Preparation and properties of ethylene/POSS copolymer with rac‐Et(Ind)2ZrCl2 catalyst

The various monovinyl‐functional polyhedral oligomeric silsesquioxane (POSS) monomers had been copolymerized with ethylene (E) using rac‐Et(Ind)₂ZrCl₂ and a modified methylaluminoxane (MMAO) cocatalyst. The unreacted POSS monomer could be removed completely by washing the copolymerization product with n‐hexane. And the copolymers were characterized with ¹H NMR, TEM, DSC, TGA, and GPC to know the composition, thermal properties, molecular weight and its distribution, respectively. According to ¹H NMR data, the monomer reactivity ratios of various POSS monomers were calculated by the Fineman‐Ross and Kelen‐Tudos methods. Thermogravimetric analysis of E/POSS copolymers exhibited an improved thermal stability with a higher degradation temperature and char yields, demonstrating that the inclusion of inorganic POSS nanoparticles made the organic polymer matrix more thermally robust. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ethylene polymerization with a silica‐supported iron‐based diimine catalyst

A supported iron‐based diimine catalyst (SC) was prepared by immobilization of 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl]pyridine iron chloride (I) on silica and employed in ethylene polymerization. The kinetic behavior of ethylene polymerization with SC was studied. The effects of the Al/Fe molar ratio, reaction temperature, and cocatalyst on the catalytic activity as well as the melting temperature, molecular weight, and morphology of the polymers obtained were also investigated. The results showed that good catalytic activities can be obtained even with a small amount of the cocatalyst methylaluminoxane (MAO) or triethylaluminum (AlEt₃). The polyethylenes obtained with a supported catalyst had higher molecular weight, higher melting temperature, and better morphology than those obtained with a homogeneous catalyst. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 466–469, 2003     

In situ copolymerization of ethylene to produce linear low‐density polyethylene by Ti(OBu)4/AlEt3‐MAO/SiO2/Et(Ind)2ZrCl2

Linear low‐density polyethylene (LLDPE) is produced in a reactor from single ethylene feed by combining Ti(OBu)₄/AlEt₃, capable of forming α‐olefins (predominantly 1‐butene), with SiO₂‐supported Et(Ind)₂ZrCl₂ (denoted MAO/SiO₂/Et(Ind)₂ZrCl₂), which is able to copolymerize ethylene and 1‐butene in situ with little interference in the dual‐functional catalytic system. The two catalysts in the dual‐functional catalytic system match well because of the employment of triethylaluminum (AlEt₃) as the single cocatalyst to both Ti(OBu)₄ and MAO/SiO₂/Et(Ind)₂ZrCl₂, exhibiting high polymerization activity and improved properties of the obtained polyethylene. There is a noticeable increment in catalytic activity when the amount of Ti(OBu)₄ in the reactor increases and 1‐butene can be incorporated by about 6.51 mol % in the backbone of polyethylene chains at the highest Ti(OBu)₄ concentration in the feed. The molecular weights (M_w), melting points, and crystallinity of the LLDPE descend as the amount of Ti(OBu)₄ decreases, which is attributed mainly to chain termination and high branching degree, while the molecular weight distribution remains within a narrow range as in the case of metallocene catalysts. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2451–2455, 2004     

Copolymerization of ethylene and in situ‐generated α‐olefins to high‐performance linear low‐density polyethylene with a two‐catalyst system supported on mesoporous molecular sieves

The manufacture of linear low‐density polyethylene (LLDPE) is of great significance in academia and industry. The employment of a single monomer, i.e. ethylene, to produce LLDPE by introducing two catalysts into one reactor to conduct ethylene copolymerization with in situ‐generated α‐olefins has proved to be an effective way in this case. Moreover, immobilization of catalysts affords LLDPE with better morphology and improved physical properties. An iron‐based diimine complex immobilized on methylaluminoxane (MAO)‐treated mesoporous molecular sieves was used to oligomerize ethylene to α‐olefins with improved selectivity to lower molar mass fractions. Based on this, zirconocene compound was also supported on mesoporous molecular sieves to comprise a two‐catalyst system to produce LLDPE from a single ethylene monomer. Copolymerization performed at both atmospheric and high pressure produced LLDPE of high molecular weight and broad molecular weight distribution without using MAO during the polymerization processes. Physical and mechanical measurements evidenced significant increases in tensile strength, tensile modulus and Izod impact strength. A marked shear‐thinning phenomenon and improved storage modulus of LLDPE produced using catalysts supported on MCM‐41 and SBA‐15 mesoporous molecular sieves indicated a stronger interfacial interaction between the molecular sieve support and the polymeric matrix. Copyright © 2010 Society of Chemical Industry     

Ethylene polymerization with iron‐based diimine catalyst supported on MCM‐41

A mesoporous molecular sieve MCM‐41 supported iron‐based diimine catalyst ( MC ) was prepared for the first time. The kinetic behavior of ethylene polymerization with MC was studied. The effects of Al/Fe molar ratio and various cocatalysts on the catalytic activity and properties of the polyethylene obtained were investigated. The results showed that good catalytic activities can be reached with cocatalyst methylaluminoxane (MAO) and triethylaluminium (TEA). Ethylene polymerization with MC gave polymers with higher molecular weight, melting temperature and onset temperatures of decomposition (T_onset) and better morphology than those obtained with the corresponding homogeneous catalyst. Copyright © 2004 Society of Chemical Industry     

Preparation of linear low‐density polyethylene by in situ copolymerization of ethylene with Zr supported on montmorillonite/Fe/methylaluminoxane catalyst system

Linear low‐density polyethylene (LLDPE) was prepared by in situ copolymerization of ethylene with dual‐functional catalysts that were composed of rac‐Et(Ind)₂ZrCl₂ supported on montmorillonite (MMT) and {[(2‐ArN?C(Me))₂C₅H₃N]FeCl₂} [Ar = 2,4‐C₆H₄(Me)₂] oligomerization catalyst. A series of polyethylenes with different degrees of branching were obtained by adjusting the ratio of Fe and Zr (Fe/Zr). DSC, NMR, GPC, SEM, and density‐gradient method were used to characterize the polymers. With increasing Fe/Zr ratio, the densities and melting points of polymers decreased, whereas the branching degrees and molecular weights increased. When the Fe/Zr ratio was increased, the activities of the catalysts decreased at atmospheric pressure and increased at 0.7 MPa ethylene pressure. SEM micrographs revealed that the morphology of branched polyethylene, produced with the catalyst supported on MMT, is better than that produced by the catalyst in a homogeneous system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1690–1696, 2004     

Recycled poly(ethylene terephthalate)/linear low‐density polyethylene blends through physical processing

Poly(styrene‐ethylene/butylene‐styrene) (SEBS) was used as a compatibilizer to improve the thermal and mechanical properties of recycled poly(ethylene terephthalate)/linear low‐density polyethylene (R‐PET/LLDPE) blends. The blends compatibilized with 0–20 wt % SEBS were prepared by low‐temperature solid‐state extrusion. The effect of SEBS content was investigated using scanning electron microscope, differential scanning calorimeter, dynamic mechanical analysis (DMA), and mechanical property testing. Morphology observation showed that the addition of 10 wt % SEBS led to the deformation of dispersed phase from spherical to fibrous structure, and microfibrils were formed at the interface between two phases in the compatibilized blends. Both differential scanning calorimeter and DMA results revealed that the blend with 20 wt % SEBS showed better compatibility between PET and LLDPE than other blends studied. The addition of 20 wt % of SEBS obviously improved the crystallizibility of PET as well as the modulus of the blends. DMA analysis also showed that the interaction between SEBS and two other components enhanced at high temperature above 130°C. The impact strength of the blend with 20 wt % SEBS increased of 93.2% with respect to the blend without SEBS, accompanied by only a 28.7% tensile strength decrease. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modifying adhesion of linear low‐density polyethylene to polypropylene by blending with a homogeneous ethylene copolymer

Adhesion of a Ziegler–Natta catalyzed ethylene copolymer (ZNPE) to polypropylene (PP) was studied by measuring the delamination toughness G of coextruded microlayers by using the T‐peel test. Low values of G compared to a homogeneous copolymer with approximately the same short chain branch (SCB) content were attributed to an amorphous interfacial layer of low molecular weight, highly branched ZNPE fractions. Blending ZNPE with a homogeneous metallocene catalyzed copolymer (mPE) increased G. In this regard, mPE with higher SCB content was more effective than mPE with slightly lower SCB content. The ZNPE interface was mimicked by microlayering ZNPE and ZNPE blends with polystyrene from which the ZNPE layers were easily separated without damage to the surface. Examination with atomic force microscopy revealed a soft coating about 8 nm thick on the surface of the ZNPE layer. Blending with mPE reduced or eliminated the amorphous interfacial layer. It was proposed that mPE increased miscibility of low molecular weight, highly branched fractions of ZNPE and prevented their segregation at the interface. After blending with mPE eliminated the interfacial layer, G increased to a value comparable to that of a homogeneous copolymer with about the same SCB content as ZNPE bulk chains. The increase in G was attributed to epitaxial crystallization of the ethylene copolymer in the absence of an amorphous interfacial layer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 109–115, 2004     

Nano‐sized silica supported Me2Si(Ind)2ZrCl2/MAO catalyst for ethylene polymerization

Nano‐sized and micro‐sized silica particles were used to support a zirconocene catalyst [racemic‐dimethylsilbis(1‐indenyl)zirconium dichloride], with methylaluminoxane as a cocatalyst. The resulting catalyst was used to catalyze the polymerization of ethylene in the temperature range of 40–70°C. Polyethylene samples produced were characterized with scanning electron microscopy (SEM), X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC). Nano‐sized catalyst exhibited better ethylene polymerization activity than micro‐sized catalyst. At the optimum temperature of 60°C, nano‐sized catalyst's activity was two times the micro‐sized catalyst's activity. Polymers obtained with nano‐sized catalyst had higher molecular weight (based on GPC measurements) and higher crystallinity (based on XRD and DSC measurements) than those obtained with micro‐sized catalyst. The better performances of nano‐sized catalyst were attributed to its large external surface area and its absence of internal diffusion resistance. SEM indicated that polymer morphology contained discrete tiny particles with thin long fiberous interlamellar links. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphology,structure, and rheological property of linear low‐density polyethylene grafted with acrylic acid

The chain structure, spherulite morphology, and rheological property of LLDPE‐g‐AA were studied by using electronspray mass spectroscopy, ¹³C–NMR, and rheometer. Experimental evidence proved that AA monomers grafted onto the LLDPE backbone formed multiunit AA branch chains. It was found that AA branch chains could hinder movement of the LLDPE main chain during crystallization. Spherulites of LLDPE became more anomalous because of the presence of AA branch chains. Rheological behavior showed that AA branch chains could act as an inner plasticizer at the temperature range of 170–200°C, which made LLDPE‐g‐AA easy to further process. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2538–2544, 2001     

Sago starch‐filled linear low‐density polyethylene (LLDPE) films: Their mechanical properties and water absorption

Composites containing various percentages of sago starch and linear low‐density polyethylene (LLDPE) have been prepared. The mechanical properties and water uptake of the composites have been determined. The tensile strength and elongation at break decreased with increase in starch content. However, the modulus of the composites increased with increase in starch content. The yield strength was not significantly affected. Moisture uptake in humid air and in water increased with increase in starch content. At higher relative humidity the composites absorbed more moisture, thus indicating that the moisture barrier properties decreased with increase in relative humidity. Moisture uptake was highest when the composites were completely immersed in water. Scanning electron microscopy (SEM) shows agglomeration of the starch granules and hence, poor wetting between the starch granules and LLDPE matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 29–37, 2001     

Study of heat shrinkability of crosslinked low‐density polyethylene/poly(ethylene vinyl acetate) blends

In this study, the heat‐shrinkage property in polymer was induced by first compounding low‐density polyethylene/poly(ethylene vinyl acetate) (LDPE/EVA) blends with various amounts of peroxide in a twin‐screw extruder at about 130°C. The resulting granules were molded to shape and chemically crosslinked by compression molding. A process of heating–stretching–cooling was then performed on the samples while on a tensile machine. Shrinkability and effective parameters were also investigated using thermal mechanical analysis. The results showed that the gel fraction was higher for the sample of higher EVA content with the same amount of dicumyl peroxide (DCP). A decrease in the melting point and heat of fusion (ΔH_f), as determined from DSC, was observed with an increase in the DCP content. Studies on the heat shrinkability of the samples showed that samples stretched above the melting point had a higher shrinkage temperature than those stretched around the crystal transition temperature. The results showed that by increasing the peroxide content, the shrinkage temperature was decreased. These could be attributed to the formation of new spherulites as well as changes in the amount and the size of crystals. Furthermore, in samples elongated at 120°C (above the melting point), the rate of stretching had no effect on the shrinkage temperature. The results showed that the extent of strain had no effect on the temperature of shrinkage, but rather on the ultimate shrinkage value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1389–1395, 2004     

In situ copolymerization of ethylene to linear low-density polyethylene (LLDPE) with calcosilicate (CAS-1) supported dual-functional catalytic system

Calcosilicate (CAS-1) was used for the first time as an effective carrier for simultaneous immobilization of a dual-functional catalytic system consisted of iron-based bis(imino) pyridyl complex (O) and zirconocene compound (C) to form heterogeneous catalyst precursor (CAS-1/O/C). The α-olefins formed form O-catalyzed ethylene oligomerization copolymerized in situ with ethylene to linear low-density polyethylene (LLDPE) under the catalysis of C in CAS-1/O/C upon addition of cocatalysts as described hereafter. Instead of methylaluminoxane (MAO), triethylaluminum (TEA) was employed to activate the copolymerization reaction with high catalytic activities and smooth kinetic process. Experimental results reflected that the selectivity for lower α-olefins was improved due to the confinement effect of the layered structures of CAS-1, hence greatly increasing the incorporation rate of α-olefins into LLDPE main chains and the branching degree accordingly during the in situ copolymerization of α-olefins and ethylene. The layered structure of CAS-1 endowed the resultant LLDPE with improved thermal stability in addition to higher molecular weights (M_n).     

Thermal properties and morphology of recycled poly(ethylene terephthalate)/maleic anhydride grafted linear low‐density polyethylene blends

Properties of recycled Poly(ethylene terephthalate) were greatly improved. Recycled PET was blended with LLDPE‐g‐MA by low‐temperature solid‐state extrusion. Mechanical properties of the blends were affected obviously by the added LLDPE‐g‐MA. Elongation at break reaches 352.8% when the blend contains 10 wt % LLDPE‐g‐MA. Crystallization behavior of PET phase was affected by LLDPE‐g‐MA content. Crystallinity of PET decreased with the increase of LLDPE‐g‐MA content. FTIR testified that maleic anhydride group in LLDPE‐g‐MA reacted with the end hydroxyl groups of PET and PET‐co‐LLDPE‐g‐MA copolymers were in situ synthesized. SEM micrographs display that LLDPE‐g‐MA phase and PET phase are incompatible and the compatibility of the blends can be improved by the forming of PET‐co‐LLDPE‐g‐MA copolymer. LLDPE‐g‐MA content was less, the LLDPE‐g‐MA phase dispersed in PET matrix fine. With the increase of LLDPE‐g‐MA content, the morphology of dispersed LLDPE‐g‐MA phase changed from spherule to cigar bar, then to irregular spherule. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Improving low‐density polyethylene/poly(ethylene terephthalate) blends with graft copolymers

Blends of low‐density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were prepared with different weight compositions with a plasticorder at 240°C at a rotor speed of 64 rpm for 10 min. The physicomechanical properties of the prepared blends were investigated with special reference to the effects of the blend ratio. Graft copolymers, that is, LDPE‐grafted acrylic acid and LDPE‐grafted acrylonitrile, were prepared with γ‐irradiation. The copolymers were melt‐mixed in various contents (i.e., 3, 5, 7, and 9 phr) with a LDPE/PET blend with a weight ratio of 75/25 and used as compatibilizers. The effect of the compatibilizer contents on the physicomechanical properties and equilibrium swelling of the binary blend was investigated. With an increase in the compatibilizer content up to 7 phr, the blend showed an improvement in the physicomechanical properties and reduced equilibrium swelling in comparison with the uncompatibilized one. The addition of a compatibilizer beyond 7 phr did not improve the blend properties any further. The efficiency of the compatibilizers (7 phr) was also evaluated by studies of the phase morphology (scanning electron microscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study on molecular chain heterogeneity of linear low‐density polyethylene by cross‐fractionation of temperature rising elution fractionation and successive self‐nucleation/annealing thermal fractionation

The molecular chain heterogeneity of commercial linear low‐density polyethylene (LLDPE) was investigated by cross‐fractionation of temperature rising elution fractionation (TREF) and successive self‐nucleation/annealing (SSA) thermal fractionation by use of DSC. The results indicate that the linear relationships between crystallinity or melting temperature and the elution temperature are confirmed by TREF fractions. Intermolecular heterogeneity exists in the original LLDPE, whereas there is less intermolecular heterogeneity in the TREF fractions. After SSA thermal fractionation, the multiple endothermic peaks for both LLDPE and their TREF fractions are mainly attributed to the heterogeneities of ethylene sequence length (ESL) and lamellar thickness. The statistical terms, including weighted mean L _w, arithmetic mean L _n, and broad index L _w/L _n, were introduced to evaluate the heterogeneities of ESL and lamellar thickness of polyethylene. The difference of broadness index indicates that TREF fractions of LLDPE have less inter‐ and intramolecular heterogeneities of both ESL and lamellar thickness than those of the original LLDPE. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1710–1718, 2004     

Copolymerization of ethylene/α‐olefins over (2‐MeInd)2ZrCl2/MAO and (2‐BzInd)2ZrCl2/MAO systems

Ethylene homopolymerization and ethylene/α‐olefin copolymerization were carried out using unbridged and 2‐alkyl substituted bis(indenyl)zirconium dichloride complexes such as (2‐MeInd)₂ZrCl₂ and (2‐BzInd)₂ZrCl₂. Various concentrations of 1‐hexene, 1‐dodecene, and 1‐octadecene were used in order to find the effect of chain length of α‐olefins on the copolymerization behavior. In ethylene homopolymerization, catalytic activity increased at higher polymerization temperature, and (2‐MeInd)₂ZrCl₂ showed higher activity than (2‐BzInd)₂ZrCl₂. The increase of catalytic activity with addition of comonomer (the synergistic effect) was not observed except in the case of ethylene/1‐hexene copolymerization at 40°C. The monomer reactivity ratios of ethylene increased with the decrease of polymerization temperature, while those of α‐olefin showed the reverse trend. The two catalysts showed similar copolymerization reactivity ratios. (2‐MeInd)₂ZrCl₂ produced the copolymer with higher M_w than (2‐BzInd)₂ZrCl₂. The melting temperature and the crystallinity decreased drastically with the increase of the α‐olefin content but T_m as a function of weight fraction of the α‐olefins showed similar decreasing behavior. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 928–937, 2000     

Crystallization of poly(ethylene oxide) embedded with surface‐modified SiO2 nanoparticles

The crystallization of poly(ethylene oxide) (PEO) in the presence of silica nanoparticles (SiO₂ NPs) was investigated in terms of heterogeneous nucleation of SiO₂ NPs using polarizing optical microscopy and differential scanning calorimetry. The content and surface functionality of SiO₂ NPs were considered as the main factors affecting crystallization, and the effect of annealing time and temperature was also examined. The SiO₂ NPs acted as heterogeneous nucleates during the crystallization process, thereby enhancing the nucleation density and limiting the spherulitic growth rate. A kinetics study of non‐isothermal crystallization showed that the crystallization rate of 5 wt% SiO₂/PEO nanocomposite was ca 2.1 times higher than that of neat PEO. In addition, among various surface‐functionalized SiO₂ nanoparticles, alkyl‐chain‐functionalized SiO₂ NPs were favorable for achieving a higher crystallization rate due to the enhanced compatibility between the SiO₂ NPs and PEO chains. © 2012 Society of Chemical Industry     

Phase structure and properties of poly(ethylene terephthalate)/high‐density polyethylene based on recycled materials

Blends based on recycled high density polyethylene (R‐HDPE) and recycled poly(ethylene terephthalate) (R‐PET) were made through reactive extrusion. The effects of maleated polyethylene (PE‐g‐MA), triblock copolymer of styrene and ethylene/butylene (SEBS), and 4,4′‐methylenedi(phenyl isocyanate) (MDI) on blend properties were studied. The 2% PE‐g‐MA improved the compatibility of R‐HDPE and R‐PET in all blends toughened by SEBS. For the R‐HDPE/R‐PET (70/30 w/w) blend toughened by SEBS, the dispersed PET domain size was significantly reduced with use of 2% PE‐g‐MA, and the impact strength of the resultant blend doubled. For blends with R‐PET matrix, all strengths were improved by adding MDI through extending the PET molecular chains. The crystalline behaviors of R‐HDPE and R‐PET in one‐phase rich systems influenced each other. The addition of PE‐g‐MA and SEBS consistently reduced the crystalline level (χ_c) of either the R‐PET or the R‐HDPE phase and lowered the crystallization peak temperature (T_c) of R‐PET. Further addition of MDI did not influence R‐HDPE crystallization behavior but lowered the χ_c of R‐PET in R‐PET rich blends. The thermal stability of R‐HDPE/R‐PET 70/30 and 50/50 (w/w) blends were improved by chain‐extension when 0.5% MDI was added. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polymerization of ethylene using a SiO2–MgCl2 supported bis(cyclopentadienyl)zirconium(IV) or titanium(IV) dichloride catalyst

Silica supported MgCl₂–Cp₂MCl₂ (M = Ti or Zr) catalysts (Si–Mg–M) were prepared by deposition of a homogeneous solution of a metallocene and anhydrous magnesium chloride in tetrahydrofuran (THF) onto a high surface area silica (SiO₂). Catalyst thus prepared show higher polymerization activity when compared to metallocenes supported on either silica or magnesium chloride alone. The molecular weight and polydispersity of the poly(ethylene)s obtained from metallocenes supported on SiO₂–MgCl₂ were found to be higher and narrower, respectively, relative to silica or MgCl₂ supported metallocene catalysts. © 2002 Society of Chemical Industry