Chain-growth mechanism

Step-growth polymerizations can be schematically represented by one of the individual reaction steps VA + B V —> Vab V with the realization that the species so connected can be any molecules containing A and B groups. Chain-growth polymerization, by contrast, requires at least three distinctly different kinds of reactions to describe the mechanism. These three types of reactions will be discussed in the following sections in considerable detail. For now our purpose is to introduce some vocabulary rather than develop any of these beyond mere definitions. The principal steps in the chain growth mechanism are the following ... 

An important application of photochemical initiation is in the determination of the rate constants which appear in the overall analysis of the chain-growth mechanism. Although we shall take up the details of this method in Sec. 6.6, it is worthwhile to develop Eq. (6.7) somewhat further at this point. It is not possible to give a detailed treatment of light absorption here. Instead, we summarize some pertinent relationships and refer the reader who desires more information to textbooks of physical or analytical chemistry. The following results will be useful ... 

In the next section we shall examine the distribution of molecular weights for polymerization which follows the chain-growth mechanism. 

Chain-Growth Associative Thickeners. Preparation of hydrophobically modified, water-soluble polymer in aqueous media by a chain-growth mechanism presents a unique challenge in that the hydrophobically modified monomers are surface active and form micelles (50). Although the initiation and propagation occurs primarily in the aqueous phase, when the propagating radical enters the micelle the hydrophobically modified monomers then polymerize in blocks. In addition, the hydrophobically modified monomer possesses a different reactivity ratio (42) than the unmodified monomer, and the composition of the polymer chain therefore varies considerably with conversion (57). The most extensively studied monomer of this class has been acrylamide, but there have been others such as the modification of PVAlc. Pyridine (58) was one of the first chain-growth polymers to be hydrophobically modified. This modification is a post-polymerization alkylation reaction and produces a random distribution of hydrophobic units. 

Acrylic adhesives cure by a free radical chain growth mechanism. In contrast, epoxy and urethane adhesives cure by a step growth mechanism. This has a major impact on the cure kinetics, as well as the composition of the adhesive during cure ([9], pp. 6-9). Cyanoacrylate adhesives (such as Super Glue ) also cure by chain growth, but the mechanism is ionic with initiation by surface moisture. 

To explain the formation of non-crosslinked polymers from the diallyl quaternary ammonium system, Butler and Angelo proposed a chain growth mechanism which involved a series of intra- and inter-molecular propagation steps (15). This type of polymerization was subsequently shown to occur in a wide variety of symmetrical diene systems which cyclize to form five or six-membered ring structures. This mode of propagation of a non-conjugated diene with subsequent ring formation was later called cyclopolymerization. 

The first step in the polymerization is the electron transfer from sodium to dichlorosilane and the formation of the corresponding radical anion. The latter upon elimination of the chloride anion is transformed to the silyl radical. To fit the chain growth mechanism, the reactivities of the macromolecular radicals must be higher than the reactivities of the monomeric radicals. The latter after electron transfer and elimination of chloride anion could be transformed to the reactive silylenes. Thus, in principle, two or more mechanisms of chain growth are possible ... 

The choice of one polymerization method over another is defined by the type of monomer and the desired properties of the polymer. Table 2.1 lists advantages and disadvantages of the different chain growth mechanisms. Table 2.2 summarizes some well known addition polymers and the methods by which they can be polymerized. 

The addition of heat shifts the equilibrium concentrations away from the products and back towards the reactants, the monomers. This is one reason why processing these types of polymers is often more difficult than processing products of chain growth mechanisms. The thermal degradation process can be dramatically accelerated by the presence of the low molecular weight condensation products such as water. Polyester, as an example, can depolymerize rapidly if processed in the presence of absorbed or entrained water. 

Low viscosity (low concentration systems). Radicals are species that normally have short lifetimes (10 2s to 10 s). In the course of a chain growth mechanism (see Figure 18) they terminate by finding a second non-paired electron to build a chemical link made of an electron pair. This requires that two radicals meet, either to pair their electrons and combine (addition) or to exchange a hydrogen, leading to the formation of one saturated bond and one double bond (disproportionation). 

The most industrially significant polymerizations involving the cationic chain growth mechanism are the various polymerizations and copolymerizations of isobutylene. In fact, about 500 million pounds of butyl rubber, a copolymer of isobutylene with small amounts of isoprene, are produced annually in the United States via cationic polymerization [126]. The necessity of using toxic chlorinated hydrocarbon solvents such as dichloromethane or methyl chloride as well as the need to conduct these polymerizations at very low temperatures constitute two major drawbacks to the current industrial method for polymerizing isobutylene which may be solved through the use of C02 as the continuous phase. 

After the first dehydration step, the reaction propagates by successive dehydration-methanolation steps, competing with poly-merization-cyclization-aromatization processes. The existence of dehydration-methanolation mechanism is inferred from the constant presence of a small amount of methanol (from in situ C-NMR observation) on the catalyst. Further evidence has been acquired in favor of the carbenium ion chain-growth mechanism from the l C-NMR study of CO incorporation into the products during the conversion of methanol (46). 

The first type, termed sequential IPN s, involves the preparation of a crosslinked polymer I, a subsequent swelling of monomer II components and polymerization of the monomer II in situ. The second type of synthesis yields materials known as simultaneous interpenetrating networks (SIN s), involves the mixing of all components in an early stage, followed by the formation of both networks via independent reactions proceeding in the same container (10,11). One network can be formed by a chain growth mechanism and the other by a step growth mechanism. 

The first steps involve coordination and cycloaddition to the metal. Insertion of a third molecule of ethene leads to a more instable intermediate, a seven-membered ring, that eliminates the product, 1-hexene. This last reaction can be a (3-hydrogen elimination giving chromium hydride and alkene, followed by a reductive elimination. Alternatively, one alkyl anion can abstract a (3-hydrogen from the other alkyl-chromium bond, giving 1-hexene in one step. We prefer the latter pathway as this offers no possibilities to initiate a classic chain growth mechanism, as was also proposed for titanium [8]. The byproduct observed is a mixture of decenes ( ) and not octenes. The latter would be expected if one more molecule of ethene would insert into the metallocycloheptane intermediate. Decene is formed via insertion of the product hexene into the metallo-cyclopentane intermediate followed by elimination. 

Copper-cobalt based catalysts induce a classical chain-growth mechanism (9-11) A heavier alcohol content ranging between 20 and 70 % wt can be obtained under moderate operating conditions. The actual target for scale-up studies is the production of alcohol mixtures containing 35-45 wt % of C (12,13). 

A similar chain-growth mechanism was said to occur with the first molybdenum-sulfur-potassium based catalysts of table I (15). For such a chain-growth mechanism, the heavier the average molecular weight of alcohols, the greater the formation of heavy compounds and, more often than not, the lower the alcohols selectivity. Furthermore, in Fischer-Tropsch type catalysts (24,25) diffusion limitations, mostly due to the presence of liquid products condensed in the micro porosity, increase with the size of diffusing molecules. These molecules are capable of... 

Preparation of hydrophobically modified, water-soluble polymer in aqueous media by a chain growth mechanism presents a unique challenge in that the hydrophobically modified monomers are surface active and form micelles. 

The chain growth mechanism for the free radical copolymerization of CO with C2H4 either through added initiators or induced by y-rays has been the subject of a number of papers 7 10). The possible propagation steps in the copolymerization... 

In addition to post-functionalizing polymers by bonding the macrocycle to the preformed polymer backbone, macrocycles can be incorporated into polymer matrices by direct polymerization of the macrocycle, either by a step-growth mechanism or a chain-growth mechanism. [46] Polymeric crown ether stationary phases were pioneered by Blasius et al. [34, 59-62] These resins were used to separate both cations (including protonated amines) with a common anion, and anions with a common cation in high... 

Table 2-2 lists the common names and structures of a few chain-growth polymers. For each of these the common name of the homopolymer and its repeat unit are also shown. Two examples of copolymers are also provided. The subscripts m and n indicate only the total number of repeat units of each monomer not the arrangement in the copolymer. In other words, these are presumed to be random, not block, copolymers. All of the monomers in Table 2, a and b, polymerize by addition to a carbon-carbon double bond by a chain-growth mechanism. 

The second type of monomer for step-growth polymerization contains two different functional groups. Examples in this category include hydroxy acids such as lactic acid (or hydroxy esters [Equations 1-3]), and amino acids. A third type includes cyclic monomers such as lactones, lactams, and cyclic ethers. Cyclic monomers polymerize by ring-opening polymerization. Some, as we said, proceed by step-growth and some by chain-growth mechanisms. 

It is important to appreciate that polymer produced by an anionic chain-growth mechanism can have drastically different properties from one made by a normal free radical reaction. Block copolymers can be synthesized in which each block has different properties. We mentioned in Chapter 4 that Michael Szwdrc of Syracuse University developed this chemistry in the 1950s. Since that time, block copolymers produced by anionic polymerization have been commercialized, such as styrene-isoprene-styrene and styrene-butadiene-styrene triblock copolymers (e.g., Kraton from Shell Chemical Company). They find use as thermoplastic elastomers (TPE), polymers that act as elastomers at normal temperatures but which can be molded like thermoplastics when heated. We will discuss TPEs further in Chapter 7. 

Many alkenes form addition polymers under the right conditions. The chain-growth mechanism involves addition of the reactive end of the growing chain across the double bond of the alkene monomer. Depending on the conditions and the structure of the monomer, the reactive intermediates may be carbocations, free radicals, or carbanions. 

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