Trommsdorff effect

The rate process for termination is hindered through the Trommsdorff effect. 

Trometh amine Trommels Trommel screens Trommsdorff effect Trona... 

Bulk Polymerization. This is the method of choice for the manufacture of poly(methyl methacrylate) sheets, rods, and tubes, and molding and extmsion compounds. In methyl methacrylate bulk polymerization, an auto acceleration is observed beginning at 20—50% conversion. At this point, there is also a corresponding increase in the molecular weight of the polymer formed. This acceleration, which continues up to high conversion, is known as the Trommsdorff effect, and is attributed to the increase in viscosity of the mixture to such an extent that the diffusion rate, and therefore the termination reaction of the growing radicals, is reduced. This reduced termination rate ultimately results in a polymerization rate that is limited only by the diffusion rate of the monomer. Detailed kinetic data on the bulk polymerization of methyl methacrylate can be found in Reference 42. 

Chain transfer to polymer is reported as a major complication and is thought to be unavoidable in the polymerization of alkyl acrylates.200 202 The mechanism is believed to involve abstraction of a tertiary backbone hydrogen (Scheme 6.32). It has been proposed that this process and the consequent formation of branches may contribute to the early onset of the gel or Norrish-Trommsdorff effect in the polymerization of these monomers. At high temperatures the radicals formed may undergo fragmentation. 

The chain termination rate varies inversely with the viscosity of the polymerization medium because of the Trommsdorff Effect (i.e., the reduction of the macroradical mobility with increasing reaction viscosity). This effect significantly influences reaction rate[ ,2, 10]. 

A kinetic study for the polymerization of styrene, initiated with n BuLi, was designed to explore the Trommsdorff effect on rate constants of initiation and propagation and polystyryl anion association. Initiator association, initiation rate and propagation rates are essentially independent of solution viscosity, Polystyryl anion association is dependent on media viscosity. Temperature dependency correlates as an Arrhenius relationship. Observations were restricted to viscosities less than 200 centipoise. Population density distribution analysis indicates that rate constants are also independent of degree of polymerization, which is consistent with Flory s principle of equal reactivity. 

The desorption and termination constants were calculated for a copolymer from the corresponding homopolymer constants as discussed in Nomura and Fujita (12.) The homopolymer desorption coefficients were calculated from the appropriate chain transfer constants and radical diffusivities in the aqueous and polymer phases using an extension of the desorption theory developed by Nomura and Fujita (12.). The homopolymer termination constants were corrected for the Trommsdorff effect by using the Friis and Hamielec (12) correlation. 

Although the basic mechanisms are generally agreed on, the difficult part of the model development is to provide the model with the rate constants, physical properties and other model parameters needed for computation. For copolymerizations, there is only meager data available, particularly for cross-termination rate constants and Trommsdorff effects. In the development of our computer model, the considerable data available on relative homopolymerization rates of various monomers, relative propagation rates in copolymerization, and decomposition rates of many initiators were used. They were combined with various assumptions regarding Trommsdorff effects, cross termination constants and initiator efficiencies, to come up with a computer model flexible enough to treat quantitatively the polymerization processes of interest to us. 

Then, they depend also on the viscosity of the system. Specific diffusion control is characteristic of fast reactions like fluorescence quenching. In polymer formation, specific diffusion control is responsible for the acceleration of chain polymerization due to the retardation of the termination by recombination of two macroradicals (Trommsdorff effect). Step reactions are usually too slow to exhibit a dependence on translational diffusion also, the temperature dependence of their rate constants is of the Arrhenius type. 

If ki and k.i are much larger than kj, the reaction Is controlled by kj. If however, ki and k.i are larger than or comparable to kz, the reaction rate becomes controlled by the translational diffusion determining the probability of collisions which Is typical for specific diffusion control. The latter case Is operative for fast reactions like fluorescence quenching or free-radical chain reactions. The acceleration of free-radical polymerization due to the diffusion-controlled termination by recombination of macroradicals (Trommsdorff effect) can serve as an example. 

When polymerizations become viscous, termination slows allowing an increase in the number of growing chains and rate of polymerization. This is known as the gel of Trommsdorff effect. If such reactions are allowed to continue without cooling, explosions are possible. 

Trommsdorff effect Decrease in termination rate in viscous media that results in higher molecular weight polymers being formed. 

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 ... 

Case 3 behavior occurs when the particle size is sufficiently large (about 0.1-1 pm) relative to kt such that two or more radicals can coexist in a polymer particle without instantaneous termination. This effect is more pronounced as the particle size and percent conversion increase. At high conversion the particle size increases and k, decreases, leading to an increase in h. The increase in h occurs at lower conversions for the larger-sized particles. Thus for styrene polymerization it increases from 0.5 to only 0.6 at 90% conversion for 0.7-pm particles. On the other hand, for 1.4-pm particles, n increases to about 1 at 80% conversion and more than 2 at 90% conversion [Chatterjee et al., 1979 Gerrens, 1959]. Much higher values of h have been reported in other emulsion polymerizations [Ballard et al., 1986 Mallya and Plamthottam, 1989]. Methyl methacrylate has a more pronounced Trommsdorff effect than styrene and vinyl acetate, and this results in a more exaggerated tendency toward case 3 behavior for methyl methacrylate. 

There is an increase in temperature as heat removal slows, along with a corresponding increase in the reaction rate. This phenomenon is known as the autoacceleration or Trommsdorff effect and can lead to catastrophic results if not properly controlled. Even with snccessfnl control of the reaction, it is difficult to remove the traces of remaining monomer from the polymer due to decreased diffusion. Similarly, it is difficult to get the reactions to proceed to completion due to limited monomer mobility. 

Frequently, even if as little as 20% of the monomer has polymerized, an autoaccelerating polymerization effect will take place. This may manifest itself in an increase in the heat evolved as the process nears completion. Particularly in large-scale, industrial polymerizations, this effect, known as the Trommsdorff effect or gel effect, may be quite dangerous. In fact, serious explosions have... 

At the lowest emulsifier concentration there is a long period of constant reaction rate which, however, is terminated at 70 to 80% conversion by a rather high maximum of the reaction rate owing to the strong gel effect (Trommsdorff effect) in the comparably large particles. 

Diffusion of the macroradicals controls can be assumed to be the termination reaction. However, that is not the case the termination rate constant is absolutely independent of the degree of polymerization, as shown in Table I. Therefore, the assumption must be that the diffusion of the segment at the end of the radical chain controls the termination process (as long as the Trommsdorff effect is not rate-determining). 

This produces a rise in the concentration of active centers and a corresponding increase in the propagation rate. Chains produced at this stage are longer, and this leads to a broadening of the molar mass distribution. The term gel effect is widely used to describe this effect, although no gel is actually formed in the system. The effect is also called the Trommsdorff effect (see Chapter 5). 

The EGDMA addition produces a significant decrease in the conversion at which the Trommsdorff effect makes its appearance. For 30 wt% EGDMA, the pseudo steady-state period has completely disappeared, which means that the concentration of free radicals increases continuously after... 

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