Polymer dienes

The use of 1 3 butadiene in the preparation of synthetic rubber is discussed in the boxed essay Diene Polymers that appears later in this chapter... 

The thiophthalimide (CTP) and sulfenamide classes of retarders differ from the organic acid types by thek abiUty to retard scorch (onset of vulcanization) without significantly affecting cure rate or performance properties. Much has been pubUshed on the mechanism of CTP retardation. It functions particularly well with sulfenamide-accelerated diene polymers, typically those used in the the industry. During the initial stages of vulcanization, sulfenamides decompose to form mercaptobenzothiazole (MBT) and an amine. The MBT formed reacts with additional sulfenamide to complete the vulcanization process. If the MBT initially formed is removed as soon as it forms, vulcanization does not occur. It is the role of CTP to remove MBT as it forms. The retardation effect is linear with CTP concentration and allows for excellent control of scorch behavior. 

It is an observed fact that with most synthetic polymers the head-to-tail structure is formed. In the case of diene polymers differences may arise in the point of addition. Reaction can take place at the 1 and 4 positions, the 1 and 2 positions or the 3 and 4 positions to give the structures indicated in Figure 4.9. 

These materials differ from the previous class of resin in that the basic structure of these molecules consists of long chains whereas the cyclic aliphatics contain ring structures. Three subgroups may be distinguished, epoxidised diene polymers, epoxidised oils, and polyglycol diepoxides. 

Typical of the epoxidised diene polymers are products produced by treatment of polybutadiene with peracetic acid. The structure of a molecular segment Figure 26.16) indicates the chemical groupings that may be present. 

In some cases, diene polymers (for instance polychloroprene rubbers) can add to the growing polymer chain by 1,2 addition (also called vinyl addition). This creates labile hydrogen or reactive halogen on tertiary carbon atoms. A few percent of this type of structure in the rubber will assist cross-linking reactions. 

As described in the box "Diene Polymers" in Chapter 10, most synthetic rubber is a copolymer of styrene and 1,3-butadiene. 

The classic chemical technique for measuring the degree of unsaturation in diene polymers is iodometry (iodine value) [102]. Kubo et al. [103] extensively measured the iodine value to determine the amount of residual double bonds present in the HNBR. However, this method exhibited significantly poorer precision as compared with IR and NMR spectroscopies [99-101]. Acid... 

Conjugated dienes can be polymerized just as simple alkenes can (Section 7.10). Diene polymers are structurally more complex than simple alkene polymers, though, because double bonds remain every four carbon atoms along the chain, leading to the possibility of cis-trans isomers. The initiator (In) for the reaction can be either a radical, as occurs in ethylene polymerization, or an acid. Note that the polymerization is a 1,4-addition of the growing chain to a conjugated diene monomer. 

Diene polymers contain occasional vinyl branches along the chain. How do you think these branches might arise ... 

The alkene and diene polymers discussed in Sections 7.10 and 14.6 are called chain-growth polymers because they are produced by chain reactions. An initiator adds to a C=C bond to give a reactive intermediate, which adds to a second alkene molecule to produce a new1 intermediate, which adds to a third molecule, and so on. By contrast, polyamides and polyesters are called step-growth polymers because each bond in the polymer is formed independently of the others. A large number of different step-growth polymers have been made some of the more important ones are shown in Table 21.2. 

Vulcanization (Section 14.6) A technique for cross-linking and hardening a diene polymer by heating with a few percent by weight of sulfur. 

Early work on the microstructurc of the diene polymers has been reviewed.1 While polymerizations of a large number of 2-substituted and 2,3-disubstituted dienes have been reported,88 little is known about the microstructure of diene polymers other than PB,89 polyisoprene,90 and polychloroprene.91... 

In spite of the proposals of large primary valence structures for rubber by Pickles and somewhat ambiguously for polybutadiene by Lebedev, prevailing opinion favored rings of moderate size for vinyl and diene polymers. Structures similar to those widely accepted for cellulose and rubber were generally assumed. 

Mechanisms depending on carbanionic propagating centers for these polymerizations are indicated by various pieces of evidence (1) the nature of the catalysts which are effective, (2) the intense colors that often develop during polymerization, (3) the prompt cessation of sodium-catalyzed polymerization upon the introduction of carbon dioxide and the failure of -butylcatechol to cause inhibition, (4) the conversion of triphenylmethane to triphenylmethylsodium in the zone of polymerization of isoprene under the influence of metallic sodium, (5) the structures of the diene polymers obtained (see Chap. VI), which differ. both from the radical and the cationic polymers, and (6)... 

This discussion of the structures of diene polymers would be incomplete without reference to the important contributions which have accrued from applications of the ozone degradation method. An important feature of the structure which lies beyond the province of spectral measurements, namely, the orientation of successive units in the chain, is amenable to elucidation by identification of the products of ozone cleavage. The early experiments of Harries on the determination of the structures of natural rubber, gutta-percha, and synthetic diene polymers through the use of this method are classics in polymer structure determination. On hydrolysis of the ozonide of natural rubber, perferably in the presence of hydrogen peroxide, carbon atoms which were doubly bonded prior to formation of the ozonide... 

No mention has been made of diene polymers in this discussion. Among 1,4 units the substituents are well separated from one another, and the steric repulsions between them should therefore be negligible. A succession of 1,2 units of isoprene (VIII), on the other hand, would form a chain structure of the sterically hindered type XI. 

The equivalent function of the degree of conversion is encountered in the cross-linking of diene polymers discussed below. It is plotted in Fig. 73 in relation to the latter problem. For present purposes it is necessary merely to replace the ordinate in Fig. 73 with p/Cp. Regardless of the absolute magnitude of the branching transfer constant, the relative amount of branching must increase rapidly with conversion. 

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