The synthesis of 1-butene oligomers with vinyl endgroups and their use in further reactions
Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007.
This study comprises the synthesis, functionalization, and characterization of 1-butene oligomers, as well as the synthesis of oligobutene-based macro-RAFT agent. The directed oligomerization of 1-butene was carried out with a Cp2ZrCl2 as a catalyst, activated with MAO as a co-catalyst (10% in toluene), in the ratio Al/Zr =1000/1. Oligomers possessing vinylidene double bonds, with low molecular weight (Mw), ranging between 800 and 2000 g.mol-1 as confirmed by gel permeation chromatography, were obtained. The oligomers were successfully functionalized by adding hydroxyl functionality to the vinylidene double bond using oxymercuration-demercuration reaction, and as a result hydroxy-terminated oligobutenes were obtained. Characterization techniques such as 1H NMR, 13C NMR, GC-MS and FTIR confirmed the successful synthesis and functionalization of 1-butene oligomers. The hydroxy-terminated oligobutenes were used to prepare an oligobutene-based macro-RAFT agent. The synthesis of the macro-RAFT agent was carried out with an esterification reaction between the hydroxy-terminated oligobutenes and an acid functionalized RAFT agent. The successful synthesis of the macro-RAFT agent was confirmed by 1H NMR, 13C NMR, FTIR, and UV spectroscopy. The chain transfer ability of the macro-RAFT agent to induce living characteristics in free radical styrene polymerization was investigated with respect to molecular weight control and kinetic behaviour. The macro-RAFT agent was identified as suitable RAFT agent, yielding polystyrene-b-oligobutnes with low polydispersities and molecular weight ranging from 3000 to 40000 g/mol.