ABSTRACT
The successful synthesis of poly(aryl cyanurate) nanofiltration membranes via the interfacial polymerization reaction between cyanuric chloride and 1,1,1-tris(4-hydroxyphenyl)ethane (TPE), atop a polyethersulfone ultrafiltration support, is demonstrated. The use of cyanuric chloride allows for the formation of a polymer that does not contain hydrolysis-susceptible amide bonds that inherently limit the stability of polyamide nanofiltration membranes. In order to achieve a thin defect-free cross-linked film via interfacial polymerization, a sufficient number of each monomer should react. However, the reactivities of the second and third chloride groups of the cyanuric chloride are moderate. Here, this difficulty is overcome by the high functionality and the high reactivity of TPE. The membranes demonstrate a typical nanofiltration behavior, with a molecular weight cutoff of 400 ± 83 g·mol-1 and a permeance of 1.77 ± 0.18 L·m-2 h-1 bar-1. The following retention behavior Na2SO4 (97.1%) > MgSO4 (92.8%) > NaCl (51.3%) > MgCl2 (32.1%) indicates that the membranes have a negative surface charge. The absence of amide bonds in the membranes was expected to result in superior pH stability as compared to polyamide membranes. However, it was found that under extremely acidic conditions (pH = 1), the performance showed a pronounced decline over the course of 2 months. Under extremely alkaline conditions (pH = 13), after 1 month, the performance was lost. After 2 months of exposure to moderate alkaline conditions (pH = 12), the MgSO4 retention decreased by 14% and the permeance increased by 2.5-fold. This degradation was attributed to the hydrolysis of the aryl cyanurate bond that behaves like an ester bond.
ABSTRACT
Poly(ethylene furanoate) (PEF) is widely advocated as a renewable alternative to the fossil-based polyester poly(ethylene terephthalate) (PET). Whereas the UV stability of PET is well-studied, little is known for PEF. Here, we compare the UV stability of both polyesters after 500 h of UV irradiation in a Q-SUN xenon arc chamber. Both the virgin and irradiated polyesters were characterized by FTIR, SEC, DSC, NMR, TGA, and MALDI-TOF MS. PET showed only minor signs of degradation under the applied test conditions, while PEF showed significant discoloration as well as evidence of both cross linking/chain extension and chain scission. Also, the thermal properties and the ability to crystallize of PEF were severely impacted by UV irradiation. Although a detailed study on the degradation mechanism is out of the scope of this work, we found indications that Norrish type I and II degradation reactions play an important role in the UV degradation of PEF.
