Laboratory of Polymer Chemistry (N16)

Since the laboratory was founded, the creation of new polymer materials with valuable practical properties has been one of the most important tasks addressed by the IOC RAS. Priority goals include the development of new methods for the synthesis of fluorine-containing heterocyclic polymers and oligomers, in particular fluorinated polyesters, polyurethanes, heteroaromatic polymers, and polyfluoroorganosiloxanes, as well as the systematic study of the basic patterns of CO2 copolymerization with oxiranes and compounds capable of undergoing ring-opening polymerization (ROP) for the synthesis of polyalkylene carbonates and polyether alkylene carbonates—environmentally friendly thermoplastics. Equally important is the search for new approaches to the synthesis of low- and ultra-low-density polymers of various structures for use in medicine and laser technologies

✓ As a result of the conducted research, the synthesis of new fluorine-containing polyurethanes from fluorine-containing alcohols and aromatic (or aliphatic) diisocyanates has been proposed:

Depending on the selected starting components, polyurethane plastics with a melting point of 98 °C and rubbers with a glass transition temperature (T_g) of up to –135 °C were obtained. The decomposition temperature of such polymers is 270–300 °C.

✓ Fluorine-containing polyethers were obtained for the first time by reacting polyfluorinated diols and the dichloroanhydride of 2,5-furandicarboxylic acid:

It has been established that such polyethers retain their characteristics in a wide range of low temperatures, from –27 to –135 °C, which provides a basis for their further application:.

✓ The study of interactions between perfluoropolyether-polyperoxides and perfluoro- and polyfluorooctyl aromatic compounds (C₆F₆, C₆F5H, C₆F₅Cl, and C₆F₅CF₃) showed that the thermolysis of these compounds at 280–290 °C results in the formation of branched and cross-linked perfluoropolymers with a glass transition temperature (T_g) of up to –140 °C and a decomposition temperature of +400 °C:

It has been established that perfluorobenzene transforms into an isomer, "Dewar's benzene", under these conditions, and its interaction with perfluoropolyperoxides (PFPP-4) leads to the formation of cross-linked thermostable polymers.

✓  Significant attention has been paid to the synthesis of materials for protecting historical monuments and monumental works of art from environmental hazards. Methods have been developed for the synthesis of a range of oligomeric perfluorinated carboxylic acid derivatives with reactive trialkoxy groups:

These substances are soluble in organic and/or organofluorine solvents. When applied to limestone, sandstone, marble, and other materials, they provide water-repellent, oil-repellent, and dirt-repellent properties. The new organofluorine silicon compounds are more effective than some organosilicon hydrophobizers, and they also have high oleophobicity. The contact angles of limestone treated with this preparation were 130-140° and 90-95° for water and decahydronaphthalene, respectively. In cooperation with the administration of the city of Moscow, a number of architectural monuments were treated with the organofluorine-silicon compound "Forsam-39". Ten years after application, no growth of algae or fungi was observed on the control objects.

✓ The Institute of Organic Chemistry of the Russian Academy of Sciences has developed a method for obtaining α-oxides of 1-vinyl-2-perfluoroalkoxy-2,3,3-trifluorocyclobutanes in the presence of m-chloronaphthalene-2-carboxylic acid (m-CPBA). The reaction was carried out in a solution of methylene chloride or perfluorooctane at 40 °C, and the yield of the target products was 45-50%:

According to the results of spectral analysis by ¹H and ¹⁹F NMR methods, the obtained compounds contain cis- and trans-isomers relative to the four-membered cycle. It has been shown that the cis-isomer exists in the form of two hindered conformations around the HC-CH bonds of the two cycles in a ratio of 3:1. The synthesized α-oxides can serve as precursors for new polymers with uniquely low glass transition temperatures.

✓ Work describes the synthesis of terpolymers with different contents of L-lactic acid in the polypropylene carbonate chain by copolymerization of CO₂, propylene oxide, and L-lactide in the presence of zinc adipate:

Due to their biocompatibility, biodegradability, and low toxicity, the synthesized polycarbonates with L-lactic acid blocks have a high potential for biomedical applications.

✓ A method has been developed for the synthesis of a biodegradable and biocompatible copolymer of propylene oxide, CO₂, and trimethylenecarbonate (TMC), consisting of propylene carbonate and TMC blocks, and its composition, chain microstructure, molecular weight, and thermal characteristics have been determined.

It has been established that trimethylenecarbonate copolymer films form uniform porous structures when exposed to SC-CO₂ (20 MPa, 80 °C), which can be used in medical practice as porous substrates. To demonstrate the potential of these materials, the conditions for imbibing ibuprofen into the TMC copolymer (35 °C, 8 MPa, 8 h) were determined, and it was found that the concentration of ibuprofen can reach ~ 30% of the weight of the copolymer.

✓ Based on cellulose triacetate, a method has been developed for producing microcellular low-density aerogels with a specified density and porosity for studying the homogeneity of plasma generated under high-energy laser conditions. For the first time, information has been experimentally obtained about density fluctuations in plasma produced by laser irradiation of low-density foams. It has been established that significant dynamic changes in plasma density can persist for up to 1 ms, which is significantly longer than the time required for plasma formation.

Experimental setup (a), image of the transmitted probe beam (b), and photo of the target before the shot (c). The targets are made of microcellular aerogels obtained from cellulose triacetate with a density of 2 and 4 mg•cm^–3 and a thickness of 140 to 330 μm.

✓ Some selected research results are presented in a review article dedicated to the 90th anniversary of the Institute.