For the first time, ATRP was successfully employed for homopolymerization of a commercial methacrylate-functionalized polyhedral oligomeric silsesquioxane (POSS) monomer, iBuPOSSMA, to high molecular weights. It was found that iBuPOSSMA has a low ceiling temperature (T c); therefore, low temperatures and/or high initial monomer concentrations need to be used in order to avoid low degrees of polymerization that had been observed previously. The values of T c, as well as of the polymerization enthalpy ΔH p and entropy ΔS p were determined to be 130 °C (at [M]0 = 1 M), −41 kJ mol–1, and −101 J mol–1 K–1, respectively. Under optimized conditions, poly(iBuPOSSMA) homopolymers having low dispersity and high M n, ranging from 23 000 to 460 000, were obtained in a well-controlled ATRP process. Moreover, various block copolymers having high-M n poly(iBuPOSSMA) blocks were prepared by copolymerization of iBuPOSSMA with methyl methacrylate and styrene.

Ionic liquid 1-butyl-3-methylimidazolium chloride (bmimCl) and its water mixtures were subjected to the temperature of −25 °C for various periods of time and then investigated by Raman and FTIR spectroscopy and WAXS. Neat bmimCl crystallized in a monoclinic lattice denoted M0. During a phase separation in samples with water concentrations of 0.44 and 2.90 wt %, a metastable monoclinic form denoted M was detected that was later converted into the monoclinic form M0 (0.44 wt %) or into an orthorhombic form (2.90 wt %). The form M existed only due to stresses imposed by hydrodynamic phenomena during the phase separation. According to Raman spectroscopy, the conformation of the butyl group in the bmim cation was identified as gauche–anti for the form M0 and as anti–anti for the orthorhombic form. Capillary forces and H-bonding affected the resultant conformation after the liquid–solid and solid–solid transitions. The ATR FTIR spectra in combination with DFT calculations unveiled further changes in the strength of hydrogen bonds between anion, cation, and water.

Cellulose-based macroinitiators with predetermined number of initiation sites were synthesized by acylation of microcrystalline cellulose AVICEL PH-101 with 2-bromoisobutyryl bromide under homogeneous reaction conditions in the N,N-dimethylacetamide/LiCl solvent system. The influence of different methods of cellulose activation on acylation efficiency and reproducibility was investigated. Best results were obtained using thermal activation under reduced pressure or the newly introduced protocol based on solvent exchange to 1,4-dioxane. Prepared macroinitiators were used for grafting with styrene and methyl methacrylate (MMA) using optimized atom transfer radical polymerization reaction conditions to achieve well-controlled polymerizations with high initiation efficiency. For MMA grafting, the initiation efficiency was shown to be dependent on certain reaction conditions, such as type of solvent, monomer concentration, or the presence of a sacrificial initiator. In addition, single-electron transfer liv-ing radical polymerization with Cu(0) as the catalyst was used for the first time to prepare cellulose-graft-polystyrene and cellulose-graft-poly(MMA) copolymers in a homogeneous phase. In summary, homogeneous reaction conditions, stoichiometric control in the preparation of macroinitiators, and controlled grafting jointly allowed for an extensive control of copolymers architecture, that is, density of grafting, composition, and molecular parameters of grafts. Moreover, some of the prepared copolymers were characterized by static and dynamic light scattering and microscopic techniques (transmission electron microscopy and atomic force microscopy).

2-Isopropenyl-2-oxazoline (IPOx) is an important double functional monomer with multiple potential applications. However, until now, the attempts at reversible-deactivation radical polymerization (RDRP) of IPOx via its double bond have met with little success, leading to low conversions and high-dispersity products. Here, we demonstrate that IPOx can be polymerized through aqueous Cu(0)-mediated RDRP in a controlled way using the 2-chloropropionitrile/CuCl­(CuCl2)/TPMA initiation and catalytic system and 0.67 M NaCl as a solvent. It is shown that the polymerization is highly sensitive to the initiator concentration and the CuCl/CuCl2 ratio; however, with careful optimization of the polymerization parameters, low-dispersity products can be obtained at quantitative conversions. The synthesized poly­(IPOx) polymers were subsequently transformed into different ATRP macroinitiators by the reaction of the pendant 2-oxazoline units with 2-bromoisobutyric or 2-chloropropionic acid under optimized reaction conditions. Styrene and methyl methacrylate were then grafted as model monomers from these macroinitiators under ATRP conditions, confirming that defined poly­(IPOx)-based graft copolymers with controlled grafting density and molecular weights of the poly­(IPOx) backbone and of the grafts are accessible by the presented method. This provides a straightforward route to a new class of 2-oxazoline-based materials.

Here, we present the first example of application of single-electron transfer living radical polymerization (SET-LRP) process to a controlled grafting of cellulose esters, cellulose diacetate (CDA), and cellulose acetate butyrate (CAB). The cellulose ester macroinitiators with various functionality densities have been prepared by acylation of the backbones with 2-bromoisobutyryl (BrIB) and dichloroacetyl (DCA) groups, respectively. Methacrylate monomers were polymerized using DCA-functionalized macroinitiators in the presence of pentamethyldiethylene triamine as a ligand. At 30 C, the reaction is rather slow, reaching about 10% conversion after 3 to 6 h of polymerization, whereas the higher temperature (60 C) perceptibly speeds up the polymerization so that methyl methacrylate (MMA) conversion is $30% after 5 h. Graft copolymers with random-type and diblock-type grafts having amphiphilic character were also synthesized. For acrylate grafting (BuA and t-BuA), BrIB-functionalized macroinitiators are more convenient in a combination with a low concentration of Cu(0) and Me 6 TREN as a ligand and polymerization is detectably faster even at the lower temperature than that of MMA. Kinetic studies show ''living'' character of both the graftings. Important advantages of SET-LRP, compared with classic ATRP, are (i) higher polymerization rate, (ii) lower extent of recombination of the growing grafts and (iii) negligible coloration of the products with catalytic residua, so that the prepared polymers do not require additional careful purification.