Polymerization mechanisms epoxy cure

Radiation curing of epoxies with cationic initiators is well known [20—28]. UV-visible light has been the predominant radiation source the process has been limited to thin coatings due to the low penetration of the visible-UV light [22,23], Thermal and mechanical properties of these materials are low and the curing is incomplete. Several studies have shown that commercially available epoxies with various cationic initiators can be polymerized with EB curing [20,29-34]. 

An analogous mechanism should also produce polymers on irradiation of epoxies. Crivello s recent mechanistic suggestions [29] are consistent with the mechanisms given above. One can conclude that radiation-induced polymerization of epoxies can proceed via several mechanisms. However, further work is needed to determine the relative contributions of the different mechanisms, which might vary from one epoxy to another. As part of the Interfacial Properties of Electron Beam Cured Composites CRADA [37], an in-depth study of the curing mechanism for the cationic-initiated epoxy polymerization is being undertaken. 

Fig. 12. C- 13 spectrum of the piperidine (PIP) cured DGEBA epoxy polymer at room temperature. The assignments have been discussed and the structure indicates a possible polymerization mechanism 2 ...

Transformation of epoxy resins, which are viscous liquids or thermoplastic solids, into network polymers is a result of interaction with alkali or acid substances by means of to polyaddition and ionic polymerization mechanisms.10 A resin solidified by to the polyaddition mechanism, is a block copolymer consisting of alternating blocks of resin and a hardener or curing agent. A resin solidified by the ionic mechanism is a homopolymer. Molecules of both resin and hardener contain more than one active group. That is why block copolymer formation is a result of multiple reactions between an epoxy resin and a curing agent.11... 

The main raw materials used in epoxy adhesive formulations (resins and curing agents) can be synthesized in a variety of ways to create many different products. Epoxies react readily via several polymerization mechanisms. The extent of crosslinking is an important determinant of the final properties of the adhesive. Crosslinking can be controlled by the choice of resin and curing agent and by the curing conditions. 

Although the major interest in experimental and theoretical studies of network formation has been devoted to elastomer networks, the epoxy resins keep apparently first place among typical thermosets. Almost exclusively, the statistical theory based on the tree-like model has been used. The problem of curing was first attacked by Japanese authors (Yamabe and Fukui, Kakurai and Noguchi, Tanaka and Kakiuchi) who used the combinatorial approach of Flory and Stockmayer. Their work has been reviewed in Chapter IV of May s and Tanaka s monograph Their experimental studies included molecular weights and gel points. However, their conclusions were somewhat invalidated by the fact that the assumed reaction schemes were too simplified or even incorrect. It is to be stressed, however, that Yamabe and Fukui were the first who took into account the initiated mechanism of polymerization of epoxy groups (polyetherification). They used, however, the statistical treatment which is incorrect as was shown in Section 3.3. 

Many different photoinitiators based on onium -type compounds with anions of low nucleophilicity also have been described in the literature as effective catalysts for the polymerization of epoxides Thus, diaryliodonium salts diaryliodosyl salts triarylsulfonium salts and related compoundstri-phenylsulfoxonium saltsdialkylphenacylsulfonium salts and dialkyl-4-hydroxyphenylsulfonium salts seem to be most suitable as photoinitiators for epoxy curing. Some of the principles of the reaction mechanism involving these initiators are discussed in detail in the following Sections. Various other onium photoinitiators such as diarylchloronium and diarylbromonium salts , thiopyrylium salts 3), triarylselenonium salts and onium salts of group Va elements >... 

Macosko and Miller (1976) and Scranton and Peppas (1990) also developed a recursive statistical theory of network formation whereby polymer structures evolve through the probability of bond formation between monomer units this theory includes substitution effects of adjacent monomer groups. These statistical models have been used successfully in step-growth polymerizations of amine-cured epoxies (Dusek, 1986a) and urethanes (Dusek et al, 1990). This method enables calculation of the molar mass and mechanical properties, but appears to predict heterogeneous and chain-growth polymerization poorly. 

Unlike epoxies, which cme by an ionic polymerization mechanism, modified acrylics cure by free-radical addition. Therefore, careful proportioning of components is not required. In two-component systems, no mixing is required because the adhesive is applied to one substrate, the activator to the other, and the substrates are joined. Handling strength is rapidly achieved with this fast-curing system. 

Pojman et al. studied binary systems with two non-interfering polymerization mechanisms (79). With a cationic/amine cured epoxy and a free-radical cured diacrylate, they observed there was a minimum in the front velocity as a function of the relative concentration of each component. No comparable study has been made with copolymerization fronts. 

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