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Whitney, Ralph

Ralph Whitney


B.Sc., 1972 University of British Columbia
Ph.D., 1975 University of Cambridge
PDF 1975-77 California Institute of Technology   


Contact Information

Department of Chemistry
Queen's University
Kingston, Ontario K7L 3N6

Tel: 613-533-2641
Email: ralph.whitney

Research Interests: Isobutylene-rich Elastomers

Butyl, brominated butyl (BIIR) and brominated isobutylene-co-paramethylstyrene (BIMS) rubbers are all isobutylene-rich elastomers that are produced commercially and are used for a wide range of applications due to their excellent barrier properties, resistance to oxidation and vibrational dampening. The presence of functionality in BIIR and BIMS that is reactive towards nucleophilic substitution makes these materials amenable to a wide variety of chemical modification strategies.  Over the past 15 years we have explored several topics in some detail; a brief description of these topics is given below along with representative publications. This work has been carried out in collaboration with Professor Scott Parent (Chemical Engineering, Queen’s University) and the Global Research & Development Butyl Rubber unit of LANXESS Inc. (London, ON), and has resulted in the commercialization of “LANXESS Butyl Ionomer


1.    Microstructure, thermal stability and sulfur cure chemistry of BIIR. Cured elastomers are difficult to characterize by conventional spectroscopic methods, consequently we have made extensive use of model compound chemistry (pentamethylnonene and brominated pentamethylnonene) to develop our understanding in this area.

  •    Can. J. Chem. (2013) 91, 420-427.
  •    Macromolecules (2010) 43, 8456-8461
  •    J Polym Sci, Pt A; Polym Chem (2003) 39, 2019-2026

2.    Amine cure chemistry. Primary amines rapidly crosslink BIIR by N-alkylation; in most cases this is too rapid to provide an effective cure. Consequently we have explored delayed-onset cures through the use of imines (Forster-Decker reaction) and through the use of CO2 salts of amines.

  •    Ind Eng Chem Res (2011) 50, 680-685
  •    Polym Eng Sci (2011) 51, 1592-1598
  •    Macromolecules (2005) 38, 4625-4629

3.    Ionomers. Reaction of tertiary amines with BIIR and BIMS leads to the formation of quaternary ammonium ionomers. We observed some thermal stability problems with these materials which led us to related materials including phosphonium and imidazolium ionomers. These materials have useful properties which include improved adhesion and filler dispersion as well as the ability to inhibit the growth of microorganisms. We have developed both thermoset imidazolium ionomers as well as reactive imidazolium ionomers that can, for example, be peroxide cured.

  •    Industrial & Engineering Chemistry Research (2014), 53(45), 17527-17536
  •    J Polym Sci, Pt A: Polym Chem (2005) 43, 5671-5679
  •    Macromol (2004) 37, 7477-7483

4.    Peroxide curable carboxylate derivatives of BIIR and BIMS. Peroxide cures of elastomers are preferred for some applications due to reduced amounts of leachables and extractables. Butyl rubber however degrades in the presence of peroxides. We have studied the chemical modification of BIIR and BIMS with carboxylate nucleophiles, and have utilized this chemistry to produce itaconate derivatives of these materials which are both functional and peroxide curable.

  •    Journal of Polymer Science, Part A: Polymer Chemistry (2015), 53(1), 123-132.
  •    J Polym Sci, Pt A: Polym Chem (2010) 48, 4691-4696
  •    Macromol (2006) 39, 2514-2520


Recent Publications and Patents

 Publications: (2010-2015)

Dakin, Jackson M.; Shanmugam, Karthik Vikram Siva; Twigg, Christopher; Whitney, Ralph A.; Parent, J. Scott , “Isobutylene-rich macromonomers: Dynamics and yields of peroxide-initiated crosslinking” Journal of Polymer Science, Part A: Polymer Chemistry (2015), 53(1), 123-132.

Dakin, Jackson M.; Whitney, Ralph A.; Parent, J. Scott “Imidazolium Bromide Derivatives of Brominated Poly(isobutylene-co-para-methylstyrene): Synthesis of Peroxide-Curable Ionomeric Elastomers”, Industrial & Engineering Chemistry Research (2014), 53(45), 17527-17536

Whitney, Ralph A.; Parent, J. Scott; McNeish, Joanne R. “Halogenated poly(isobutylene-co-isoprene): influence of halogen leaving-group and polymer microstructure  on chemical reactivity” Can. J. Chem. (2013) 91, 420-427.

Ozvald, A.; Parent, J.S.; Whitney, R.A. "Hybrid Ionic/Covalent Polymer Networks Derived from Functional Imidazolium Ionomers" Journal of Polymer Science, Part A: Polymer Chemistry (2013), 51(11), 2438-2444.

Wei J. Cui, Kimberley B. McAuley, Ralph A. Whitney, Rupert E. Spence, Tuyu Xie (deceased) “Mathematical Model of Polyether Production from 1,3-Propanediol" Macromolecular Reaction Engineering, (2013), 7(6), 237-253.

Shanmugam, Karthik; Parent, J Scott; Whitney, Ralph "Design, Synthesis and Characterization of Bismaleimide Co-curing Elastomers" Industrial & Engineering Chemistry Research (2012), 51(26), 8957-8965.

KV Siva Shanmugam, JS Parent, RA Whitney “C-H Bond Addition and Copolymerization Reactions of N-Arylmaleimides: Fundamentals of Coagent-assisted Polymer Cross-linking” European Polymer Journal, (2012), 48(4), 841-849.

Parent, J. Scott; Porter, Anthony M. J.; Kleczek, Monika R.; Whitney, Ralph A. “Imidazolium bromide derivatives of poly(isobutylene-co-isoprene): A new class of elastomeric ionomers” 
Polymer (2011), 52(24), 5410-5418.

Parent, J. Scott; Malmberg, Sean M.; Whitney, Ralph A. “Auto-catalytic chemistry for the solvent-free synthesis of isobutylene-rich ionomers” Green Chemistry (2011), 13(10), 2818-2824.

MAJ Faba; JS Parent; RA Whitney, “CO2-derived Latent Nitrogen Nucleophiles for Controlled Cross-linking of Brominated Poly(isobutylene-co-isoprene)” Polymer Engineering & Science, (2011), 51(8), 1592-1598.

MAJ Faba;  JS Parent;  R A Whitney, “Reactions of N-Alkylbenzaldimines with Brominated Poly(isobutylene-co-isoprene): Delayed Onset Cure Chemistry” Industrial and Engineering Chemistry Research, (2011),  50(2),  680-685.

SM Malmberg; JS Parent; DA Pratt; R A Whitney “Isomerization and Elimination Reactions of Brominated Poly(isobutylene-co-isoprene)” Macromolecules, (2010),  43(20),  8456-8461.

S Xiao; JS Parent; RA Whitney; LM Knight, “Synthesis and Characterization of Poly(isobutylene-co-isoprene)-derived Macro-monomers” Journal of Polymer Science, Part A: Polymer Chemistry (2010) 48, 4691-4696.


Butyl ionomers for use in reducing a population of and/or preventing accumulation of organisms and coatings made therefrom. U.S. Patent 8946319 (Feb. 3, 2015).
Adkinson, Dana A.; Ferrari, Lorenzo P.; Parent, J. Scott; Whitney, Ralph A., Resendes, Rui.
• Assigned to LANXESS Dec. 14, 2009.
• Commercialised as “LANXESS Butyl Ionomer”.

S Parent, R Whitney, S Guillen-Castellanos, R Resendes, “Novel Methods for the Preparation of Butyl Graft Copolymers”, US Patent No. 7629418 (2009).
• Assigned to LANXESS Dec. 14, 2009.

S Parent, R Whitney, A Liskova, R Resendes, “Process to Produce Silica-Filled Elastomeric Compounds.” Canadian Patent 2465301 (Feb. 7, 2012); US Patent 7238736 (July 3, 2007); European Patent 1591480 (Sept. 9, 2009); Japanese Patent 5067826 (Nov. 7, 2012); Argentina Patent 442408 (Sept. 15, 2009); Chinese Patent 1690109 (June 16, 2010); Russian Patent 2407758 (Dec. 27, 2010).
• Assigned to LANXESS Dec. 14, 2009.
• Commercialised as “LANXESS Butyl Ionomer”.