Radical Polymerization of Acrylates, Methacrylates, and Styrene: Biobased Approaches, Mechanism, Kinetics, Secondary Reactions, and Modeling

Abstract

Biobased polymer molecules are a goal for the future. Here, the different intermediate pathways toward renewable structural constituents, which can substitute petrochemically derived unsustainable ones, are evaluated. Various biomass resources are covered, such as cellulose, hemicellulose, lignin, lipids, and proteins, as well as their building blocks, such as sugars, glycerol, or itaconic acid. Further emphasis is put on the impact of the impurities in the biobased monomers and the possible separations steps to remove them. The kinetics of the radical polymerization process of reacting acrylic monomers, methacrylic monomers, and styrene is reviewed. Classical elementary mechanisms are briefly discussed, while focus is put on secondary chemical reactions that influence rates greatly at elevated system temperatures, starved-feed conditions, and unideal-mixed reactor units. These functional measures have now become a common standard practice in resin production manufacturing. Described breaking/forming transformations are the styrene self-initiation step, macromonomer carrier propagation, backbiting, long chain branching, β-scission, and methacrylate continuous depropagation. The effect of the copolymerization on involved occurring changes is also overviewed. Likewise, functionality now plays a much greater role than it used to, is linked to final formulation characteristics, and is thus an integral related part of this theoretical methodology. Cross-linking mechanisms are briefly discussed. Last but not least, an insight into modeling is presented with an emphasis on lumping, the method of moments, Monte Carlo applications, and simulating conversions, as well as correlated molecular mass distributions.

Polymers without Petrochemicals: Sustainable Routes to Conventional Monomers

“…Acrylic acid is one of the most important industrial chemicals and its alkyl esters are widely used in products such as paints, coatings and adhesives. − Acrylic acid is produced from petrochemicals through the oxidation of propene. ,− Nonetheless, acrylic acid can be produced sustainably from bio-sources including glycerol, lactic acid, 3-HPA and acetic acid, as illustrated in Figure . ,− …”

“…The value of using glycerol has increased as it is a readily available bio-source due to its formation as a by-product in biodiesel production. ,, Acrylic acid can be synthesized from glycerol by either a two- or one-step process (Figure ). , In one reported two-step synthesis, a double dehydration forms the intermediate acrolein, which then undergoes an oxidation to form acrylic acid.…”

Effect of Copolymer on the Wrinkle Structure Formation and Gloss of a Phase-Separated Ternary Free-Radical/Cationic Hybrid System for the Application of Self-Matting Coatings

“…On the other hand, the (meth)acrylate conversion (Figure 6B) was rather consistent throughout the film thickness, with a relatively low average conversion close to 20%. This low conversion is characteristic of a methacrylate system, with a rate of polymerization rate much lower than its acrylate equivalent, due to the formation of stable ternary radicals [53].…”

Nanoplastic Labelling with Metal Probes: Analytical Strategies for Their Sensitive Detection and Quantification by ICP Mass Spectrometry

“…For instance, the pH of the resulting mixture represents a pivotal parameter since the labelling of nanoplastics through electrostatic interactions using AuNPs@gel requires negatively charged nanoplastics (i.e., carboxylated) and positively charged gold nanoparticles. The literature reports pKa of 4.1 and 4.5, respectively, for the acrylic acid monomer and the poly(acrylic acid) [ 38 , 39 ]. As a consequence, at a pH of 5.5, carboxylic groups are overwhelmingly deprotonated.…”