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 LiBF
4
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
.
Polyurethanes based on the aminoethers of
ortho
-phosphoric acid and polyisocyanates of an aliphatic nature were studied as a substrate for the preparation of a new polymer electrolyte.
It is well-known that various mixtures that require separation have to be dealt with in many branches of industry, especially the chemical and petrochemical industries ....
The hyperbranched polymers have drawn intensive attention in the design of macromolecules and functional materials because of their unique physical and chemical properties resulting from the branched ...architecture and the high number of functional groups. In the present study, by means of light scattering, viscosimetry, thermomechanical analysis, tensile stress-strain, mechanical loss tangent and water vapor permeability measurements, we demonstrate the hierarchical macromolecular organization of organoboron polyurethanes synthesized using sterically hindered amino ethers (AEBA) of boric acid. 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, which can exhibit an ionomeric nature and the presence of steric hindrances created in the hyperbranched structure of AEBA, which can lead to an increase in free volume in such polyurethanes.
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 influence of stable-to-self-condensation Cu(II)-coordinated polyoxyethylene-substituted silicas (ASiP-Cu-0.5) on the synthesis of microporous block copolymers (OBCs) whose structural feature is ...the existence of coplanar polyisocyanate blocks of acetal nature (O-polyisocyanates) and a flexible-chain component of amphiphilic nature was studied. The use of ASiP-Cu-0.5 increased the yield of O-polyisocyanate blocks and the microphase separation of OBC. The resulting OBCs turned out to be effective sorbents for the analytical reagents PAN and PHENAZO, which, being in the micropore cavity, interacted with copper(II) and magnesium ions. To reduce the thickness of the selective OBC layer ten-fold and simplify the technology for obtaining analytical test systems, polyethylene terephthalate was used as a substrate for applying OBC. It was found that the increased sensitivity of the resulting test systems was due to the fact that in thin reaction layers, the efficiency of the formation of O-polyisocyanate blocks noticeably increased.
New crosslinked (polydimethylsiloxane-ethylene-propylene oxide)-polyisocyanurate multiblock copolymers (MBCs) were synthesized, and their supramolecular structure and sorption characteristics were ...studied. It was found that the interaction of PPEG and D4 leads to polyaddition of D4 initiated by potassium-alcoholate groups. The use of the amphiphilic silica derivatives associated in an oligomeric medium (ASiPs) leads to structuring of the MBC due to the transetherification reaction of the terminal silanol groups of the MBC with ASiPs. It was established that the supramolecular structure of an MBC is built according to the “core-shell” structure. The obtained polymers were tested as sorbents for the development of new methods for the concentration and determination of inorganic compounds. The efficiency of sorption of reagents increased with an increase in the “thickness” of the polydimethylsiloxane component of the “shell” and with a decrease in the size of the polyisocyanurate “core”. The use of the obtained polymers as adsorbents of organic reagents is promising for increasing the efficiency of field methods of chemical testing and inorganic analysis, including the determination of the elemental composition and the detection of traces of contamination.
On the basis of aminoethers of boric acid (AEBA), polyurethane vapor-permeable and pervaporative membranes were obtained. AEBAs, the structure of which is modified by bulk adducts (EM) of diphenylol ...propane diglycidyl ether and ethanolamine, were studied. It turned out that AEBA exists in the form of clusters, and the use of EM as a result of partial destruction of associative interactions leads to a significant decrease in the size of AEBA-EM particles and their viscosity compared to unmodified AEBA. The introduction of EM into the composition of AEBA leads to a threefold increase in the vapor permeability of polyurethanes obtained on their basis. The observed effect is explained by the fact that a decrease in the size of clusters leads to loosening of their dense packing. Areas of clustering due to associative interactions of hydroxyl groups, together with the hydrophilic nature of polyoxyethylene glycol, create channels through which water molecules can penetrate. The increase in vapor permeability is accompanied by a multiple increase in the permeability coefficients in the pervaporative dehydration of isopropanol.
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.
Organophosphorus polyurethane ionomers (AEPA-PU) based on aminoethers of
-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 of
-phosphoric acid with triethanolamine and polyoxypropylene glycol is studied. The reaction process is accompanied by the formation of hyperbranched amino ethers of
-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
-phosphoric acid with glycols becomes possible through the use of tertiary amines. The amino ethers of
-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
-phosphoric acid amino ethers to polymers of ionomeric nature.
We have synthesized cubic and linear polysiloxanes containing polyoxyethylene branches (ASiP-Cu) using tetraethoxysilane, polyoxyethylene glycol, and copper chloride as precursors; the products are ...stable to self-condensation. The effect of copper chloride content on the chemical structure of ASiP-Cu has been established. A special study was aimed at defining the modifying effect of ASiP-Cu on the sorption characteristics of membranes based on microporous, optically transparent block copolymers (OBCs). These OBCs were produced using 2,4-toluene diisocyanate and block copolymers of ethylene and propylene oxides. The study demonstrated significantly increased sorption capacity of the modified polymers. On the basis of the modified microporous block copolymers and 1-(2-pyridylazo)-2-naphthol (PAN) analytical reagent, an analytical test system has been developed. Additionally, the modified OBCs have the benefit of high diffusion permeability for molecules of organic dyes and metal ions. It has been shown that the volume of voids and structural features of their internal cavities contribute to the complex formation reaction involving PAN and copper chloride.
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