Brillouin scattering and optical Kerr effect study of dimethacrylates: temperature effects

In this paper we report a temperature study of Brillouin scattering and optical Kerr effect in the ethane-1,2-diol dimethacrylate, pentane-1,5-diol dimethacrylate and hexane-1,6-diol dimethacrylate belonging to the series of dimethacrylate homologues. Using these methods we have studied the temperature behaviour of the hypersonic velocity, adiabatic compressibility and optical Kerr constant in the temperature range from 283 to 323 K.

The obtained results are compared to those obtained earlier from Brillouin scattering and optical Kerr effect experiments for butane-1,4-diol dimethacrylate and 2,2′-thiodiethyl dimethacrylate (a sulfur-containing monomer). The results are also discussed in terms of changes in the intermolecular interactions and arrangement in the liquid compounds under study.     

Methacrylate-based polymer blends containing oligomeric 1,2-polybutadienes

Partly miscible polymer blends with semi-IPNs structure built from polydimethacrylate networks and hydroxyl-terminated liquid polybutadienes with predominant 1,2-structure (LBH) were prepared by photopolymerization method. Photopolymerization kinetics of dimethacrylate–LBH mixtures were monitored by DSC technique under isothermal conditions. Kinetic curves and related parameters, like polymerization rate and degree of double bond conversion were determined as functions of dimethacrylate structure, LBH molecular mass, and its content in the mixture as well as polymerization temperature. The photopolymerization kinetics and activation energy for the polymerization rate were discussed taking into account the phase separation occurring during the curing reaction. The extent of phase separation (based on T _g’s measurements) depended on LBH content and dimethacrylate chemical structure. The effect of LBH content on hardness of polymer blends was also examined.     

The influence of aliphatic sulfides on the photoinduced polymerization of butanediol-1,4 dimethacrylate

The photoinduced polymerization of butanediol-1,4 dimethacrylate was investigated in the presence of various linear sulfides and cyclic dithioacetals. Benzophenone was used as a sensitizer. It was found that the addition of small amounts of sulfides to the polymerization mixture causes, depending on the sulfide structure and concentration, reduction or full elimination of an induction period as well as an increase in the reaction rate and yield both in air and argon-saturated systems. The explanation of the obtained results is based on the propensity of sulfides to act as hydrogen donors, chain-transfer agents, and highly oxidizable compounds.     

Brillouin study of photopolymerization process of two-monomer systems

The results of Brillouin scattering investigations of two-component system: 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane/polyethylene glycol methacrylate (bis-GMA/PEGMM) containing 0, 30, 50, 70, 85 and 100 mol% of PEGMM are presented. For the first time the Brillouin spectroscopy was used to monitor the progress of the polymerization process. The polymerization was initiated by ultraviolet radiation (λ=365 nm), at temperature 20°C and 40°C. Some of the physical parameters characteristic for this system such as velocity V, adiabatic compressibility β(ad) and attenuation coefficient α of the acoustic waves have been estimated from Brillouin spectra as a functions of the polymerization time. The obtained results have been discussed in terms of changes of the elastic properties of the two-component system occurring during polymerization process and their dependence on bis-GMA/PEGMM system composition.     

Polymerization of 1,3,5-trithiane in the solid state initiated by UV-irradiation. II. Investigation of the initiation process

The influence of the irradiation and polymerization atmosphere on polymer yield was observed. It was shown that in the initiation process oxygen presence is necessary. ESR studies of UV-and γ-irradiated 1,3,5-trithiane were done. The influence of the irradiation atmosphere on generated radicals and the influence of UV-action on radicals formed by γ-irradiation was also investigated. The possible initiation mechanism of cationic polymerization of 1,3,5-trithiane is discussed. A comparison of the 1,3,5-trithiane is polymerizations initiated chemically and by UV- or γ-irradiation is also given.     

Polymerization kinetics of photocurable acrylic resins

The polymerization kinetics of photocurable compositions based on an epoxyacrylate oligomer and three analogous diacrylate monomers were investigated. The effects of the oligomer-to-monomer ratio, curing conditions, and monomer structure were considered. The polymerization is characterized by a synergistic effect observed in a wide temperature range and occurring for the polymerization rate both in air and Ar and for final conversions in air. The final conversion in Ar is determined by viscosity of a formulation. The presence of a heteroatom (S or O) in the ester group of the reactive diluent is beneficial for the polymerization course, especially in air atmosphere. The best results were obtained for the sulfur-containing monomer. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 665–673, 1998     

Theoretical study of the accuracy of the pulse method,frontal analysis,and frontal analysis by characteristic points for the determination of single component adsorption isotherms

The adsorption isotherms of selected compounds are our main source of information on the mechanisms of adsorption processes. Thus, the selection of the methods used to determine adsorption isotherm data and to evaluate the errors made is critical. Three chromatographic methods were evaluated, frontal analysis (FA), frontal analysis by characteristic point (FACP), and the pulse or perturbation method (PM), and their accuracies were compared. Using the equilibrium-dispersive (ED) model of chromatography, breakthrough curves of single components were generated corresponding to three different adsorption isotherm models: the Langmuir, the bi-Langmuir, and the Moreau isotherms. For each breakthrough curve, the best conventional procedures of each method (FA, FACP, PM) were used to calculate the corresponding data point, using typical values of the parameters of each isotherm model, for four different values of the column efficiency (N=500$N=500$, 1000, 2000, and 10,000). Then, the data points were fitted to each isotherm model and the corresponding isotherm parameters were compared to those of the initial isotherm model. When isotherm data are derived with a chromatographic method, they may suffer from two types of errors: (1) the errors made in deriving the experimental data points from the chromatographic records; (2) the errors made in selecting an incorrect isotherm model and fitting to it the experimental data. Both errors decrease significantly with increasing column efficiency with FA and FACP, but not with PM.     

Surface‐dependent effect of functional silica fillers on photocuring kinetics of hydrogel materials

Two types of silica: precipitated (P, prepared in non‐polar media, a new type, submicrometer sized) and fumed (F, nanosized), both unmodified and surface modified are investigated as functional fillers for potential applications in nanocomposites with poly(2‐hydroxyethyl methacrylate) matrix. Special attention is paid to the kinetics of composite formation in an in situ photopolymerization process. Silica‐containing formulations polymerize faster; this effect is much stronger for silica P having much larger particle size than silica F. Surface treatment leads to further acceleration of the polymerization in case of silica P but to retardation in case of silica F; the effect of modification of the filler surface on properties of composites is different for each of the silicas. The obtained results are discussed in terms of effects of curvature of silica particles, surface properties, solvation cell, interphase region, viscosity changes, and morphology of the resulting composites. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3472–3487     

Spectroscopic and photopolymerization studies of benzyl methacrylate/poly(benzyl methacrylate) two‐component system

The influence of the viscosity of a two‐component system on its molecular dynamics (on the basis of hypersonic wave velocity and attenuation coefficient) and photopolymerization kinetics was studied. The system investigated represented the solution of poly(benzyl methacrylate), PBzMA (MW = 70000) in its monomer, benzyl methacrylate (BzMA). The viscosity of the system was varied by adding various amounts of the polymer to the monomer (10–50 wt %). The molecular dynamics in the neat BzMA was studied by the proton Nuclear Magnetic Resonance (NMR) spin‐lattice relaxation time measurements and the wide‐line ¹H NMR spectroscopy in a wide range of temperature. Information on the local dynamics in liquid BzMA above its melting temperature was gained from the high‐resolution ¹H and ¹³C NMR spectra. The hypersonic wave velocity and the attenuation coefficient were investigated in the appropriate temperature range related to a viscoelastic relaxation process by the Brillouin light scattering method. The kinetic measurements have demonstrated that the photopolymerization rate rapidly increases and the monomer conversion decreases with increasing polymer‐to‐monomer ratio; this effect has been noted in the whole range of polymer concentration and reaction temperature studied. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1336–1348, 2010