Bulk polymerization Viscosity

Although bulk polymerization of acrylonitrile seems adaptable, it is rarely used commercially because the autocatalytic nature of the reaction makes it difficult to control. This, combined with the fact that the rate of heat generated per unit volume is very high, makes large-scale commercial operations difficult to engineer. Lastiy, the viscosity of the medium becomes very high at conversion levels above 40 to 50%. Therefore commercial operation at low conversion requires an extensive monomer recovery operation. 

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. 

Bulk Polymerizations. In the bulk polymerization of vinyl acetate the viscosity increases significantly as the polymer forms making it difficult to remove heat from the process. Low molecular weight polymers have been made in this fashion. Continuous processes are known to be used for bulk polymerizations (68). 

Bulk Polymerization The monomer and initiators are reacted without or with mixing without mixing to make useful shapes direcily, like bakelite products. Because of viscosity hmitations, stirred bulk polymerization is not carried to completion but only to 30 to 60 percent or so, with the remaining monomer stripped out and recycled. A... 

In solution polymerization, an organic solvent dissolves the monomer. Solvents should have low chain transfer activity to minimize chain transfer reactions that produce low-molecular-weight polymers. The presence of a solvent makes heat and viscosity control easier than in bulk polymerization. Removal of the solvent may not be necessary in certain applications such as coatings and adhesives. 

Some of the results of bulk polymerization of 61 by using different anionic catalysts are summarized in Table 858 It was easily polymerized in the presence of alkali metal compounds above 60 °C. The polymerization at 150 °C was too fast to be controlled. The yield and the viscosity number, i gp/c, of the resulting polyamide increased with the reaction time. The initial rate of the polymerization became higher with the size of the countercation, in analogy to the case of anionic polymerization of e-caprolactam59. The rate increased also with raising temperature as shown in Fig. 658. ... 

Bulk polymerization of di-n-butyl-bis-(y-glycidyloxypropyl)stannane in the air or in benzene as reaction medium at 30 °C results in a gradual increase in viscosity and precipitation of a white powder in quantitative yield. The polymerization product... 

Chain-growth polymerizations are diffusion controlled in bulk polymerizations. This is expected to occur rapidly, even prior to network development in step-growth mechanisms. Traditionally, rate constants are expressed in terms of viscosity. In dilute solutions, viscosity is proportional to molecular weight to a power that lies between 0.6 and 0.8 (22). Melt viscosity is more complex (23) Below a critical value for the number of atoms per chain, viscosity correlates to the 1.75 power. Above this critical value, the power is nearly 3 4 for a number of thermoplastics at low shear rates. In thermosets, as the extent of conversion reaches gellation, the viscosity asymptotically increases. However, if network formation is restricted to tightly crosslinked, localized regions, viscosity may not be appreciably affected. In the current study, an exponential function of degree of polymerization was selected as a first estimate of the rate dependency on viscosity. 

The data in Table I are not directly comparable, since the viscosity of the 3-isomer was determined in benzene while the others were measured in DMSO. In addition, the first two polymers were prepared in bulk polymerizations, while the polymerization of methyl 3-vinylsalicylate was carried out with the monomer diluted 1 1 with benzene. Thus no certain conclusion can be drawn the data are, however, an indication of possible difficulty in radical polymerization of substituted styrenes bearing a phenol ortho to the vinyl group. 

In general, for solutions and bulk polymeric materials, viscosity follows the general relationship shown in Figure 7.7 where viscosity is constant over much of the fluid range but sharply increases near Tg. 

This was derived assuming uniform concentration because good mixing is important for this relationship to hold. It also assumes a constant temperature. Both these assumptions are only approached in most batch systems. Further, stirring becomes more difficult as conversion increases so that both control of localized temperature and concentration become more difficult. In reality, this relationship holds for only a few percentage points of conversion. Overall, temperature is a major concern for vinyl polymerizations because they are relatively quite exothermic. This is particularly important for bulk polymerizations. This, coupled with the general rapid increase in viscosity, leads to the Trommsdorff-like effects. 

Polymerization of a monomer in a solvent overcomes many of the disadvantages of the bulk process. The solvent acts as diluent and aids in the transfer of the heat of polymerization. The solvent also allows easier stirring, since the viscosity of the reaction mixture is decreased. Thermal control is much easier in solution polymerization compared to bulk polymerization. On the other hand, the presence of solvent may present new difficulties. Unless the solvent is chosen with appropriate consideration, chain transfer to solvent can become a problem. Further, the purity of the polymer may be affected if there are difficulties in removal of the solvent. Vinyl acetate, acrylonitrile, and esters of acrylic acid are polymerized in solution. 

The emulsion polymerization process has several distinct advantages. The physical state of the emulsion (colloidal) system makes it easy to control the process. Thermal and viscosity problems are much less significant than in bulk polymerization. The product of an emulsion polymerization, referred to as a latex, can in many instances be used directly without further separations. (However, there may be the need for appropriate blending operations,... 

Some effect of viscosity on r has been observed [Kelen and Tudos, 1974 Rao et al., 1976]. Copolymerization of styrene (Mil-methyl methacrylate (M2) in bulk leads to a copolymer containing less styrene than when reaction is carried out in benzene solution [Johnson et al., 1978]. The gel effect in bulk polymerization decreases the mobility of styrene resulting in a decrease in r and an increase in r%. 

Bulk Polymerization. Monomer and polymer (with traces of initiator) are the only constituents in bulk polymerizations. Obviously, the monomer must be soluble in the polymer for this type of process to effectively proceed. Bulk polymerization, also called mass or block polymerization, can occur in stirred-tank reactors, or can be unstirred, in which instance it is called quiescent bulk polymerization. The primary difficulty with bulk polymerizations is that as the polymerization proceeds and more polymer is formed, the viscosity increases, thermal conductivity decreases, and heat removal becomes difficult. 

The bulk polymerization effects the special needs to remove the heat of reactions, and moreover, high conversions cannot be reached because the viscosity of the polymer increases drastically with conversion. In order to avoid a high viscosity of the end product before discharging, the mass polymerization is carried out in solution. Ethylbenzene is a common solvent. 

Solution Polymerization. In this process an inert solvent is added to the reaction mass. The solvent adds its heat capacity and reduces the viscosity, facilitating convective heat transfer. The solvent can also be refluxed to remove heat. On the other hand, the solvent wastes reactor space and reduces both rate and molecular weight as compared to bulk polymerization. Additional technology is needed to separate the polymer product and to recover and store the solvent. Both batch and continuous processes are used. 

Figure 5. Variation of intrinsic viscosity with conversion during bulk polymerization of propylene oxide with Zns[Co(CN)e]2 glyme ZnCU (0.01 wt %) at 30°C...

Table 3. Intrinsic Viscosity vs. Temperature Bulk Polymerization with 0.008 Molar Benzoyl Peroxide...

Viscometry The specific viscosity of each polymer from the bulk polymerization was measured in acetone at 30°C using an Ubbelohde dilution viscometer. Five concentrations in the range of 1.120 to 0.242 g/d poly(vinyl acetate) and polyvinyl trideuteroacetate) and 0.385 to 0.084 g/dl (poly(trideu-terovinyl acetate)) were run. Intrinsic viscosity was calculated by extrapolation of the Tlsp/c versus c plot to zero concentration. Number average molecular weights were calculated using the equation(20) [q] =1,0 x 10 1 [Mn] 0 72 which is in the mid range of the equations listed. 

Kinetics and Phase Behavior - Table IV represents a simplified picture of the situation however, some polymerizations go through several phase changes in the course of the reaction. For example, in the bulk polymerization of PVC, the reaction medium begins as a low viscosity liquid, progresses to a slurry (the PVC polymer, which is insoluble in the monomer, precipitates), becomes a paste as the monomer disappears and finishes as a solid powder. As might be expected, modelling the kinetics of the reaction in such a situation is not a simple exercise. 

Living free-radical polymerization represents a promising technique to produce polymers with highly controlled structures. Different possible systems known from bulk polymerizations have been used in miniemulsions. The living free radical polymerization of, e.g., styrene via the miniemulsion approach allows one to eliminate the drawback of the bulk system where an increase in polydis-persity was found at high conversions due to the very high viscosity of the reaction medium [90]. 

This is one of the simplest methods of polymerization. It is often used in the polymerization of step-growth polymers.28 In these types of systems the viscosity remains low for a large portion of the reaction and heat transfer is easily controlled. Chain-growth polymers are more difficult to polymerize by this method due to the rapid and highly exothermic reactions. As the viscosity increases, thermal control becomes more difficult and may result in thermal runaway or localized hot spots. Commercial use of bulk polymerization for vinyl polymers is rather limited for... 

In the case of bulk polymerization, the initiator is dissolved in the monomer and the viscosity of the system increases with progressing polymerization from liquid, through the state of gel ("gel-effect") to solid polymer. This polymerization technique has many disadvantages, among others the transfer of exothermic reaction heat from the system is very complicated. The reaction heat reaches values as high as 85 kj/ mol, and because polymers are poor heat conductors, this may cause the temperature of the system to reach the boiling point of monomer and consequently the polymer is foamed by vapours of monomer. 

For the bulk polymerization of styrene using thermal initiation, the kinetic model of Hui and Hamielec (13) was used. The flow model (Harkness (1)) takes radial variations in temperature and concentration into account and the velocity profile was calculated at every axial point based on the radial viscosity at that point. The system equations were solved using the method of lines with a Gear routine for solving the resulting set of ordinary differential equations. 

In a bulk polymerization only reactants (and added catalyst, if necessary) are included in the reaction vessel, This type of process is widely used for step-growth polymerizations where high molecnlar weight polymer is ouly produced in the last stages of the polymerization. As a result, the viscosity of the reaction medium stays low throughout most of the reaction. However, crystallization of the polymer that is formed can lead to all sorts of... 

Chain polymerizations are less often performed in die bulk, because of problems with the control of the reaction. [An interesting exception is poly(methyl methacrylate), a polymer that is soluble in its own monomer (not all polymers are), and which is synthesized commercially by chain (free radical) polymerization very slowly in bulk (Figure 3-44). The resulting polymer has outstanding optical properties (clarity) because there are very few impurities.] In bulk polymerizations there is a tendency for the reaction mass to form a gel (i.e., have an extraordinarily high viscosity) and hot spots can develop. At the extreme, the reaction rate can accelerate to runaway proportions (for reasons we will discuss when we consider kinetics) with potentially disastrous (explosive) consequences. Viscosity and heat control can be achieved, if necessary, by carrying out the polymerizations to a relatively low conversion, with the unreacted monomer being separated and recycled. Another way to control the viscosity and heat transfer problems of chain polymerizations is to perform the polymerization in solution A major concern with this method is that chain transfer to sol-... 

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