Space-network polymer

Nonlinear addition polymers are readily obtained by copolymerizing a divinyl compound (e.g., divinylbenzene) with the vinyl monomer (e.g., styrene), as already mentioned. Products so obtained exhibit the insolubility and other characteristics of space-network structures and are entirely analogous structurally to the space-network polymers produced by the condensation of polyfunctional compounds. Owing to... 

Thermosetting space-network polymers can be prepared through the reaction of polybasic acid anhydrides with polyhydric alcohols. A linear polymer is obtained with a bifunctional anhydride and a bifunctional alcohol, but if either reactant has three or more reactive sites, then formation of a three-dimensional polymer is possible. For example, 2 moles of 1,2,3-propane-triol (glycerol) can react with 3 moles of 1,2-benzenedicarboxylic anhydride (phthalic anhydride) to give a highly cross-linked resin, which usually is called a glyptal ... 

If the monomers are bifunctional, as in the above example, then a linear polymer is formed. Terminating monofunctional groups will reduce the average degree of polymerisation. Polyfunctional monomers, such as glycerol and phthalic acid, are able to form branching points, which readily leads to irreversible network formation (see Chapter 9). Bakelite, a condensation product of phenol and formaldehyde, is an example of such a space-network polymer. Linear polymers are usually soluble in suitable solvents and are thermoplastic - i.e. they can be softened by heat without decomposition. In contrast, highly condensed network polymers are usually hard, are almost completely insoluble and thermoset - i.e. they cannot be softened by heat without decomposition. 

If each monomer molecule contains just two functional groups, growth can occur in only two directions, and a linear polymer is obtained, as in nylon 66 or Dacron. But if reaction can occur at more than two positions in a monomer, there is formed a highly cross-linked space network polymer, as in Glyptal, an alkyd resin. Dacron and Glyptal are both polyesters, but their structures are quite different and, as we shall see, so are their uses. 

Urea reacts with formaldehyde to form the urea-formahlehyde resins, highly important in molded plastics. Here, too, a space-network polymer is formed. 

The amine has three distinct sites where it can react with the epoxide thus generating crosslinkages and forming a space-network polymer. 

As Fig. 1.5 shows, the maximum for some systems does not show up at high temperatures. This can be explained by the increase of the tan 6 value caused by low-molecular weight impurities of the polymer serving as centers of conductivity. The change in the tan 6 values for the epoxy system in the range of 333-383 K measured after 2 h thermal treatment is explained by the increase of the crosslink density of the space-network polymer and by the volatilization of the low-molecular weight impiuities. 

The ladder, sheet, and some of the space network polymers shown are listed under letters B, C, and D in Fig. 1.21. They are often rigid, and are thus class 3 macromolecules (see Sect. 1.1.3). The flexible molecules of interest, however, are difficult to make with a specific stmcture so that they can be named (for a ladder polymer, see the isomers of polybutadiene in Fig. 1.20). Even epoxies and rubbers are usually so poorly characterized, that precise naming is impossible. 

Plastic is a material that can be plasticized into certain shapes under certain conditions (temperature, pressure, etc.) and can keep its shape unchanged at room temperature and normal atmosphere pressure. According to their performance after heat treatment, plastics can be divided into thermoplastic and thermosetting plastics. A thermoplastic plastic is generally a linear or branched polymer. It melts when heated and solidifies when cooled, and this kind of behavior can be repeated, so the plastic can be used multiple times. The main varieties are polyethylene, polypropylene, polyvinyl chloride, polystyrene, and acrylonitrile-butadiene-styrene terpolymer. Thermosetting plastic is a space network polymer, which is formed by direct polymerization of monomers or by cross-linking of linear prepolymers. Once the solidification is finished, the polymer cannot be heated back to the plasticizing state. The main varieties are phenolic resin, epoxy resin, amino resin, and unsaturated polyester. 

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