Alexey P. Sivokhin

Anionic thermo- and pH-responsive copolymers were synthesized by photoiniferter reversible addition–fragmentation chain transfer polymerization (PI-RAFT). The thermo-responsive properties were provided by oligo(ethylene glycol)-based macromonomer units containing hydrophilic and hydrophobic moieties. The pH-responsive properties were enabled by the addition of 5–20 mol% of strong (2-acrylamido-2-methylpropanesulfonic) and weak (methacrylic) acids. Upon initiation by visible light at 470 nm and in the absence of radical initiators, yields from the ternary copolymers reached 94% in 2.5 h when the process was carried out in continuous flow mode using 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid as a light-sensitive RAFT agent. The polymers were characterized using size exclusion chromatography, IR and NMR spectroscopy, and differential scanning calorimetry. The copolymers featured a sufficiently high molecular weight (93–146 kDa) consistent with theoretical values and satisfactory dispersities in the range of 1.18–1.45. The pH-responsive properties were studied in deionized water, saline, and buffer solutions. Dramatic differences in LCST behavior were observed in strong and weak acid-based polyelectrolytes. The introduction of sulfonic acid units, even in very small amounts, completely suppressed the LCST transition in deionized water while maintaining it in the saline and buffer solutions, with a negligible LCST dependence on the pH. In contrast, the incorporation of weak methacrylic acid demonstrated a pronounced pH dependence. The peculiarities of micelle formation in aqueous solutions were investigated and critical micelle concentrations and their ability to retain pyrene, a hydrophobic drug model, were determined. It was observed that anionic molecular brushes formed small micelles with aggregation numbers of 1–2 at concentrations in the order of 10⁻⁴ mg/mL. These micelles have a high ability to entrap pyrene, which makes them a promising tool for targeted drug delivery.

Herein, a series of ternary amphiphilic amide-containing bottlebrushes were synthesized by photoiniferter (PI-RAFT) polymerization of macromonomers in continuous-flow mode using trithiocarbonate as a chain transfer agent. Visible light-mediated polymerization of macromonomers under mild conditions enabled the preparation of thermoresponsive copolymers with low dispersity and high yields in a very short time, which is not typical for the classical reversible addition–fragmentation chain transfer process. Methoxy oligo(ethylene glycol) methacrylate and alkoxy(C₁₂–C₁₄) oligo(ethylene glycol) methacrylate were used as the basic monomers providing amphiphilic and thermoresponsive properties. The study investigated how modifying comonomers, acrylamide (AAm), methacrylamide (MAAm), and N-methylacrylamide (-MeAAm) affect the features of bottlebrush micelle formation, their critical micelle concentration, and loading capacity for pyrene, a hydrophobic drug model. The results showed that the process is scalable and can produce tens of grams of pure copolymer per day. The unmodified copolymer formed unimolecular micelles at temperatures below the LCST in aqueous solutions, as revealed by DLS and SLS data. The incorporation of AAm, MAAm, and N-MeAAm units resulted in an increase in micelle aggregation numbers. The resulting bottlebrushes formed uni- or bimolecular micelles at extremely low concentrations. These micelles possess a high capacity for loading pyrene, making them a promising choice for targeted drug delivery.

High-molecular weight amphiphilic PEG-based bottlebrushes have been synthesized via continuous flow photoiniferter polymerization of macromonomers using trithiocarbonates as chain transfer agents.

The performance of polyalkyl acrylate additives of various compositions in low-temperature dewaxing of 11 oil fractions differing in the viscosity and content of waxes, aromatic hydrocarbons, and resins was studied. The dewaxing was performed in a methyl ethyl ketone–toluene mixed solvent. For polyalkyl acrylate with pendant C_16–10 alkyl chains, the raffinates can be subdivided into three groups with respect to an increase in the yield of dewaxed oils (relative to the process without additives): increase by 12–13, 5–8, and 3–4%. In most cases, introduction into such polymer of 5–30% polar groups (amino ester, amino amide, amide, oligoethylene glycol) allowed the oil yield to be additionally increased.

Betulin, a natural triterpene possessing a wide range of biological activities, has been modified via Steglich esterification to produce a methacrylate derivative capable of participating in radical polymerization. The modification is intended to increase the solubility of betulin, which is almost insoluble in water, by incorporating into the composition of an amphiphilic copolymer. The resulting solubility of betulin in water increased from 8·10⁻⁵ mg/mL to more than 10 mg/mL per betulin. For this, well‐defined biocompatible thermoresponsive copolymers with high betulin content have been synthesized through the conventional and RAFT copolymerizations of betulin methacrylate (BeMA) with methoxy oligo(ethylene glycol) methacrylate (MOEGMA). BeMA was more reactive in the BeMA‐MOEGMA pair; the resulting copolymers were slightly enriched with BeMA units (r₁ = 1.70, r₂ = 0.93). The copolymers exhibited LCST‐type behavior. LCST was tuned by balancing the hydrophobic betulin and hydrophilic OEG fragments. The molecular weight characteristics of polymers and their behavior in aqueous and organic solutions have been studied. Copolymers obtained by conventional polymerization had lower cloud points than RAFT copolymers of the same composition. The copolymers are characterized by low critical micelle concentrations that decrease as the BeMA fraction in the copolymers increases. RAFT copolymers were shown to form unimolecular micelles resistant to dissociation, which is promising for their use in targeted drug delivery.

Amphiphilic random and diblock thermoresponsive oligo(ethylene glycol)-based (co)polymers were synthesized via photoiniferter polymerization under visible light using trithiocarbonate as a chain transfer agent. The effect of solvent, light intensity and wavelength on the rate of the process was investigated. It was shown that blue and green LED light could initiate RAFT polymerization of macromonomers without an exogenous initiator at room temperature, giving bottlebrush polymers with low dispersity at sufficiently high conversions achieved in 1–2 h. The pseudo-living mechanism of polymerization and high chain-end fidelity were confirmed by successful chain extension. Thermoresponsive properties of the copolymers in aqueous solutions were studied via turbidimetry and laser light scattering. Random copolymers of methoxy- and alkoxy oligo(ethylene glycol) methacrylates of a specified length formed unimolecular micelles in water with a hydrophobic core consisting of a polymer backbone and alkyl groups and a hydrophilic oligo(ethylene glycol) shell. In contrast, the diblock copolymer formed huge multimolecular micelles.

Benzene and toluene are commonly used reference substances for static light scattering (SLS) measurements. However, due to the appearance and wide availability of solid‐state lasers with various wavelengths, there is a need for data on the Rayleigh ratios for references at various wavelengths. Thermoresponsive polymers, which are widely researched now, can have lower critical solution temperature (LCST) values very close to the human body temperature (30–36 °C). Such polymers can be used to develop efficient means for targeted drug delivery. In this paper, we report how to accurately determine the absolute molecular weights of thermoresponsive polymers by the SLS method. This is especially important when the LCST value of a polymer is close to the room temperature (at which SLS measurements are usually taken), which can lead to overestimated results due to the aggregation of macromolecules. So, it is necessary to carefully select the measurement temperature and, accordingly, data are needed on the temperature dependence of the Rayleigh ratios for a reference sample. The Rayleigh ratios and depolarization factors, ρ _u and ρ _v , were first determined for toluene within a wide temperature range (10–50 °C). The temperature dependencies of these parameters were shown to be linear in the whole range investigated. Temperature coefficients for the calculation of the Rayleigh ratios at different scattering geometries were obtained. The particular importance of choosing the optimal measurement temperature when determining the molecular weights of thermoresponsive polymers with low values of LCST using the static light scattering method was demonstrated.

Thermoresponsive PEG‐based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)‐ or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate‐ and methoxy oligo(propylene glycol)‐block‐oligo(ethylene glycol) (meth)acrylate‐based macromonomers with high yields (80%–98.7%) by the acid‐catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p‐Toluene sulphonic acid (pTSA), alkyl(C₁₂–C₁₄)benzene sulfonic acid (ABSA) and H₂SO₄ were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%.

The review summarises the trends in the development of research on the synthesis of polymethacrylimides (PMIs) and polyacrylimides by the method of intramolecular thermal imidisation of (meth)acrylic polymers. Along with the widely used industry variant of PMI foam of the ‘Rohacell’ series based on bulk copolymers of methacrylonitrile and methacrylic acid, intensive research on alternative variants began after 2005. This review describes the main and side reactions when using polymer precursors of different structures as well as the effect of precursor composition and structure on the properties of the resulting poly(meth)acrylimides. It has been shown that the achievements of the last 15 years provide a basis for reducing the cost of poly(meth)acrylimides which will significantly expand the areas and scale of their application.

Concentration effects in the base-catalyzed hydrolysis of water-soluble methacrylates (3-(N,N-dimethylaminoethyl) methacrylate (DMAEMA), 2-hydroxyethyl methacrylate (HEMA) and oligo(ethylene glycol) methacrylates (OEGMAs)) have been studied. These monomers are rapidly hydrolyzed in the presence of bases at the room temperature in dilute aqueous solutions, but the reaction rate decreases sharply in highly concentrated solutions. A clear correlation was found between a form of the viscosity isotherm for DMAEMA solutions and the concentration dependence of the autocatalytic hydrolysis rate which indicates the connection of process kinetics with the structure of solutions. These data should be considered when carrying out homo- and copolymerization of the previously mentioned monomers in aqueous solutions.