Control on the topological structure of polyolefin elastomer by reactive processing

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 (D_LCB) 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).     

The effect of shear flow on reaction of melt poly(ethylene-α-octene) elastomer with dicumyl peroxide

The reaction of melt poly(ethylene-α-octene) (POE) initiated by dicumyl peroxide (DCP) was studied at elevated temperature in both oscillatory and transient shear flow fields. In oscillatory shear flow, the storage modulus evolution was monitored by parallel plate rheometer with certain oscillatory frequencies and different strains, which were chosen to represent different flow fields. Our results indicated that at low frequencies (0.1 and 0.4 Hz) the dominant reaction was coupling with small strain amplitudes within the linear viscoelastic regime. However, the degradation, which was caused by β-scission of tertiary carbon macromolecular radicals, also occurred when large strains were applied, which were out of the linear viscoelastic regime. The threshold strain of degradation was only 8% at 1.5 Hz, still within the linear viscoelastic regime. The mechanisms of how the frequency and strain affected the degradation were different. On the other hand, in transient shear flow the degradation could hardly take place when the shear rate was lower than the critical value of 0.0025 s⁻¹. Moreover, the larger the shear rate, the more distinct was the degradation.     

Supercritical carbon dioxide-assisted reactive extrusion for preparation long-chain branching polypropylene and its rheology

An environmental benign process, which uses supercritical carbon dioxide (ScCO₂) as a processing aid, is developed in this work to prepare long chain branching polypropylene (LCB-PP). Results from the oscillatory shear rheology, melt elongational behavior and Fourier transformed infrared spectroscopy (FTIR) show that long chains have been linked as branches to the original linear PP chains using scCO₂-assisted reactive extrusion in the presence of cumene hydroperoxide and 1,6-hexanediol diacrylate. Compared to the initial linear PP, the branched samples show higher storage modulus (G′) at low frequency, distinct strain hardening of elongational viscosity, lower melt flow rate, increased crystallization temperature and improvement of the melt strength. ScCO₂ can improve the branching efficiency of modified PPs. The elastic response, melt strength and strain hardening parameter of the modified PPs increase with increasing scCO₂ concentration, which is ascribed to scCO₂ acting as a plasticizer for reducing PP viscosity and a carrier for active chemical species.     

Dynamic mechanical and rheological properties of metallocene-catalyzed long-chain-branched ethylene/propylene copolymers

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(SiMe₂N^tBu)]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.     

Structure and melt rheology of long‐chain branching polypropylene/clay nanocomposites

Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Triple-detector GPC characterization and processing behavior of long-chain-branched polyethylene prepared by solution polymerization with constrained geometry catalyst

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.     

Effect of oscillatory shear on the interfacial morphology of a reactive bilayer polymer system

We investigated, via atomic force microscopy and transmission electron microscopy, the effect of oscillatory shearing amplitude (γ₀) and frequency (ω) on the interfacial morphology of a reactive bilayer polymer system composed of end-functionalized polystyrene with carboxylic acid (PS-mCOOH) and poly(methyl methacrylate-ran-glycidylmethacrylate) (PMMA-GMA). It has been observed that in the absence of oscillatory shearing (or at very small values of γ₀ and ω), the roughness of the interface increased with reaction period, while at large values of γ₀ and ω it became less than that observed in the absence of oscillatory shearing. This observation may be attributable to the possibility that oscillatory shearing might have hindered the diffusion of polymer chains, which are located away from the interface, to the interface of the layers. However, the effect of γ₀ and ω on the roughness of the interface of (PS-mCOOH)/(PMMA-GMA) bilayer is found to be quite different. Specifically, when a large γ₀ was first applied to the bilayer, followed by application of a low γ₀, the reactive polymer chains diffused into the interface of the (PS-mCOOH)/(PMMA-GMA) bilayer; and then the roughness of the interface increased. However, when a high ω of oscillatory shear flow was first applied to a specimen, followed by application of a low ω of oscillatory shear flow to the same specimen, a relatively low degree of roughness of the interface was observed. This is attributable to the fact that the oscillatory shear with a large ω generated a multilayer microstructure consisting of PS and PMMA layers, which apparently played the role of an obstacle (or diffusion barrier) that hindered the diffusion of both reactive polymer chains to the interface for chemical reactions.     

Effect of sparse long‐chain branching on the step‐strain behavior of a series of well‐defined polyethylenes

The effect of sparse long chain branching, LCB, on the shear step‐strain relaxation modulus is analyzed using a series of eight high‐density polyethylene (HDPE) resins. Strains of 1 to 1250% are imposed on materials with LCB content ranging from zero to 3.33 LCB per 10,000 carbon atoms. All materials are observed to obey time–strain separation beyond some characteristic time, τ_k. The presence of LCB is observed to increase the value of τ_k relative to the linear resin. The behavior of the relaxation modulus at times shorter than τ_k is investigated by an analysis of the enhancement seen in the linear relaxation modulus, G⁰(t), as a function of strain and LCB content. This enhancement is seen to (1) increase with increasing strain in all resins, (2) be significantly larger in the sparsely branched HDPE resins relative to the linear HDPE resin, and (3) increase in magnitude with increasing LCB content. The shape and smoothness of the damping function is also investigated. The finite rise time to impose the desired strain is compared to the Rouse relaxation time of linear HDPE resins studied. Sparse LCB is found to increase the magnitude of the relaxation modulus at short times relative to the linear resin. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Preparation of long‐chain branched poly(ethylene terephthalate): Molecular entanglement structure and toughening mechanism

Poly(ethylene terephthalate) (PET) was long‐chain branched (LCB) by ring‐opening reaction with both pyromellitic dianhydride and tetrahydrophthalic acid diglycidyl ester as chain extenders through reactive melt processing. It was found that with the increase of chain extenders dosage, the intrinsic viscosity of PET increased and melt index decreased greatly, while both the tensile strength and impact strength of PET were remarkably improved. The elastic modulus (G′) and viscous modulus (G″) were enhanced by chain branching. Compared with PET, the complex viscosities of LCB‐PET were much higher at full frequency range, and obvious shear thinning was presented. The Cole–Cole curve deviated from the semicircular shape and the curve end was inclined to upward in high viscosity region, indicating the formation of the multiple hierarchical structures. The molecular weight of the branch (M_B) was much greater than critical entanglement molecular weight (M _e), which essentially confirmed the existence of LCB structure and fairly strong molecular entanglement in the LCB‐PET molecular chain. When subjected to external force, the entanglement point, acting as physical crosslinking point between the molecules, was in favor of increasing the molecular interaction, reducing the molecular slippage, and bearing a large deformation. POLYM. ENG. SCI., 59:1190–1198 2019. © 2019 Society of Plastics Engineers     

Rheology of a low‐filled polyamide 6/montmorillonite nanocomposite

The rheological properties of a polyamide 6/clay nanocomposite with a low loading of clay (1 wt %) were studied. Linear viscoelastic measurements in oscillatory and steady shear with small strain amplitudes were carried out. The nanocomposite exhibited a higher elastic modulus, viscous modulus, and complex viscosity than neat polyamide 6 during dynamic and steady shear tests. Moreover, the addition of clay resulted in a reduction of the critical strain amplitude, an increase of the loss angle, and a reduction of the frequency at the intersection of the elastic and viscous moduli. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and characterization of high melt strength polypropylene with long chain branched structure by the reactive extrusion process

The reactive extrusion of maleic anhydride grafted polypropylene (PP‐g‐MAH) with ethylenediamine (EDA) as coupling agent is carried out in a corotating twin‐screw extruder to produce long chain branched polypropylene (LCBPP). Part of PP‐g‐MAH is replaced by maleic anhydride grafted high‐density polyethylene (HDPE‐g‐MAH) or linear low‐density polyethylene (LLDPE‐g‐MAH) to obtain hybrid long chain branched (LCB) polyolefins. Compared with the PP‐g‐MAH, PE‐g‐MAH, and their blends, the LCB polyolefins exhibit excellent dynamic shear and transient extensional rheological characteristics such as increased dynamic modulus, higher low‐frequency complex viscosity, broader relaxation spectra, significantly enhanced melt strength and strain‐hardening behaviors. The LCB polyolefins also have higher tensile strength, tensile modulus, impact strength and lower elongation at break than their blends. Furthermore, supercritical carbon dioxide (scCO₂) is constructively introduced in the reactive extrusion process. In the presence of scCO₂, the motor current of the twin extruder is decreased and LCB polyolefins with lower melt flow rate (MFR), higher complex viscosity and increased tensile strength and modulus can be obtained. This indicates that the application of scCO₂ can reduce the viscosity of melt in extruder, enhance the diffusion of reactive species, and then facilitate the long chain branching reaction between anhydride group and primary amine group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Rheological and thermomechanical properties of long‐chain‐branched polyethylene prepared by slurry polymerization with metallocene catalysts

A series of polyethylene (PE) samples were prepared in a slurry polymerization with bis(cyclopentadienyl) zirconium dichloride (Cp₂ZrCl₂)/modified methylaluminoxane (MMAO) using a semibatch reactor. The samples had long‐chain branch densities (LCBDs) of a 0.03–1.0 branch per 10,000 carbons and long‐chain branch frequencies (LCBFs) up to a 0.22 branch per polymer molecule. The rheological and dynamic mechanical behaviors of these long‐chain branched PE samples were evaluated. Increasing the LCBF significantly increased the η₀'s and enhanced shear thinning. Long‐chain branching (LCB) also influenced the loss modulus and storage modulus. Increasing the LCBF led to enhanced G′ and G″ values at low shear rates and broader relaxation spectrums. The samples exhibited thermorheologically complex behavior. LCB also played a significant role in the dynamic mechanical behavior. Increasing the LCBF increased the stiffness of the polymer and enhanced the damping or energy dissipation. However, LCB had little influence on the crystalline structure of the PE. The α‐ and γ‐relaxations showed little dependence on the LCBF. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 307–316, 2004     

The preparation and rheology characterization of long chain branching polypropylene

In order to study the rheological behavior of long chain branching (LCB) polypropylene (PP), linear polypropylene was modified by melt grafting reaction in the presence of 2,5-dimethyl-2,5(tert-butylperoxy) hexane peroxide and pentaerythritol triacrylate (PETA) in mixer. The transient torque curves and Fourier transformed infrared spectroscopy (FTIR) results indicated that macroradical recombination reactions took place and PETA had been grafted onto PP backbone. Various rheological plots including viscosity curve, storage modulus, loss angle, Han plot, Cole-Cole plot were used to distinguish LCB PP from linear PP. On the other hand, to quantify the LCB level in modified PPs, a new method was suggested on the basis of macromolecular dynamics models. The results showed that the level of LCB was in the range of 0.025-0.38/10⁴ C . Moreover, the length of the branched chains and the content of the branched component increase with PETA concentration. Furthermore, the LCB efficiency of monomer can also be calculated, less than 20% of grafting monomers was used to form branch structure.     

SEC-MALS method for the determination of long-chain branching and long-chain branching distribution in polyethylene

This paper systematically describes a LCB determination method that can quantify both LCB content and LCB distribution across the molecular weight distribution in polyethylene homopolymers as well as copolymers. Coupling size-exclusion chromatography with multi-angle light scattering (SEC-MALS), this method quantifies molecular weights (MW) and radii of gyration (R_g) simultaneously. The number of LCB per molecule and LCB frequency as a function of MW can be calculated by comparing R_g of a branched polymer with that of a linear control at the same MW using the Zimm-Stockmayer approach. Because the presence of short-chain branching in copolymers results in changes in R_g of the copolymers, their LCB contents cannot be obtained before the short-chain branching (SCB) effect is corrected. Using well-characterized linear PE copolymers as standards, an empirical method is successfully established in this paper to correct the SCB effect. Consequently, this method can be applied to determine LCB in PE copolymers as well. Some practical aspects, such as the selection of formalism for data processing, the LCB detection sensitivity and precision, and long-term reproducibility of this method are also discussed. Finally, examples are given to demonstrate how this method is applied to determine LCB and LCB distribution in practical PE homopolymers and copolymers.     

Dynamic rheology of branched poly(ethylene terephthalate)

Branched poly(ethylene terephthalate)s (BPET) of varying molar mass have been synthesized with glycerol and pentaerythritol as branching comonomers, and their rheological behaviour has been measured. In this study, we describe the use of dynamic and steady shear measurements to examine the influence of the proportion and type of branching comonomers on the melt viscosity of BPET. Steady shear rheology has been used to measure the shear rate dependence on the apparent viscosity. Dynamic (oscillatory) measurements have been used to obtain the complex viscosity η* (ω) and the storage modulus G′ (ω) as a function of frequency. G′ (ω) represents the elastic component of the viscoelastic melt; this variable was measured as a function of frequency at various temperatures in the linear viscoelastic domain. Linear poly(ethylene terephthalate) (LPET) exhibited nearly Newtonian behaviour, while BPET became shear thinning at relatively low shear rates. The viscosity and elasticity increased with increase in molar mass and specific branching composition. This was attributed to increasing chain entanglements at higher molar mass and to increasing branching of the BPET. At higher shear rates or frequencies, the BPET show much greater shear thinning character than LPET and this is more pronounced with higher branching proportions. © 2000 Society of Chemical Industry     

Oscillation effects on the crystallization behavior of iPP

The oscillation effects on the crystallization behavior of the iPP were studied by shear stage, wide-angle X-ray diffraction and DSC. The effects of strain and frequency on the crystallization behavior and morphology of iPP were also investigated. The β form crystals were found after oscillatory shearing at the fixed frequency (2 Hz), and the β crystallinity increased with the strains. At the fixed strain (100%), the β crystallinity changed little with the increased frequencies. The orientation degree of the molecule chains increased with the strains. If the strain is high enough, the fiber crystals emerge. It is difficult to find the effect of frequency on the crystallization morphology of iPP. The orientation degree of the molecule chains changed little with different oscillatory frequencies.     

Shear-induced gelation of associative polyelectrolytes

Copolymer of N,N-dimethylacrylamide (DMA) and acrylic acid (AA) was functionalized with pendant alkyl groups. Their dynamic mechanical properties in aqueous solution were investigated using continuous shear and oscillatory shear. Shear flow showed an abrupt divergence of the viscosity at a critical shear stress (σ_c). Oscillatory shear showed, with increasing applied stress, slight shear thinning followed by strong shear thickening above σ_c. The effect of the polymer concentration and the oscillation frequency (ω) was investigated. The behaviour at all concentrations and frequencies was fully determined by the product of the oscillation frequency and the terminal relaxation time (τ) of the systems at rest. Master curves of the data determined at different concentrations and frequencies were obtained if the reduced shear modulus was plotted versus the reduced applied stress at constant ω.τ. The effect of shear increased with decreasing value of ω.τ. At low frequencies the storage shear modulus crossed the loss modulus with increasing shear. A model is proposed for this phenomenon of shear-induced gelation.     

Viscoelasticity of randomly crosslinked EPDM networks

The network structure of plasticized EPDM compounds, crosslinked with resol at different concentrations, was studied by means of rheological methods consisting in oscillatory shear tests, to determine the equilibrium modulus G_e, and long-time relaxation tests in compression followed by strain recovery (a protocol that also yielded values of the compression set of the samples). G_e results were analyzed with respect to the phenomenological model of Langley and Graessley which takes into account the contribution of crosslinks and trapped entanglements to the shear equilibrium modulus. A correction was introduced in order to take into account the presence of plasticizer. The measurement of the soluble polymer fraction in the different samples allowed a more detailed characterization of the networks to be carried out, following a molecular approach by Pearson and Graessley. This method enabled to calculate the crosslink density and trapping factor, but also to compute the probability ψ₁ for an un-crosslinked polymer unit to belong to a dangling chain. This probability was shown to increase as resol concentration, and then crosslink density, decreased. The empirical Chasset-Thirion equation was used to model the long-time relaxation data for each sample. Chasset-Thirion parameters were interpreted by Curro and Pincus within a theoretical framework based on the idea that the longest relaxation times are associated with the pendent chains of the network. The relaxation times, obtained from the fitting of experimental relaxation moduli, dramatically increased as the crosslink density decreased. This result corroborates the evolution of ψ₁: both tend to demonstrate that in the present compounds, the decrease of crosslink density is accompanied by an increase of the number and length of the dangling chains, leading to increasing relaxation times. The large soluble fraction and long pendent chains of samples showing the lowest crosslink densities were responsible for their poor elastic recovery. The relaxation data were used to model the elastic recovery of the compounds and predict their compression set profiles. Very satisfactory agreement was obtained between experimental data and computations.     

Shear thickening behavior of dilute poly(diallyl dimethyl ammonium chloride) aqueous solutions

Using dynamic light scattering (DLS) and capillary dynamic viscoelasticity (DVE) analyzer, we investigated dilute (0.5 mg/ml) poly(diallyl dimethyl ammonium chloride) (PDADMAC) aqueous solution properties for three different molecular weights of PDADMACs mixed with various concentrations of NaCl. The dependence of PDADMAC molecular chain conformations in aqueous solutions on polymer molecular weight and NaCl concentration were studied. By analyzing dynamic shear viscosity η′(ω), viscoelastic relaxation times t_r, and shear rate at tube wall ?_a(ω) of PDADMAC aqueous solutions in oscillatory flows, we proposed that polymer chain conformations varied with increasing shear frequency ω via the following steps: intra-polymer associations, dissociation of intra-polymer associations, stretching of polymer chains, inter-polymer aggregations, and dissociations of inter-polymer aggregations. The intra-polymer associations lowered the n′ exponent of storage modulus G′(ω) (G′(ω) ∼ ω^n′) with n′ < 2, and the polymer chain stretching and inter-polymer aggregations caused shear thickening (i.e. upturn of η′(ω)) of PDADMAC aqueous solutions. The behaviors of the lowering of n′ exponent with n′ < 2 and the shear thickening were favored by increasing ionic strength of solutions. By comparing η′(ω) data with DLS hydrodynamic radii (R_h) data, we also confirmed the possibility of inter-polymer aggregations in dilute solutions when polymer chains were stretched in oscillatory flows.     

The melt grafting preparation and rheological characterization of long chain branching polypropylene

To study the rheological properties of long chain branching (LCB) polypropylene (PP), long chain branches (LCB) were grafted onto the linear PP by melt grafting reaction in the presence of a novel chain extender, poly(hexamethylendiamine-guanidine hydrochloride) (PHGH). The branching reactions between the functionalized PP and PHGH were confirmed by transient torque curves and FTIR. By differential scanning calorimetry (DSC) and polarized microscope measurements, the presence of long chain branching structures was further confirmed. Also, the viscoelastic properties of the LCB PP and linear PP under shear flow were investigated for distinguishing LCB PP from linear PP. It was found that the elastic response of LCB PP at low frequencies was significantly enhanced in comparison with that of the linear PP, implying a presence of a long relaxation time mode that was not revealed in linear PP. Moreover, the branching levels of LCB PP were quantified using a detailed method, which was in correspondence with the molar amount of PHGH grafted on PP.