Crystalline characteristics of ethylene/propylene/1,4-hexadiene terpolymers and related ethylene copolymers

An improved differential thermal analytical technique which permits the rapid, convenient characterization of the thermal behavior of crystalline polymers free of any influence of prior thermal history is presented. Characterization of both crystallization and fusion phenomena is described for ethylene/propylene copolymers subjected to well-controlled thermal scanning techniques. Parameters describing these phenomena are derived. While they are nonequilibrium parameters, they are reproducible and capable of correlation with polymer composition. the crystallization onset temperature determined by this cooling technique was found to relate to the molar ethylene content of the copolymers by an equation similar to the one derived by Flory⁵ based on equilibrium melting point. The relationship was found to hold true for a number of ethylene copolymers, including samples of linear and branched polyethylene, commercial EPDM, and ethylene/vinyl acetate copolymers.     

Effect of damp‐heat aging on the structures and properties of ethylene‐vinyl acetate copolymers with different vinyl acetate contents

We reported herein the damp‐heat aging of ethylene‐vinyl acetate copolymers (EVA) with different vinyl acetate (VAc) contents simultaneously for weeks. The aging was carried out under temperature of 40°C and relative humidity of 93% in air atmosphere. The changes of copolymers' structures and properties were investigated by means of FTIR, wide angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) and mechanical tests. CI values derived from ATR‐FTIR spectra have a decrease when aging time is 1 week and then increase during damp‐heat aging process which suggests the first loss then incorporation of O?C group. WAXD infer that the narrowing trend of FWHM and increase of crystal sizes may attribute to the melting and re‐crystallization of secondary crystallization, which is also confirmed by DSC results. Mechanical tests including Shore A and Shore D hardness, modulus at 100%, tensile strength and elongation at break, are all depending on the primary crystallization and influenced little by damp‐heat aging. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Copolymerization of ethylene with vinyl acetate. I. Effect of polymerization temperature on degree of branching

The degree of branching of a series of ethylene–vinyl acetate copolymers was found to be strongly dependent upon polymerization temperature. The copolymers were prepared by free-radical polymerization and had low molecular weights and molar ratios of ethylene: vinyl acetate greater than 3:1. Nuclear magnetic resonance and infrared studies showed that copolymers prepared at 150°C were highly branched and had little crystallinity. Branches were mainly alkyl groups on the polymethylene backbone segments. There was no evidence of δ-acetoxyalkyl branches. Long branches originating by intermolecular H abstraction from the acetylmethyl groups were also expected but could not be detected. These results were consistent with an intramolecular “backbiting” mechanism similar to that found in ethylene homopolymerizations. There was little or no participation by the vinyl acetate moiety in the branching scheme. Copolymers prepared at about 90°C had very few long or short branches and were more crystalline. Copolymers prepared between these temperatures had intermediate degrees of branching and crystallinity.     

Bulk polymer/solvent interactions for polyethylene and EVA copolymers,below their melting temperatures

In this work, the Flory–Huggins parameters corresponding to the amorphous phase of a polyethylene (PE) and two ethylene–vinyl acetate (EVA) copolymers (with 18 and 33 % vinyl acetate content, respectively) samples, with different solvents have been determined below the melting temperature of the polymers, in order to quantify the bulk interactions of these polymer/solvent systems. The employed solvents were a dispersion solvent (cyclohexane), a polar solvent (vinyl acetate) and an association solvent (methanol). Initially, the inverse gas chromatography measurements allowed obtaining the retention volumes, activity coefficients and overall Flory–Huggins parameters of every polymer/solvent system. According to these parameters, in all cases, the more compatible solvent was cyclohexane, so it was selected as the probe to calculate the percentages of crystallinity at room temperature, whose results were in agreement the literature data (35 % for PE, 29 % for EVA18, and 12 % for EVA33). The percentage of crystallinity allowed determining the amorphous Flory–Huggins parameters which are the ones which take into account just the bulk interactions in a polymer/solvent mixture. The Flory–Huggins parameter results show that, to accurately study the vapor–liquid equilibrium between a polymer and a solvent (bulk interactions), when the range of studied temperatures is below the melting point of the polymer, it is crucial to calculate the amorphous contribution (χ _amorphous) on the overall Flory–Huggins parameter. In the case of this study, the lower the vinyl acetate content (higher crystallinity), the higher the difference between the overall and amorphous Flory–Huggins parameters is. Analyzing the interactions between the three polymeric materials and the solvents it can be noticed that, for the most compatible solvent (cyclohexane), χ _amorphous represents the less contribution, or the highest correction, to the overall Flory–Huggins parameter (around 50 % for PE and EVA18, and 79 % for EVA33, the less crystalline polymer).     

Turbidimetric thermal gradient technique for the estimation of compositional distribution of ethylene copolymers

A new experimental technique has been developed for determining the compositional distribution of ethylene copolymers and blends of ethylene homopolymers and copolymers. The method is similar to the turbidimetric titration procedure, but with crystalline precipitation of the various structural species effected by lowering of the temperature. Experimentally, a Brice-Phoenix light-scattering photometer, equipped with a stirred heated cylindrical cell is used as a turbidimeter for measuring the light transmission through a liquid system. The decreasing light transmission of a 0.01% solution in a fixed ratio of solvent and nonsolvent of α-chloronaphthalene and dimethyl phthalate, with a temperature drop of 2°C./min., is plotted against temperature on an X-Y recorder. The more highly branched molecules, that is, those containing higher comonomer content, are the less crystalline, hence are more soluble and precipitate at the lower temperatures. Compositional distribution is estimated from the cooling curves by two procedures: (1) the broader temperature range over which a nonuniform resin precipitates out of solution is compared to that of a more uniform resin, and (2) the higher initial cloud point of a mixture or nonuniform copolymer is compared to the cloud point–comonomer content relationship developed for uniform resins. The effects of molecular weight and molecular weight distribution are shown to be small relative to the effects of structural distribution. The compositional distribution of the ethylenepropylene copolymers studied varies from narrow to broad, depending on the specific coordination catalyst and polymerization method used. Ethylene–vinyl acetate copolymers, on the other hand, are uniform because of the 1:1 reactivity ratios of ethylene and vinyl acetate. Synthetic mixtures of ethylene–vinyl acetate resins of varying vinyl acetate content exhibit the expected nonuniformity. This technique has also been successfully applied to mixtures of high- and low-density polyethylenes, further demonstrating the utility of this new rapid tool for structural characterization. Experimental time is about 2 hr.     

Emulsion copolymerization of vinyl acetate-ethylene in high pressure reactor-characterization by inline FTIR spectroscopy

The objective of this research was to investigate the effect of temperature, pressure, initiator concentration and agitation rate, in ethylene-vinyl acetate emulsion copolymerization, on copolymer composition. The inline React-IR ATR system was used to monitor the reaction as well as to determine residual free vinyl acetate. Pressure, temperature and agitation rate have great influence on mass transfer of ethylene monomer to the reaction sites. The vinyl acetate was introduced in semi-batch mode as well as ethylene since the copolymerization was carried out under a constant pressure of ethylene. The higher temperature results in lower content of ethylene incorporated in copolymer. Increase of pressure has a direct effect on the ethylene content in the copolymers through increasing solubilization of ethylene monomer which in turn increases ethylene content in the copolymers. Copolymers of up to 15 wt.% of ethylene content have been synthesized at an ethylene pressure of 30 bar and a temperature of 75 °C. Analytical methods, such as differential scanning calorimetry, nuclear magnetic resonance, thermogravimetric analysis, and infrared spectroscopy were used for characterization of copolymers.     

Shape memory effect of ethylene–vinyl acetate copolymers

Crosslinked ethylene–vinyl acetate (EVA) copolymers with VA content of 28% by weight were prepared by a two‐step method by evenly dispersing the crosslinking agent (dicumyl peroxide) into the EVA matrix and then crosslinking at elevated temperatures. The crosslinking features of the samples were analyzed by Soxhlet extraction with xylene and dynamic mechanical measurements. All the samples were crystalline at room temperature, and the chemical crosslinks seemed to have little effect on the melting behavior of polyethylene segment crystals in the EVA copolymers. The shape recovery results indicated that only those specimens that had a sufficiently high crosslinking degree (gel content higher than about 30%) were able to show the typical shape memory effect, a large recoverable strain, and a high final recovery rate. The degree of crosslinking can be influenced by the amount of the peroxide and the time and temperature of the reaction. The response temperature of the recovery effect (about 61°C) was related to the melting point of the samples. The EVA shape memory polymer was characterized by its low recovery speed that resulted from the wide melting range of the polyethylene segment crystals. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1063–1070, 1999     

Carbon black‐filled poly(ethylene‐co‐alkyl acrylate) composites: Calorimetric studies

The calorimetric characteristics of carbon black (CB)/poly(ethylene‐co‐alkyl acrylate) composites depend on both the CB and acrylate contents. An increase of the acrylate content in the pure copolymers tends to decrease all the crystalline characteristics: T_c,n, the nonisothermal crystallization temperature; T_m, the melting temperature, and ΔH_m, the melting enthalpy. CB modifies the crystallization kinetics of poly(ethylene‐co‐ethyl acrylate) (EEA) alone and in blends with poly(ethylene‐co‐24% w/w methyl acrylate) (24EMA) and poly(ethylene‐co‐35% w/w methyl acrylate) (35EMA). In the presence of CB, T_c,n, the nonisothermal crystallization temperature of EEA, increases and t_1/2, the half‐crystallization time, decreases for a given isothermal crystallization temperature, T_c,i. The thermograms obtained during the melting of EEA after isothermal crystallization show multiple endotherms, suggesting that crystalline‐phase segregation has occurred. The existence of different crystalline species can be explained by the presence of fractions of different acrylate content in the copolymers as shown by SEC. Therefore, CB does not seem to have much effect on the subsequent melting temperature of EEA, T_m,s. CB also induces a lower melting enthalpy, Δ H_m, in the blends. This decrease of ΔH_m appears to be constant whatever the compound, but when reported to the melting enthalpy of the polymer without CB, δΔH_m/ΔH_m increases with the acrylate content. A slight increase of the amorphous phase stiffness after CB introduction is noticed: The T_g of EEA/24EMA and EEA/35EMA blends increases by several degrees. Therefore, plotting ΔH_m versus ΔC_p shows that for the same ΔH_m the ΔC_p is lower in CB‐filled samples, suggesting there is some kind of rigid amorphous phase not contributing to the glass transition. We propose to explain the CB activity during the crystallization process by the existence of molecular interactions between CB and acrylate groups rather than by a pure nucleating effect. Thus, the increase of T_c,n and the decrease of ΔH_m could be explained by the fact that CB separates acrylate‐rich chains from the crystallization medium, accelerating the crystallization of the acrylate‐poor chains. During such a crystallization process, CB may be preferentially localized in the more polar amorphous phase and scattered between the two crystalline phases of EEA and EXA. These blends of poly(ethylene‐co‐alkyl acrylate) copolymers with CB provide interesting materials with adjustable properties depending on the acrylate and CB contents and on the thermomechanical treatments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 779–793, 2001     

PP/PE blends. IV. Characterization and compatibilization of blends of postconsumer resin with virgin PP and HDPE

The mechanical properties of blends of isotactic polypropylene and high-density polyethylene with a postconsumer resin (recycled dairy containers) were investigated over the entire composition range. Modification of these blends with an ethylene/propylene/diene copolymer or an ethylene/vinyl acetate copolymer was also investigated. Isotactic polypropylene/postconsumer resin blends have satisfactory impact and tensile properties at postconsumer resin contents of less than 50% for certain applications. At higher postconsumer resin contents, the tensile properties were adversely affected. The impact properties remained satisfactory. Addition of an ethylene/propylene/diene copolymer improved the mechanical properties of these blends to levels equal to or greater than those for neat isotactic polypropylene. Ethylene/vinyl acetate copolymers were also able to improve the mechanical properties, but not as efficiently as did the ethylene/propylene/diene copolymer. Blends of high-density polyethylene and a postconsumer resin had poor impact and tensile properties. Although the ethylene/propylene/diene copolymer and ethylene/vinyl acetate copolymers were able to improve these properties, the improvement was insufficient for general recycling, except at lower (≤25%) postconsumer resin contents. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2081–2095, 1998     

Lithium ion conducting polymeric electrolytes based on poly(ethylene adipate)

We report the preparation and properties of polymeric lithium ion conducting films based on poly(ethylene adipate) with lithium trifluoromethanesulfonate and blends of poly(ethylene adipate) and poly(vinyl acetate) with lithium triflouromethanesulfonate.The conductivity/temperature behaviour of these films was found to be very similar to those based on poly(ethylene oxide), with Arrhenius behaviour above the crystalline melting point and slight hysteresis below this temperature.     

Reversible gelation of acrylonitrile–vinyl acetate copolymer solutions

The reversible gelation of acrylonitrile–vinyl acetate copolymers in concentrated solutions has been studied with the use of various solvents. These concentrated solutions gel or become rigid with time, but they become fluid again when heated above a certain temperature called the gel melting point. A technique involving the use of mercury drops was developed to measure this transition. This temperature was evaluated as a function of solids level, water content in the solvent, and the amount of vinyl acetate in the copolymer, dimethylacetamide being used as the solvent. Four other solvents were used to obtain limited data. Gel melting was studied further by differential thermal analysis and shear modulus measurements. The results are discussed in terms of network formation and solubility. The x-ray diffraction results imply that the tie points of the gel are crystalline.     

Multiple melting and partial miscibility of ethylene‐vinyl acetate copolymer/low density polyethylene blends

Multiple melting behaviors and partial miscibility of ethylene‐vinyl acetate (EVA) copolymer/low density polyethylene (LDPE) binary blend via isothermal crystallization are investigated by differential scanning calorimetry (DSC) and wide angle X‐ray diffraction (WAXD). Crystallization temperature T (°C) is designed as 30, 50, 70, 80°C with different crystallization times t (min) of 10, 30, 60, 300, 600 min. The increase of crystallization temperature and time can facilitate the growth in lateral crystal size, and also the shift of melting peak, which means the completion of defective secondary crystallization. For blends of various fractions, sequence distribution of ethylene segments results in complex multiple melting behaviors during isothermal crystallization process. Overlapping endothermic peaks and drops of equilibrium melting points of LDPE component extrapolated from Hoffman–Weeks plots clarify the existence of partial miscibility in crystalline region between EVA and LDPE. WAXD results show that variables have no perceptible influence on the predominant existence of orthorhombic crystalline phase structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Comparison of chain structure and morphology of an olefinic blocky copolymer and a Ziegler–Natta‐based ethylene random copolymer

The microstructure and morphology of an olefinic blocky copolymer (OBC) and an ethylene‐hexene copolymer prepared by conventional Ziegler‐Natta catalysis (ZNEH) are compared. It is found that these two samples have similar melting temperatures, but the overall comonomer content in OBC is slightly higher. The crystallization temperature and crystallinity of OBC are markedly lower than those of ZNEH. A successive self‐nucleation annealing experiment reveals that OBC has a more uniform distribution of crystal thickness, indicating a more homogeneous composition distribution in its hard blocks. Small‐angle X‐ray scattering (SAXS) results show that the long period of OBC hardly changes with temperature in the low‐temperature range, whereas that of ZNEH increases gradually with temperature due to melting of the less perfect crystals. The average lamellar thickness of crystals is larger for OBC than for ZNEH, but the thickness of the thickest crystals is comparable in the two. The SAXS profiles were analyzed using a one‐dimensional correlation function. The result reveals that the partially ordered interphases in OBC are mainly located at the interface of the crystalline and amorphous phases. In contrast, the interface of the crystalline and amorphous phases in ZNEH is quite sharp and it is inferred that the partially ordered interphases are distributed in the bulk as separated domains. Scattered tiny crystals are formed in ZNEH, but OBC exhibits a macroscopic morphology of large spherulites. It is also observed that more amorphous phases are rejected outside of the lamellar stacks and spherulites in OBC. © 2012 Society of Chemical Industry     

Interphases in ethylene–vinyl acetate copolymer/steel sandwiches

The properties of a polymer near an interface with a substrate can be different from the bulk properties. To characterize the interphasial zone, the influence of the thickness of a polymer inserted between two steel sheets is carried out. The chosen polymer is a semi-crystalline ethylene–vinyl acetate copolymer with different amounts of vinyl acetate. Dynamic mechanical spectroscopy measurements were performed directly on the assemblies using a three-point flexure test in order to characterize the mobility of the amorphous phase. The crystalline properties were analyzed by differential scanning calorimetry. The mechanical transition temperature, T_mech, corresponding to the temperature at which the loss factor goes through a maximum was examined. The results show that at high thicknesses T_mech remains constant. However, when the polymer thickness decreases, T_mech increases greatly, indicating a decrease of mobility of the chains. This effect is seen whatever the vinyl acetate content. The crystalline properties are also modified with a higher proportion of small crystals for thin layers. For interfacial energy-minimization reasons, the vinyl acetate groups of the copolymer chains are oriented toward the polar steel surface. These orientation phenomena probably induce some reorganization of the phases, leading to more crystals that constitute physical ties, reducing the mobility of the amorphous phase. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:347–353, 1997     

Rheological properties of partially hydrolyzed ethylene–vinyl acetate copolymers

Studies have been made of steady-shear and dynamic viscosities for melts of two ethylene–vinyl acetate copolymers and their partially hydrolyzed derivatives using a Weissenberg rheogoniometer over the temperature range of 123–150°C with some tests at 160°C. The flow activation energy of all samples studied was essentially independent of shear stress. The introduction of hydroxyl groups in controlled concentrations, however, produced a complicated flow behavior. At low concentrations, there is a marked increase in Newtonian viscosity, flow activation energy, and shear dependence of viscosity. In contrast to previous reports, a further increase in all three functions was not observed with increasing vinyl alcohol concentration. Dynamic viscosities, in contrast, show monotonic increases with increasing hydroxyl group content, as do activation energies derived from the temperature dependence of the dynamic viscosity. These data may result from an increased chain cohesion due to hydrogen bonding of hydroxyl groups.     

Polyamide4‐block‐poly(vinyl acetate) via a polyamide4 azo macromolecular initiator: Thermal and mechanical behavior,biodegradation, and morphology

A series of polyamide4‐block‐poly(vinyl acetate)s were synthesized by the radical polymerization of vinyl acetate (VAc) using an azo macromolecular initiator composed of polyamide4 (PA4). The block copolymers were investigated by examining their molecular weight, structure, thermal and mechanical properties, biodegradation, and the morphology of the film surface. The compositions and molecular weights (Mw) ranging from 46,800 to 163,700 g mol^?1 of the block copolymers varied linearly with increasing molar ratio of VAc to azo‐PA4. The block copolymers have high melting points of 248.2–262.5°C owing to PA4 blocks and heats of fusion, which were linearly dependent on the PA4 content. The mechanical properties of the block copolymers were monotonically dependent on the composition, i.e., increasing the PA4 content increased the tensile strength, whereas increasing the poly(vinyl acetate) content increased the elongation at break. The morphology of the block copolymers suggested the appearance of microphase separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42466.     

Crystallinity and fusion of ethylene oxide/propylene oxide block copolymers: 1. Type PE copolymers

Lamella spacings, specific volumes and melting points have been determined for a series of well characterized poly(propylene oxide)/poly(ethylene oxide) type PE block copolymers with E-block length 40 chain units and P-block lengths 0 to 11 chain units. These properties are interpreted in terms of a stacked lamella model with alternating amorphous and crystalline layers. The crystalline lamella thickness is found to be about 25 E chain units, i.e. the crystals are predominantly of extended-chain type. The specific volume of the polymer in the amorphous lamellae is found to be lower than that of polymer of corresponding composition in the supercooled melt. The melting points are low compared to that of perfectly crystalline poly(ethylene oxide), i.e. 47 to 51°C compared with T⁰_m = 76°C. This is due to the positive free energy of formation from the melt of the amorphous layer (σ₅ 3.5 kJ/mol) and the crystalline/amorphous) interface (σ_o 3 kJ/mol).     

Permeation of Phenol through Ethylene Copolymer Hollow Fibers

Abstract

Hollow fibers were spun from low-density polyethylene, an ethylene/propylene copolymer, ethylene/vinyl acetate copolymers, and ethylene/ethyl acrylate copolymers. The phenol permeation rates through these hollow fibers by reactive dialysis were measured over a range of temperatures, allowing the calculation of the apparent activation energies for transport. The permeation rates for phenol transport were found to be dependent upon the degree of crystallinity in the hollow fiber and the increased solubility of phenol in the hollow fiber due to the presence of the polar ethyl acrylate and vinyl acetate groups in the amorphous phase.     

Terpolymers. III. Isochronal viscoelastic parameters for terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Isochronal viscoelastic parameters were collected for many of the copolymers, terpolymers, and diluent mixtures whose mechanical properties at ambient temperatures were reported in the preceding paper. In the polymeric systems, vinyl stearate, acting as the primary internal plasticizer, was introduced into terpolymers by displacing vinyl acetate from base copolymers of vinyl acetate and vinyl chloride, across the range of composition. In the diluent mixtures, poly(vinyl chloride) was plasticized by di-2-ethylhexyl phthalate across the range of compositions. For direct comparison with the mixtures, vinyl chloride was plasticized by copolymerization with vinyl stearate across the same range of compositions. Moduli for the co- and terpolymers reached the low values characteristic of soft materials at room temperature only through a short range of vinyl stearate composition. At higher internal plasticizer compositions, side-chain crystallization stiffened the samples and raised their moduli. In contrast, moduli for the mixtures decreased steadily with increase in diluent at ambient temperature. The effective use temperature ranges were narrow for the co- and terpolymers but broad for the mixtures. Curve broadening was similar for both types of systems, but reached a maximum at about 40 weight-% plasticizer for the diluent mixtures. The slopes of the glassy modulus with decreasing temperature at 50°C below T_g for the vinyl stearate copolymers were relatively large. However, moduli close to that of poly(vinyl chloride) were reached only near the temperature range associated with the γ-transition. Consequently, this behavior was attributed to motions of the side chains in the glassy matrix. Room temperature moduli, which could be obtained before the onset of melting, were correlated with the fractional side-chain crystallinity for polymers having a high vinyl stearate content. From this relation, the modulus for the hexagonal crystal form of the side-chain crystallites of poly(vinyl stearate) was estimated to be 1.2×10¹⁰ dynes/cm². Moduli for the glassy amorphous phase of this same polymer appeared to have one sixth of this value at 40°C below the glass transition. The glass transition temperature occurred about 10° below the inflection temperature at 10⁹ dynes/cm², as an average for all of the systems studied.     

Procedure for calculating the crystallinity of ethylene–vinyl acetate copolymers and low-density polyethylene as a function of temperature

A method is described for determining the x-ray crystallinity of ethylene–vinyl acetate copolymers at differing temperatures. An equation is derived for the symmetrical curves of crystallinity versus temperature thus obtained, from which the crystallinity at any temperature can be calculated. In order to determine the constants of the equation for a particular polymer, it is only necessary to determine the melting point and per cent crystallinity of the resin at a known temperature. The equation can also be applied to conventional polyethylenes, but not to linear polyethylenes. It is suggested that this is due to the former resins having a broad crystallite size distribution compared with the narrow distribution present in high-density polyethylene.