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FIGURE 32.2 Monomers: Small unsaturated (double-bonded) molecules that are building units for large polymer molecules. (a) Ethylene; (b) vinyl chloride; (c) urea; (d) benzene; (e) phenol; (f) formaldehyde.
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fluoride. The vinyl chloride monomer, as shown in Fig. 32.2b, is similar to ethylene except that one of the hydrogen atoms is replaced with a chlorine atom. The polymerization of this monomer results in polyvinyl chloride. These macromolecules resemble, more or less, smooth strings or chains, as can be seen from their structural arrangement. Some macromolecules resemble rough chains that is, chains with many short side arms branching from them. Polystyrene, which is a very important industrial polymer, is of this type. The styrene monomer is made from the benzene ring (C6H6) with one of the hydrogen atoms replaced with a CH CH2 molecule, as shown in Fig. 32.4a. Polymerization then occurs by breaking the double bond in the CH CH2 group with the help of a peroxide catalyst and joining two of them together, as shown in Fig. 32.4b. The polymers just described are thermoplastic; they melt or soften when they are heated. This is due to the fact that the individual macromolecules are stable and the linkages to other macromolecules are loose (since they are attracted to each
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FIGURE 32.3 Addition polymerization. (a) Three individual monomers of ethylene; (b) a portion of a polyethylene molecule formed when each double bond of the monomers is broken by a catalyst to form two single bonds and join the individual molecules together.
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Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
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FIGURE 32.4 (a) Styrene structure; (b) polystyrene structure. The polymerization takes place in the presence of a peroxide catalyst.
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other by weak van der Waals forces). Some polymers are thermosetting; they do not soften when they are heated, but retain their set or shape until charred. This is due to the fact that the individual macromolecules unite with each other and form many cross-linkages. Bakelite (phenol formaldehyde) is such a polymer. Figure 32.5 shows how each formaldehyde monomer joins two phenol monomers together, under suitable heat and pressure, to form a macromolecule. This is a condensation type of polymerization because one water molecule is formed from the oxygen atom of each formaldehyde molecule and a hydrogen atom from each of the two phenol molecules.
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Mechanical Properties of Molecular Structures
The mechanical properties of polymers are determined by the types of forces acting between the molecules. The polymers are amorphous with random chain orientations while in the liquid state. This structure can be retained when the polymer is cooled rapidly to the solid state. In this condition, the polymer is quite isotropic. However, with slow cooling or plastic deformation, such as stretching or extruding, the molecules can become aligned. That is, the long axes of the chains of all the molecules tend to be parallel. A material in this condition is said to be oriented or crystalline, the degree of orientation being a measure of the crystallinity.When the molecular chains of a polymer have this type of directionality, the mechanical properties are also directional and the polymer is anisotropic. The strength of an aligned polymeric material is stronger along the axis of the chains and much lower in the perpendicular directions. This is due to the fact that only weak van der Waals forces hold the individual, aligned macromolecules together, whereas the atoms along the axes of the chains are held together by strong and covalent bonds. The intermolecular strength of linear polymers can be increased by the addition of polar (dipole) groups along the length of the chain. The most frequently used polar groups are chlorine, fluorine, hydroxyl, and carboxyl. The thermosetting (cross-linked) types of polymers have all the macromolecules connected together in three directions with strong covalent bonds. Consequently, these polymers are stronger than thermoplastic ones, and they are also more isotropic.
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