Chemical modification of polyolefin blends

The effect of crosslinking on the properties of low density polyethylene / polypropylene blends was investigated. It was found that crosslinking results in much higher deformability of the blends compared to uncrosslinked materials. A decrease in crystalline portion determined by DSC leads to lower modulus in crosslinked samples. High drawability of crosslinked samples is mainly attributed to peculiar behaviour of PE part of the crosslinked blend where thicker lamellae are formed during drawing.     

Local friction in polyolefin blends

Processes on different length scales affect the dynamics of chain molecules. The friction experienced by a short chain segment depends on both small-scale chain properties and on the local environment of the segment. As a consequence, the (monomeric) friction coefficients of the two components of a binary polymer blend will, in general, differ from each other and from the friction coefficients of the corresponding melts. In this work, we investigate local friction in polyolefin blends with the aid of a small-scale simulation approach. The polymer chains, in united atom representation, are assumed to occupy the sites of a partially filled simple cubic lattice. The simulation focuses on short chain sections with straight backbones and enumerates all possible binary contacts and relative movements of such sections. By evaluating the exact enumeration results in conjunction with equations of state for the blends, we are able to make predictions about the variation of the friction coefficients with local chain architecture and thermodynamic state (temperature, pressure, and composition). We calculate relative values of friction coefficients at temperatures well above the glass transition for blends of PEP, an alternating copolymer of polyethylene and polypropylene, with polyethylene and polyisobutylene and for blends of polyethylene and atactic polypropylene. We also investigate a blend of PEP with head-to-head polypropylene and compare our results with experimental data.     

Thermal properties of binary polyolefin blends

The thermal properties of binary polyolefin blends (LDPE/HDPE, LDPE/PP, HDPE/PP) were examined by differential scanning calorimetry. The additon of a second polymer lowers the melting temperature although the melting temperature depression is not a defined function of the blend composition. DSC curves show two melting and two crystallization temperatures. The difference between crystallization temperatures for blends containing PP is smaller than the difference between melting temperatures. The enthalpies of fusion are nearly monotonic functions of blend composition.

---

Zusammenfassung Die thermischen Eigenschaften binärer Polyolefinmischungen (LDPE/HDPE, LDPE/PP, HDPE/PP) wurden mittels DSC untersucht. Durch Zugabe eines zweiten Polymers wird die Schmelztemperatur erniedrigt, obwohl die Erniedrigung der Schmelztemperatur keine Funktion der Mischungszusammensetzung ist. Die DSC-Kurven zeigen zwei Schmelz- und zwei Kristallisationspeaks. Bei PP enthaltenden Mischungen ist der Unterschied zwischen den Kristallisationstemperaturen geringer als zwischen den Schmelztemperaturen. Die Schmelzenthalpie ist eine nahezu monotone Funktion der Mischungszusammensetzung.

---

— , — , — . , . . , . .

     

Design of miscible polyolefin copolymer blends

Theoretical guidelines are established for designing miscible blends of amorphous polyolefin copolymers. On the basis of calculations for an athermal and incompressible model of copolymer melts, limits are placed on the compositions and structural differences between blend components that are consistent with thermodynamic stability of a single liquid phase. Specific cases analyzed include binary blends of random copolymers containing short branches and blends of graft polymers with long flexible branches, either periodically or randomly placed. The predictions are shown to be in good agreement with recent experimental studies of miscibility in model polyolefin copolymer blends. © 1995 John Wiley & Sons, Inc.     

Wetting transition in polyolefin blends studied by profiling techniques

Based on segregation data, determined with profiling techniques, we analyze surface phase diagram of binary liquid mixtures composed of random olefinic copolymers. Blends with extended‐ and small‐critical point wetting regimes are discussed. First observation of wetting transition is presented. Surface enrichment‐depletion duality, a phenomenon prerequisite to the 2^nd order wetting transition, is described.     

Ostwald ripening in immiscible polyolefin blends

The coarsening in the quiescent melt of the phase-segregated particles of a polymer blend, composed of a narrow molecular weight fraction of an unbranched high-density polyethylene (HDPE) and a highly branched (100 ethyl branches/1000 C atoms) hydrogenated polybutadiene (HPB) was studied. The system was effectively binary, due to the narrow molecular weight and composition distributions of each component. The system was composed of 90 wt % of the HDPE and 10 wt % of the HPB and it formed a two-phase system in the melt at 177°C. The blend was precipitated from xylene solution in order to obtain an initially intimately mixed system. This was the third study in a series of studies of the coarsening of phase-segregated particles in polymer blends. This study was unique in that the system studied was binary in this case while the previous systems were multicomponent. Since the present system was binary, exact thermodynamic calculations of the phase state of this system could be applied with a high level of confidence. The droplet phase particles, which were mainly composed of the HPB, were observed to coarsen on storage in the melt for times of from 5 s to 1 h. At the shortest storage time of 5 s the particles had an average radius of about 0.05 μm and coarsened to about 0.2 μm after 1 h storage in the melt state. Particle dimensions were measured by scanning electron microscopy of n-heptane-etched and gold-coated sections. It was found that the volume of the particles increased linearly with time and that the rate constant of coarsening was K_exp = 1.23 × 10^?18 cm³/s and this agreed fairly well with the rate constant calculated from Ostwald ripening theory of K_ce = 0.86 × 10^?18 cm³/s. In contrast the rate constant for direct particle diffusion and coalescence was K_c = 3.6 × 10^?20 cm³/s. Since this was two orders of magnitude smaller than the rate constant for Ostwald ripening, it was concluded that, although the linear increase of volume with time was also consistent with the particle diffusion and coalescence mechanism, this was not a significant contributor to the coarsening mechanism. The major cause for the insignificance of the particle diffusion and coalescence mechanism was the high melt viscosity of the matrix polymers. The application of the Ostwald ripening theory to this system could be made with a high level of confidence because it was binary. It was found that the phase concentration of the droplet phase apparently underwent a rapid increase during the first 1-2 min of storage in the melt, indicating that the system did not reach phase equilibrium (i.e., did not completely phase-segregate) for about 1-2 min. This further indicated that the long-time coarsening regime was not entered until after this length of time. The particle size distributions remained approximately self-similar over the period of coarsening, as predicted by Ostwald ripening theory. © 1995 John Wiley & Sons, Inc.     

The effects of ageing by ultraviolet degradation of recycled polyolefin blends

Products manufactured from recycled polyolefin blends were subjected to accelerate weathering conditions and subsequent tests. Field-aged products were also tested.Samples were analysed for changes in mechanical, rheological and chemical properties. Data obtained in this study, by means of tensile, impact, and melt flow tests, GPC, gloss and colour analyses showed that the effect of UV exposure, whether in the field or artificial environments, was not significant as far as the mechanical properties of the materials were concerned. There was some change in the surface characteristics but such surface effects would not compromise the mechanical integrity of the product when recycled. During reprocessing of the materials, it is likely that stabilizer is redistributed at the surface of any new moulding, thus renewing the surface characteristics. Hence damaged or end-of-life products need not be discounted from recycling.     

Ozonization of polyolefin blends with a minor component

Some regularities of degradation of PE-PP blends low in content (up to 5 wt %) of one of the components under the action of electric discharge and ozonization were studied. The electric aging is mainly explained by the effect of oxidation processes, which were investigated via estimation of the content of C=O groups, which depends on the blend composition. The data on changes in the dielectric characteristics of blends subjected to the action of electric discharge and ozone were obtained. It was shown that the blends of PE low in PP content have the highest tolerance against the electric discharge and ozonization, whereas the blends of PP with a low content of PE demonstrate the minimum stability.     

CRYSTAF Analysis of Polyethylene Synthesized with Phillips Catalyst

Crystallization analysis fractionation (CRYSTAF) was used for the first time to investigate the solution crystallization behavior of ethylene homopolymers and copolymers made with Phillips CrO_x/SiO₂ catalyst. Interestingly, the crystallization peak temperatures (T_p) of copolymers of ethylene and cyclopentene increased with increasing cyclopentene molar fraction in the copolymer. Comparing two factors (short chain branches (SCBs) and cyclopentene incorporation), decreasing SCB frequency is proposed as the dominant factor to explain the increase of crystallization peak temperatures with increasing cyclopentene incorporation. In addition, SCB frequency and molecular weight might be the two significant factors determining the crystallization temperature of polyethylene made with Phillips CrO_x/SiO₂ catalyst with different cocatalysts (triethylaluminum and diethylaluminum ethoxide).     

Recent developments in phase separation of polyolefin melt blends

Saturated hydrocarbon polymers may be differentiated by the relative amount and placement of methylene, methyl, methine, and quaternary carbon moieties. While it has been known or suspected for some time that polyolefins of conventional molecular weight (M_w ≈ 100 kg/mol) with dissimilar chemical microstructures are most often immiscible in the liquid state, recent experiments with binary blends of model polyolefins have increased greatly our understanding of thermodynamic interactions between unlike chains. Model systems with methyl (−CH₃) and ethyl (−C₂H₅) short-chain branches give results, expressed as the Flory-Huggins interaction parameter χ, that are nearly universal; repulsive interactions (χ > 0) are more pronounced at low temperatures, leading to liquid-liquid phase separation at an upper critical solution temperature. Phase behavior of more complex systems (with distributions of chain microstructures and/or molecular weight) is generally consistent with predictions from model systems. An interesting exception is from work at Bristol on blends of lightly branched ethylene − α-olefin copolymers with unbranched polyethylene as the minority species. Here the presence of two liquid phases is inferred under conditions not expected from model studies; effects of copolymer composition and molecular weight are also unusual. Recent theoretical work points to the importance of chain stiffness (established by short-chain branching) in determining the thermodynamics of model blends. Nonrandom mixing of chains with different stiffness gives rise to an enthalpic χ, which may be negative under certain conditions. Other limitations of the Flory-Huggins approach to describing blend energetics are considered. At present there is no theoretical basis for liquid-liquid phase separation reported by the Bristol group. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2329–2353, 1997     

Reactive compatibilization of polyolefin/PET blends by melt grafting with glycidyl methacrylate

The melt free radical grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE) was carried out in Brabender internal mixer. The GMA content of the grafted HDPE (HDPE‐g‐GMA) was determined through FTIR by means of a calibration curve. The influence of reaction procedure, radical initiator concentration and addition of a co‐monomer (styrene) on the grafting efficiency was examined. Blends of poly(ethylene terephthalate) (PET) with HDPE and HDPE‐g‐GMA (75/25 w/w) were prepared by melt mixing in internal mixer. The morphology of the blends was then analysed by SEM microscopy. PET/HDPE‐g‐GMA blends displayed improved phase dispersion and interfacial adhesion as compared to unfanctionalized PET/HDPE blend.     

Orientational effects in novel side-chain liquid crystalline polyolefin blends

The paper is concerned with an analysis of the dynamic properties of novel comb-like liquid crystalline polycarbosilane, which are related to the reorientational processes responding to the applied ac electric field. Electro-optical and switching effects of the polymer are estimated basing on the measurements of the transmitted light intensity as a function of temperature and ac electric field. The threshold voltage, rise and decay times are measured and discussed.     

The role of lubricants in reactive compatibilization of polyolefin blends

Reactive compatibilization using liquid polybutadienes and dialkyl peroxides was studied in model low‐density polyethylene/polystyrene (4/1) blends and the commingled waste of composition similar to these blends. The influence of three types of lubricants (Ca stearate, stearic acid ‐ Loxiol G20 and paraffin ‐ Loxiol G22) on the structure and toughness of these blends was determined. In spite of the fact that in the waste material, a coarse morphology and poor toughness were found in comparison with the blend of virgin polyolefins, reactive compatibilization has approximately the same effect in both types of the blends as far as the structure parameters and mechanical behaviour are concerned. This effect is enhanced by addition of lubricants, the most efficient being the paraffin in the model blends, probably due to its partial miscibility with LDPE. In the commingled waste, liquid polybutadienes supported on precipitated SiO₂ appear to be quite efficient. No influence of the reactive compatibilization on both the crystal modification and the crystalline content was observed in both types of these blends.     

Monitoring thermo-oxidative degradation of polypropylene by CRYSTAF and SEC-FTIR

Samples of a polypropylene homopolymer have been degraded and analysed with regard to chemical composition, molecular weight distribution and chemical composition distribution. FTIR shows the progress of degradation and a decrease in molecular weight can be observed from SEC. CRYSTAF shows that the chemical heterogeneity of the samples broadens with continuing degradation. SEC-FTIR reveals that the degraded species are mainly found in the low molecular end of the molecular weight distribution. The spatial heterogeneity of the degradation process has been proven by the analysis of abrased layers.     

Entropically driven phase separation of highly branched/linear polyolefin blends

Small‐angle neutron scattering (SANS) was used to examine the melt phase behavior of a heavily branched comb PEE polymer blended separately with two linear PEE copolymers. In this case, PEE refers to poly(ethylene‐r‐ethylethylene) with 10% ethylene units; therefore, the molecular architecture was the only difference between the two components of the blends. The molecular weights of the two linear random copolymers were 60 and 220 kg/mol, respectively. The comb polymer contained an average of 54 long branches, with a molecular weight of 13.7 kg/mol, attached to a backbone with a molecular weight of 10 kg/mol. Three different volume compositions (25/75, 50/50, and 75/25) were investigated for both types of blends. SANS results indicate that all the blends containing the lower molecular weight linear polymer formed single‐phase mixtures, whereas all the blends containing the high molecular weight linear polymer phase‐separated. These results are discussed in the context of current theories for polymer blend miscibility. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2965–2975, 2000     

The influence of thermoplastic elastomers on structure and crystallisation behaviour of polyolefin blends

The influence of a styrene-ethylene/butylene-styrene triblock copolymer (SEBS) on an isotactic polypropylene / polyethylene blend was investigated. For comparison binary blends with polypropylene and SEBS alone were also prepared. The blends obtained by solution mixing were characterised by small-angle x-ray scattering, light microscopy and dynamic mechanical analysis. The role of SEBS as matrix reinforcer or interfacial agent is composition dependent. Experimental data also reveal a different influence of SEBS on the binary blends than on the ternary blends containing polyethylene.     

Polymorphism of nylon-6 in nylon-6/nanoclay/functionalized polyolefin blends

The crystallization behavior of Nylon-6 and the interaction in Nylon-6/nanoclay/functionalized polyolefin blends were investigated by X-ray diffraction and Fourier transform infrared spectroscopy. For samples without any thermal history, the interaction between Nylon-6 and nanoclay or the interaction between Nylon-6 and functionalized polyolefin favors the formation of γ form crystal. In contrast, the presence of both nanoclay and functionalized polyolefin together in Nylon-6 was found to have an antagonistic effect on each other's ability to promote the formation of γ form crystal. This was attributed to the complex interactions between the constituents. The crystallization behavior of Nylon-6 in Nylon-6/nanoclay/functionalized polyolefin blends is clearly affected by the cointeraction of these effects. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1494–1502, 2007     

Syntheses of graft and star copolymers possessing polyolefin branches by using polyolefin macromonomer

Graft and star copolymers having poly(methacrylate) backbone and ethylene–propylene random copolymer (EPR) branches were successfully synthesized by radical copolymerization of an EPR macromonomer with methyl methacrylate (MMA). EPR macromonomers were prepared by sequential functionalization of vinylidene chain‐end group in EPR via hydroalumination, oxidation, and esterification reactions. Their copolymerizations with MMA were carried out with monofunctional and tetrafunctional initiators by atom transfer radical polymerization (ATRP). Gel‐permeation chromatography and NMR analyses confirmed that poly(methyl methacrylate) (PMMA)‐g‐EPR graft copolymers and four‐arm (PMMA‐g‐EPR) star copolymers could be synthesized by controlling EPR contents in a range of 8.6–38.1 wt % and EPR branch numbers in a range of 1–14 branches. Transmission electron microscopy of these copolymers demonstrated well‐dispersed morphologies between PMMA and EPR, which could be controlled by the dispersion of both segments in the range between 10 nm and less than 1 nm. Moreover, the differentiated thermal properties of these copolymers were demonstrated by differential scanning calorimetry analysis. On the other hand, the copolymerization of EPR macromonomer with MMA by conventional free radical polymerization with 2,2′‐azobis(isobutyronitrile) also gave PMMA‐g‐EPR graft copolymers. However, their morphology and thermal property remarkably differed from those of the graft copolymers obtained by ATRP. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5103–5118, 2005