A generalized equation for the prediction of melting temperatures of homopolymers and copolymers

A generalized equation was derived to calculate the melting temperatures of homopolymers and copolymers. The Gibbs‐Thomson equation for homopolymers and a modified application to copolymers were derived using the proposed equation. The melting temperature T_m⁰ in the Flory equation corresponds to the melting temperature T_m^C,∞ of copolymer crystals with stems of infinite length. Also, T_m^C,n*, the melting temperature for copolymer crystals with stems containing the maximum possible number of structural units, n*, should be used instead of T_m⁰ as the basis of supercooling in crystallization. The proposed equation shows good agreement with experimental data for α‐alkene‐ethylene homogeneous copolymers.     

On the use of pressure‐volume‐temperature data of polyethylene liquids for the determination of their solubility and interaction parameters

Specific volumes of high‐density and low‐density polyethylene liquids at several elevated temperatures and pressures were measured. The measured specific volumes were then used to estimate the thermal expansion coefficients $\left( {{\rm \alpha = }\frac{{\rm 1}}{v}\left( {\frac{{\partial v}}{{\partial T}}} \right)_P } \right)$ and isothermal compressibility $\left( {{\rm \beta = } - \frac{{\rm 1}}{v}\left( {\frac{{\partial v}}{{\partial P}}} \right)_T } \right)$ of the polymers. Two different approaches were used in which one was simply to fit the raw data by second order polynomials to obtain (?v/?T)_P and (?v/?P)_T, while the other by the Sanchez‐Lacombe (S‐L) equation of state. It was found that the resultant α and β obtained from the above methods differ significantly, indicating that the S‐L equation of state may not be suitable for determining α and β at elevated temperatures. When these two sets of α and β were used to calculate the corresponding solubility parameters and then the Flory‐Huggins interaction parameters (χ) of the polymers, the results also differ considerably. Nonetheless, χ obtained from the first method agrees well with the results obtained from small angle neutron scattering measurements while the S‐L equation of state method does not. The current results suggest that solubility and interaction parameters obtained from pressure‐volume‐temperature experiments depend critically on the manner by which the data analysis is performed. Polym. Eng. Sci. 44:853–860, 2004. © 2004 Society of Plastics Engineers.     

Investigations Towards the Chemoselective Thioacetaliztion of Carbonyl Compounds by Using Ionic Liquid [bmim]Br as a Recyclable Catalytic Medium

The ionic liquid based on the 1‐n‐butyl‐3‐methylimidazolium cation has been prepared and used as an efficient catalytic medum for the chemoselective thioacetalization of carbonyl compounds. Furthermore, recycling and reuse of this ionic liquid medium has been demonstrated. Moreover, the use of this catalytic medium not only avoids the generation of waste but also provides a green process with minimal hazards.     

Epoxy‐montmorillonite clay nanocomposites: Synthesis and characterization

Nanocomposites of epoxy resin with montmorillonite clay were synthesized by swelling of different proportions of the clay in a diglycidyl ether of bisphenol‐A followed by in situ polymerization with aromatic diamine as a curing agent. The montmorillonite was modified with octadecylamine and made organophilic. The organoclay was found to be intercalated easily by incorporation of the epoxy precursor and the clay galleries were simultaneously expanded. However, Na‐montmorillonite clay could not be intercalated during the mixing or through the curing process. Curing temperature was found to provide a balance between the reaction rate of the epoxy precursor and the diffusion rate of the curing agent into the clay galleries. The cure kinetics were studied by differential scanning calorimetry. The exfoliation behavior of the organoclay system was investigated by X‐ray diffraction. Thermogravimetric analysis was used to determine the thermal stability, which was correlated with the ionic exchange between the organic species and the silicate layers. The morphology of the nanocomposites was evaluated by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2201–2210, 2004     

Distributions of Crystal Size from DSC Melting Traces for Polyethylenes

Melting curves, obtained by differential scanning calorimetry, are used to estimate crystal size distributions. The proposed theoretical analysis is applied to different types of polyethylene, including high‐density polyethylene (HDPE), metallocene catalyzed linear low‐density polyethylenes (m‐LLDPE), blends of m‐LLDPEs, and Ziegler‐Natta catalyzed LLDPEs (ZN‐LLDPE). Theoretical predictions are in agreement with experimental results. A generalized melting temperature equation successfully predicts the melting temperatures of all the LLDPEs, although it was initially proposed for homogeneous copolymers with excluded comonomers. A new definition of the heat of fusion for pure crystals is proposed. This heat of fusion can be calculated from the average crystal size or the crystal size number distribution.     

Synthesis,Characterization and Surface Properties of Amidosulfobetaine Surfactants Bearing Odd-Number Hydrophobic Tail

Three amidosulfobetaine surfactants were synthesized namely: 3-(N-pentadecanamidopropyl-N,N-dimethyl ammonium) propanesulfonate (2a); 3-(N-heptadecanamidopropyl-N,N-dimethyl ammonium) propanesulfonate (2b), and 3-(N-nonadecanamidopropyl-N,N-dimethyl ammonium) propanesulfonate (2c). These surfactants were prepared by direct amidation of commercially available fatty acids with 3-(dimethylamino)-1-propylamine and subsequent reaction with 1,3-propanesultone to obtain quaternary ammonium salts. The synthesized surfactants were characterized by IR, NMR and mass spectrometry. Thermogravimetric analysis (TGA) results showed that the synthesized surfactants have excellent thermal stability with no major thermal degradation below 300 °C. The critical micelle concentration (CMC) values of the surfactants 2a and 2b were found to be 2.2 × 10^?4 and 1.04 × 10^?4 mol/L, and the corresponding surface tension (γ_CMC) values were 33.14 and 34.89 mN m^?1, respectively. The surfactants exhibit excellent surface properties, which are comparable with conventional surfactants. The intrinsic viscosity of surfactant (2b) was studied at various temperatures and concentrations of multi-component brine solution. The plot of natural logarithm of relative viscosity versus surfactant concentration obtained from Higiro et al. model best fit the surfactant behavior. Due to good salt resistance, excellent surface properties and thermal stability, the synthesized surfactant has potential to be used in various oil field applications such as enhanced oil recovery, fracturing, acid diversion, and well stimulation.     

Zirconia Nanoparticles Made in Spray Flames at High Production Rates

Synthesis of zirconia nanoparticles by flame spray pyrolysis (FSP) at high production rates is investigated. Product powder is collected continuously in a baghouse filter unit that is cleaned periodically by air-pressure shocks. Nitrogen adsorption (BET), X-ray diffractometry (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA) are used to characterize the product powder. The effect of powder production rate (up to 600 g/h), dispersion gas flow rate, and precursor concentration on product particle size, crystallinity, morphology, and purity is investigated. The primary particle size of zirconia is controlled from 6 to 35 nm, while the crystal structure consists of mostly tetragonal phase (80–95 wt%), with the balance monoclinic phase at all process conditions. The tetragonal crystal size is close to the primary particle size, which indicates weak agglomeration of single crystals.     

Effect of N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine antioxidant on the adhesion properties of (zinc oxide)‐filled (epoxidized natural rubber 25)‐based pressure‐sensitive adhesives

The effect of antioxidant, namely, N‐isopropyl‐N′‐phenyl‐p‐phenylenediamine (IPPD), on the adhesion properties of epoxidized natural rubber (ENR 25)‐based pressure‐sensitive adhesive was investigated. The concentration of the IPPD was varied from 0 to 5 parts by weight per hundred parts of rubber (phr). Coumarone‐indene resin, zinc oxide, toluene, and polyethylene terephthalate were used as the tackifier, filler, solvent, and substrate, respectively. A Lloyd Adhesion Tester operating at different testing rates (10–60 cm/min) was used to determine the loop tack, peel strength, and shear strength at 60‐µm and 120‐µm coating thicknesses. Results indicate that adhesion properties increase with IPPD up to 2 phr of content, after which it decreases with further addition of the antioxidant. This observation is attributed to the culmination of wettability and compatibility at the optimum IPPD concentration. The 60‐µm coated sample consistently shows higher adhesion strength than that of 120‐µm coated sample. Loop tack and peel strength increase with testing rate up to 30 cm/min. However, shear strength increases with increasing testing rate in the testing rate investigated in this study. J. VINYL ADDIT. TECHNOL., 21:111–115, 2015. © 2014 Society of Plastics Engineers