Polymerizations, anionic methacrylates

Despite numerous efforts, there is no generally accepted theory explaining the causes of stereoregulation in acrylic and methacrylic anionic polymerizations. Complex formation with the cation of the initiator (146) and enolization of the active chain end are among the more popular hypotheses (147). Unlike free-radical polymerizations, copolymerizations between acrylates and methacrylates are not observed in anionic polymerizations however, good copolymerizations within each class are reported (148). 

Anionic and cationic polymerizations are often associated. Feldthusen et al. [5f] prepared copolymers containing linear and star-shaped blocks a living polyisobutylene chain was prepared by cationic polymerization, its ends were converted into 2,2-diphenylvinyl groups, then metallated and used as initiators of the ferf-butyl methacrylate anionic polymerization. 

The vast majority of commercial apphcations of methacryhc acid and its esters stem from their facile free-radical polymerizabiUty (see Initiators, FREE-RADICAl). Solution, suspension, emulsion, and bulk polymerizations have been used to advantage. Although of much less commercial importance, anionic polymerizations of methacrylates have also been extensively studied. Strictiy anhydrous reaction conditions at low temperatures are required to yield high molecular weight polymers in anionic polymerization. Side reactions of the propagating anion at the ester carbonyl are difficult to avoid and lead to polymer branching and inactivation (38—44). 

Unlike ftee-tadical polymerizations, copolymerizations between acrylates and methacrylates ate not observed in anionic polymerizations however, good copolymerizations within each class ate reported (99). 

The anionic polymerization of methacrylates using a silyl ketene acetal initiator has been termed group-transfer polymerization (GTP). First reported by Du Pont researchers in 1983 (100), group-transfer polymerization allows the control of methacrylate molecular stmcture typical of living polymers, but can be conveniendy mn at room temperature and above. The use of GTP to prepare block polymers, comb-graft polymers, loop polymers, star polymers, and functional polymers has been reported (100,101). 

Group-Transfer Polymerization. Du Pont has patented (29) a technique known as group-transfer polymerization and appHed it primarily to the polymerization of acrylates and methacrylates. It is mechanistically similar to anionic polymerization, giving living chains, except that chain transfer can occur (30). 

There are some indications that the situation described above has been realized, at least partially, in the system styrene-methyl methacrylate polymerized by metallic lithium.29 29b It is known51 that in a 50-50 mixture of styrene and methyl methacrylate radical polymerization yields a product of approximately the same composition as the feed. On the other hand, a product containing only a few per cent of styrene is formed in a polymerization proceeding by an anionic mechanism. Since the polymer obtained in the 50-50 mixture of styrene and methyl methacrylate polymerized with metallic lithium had apparently an intermediate composition, it has been suggested that this is a block polymer obtained in a reaction discussed above. Further evidence favoring this mechanism is provided by the fact that under identical conditions only pure poly-methyl methacrylate is formed if the polymerization is initiated by butyl lithium and not by lithium dispersion. This proves that incorporation of styrene is due to a different initiation and not propagation. 

In a similar manner polyisoprene-polyethylene oxide block copolymers can prepared301. It is surprising that the poly(methyl methacrylate) anion can be successfully used for the polymerization of ethylene oxide without chain transfer302. Graft copolymers are also prepared by successive addition of ethylene oxide to the poly-... 

Surprisingly, after this very first example, there was a 20 year delay in the literature in the appearance of the second report on siloxane macromonomers. However, during this period there have been numerous studies and developments in the vinyl and diene based macromonomers91 -94). The recent approach to the synthesis of siloxane macromonomers involves the lithiumtrimethylsilanolate initiated anionic polymerization of hexamethyltrisiloxane in THF 95,123). The living chain ends were then terminated by using styrene or methacrylate functional chlorosilanes as shown in Reaction Scheme X. 

Anionic Polymerization of Methyl Methacrylate 3.1 Basic Observations... 

Our understanding of the intricacies of anionic polymerization of methyl methacrylate was greatly improved during the last 15years by the meticulous and persistent work of the Mainz group. To appreciate fully the progress made in this field it is advisable to summarize the older studies and the ideas developed in those days. 

The difficulties encountered in the early studies of anionic polymerization of methyl methacrylate arose from the unfortunate choice of experimental conditions the use of hydrocarbon solvents and of lithium alkyl initiators. The latter are strong bases. Even at —60 °C they not only initiate the conventional vinyl poly-addition, but attack also the ester group of the monomer yielding a vinyl ketone1, a very reactive monomer, and alkoxide 23). Such a process is described by the scheme. 

Kinetic studies of the polymerization of mono-functional polymethyl methacrylate led to the determination of the propagation constants, k , of the sodium, potassium, and cesium salts 29- 35 36) of polymethyl methacrylates anions. Surprisingly, they... 

Fig. 2. Arrhenius plots of the rate constants of the anionic polymerization of methyl methacrylate in THF as the solvent and with Na+ orCs+ as the counterion. (R. Kraft, A. H. E. Muller, V. Warzelhan, H. Hocker, G. V. Schulz, Ref.35>)...

Anionic Polymerization of Other Methacrylates and Their Copolymerization... 

The striking simplicity of the methacrylate polymerization caused by the introduction of a t-butyl group was noted also in anionic polymerization of related monomers such as t-butyl acrylate57), t-butyl crotonate 58) and t-butyl vinyl ketone. 

Okamoto and his colleagues60) described the interesting polymerization of tri-phenylmethyl methacrylate. The bulkiness of this group affects the reactivity and the mode of placement of this monomer. The anionic polymerization yields a highly isotactic polymer, whether the reaction proceeds in toluene or in THF. In fact, even radical polymerization of this monomer yields polymers of relatively high isotacticity. Anionic polymerization of triphenylmethyl methacrylate initiated by optically active initiators e.g. PhN(CH2Ph)Li, or the sparteine-BuLi complex, produces an optically active polymer 60). Its optical activity is attributed to the chirality of the helix structure maintained in solution. 

To be eligible to living anionic polymerization a vinylic monomer should carry an electron attracting substituent to induce polarization of the unsaturation. But it should contain neither acidic hydrogen, nor strongly electrophilic function which could induce deactivation or side reactions. Typical examples of such monomers are p-aminostyrene, acrylic esters, chloroprene, hydroxyethyl methacrylate (HEMA), phenylacetylene, and many others. 

In some cases hydrogen donating functions can be protected hydroxyethyl methacrylate and glyceryl methacrylate 16,17) can undergo anionic polymerization as silyl-ether or-acetal, respectively. After polymerization the OH functions are recovered by mild acid hydrolysis. Similarly, p-hydroxyethylstyrene can be polymerized an-... 

Some tailor-made homopolymers can serve as starting points for chemical modifications to yield new species. Poly(hydroxyethyl methacrylate) and poly(glyceryl methacrylate) 16), already mentioned, are obtained upon hydrolysis of the OH-protecting groups that allow the anionic polymerization to proceed. Another example is the acid hydrolysis of poly(t-butyl methacrylate), a reaction which proceeds easily to completion, yielding poly(methacrylic acid) of known degree of polymerization and narrow molecular weight distribution 44 45). 

Yijin X. and Caiyaun P., Block and star-hlock copolymers by mechanism transformation. 3. S-(PTHF-PSt)4 and S-(PTHF-PSt-PMMA)4 from living CROP to ATRP, Macromolecules, 33, 4750, 2000. Feldthusen J., Ivan B., and Mueller A.H.E., Synthesis of linear and star-shaped block copolymers of isobutylene and methacrylates hy combination of living cationic and anionic polymerizations. Macromolecules, 31, 578, 1998. 

Interestingly, Reggelin et al. [147] prepared helical chiral polymers by helix-sense selective anionic polymerization of methacrylates, using an asymmetric base mixture as initiator (Scheme 61). 

Polystyrene standards used were narrow molecular weight distribution sample produced by anionic polymerization and available from Pressure Chemical Co. Also sample NBS7C from the National Bureau of Standards was used. The sample of poly n-butyl methacrylate was obtained from Aldrich Chemical. It was produced by free radici polymerization with an Mw of 320,(XK) and an Mn of 73,500 (Cat. No. 18,153-6). 

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