The thermal stability of brominated isobutylene–isoprene rubber (BIIR) was investigated through studies of the elastomer and a model compound that accurately represented the reactive functionality within the polymer. An analysis of commercial BIIR and reaction products of brominated 2,2,4,8,8‐pentamethyl‐4‐nonene (BPMN) by NMR demonstrated that bromination of isobutylene–isoprene rubber by 1,3‐dibromo‐5,5‐dimethylhydantoin yielded a kinetically favored exomethylene substitution product, 3‐bromo‐6,6‐dimethyl‐2‐(2,2‐dimethylpropyl)‐1‐heptene (2), as opposed to the more stable endo‐isomer, (E,Z)‐4‐(bromomethyl)‐2,2,8,8‐tetramethyl‐4‐nonene (3). The exposure of BIIR and the brominated model compound BPMN to vulcanization temperatures led to the isomerization of 2 to 3 at a rate strongly dependent on HBr concentration. The elimination of HBr from these allylic bromides to produce exo‐ and endo‐conjugated dienes proceeded concurrently with isomerization, and the kinetics of these processes could be rationalized on the basis of a polar reaction mechanism. The product distributions obtained from both the model system and BIIR were consistent, thereby justifying an extension of the model compound approach to an analysis of BIIR vulcanization chemistry. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2019–2026, 2001

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-4nonene (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.

The sulfuration and reversion products of brominated poly(isobutylene-coisoprene) (BIIR) were characterized through the use of a model compound, brominated 2,2,4,8,8-pentamethyl-4-nonene (BPMN). The reaction of BPMN with S 8 produced bisallylic polysulfides of various ranks, yielding sulfur bromide intermediates that likely contributed to the rapid oxidation of allylic sulfides into thiophenes. Reductive cure reversion to pentamethylnonene was also observed in the latter stages of vulcanization. The reaction of 2,2Ј-dithiobisbenzothiazole with BIIR and BPMN produced a stable adduct that reduced the concentration of allylic bromide available for vulcanization.

Thioether derivatives of brominated poly(isobutylene‐co‐isoprene) (BIIR) were prepared through base‐mediated nucleophilic substitution reactions of the elastomer with thiolate ions formed in situ from thiols. The characterization of the reaction products was accomplished with studies of a model compound, brominated 2,2,4,8,8‐pentamethyl‐4‐nonene, the reactivity of which was shown to be consistent with that of the polymer. The reaction of aliphatic thiols with the allylic bromide functionality of BIIR required a strong base, and base‐catalyzed air oxidation of the thiol to disulfide operated concurrently to reduce the yield of the desired substitution products. An efficient and direct method of coupling BIIR to silica with (3‐mercaptopropyl)trimethoxysilane improved filler dispersion, thereby overcoming problematic agglomeration of reinforcing siliceous fillers in these compounds. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2937–2944, 2002