Skip to main content

Research Repository

Advanced Search

Rate of Formation of Industrial Lubricant Additive Precursors from Maleic Anhydride and Polyisobutylene

Streets, Jessica; Proust, Nicolas; Parmar, Dixit; Walker, Gary; Licence, Peter; Woodward, Simon


Jessica Streets

Nicolas Proust

Dixit Parmar

Gary Walker

Professor of Synthetic Organic Chemistry


The Alder-ene reaction of neat polyisobutylene (PIB) and maleic anhydride (MAA) to produce the industrially important lubricant additive precursor polyisobutylene succinic anhydride (PIBSA) is studied at 150-180 °C. Under anaerobic conditions with [PIB] ∼1.24 M (550 g mol-1 grade, >80% exo alkene) and [MAA] ∼1.75 M, conversion of exo-PIB and MAA follows second-order near-equal rate laws with kobs up to 5 × 10-5 M-1 s-1 for both components. The exo-alkene-derived primary product PIBSA-I is formed at an equivalent rate. The less reactive olefinic protons of exo-PIB also react with MAA to form isomeric PIBSA-II (kobs up to 6 × 10-5 M-1 s-1). Some exo-PIB is converted to endo-PIB (containing trisubstituted alkene) in a first-order process (kobs ∼1 × 10-5 s-1), while PIBSA-I is difunctionalized by MAA to bis-PIBSAs very slowly. The MAA- and PIB-derived activation parameter ΔG‡(150 °C) 34.3 ± 0.3 kcal mol-1 supports a concerted process, with that of PIBSA-I suggesting a late (product-like) transition state.


Streets, J., Proust, N., Parmar, D., Walker, G., Licence, P., & Woodward, S. (2022). Rate of Formation of Industrial Lubricant Additive Precursors from Maleic Anhydride and Polyisobutylene. Organic Process Research and Development, 26(9), 2749-2755.

Journal Article Type Article
Acceptance Date Aug 12, 2022
Online Publication Date Aug 30, 2022
Publication Date Aug 30, 2022
Deposit Date Sep 12, 2022
Publicly Available Date Sep 12, 2022
Journal Organic Process Research and Development
Print ISSN 1083-6160
Electronic ISSN 1520-586X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 26
Issue 9
Pages 2749-2755
Keywords Article, kinetics, ene reaction, thermal, mechanism, energetics, lubricant
Public URL
Publisher URL


You might also like

Downloadable Citations