New stimuli-responsive polyampholyte: Effect of chemical structure and composition on solution properties and swelling mechanism

• Published in: Polymer (Guilford) 2016-11, Vol.104, p.91-103
• Main Authors: Deen, G. Roshan, Wei, Teo Tee, Fatt, Lee Kim
• Format: Article
• Language: English
• Subjects: Calorimetry; Charge density; Composition effects; Copolymerization; Copolymers; Crosslinking; Differential scanning calorimetry; Diffusion; Dye adsorption; Dyes; Gels; Heat measurement; Hydrogels; Hydrogen ions; Ionic strength; Ionization; Isoelectric points; Kinetics; Maleic acid; Mathematical models; Monomers; pH effects; Piperazine; Polyampholyte hydrogels; Polyampholytes; Polyelectrolytes; Polymerization; Polymers; Properties (attributes); Reaction kinetics; Salts; Solution polymerization; States of water; Studies; Swelling; Swelling ratio
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/j.polymer.2016.09.094

New polyampholyte linear polymers and hydrogels based on N-acryloyl-N′-ethyl piperazine (AcrNEP) and maleic acid (MaA) were prepared by free-radical solution polymerization. The microstructure of copolymers was statistically estimated by the terminal copolymerization model. A maximum tendency (80%) of alternating sequence of monomers units occurred at about 85 mol % of AcrNEP in the reaction feed. The copolymers at definite monomer compositions (40 mol % of AcrNEP and 59.6 mol % of MaA) exhibited lower critical solution temperature (LCST) behavior in water. The LCST was dependent on monomer composition, pH of external solution, type and concentration of simple salts. The isoelectric points (IEP) of copolymers were found to be influenced by the overall composition of ionic monomer units. The influence of high maleic acid content (14 mol % and 59 mol %) and the type of chemical crosslinker on pH-responsive swelling behavior, water diffusion and dye sorption properties of the hydrogels were studied in detail. The gels exhibited interesting swelling behavior as function of pH (ionic strength = 0.01 M) due to a combination of factors such as pKa of the monomers, charge density, and type of crosslinker. The IEP of the gels were also determined from swelling experiments. The swelling ratio of the gels increased at the IEP with increase in ionic strength of the solution due to anti-polyelectrolyte effect. However below the IEP, the swelling ratio decreased considerably. Dynamic swelling properties of the amphoteric gels in water without added salt were measured. The swelling behavior was found to depend on the ionization state of the monomers, and the swelling followed non-Fickian (anomalous) mechanism. The swelling process of the hydrogels in water followed second-order kinetics. The amount of bound and unbound water in swollen gels was quantified using differential scanning calorimetry. Dye adsorption capacity of the new hydrogels was investigated using a Congo red as a model dye and was in the range 8.37–11.45 mg g−1. This corresponds to an absorption efficiency of range 68–93%. The solution properties and swelling behavior of new smart polyampholytes were investigated. The swelling behavior was found to depend on the ionization state of the monomers and their composition. The gels showed promise in dye removal applications and can be exploited in the development of stimuli-responsive sorbents. [Display omitted] •New stimuli-responsive polyampholytes (linear an