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Several polymers based on 1,3-dienes are used as elastomers. These include styrene 1,3butadiene (SBR), styrene 1,3-butadiene terpolymer with an unsaturated carboxylic acid (carboxylated SBR), acrylonitrile-1,3-butadiene (NBR or nitrile rubber) (Secs. 6-8a, 6-8e), isobutylene isoprene (butyl rubber) (Sec. 5-2i-1), and block copolymers of isoprene or 1,3-butadiene with styrene (Sec. 5-4a). cis-1,4-Polyisoprene is produced using alkyllithium and Ti/Al Ziegler Natta initiators. About 100 million pounds are produced annually in the United States to supplement the 2 billion pounds of natural rubber that are used. trans-1,4-Polyisoprene is a specialty material produced in small amounts by means of V/Al Ziegler Natta initiators. The uses for these materials were discussed in Sec. 8-2a-2. About 1.5 billion pounds of cis-1,4-poly(1,3-butadiene) were produced in the United States in 2001. This polymer has a lower Tg and, therefore, higher resilience but poorer tear resistance and tensile strength than does natural rubber. For this reason, cis1,4-polybutadiene is not used alone but is blended with either natural rubber or SBR to produce tires for trucks and passenger automobiles. Considerable amounts of cis-1,4-polybutadiene are also used in producing ABS materials (Sec. 6-8a). More than 100 million pounds of polychloroprene (trade name: Neoprene) are produced annually in the United States by the radical (emulsion) polymerization of chloroprene. Polychloroprene, highly trans 1,4 in structure, is surpassed in oil and fuel resistance only by nitrile rubber, while its strength is superior to all except cis-1,4-polyisoprene. The high cost of polychloroprene limits its use to applications requiring its unique combination of properties. It is used for wire and cable coatings and jackets, industrial belts and hoses, seals for buildings and highway joints, roof coatings, adhesives, gloves, and coated fabrics.



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(V A X~,s) . B,

8-12

A Xn,sbn,s'

Polar monomers such as methacrylates and vinyl ethers undergo stereoselective polymerization when there is an appropriate balance between monomer, initiator, solvent, and temperature. Under conditions where the propagating species is free (uncoordinated), syndiotacticity is increasingly favored with decreasing reaction temperature (Sec. 8-3). This is the case for all radical polymerizations and for those ionic polymerizations that take place in highly solvating media. Isoselective polymerization can occur in poorly solvating media where the propagating species is coordinated to the counterion. Many of the homogeneous polymerizations described in Chap. 5 result in stereoselective polymerization, although the degree of stereoselectivity generally is less than that observed in polymerizations with the traditional Ziegler Natta, metallocene, and chelate initiators. 8-12a Methyl Methacrylate





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The stereoselective polymerization of various acrylates and methacrylates has been studied using initiators such as alkyllithium [Bywater, 1989; Pasquon et al., 1989; Quirk, 1995, 2002]. Table 8-12 illustrates the effects of counterion, solvent, and temperature on the stereochemistry of the anionic polymerization of methyl methacrylate (MMA). In polar solvents (pyridine and THF versus toluene), the counterion is removed from the vicinity of the propagating center and does not exert an in uence on entry of the next monomer unit. The tendency is toward syndiotactic placement via chain end control. The extent of syndiotacticity

(A39)

TABLE 8-12 Effect of Counterion, Solvent, and Temperature of Polymerization of Methyl Methacrylate Triad Tacticity (mm) (mr) (rr) 0.72 0.08 0.87 0.97 0.23 0.01 0.05 0.78 0 0.57 0.12 0.35 0.14 0.10 0 0.17 0.32 0.10 0.03 0.16 0.15 0.33 0.16 0.10 0.31 0.46 0.42 0.53 0.56 0.40 0.11 0.60 0.03 0 0.61 0.84 0.61 0.06 0.90 0.12 0.42 0.23 0.33 0.34 0.60

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In this mode space, Maxwell's equations then become much simpler. In fact, they reduce to just two coupled ordinary differential equations:

Solvent Toluenea Pyridinea Tolueneb Tolueneb Tolueneb THFb THFc Toluenec Toluenec Toluenea Pyridinea Toluenea Pyridinea THFe THFe

= -cknen,s, = cknbn,s,

Temperature ( C) 0 0 78 78 78 85 78 78 78 0 0 0 0 20 100

(A40) (A41)

Data from Braun et al. [1962]. Data from Bywater [1989]. c Data from Kitayama et al. [1989]. d Initiator t-C4 H9 Li Al(C2 H5 )3 . e Data from Muller et al. [1977], Kraft et al. [1980a,b].

as can be seen by substituting (A.38) and (A.39) in (AI) to (A.4) and using the orthogonality properties of the mode functions. Together, these equations yield harmonic oscillator equations for the electric and magnetic fields, like (2.51) and (2.52): (A.42) (A43)

decreases in the order Li > Na > K, corresponding to the relative extents of solvation of different ions. The smallest ion Li is the most highly solvated and furthest removed from the propagating center. (This is analogous to the effect of polar solvent on propagation rate constants for anionic polymerization of styrene with different counterions. The ion-pair propagation rate constant for styrene is largest for Li and smallest for Cs, which is the reverse of the order in less polar solvent Sec. 5-3d-2-b.) The extent of syndiotacticity increases with decreasing temperatures, as is evident in the data for polymerization with cesium as the counterion. The level of syndioselectivity is similar to that observed in radical polymerization of MMA, (rr) 0.79 at 55 C [Hatada et al., 1988]. When nonpolar solvents are employed, polymerization proceeds by an anionic coordination mechanism. The counterion directs isotactic placement of entering monomer units into the polymer chain. The extent of isotactic placement increases with the coordinating power of the counterion (Li > Na ) K, Cs). The small lithium ion has the greatest coordinating power and yields the most stereoselective polymerization. Increased reaction temperature decreases the isoselectivity. Mechanisms proposed to explain the isoselective polymerization of methyl methacrylate involve rigidi cation of the enolate propagating species by coordination of counterion with the terminal monomer unit (and possibly also the penultimate monomer unit) [Braun et al., 1962; Leitereg and Cram, 1968; Wiles and Bywater, 1965]. The rigid propagating chain end imposes stereoselectivity on monomer insertion in a manner analogous to that for a traditional Ziegler Natta, metallocene, or chelate propagating species in alkene polymerizations. The delicate nature of this stereoselectivity is evident when noting that the presence of triethylaluminum coinitiator changes the t-C4 H9 Li polymerization of MMA in toluene from

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