Synthesis and characterization of furan based polyamides and polyureas

Abstract

Aromatic polyamides (PAs) are widely used as high-performance polymers in technical applications due to their unique combination of outstanding thermal, optical, mechanical and chemical properties. Although PAs are mostly utilized where strength or heat resistance is of primary concern, they also find use in other important applications such as in NOMEX membranes for desalination of brackish water or seawater. PAs do however have some disadvantages such as high melting points, high glass transition temperatures (T 9) and a limited solubility in most organic solvents, wh.ich makes their processing difficult. Polyureas (PUs) are generally known for their excellent thermal stability and high chemical resistance due to the presence of thermally stable bonds of aromatic or heterocyclic ring systems along their backbone. Both polymer systems are poorly researched when it comes*' the introduction of furan units into the chains. The same is valid for cases where two or more different diacids or diamines are incorporated. The aim of this study was therefore to investigate the influence of furan units in the polymer chains and the change in properties if the composition of starting materials is varied further. Nineteen PAs were prepared via the interfacial polymerization method and the homogeneous phase polymerization method. These polymers were prepared either with furan- or isophthalic acids in their chains and then compared with the copolymers, containing both diacids in different ratios. Products were characterized by various analytical techniques. Furanoyl-2,5-dichloride (FDC) and different amounts of isophthaloyl chloride (IPDC) - 0, 10, 30 and 50% - as the basic starting monomers were reacted individually with four diamines: m-phenylen diamine (MPD), 4,4'-diamino diphenylsulfone (DDS), 4,4'-diamino diphenylether (ODE) and 2,4-bis(4-aminophenyl)-6-phenyl-1,3,5-triazine-2,4,6-triamine (BAT) by interfacial or homogeneous polycondensation reactions.

Two polyureas, starting with furanoyl-2,5-diazide (FDZ) and transformed into the diisocyanate were prepared by reaction with two diamines, namely MPD and DDS in homogeneous solution. The PAs and PUs were characterized by Fourier-Transform Infrared Spectroscopy (FTIR), Proton NMR CH), Carbon NMR C3C), Gel Permeation Chromatography (GPC), Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC). The water up-take per polymer unit (mol water I repeat unit of the polymer) was measured. The values for 70% Relative Humidity (RH) were between 0.87 and 1 ~80 moles of water per repeat unit and for 43% RH between 0.40 and 1.35 mols.