Structure–Property Relationships in CO₂-philic (Co)polymers: Phase Behavior, Self-Assembly, and Stabilization of Water/CO₂ Emulsions

Abstract

This Review provides comprehensive guidelines for the design of CO2-philic copolymers through an exhaustive and precise coverage of factors governing the solubility of different classes of polymers. Starting from computational calculations describing the interactions of CO2 with various functionalities, we describe the phase behavior in sc-CO2 of the main families of polymers reported in literature. The self-assembly of amphiphilic copolymers of controlled architecture in supercritical carbon dioxide and their use as stabilizers for water/carbon dioxide emulsions then are covered. The relationships between the structure of such materials and their behavior in solutions and at interfaces are systematically underlined throughout these sections.

Synthesis of fluorinated nanoparticles via RAFT dispersion polymerization-induced self-assembly using fluorinated macro-RAFT agents in supercritical carbon dioxide

“…According to the literature, 33,34 uorinated polymers exhibit high solubility (>10 wt%) at 25-65 C under 35 MPa, such as polyuoroacrylates or polyuoroethers. On the contrary, other hydrocarbon-based polymers except some poly(propylene oxide) (PPO)-based oligomers or poly(ethylene oxide) (PEO)-based oligomers show solubility lower than 0.1 wt% (or completely insoluble) even at the molecular weight as low as 1700, such as polystyrene, poly(methyl methacrylate), etc.…”

Modeling Solvation in Supercritical CO2

“…[132] The importance of structure-property relationships in the design of new co-polymers that are soluble in scCO 2 has been recentlys tressed by somec omprehensive review work. [133] A detailedd escription of the studies that have been performed to investigate the interactions of CO 2 with molecules containing fluorine,n itrogen and oxygen atoms, as well as those containing phosphate or sulfoxideg roups can be found in that paper.I nt he followings ections, we focus on theoretical analysis of the interactions with fluorinated and carbonyl compounds,w ith special attention paid to sugar acetate derivatives, because these molecules and groups have been particularly relevant for chemicalapplicationsofs cCO 2 .…”

Scalable synthesis of an architectural library of well‐defined poly(acrylic acid) derivatives: Role of structure on dispersant performance

“…As an illustrative example, polyethylene, one of the simplest and most widely used commodity polymers, can be either a high strength or ductile material, depending on the degree of backbone branching . Significantly, solubility, crystallinity, and morphology are also dictated by polymer architecture . While a systematic understanding of the influence of these structural features on polymer properties would be highly beneficial, studies that tune and compare architectural isomers are synthetically challenging.…”

“…4 Significantly, solubility, crystallinity, and morphology are also dictated by polymer architecture. [5][6][7][8][9][10][11][12] While a systematic understanding of the influence of these structural features on polymer properties would be highly beneficial, studies that tune and compare architectural isomers are synthetically challenging. and filler particles (e.g., calcium carbonate, CaCO 3 ), with the specific aim of achieving uniform dispersions, improving particle stability, and increasing the dispersant efficiency.…”