Gelation thermosetting

Polyester Resins. Reinforced polyester resins are thermosets based on unsaturated polyesters from glycols and dibasic acids, either or both of which contain reactive double bonds. The ratio of saturated to unsaturated components controls the degree of cross-linking and thus the rigidity of the product (see Polyesters, unsaturated). Typically, the glycols and acids are esterified until a viscous Hquid results, to which an inhibitor is added to prevent premature gelation. Addition of the monomer, usually styrene, reduces the viscosity to an easily workable level. 

Control of crosslinking is critical for processing thermoset plastics, both the reaction prior to the gel point and that subsequent to the gel point. The period after the gel point is usually referred to as the curing period. Too slow or too rapid crosslinking can be detrimental to the properties of a desired product. Thus, in the production of a thermoset foamed product, the foam structure may collapse if gelation occurs too slowly. On the other hand, for reinforced and laminated products the bond strength of the components may be low if crosslinking occurs too quickly. 

The chemical structure of the epoxy matrix constituent as well as processing are reported to strongly influence 11 -I3> the thermoset network and hence the properties and durability of the crosslinked polymer 11 ,4-16). The cure of a reactive prepolymer involves the transformation of low-molecular-weight reactive substances from liquid to rubber and solid states as a result of the formation of a polymeric network by chemical reaction of some groups in the system. Gelation and vitrification are the two macroscopic phenomena encountered during this process which strongly alter the viscoelastic behavior of the material. 

Figure 3.13 shows the variation of the gel conversion of the limiting reactant as a function of the stoichiometric ratio. For r > 3, no gel is formed and the polymer remains in the liquid state after complete reaction of epoxy groups. If the amount of epoxy monomer necessary to obtain a stoichiometric system is added in a second step, polymerization restarts, leading to gelation and the formation of a network. The two-step polymerization is the basis of several commercial thermosetting polymers. 

Thermosetting polymers represented in Figs 6.4, 6.5, and also 6.6 were cured at T > Tgw In many cases and particularly for high-Tg networks, a precure step is performed at Tj < Tgco. In this case the two transformations, gelation and vitrification, occur and the rheology in the vicinity of the critical gel point could be affected by vitrification. 

A secondary phase separation may take place inside the (3-phase, and due to diffusion effects it leads to a sub-structure of thermoset-rich domains. Secondary phase separation may be arrested by gelation or vitrification of the (3-phase. 

In Section 4, we have examined, from a fundamental point of view, how temperature and cure affect the dielectric properties of thermosetting resins. The principal conclusions of that study were (1) that conductivity (or its reciprocal, resistivity) is perhaps the most useful overall probe of cure state, (2) that dipolar relaxations are associated with the glass transition (i.e., with vitrification), (3) that correlations between viscosity and both resistivity and dipole relaxation time are expected early in cure, but will disappear as gelation is approached, and (4) that the relaxed permittivity follows chemical changes during cure but is cumbersome to use quantitatively. 

Dusek, K. and Matejka, L., Transesterification and Gelation of Polyhydroxy Esters Formed from Diepoxides and Dicarboxylic Acids, in Rubber Modified Thermoset Resins, Riew, C. K. and Gillham, J. K. (Eds), Am. Chem. Soc., Adv. Chem. Series 208 (l984), pp. 15-26. 

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