9

CROSS-LINKED POLYMERS AND RUBBER ELASTICITY

An elastomer is dened as a cross-linked amorphous polymer above its glass transition temperature. Elastomers may be stretched substantially reversibly to several hundred percent. While most of this chapter explores the behavior of elastomers, the study of cross-linking is more general. If the cross-linked polymer is glassy, it is often called a thermoset. Below, the terms elastomer and rubber are often used interchangably. 9.1 CROSS-LINKS AND NETWORKS

During reaction, polymers may be cross-linked to several distinguishable levels. At the lowest level, branched polymers are formed. At this stage the polymers remain soluble, sometimes known as the sol stage. As cross-links are added, clusters form, and cluster size increases. Eventually the structure becomes innite in size; that is, the composition gels.At this stage a Maxwellian demon could, in principle, traverse the entire macroscopic system stepping on one covalent bond after another. Continued cross-linking produces compositions where, eventually, all the polymer chains are linked to other chains at multiple points, producing, in principle, one giant covalently bonded molecule. This is commonly called a polymer network. 9.1.1 The SolGel Transition

The reaction stage referred to as the solgel transition (13) is called the gel point. At the gel point the viscosity of the system becomes innite, and the
Introduction to Physical Polymer Science, by L.H. Sperling ISBN 0-471-70606-X Copyright 2006 by John Wiley & Sons, Inc.

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equilibrium modulus climbs from zero to nite values. In simple terms the polymer goes from being a liquid to being a solid. There are three different routes for producing cross-linked polymers: 1. Step polymerization reactions, where little molecules such as epoxies (oxiranes) react with amines, or isocyanates react with polyols with functionality greater than two to form short, branched chains, eventually condensing it into epoxies or polyurethanes, respectively. Schematically B nA A + mB B BA AB BA AB AB (9.1)

2. Chain polymerization, with multifunctional molecules present. An example is styrene polymerized with divinyl benzene. 3. Postpolymerization reactions, where a linear (or branched) polymer is cross-linked after synthesis is complete. An example is the vulcanization of rubber with sulfur, which will be considered further below. The general features of structural evolution during gelation are described by percolation (or connectivity) theory, where one simply connects bonds (or lls sites) on a lattice of arbitrary dimension and coordination number (46). Figure 9.1 (6) illustrates a two-dimensional system at the gel point. It must be noted that gels at and just beyond the gel point usually coexist with sol clusters. These can also be seen in Figure 9.1. It is common to speak of the con-

Figure 9.1 A square lattice example of percolation, at the gel point (6). Note structures that span the whole sample.

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version factor, p, which is the fraction of bonds that have been formed between the mers of the system; see Section 3.7. For the two-dimensional 1 schematic illustrated in Figure 9.1, p = yields the gel point. 2 9.1.2 Micronetworks

A special type of network exists that involves only one or a few polymer chains. Thus microgels may form during specialized reaction conditions where only a few chains are interconnected. Globular proteins constitute excellent examples of one-molecule micronetworks (7), where a single polymer chain is intramolecularly cross-linked; see Figure 9.2 (8). Here, disulde bonds help keep the three-dimensional structure required for protein biopolymer activity. Such proteins may be denatured by any of several mechanisms, especially heat. Thus, when globular proteins are cooked, the intramolecular cross-links become delocalized, forming intermolecular bonds instead. This is the major difference between raw egg white and hard-boiled egg white, for example. Fully cross-linked on a macroscopic scale, polymer networks fall into different categories. It is convenient to call such polymers, which are used below

Figure 9.2 The structure of ribonuclease A, a micronetwork of one chain. Note cysteine cysteine bonds (8).

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their glass transition temperature, thermosets, since they are usually plastics incapable of further ow. On the other hand, those networks that are above their glass transition temperature are rubbery unless very heavily cross-linked. While all these kinds of cross-linked polymers are important, the remainder of this chapter is devoted primarily to amorphous, continuous polymer networks above their glass transition temperature, the regime of rubber elasticity. While the rubber elasticity theory to be described below presumes a randomly cross-linked polymer, it must be noted that each method of network formation described above has distinctive nonuniformities, which can lead to signicant deviation of experiment from theory. For example, chain polymerization leads rst to microgel formation (9,10), where several chains bonded together remain dissolved in the monomer. On continued polymerization, the microgels grow in number and size, eventually forming a macroscopic gel. However, excluded volume effects, slight differences in reactivity between the monomer and cross-linker, and so on lead to systematic variations in crosslink densities at the 100- to 500- level.

9.2 9.2.1

HISTORICAL DEVELOPMENT OF RUBBER Early Developments

A simple rubber band may be stretched several hundred percent; yet on being released, it snaps back substantially to its original dimensions. By contrast, a steel wire can be stretched reversibly for only about a 1% extension. Above that level, it undergoes an irreversible deformation and then breaks. This longrange, reversible elasticity constitutes the most striking property of rubbery materials. Rubber elasticity takes place in the third region of polymer viscoelasticity (see Section 8.2) and is especially concerned with cross-linked amorphous polymers in that region. Columbus, on his second trip to America, found the American Indians playing a game with rubber balls (11,12) made of natural rubber. These crude materials were un-cross-linked but of high molecular weight and hence were able to hold their shape for signicant periods of time. The development of rubber and rubber elasticity theory can be traced through several stages. Perhaps the rst scientic investigation of rubber was by Gough in 1805 (13). Working with unvulcanized rubber, Gough reached three conclusions of far-reaching thermodynamic impact: 1. A strip of rubber warms on stretching and cools on being allowed to contract. (This experiment can easily be conrmed by a student using a rubber band. The rubber is brought into contact with the lips and stretched rapidly, constituting an adiabatic extension. The warming is easily perceived by the temperature-sensitive lips.)

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2. Under conditions of constant load, the stretched length decreases on heating and increases on cooling. Thus it has more retractive strength at higher temperatures. This is the opposite of that observed for most other materials. 3. On stretching a strip of rubber and putting it in cold water, the rubber loses some of its retractile power, and its relative density increases. On warming, however, the rubber regains its original shape. In the light of present-day knowledge, this last set of experiments involved the phenomenon known as strain-induced crystallization, since unvulcanized natural rubber crystallizes easily under these conditions. In 1844 Goodyear vulcanized rubber by heating it with sulfur (14). In modern terminology, he cross-linked the rubber. (Other terms meaning crosslinking include tanning of leather, drying of oil-based paints, and curing of inks.) Vulcanization introduced dimensional stability, reduced creep and ow, and permitted the manufacture of a wide range of rubber articles, where before only limited uses, such as waterproong, were available (15). (The MacIntosh raincoat of that day consisted of a sandwich of two layers of fabric held together by a layer of unvulcanized natural rubber.) Using the newly vulcanized materials, Goughs line of research was continued by Kelvin (16). He tested the newly established second law of thermodynamics with rubber and calculated temperature changes for adiabatic stretching. The early history of rubber research has been widely reviewed (17,18). All of the applications above, of course, were accomplished without an understanding of the molecular structure of polymers or of rubber in particular. Beginning in 1920, Staudinger developed his theory of the long-chain structure of polymers (19,20). [Interestingly Staudingers view was repeatedly challenged by many investigators tenaciously adhering to ring formulas or colloid structures held together by partial valences (21).] See Appendix 5.1. 9.2.2 Modern Developments

In the early days the only elastomer was natural rubber. Starting around 1914, a polymer of 2,3-dimethylbutadiene known as methyl rubber was made in Germany. This was replaced by a styrenebutadiene copolymer called Buna-S (butadienenatriumstyrene), where natrium is, of course, sodium. This sodium-catalyzed copolymer, as manufactured in Germany in the period from about 1936 to 1945 had about 32% styrene monomer (22). In 1939 the U.S. government started a crash program to develop a manufactured elastomer, called the Synthetic Rubber Program (23). The new material was called GR-S (government rubber-styrene). GR-S was made by emulsion polymerization. While the Bunas was catalyzed by sodium, the latter was catalyzed by potassium persulfate. Incidentally, the emulsier in those

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days was ordinary soap akes. Both materials played crucial roles in World War II, a story told many times (2325). While Buna-S had about 32% styrene monomer (22), the GR-S material, started a few years later with the benet of the German recipe, had about 25% styrene (26). This difference in the composition was important for lowering the glass transition temperature. Using the Fox equation, equation (8.73), with a Tg of polystyrene of 373 K, and that of polybutadiene of 188 K, Table 8.7, values of Tg for Buna-S and GR-S are estimated at -47 and -58C, respectively. Noting that winter temperatures in European Russia reach -40 to -51C (27), lore has it that use of Buna-S seriously inuenced the winter Russian campaigns. Today, SBR elastomers are widely manufactured with only minor improvements in the GR-S recipe. One such is the use of synthetic surfactants as emulsiers. These and other improvements allow the production of more uniform latex particles.

9.3

RUBBER NETWORK STRUCTURE

Once the macromolecular hypothesis of Staudinger was accepted, a basic understanding of the molecular structure was possible. Before cross-linking, rubber (natural rubber in those days) consists of linear chains of high molecular weight. With no molecular bonds between the chains, the polymer may ow under stress if it is above Tg. The original method of cross-linking rubber, via sulfur vulcanization, results in many reactions. One such may be written CH3 2 CH2 CH S S CH CH CH3 C CH S S R C CH CH3 C CH CH2 CH2 (9.1a) + sulfur

where R represents other rubber chains. Two other methods of cross-linking polymers must be mentioned here. One is radiation cross-linking, with an electron beam or gamma irradiation. Using polyethylene as an example,