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511. 512. 513. 514. 515. 516. 517. 518. 519. Wright, op. cit., p. 876. Childs, op. cit., p. 112. Ibid., p. 120. Wright, op. cit., p. 882. Childs, op. cit., p. 138. Durand, David. Basic Yields of Corporate Bonds, 1900 1942 (and supplements). New York: National Bureau of Economic Research, 1942. Hickman, W. Braddock. The Term Structure of Interest Rates. New York: National Bureau of Economic Research, 1942. Kaufman, Henry. Interest Rates, the Markets, and the New Financial World. New York: Times Books, 1986. Chs. 3, 14. Niefeld, M. R. The Personal Finance Business. New York: Harper & Brothers, 1933; and Trends in Consumer Finance. Easton: Mack Publishing Co., 1954. p. 59. Niefeld, op. cit., p. 292. Niefeld, op. cit., p. 209. Encyclopedia of the Social Sciences, op. cit., vol. 8, p. 139. New York Times, Feb. 19, 1959, p. 1. An exact formula for the one-year real rate is (1 + i)/(1 + p) 1, where i is the nominal, or market, rate of interest per annum and p is the expected oneyear inflation rate. The formula is equivalent mathematically to a real rate of (i p)/(1 + p). It is often stated that the real rate of interest is the nominal, or market, rate less the inflation rate. Clearly, this is an approximation that is only roughly correct for low rates of inflation. An excellent book-length study of real rates the first of its kind appeared in 1989, the last full year of this HISTORY. See Peter S. Spiro, Real Interest Rates and Investment and Borrowing Strategy. New York, Westport, CT, and London: Quorum Books, 1989. This is discussed by Henry Kaufman, op. cit., p. 19. See Spiro, op. cit., ch. 7. Macaulay, op. cit., pp. 85ff. Durand, op. cit. See Table 53 for additional sources.

For most step polymerizations, for example, in the synthesis of poly(hexamethylene adipamide) or poly(ethylene terephthalate), two reactants or monomers are used in the process, and the polymer obtained contains two different kinds of structures in the chain. This is not the case for chain polymerizations, where only one monomer need be used to produce a polymer. However, chain polymerizations can be carried out with mixtures of two monomers to form polymeric products wiht two different structures in the polymer chain. This type of chain polymerization process in which two monomers are simultaneously polymerized is termed a copolymerization, and the product is a copolymer. It is important to stress that the copolymer is not an alloy of two homopolymers but contains units of both monomers incorporated into each copolymer molecule. The process can be depicted as

6-1

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3. Solder two power extension wires to the new power jack: positive wire to the lug that goes to the center, or tip connector, of the jack, and negative to the other lug (see Figure 10-15).

The two monomers enter into the copolymer in overall amounts determined by their relative concentrations and reactivities. The simultaneous chain polymerization of different monomers can also be carried out with mixtures of three or more monomers. Such polymerizations are generally referred to as multicomponent copolymerizations; the term terpolymerization is speci cally used for systems of three monomers. Copolymerization is also important in step polymerization. Relatively few studies on step copolymerization have been carried out, although there are considerable commercial applications. Unlike the situation in chain copolymerization, the overall composition of the copolymer obtained in a step copolymerization is usually the same as the feed composition since step reactions must be carried out to close to 100% conversion for the synthesis of

520. 521. 522. 523. 524.

Principles of Polymerization, Fourth Edition. By George Odian ISBN 0-471-27400-3 Copyright # 2004 John Wiley & Sons, Inc.

high-molecular-weight polymers. Further, most step polymerizations are equilibrium reactions and the initially formed copolymer composition is rapidly changed by equilibration. This chapter is concerned entirely with chain copolymerization. The main features of step copolymerization have been covered in Sec. 2-13.

526. 527. 528. 529.

Chain copolymerization is important from several considerations. Much of our knowledge of the reactivities of monomers, free radicals, carbocations, and carbanions in chain polymerization comes from copolymerization studies. The behavior of monomers in copolymerization reactions is especially useful for studying the effect of chemical structure on reactivity. Copolymerization is also very important from the technological viewpoint. It greatly increases the ability of the polymer scientist to tailor-make a polymer product with speci cally desired properties. Polymerization of a single monomer is relatively limited as to the number of different products that are possible. The term homopolymerization is often used to distinguish the polymerization of a single monomer from the copolymerization process. Copolymerization allows the synthesis of an almost unlimited number of different products by variations in the nature and relative amounts of the two monomer units in the copolymer product. A prime example of the versatility of the copolymerization process is the case of polystyrene. More than 11 billion pounds per year of polystyrene products are produced annually in the United States. Only about one-third of the total is styrene homopolymer. Polystyrene is a brittle plastic with low impact strength and low solvent resistance (Sec. 3-14b). Copolymerization as well as blending greatly increase the usefulness of polystyrene. Styrene copolymers and blends of copolymers are useful not only as plastics but also as elastomers. Thus copolymerization of styrene with acrylonitrile leads to increased impact and solvent resistance, while copolymerization with 1,3-butadiene leads to elastomeric properties. Combinations of styrene, acrylonitrile, and 1,3-butadiene improve all three properties simultaneously. This and other technological applications of copolymerization are discussed further in Sec. 6-8. 6-1b Types of Copolymers

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