicals formed are not oxidized even by much stronger oxidants such as iodonium ions as was demonstrated by laser flash photolysis studies [51, 52]. The electron donor radical generating process involves either hydrogen abstraction or the addition of phosphorus centered or benzoyl radicals to vinyl ether monomers [53]. Typical reactions for the photoinitiated cationic polymerization of butyl vinyl ether by using acylphosphine oxide-pyridinium salt combination are shown in Scheme 10. 

A similar study has been performed on EPI blends in which the vinyl ether was replaced by an acrylate monomer (HDDA) to produce, by different mechanisms, two interpenetrating polymer networks. With the onium salt as sole photoinitiator, the cationic polymerization of the EPI epoxy groups occurred as fast in the formulation containing 20% of HDDA by weight as in the EPI/DVE-3 blend, to reach nearly 100% conversion within 0.6 s (Fig. 11). The polymerization quantum yield was found to be similar to that measured in the EPI/vinyl ether blend Op 650 mol E. By contrast, the acrylate double bonds were found to polymerize at a much slower pace, most probably because of the low reactivity of the free radicals generated by the cationic-type photoinitiator. 

In systems 1-4 radical polymerization takes place. Decomposition of the photoinitiator (e.g., benzoin and its derivatives) leads to formation of free radicals which react with the carbon-carbon double bonds. In system 5 acidic reactive species are formed which react with cycloaliphatic epoxy compounds and vinyl ethers to form a cross-linked network. Sulfonium, and iodonium salts are used to initiate this cationic polymerization, a typical example is PhjS PFg. ... 

The virtues of photoinitiated cationic polymerization are rapid polymerization without oxygen inhibition, minimal sensitivity to water, and the ability to polymerize vinyl ethers, oxiranes (epoxides), and other heterocyclic monomers (see Table 10.7) that do not polymerize by a free radical mechanism. 

There are definite attractions for monomers that can be used without the aid of initiators. Such monomers are maleimides. The monomers based on vinyl acrylate are also capable of self initiation. The vinyl ester itself, however, is too volatile for practical use and its initiation of polymerization is slower than obtained with the traditional photoinitiators. When the acrylate group is replaced by crotonate, cinnamate, fumarate, or maleate chromophores, these monomers copolymerize readily with thiol and vinyl ether monomers and initiate free-radical polymerization upon direct excitation in the absence of any added photoinitiator. 

Free radical polymerization is disturbed by oxygen, as shown in Chapter 1, while cationic polymerization shows no effect from oxygen. Epoxy or vinyl-ether compounds are used for cationic polymerization. Typical cationic polymers are shown in Figure 4.10. Photoinitiators are photoacid-generating compounds, di-(p-toluene)iodonium hexafluoroantimonate and triphenyl-sulfonium hexafluorophosphate, as shown in Figure 4.11. 

The efficiency of cationic photoinitiators can be enhanced by the use of free-radical sources such as benzoin alkyl ethers and alkoxyacetophenones. In the presence of THF, photo-active radical sources and diaryliodonium salts would be expected to yield cations as outlined in Scheme 1. The neral method of producing cations by the oxidation of radicals produced from any source has been demonstrated for the polymerization of vinyl ethers and THF. ... 

Decker C, Morel F, Jdnsson S, et al. Light-induced polymerization of photoinitiator-free vinyl-ether-maleimide systems. Macromol ChemPhys. 1999 200 1005-1013. 

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