Structure of cyclopentene unit in the copolymer with propylene obtained by stereospecific zirconocene catalysts

Copolymerization of propylene and cyclopentene (CPE) was carried out using as a catalyst isospecific rac-ethylenebis(indenyl)zirconium dichloride (1), rac-dimethylsilylenebis(indenyl)zirconium dichloride (2), rac-dimethylsilylenebis(2-methylindenyl)zirconium dichloride (3), or syndiospecific diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (4) with methylaluminoxane as a cocatalyst. Isospecific zirconocene catalysts 1-3 produced copolymers having narrow molecular weight distribution, while syndiospecific catalyst 4 effected propylene homopolymerization. Microstructures of the copolymers were studied by ¹³C NMR and distortionless enhancement of polarization transfer (DEPT) spectroscopy. CPE was found to be incorporated in the copolymer preferentially via 1,2-insertion mechanism in the copolymerization with the catalyst 3. The catalyst 1 and 2 gave copolymers containing CPE units formed by either 1,2-insertion or 1,3-insertion mechanism. The proportion of 1,3-insertion units increased with increasing CPE content in the copolymers. The isomerization reaction from 1,2-insertion to 1,3-insertion CPE units was discussed on the basis of kinetic parameters.     

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     

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.     

Behavior of poly(ethylene‐co‐olefin) polymers as elastomeric materials

The properties of two new ethylene‐α‐olefin copolymers, namely, ethylene–1‐hexene copolymer (EHC) and ethylene–1‐octadecene copolymers (EOC), synthesized via metallocene catalysts were evaluated. The copolymerization was carried out in an autoclave reactor with Et(Indenyl)₂ZrCl₂/methylaluminoxane as a catalyst system. These single‐site catalysts (metallocene type) allow one to obtain very homogeneous copolymers with excellent control of the molecular weight distribution and proportion of comonomer incorporation. So, copolymers with 18 mol % comonomer in the case of EHC and 12 mol % for EOC were shaped, and activities around 100,000 kg of polymer mol^?1 of Zr bar^?1 h^?1 were reached. The properties of these copolymers were compared with other commercial elastomers, such as ethylene–propylene copolymers synthesized by Ziegler–Natta catalysts and an ethylene–octene copolymer obtained via metallocene catalysts. The results show that these new copolymers, in particular, EOC, had excellent elastomeric properties. Furthermore, they had a relatively low viscosity, which implied a good response during processing. Moreover, the effectiveness of these copolymers as impact modifiers for polyolefins was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3008–3015, 2004     

Influence of the longest ethylene and isotactic propylene sequences on crystallization elution fractionation of ethylene/propylene copolymers

Crystallization elution fractionation (CEF) is the newest crystallization-based technique for estimating the chemical composition distribution of ethylene/1-olefin copolymers. Understanding the separation mechanism of CEF for ethylene/propylene copolymers over their full compositional range is challenging because the crystallizabilities of the copolymer chains depend on the longest ethylene sequence and on longest isotactic propylene sequence. We developed a mathematical model to describe the CEF mechanism for ethylene/propylene copolymers over the entire compositional range using population balances for the crystallization and dissolution stages. The joint distribution of longest ethylene and isotactic propylene sequences determines how the copolymer populations crystallize and dissolve. The model was validated with experimental CEF profiles of ethylene/propylene copolymers varying from pure ethylene to propylene homopolymers.     

Copolymerization of ethylene and propylene catalyzed by novel magnesium chloride supported,vanadium‐based catalysts

Two novel magnesium chloride supported, vanadium‐based Ziegler–Natta catalysts with 9,9‐bis(methoxymethyl)fluorene and di‐i‐butyl phthalate as internal donors were prepared and used in the copolymerization of ethylene and propylene. The catalytic behaviors of these catalysts were investigated and compared with those of traditional magnesium chloride supported, vanadium‐based catalysts without internal donors. Differential scanning calorimetry, gel permeation chromatography, and ¹³C‐NMR spectroscopy analysis were performed to characterize the melting temperatures, molecular weights, and molecular weight distributions as well as structures and compositions of the products. The copolymerization kinetic results indicated that the novel catalyst with 9,9‐bis(methoxymethyl)fluorene as an internal donor had the highest catalytic activity and optimal kinetic behavior in ethylene–propylene copolymerization with an ethylene/propylene molar ratio of 44/56. Low‐crystallinity and high‐molecular‐weight copolymers were obtained with these novel magnesium chloride supported, vanadium‐based catalysts. The reactivity ratio data indicated that the catalytic systems had a tendency to produce random ethylene–propylene copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Graft copolymers of poly(methyl methacrylate) backbone and poly(propylene oxide-b-ethylene oxide) branches

Summary Two mono-functional macromonomers of poly (propylene oxide-b-ethylene oxide) were synthesized by reaction with methacryloyl chloride. The macromonomers have the same molecular weight and ratio of ethylene oxide and propylene oxide sequences. The reactive methacrylate group can be linked to the ethylene oxide (BuPPOPEO) or to the propylene oxide (BuPEOPPO). These macromonomers showed self-gelling in one week even at low temperature and under a dry atmosphere. Graft copolymers were obtained by reaction of these macromonomers with methyl methacrylate upon free-radical initiation and they were characterized by GPC, VPO, IR and ¹H NMR spectra.     

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     

Determination of monomer sequence distribution in EPDM by 13C‐NMR: Third monomer effects

The methods for sequencing ethylene–propylene copolymers (EPMs) by ¹³C‐NMR were extended to account for third monomer effects. The equations for calculating the ethylene content and monomer sequence distribution in EPMs were corrected for the presence of the third monomers 1,4 hexadiene, 2‐ethylidene‐5‐norbornene, and 5,8‐dicyclopentadiene that display resonances that overlap with the main chain EPM carbons. These corrections dramatically reduce the standard deviation among equivalent calculation methods. We also examined the effects of experimental conditions on the sequencing data including the choice of solvent, Cr³⁺ doping, and the presence of the nuclear Overhauser effect. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 523–530, 1999     

Polymerization and characterization of ethylene/propylene and ethylene/1-octene copolymers produced with bridged Zr- and Hf-based metallocenes

Ethylene/propylene (E/P) and ethylene/1-octene (E/O) copolymers were polymerized with two bridged metallocene catalyst systems, Et(Ind)₂ZrCl₂/MAO and Et(Ind)₂HfCl₂/MAO, respectively. The copolymers produced and some commercial reference copolymers were characterized by DSC, SEC, DMA and ¹³C NMR. The Hf-catalysed E/P polymerizations showed much lower activities than the corresponding Zr-catalysed polymerizations but gave polymers with high molar mass. The Hf-based copolymers also showed two melting peaks which may be indicative of several active sites of the catalyst. A comparison of E/P copolymers, containing about 20 mol-% propylene and produced with Zr, Hf and homogeneous V-catalysts, respectively, indicated that the Hf and V-catalysts gave material more similar to each other. The E/O copolymers produced with Zr-catalysts gave very low molar masses and the reactivity ratios, calculated from the NMR data, indicated that the Hf-catalyst has a slightly higher reactivity for 1-octene and the Zr-catalyst some better reactivity for ethylene. Segregation fractionation studies by DSC indicated that a lower 1-octene feed gives more heterogeneous copolymers and the DMA measurements reveal the existence of a linear correlation between the 1-octene content and the intensity of the tan δ_max peak.     

Dynamic mechanical and rheological properties of metallocene-catalyzed long-chain-branched ethylene/propylene copolymers

The dynamic mechanical and rheological properties of five long-chain branched (LCB) and three linear ethylene/propylene (EP) copolymers were investigated and compared using a dynamic mechanical analyzer (DMA) and an oscillatory rheometer. The novel series of LCB EP copolymers were synthesized with a constrained geometry catalyst (CGC), [C₅Me₄(SiMe₂N^tBu)]TiMe₂, and had various propylene molar fractions of 0.01-0.11 and long-chain branch frequencies (LCBF) of 0.05-0.22. The linear EP copolymers were synthesized with an ansa-zirconocene catalyst, rac-Et(Ind)₂ZrCl₂ (EBI), and contained similar levels of propylene incorporation as the CGC copolymers, but no LCB. In dynamic mechanical analysis, the dynamic storage moduli (G′) and loss moduli (G″) of the copolymers decreased with an increase of propylene molar fraction. The α- and β-transitions of the CGC copolymers were overlaid with each other. High damping (tan δ) values were found with the CGC copolymers at temperatures below 0 °C. In oscillatory rheological analysis, compared to the linear EBI counterparts, the LCB CGC copolymer melts showed higher zero shear activation energies, broader plateaus of δ and larger elastic contributions, which are essential characteristics of LCB polymers. It was found that the long chain branching was the determining factor in controlling rheological properties of the polymer melts while the short chain branching from propylene incorporation played a decisive role in affecting dynamic mechanical properties. This work represents the first rheological evidence of LCB in EP copolymers synthesized with CGC.     

Influence of the structure and composition on surface tension of aqueous solution of graft copolymers of polyacrylamide backbone and polyalkyleneoxide branches

Polyacrylamide homopolymers and graft copolymers of poly(acrylamide-g-ethylene oxide) and poly(acrylamide-g-propylene oxide) were synthesized, characterized by SEC, FTIR and ¹³C-NMR and the behavior of their aqueous solutions was evaluated by surface tension measurements. By using the macromonomer technique, it is more difficult to incorporate poly(propylene oxide) branches than poly(ethylene oxide) branches. Graft copolymers of polyacrylamide and poly(propylene oxide) showed higher reduction of surface tension than poly(acrylamide-g-ethylene oxide) since they present a structure made up of hydrophilic and hydrophobic segments. Poly(acrylamide-g-propylene oxide) exhibits surfactant behavior, and the surface tension of its aqueous solution depends on the poly(propylene oxide) graft chain length and amount. Received: 9 December 1996/Revised: 15 May 1997/Accepted: 23 May 1997     

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.     

Crystalline characteristics of ethylene/propylene/1,4-hexadiene terpolymers and related ethylene copolymers

An improved differential thermal analytical technique which permits the rapid, convenient characterization of the thermal behavior of crystalline polymers free of any influence of prior thermal history is presented. Characterization of both crystallization and fusion phenomena is described for ethylene/propylene copolymers subjected to well-controlled thermal scanning techniques. Parameters describing these phenomena are derived. While they are nonequilibrium parameters, they are reproducible and capable of correlation with polymer composition. the crystallization onset temperature determined by this cooling technique was found to relate to the molar ethylene content of the copolymers by an equation similar to the one derived by Flory⁵ based on equilibrium melting point. The relationship was found to hold true for a number of ethylene copolymers, including samples of linear and branched polyethylene, commercial EPDM, and ethylene/vinyl acetate copolymers.     

Thermal fractionation and effect of comonomer distribution on the crystal structure of ethylene-propylene copolymers

In this paper the comonomer distributions of two series of ethylene-propylene copolymers with different propylene contents, which were prepared by a fluorinated bis(phenoxyimine) Ti catalyst (FI-EP copolymers) and a conventional Ziegler-Natta catalyst (ZN-EP copolymers), respectively, were characterized. It is found that the comonomer distribution of ethylene-propylene copolymers can still be characterized by thermal fractionation at a long scale, though the propylene units can be incorporated into the PE crystal lattice. The FI-EP copolymers exhibit a narrow and random comonomer distribution, whereas a broad comonomer distribution is observed for the ZN-EP copolymers. The crystal structures of the FI-EP and ZN-EP copolymers were studied by WAXD. The a-axis of the PE crystals of the FI-EP copolymers increases rapidly with propylene content, indicating that more propylene units are incorporated into the PE crystal lattice, whereas only a slight expansion in a-axis is observed for the ZN-EP copolymers. WAXD result also shows the presence of hexagonal phase in the FI-EP copolymers and the relative content of the hexagonal phase increases with the propylene content, while in the ZN-EP copolymers the hexagonal phase is negligible.     

Stepwise polymerization of propylene and ethylene with Cr(acetylacetonate)3/MgCl2–ethylbenzoate/diethylaluminium chloride catalyst system

During propylene polymerization with the Cr(acetylacetonate)₃/MgCl₂–Et₂AlCl–ethylbenzoate catalyst system which shows high isospecificity for propylene polymerization, it was found that the chain transfer and termination reactions can be neglected. Based on this result, some stepwise polymerizations of propylene and ethylene were carried out with the same catalyst system varying polymerization conditions. The resulting copolymers were separated by temperature rising elution fractionation (TREF) and afforded two fractions which were eluted at different temperatures. From the ¹³C NMR, DSC and GPC analyses of each fraction, it was considered that the corresponding block copolymer existed in the fraction eluted at higher temperature. © 2003 Society of Chemical Industry     

Synthesis,characterization, and properties of two‐component amphiphilic polyoxyethylene–containing multiblock copolymers

Amphiphilic (oxyethylene–oxypropylene) and (oxyethylene–styrene) multiblock copolymers, both with high molecular weights, were synthesized by coupling poly(ethylene glycol) (PEG) with poly(propylene glycol) (PPG) or with telechelic dihydroxy polystyrene using 2,4‐toluene diisocyanate as a coupling agent, respectively. The polymerization conditions were investigated. The products were purified and characterized by IR, ¹H‐NMR spectroscopy, and membrane osmometry and identified as multiblock copolymers. Crystallinity of the two kinds of multiblock copolymers was determined by DSC. They showed good emulsifying properties. Their complexes with LiClO₄ showed high room‐temperature conductivities from 3 × 10⁻⁵ to 4 × 10⁻⁴ S/cm at 30°C. High molecular weight (oxyethylene–oxypropylene) multiblock copolymers, at a weight ratio of PEG/PPG = 6/4, behave like thermoplastic elastomers. The (oxyethylene–styrene) copolymer functions as a good compatibilizer for the blend of chlorohydrin rubber and polystyrene. An amount of only 3 wt %, based on the blend, is needed to increase the tensile strength of the blend almost sixfold. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1295–1301, 2005     

Determination methods of the grafting yield in glycidyl methacrylate‐grafted ethylene/propylene/diene rubber (EPDM‐g‐GMA): Correlation between FTIR and 1H‐NMR analysis

A normalized and universally applicable calibration function for the Fourier‐transformed infrared (FTIR) quantification of the glycidyl methacrylate (GMA) grafting yield in polymers of known compositions having ethylene block sequences was established. The ¹H nuclear magnetic resonance (¹H‐NMR) spectroscopy results achieved on different GMA‐grafted ethylene/propylene/diene rubber (EPDM‐g‐GMA) and ethylene/GMA copolymers were correlated to their FTIR data to calibrate the relative determination of the FTIR method. Both direct and indirect standardization approaches were followed and evaluated. The calibration deduced was used to investigate the free radical grafting reaction of GMA on EPDM rubber in the melt phase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2616–2624, 1999     

Synthesis of polar vinyl monomer–olefin copolymers by α‐diimine nickel catalyst

Vinyl acetate, methyl methacrylate, acrylonitrile and methyl vinyl ketone were investigated for co‐ and terpolymerization with ethylene and ethylene–propylene. Precursor [bis(N,N ′‐dimesitylimino)acenaphthene]dibromonickel, activated by methylaluminoxane was used as a catalyst system and trialkylaluminium was employed to block the polar groups for these polymerizations. Polymerization activities of the order of magnitude of 10⁶ in the case of vinyl acetate and methyl methacrylate, and 10⁵ in the case of acrylonitrile were achieved. Microanalysis and GPC of acrylonitrile copolymers found about 17 units of acrylonitrile per polymer chain. Copolymers with very different properties from the parent homopolymers were obtained in all cases except that of methyl vinyl ketone. © 2001 Society of Chemical Industry     

Multilayered core–shell structure of the dispersed phase in high‐impact polypropylene

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