Influence of long‐chain branching on the rheological behavior of polyethylene in shear and extensional flow

In this work, a study of the influence of molecular structure on the viscoelastic behavior of melts of commercial polyethylene (PE) copolymers, particularly in extensional flows, will be performed. To enable this study to be performed, a series of four very low‐density polyethylenes (VLDPEs) (film and blow molding grades) with different parameters of molecular weight (M_W), molecular weight distribution (MWD), and degree of long‐chain branching (LCB) will be used. Experiments in shear flow (steady state and oscillatory regime) are complemented with experiments in uniaxial extension (constant strain rate and stress relaxation after a step strain). It will be shown that a qualitative correlation exists between both types of experiments; the stress relaxation experiments being particularly sensitive to the different molecular features of the polymers. In addition, the failure behavior in extension was also investigated and the results indicate that, within experimental error, the Hencky strain to failure is sensitive to the type of molecular structure but the corresponding tensile stress is not. POLYM. ENG. SCI., 45:984–997, 2005. © 2005 Society of Plastics Engineers     

Detection of low levels of long‐chain branching in polydisperse polyethylene materials

Creep experiments have been applied to probe the zero‐shear viscosity, η₀, of polyethylene chains directly and precisely in a constant‐stress rheometer at 190°C. Such experiments, when combined with precise measurements of the weight‐average molecular weight, M_w, calibrated relative to linear chains of high‐density polyethylene, are shown to provide a very sensitive approach to detect low levels (0.005 branches per 1000 carbons) of long‐chain branching (LCB). This detection limit is shown to be insensitive to whether the molecular weight distribution (MWD) breadth, M_w/M_n, rises from about two to ten. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Molecular characterization and rheological properties of modified poly(ethylene terephthalate) obtained by reactive extrusion

The use of a tetrafunctional epoxy‐based additive to modify the molecular structure of poly(ethylene terephthalate) (PET) was investigated with the aim of producing PET foams by an extrusion process. The molecular structure analysis and shear and elongation rheological characterization showed that branched PET is obtained for 0.2, 0.3 and 0.4 wt% of a tetrafunctional epoxy additive. Gel permeation chromatography (GPC) analysis led to the conclusion that a randomly branched structure is obtained, the structure being independent of the modifier concentration. The evolution of shear and extensional behavior as a function of molecular weight (M_w), degree of branching, and molecular weight distribution (MWD) were studied, and it is shown that an increase in the degree of branching and M_w and the broadening of the MWD induce an increase in Newtonian viscosity, relaxation time, flow activation energy and transient extensional viscosity, while the shear thinning onset and the Hencky strain at the fiber break decrease markedly.     

Thermal and rheological studies on the molecular composition and structure of metallocene‐ and Ziegler–Natta‐catalyzed ethylene–α‐olefin copolymers

The relationship between the molecular structure and the thermal and rheological behaviors of metallocene‐ and Ziegler–Natta (ZN)‐catalyzed ethylene copolymers and high‐density polyethylenes was studied. Of special interest in this work were the differences and similarities of the metallocene‐catalyzed (homogeneous) polymers with conventional coordination‐catalyzed (heterogeneous) polyethylenes and low‐density polyethylenes. The short‐chain branching distribution was analyzed with stepwise crystallization by differential scanning calorimetry and by dynamic mechanical analysis. The metallocene copolymers exhibited much more effective comonomer incorporation in the chain than the ZN copolymers; they also exhibited narrower lamellar thickness distributions. Homogeneous, vanadium‐catalyzed ZN copolymers displayed a very similar comonomer incorporation to metallocene copolymers at the same density level. The small amplitude rheological measurements revealed the expected trend of increasing viscosity with weight‐average molecular weight and shear‐thinning tendency with polydispersity for the heterogeneous linear low‐density polyethylene and very‐low‐density polyethylene resins. The high activation energy values (34–53 kJ/mol) and elevated elasticity found for some of our experimental metallocene polymers suggest the presence of long‐chain branching in these polymers. This was also supported by the comparison of the relationship between low shear rate viscosity and molecular weight. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1140–1156, 2002     

Higher‐molecular‐weight hyperbranched polyethylenes containing crosslinking structures as lubricant viscosity‐index improvers

As a new grade of polyethylene materials with unique chain architectures, hyperbranched polyethylenes synthesized by chain walking ethylene polymerization have great potential for industrial application as novel viscosity index (VI) improver in lubricant formulation. Although high‐molecular‐weight hyperbranched polyethylenes (weight‐average molecular weight of about 10⁵ g/mol) possess high shear stability, their viscosity thickening properties are compromised due to their compact chain architectures. In this work, we aim at improving their viscosity thickening property by increasing polymer molecular weight. A range of hyperbranched polymers of various enhanced molecular weights were synthesized by chain walking ethylene polymerization in the presence of small amounts of 1,4‐butanediol diacrylate as a difunctional crosslinker. The molecular weight dependences of viscosity thickening power and shear stability of these polymers containing crosslinking structures were evaluated. It is found that, with the increase of molecular weight via crosslinking, these polymers showed consistently enhanced viscosity thickening power, but with the reduced shear stability. However, their shear stability was still significantly better compared to linear polymers. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Microporous membranes of polyoxymethylene from a melt‐extrusion process: (I) effects of resin variables and extrusion conditions

A two‐part study utilizing polyoxymethylene (POM) was undertaken to investigate a three stage process (melt extrusion/annealing/uniaxial stretching) (MEAUS) employed to produce microporous films. In this first part, three POM resins (D, E, and F) were melt extruded into tubular films (blowup ratio; BUR = 1), where resin D has a higher weight average molecular weight (M_w) than resin E, but both possess similar and relatively narrow molecular‐weight distributions (MWD). In contrast, resin F is characterized by a distinctly broader MWD while its M_w is slightly higher than resin D. Specific attention was focused upon the morphological and crystal orientation results as a function MWD and M_w. A stacked lamellar morphology was obtained in each case from the melt extrusion; however, the type of stacked lamellar morphology, planar or twisted, and the orientation state was found to depend upon both the resin characteristics and the melt‐extrusion conditions. Atomic force microscopy and wide‐angle X‐ray scattering were the main techniques utilized to study the melt‐extruded films while dynamic melt rheometry in conjunction with the Carreau‐Yasuda model aided in differentiating the melt‐flow behavior of the three resins. Small‐angle light scattering (SALS) was also employed to characterize the morphological state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2944–2963, 2001     

Scale‐Free Power‐Law Distribution of Emulsion‐Polymerized Branched Polymers: Power Exponent of the Molecular Weight Distribution

Summary: The molecular weight distribution (MWD), formed in emulsion polymerization that involves the polymer transfer reaction during Interval II, may approach the power‐law distribution as polymerization proceeds. The power exponent, α, of the weight fraction distribution W(M) = M^?α conforms to the relationship, α = 1/P_b, where P_b is the probability that the chain end is connected to a backbone chain. The MWD of emulsion‐polymerized polyethylene reported in literature agrees reasonably well with the relationship, W(M) = M^?α with α = 1/P_b. This simple relationship could be used to estimate the P_b value from the MWD data, possibly leading to determining the polymer transfer constant under well‐designed experimental conditions. Because α > 1, the number‐average MW always approaches a finite value, but the weight‐ and higher order‐averages of MWD may continue to increase as the particle grows without limit depending on the magnitude of P_b. The power‐law distributions are self‐similar, possessing the nature of fractals and lacking a characteristic scale. The i‐th moment of the MWD for the present reaction system continues to increase without limit during Interval II for P_b ≥ 1/i.

Molecular weight distribution of the emulsion‐polymerized polyethylene.     

Influence of molecular structure on the rheological and processing behavior of polyethylene resins

The rheological and processing behavior (melt fracture performance) of linear lowdensity polyethylenes (LLDPEs) is studied as a function of both the weight average molecular weight (M_w) and its distribution (MWD). A number of LLDPE resins having different molecular characteristics were tested, with essentially one characteristic (M_w or MWD) changing at a time. The first series of resins consisted of nine samples having a wide range of polydispersities (3.3–12.7) and nearly constant M_w and short chain branching. The second series had six resins with varying M_w (51,000–110,000) but fixed MWD (about 4). The influence of M_w and MWD on the viscosity profiles, linear viscoelastic moduli as expressed by means of a discrete spectrum of relaxation times, extrudate swell, and melt fracture behavior for these resins is reported. Correlations between the molecular characteristics of the resins and their rheological and processing behavior are also reported. It is found that for a given molecular weight, the optimum melt fracture performance is obtained at a specific polydispersity value, and it is characterized by a minimum relaxation time for the resin defined in terms of recoverable shear.     

Non‐newtonian rheological behavior of semi‐dilute ultra‐high molecular weight polyethylene solution in gel‐spinning process. 1: Concentration effect on the fundamental rheological properties

The rheological properties of a semi‐dilute ultra‐high molecular weight polyethylene (UHMw‐PE)/paraffin wax solution were investigated by mainly focusing on the influence of its concentration on the shear flow viscosity. It was found that the UHMw‐PE solution exhibits a shear‐thinning behavior at a very wide shear rate range from 10^?4 to higher than 10³ sec^?1. Furthermore, this typical non‐Newtonian behavior was more obvious with a concentration increase. From the concentration dependence of the zero‐shear creep compliance or other rheological factor, it was found that the extremely large M_e value of the system gives rise to various kinds of non‐Newtonian behaviors, especially those highly elastic in nature. Finally, the origin of the abnormal stress fluctuation during the steady shear measurement was found to be related to the shear‐induced structural development of the solution.     

Heterogeneity of active sites of Ziegler‐Natta catalysts: The effect of catalyst composition on the MWD of polyethylene

Experimental data on the molecular weight distribution (MWD) of polyethylene (PE) produced over a broad number of Ziegler‐Natta catalysts differing in composition and preparation procedure are presented. These catalysts include nonsupported TiCl₃ catalyst, four types of supported titanium‐magnesium catalysts (TMC) differing in the content of titanium and the presence of various modifiers in the composition of the support, and a supported catalyst containing VCl₄ as an active component instead of TiCl₄. The studied catalysts produce PE with different molecular weights within a broad range of polydispersity (M_w/M_n = 2.8–16) under the same polymerization conditions. The heterogeneity of active sites of these catalysts was studied by deconvolution of experimental MWD curves into Flory components assuming a correlation between the number of Flory components and the number of active site types. Five Flory components were found for PE produced over nonsupported TiCl₃ catalysts (M_w/M_n = 6.8), and three–four Flory components were found for PE produced over TMC of different composition. A minimal number of Flory components (three) was found for PE samples (M_w/M_n values from 2.8 to 3.3) produced over TMC with a very low titanium content (0.07 wt %) and TMC modified with dibutylphtalate. It was shown that five Flory components are sufficient to fit the experimental MWD curve for bimodal PE (M_w/M_n = 16) produced over VMC. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Rheology and enhancement of extrusion of linear and branched polyethylenes using low amount of organoclay

Interaction between 0.05 wt % organoclay and polyethylenes of different short chain branching (SCB) was studied. Linear rheology (van Gurp‐Palmen plot) was used to study the effect of organoclay on the rheology of polyethylenes. Organoclay had effect only on the van Gurp‐Palmen plot of linear polyethylene. Fourier transform (FT) rheology, extrusion at high‐shear rates in a slit rheometer, transient stress growth analysis, and extensional rheology were conducted to examine the potential of organoclay as a processing aid. Organoclay reduced the transient stress overshoot, normal stress difference, ηo, onset of shear thinning, and extrusion pressure of polyethylene. The reduction was more pronounced in linear polyethylene without branching. Such effects gradually decreased as the branch content increased. The trend was independent of the type of flow (shear or extensional). It was interesting to note that FT rheology was not effective in explaining the impact of organoclay on polyethylene. The work concluded with the proposition that organoclay (as low as 0.05 wt %) was a good processing aid for linear polyethylene and polyethylenes with low content of SCB. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydrolytic degradation and crystallization behavior of linear 2‐armed and star‐shaped 4‐armed poly(l‐lactide)s: Effects of branching architecture and crystallinity

“Linear” aliphatic polyesters composed of two poly(l ‐lactide) arms attached to 1,3‐propanediol and “star‐shaped” ones composed of four poly(l ‐lactide) arms attached to pentaerythritol (2‐L and 4‐L polymers, respectively) with number‐average molecular weight (M_n) = 1.4–8.4 × 10⁴g/mol were hydrolytically degraded at 37°C and pH = 7.4. The effects of the branching architecture and crystallinity on the hydrolytic degradation and crystalline morphology change were investigated. The degradation mechanism of initially amorphous and crystallized 2‐L polymers changed from bulk degradation to surface degradation with decreasing initial M_n; in contrast, initially crystallized higher molecular weight 4‐L polymer degraded via bulk degradation, while the degradation mechanism of other 4‐L polymers could not be determined. The hydrolytic‐degradation rates monitored by molecular‐weight decreases decreased significantly with increasing branch architecture and/or higher number of hydroxyl groups per unit mass. The hydrolytic degradation rate determined from the molecular weight decrease was higher for initially crystallized samples than for initially amorphous samples; however, that of 2‐L polymers monitored by weight loss was larger for initially amorphous samples than for initially crystallized samples. Initially amorphous 2‐L polymers with an M_n below 3.5 × 10⁴g/mol crystallized during hydrolytic degradation. In contrast, the branching architecture disturbed crystallization of initially amorphous 4‐L polymers during hydrolytic degradation. All initially crystallized 2‐L and 4‐L polymers had δ‐form crystallites before hydrolytic degradation, which did not change during hydrolytic degradation. During hydrolytic degradation, the glass transition temperatures of initially amorphous and crystallized 2‐L and 4‐L polymers and the cold crystallization temperatures of initially amorphous 2‐L and 4‐L polymers showed similar changes to those reported for 1‐armed poly(l ‐lactide). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41983.     

Rheology of metallocene-catalyzed monomodal and bimodal polyethylenes

The effect of molecular architecture on the dynamic viscoelastic properties of new metallocene high density polyethylenes has been analyzed. Bimodal molecular weight distribution metallocene polyethylenes show features different from conventional polydisperse and bimodal polyethylenes. Higher values of Newtonian viscosity (η_o) at the same values of weight average molecular weight (M_w) and stronger frequency dependence of dynamic viscosity (η′) than in conventional HDPE-s have been observed; this leads to lower values of the characteristic frequency for the onset of non-Newtonian behavior (ω_o) and higher values of the power law index (α). These features are probably due to the presence of very small amounts of long chain branching (LCB). The implications of these results in polymer processing are analyzed comparing extrusion rheometer data, which leads to the conclusion that extrusion difficulties in metallocene catalyzed polyethylenes can be overcome with bimodal molecular weight distributions.     

Molecular Weight Polydispersity Effects on Diffusion at Polymer/Polymer Interfaces

The effect of molecular weight distribution (MWD) on diffusion at symmetric polymer/polymer interfaces is investigated by rheological tools. A new model allowing the determination of a self‐diffusion coefficient of polydisperse polymer systems is presented. The model is based on the double reptation theory and Doi and Edwards' molecular dynamics applied to A/A polymers brought into intimate contact in the molten state. The material parameters for the model are obtained from linear oscillatory shear experiments, in which the dynamic shear modulus is measured in parallel plate geometry under a small amplitude of deformation as a function of time and frequency for a sandwich‐like assembly. The experiments were conducted on polystyrene (PS) blends with constant weight average molecular weight (M_w) but with variable number average molecular weights (M_n). The measured self‐diffusion coefficients showed that the presence of short molecules in the blend increases the mean value of the self‐diffusion coefficient and the magnitude of such increase can be quantitatively evaluated by the proposed model.     

Effects of polymer structure on the onset of processing defects in linear low density polyethylenes

Linear low density polyethylenes are manufactured by copolymerizing ethylene with 1-alkenes, yielding a linear polyethylene backbone with short side chains. Due to the nature of the catalyst used in the polymerizaton, multimodal branching distributions are typically obtained. In this report, we have investigated the processability of four 1-octene linear low density polyethylenes as a function of the short chain branching distribution. Analytical techniques such as ¹³C nuclear resonance spectroscopy, size exclusion chromatography, differential scanning calorimetry, and temperature rising elution fractionation, in particular were used to elucidate the molecular structure. Processability measurements were made using various extrusion techniques and dynamic mechanical analyses.It was determined that in the absence of any variations in molecular weight, the polymers with the higher proportions of linear polyethylene showed inferior processability In terms of onset of surface imperfections at lower extrusion rates. Polymers with worse processability characteristics also exhibited higher zero shear viscosities.     

FI Catalysts: A New Family of High Performance Catalysts for Olefin Polymerization

This paper reviews a new family of olefin polymerization catalysts. The catalysts, named FI catalysts, are based on non‐symmetrical phenoxyimine chelate ligands combined with group 4 transition metals and were developed using “ligand‐oriented catalyst design”. FI catalysts display very high ethylene polymerization activities under mild conditions. The highest activity exhibited by a zirconium FI catalyst reached an astonishing catalyst turnover frequency (TOF) of 64,900 s ^–1 atm ^–1, which is two orders of magnitude greater than that seen with Cp₂ZrCl₂ under the same conditions. In addition, titanium FI catalysts with fluorinated ligands promote exceptionally high‐speed, living ethylene polymerization and can produce monodisperse high molecular weight polyethylenes (M_w/M_n<1.2, max. M_n>400,000) at 50 °C. The maximum TOF, 24,500 min ^–1 atm ^–1, is three orders of magnitude greater than those for known living ethylene polymerization catalysts. Moreover, the fluorinated FI catalysts promote stereospecific room‐temperature living polymerization of propylene to provide highly syndiotactic monodisperse polypropylene (max. [rr] 98%). The versatility of the FI catalysts allows for the creation of new polymers which are difficult or impossible to prepare using group 4 metallocene catalysts. For example, it is possible to prepare low molecular weight (M_v∼10³) polyethylene or poly(ethylene‐co‐propylene) with olefinic end groups, ultra‐high molecular weight polyethylene or poly(ethylene‐co‐propylene), high molecular weight poly(1‐hexene) with atactic structures including frequent regioerrors, monodisperse poly(ethylene‐co‐propylene) with various propylene contents, and a number of polyolefin block copolymers [e.g., polyethylene‐b‐poly(ethylene‐co‐propylene), syndiotactic polypropylene‐b‐poly(ethylene‐co‐propylene), polyethylene‐b‐poly(ethylene‐co‐propylene)‐b‐syndiotactic polypropylene]. These unique polymers are anticipated to possess novel material properties and uses.     

Microporous membranes of isotactic poly(4‐methyl‐1‐pentene) from a melt‐extrusion process. I. Effects of resin variables and extrusion conditions

A study utilizing isotactic poly(4‐methyl‐1‐pentene) (PMP) was undertaken to investigate a three‐stage process (melt‐extrusion/annealing/uniaxial‐stretching) (MEAUS) employed to produce microporous films. The results of this study will be reported in the course of two articles. In this first part, three PMP resins were melt‐extruded into tubular films (blowup ratio; BUR = 1), where the resins each differ in weight‐average molecular weight (M_w). Specific attention was focused upon the morphological and crystal orientation results as a function of the melt‐relaxation times as influenced by the resin characteristics and the processing parameters. The results of a number of melt‐extrusion conditions are presented. A stacked lamellar morphology was obtained in each case; however, the type of stacked lamellar morphology, planar or twisted, and the orientation state was found to depend upon both the resin characteristics, specifically M_w, and the melt‐extrusion conditions. Atomic force microscopy and wide‐angle X‐ray scattering (WAXS) were the main techniques utilized to study the melt‐extruded films, while oscillatory shear measurements, in conjunction with a Carreau–Yasuda analysis, aided in differentiating the melt‐flow behavior of the three resins. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2095–2113, 2002     

Synthesis and molecular weight characterization of rubber seed oil‐modified alkyd resins

Alkyd resins of 40% (I), 50% (II), and 60% (III) oil length (OL) were prepared with rubber seed oil (RSO), phthalic anhydride (PA), and glycerol (GLY), employing the two‐stage alcoholysis method. Changes in the physical characteristics of the reaction medium were monitored by determination of the acid value and the number‐average molecular weight, M_n , of in‐process samples withdrawn at different stages of the reaction. The mode of variation of these properties denotes that the preparation of RSO alkyds is complex. Molecular weight averages and the molecular weight distribution (MWD) of the finished alkyds were determined by GPC, cryoscopy, and end‐group analysis. Molecular weight averages and the MWD vary with differences in the formulation, with sample II exhibiting the narrowest size distribution. Values of M_n with the corresponding polydispersities in brackets are 3234 (1.91), 1379 (1.56), and 3304 (2.56) for samples I, II, and III respectively. M_n values obtained by cryoscopy are comparable to those obtained by gel permeation chromatography (GPC), while end‐group analysis seems to grossly overestimate their molecular weights. Correlation of M_n and the MWD with the quality of the finished alkyds shows that the narrower the size distribution the better the quality of the alkyd. Properties such as the rate of drying and resistance of the alkyds are optimum at 50% OL. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2431–2438, 2001     

Rheological behaviors and molecular weight distribution characteristics of bimodal high‐density polyethylene

A series of bimodal high density polyethylene (PE) with different molecular weight distributions (MWDs) were prepared by melt blending, and the fitting multipeaks on Gaussian were used to analyze the MWD curves, and the ratio of the areas under unimodal curves was as a tool to characterize the MWD; the phase behaviors and rheological behaviors were studied by dynamic rheological. The results showed that homogeneous bimodal high density PEs could be successfully prepared via melt blending, and the bimodal characteristic could be adjusted as expected. For samples with the MWD peak positions unvaried, the storage modulus, complex viscosity, and zero‐shear viscosity decreased rapidly with the value of A_L/U increasing. Especially in the low frequency region, the loss modulus surpassed the storage modulus (G″ > G′) when A_L/U > 10.17 and the dynamic cross‐point Gx appeared and increased with increasing A_L/U, with an increasing extent much larger than that due to the width of MWD. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011