Polymerization photoinitiated

Photoinitiation is not as important as thermal initiation in the overall picture of free-radical chain-growth polymerization. The foregoing discussion reveals, however, that the contrast between the two modes of initiation does provide insight into and confirmation of various aspects of addition polymerization. The most important application of photoinitiated polymerization is in providing a third experimental relationship among the kinetic parameters of the chain mechanism. We shall consider this in the next section. 

When results are compared for polymerization experiments carried out at different frequencies of blinking, it is found that the rate depends on that frequency. To see how this comes about, we must examine the variation of radical concentration under non-stationary-state conditions. This consideration dictates the choice of photoinitiated polymerization, since in the latter it is almost possible to turn on or off—with the blink of a light—the source of free radicals. The qualifying almost in the previous sentence is actually the focus of our attention, since a short but finite amount of time is required for the radical concentration to reach [M-] and a short but finite amount of time is required for it to drop back to zero after the light goes out. 

Dry-Film Resists Based on Radical Photopolymerization. Photoinitiated polymerization (PIP) is widely practiced ia bulk systems, but special measures must be taken to apply the chemistry ia Hthographic appHcations. The attractive aspect of PIP is that each initiator species produced by photolysis launches a cascade of chemical events, effectively forming multiple chemical bonds for each photon absorbed. The gain that results constitutes a form of "chemical amplification" analogous to that observed ia silver hahde photography, and illustrates a path for achieving very high photosensitivities. 

In the case of photoinitiated polymerization, an oxygen-free aqueous solution of acrylamide with a concentration of about 50% mixed with a photosensibilizer and other required additives is passed through a column-type apparatus with exterior water-cooling. A thin layer of the solution is exposed to a mercury lamp, acquires the consistency of a plastic film, which then can be passed through a second exposure zone, and is crushed and dried. Acrylamide polymers produced by this method are easily soluble and have a low residual monomer content. 

Bosch P, Peinado C, Martin V, Catalina F, Corrales T (2006) Fluorescence monitoring of photoinitiated polymerization reactions synthesis, photochemical study and behaviour as fluorescent probes of new derivatives of 4-dimethylaminostyryldiazines. J Photochem Photobiol A Chem 180(1-2) 118-129... 

Light Intensity and Temperature Effect in Photoinitiated Polymerization... 

In considering the potential candidates for donor/acceptor photoinitiated polymerization in the absence of an added photoinitiator, we have evaluated a number... 

See also Epoxy coatings Epoxy chalcone, 10 450 12,13-Epoxy-cis-9-octadecenoic (vernolic) acid, physical properties, 5 35t Epoxy coatings, 10 436 450 17 845. See also Epoxy can coatings for corrosion protection, 7 199 markets for, 10 442-449 performance of, 10 423 waterborne, 10 439 Epoxy composites, 10 450, 451 Epoxy compounds, photoinitiated polymerization of, 23 716 Epoxy content analysis, 10 385 Epoxy cresol novolac (ECN) resins, 10 367, 369... 

Three-dimensional engineering, prototyping photoinitiated polymerization in, 19 117 Three-dimensional food packaging, 18 48-49... 

Photochemical or photoinitiated polymerizations occur when radicals are produced by ultraviolet and visible light irradiation of a reaction system [Oster and Yang, 1968 Pappas, 1988]. In general, light absorption results in radical production by either of two pathways ... 

The radiolysis of olefinic monomers results in the formation of cations, anions, and free radicals as described above. It is then possible for these species to initiate chain polymerizations. Whether a polymerization is initiated by the radicals, cations, or anions depends on the monomer and reaction conditions. Most radiation polymerizations are radical polymerizations, especially at higher temperatures where ionic species are not stable and dissociate to yield radicals. Radiolytic initiation can also be achieved using initiators, like those used in thermally initiated and photoinitiated polymerizations, which undergo decomposition on irradiation. 

---