Racemic dyads

Table 7.8 The Splitting of Meso and Racemic Dyads into Six Tetrads...

The hydrogens of the methylene group in the backbone of the poly (methyl methacrylate) produce a single peak in a racemic dyad, as illustrated by structure [XVI]. 

The area under the methylene peaks is proportional to the dyad concentration The singlet gives the racemic dyads and the quartet gives the meso dyads. 

Table 7.9 The Fractions of Meso and Racemic Dyads and Iso, Syndio, and Hetero Triads for the Data in Fig. 7.10...

The number of racemic dyads in a sequence is the same as the number of syndiotactic units n. The number of meso dyads in a sequence is the same as the number of iso units nj. These can also be verified from structure [XVIII] above. 

Figure 4.1 Representation of meso (m) and racemic / ) dyads with polymer...

In figure 1 we present the experimental and calculated mK values of the copolymer poly(styrene-co-p-bromostyrene). From this study (3) we were able to show unequivocally that the tacticity of this polystyrene sample is pr — 0.55, where pr is the probability of racemic dyad replication. 

When measuring vinyl polymer tactlclty, one prefers the longest complete n-ad distribution available as well as the translated simplest comonomer distribution, possibly m versus r. An alternative exists to the m versus r distribution In the form of number average or mean sequence lengths. If any vinyl homopolymer Is viewed conceptually as a copolymer of meso and racemic dyads, mean sequence lengths can be determined for continuous runs of both meso and racemic configurations (32), that Is,... 

In addition to viewing a vinyl homopolymer conceptually as a copolymer of meso and racemic dyads, one may also consider the mean sequence length of "like" configurations (M). In this Instance, the polymer chain Is seen as a succession of different lengths of co-orlented configurations from one to "n", the longest sequence of like configurations, that Is,... 

As was true in the case of mean sequence lengths for meso and racemic dyads, the necessary relationships can be used to develop corresponding equations for any particular n-ad distribution. A favorable point concerning the concept of "like" configurations is that it attaches a physical significance to the racemic distribution. 

Consider the description of the sequence distribution of isotactic and syndiotactic placements in the polymerization of a monosubstituted ethylene. The approach is general and can be applied with appropriate modification to the 1,4-polymerization of a 1,3-diene. Dyad tac-ticity is defined as the fractions of pairs of adjacent repeating units that are isotactic or syndiotactic to one another. The isotactic and syndiotactic dyads (XV) are usually referred to as meso and racemic dyads. The horizontal line in XV represents a segment of the polymer... 

These definitions are clarified by considering a portion of a polymer chain such as XVII. Chain segment XVII has a total of 9 repeating units but only 8 dyads and 7 triads. There are 6 meso dyads and 2 racemic dyads (m) —, (r) —, There are 4 isotactic, 2 heterotactic, and 1 syndiotactic triads mm) = (mr) — j, (rr) — A. 

C NMR of isotactic polypropene shows the main error is pairs of racemic dyads instead of isolated racemic dyads (Table 8-3) [Heatley et al., 1969 Resconi et al., 2000 Wolfsgruber et al., 1975]. A stereoerror in the addition of a monomer molecule is immediately corrected when stereocontrol is by the chiral active site. If stereocontrol was due to the propagating chain end, an error would continue to propagate in an isotactic manner to yield a polymer, referred to as an isotactic stereoblock, containing long isotactic all-R and all-5 stereoblocks on each side of the error. 

Probahilities Pm and Pr, the transition or conditional probabilities of forming meso and racemic dyads, respectively, are defined by... 

The first-order markov model describes a polymerization where the penultimate unit is important in determining subsequent stereochemistry. Meso and racemic dyads can each react in two ways ... 

An unambiguous stereochemical assignment of the alpha methyl absorptions is difficult to make. On the basis of the similarity of the observed spectra to the closely similar poly (alphamethylstyrene) ( , 10, Jl ), it is tempting to assign the upfield and downfield absorptions to syndiotactic and isotactic triads, respectively. This assignment would be supported by the 300 and 600 MHz 1h spectra of tetramer [14] that suggest predominant (>90%) formation of a racemic dyad. 

Table I Tacticities of samples obtained in DME and THF, using mono- and bifunctional initiators and Na+ and Cs+ as the counterions. I,H,S isotactic (ami), heterotactic (mr/rm) and syn-diotactic (rr) triads m,r meso and racemic dyads p 2mr/H persistence ratio ( p 1 for Bernoullian statistics).

Conformational energies of meso and racemic diads of PS are computed as functions of skeletal bond rotations. Confinement of rotations of the phenyl groups to a small range within which they are nearly perpendicular to the plane defined by the two adjoining skeletal bonds is confirmed. Steric interactions involving the relatively large planar phenyl group virtually preclude"g" conformations. A simple, two-state RIS scheme is applicable with states at 170° and 70° for both meso and racemic dyads. 

Because the transition state of electrophilic addition is rather open or only very weakly bridged, the stereoselectivity is poor, resulting in primarily atactic polymers. Polystyrene and most poly(vinyl ether)s prepared cationically at ambient temperature are atactic with similar proportions of meso and racemic dyads [243,244]. However, meso addition is slightly preferred with vinyl ethers, and varies from 60 to 70% for most monomers, including isobutyl, neopentyl, n-butyl, and ethoxyethyl vinyl ethers [245]. It is higher with benzyl vinyl ether (89%). This tendency to... 

The conpling constant of the AA BB portion of bisphenol A-neopentyl glycoltereph-thalate copolyesters (20) was determined in the presence of Pr(fod)3". The compositional tetrads of a 3,3 -dimethylbisphenol A-phenolphthalein copolyterephthalate (21) were resolved in the presence of En(fod)3 . The meso and racemic dyads of a poly(/l-snbstitnted- S-propiolactone) were distinguishable in the NMR in the presence of Eu(dpm)3". The H and NMR spectra of ethylene-vinyl acetate copolymers were assigned on the basis of two-dimensional NMR methods and lanthanide-induced shift data in the presence of Eu(fod)3". ... 

The amount of meso and racemic dyads in PS was 0.43 and 0.57, respectively. The conformational parameters for PDMS were taken from ref. 112.) The strong difference in the half-peak widths q /2 is a clear indication of a higher conformational rigidity for PS, which is also suggested by the characteristic ratios relative to the freely rotating chain = o/ [see Eqn. (3.3.4)], the value of which is 4.4 and 1.9 for PS and PDMS, respectively. 

PVA samples with different tacticities, such as isotactic (iso-), atactic (at-) and syndiotactic (syn-) ones were used. The degree of polymerization, and the fractions of mm, mr and rr triads, are shown in Table 20.2, where m and r indicate the meso and racemic dyads, respectively. The CP/MAS NMR spectra for the three kinds of PVA gels with different tacticity (9% of polymer concentration) are shown in Fig. 20.7. As described in Section 20.4.1, the CH peaks are composed of both the three sharp peaks corresponding to the triad configurations (mm, mr and rr) and the three broad peaks (I, II and III at about 77, 71 and 65 ppm, respectively). 

Denoting the rates of meso and racemic dyad placements by i , and Rr, respectively, the probabilities Pm and P,- can be defined by... 

Much literature precedent supports the assignment of tacticity in methyl acrylate polymers using NMR techniques [40,41]. In the H-NMR spectrum, the shift of the methylene protons is sensitive to dyad stereochemistry. For example, in an isotactic (meso) dyad 28, the methylene protons are chemically non-equivalent and appear as two separate sets of signals, whereas in a syndiotactic (racemic) dyad 29, the methylene protons are equivalent. The H-NMR spectrum of 27 showed multiplets at 1.89 and 1.5 ppm due to the two diastereotopic methylene protons of the isotactic dyad. The rest of the spectrum is consistent with the structure of the n=4 tetrad 27. A racemic dyad structure would have been expeeted to give resonances of intermediate shift to that of the two resonances observed for the telomer 27. This evidence strongly implies that 27 has the allisotactic configuration shown in Scheme 8-12. 

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