Comb dispersants suitable for stabilization of carbonaceous deposits found in automotive lubricating oils were derived from the copolymerization of vinyl‐ether terminated polyisobutylene (VE‐PIB) macromonomers with maleic anhydride (MAH). The rate and degree of copolymerization of VE‐PIB with MAH was greatly influenced by the molecular weight of the VE‐PIB. Longer PIB tails imposed greater hindrance of the chain end resulting in slower propagation and lower degrees of copolymerization for PIB‐alt‐MAH copolymers. Functionalization of PIB‐alt‐MAH with a polyamine proceeded smoothly at elevated temperatures as evidenced by disappearance of anhydride stretches via Fourier transform infrared spectroscopy. Analogous linear and grafted dispersants were prepared to investigate the influence of architecture on the physical properties of the dispersants. Characterization of the intermediates and final dispersants was conducted by nuclear magnetic resonance, gel permeation chromatography, thermogravimetric analysis, and ultraviolet–visible. Using Langmuir adsorption studies and carbon black as a substitute for carbonaceous deposits, it was found that comb and grafted dispersants exhibit greater affinities for adsorption but decreased packing efficiencies in comparison to linear dispersants. Rheological studies investigating viscosity as a function of loading for dispersant/oil mixtures with carbon black present a similar finding. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1682–1696

Lubricating oils for gasoline and diesel engines are formulated to include amphiphilic dispersants for soot particle stabilization and prevention of particle aggregation. Primary and secondary amines used within the polar group of traditional dispersants provide basic nitrogen, which is able to neutralize acidic by‐products from combustion and does not contribute to sulfated ash. However, these active‐hydrogen‐containing amines present significant problems for fluoroelastomer seals and metals in terms of degradation and corrosion. Polyisobutylene (PIB)‐based dispersants containing only tertiary amines, intended to remediate these problems, were synthesized from primary‐bromide‐terminated PIB, 1‐(2‐aminoethyl)piperazine, and an anhydride such as phthalic anhydride. Intermediates and final dispersant molecules were characterized by NMR, GPC, TGA, and MALDI‐TOF MS. Using Langmuir adsorption studies with carbon black as a surrogate for soot, a direct dependence on the affinity for adsorption of the dispersant with respect to the number of phenyl rings present was identified. Performance testing revealed increased compatibility of the dispersants, including limited degradation of seals and corrosion of metals, while retaining total base number. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1657–1675