Developing (Quantitative Structure Property Relationships) QSPR Techniques to Predict the Char Formation of Polybenzoxazines

This study uses the Molecular Operating Environment software (MOE) to generate models to calculate the char yield of polybenzoxazines (PBz). A series of benzoxazine (Bz) monomers were constructed to which a variety of parameters relating to the structure (e.g., water accessible surface, negative van der Waals surface area and hydrophobic volume, etc.) were obtained and a quantitative structure property relationships (QSPR) model was generated. The model was used to generate data for new Bz monomers with desired properties and a comparison was made of predictions based on the QSPR model with the experimental data. This study shows the quality of predictive models and confirms how useful computational screening is prior to synthesis

Predicting Glass Transition Temperatures of Polyarylethersulphones Using QSPR Methods

The technique of Quantitative Structure Property Relationships has been applied to the glass transition temperatures of polyarylethersulphones. A general equation is reported that calculates the glass transition temperatures with acceptable accuracy (correlation coefficients of between 90–67%, indicating an error of 10–30% with regard to experimentally determined values) for a series of 42 reported polyarylethersulphones. This method is quite simple in assumption and relies on a relatively small number of parameters associated with the structural unit of the polymer: the number of rotatable bonds, the dipole moment, the heat of formation, the HOMO eigenvalue, the molar mass and molar volume. For smaller subsets of the main group (based on families of derivatives containing different substituents) the model can be simplified further to an equation that uses the volume of the substituents as the principal variable

Single Ion Free Energy Calculation in ASIC1: The Importance of the HG loop

Acid Sensing Ion Channels (ASICs) are one of the most studied channels of the Epithelial Sodium Channel/Degenerin (ENaC/DEG) superfamily. They are responsible for excitatory responses following acidification of the extracellular medium and are involved in several important physiological roles. The ASIC1 subunit can form a functional homotrimeric channel and its structure is currently the most characterised of the whole ENaC/DEG family. Here we computed the free energy profiles for single ion permeation in two different structures of ASIC1 using both Na+ and Cl- as permeating ions. The first structure is the open structure of the channel from the PDB entry 4NTW, and the second structure is the closed structure with the re-entrant loop which contains the highly conserved `HG' motif form PDB entry 6VTK. Both structures show cation selective free energy profiles, however the profiles of the permeating Na+ differ significantly between the two structures. Indeed, whereas there is only a small energetically favorable (-0.5 kcal mol-1) location for Na+ in the open channel (4NTW) near the end of the pore, we observed a clear ion binding site (-7.8 kcal mol-1) located in between the `GAS' belt and the `HG' loop for the channel containing the re-entrant loop (6VTK). Knowing that the `GAS' motif was determined as the selectivity filter, our results support previous observations while addressing the importance of the `HG' motif for the interactions between the pore and the permeating cations

A Novel Approach to Atomistic Molecular Dynamics Simulation of Phenolic Resins Using Symthons

Materials science is beginning to adopt computational simulation to eliminate laboratory trial and error campaigns—much like the pharmaceutical industry of 40 years ago. To further computational materials discovery, new methodology must be developed that enables rapid and accurate testing on accessible computational hardware. To this end, the authors utilise a novel methodology concept of intermediate molecules as a starting point, for which they propose the term ‘symthon’a rather than conventional monomers. The use of symthons eliminates the initial monomer bonding phase, reducing the number of iterations required in the simulation, thereby reducing the runtime. A novel approach to molecular dynamics, with an NVT (Canonical) ensemble and variable unit cell geometry, was used to generate structures with differing physical and thermal properties. Additional script methods were designed and tested, which enabled a high degree of cure in all sampled structures. This simulation has been trialled on large-scale atomistic models of phenolic resins, based on a range of stoichiometric ratios of formaldehyde and phenol. Density and glass transition temperature values were produced, and found to be in good agreement with empirical data and other simulated values in the literature. The runtime of the simulation was a key consideration in script design; cured models can be produced in under 24 h on modest hardware. The use of symthons has been shown as a viable methodology to reduce simulation runtime whilst generating accurate models

On the use of benzaldehyde to improve the storage stability of one-pot, epoxy ionic liquid formulations

A series of adducts were prepared based on the reaction of 1-ethyl-3-methylimidazolium acetate and benzal- dehyde in various stoichiometries (from equimolar reaction to benzaldehyde in 10-fold excess) and the resulting adducts were characterized using nuclear magnetic resonance spectroscopy (¹H, ¹³C, DEPT, and HQSC experi- ments). Differential scanning calorimetry was used to examine the initiating behaviour of the adducts towards mono- and di-functional epoxy resins and the data were used to determine kinetic parameters for the poly- merization. The lower temperature peak, due to carbene formation, is sensitive to adduct concentration; the residual ionic liquid in the adduct mixture contributes towards the initiation of the curing reaction. When a monofunctional epoxy and the 1:1 adduct was subjected to a 2-week period of storage at room temperature and sub-zero temperatures in the freezer, the profiles of the thermograms for the frozen samples do not change considerably over the storage period and the formulation retains a light yellow colour (rather than the viscous, dark red appearance of the formulation stored at room temperature)

Examining the Influence of Bisphenol A on the Polymerisation and Network Properties of An Aromatic Benzoxazine

A series of reactive blends, comprising a commercial benzoxazine monomer, 2,2-bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine)propane, and bisphenol A is prepared and characterized. Thermal analysis and dynamic rheology reveal how the introduction of up to 15 wt % bisphenol A lead to a significant increase in reactivity (the exothermic peak maximum of thermal polymerization is reduced from 245 °C to 215 °C), with a small penalty in glass transition temperature (reduction of 15 K), but similar thermal stability (onset of degradation = 283 °C, char yield = 26%). With higher concentrations of bisphenol A (e.g. 25 wt %), a significantly more reactive blend is produced (exothermic peak maximum = 192 °C), but with a significantly lower thermal stability (onset of degradation = 265 °C, char yield = 22%) and glass transition temperature (128 °C). Attempts to produce a cured plaque containing 35 wt % bisphenol A were unsuccessful, due to brittleness. Molecular modelling is used to replicate successfully the glass transition temperatures (measured using thermal analysis) of a range of copolymers

Exploring Structure–Property Relationships in Aromatic Polybenzoxazines Through Molecular Simulation

A series of commercial difunctional benzoxazine monomers are characterized using thermal and thermo-mechanical techniques before constructing representative polymer networks using molecular simulation techniques. Good agreement is obtained between replicate analyses and for the kinetic parameters obtained from differential scanning calorimetry data (and determined using the methods of Kissinger and Ozawa). Activation energies range from 85 to 108 kJ/mol (Kissinger) and 89 to 110 kJ/mol (Ozawa) for the uncatalyzed thermal polymerization reactions, which achieve conversions of between 85% and 97%. Glass transition temperatures determined from differential scanning calorimetry and dynamic mechanical thermal analysis are comparable, ranging from BA-a (151 °C, crosslink density 3.6 × 10−3 mol cm−3) containing the bisphenol A moiety to BP-a, based on a phenolphthalein bridge (239 to 256 °C, crosslink density 5.5 to 18.4 × 10−3 mol cm−3, depending on formulation). Molecular dynamics simulations of the polybenzoxazines generally agree well with empirical data, indicating that representative networks have been modelled

Exploring the thermal degradation mechanisms of some polybenzoxazines under ballistic heating conditions in helium and air

The degradation behaviour of five polybenzoxazines (PBZs) is studied using pyrolysis-GC/MS. Upon heating to 800 °C in helium the PBZs generate a variety of similar pyrolysis products including aniline (the major product in all cases), substituted phenols, acridine, and 9-vinylcarbazole. During the initial stages of heating (200–300 °C) aniline is the dominant pyrolysis product; from 350 °C onwards substituted phenols are released, particularly 2-methylphenol and 2,6-dimethyl phenol. The same major species are produced on heating in air, but in addition isocyanatobenzene is observed which results from the oxidation of Mannich bridges, along with a number of sulphurous species from the monomer containing a thioether bridge. This suggests that sulphur is more likely to be retained in the char in a helium atmosphere, but takes part in oxidative reactions to form pyrolysis fragments in air. During the ramped temperature cycles in both air and helium atmospheres the release of aniline was observed to rise, fall and then to rise again. This may be due a combination of the very high heating rate, poor thermal conduction of the polymer and the availability of the Mannich bridges to undergo breakdown

Improving the hydrolytic stability of aryl cyanate esters by examining the effects of extreme environments on polycyanurate copolymers

Three cyanate ester monomer or oligomer species: 2,2-bis(4-cyanatophenyl)propane 1, 1-1-bis(4-dicyanatophenyl)ethane 2, and the oligomeric phenolic cyanate 3, are blended in various ratios to form binary mixtures (18 in total), formulated with copper(II) acetylacetonate (200 ppm) in dodecylphenol (1 % w/v active copper suspension) and cured (3 Kmin-1 to 150 °C + 1 hour; 3 Kmin-1 to 200 °C + 3 hours) followed by a post cure (3 Kmin-1 to 260 °C + 1 hour). Cured copolymers were exposed to environments of elevated relative humidity (75 % RH) and parallel immersion testing in H2O, H2SO4 (10 %) and NaOH (10 %) at 25 °C for a period of up to 2 years and accelerated ageing in boiling water (14 days). Periodic measurements are made of moisture gain along with infrared spectra and compared with cured homopolymers. Changes in mass are recorded periodically throughout exposure, prior to destructive thermo-mechanical analyses. Dynamic mechanical thermal analysis data comparing neat and exposed blends demonstrate the detrimental effect of moisture ingress whilst data from thermogravimetric analysis demonstrate no change in degradation onset between neat and exposed materials. An optimised blend of 1:1 of monomer units 1 and 2 was found to absorb less moisture than blends of different stoichiometry or between other respective monomeric units, consequently limiting the deleterious effect of moisture ingress