Paulina Maksym

• PhD in Polymer Chemistry; M. Eng. in Chemical Technology
• Researcher at Carnegie Mellon University

Using high-pressure and light irradiation, we innovatively synthesized UHMW polymers, overcoming traditional ATRP limitations.

We investigate the effect of a high electric field on the free-radical polymerization (FRP) of acrylate monomer with a large steric hindrance that comes from the isobornyl pendant group. In...

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...

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-pre...

This work demonstrates the effect of a high dc bias field (up to 160 kV/cm) on the polyaddition reaction of the modeled epoxy resin system. Polymerization of bisphenol A diglycidyl ether (DGEBA) supported by high electric field results in obtaining epoxides with significantly increased molecular weight, which is seven-fold higher than the zero-fiel...

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 oligome...

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...

Star-shaped glycopolymers due to the attractive combination of the physicochemical, morphological, self-assembly properties along with biological activity have gained increased attention as innovative agents in novel cancer therapies. Unfortunately, the production of these highly desirable biomaterials remains a challenge in modern macromolecular c...

In macromolecular science, tunning basic polymer parameters, like molecular weight (M n ) or molecular weight distribution (dispersity, Đ), is an active research topic. Many prominent synthetic protocols concerning chemical modification of...

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 hard...

In this paper, we report 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) supported high-pressure approach enforcing Ring-Opening Polymerization (ROP) of γ-butyrolactone (GBL), that due to unfavorable thermodynamics and low ring strain, is considered as a hardly polymerizable monomer. Application of Broadband Dielectric Spectroscopy (BDS) allowed us to fi...

Poly(1-vinyl-2-pyrrolidone) (Povidone, PVP) is one of the most interesting and versatile synthetic polymers utilised in the pharmaceutical and cosmetic industries. Its large-scale commercial production offers an assortment of products in a wide range of molecular weights but poorly-controlled (macro)structural parameters (i.e., dispersity, function...

The subject of the invention is a method of pressure polymerization of γ-butyrolactone (GBL), enabling the production of chemically pure poly(γ-butyrolactone) PGBL, consisting in mixing the monomer in the form of γ-butyrolactone with a catalyst in the form of 1,5,7-triazabicyclo[ 4.4.0]dec-5-ene, preferably dried, in a catalyst to monomer ratio ran...

This work highlights the development of a robust and universal route towards gaining control over macromolecule molecular weight, molecular weight distribution, and more importantly, morphology through the implementation of photoiniferter-mediated RAFT (photo-RAFT) carried out in mesoporous materials varying in the composition, pore arrangement, an...

The innovative combination of light and high-pressure allowed us to effectively polymerize for the first time challenging ionic 1,2,4-triazolium-based ionic liquid (IL) with fluorinate anion (MetTRI/NTF) and non-ionic vinyl acetate...

The invention relates to a method for producing poly(N-vinylpyrrolidone) through pressure-induced free-radical polymerization of N-vinylpyrrolidone (NVP) initiated by light, either in bulk or in a solvent, under favorable pressure and temperature conditions (p and T). The method involves adding a radical photoinitiator to the monomer in the form of...

We examined the behavior of poly(mercaptopropyl)methyl-siloxane (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 diffracti...

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 Mn = 340 g/mol). Further physicochemical properties (i.e., glass transition temperature, Tg, and conductivity,...

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...

Star‐shaped 1‐vinyl‐2‐pyrrolidone (VP)‐based polymers having four pendant arms were produced via high‐pressure RAFT using the trithiocarbonate‐functionalized core. The use of compression (p = 250 MPa) significantly reduced or eliminated star‐star/star‐chain coupling side reactions and termination process characteristics the for “core‐first” R‐type...

In this paper, we present facile synthetic strategies enabling production of well-defined poly(ionic liquids) PILs based on 1-vinyl-4-benzyl-3-methylimidazolium- (VBIm) and 1-vinyl-4-benzyl-3-methylpyrrolidium (VBPy) ionic liquids (IL) possessing different counterions (chloride Cl􀀀 vs. bis(trifluoromethanesulfonyl)imide NTf2 - ) (VBIm/NTf2,VBIm/Cl,...

In this paper, catalyzed and non-catalyzed water-initiated Ring-Opening Polymerization (ROP) of ε-caprolactone (ε-CL) at varying thermodynamic conditions (T=293-393 K and p=0.1-500 MPa) was carried out. As organocatalysts, two non-nucleophilic bases characterized by a different mode of action, i.e. 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU) and 1,5,7...

The subject of the invention is a method of pressure polymerization of 1-vinyl-2-pyrrolidone (VP), enabling the production of chemically pure poly(1-vinyl-2-pyrrolidone) PVP, consisting in the monomer in the form of 1-vinyl-2-pyrrolidone (VP ) with a purity preferably above 99%, is mixed with a thermoinitiator in the form of azobis(isobutyronitrile...

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 and narrow dispersities via thermal and photo-induced...

The effect of hard confinement and high pressure on the progress of free-radical and reversible addition-fragmentation chain transfer polymerizations of sterically hindered 1-octyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide ([OVIM][NTf2]) has been investigated.

Method of pressure polymerization of ε-caprolactone The subject of the invention is a method of pressure polymerization of ε-caprolactone (ε-CL), enabling the production of linear polycaprolactone (PCL), in which an initiator in the form of water is added to the ε-caprolactone (ε-CL) monomer with a purity preferably above 90%. or anhydrous alcohol...

The synthesis of tailored [2‐(methacryloyloxy)ethyl]‐trimethylammonium chloride (ChMA/Cl⁻) and bis(trifluoromethanesulfonate) imide (ChMA/NTf2⁻)‐based ionic homopolymers by sustainable activators generated by electron transfer atom transfer radical polymerization (ATRP) method has been demonstrated. Linear and four‐arm star‐shaped macromolecules we...

The effect of the chemical modification of poly(propylene glycol) (PPG) end groups on the molecular dynamics under 2D confinement and the polymer/matrix interactions (including interfacial energies) was investigated by a combination of differential scanning calorimetry (DSC), broadband dielectric spectroscopy (BDS), surface tension and contact angl...

Efficient ROP polymerization of ϵ-caprolactone, resulting in products characterized by high molecular weight of low dispersities, remains a challenging task and is currently an important matter of ongoing research, mostly due to the accompanying side reactions, i.e., hydrolysis and transesterification. Herein, we studied in detail the impact of 2D...

For the first time, RAFT polymerization of monomeric ionic liquid under hard confinement was successfully carried out. Consequently, macromolecules of well-defined chemical structure and narrow molecular weight distribution were obtained. Additionally, we reported the unique possibility of triggering RAFT polymerization at 30oC. This novel strategy...

The effect of nanoscale confinement on the formation of glacial phase in triphenyl phosphite (TPP), usually assigned to liquid-liquid transition (LLT), was investigated by a combination of differential scanning calorimetry (DSC), broadband dielectric (BDS) and Raman spectroscopy. Although the application of micronscale confinement revealed the prese...

The synthesis of well-defined imidazolium-based poly(ionic liquid)s (PILs) by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization is demonstrated. Two specially designed monomeric ionic liquids (MILs), such as 1-methyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide [MVIM][NTf2] and 1-ethyl-3-vinylimidazolium bis(trifluorom...

Development of green ε-caprolactone (CL) polymerization method is the most important challenge of modern polymer chemistry. Herein, we propose a novel way to produce polyesters of well-defined chemical structure, narrow molecular weight distributions by using combination of high pressure, temperature and water. We found two competitive phenomena: p...

The kinetics of polymerization of Bisphenol-A diglycidyl ether (DGEBA), a well-known epoxy resin, with two ionic amines 1-(3-aminopropyl)-3-butylimidazolium bis(trifluoromethylsulfonyl)imide ([apbim][NTf2]) and the tetrabutylammonium leucine ([N4444][Leu]) have been studied with the use of differential scanning calorimetry (DSC) and broadband diele...

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 funct...

Copolymers with semigrafted topology, consisting of a linear block of poly(ethylene glycol) (PEG) and polymethacrylic segments with loosely distributed oligo(propylene glycol) (OPG) grafts, were obtained by atom transfer radical polymerization (ATRP). The synthesis was performed with the use of a monofunctional macroinitiator (bromoester functional...

The amphiphilic graft copolymers containing polyether-b-polymethacrylate side chains are proposed as carriers for a non-steroidal anti-inflammatory drug, indomethacin (IMC). Two series of copolymers, poly((methyl methacrylate)-co-(poly(ethylene glycol methacrylate)-graft-poly((methacrylic acid)-co-(tert-butyl methacrylate)))) (P(MMA-co-(PEGMA-graft...

(Co)polymerization of four pairs of monomers, that is methyl methacrylate (MMA) and tert-butyl methacrylate (tBMA) or tert-butyl acrylate (tBA), methyl acrylate (MA) and tBMA or tBA, was initiated by pentaerythritol tetrakis(2-bromoisobutyrate) to obtain a four-armed star shaped co-polymers. Reactions were carried out by atom transfer radical polym...

Otrzymano dwie serie gwiaździstych polimerów statystycznych, poli(MA-co-TBA) i poli(MA-co-TBMA) zawierających różny udział grup tert-butylowych regulowanych przez określone początkowe stężenie komonomerów. Badania wykazały stosunkowo niską konwersję (~20%) w przypadku kopolimeryzacji z TBA po 3-4h, zaś użycie bardziej reaktywnego komonomeru, tj. TB...

The core-shell micelles in aqueous solutions were prepared at low CAC values (<0.1 mg · mL(-1) ) from amphiphilic graft copolymers consisting of poly(methyl methacrylate) backbone (120-165 units) with loosely grafted (17-40%) hydroxyl-capped PEG (9 vs 6 units in side chain) for drug loading. Hydrophobic indomethacin (IMC) was loaded into the micell...

A series of the well-defined amphiphilic graft copolymers based on poly(propylene glycol) methacrylate (PPGMA) extended with polymethacrylate segment containing methacrylic acid units was successfully synthesized combining atom transfer radical polymerization (ATRP), esterification, “grafting from” polymerization, and acidolysis. The multistep proc...

The synthesis of monomodal copolymers with poly(ethylene glycol) (PEG) side chains from commercial poly(ethylene glycol) methacrylates (PEGMA) by atom transfer radical polymerization (ATRP) is verified. Two hydroxy-functionalized PEGMA macromonomers (520 g/mol and 360 g/mol) were copolymerized with methyl methacrylate (MMA) using various initial fe...

The reactive oxirane groups were incorporated into the macromolecule as substituents in the side chains of loosely-grafted copolymer or in the arms of star-shaped copolymer using glycidyl methacrylate (GMA) in the controlled atom transfer radical polymerization (ATRP). The branched GMA copolymers with various architectures were obtained by using hy...

Linear and star-shaped poly(ε-caprolactone) (PCL) block copolymers containing poly(meth)acrylate segments with glycidyl, 2-(trimethylsilyloxy)ethyl and tert-butyl pendant groups were synthesized using mono-, di- and trifunctional PCL macroinitiators and appropriate (meth)acrylate monomers by controlled radical polymerization. The well-defined struc...