Heterotacticity

A heterotactic traid [XVII] is generated by mr and rm sequences of additions ... 

Use zero-order Markov statistics to evaluate the probability of isotactic, syndio-tactic, and heterotactic triads for the series of p values spaced at intervals of... 

Fig. 1. Triad sequences for stereoregular poly(propylene oxide) where (a) shows isotactic (RRR or SSS), (b) syndiotactic (RSR or SRS), and (c) heterotactic...

The nmr spectmm of PVAc iu carbon tetrachloride solution at 110°C shows absorptions at 4.86 5 (pentad) of the methine proton 1.78 5 (triad) of the methylene group and 1.98 5, 1.96 5, and 1.94 5, which are the resonances of the acetate methyls iu isotactic, heterotactic, and syndiotactic triads, respectively. Poly(vinyl acetate) produced by normal free-radical polymerization is completely atactic and noncrystalline. The nmr spectra of ethylene vinyl acetate copolymers have also been obtained (33). The ir spectra of the copolymers of vinyl acetate differ from that of the homopolymer depending on the identity of the comonomers and their proportion. 

It has been postulated that the syn TT-ahyl stmcture yields the trans-1 4 polymer, and the anti TT-ahyl stmcture yields the cis-1 4 polymer. Both the syn and anti TT-ahyl stmctures yield 1,2 units. In the formation of 1,2-polybutadiene, it is beheved that the syn TT-ahyl form yields the syndiotactic stmcture, while the anti TT-ahyl form yields the isotactic stmcture. The equihbtium mixture of syn and anti TT-ahyl stmctures yields heterotactic polybutadiene. It has been shown (20—26) that the syndiotactic stereoisomers of 1,2-polybutadiene units can be made with transition-metal catalysts, and the pure 99.99% 1,2-polybutadiene (heterotactic polybutadiene) [26160-98-5] can be made by using organolithium compounds modified with bis-pipetidinoethane (27). At present, the two stereoisomers of 1,2-polybutadiene that are most used commercially are the syndiotactic and the heterotactic stmctures. 

Millan (98) studied the effect of tacticity on the ionic dehydrochlorination and chlorination of PVC. For the dehydrochlorination reaction, both the reaction rate and the polyence sequence distribution depend markedly on the syndiotactic content. Chlorination appeared to be easier through heterotactic parts than through syndiotactic sequences as shown by C-NMR. 

Millan and coworkers (99-101) also studied the effect of tacticity on the nucleophilic substitution reactions of PVC. Sodium thiophenate and phenol were used for these reactions. The central chlorine in isotactic triads and, to a lesser extent, in heterotactic triads was found to be most reactive. It was concluded that initiation of degradation may occur by normal structures, and polyene build-up may be favored by syndiotic sequence. This... 

Cyclopolymerization of the bis-methacrylates (10, ll)6" 6j or bis-styrene derivatives (12)64 has been used to produce heterotactic polymers and optically active atactic polymers. Cyclopolymcrization of racemic 13 by ATRP with a catalyst based on a chiral ligand (Scheme 8.12) gave preferential conversion of the (S, )-enantiomer. 66... 

Such configurational as well as conformational effects have been also reported by MILLAN et al. in the case of nucleophilic substitution of poly(vinyl chloride) with sodium thiophenate (14) and with sodium isooctylthioglycolate or isooctylthiosalicylate (15). The authors have shown that these reactions proceed selectively on the isotactic TT diads which can only exist either in the GTTG isotactic or in the TTTG heterotactic triads, the former ones being much more reactive than the latter ones. 

Compositional sequences were assigned in the carbonyl region of the 3C spectra of poly(MAA/MMA) and in the 3 9Sn spectra of poly (TBTM/MMA). Both syndiotactic and heterotactic splittings were observed in the carbonyl spectrum. In the 9Sn spectrum only the syndiotactic compositional triad was observed. 

Copolymer Designation COOCH3 COOH Isotactic (%) Heterotactic (%) Syndiotactic (%)... 

By contrast, the synthesis of syndiotactic PP, s-PP, is generally catalyzed by Cs-symmetry ansa- metallocenes. For example, (16)/MAO affords PP with a pentad (rrrr) content of 86% at 25 °C.77 The stereoselectivity is highly sensitive to ligand variation. For example, substitution at the 3-position of the Cp ring with a methyl group affords heterotactic PP,78 whilst the Bu analog favors i-PP production.50,75,79... 

Lactide (LA), the cyclic diester of lactic acid, has two stereogenic centers and hence exists as three stereoisomers L-lactide (S,S), D-lactide (R,R), and meso-lactide (R,S). In addition, rac-lactide, a commercially available racemic mixture of the (R,R) and (S,S) forms, is also frequently studied. PLA may exhibit several stereoregular architectures (in addition to the non-stereoregular atactic form), namely isotactic, syndiotactic, and heterotactic (Scheme 15). The purely isotactic form may be readily prepared from the ROP of L-LA (or D-LA), assuming that epimerization does not occur during ring opening. The physical properties, and hence medical uses, of the different stereoisomers of PLA and their copolymers vary widely and the reader is directed to several recent reviews for more information.736 740-743... 

The enantiomorphic site selectivity of (R)-(—)-(263) allows highly syndiotactic PLA to be prepared via the polymerization of meso-LA (Mn = 12,030, Mn calc= 13,540, Mw/Mn= 1.05).802 The ring opening of meso-LA by (R)-(—)-(263) occurs to produce a syndiotactic propagating chain bound to the metal via an (S)-lactic acid unit.803 Attempts to produce syndiotactic PLA via the ROP of meso-LA using rac-( )-(263) instead afforded heterotactic-biased material. 

A more active zinc catalyst has been developed containing a /3-diketiminate ancillary ligand.823 Complex (272) converts 200 equivalents rac-LA. in less than 20 min at room temperature to highly heterotactic PLA (the probability of a racemic junction between monomer units, PR = 0.90 at 25 °C and 0.94 at 0°C) of narrow polydispersity (Mn = 37,900, Mn calc = 28,800, Mw/Mn= 1.10). Kinetic studies reveal that the zinc initiators display a fractional rate law order (1.56 0.06). In accord with the observation that kR/ss > kR/RR (or ks/RR > ks/ss), the polymerization of L-LA proceeds significantly slower than rac-LA (kapp L-LA = 0.031 min-1 kapp rac-LA = 0.22 min-1).824... 

The magnesium initiators (273) and (274) do not display the same stereocontrol as their zinc analogs over the ROP of rac-LA in either CH2C12 or benzene. However, in THF highly heterotactic PLA is produced.826 In non-coordinating solvents the Mg and Zn initiators are believed to adopt dimeric and monomeric resting states respectively, whereas both exist as monomeric forms in THF and hence give rise to similar stereoselectivity. 

Jensen et al. reported the stereoselective polymerization of D,L-lactide with dibenzyloxidezinc(2,4,6-trimetylphe-nyimidazol-2-ylidene), which was synthesized as shown in Scheme 39.100 Surprisingly, a mixture of the heterocarbene and benzyl alcohol was a better catalyst for polylactide formation than the zinc complex, and unlike 50 the mixture produced heterotactically enriched polylactide. 

Fig Planar zigzag structure of polymer molecules showing (I) isotactic, (II) syndiotactic, and (III) heterotactic configurations, (Hydrogen atoms are not shown for the purpose of clarity.)... 

Several experiments gave evidence against homotactic or heterotactic association of diene and dienophile. Vapor-pressure measurement for cyclopentadiene (CPD) (Figure 7.2), in pure water and in 10% (w/w) n-PrOH/water, show that Henry s law is obeyed (vapor pressure varies linearly with solute concentration) until [CPD] is 0.03 M in pure water and 0.06 M in ri-PrOH/water. In kinetic measurement the concentration of CPD was always below 0.002 M, indicating that association is highly unlikely. Similar results have been obtained with methyl vinyl ketone, ethyl vinyl ketone, and naphthoquinone. 

In stereoregular polymers there is only one type of sequence, or, at the most, a very limited number (in a regular heterotactic. . . mrmrmrmr. . . polymer both mrm and rmr tetrads are present) (44). 

In a recent study on poly(a-methyl-a-ethyl-piopiolactone) and poly(a-methyl-a-propyl-propiolactone) (112) Spassky et al. extended the earlier examination carried out on oxiranes and thiiranes (113) to the tetrad and pentad level. Because of the chirality of these polymers, Spassky avoids the use of the terms m and r as being inapplicable (21). To indicate the dyads RR (or SS) and RS (or SR) 64 he used the symbols ij and Sj where the indices stand for dyad. In their turn the triads RRR (or SSS) are indicated with i, RSR (or SRS) with s, RRS (or SRR) with hi (heterotactic triad beginning with an dyad) and RSS (or SRR) with (heterotactic triad beginning with a dyad), 65 (Scheme 14) (114). 

To prove the correctness of this analysis we shall try to look for alternative explanations. A stereoregular heterotactic polymer. . . mrmrmr. . . could also explain the presence of a methyl singlet and a well-separated doublet of doublets for methylene protons, in agreement with the spectrum of the first sample in fact, there would be present the mr triad and the rmr tetrad with diastereotopic protons. However, in addition, an equal amount of the mrm tetrad should be present, yet the corresponding singlet is not visible with the required intensity. In the same way other hypothetical structures can be rejected. 

When it is necessary to specify the internal stereochemistry of the group, a prefix is required. In vinyl polymers there are meso (m) and racemic (r) diads and mm, mr, rr triads. The latter may be called isotactic, heterotactic and syndiotactic triads, respectively. Stereoregular vinyl polymers can be defined in terms of the regular sequences of diads thus an isotactic vinyl polymer consists entirely of m diads, i.e., it corresponds to the following succession of relative configuration -mmmmmm-, whereas a syndiotactic vinyl polymer consists entirely of r diads, corresponding to the sequence -rrrrrrr-. Similarly, a vinyl polymer consisting entirely of mr (= rm) triads is called a heterotactic polymer. 

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