Cross-Linking and Evaluation of the Thermo-Mechanical Behavior of Epoxy Based Poly(ionic Liquid) Thermosets

Poly(ionic liquids) (PILs) and ionenes are polymers containing ionic groups in their repeating units. The unique properties of these polymers render them as interesting candidates for a variety of applications, such as gas separation membranes and polyelectrolytes. Due to the vast number of possible structures, numerous synthesis protocols to produce monomers with different functional groups for task-specific PILs are reported in literature. A difunctional epoxy-IL resin was synthesized and cured with multifunctional amine and anhydride hardeners and the thermal and thermomechanical properties of the networks were assessed via differential scanning calorimetry and dynamic mechanical analysis. By the selection of suitable hardeners, the glass transition onset temperature (Tg,onset) of the resulting networks was varied between 18 °C and 99 °C. Copolymerization of epoxy-IL with diglycidyl ether of bisphenol A (DGEBA) led to a further increase of the Tg,onset. The results demonstrate the potential of epoxy chemistry for tailorable PIL networks, where the hardener takes the place of the ligands without requiring an additional synthesis step and can be chosen from a broad range of commercially available compounds.

Simple linear ionic polysiloxane showing unexpected nanostructure and mechanical properties

Polysiloxanes are ubiquitous materials in industry and daily life derived from silicates, an abundant resource. They exhibit various properties, which depend on the main-chain network structure. Linear (1D backbone) polysiloxanes provide amorphous materials. They are recognized as fluid materials in the form of grease or oil with a low glass transition temperature. Herein we report that a simple linear polysiloxane, poly(3-aminopropylmethylsiloxane) hydrochloride, shows an elastic modulus comparable to that of stiff resins such as poly(tetrafluoroethylene). By introducing an ammonium salt at all the units of this polysiloxane, inter- and intramolecular ionic aggregates form, immensely enhancing the elastic modulus. This polysiloxane is highly hygroscopic, and its modulus can be altered reversibly 100 million times between moist and dry atmospheres. In addition, it works as a good adhesive for glass substrates with a shear strength of more than 1 MPa in the dry state. Despite its simple structure with a flexible backbone, this polymer unexpectedly self-assembles to form an ordered lamellar nanostructure in dry conditions. Consequently, this work reveals new functions and possibilities for polysiloxanes materials by densely introducing ionic groups.

Transition Metal (II) Complexes of (E)-N-(4-methylbenzylidene)-2-((Z)-(4-methylbenzylidene)amino)benzamides: Synthesis, Characterization and their Biological Evaluation

In this paper, cerium sulfate tetrahydrate (Ce(IV)) dissolved in acid-aqueous medium and mercaptosuccinic acid (MSA) redox couple was used to synthesize the crosslinked copolymer of acrylamide (AAm), lithium methacrylate (LiMA), and N,N’-methylene bisacrylamide (MBAAm) in the presence of ethylenediaminetetraacetic acid tetrasodium salt (EDTANa4). The effects of various mole amounts of AAm and LiMA at constant crosslinker concentration and mole amounts of total monomer/MBAAm at constant amounts of AAm and LiMA on the swelling behaviors and swelling kinetics of synthesized hydrogels were investigated in distilled water. The use of hydrogel, including lithium methacrylate ionic groups, for the removal of copper ions from aqueous solutions was examined by using the batch adsorption method. In the adsorption process of copper ions on hydrogels containing LiMA groups, the effects of parameters such as the amount of hydrogel, initial Cu(II) concentration, adsorption time, and pH of solution were investigated.

Synthesis and Swelling Behaviors of Hydrogels Containing LiMA Groups and its Use in Cu(II) Adsorption from Aqueous Solution

In this paper, cerium sulfate tetrahydrate (Ce(IV)) dissolved in acid-aqueous medium and mercaptosuccinic acid (MSA) redox couple was used to synthesize the crosslinked copolymer of acrylamide (AAm), lithium methacrylate (LiMA), and N,N’-methylene bisacrylamide (MBAAm) in the presence of ethylenediaminetetraacetic acid tetrasodium salt (EDTANa4). The effects of various mole amounts of AAm and LiMA at constant crosslinker concentration and mole amounts of total monomer/MBAAm at constant amounts of AAm and LiMA on the swelling behaviors and swelling kinetics of synthesized hydrogels were investigated in distilled water. The use of hydrogel, including lithium methacrylate ionic groups, for the removal of copper ions from aqueous solutions was examined by using the batch adsorption method. In the adsorption process of copper ions on hydrogels containing LiMA groups, the effects of parameters such as the amount of hydrogel, initial Cu(II) concentration, adsorption time, and pH of solution were investigated.

Simple Linear Ionic Polysiloxane Showing Unexpected Nanostructure and Mechanical Properties

Polysiloxanes are ubiquitous materials in industry and daily life derived from silicates, an abundant resource. They exhibit various properties, which depend on the main-chain network structure. Linear (1D backbone) polysiloxanes provide amorphous materials. They are recognized as fluid materials in the form of grease or oil with a low glass transition temperature. Herein we report that a simple linear polysiloxane, poly(3-aminopropylmethylsiloxane) hydrochloride, shows an elastic modulus comparable to that of stiff resins such as poly(tetrafluoroethylene). By introducing an ammonium salt at all the units of this polysiloxane, inter- and intramolecular ionic aggregates form, immensely enhancing the elastic modulus. This polysiloxane is highly hygroscopic, and its modulus can be altered reversibly 100 million times between moist and dry atmospheres. In addition, it works as a good adhesive for glass substrates with a shear strength of more than 1 MPa in the dry state. Despite its simple structure with a flexible backbone, this polymer unexpectedly self-assembles to form an ordered lamellar nanostructure in dry conditions. Consequently, this work reveals new functions and possibilities for polysiloxanes materials by densely introducing ionic groups.

Enzyme-induced mineralization of hydrogels with amorphous calcium carbonate for fast synthesis of ultrastiff, strong and tough organic–inorganic double networks

Hydrogels with good mechanical properties have great importance in biological and medical applications. Double-network (DN) hydrogels were found to be very tough materials. If one of the two network phases is an inorganic material, the DN hydrogels also become very stiff without losing their toughness. So far, the only example of such an organic–inorganic DN hydrogel is based on calcium phosphate, which takes about a week to be formed as an amorphous inorganic phase by enzyme-induced mineralization. An alternative organic–inorganic DN hydrogel, based on amorphous CaCO3, which can be formed as inorganic phase within hours, was designed in this study. The precipitation of CaCO3 within a hydrogel was induced by urease and a urea/CaCl2 calcification medium. The amorphous character of the CaCO3 was retained by using the previously reported crystallization inhibiting effects of N-(phosphonomethyl)glycine (PMGly). The connection between organic and inorganic phases via reversible bonds was realized by the introduction of ionic groups. The best results were obtained by copolymerization of acrylamide (AAm) and sodium acrylate (SA), which led to water-swollen organic–inorganic DN hydrogels with a high Young’s modulus (455 ± 80 MPa), remarkable tensile strength (3.4 ± 0.7 MPa) and fracture toughness (1.1 ± 0.2 kJ m−2). Graphical Abstract The present manuscript describes the method of enzymatic mineralization of hydrogels for the production of ultrastiff and strong composite hydrogels. By forming a double-network structure based on an organic and an inorganic phase, it is possible to improve the mechanical properties of a hydrogel, such as stiffness and strength, by several orders of magnitude. The key to this is the formation of a percolating, amorphous inorganic phase, which is achieved by inhibiting crystallization of precipitated amorphous CaCO3 with N-(phosphonomethyl)glycine and controlling the nanostructure with co polymerized sodium acrylate. This creates ultrastiff, strong and tough organic–inorganic double-network hydrogels.

Silver- and Zinc-Decorated Polyurethane Ionomers with Tunable Hard/Soft Phase Segregation

Segmented polyurethane ionomers find prominent applications in the biomedical field since they can combine the good mechanical and biostability properties of polyurethanes (PUs) with the strong hydrophilicity features of ionomers. In this work, PU ionomers were prepared from a carboxylated diol, poly(tetrahydrofuran) (soft phase) and a small library of diisocyanates (hard phase), either aliphatic or aromatic. The synthesized PUs were characterized to investigate the effect of ionic groups and the nature of diisocyanate upon the structure–property relationship. Results showed how the polymer hard/soft phase segregation was affected by both the concentration of ionic groups and the type of diisocyanate. Specifically, PUs obtained with aliphatic diisocyanates possessed a hard/soft phase segregation stronger than PUs with aromatic diisocyanates, as well as greater bulk and surface hydrophilicity. In contrast, a higher content of ionic groups per polymer repeat unit promoted phase mixing. The neutralization of polymer ionic groups with silver or zinc further increased the hard/soft phase segregation and provided polymers with antimicrobial properties. In particular, the Zinc/PU hybrid systems possessed activity only against the Gram-positive Staphylococcus epidermidis while Silver/PU systems were active also against the Gram-negative Pseudomonas aeruginosa. The herein-obtained polyurethanes could find promising applications as antimicrobial coatings for different kinds of surfaces including medical devices, fabric for wound dressings and other textiles.