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Several other types of monomers are capable of yielding stereoisomeric polymer structures. Ordered structures are possible in the polymerization of carbonyl monomers (RCHO and RCOR0 ) and the ring-opening polymerizations of certain monomers. Thus, for example, the polymers from acetaldehyde and propylene oxide can have isotactic and syndiotactic structures as shown in Figs. 8-3 and 8-4.

Fig. 8-4

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Polyacetaldehyde [IUPAC: Poly(oxy[methylmethylene])], like the systems described previously, contains stereocenters that are achirotopic. Both the isotactic and syndiotactic polymers are achiral and do not possess optical activity. The repeat unit (III) in poly(propylene oxide) [IUPAC: poly(oxy[1-methylethylene])], on the other hand, possesses stereocenters that are chirotopic since the two chain segements

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we see that divisor of z; can be canceled and so the combined influence curve will not be unbounded because of (8.12). Here it is natural to consider combining the residual and position influences into H combined influence curve. The combined curve acts in many ways like a position influence curve in that it may still be unbounded in certain directions because of other terms. 1 For a single fixed input pattern we have, for q = 1,. . . ,Q and h = 1 , . . . ,

attached to C* are very different one is attached via an oxygen and the other via a methylene. Isotactic poly(propylene oxide) contains no symmetry element, is not superposable on its mirror image, and possesses optical activity. The syndiotactic polymer is incapable of optical activity since it possesses a mirror glide plane of symmetry. The stereochemistry of step polymerization is considered now. Bond formation during step polymerization almost never results in the formation of a stereocenter. For example, neither the ester nor the amide groups in polyesters and polyamides, respectively, possess stereocenters. Stereoregular polymers are possible when there is a chiral stereocenter in the monomer(s) [Oishi and Kawakami, 2000; Orgueira and Varela, 2001; Vanhaecht et al., 2001]. An example would be the polymerization of (R) or (S)-H2 NCHRCOOH. Naturally occurring polypeptides are stereoregular polymers formed from optically active a-amino acids.

8-1d 8-1d-1

The polymerization of a 1,3-diene such as 1,3-butadiene, isoprene, and chloroprene can lead to cis and trans isomers when polymerization occurs by a 1,4-polymerization. On the

and for h = 1,. . .

other hand, 1,2-polymerization through one or the other double bond can yield isotactic, syndiotactic, or atactic polymers, for example, for 1,3-butadiene

6

8-1

The situation is exactly analogous to the polymerization of monosubstituted alkenes; the var ious polymer structures would be those in Fig. 8-1 with R CH2 . With chloroprene CH and isoprene, the possibilities are enlarged since the two double bonds are substituted differently. Polymerizations through the 1,2- and 3,4-double bonds do not yield the same product as they would in 1,3-butadiene polymerization. There are, therefore, a total of six structures possible corresponding to isotactic, syndiotactic, and atactic structures for both 1,2- and 3,4-polymerizations; for instance, for isoprene, one has the situation shown in Eq. 8-2 with polymers V and VI capable of exhibiting the structures in Fig. 8-1 with R CH2 CH CH2 and C(CH3 ) CH2 , respectively.

8-2

and p = 1,. . . ,

8-1d-2

From the practical viewpoint, the more important products from 1,3-dienes are those that occur by 1,4-polymerization of the conjugated diene system, for example, for isoprene, we obtain

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8-3

Following this argument along the same lines as the argument in Section 8.5, we conclude that the behavior of I C ( r l w p ) is as described in equations (8.5) and (8.6) (p. 131). That is, it is unbounded in the general case along paths parallel t o the decision boundary, L J ~ X 0. =

1,4-Polymerization leads to a polymer structure (VII) with a repeating alkene double bond in the polymer chain. The double bond in each repeating unit of the polymer chain is a site of steric isomerism since it can have either a cis or a trans con guration. The polymer chain segments on each carbon atom of the double bond are located on the same side of the double

bond in the cis con guration (VIII) and on opposite sides in the trans con guration (IX), for example, for polyisoprene.

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