Syndiotacticity

In polymers made of dis-symmetric monomers, such as, for example, poly(propylene), the stmcture may be irregular and constitutional isomerism can occur as shown in figure C2.1.1(a ). The succession of the relative configurations of the asymmetric centres can also vary between stretches of the chain. Configuration isomerism is characterized by the succession of dyads which are named either meso, if the two asymmetric centres have the same relative configurations, or racemo if the configurations differ (figure C2.1.1(b )). A polymer is called isotactic if it contains only one type of dyad and syndiotactic if the dyad sequence strictly alternates between the meso and racemo fonns. 

FIGURE 7 16 Poly mers of propene The mam chain IS shown in a zigzag conformation Every other carbon bears a methyl sub stituent and is a chirality center (a) All the methyl groups are on the same side of the carbon chain in isotactic polypropylene (b) Methyl groups alternate from one side to the other in syndiotactic polypropy lene (c) The spatial orienta tion of the methyl groups IS random in atactic polypropylene... 

When propene is polymerized under free radical conditions the polypropylene that results IS atactic Catalysts of the Ziegler-Natta type however permit the preparation of either isotactic or syndiotactic polypropylene We see here an example of how proper choice of experimental conditions can affect the stereochemical course of a chemical reaction to the extent that entirely new materials with unique properties result... 

Atactic polymer (Section 7 15) Polymer characterized by ran dom stereochemistry at its chirality centers An atactic polymer unlike an isotactic or a syndiotactic polymer is not a stereoregular polymer... 

Syndiotactic polymer (Section 7 15) Stereoregular polymer in which the configuration of successive chirality centers alternates along the chain... 

In a syndiotactic arrangement, the substituents are in an ordered alternating sequence, appearing alternately on one side and then on the other side of the chain, thus... 

Syndiotactic. Substituents on the fully extended chain lie on alternating sides of the backbone. This alternation of configuration can be represented as -DLDLDLDLDLDL-. 

Polymers of different tacticity have quite different properties, especially in the solid state. One of the requirements for polymer crystallinity is a high degree of microstructural regularity to enable the chains to pack in an orderly manner. Thus atactic polypropylene is a soft, tacky substance, whereas both isotactic and syndiotactic polypropylenes are highly crystalline. 

Figure 1.2 Sections of polymer chains of differing tacticity (a) isotactic (b) syndiotactic (c) atactic.

In this representation the X indicates the substituent other bonds involve only hydrogens. This formalism also applies to 1,1-disubstituted ethylenes in whicli the substituents are different. With these symbols, the isotactic, syndiotactic, and atactic structures shown in Fig. 1.2 are represented by structures [VI]-[VIII], respectively ... 

The successive repeat units in strucutres [VI]-[VIII] are of two different kinds. If they were labeled Mj and M2, we would find that, as far as microstructure is concerned, isotactic polymers are formally the same as homopolymers, syndiotactic polymers are formally the same as alternating copolymers, and atactic polymers are formally the same as random copolymers. The analog of block copolymers, stereoblock polymers, also exist. Instead of using Mj and M2 to differentiate between the two kinds of repeat units, we shall use the letters D and L as we did in Chap. I. 

The statistical nature of polymers and polymerization reactions has been illustrated at many points throughout this volume. It continues to be important in the discussion of stereoregularity. Thus it is generally more accurate to describe a polymer as, say, predominately isotactic rather than perfectly isotactic. More quantitatively, we need to be able to describe a polymer in terms of the percentages of isotactic, syndiotactic, and atactic sequences. 

What is significant about these reactions is that only two possibilities exist addition with the same configuration (D -> DD or L LL) or addition with th< opposite configuration (D DL or L LD). We shall designate these isotactic (subscript i) or syndiotactic (subscript s) additions, respectively, and shal define the rate constants for the two steps kj and k. Therefore the rates o isotactic and syndiotactic propagation become... 

A syndiotactic triad [XVI] is generated by two successive racemic additions X... 

The probability of the syndiotactic triad is given by p. , which becomes... 

Figure 7.10 shows the 60-MHz spectra of poly (methyl methacrylate) prepared with different catalysts so that predominately isotactic, syndiotactic, and atactic products are formed. The three spectra in Fig. 7.10 are identified in terms of this predominant character. It is apparent that the spectra are quite different, especially in the range of 5 values between about 1 and 2 ppm. Since the atactic polymer has the least regular structure, we concentrate on the other two to make the assignment of the spectral features to the various protons. 

The peaks centered at 5 = 1.84 ppm-a singlet in the syndiotactic and a quartet in the isotactic polymers-are thus identified with these protons. This provides an unambiguous identification of the predominant stereoregularity of these samples. 

Table 7.9 lists the estimated fractions of dyads of types m and r and the fractions of triads of types i, s, and h. These fractions represent the area under a specific peak (or four peaks in the case of the meso dyads) divided by the total area under all of the peaks in either the dyad or triad category. As expected for the sample labeled isotactic, 89% of the triads are of type i and 87% of the dyads are of type m. Likewise, in the sample labeled syndiotactic, 68% of the triads are s and 83% of the dyads are r. 

Figure 7.11 Methylene proton portion of the 220-MHz NMR spectrum of poly(methyl methacrylate) (a) predominately syndiotactic and (b) predominately isotactic. [From F. A. Bovey, High Resolution NMR of Macro molecules, Academic, New York, 1972, used with permission.]...

With this kind of information it is not difficult to evaluate the average lengths of isotactic and syndiotactic sequences in a polymer. As a step toward this objective, we define the following ... 

The number of syndiotactic sequences containing n syndic repeat units is Nn. ... 

Since isotactic and syndiotactic sequences must alternate, it follows that... 

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. 

Use the dyad and triad fractions in Table 7.9 to calculate the average lengths of isotactic and syndiotactic sequences for the polymers of Fig. 7.10. Comment on the results. 

Tacticity of products. Most solid catalysts produce isotactic products. This is probably because of the highly orienting effect of the solid surface, as noted in item (1). The preferred isotactic configuration produced at these surfaces is largely governed by steric and electrostatic interactions between the monomer and the ligands of the transition metal. Syndiotacticity is mostly produced by soluble catalysts. Syndiotactic polymerizations are carried out at low temperatures, and even the catalyst must be prepared at low temperatures otherwise specificity is lost. With polar monomers syndiotacticity is also promoted by polar reaction media. Apparently the polar solvent molecules compete with monomer for coordination sites, and thus indicate more loosely coordinated reactive species. 

Fig. 7.13, this shifts the vacancy—represented by the square-in the coordination sphere of the titanium to a different site. Syndiotactic regulation occurs if the next addition takes place via this newly created vacancy. In this case the monomer and the growing chain occupy alternating coordination sites in successive steps. For the more common isotactic growth the polymer chain must migrate back to its original position. 

Poly(acrylic acid) and Poly(methacrylic acid). Poly(acryHc acid) (8) (PAA) may be prepared by polymerization of the monomer with conventional free-radical initiators using the monomer either undiluted (36) (with cross-linker for superadsorber appHcations) or in aqueous solution. Photochemical polymerization (sensitized by benzoin) of methyl acrylate in ethanol solution at —78° C provides a syndiotactic form (37) that can be hydrolyzed to syndiotactic PAA. From academic studies, alkaline hydrolysis of the methyl ester requires a lower time than acid hydrolysis of the polymeric ester, and can lead to oxidative degradation of the polymer (38). Po1y(meth acrylic acid) (PMAA) (9) is prepared only by the direct polymerization of the acid monomer it is not readily obtained by the hydrolysis of methyl methacrylate. 

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