The global market size of paints and coatings (P&C) was US$164 Billion in 2022 and is forecast to grow to US$241Billion by 2030. A fast-growing sector in the P&C industries is acrylics. P&C should contain a solvent in order to be brushable/sprayable. However, in the case of solvent-borne P&C, their improved sustainability requires decreasing their organic solvent contents. This sustainability-applicability tradeoff can be addressed by preparing P&C from polymers with lower average molecular weights, which can be produced via high-temperature (> 130 °C)free-radical polymerization. However, at these temperatures, several reactions — that are of little significance at low temperatures — strongly affect the polymer product quality. These so-called secondary reactions include monomer self-initiation, monomer-solvent and monomer-molecular oxygen co-initiation, depropagation, β-scission, and backbiting. We have made advances in quantum-level polymerization reaction modeling — that have enabled us to discover new reactions and fundamentally study previously known reactions in thermal polymerization of acrylates — as well as in macroscopic-scale mechanistic modeling and optimization of high-temperature polymerization reactors. Sample results from these studies will be presented. They will include new theoretical and experimental insights that can be used to produce more sustainable, higher-quality acrylic P&C at lower costs. The self-initiation of acrylates at high temperatures improves the polymer quality and reduces the operating costs due to less or no use of relatively expensive conventional initiators.