Polymerization, reactions

Polymerization reactions. There are two broad types of polymerization reactions, those which involve a termination step and those which do not. An example that involves a termination step is free-radical polymerization of an alkene molecule. The polymerization requires a free radical from an initiator compound such as a peroxide. The initiator breaks down to form a free radical (e.g., CH3 or OH), which attaches to a molecule of alkene and in so doing generates another free radical. Consider the polymerization of vinyl chloride from a free-radical initiator R. An initiation step first occurs ... 

Polymerization reactions. Polymers are characterized by the distribution of molecular w eight about the mean as well as by the mean itself. The breadth of this distribution depends on whether a batch or plug-flow reactor is used on the one hand or a continuous well-mixed reactor on the other. The breadth has an important influence on the mechanical and other properties of the polymer, and this is an important factor in the choice of reactor. 

This is an exothermic, reversible, homogeneous reaction taking place in a single liquid phase. The liquid butadiene feed contains 0.5 percent normal butane as an impurity. The sulfur dioxide is essentially pure. The mole ratio of sulfur dioxide to butadiene must be kept above 1 to prevent unwanted polymerization reactions. A value of 1.2 is assumed. The temperature in the process must be kept above 65°C to prevent crystallization of the butadiene sulfone but below lOO C to prevent its decomposition. The product must contain less than 0.5 wt% butadiene and less thM 0.3 wt% sulfur dioxide. 

When exposed to sunlight, it is converted to a white insoluble resin, disacryl. Oxidized by air to propenoic acid small amounts of hy-droquinone will inhibit this. Bromine forms a dibromide which is converted by barium hydroxide into DL-fructose. The acrid odour of burning fats is due to traces of propenal. It is used in the production of methionine and in controlled polymerization reactions to give acrolein polymers. ... 

The successful preparation of polymers is achieved only if tire macromolecules are stable. Polymers are often prepared in solution where entropy destabilizes large molecular assemblies. Therefore, monomers have to be strongly bonded togetlier. These links are best realized by covalent bonds. Moreover, reaction kinetics favourable to polymeric materials must be fast, so tliat high-molecular-weight materials can be produced in a reasonable time. The polymerization reaction must also be fast compared to side reactions tliat often hinder or preclude tire fonnation of the desired product. 

Figure C2.1.3. Schematic dependence of tire molecular weight of a polymer as a function of tire degree of monomer conversion for different polymerization reactions.

The second category of polymerization reactions does not involve a chain reaction and is divided into two groups poly addition and poly condensation [4]. In botli reactions, tire growth of a polymer chains proceeds by reactions between molecules of all degrees of polymerization. In polycondensations a low-molecular-weight product L is eliminated, while polyadditions occur witliout elimination ... 

The synthesis of five-, six-, and seven-membered cyclic esters or timides uses intramolecular condensations under the same reaction condifions as described for intermolecular reactions. Yields are generally excellent. An example from the colchicine synthesis of E.E. van Ta-melen (1961) is given below. The synthesis of macrocyclic lactones (macrolides) and lactams (n > 8), however, which are of considerable biochemical and pharmacological interest, poses additional problems because of competing intermolecular polymerization reactions (see p. 246ff.). Inconveniently high dilution, which would be necessary to circumvent this side-... 

The cyclization reactions discussed here either involve the intramolecular reaction of a donor group D with an acceptor group A or a cyclizing dimerization of two molecules with two terminal acceptors and two donors. A polymerization reaction will always compete with cyclization. For macrolides see p. 146 and p. 319 — 329. 

The expression template reaction indicates mostly a reaction in which a complexed me) ion holds reactive groups in the correct orientation to allow selective multi-step reactions. T1 template effect of the metal is twofold (i) polymerization reactions are suppressed, since th local concentration of reactants around the metal ion is very high (ii) multi-step reactions are possible, since the metal holds the reactants together. In the following one-step synthesis eleven molecules (three ethylenediamine — en , six formaldehyde, and two ammonia molecules) react with each other to form one single compound in a reported yield of 95%. It is ob vious that such a reaction is dictated by the organizing power of the metal ion (I.I. Creasei 1977),... 

Our purpose in this introduction is not to trace the history of polymer chemistry beyond the sketchy version above, instead, the objective is to introduce the concept of polymer chains which is the cornerstone of all polymer chemistry. In the next few sections we shall introduce some of the categories of chains, some of the reactions that produce them, and some aspects of isomerism which multiply their possibilities. A common feature of all of the synthetic polymerization reactions is the random nature of the polymerization steps. Likewise, the twists and turns the molecule can undergo along the backbone of the chain produce shapes which are only describable as averages. As a consequence of these considerations, another important part of this chapter is an introduction to some of the statistical concepts which also play a central role in polymer chemistry. 

One type of polymerization reaction is the addition reaction in which successive repeat units add on to the chain. No other product molecules are formed, so the weight of the monomer and that of the repeat unit are identical in this case. A second category of polymerization reaction is the condensation reaction, in which one or two small molecules like water or HCl are eliminated for each chain linkage formed. In this case the molecular weight of the monomer and the... 

In the last section we examined some of the categories into which polymers can be classified. Various aspects of molecular structure were used as the basis for classification in that section. Next we shall consider the chemical reactions that produce the molecules as a basis for classification. The objective of this discussion is simply to provide some orientation and to introduce some typical polymers. For this purpose a number of polymers may be classified as either addition or condensation polymers. Each of these classes of polymers are discussed in detail in Part II of this book, specifically Chaps. 5 and 6 for condensation and addition, respectively. Even though these categories are based on the reactions which produce the polymers, it should not be inferred that only two types of polymerization reactions exist. We have to start somewhere, and these two important categories are the usual place to begin. 

Although the conditions of the polymerization reaction may be chosen to optimize the formation of one specific isomer, it is typical in these systems to have at least some contribution of all possible isomers in the polymeric product, except in the case of polymers of biological origin, like natural rubber and gutta-percha. 

In the next group of chapters we shall discuss condensation or step-growth polymers and polymerizations in Chap. 5, addition or chain-growth polymers and polymerizations in Chap. 6, and copolymers and stereoregular polymers in Chap. 7. It should not be inferred from this that these are the only classes of polymers and polymerization reactions. Topics such as ring-opening polymeri-... 

The stoichiometry of the polymerization reaction (small molecule eliminated ). 

The chapter is organized in a spiral fashion. First, we examine how the degree of polymerization and its distribution vary with the progress of the polymerization reaction, with the latter defined both in terms of stoichiometry and time. In the first round, we consider these topics for simple reaction... 

One of the most sensitive tests of the dependence of chemical reactivity on the size of the reacting molecules is the comparison of the rates of reaction for compounds which are members of a homologous series with different chain lengths. Studies by Flory and others on the rates of esterification and saponification of esters were the first investigations conducted to clarify the dependence of reactivity on molecular size. The rate constants for these reactions are observed to converge quite rapidly to a constant value which is independent of molecular size, after an initial dependence on molecular size for small molecules. The effect is reminiscent of the discussion on the uniqueness of end groups in connection with Example 1.1. In the esterification of carboxylic acids, for example, the rate constants are different for acetic, propionic, and butyric acids, but constant for carboxyUc acids with 4-18 carbon atoms. This observation on nonpolymeric compounds has been generalized to apply to polymerization reactions as well. The latter are subject to several complications which are not involved in the study of simple model compounds, but when these complications are properly considered, the independence of reactivity on molecular size has been repeatedly verified. 

These last expressions provide two very useful views of the progress of a condensation polymerization reaction with time. Equation (5.14) describes how the concentration of A groups asymptotically approaches zero at long times Eq. (5.17) describes how the degree of polymerization increases linearly with time. 

What we seek next is a quantitative relationship between the extent of the polymerization reaction, the composition of the monomer mixture, and the point of gelation. We shall base our discussion on the system described by reaction (5.U) other cases are derived by similar methods. To further specify the system we assume that A groups limit the reaction and that B groups are present in excess. Two parameters are necessary to characterize the reaction mixture ... 

Equation (5.47) is of considerable practical utility in view of the commercial importance of three-dimensional polymer networks. Some reactions of the sort we have considered are carried out on a very large scale Imagine the consequences of having a polymer preparation solidify in a large and expensive reaction vessel because the polymerization reaction went a little too far Considering this kind of application, we might actually be relieved to know that Eq. (5.47) errs in the direction of underestimating the extent of reaction at... 

In this section we examine some examples of cross-linked step-growth polymers. The systems we shall describe are thermosetting polymers of considerable industrial importance. The chemistry of these polymerization reactions is more complex than the hypothetical AB reactions of our models. We choose to describe these commercial polymers rather than model systems which might conform better to the theoretical developments of the last section both because of the importance of these materials and because the theoretical concepts provide a framework for understanding more complex systems, even if they are not quantitatively successful. 

Even at the qualitative level of the discussion above, it is difficult to make predictions regarding the spontaneity of the ring-opening polymerization reaction (5.FF) ... 

Evaluate AG° and at 25°C for each of the polymerization reactions and comment on the results. 

Table 5.8 Values for AH and AS for the Ring-Opening Polymerization, Reaction (5.FF), for Monomers with the Indicated Values of 1...

Table 5.9 Some Typical Ring-Opening Polymerization Reactions...

All of the reactions listed in Table 6.1 produce free radicals, so we are presented with a number of alternatives for initiating a polymerization reaction. Our next concern is in the fate of these radicals or, stated in terms of our interest in polymers, the efficiency with which these radicals initiate polymerization. Since these free radicals are relatively reactive species, there are a variety of... 

Throughout this section we have used mostly p and u to describe the distribution of molecular weights. It should be remembered that these quantities are defined in terms of various concentrations and therefore change as the reactions proceed. Accordingly, the results presented here are most simply applied at the start of the polymerization reaction when the initial concentrations of monomer and initiator can be used to evaluate p or u. The termination constants are known to decrease with the extent of conversion of monomer to polymer, and this effect also complicates the picture at high conversions. Note, also, that chain transfer has been excluded from consideration in this section, as elsewhere in the chapter. We shall consider chain transfer reactions in the next section. 

We conclude this section by noting an extreme case of chain transfer, a reaction which produces radicals of such low reactivity that polymerization is effectively suppressed. Reagents that accomplish this are added to commercial monomers to prevent their premature polymerization during storage. These substances are called either retarders or inhibitors, depending on the degree of protection they afford. Such chemicals must be removed from monomers prior to use, and failure to achieve complete purification can considerably affect the polymerization reaction. 

Bulk and solution polymerizations are more or less self-explanatory, since they operate under the conditions we have assumed throughout most of this chapter. A bulk polymerization may be conducted with as few as two components monomer and initiator. Production polymerization reactions are carried out to high conversions which produces several consequences we have mentioned previously ... 

In some cases may be larger than E- + Ep, which leads to the unusual situation where the rate of the polymerization reaction decreases with increasing temperature. The specifics here depend on the reaction system, including the solvent. 

We saw in the last chapter that the stationary-state approximation is apphc-able to free-radical homopolymerizations, and the same is true of copolymerizations. Of course, it takes a brief time for the stationary-state radical concentration to be reached, but this period is insignificant compared to the total duration of a polymerization reaction. If the total concentration of radicals is constant, this means that the rate of crossover between the different types of terminal units is also equal, or that R... 

The statistical nature of polymers and polymerization reactions has been illustrated at many points throughout this volume. It continues to be important in the discussion of stereoregularity. Thus it is generally more accurate to describe a polymer as, say, predominately isotactic rather than perfectly isotactic. More quantitatively, we need to be able to describe a polymer in terms of the percentages of isotactic, syndiotactic, and atactic sequences. 

In general, acryUc ester monomers copolymerize readily with each other or with most other types of vinyl monomers by free-radical processes. The relative ease of copolymerization for 1 1 mixtures of acrylate monomers with other common monomers is presented in Table 7. Values above 25 indicate that good copolymerization is expected. Low values can often be offset by a suitable adjustment in the proportion of comonomers or in the method of their introduction into the polymerization reaction (86). 

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