RESUMEN
The development of cleaner, more environmentally friendly processes in polymerization technology is crucial due to the prevalent use of volatile organic solvents (VOCs), which are harmful and toxic. Future regulations are likely to limit or ban VOCs. This review explores the use of supercritical solvents, specifically supercritical CO2 (scCO2), in polymerization processes. The study focuses on reversible addition-fragmentation chain-transfer (RAFT) induced homo-polymerization of various monomers using specific chain transfer agents (CTAs) in scCO2. RAFT polymerization, a reversible deactivation radical polymerization (RDRP) polymerization, relies heavily on the choice of CTA, which significantly influences the dispersity and molar mass of the resulting polymers. Stabilizers are also crucial in controlling product specifications for polymerizations in supercritical CO2, except for fluor-based polymers, although they must be removed and preferably recycled to ensure product purity and sustainability. The review notes that achieving high molar mass through RAFT polymerization in scCO2 is challenging due to solubility limits, which lead to polymer precipitation. Despite this, RAFT polymerization in scCO2 shows promise for sustainable, circular production of low molar mass polymers, although these cannot yet be fully considered green products.
RESUMEN
A biorenewable polymer is synthesized via a green process using the RAFT principle for the first time in supercritical CO2 at 300 bar and 80 °C. α-Methylene-γ-butyrolactone polymers of various chain lengths and molecular weights are obtained. The molecular weights vary from 10 000 up to 20 000 with low polydispersity indexes (PDI <1.5). Furthermore, the monomer conversion in supercritical CO2 is substantially higher, respectively 85% for ScCO2 compared to ≈65% for polymerizations conducted in dimethyl formamide (DMF) solvent. Chain extensions are carried out to confirm the livingness of the formed polymers in ScCO2 . This opens up future possibilities of the formation of different polymer architectures in ScCO2 . The polymers synthesized in ScCO2 have glass transition temperature (Tg ) values ranging from 155 up to 190 °C. However, the presence of residual monomer encapsulated inside the formed polymer matrix affects the glass transition of the polymer that is lowered by increasing monomer concentrations. Hence, additional research is required to eliminate the remaining monomer concentration in the polymer matrix in order to arrive at the optimal Tg .
Asunto(s)
Dióxido de Carbono , Polímeros , Peso Molecular , Polimerizacion , TemperaturaRESUMEN
We have developed a cross-linked polyethyleneimine non-porous material (PEI "snow") for direct air capture (DAC) of CO2. This new hydrogel is green, inexpensive, readily scalable and can be fabricated through simple crosslinking of PEI with triglycidyl trimethylolpropane ether (TTE) in 10 minutes. It demonstrates outstanding DAC performance (overall CO2 uptake efficiency of approximately 50 mg g-1 of sorbent) at lab scale (sorbent weight roughly 60 g, air flow rate 2000 ml min-1) and the CO2 can be desorbed using low-grade waste steam.