Tosyl iodide – a new initiator for the photo-controlled iodine transfer polymerization of methacrylates under sunlight irradiation

A very simple photo-controlled iodine transfer polymerization system consisting only of methacrylate monomers, solvent (dimethylacetamide), and initiator (tosyl iodide) under violet and sunlight irradiation is reported. In this report, the...

The Role of Polymer Structure in Formation of Various Nano- and Microstructural Materials: 30 Years of Research in the Laboratory of Nano- and Microstructural Materials at the Centre of Polymer and Carbon Materials PAS

The review summarizes the research carried out in the Laboratory of Nano- and Microstructural Materials at the Centre of Polymer and Carbon Materials, Polish Academy of Sciences (CMPW PAS). Studies carried out for many years under the guidance of Professor Andrzej Dworak led to the development and exploration of the mechanisms of oxirane and cyclic imine polymerization and controlled radical polymerization of methacrylate monomers. Based on that knowledge, within the last three decades, macromolecules with the desired composition, molar mass and topology were obtained and investigated. The ability to control the structure of the synthesized polymers turned out to be important, as it provided a way to tailor the physiochemical properties of the materials to their specific uses. Many linear polymers and copolymers as well as macromolecules with branched, star, dendritic and hyperbranched architectures were synthesized. Thanks to the applied controlled polymerization techniques, it was possible to obtain hydrophilic, hydrophobic, amphiphilic and stimulus-sensitive polymers. These tailor-made polymers with controlled properties were used for the construction of various types of materials, primarily on the micro- and nanoscales, with a wide range of possible applications, mainly in biomedicine. The diverse topology of polymers, and thus their properties, made it possible to obtain various types of polymeric nanostructures and use them as nanocarriers by encapsulation of biologically active substances. Additionally, polymer layers were obtained with features useful in medicine, particularly regenerative medicine and tissue engineering.

Assemblies of Polyacrylonitrile-Derived Photoactive Polymers as Blue and Green Light Photo-Cocatalysts for Cu-Catalyzed ATRP in Water and Organic Solvents

Photoluminescent nanosized quasi-spherical polymeric assemblies prepared by the hydrothermal reaction of polyacrylonitrile (PAN), ht-PLPPAN, were demonstrated to have the ability to photo-induce atom transfer radical polymerization (ATRP) catalyzed by low, parts per million concentrations of CuII complex with tris(2-pyridylmethyl)amine (TPMA). Such photo induced ATRP reactions of acrylate and methacrylate monomers were performed in water or organic solvents, using ht-PLPPAN as the photo-cocatalyst under blue or green light irradiation. Mechanistic studies indicate that ht-PLPPAN helps to sustain the polymerization by facilitating the activation of alkyl bromide species by two modes: 1) green or blue light-driven photoreduction of the CuII catalyst to the activating CuI form, and 2) direct activation of dormant alkyl bromide species which occurs only under blue light. The photoreduction of the CuII complex by ht-PLPPAN was confirmed by linear sweep voltammetry performed under illumination. Analysis of the polymerization kinetics in aqueous media indicated even though CuI complexes comprised only 1–1.4% of all Cu species at equilibrium, they exhibited high activation rate constant and activated the alkyl bromide initiators five to six orders of magnitude faster than ht-PLPPAN.

UV Polymerization of Methacrylates—Preparation and Properties of Novel Copolymers

More environmentally friendly polymeric materials for use in corrosive conditions were obtained in the process of UV polymerization of terpene methacrylate monomers: geranyl methacrylate and citronellyl methacrylate and the commercially available monomer methyl methacrylate. Selected properties (solvent resistance, chemical resistance, glass transition temperature, thermal stability, and decomposition course during heating) were evaluated. It was found that the properties of the materials directly depended on the monomer percentage and the conditioning temperatures used. An increase in the geranyl or citronellyl methacrylate monomer content in the copolymers reduced the solubility and chemical resistance of the materials post-cured at 50 °C. The samples post-cured at 120 °C were characterized by high resistance to polar and non-polar solvents and the chemical environment, regardless of the percentage composition. The glass transition temperatures for samples conditioned at 120 °C increased with increasing content of methyl methacrylate in the copolymers. The thermal stability of copolymers depended on the conditioning temperatures used. It was greater than 200 °C for most copolymers post-cured at 120 °C. The process of pyrolysis of copolymers led to the emission of geranyl methacrylate, citronellyl methacrylate, and methyl methacrylate monomers as the main pyrolysis volatiles.

Enhancement of Polymer Structural Ordering in Polymer-Stabilised Blue Phases for Improved Electro-Optical Properties

Polymer-stabilised blue phase (PSBP) could be employed in novel fast response optical and photonic devices. It is inferred that inside PSBPs, the polymers are selectively aggregated by location in −1/2 disclinations, which are defects coexisting with the blue phase as a periodic lattice, thereby extending the temperature range of the blue phase. The polymer aggregate structure in PSBPs strongly affects their physical properties. In this study, we employed a non-destructive synchrotron ultra-small-angle X-ray diffraction analysis to investigate the effect of polymerisation rates on the polymer aggregate structure in PSBPs prepared with monomers of different polymerisation rates and examined the structure formation process of the polymer during polymerisation. When methacrylate monomers, which exhibit a relatively low polymerisation rate, were used to form polymers in PSBP, the resulting polymer was more selectively aggregated at disclinations in the PSBP. Furthermore, the electro-optical effect in the PSBP was successfully improved by reducing the polymer concentration in the PSBPs prepared with the optimised monomer combinations.

Applications of the Poly(methyl methacrilate) (PMMA) in Cranioplasty

Cranioplasty is a surgical procedure that is used to correct any defect in skull bones after a previous decompresive craniectomy, usually made for traumatic brain injuries, with ischemic or hemorragic nature, or after a tumor removal. A composite for modeling on a defect in skull bones was prepared by crosslinking poly(methyl methacrylate) in the presence of barium sulfate. The crosslinking rate of methyl polymethacrylate in the presence of the benzoyl peroxide initiator, the N, N-dimethyl-β-toluidine polymerization accelerator and the hydroquinone polymerization inhibitor allows modeling according to the location and size of the defect. Thus, the concentration of composite precursor components was optimal for this purpose. The TGA diagram shows the almost total consumption of methyl methacrylate and butyl methacrylate monomers in the crosslinking process of methyl polymethacrylate with the formation of the composite. This technical study demonstrate the efficacy of this treatment, as well as to show all the possible scenarios in such procedures.

Modelling ATR-FTIR Spectra of Dental Bonding Systems to Investigate Composition and Polymerisation Kinetics

Component ratios and kinetics are key to understanding and optimising novel formulations. This warrants investigation of valid methods. Attenuated Total Reflectance Fourier Transform Infra-Red (ATR)-FTIR spectra of separate primers/adhesives were modelled using summed spectra of solvents (water, ethanol), methacrylate monomers (HEMA (hydroxyethyl methacrylate), Bis-GMA (bisphenol A glycidyl methacrylate), and 10-MDP (10-methacryloyloxydecyl dihydrogen phosphate)), and fillers, multiplied by varying fractions. Filler loads were obtained following their separation from the adhesives, by analysing three repetitions (n = 3). Spectral changes during light exposure at 37 °C (20 s, LED 1100–1330 mW/cm2) were used to determine polymerisation kinetics (n = 3). Independent samples T-test was used for statistical analysis (significance level of 5%). FTIR modelling suggested a primer solvent percentage of OBFL (Optibond FL) (30%) was half that of CFSE (Clearfil SE 2) (60%). OBFL included ethanol and water, while CFSE included only water. Monomer peaks were largely those of HEMA with lower levels of phosphate monomers. OBFL/CFSE adhesive model spectra suggested that both contained equal volumes of Bis-GMA/HEMA, with CFSE having 10-MDP. Filler levels and spectra from OBFL (48 wt.%) and CFSE (5 wt.%) were different. Both systems reached a 50% conversion rate within seconds of light exposure. The final conversion for OBFL (74 ± 1%) was lower compared to CFSE (79 ± 2%) (p < 0.05). ATR-FTIR is a useful method to investigate relative levels of main components in bonding systems and their polymerisation kinetics. Such information is valuable to understanding such behaviour.

Visible light-induced controlled surface grafting polymerization of hydroxyethyl methacrylate from isopropylthioxanthone semipinacol-terminated organic monolayers

Reaction scheme of the visible light-induced controlled surface grafting polymerization of methacrylate monomers onto organosilane-coated silicon initiated by previously coupled dormant ITXSP groups.