Propylene copolymerization with non-conjugated dienes and α-olefins using supported metallocene catalyst

Propylene was copolymerized with 7-methyl-1,6-octadiene, 1,9-decadiene and α-olefins using dimethylsilanylbis(2-methyl-4-phenyl-1-indenyl)zirconium dichloride supported on methylaluminoxane modified silica. Additional methylaluminoxane was needed to activate the catalyst. Comonomer incorporations were 1.5 mol% or less. In propylene/7-methyl-1,6-octadiene copolymers there was no indication of long-chain branching and molar masses were low. Adding a small amount of 1,9-decadiene caused very high molar masses and broad molar mass distributions. A possible long-chain branching in propylene/1,9-decadiene copolymers was evaluated by stress-controlled dynamic rheometer. Changed rheological behavior and especially raised Arrhenius-type flow activation energy along with change in polymer properties indicated long-chain branching in propylene/1,9-decadiene copolymers.     

Physical gelation in ethylene-propylene copolymer melts induced by polyhedral oligomeric silsesquioxane (POSS) molecules

The rheological behavior of ethylene-propylene (EP) copolymers containing polyhedral oligomeric silsesquioxane (POSS) molecules was investigated by means of wide-angle X-ray diffraction (WAXD), oscillatory shear, stress and strain controlled rheology in the molten state and dynamic mechanical analysis (DMA) in the solid state. WAXD results showed that the majority of POSS molecules in the EP melt were present in the crystal form. Oscillatory shear results showed that the EP/POSS nanocomposites exhibited a solid-like rheological behavior compared with the liquid-like rheological behavior in the neat resin, i.e. POSS caused physical gelation in EP. While POSS exhibited only a minimum effect on the flow activation energy of EP, the high POSS concentration samples were found to induce higher yield stress than the neat resin. This behavior was similar to the Bingham rheology, indicative of a structured fluid. DMA results indicated that the presence of POSS increased the Young's modulus as well as the T_g of the EP copolymer. These results suggested that two types of interactions contributed to the physical gelation in EP/POSS melts were present: the strong particle-to-particle interactions between the POSS crystals and the weak particle-to-matrix interactions between the POSS crystals and the EP matrix.     

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.     

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     

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.     

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.     

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     

Unique microstructure analysis of ethylene-propylene copolymer synthesized using catalytic system based on α-diimine nickel complexes: a comparative study by 13C NMR technique

The microstructure of rubber-like ethylene-propylene copolymer (MN4) produced by a mixed nickel-based system (MN) containing catalysts of dibromo[N,N′-bis(2,6-diisopropylphenyl)-2,3-butanediimine]nickel(II) n1 and dibromo[N,N′-(phenanthrene-9,10-diylidene)bis(2,6-diisopropylaniline)]nickel(II) n2 was determined by ¹³C NMR technique. Sequences distribution of ethylene (E), propylene (P), EP, inverted propylene and uninterrupted methylene and also methylene number-average sequence lengths for the copolymer (MN4) were estimated. The results obtained from the MN4 EP copolymer were compared with reported copolymers which had been synthesized using constrained geometry catalyst (CGC) and vanadium-based Ziegler-Natta catalyst. The results demonstrated that the MN4 EP copolymer had fewer alternating comonomer sequences than ethylene-propylene elastomers obtained by CGC and vanadium-based (V) catalysts. A large number of the inversion structures (66 %) and high mole percent of sequences containing a long branch (3.2 mol%) were also observed in unique microstructure of the copolymer (MN4).     

Rheological control in foaming polymeric materials: I. Amorphous polymers

The influence of rheological properties, especially melt strength, on foam structures, such as cell size, cell density and cell size distribution, of amorphous polymer was investigated. The rheology of polystyrene (PS) was controlled by molecular modification with free radical reaction, and PS with long chain branching (LCB) level ranging from 0.15 to 1.6 branching point per 10⁴ carbon atom was gotten. The shear and elongational rheology were found to be dependent on the LCB structure, and the strain hardening behavior of modified samples in transient elongational viscosity confirmed the existence of long branched chain. The effects of chain structure and foaming conditions such as temperature and pressure were studied by the analysis on the foam structures obtained by supercritical CO₂. The experimental results revealed that increasing LCB level would decrease cell size, make cell size distribution narrower and slightly increase cell density. The effects of chain topology on the foam structures were also investigated by numerical simulation, where Pom-Pom model was used to describe the effect of backbone length and arm length. The dependence of cell size on the arm length was consistently observed in experiments and simulation. It suggested that the arm length had greater influence on the cell radius than the backbone length. Therefore, the relationship among foam structures, rheological properties and molecular structures can be established from both experiments and simulation, which can be used as a guidance to control the foam structure by designing and controlling the molecular structures and the corresponding rheological properties.     

Facile synthesis of ethylene–propylene fully alternating copolymer and comparison with random copolymer of similar composition

A precisely sequenced ethylene–propylene (EP) fully alternating copolymer was synthesized via trans‐1,4‐polymerization of isoprene catalyzed by Ziegler–Natta catalyst followed by hydrogenation. This EP copolymer was used as model polymer for studying structure–property relationship. An ethylene–propylene random copolymer (ethylene–propylene rubber [EPR]) with similar ethylene content was also prepared for comparison, and the effect of comonomer sequence distribution on properties was investigated. The copolymer chain structures were monitored by ¹H and ¹³C NMR and Fourier translation infrared. Differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and tensile tests were employed to determine the thermal and mechanical properties. The fully alternating copolymer EP gives a more precise glass transition comparing than EPR. Further understanding on thermal properties and aggregation behavior of ethylene–propylene copolymers is made possible by this comparative study. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45816.     

A rheology theory and method on polydispersity and polymer long-chain branching

Model calculations were performed to investigate the sensitivity of zero-shear melt viscosity (η₀ or Eta0) on the molecular weight (MW) polydispersity of linear polymers. Simulated MW distributions (MWD) were generated with the generalized exponential (GEX) distribution function for various levels of polydispersity M_w/M_n and M_z/M_w. For linear entangled polymeric chains in the melt, the linear viscoelastic properties were predicted by using the double reptation blending rule and the so-called BSW relaxation time spectrum, named after the authors: Baumgaertel, Schausberger and Winter [Baumgaertel M, Schausberger A, Winter HH. Rheol Acta 1990;29:400-8]. Published rheological parameters appropriate for polyethylene were used in the calculations. It was found that Eta0 depended mostly on M_w, but it also significantly depended on the extent of high-MW polydispersity M_z/M_w. A revision to the fundamental MW dependency of Eta0 was proposed to compensate for this polydispersity effect. To offset the polymer polydispersity differences, we propose a new MW average (M_HV or M_x with x = 1.5) to replace M_w in the historical rheological power-law equation of Eta0 ∝ M_w^a, where the literature value of exponent “a” ranges from 3.2 to 3.6. The use of M_HV instead of M_w in the power-law equation made the calculated Eta0 independent of the sample high-MW polydispersity. With the removal of the complication from polydispersity effect, the new Eta0 power law can now provide a more robust base for studying polymer long-chain branching (LCB). A new LCB index is thus proposed based on this new melt-viscosity power law. The values of M_HV in the new power law can be calculated for polymer samples from the conventional gel permeation chromatographic (GPC) slice data.     

Correlation of low density polyethylene rheological measurements,with optical and processing properties

The processing properties of low density polyethylene melts, such as drawdown and neck-in, and the final product properties, such as film haze and gloss, have been successfully correlated with rheological functions and the level of longchain branching. The rheological functions employed are the entrance pressure drop ΔP_o and the swell ratio S_o, determined at a specified shear stress using aft-orifice with a length/ diameter (L/D) ratio of zero. The calculation of shear stress requires additional measurements using adie with a finite L/D e.g. 20. The rheological functions ΔP_o, and S_o are governed by the level of high molecular weight species and/or the level of long-chain branching(LCB). If determined at a constant shear stress, in order to eliminate the effect of viscosity, they are a relative measure of elasticity. Higher ΔP₀ and S_o indicate a higher level of LCB and correlate with poorer optical properties and drawdown in films.     

Influence of morphology on the properties of segmented block copolymers

A comparison was carried out regarding the structure and properties of segmented block copolymers with either non-crystallisable or crystallisable rigid segments. The flexible segment in the block copolymers was a linear poly(propylene oxide) end capped with poly(ethylene oxide), with a segment molecular weight of 2300 g/mol. The rigid segments were either non-crystallisable or monodisperse crystallisable polyamides of varying lengths. The morphologies were studied by TEM and AFM, the thermal mechanical properties by DMA and the elastic properties by compression set and tensile measurements. A direct comparison was made of segmented block copolymers with either liquid-liquid demixed or crystallised structures. The crystallised amide segments were more efficient in increasing the modulus and improving the elastic properties than the non-crystallisable ones. The copolymers with crystallised structures were transparent, had a low glass transition temperature of the polyether phase and a modulus that was independent of temperature between T_g and T_m. These copolymers also displayed a very low loss factor (tan δ), suggesting excellent dynamic properties. The hard phase in segmented block copolymers should thus preferably be crystalline.     

Influence of epoxy resin on the morphological and rheological properties of PBT/ABS blends compatibilized by ASMA

Polybutylene terephthalate (PBT)/acrylonitrile–butadiene–styrene (ABS) copolymer blends compatibilized by a mixture of styrene–acrylonitrile–maleic anhydride (ASMA) copolymers and epoxy resin (EP) were prepared through melt reactive extrusion. The morphological, rheological, and mechanical properties of these blends were studied. The epoxy functional groups of EP can react with anhydride groups of ASMA and the PBT terminal groups (? OH and ? COOH) simultaneously, leading to the formation of ASMA–EP–PBT graft copolymers. Because of the effective compatibilization of these copolymers at the interface, finer dispersed phase morphologies were obtained. Compared with PBT/ABS/ASMA blends, the addition of EP induced a more stable molten phase structure, with increases of storage moduli, loss moduli, and dynamic viscosities. Results indicated that 1.5 wt% of the EP in the blends was most suited for the compatibilization. Impact properties of these blends were also investigated. POLYM. ENG. SCI., 47:1943–1950, 2007. © 2007 Society of Plastics Engineers     

Thermal oxidation‐induced long chain branching and its effect on phase separation kinetics of a polyethylene blend

Thermal oxidation‐induced long chain branching (LCB) during the molding processes for polyolefin copolymer poly(ethylene‐co‐butene) (PEB) and its blend with another polyolefin copolymer poly(ethylene‐co‐hexene) (PEH/PEB 50/50 blend, denoted as H50) was investigated mainly by rheological measurements. LCB with different levels could be introduced on PEB backbones by changing the molding temperature and/or molding time, which could be sensitively characterized by changes of rheological parameters, that is, storage modulus G′ and complex viscosity η*. Thermal oxidation‐induced LCB of PEB in H50 samples could largely influence the phase separation kinetics. Rheological measurements and phase‐contrast optical microscope observations coherently indicated that thermal oxidation‐induced LCB of PEB more or less retarded the development of phase separation and once it reached a certain level, the reduced chain diffusion even arrested phase separation. The decrease of mass‐averaged molecular mass in H50 with high LCB level was ascribed to the reduced hydrodynamic volume. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Good extrusion foaming performance of long-chain branched PET induced by its enhanced crystallization property

Poly(ethylene terephthalate) (PET) was modified by regulating different contents of branching agent epoxy-based multifunctional oligomer and chain extender pyromellitic dianhydride in reactive extrusion process. The modified PET with better long-chain branched (LCB) structure boosted its rheological properties, and its enhancement of melt viscoelasticity resulted in excellent foamability in molten-state foaming process using supercritical CO₂ as blowing agent. More importantly, the branched structures acted as crystal sites to accelerate the crystallization kinetic of LCB PET whether under atmospheric pressure or high-pressure CO₂. The shear and elongation flow inside die further quickly induced the crystallization of LCB PET. The rapidly generated fine crystals could both introduce heterogeneous cell nucleation and suppress CO₂ escape, so the cell morphology of LCB PET in continuous extrusion foaming process exhibited a three-fold increase in cell density and smaller uniform cell size with respect to those of other foam-grade PET with long-chain structure.     

Melting of ethylene oxide - propylene oxide type P(EP)n block copolymers

Multiblock copolymers of poly(ethylene oxide) and poly(propylene oxide), type P(EP)_n, have been prepared by condensation of hydroxy- and chlorocarboxy-ended polymers. Small-angle X-ray scattering and dilatometry have been used to determine lamella spacings and melting points of the copolymers. The melting points of the multiblock copolymers can be predicted from the melting points of corresponding triblock (PEP) copolymers.     

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).     

Morphology and mechanical properties in the binary blends of isotactic polypropylene and novel propylene-co-olefin random copolymers with isotactic propylene sequence 1. Ethylene-propylene copolymers

The additive effects of the novel ethylene-propylene random (EP) copolymers with high isotacticity in propylene sequence on the morphology and mechanical properties of isotactic polypropylene (iPP) were investigated using polarized optical microscopy, transmission electron microscopy, dynamic mechanical analysis and tensile behavior. According to these results, the EP copolymers with a propylene content of more than 84 mol% were miscible with iPP, in which the crystallizable PP sequences in these EP copolymers were incorporated in crystal lattice of iPP and the other portions in the EP chains were excluded to the amorphous phases. Consequently, they act as tie molecules linking between adjacent lamellae, leading to enhancement of yield toughness of iPP. On the other hand, the EP copolymers with a propylene-unit content of less than 77 mol% were incompatible with iPP. The iPP/EP blends showed the phase-separated morphology.     

Structure‐rheology responses of polylactide/calcium carbonate composites

Polylactide (PLA) and calcium carbonate (CaCO₃) were melt blended using a twin‐screw extruder. The morphology of PLA/CaCO₃ composites was observed by scanning electronic microscopy. The linear and nonlinear shear rheological behaviors of PLA/CaCO₃ melts were investigated by an advanced rheology expended system. The results show that the CaCO₃ particles are evenly dispersed in the PLA matrix. The incorporation of low CaCO₃ content (<20%) causes the reduction of the storage moduli, loss moduli, and dynamic viscosities whereas high CaCO₃ content (>30%) leads to the increase of the storage moduli, loss moduli, and dynamic viscosities. The composites with high CaCO₃ content show pseudo‐solid‐like behaviors at low frequency. High CaCO₃ content also results in a significant increase of flow activation energy and a dramatic decrease of flow index n, which is in consistent with the more serious shear‐thinning tendency of high‐filled PLA composites melts. The particular rheological responses might be attributed to the formation and destruction of the percolating network. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009