Methyl methacrylate isothermal polymerization

In this work, a comprehensive kinetic model, suitable for simulation of inilticomponent aiulsion polymerization reactors, is presented A well-mixed, isothermal, batch reactor is considered with illustrative purposes. Typical model outputs are PSD, monomer conversion, multivariate distritution of the i lymer particles in terms of numtoer and type of contained active Chains, and pwlymer ccmposition. Model predictions are compared with experimental data for the ternary system acrylonitrile-styrene-methyl methacrylate. 

Figure 2. Isothermal polymerization of methyl methacrylate in a CSTR (1 5). a. Predicted steady-state monomer conversion vs. reactor residence time for the solution polymerization of MMA in ethyl acetate at 86 °C. h. Steady-state and dynamic experiments for the isothermal solution polymerization of MMA in ethyl acetate (solvent fraction O.k) ( ) steady states,...

Figure 7- Isothermal multiplicity for the emulsion polymerization of methyl methacrylate in a CSTR (20h). S = 0.03...

In view of Eq. (6.26) for ideal polymerization kinetics one would normally expect the reaction rate to fall with time, since the monomer and initiator concentrations decrease with conversion. However, the exact opposite behavior is observed in many polymerizations where the rate of polymerization increases with time. A typical example of this phenomenon is shown in Fig. 6.10 for the polymerization of methyl methacrylate in benzene solution at 50°C [49], At monomer concentrations less than about 40 wt% in this case, the rate (slope of conversion vs. time) is approximately as anticipated from the ideal kinetic scheme described in this chapter, that is, the rate decreases gradually as the reaction proceeds and the concentrations of monomer and initiator are depleted. An acceleration is observed, however, at higher monomer concentrations and the curve for the pure monomer shows a dramatic autoacceleration in the polymerization rate. Such behavior is referred to as the gel effect. (The term gel used here is different than the usage in Chapter 5 as it refers only to the sharp increase in viscosity and not to the formation of a cross-linked polymer.) The autoaccelerative gel effect is also known as the Tromsdorff effect or Norrish-Smith effect after pioneering workers in this field. It should be noted that the gel effect is observed under isothermal conditions. It should thus not be confused with the acceleration that would be observed if a polymerization reaction were carried out under nonisotherraal conditions such that the reaction temperature increased with conversion due to exothermicity of the reaction. 

A series of close-to-spherical styrene/DVB resins of varying particle size and pore diameter were employed as supports for non-covalent adsorptive attachment of CALB by hydrophobic interaction. The effect of matrix particle and pore size on CALB i) adsorption isotherms, ii) fraction of active sites, iii) distribution within supports, and iv) catalytic activity for s-CL ring-opening polymerizations and adipic acid/l,8-octanediol polycondensations is reported. Important differences in the above for CALB immobilized on methyl methacrylate and styrene/DVB resins were found. The lessons learned herein provide a basis to others that seek to design optimal immobilized enzyme catalysts for low molar mass and polymerization reactions. 

Observe that for monomer concentrations of up to 40%, plots show that first-order kinetics is followed. However, at higher initial monomer concentrations, a sharp increase in rate is observed at an advanced stage of polymerization. At the same time, high-molecular-weight polymers are produced. Autoacceleration is particularly pronounced with methyl methacrylate, methyl acrylate, and acryhc acid. It occurs independent of an initiator and is observed even rmder isothermal conditions. In fact, where there is no effective dissipation of heat, autoacceleration results in a large increase in temperature. 

When direct measurements of polymerization heats are made, earo must be taken to estimate the amount of monomer which has been converted to polymer. For methyl methacrylate there is a discrepancy of 0 9 kcal/mole between the two directly measured heats, using isothermal calorimetry. Thus Ekegren et obtain... 

Isothermal frontal polymerization (IFP) is a self-sustaining, directional polymerization that can be used to produce gradient refractive index materials. Accurate detection of frontal properties has been difficult due to the concentration gradient that forms from the diffusion and subsequent polymerization of the monomer solution into the polymer seed. A laser technique that detects tiny differences in refractive indices has been modified to detect the various regions in propagating fronts. Propagation distances and gradient profiles have been determined both mathematically and experimentally at various initiator concentrations and cure temperatures for IFP systems of methyl methacrylate with poly(methyl methacrylate) seeds and wilh the thermal initiator 2,2 -azobisisobutryonitrile. 

Jaisinghani and Ray (40) also predicted the existence of three steady states for the free-radical polymerization of methyl methacrylate under autothermal operation. As their analysis could only locate unstable limit cycles, they concluded that stable oscillations for this system were unlikely. However, they speculated that other monomer-initiator combinations could exhibit more interesting dynamic phenomena. Since at that time there had been no evidence of experimental work for this class of problems, their theoretical analysis provided the foundation for future experimental work aimed at validating the predicted phenomena. Later studies include the investigations of Balaraman et al. (43) for the continuous bulk copolymerization of styrene and acrylonitrile, and Kuchanov et al. (44) who demonstrated the existence of sustained oscillations for bulk copolymerization under non-isothermal conditions. Hamer, Akramov and Ray (45) were first to predict stable limit cycles for non-isothermal solution homopolymerization and copolymerization in a CSTR. Parameter space plots and dynamic simulations were presented for methyl methacrylate and vinyl acetate homopolymerization, as well as for their copolymerization. The copolymerization system exhibited a new bifurcation diagram observed for the first time where three Hopf bifurcations were located, leading to stable and unstable periodic branches over a small parameter range. Schmidt, Clinch and Ray (46) provided the first experimental evidence of multiple steady states for non-isothermal solution polymerization. Their... 

In experimental work, however, it is frequently noticed that after a linear decrease in with u the rate of polymerization again increases and goes through a maximum, only to fall again to zero (at u = 1). This effect is seen at 60°C with methyl methacrylate for yields as low as 20% with styrene, by contrast, it does not occur until 65%. The effect is also observed when reactions are carried out isothermally. Therefore, it cannot primarily be caused by liberation of heat. The effect is accentuated when the medium is more viscous (addition of otherwise inert polymer, low initiator concentrations, poor solvent). Therefore, it must originate from some kind of diffusion control, and is called the gel effect or Trommsdorf-Norrish effect. 

Lewis and Volpert continue the discussion of the isothermal form of frontal polymerization in Chapter 5. Isothermal frontal polymerization is also a localized reaction zone that propagates but because of the autoacceleration of the rate of free-radical polymerization with conversion. A seed of poly(methyl methacrylate) is placed in contact with a solution of a peroxide or nitrile initiator, and a front propagates from the seed. The monomer diffuses into the seed, creating a viscous zone in which the rate of polymerization is faster than in the bulk solution. The result is a front that propagates but not with a constant velocity because the reaction is proceeding in the bulk solution at a slower rate. This process is used to create gradient refractive index materials by adding the appropriate dopant. 

The calculated values of agreed well with the limiting convorsion values for bulk polymerization of methyl methacrylate estimated by isothermal differential scanning calcainKtry (DSQ and gravimetry The theory can be ap(Aed not only to radical... 

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