Tailor‐made controlled rheology polypropylenes from metallocene and Ziegler–Natta resins

Production of controlled rheology polypropylenes (CRPPs) is practiced industrially by modifying existing commodity Ziegler–Natta resins through peroxide‐induced β‐scission reactions, resulting in materials with controlled rheological properties and accompanying narrower molecular weight distributions (MWDs). In this work, this methodology was studied using both metallocene‐based polypropylenes (mPPs) and Ziegler–Natta‐based polypropylenes (ZN‐PPs). Numerical simulations based on a previously proposed kinetic model indicated that the nature of the starting resin has a significant effect on the control of MWD polydispersity index (PDI) and weight‐average molecular weight ( ${\overline{M}}_W$) of the resulting CRPP. Based on these observations, experiments were carried out to demonstrate the feasibility of producing CRPP with targeted molecular and rheological characteristics. Commercial mPP and ZN‐PP resins were selected to produce CRPP with similar ${\overline{M}}_W$ or melt flow rates (MFRs) but varying PDIs. The rheological properties and MWDs of these materials were evaluated through oscillatory shear and gel permeation chromatography (GPC) measurements and their extrusion behavior was briefly studied and assessed with respect to these properties. POLYM. ENG. SCI., 59:1114–1121 2019. © 2019 Society of Plastics Engineers     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. I. Temperature dependence

Polypropylene (PP)‐type resins with narrow molecular weight distribution, such as PP‐type thermoplastic elastomer PER and controlled‐rheology PP (CRPP) made by peroxide degradation of high molecular weight PP, have a problem of easy generation of skin roughness at extrusion. To examine the present state, the occurrence of skin roughness in PER and CRPP at extrusion was investigated with a capillary rheometer in a shear rate range of 12–6100 s^?1 and a temperature range of 180–280°C. A homo‐PP (HPP) and a block‐PP (BPP) with usual molecular weight distributions were used for comparison. HPP and BPP with usual molecular weight distributions show smooth extrudates at low shear rates and abruptly generate severe skin roughness “elastic failure” originating at the die entrance at a higher shear rate. PER and CRPP with narrow molecular weight distributions easily generate “sharkskin” melt fracture originating at the die exit, from a shear rate nearly one decade lower than rates of elastic failure of HPP and BPP. The sharkskin becomes more severe, with increasing shear rate, and attains to the elastic failure. The critical shear rate at which sharkskin occurs increases with increasing extrusion temperature. The critical shear rate is about 20 s^?1 at 180°C and about 120 s^?1 at 280°C, which is in the range encountered by the molten resin at extrusion processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2111–2119, 2002     

Gross melt fracture of polyethylene. II: Effects of molecular structure

The effect of molecular structure (MW, MWD and LCB) on the critical tensile stress (σ_c) for the onset of gross melt fracture (OGMF), proposed in Part I (1) as a material‐dependent criterion for fracture, was determined for a group of polyethylenes varying in structure. These included linear low and high‐density polyethylenes and several materials produced using metallocene and constrained geometry catalysts. It was found that the critical stress is independent of M_W, for constant polydispersity but increases with increasing long chain branching and polydispersity. The addition of boron nitride particles had no effect on the σ_c up to a level of 0.5% by weight.     

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.     

Flow properties of molten ethylene–vinyl acetate copolymer and melt fracture

In an investigation of the behavior and formation mechanism of melt fracture the flow properties of molten ethylene–vinyl acetate (EVA) copolymer in the region of high shear rate were measured with a capillary-type rheometer. EVA copolymer differs slightly in flow curve from low-density polyethylene (LDPE); it seems, however, that the difference is due to the difference in molecular weight distribution (MWD) rather than to the materials themselves. The fluidity of molten EVA copolymer having a narrow MWD is equivalent to that of LDPE having a broad MWD and, generally, EVA copolymer has a higher fluidity than LDPE. It is expected that the fluidity increases with incorporation of vinyl acetate at the same MWD and the same M?_w. The critical shear rate increases with melt index and temperature. It cannot be found that the materials themselves and the MWD directly influence the critical point of melt fracture formation when the melt index is taken as a parameter. The critical viscosity (η_c) at which melt fracture forms decreases in an almost straight line with an increase of melt index. It was found from the studies of end correction and behavior of melt fracture formation that melt fracture occurs at the inlet of the die, and it is supposed that the melt fracture formation is caused by the elastic turbulence in the flow pattern due to a failure of recoverable shear strain at the die inlet.     

Critcal stress and recoverable shear for polymer melt fracture

The phenomenon of extrudate distortion, which is called melt fracture, was studied for polystyrene samples of narrow and broad molecular weight distribution, and commerical samples of polypropylene and linear and branched polyethylene. It was experimentally found that the shear stress at the onset of melt fracture (τ_cr) is of the order of 10⁶ dynes/cm² and independent of the distribution of molecular weights. As the weight average molecular weight increases the shear stress τ_cr decreases. For polystyrene extruded at τ_cr the recoverable shear strain, which is defined to be half the ration (first normal stress difference/shear stress), was found proportional to the factor M _zM _z+1/M _w² which represents the distrubution of molecular weights. The proportionality is expected to hold for other polymer systems. The polymer behavior at the onset of melt fracture was explained in terms of Graessley's entanglement theory and his correlation between true and Rouse shear compliance.     

A study on the onset surface melt fracture of polypropylene materials with foaming additives

The melt fracture behaviors of linear and branched polypropylene resins with foaming additives were investigated. The effects of branching, processing temperature, additives, and blowing agent on the surface melt fracture of polypropylene materials were thoroughly studied. A CCD camera was installed at the die exit to precisely observe the onset of surface melt fracture of extruded foams. The critical wall shear stress was determined for various linear and branched polypropylene resins using a capillary die. It was found that the branching required to foam polypropylene resins also promotes melt fracture: the critical shear stress was decreased by 0.0175 MPa with an increase of 0.1 n/1000c in long‐chain branching. It was also observed that the dissolved blowing agent (butane) significantly suppressed the melt fracture of both linear and branched polypropylene resins. On the other hand, a noticeable increase in the critical shear stress of branched polypropylene materials was observed with the nucleating agent (talc) and the aging modifier (glycerol mono stearate), whereas almost negligible effect of the additives on the critical shear stress was observed for linear polypropylene materials. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Concentrated solution and melt rheology of poly(vinylidene fluoride)

The concentrated solution and melt rheology of poly(vinylidene fluoride) [PVDF] were studied by using a falling needle solution viscometer, a Brookfield viscometer, and a Kayeness capillary rheometer. It was found that the concentrated solution (15 wt% in N-dimethyl acetamide) rheology exhibited a different behavior for various grades of PVDF produced by different types of polymerization. While Newtonian behavior was found in one type of PVDF, shear thinning was found in another type. The power law model was used to describe the general solution behavior of these materials. Zero shear rate viscosity correlated well with the molecular weight (M_w) of the material. Melt viscosity of PVDF exhibited continuous shear thinning behavior throughout the whole range of shear rates. The data were best fitted by a second-degree polynomial curve. Correlations were established between the molecular weight, molecular weight distribution, and the parameters of the polynomial curve. These correlations are useful for the prediction of various grades of PVDF designated for specific engineering applications. The correlations obtained from solution provided better and more accurate correlations to M_w parameters than those of melt rheology.     

Molecular weight–viscosity relationships for poly(1,4-butylene terephthalate)

The correlation between number-average molecular weight and intrinsic viscosity in 60:40 phenol-sym-tetrachloroethane at 30°C for poly(1,4-butylene terephthalate) was established from endgroup determinations as well as by gel permeation chromatography, eqs. (1) and (10a). The GPC data also yielded relationships between weight- and z-average molecular weight and intrinsic viscosity, eqs. (10b) and (10c). Melt viscosities, corrected for the thermal history of the melt, were measured at shear stresses in the range of 0.02–0.55 MPa. Linear PBT melts were found to become non-Newtonian at a shear stress of approximately 0.11 MPa, independent of molecular weight within the range studied. Correlations between melt viscosity at low shear stress versus intrinsic viscosity are presented, as well as the dependence of melt viscosity in the non-Newtonian region on shear stress and low-stress (Newtonian) melt viscosity.     

Shear viscosity,extensional viscosity,and die swell of polypropylene in capillary flow with pressure dependency

The shear and extensional viscosities of a polypropylene resin were studied using a capillary rheometer and capillary dies of 1‐mm diameter and length of 10, 20, and 30 mm. Melt temperatures at 190, 205, and 220°C and shear rates between 100 and 5000 s^?1 were used. At the highest shear rate a visible melt fracture was observed. An equation relating the pressure drop and die length was derived with consideration of pressure effects on melt viscosities and the end effect. After the correction for pressure effects the true wall shear stress and end effect at zero pressure were calculated. The end effect showed a critical stress of melt fracture around 10⁵ Pa, and increased rapidly when shear stress increased above the critical stress. From shear stress the shear viscosity was calculated, and a power law behavior was observed. Extensional viscosity was calculated from the end effect and showed a decreasing trend when strain rate increased. After time–temperature superposition shift shear viscosity data correlated well, but an upward trend was observed in extensional viscosity when melt fracture occurred. Die swell ratio at different temperatures can be plotted as a function of wall shear stress and was higher for shorter dies. © 2002 Wiley Perioodicals, Inc. J Appl Polym Sci 84: 1269–1276, 2002; DOI 10.1002/app.10466     

Observation of melt fracture of polypropylene resins in capillary flow

Melt fracture, shear viscosity, extensional viscosity, and die swell of two polypropylene resins were studied using a capillary rheometer. A modified Bagley plot with consideration of pressure effects on melt viscosity and end effect was used. From the true wall shear stress the shear viscosity was calculated. Extensional viscosity was calculated from the end effect. Both shear and extensional viscosities of different molecular weights and temperatures correlated well under the time-temperature Williams-Landel-Ferry (WLF) superposition. Die swell increased when shear stress increased, and was higher for shorter dies at a given shear rate. When shear rates increased the extrudate staged from smooth to gross melt fracture with regular patterns (spurt), and then turned into irregular shapes. In the regular stage the wavelength of extrudates was measured, and corresponding frequency was calculated. The frequency increased when molecular weight decreased and when melt temperature increased. The shift factor based on shear viscosity also brought frequency data of different molecular weights and temperatures into master curves. The frequency decreased slightly when die lengths increased from L/R=10 to 60. A small maximum was observed when shear rates increased.     

Charakterisierung von Polyethylenen hoher Dichte mittels rheologischer Messungen

The melt rheological behaviour of three homologous HDPE-series, differing substantially in molecular weight distribution and each encompassing a broad molecular weight range, was investigated. The viscoelastic properties were measured by means of a sandwich-type creep rheometer and capillary viscosimeters. The zero shear viscosity is found to be proportional to the 3.6 power of the weight average molecular weight. The shear stress dependence of viscosity is related to the molecular weight distribution and is not influenced by molecular weight. The elastic behaviour (shear compliance) is also only effected by molecular polydispersity. This normal behaviour of PE is easily obscured by long chain branching. Few long chain branches cause considerable deviations of the rheological properties.     

Prediction of high density polyethylene processing behavior from rheological measurements

In order to predict the processing behavior of a high density polyethylene resin one must know the resin flow behavior over a wide range of shear rates. Low shear properties are important in applications where melt strength, sagging, etc. are critical. On the other hand, high shear flow properties are a determining factor in applications where melt instability, melt fracture and heat generation are important. The flow behavior of a resin can be established by measuring the zero shear viscosity, η₀, the maximum relaxation time, τ₀, and the shape of the flow curve. We have measured these basic rheological parameters on a large number of high density polyethylene resins. A shear sensitivity parameter which is independent of molecular weight was derived from a correlation between η₀ and τ₀. This parameter, together with η₀, provide the vital information needed in order to predict the processing behavior of the resin. This method is applicable to other polymer systems provided that the rheological parameters η₀ and τ₀ can be experimentally obtained.     

Structural and rheological investigation of low density polyethylenes

Some low density polyethylenes (LDPE) with different melt flow index (MFI) or produced by different producers have been examined in detail by solvent gradient fractionation, ¹³C NMR analysis, FTIR spectroscopy and melt rheological measurements. It was found that the distribution curves of the samples resemble Wesslau's logarithmic-normal model. From branching analyses it can be concluded that the branching content in the analyzed LDPEs is independent from the molecular weight. Relations between viscosity curve parameters and molecular structure have been investigated. It has been found that the dependence of the first normal stress difference on the shear stress is influenced by polydispersity as well as by the character of samples branching.     

ELASTIC FRACTURE OF POLYMERIC FLUIDS

The elastic fracture of polystyrene solutions and melts was investigated using a plunger driven viscometer. The polymeric extrudate emerging from a circular capillary was photographed to determine the onset of fracture, and an effort was made to relate this information to the shear stress at the capillary wall, the recoverable shear strain, the entanglement density and the geometrical parameters characterizing the system. It was found that narrow molecular weight distribution polystyrenes dissolved in benzene clearly fractured as reported in the literature, but the onset of fracture could not be predicted by available criteria. As opposed to this, highly concentrated (polymer volume fraction up to 0.57) and elastic solutions of a wide molecular weight distribution polystyrene in benzene showed no fracture when judged using similar criteria. Nonetheless, this latter polymer fractured as a melt at a value of the wall shear stress less than that achieved in the solution runs. From an examination of the polymer rheology, it is concluded that the recoverable shear strain is the key quantity influencing the onset of elastic fracture. Also, the recoverable shear-shear rate behavior is different for the melt and the solution and it depends not only on the polymer molecular weight and its distribution but also on the solvent used. The surprising absence of elastic fracture for highly viscoelastic solutions can be understood if one realizes that a critical value of the recoverable shear strain is needed for fracture to occur.     

Influence of molecular weight distribution on the structure and properties of melt-spun polypropylene filaments

The role of molecular weight distribution on the spinnability, structure, and properties of melt-spun isotactic polypropylene filaments was studied with the aim of clearly distinguishing the effect of the breadth of the distribution from the effect of the average molecular weight and resin melt flow rate (MFR). Nine resins were chosen for this purpose, ranging in MFR from 16 to 78 and in polydispersity from 2.6 to 5.4. It was observed that the spinnability, structure, and properties of the spun filaments were all strong functions of the breadth of the distribution. Spinnability decreased with increasing breadth. At given spinning conditions and polydispersity, an increase in the weight-average molecular weight (decrease in MFR) produces an increase in crystallinity, birefringence, tensile strength, and tensile modulus. But at given spinning conditions and resin MFR, broadening the molecular weight distribution (increasing the polydispersity) produces an increase in crystallinity, tensile modulus, and elongation-to-break while birefringence and tensile strength decrease. The major influence of the polydispersity on the structure and properties developed was attributed to its effect on both the elongational viscosity of the resin and the ability of high molecular weight tails in the distribution to influence the stress-induced crystallization that occurs in the spinline. © 1995 John Wiley & Sons, Inc.     

Study on long fiber–reinforced thermoplastic composites prepared by in situ solid‐state polycondensation

Long glass fiber–reinforced thermoplastic composites were prepared by a new process, in situ solid‐state polycondensation (INSITU SSP). In this process reinforcing continuous fibers were impregnated by the oligomer of PET melt, and then the impregnated continuous fibers were cut to a desired length (designated prepreg); finally, the prepreg was in situ polymerized in the solid state to form the high molecular weight matrix. SEM, FTIR spectra, short‐beam shear stress test, flexural strength test, impact strength test, and the intrinsic viscosity measurement were used to investigate the wetting and interfacial adhesion, the mechanical properties of the composite, and the molecular weight of matrix resin in the composite. The results showed that the molecular weight of PET in the matrix resin and mechanical properties could be adjusted by controlling the SSP time and that the high level of interfacial adhesion between reinforcing fibers and matrix resin could be achieved by this novel INSITU SSP process, which are attributed to the good wetting of reinforcing fibers with low molecular weight oligomer melt as the impregnation fluid, the in situ formation of chemical grafting of oligomer chains onto the reinforcing fiber surface, and the in situ formation of the high molecular weight PET chains in the interphase regions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91:3959–3965, 2004     

Extrude distortion in the capillary/slit extrusion of a molten polypropylene

Experiments were carried out in both sliding plate and capillary rheometers with a polypropylene resin to determine the conditions for the onset of slip, surface, and gross melt fracture. It was found that there was no distinction between surface and gross melt fracture, which is commonly observed in the case of polyethylenes. Furthermore, the flow curves determined by using capillaries having various diameters are diameter independent implying the absence of slip. However, experiments with slit dies having rough surfaces suggest wall slip. Further analysis has shown that the effect of viscous heating masks the detection of slip from the diameter-dependency of the flow curves. The effect of a thin layer of fluoropolymer (Teflon PA, DuPont) on the critical shear stress for the onset of wall slip and melt fracture, as well as on the relationship between the wall shlip and the shear stress, were also examined. It was found that the presence of such layers increases the slip velocity, while it decreases the critical shear stress for the onset of slip.     

The effect of random branching on the balance between flow and mechanical properties of polyamide-6

The rheological and mechanical properties of a series of linear and randomly branched polyamide 6 samples, with varying molar mass and varying degree of moderate branching, have been investigated.As expected, it was found that random long-chain branching has a pronounced effect on the rheological behaviour of the materials in both shear and extensional flow. The zero shear viscosity increases with branching while the flow curve becomes more shear thinning. Randomly branched materials have an enhanced melt strength in elongational flow. Although branched, the materials show perfect melt stability in their rheology.The mechanical properties show minor differences between the linear and the moderately branched samples and are mainly dependent on the weight average molar mass. A small increase in modulus, yield stress and failure stress and a decrease in the strain at break are found, which is probably due to increased molecular orientation in the plane of injection moulding. The IZOD impact strength is similar to what is normally found for linear polyamide-6, and independent of branching. Also the fracture toughness K_IC is not affected by the incorporation of random branching. However, it is clearly dependent on the weight average molar mass.By using random branched polyamide-6, molecular weights and related mechanical properties can be obtained that are out of reach for linear polyamide-6.     

The rheology of polysulfone

The viscosity-shear rate functions for polysulfone (PSF) condensates ranging from 0.4RV to 0.95RV were determined using capillary rheometry, The most probable distribution of molecular weights of these resins allowed facile comparison with the polydisperse Bueche theory for viscosity, The agreement in shape of the viscosity function with theory was good but the data were displaced by a factor of 3 to 4 to higher reduced shear rate, a fairly common occurrence for melts. The high absolute value of PSF viscosity was explained with existing empirical correlations as a combination of low critical molecular weight and strong intermolecular interactions. The temperature dependence of viscosity was found to be close to that for polystyrene in the temperature range, T_g + 90 to T_g + 190°C. The die swell, end corrections, and melt fracture characteristics were also determined. The latter was found to occur at a constant wall shear stress of about 6 × 10⁶ dynes/cm² while the die swell and end corrections were found to be small.