Block co-polymerization by transformation reactions

  • Dorothy G. Amass

Student thesis: Doctoral ThesisDoctor of Philosophy


The aim of this study was to use the transformation of anionic to metathesis
polymerization to produce block co-polymers of styrene-b-pentenylene using
WC16 /PStLi and WC16/PStLi/ AlEtC12 catalyst systems. Analysis of the products
using SEC and 1H and 13C NMR spectroscopy enabled mechanisms for
metathesis initiation reactions to be proposed.
The initial work involved preparation of the constituent homo-polymers.
Solutions of polystyryllithium in cyclohexane were prepared and diluted so that the [PStLi]o<2x10-3M. The dilution produced initial rapid decay of the active species, followed by slower spontaneous decay within a period of days. This was investigated using UV / visible spectrophotometry and the wavelength of maximum absorbance of the PStLi was found to change with the decay from an initial value of 328mn. to λmax of approximately 340nm. after 4-7 days. SEC analysis of solutions of polystyrene, using RI and UV / visible (set at 254nm.) detectors; showed the UV:RI peak area was constant for a range of polystyrene samples of different moleculor weight.
Samples of polypentenylene were prepared and analysed using SEC.
Unexpectedly the solutions showed an absorbance at 254nm. which had to be
considered when this technique was used subsequently to analyse polymer
samples to determine their styrene/ pentenylene co-polymer composition.
Cyclohexane was found to be a poor solvent for these ring-opening metathesis
polymerizations of cyclopentene.
Attempts to produce styrene-b-pentenylene block co-polymers, using a range of
co-catalyst systems, were generally unsuccessful as the products were shown to
be mainly homopolymers. The character of the polymers did suggest that
several catalytic species are present in these systems and mechanisms have been suggested for the formation of initiating carbenes. Evidence of some low molecular weight product with co-polymer character has been obtained. Further investigation indicated that this is most likely to be ABA block copolymer,
which led to a mechanism being proposed for the termination of the

Date of AwardApr 1996
Original languageEnglish
SupervisorAllan J Amass (Supervisor)


  • ring-opening metathesis polymerization
  • anionic polymerization
  • cyclopentene
  • styrene

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