Amine Substitution Reactions of Brominated Poly(isobutylene-c o-isoprene):  New Chemical Modification and Cure Chemistry

• Published in: Macromolecules Vol. 35; no. 9; pp. 3374 - 3379
• Main Authors: Parent, J. Scott, White, Greg D. F, Whitney, Ralph A, Hopkins, William
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 23.04.2002
• Subjects: Applied sciences; Chemical modifications; Chemical reactions and properties; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Liquid liquid reaction; Crosslinking; Bromobutyl rubber; Experimental study; Chemical modification; Amination; Tertiary amine; Reaction mechanism; Model reaction; Kinetics; Growth from melt; Nucleophilic substitution; Primary amine
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma0120106

Nucleophilic substitution reactions of brominated poly(isobutylene-co-isoprene) (BIIR) with amines are characterized through studies of a model compound, brominated 2,2,4,8,8-pentamethyl-4-nonene (BPMN), and analysis of BIIR cure rheology. Nucleophilic amines do not accelerate HBr elimination from the allylic bromide within BIIR but readily engage in N-alkylation reactions with this functional group. N-Alkylation and accompanying proton-transfer reactions are shown to be reversible, and the distribution of allylic bromide, ammonium bromide salts, and their corresponding amines is dictated by equilibrium thermodynamics. N,N-Dimethyloctylamine and N-methyloctadecylamine undergo a single N-alkylation reaction with BPMN, while octylamine forms bis-N-alkylation products that can be used to generate stable cross-linked BIIR networks.