Synthesis of nanosized ethylene–propylene rubber latex via polyisoprene hydrogenation

Nanosized ethylene–propylene rubber (EPM) latex with a particle size of 47 nm was synthesized via an alternative route consisting of isoprene (IP) polymerization followed by hydrogenation. First, the IP monomer was polymerized by differential microemulsion polymerization to obtain polyisoprene (PIP) rubber latex with a particle size of 42 nm. The structure of synthetic PIP was hydrogenated at the carbon–carbon double bonds to produce an ethylene–propylene copolymer by diimide reduction in the presence of hydrazine and hydrogen peroxide using boric acid as promotor. The degree of hydrogenation was determined by proton nuclear magnetic resonance (¹H‐NMR) spectroscopy and the structure of the ethylene–propylene copolymer was identified by ¹³C‐NMR spectroscopy. In nanosized PIP hydrogenation, the hydrogenation level was found to be increased by boric acid addition. An EPM yield of 94% was achieved using a hydrogen peroxide : hydrazine ratio of 1.5 : 1. The EPM produced from PIP has high thermal stability with the maximum decomposition temperature of 510°C and a glass transition temperature of ‐42.4°C close to commercial ethylene–propylene diene rubber. Dynamic mechanical analysis indicated that EPM had a maximum storage modulus due to the saturated carbons domains of the ethylene segments in the polymer chains. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

(Ind)₂ZrCl₂ catalyst was synthesized and used for copolymerization of ethylene and propylene (EPR) and terpolymerization of ethylene propylene and 5‐ethyldiene‐2‐norbornene (ENB). Methylaluminoxane (MAO) was used as cocatalyst. The activity of the catalyst was higher in copolymerization of ethylene and propylene (EPR) rather than in terpolymerization of ethylene, propylene and diene monomers. The effects of [Al] : [Zr] molar ratio, polymerization temperature, pressure ratio of ethylene/propylene and the ENB concentration on the terpolymerization behavior were studied. The highest productivity of the catalyst was obtained at 60°C, [Al] : [Zr] molar ratios of 750 : 1 and 500 : 1 for copolymerization and terpolymerization, respectively. Increasing the molar ratio of [Al] : [Zr] up to 500 : 1 increased the ethylene and ENB contents of the terpolymers, while beyond this ratio the productivity of the catalyst dropped, leading to lower ethylene and ENB contents. Terpolymerization was carried out batchwise at temperatures from 40 to 70°C. Rate time profiles of the polymerization were a decay type for both copolymerization and terpolymerization. Glass transition temperatures (T_g) of the obtained terpolymers were between ?64 and ?52°C. Glass transition temperatures of both copolymers and terpolymers were decreased with increased ethylene content of the polymers. Dynamic mechanical and rheological properties of the obtained polymers were studied. A compounded EPDM showed good thermal stability with time. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of the Form II/Form I crystal polymorphism of random copolymers of butene‐1 with ethylene or propylene on the peel behavior of peel films

Peel films of blends of low density polyethylene (LDPE) and random isotactic copolymers of butene‐1 with either ethylene (iPB‐Eth) or propylene (iPB‐Prop) were investigated regarding the effect of the copolymer composition on both the Form II mesophase to Form I crystal transformation of the copolymers, and the time‐dependent peel behavior of their blends with LDPE in peel films. In general, there is observed a decrease of the peel force with increasing concentration of both ethylene and propylene co‐units in random iPB‐1 based copolymers and their blends with LDPE, after completion of the Form II to Form I transformation. Thus, to tailor the peel force, either the content of the peel component in the blends, or the concentration of ethylene or propylene co‐units in the peel component may be varied. The effect of ethylene co‐units in the random copolymers on the peel force is distinctly larger than that of propylene co‐units. Parallel to the Form II to Form I transition of butene‐1 based copolymers, the peel force decreases with a rate which depends on the copolymer composition. The Form II to Form I transition in iPB‐Prop copolymers proceeds distinctly faster than in iPB‐Eth copolymers of identical concentration of co‐units. POLYM. ENG. SCI., 55:1749–1757, 2015. © 2014 Society of Plastics Engineers     

Morphology–toughness correlation of polypropylene/ethylene–propylene rubber blends

A polypropylene homopolymer was blended with ethylene–propylene rubber in different mixing ratios. The influence of the ethylene–propylene rubber content on the toughness behavior was investigated. According to the results of instrumented impact tests, brittle‐to‐tough transition temperatures were found for different ethylene–propylene rubber contents. Critical transition temperatures could be determined not only in the region of predominantly unstable crack propagation but also in the region of stable crack initiation. In situ measurements provided information on the deformation processes on the crack tip. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3364–3371, 2006     

Phase interactions and structure evolution of heterophasic ethylene–propylene copolymers as a function of system composition

Heterophasic copolymers comprised of polypropylene (PP) matrix and ethylene–propylene copolymer (EPC) dispersed phase were investigated with respect to the dispersed phase composition, i.e., ethylene/propylene ratio. The rheological properties, morphology, as well as thermal and mechanical relaxation behavior were studied to describe the structure evolution and phase interactions between the components of the PP copolymers. Decrease of the ethylene content of the EPC leads to a higher matrix‐dispersed phase compatibility, as evaluated by the shift of the glass transition temperatures of EPC and PP towards each other. At ethylene content of EPC of 17 wt %, the glass transition temperatures of the both phases merged into a joint relaxation. The effect of the EPC composition on the internal structure of the dispersed domains and on the morphology development of the heterophasic copolymers was demonstrated. Decreasing ethylene content was found to induce a refinement of the dispersed phase with several orders of magnitude down to 0.18 μm for propylene‐rich EPC. Optical microscopy observations showed that the dispersed propylene‐rich phase is preferably rejected at the interlamellar regions of the spherulites and/or at the interspherulitic regions, while the ethylene‐rich domains are engulfed within the PP spherulites. Both of these processes impose an additional energetic barrier and influence the spherulite growth rate of the heterophasic materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2825–2837, 2006     

Influence of copolymerization conditions on the structure and properties of polyethylene/polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys synthesized in gas‐phase with spherical ziegler‐natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of polyethylene/polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys by sequential homopolymerization of ethylene, homopolymerization of propylene, and copolymerization of ethylene and propylene in gas‐phase. Different conditions in the third stage, such as the pressure of ethylene–propylene mixture and the feed ratio of ethylene, were investigated, and their influences on the compositions, structural distribution and properties of the in‐reactor alloys were studied. Increasing the feed ratio of ethylene is favorable for forming random ethylene–propylene copolymer and segmented ethylene–propylene copolymer, however, slightly influences the formation of ethylene‐b‐propylene block copolymer and homopolyethylene. Raising the pressure of ethylene–propylene mixture results in the increment of segmented ethylene–propylene copolymer, ethylene‐b‐propylene block copolymer, and PE fractions, but exerts a slight influence on both the random copolymer and PP fractions. The impact strength of PE/PP/EPR in‐reactor alloys can be markedly improved by increasing the feed ratio of ethylene in the ethylene–propylene mixture or increasing the pressure of ethylene–propylene mixture. However, the flexural modulus decreases as the feed ratio of ethylene in the ethylene–propylene mixture or the pressure of ethylene–propylene mixture increases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2481–2487, 2006     

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.     

FI Catalysts: A New Family of High Performance Catalysts for Olefin Polymerization

This paper reviews a new family of olefin polymerization catalysts. The catalysts, named FI catalysts, are based on non‐symmetrical phenoxyimine chelate ligands combined with group 4 transition metals and were developed using “ligand‐oriented catalyst design”. FI catalysts display very high ethylene polymerization activities under mild conditions. The highest activity exhibited by a zirconium FI catalyst reached an astonishing catalyst turnover frequency (TOF) of 64,900 s ^–1 atm ^–1, which is two orders of magnitude greater than that seen with Cp₂ZrCl₂ under the same conditions. In addition, titanium FI catalysts with fluorinated ligands promote exceptionally high‐speed, living ethylene polymerization and can produce monodisperse high molecular weight polyethylenes (M_w/M_n<1.2, max. M_n>400,000) at 50 °C. The maximum TOF, 24,500 min ^–1 atm ^–1, is three orders of magnitude greater than those for known living ethylene polymerization catalysts. Moreover, the fluorinated FI catalysts promote stereospecific room‐temperature living polymerization of propylene to provide highly syndiotactic monodisperse polypropylene (max. [rr] 98%). The versatility of the FI catalysts allows for the creation of new polymers which are difficult or impossible to prepare using group 4 metallocene catalysts. For example, it is possible to prepare low molecular weight (M_v∼10³) polyethylene or poly(ethylene‐co‐propylene) with olefinic end groups, ultra‐high molecular weight polyethylene or poly(ethylene‐co‐propylene), high molecular weight poly(1‐hexene) with atactic structures including frequent regioerrors, monodisperse poly(ethylene‐co‐propylene) with various propylene contents, and a number of polyolefin block copolymers [e.g., polyethylene‐b‐poly(ethylene‐co‐propylene), syndiotactic polypropylene‐b‐poly(ethylene‐co‐propylene), polyethylene‐b‐poly(ethylene‐co‐propylene)‐b‐syndiotactic polypropylene]. These unique polymers are anticipated to possess novel material properties and uses.     

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene (hiPP) were studied by solvent extraction fractionation, transmission electron microscopy (TEM), selected area electron diffraction (SAED), nuclear magnetic resonance (¹³C‐NMR), and selected reblending of different fractions of hiPP. The results indicate that hiPP contains, in addition to polypropylene (PP) and amorphous ethylene‐propylene random copolymer (EPR) as well as a small amount of polyethylene (PE), a series of crystallizable ethylene‐propylene copolymers. The crystallizable ethylene‐propylene copolymers can be further divided into ethylene‐propylene segmented copolymer (PE‐s‐PP) with a short sequence length of PE and PP segments, and ethylene‐propylene block copolymer (PE‐b‐PP) with a long sequence length of PE and PP blocks. PE‐s‐PP and PE‐b‐PP participate differently in the formation of multilayered core‐shell structure of the dispersed phase in hiPP. PE‐s‐PP (like PE) constructs inner core, PE‐b‐PP forms outer shell, while intermediate layer is resulted from EPR. The main reason of the different functions of the crystallizable ethylene‐propylene copolymers is due to their different compatibility with the PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fracture characteristics and deformation behavior of heterophasic ethylene-propylene copolymers as a function of the dispersed phase composition

The deformation and fracture behavior of in reactor produced heterophasic copolymers, comprising a polypropylene (PP) matrix and an ethylene propylene copolymer (EPC) dispersed phase, have been studied as a function of the dispersed phase composition (ethylene/propylene ratio). Conventional and instrumented Charpy as well as instrumented drop weight tests were employed to quantify the response of the materials to impact loading. Scanning and high-voltage electron microscopy was used for characterization of the deformation mechanisms. Decreasing ethylene content of the EPC led to an enhancement of the matrix/dispersed phase compatibility, reduction of the dispersed phase particle size and therewith to a systematic increase of the impact strength at room temperature and a decrease of the brittle-to-tough transition temperature (T_BTT) of the materials. The low temperature impact strength was predominantly dependent upon the glass transition temperature of the EPC phase. The results are discussed from the viewpoint of interfacial interactions, size and spatial packing of the dispersed phase domains and the observed deformation mechanisms.     

Comparison of propylene/ethylene copolymers prepared with different catalysts

This study compared a series of experimental propylene/ethylene copolymers synthesized by a transition metal‐based, postmetallocene catalyst (xP/E) with homogeneous propylene/ethylene copolymers synthesized by conventional metallocene catalysts (mP/E). The properties varied from thermoplastic to elastomeric over the broad composition range examined. Copolymers with up to 30 mol % ethylene were characterized by thermal analysis, density, atomic force microscopy, and stress–strain behavior. The xP/Es exhibited noticeably lower crystallinity than mP/Es for the same comonomer content. Correspondingly, an xP/E exhibited a lower melting point, lower glass transition temperature, lower modulus, and lower yield stress than an mP/E of the same comonomer content. The difference was magnified as the comonomer content increased. Homogeneous mP/Es exhibited space‐filling spherulites with sharp boundaries and uniform lamellar texture. Increasing comonomer content served to decrease spherulite size until spherulitic entities were no longer discernable. In contrast, axialites, rather than spherulites, described the irregular morphological entities observed in xP/Es. The lamellar texture was heterogeneous in terms of lamellar density and organization. At higher comonomer content, embryonic axialites were dispersed among individual randomly arrayed lamellae. These features were characteristic of a copolymer with heterogeneous chain composition. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1651–1658, 2006     

Polymeric proton conducting systems based on commercial elastomers. II. Synthesis and microstructural characterization of films based on HSBR/EPDM/PP/PS/silica

This article reports on the synthesis and structural characterization of films containing hydrogenated poly(butadiene‐styrene) block copolymer/ethylene‐propylene terpolymer/polypropylene, hydrogenated poly(butadiene‐styrene) block copolymer/ethylene‐propylene terpolymer/polystyrene, and hydrogenated poly(butadiene‐styrene block copolymer/ethylene‐propylene terpolymer/silica) crosslinked with peroxides and heterogeneously sulfonated. Sulfonation of the different polymeric systems gives rise to materials with high proton conductivity and great dimensional stability, suited for application in a variety of electronic devices. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2394–2402, 2004     

Minor‐phase particles evolution in a polyethylene/ethylene–propylene copolymer (80/20) blend across mixing: Breakup and coalescence

On the basis of an online sampling microscopy method, the morphological evolution of a metallocene polyethylene/metallocene ethylene–propylene copolymer system (80/20 vol %) across various mixing regimes was investigated and treated statistically. The size distributions of the minor‐phase metallocene ethylene–propylene (mEP) droplets were described with principles of irreversible thermodynamics. Such an approach allowed us to find two superimposed statistical ensembles involving primary (broken) and secondary (coalesced) mEP particles. The mean size and relative number of both broken and coalesced mEP particles were calculated. The evolution of these characteristics across melt mixing, static coalescence, and flow‐driven coalescence was analyzed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3421–3431, 2013     

Millimeter‐size polyethylene hollow spheres synthesized with MgCl2‐supported Ziegler‐Natta catalyst

Polyethylene hollow spheres with diameters of 0.4–2 mm were synthesized by a two‐step slurry polymerization in a single reactor with a spherical MgCl₂‐supported Ziegler‐Natta catalyst activated by triethylaluminum, in which the first step was prepolymerization with 0.1 MPa propylene and the second step was ethylene polymerization under 0.6 MPa. The prepolymerization step was found necessary for the formation of hollow spherical particles with regular shape (perfectly spherical shape). The effects of adding small amount of propylene (propylene/ethylene < 0.1 mol/mol) in the reactor after the prepolymerization step were investigated. Average size of the polymer particles was increased, and the polymerization rate was markedly enhanced by the added propylene. Development of the particle morphology with polymerization time was also studied. The polymer particles formed by less than 20 min of ethylene polymerization showed hollow spherical morphology with thin shell layer. Most of the particles had ratio of shell thickness/particle radius smaller than 0.5. By prolonging the ethylene polymerization, the shell thickness/particle radius ratio gradually approached 1, and the central void tended to disappear. Central void in polymer particles formed from smaller catalyst particles disappeared after shorter time of polymerization than those formed from bigger catalyst particles. The shell layer of the hollow particles contained large number of macro‐, meso‐ and micro‐pores. The mesopore size distributions of four typical samples were analyzed by nitrogen adsorption–desorption experiments. A simplified multigrain model was proposed to explain the morphogenesis of the hollow spherical particles. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43207.     

Improvement of the compatibility of natural rubber/ethylene–propylene diene monomer rubber blends via natural rubber epoxidation

The longitudinal ultrasonic velocity, longitudinal ultrasonic absorption (attenuation coefficient), glass‐transition temperature, and Mooney viscosity for epoxidized natural rubber/ethylene–propylene diene monomer blends were measured. The variation of the longitudinal ultrasonic velocity with the blend ratios was linear, indicating a compatible system in comparison with the same system without epoxidation (natural rubber/ethylene–propylene diene monomer), which was incompatible. Also, the behavior was confirmed by heat of mixing calculations as well as Mooney viscosity measurements. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2816–2819, 2002     

Compatibilizer‐induced microstructural changes in poly(trimethylene terephthalate)/EPDM blends studied by the positron annihilation lifetime technique and differential scanning calorimetry

Blends of poly(trimethylene terephthalate) (PTT) and ethylene propylene diene monomer (EPDM) with and without the compatibilizer poly (EPM‐graft‐MA) were investigated by positron annihilation lifetime spectroscopy (PALS) and differential scanning calorimetric (DSC) measurements. The DSC results for the blend with 50/50 composition revealed two glass transition temperatures, indicating a two‐phase system. In the presence of compatibilizer, the two glass transition temperatures shifts towards each other, suggesting an increased interaction between the blend components. The PALS results for the blends without compatibilizer showed an increase in free volume hole size and concentration with increasing EPDM content in the blend, suggesting the coalescence of free volumes of EPDM with the PTT to some extent, but the phase‐separation behaviour continued. The free volume of these blends exhibited positive deviation from the known free volume linear additivity rule. However, poly(EPM‐graft‐MA) compatibilized blends of PTT/EPDM had a noticeable decrease in the free volume parameters, which was clearly due to the compatibilizing effect through increased interaction between blend components. Copyright © 2005 Society of Chemical Industry     

Toughening effects of nucleating agent on impact polypropylene copolymer

In this study, the impact polypropylene copolymer (IPC) blended with the sorbitol‐based nucleating agent (NA) NX8000 was prepared and then characterized using a wide range of instrumentations. The results showed that the NA formed a fibril network which resulted in the increased viscosity of system and the decreased size of ethylene–propylene random copolymer (EPR) phase. The results of mechanical tests revealed “the brittle–ductile transition (BDT)” occurred while the ethylene content was between 3.5 wt % and 6 wt % and indicated that the impact strength of IPC was greatly improved by the addition of NX8000 when the EPR content was right over the critical value of BDT. The investigations provided valuable information for the further development of IPC materials and boarded its potential industrial applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40705.     

Study of crystallization and melting behavior of polypropylene‐block‐polyethylenes copolymers fractionated from polypropylene and polyethylene mixtures

A series of ethylene–propylene block copolymer fractions of differing compositions, while still retaining broad molecular weight distributions, were obtained by fractionation of polypropylene (PP) and polyethylene (PE) copolymers prepared by sequential polymerization of ethylene and propylene. The crystallization and melting behavior of the polypropylene‐block‐polyethylene fractions were studied. It was observed that the major component could suppress crystallization of the minor component, leading to a decrease in crystallinity and melting temperature. Non‐isothermal crystallization showed that crystallization of the ethylene block was less influenced by composition and cooling rate than the propylene block. At fast cooling rates, the ethylene block could crystallize prior to the propylene block. Isothermal crystallization kinetics experiments were also conducted. We found that the block copolymers with minor ethylene components had smaller Avrami exponents (n ≈ 1.0), hence indicating a reduced growth dimension of the PE crystals by the pre‐existing PP crystals. On the other hand, the ethylene block exhibited much larger Avrami exponents in those block copolymers with major ethylene contents. Copyright © 2004 Society of Chemical Industry     

Structure and morphology of a commercial high‐impact polypropylene in‐reactor alloy synthesized using a spherical Ziegler–Natta catalyst

A commercial high‐impact polypropylene (hiPP) was fractionated by temperature‐gradient elution fractionation into nine fractions. All fractions were studied using Fourier transform infrared spectroscopy and differential scanning calorimetry. The amount of ethylene in the fractions was also determined. The results demonstrate that the ethylene–propylene statistical copolymer (or ethylene–propylene rubber, EPR) content in this hiPP is rather low and the amounts of ethylene–propylene segmented copolymer and ethylene–propylene block copolymer (that act as adhesive and compatibilizer between elastomeric phase and matrix, respectively) are negligible. Furthermore, the morphology of the resin was studied using scanning electron microscopy observations of microtome‐cut original and etched samples, which reveals that EPR particles are too large and their distribution inside the matrix is not uniform. Copyright © 2010 Society of Chemical Industry     

Effect of composition and component structure on thermal behavior and miscibility of polypropylene catalloys

The thermal behavior and the miscibility of an in‐situ polypropylene blend named polypropylene catalloys (PP‐cats) were investigated by using modulated differential scanning calorimeter (MDSC). It is found that all PP‐cats samples present two glass transitions, one of which is ascribed to the ethylene‐propylene random copolymer (EPR), and the other, to isotactic polypropylene (PP). However, no glass transition of ethylene‐propylene block copolymer (E‐b‐P) responsible for a third component in PP‐cats could be found. With the increase of EPR, the glass transition temperatures responding to PP and EPR components, T_g, _PP and T_g, _EPR, shift to low temperature, because of the enhancement of the interaction between PP and EPR component and the increase of ethylene content in EPR, respectively. Furthermore, the difference between T_g, _PP and T_g, _EPR remarkably decreases with the increase of the total ethylene content in PP‐cats, which indicates that the miscibility of PP‐cats is strongly dependent on the composition. Comparing the T_g, _PP and T_g, _EPR with T_g of fractionated PP and EPR, we ascribe the T_g change of PP fraction to the increase of EPR content; while that of EPR, to the increase of ethylene content in EPR. These experimental results suggest that the existence of E‐b‐P plays an important role in improving the miscibility between propylene homopolymer and EPR in PP‐cats. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007