Phase relationships and thermodynamic interactions in isotactic polypropylene–diluent systems

Phase relationships of isotactic polypropylene in various organic diluents were investigated. The diluents used were aliphatic alcohols, alkyl phenols, aryl phenols, diphenyl derivatives, alkyl aryl ethers, esters, and others. Among the diluents examined, n-butyl alcohol, p-tert-butyl phenol, p-tert-amyl phenol, diphenyl, diphenyl ether, benzyl phenyl ether, dibenzyl ether, and benzyl propionate were found to be theta solvents for isotactic polypropylene at temperatures in the range 120–190°C. For these theta solvents, the thermodynamic interaction parameters were determined. The results are discussed in relation to the type of diluent.     

Bisphenol-A polycarbonate–diluent interactions

The effect of low-molecular-weight miscible additives on the sub-T_g (β) relaxation process in bisphenol-A polycarbonate (BPAPC) was studied using high-resolution carbon-13 solid-state NMR. The trend of the spin-lattice relaxation times T₁ at 50 MHz suggests that strong intermolecular interactions occur upon mixing when BPAPC is physically stiffened by the antiplasticizing diluent, diphenylphthalate. The values of ¹³C T₁ at 15 MHz in d-chloroform solutions for similar BPAPC-diluent mixtures suggest that diluent effects on the megahertz mobility of the polymer occur exclusively in the solid state. These results are explained using equilibrium thermodynamics, in the Ehrenfest sense, at the second-order glass transition temperature T_g. Theory predicts that the temperature dependence of the Flory–Huggins interaction parameter ?χ/?T changes abruptly as the polymer-diluent blends are cooled below T_g from the molten state. The difference between ?χ/?T in the liquid and glassy states is the major factor which determines the diluent concentration dependence of T_g. A method is developed to estimate the relative magnitudes of χ for polymerdiluent blends in the glassy state.     

Phase relationships and thermodynamic interactions of isotactic poly(1-butene) and organic solvent systems

Isotactic crystalline low-molecular-weight poly(1-butene), iPBu-1, was synthesised by using a metallocene catalyst. The molecular weight was determined by GPC. The chemical structure of iPBu-1 was verified by using high-temperature (13)C NMR spectroscopy and the thermal properties by differential scanning calorimetry (DSC). The (solid+liquid) equilibria, SLE, of iPBu-1 with different hydrocarbons (n-hexadecane, 1-heptene, 1-heptyne, cyclopentane, cyclohexane, cycloheptane, cyclooctane, benzene and propylbenzene) were studied by a dynamic method. By performing these experiments over a large concentration range, the temperature-mole fraction phase diagrams of the polymer-solvent systems could be constructed. From these diagrams it was found that iPBu-1 had the highest solubility in small-ring cycloalkanes and the lowest in n-hexadecane, 1-heptyne and benzene in the mole fraction range measured. The excess Gibbs energy models were used to describe the nonideal behaviour of the liquid phase and to estimate the solubility of iPBu-1 in the whole mole fraction range. Activity coefficients at infinite dilution of polymer and solvent were determined from the solubility measurements and were predicted by using the UNIFAC FV model and molecular Monte Carlo simulations.     

Phase equilibria in polymer–liquid–liquid systems

The phase equilibria in polymer–liquid 1–liquid 2 ternary systems have been calculated on the basis of the Flory-Huggins theory of polymer solutions. A new approximation method based on the “cluster” concept has been introduced for mixed solvents comprising a solvent and a nonsolvent. This concept has been verified with polystyrene–solvent–methanol systems.     

Phase transitions in segmented polyesterurethane–DMSO–water systems

The phase separation processes occurring in polyurethane/DMSO/water mixtures were studied using DSC and cloud point measurements. It is demonstrated that liquid–liquid demixing occurs in ternary solutions of segmented polyesterurethanes at sufficiently high water concentrations. It is also shown that the hard segment can crystallize from solution when cooled to room temperature; while if the mixture is cooled to sufficiently low temperatures, DMSO partially freezes, which also induces crystallization of the soft segment. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 716–723, 2005     

Morphology of polyethylene–carbon black composites

Carbon black is a common polymer additive that is used for reinforcement and for its ability to enhance physical properties, such as conductivity. This article pertains to an X‐ray scattering (SAXS) study of a conductive grade of carbon black and carbon black–polymer composites. The scattering pattern for such blacks displays a surface‐fractal‐like power‐law decay over many decades in scattering vector q. It is often assumed that small‐angle scattering from carbon black aggregates can be described in terms of surface‐fractal models, related to particles with fractally rough surfaces. Such self‐similar surface roughness is usually easy to identify by microscopy; however, electron microscopy from these blacks fails to support this assumption. It is proposed here that this apparent surface‐fractal scattering actually represents a more complicated morphology, including overlapping structural features and a power‐law scaling of polydispersity. One use of conductive black–polyethylene composites is in circuit protection devices where resistive heating leads to a reversible association of carbon black aggregates that controls switching between a conductive and a nonconductive state. Scattering can be used as an in situ tool to observe the morphological signature of this reversible structural change. Scattering patterns support a model for this switching based on local enhancement of concentration and the formation of linear agglomerates associated with the matrix polymer's semicrystalline morphology. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1105–1119, 1999     

Kinetic approach to radiation–induced grafting in the polyethylene–styrene system

To investigate the mechanism of radiation-induced grafting in this system, the increase of monomer concentration in the polyethylene film in styrene vapor was evaluated by measuring the weight increase and formulated to be V([M_∞] ? [M]). The decay of radical concentration was also measured by ESR and the rate constant of the decay was determined. The alkyl type radical was affected only a little by styrene, while the allyl type radical was much affected by styrene. A new computer investigation method was proposed to clarify the reaction mechanism. The data obtained were substituted into differential equations and used to calculate the pattern of increase of the degree of grafting for the preirradiation method with reaction in the vapor phase. Results of these calculations suggest that only allyl type radicals induce grafting reactions and that the grafting reaction seldom occurs in the region of grafted polystyrene.     

Phase studies of surfactant–water systems

Significant advances have been made in establishing phase behavior of a number of nonionic, cationic, anionic, catanionic and fluorinated surfactants in water. An interest in phase equilibria existing at sub-ambient temperatures is developing. The study of cubic, intermediate, defective lamellar and sponge phases is an active field of research at present. Further work is needed in exploring thermodynamic stability of rigid nanodisks and densely packed vesicles. Colloidal aspects, thermodynamic and volumetric properties of the surfactant-containing systems deserve special attention.     

Flexural behavior of unidirectional polyethylene–glass fiber–PMMA hybrid composites

Unidirectional hybrid laminates based on glass fibers (GF) and high performance polyethylene fibers (PEF) were prepared with a partially polymerized methyl methacrylate (MMA) matrix at room temperature followed by heating at 55°C for the stipulated time (well below the softening point of PEF). The ultimate flexural strength (UFS), flexural modulus (FM) and interlaminar shear strength (ILSS) of the composites were determined and analyzed. An interesting observation of the study was the change in flexural behavior, which was largely dependent on the position of GF and PEF ply/plies in the compression and tension sides. When the ply/plies of PEF were at the tension side, the UFS and FM showed a higher value than that when GF plies were in the tension side of the hybrid composites. The ILSS also follows the same trend regarding the position of the GF and PEF plies.     

The crystallization of polymer–diluent mixtures

A theory pertinent to the nucleation of polymer-diluent systems for molecules of finite molecular weight has been developed. These results have been applied to the crystallization from polyethylene-α-chloronaphthalene mixtures using molecular weight fractions of polyethylene ranging from 4,000 to 250,000. This analysis is carried out over the composition range extending from pure polymer to a polymer fraction of 0.30. According to this theory, the interfacial basal free energy decreases as either the molecular weight or diluent concentration decreases.     

Study of physicochemical interactions in metal–polymer systems

This article deals with the investigation of adhesive joints of unlike metals separated by layers of thermoplastics. Experimental data are presented on electrical conductivity of polymers at temperatures of 333–573 K in the electric field of 1–10² V/cm. Infrared (IR) spectroscopy data have been used to establish correlation between the parameters of the voltage generated on the metal–polymer specimens and the existence of groups that can form hydrogen bonds. Adhesive strength of the adhesive joints is discussed in connection with the performance of a metal–polymer–metal voltaic couple when the adhesive joints are being formed. The results presented allow a conclusion that polymeric dielectrics exhibit properties of electrolytes when heated in contact with metals. Therefore electrochemical interactions between components of metal–polymer systems should be taken into consideration when predictions are made of performance characteristics of industrial materials based on polymers and metals.     

Organic–inorganic polymeric nanocomposites involving novel titanium tetraisopropylate in polyethylene–octene elastomer

The new nanocomposites, by means of an in situ sol–gel process consisting of metallocene polyethylene–octene elastomer (POE) and titanium tetraisopropylate (TTIP), were investigated. In addition, the acrylic acid grafted POE (POE‐g‐AA) was studied as an alternative to POE. Fourier transform infrared (FTIR) spectroscopy, a dynamic mechanical analyzer (DMA) spectrometer, an X‐ray diffractometer (XRD), differential scanning calorimetry (DSC), a thermogravimetric analyzer (TGA), an Instron mechanical tester, and a scanning electron microscope (SEM) were used to characterize and examine the samples. The results indicate that the POE‐g‐AA/TiO₂ hybrid could have a positive effect on the properties of the POE/TiO₂ hybrid because the carboxylic acid groups of acrylic acid should act as coordination sites for the titania phase to form a Ti? O? C chemical bond. The strength of interfacial bonding between the polymer chains and the ceramic phase depended on the amount of TiO₂, as shown by the change in glass‐transition temperature (T_g) with TiO₂ content. The result of mechanical and thermal tests showed that both the tensile strength and the T_g increased to a maximum value and then decreased with an increasing of TiO₂ because excess particles (e.g., greater than 10 wt % TiO₂) might cause separation or segregation between the organic and inorganic phases. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4272–4280, 2004     

Isochronal temperature–concentration diagram for a polymer–diluent system

The results of an investigation of the viscoelastic and thermal properties of the gelatin–glycerol system are presented in the form of a complete temperature–composition diagram. This diagram shows the isochronal (10-sec.) mechanical behavior of the system along lines of constant modulus and thereby affords a convenient assessment of variation in viscoelastic behavior along any isotherm or isopleth of interest. Comparison of the results with previously obtained limited sets of data on a number of other polymer–dilent systems indicates the applicability and utility of such a presentation.     

Well‐defined non‐linear polyethylene‐based macromolecular architectures

Polyethylene (PE)‐based 3‐ and 4‐miktoarm star [PE(PCL)₂, PE(PCL)₃] and H‐type [(PCL)₂PE(PCL)₂] block copolymers [polycaprolactone (PCL)] were synthesized by a combination of polyhomologation, chlorosilane chemistry, and ring opening polymerization (ROP). The following steps were used for the synthesis of the miktoarm stars: (a) reaction of a hydroxy‐terminated polyethylene (PE‐OH), prepared by polyhomologation of dimethylsulfoxonium methylide with a monofunctional boron initiator followed by oxidation/hydrolysis, with chloromethyl(methyl)dimethoxysilane or chloromethyltrimethoxysilane; (b) hydrolysis of the produced ω‐di(tri)methoxysilyl‐polyethylenes to afford ω‐dihydroxy‐polyethylene (difunctional initiator) and ω‐trihydroxy‐polyethylene (trifunctional initiator); and (c) ROP of ɛ‐caprolactone with the difunctional (3‐miktoarm star) or trifunctional macroinitiator (4‐miktoarm star), in the presence of 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2λ⁵,4λ⁵‐catenadi(phosphazene) (t‐BuP₂). The H‐type block copolymers were synthesized using the same strategy, but with a difunctional polyhomologation initiator. All intermediates and final products were characterized by HT‐GPC, ¹H NMR and FTIR analyses. Thermal properties of the PE precursors and all final products were investigated by DSC and TGA. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2129–2136     

Improving polyethylene–octene elastomer/chitosan by graftation of acrylic acid onto polyethylene–octene elastomer—mechanical properties and biodegradability examination and composites characterization

In this study, the properties of polyethylene–octene elastomer/chitosan (POE/chitosan) and acrylic acid (AA)‐grafted‐polyethylene–octene elastomer/chitosan (POE‐g‐AA/chitosan) were examined using various characterizing instruments. Mechanical and thermal properties of POE deteriorated noticeably when it was blended with chitosan, due to the unsatisfactory compatibility between the two phases. The greater compatibility of POE‐g‐AA with chitosan, due to the formation of ester carbonyl and imide groups, led to a much better dispersion and homogeneity of chitosan in the POE‐g‐AA matrix and consequently to noticeably better mechanical properties. Furthermore, with a lower melting point temperature, the POE‐g‐AA/chitosan blend was more easily processed than POE/chitosan. POE‐g‐AA/chitosan had a higher water resistance than POE/chitosan. Both blends suffered weight loss when buried in soil, especially at high levels of chitosan substitution, indicating that both were biodegradable. The mechanical properties of both blends, such as tensile strength and elongation at break, also deteriorated after being buried in soil. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3882–3891, 2003     

Determination of thermodynamic parameters of polymer–solvent systems from sedimentation–diffusion equilibrium in the ultracentrifuge

Sedimentation equilibrium in the ultracentrifuge means that there is such a distribution of molecular species throughout the cell, that the centrifugal forces are balanced by differences in the activities. This provides a method for determination of the activities and the chemical potentials in polymer solutions which, in principle, is very simple and reliable. A complication is caused by polydispersity of the dissolved polymer. If one assumes that the interaction parameter depends on concentration and temperature, but not on molecular weight, it is possible to determine the chemical potential of polymer and solvent from the ultracentrifugal data. Experiments have been carried out on the systems polystyrene–toluene and polystyrene–cyclohexane at different temperatures and in the concentration range 0–80 wt-%. The results are expressed in the data for the chemical potential of the solvent, the number average chemical potential of the polymer and the interaction parameter χ.     

Phase behaviors of nematic liquid crystal/linear polymer systems: Effect of specific interactions

A new model has been proposed that takes into account the specific interaction between nematic liquid crystal and polymer. A generalized lattice fluid model was employed to describe the specific interaction between liquid crystal and polymer. The proposed model postulates that a specific interaction between dissimilar components in a mixture has both an energetic and an entropic component. A degeneracy parameter and an interaction parameter are also discussed, followed by a comparison of the experimental data to the model. The results show that that a specific interaction plays an important role in the phase behaviors of the given systems. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4128–4136, 2000     

Thermodynamic interactions in polymer systems by gas–liquid chromatography. III. Polyethylene–hydrocarbons

Thermodynamic interaction parameters have been calculated from gas–liquid chromatographic measurements for linear and branched polyethylene interacting with selected hydrocarbons. The values of the interaction parameter χ are substantial in spite of chemical similarities between the polymer and low molecular weight hydrocarbon species, a fact attributed to significant differences in the respective thermal expansion coefficients. A systematic increase of χ is observed in going from branched to linear polyethylene systems. The thermal expansion coefficients of these polymer homologs therefore may not be identical. The present χ values differ substantially from those reported in earlier literature. The comparison confirms suspicions that some older data, based on equilibrium sorption experiments, were erroneously low because of an underestimate in the reduced melting temperature of polymer in the presence of excess solvent.     

A Flory–Huggins thermodynamic approach for predicting sorption equilibrium in ternary polymer systems

The Flory–Huggins theory as modified by Pouchlý has been applied to calculate preferential (λ) and total (Y) sorption coefficients for a ternary polymer system. The ternary interaction function (?₁?₂?₃G_T(u₁, ?₃)) is described as the product of three independent binary functions. This expression allows prediction of λ and Y from binary interaction parameters χ, χ, g, g, and g₁₂(?₁₀). Three ternary polymer systems are used to check the validity of the expression. Moreover for polymer systems in which the parameters g and/or g are unknown, a procedure to evaluate them has been developed and verified on systems for which sufficient experimental information is available.