Molecular heterogeneity of ethylene‐propylene rubbers: New insights through advanced crystallization‐based and chromatographic techniques

For a long time ethylene‐propylene rubber (EPR) copolymers with high comonomer contents were believed to be amorphous materials with a random copolymer composition. This is not completely correct as has been shown by temperature rising elution fractionation (TREF) combined with differential scanning calorimetry (DSC), crystallization analysis fractionation (CRYSTAF), and high temperature–high‐performance liquid chromatography (HT‐HPLC). When using only conventional crystallization‐based fractionation methods, the comprehensive compositional analysis of EPR copolymers was impossible due to the fact that large fractions of these copolymers do not crystallize under CRYSTAF conditions. In the present work, HT‐HPLC was used for the separation of the EPR copolymers according to their ethylene and propylene distributions along the polymer chains. These investigations showed the existence of long ethylene sequences in the bulk samples which was further confirmed by DSC. The results on the bulk samples prompted us to conduct preparative fractionations of EPR copolymers having varying ethylene contents using TREF. Surprisingly, significant amounts of crystallizing materials were obtained that were analyzed using a multistep protocol. CRYSTAF and DSC analyses of the TREF fractions revealed the presence of components with large crystallizable sequences that had not been detected by the bulk samples analyses. HT‐HPLC provided a comprehensive separation and characterization of both the amorphous and the crystalline TREF fractions. The TREF fractions eluting at higher temperatures showed the presence of ethylene‐rich copolymers and PE homopolymer. In order to obtain additional structural information on the separated fractions, HT‐HPLC was coupled to Fourier transform‐infrared (FT‐IR) spectroscopy. The FT‐IR data confirmed that the TREF fractions were separated according to the ethylene contents of the eluted samples. Preparative TREF analysis together with a combination of various analytical methods proved to be useful tools in understanding the complex molecular composition of these rubber samples. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 863–874     

Sorption and partial molar volumes of C2 and C3 hydrocarbons in polypropylene copolymers

The sorption of C₂ and C₃ hydrocarbons in two ethylene–propylene copolymers and a propylene homopolymer and the simultaneous dilation of the polymers were measured at temperatures of 287–363 K and pressures up to 4 MPa. The sorption isotherms were well described by the Flory–Huggins theory of dissolution. Dilation isotherms in the form of elongation versus pressure were similar in shape to the corresponding sorption isotherms. Solubility coefficients, partial molar volumes, and Flory–Huggins interaction parameters were determined from these isotherms. The thermal expansivities of the hydrocarbons dissolved in the polymers were 0.002–0.005 K^?1, and the Flory–Huggins interaction parameters depended not only on temperature but also on concentration. At 323 K, the calculated solubilities of propylene in the ethylene–propylene‐rubber regions of the copolymers were 1.8 times higher than in the amorphous regions of the propylene homopolymer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1255–1262, 2001     

Structural characterization of radiation‐grafted block copolymer films,using SANS technique

We report small‐angle neutron scattering studies of grafted copolymer films of perfluorinated poly(ethylene propylene), FEP, base polymer and polystyrene, PS, grafted blocks. The films show highly anisotropic scattering patterns, revealing nematic‐like ordering of the crystalline domain structure as a consequence of the processing conditions. Upon grafting, the styrene swells the amorphous domains in the copolymer formation. For styrene content beyond roughly 15%, the amorphous regimes increase on the cost of crystalline domains. To stabilize the rather well‐defined domain structure already given by the original FEP base material, the samples need to be cross‐linked. Without cross‐linking, the nanometer length scale domains vanish, and some large scale structure takes over, likely driven by the immiscibility between FEP and PS. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1660–1668, 2008     

Development of novel elastomeric blends derived from chlorinated nitrile rubber and chlorinated ethylene propylene diene rubber

Chlorinated nitrile rubber (Cl-NBR) has been blended with chlorinated ethylene propylene diene rubber (Cl-EPDM) in different ratios by a conventional mill mixing method. The effect of the blend ratio on processing characteristics, mechanical properties (such as tensile and tear strength, elongation at break, hardness, abrasion resistance, heat build-up and resilience), structure, morphology, glass transition temperature (Tg), thermal stability, flame retardancy, oil resistance, AC conductivity, dielectric properties and transport behavior of petrol, diesel and kerosene were investigated. The shift in absorption bands of blends studied from FTIR spectra, single Tg from DSC analysis and decrease in amorphous nature from XRD showed the molecular miscibility in Cl-NBR/Cl-EPDM blends. SEM images showed the uniform mixing of both Cl-NBR and Cl-EPDM in a 50/50 blend ratio. The TGA curves indicated the better thermal stability of the polymer blend. The elongation at break, heat build-up, resilience and hardness of the polymer blend decreases with an increase in Cl-NBR content in the blend whereas the flame and oil resistance were increased with increase in Cl-NBR content. Among the polymer blends, the maximum torque, tensile strength, tear and abrasion resistance was obtained for the 50/50 blend ratio because of the effective interfacial interactions between the blend components. AC conductivity and dielectric properties of polymer blend increased with increase in the ratio of Cl-NBR in the blend. Different transport properties such as diffusion, permeation and sorption coefficient were measured with respect to nature of solvent and different blend ratios. Temperature dependence of diffusion was used to estimate the activation parameters and the mechanism of transport found to be anomalous.     

The effect of electron beam irradiation on dynamic shear rheological behavior of a poly (propylene‐co‐ethylene) heterophasic copolymer

In this study the effect of electron beam irradiation on rheological properties of a poly (propylene‐co‐ethylene) heterophasic copolymer is evaluated. Using dynamic viscoelastic measurement in the linear viscoelastic range of deformation, it is observed that the complex viscosity and dynamic modulus of polypropylenes were decreased by increasing the irradiation dose. Polypropylene heterophasic copolymers consist of ethylene propylene rubber phase dispersed in polypropylene homopolymer matrix. The high energy electron beams simultaneously affect both isotactic polypropylene (iPP) matrix and ethylene propylene dispersed phase. The molecular chains of polypropylene homopolymer phase breakdown to smaller species, those are prone to degradation and branching as well. Increase in the melt flow rate behavior and shifting the cross‐over point to higher frequencies and increase in melt strength are due to this phenomenon. At the same time, the ethylene propylene phase of the polypropylene copolymer cross‐links due to irradiation, and a significant effect on the rheological behavior of samples are observed. The mathematical modeling of complex viscosity behavior revealed the conformity of experimental data with modified Carreau equation. Copyright © 2010 John Wiley & Sons, Ltd.     

Influence of reaction parameters on the structure of in situ rubber/silica compounds synthesized via sol–gel reaction

In situ silica was synthesized in three non‐vulcanized rubber matrices, namely natural rubber, styrene‐butadiene rubber, and EPDM (ethylene‐propylene diene ter‐polymer), using the sol–gel method with tetra‐ethoxysilane (TEOS) as silica precursor and hexylamine as catalyst. The effect of the reaction parameters such as the amount of TEOS, the reaction time (15–120 min), and the type of rubber was explored. Transmission electron microscopy was used to study the gradient in silica content and particle size over the sample thickness. The diffusion gradient of TEOS and catalyst solution in the rubber matrix responsible for the gradient was studied with Fick's law. An excellent dispersion of silica was obtained for all rubbers, even for the very non‐polar EPDM, without the use of any additives to improve the dispersion. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 967–978     

The rheological,thermal, and mechanical properties for polypropylene and amorphous poly alpha olefin blends

Rheological, thermal, and mechanical properties of polypropylene homo polymer (PPH)/amorphous poly alpha olefin (APAO) blends as a function of molecular weight, comonomer type and content, and blend composition have been investigated. Homo APAO grade showed better compatibility than copolymerized ones in terms of rheological and thermal properties. The mechanical strength showed strong dependence on APAO content and type, and the impact strength and melt index rapidly increased for certain types of APAO at and above 30 wt%. On comparison with commercially used PPH/ethylene–propylene rubber (EPR) blend system, it is supposed that PPH/APAO blend can be successfully used in thermoplastic polyolefin applications. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis,physical characterization,and acetone sorption kinetics in random copolymers of poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalate)

Random copolymers of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6-naphthalate) (PEN) were synthesized by melt condensation. In a series of thin, solvent cast films of varying PEN content, acetone diffusivity and solubility were determined at 35°C and an acetone pressure of 5.4 cm Hg. The kinetics of acetone sorption in the copolymer films are well described by a Fickian model. Both solubility and diffusivity decrease with increasing PEN content. The acetone diffusion coefficient decreases 93% from PET to PET/85PEN, a copolymer in which 85 weight percent of the dimethyl terephthalate in PET has been replace by dimethyl naphthalate 2,6-dicarboxylate. The acetone solubility coefficient in the amorphous regions of the polymer decreases by approximately a factor of two over the same composition range. The glass/rubber transition temperatures of these materials rise monotonically with increasing PEN content. Copolymers containing 20 to 80 wt % PEN are amorphous. Samples with <20% or >80% PEN contain measurable levels of crystallinity. Estimated fractional free volume in the amorphous regions of these samples is lower in the copolymers than in either of the homopolymers. Relative free volume as probed by positron annihilation lifetime spectroscopy (PALS) decreases systematically with increasing PEN content. Acetone diffusion coefficients correlate well with PALS results. Infrared spectroscopy suggests an increase in the fraction of ethylene glycol units in the trans conformation in the amorphous phase as the concentration of PEN in the copolymer increases. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2981–3000, 1998     

Characterization of ethylene–propylene block copolymers by proton magnetic resonance

A high-resolution proton magnetic resonance compositional analysis has been developed for propylene polymers containing 0–40 wt.-% ethylene as either homopolymer or copolymer blocks. The test is independent of tacticity and provides qualitative information on copolymer sequencing and propylene chain structure. The analysis was developed using a series of standard reference polymers synthesized to contain various ratios of C¹⁴-tagged ethylene and propylene. The compositional standards were established by radiotracer analysis for C¹⁴ and by preparing weighed physical mixtures of homopolymers. Spectra were obtained at 200 ± 10°C. by placing externally heated polymer solutions into a conventional probe of a Varian A-60 proton spectrometer. All measurements were made on ± 10% polymer solutions in diphenyl ether. Analyses are accurate to about ± 10% at higher ethylene concentrations. The method is sensitive, with less precision, to below 1% for ethylene either as blocks or homopolymer.     

Polymer adsorption onto a micro-sphere from optical tweezers electrophoresis

We explore the design and operation of an optical-tweezers electrophoresis apparatus to resolve polymer adsorption dynamics onto a single micro-sphere in a micro-fluidic environment. Our model system represents a broader class of micro-fluidic electrophoresis experiments for biosensing and fundamental colloid and surface science diagnostics. We track the adsorption of 100 kDa poly(ethylene oxide) homopolymer onto a colloidal silica sphere that is optically trapped in a crossed parallel-plate micro-channel. The adsorption dynamics are probed on the ～1 μm particle length scale with ～1 s temporal resolution. Because the particle electrophoretic mobility and channel electro-osmotic flow are exquisitely sensitive to the polymer layer hydrodynamic thickness, particle dynamics can be complicated by polymer adsorption onto the micro-channel walls. Nevertheless, using experiments and a theoretical model of electro-osmotic flow in channels with non-uniform wall ζ-potentials, we show that such influences can be mitigated by adopting a symmetrical flow configuration. The equilibrium hydrodynamic layer thickness of 100 kDa poly(ethylene oxide) on colloidal silica is ～10 nm at polymer concentrations ?10 ppm (weight percent), with the dynamics reflecting polymer solution concentration, flow rate, and polydispersity.     

Aging and degradation of polyolefins. III. Polyethylene and ethylene–propylene copolymers

Rates of oxygen absorption and formation of oxidation products were determined in γ-initiated oxidations of thin films of high- and low-density polyethylene, atactic and isotactic polypropylene, and of three ethylene–propylene copolymers. Radiation yields G for O₂ absorbed and formation of hydroperoxides depend on dose rates and decrease sharply with increasing ethylene content of the copolymers and moderately with increasing crystallinity of any base polymer. G values for dialkyl peroxide and carbonyl formation, and therefore for chain initiation and termination, do not change much with polymer composition and crystallinity and not at all with dose rates. A few experiments with atactic polypropylene and an amorphous ethylene–propylene copolymer, initiated by di-tert-butylperoxy oxalate, indicate that 37 mole-% of ethylene in the polymer increases the efficiency of initiation and the tendency toward crosslinking.     

Composite Materials Based on Polylactide and Poly-3-hydroxybutyrate “Green” Polymers

Blends of polylactide with low-density polyethylene and of poly-3-hydroxybutyrate with synthetic ethylene–propylene rubber with the component weight ratios of 30 : 70, 50 : 50, and 70 : 30 were prepared and studied in comparison with the pure components. The thermal characteristics of these blends were determined by differential scanning calorimetry. The melting point of polyhydroxybutyrate and polylactide in the blends changes insignificantly, by 1–2°C. The dependence of the morphology on the composition for both polymer systems was examined by scanning electron microscopy. The physicomechanical properties of the samples are determined by the major phase. The blends undergo biodegradation in soil at 20 ± 3°С. The process occurs faster for blends of polyhydroxybutyrate with ethylene–propylene rubber of all the compositions studied.     

Study and Control of the Distribution of Elastomer in High Impact Polypropylene

In an initial step, different techniques were used to investigate the distribution and properties of the rubbery domains inside individual high impact polypropylene particles. Both Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM) were used to visualise the local of rubber nodules as a function of the quantity of ethylene propylene rubber (EPR) in the final product. It was demonstrated that the EPR forms first as nodules near the centre of the homopolymer particles, and then accumulates as the rubber quantity increases.     

Synthesis and Characterization of Ethylene/Propylene Copolymers in the Whole Composition Range

Summary: The incorporation of comonomer molecules in the backbone of a homopolymer can influence the final properties of the material, decreasing its crystallinity and the melting and glass transition temperatures, and increasing its impact resistance and transparency. In the present work, ten ethylene/propylene copolymers have been synthesized using a supported metallocene catalytic system covering the whole composition range. Any desired composition was obtained by controlling the feed composition during the reaction. These synthesized copolymers have been characterized by different techniques in order to study the effect of the comonomer incorporation onto their final properties. When the comonomer content is low, the behaviour of the copolymer is similar to that of the corresponding homopolymer. Nevertheless, if the comonomer content increases, the copolymer becomes more amorphous (low crystallization temperature and soft XRD signals) and easily deformable, reaching a behaviour close to that corresponding to an elastomeric material. In order to corroborate these results the samples have been characterized by TREF and GPC-MALS. TREF analysis showed that copolymers containing less than 10% and more than 80% of ethylene are semicrystalline, with elution temperatures typical of this kind of polymers. Molecular weights are higher for homopolymers and they decrease as the comonomer concentration increases, whereas the polydispersity index keeps almost constant at the expected value for this kind of samples.     

The Effect of multi-reprocessing on the structure and characteristics of thermoplastic elastomers based on recycled polymers

The effect of multi-reprocessing on the phase structure and characteristics is studied for thermoplastic elastomers based on recycled high-density polyethylene (HDPE), ethylene-propylene-diene rubber (ternary copolymer of ethylene, propylene, and 5-ethylidene-2-norbornene) (EPDM), and recycled ground tire rubber (RGTR). Analysis of the viscous flow characteristics of thermoplastic elastomers shows that, independently of the number of processing cycles, all samples are characterized by the required flow characteristics at elevated temperatures. Processing of thermoplastic elastomers is accompanied by the competing processes of crosslinking and degradation of macromolecules in a polymer mixture. The results of DSC study and dynamic mechanical thermal analysis show that, as the number of processing cycles is increased, phase separation between amorphous and crystalline phases in thermoplastic elastomers decreases. Insignificant intermolecular crosslinking induced by the processing of thermoplastic elastomers appears to have almost no effect on the physicomechanical characteristics of the final material.     

Melting behavior of ethylene oxide–propylene oxide (sym-PEP) block copolymers

Melting points and lamellar thicknesses have been measured for ethylene oxide–propylene oxide block copolymers (sym-PEP) with central poly(ethylene oxide) block lengths of 70–100 chain units and end poly(propylene oxide) block lengths of 0–30 chain units. Melting points of the block copolymers are lower than those of the corresponding poly(ethylene oxide) homopolymer by an amount (up to 15°C) which increases as the poly(propylene oxide) block length increases. Most samples have more than one melting transition, which can be assigned to variously folded chain crystals. End interfacial free energies σ_e for the various crystals have been estimated by use of Flory's theory of melting of block copolymers. For a given crystal type (e.g., once-folded-chain) σ_e is higher the longer the chain length of the end poly(propylene oxide) blocks. For a given copolymer σ_e is lower, the more highly folded the poly(ethylene oxide) chain.     

Reaction of chlorine-containing polymers with living polymers

A graft polymer was prepared by means of the coupling reaction of chlorinated ethylene–propylene terpolymer with living polystyrene, obtained with a sodium–naphthalene complex as initiator, under various conditions; the grafting efficiency and the percentage of grafting are discussed. Poly(chloroprene), chlorinated butyl rubber, poly(vinyl chloride), poly(epichlorohydrin), and epichlorohydrin–ethylene oxide copolymer were also used as chlorine-containing polymers. The grafting efficiencies were found to be in the following order: chlorinated butyl rubber > poly(epichlorohydrin) > epichlorohydrin-ethylene oxide copolymer > chlorinated ethylene-propylene terpolymer > poly(chloroprene) > poly(vinyl chloride). A graft polymer was obtained from the reaction between chlorinated ethylene–propylene terpolymer and living poly(isoprene), with butyllithium in benzene. The undesirable metal–halogen interchange reaction was considerable.     

Effect of copolymerization and heat treatment on the structure and x-ray diffraction of polyacrylonitrile

Wide-angle x-ray diffraction studies are reported on polyacrylonitrile (PAN) (homopolymer powder and fiber samples) and its random copolymers with methyl methacrylate (MMA) and methacrylonitrile (MAN). A new method of determination of degree of order which involves resolution of the individual maxima in the diffraction pattern is described and compared with the methods used in the literature. Comparison of the results on untreated fibers with those on untreated homopolymer powder samples, and the effect of heat treatment, suggest the molecular rod conformation of the PAN molecules in the amorphous phase. Heat treatment or the orientation induces a parallel alignment of the molecular rods in the amorphous phase, similar to the cyrstalline structure of PAN. Copolymerization with both the comonomers MMA and MAN produces qualitatively similar effect on the structure of PAN, which depends on the comonomer content. Below a critical comonomer content c* (c* = 12 mol % for MMA and 25 mol % for MAN comonomer), the crystalline lattice remains that characteristic of PAN, whereas above the critical comonomer content some modification in the crystalline lattice is apparent.     

Anionic synthesis of poly[ethylene methylene bis(4-phenyl-carbamate)-g-acrylonitrile]

A relatively high-molecular-weight polyurethane based on MDI and ethylene glycol was prepared and characterized. This polymer was metalated with sodium hydride in N,N-dimethylformamide (DMF) at about 0°C. Metalation was confirmed principally by spectroscopic identification of the N-methyl derivative obtained by coupling the metalated polymer with methyl iodide. Under appropriate reaction conditions the metalated polyurethane was used for the anionic graft polymerization of the reactive monomers acrylonitrile and ethylene and propylene sulfides. Attempted anionic graft polymerizations with other monomers, including styrene and ethylene and propylene oxides, were unsuccessful. The polyurethane grafted with acrylonitrile was separated by fractionation from accompanying small amounts of polyacrylonitrile, a low-molecular-weight homopolymer. One sample of polyurethane grafted with acrylonitrile was identified by microanalysis, IR, NMR, and increase in weight and was also characterized by differential thermal analysis.