HDPE/LLDPE reactor blends with bimodal microstructures—Part II: rheological properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and vice versa HMW homopolymer to LMW copolymer. The shear flow characteristics of these polymers in the typical processing range mostly depend on the molecular weight and MWD of the polymer and are independent of the short chain branch content. From oscillatory shear measurements, it was observed that the viscosity of HMW polymers was reduced with the addition of LMW material. For the polymers produced with this two-step polymerization process, the LMW homopolymer and HMW copolymer blends and HMW homopolymer and LMW copolymer blends were melt miscible, despite the large viscosity differences of the pure components.     

Molecular weight distribution of living polymers in a semi-batch reactor

For anionic polymerization with slow initiation and rapid propagation step analytical expressions are presented to calculate average molecular weights and molecular weight distributions for a semi-batch process, in which a monomer solution contaminated by impurities is fed to an initiator solution in the reactor. The validity of the model was checked for the case of the polymerization of isoprene by n-butyllithium in n-heptane. The differences observed between theoretical and experimental values are explained by the changes in the rate constants of the initiation and the propagation step caused by the change in the polarity of the reaction solution by the continuously fed impurities. Furthermore it is shown that polymers with bimodal molecular weight distributions are formed if the semi-batch procedure is followed by a batch one to increase the monomer conversion.     

乙烯气相聚合过程中氢气振荡操作制备双峰聚乙烯

在单一气相反应器中,采用国产APE-1G(Cp*₂ZrCl₂·2LiCl·THF)型茂金属催化剂,通过强制振荡反应器内的氢气浓度制备双峰聚乙烯。实验考察了氢气浓度、振荡时间分配和振荡周期对聚乙烯分子量分布的影响。实验结果表明,氢气的加入使得催化剂活性降低,产物分子量也减小。通过强制振荡氢气的浓度可以得到双峰分布的聚乙烯,M_w/M_n达到11.2～34.2。研究表明,通过调节氢气振荡操作的实验条件,尤其是调节振荡时间分配,可以很好地控制双峰聚乙烯的分子量分布。     

High performance gel permeation chromatography of polystyrene

Microparticulate crosslinked polystyrene packings in short columns have been investigated with high performance liquid chromatography instrumentation. Reliable molecular weight data for six polystyrene standards having narrow molecular weight distributions and for a polystyrene having a broad distribution have been obtained by optimizing the injection procedure, using a constant flow pump, and incorporating an internal standard into each injected solution. Experimental determinations of the dependence of the polydispersity for polystyrene standards on eluent flow rate and polymer diffusion coefficient were in agreement with a relation predicted from theoretical considerations of chromotogram broadening. Because of the dependence of chromatogram broadening on polystyrene molecular weight, high efficiency separations for high polymers were only obtained at low eluent flow rates. For low polymers, high efficiency separations may be performed at fast eluent flow rates. It was concluded that accurate molecular weight distributions can only be determined from chromatograms obtained at low eluent flow rates, which was supported by experimental measurements of polydispersity on polystyrene sample prepared by a radical polymerization at low monomer conversion. A differential weight distribution calculated from an experimental chromatogram for the polydisperse polystyrene determined at the lowest eluent flow rate (0.1 cm³min^?1) was compared with distributions predicted theoretically for polystyrenes prepared by radical polymerization. It was concluded that the experimental distribution contained a small contribution from chromatogram broadening and that most of the radicals in the polymerization of styrene terminated by combination.     

HDPE/LLDPE reactor blends with bimodal microstructures—part I: mechanical properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and, vice versa, HMW homopolymer to LMW copolymer. The physical properties of the blends were found to be consistent with the nature of the individual components. For the tensile properties, the stiffness decreases with increasing the fraction of the copolymer, regardless of the molecular weight of the homopolymer fraction. For these blends with bimodal microstructures, it was confirmed that the degree of crystallinity governs the stiffness of the polymer. However, the energy dampening properties of the polymers benefit from the presence of the copolymer. A balance of stiffness and toughness can be obtained by altering the composition of the blends. For some blends, the presence of HMW homopolymer can dominate the tensile properties, showing little variation in the stiffness with increased addition of copolymer. It was also demonstrated that the testing conditions and thermal treatment of the polymer greatly influence the resulting elastic and energy dampening properties. Depending on the desired application, annealing these polymers (especially very low density copolymers) not only increases the crystallinity and stiffness, but also changes the frequency response of the dynamic mechanical properties.     

Modality of molecular weight distributions

Even restricting attention to weight distributions, it is ambiguous to merely say that a polymer is “not bimodal.” A simple example is shown wherein the weight distribution of log (molecular weight) is bimodal, but the weight distribution of molecular weight is not bimodal.     

Coagent-induced transformations of polypropylene microstructure: Evolution of bimodal architectures and cross-linked nano-particles

Polypropylene is transformed by simultaneous, radical-mediated chain scission and cross-linking to generate branched architectures. While macroradical fragmentation reduces the molar mass of the dominant chain population, cross-linking by triallyl trimesate (TAM) activation yields a minority population of hyper-branched chains that is less susceptible to molecular weight loss. This disparity in chain reactivity leads to bimodal molecular weight and branching distributions. Furthermore, a precipitation polymerization of TAM can proceed concurrently with PP branching to produce a low yield of cross-linked, TAM-rich nano-particles. The mechanisms through which unimodal composition and molecular weight distributions evolve toward a bimodal condition are discussed, along with the factors that lead to particle formation.     

Polarization-optical investigation of normal and shear stresses in flow of polymers

A method has been suggested for calculating the first difference of normal stresses characterizing the flow of polymers at high shear stresses. The calculations are based on the results of rheooptical measurements in a slit of rectangular cross section. It has been found, for several samples of high molecular weight polybutadienes and polyisoprenes, that the flow behavior of the representatives of the given polymer homologous series having different molecular weights is characterized by a general relationship between the first normal stress differences and the shear stresses in those cases where the polymers are characterized by narrow molecular weight distributions. It has also been established that the first normal stress difference sharply increases in the region of shear stresses which immediately precedes the spurt—a jumpwise increase of the flow rate at a certain critical value of shear stress; while for polymers of wide molecular weight distribution the increase of the normal stress difference in the region of high values of shear stresses is retarded. Equilibrium swell of the extrudate has been measured and the first normal stress difference determined by the rheo-optical method has been found to agree satisfactorily with the values calculated from the swelling ratios according to theoretical models.     

Poly[bis(m-chlorophenoxy)phosphazene]. Macromolecular characterization and degradation studies

The macromolecular structures of five poly[bis(m-chlorophenoxy)phosphazene] samples are critically analyzed. There are significant variations in the solubility behavior and physical properties of the polymers. Property differences are attributed mainly to the incomplete nucleophilic substitution of the dichlorophosphazene polymer precursor. All the polymers are found to have high molecular weights and broad, bimodal molecular weight distributions. However, differences in branching are noted and the presence of thermally labile “weak links” on the polymer chain backbones is suspected. At 165°C in static air, the polyphosphazene degrades by a random degradation mechanism and for long exposure times is considerably more stable than polystyrene.     

Splitting for strength: Manipulating polymerization reactor split ratios to control mechanical and rheological properties in bimodal polyethylene resins

This study integrates advanced mathematical modeling and experimental methodologies to investigate the simultaneous impact of modifications in the split ratio and molecular weight (MW) of chains on the rheological and mechanical properties of bimodal polyethylene (BiPE) resins. The outcomes underscored the viability of fine-tuning the molecular weight distribution (MWD) of a BiPE resin by augmenting the MW of high molecular weight (HMW) chains while simultaneously diminishing their proportion in the final alloy formulation. In addition, the experimental results illuminated the prospect of attaining a targeted melt flow index for the final polymers by elevating the MW of HMW chains alongside an increase in the proportion of low molecular weight chains. Significantly, these adjustments resulted in remarkable enhancements in the shear thinning index and strain hardening modulus of the fabricated resins.     

Calibration of size-exclusion chromatography columns with polydisperse polymer standards. II. Applications

New methods for calibrating SEC columns by means of polydisperse polymer samples with known M_n and M_w have been tested with computer-generated chromatograms and with experimental data of high-performance SEC. Calculations with the artificial chromatograms show that accurate calibration dependences can be recovered even when polymers with broad and/or bimodal molecular weight distributions are used as standards. Polystyrene calibration calculated by the proposed method from chromatograms of five polydisperse polystyrenes follows closely the curve obtained in a conventional manner from nine narrow polystyrene standards. The dependence log M vs. ν for PMMA determined from chromatograms of six PMMA samples with moderately broad molecular weight distributions agrees well with the curve obtained by shifting the dependence for polystyrene using the universal calibration concept. The new method is particularly useful when SEC columns are to be calibrated for dextrans in water, where only a few standards having a rather broad molecular weight distribution are available, and can considerably improve the accuracy of molecular weight determination by SEC.     

Accurate molecular weight distribution of polymers using thermal field-flow fractionation with deconvolution to remove system dispersion

Thermal field-flow fractionation (ThFFF) is an elution process that separates polymeric materials by molecular weight. Elution profiles thus provide approximations to the molecular weight distributions of polymers. The accuracy of such approximate distributions is expected to be improved by accounting for the effect on the elution profile of band-broadening processes in the FFF system. Fortunately this intrinsic band broadening, referred to as system dispersion, is theoretically well-defined in ThFFF. In this article we present an algorithm that corrects ThFFF elution profiles by removing system dispersion. The program is applied to ThFFF fractograms of standard polymers having both narrow and broad molecular weight distributions. The increased accuracy obtained by accounting for system dispersion is demonstrated. For the narrow standard, deconvolution shows that the polydispersity (weight/number-average mol. wt.) is only 1.004. For the broad standard, NBS 706, the molecular weight distribution and parameters obtained agree well with previously published results. Application to a simulated fractogram resulting from mixing five narrow standards helps define the conditions under which accurate molecular weight information can be recovered.     

ansa‐Zirconocenes with Bridge‐tethered Donors: Synthesis and Application as Catalysts in Solution Polymerization of Ethylene

Four new donor‐functionalized ansa‐zirconocenes have been synthesized from the XMeSiCp₂ZrCl₂ and X₂SiCp₂ZrCl₂ general formula (where X = (CH₂)₃OEt, C₈H₄SCH₂OMe, and CH₂(2‐MeO‐3‐Me‐C₆H₃)). In each of these metallocenes, alkoxy groups are linked by a three‐carbon chain to the silicon atom. To study the influence of the functionalized side chains, these metallocenes were activated with methylalumoxane (MAO) and utilized in solution polymerization of ethylene. The molecular weight distributions of the polymers formed show a bimodal shape which can be described as a superposition of two Schultz‐Flory distributions, synonymous to at least two different catalytic species. Unimodal polymers with M_w/M_n = 2 were formed with the Me₂SiCp₂ZrCl₂/MAO catalyst system, indicating that the unusual bimodal molecular weight distributions are due to the functionalized side chains tethered to the Si‐bridge.     

Heterogeneous catalyst mixtures for the polymerization of ethylene

Heterogeneous cocatalysts, catalysts, and catalyst mixtures for the polymerization of ethylene were prepared applying “fumed silica” and mesoporous MCM-41 support materials and zirconocene dichloride, titanocene dichloride, and a bis(arylimino)pyridine iron complex as catalyst precursors. The catalyst mixtures produced polyethylenes which exhibit the properties of two single polymers. Polyethylenes with the desired bimodal molecular weight distributions could be obtained with a series of ternary Zr/Ti/Fe catalysts. The ability of the zirconium and titanium species to copolymerize short-chain 1-olefins produced by the iron centers (“in situ” copolymerization) is useful for the production of copolymers from only one monomer (ethylene).     

A study on the rheological properties and processability of polycarbonate

The transport theory for the solids conveying zone in a single‐screw extruder was applied to calculate the pressure distributions along the screw channel for several bisphenol A polycarbonate resins based on the screw revolution speed and the flow rate. The pressure distributions and the flow rates of the resins were related to the structural and rheological properties. When polymers have the same chemical structure and number‐average molecular weight and the same mechanical properties, the polymer having a broader molecular weight distribution showed a lower glass transition temperature. For the polymer with broader MWD a relatively low pressure was developed along the screw channel, and an increased flow rate was observed. A relatively short melting length was also observed for this polymer and, accordingly, it was concluded that the polymer with a broader MWD has a better processability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2921–2929, 2002     

Shear properties of polystyrenes in the transition region

Shear properties of commercially available polystyrenes with narrow molecular weight distribution have been measured in the transition region from 100°C to 150°C and over a frequency range from 50 Hz to 1000 Hz. The effect of molecular weight or shear properties is established with four polymers ranging in molecular weight from 20,000 to 860,000. A broad, bimodal distribution is also studied. The properties of these polymers, with two different diluents added, illustrate the rather marked qualitative difference in effects caused by diluents.     

Melting Properties of Syndiotactic Polystyrenes and Effect of Hydrogen on Molecular Weight Distribution

Summary: The melting properties of syndiotactic polystyrenes are significantly affected by the structural molecular properties of the polymers. The most important influences on the melting behavior are stereoregularity, molecular weight and molecular weight distribution of the polymers. The melting temperature is increased by an enhanced syndiotacticity at sufficiently high molecular weights and at narrow molecular weight distributions. The degree of syndiotacticity obtained primarily depends on the kind and structure of the cyclopentadienyl ligand of the transition metal catalyst, whereas the effect of the other ancillary ligands on stereoregularity is negligible at the same cyclopentadienyl ligand. At narrow molecular weight distributions with below 2.8 and at constant stereoregularities, the molecular weight has a remarkable effect on the melting behavior at weight‐average molecular weights lower than about 80 000 g · mol^?1, resulting in a significant decrease of the melting temperature until below 230 °C. The presence of hydrogen during polymerization leads to a significant shift to lower molecular weights at comparably small amounts of hydrogen, but results in the occurrence of an additional peak in the molecular weight distribution at larger hydrogen concentrations giving evidence for the formation of a second active polymerization site producing lower molecular weight polymers. At constant stereoregularity, the broadening of the molecular weight distribution leads to decreased melting temperatures and to improved flow properties of the syndiotactic polystyrenes with increasing shear rates at moderate molecular weight distributions.

Detailed molecular weight distributions of syndiotactic polystyrenes in dependence on the hydrogen concentration.     

Molecular structure of high melt strength polypropylene and its application to polymer design

We report a numerical technique to investigate the branching process of linear Ziegler-Natta polypropylenes. Using an iterative procedure, linear chains are created based on the molecular weight distribution (MWD) of linear Ziegler-Natta polypropylenes as determined by GPC. By varying one parameter, MWDs of polymers with various levels of branching are simulated, and the simulated MWDs agree very well with experimental GPC data of branched polymers. From the simulation, the average branching parameters as well as the branching distributions of the polymers can be obtained. The branching information is related to the moments of the MWD, and a criterion of the onset of gelation is proposed. The melt flow rate (MFR) is correlated with the weight-average molecular weight. These relationships make it possible to design a polymer having a prescribed MFR.     

Mechanical properties of ethylene/1-hexene copolymers with tailored short chain branching distributions

Recently, we have investigated a metallocene catalyst system that can produce polyethylene and ethylene/α-olefin copolymers with tailored molecular weight and short chain branching distributions (SCBD). Ethylene/α-olefin copolymers produced with this system have narrow molecular weight distributions as expected from metallocene catalysts. However, these copolymers are quite unique in that their SCBDs are broad and sometimes bimodal, similar to Ziegler-Natta LLDPE.To examine the effect of these broad SCBDs on the polymer properties, a series of poly(ethylene-co-1-hexene) resins with very distinct, and in some cases bimodal crystalline distributions, were synthesized. The attractive feature of the resins in this study is that their molecular weight distributions are similar but each possesses a different SCBD, thus effectively minimizing the effect of molecular weight on the properties investigated.It was found that the tensile properties of a copolymer could be controlled by the ratio of the crystalline species present in the sample. In this study, a balance of stiffness and toughness was exhibited by a copolymer containing a large proportion of crystalline material and a small fraction of material of lower crystallinity.     

Crosslinking of bimodal polyethylene

Two bimodal polyethylenes, differing only in polymerisation order, were investigated with respect to crosslinking behaviour and network properties. The crosslinked materials were examined using size exclusion chromatography (SEC), gel-content measurements, and calculations of the network density. Dynamic mechanical analyses in the melt were performed to monitor the crosslinking and to provide another measure of the network density. The experiments were performed to investigate any potential influence of the polymerisation order on the crosslinking as well as to study the network formation in the crosslinked polymers. The bimodal polyethylenes were also compared to two monomodal polyethylenes representing the short chain branched, high molecular weight fraction, and the linear, low molecular weight fraction, respectively. The SEC measurements clearly showed how the crosslinking starts with the consumption of the high molecular weight fraction. The gel-content measurement showed the importance of a high molecular weight material for the gel formation. The network density calculations demonstrated how long chains can give rise to apparent networks which are mainly due to chain entanglements. The experiments showed that the polymerisation order for the bimodal polyethylenes has no effect on the crosslinking.