Rheology modifier additive for enhanced processability of polyethylene for blown-Film applications

Polyethylene is a versatile polymer suitable for a large variety of flexible and rigid packaging applications. Its mechanical and rheological properties can be tuned across a wide range by controlling its molecular architecture, such as the amount and distribution of olefinic comonomers (short chain branching), long chain branching, and molecular weight distribution. Linear low-density polyethylene (LLDPE) is known for its high toughness which enables downgauged film structures and low-density polyethylene (LDPE) is known for its excellent shear thinning and melt strength which enables enhanced processability and high throughput, such as on blown film lines. In order to obtain a balance of toughness and processability on films produced on blown film lines, blends of LLDPE and LDPE are commonly used. In this paper, we describe additive-based approaches, including a new product, DOWLEX™ (TM = trademark of the Dow Chemical Company (“Dow”) or an affiliated company of Dow) GM AX01, which enhances melt strength and other rheological properties of polyethylene, enabling fabrication of films with lower LDPE content while still maintaining excellent rheological properties and higher toughness versus conventional LLDPE/LDPE blends. The higher toughness enables downgauging without loss of mechanical properties, which in turn reduces consumption of polymer resulting in a more sustainable solution.     

Processability of LLDPE/LDPE blends: Capillary extrusion studies

The processing behavior of a number of linear low‐density polyethylenes/low density polyethylene (LLDPE/ LDPE) blends with emphasis on the effects of long chain branches is presented. A Ziegler‐Natta linear low‐density polyethylene was blended with four low‐density polyethylene LDPE's having distinctly different molecular weights. The weight fractions of the LDPEs used in the blends were 1, 5, 10, 20, 50, and 75 wt%. Capillary extrusion reveals that the onset of sharkskin and gross melt fracture are slightly influenced with the addition of LDPE into LLDPE. However, the amplitude of the oscillations in the stick‐slip flow regime was found to scale well with the weight fraction of LDPE. Amounts as low as 1 wt% LDPE have a significant effect on the amplitude of pressure oscillations. These effects are clearly due to the presence of long chain branching (LCB); furthermore, it was observed that the onset of this flow regime was shifted to higher shear rates with increase of LDPE content. On the other hand, shear rheology is not sensitive to detect addition of small levels of LDPE up to 20 wt%. Extensional rheology can detect levels of LDPE as small as 1 wt% only at high Hencky strain rates (typically greater than 5s^?1) and only for certain blends, typically those that contain LDPE of high molecular weight. It is suggested that the magnitude of oscillations in the oscillating melt fracture flow regime is a sensitive method capable of detecting low levels of LCB. POLYM. ENG. SCI., 47:1317–1326, 2007. © 2007 Society of Plastics Engineers     

Linear-low-density polyethylene melt rheology: Extensibility and extrusion defects

This paper investigates three aspects of linear-low-density polyethylene (LLDPE) rheological properties: shear viscosity variations with shear rate and temperature, tensile behavior determined with an extensiometer, and extrusion defects. The differences in shear viscosity variation with shear rate and temperature between LLDPE and LDPE (low-density polyethylene) are shown. These differences, attributed to wider molecular weight distribution and to long chain branching (LCB) in LDPE, involve different extrusion behaviors. The lack of LCB in LLDPE can be demonstrated by comparison of the measured Newtonian viscosity with the value of the same parameter calculated from molecular weight distribution and composition law of Newtonian viscosities. The lack of LCB leads to good melt extensibility, which is shown by tensile properties of polyethylene melts determined with a non-isothermal extensiometer. The melt fracture phenomenon is studied because it promotes surface defects on bubbles in film application. Extrudate distortions are examined at the laboratory extruder outlet. This test shows differences between LLDPE and LDPE, but also between some LLDPE samples.     

Influence of molecular architecture and melt rheological characteristic on the optical properties of LDPE blown films

A systematic investigation on the origin of the haze of LDPE blown films was conducted, aiming to correlate the film haze with the molecular architecture and melt rheological properties. First of all, the haze measurement indicated that the surface haze, rather than the bulk haze, is the dominating factor for the total haze of the investigated films. No spherulitic crystals or other superstructures were observed for the LDPE blown films, implying that the crystallites formed in the film-blowing process are too small to be responsible for the optical haze. Rheological study revealed that the surface roughness was originated from the irregular flow of LDPE melt during the extrusion process. NMR, GPC and parallel-plate rheology were applied to study the molecular architecture of the LDPE resins. It was found that the LDPE sample with higher haze value exhibits distinctly larger portion of higher molecular weight component, broader molar mass distribution, significantly higher side chain branch density.     

LDPE收缩膜专用树脂性能的研究

研究了低密度聚乙烯收缩膜专用树脂LD163的分子链结构、结晶性能及收缩性能。结果表明,LD163具有较高的相对分子质量、适中的相对分子质量分布,总体支化度低、长链支化度较高,结晶度高、结晶速率快。因此,LD163具有优良的力学性能,良好的加工性能,其薄膜制品的收缩性能及综合性能优异。     

Study of polyethylene solution fractionation and resulting fractional crystallization behavior

Solution fractionation for four different polyethylenes including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low‐density polyethylene (VLDPE) are conducted by stepwise controlling both the temperature and the amount of precipitant. The size exclusion chromatograph (SEC) measurements indicate that solution fractionation technique can successfully separate all the polyethylene samples in accordance with their molecular weight and molecular‐weight distributions. In addition, infrared spectroscopy analysis shows that the degree of short‐chain branching for each fraction of each polyethylene varies with the fraction's molecular weight. The effect of the molecular weight with different short‐chain branching on each fraction's crystallinity represents the characteristics of chain components for different polyethylenes. The crystallinities of HDPE, LLDPE, and LDPE decrease with the increase in their molecular weights; however, for VLDPE, its crystallinity increases with the increase in the molecular weight. The research revealed that the degree of short‐chain branching, together with the molecular weight, can greatly affect the crystallinity of polyethylene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2542–2549, 2004     

管式法挤出涂层专用LDPE的性能及质量改进

针对管式工艺生产的挤出涂层专用低密度聚乙烯(LDPE)产品存在涂层与基材的黏结强度低、淋膜缩幅大等问题,通过与同类釜式产品的性能和结构的对比研究发现,管式产品的分子支化程度过低是造成其性能不佳的主要原因。分析了影响产品长链支化程度的工艺因素,并提出了增加产品长支链含量的方法。初步试生产表明:适当提高反应温度、降低反应压力并改变分子量调节剂的注入速度,可以有效地改善挤出涂层产品的性能。     

Correlations between processing parameters,morphology, and properties of blown films of LLDPE/LDPE blends,part 2: Crystalline and amorphous biaxial orientation by WAXD pole figures

The biaxial molecular orientation of blown films made of blends of linear low density polyethylene (LLDPE) with low density polyethylene (LDPE) was characterized by two different methods: complete pole figures obtained by wide angle X‐rays diffraction (WAXD) and polarized infrared spectroscopy (IR) using the Krishnaswamy approach. The molecular orientation of the blends amorphous phase was also evaluated by polarized IR. The crystallinity of the blown films was determined by WAXD. A good correlation between the X‐ray pole figures and the polarized IR results was obtained. At all blends compositions, it was shown that the a‐axis of the polyethylene orthorhombic cell was preferentially oriented along the machine direction, the orientation degree along this direction increasing with the increase of the LDPE amount in the blends. The b‐axis changed its preferential orientation from film thickness in the 100/0 LLDPE/LDPE film to along the transverse direction with increasing LDPE in the blends. The c‐axis changed its orientation from orthogonal to normal direction in the 100/0 LLDPE/LDPE film to along the film thickness with increasing LDPE in the blends. Polarized IR characterization showed a negligible orientation of the amorphous phase. The amount of crystallinity was dependent on blend composition decreasing with the increase of LDPE content in the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2760–2767, 2006     

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.     

HDPE 5000S在共混挤出板材中的应用

对不同装置生产的高密度聚乙烯5000S的分子链结构、基础物性、旋转流变性能及加工流变性能等进行了对比分析。结果表明:由于5000S-3的相对分子质量较高,支化度较小,导致其储能模量及熔体拉伸强度较大,5000S-3与线型低密度聚乙烯7042共混挤出的板材没有出现破洞;5000S-3的高相对分子质量(大于10×10^5)部分含量较5000S-2低,低相对分子质量(小于1×10^4)部分含量较5000S-1高,且其相对分子质量分布较宽,所以加工性能最好,提高温度可改善原料在加工过程中的不稳定流动现象。     

The effect of molecular weight distribution on polyethylene film properties

Polymer molecular weight heterogeneity affects the rheological properties of polymer melts such as melt viscosity, fracture and die swell. These rheological properties affect the conversion of the polymer from the bulk resin state to its final usable form. In this particular study, the effect of molecular weight distribution on polyethylene blown film characteristics was studied. The effect of the molecular weight heterogeneity on the rheological characteristics of the polymer in the molten state and its effect on the film properties is presented. The properties studied included film gloss, haze, tear resistance and film impact strength. This study shows that broadening the molecular weight distribution increases haze and reduces film gloss. Further, it was shown that a linear relationship exists between film gloss and external haze. Both values are measures of surface irregularities in the film which are affected by the drawing characteristics of the polymer. A broader molecular weight distribution results in increased impact strength as measured by the Dart Drop Impact Test. This is, it is believed, a result of the increase in long chain branching of the higher molecular weight fractions of the polymer which cause a higher degree of molecular weight entanglement at the branch sites. In contrast the tear strength is reduced as the molecular weight distribution broadens because of the low molecular weight fraction in the broad spectrum material which tend to decrease resistance to tear.     

Effect of clay on mechanical and gas barrier properties of blown film LDPE/clay nanocomposites

Low density polyethylene (LDPE)/clay nanocomposites, which can be used in packaging industries, were prepared by melt‐mix organoclay with polymer matrix (LDPE) and compatibilizer, polyethylene grafted maleic anhydride (PEMA). The pristine clay was first modified with alkylammonium salt surfactant, before melt‐mixed in twin screw extruder attached to blown‐film set. D‐spacing of clay and thermal behavior of nanocomposites were characterized by Wide‐Angle X‐ray Diffraction (WAXD) and differential scanning calorimetry (DSC), respectively. WAXD pattern confirmed the increase in PEMA contents exhibited better dispersion of clay in nanocomposites. Moreover, DSC was reported the increased PEMA contents caused the decrease in degree of crystallinity. Mechanical properties of blown film specimens were tested in two directions of tensile tests: in transverse tests (TD tests) and in machine direction tests (MD tests). Tensile modulus and tensile strength at yield were improved when clay contents increased because of the reinforcing behavior of clay on both TD and MD tests. Tensile modulus of 7 wt % of clay in nanocomposite was 100% increasing from neat LDPE in TD tests and 17% increasing in MD tests. However, elongation at yield decreased when increased in clay loading. Oxygen permeability tests of LDPE/clay nanocomposites also decreased by 24% as the clay content increased to 7 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effects of a mixture of stabilizers on the structure and mechanical properties of polyethylene during reprocessing

The properties of two polyethylenes [a high‐density polyethylene (HDPE) and a low‐density polyethylene (LDPE)] were studied after several extrusion cycles. To reduce the degradation effects during the reprocessing, a mixture of two stabilizers was added to the formulations. The predominant degradation mechanism was chain scission for the HDPE and chain branching and crosslinking for the LDPE. For both polyethylenes the FTIR spectra exhibited a growth in the number of carbonyl groups as a function of the number of extrusion cycles. Their tensile properties were degraded with the reprocessing but both polyethylenes maintained their nearly constant thermal behavior and crystallinity. The addition of a primary phenolic antioxidant and a secondary phosphite antioxidant preserved the melt behavior of virgin materials after the reprocessing and reduced the degradation effects. From the tensile tests, the efficiency of the antioxidants in the LDPE was very high and, after the reprocessing, the material retained the mechanical properties of virgin LDPE. The efficiency of the antioxidants for the HDPE was not significant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3910–3916, 2004     

Highly active peroxides in the radical polymerization of ethylene under high pressure. Properties of the polymers

Using highly active peroxide initiators, a number of polyethylene samples were prepared at low temperatures of 70–140°C and a pressure of 1900 bar. The average molecular weight and the melt flow index were adjusted by adding propionaldehyde as modifier. The characteristic properties of the samples as regards the molecular weight distribution, the average molecular weight, the frequency of long chain branching, the crystallinity and the density were determined. As expected, the polymers are characterized by density values of more than 0.955 g/ml and crystallinity values of 65–80% which are characteristic of PE-HD. The molecular weight distribution, too, remains within narrow limits. On the other hand, rather surprisingly, a relatively high frequency of long chain branching typical of PE-LD is obtained. The investigation of the phase behaviour has shown that polymerization under high pressure at temperatures above 115–118°C takes place in the homogeneous range. The samples polymerized in the transition zone between the single and the two phase area exhibit maximum crystallinity and melt enthalpy. The frequency of long chain branching passed through a minimum.     

A molecular dynamics study of the effects of branching characteristics of LDPE on its miscibility with HDPE

The effects of branching characteristics of low-density polyethylene (LDPE) on its melt miscibility with high-density polyethylene (HDPE) were studied using molecular simulation. In particular, molecular dynamics (MD) was applied to compute Hildebrand solubility parameters (δ) of models of HDPE and LDPE with different branch contents at five temperatures that are well above their melting temperatures. Values computed for δ agreed very well with experiment. The Flory-Huggins interaction parameters (χ) for blends of HDPE and different LDPE models were then calculated using the computed δ values. The level of branch content for LDPE above which the blends are immiscible and segregate in the melt was found to be around 30 branches/1000 long chain carbons at the chosen simulation temperatures. This value is significantly lower than that of butene-based linear low-density polyethylene (LLDPE) (40 branches/1000 carbons) in the blends with HDPE computed by one of the authors (polymer 2000; 41:8741). The major difference between LDPE and LLDPE models is that each modeled LDPE molecule has three long chains while each modeled LLDPE molecule had only one long chain. The present results together with those of the LLDPE/HDPE blends suggest that the long chain branching may have significant influence on the miscibility of polyethylene blends at elevated temperatures.     

Influence of low density polyethylene quality on extrusion coating processability

In order to obtain explicit information about the influence of different low density polyethylene (LDPE) quality parameters on extrusion coating processability, a test run was made with an autoclave reactor and the products were investigated. All the grades manufactured had melt indices (MI), densities, molecular weight distributions (MWD), and degrees of long chain branching(LCB) typical of commercial extrusion coating grades. The processability characteristics studied were maximum line speed and neck-in. The influence of MI, density, and extrusion melt temperature were systematically investigated. It was found that the maximum line speed rose with increasing MI, density, and extrusion melt temperature, and that an increasing extrusion melt temperature led to a growing difference between the maximum line speed at a constant coating thickness and the maximum line speed at a constant screw speed. Neck-in was found to increase with increasing MI, increasing density, and increasing coating thickness. These effects were more pronounced at higher extrusion melt temperatures. When using the extrusion temperature needed to achieve a certain line speed for each grade, the influence of MI on neck-in was practically non-existent.     

Rheological,physical, and thermal characterization of single‐site catalyst based polyethylenes for seal layer applications

Four single‐site metallocene catalyst based polyethylenes (mPEs), one ultra low density polyethylene, one conventional linear low density polyethylene (LLDPE), and one low density polyethylene (LDPE) were selected to characterize the effect of side chain branches on physical and mechanical properties. Rheological experiments were carried out to extract complex viscosity and elasticity as a function of frequency. Elongational viscosity tests were also performed to assess long chain branching. For some mPEs, sparse long chain branching improved shear thinning and elasticity of the chains in melt state. During elongation, mPEs with a narrow linear chain distribution showed initially greater melt strength whereas for longer elongation, the mPEs with long chain branching lead over in strength. Cast films were produced from the mPEs and their physical (such as crystallinity, crystal size) and mechanical properties were tested. A double melting peak was observed in the differential scanning calorimetry thermograms of the mPE films. A relatively sharp strain hardening behavior in tensile tests was observed for the mPEs films when compared to LLDPE. Fourier transform infrared was used as an effective and fast method to investigate side chain length. It was found that the positioning of side chain, co‐monomer length, and content influence the melting behavior of mPE films. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Effects of the processing conditions and blending with linear low-density polyethylene on the properties of low-density polyethylene films

Effects of blending low-density polyethylene (LDPE) with linear low-density polyethylene (LLDPE) were studied on extrusion blown films. The tensile strength, the tear strength, the elongation at break, as well as haze showed more or less additivity between the properties of LDPE and LLDPE except in the range of 20–40% where synergistic effects were observed. The LLDPE had higher tensile strength and elongation at break than did the LDPE in both test directions, as well as higher tear strength in the transverse direction. The impact energies of the LLDPE and the LDPE were approximately the same, but the tear strength of the LLDPE was lower than that of LDPE in the machine direction. The comparative mechanical properties strongly depend on the processing conditions and structural parameters such as the molecular weight and the molecular weight distribution of both classes of materials. The LLDPE in this study had a higher molecular weight in comparison to the LDPE of the study, as implied from its lower melt flow index (MFI) in comparison to that of the LDPE. The effects of processing conditions such as the blow-up ratio (BUR) and the draw-down ratio (DDR) were also studied at 20/80 (LLDPE/LDPE) ratio. Tensile strength, elongation at break, and tear strength in both directions became equalized, and the impact energy decreased as the BUR and the DDR approached each other.     

Shear and elongational rheology of polyethylenes with different molecular characteristics. I. Shear rheology

Four metallocene polyethylenes (PE), one conventional low density polyethylene (LDPE), and one conventional linear low density polyethylene (LLDPE) were characterized in terms of their complex viscosity, storage and loss moduli, and phase angle at different temperatures. The effects of molecular weight, breadth of molecular weight distribution, and long‐chain branching (LCB) on the shear rheological properties of PEs are studied. For the sparsely long‐chain branched metallocene PEs, LCB increases the zero‐shear viscosity. The onsets of shear thinning are shifted to lower shear rates. There is also a plateau in the phase angle, δ, for these materials. Master curves for the complex viscosity and dynamic moduli were generated for all PE samples. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of different film preparation procedures on the thermal,morphological and mechanical properties of pure and calcite‐filled HDPE films

The effect of different film preparation procedures on the thermal, morphological and mechanical properties of high density polyethylene (HDPE) films have been studied using differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXRD), atomic force microscopy (AFM), scanning electron microscopy (SEM) and ultimate tensile testing. Film preparation procedures included variation in cooling methods, including quenching, forces (fanning) and natural cooling and techniques such as extrusion followed by melt squeezing and compression molding. The heat of fusion (from DSC), the degree of crystallinity (from WAXRD) and the crystallite size (from WAXRD and AFM) were found to be highest for naturally cooled specimens, followed by fan‐cooled and quenched ones. AFM images of surface topology exhibit stacked lamellar morphology for forcefully cooled (fan‐cooled and quenched) samples and spherulitic ‘lozenges’ for naturally cooled ones. The Young's modulus and yield stress [from the universal testing machine (UTM)] were highest for naturally cooled samples, followed by fan‐cooled and quenched ones. Among the calcite‐filled composites, the ‘base film,’ which was prepared by extrusion followed by melt squeezing and natural cooling, exhibited the lowest heat of fusion and degree of crystallinity and a similar crystallite size relative to compression‐molded films. Lower yield stress, tensile strength and Young's modulus and higher elongation at break were observed for the base film in comparison to the naturally cooled composite film. The low degree of crystallinity and crystallite size in the ‘base film’ explain all of its mechanical and morphological properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1427–1434, 2004