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     

Chain structure and mechanical properties of polyethylene/polypropylene/poly(ethylene‐co‐propylene)in‐reactor alloys synthesized with a spherical Ziegler–Natta catalyst by gas‐phase polymerization

Two polyethylene/polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloy samples with a good polymer particle morphology were synthesized by sequential multistage gas‐phase polymerization with a spherical Ziegler–Natta catalyst. The alloys showed excellent mechanical properties, including both toughness and stiffness. With temperature‐gradient extraction fractionation, both alloys were fractionated into five fractions. The chain structures of the fractions were studied with Fourier transform infrared, ¹³C‐NMR, and thermal analysis. The alloys were mainly composed of polyethylene, polyethylene‐b‐polypropylene block copolymer, and polypropylene. There also were minor amounts of an ethylene–propylene segmented copolymer with very low crystallinity and an ethylene–propylene random copolymer. The block copolymer fraction accounted for more than 44 wt % of the alloys. The coexistence of these components with different structures was apparently the key factor resulting in the excellent toughness–stiffness balance of the materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 640–647, 2005     

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     

Morphology and mechanical properties of biaxially oriented films of polypropylene and HDPE blends

Biaxially oriented films of blends of high-density polyethylene (HDPE) with polypropylene (PP) homopolymer and PP copolymers prepared by twin-screw extrusion and lab-stretcher have been investigated by scanning electron microscopy (SEM), polarized microscopy, differential-scanning calorimeter, and universal testing machine. Three different kinds of PP copolymers were used: (i) ethylene–propylene (EP) random copolymer; (ii) ethylene–propylene (EP) block copolymer; (iii) ethylene–propylene–buttylene (EPB) terpolymer. In the SEM study of the morphology of films of HDPE with various PP blends, phase separation is observed between the PP phase and the HDPE phase for all blends and compositions. In all blends, HDPE serves to reduce the average spherulites size, probably acting as a nucleating agent for PP. The reduction of spherulite size appeared most significantly in the blend of EPB terpolymer and HDPE. A large increase of crystallization temperature was found in the blend of EPB terpolymer and HDPE compared with the unblended EPB terpolymer. For the blend of EPB terpolymer and HDPE, the improvement of tensile strength and modulus is observed with an increase of HDPE content, and this can be considered as a result of the role of HDPE in reducing average spherulite size. © 1994 John Wiley & Sons, Inc.     

Study on thermal behavior of impact polypropylene copolymer and its fractions

An impact polypropylene copolymer (IPC) was fractionated into three fractions using n‐octane as solvent by means of temperature‐gradient extraction fractionation. The glass transitions, melting, and crystallization behavior of these three fractions were studied by modulated differential scanning calorimeter (MDSC) and wide‐angle X‐ray diffraction (WAXD). In addition, successive self‐nucleation and annealing (SSA) technique was adopted to further examine the heterogeneity and the structure of its fractions. The results reveal that the 50°C fraction (F₅₀) mainly consists of ethylene‐propylene random copolymer and the molecular chains may contain a few of short but crystallizable propylene and/or ethylene unit sequences; moreover, the lamellae thicknesses of the resulting crystals are extremely low. Furthermore, 100°C fraction (F₁₀₀) mainly consist of some branched polyethylene and various ethylene‐propylene block copolymers in which some ethylene and propylene units also randomly arrange in certain segments, and some polypropylene segments can form crystals with various lamellae thickness. An obvious thermal fractionation effect for F₁₀₀ samples after being treated by SSA process is ascribed to the irregular and nonuniform arrangement of ethylene and propylene segments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and morphology of polyethylene/polypropylene in‐reactor alloys synthesized by spherical high‐yield Ziegler–Natta catalyst

A series of spherical polyethylene/polypropylene (PE/PP) in‐reactor alloys were synthesized with spherical high‐yield Ziegler–Natta catalyst by sequential multistage polymerization in slurry. The morphology of PE/PP alloy granule was evaluated by optical microscopy, scanning electron microscopy, and transmission electron microscopy. The results show PE/PP in‐reactor alloy with excellent morphology, high porosity, and narrow distribution of the particle size. The PE/PP in‐reactor alloys show excellent mechanical properties with good balance between toughness and rigidity. It was fractionated into five fractions by temperature‐gradient extraction fractionation, and every fractionation was analyzed by FTIR, ¹³C‐NMR, DSC, and WAXD. The PE/PP in‐reactor alloy was found to contain mainly five portions: PP, PE, segmented copolymer with PP and PE segment of different length, ethylene‐b‐propylene copolymer, and an ethylene–propylene random copolymer. The characteristic chain structure leads to good compatibility between the fractions of the alloy that shows a multiphase structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2075–2085, 2007     

Structure and properties of polypropylene alloy in situ blends

A series of polypropylene (PP) alloys containing different ethylene contents have been prepared by the in situ sequential polymerization technique, using Ziegler–Natta catalyst (MgCl₂/TiCl₄/BMF; BMF is 9,9‐bis(methoxymethyl)fluorine, as an internal donor) without any external donor. The structure and properties of PP alloys obtained have been investigated by nuclear magnetic resonance, Fourier transform infrared spectroscopy, dynamic mechanical analysis, differential scanning calorimetry, and scanning electron microscopy (SEM). The results have suggested that PP alloys are the complex mixtures containing PP, the copolymer with long sequence ethylene chain, ethylene‐propylene rubber (EPR), and block copolymer etc. In the alloys, PP, EPR, and the copolymer with long sequence ethylene chain are partially compatible. The investigation of the mechanical properties indicates that notched Izod impact strength of PP alloy greatly increases at 16°C/?20°C in comparison with that of pure PP. The noticeable plastic deformation is observed in SEM photograph. The increase in the toughness, the mechanical strength of PP alloy decreases to a certain extent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4804–4810, 2006     

Structure and properties of impact copolymer polypropylene. I. Chain structure

In this work, impact copolymer polypropylene (ICPP) was fractionated into 4 fractions. ICPP and the 4 fractions were studied using Fourier transform infrared and ¹³C nuclear magnetic resonance analysis. The results demonstrate that fraction A is ethylene–propylene rubber, fraction B is ethylene–propylene (EP) segmented copolymer, fraction C is ethylene–propylene block copolymer, and fraction D is polypropylene with a few ethylene monomers in the chain. The differences in properties between different impact copolymer polypropylenes should be due to their fractions' differences in composition and chain sequence structure. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 93–101, 1999     

Blends of polypropylene resins with a liquid crystalline polymer. I. Isothermal crystallization

The isothermal crystallization kinetics of blends of different polypropylene (PP) resins and a liquid crystalline polymer (LCP) after two different melting conditions (200 and 290°C) were studied by DSC and polarized light optical microscopy. The resins were a homopolymer (hPP), a random copolymer with ethylene (cPP), and a maleic anhydride grafted PP (gPP). The LCP was Vectra A950, a random copolymer made of 75 mol % of 4‐hydroxybenzoic acid and 25 mol % of 2‐hydroxy,6‐naphthoic acid. It was observed that the overall crystallization rates of all the blends after melting at 200°C were higher than those after melting at 290°C. The LCP acted as a nucleating agent for all the PP resins; however, its nucleating effect was stronger for the hPP than for the cPP and gPP resins. After both melting conditions, an increase was observed in the overall crystallization rate of the hPP and gPP resins with the increase in the amount of LCP, but not in the cPP crystallization rate. The fold surface free energy σ_e of hPP and cPP in the blends decreased, but increased in the gPP blends. Finally, all the PP resins formed transcrystallites on the LCP domain surfaces. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 916–930, 2003     

Chain structure of polyethylene/polypropylene in‐reactor alloy synthesized in gas phase with spherical Ziegler–Natta catalyst

Two polyethylene/polypropylene (PE/PP) in‐reactor alloy samples were synthesized by multi‐stage gas‐phase polymerization using a spherical Ziegler–Natta catalyst. The alloys show excellent toughness and stiffness. FTIR, ¹³C‐NMR and thermal analysis proved that the alloys are mainly composed of polyethylene, PE‐block‐PP copolymer and polypropylene. There are also a few percent of ethylene‐propylene segmented copolymer with very low crystallinity. The block copolymer fraction accounts for more than 25 % of the alloy. The role of the block copolymer as compatibilizer between PE and PP is believed to be the key factor that results in the excellent toughness–stiffness balance of the material. Copyright © 2004 Society of Chemical Industry     

Effect of thermomechanical history on the crystallization of poly(ether‐block‐amide)

The quiescent and flow‐induced crystallization of a poly(ether‐block‐amide) is studied by means of rheo‐optical methods. Both optical microscopy and small angle light scattering have been used. The multiblock copolymer has a microphase‐separated structure with an order–disorder transition at 180–185°C, as measured with rheometry and SAXS. The number of nuclei, spherulitic growth rates, and the characteristic time scale for crystallization are compared with that of a polyamide of similar molar mass. For the poly(ether‐block‐amide)—containing a majority of amide segments—the growth rates of the spherulites during quiescent crystallization are similar for the block copolymer and the homopolymer, even if the spherulitic structures are not the same. When flow is applied, the two materials behave differently. The flow increased the nucleation density in the homopolymer but not in the block copolymer. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Characterization of microstructure of polypropylene alloys

Two polypropylene (PP) alloys, which have similar composition, molecular weight and molecular weight distribution, but different processing and application properties, were fractionated using a preparative temperature rising elution fractionation (TREF) technique. It was found that PP alloys are mainly composed of four components: ethylene–propylene random copolymer, block-type copolymer, transition copolymer and propylene homopolymer. However, the fractionation data show that the distribution and the composition are different for these two samples. A possible mechanism is proposed for the formation of PP alloys of different compositions. Based on this mechanism, some possible adjustment of the polymerization parameters is suggested to control the microstructure. © 1998 Society of Chemical Industry     

SBS and SEBS block copolymers as impact modifiers for polypropylene compounds

Blends of polypropylene (PP) and thermoplastic elastomers (TPE), namely SBS (styrene‐butadiene‐styrene) and SEBS (styrene‐ethylene/1‐butene‐styrene) block copolymers, were prepared to evaluate the effectiveness of the TPE type as an impact modifier for PP and influence of the concentration of elastomer on the polymer properties. Polypropylene homopolymer (PP‐H) and ethylene–propylene random copolymer (PP‐R) were evaluated as the PP matrix. Results showed that TPEs had a nucleating effect that caused the PP crystallization temperature to increase, with SBS being more effective than SEBS. Microstructure characterization tests showed that in most cases PP/SEBS blends showed the smallest rubber droplets regardless of the matrix used. It was seen that SEBS is a more effective toughening agent for PP than SBS. At 0°C the Izod impact strength of the PP‐H/SEBS 30% b/w blend was twofold higher than the SBS strength, with the PP‐R/SEBS 30% b/w blend showing no break. A similar behavior on tensile properties and flexural modulus were observed in both PP/TPE blends. Yield stress and tensile strength decreased and elongation at break increased by expanding the dispersed elastomeric phase in the PP matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 254–263, 2005     

Crystallization behavior of dry‐brush PEO‐PS block copolymer and PEO homopolymer blend

The crystallization behavior of semicrystalline PEO homopolymer/triblock PS‐PEO‐PS copolymer blend system, which exhibited “Dry‐Brush” in the melt. A symmetric polystyrene–poly(ethylene oxide)–polystyrene triblock copolymer was blended with PEO homopolymer (h‐PEO) having the same molecular weight as that of the PEO block in the copolymer. Considering the composition of the blend (W_ps ≥ 0.8), PEO spheres were formed in the blend. Because of the dry‐brush phase behavior of this blend, h‐PEO added was localized in the PEO microdomains, which increases the domain size without changing the microdomain morphology. The crystallization of PEO block was confined within the microdomains and the crystallization temperature was about 60°C lower than normal. Self‐seeding tests were performed to clarify the nucleation mechanism of the blend. Because the droplets size varies greatly, multicrystallization peaks were witnessed in the self‐seeding process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Studies of thermal oxidative degradation of polypropylene impact copolymer using the temperature rising elution fractionation method

Thermal oxidative degradation of polypropylene impact copolymer has been studied with its fractions obtained using the temperature rising elution fractionation method. The fractions were analyzed using ¹³C NMR, Fourier transform infrared and differential scanning calorimetry measurements, and the chemical structure, isotacticity, conformation and melting point were investigated. It is found that these fractions are composed of a homopolymer or a polymer blend of polypropylene, polyethylene and ethylene–propylene copolymer. The thermal oxidative degradation of each fraction was carried out at 130 °C, and the degradation progress was estimated by the change of molecular weight distribution (from gel permeation chromatography curves). The rate of degradation is found to be dominated by the content of tertiary C? H bonds (propylene unit) and the existence of 3₁ helix conformation corresponding to a crystalline polypropylene part in each fraction. The latter is more evident leading to the degradation reaction path with a lower activation energy. Copyright © 2007 Society of Chemical Industry     

Influence of polymerization conditions on the structure and properties of polyethylene/polypropylene in‐reactor alloy synthesized in the gas phase with a spherical Ziegler–Natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of in‐reactor polyethylene/polypropylene alloys by polyethylene homopolymerization and subsequent homopolymerization of propylene in the gas phase. Different conditions in the ethylene homopolymerization stage, such as monomer pressure and polymerization temperature, were investigated, and their influences on the structure and properties of in‐reactor alloys were studied. Raising the polymerization temperature is the most effective way of speeding up polymerization and regulating the ethylene content of polyethylene (PE)/polypropylene (PP) alloys, but it will cause a greater increase in the PE‐b‐PP block copolymer fraction (named fraction D) than in the fraction of PP‐block‐PE in which the PP segments have low or medium isotacticity (named fraction A). Although changing ethylene monomer pressure could influence the ethylene content of PE/PP alloys slightly, it is an effective way of regulating the structural distribution. Reducing the monomer pressure will evidently increase fractions A and D. The mechanical properties of the alloys, including impact strength and flexural modulus, can be regulated in a broad range with changes in polymerization conditions. These properties are highly dependent on the amount, distribution, and chain structure of fractions A and D. The impact strength is affected by both fraction A and fraction D in a complicated way, whereas the flexural modulus is mainly determined by the amount of fraction A. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2136–2143, 2006     

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     

Crystallization,melting behavior,and morphology of BPP/HDPE blend

The crystallization, melting behavior, and morphology of a low ethylene content block propylene–ethylene copolymer (BPP) and a high-density polyethylene (HDPE) blend were studied. It was found that the existence of ethylene–propylene rubber (EPR) in BPP has more influence on the crystallization of HDPE than on that of PP. This leads to the decreasing of the melting temperature of the HDPE component in the blends. It is suggested that the EPR component in BPP shifted to the HDPE component during the blending process. The crystallinity of the HDPE phase in the blends decreased with increasing BPP content. The morphology of these blends was studied by polarized light microscopy (PLM) and SEM. For a BPP-rich blend, it was observed that the HDPE phase formed particles dispersed in the PP matrix. The amorphous EPR chains may penetrate into HDPE particles to form a transition layer. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2469–2475, 1998     

Fractionation and characterization of an ethylene–propylene copolymer produced with a MgCl2/SiO2/TiCl4/diester‐type ziegler–natta catalyst

An ethylene–propylene copolymer synthesized with a Ziegler–Natta catalyst was fractionated by a combination of dissolution/precipitation and temperature‐gradient extraction fractionation. The fractions were characterized with ¹³C‐NMR, differential scanning calorimetry, and wide‐angle X‐ray diffraction. The fractionation was carried out mainly with respect to the content of ethylene, but the crystallizable propylene sequences could also exert an influence on the fractionation. The copolymer contained a series of components with wide variations in the compositions. With an increase in the ethylene content, the structure of the fractions became blockier and blockier, and the fraction extracted at 111°C had the blockiest structure. A further increase in the ethylene content led to a decrease in the length and number of the propylene sequences. Differential scanning calorimetry results showed that the composition distribution in single fractions was not homogeneous, and multiple melting peaks were observed. Wide‐angle X‐ray diffraction results revealed both polyethylene and polypropylene crystals in most of the fractions. Short propylene sequences could be included in the polyethylene crystals, and short ethylene sequences could also be incorporated into the polypropylene crystals. The incorporation of propylene sequences into polyethylene crystals strongly depended on the sequence distribution and crystallization conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Evaluation of olefinic block copolymer blends with amorphous polyolefins—effect of different unsaturated and saturated hydrocarbon tackifier resins on blend miscibility

Blends of ethylene–octene based olefinic block copolymer (OBC) with two amorphous polyolefin (APO) polymers [atactic propylene homopolymer (PP) and ethylene–propylene copolymer (PE–PP)] were evaluated at three different ratios. Dynamic mechanical analysis (DMA) and transmission electron microscopy (TEM) evaluations were performed to determine the blend miscibility characteristics. Viscoelastic properties of both OBC blends with PP polymer, and OBC blends with PE–PP copolymer showed incompatibility. Analysis revealed that both blends formed two phase morphologies. The effect of three unsaturated aliphatic hydrocarbon resins with varying aromatic content and two saturated hydrocarbon resins with different chemistries were evaluated as compatibilizing agent for OBC/PP and OBC/PE–PP blends. A 1 : 1 polymer blend ratio of OBC/PP and OBC/PE–PP was selected to better understand the influence of resin addition at three different levels 20, 30, and 40 wt %. The fully aliphatic unsaturated resin seems to improve the miscibility of the OBC/PP blends at higher resin addition levels, but reduced the miscibility as the aromatic content of the resin increases. However, OBC/PE–PP blends showed improved miscibility with increasing aromatic content. A ternary phase morphology was particularly observed for both OBC/PP and OBC/PE–PP blends with highly aromatic (14%) unsaturated hydrocarbon resin, in which OBC formed the continuous phase, and PP, PE–PP, and unsaturated hydrocarbon resins formed the dispersed phase. Interestingly, we did not observe much difference in miscibility characteristics between the two saturated resin chemistries in both blend systems (OBC/PP and OBC/PE–PP). The Harkins spreading coefficient concept was used to better understand the ternary blend dispersed phase morphology. Spreading coefficients indicate that the free hydrocarbon resins (both unsaturated and saturated) were encapsulated by the amorphous PP or amorphous PE–PP polymer in the dispersed phase for the respective blend compositions. Overall OBC–PP and OBC/PE–PP blends showed better miscibility characteristics with both saturated aliphatic hydrocarbon resins, irrespective of the difference in resin chemistries. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2624–2644, 2013