Polymerization, heat transfer

It is commonly assumed that, in suspension polymerization, heat transfer between polymerizing drops and the continuous phase is rapid and both phases have the same temperature. However, Lazrak and Ricard [115] showed that, with methyl methacrylate polymerization, the internal temperature of drops could be... 

Computer modelling provides powerful and convenient tools for the quantitative analysis of fluid dynamics and heat transfer in non-Newtonian polymer flow systems. Therefore these techniques arc routmely used in the modern polymer industry to design and develop better and more efficient process equipment and operations. The main steps in the development of a computer model for a physical process, such as the flow and deformation of polymeric materials, can be summarized as ... 

Emulsion polymerization also has the advantages of good heat transfer and low viscosity, which follow from the presence of the aqueous phase. The resulting aqueous dispersion of polymer is called a latex. The polymer can be subsequently separated from the aqueous portion of the latex or the latter can be used directly in eventual appUcations. For example, in coatings applications-such as paints, paper coatings, floor pohshes-soft polymer particles coalesce into a continuous film with the evaporation of water after the latex has been applied to the substrate. 

The enthalpy of the copolymerization of trioxane is such that bulk polymerization is feasible. For production, molten trioxane, initiator, and comonomer are fed to the reactor a chain-transfer agent is in eluded if desired. Polymerization proceeds in bulk with precipitation of polymer and the reactor must supply enough shearing to continually break up the polymer bed, reduce particle size, and provide good heat transfer. The mixing requirements for the bulk polymerization of trioxane have been reviewed (22). Raw copolymer is obtained as fine emmb or flake containing imbibed formaldehyde and trioxane which are substantially removed in subsequent treatments which may be combined with removal of unstable end groups. 

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). 

Aqueous media, such as emulsion, suspension, and dispersion polymerization, are by far the most widely used in the acryUc fiber industry. Water acts as a convenient heat-transfer and cooling medium and the polymer is easily recovered by filtration or centrifugation. Fiber producers that use aqueous solutions of thiocyanate or zinc chloride as the solvent for the polymer have an additional benefit. In such cases the reaction medium can be converted directiy to dope to save the costs of polymer recovery. Aqueous emulsions are less common. This type of process is used primarily for modacryUc compositions, such as Dynel. Even in such processes the emulsifier is used at very low levels, giving a polymerization medium with characteristics of both a suspension and a tme emulsion. 

Copolymerization is effected by suspension or emulsion techniques under such conditions that tetrafluoroethylene, but not ethylene, may homopolymerize. Bulk polymerization is not commercially feasible, because of heat-transfer limitations and explosion hazard of the comonomer mixture. Polymerizations typically take place below 100°C and 5 MPa (50 atm). Initiators include peroxides, redox systems (10), free-radical sources (11), and ionizing radiation (12). 

In order to faciUtate heat transfer of the exothermic polymerization reaction, and to control polymerizate viscosity, percent reactives are adjusted through the use of inert aromatic or aUphatic diluents, such as toluene or heptane, or higher boiling mixed aromatic or mixed aUphatic diluents. Process feed streams are typically adjusted to 30—50% polymerizable monomers. 

In a suspension polymerization, monomer is suspended ia water as 0.1—5 mm droplets, stabilized by protective coUoids or suspending agents. Polymerization is initiated by a monomer-soluble initiator and takes place within the monomer droplets. The water serves as both the dispersion medium and a heat-transfer agent. Particle size is controlled primarily by the rate of agitation and the concentration and type of suspending aids. The polymer is obtained as small beads of about 0.1—5 mm in diameter, which are isolated by filtration or centrifugation. 

Polymerization in Hquid monomer was pioneered by RexaH Dmg and Chemical and Phillips Petroleum (United States). In the RexaH process, Hquid propylene is polymerized in a stirred reactor to form a polymer slurry. This suspension is transferred to a cyclone to separate the polymer from gaseous monomer under atmospheric pressure. The gaseous monomer is then compressed, condensed, and recycled to the polymerizer (123). In the Phillips process, polymerization occurs in loop reactors, increasing the ratio of available heat-transfer surface to reactor volume (124). In both of these processes, high catalyst residues necessitate post-reactor treatment of the polymer. 

Solution Polymerization. In this process an inert solvent is added to the reaction mass. The solvent adds its heat capacity and reduces the viscosity, faciUtating 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 polymerisation. Additional technology is needed to separate the polymer product and to recover and store the solvent. Both batch and continuous processes are used. 

Catalyst Development. Traditional slurry polypropylene homopolymer processes suffered from formation of excessive amounts of low grade amorphous polymer and catalyst residues. Introduction of catalysts with up to 30-fold higher activity together with better temperature control have almost eliminated these problems (7). Although low reactor volume and available heat-transfer surfaces ultimately limit further productivity increases, these limitations are less restrictive with the introduction of more finely suspended metallocene catalysts and the emergence of industrial gas-phase fluid-bed polymerization processes. 

K. H. Reichert and R. Michael, "Polymerization iu Bubble Columns, Problems of Mass and Heat Transfer at High SoHd Contents," Inst. Chem. 

Reaction and Heat-Transfer Solvents. Many industrial production processes use solvents as reaction media. Ethylene and propylene are polymerized in hydrocarbon solvents, which dissolves the gaseous reactant and also removes the heat of reaction. Because the polymer is not soluble in the hydrocarbon solvent, polymer recovery is a simple physical operation. Ethylene oxide production is exothermic and the catalyst-filled reaction tubes are surrounded by hydrocarbon heat-transfer duid. 

Continuous polymerization systems offer the possibiUty of several advantages including better heat transfer and cooling capacity, reduction in downtime, more uniform products, and less raw material handling (59,60). In some continuous emulsion homopolymerization processes, materials are added continuously to a first ketde and partially polymerized, then passed into a second reactor where, with additional initiator, the reaction is concluded. Continuous emulsion copolymerizations of vinyl acetate with ethylene have been described (61—64). Recirculating loop reactors which have high heat-transfer rates have found use for the manufacture of latexes for paint appHcations (59). 

Suspension Polymerization. This method (10) might be considered as a number of bulk polymerizations carried out simultaneously in the monomer droplets with water acting as a heat-transfer medium. A monomer-soluble initiator, eg, a peroxide or azo compound, and a protective coUoid like poly(vinyl alcohol) or bentonite, are requited. After completion of the polymerization, the excess of monomer(s) is steam stripped, and the beads of polymer are collected and washed on a centrifiige or filter and dried on a vibrating screen or by means of an expeUer—extmder. 

In the recipes shown in Table 2, the amount of water can vary widely, depending on the available heat-transfer capacity of the reactor and the rate of polymerization. Each of the monomers has a heat of polymerization of about 75 kj/ mol (18 kcal/mol), so removing the heat of polymerization to control temperature is often the limiting factor on rate of polymerization. 

The inside of the convection tubes rarely foul, but occasionally the Hquid unsaturates in feedstocks tend to polymerize and stick to the walls and thus reduce the heat transfer. This soft coke is normally removed by mechanical means. In limited cases, the coke can also be burnt off with air and steam. Normally, the outside surface of the convection section fouls due to dust and particles in the flue gas. Periodically (6 to 36 months), the outside surface is cleaned by steam lancing. With Hquid fuel firing, the surface may require more frequent cleaning. 

For laminar flow of power law fluids in channels of noncircular cross section, see Schecter AIChE J., 7, 445 48 [1961]), Wheeler and Wissler (AJChE J., 11, 207-212 [1965]), Bird, Armstrong, and Hassager Dynamics of Polymeric Liquids, vol. 1 Fluid Mechanics, Wiley, New York, 1977), and Skelland Non-Newtonian Flow and Heat Transfer, Wiley, New York, 1967). 

Topics that acquire special importance on the industrial scale are the quality of mixing in tanks and the residence time distribution in vessels where plug flow may be the goal. The information about agitation in tanks described for gas/liquid and slurry reactions is largely apphcable here. The relation between heat transfer and agitation also is discussed elsewhere in this Handbook. Residence time distribution is covered at length under Reactor Efficiency. A special case is that of laminar and related flow distributions characteristic of non-Newtonian fluids, which often occiu s in polymerization reactors. 

Polymerization processes are characterized by extremes. Industrial products are mixtures with molecular weights of lO" to 10. In a particular polymerization of styrene the viscosity increased by a fac tor of lO " as conversion went from 0 to 60 percent. The adiabatic reaction temperature for complete polymerization of ethylene is 1,800 K (3,240 R). Heat transfer coefficients in stirred tanks with high viscosities can be as low as 25 W/(m °C) (16.2 Btu/[h fH °F]). Reaction times for butadiene-styrene rubbers are 8 to 12 h polyethylene molecules continue to grow lor 30 min whereas ethyl acrylate in 20% emulsion reacts in less than 1 min, so monomer must be added gradually to keep the temperature within hmits. Initiators of the chain reactions have concentration of 10" g mol/L so they are highly sensitive to poisons and impurities. 

One such monolithic carbon has been produced by Sutcliffe Speakman Carbons and is described by Tamainot-Telto and Critoph [17]. Powdered activated carbon is mixed with a polymeric binder, compressed in a die and fired to produce a monolith of the desired shape, with a density of 713 kg/m and conductivity of 0.33 W/mK. A heat transfer coefficient of 200 W/m K has been measured between the blocks and aluminium fins. 

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