Isothermal polymerization

Polymerization. Isothermal polymerizations were conducted in 1/8" molds controlled at the stated isothermal temperature. Below lOO C circulating water was the temperature control medium whereas circulating air was used above 100 C. Reactants were... 

Hint 2. An increase in temperature will increase the limiting conversion. Following the MMA polymerization example, polymerizing isothermally at 80 °C will give a limiting conversion about 93%. At 100 °C, the limiting conversion will go up to about 97-98%. If the temperature is 120 °C, the polymerization will almost go to completion, that is, there is no limiting conversion (within experimental error). 

Radical polymerization Isothermal solution polymerization in cyclohexane with AIBN initiator (7)... 

The majority of polymer flow processes involve significant heat dissipation and should be regarded as nou-isothermal regimes. Therefore in the finite element modelling of polymeric flow, in conjunction with the equations of continuity... 

Solution Polymerization. Plant scale polymerizations ia water are conducted either adiabaticaHy or isotherm ally. Molecular weight control, exotherm control, and reduction of residual monomer are factors which limit the types of initiators employed. Commercially available high molecular weight solution polyacrylamides are usually manufactured and sold at about 5% soHds so that the viscosities permit the final product to be pumped easily. 

Isothermal polymerizations are carried out in thin films so that heat removal is efficient. In a typical isothermal polymerization, aqueous acrylamide is sparged with nitrogen for 1 h at 25°C and EDTA (C2QH2 N20g) is then added to complex the copper inhibitor. Polymerization can then be initiated as above with the ammonium persulfate—sodium bisulfite redox couple. The batch temperature is allowed to rise slowly to 40°C and is then cooled to maintain the temperature at 40°C. The polymerization is complete after several hours, at which time additional sodium bisulfite is added to reduce residual acrylamide. 

Adsorption of dispersants at the soHd—Hquid interface from solution is normally measured by changes in the concentration of the dispersant after adsorption has occurred, and plotted as an adsorption isotherm. A classification system of adsorption isotherms has been developed to identify the mechanisms that may be operating, such as monolayer vs multilayer adsorption, and chemisorption vs physical adsorption (8). For moderate to high mol wt polymeric dispersants, the low energy (equiUbrium) configurations of the adsorbed layer are typically about 3—30 nm thick. Normally, the adsorption is monolayer, since the thickness of the first layer significantly reduces attraction for a second layer, unless the polymer is very low mol wt or adsorbs by being nearly immiscible with the solvent. 

Adsorption for gas purification comes under the category of dynamic adsorption. Where a high separation efficiency is required, the adsorption would be stopped when the breakthrough point is reached. The relationship between adsorbate concentration in the gas stream and the solid may be determined experimentally and plotted in the form of isotherms. These are usually determined under static equilibrium conditions but dynamic adsorption conditions operating in gas purification bear little relationship to these results. Isotherms indicate the affinity of the adsorbent for the adsorbate but do not relate the contact time or the amount of adsorbent required to reduce the adsorbate from one concentration to another. Factors which influence the service time of an adsorbent bed include the grain size of the adsorbent depth of adsorbent bed gas velocity temperature of gas and adsorbent pressure of the gas stream concentration of the adsorbates concentration of other gas constituents which may be adsorbed at the same time moisture content of the gas and adsorbent concentration of substances which may polymerize or react with the adsorbent adsorptive capacity of the adsorbent for the adsorbate over the concentration range applicable over the filter or carbon bed efficiency of adsorbate removal required. 

Polymerization in aqueous solution of acrylamide can also be fulfilled in thin layers (up to 20 mm) applied on a steel plate or a traveling steel band. Polymerization is initiated by persulfates, redox system, UV or y radiation. Polymerization proceeds in isothermal conditions as the heat of polymerization is dissipated in the environment and, additionally, absorbed by the steel carrier. Nonadhesion of the polymer to the carrier is ensured by the addition of glycerol to isopropyl alcohol or by precoating the steel band with a film based on fluor-containing polymers. This makes polymerization possible at a high concentration of the monomer (20-45%) and in a wider process temperature range. This film of polyacrylamide is removed from the band, crushed, dried, and packed. 

The objectives of this presentation are to discuss the general behavior of non isothermal chain-addition polymerizations and copolymerizations and to propose dimensionless criteria for estimating non isothermal reactor performance, in particular thermal runaway and instability, and its effect upon polymer properties. Most of the results presented are based upon work (i"8), both theoretical and experimental, conducted in the author s laboratories at Stevens Institute of Technology. Analytical methods include a Semenov-type theoretical approach (1,2,9) as well as computer simulations similar to those used by Barkelew LS) ... 

The rate of polymerization can he shown to he in the case of isothermal hulk polymerization... 

Peaking and Non-isothermal Polymerizations. Biesenberger a (3) have studied the theory of "thermal ignition" applied to chain addition polymerization and worked out computational and experimental cases for batch styrene polymerization with various catalysts. They define thermal ignition as the condition where the reaction temperature increases rapidly with time and the rate of increase in temperature also increases with time (concave upward curve). Their theory, computations, and experiments were for well stirred batch reactors with constant heat transfer coefficients. Their work is of interest for understanding the boundaries of stability for abnormal situations like catalyst mischarge or control malfunctions. In practice, however, the criterion for stability in low conversion... 

There is very little experimental data available on values of p for these reactants. Some isothermal data indicates that values in the neighborhood of 3 to 4 are reasonable (1 ), but virtually nothing is reported in the literature on the temperature dependence. This makes quantitative comparison with data more difficult, however certain aspects such as the polydisper-sity prediction of 2 are easily checked. Thus, we now will examine the utility of this model under various experimental polymerization conditions. 

In order to get a quantitative idea of the magnitude of the effects of these temperature variations on molecular structure and morphology an experimental study was undertaken. Two types of polymerizations were conducted. One type was isothermal polymerization at fixed reaction time at a series of temperatures. The other type was a nonisothermal polymerization in the geometry of a RIM mold. Intrinsic viscosities, size exclusion chromotograms (gpc) and differential scanning calorimetry traces (dsc) were obtained for the various isothermal products and from spatially different sections of the nonisothermal products. Complete experimental details are given below. 

Figure 9. GPC results on isothermal samples (top) CC/BB/AA = 1/5/6 (bottom) CC/BB/AA — 1/2/3/, Numbers by curves indicate polymerization temperature in degrees C.

A mathematical model for this polymerization reaction based on homogeneous, isothermal reaction is inadequate to predict all of these effects, particularly the breadth of the MWD. For this reason a model taking explicit account of the phase separation has been formulated and is currently under investigation. 

One must now realize that extreme caution should be exercized in drawing conclusions about RIM polymerization from batch isothermal reactions at high temperature. 

There is less information available in the scientific literature on the influence of forced oscillations in the control variables in polymerization reactions. A decade ago two independent theoretical studies appeared which considered the effect of periodic operation on a free radically initiated chain reaction in a well mixed isothermal reactor. Ray (11) examined a reaction mechanism with and without chain transfer to monomer. 

The most comprehensive simulation of a free radical polymerization process in a CSTR is that of Konopnicki and Kuester (15). For a mechanism which includes transfer to both monomer and solvent as well as termination by combination and disproportionation they examined the influence of non-isothermal operation, viscosity effects as well as induced sinuoidal and square-wave forcing functions on initiator feed and jacket temperature on the MWD of the polymer produced. 

Yu. F.C.L., Periodic Operation of a Non-Isothermal Polymerization Reactor, M.Sc. Thesis, University of Massachusetts, 1969. 

The research programme into n-butyl lithium initiated, anionic polymerization started at Leeds in 1972 and involved the construction of a pilot scale, continuous stirred tank reactor. This was operated isothermally, to obtain data under a typical range of industrial operating conditions. 

Several studies have been published to assess the kinetics of polymerization reactions at high temperatures. (irZ) However, most of these studies only describe experiments conducted at isothermal conditions. Only a few papers are based on adiabatic runaways. This paper is one of the first studies based on "first principles" characterizing adiabatic runaway reactions. 

Most published studies relate only to isothermal experiments. Hence, in order to make such comparisons we modified our computations to assume isothermal conditions. Figure 11 compares our kinetic model with data by Hui and Hamielec for styrene thermal polymerization at 1A0°C. Figure 12 compares out kinetic model with data by Balke and Hamielec (7) for MMA at 90 C using 0.3 AIBN. Figure 13 compares our kinetic model with data by Lee and Turner ( ) for MMA at 70°C using 2% BPO. Our model compares quite favorably with these published experiments. The percent error was less than S% in most of the ranges of conversions. 

In conclusion, we have reviewed how our kinetic model did simulate the experiments for the thermally-initiated styrene polymerization. The results of our kinetic model compared closely with some published isothermal experiments on thermally-initiated styrene and on styrene and MMA using initiators. These experiments and other modeling efforts have provided us with useful guidelines in analyzing more complex systems. With such modeling efforts, we can assess the hazards of a polymer reaction system at various tempera-atures and initiator concentrations by knowing certain physical, chemical and kinetic parameters. 

Example 3.6 The isothermal batch polymerization in Example 2.8 converted 80% of the monomer in 2h. You want to do the same thing in... 

Unsteady behavior in an isothermal perfect mixer is governed by a maximum of -I- 1 ordinary differential equations. Except for highly complicated reactions such as polymerizations (where N is theoretically infinite), solutions are usually straightforward. Numerical methods for unsteady CSTRs are similar to those used for steady-state PFRs, and analytical solutions are usually possible when the reaction is first order. 

As suggested by Barrett (2), it is assumed that following the particle nucleation stage, the polymerization proceeds in the particle (monomer/polymer) phase with no mass transfer limitation. Therefore, the dispersion polymerization is similar to a mass or suspension polymerization, and kj can not be assumed to be constant even at isothermal conditions, since kp and even kp are dependent on the degree of polymerization because of a gel effect. (2., ,D However, since the application of the model is for a finishing step, with polymer molecular weight and viscosity fairly well established, further changes in kp and kp should be minimal. 

MODEL TO PREDICT RESIDUAL MONOMER FOR AN ISOTHERMAL SEMI-BATCH POLYMERIZATION AND AN ISOTHERMAL BATCH FINISHING STEP. 

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