Reactor conversion-molecular weight

Hamielec and coworkers (, 42, 43) have conducted extensive experimental and theoretical studies with styrene polymerization in CSTR s. Theirs represent probably the first published work in this area at commercially interesting temperatures and conversions relating theory to experiment, and determining the effects of reactor configuration and conditions on conversion, molecular weight and MWD. 

The study of the peak temperature sensitivity to the reactor operating parameters and the construction of sensitivity boundary curves for stable reactor operation were previously reported ( l). This paper presents a computer study on conceptual relationships between the conversion-product properties and the reactor operating parameters in a plug flow tubular reactor of free radical polymerization. In particular, a contour map of conversion-molecular weight relationships in a reactor of fixed size is presented and the sensitivity of its relationship to the choice of initiator system, solvent system and heat transfer system are discussed. 

This work particularly emphasizes the importance of selecting the initiator system for optimum reactor operation and reveals general concepts which specify the desired properties and operational modes of an optimum initiator system. In addition, the effects of the system heat transfer and the CTA (chain transfer agent) level on the conversion-molecular weights relationships are presented. 

Equation (8) provides a general relationship between the reactor temperature profile and the operating parameters. In relating the system heat transfer to the conversion-molecular weights relationship for a reactor of fixed size, the heat transfer coefficient emerges as the correlating parameter. 

Emulsion Process. The emulsion polymerization process utilizes water as a continuous phase with the reactants suspended as microscopic particles. This low viscosity system allows facile mixing and heat transfer for control purposes. An emulsifier is generally employed to stabilize the water insoluble monomers and other reactants, and to prevent reactor fouling. With SAN the system is composed of water, monomers, chain-transfer agents for molecular weight control, emulsifiers, and initiators. Both batch and semibatch processes are employed. Copolymerization is normally carried out at 60 to 100°C to conversions of - 97%. Lower temperature polymerization can be achieved with redox-initiator systems (51). 

Recycle and Polymer Collection. Due to the incomplete conversion of monomer to polymer, it is necessary to incorporate a system for the recovery and recycling of the unreacted monomer. Both tubular and autoclave reactors have similar recycle systems (Fig. 1). The high pressure separator partitions most of the polymers from the unreacted monomer. The separator overhead stream, composed of monomer and a trace of low molecular weight polymer, enters a series of coolers and separators where both the reaction heat and waxy polymers are removed. Subsequendy, this stream is combined with fresh as well as recycled monomers from the low pressure separator together they supply feed to the secondary compressor. 

The early attempts at NMP of S in emulsion used TEMPO and related nitroxides and needed to be carried out at high temperatures (100-130 °C) necessitating a pressure reactor. Problems with colloidal stability and molecular weight control and limiting conversions were reported.215 217... 

Low Conversion Reactors. The major problem in temperature control in low conversion reactors is the orders cf magnitude increase in viscosity as the conversion increases. Fig.8 shows the viscosity of a polystyrene solution as the function of percent PS. The data are for polystyrene with a Staudinger molecular weight of 60,000 at 100 C and 150 C in a cumene solution, a satisfactory analog for styrene monomer solutions. As the polymer concentration increases from 0 to 60%, viscosity increases from about 1 cp to 10 cp. 

It is noted that the maximum value of rp in the helically coiled reactor is larger than the maximum observed in the straight tube reactor. The rp increases with increasing Reynolds number while the molecular weight (at a given conversion) decreases. 

Free-Radical Polymerization Sensitivity of Conversion and Molecular Weights to Reactor Conditions... 

Figure 5. Molecular weight-conversion contour map for various concentrations of a free-radical initiator operating in a tubular-addition polymerization reactor of fixed size. Curves were constructed using varying jacket temperatures (kinetic parameters for the initiator Ea = 32.921 Kcal/mol In k/ = 26.494 In sec f = 0.5 (------------------------) optimum operating line)...

Effects of Initiator Parameters. Initiator types can best be characterized by the frequency factor (k ) and the activation energy (E ), and the effect of these parameters on the molecular weight-conversion relationship is shown in Figures 7 and 8. The curves shown are the result of choosing the jacket temperature-inlet initiator concentration combination which maximizes the reactor conversion for each initiator type investigated. 

Figure 7 shows the limiting maximum molecular weight of products from a reactor of fixed size varies directly with the frequency factor of the initiator at a fixed activation energy, while the limiting conversion varies inversely with the frequency factor. In addition, the length of the chain-transfer controlled zone is increased inversely with the frequency factor. 

Figure 7. Tubular plug-flow addition polymer reactor effect of the frequency factor (ka) of the initiator on the molecular weight-conversion relationship at constant activation energy (Ea). Each point along the curves represents an optimum initiator feed concentration-reactor jacket temperature combination and their values are all different, (Ea = 32.921 Kcal/mol In ka = 35,000 In sec ...

Figure 9, Effect of the initiator activation energy on the molecular weight distribution of an addition polymer produced in a tubular reactor constant frequency factor and at widely different values of initiator—jacket temperature combination (the conversion is optimized In k/ = 26.492...

The LDPE reactor is sometimes termed heat transfer limited in conversion. While this is true, the molecular weight (or melt index)—conversion relationship is not since this work shows that a selected initiator can allow conversion improvements to be made under adiabatic conditions for a specified molecular weight. The actual limitation to conversion is the decomposition temperature of the ethylene and given that temperature as a maximum limitation, an initiator (not necessarily commercial or even known with present initiator technology) can be found which will allow any product to be made at the rate dictated by this temperature. Conceptually, this is a constant (maximum) conversion reactor, runnirg at constant operating conditions where the product produced dictates the initiator to be used. 

Figure 14, Molecular weight-conversion relationship (computer simulation— reactor of a fixed geometry for a given initiator system) (h) heat transfer coefficient...

The computer simulation study of the operation of the tubular free radical polymerization reactor has shown that the conversion and the product properties are sensitive to the operating parameters such as initiator type, jacket temperature, and heat transfer for a reactor of fixed size. The molecular weight-conversion contour map is particularly significant and it is used in this paper as a basis for a comparison of the reactor performances. 

The type of initiator used affects the molecular weight and conversion limits in a reactor of fixed size and the molecular weight distribution of the material produced at a given conversion level. The initiator type also dictates the amount of initiator which is necessary to yield a given conversion to polymer, the operating temperature range of the reactor and the sensitivity of the reactor to an unstable condition. Clearly, the initiator is the most important reaction parameter in the polymer process. 

The full utilization of improved heat transfer in a given reactor can only be made when the molecular weight-conversion relationships are carefully studied with various initiator types at different heat transfer levels. Then a particular initiator system must be selected for a maximum conversion improvement for a specified product. 

There exists an optimum jacket temperature for maximizing conversion at a given average molecular weight product. The study further suggests that an unstable operating region exists where wide conversion fluctuations result from attempts to increase the reactor conversion by minor adjustments in initiator amount or jacket temperature. 

Reactor Conditions for Experimental Runs. Operating conditions for the continuous, stirred tank reactor runs were chosen to study the effects of mixing speed on the monomer conversion and molecular weight distribution at different values for the number average degree of polymerization of the product polymer. 

The micro-mixed reactor with dead-polymer model was developed to account for the large values of the polydispersity index observed experimentally. The effect of increasing the fraction of dead-polymer in the reactor feed while maintaining the same monomer conversion is to broaden the product polymer distribution and therefore to increase the polydispersity index. As illustrated in Table V, this model, with its adjustable parameter, can exactly match experiment average molecular weights and easily account for values of the polydispersity index significantly greater than 2. 

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