Visible-light-induced ATRP under high-pressure: synthesis of ultra-high-molecular-weight polymers.

In this study, a high-pressure-assisted photoinduced atom transfer radical polymerization (p ≤ 250 MPa) enabled the synthesis of ultra-high-molecular-weight polymers (UHMWPs) of up to 9 350 000 and low/moderate dispersity (1.10 < D < 1.46) in a co-solvent system (water/DMSO), without reaction mixture deoxygenation.

The unique role of pore wall nanostructurization in the intrachannel photo-ATRP for fine-tuning PMMA tacticity.

In this paper, efficient MMA photo O-ATRP protocols conducted inside nanoreactors varying in nanostructured interfaces are reported for the first time. We showed that the microstructure of recovered polymers could be easily tuned just by implementing a given type of nanochannel (d = 10, 19-28, 35, 160 nm).

The Effect of Various Poly (N-vinylpyrrolidone) (PVP) Polymers on the Crystallization of Flutamide.

In this study, several experimental techniques were applied to probe thermal properties, molecular dynamics, crystallization kinetics and intermolecular interactions in binary mixtures (BMs) composed of flutamide (FL) and various poly(N-vinylpyrrolidone) (PVP) polymers, including a commercial product and, importantly, samples obtained from high-pressure syntheses, which differ in microstructure (defined by the tacticity of the macromolecule) from the commercial PVP. Differential Scanning Calorimetry (DSC) studies revealed a particularly large difference between the glass transition temperature (Tg) of FL+PVPsynth. mixtures with 10 and 30 wt% of the excipient. In the case of the FL+PVPcomm. system, this effect was significantly lower. Such unexpected findings for the former mixtures were strictly connected to the variation of the microstructure of the polymer. Moreover, combined DSC and dielectric measurements showed that the onset of FL crystallization is significantly suppressed in the BM composed of the synthesized polymers. Further non-isothermal DSC investigations carried out on various FL+10 wt% PVP mixtures revealed a slowing down of FL crystallization in all FL-based systems (the best inhibitor of this process was PVP Mn = 190 kg/mol). Our research indicated a significant contribution of the microstructure of the polymer on the physical stability of the pharmaceutical-an issue completely overlooked in the literature.

Supramolecular structures of self-assembled oligomers under confinement.

We study the molecular origin of a prepeak (PP) observed at low q values in the structure factors of three oligomers in a bulk (poly(mercaptopropyl)methylsiloxane, PMMS, poly(methylmercaptopropyl)-grafted-hexylmethacrylate, PMMS-g-HMA, and poly(methylphenyl)siloxane, PMPS) in order to understand the lowering of the PP intensity detected for oligomers confined in cylindrical pores with low diameter. For this purpose, we use a combination of X-ray diffraction measurements and coarse-grained bead-spring molecular dynamics simulations. Our molecular modelling demonstrated that the planarity of the pendant groups triggers the self-association of oligomers into nanoaggregates. However, the formation of oligomeric nanodomains is not sufficient for building-up the PP. The latter requires spatial disturbance in the arrangement of the side groups of oligomers within clusters. Importantly, our numerical analysis revealed that the increasing degree of the confinement of oligomers limits their aggregation and consequently lowers the amplitude of the PP observed in the experimental data.

Stereoregulation, molecular weight, and dispersity control of PMMA synthesized via free-radical polymerization supported by the external high electric field.

We show the remarkable effect of using static (DC) and alternating (AC) electric fields to control the free-radical polymerization of methyl methacrylate (MMA). The magnitude and/or frequency of the applied electric field (up to 154 kV cm-1) were found to control the molecular weight, dispersity, and stereochemistry of the produced polymers.

High pressure as a novel tool for the cationic ROP of γ-butyrolactone.

In this study, we report the acid-catalyzed and high pressure assisted ring-opening polymerization (ROP) of γ-butyrolactone (GBL). The use of a dually-catalyzed approach combining an external physical factor and internal catalyst (trifluoromethanesulfonic acid (TfOH) or p-toluenesulfonic acid (PTSA)) enforced ROP of GBL, which is considered as hardly polymerizable monomer still remaining a challenge for the modern polymer chemistry. The experiments performed at various thermodynamic conditions (T = 278-323 K and p = 700-1500 MPa) clearly showed that the high pressure supported polymerization process led to obtaining well-defined macromolecules of better parameters (M n = 2200-9700 g mol-1; D = 1.05-1.46) than those previously reported. Furthermore, the parabolic-like dependence of both the molecular weight (M W) and the yield of obtained polymers on variation in temperature and pressure at either isobaric or isothermal conditions was also noticed, allowing the determination of optimal conditions for the polymerization process. However, most importantly, this strategy allowed to significantly reduce the reaction time (just 3 h at room temperature) and increase the yield of obtained polymers (up to 0.62 gPGBL/gGBL). Moreover, despite using a strongly acidic catalyst, synthesized polymers remained non-toxic and biocompatible, as proven by the cytotoxicity test we performed in further analysis. Additional investigation (including MALDI-TOF measurements) showed that the catalyst selection affected not only M W and yield but also the linear/cyclic form content in obtained macromolecules. These findings show the way to tune the properties of PGBL and obtain polymer suitable for application in the biomedical industry.

Correlation between Locally Ordered (Hydrogen-Bonded) Nanodomains and Puzzling Dynamics of Polymethysiloxane Derivative.

We examined the behavior of poly(mercaptopropyl)methylsiloxane (PMMS), characterized by a polymer chain backbone of alternate silicon and oxygen atoms substituted by a polar pendant group able to form hydrogen bonds (-SH moiety), by means of infrared (FTIR) and dielectric (BDS) spectroscopy, differential scanning calorimetry (DSC), X-ray diffraction (XRD), and rheology. We observed that the examined PMMS forms relatively efficient hydrogen bonds leading to the association of chains in the form of ordered lamellar-like hydrogen-bonded nanodomains. Moreover, the recorded mechanical and dielectric spectra revealed the presence of two relaxation processes. A direct comparison of collected data and relaxation times extracted from two experimental techniques, BDS and rheology, indicates that they monitor different types of the mobility of PMMS macromolecules. Our mechanical measurements revealed the presence of Rouse modes connected to the chain dynamics (slow process) and segmental relaxation (a faster process), whereas in the dielectric loss spectra we observed two relaxation processes related most likely to either the association-dissociation phenomenon within lamellar-like self-assemblies or the sub-Rouse mode (α'-slower process) and segmental (α-faster process) dynamics. Data presented herein allow a better understanding of the peculiar dynamical properties of polysiloxanes and associating polymers having strongly polar pendant moieties.

Impact of Imidazolium-Based Ionic Liquids on the Curing Kinetics and Physicochemical Properties of Nascent Epoxy Resins.

We investigated the influence of anion type (salicylate, [(MOB)MIm][Sal], vs chloride, [(MOB)MIm][Cl]) of imidazolium-based ionic liquid (IL) and its content on the curing kinetics of bisphenol A diglicydyl ether (DGEBA of molecular weight M n = 340 g/mol). Further physicochemical properties (i.e., glass transition temperature, T g, and conductivity, σdc) of produced polymers were investigated. The polymerization of the studied systems was examined at various molar ratios (1:1, 10:1, and 20:1) at different reaction temperatures (T reaction = 353-383 K) by using differential scanning calorimetry (DSC). Interestingly, both DGEBA/IL compositions studied herein revealed significantly different reaction kinetics and yielded materials of completely distinct physical properties. Surprisingly, in contrast to [(MOB)MIm][Cl], for the low concentration of [(MOB)MIm][Sal] in the reaction mixture, an additional step in the kinetic curves, likely due to the combined enhanced initiation activity of anion (salicylate)-cation (imidazolium-based), was noted. To thoroughly analyze the kinetics of all studied systems, including the two-step kinetics of DGEBA/[(MOB)MIm][Sal], we applied a new approach that relies on the combination of the two phenomenological Avrami equations. Analysis of the determined constant rates revealed that the reaction occurring in the presence of the salicylate anion is characterized by higher activation energy with respect to those with the chloride. Moreover, DGEBA/[(MOB)MIm][Sal] cured materials have higher T g in comparison to DGEBA polymerized with [(MOB)MIm][Cl] independent of the IL concentration. This fact might indicate that, most likely, the products of hardening are highly cross-linked (high T g) or oligomeric linear polymers (low T g) in the former and latter cases, respectively. Such a change in the chemical structure of the polymer is also reflected in the dc conductivity measured at the glass transition temperature, which is much higher for DGEBA cured with [(MOB)MIm][Cl]. Herein, we have clearly demonstrated that the type of anion has a crucial impact on the polymerization mechanism, kinetics, and properties of produced materials.

Pressure-assisted solvent- and catalyst-free production of well-defined poly(1-vinyl-2-pyrrolidone) for biomedical applications.

In this work, we developed a fast, highly efficient, and environmentally friendly catalytic system for classical free-radical polymerization (FRP) utilizing a high-pressure (HP) approach. The application of HP for thermally-induced, bulk FRP of 1-vinyl-2-pyrrolidone (VP) allowed to eliminate the current limitation of ambient-pressure polymerization of 'less-activated' monomer (LAM), characterized by the lack of temporal control yielding polymers of unacceptably large disperisites and poor result reproducibility. By a simple manipulation of thermodynamic conditions (p = 125-500 MPa, T = 323-333 K) and reaction composition (two-component system: monomer and low content of thermoinitiator) well-defined poly(1-vinyl-2-pyrrolidone)s (PVP) in a wide range of molecular weights and low/moderate dispersities (M n = 16.2-280.5 kg mol-1, D = 1.27-1.45) have been produced. We have found that HP can act as an 'external' controlling factor that warrants the first-order polymerization kinetics for classical FRP, something that was possible so far only for reversible deactivation radical polymerization (RDRP) systems. Importantly, our synthetic strategy adopted for VP FRP enabled us to obtain polymers of very high M n in a very short time-frame (0.5 h). It has also been confirmed that VP bulk polymerization yields polymers with significantly lower glass transition temperatures (T g) and different solubility properties in comparison to macromolecules obtained during the solvent-assisted reaction.

The application of spatially restricted geometries as a unique route to produce well-defined poly(vinyl pyrrolidones) via free radical polymerisation.

We report, for the first time, the metal-free green synthesis of linear poly(vinyl pyrrolidone) (PVP) homopolymers of molecular weight higher than 100 kg mol-1 and narrow dispersities via thermal and photo-induced free radical polymerisation carried out within alumina nanoporous membranes acting as "nanoreactors".

Efficient metal-free strategies for polymerization of a sterically hindered ionic monomer through the application of hard confinement and high pressure.

In this paper, we have studied the effect of both hard confinement (nanoporous membranes treated as nanoreactors) and high pressure (compression of system) on the progress of free-radical (FRP) and reversible addition-fragmentation chain transfer (RAFT) polymerizations of selected hardly polymerizable, sterically hindered imidazolium-based ionic monomer 1-octyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide ([OVIM][NTf2]). These two innovative approaches, affecting (in a different way) the free volume of the polymerizing system, allows the reduction of the number of toxic substrates/catalysts, satisfying the requirement of green chemistry. It was found that at both conditions (high compression and confinement) the polymerizability of monomer, as well as the control over the reaction and the properties of the produced polyelectrolytes, have increased significantly. However, it should be added that there were noticeable differences between FRP carried out under confinement and at high pressures. Interestingly, by appropriate variation in thermodynamic conditions, it was possible to synthesize polymers of moderate molecular weight (M n ∼ 58 kg mol-1) and relatively low dispersity (D ∼ 1.7); while for the reaction performed within AAO pores of varying diameter (d = 35 nm and d = 150 nm), macromolecules of higher M n but slightly broader dispersity indices (D ∼ 2.2-2.7) were recovered. On the other hand, RAFT polymerization carried out under confinement and at elevated pressures yielded polymers with well-defined properties. Noteworthy is also the fact that nanopolymerization leads to polymers of comparable M n to those obtained at high-pressure studies but at significantly shorter reaction time (t ∼ 2 hours). We believe that the presented data clearly demonstrated that both examined approaches (the compression and application of alumina templates, treated as nanoreactors) could be successfully used as additional driving forces to polymerize sterically hindered monomers and produce well-defined polymers in relatively short times. At the same time, it should be mentioned that both proposed polymerization methods enabled us to omit the addition of metal-based initiators/catalysts, which seem to be a crucial step towards further development of the alternative green synthesis of polyelectrolytes in the future.

Polymerization of Monomeric Ionic Liquid Confined within Uniaxial Alumina Pores as a New Way of Obtaining Materials with Enhanced Conductivity.

Broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC) have been employed to probe dynamics and charge transport of 1-butyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide ([bvim][NTf2]) confined in native uniaxial AAO pores as well as to study kinetics of radical polymerization of the examined compound as a function of the degree of confinement. Subsequently, the electronic conductivity of the produced polymers was investigated. As observed, polymerization carried out at T = 363 K proceeds faster under confinement with some saturation effect observed for the sample in pores of smaller diameter. Obtained results were discussed in the context of the very recent reports showing that the free volume of the confined material is higher with respect to the bulk one. It was also noted that conductivity of poly[bvim][NTf2] is significantly higher with respect to the macromolecules obtained upon bulk polymerization. Moreover, charge transport of the confined macromolecules is even higher when compared to the bulk monomeric ionic liquid at some thermodynamic conditions. Additionally, the molecular weight, Mw, of the confined-synthesized polymers is significantly higher with respect to the bulk-synthesized material. Interestingly, both parameters, (i) the enhancement of σdc and (ii) the increase in Mw, can be tuned and controlled by the application of the appropriate confinement. Consequently, those results are quite promising in the context of development of the fabrication of polymerized ionic liquids (PILs) nanomaterials with unique properties and morphologies, which can be further easily applied in the field of nanotechnology.