Free-Radical Chain-Growth Polymerization Process

1 Free-Radical Chain-Growth Polymerization Process 

Polymerizations by free-radical mechanism are typical free-radical reactions. That is to say, there is an initiation, when the radicals are formed, a propagation, when the products are developed, and a termination, when the free-radical chain reactions end. In the polymerizations, the propagations are usually chain reactions. A series of very rapid repetitive steps follow each single act of initiation, leading to the addition of thousands of monomers. 

This process of polymerization of vinyl monomers takes place at the expense of the double bonds, —C=C------ -C-C-. Table 3.1 illustrates the steps in this process. 

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Free-radical polymerization is the most widely used process for polymer synthesis. It is much less sensitive to the effects of adventitious impurities than ionic chain-growth reactions. Free-radical polymerizations are usually much faster than those in step-growth syntheses, which use diFFereiit monomers in any case. Chapter 7 covers emulsion polymerization, which is a special technique of free-radical chain-growth polymerizations. Copolymerizalions are considered separately in Chapter 8. This chapter focuses on the polymerization reactions in which only one monomer is involved. 

It has been stated that the propagation processes in die thiol-ene reactions are less sensitive to oxygen than are typical free radical chain-growth polymerizations. In the presence of excess oxygen, however, peroxy radicals... 

Heterogeneous processes are of great importance for the free-radical chain-growth polymerization of CH2=CRR monomers on an industrial scale. In comparison with bulk polymerization, they allow us to overcome the rapid viscosity increase of the reaction medium with conversion, as well as its consequences, such as the difficult heat removal and the autoacceleration phenomenon. Because in many cases the continuous phase is water, they are also more environmentally friendly techniques than solution polymerization methods, where the use of organic solvents remains hazardous and expensive. Ultimately, heterophase polymerization techniques are the original routes to polymer particles ranging from a few tens of nanometers to a few millimeters in diameter. 

Bulk polymerizations of monomers like acrylates, methacrylates, and styrene belong to the class of free-radical chain-growth polymerizations (or addition polymerizations). With this type of reaction, each polymer chain is formed in a relatively short time and subsequently excluded from further participation in the reaction process. As a consequence, at the beginning of the reaction when the monomer concentration is high, large chains are formed in a monomeric environment, and while the reaction progresses until a certain conversion, the chains formed become shorter. The chain formation can be divided into three steps ... 

Both the monomer and polymer are soluble in the solvent in these reactions. Fairly high polymer concentrations can be obtained by judicious choice of solvent. Solution processes are used in the production of c(5-polybutadiene with butyl lithium catalyst in hexane solvent (Section 9.2.7). The cationic polymerization of isobutene in methyl chloride (Section 9.4.4) is initiated as a homogeneous reaction, but the polymer precipitates as it is formed. Diluents are necessary in these reactions to control the ionic polymerizations. Their use is avoided where possible in free-radical chain growth or in step-growth polymerizations because of the added costs involved in handling and recovering the solvents. 

The exact arrangement of monomers along a copolymer chain will depend on a number of factors. One of these is the relative reactivity of the two monomers. Let us assume that we polymerize a 1 1 mixture of A and B by a free-radical chain-growth process. Here are some of the possibilities ... 

Chain gro tvth polymerization begins when a reactive species and a monomer react to form an active site. There are four principal mechanisms of chain growth polymerization free radical, anionic, cationic, and coordination polymerization. The names of the first three refer to the chemical nature of the active group at the growing end of the monomer. The last type, coordination polymerization, encompasses reactions in which polymers are manufactured in the presence of a catalyst. Coordination polymerization may occur via a free radical, anionic, or cationic reaction. The catalyst acts to increase the speed of the reaction and to provide improved control of the process. 

The process of forming an addition polymer by chain-growth polymerization involving a free radical at the end of the growing chain, (p. 372)... 

The most common type of chain-growth polymerization is free-radical polymerization. An initiator or a photochemical reaction produces a free radical that attaches itself to a monomer molecule, creating a group with odd-electron configuration (reactive center) at which monomer molecules are added until two such centers react with one another or, more rarely, a center is deactivated by some other process. This is a mechanism much like that of ordinary chain reactions (see Chapter 9 the term "chain" in chain growth refers to that kind of mechanisms, not to the growing molecular chain of repeating units in the polymer.)... 

The active site in chain-growth polymerizations can be an ion instead of a free-radical. Ionic reactions are much more sensitive than free-radical processes to the effects of solvent, temperature, and adventitious impurities. Successful ionic polymerizations must be carried out much more carefully than normal free-radical syntheses. Consequently, a given polymeric structure will ordinarily not be produced by ionic initiation if a satisfactory product can be made by less expensive free-radical processes. Styrene polymerization can be initiated with free radicals or appropriate anions or cations. Commercial atactic styrene polymers are, however, all almost free-radical products. Particular anionic processes are used to make research-grade polystyrenes with exceptionally narrow molecular weight distributions and the syndiotactic polymer is produced by metallocene catalysis. Cationic polymerization of styrene is not a commercial process. 

Living polymerizations are limited to the realm of chain-growth polymerizations, in which a monomer is transformed to a polymer by a reactive species (an initiator, I) via a kinetic chain reaction (Scheme 15.1). An intrinsic limitation of a typical chain-growth process, such as free-radical polymerization, is the occurrence of termination reactions that lead to the formation of dead chains, chains that are incapable of further growth. 

Chain-growth polymerization involves the sequential step-wise addition of monomer to a growing chain. Usually, the monomer is unsaturated, almost always a derivative of ethene, and most commonly vinylic, that is, a monosubstituted ethane, 1 particularly where the growing chain is a free radical. For such monomers, the polymerization process is classified by the way in which polymerization is initiated and thus the nature of the propagating chain, namely anionic, cationic, or free radical polymerization by coordination catalyst is generally considered separately as the nature of the growing chain-end may be less clear and coordination may bring about a substantial level of control not possible with other methods. ... 

Chain growth polymerization has the characteristic of having an intermediate within the process that cannot be isolated [5], The intermediate can be a metal complex, a free radical, or an ion. These intermediates are transient to the process. The terms vinyl, olefin, and addition polymerization have been associated with this process [13], Monomer units add to a chain very rapidly once it has been initiated. Initiation is the creation of an active center such as a free radical or carbanion [13], An example is the thermal decomposition of benzoyl peroxide shown in Figure 3.4. To propagate the chain, an additional monomer is added at a very rapid rate as monomer concentration is reduced. Figure 3.5 shows the propagation of polystyrene. 

Polymerization rapidly occurs only with chains possessing a free radical, cation, or anion (referred to as active chains), with rapid addition of units and subsequent chain growth. This process results in a reaction mixture largely composed of polymer and monomer throughout the entirety of the polymerization process. Polymerization occurs until the reactive end is terminated by chemical or physical means. 

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