Methyl methacrylate anionic tactic polymerization

The same type of addition—as shown by X-ray analysis—occurs in the cationic polymerization of alkenyl ethers R—CH=CH—OR and of 8-chlorovinyl ethers (395). However, NMR analysis showed the presence of some configurational disorder (396). The stereochemistry of acrylate polymerization, determined by the use of deuterated monomers, was found to be strongly dependent on the reaction environment and, in particular, on the solvation of the growing-chain-catalyst system at both the a and jS carbon atoms (390, 397-399). Non-solvated contact ion pairs such as those existing in the presence of lithium catalysts in toluene at low temperature, are responsible for the formation of threo isotactic sequences from cis monomers and, therefore, involve a trans addition in contrast, solvent separated ion pairs (fluorenyllithium in THF) give rise to a predominantly syndiotactic polymer. Finally, in mixed ether-hydrocarbon solvents where there are probably peripherally solvated ion pairs, a predominantly isotactic polymer with nonconstant stereochemistry in the jS position is obtained. It seems evident fiom this complexity of situations that the micro-tacticity of anionic poly(methyl methacrylate) cannot be interpreted by a simple Bernoulli distribution, as has already been discussed in Sect. III-A. 

In polar solvents such as THF anionic polymerization of methyl methacrylate at low temperature is classically assumed to proceed via free anions and the products are syndiotactic. Indeed the structure of such polymers has been confirmed recently and tactic addition shown to conform to Bernoullian... 

We have been concerned with the precision and accuracy of NMR data of polymers since we first started NMR studies on polymers.1-4 Using continuous-wave (CW) spectrometers, the effects of measurement conditions including temperature, sample concentration and radiofrequency (rf) field strength, were examined using several polymer and copolymer samples. Since our research group have been deeply involved in stereospecific polymerization of methacrylates, one of the main concerns about NMR measurement was the precision of tacticity determination by NMR. The errors in determining the tacticity of poly(methyl methacrylate) (PMMA) and those in the results of polymerization of methyl methacrylate (MMA) by radical and anionic initiators were examined and found to be satisfactorily small.4 Although there... 

Needless to say, vinyl polymerization is one of the most important methods for polymer synthesis. A variety of carbon-carbon (C-C) main chain polymers have been prepared by the vinyl polymerization of monomers with diverse substituents, via radical, cationic, anionic, or coordination mechanism. Furthermore, with the technological achievement such as living and stereoselective (or stereospecific) polymerizations, fine-tuning of the polymer structure with respect to molecular weight and tacticity has been realized in a number of examples. In particular, polymers obtained with vinyl polymerization (vinyl polymer) as represented by polyethylene, polypropylene, polystyrene, and poly(methyl methacrylate) have contributed to the progress of modern society in various aspects as useful synthetic materials. 

Derivation of polymer also serves as a useful method for tacticity determination. Poly(triphenylmethyl methacrylate) is easily converted to PMMA by hydrolysis and the subsequent methylation with diazomethene. The polymers obtained by anionic polymerization not only in toluene but also in tetrahydrofuran are highly isotactic.189 Even the radical polymerization of the monomer gives an isotactic polymer. 

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