Tomasz Fronczyk

A series of star-shaped poly[2-(methacryloyloxy)ethyl trimethylammonium chloride]s with different arm lengths were synthesized via open-aired enzymatically assisted ATRP using the 2-hydroxypropyl β-cyclodextrin derivative as an initiator. The resulting PMETAs with narrow molecular weight distribution (Đ = 1.06–1.12) created thin hydrophilic films with thickness < 40 nm exhibiting water contact angle (WCA) values < 50°. Higher interfacial tension values obtained for star-shaped polymers in comparison with the linear analog indicate that surface wettability can be modified by changing the polymer topology. AFM was used to analyze the relationship between macromolecule topology, surface roughness, and WCA.

We report a one-pot synthesis of well-defined A₅B and A₈B miktoarm star-shaped polymers where N,N-dimethylaminoethyl methacrylate (DMAEMA) and various cyclic esters such as ε-caprolactone (ε-CL), lactide (LA) and glycolide (GA) were used for the synthesis. Miktopolymers were obtained by simultaneously carrying out atom transfer radical polymerization (ATRP) of DMAEMA, ring-opening polymerization (ROP) of cyclic esters, and click reaction between the azide group in gluconamide-based (GLBr₅-Az) or lactonamide-based (GLBr₈-Az) ATRP initiators and 4-pentyn-1-ol. The relatively low dispersity indices of the obtained miktoarm stars (Đ = 1.2–1.6) indicate that control over the polymerization processes was sustained despite almost complete monomers conversions (83–99%). The presence of salts from phosphate-buffered saline (PBS) in polymer solutions affects the phase transition, increasing cloud point temperatures (T_CP) values. The critical aggregation concentration (CAC) values increased with a decreasing number of average molecular weights of the hydrophobic fraction. Hydrolytic degradation studies revealed that the highest reduction of molecular weight was observed for polymers with PCL and PLGCL arm. The influence of the composition on the miktopolymers hydrophilicity was investigated via water contact angle (WCA) measurement. Thermogravimetric analysis (TGA) disclosed that the number of arms and their composition in the miktopolymer affects its weight loss under the influence of temperature.

This study explores the synthesis, characterization, and application of a heterofunctional initiator derived from 2-hydroxypropyl cyclodextrin (HP-β-CD), having eight bromoester groups and thirteen hydroxyl groups allowing the synthesis of mikto-arm star-shaped polymers. The bromoesterification of HP-β-CD was achieved using α-bromoisobutyryl bromide as the acylation reagent, modifying the cyclodextrin (CD) molecule as confirmed by electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (NMR), attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy analysis, and differential scanning calorimetry (DSC) thermograms. The initiator’s effectiveness was further demonstrated by obtaining star-comb and mikto-arm polymers via an enzymatically assisted atom transfer radical polymerization (ATRP) method and subsequent ring-opening polymerization (ROP). The ATR polymerization quality and control depended on the type of monomer and was optimized by the way of introducing the initiator into the reaction mixture. In the case of ATRP, high conversion rates for poly(ethylene oxide) methyl ether methacrylate (OEOMA), with molecular weights (Mn) of 500 g/mol and 300 g/mol, were achieved. The molecular weight distribution of the obtained polymers remained in the range of 1.23–1.75. The obtained star-comb polymers were characterized by different arm lengths. Unreacted hydroxyl groups in the core of exemplary star-comb polymers were utilized in the ROP of ε-caprolactone (CL) to obtain a hydrophilic mikto-arm polymer. Cloud point temperature (T_CP) values of the synthesized polymers increased with arm length, indicating the polymers’ reduced hydrophobicity and enhanced solvation by water. Atomic force microscopy (AFM) analysis revealed the ability of the star-comb polymers to create fractals. The study elucidates advancements in the synthesis and utilization of hydrophilic sugar-based initiators for enzymatically assisted ATRP in an aqueous solution for obtaining complex star-comb polymers in a controlled manner.

In this paper, the influence of hydrodynamic conditions in Kenics static mixer, which acts as a multifunctional reactor, on precipitation kinetics of barium sulfate is investigated. The investigated range of the Reynolds number varied between 500 and 5000, which covered both laminar and turbulent flow regimes. In all experiments, the relative supersaturation was maintained at the constant level (σ = 205). The obtained precipitate was collected and used for crystal size distribution (CSD) determination. On that basis, the kinetic parameters of the process were calculated using the mixed suspension mixed product removal (MSMPR) mathematical model of the process. It was found that for the whole investigated range of Reynolds number, the mixing conditions were satisfactory. CSD analysis showed that in the laminar regime, a clear tendency in crystal behavior could not be noticed. However, during the analysis of the turbulent regime, the presence of a critical Reynolds number was noticed. Above this value, there is a change in the flow pattern, which results in a change of kinetic parameters (B, G), as well as manifests in a form of a decrease in the value of mean diameters of crystals. The flow pattern change is caused by the geometry of the reactor’s inserts.