Tacticity random

In order to determine whether MMA pol)nnerization time affects block integrity, two experiments were carried out in which only the polymerization time of MMA was varied. These results are listed as PMT-1 and PMT-2 in Table 7. Both PMT-1 and PMT-2 show good agreement between actual and expected triad tacticities. Random copolymerization between monomers is not observed in either case. This is not surprising, since the polymerization of MMA is expected to occur much faster than, for instance, that of DMA or TrMA. Table 7 also lists additional PMMA stereoblock polymers synthesized... 

All polymer molecules have unique features of one sort or another at the level of individual repeat units. Occasional head-to-head or tail-to-tail orientations, random branching, and the distinctiveness of chain ends are all examples of such details. In this chapter we shall focus attention on two other situations which introduce variation in structure into polymers at the level of the repeat unit the presence of two different monomers or the regulation of configuration of successive repeat units. In the former case copolymers are produced, and in the latter polymers with differences in tacticity. Although the products are quite different materials, their microstructure can be discussed in very similar terms. Hence it is convenient to discuss the two topics in the same chapter. 

Isoprene can be polymerized using free radical initiators, but a random polymer is obtained. As with butadiene, polymerization of isoprene can produce a mixture of isomers. However, because the isoprene molecule is asymmetrical, the addition can occur in 1,2-, 1,4- and 3,4- positions. Six tactic forms are possible from both 1,2- and 3,4- addition and two geometrical isomers from 1,4- addition (cis and trans) ... 

Copolymers involving only monosubslihited monomers are usually assumed lo have random tacticity (i.e. oAr = = 0.5). 

The results for arylsilanes are not fully understood, but the spectra may reflect partial tacticity in these polymers. Further work is needed studies of model compounds with known relative configuration would be particularly helpful. Silicon-29 NMR of polysilane copolymers also shows great promise, especially for distinguishing block-like from fully random copolymers. 

The term tactidty refers to the configuration of polymer chains when their constituent monomer residues contain a steric center. Figure 1.8 illustrates the three principal classes of tacticity as exemplified by polypropylene. In isotactic polypropylene, the methyl groups are all positioned on the same side of the chain, as shown in Fig. 1.8 a). In syndiotactic polypropylene, the methyl groups alternate from one side to the other, as shown in Fig. 1.8 b). Random placement of the methyl groups results in atactic polypropylene, which is shown in Fig. 1.8 c). We can readily observe the effects of tacticity on the properties of polypropylene isotactic polypropylene is hard and stiff at room temperature, syndiotactic polypropylene is soft and flexible, and atactic polypropylene is soft and rubbery. 

We have designed PBUILD, a new CHEMLAB module, for easy construction of random copolymers. A library of monomers has been developed from which the chemists can select a particular sequence to generate a polymeric model. PBUILD takes care of all the atom numbering, three dimensional coordinates, and knows about stereochemistry (tacticity) as well as positional isomerism (head to tail versus head to head attachment). The result is a model of the selected polymer (or more likely a polymer fragment) in an all trans conformation, inserted into the CHEMLAB molecular workspace in literally a few minutes. 

The algorithm also incorporates tacticity control for vinyl chains. The random number generator is used to choose between d- and l-versions of the transformation matrix. A single parameter controls the relative probability of d- and l-residues. The poly(p-fluorostyrene) results presented here are for atactic (stereochemically irregular) chains. 

There are, however, things about the polymer structure which are not known for certain. We assume that the reaction occurs in a random manner along the polymer backbone but there is little evidence at all concerning this problem and a detailed analysis must await future research. In addition, we know very little about the effects of polymer tacticity on the reaction shown in Equation 21. This also remains to be studied. On the other hand, we are confident that this reaction does not lead to a novel crosslinking reaction sequence since these polymers are soluble in a number of different solvents (Table II). 

In addition to isotactic, syndiotactic and atactic polymers (and other well-defined types of tactic polymers), there exists the whole range of possible arrangements between the completely ordered and the eompletely random distributions of configurational base units,... 

For disubstituted ethylenes, the presence and type of tacticity depends on the positions of substitution and the identity of the substituents. In the polymerization of a 1,1-disubstituted ethylene, CH2=CRR, stereoisomerism does not exist if the R and R groups are the same (e.g., isobutylene and vinylidene chloride). When R and R are different (e.g., —CH3 and —COOCH3 in methyl methacrylate), stereoisomerism occurs exactly as in the case of a monosubstituted ethylene. The methyl groups can be located all above or all below the plane of the polymer chain (isotactic), alternately above and below (syndiotactic), or randomly (atactic). The presence of the second substituent has no effect on the situation since steric placement of the first substituent automatically fixes that of the second. The second substituent is isotactic if the first is isotactic, syndiotactic if the first substituent is syndiotactic, and atactic if the first is atactic. 

TACTICITY. The regularity of symmetry in the molecular arrangement of structure of a polymer molecule. Contrasts with random positioning of substituent groups along the polymer backbone, or random position with icspcct to one another of successive atoms in the backbone chain of a polymer molecule. 

The addition of monomer fixes the tactidty of the previous monomer unit. The tacticity of PVC is nearly random, with syndiotactidty slightly favored at lower polymerization temperature,... 

ZIEGLER-NATTA POLYMERIZATION. Polymerization of vinyl monomers under mild conditions using aluminum alkyls and TiCL lor other transition element halide) catalyst to give a stereoregulated, or tactic, polymer. These polymers, in which the stereochemistry of the chain is not random have very useful physical properties. 

Today, the majority of all polymeric materials is produced using the free-radical polymerization technique [11-17]. Unfortunately, however, in conventional free-radical copolymerization, control of the incorporation of monomer species into a copolymer chain is practically impossible. Furthermore, in this process, the propagating macroradicals usually attach monomeric units in a random way, governed by the relative reactivities of polymerizing comonomers. This lack of control confines the versatility of the free-radical process, because the microscopic polymer properties, such as chemical composition distribution and tacticity are key parameters that determine the macroscopic behavior of the resultant product. 

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