Polarity-balanced binary-solvent route for solvent-limited synthesis of low-viscosity polyanionic cellulose (PAC-LV)
摘要
We present an industrially relevant route for producing low-viscosity polyanionic cellulose (PAC-LV) at a fixed solvent-to-cellulose ratio of 1:1 (w/w) by tuning binary-solvent polarity to sustain the semi-biphasic environment required for selective alkalization and uniform etherification. Forty-five alcohol/ketone combinations were screened under constant stoichiometry (≈48% NaOH; NaMCA≈1:1 per glucose residue). Performance depended non-linearly on polarity: very low polarity limited NaOH/NaMCA diffusion, whereas over-polar media lost interfacial structure and reduced substitution efficiency. A narrow intermediate window—best exemplified by isopropanol–ethanol (40:60, w/w)—delivered DS ≈ 0.85, FV ≈ 13–14 mL, and active matter ≈ 73–75%, fully meeting API 13A filtration requirements. Mixed alcohol–ketone systems (MEK–EtOH 50:50; acetone–EtOH 50:50) also achieved low FV with high purity, while methanol-rich systems underperformed. An inverse DS–FV relationship held across classes but plateaued near DS ≈ 0.85; forcing DS higher via reagent excess increased by-products (NaCl, sodium glycolate) and lowered active matter, indicating the functional optimum is the DS that secures API-compliant FV while maximizing purity. Robustness was confirmed by independent repeats (n = 5 per top system) and benchmarking versus a commercial PAC-LV reference (similar FV at markedly higher purity under the same 1:1 solvent load). Pilot-scale runs (≈10 kg cellulose/batch) reproduced laboratory trends. Overall, polarity balance governs phase stability, reagent accessibility, and product quality, enabling a scalable, energy-efficient PAC-LV process whose higher initial active matter also reduces the downstream burden when purified grades (≥ 95%) are required.
Graphical abstract