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5-6 CARBONYL POLYMERIZATION The polymerization of the carbonyl group in aldehydes yields polymers, referred to as polyacetals, since they contain the acetal repeating structure

where F(r, t) is an arbitrary function of rand t. Indeed, when a particular gauge is chosen, the redundant degrees of freedom can be eliminated using the constraint

5-125

7Here we are referring to the transverse component of the vector potential. which is gauge invariant. This component can give rise to an observable physical effect in a region where there are no fields (BohmAharonov effect [9]).



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Besides the carbon carbon double bond, this is the only other unsaturated linkage whose polymerization has been successfully carried out to an appreciable extent [Furukawa and Saegusa, 1963; Kubisa et al., 1980; Vogl, 1967, 1976, 2000]. The polymerization of formaldehyde has been studied much more intensely than that of other aldehydes. Although formaldehyde was successfully polymerized over a hundred years ago, it was not until much later that high-molecular-weight polymers of other aldehydes were obtained. Progress in the polymerization of the carbonyl linkage did not result until there was an understanding of the effect of ceiling temperature (Tc ) on polymerization (Sec. 3-9c). With the major exception of formaldehyde and one or two other aldehydes, carbonyl monomers have low ceiling temperatures (Table 5-13). Most carbonyl monomers have ceiling temperatures at or appreciably below room temperature. The low Tc values for carbonyl polymerizations are due primarily to the H factor. The entropy of polymerization of the carbonyl double bond in aldehydes is approximately the same as that for the alkene double bond. The enthalpy of polymerization for the carbonyl double bond, however, is appreciably lower. Thus H for acetaldehyde polymerization is only about 29 kJ mol 1 compared to the usual 80 90 kJ mol 1 for polymerization of the carbon carbon double bond (Table 3-14) [Hashimoto et al., 1076, 1978]. Most of the early attempts to polymerize carbonyl compounds were carried out at temperatures that were, in retrospect, too high. The use of temperatures above Tc resulted in the absence of polymer formation, due to the unfavorable equilibrium between monomer and polymer. Carbonyl monomers were successfully polymerized to high polymer when the





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relations introduced by the choice of gauge. Depending on the choice of gauge. however. the separation of the truly independent degrees of freedom of the fields from the rest might not be so straightforward as when we were dealing with the fields themselves. In non relativistic quantum electrodynamics. such a separation is possible by the adoption of the Coulomb gauge. The Coulomb gauge is the gauge where the vector potential A is transverse:

TABLE 5-13 Ceiling Temperaturesa Monomer Formaldehyde Tri uoroacetaldehyde Trichloroacetaldehyde Propanal Acetaldehyde Pentanal

A(k, t) = A-L(k, t).

Data from Brandup and Immergut [1989], Kubisa et al. [1980], Vogl [1976, 2000]. b Monomer concentration 1 atm (gaseous); all other data are for neat liquid monomer.

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polymerization reactions were carried out at temperatures below the ceiling temperatures of the monomers. Both anionic and cationic initiators, of the types used in alkene polymerizations, can be used to initiate the polymerization of the carbonyl double bond. These polymerizations are similar in their general characteristics to the ionic polymerizations of alkene monomers. The number of detailed mechanistic studies of carbonyl polymerizations is, however, very small. A characteristic of aldehyde polymerization is the precipitation, often with crystallization, of the polymer during polymerization. Depending on the solvent used, polymerization rate, state of agitation, and other reaction conditions, the polymerization can slow down or even stop because of occlusion of the propagating centers in the precipitated polymer. The physical state and surface area of the precipitated polymer in uence polymerization by their effect on the availability of propagating centers and the diffusion of monomer to those centers. 5-6a Anionic Polymerization

(5.92)

The carbonyl group is polymerized by a variety of anionic initiators. The strength of the base required to initiate polymerization depends on the substituent(s) attached to the carbonyl group. 5-6a-1 Formaldehyde

The transverse vector potential. however. has only two independent components in reciprocal space. These are components along two orthogonal directions on the plane perpendicular to k. We will denote a given choice of two such directions by the normalized vectors } (k) and 2(k). The components will be indicated by the subscripts } and 2. In the Coulomb gauge. the transverse fields depend on the vector potential only: 1 . (5.93) E-L(k,t) = -- A(k,t),

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