Polymerisation mechanisms models

The model with different end-groups is not realistic in all cases isotactic polypropylene and syndiotactic polypropylene are chiral, or more precisely, their structure is cryptochiral. This model is to be chosen when examining oligomers, and especially when studying the polymerisation mechanism where the structure of the reactive chain end is of extreme importance [16]. 

Catalysts, Models of Active Sites and the Polymerisation Mechanism... 

Models of the Active Sites, Epoxide Polymerisation Mechanism and Stereochemistry... 

Thus, ellipsometry gives direct evidence for a model of the initial stages of polythiophene growth, disproving the conclusions based purely on coulo-metry. In the same paper, Hamnett and Hillman were able to obtain valuable and complementary information not just on the initial stages of the polymerisation but also on the mechanism of the subsequent nucleation and growth. The unique piece of information that the ellipsometer was able to extract, the changes in film thickness (in real time), when combined with coulometric data allowed a wealth of information to be deduced, e.g. with respect to the film composition, and ably showed the power of the technique. 

The rearrangement of platinacyclobutanes to alkene complexes or ylide complexes is shown to involve an initial 1,3-hydride shift (a-elimina-tion), which may be preceded by skeletal isomerization. This isomerization can be used as a model for the bond shift mechanism of isomerization of alkanes by platinum metal, while the a-elimination also suggests a possible new mechanism for alkene polymerisation. New platinacyclobutanes with -CH2 0SC>2Me substituents undergo solvolysis with ring expansion to platinacyclopentane derivatives, the first examples of metallacyclobutane to metallacyclopentane ring expansion. The mechanism, which may also involve preliminary skeletal isomerization, has been elucidated by use of isotopic labelling and kinetic studies. 

It was thus worth finding a model of the synthesis of fluoropolymers in order to predict their degree of polymerisation, their structure, and the mechanism of the reaction. 

The reaction model assumed is one in which free-radical polymerisation is compartmentalised within a fixed number of reaction loci, all of which have similar volumes. As has been pointed out above, new radicals are generated in the external phase only. No nucleation of new reaction loci occurs as polymerisation proceeds, and the number of loci is not reduced by processes such as particle agglomeration. Radicals enter reaction loci from the external phase at a constant rate (which in certain cases may be zero), and thus the rate of acquisition of radicals by a single locus is kinetic-ally of zero order with respect to the concentration of radicals within the locus. Once a radical enters a reaction locus, it initiates a chain polymerisation reaction which continues until the activity of the radical within the locus is lost. Polymerisation is assumed to occur almost exclusively within the reaction loci, because the solubility of the monomer in the external phase is assumed to be low. The volumes of the reaction loci are presumed not to increase greatly as a consequence of polymerisation. Two classes of mechanism are in general available whereby the activity of radicals can be lost from reaction loci ... 

Since olefin insertion into the metal carbon bond has been established to be of the cis type, it has been considered to proceed by a concerted mechanism involving the formation of a four-membered transition state. However, various models of active centres and of the insertion mechanism have been proposed for olefin polymerisation systems with coordination catalysts. 

It should be emphasised that strong support has been provided for this mechanism of 7-olefin polymerisation, involving sites located on lateral a-TiCb faces, from molecular orbital calculations [268]. Analogous model sites, but located on layers in relief with respect to lateral faces of layered TiCfi structures [279-282], as well as for catalysts with the MgCT/TiCU precursor [279], have also been considered in molecular mechanics studies. 

A detailed molecular mechanics analysis of model catalytic sites has rationalised these observed behaviours for homogeneous propylene isospecific polymerisation catalysts based on bridged rac.-metallocene [357], It is interesting that, in contrast to the discussed case of enantioselectivity of the models for the primary insertion of propylene, the enantioselectivity of the models for the secondary insertion of propylene is due to direct interactions of the... 

Considering the above stereochemical model for syndiospecific styrene polymerisation, one may conclude reasonably that tf coordination of the monomer at the active site could hardly be possible, and r 2 coordination would always be involved in the syndiospecific polymerisation of this monomer [87]. One should note that preliminary concepts concerning the stereoregulation mechanism of syndiospecific styrene polymerisation assumed the styrene monomer to undergo only t]4 coordination at the titanium centre, the propagating chain being anchored via a benzylic bond as an t]3 ligand at the titanium [44,55,70]. 

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