4.5.1 The copolymer equation

It can be shown that the rate of change of monomer concentration in any copolymerization is given by the equation

where [M1] and [M2] are the concentrations of monomers 1 and 2 at any instant and r1 and r2., are reactivity ratios. The reactivity ratios represent the rate at which one type of gr
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4.5 Copolymerization

The alloying of metals to improve their properties is widespread and although many polymers used today are relatively pure (e.g. polystyrene, nylon), an increasing number are mixtures of two or more polymers. As with metals, one reason for doing this is to increase the range of properties. The major practical problem, however, is that homopolymers blend together with difficulty and even where blends are possible, as in some thermoplastics, phase separation can occur readily.

This proble
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4.4 Step growth polymerization

Figure 41
Figure 41 Molecular mass distrib
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4.3.5 Co-ordination polymerization

While most free radical and ionic polymerizations are carried out homogeneously, there is another important class of reaction which is often performed with solid catalysts. These reactions, discovered in the mid-fifties, have revolutionized polymer manufacture by permitting much less severe polymerization conditions than with other systems and by allowing a greater degree of control of polymer structure. Ziegler-Natta catalysts, as they are called, will convert vinyl and diene monomers
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4.3.4 Ionic polymerization

Free radicals are indiscriminate in the compounds they attack, and their non-selective nature in polymerization reactions leads to problems such as chain branching and transfer which affect the structure of the polymer produced. Anionic polymerization overcomes many of these problems.

A typical commercial (but also see Box 8) anionic reaction is the polymerization of styrene using butyllithium, C4H9
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4.3.3 Termination and transfer

There are basically three ways in which chains terminate.

The first is known as coupling and occurs when two free radicals join together. This can be represented by the general equation

Such a mechanism significantly increases molecular mass, if it results in two polymer chains joining. This is the main mechanism which terminates the po
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4.3.2 Propagation

Once a small number of chains have been started, propagation involves successive addition of monomer units to achieve chain growth. At each step the free radical is regenerated as it reacts with the double bond. So in the case of styrene the propagation step is

The free radical can also add on in a different way to produce

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4.3.1 Initiation

Initiation is the mechanism which starts the polymerization process. Vinyl monomers are quite easily polymerized by a variety of activating methods. Styrene, for example, can be converted to solid polymer simply by heating, and ultraviolet light can have exactly the same effect. Usually, however, an activating agent is used. This is an unstable chemical which produces active species that attack the monomer. A good example is benzoyl peroxide which splits up when heated:

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4.3 Chain growth polymerization

Chain growth polymerization is basically a three-stage process, involving initiation of active molecules, their propagation and termination of the active chain ends.

4.2 Chain and step growth

There are two basic ways of making chains. The first is to activate a small number of monomer units M which then successively consume other monomers. This mechanism is known as chain growth and is shown schematically in Figure 36 (a), where a monomer unit is activated by initiator I and forms a chain very quickly. After 75 per cent of the monomer molecules have reacted in this case the degree of polymerization n =
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4.1 Understanding the polymerization process

Converting monomer to long chain polymer is the final step in the polymer manufacturing sequence. Polymerization is usually highly favourable in thermodynamic terms, mainly on energetic grounds because ordering molecules into linked chains is a process where the entropy is decreased. Heat is always given out during polymerization owing to the very favourable energetics of reaction, a point you may have noticed if you have ever made GRP parts for your car, for example!

Advances in cataly
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3.4 The petrochemical industry

The four-fold increase in the price of oil in 1973–4, together with associated political events, proved a powerful stimulus in the development and exploitation of North Sea crude oil. Increasing the price of oil does not mean that the price of the final plastic moulding increases by the same amount. For example if oil prices were doubled again then naphtha prices would typically increase by about 80 per cent, although there is no simple and fixed gearing mechanism between the two prices. Th
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3.3.3 Higher aromatics

Benzene rings can be fused in various ways to create component parts for some of the complex aromatic repeat units shown in Table 5. One of the most important is bisphenol A, made by fusing two phenol rings with acetone:

This intermediate is important for a number of speciality polymers, for example, polycarbonate and epoxy resi
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3.3.2 Benzene, toluene and xylene

In addition to benzene itself, the catalytic reformer also produces ethylbenzene, toluene and the isomeric xylenes directly. The demand for ethylbenzene is always great as a source of styrene monomer, but toluene does not find great use apart from a relatively small application in polyurethane. This is why most toluene is de-alkylated to increase overall benzene production. A similar problem exists with the xylenes:

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3.3.1 Ethylene, propylene and butadiene

Nowadays ethylene is the most important building block for the chemical industry, particularly as a monomer in its own right, as a co-monomer with other vinyls, and as a source of vinyl monomers. It is the prime source for ethylene oxide, which is another major source of polymers, glycols and ethers. They can also be used to build up more complex C4 molecules and aromatics.

Some of the ways in which the ethylene molecule is modified to create other chemicals and polymers are
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3.3 Petrochemical intermediates and monomers

About 80 per cent of all petrochemicals end up in polymers, the most important building blocks being ethylene, propylene, butadiene and benzene. The first three can be polymerized directly but an important slice of their production is used to create more complex monomers. Ethylene is the progenitor of most vinyl monomers (Figure 35), so the pressure on ethylene supply is particularly strong compared for example to propyle
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3.2.2 Ethane cracking

Although ethane can be cracked thermally, the reaction is slow and does not necessarily yield ethylene at high severity. Careful control of reaction conditions, however, allows the reaction to occur

The yield of ethylene is typically nearly 50 wt% with the rest composed of unreacted ethane (40 per cent) and some methane and hydrogen (10 per cent). T
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3.2.1 Thermal cracking

The bulk of the major monomer and intermediate, ethylene (C2H4), is still produced in the UK by steam cracking without the use of catalysts. Paraffinic feedstocks are best for optimising ethylene yields, and the severity of cracking is specified by the rate of disappearance of a marker compound, usually n-pentane. The severity of the reaction can then be defined as follows:

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1 Learning to learn
How do we learn? Understanding ‘how’ is the key to learning more effectively. This unit looks at the three main categories of theories: the acquisitive, constructivist and experiential models of learning. There is no right way to learn but developing an active approach will ensure that you are open to new ideas.
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2.3 Choosing your voice: exercise
In this unit we will consider how language can be used in different ways for different purposes. To do this we will use the theme of memorial and commemoration. In the first section we briefly discuss the life of the poet Siegfried Sassoon before examining both his poetry and prose. Through this we will see how he conveys meaning in different ways for different audiences using different forms. Following this we discuss more generally how different meanings can be conveyed using prose and poetic
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