Nonaqueous Interfacial Polymerization-Derived Polyphosphazene Films for Sieving or Blocking Hydrogen Gas

A series of cyclomatrix polyphosphazene films have been prepared by nonaqueous interfacial polymerization (IP) of small aromatic hydroxyl compounds in a potassium hydroxide dimethylsulfoxide solution and hexachlorocyclotriphosphazene in cyclohexane on top of ceramic supports. Via the amount of dissolved potassium hydroxide, the extent of deprotonation of the aromatic hydroxyl compounds can be changed, in turn affecting the molecular structure and permselective properties of the thin polymer networks ranging from hydrogen/oxygen barriers to membranes with persisting hydrogen permselectivities at high temperatures. Barrier films are obtained with a high potassium hydroxide concentration, revealing permeabilities as low as 9.4 × 10-17 cm3 cm cm-2 s-1 Pa-1 for hydrogen and 1.1 × 10-16 cm3 cm cm-2 s-1 Pa-1 for oxygen. For films obtained with a lower concentration of potassium hydroxide, single gas permeation experiments reveal a molecular sieving behavior, with a hydrogen permeance of around 10-8 mol m-2 s-1 Pa-1 and permselectivities of H2/N2 (52.8), H2/CH4 (100), and H2/CO2 (10.1) at 200 °C.ChemE/Advanced Soft MatterOLD ChemE/Organic Materials and Interface

Extraction of low molecular weight polyhydroxyalkanoates from mixed microbial cultures using bio-based solvents

(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) obtained from waste/wastewater using a mixed microbial culture (MMC) usually varies in its properties due to daily variation in the waste/wastewater composition applied as feedstock. In the current study, the average molecular weight (MW) of PHBV was purposely reduced from about 1 MDa to about 200 kDa by drying the PHBV-rich biomass at elevated temperature of 120 °C for 18 h to ease extraction and handling. Furthermore, conversion into value-added chemicals such as trans-crotonic acid (trans-CA) and trans-2-pentenoic acid (2-PA) by thermal decomposition (pyrolysis) benefits from the lower MW. For the extraction of low MW PHBV, the use of the bio-based solvents 2-methyltetrahydroxyfuran (2-MTHF) and dihydrolevoglucosenone (cyrene) was studied. The maximum extraction yield of 62 ± 3 % with purity of > 99 % was achieved with 2-MTHF at 80 °C for an hour with high biomass to solvent ratio of 5 % (g/mL). Cyrene-based extractions resulted in the highest yield of 57 ± 2 % with purity of > 99 % at 120 °C in 2 h with 5 % (g/mL) biomass to solvent ratio. The mass balance closure over the extraction process indicated that about 15 % and 10 % of polymer has remained in the residual biomass after extraction by 2-MTHF and cyrene, respectively. The performance of these new solvents to extract polymers with various average MW was compared to the benchmark extractions using chloroform and dimethyl carbonate (DMC). It was found that for the polymers with low average MW the extraction efficiency of the proposed solvents exceeds the benchmark solvents.ChemE/Advanced Soft Matte