Studies of the cationic polymerisation of vinylic and energetic cyclic ether monomers

  • Hemant Desai

Student thesis: Doctoral ThesisDoctor of Philosophy


The cationic polymerisation of various monomers, including cyclic ethers bearing energetic nitrate ester (-ON02) groups, substituted styrenes and isobutylene has been investigated. The main reaction studied has been the ring-opening polymerisation of 3- (nitratomethyl)-3-methyl oxetane (NIMMO) using the alcohol/BF3.0Et2 binary initiator system. A series of di-, tri- and tetrafunctional telechelic polymers has been
synthesised. In order to optimise the system, achieve controlled molecular weight polymers and understand the mechanism of polymerisation the effects of certain parameters on the molecular weight distribution, as determined by Size Exclusion
Chromatography, have been examined. This shows the molecular weight achieved depends on a combination of factors including -OH concentration, addition rate of monomer and, most importantly, temperature. A lower temperature and OH
concentration tends to produce higher molecular weight, whereas, slower addition rates of monomer, either have no significant effect or produce a lower molecular weight polymer. These factors were used to increase the formation of a cyclic oligomer, by a
side reaction, and suggest, that the polymerisation of NIMMO is complicated with endbiting and back biting reactions, along with other transfer/termination processes. These observations appear to fit the model of an active-chain end mechanism. Another cyclic monomer, glycidyl nitrate (GLYN), has been polymerised by the activated monomer mechanism. Various other monomers have been used to end-cap the polymer chains to produce hydroxy ends which are expected to form more stable urethane links, than the glycidyl nitrate ends, when cured with isocyanates. A novel monomer, butadiene oxide dinitrate (BODN), has been prepared and its homopolymerisation and copolymerisation with GL YN studied.
In concurrent work the carbocationic polymerisations of isobutylene or substituted
styrenes have been studied. Materials with narrow molecular weight distributions have
been prepared using the diphenyl phosphate/BCl3 initiator.
These systems and monomers are expected to be used in the synthesis of thermoplastic
Date of AwardJun 1995
Original languageEnglish
SupervisorAllan J Amass (Supervisor)


  • cationic polymerisation
  • energetic cyclic ether monomers
  • nitrato or nitrate ester groups
  • linear and cyclic oligoethers
  • polyethers
  • vinylic monomers

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