Course of Polymerization

Radical chain polymerizations are characterized by the presence of an autoacceleration in the polymerization rate as the reaction proceeds [North, 1974], One would normally expect a reaction rate to fall with time (i.e., the extent of conversion), since the monomer and initiator concentrations decrease with time. However, the exact opposite behavior is observed in many polymerizations—the reaction rate increases with conversion. A typical example is shown in Fig. 3-15 for the polymerization of methyl methacrylate in benzene solution [Schulz and Haborth, 1948]. The plot for the 10% methyl methacrylate solution shows the behavior that would generally be expected. The plot for neat (pure) monomer shows a dramatic autoacceleration in the polymerization rate. Such behavior is referred to as the gel effect. (The term gel as used here is different from its usage in Sec. 2-10 it does not refer to the formation of a crosslinked polymer.) The terms Trommsdorff effect and Norrish-Smith effect are also used in recognition of the early workers in the field. Similar behavior has been observed for a variety of monomers, including styrene, vinyl acetate, and methyl methacrylate [Balke and Hamielec, 1973 Cardenas and O Driscoll, 1976, 1977 Small, 1975 Turner, 1977 Yamamoto and Sugimoto, 1979]. It turns out that the gel effect is the normal  

A more critical analysis of accurate polymerization data indicates that the situation is complicated three stages can be distinguished in some polymerizations when is plotted against time (or conversion) (Fig. 3-16) [Dionisio et al, 1979 Dionisio and O Driscoll, 1980 Sack et al., 1988]. Plotting i p/[M] [I] instead of percent conversion takes 

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Synthetic Fiber and Plastics Industries. In the synthetic fibers and plastics industries, the substrate itself serves as the solvent, and the whitener is not appHed from solutions as in textiles. Table 6 Hsts the types of FWAs used in the synthetic fibers and plastic industries. In the case of synthetic fibers, such as polyamide and polyester produced by the melt-spinning process, FWAs can be added at the start or during the course of polymerization or polycondensation. However, FWAs can also be powdered onto the polymer chips prior to spinning. The above types of appHcation place severe thermal and chemical demands on FWAs. They must not interfere with the polymerization reaction and must remain stable under spinning conditions. 

The relative importance of combination and disproportionation in relevant model systems and in polymerizations of some common monomers is considered in Sections 5,2.2.1 and 5.2.2.2 respectively. The significance of the termination mechanism on the course of polymerization and on the properties of polymers is discussed briefly in Section 5.2.2 and is further discussed in Section 8.2. 

It has been proposed that transfer to monomer may not involve the monomer directly but rather the intermediate (110) formed by Diels-Alder dimerization (Scheme 6.28). 70 Since 110 is formed during the course of polymerization, its involvement could be confirmed by analysis of the polymerization kinetics. 

Since intermediates usually cannot be observed directly, the exact nature of the donor-acceptor complex and the mechanisms for their interaction with radicals are speculative. At least three ways may be envisaged whereby complex formation may affect the course of polymerization ... 

In applying equation (l) Cardenas and 0 Driscoll use Xq as the critical chain length for chain entanglement and permit Xq to decrease as ( )p increases during the polymerization according to equation (l). Therefore, during the course of polymerization they note three kinds of termination reactions ... 

Polymerization reactions of olefins and dienes cannot be treated here in detail. Knowledge of the early steps which occur on nickel, as in oligomerization reactions, help explain the course of polymerization reactions and particularly their stereospecific character, as in Ziegler-Natta polymerization. 

Interest in optically active polymers arose from analogy with macromolecules of biological origin. In addition, there was the hope to obtain new information to clarify the stereochemical features of synthetic polymers this, in fact, did come about. Attempts to direct the course of polymerization using chiral reagents had been made already prior to the discovery of stereospecific polymerization. It was only after the 1950s, however, that the problem of polymer chirality was tackled in a rational way. The topic has been reviewed by several authors (251-257). In this section I shall try to illustrate three distinct aspects the prediction of chirality in macromolecular systems, the problems regarding the synthesis of optically active polymers, and polymer behavior in solution. 

For high molecular weight, Mn and M /Mn do not change in the course of polymerization up to about 60% conversion. These results confirm that under proper conditions (polymerization at moderate temperature, template of high enough molecular weight, moderate concentration of substrates) ladder-type polymers can be obtained by template polymerization of multiacrylates or methacrylates. 

Dilatometric technique can also be used for determination of polymerization rate in the case of multimonomer polymerization. However, in this case calibration of the dilatometric method is more complex. The substrates and products are both polymers with similar molecular weights. Difference in density during the course of polymerization is connected only with the conversion of double bonds to the single bonds. It is difficult to obtain a macromolecular product in which double bonds are fully converted to single bonds. Calibration must be based on simultaneous measurements of Ah and independent method (e.g., IR spectroscopy) and calculation of (1/dp l/d]vi). 

Polymerization Kinetics and Cure Studies [2,4,25] Infrared spectra of monomers differ markedly from spectra of the polymers [2], As a consequence, it is possible to use infrared spectroscopy to follow the course of polymerization reactions and to simultaneously analyze the structure of the polymer [2]. 

Common thermosets are cured by a free radical addition mechanism. These types of composites are cured by heat initiators, such as peroxides, or by photo initiators, such as a-diketones. A characteristic of cured acrylates is large shrinkage in the course of polymerization, which is undesirable for many uses. Another undesirable characteristic of acrylates is the formation of an oxygen-inhibited layer on the surface upon curing. 

Multi-component catalyst systems based on palladium compounds and phosphorus compounds show a particularly high activity (35). The high catalytic activity is not deteriorated in the course of polymerization. Substituted norbornene derivates can be used that are otherwise difficult to polymerize. 

At this point, the phenomenon of phase inversion occurs and the rubber in monomer phase becomes dispersed as discrete particles in a matrix of the polymer in monomer phase. Usually in a mass polymerization process, the rubber will contain occlusions of polymer/monomer, which serve to swell the volume of the rubber particle. In the course of polymerization, monomer is converted to polymer, the viscosity of the mixture increases and greater power is needed to maintain the temperature and the compositional uniformity throughout the polymerized material (8). 

The small reactivity ratio for AN indicates that a growing AN radical is reluctant to react with an AN monomer, but rather will react with a styrene monomer. On the other hand, even when a growing styrene radical reacts rather with an AN monomer, the tendency is not as marked. In the limiting case, if both monomer reactivity rations are going to zero, this effects the formation of strictly alternating polymers. The composition of the polymer can be controlled by the ratio of monomers in the monomer feed. In particular, since one of the monomers will be consumed faster that the other in a discontinuous process, the monomer feed can be adjusted accordingly in the course of polymerization. Also in a continuous process, in a cascade of reaction vessels, monomer can be fed into certain stages. 

Assuming that we are dealing with so-called "living" polymerization (in the absence of chain termination in the course of polymerization), the kinetic mechanism of (o-dodecalactam polymerization with instantaneous initiation can be written as... 

For some particular formulations (e.g., unsaturated polyesters formulated with a high styrene concentration), the primary chains that are first generated are not miscible with the unreacted monomers. In this case, there is a phase separation phenomenon characterized by the appearance of relatively large polymer-rich particles. These microgels are formed by a thermodynamic driving force and their sizes are large enough to be detected in both the course of polymerization and the final materials. 

For formulations rich in styrene, phase separation takes place in the course of polymerization (Hsu and Lee, 1991). In this case it would be necessary to account for the different compositions of both phases and the partition of the initiators and radicals between them. 

Many thermosets are inhomogeneous. This may be the result of the polymerization mechanism (chemically induced inhomogeneities, such as those produced by the free-radical crosslinking polymerization of multifunctional monomers or by the step polymerization of three different monomers), or of the decrease of solubility of reaction products (thermodynamic driving force) or of both factors acting simultaneously, such as the case of several UP formulations. Inhomogeneities formed in the course of polymerization are fixed by the crosslinking reactions. 

The thermoplastic-rich phase may be separated in the course of polymerization (Sec. 13.4.2) or can be incorporated as a dispersed powder in the initial formulation (Sec. 13.4.3). A strong drawback of the in situ-phase separation for processing purposes is the high viscosity of the initial solution which results from the much higher average molar mass of the TP compared with the liquid rubbers. Also, for the same reason, the critical concentration crit has a smaller value (phase inversion is observed at smaller concentrations of modifier). 

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