Oligomer Oligomerisation

The reaction mixture consisted only of glycine and water, without the addition of salts or other condensation catalysts. A stepwise, time-dependent synthesis of oligomers up to hexaglycine was observed. On addition of Ca2+ ions (pH 2.5), the oligomerisation continued further to give octaglycine. 

In a closer examination of the formation of oligomers, Ferris and co-workers found that the reaction is favoured by relatively high salt concentrations (e.g. 1M NaCl), while the presence of divalent cations is not necessary. The formation of RNA oligomers was found to be temperature sensitive the yields decrease when the temperature is raised from 4°C to 50° C. The addition of meteorite material (from 3 meteorites) does not catalyse the polymerisation reaction only galena (PbS) can do this. The authors thus assume that RNA oligomers could have been formed on the young Earth in solutions of alkali metal salts in the presence of montmorillonite and a pH value of 7-9 (Miyakawa et al., 2006). Ferris (2006) has provided a short but up-to-date survey of montmorillonite-catalysed RNA oligomerisation. 

Since the proton affinity P(Rn=) of the branched olefin Rn= is certainly greater than P(C2H4), the reaction would be endothermic a similar argument applies to the transfer of carbonium ions. This may account for the low yields observed even in the heterogeneous cationic oligomerisation of ethylene. The most likely transfer reactions are hydride ion and methide ion transfers between oligomer ions and molecules (see below), leading to conjunct polymerisation [12]. 

Our studies have confirmed that the oligomerisation of styrene by perchloric acid is both chemically and kinetically simple. However, the reactions which follow completion of the polymerisation, and during which carbonium ions are formed and destroyed, are complicated. They can be rationalised in terms of equilibria involving ions, acid, double bonds, and esters cyclisation of olefinic oligomers and formation of polyenes by way of allylic ions add further complications. We have thus shown in some detail just why such systems must be treated with the greatest circumspection if they are to yield valid information. 

When chain transfer is very fast, the reaction observed is the alkoxycarbonylation of ethene, which is nothing but a perfect chain transfer after the insertion of just two monomers. In recent years several very fast catalysts for this reaction have been reported as we will see in the next section. The first effective catalysts reported by Sen [8] (Pd(BF4)2 and PPh3) also give relatively fast chain transfer as the Flory-Schulz constant for their product was only 0.3-0.4 (see Chapter 9.2.1 on oligomerisation) and the product is an oligomer rather than a polymer. 

Various oligomers of fluorinated alkenes and cycloalkenes have been prepared by fluoride ion induced oligomerisation of various monomers (Sect. 5.3), and the chemistry of these systems provides some unique reactions. The oligomers of special interest here may be described as of types (95) or (96) (Scheme 59), i. e. systems with either four (95) or three (96) perfluoro-alkyl or -cycloalkyl groups attached to the double bond, whereas systems with two perfluoroalkyl groups attached, i. e. (97) and (98), have a chemistry more similar to fluorinated alkenes that may be derived from other sources. 

At higher temperature (T>250°C), a small part of trapped isopentane molecules are transformed into coke (oligomers and aromatic compounds) by successive reaction such as cracking, oligomerisation, cycUsation and hydrogen transfer on the weak acid sites of 5A zeolite. 

A besetting problem with the industrial process to remove traces of alkynes alkadienes from alkene streams using palladium catalysts has been the formation of higher hydrocarbons by oligomerisation. Although in this respect palladium is better than base metals such as nickel (which presumably explains why this cheaper metal is not used), and while the fraction of ethyne that reacts in this manner is small, nevertheless in a continuous operation these higher products accumulate, and cause problems. The carbonaceous deposits, so often mentioned, may be partly C2 species such as ethylidyne, but they also comprise adsorbed forms of oligomers in the steady state their formation is followed by release into the fluid phase. 

---