Tacticities

Unfortunately this route gives only a 40% yield IJ. Amer. Cham. Soc 1951, 73, 3237) in the Grignard reaction, largely because benzyl Grignard reagents easily give radicals which polymerise. In any case, it s poor tactics to chop off carbon atoms one at a time, and a better disconnection would be ... 

Analysis The functional group is an acetal - once we ve removed this, we can follow straightforward tactics. 

Thus mixed aldol additions can be achieved by the tactic of quantitative enolate for matron using LDA followed by addition of a different aldehyde or ketone... 

Generally polymers involve bonding of the most substituted carbon of one monomeric unit to the least substituted carbon atom of the adjacent unit in a head-to-tail arrangement. Substituents appear on alternate carbon atoms. Tacticity refers to the configuration of substituents relative to the backbone axis. In an isotactic arrangement, substituents are on the same plane of the backbone axis that is, the configuration at each chiral center is identical. 

Figure 1.2 shows sections of polymer chains of these three types the substituent R equals phenyl for polystyrene and methyl for polypropylene. The general term for this stereoregularity is tacticity, a term derived from the Greek word meaning to put in order. ... 

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.

These differences do not arise from 1,2- or 3,4-polymerization of butadiene. Structures [XIII] and [XIV] can each exhibit the three different types of tacticity, so a total of six structures can result from this monomer when only one of the olefin groups is involved in the backbone formation. 

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. 

For both copolymers and stereoregular polymers, experimental methods for characterizing the products often involve spectroscopy. We shall see that nuclear magnetic resonance (NMR) spectra are particularly well suited for the study of tacticity. This method is also used for the analysis of copolymers. 

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... 

Figure 7.10 Nuclear magnetic resonance spectra of three poly(methyl methacrylate samples. Curves are labeled according to the preominant tacticity of samples. [From D. W. McCall and W. P. Slichter, in Newer Methods of Polymer Characterization, B. Ke (Ed.), Interscience, New York, 1964, used with permission.]...

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. 

From appropriate ratios of these sequence lengths, what conclusions can be drawn concerning terminal versus penultimate control of addition The following are experimental tacticity fractions of polymers prepared from different monomers and with various catalysts. On the basis of Fig. 7.9, decide whether these preparations are adequately described (remember to make some allowance for experimental error) by a single parameter p or whether some other type of statistical description is required ... 

B. D. Nahloosky and G. A. Zimmerman, Thermoplastic Elastomers for S olid Propellant Binders, AERPL-TR-86-069, Aerojet Tactical Systems Co., Sacramento, Calif., Dec. 1986. 

J. E. Tormey, "Processing and Manufactuie of Composite Propellants," Proceedings of the AGARD Colloquim, Advances in Tactical Rocket Propulsion, CIRA Pub., Pelham, New York, 1968. 

National Academy of Sciences, Pesticide Resistance Strategies and Tactics for Management, Washiagton, D.C., 1986. 

R. Goldscheider, "The Art of Licensiag Out", Technology Management Eaw, Tactics, Forms, Clark Boardman Callaghan, New York, 1988, Chapt. 6. 

The nature of the alkyl group from the esterifying alcohol, the molecular weight, and the tacticity determine the physical and chemical properties of methacrylate ester polymers. 

Transformations in the Solid State. From a practical standpoint, the most important soHd-state transformation of PB involves the irreversible conversion of its metastable form II developed during melt crystallization into the stable form I. This transformation is affected by the polymer molecular weight and tacticity as well as by temperature, pressure, mechanical stress, and the presence of impurities and additives (38,39). At room temperature, half-times of the transformation range between 4 and 45 h with an average half-time of 22—25 h (39). The process can be significantly accelerated by annealing articles made of PB at temperatures below 90°C, by ultrasonic or y-ray irradiation, and by utilizing various additives. Conversion of... 

Specialty Polystyrenes. These include ionomers and PS of specified tacticity, as well as stabilized PS. 

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