Temperature control free-radical polymerization

Temperature-controlled free radical polymerization of vinyl monomers such as butyl acrylate, methyl methacrylate, and styrene has been carried out in the reactor shown in Figure 8.3. Following mixing of the initiator 2,2-azobis(isobutylronitrile)... 

B. Charleux, S. R. A. Marque, D. Bertin, S. Magnet, L Couvreur, Living character of polymer chains prepared via nitroxide-mediated controlled free-radical polymerization of methyl methacrylate in the presence of a small amount of styrene at low temperature, Macromolecules 2006,... 

The previous sections show that certain ionic liquids, namely the chloroalumi-nate(III) ionic liquids, are capable of acting both as catalyst and as solvent for the polymerization of certain olefins, although in a somewhat uncontrolled manner, and that other ionic liquids, namely the non-chloroaluminate(III) ionic liquids, are capable of acting as solvents for free radical polymerization processes. In attempts to carry out polymerization reactions in a more controlled manner, several studies have used dissolved transition metal catalysts in ambient-temperature ionic liquids and have investigated the compatibility of the catalyst towards a range of polymerization systems. 

A number of different materials were used as chain transfer agents to control molecular weight. These results are shown in Table 6.1. The effect of varying concentration of t-butyl alcohol and reaction temperature is shown in Figure 6.1. The results are consistent with normal free radical polymerizations. Polymer output was characterized by inherent viscosity and ZST tests. 

Rasmussen and co-workers. Chapter 10, have shown that many free-radical polymerizations can be conducted in two-phase systems using potassium persulfate and either crown ethers or quaternary ammonium salts as initiators. When transferred to the organic phase persulfate performs far more efficiently as an initiator than conventional materials such as azobisisobutyronitrile or benzoyl peroxide. In vinyl polymerizations using PTC-persulfate initiation one can exercise precise control over reaction rates, even at low temperatures. Mechanistic aspects of these complicated systems have been worked out for this highly useful and economical method of initiation of free-radical polymerizations. 

Apart from ATRP, the concept of dual initiation was also applied to other (controlled) polymerization techniques. Nitroxide-mediated living free radical polymerization (LFRP) is one example reported by van As et al. and has the advantage that no further metal catalyst is required [43], Employing initiator NMP-1, a PCL macroinitiator was obtained and subsequent polymerization of styrene produced a block copolymer (Scheme 4). With this system, it was for the first time possible to successfully conduct a one-pot chemoenzymatic cascade polymerization from a mixture containing NMP-1, CL, and styrene. Since the activation temperature of NMP is around 100 °C, no radical polymerization will occur at the reaction temperature of the enzymatic ROP. The two reactions could thus be thermally separated by first carrying out the enzymatic polymerization at low temperature and then raising the temperature to around 100 °C to initiate the NMP. Moreover, it was shown that this approach is compatible with the stereoselective polymerization of 4-MeCL for the synthesis of chiral block copolymers. 

The various properties exhibited by ILs make them ideal stahonary phases in GLC. ILs exhibit a unique dual-nature selechvity that allows them to separate polar molecules like a polar stationary phase and nonpolar molecules like a nonpolar stationary phase. In addition, the combination of cations and anions can be tuned to add further selectivity for more complex separations. Viscosity, thermal stability, and surface tension are vital properties that dictate the quality and integrity of the stationary phase coating and are additional characteristics that can be controlled when custom designing and synthesizing ILs. Furthermore, thermal stability and the integrity of stationary phase film can be improved by immobilizing the IL by free radical polymerization to form stationary phases suitable for low- moderate-, and high-temperature separations. Chiral ILs have been shown to enantioresolve chiral analytes with reasonable efficiency. 

Free-radical initiation of emulsion copolymers produces a random polymerization m which the trans/ds ratio cannot be controlled. The nature of ESBR free-radical polymerization results in the polymer being heterogeneous, with a broad molecular weight distribution and random copolymer composition. The microstructurc is not amenable to manipulation, although the temperature of the polymerization affects the ratio of trans to cis somewhat... 

Homopolymerization. The free-radical polymerization of VDC has been carried out by solution, slurry, suspension, and emulsion methods. Slurry polymerizations are usually used only in the laboratory. The heterogeneity of the reaction makes stirring and heat transfer difficult consequently, these reactions cannot be easily controlled on a large scale. Aqueous emulsion or suspension reactions are preferred for large-scale operations. The spontaneous polymerization of VDC, so often observed when the monomer is stored at room temperature, is caused by peroxides formed from the reaction of VDC with oxygen, fery pure monomer does not polymerize under these conditions. Heterogeneous polymerization is characteristic of a number of monomers, including vinyl chloride and acrylonitrile. 

Many polymer reactions, for example, are highly exothermic, so the temperature control concepts outlined in this book must be applied. At the same time, controlling just the temperature in a polymer reactor may not adequately satisfy the economic objectives of the plant, since many of the desired polymer product properties (molecular weight, composition, etc.) are created within the polymerization reactor. These key properties must be controlled using other process parameters (i.e. vessel pressure in a polycondensation reactor or chain transfer agent composition in a free-radical polymerization reactor). 

The key problems in a polymerization CSTR are the determination and characterization of micro- and macromixing, and the possibility of multiple steady states due to the exothermic nature of the reactions. Recent studies of CSTRs for bulk or solution free-radical polymerization indicate the possibility of multiple steady states due to the large heat evolution and difficult heat transfer that are characteristic of the reactors. Furthermore, even in simple solution polymerization (for example, in methyl methacrylate polymerization in ethyl acetate solvent), autocatalytic kinetics can lead to runaway conditions even with perfect temperature control for certain combinations of solvent concentration and reactor residence time. In practice, the heat evolution can be an additional source of autocatalytic behavior. 

Under suitable conditions, anionic polymerization is faster than free-radical polymerization and so can be conducted at lower temperatures. The main reasons are fast initiation by an ionic reaction and absence of an effective termination mechanism. However, the sensitivity to impurities is much greater and choice and control of reaction conditions are more delicate. Water, oxygen, carbon dioxide, and other substances able to react with carbanion chain carriers must be strictly excluded. 

Polymerization. The monomer (or comonomers) and polymerization solvents were passed through a column packed with neutral-grade alumina to remove the inhibitor and other impurities. The monomer(s) and a solvent were degassed by several freeze-thaw cycles by using a vacuum line and were distilled at room temperature into an ampoule containing a known amount of AIBN (azobisisobutyroni-trile), a free-radical-polymerization initiator. After additional degassing, the ampoule was sealed, wrapped in aluminum foil, and placed in a thermostatically controlled bath. Several examples of reaction conditions are given in Table I. 

A combination of variables controls the outcome of the copolymerization of two or more unsaturated monomers by CCT free-radical polymerization.382 Of course, all of the features that control the outcome of a normal free-radical polymerization come into effect.40 426 429 These include the molar ratio of monomers, their relative reactivity ratios and their normal chain-transfer constants, the polymerization temperature, and the conversion. In the presence of a CCT catalyst, the important variables also include their relative CCT chain-transfer constants and the concentration of the Co chain-transfer agent. The combination of all of these features controls the molecular weight of the polymer and the nature of the vinyl end group. In addition, they can also control the degree of branching of the product. 

Free radical polymerization of neat monomer in the absence of solvent and with only initiator present is called bulk or mass polymerization. Monomer in the liquid or vapor state is well mixed with initiator in a heated or cooled reactor as appropriate. The advantages of this method are that it is simple, and because of the few interacting components present, there is less possibility for contamination. However, vinyl-type polymerizations are highly exothermic so that control of the temperature of bulk polymerization may be difficult. Also, in the absence of a solvent viscosities may become very high toward the end of a polymerization, which could make stirring difficult, and add to the difficulty of heat removal from the system. The advantages of this system, however, are sufficiently attractive for this to be used commercially for the free radical polymerization of styrene, methyl methacrylate, vinyl chloride, and also for some of the polymerization processes of ethylene [7]. 

Free radical polymerization of a monomer in solution is often more versatile and more amenable to temperature control than bulk polymerization. The presence of the solvent avoids any potential viscosity or stirring problems. Also the exotherm of the polymerization is moderated by the lower monomer concentrations under these conditions, which slows down rates, and by the thermal mass contributed by the solvent. Sometimes the polymerization temperature will be conveniently controlled by the reflux temperature of the solvent used. 

Commercially, PFA is polymerized by free-radical polymerization mechanism usually in an aqueous media via addition polymerization of TFE and perfluoropropyl vinyl ether. The initiator for the polymerization is usually water-soluble peroxide, such as ammonium persulfate. Chain transfer agents such methanol, acetone and others are used to control the molecular weight of the resin. Generally, the polymerization regime resembles that used to produce PTFE by emulsion polymerization. Polymerization temperature and pressure usually range from 15 to 95°C and 0.5 to 3.5 MPa. 

While possessing many of the key advantages of controlled/ living polymerization methods, nitroxide-mediated free-radical polymerizations do exhibit several limitations. The range of monomers that have been polymerized using nitroxide-mediated techniques include styrenics. acrylamides and (meth)acrylates but these have predominantly been reported in bulk polymerizations (i.e. without solvent) and are conducted at elevated temperature for long time periods. In addition, synthesis of the unimolecular initiator can prove troublesome (dependent upon the type required) and often requires extensive purification in order to attain sufficient purity levels to allow molecular weight control. 

Bhat, S. A., Gupta, S., Saraf, D. N. and Gupta, S. K. (2006). On-line optimizing control of bulk free radical polymerization reactors under temporary loss of temperature regulation experimental study on a 1-L batch reactor, Ind. Eng. Chem. Res., 45, pp. 7530-7539. 

In Chapter 9, we mentioned that the use of microreactors leads to a significant improvement in the control of the molecular-weight distribution in free radical polymerization by virtue of superior heat-transfer efficiency.Free-radical polymerization reactions are usually highly exothermic, so precise temperature control is essential to carry out these reactions in a highly controlled manner. Thus, from an industrial viewpoint, a major concern with free-radical polymerization is the controllability of the reaction temperature. Temperature control often arises as a serious problem during the scale-up of a bench process to industrial production. In this section, we will discuss the numbering-up of microreactors to increase production volumes in radical polymerization in industry. 

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