Cationic polymerization termination processes

For monomers that undergo cationic polymerization, the process is terminated when the carbocation intermediate is deprotonated by a base or attacked by a nucleophile other than an alkene (such as water). 

This reaction corresponds to the basic process during the initiation of cationic polymerizations by RX/MtXn and when reversed is the termination reaction. It will be handled more in detail in part 4.2. When X = H, the reaction enthalpy of the previous equation is equal to the hydride ion affinity (HIA) which is shown for various relevant... 

Such a mechanism is open to serious objections both on theoretical and experimental grounds. Cationic polymerizations usually are conducted in media of low dielectric constant in which the indicated separation of charge, and its subsequent increase as monomer adds to the chain, would require a considerable energy. Moreover, termination of chains growing in this manner would be a second-order process involving two independent centers such as occurs in free radical polymerizations. Experimental evidence indicates a termination process of lower order (see below). Finally, it appears doubtful that a halide catalyst is effective without a co-catalyst such as water, alcohol, or acetic acid. This is quite definitely true for isobutylene, and it may hold also for other monomers as well. 

In both anionic and cationic polymerization it is possible to create living polymers . In this process, we starve the reacting species of monomer. Once the monomer is exhausted, the terminal groups of the chains are still activated. If we add more monomer to the reaction vessel, chain groivth will restart. This technique provides us with a uniquely controllable system in which we can add different monomers to living chains to create block copolymers. 

A hypothesis which may explain the experimental observations can be developed as follows Transfer has been assumed to occur by proton transfer to monomer. Previous studies (18,19) indicate that propagation and transfer have similar transition states in cationic polymerizations. For this reason it is possible that these two processes may both occur within the ion-counterion-monomer complex. Termination has been assumed to occur by ion-counterion collapse (20), for example, for EtAlCl2 ... 

Mention should be made of a process first described by Watanabe et al. 62) in which cationic polymerization of alkylene oxides was initiated by Lewis acids and carried out in the presence of methacrylic acid or 2-hydroxyethyl methacrylate (HEMA). The products obtained were characterized and found to contain one terminal methacrylic ester function per chain ... 

The reaction of an unsaturated compound with an antagonist function located at the end of a polymer chain is still the most commonly used method to synthesize macromonomers. We have already mentioned some processes that can be used to introduce into the chain end of a macromolecule a functional group, e.g. by deactivation of living carbanionic sites and transfer reactions of various kinds in cationic polymerization. We have also described some methods used to link an active terminal double bond to the chain end originally bearing hydroxy groups. 

All these circumstances cause cationic polymerization to be a very sensitive process, despite the fact that it may also be living, i.e. without being subject to transfer and termination [123, 124], Monomer addition to carbocations usually yields an atactic polymer. 

The scope of the living cationic polymerizations and synthetic applications of these functionalized monomers will be treated in the next chapter on polymer synthesis (see Chapter 5, Section III.B). One should note that the feasibility of living processes for these polar monomers further attests to the formation of controlled and stabilized growing species. Conventional nonliving polymerizations, esters, ethers, and other nucleophiles are known to function as chain transfer agents and sometimes as terminators. In addition, the absence of other acid-catalyzed side reactions of the polar substituents, often sensitive to hydrolysis, acidolysis, etc., demonstrates that these polymerization systems are free from free protons that could arise either from incomplete initiation (via addition of protonic acids to monomer) or from chain transfer reactions (/3-proton elimination from the growing end). 

The process based on cationic polymerization of 1,3,5-trioxane employs a different principle for stabilization of polymer. Trioxane is copolymerized with a few percent of 1,3-dioxolane (or ethylene oxide). The sequence of —OCH2— units is then separated from time to time by —OCH2CH2— units. The product of copolymerization is subsequently heated to eliminate the terminal units (unstable fraction). Depropagation proceeds until the stable —CH2CH2OH group is reached ... 

Figure 14 Transfer and/or termination processes in/3-pinene cationic polymerization. (From Refs. 93 and 94.)...

We can detect a further complication from observations that some cationic polymerizations exhibit bimodal (two peaks) molecular weight distributions. This can happen if different active species (say, free ions and some form of ion pairs) engage in propagation or transfer reactions faster than they can come to equilibrium with each other. Under these circumstances there can be two effectively independent processes that govern the size of the macromolecules that are produced. If we ignore all these important complications we can write the following expressions for the rates of initiation (/ i), propagation (/ p), termination (R,), and transfer to monomer (Rv,m) ... 

Initiation of Poly merization of Vinyl Monomers Propagation Reactions Termination and Transfer Processes Kinetics of Cationic Polymerization of Olefins Temperature Effects... 

The above kinetic expressions illustrate some basic differences between cationic and free radical processes. In the cationic polymerization, the propagation rate is of first order with respect to the initiator concentration, whereas in free radical polymerization it is proportional to the square root of initmtor concentration (Eq. [34]). Furthermore, the molecular weight (or DP) of the polymer synthesized by the cationic process is independent of the concentration of the initiator, regardless of how termination takes place, unlike free radical polymerization where DP is inversely proportional to [I] in the absence of chain transfer (Eq. [35]). 

Recently, Higashimura [7] has reviewed the data on elementary rate coefficients (fej, fep, fet and fej) in cationic polymerization of vinyl monomers. Information available on initiation and termination reactions is extremely limited, and virtually no attempt [50] has been made to elucidate, either qualitatively or quantitatively the role of free ions and ion pairs in these processes. Numerical data on the separate contributions to propagation by free ions and ion pairs is slowly becoming available, though in a less ordered fashion than in the case of anionic systems. It seems likely that the most fruitful approach to the problem of absolute reactivity, in initiation processes at least, will be an examination of reactions of non-polymerizable monomer models, where electronic factors... 

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