Block Copolymer Nanoparticles Prepared via Polymerization-Induced Self-Assembly Provide Excellent Boundary Lubrication Performance for Next-Generation Ultralow-Viscosity Automotive Engine Oils

Core cross-linked poly(stearyl methacrylate)–poly(benzyl methacrylate)–poly(ethylene glycol dimethacrylate) [S31–B200–E20] triblock copolymer nanoparticles were synthesized directly in an industrial mineral oil via polymerization-induced self-assembly (PISA). Gel permeation chromatography analysis of the S31–B200 diblock copolymer precursor chains indicated a well-controlled reversible addition–fragmentation chain transfer dispersion polymerization, while transmission electron microscopy, dynamic light-scattering (DLS), and small-angle X-ray scattering studies indicated the formation of well-defined spheres. Moreover, DLS studies performed in THF, which is a common solvent for the S and B blocks, confirmed successful covalent stabilization because well-defined solvent-swollen spheres were obtained under such conditions. Tribology experiments using a mini-traction machine (MTM) indicated that 0.50% w/w dispersions of S31–B200–E20 spheres dramatically reduce the friction coefficient of base oil within the boundary lubrication regime. Given their efficient and straightforward PISA synthesis at high solids, such nanoparticles offer new opportunities for the formulation of next-generation ultralow-viscosity automotive engine oils

Well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures as pour point and viscosity modifiers for lubricating oil

A series of well-defined poly(styrene-co-maleic anhydride) copolymers (PSMA) allowing controlled grafting density and distribution of long alkyl side chains (C12 and C22) was synthesized and investigated as viscosity modifiers for two mineral base oils (API Group II and III). The PSMA copolymer backbones (multisite, multiblock, diblock, alternating linear, alternating star) were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization using an industrial chain transfer agent (CTA-Ester) and subsequently esterified using long alkyl alcohols (lauryl and behenyl alcohol). The influence of grafting density and distribution, backbone, and side chain length of the polymers on the pour point (PPT) of blended fluids was investigated. The viscosity index (VI) and thickening efficiency (TE) were also studied. All the polymers showed improvement of base oil properties (PPT, VI, and TE). The alternating PSMA materials (high density of side chains) functionalized with shorter alkyl chains (C12) were found to be more efficient as pour point depressants (PPDs), regardless of the oil type and the molar mass or architecture of the polymer tested (ΔPPT = −36 °C and −30 °C in oil groups II and III, respectively). A poly(lauryl acrylate) (PLAc) sample was also synthesized and used for comparison, showing the benefit of having styrene in the copolymer additive composition. The VI and TE properties were shown to be dependent on molar mass and architectures used, where the best results were obtained for the high molar mass PSMA star

Influence of grafting density and distribution on material properties using well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures synthesized by RAFT

Poly(styrene-co-maleic anhydride) copolymers (PSMA) with controlled number and distribution of maleic anhydride (MAnh) units were synthesized by reversible addition–fragmentation chain transfer polymerization using chain-transfer agents (CTA) suitable for industrial scale processes. Linear- and star-shaped alternating PSMA polymers were prepared in a single-step synthesis, while a one-pot sequential chain-extension strategy was utilized to prepare diblock, multiblock, and multisite copolymer architectures. A library of grafted PSMAs with controlled density and distribution of side chains was achieved by the subsequent grafting of long aliphatic alcohol chains (C22) to the MAnh units. The influence of structure, composition, and long alkyl chain addition on PSMAs behavior in solution was studied with triple-detection size exclusion chromatography, while their thermal properties were examined by thermogravimetric analysis and differential scanning calorimetry. Overall, the side chain density and distribution did not impact the polymer conformations in solution (random coil); however, an effect on the molecular size (Rh) and structure density (intrinsic viscosity) were observed. The materials density was shown to be dependent on polymer architectures as lower intrinsic viscosity was observed for the star copolymer. All the materials had similar degradation points (400 °C), while the rate of degradation showed a dependence on the MAnh content and polymeric architecture. Ultimately, the grafting of long aliphatic side chains (crystalline) onto the PSMA backbone, even at low density, was shown to drastically change the microphase ordering, as all the grafted copolymers became semicrystalline. The difference of the crystallization temperature between low density multisite materials (Tc ≈ 8 °C) and the high density alternating material (Tc ≈ 40 °C) highlights the major importance of controlling copolymer composition and structure to tune material properties

Evaluating the evidence base for relational frame theory: A citation analysis

Relational frame theory (RFT) is a contemporary behavior-analytic account of language and cognition. Since it was first outlined in 1985, RFT has generated considerable controversy and debate, and several claims have been made concerning its evidence base. The present study sought to evaluate the evidence base for RFT by undertaking a citation analysis and by categorizing all articles that cited RFT-related search terms. A total of 174 articles were identified between 1991 and 2008, 62 (36%) of which were empirical and 112 (64%) were nonempirical articles. Further analyses revealed that 42 (68%) of the empirical articles were classified as empirical RFT and 20 (32%) as empirical other, whereas 27 (24%) of the nonempirical articles were assigned to the nonempirical reviews category and 85 (76%) to the nonempirical conceptual category. In addition, the present findings show that the majority of empirical research on RFT has been conducted with typically developing adult populations, on the relational frame of sameness, and has tended to be published in either The Psychological Record or the Journal of the Experimental Analysis of Behavior. Overall, RFT has made a substantial contribution to the literature in a relatively short period of time