It is shown that the water vapor permeability of polyurethanes obtained on the basis of sterically hindered aminoethers of boric acid is due to the peculiarities of the chemical structure of AEBA.
The etherification of ortho-phosphoric acid with triethanolamine and polyoxypropylene glycol is studied. The reaction process is accompanied by the formation of hyperbranched amino ethers of ortho-phosphoric acid terminated by hydroxyl groups. A specific feature of the chemical structure of the compounds obtained is the existence of ion pairs in their structure separated in space. The reaction of the etherification of ortho-phosphoric acid with glycols becomes possible through the use of tertiary amines. The amino ethers of ortho-phosphoric acid are investigated as a polyol component for the synthesis of polyurethanes with high adhesion characteristics and strength properties. The experimental results presented allow us to relate polyurethanes obtained on the basis of ortho-phosphoric acid amino ethers to polymers of ionomeric nature.
Polyurethanes based on the aminoethers of ortho-phosphoric acid and polyisocyanates of an aliphatic nature were studied as a substrate for the preparation of new polymer electrolyte. The conductivity of polyurethane ionomer samples obtained using the optimal amount of aliphatic polyisocyanates and after keeping them in a 1 M LiBF4 solution in γ-butyrolactone reaches 0.62 mS cm−1. It has been established that the transport of positively charged ions through the polymer matrix is due to the formation of clusters of phosphate ions and their association into the conducting channels. The introduction of carboxylate ions into the conducting channels by modifying the aminoethers of ortho-phosphoric acid with phthalic anhydride leads to an increase in their size and rise in the mobility of cations. As a result, the conductivity of polyurethane gel electrolytes increased to 2.1 mS cm−1.
Organophosphorus polyurethane ionomers (AEPA-PU) based on aminoethers of ortho-phosphoric acid (AEPA) were obtained and studied as pervaporation membrane materials for separating isopropanol/water mixtures. The regularities of the change in the water vapor permeability of AEPA-PU were also investigated. It has been established that an increase of solute content in the composition of the urethane-forming system and the content of ionogenic groups in AEPA leads to a noticeable increase in the vapor permeability of the resulting film materials. An increase in water vapor permeability values is accompanied by a significant increase in the pervaporation characteristics of AEPU-PU. It was shown that the conditions promoting clustering of phosphate anions cause an increase in the values of the vapor permeability coefficient of AEPA-PU obtained using polyoxypropylene glycol. However, the hydrophobicity of the polypropylene glycol surrounding the clusters makes it difficult for water to move through the polymer matrix. Due to the hydrophilicity of polyoxyethylene glycol, the highest values of water vapor permeability and pervaporation characteristics are achieved for AEPA-PU synthesized using PEG.
The etherification reaction of ortho-phosphoric acid (OPA) with polyoxypropylene glycol in the presence of tertiary amines was studied. The reaction conditions promoting the catalytic activity of triethanolamine (TEOA) and triethylamine (TEA) in the low-temperature etherification of OPA were established. The catalytic activity of TEOA and TEA in the etherification reaction of phosphoric acid is explained by the hydrophobic-hydrophilic interactions of TEA with PPG, leading, as a result of collective interactions, to a specific orientation of polyoxypropylene chains around the tertiary amine. When using triethylamine, complete etherification of OPA occurs, accompanied by the formation of branched OPA ethers terminated by hydroxyl groups and even the formation of polyphosphate structures. When triethanolamine is used as a catalyst, incomplete etherification of OPA with polyoxypropylene glycol occurs and as a result, part of the phosphate anions remain unreacted in the composition of the resulting aminoethers of ortho-phosphoric acid (AEPA). In this case, the hydroxyl groups of triethanolamine are completely involved in the OPA etherification reaction, but the catalytic activity of the tertiary amine weakens due to a decrease in its availability in the branched structure of AEPA. The kinetics of the etherification reaction of OPA by polyoxypropylene glycol catalyzed by TEOA and TEA were studied. It was shown that triethanolamine occupies a central position in the AEPA structure. The physico-mechanical and thermomechanical properties of polyurethane ionomer films obtained on the basis of AEPA synthesized in a wide temperature range were studied.
Polymers with micro- and mesoporous structure are promising as materials for gas storage and separation, encapsulating agents for controlled drug release, carriers for catalysts and sensors, precursors of nanostructured carbon materials, carriers for biomolecular immobilization and cellular scaffolds, as materials with a low dielectric constant, filtering/separating membranes, proton exchange membranes, templates for replicating structures, and as electrode materials for energy storage. Sol–gel technologies, track etching, and template synthesis are used for their production, including in micelles of surfactants and microemulsions and sublimation drying. The listed methods make it possible to obtain pores with variable shapes and sizes of 5–50 nm and achieve a narrow pore size distribution. However, all these methods are technologically multi-stage and require the use of consumables. This paper presents a review of the use of macromolecular architecture in the synthesis of micro- and mesoporous polymers with extremely high surface area and hierarchical porous polymers. The synthesis of porous polymer frameworks with individual functional capabilities, the required chemical structure, and pore surface sizes is based on the unique possibilities of developing the architecture of the polymer matrix.