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1.
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  相似文献   

2.
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  相似文献   

3.
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  相似文献   

4.
Four polyolefin in‐reactor alloys with different compositions and structures were prepared by sequential polymerization. All the alloys were fractionated into five fractions: a random copolymer of ethylene and propylene (25°C fraction), an ethylene–propylene segmented copolymer (90°C fraction), an ethylene homopolymer (110°C fraction), an ethylene–propylene block copolymer (120°C fraction), and a propylene homopolymer plus a minor ethylene homopolymer of high molecular weight (>120°C fraction). The effect of the structure on the morphology and spherulitic growth kinetics of the polypropylene (PP) component in the alloys was investigated. The polyolefin alloys containing a suitable block copolymer fraction and a larger amount of PP had a more homogeneous morphology, and the crystalline particles were smaller. Quenching the polyolefin alloys led to smaller crystallites and a more homogeneous morphology as well. Isothermal crystallization was carried out above the melting temperature of polyethylene, and the growth of PP spherulites was monitored with polarized optical microscopy with a hot stage. The alloys with higher propylene contents exhibited a faster spherulitic growth rate. The fold surface free energy was derived, and it was found that a large amount of block copolymer fractions and random copolymer fractions could reduce the fold surface free energy. The structure of the alloys also affected the crystallization regime of PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 632–638, 2005  相似文献   

5.
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  相似文献   

6.
In this work, high melt flow rate (MFR) polypropylene (HF‐PP) and polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys (HF‐PP/EPR) with MFR ≈ 30 g/10 min were synthesized by spherical MgCl2‐supported Ziegler–Natta catalyst with cyclohexylmethyldimethoxysilane (CHMDMS) or dicyclopentyldimethoxysilane (DCPDMS) as external donor (De). The effects of De on polymerization activity, chain structure, mechanical properties, and phase morphology of HF‐PP and HF‐PP/EPR were studied. Adding CHMDMS caused more sensitive change of the polymers MFR with H2 than DCPDMS, and produced PP/EPR alloys containing more random ethylene‐propylene copolymer (r‐EP) and segmented ethylene‐propylene copolymer (s‐EP). CHMDMS also caused formation of s‐EP with higher level of blockiness than DCPDMS. HF‐PP/EPR alloy prepared in the presence of DCPDMS exhibited higher flexural properties but lower impact strength than that prepared with CHMDMS. Toughening efficiency of the rubber phase was nearly the same in the alloys prepared using CHMDMS or DCPDMS as De, but stiffness of the alloy can be improved by using DCPDMS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42984.  相似文献   

7.
The multiphase morphology of high impact polypropylene (hiPP), which is a reactor blend of polypropylene (PP) with ethylene–propylene copolymer, was investigated by transmission electron microscopy, selected area electron diffraction, atomic force microscopy, and field‐emission scanning electron microscopy techniques in conjunction with an analysis of the hiPP composition and chain structure based on solvent fractionation, 13C‐NMR, and differential scanning calorimetry measurements. A multilayered core–shell structure of the dispersed phase of hiPP in solution‐cast films and the bulk was observed. The inner core was mainly composed of polyethylene (including its long blocks) together with part of PP, the intermediate layer was ethylene–propylene random copolymer, and the outer shell consisted of ethylene–propylene multiblock copolymers. The formation process and controlling factors of the multilayered core–shell structure are discussed. This kind of multiphase morphology of hiPP caused the material to possess both a high rigidity and high toughness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

8.
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  相似文献   

9.
Blends of isotactic polypropylene (PP), ethylene‐propylene rubber copolymer (EPR), and ethylene‐propylene crystalline copolymer (EPC) can be produced through in situ polymerization processes directly in the reactor and blends with different structure and composition can be obtained. In this work we studied the structure of five reactor‐made blends of PP, EPR, and EPC produced by a Ziegler‐Natta catalyst system. The composition of EPR was related to the ratio between ethylene and propylene used in the copolymerization step. The ethylene content in the EPR was in the range of 50–70 mol %. The crystallization behavior of PP and EPC in the blends was influenced by the presence of the rubber, and some specific interactions between the components could be established. By preparative temperature rising elution fractionation (P‐TREF) analysis, the isolation and characterization of crystalline EPC fractions were made. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2155–2162, 2004  相似文献   

10.
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  相似文献   

11.
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  相似文献   

12.
In this work, a series of polypropylene/poly(ethylene‐co‐propylene) (iPP/EPR) in‐reactor alloys were prepared by MgCl2/TiCl4/diester type Ziegler‐Natta catalyst with triethylaluminium/triisobutylaluminium (TEA/TIBA) mixture as cocatalyst. The influence of cocatalyst and external electron donor, e.g., diphenyldimethoxysilane (DDS) or dicyclopentyldimethoxysilane (D ‐donor), on the structure and mechanical properties of iPP/EPR in‐reactor alloys were studied and discussed. According to the characterization results, PP/EPR was mainly composed of random poly(ethylene‐co‐propylene), segmented poly(ethylene‐co‐propylene), and high isotactic PP. Using TEA/TIBA mixture as cocatalyst and DDS as external electron donor, as TEA/TIBA ratio increased, the impact strength of iPP/EPR in‐reactor alloys had an increasing trend. Using TEA/TIBA mixture as cocatalyst and D ‐donor as external electron donor, the impact strength of iPP/EPR in‐reactor alloy were dramatically improved. In this case, the iPP/EPR in‐reactor alloy prepared at TEA: TIBA = 4 : 1 was the toughest. The influence of cocatalyst and external electron donor on the flexural modulus and flexural strength could be ignored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

13.
In this research, the reinforcement of polypropylene (PP) was studied using a new method that is more practical for synthesizing polypropylene‐block‐poly(ethylene‐propylene) copolymer (PP‐co‐EP), which can be used as a rubber toughening agent. This copolymer (PP‐co‐EP) could be synthesized by varying the feed condition and changing the feed gas in the batch reactor system using Ziegler–Natta catalysts system at a copolymerization temperature of 10°C. The 13C‐NMR tested by a 21.61‐ppm resonance peak indicated the incorporation of ethylene to propylene chains that could build up the microstructure of the block copolymer chain. Differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and dynamic mechanical analysis (DMA) results also confirmed these conclusions. Under these conditions, the morphology of copolymer trapped in PP matrix could be observed and the copolymer Tg would decrease when the amount of PP‐co‐EP was increased. DMA study also showed that PP‐co‐EP is good for the polypropylene reinforcement at low temperature. Moreover, the PP‐co‐EP content has an effect on the crystallinity and morphology of polymer blend, i.e., the crystallinity of polymer decreased when the PP‐co‐EP content increased, but tougher mechanical properties at low temperature were observed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3609–3616, 2007  相似文献   

14.
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  相似文献   

15.
A series of isotactic polybutene‐1/polypropylene (PB/PP) alloys with spherical morphology were prepared by MgCl2‐supported Ziegler‐Natta catalyst with sequential two‐stage polymerization technology. The first formed PP particles were used as micro‐reactors to initiate the bulk precipitation polymerization of butene‐1 further. The porous PP particles as a hard framework may prevent the adhesion of PB particles during the bulk precipitation polymerization process. At the same time, the bulk precipitation polymerization process allows for maximization of the butene‐1 polymerization rate and simplifies the butene‐1 polymerization process considerably. Finally, spherical PB alloys with a super‐high molecular weight PB component and adjustable PP component were synthesized in situ within the reactor. The structures and properties of the PB/PP alloys were characterized by gel permeation chromatography, 13C nuclear magnetic resonance, Fourier transform IR, scanning electron microscopy, differential scanning calorimetry and X‐ray diffraction. The results showed that the MgCl2‐supported Ziegler‐Natta catalyst showed relatively high stereospecificity and efficiency for both propylene and butene‐1 polymerization. The incorporation of propylene on the PB matrix affects the properties of the final products markedly. The PB/PP alloys are expected to have a broader range of applications as a new family of high performance materials. Copyright © 2012 Society of Chemical Industry  相似文献   

16.
Some polyolefin elastomers were compared as compatibilizers for blends of polypropylene (PP) with 30 wt % high‐density polyethylene (HDPE). The compatibilizers included a multiblock ethylene–octene copolymer (OBC), two statistical ethylene–octene copolymers (EO), two propylene–ethylene copolymers (P/E), and a styrenic block copolymer (SBC). Examination of the blend morphology by AFM showed that the compatibilizer was preferentially located at the interface between the PP matrix and the dispersed HDPE particles. The brittle‐to‐ductile (BD) transition was determined from the temperature dependence of the blend toughness, which was taken as the area under the stress–strain curve. All the compatibilized blends had lower BD temperature than PP. However, the blend compatibilized with OBC had the best combination of low BD temperature and high toughness. Examination of the deformed blends by scanning electron microscopy revealed that in the best blends, the compatibilizer provided sufficient interfacial adhesion so that the HDPE domains were able to yield and draw along with the PP matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

17.
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  相似文献   

18.
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  相似文献   

19.
The solution fractionation of ethylene–propylene copolymerization products was simulated by assuming an appropriate partition relationship for the polymer distribution between the two liquid phases and by using data for the molecular weight dependence of the solubility. Bivariate and log normal distribution functions were assumed for the polydispersities of the copolymer and the homopolymers, respectively. The products can be classified into five types: copolymer (EP), polyethylene–polypropylene (PE–PP), polypropylene–copolymer (PP–EP), polypropylene–copolymer–polyethylene(PP–EP–PE), and copolymer–polyethylene (EP–PE). The present work is mainly concerned with the latter three types. The experimental results, which could not be explained earlier in terms of pure EP or PE–PP blends, could be explained by the present computer analysis. Thus, even though the distribution curves vary in a complicated way with the component types and the ratios of amounts present, analysis of this kind should be useful for understanding the nature of unknown samples. Finally, the possibility of isolating pure components by solution fractionation is discussed.  相似文献   

20.
The effect of addition of propylene copolymer, produced by metallocene catalysts, on the mechanical, rheological, and morphological properties of blends based on poly(propylene) (PP) and ethylene–1‐octene copolymer (EOC) was evaluated. It was observed that the addition of 2 wt % propylene–1‐octene copolymer (POC) improved the impact strength of the EOC/PP blends. The rheological analysis indicated that the addition of propylene copolymer produced materials with improved processability. Thermal and morphological analysis showed that the POC acts as a compatibilizer on the EOC/PP blends. © 2003 Wiley Periodicals, J Appl Polym Sci 89: 1690–1695, 2003  相似文献   

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