Large enhancements of the melt strength of polypropylene (PP) were achieved by the introduction of specific unsaturated linear
polyester (ULP) branches using melt grafting. The transient torque curves and optical rheology microscope images indicated
that branching reactions took place and the ULP had been grafted onto the PP backbone. Shear rheological behaviors of three
kinds of PP were investigated using rotational rheometer under dynamic shear mode with periodic shear rate. These PP samples
are foamable PP (FPP) with sparse branches obtained by grafting ULP, commercial high melt strength PP (HMS PP) for foaming
and conventional linear PP (EPS). It was found that the rheological properties of FPP, the HMS PP, were distinctly different
from those of conventional PP. Storage modulus, steady state compliance and zero shear viscosity increased in comparison with
EPS, while shear viscosity decreased. This result implied the presence of branching structures that was not revealed in conventional
PP. In melt flow measurements, extrusion swell that was a prominent behavior of branching PP was observed also for FPP and
PF. Compared to linear PP, FPP and PF showed distinct sag-resistant property and lower melt flow index. On the other hand,
to estimate the extent of branching, a detailed method was applied using the obtained zero shear viscosity. The result showed
that FPP was grafted by sparse ULP. From these results, it was found that FPP showed obvious enhancements in rheological behaviors
similar to PF, although its melt strength was lower than that of PF due to the presence of shorter branching chains grafted
on the backbone of FPP. 相似文献
This paper compares the molecular structure and rheological properties of a commercial poly(ethylene terephthalate) (PET) after reactive processing with different concentrations of either pyromellitic dianhydride (PMDA) or a multifunctional epoxide (Joncryl®ADR-4368) as a chain extender. By size exclusion chromatography with triple detection, an increase of molar mass, a broadening of molar mass distribution, and the generation of long-chain branched molecules were found for both chain extenders. While gel-free materials were obtained with PMDA, the processing with Joncryl leads to the formation of gels. The effect of branching, indicated by the Mark–Houwink exponent, is more pronounced for materials with Joncryl compared to PMDA and points to a more compact branching structure of the PET/Joncryl molecules. Rheological measurements in shear and elongation support the analysis from SEC and reveal a complex tree-like branching structure for both chain extenders. In addition, the role of the two modifiers with respect to processing was assessed. 相似文献
The rheology of blends of linear and branched poly(lactic acid) (PLA) architectures is comprehensively investigated. Measurement of the melt rheological properties of PLA is complicated by degradation effects but the addition of 0.35 wt% tris(nonylphenyl) phosphite (TNPP) provides excellent stabilization over a range of temperatures. Master curves of dynamic viscosity constructed using time‐temperature superposition show significant dispersion for unstabilized samples; this behavior is accompanied by a loss of molecular weight. TNPP stabilized samples show excellent superposition throughout the entire frequency range and minimal loss in molecular weight. For the linear architecture, the Cox‐Merz rule is valid for a large range of shear rates and frequencies. The branched architecture deviates from the Cox‐Merz equality and blends show intermediate behavior. Both the zero shear viscosity and the elasticity (as measured by the recoverable shear compliance) Increase with increasing branched content. The viscosities of both the unstabilized samples and the TNPP stabilized samples roughly obey a log additivity mixing rule. The recoverable shear compliance is monotonic in blend composition and a mixing rule for this property is also presented. For the linear chain, the compliance is independent of temperature but this behavior is apparently lost for the branched and blended materials. Tensile and thermal properties of the blends are also measured and found to be roughly equal within the statistical error of the experiments. The results suggest that excellent control over rheological behavior of PLA is possible through blending chain architectures without compromising mechanical properties. 相似文献
Commodity linear and branched polypropylene resins have been modified by means of peroxide initiated chemical degradation in a reactive extrusion process. Data collected from molar mass and linear viscoelastic property measurements have been used to evaluate the L“crossover modulus” and “modulus separation” rheological polydispersity measures and a theoretical justification is provided for the modulus separation index. In the past, these empirical methods have been used successfully to relate molar mass characteristics to rheological properties. Results obtained in this study confirm the validity of the modulus separation index for linear polymers and suggest that it should be used carefully in the analysis of data from branched polymers. Linear viscoelastic data are used to estimate the terminal relaxation time spectra of both the linear and branched materials and a new correlation between modulus separation and relaxation time polydispersity is given. 相似文献
An empirical model suggested earlier by B. H. Bersted predicting the rheological properties of linear polyethylene from the molecular weight distribution is modified to account for the rheological properties in steady shear flow of branched polyethylene as well. The shear dependent viscosity, the steady shear compliance, and extrudate swell could be calculated from the distributions of molecular weight and long-chain branching in good agreement with experimental data for eight commercial low density polyethylenes. Tanner's equation was used to calculated die-swell from the modified Bersted model. The steady shear compliance was found to be related to \documentclass{article}\pagestyle{empty}\begin{document}$(\overline {gM} )_z .(\overline {gM} )_{z + 1} /(\overline {gM} )_w^2 .$\end{document}. 相似文献
Summary: The rheological behavior of polyethylenes is mainly dominated by the molecular weight, the molecular weight distribution and by the type, the amount and the distribution of the chain branches. In this work a linear metallocene catalyzed polyethylene (m‐PE), a branched metallocene catalyzed polyethylene (m‐bPE), a conventional linear low density polyethylene (LLDPE) and a low density polyethylene (LDPE) have been investigated in order to compare their rheological behavior in shear and in elongational flow. The four samples have similar melt flow index and in particular a value typical of film blowing grade. The melt viscosity has been studied both in shear and in isothermal and non‐isothermal elongational flow. The most important features of the results are that in shear flow the m‐PE sample shows less pronounced non Newtonian behavior while in the elongational flow the behavior of m‐PE is very similar to that of the linear low density polyethylene: the narrower molecular weight distribution and the better homogeneity of the branching distribution are reasonably responsible for this behavior. Of course the most pronounced non‐linear behavior is shown, as expected, by the LDPE sample and by the branched metallocene sample. This similar behavior has to be attributed to the presence of branching. Similar comments hold in non‐isothermal elongational flow; the LDPE sample shows the highest values of the melt strength and the other two samples show very similar values. As for the breaking stretching ratio the opposite is true for LDPE while m‐PE and LLDPE show higher values. The transient isothermal elongational viscosity curves show that the branched samples show a strain hardening effect, while LLDPE and m‐PE samples present a linear behavior.
Dimensionless flow curves of different polyethylene samples. 相似文献
Fourteen long-chain branched (LCB) polyethylene (PE) samples were prepared by a constrained geometry catalyst. The PE samples had average branching frequencies of 0.06-0.98 branches per polymer chain, as determined by the nuclear magnetic resonance spectroscopy (13C NMR). These samples, as well as five linear PEs were characterized using a gel permeation chromatography (GPC) coupled with online three-angle laser light scattering (LS), differential refractive index (DRI), and viscosity (CV) detectors. The root mean-square radius of gyration intrinsic viscosity ([η]), and molecular mass (M) of the PEs were measured for each elution fraction. Based on the comparison of the long-chain branching (LCB) PEs with their linear counterparts and the Zimm-Stockmayer equation, the distributions of long-chain branch frequency (LCBF) and density (LCBD) as function of molecular mass were estimated. It was found that although the LCBF increased with the increase of molecular mass, the LCBD showed a maximum value in the medium molecular mass range for most of the PE samples. The average LCBD data from the GPC analysis were in good agreement with the 13C NMR measurements. The rheological properties and processing behavior of these samples were also assessed. While the long chain branching showed significant effects on the modulus and viscosity, it did not improve the processing. Compared to linear PE, polymer melt flow instabilities such as sharkskin, stick-slip and gross melt fracture developed in extrusion of LCB PEs occurred at lower wall shear stresses and apparent shear rates. 相似文献
The dynamic mechanical and rheological properties of five long-chain branched (LCB) and three linear ethylene/propylene (EP) copolymers were investigated and compared using a dynamic mechanical analyzer (DMA) and an oscillatory rheometer. The novel series of LCB EP copolymers were synthesized with a constrained geometry catalyst (CGC), [C5Me4(SiMe2NtBu)]TiMe2, and had various propylene molar fractions of 0.01-0.11 and long-chain branch frequencies (LCBF) of 0.05-0.22. The linear EP copolymers were synthesized with an ansa-zirconocene catalyst, rac-Et(Ind)2ZrCl2 (EBI), and contained similar levels of propylene incorporation as the CGC copolymers, but no LCB. In dynamic mechanical analysis, the dynamic storage moduli (G′) and loss moduli (G″) of the copolymers decreased with an increase of propylene molar fraction. The α- and β-transitions of the CGC copolymers were overlaid with each other. High damping (tan δ) values were found with the CGC copolymers at temperatures below 0 °C. In oscillatory rheological analysis, compared to the linear EBI counterparts, the LCB CGC copolymer melts showed higher zero shear activation energies, broader plateaus of δ and larger elastic contributions, which are essential characteristics of LCB polymers. It was found that the long chain branching was the determining factor in controlling rheological properties of the polymer melts while the short chain branching from propylene incorporation played a decisive role in affecting dynamic mechanical properties. This work represents the first rheological evidence of LCB in EP copolymers synthesized with CGC. 相似文献
The feasibility of preliminary tailoring of the long chain branched (LCB) polymer through complex flow field was evaluated in the torque rheometer, for the reaction of melt polyolefin elastomer (POE) with peroxides at elevated temperatures. With the compensation of temperature, the strength of complex shear flow could be the only factor affecting the reaction kinetics and mechanism. The results of sample characterization by the rheological and dilute polymer solution methods indicated that the degradation mainly made the length of LCB arm shorter and shorter as the rotational speed increases. Extremely, a certain amount of LCB degraded to be linear chains again due to the scission approaching the branching point at intense mixing condition. One new LCB index (DLCB) was defined from nonlinear oscillatory shear, and a nearly linear relationship between it and long chain branching index (LCBI) was found, which can be a map to quantify LCB level by Fourier Transform Rheology (FTR). 相似文献