Showing papers in "Journal of Polymer Science Part B in 1982"

Determination of branching distributions in polyethylene and ethylene copolymers

Abstract: A description is given of an analytical temperature-rising elution fractionation (TREF) system for the purpose of determining short-chain branching (SCB) or copolymer distributions in poly-ethylenes and ethylene copolymers. The system achieves fractionation on the basis of crystallizability and is shown to be very little influenced by molecular weight in the normal high polymer range. Sample preparation by slow cooling from relatively dilute solution followed by continuous elution with a simultaneous and fairly rapid rate of temperature rise proves to be an efficient fractionation process. An on-line detector and data system allows application of a calibration curve to give realistic SCB distribution data in a convenient manner. The potential value of the TREF technique for providing structural information is illustrated by examples which include low-density high-pressure resins made by both tubular and autoclave reactors, high- and low-density resins made by low-pressure processes, and copolymers of ethylene with vinyl acetate and ethyl acrylate.

Effect of molecular entanglements on craze microstructure in glassy polymers

Abstract: Thin films of ten glassy polymers are bonded to copper grids and strained in tension to produce crazes, which are then examined in the transmission electron microscope. The average craze fibril extension ratio λ for each polymer is determined from microdensitometer measurements of the mass thickness contrast of the crazes. The extension ratio λ is found to increase approximately linearly with the chain contour length le between entanglements, as determined from melt elasticity measurements of the entanglement molecular weight of these polymers. These results are analyzed by comparing them with λmax, the maximum extension ratio of an entanglement network in which polymer chains neither break nor reptate (i.e., permanent entanglement crosslinks are assumed). The values of λmax are given by le/d where d, the entanglement mesh spacing in the unoriented glass, is computed from d = k(Me)1/2 with k determined either from small-angle neutron scattering results on isolated chains in the glass or from coil size measurements in dilute solutions of a θ solvent. The craze extension ratios fall somewhat below λmax at low λ but increase to well above λmax for polymers with high le. This comparison suggests a significant contribution due to chain breakage (or reptation) in the higher-λ crazes of large-le polymers, which may arise from the higher true stresses in the craze fibrils (which for a given applied stress increase proportionally to λ). The results also imply that a useful way to increase the “brittle” fracture stress and decrease the ductile-to-brittle transition temperature of a glassy polymer is to decrease its entanglement contour length le.

Bisphenol‐A polycarbonate–poly(butylene terephthalate) transesterification. I. Theoretical study of the structure and of the degree of randomness in four‐component copolycondensates

Abstract: This article is the first of a series devoted to various aspects of exchange reactions in molten bisphenol-A polycarbonate–poly(butylene terephthalate) mixtures. The statistical aspects of exchange reactions between two polycondensates of different chemical structure are considered. This theoretical approach enables us to calculate the mean lengths of the various sequences as well as several expressions for the degree of randomness in four-component copolycondensates from triad or dyad concentrations as determined by NMR spectroscopy.

Molecular design of multicomponent polymer systems. III. Comparative behavior of pure and tapered block copolymers in emulsification of blends of low‐density polyethylene and polystyrene

Abstract: Poly(hydrogenated butadiene-b-styrene) copolymers are very effective emulsifiers for blends of polystyrene and low-density or high-density polyethylene. It is shown that the extent of improvement in mechanical properties is dependent not only on the molecular weight but also on the structure of the diblock copolymer. A comparative study of the morphology and the mechanical behavior of modified low-density polyethylene/polystyrene blends demonstrates that a tapered diblock is more efficient than a pure diblock with the same composition and molecular weight. It is assumed that the unique behavior of the tapered sample results from its particular miscibility characteristics at the blend interface. The tapered copolymer could behave essentially as a solu-bilizing agent for the homopolymers at the interface and provide a “graded” modulus responsible for the improved mechanical response of the material.

Bisphenol‐A polycarbonate–poly(butylene terephthalate) transesterification. II. Structure analysis of the reaction products by IR and 1H and 13C NMR

Abstract: The structure of the four-component copolyester resulting from the exchange reaction between molten bisphenol-A polycarbonate and poly(butylene terephthalate) is analyzed as a function of the reaction time by infrared and nuclear magnetic resonance spectroscopy. By applying a statistical method developed earlier, the mean chain length of the various sequences as well as the degree of randomness is computed. The exchange reaction leads initially to the formation of a block copolyester with reduced solubility. As the reaction proceeds, a soluble random copolycondensate is progressively formed.

Rheology of a thermotropic polyester in the nematic and isotropic states

Abstract: The rheological properties of a thermotropic polyester were determined in the nematic and isotropic states. In the isotropic state, the viscosity is almost constant and the polymer is only slightly elastic. The nematic phase has a lower viscosity than the isotropic, except at low frequencies or shear rates, where the viscosity increases as though the polymer had a yield stress. There is a marked dependence of the rheology on shear history. The effects of shearing can be erased by returning the material first to the isotropic state and then back to the nematic state. The results are discussed with reference to analogous observations in small-molecule liquid crystals and in thermotropic aromatic co-polyesters.

A study of the pressure‐volume‐temperature relationships of four related amorphous polymers: Polycarbonate, polyarylate, phenoxy, and polysulfone

Abstract: The pressure-volume-temperature (PVT) relationships of bisphenol-A polycarbonate, polyarylate, and phenoxy were studied at pressures to 1800 kg/cm2 and in both the glassy and melt states. Earlier data on polysulfone are included in the analysis and discussion of the results. All four polymers contain the bisphenol-A residue in their repeat unit, together with a moiety of varying complexity, and are therefore somewhat related. At the glass transition, equations of the Ehrenfest type hold, provided the pressure dependence of the glass transition temperature is defined from the line obtained by intersecting the quasiequilibrium PVT relationship of the glass with the equilibrium PVT surface of the melt. The Prigogine-Defay ratio r = ΔκΔCp/TgVg(Δα)2 at P = O is unity within experimental error for all four polymers. The melt data were fitted successfully to the Simha-Somcynsky theory. Molecular parameters deduced from the reducing parameters vary in a reasonable manner among these four related polymers, lending support to the foundations of the theory.

Nematic and cholesteric thermotropic polyesters with azoxybenzene mesogenic units and flexible spacers in the main chain

Abstract: Properties of linear polyesters based on azoxybenzene and 2,2′-methylazoxybenzene moieties with linear, flexible spacers based on mixtures of dodecanedioic acid (DDA) and methyladipic acid (MAA), chiral or racemic, of various compositions (system MAA/DDA-8 and MAA/DDA-9, respectively) have been described Substitution of methyl groups in the 2,2′ or 3,3′ positions of the mesogenic core leads to soluble and relatively low-melting-point polyesters The viscosity law for (MAA/DDA-9) polyesters in 1,1,2,2 tetrachloroethane gives an exponent 076, indicating well-sol-vated, coiled chain conformations in dilute solution Calorimetric data show an increase in isotropization entropy ΔSNI with increasing average length of the spacer This suggests a nonrandom conformation of the spacer in the nematic melt with a degree of order superior to that of low-molecular-weight analogs X-ray data obtained with an oriented nematic glass quenched from the nematic melt of DDA-9 subjected to a magnetic field of 10–12 T also support the extended-chain model in the nematic phase of DDA-9 Oriented fibers can be produced by subjecting nematic melts of polyesters 8 and 9 either to magnetic fields of high intensity or to shear fields The x-ray data obtained from these fibers also support the extended-chain model Cholesteric systems do not orient in the magnetic field of 10–12 T The study of mesophases of systems 8 and 9 indicates a dramatic influence of the position of the ester group on the stability of the mesophase in the azoxybenzene polyesters The results are interpreted in terms of geometric factors influencing the colinearity of the mesogenic core and of the extended spacer

Miscibility of polycaprolactone/chlorinated polyethylene blends

Abstract: Blends of polycaprolactone (PCL) with chlorinated polyethylenes (PECls) having chlorine contents of 25,30,36,42, and 48% by weight were prepared and studied by differential scanning calorimetry and small-angle light scattering (SALS). It was found that blends made with PECls containing 30% or more chlorine are completely miscible with PCL (a single glass transition temperature Tg is found) while the PCL/PECl(25) blends are immiscible. PCL crystallizes in the miscible blends at any composition and it has an enthalpy of fusion which decreases only slightly with PECl content. Blends in the PECl composition interval of 0 4 0 % are spherulitic, as shown by SALS, but a rodlike morphology is found at the 85% composition and dispersed crystals are observed at higher compositions. It is suggested that the k parameter of the Gordon-Taylor equation can be taken as a measure of the strength of the specific interaction between PCL and PECl. Low values of k (0.26 and 0.35) are found for PCL/PECl blends but a higher value of k (0.51) has been reported for PCL/poly(vinyl chloride) (PVC) blends, indicating a stronger interaction in the latter mixtures. In agreement with these findings poly(cY-methyl-a-n-propyl-8-propiolactone) and poly(valero1actone) are not miscible with PECl, whereas they were previously shown to be miscible with PVC.

Behavior of concentrated polystyrene solutions in large‐amplitude oscillating shear fields

Abstract: The limits of linear viscoelastic behavior of polystyrene solutions have been investigated by subjecting them to large-amplitude oscillatory strains, γ0. At strains less than one we find that the dynamic storage modulus G′(ω,γ0) and the dynamic loss modulus G″(ω,γ0) decrease quadratically with increasing strain. As a measure of the size of the linear viscoelastic region, we have determined the strain at which the moduli have fallen 5% below their zero-strain values. This strain, γNL, is found to be independent of frequency ω at high frequencies but to increase with decreasing frequency at low frequencies. Behavior of this type is in qualitative agreement with the recent constitutive equation developed by Doi and Edwards. More specifically, we find that the rate of decrease of the storage modulus with increasing strain is quite similar to that predicted by their theory, but that the rate of decrease of the loss modulus is much slower. Some possible approaches for improving the agreement with experimental results are suggested. In the course of our work an interesting hydrodynamic instability was observed. The nature of this instability and methods to avoid it are discussed.

Mechanical relaxation mechanism of epoxide resins cured with aliphatic diamines

Abstract: The mechanism of low-temperature relaxations in bisphenol-A-type epoxide resins cured with aliphatic diamines, with aliphatic diamines in the presence of salicylic acid as an accelerator, and with tertiary amines was investigated to compare the dynamic mechanical properties and the chemical structure of these networks. Mechanical relaxations are observed at about −140 and −60°C. The former relaxation is denoted the γ relaxation and the latter the β relaxation. The β relaxation of the cured epoxide resins containing hydroxyether groups is a sum of contributions from the relaxation of these groups and of other parts of the network structure. A new relaxation due only to the motion of the hydroxyether group can be estimated from the difference of tanδ curves between the aminecrosslinked and ether-crosslinked systems. The γ relaxation is attributed to the motion of a polymethylene sequence consisting of at least four carbon atoms.

Threshold tear strength of elastomers

Abstract: : Tear strengths have been measured for a wide variety of molecular networks under threshold conditions; i.e., at high temperatures, low rates of tearing, and with swollen samples. For all of the polymers examined, the threshold tear strength was found to be proportional to the square root of the average molecular weight M sub c of network strands, in agreement with theory. However, for the same M sub c and hence for similar values of elastic modulus, different polymers showed major differences in threshold tear strength. The tear strength of polydimethylsiloxane networks was only about one-third as large as that for networks of polybutadiene and cis-polyisoprene and the values obtained for polyphosphazene networks were only about one-fifth as large as the same M sub C. These striking differences are attributed to differences in network strand length and extensibility for the same molecular weight. The threshold tear strengths are shown to be in satisfactory quantitative agreement with theoretically predicted values on this basis. (Author)

Tensile strength of highly oriented polyethylene. II. Effect of molecular weight distribution

Abstract: The tensile strength of oriented polyethylene filaments is discussed in relation to molecular weight. Short-term tensile properties at room temperature were obtained in our laboratory and from the literature for polymer samples covering the molecular weight (Mw) range from 54 × 103 to 4 × 106, and polydispersities ranging from 1.1 to 15.6, oriented by solid-state extrusion, melt spinning/drawing, solution spinning/drawing, and “surface growth.” It was found that both the molecular weight and its distribution markedly affected tensile strength. The breaking stress σ of highly oriented fibers varied with molecular weight roughly as σ ∝, M0.4, at constant Mw/Mn over the entire range studied. Reduction of polydispersity from 8 to 1.1 by an increase of Mn with Mw approximately constant at 105 increased tensile strength of oriented polyethylene filaments by a factor of nearly 2.

A new look at the crystallization of polyethylene. III. Crystallization from the melt at high supercoolings

Abstract: This article is part of the general project laid out in Part I (ref. 9) and is concerned with obtaining information on primary (unthickened) crystals of polyethylene formed at low supercoolings. For this, a technique had to be devised by which crystallization could be speeded up so as to eliminate or at least reduce lamellar thickening. Indeed we were able to increase the rate of crystallization by an order of magnitude using a technique which we have called enhanced self-nucleation. Using this technique we find that when viewed under an optical microscope, spherulites crystallize uniformly over the field of view, and not, as is usual, by a radial growth process. Isothermal crystallization in bulk linear polyethylene has been studied by means of the enhanced self-nucleation technique as a function of crystallization time by using Raman LAM and melting points to assess variations of fold length Data have been obtained at very much shorter times than before. At short times, we find a constant fold length; at longer times the crystals thicken linearly with the logarithm of time. Values of the initial fold length for crystallization temperatures between 118 and 130°C are presented. Associated with the thickening at short times we find an induction time which increases with temperature.

Bisphenol-A polycarbonate-poly(butylene terephthalate) transesterification. III. Study of model reactions

Abstract: Exchange reactions in molten bisphenol-A polycarbonate–poly(butylene terephthalate) mixtures are investigated by means of model reactions. Transesterification can result either from direct ester-ester interchange or via alcoholysis or acidolysis. Among the various reactions investigated, only the PBTP alcoholysis by phenol is not found to occur. Taking into account that bisphenol-A terephthalate units (A2B1) and butylene carbonate units (A1B2) are formed in equimolecular amounts, it is concluded that direct ester-ester interchange is the most likely mechanism for PC-PBTP transesterification.

Pressure‐volume‐temperature properties of blends of poly(2,6‐dimethyl‐1,4‐phenylene ether) with polystyrene

Abstract: The pressure-volume-temperature (PVT) properties of blends of poly(2,6-dimethyl-1,4-phenylene ether) (PPO) with polystyrene (PS) have been studied experimentally in both the glassy and melt states at 0, 20, 40, 50, 60, 80, and 100% PPO content. In all compositions a strong glass transition was observed varying linearly with composition. For all but the 40% PPO composition this was the only transition, indicating molecular compatibility of the components in these blends. The 40% PPO composition showed a very weak second transition near the glass transition of pure PS. A small amount of phase separation may have occurred in this blend. The data for the glassy and melt states were fitted to an empirical equation of state based on the Tait equation. The volume of the melts at constant pressure and temperature showed a virtually linear dependence on composition. Any negative excess volume of mixing compatible with the data would have to be very small, smaller than expected from previous measurements in the glassy state. Various properties relating to the glassy and melt states and to the glass transition were evaluated and are discussed as a function of composition. It was found that most properties of the glasses could not be modeled by simple functions of composition.

Bisphenol-A polycarbonate–poly(butylene terephthalate) transesterification. IV. Kinetics and mechanism of the exchange reaction

Abstract: The kinetic aspects of the bisphenol-A polycarbonate–polybutylene terephthalate exchange reaction are considered as a function of temperature and of the PC/PBTP ratio. The most likely mechanism is a direct reversible ester-ester interchange reaction catalyzed by titanium residues present in commercial PBTP.

The entanglement network and craze micromechanics in glassy polymers

Abstract: Crazes have been grown from crack tips in thin films of the following five polymers: polytertbutylstyrene (PTBS), polystyrene (PS), poly(styrene-acrylonitrile) (PSAN), poly(phenylene oxide) (PPO), and poly(styrene-methyl methacrylate) (PSMMA). These polymers represent a wide range of le values, where le is the chain contour length between entanglements. Quantitative transmission electron microscopy has been used to analyze the extension ratio λcraze and displacement profiles for these crazes. From these measurements the craze surface stresses have been computed by using the method of distributed dislocations. This analysis also permits an accurate measure of the level of the applied stress σ∞. These measurements show that the stress necessary for crazing increases as le decreases and that the higher surface stresses present at crack tips generate crazes that have higher λs than isolated crazes in the same polymers. Surface drawing is shown to be the dominant mechanism for craze thickening in all five polymers.

Phase separation in perfluorosulfonate ionomer membranes

Abstract: The extent of phase separation in Nafion® perfluorosulfonate ionomer membranes has been studied by small-angle neutron scattering (SANS). These polymers, which consist of a perfluorocarbon main chain and a sulfonate-containing side group, can absorb up to 30% by weight of water. Previous studies have shown that clustering of water occurs, forming particles in the size range observable by SANS. The current study is concerned with the fraction of water molecules which participate in the clustering and the chemical composition of the phases present. Experiments have been made on melt-quenched samples which have no fluorocarbon crystallinity. The analysis is based on isotopic replacement experiments in which SANS measurements are made on samples hydrated with mixtures of H2O and D2O. Values of the small-angle x-ray scattering (SAXS), mean-square electron density fluctuation, and mass density are used as additional criteria. It is shown that at high water content (more than 15% absorption by weight), a two-phase model can explain the data with a majority (>60%) of the water molecules in one phase and most (>90%) of the perfluorocarbon in the other phase; a sample hydrated to a lower extent (8% by weight) shows deviations from the two-phase model. These results are consistent with the scattering behavior at large angles observed by SAXS.

Morphological studies of poly(vinylidene fluoride) and its blends with poly(methyl methacrylate)

Abstract: Both pure poly(vinylidene fluoride) (PVF2) and its blends with poly(methyl methacrylate) (PMMA) develop a variety of morphologies when they are crystallized above the 420–424 K range. Two populations of spherulites as well as axialitelike growths are observed. Addition of the PMMA lowers the temperature where these new morphologies develop, makes the spherulites more open, causes the banding periodicity to decrease, and increases the number of small, coarse spherulites. These structures melt in three regimes. The highest-melting-point crystals arise only from a solid-solid transformation of the lowest-melting-point ones. This solid-state transition sometimes causes mixed spherulites to be formed in the blends. Electron and wide-angle x-ray diffraction show the lowest-melting-point species to be α crystals, while the other two are γ crystals. The highest-melting-point species, labeled γ′, and the α crystals seem to be more ordered than the other γ crystals.

Phase transitions in mesophase macromolecules. III. The transitions in poly(ethylene terephthalate‐co‐p‐oxybenzoate)

Abstract: The glass and melting transitions of poly(ethylene terephthalate-co-p-oxybenzoate)s have been studied by differential scanning calorimetry. Despite the higher glass transition expected for polyoxybenzoate, there is almost no change in the glass transition temperature up to 63 mol % oxybenzoate (353 ± 4 K). At high oxybenzoate concentration there seems to be a discontinuous jump to a glass transition of 450 K. This high glass transition has been observed in two-phase materials down to 30 mol % oxybenzoate. The melting transition shows signs of isodimorphism with a minimum in melting temperature at about 60–70 mol % oxybenzoate, 60 K below the melting temperature of poly(ethylene terephthalate). The thermal properties are little affected by the change of the noncrystalline parts of the molecules to a mesophase structure. The transition to the isotropic phase could not be analyzed because of prior decomposition.

The structure of an aminosilane coupling agent in aqueous solutions and partially cured solids

Abstract: The molecular structures of partially cured polyaminopropylsilsesquioxane and aminopropyltriethoxysilane in water have been studied using Fourier-transform infrared, laser Raman, and quasielastic laser light-scattering spectroscopy. A multiply hydrogen-bonded structure is proposed for the intramolecularly interacting amine and silanol groups on the basis of isotope exchange experiment and conformational energy calculations. Conformational restrictions are rather low for the proposed structure, which is thus suitable for the partially cured solid where there are slight perturbations by the surrounding amine and silanol groups. The O.…N distance was experimentally determined to be in the range 2.70–2.67 A and estimated theoretically as 2.49–2.45 A. The aminosilane in very dilute solution is found to be mostly monomeric. The isolated monomer-oligomer transition lies around 0.15% by weight and this transition influences the amount of silane uptake by glass fibers. It is also proposed that this phenomenon may be general for surface treatments by silane coupling agents. Hydrolyzed aminosilane oligomers exist in part as submicron aggregates which can be broken up by the addition of an alcohol. The neutralized aminosilane hydrolyzes very slowly although it dissolves in water instantaneously. Micelle formation is also proposed.