Mechanism of chain initiation

It is commonly found that polymers are less stable particularly to molecular breakdown at elevated temperatures than low molecular weight materials containing similar groupings. In part this may be due to the constant repetition of groups along a chain as discussed above, but more frequently it is due to the presence of weak links along the chain. These may be at the end of the chain (terminal) arising from specific mechanisms of chain initiation and/or termination, or non-terminal and due to such factors as impurities which becomes built into the chain, a momentary aberration in the modus operandi of the polymerisation process, or perhaps, to branch points. 

The mechanism of chain initiation in cyclohexanol by the reaction with dioxygen was studied by the inhibitor method [57]. It was established that... 

The Catalyst System Eleven years ago, Kaminsky invented a novel olefin polymerization catalyst derived from Cp2ZrCl2 (Cp = 7 -5-C5H5) and methylaluminoxane (1), a result that has stimulated intense interest in synthesis and reactions of metallocenium ions. Important questions still remain, however, regarding the nature of the Kaminsky catalyst. These include (1) what is methylaluminoxane and how does it interact with Cp2ZrMe2 to initiate polymerization and (2.) what are the mechanisms of chain initiation, propagation, transfer and termination A collateral question is how these steps may be controlled. 

Using the technique of differential calorimetry, Kapralova has found evidence that, the initiation and termination of chains in 1,2-dichloroethane pyrolysis occurs on the reaction vessel walls instead of in the homogeneous gas phase. It has also beenproposed - that the inhibitory effect of propene may be associated with its absorption on the vessel walls causing a reduction in the rate of the initiation of chains on the surface. The mechanism of chain initiation and the action of inhibitors and sensitisers in 1,2-dichloroethane pyrolysis have been further discussed in papers by Kapralova and Semenov > Kitabatake and Onouchi and Smolyan . 

Initiation, as noted above, involves the generation of active species, which can be through free-radical, ionic, or coordination mechanism. This mechanism of chain initiation is the essential distinguishing feature between different polymerization processes. Quite expectedly, therefore, addition polymerization of vinyl... 

Small, B. L. Brookhart, M. Polymerization of propylene by a new generation of iron catalysts Mechanisms of chain initiation, propagation, and termination. Macromolecules 1999, 32, 2120-2130. 

Scheme 62 Mechanism of chain initiation and propagation for lipase-catalyzed TMC polymerization.

The first of these problems—the mechanism of chain initiation—is intimately connected wdth the question of the temporal relationship between protein and polysaccharide synthesis. A number of alternatives may obviously be envisaged for the time sequence of the formation of these two components and their combination to the covalently linked end product. Some of these are outlined below (see also Yamashina, 1966) ... 

Chitosan, having a similar chemical backbone as cellulose, is a linear polymer composed of a partially deacety-lated material of chitin [(l-4)-2-acetamide-2-deoxy-/3-D-glucan]. Grafting copolymer chains onto chitosan can improve some properties of the resulting copolymers [48-50]. Yang et al. [16] reported the grafting reaction of chitosan using the Ce(IV) ion as an initiator, but no detailed mechanism of this initiation has been published so far. 

The general mechanism of chain transfer as first proposed by Flory,1,2 may be written schematically as shown in Scheme 6.2. The overall process involves a propagating chain (Pn ) reacting with a transfer agent (T) to terminate one polymer chain and produce a radical (T ) that initiates a new chain (IV). 

Variable valence transition metal ions, such as Co VCo and Mn /Mn are able to catalyze hydrocarbon autoxidations by increasing the rate of chain initiation. Thus, redox reactions of the metal ions with alkyl hydroperoxides produce chain initiating alkoxy and alkylperoxy radicals (Fig. 6). Interestingly, aromatic percarboxylic acids, which are key intermediates in the oxidation of methylaromatics, were shown by Jones (ref. 10) to oxidize Mn and Co, to the corresponding p-oxodimer of Mn or Co , via a heterolytic mechanism (Fig. 6). 

Eqs. (3), (4), (5), and (7) describe the mechanism of an initiated free radical polymerization in a form amenable to general kinetic treatment. The rate of initiation of chain radicals according to Eqs. (3) and (4) may be written... 

Figure 26 Overall anionic chain polymerisation mechanism of styrene initiated by n-butyllithium.

On the basis of the nature of CO adsorption and of the nature of chain initiator intermediates, popular mechanistic proposals include the carbide mechanism,1-2 wherein CO adsorbs dissociatively and the carbide (C ) is the chain initiator intermediate, and the enolic mechanism,3 involving molecular adsorption of CO and the formation of an oxygen intermediate, the enol (HC OH). 

The border conditions between chain and nonchain mechanisms of oxidation depends not only on temperature but also on the hydrocarbon concentration and the rate of chain initiation. The following equation describes this dependence ... 

Phosphites can react not only with hydroperoxides but also with alkoxyl and peroxyl radicals [9,14,17,23,24], which explains their susceptibility to a chain-like autoxidation and, on the other hand, their ability to terminate chains. In neutral solvents, alkyl phosphites can be oxidized by dioxygen in the presence of an initiator (e.g., light) by the chain mechanism. Chains may reach 104 in length. The rate of oxygen consumption is proportional to v 1/2, thus indicating a bimolecular mechanism of chain termination. The scheme of the reaction... 

The hydrogen-chlorine chain reaction has proved to be one of the most controversial systems yet studied. After thirty years of investigation Bodenstein43 was able to say in 1931 that every worker on the photochemical synthesis of HC1 had produced his own mechanism even as late as 1940 little positive information had been obtained. However, the accumulated techniques and experience had firmly established the importance of atom chain reactions. The mechanism of photo-initiation and propagation is the same as for the hydrogen bromide photosynthesis, a non-branching chain reaction... 

The block mechanism of chain assembly is characteristic for polymeric chains of the UGT type (see Salmonella O-specific polysaccharides 10-12 and 18) and the UG type (see capsular polysaccharides 25, 27, and 33), with UDP-activated sugars serving as initiators of chain growth. It seems rather safe to suggest that the biosynthesis of other polymers of these types occurs through a block mechanism as well. 

Mayo, F. R. Chain transfer in the polymerization of styrene. VIII. Chain transfer with bromobenzenc and mechanism of thermal initiation. J. Am. Chem. Soc. 75, 6133 (1953). 

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