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Unsaturated polyesters in which the alkene double bond resides in a fatty acid component such as oleic (IX) and linoleic (X) acids are referred to as alkyds or alkyd resins (Sec. 2-12a).

(C.77)



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Alkyds are crosslinked via oxidation by atmospheric oxygen [Marshall et al., 1987; Solomon, 1967]. The process is usually referred to as drying or air-drying. Varnishes and other surface coatings based on these polymers are crosslinked by standing in air. The crosslinking process is different depending on whether the unsaturation is an unconjugated double bond as in oleic acid or a conjugated double bond as in linoleic acid. Unconjugated double bonds undergo crosslinking by the initial formation of an allylic hydroperoxide

Now, for an infinitesimal boost, U will differ from 1 by something on the order of 8f3 and higher. To first order in 8f3,

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9-7

(C.78)

9-8 9-9 9-10 9-11 9-12 9-13 9-14

'R' =





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OOH and H represent the oxidized and unoxidized polymer molecules. In where order to achieve practical crosslinking rates, the reaction is catalyzed by hydrocarbon-soluble salts (usually octanoates, naphthenates, and linoleates) of metals (cobalt, lead, and manganese). The metal ions accelerate hydroperoxide decomposition in a manner analogous to the redox initiator systems discussed in Sec. 3-4b. The relative amounts of carbon carbon (Eq. 9-12), ether (Eq. 9-13), and peroxide (Eq. 9-14) crosslinks depend on the reaction conditions. Crosslinking of alkyds containing conjugated double bonds results in more carbon carbon bonds in the crosslinks than in the alkyds containing unconjugated double bonds. The crosslinking mechanism involves the formation and decomposition of cyclic peroxides, to yield radicals that initiate crosslinking by 1,4-polymerization of the polymer molecules.

(C.79)

9-15

(C.80)

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Various homo- and copolymers of 1,3-dienes make up the large bulk of polymers used as elastomers. Crosslinking is an absolute requirement if elastomers are to have their essential property of rapidly and completely recovering from deformations. The term vulcanization is used synonymously with crosslinking in elastomer technology. Crosslinking or vulcanization can be achieved by using sulfur, peroxides, other reagents, or ionizing radiation [Alliger and Sjothun, 1964; Bateman, 1963; Coran, 1978; Engels et al., 2002; Morrison and Porter, 1984; Roberts, 1988]. Heating with sulfur is used almost exclusively for the commercial crosslinking of most elastomers based on 1,3-dienes. This includes 1,4-polyisoprene (synthetic and natural), 1,4-poly(1,3-butadiene), ethylene propene diene terpolymer (EPDM), 1,3butadiene copolymers with styrene (SBR) and acrylonitrile (nitrile rubber or NBR), and isobutylene isoprene copolymer [butyl rubber (BR)]. Poly(oct-1-ene-1,8-diyl) and polynorbornene are also vulcanized by sulfur.

9-2b-1

A boost with a finite speed cf3 in the direction V can be approximated by a series of N infinitesimal boosts applied in succession. This approximation will be exact when N - t 00 and f3 - t 0, with the sum of all the N infinitesimal velocities yielding the desired finite velocity, that is, in the limit

Although sulfur vulcanization has been studied since its discovery in 1839 by Goodyear, its mechanism is not well understood. Free-radical mechanisms were originally assumed but most evidence points to an ionic reaction [Bateman, 1963]. Neither radical initiators nor inhibitors affect sulfur vulcanization and radicals have not been detected by ESR spectroscopy. On the other hand, sulfur vulcanization is accelerated by organic acids and bases as well as by solvents of high dielectric constant. The ionic process can be depicted as a chain reaction involving the initial formation of a sulfonium ion (XI) by reaction of the polymer with polarized sulfur or a sulfur ion pair. The sulfonium ion reacts with a polymer molecule by hydride

U(f3)

A 4 5

9-16

(C.81)

abstraction to yield the polymeric (allylic) carbocation XII, which undergoes crosslinking by reacting with sulfur followed by addition to a polymer double bond. A subsequent reaction

To calculate this limit, we must find the 8f3 such that the sum of N of them add up to f3. Notice that we cannot simply write N8f3 = f3 as in classical Newtonian mechanics because relativistic velocities add in a different way. Given two velocities, VI Y and V2Y, along the same direction Y, their sum is VY with the speed V given by (see pp. 42-44 in 4 of [48])

9-17

(C.82)

9-2b-2

Then for our succession of infinitesimal boosts, we can write the following relation between f3n, the resulting speed in units of the speed of light for the nth application of the infinitesimal boost, and f3n-I, for the (n - 1 )th application:

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