Copolymerization of propylene with 1‐octene catalyzed by MgCl2/TiCl4/diether catalyst

MgCl₂/TiCl₄/diether is a fifth‐generation Ziegler–Natta catalyst for the commercial polymerization of propylene. The outstanding features of this catalyst are the high activity and high isotacticity for propylene polymerization without using an external electron donor. In this study, we explored the copolymerization of propylene and 1‐octene with MgCl₂/TiCl₄/diether catalyst. It was found that MgCl₂/TiCl₄/diether catalyst showed higher polymerization activity and led to greater 1‐octene content incorporation, compared with a fourth‐generation Ziegler–Natta catalyst (MgCl₂/TiCl₄/diester). With an increase in 1‐octene incorporation in polypropylene chains, the melting temperature, glass transition temperature and crystallinity of the copolymers decreased distinctly. The microstructures of the copolymers were characterized using ¹³C NMR spectroscopy, and the copolymer compositions and number‐average sequence lengths were calculated from the dyad concentration and distribution. This result is very important for the in‐reactor polyolefin alloying process, especially for the case of a single catalyst and two‐step (or two‐reactor) process. Copyright © 2011 Society of Chemical Industry     

Synthesis mechanisms of poly[styrene‐co‐(acrylic acid)]‐supported TiCl4 catalysts modified by magnesium compounds

Soluble poly[styrene‐co‐(acrylic acid)] (PSA) modified by magnesium compounds was used to support TiCl₄. For ethylene polymerization, four catalysts were synthesized, namely PSA/TiCl₄, PSA/MgCl₂/TiCl₄, PSA/(n‐Bu)MgCl/TiCl₄, and PSA/(n‐Bu)₂Mg/TiCl₄. The catalysts were characterized by a set of complementary techniques including X‐ray photoelectron spectroscopy, Fourier‐transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy, and element analysis. Synthesis mechanisms of polymer‐supported TiCl₄ catalysts were proposed according to their chemical environments and physical structures. The binding energy of Ti 2p in PSA/TiCl₄ was extremely low as TiCl₄ attracted excessive electrons from ? COOH groups. Furthermore, the chain structure of PSA was destroyed because of intensive reactions taking place in PSA/TiCl₄. With addition of (n‐Bu)MgCl or (n‐Bu)₂Mg, ? COOH became ? COOMg‐ which then reacted with TiCl₄ in synthesis of PSA/(n‐Bu)MgCl/TiCl₄ and PSA/(n‐Bu)₂Mg/TiCl₄. Although MgCl₂ coordinated with ? COOH first, TiCl₄ would substitute MgCl₂ to coordinate with ? COOH in PSA/MgCl₂/TiCl₄. Due to the different synthesis mechanisms, the four polymer‐supported catalysts correspondingly showed various particle morphologies. Furthermore, the polymer‐supported catalyst activity was enhanced by magnesium compounds in the following order: MgCl₂ > (n‐Bu)MgCl > (n‐Bu)₂Mg > no modifier. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Temperature programmed decomposition of sillica-supported MgCl2/THF/TiCl4 catalyst and effect of thermal treatment on ethylene polymerization rate

Silica supported MgCl₂/THF/TiCl₄ catalyst (SiO₂/MgCl₂/THF/TiCl₄) was prepared, and then decomposed thermally. The amount of produced gas [tetrahydrofuran (THF) and 1,4-dichlorobutane (DCB)] was measured with gas chromatography (GC) and mass spectrometer. SiO₂/MgCl₂/THF/TiCl₄ catalyst started to decompose around 85‡C, and further decomposed at 113, 150 and 213‡C. THF was mainly produced, but very small amount of DCB evolved during temperature programmed decomposition (TPD), while unsupported MgCl₂THF/TiCl₄ produced DCB significantly. Polymerization rate of ethylene with SiO₂/MgCl₂/THF/TiCl₄ decreased when it was preheated at 85 and 110‡C for 5 and 60 min, respectively, while that of unsupported MgCl₂/THF/TiCl₄ increased after same pretreatment condition. It can be suggested that Mg/Ti bimetallic complex anchored on the surface of silica through OH group of it has weak interaction between Mg and Ti species.     

Hybrid titanium catalyst supported on core‐shell silica/poly(styrene‐co‐acrylic acid) carrier

Hybrid titanium catalysts supported on silica/poly(styrene‐co‐acrylic acid) (SiO₂/PSA) core‐shell carrier were prepared and studied. The resulting catalysts were characterized by Fourier transform infrared (FTIR) spectroscopy, laser scattering particle analyzer and scanning electronic microscope (SEM). The hybrid catalyst (TiCl₃/MgCl₂/THF/SiO₂·TiCl₄/MgCl₂/PSA) showed core‐shell structure and the thickness of the PSA layer in the two different hybrid catalysts was 2.0 μm and 5.0 μm, respectively. The activities of the hybrid catalysts were comparable to the conventional titanium‐based Ziegler‐Natta catalyst (TiCl₃/MgCl₂/THF/SiO₂). The hybrid catalysts showed lower initial polymerization rate and longer polymerization life time compared with TiCl₃/MgCl₂/THF/SiO₂. The activities of the hybrid catalysts were enhanced firstly and then decreased with increasing P/P. Higher molecular weight and broader molecular weight distribution (MWD) of polyethylene produced by the core‐shell hybrid catalysts were obtained. Particularly, the hybrid catalyst with a PSA layer of 5.0 μm obtained the longest polymerization life time with the highest activity (2071 kg PE mol^?1 Ti h^?1) and the resulting polyethylene had the broadest MWD (polydispersity index = 11.5) under our experimental conditions. The morphology of the polyethylene particles produced by the hybrid catalysts was spherical, but with irregular subparticles due to the influence of PSA layer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The roles for a Lewis base and MgCl2 in third-generation Ziegler-Natta catalysts

Activity of a titanium catalyst supported on a bimetallic magnesium–aluminium system, involving a Lewis base [MgCl₂(THF)₂/Al(C₂H₅)₂Cl], was studied in ethylene polymerization, and the effect of the catalyst composition on the properties of the final polymer produced was investigated. Analysis and discussion of the findings covering also some part of the kinetic study, resulted in defining the roles for MgCl₂ and a Lewis base in the third-generation Ziegler-Natta catalysts. MgCl₂ forms a bimetallic complex with an organoaluminium compound, which involves also a Lewis base. Its reaction with TiCl₄ yields a very active catalyst wherein the Mg : Ti molar ratio is close to 1. This means that MgCl₂ is involved in creating catalytic active sites. The structure of these catalytic sites were suggested. Hence, the role for MgCl₂ can be twofold: it is a component of a catalytic active site, and it is a support if Mg : Ti > 5. It was found in the study that the catalytic function of MgCl₂ can be maintained while its supporting function can be omitted. Thus, MgCl₂ can be substituted for Al₂O₃ and the catalytic system obtained will have the same activity. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1005–1011, 1998     

Ethylene/1‐octadecene copolymerization using [η5:η1‐C5Me4‐4‐R1‐6‐R‐C6H2O]TiCl2 catalysts

Copolymerization of ethylene with 1‐octadecene was studied using [η⁵:η¹‐C₅Me₄‐4‐R₁‐6‐R‐C₆H₂O]TiCl₂ [R₁ = ^tBu (1), H (2, 3, 4); R = ^tBu (1, 2), Me (3), Ph (4)] as catalysts in the presence of Al(i‐Bu)₃ and [Ph₃C][B(C₆F₅)₄]. The effect of the concentration of comonomer in the feed and Al/Ti molar ratio on the catalytic activity and molecular weight of the resultant copolymer were investigated. The substituents on the phenyl ring of the ligand affect considerably both the catalytic activity and comonomer incorporation. The 1 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system exhibits the highest catalytic activity and produces copolymers with the highest molecular weight, while the 2 /Al(i‐Bu)₃/[Ph₃C][B(C₆F₅)₄] catalyst system gives copolymers with the highest comonomer incorporation under similar conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of temperature,solvent, Lewis acid and additives on the polymerization of tert‐butyl vinyl ether using Lewis acid‐induced N‐methyleneamines as cationic initiators

N‐Methyleneamines, formed by treating 1,3,5‐trimethylhexahydro‐1,3,5‐triazines with Lewis acids, have been shown to be capable initiators in the cationic polymerization of tert‐butyl vinyl ether, yielding polymers with amine functionality at the chain ends. Previous work was limited to titanium(IV) chloride (TiCl₄) as the Lewis acid in dichloromethane solvent at 0 °C (with resulting polymers possessing relatively broad polydispersity index (PDI) values near 2), while this contribution details the effect of reaction parameters on the polymeric products; specifically, the role of temperature, solvent, Lewis acid and additives. Ultimately, performing the polymerization at ?78 °C in dichloromethane with TiCl₄ as the Lewis acid and tetra‐n‐butylammonium chloride (nBu₄NCl) as the additive afforded the best control over the system, with polymers formed possessing low PDI values (<1.2). Dramatic changes in number‐average molecular weight and PDI were observed in polymers formed by initiating systems of Lewis acid‐induced N‐methyleneamines, with temperature, solvent, Lewis acid and additives all playing a role. By varying single parameters, optimization of the system was achieved. Copyright © 2009 Society of Chemical Industry     

Kinetic study of ethylene polymerization by highly active silica supported TiCL4/MgCl2 catalysts

The kinetics of ethylene polymerization with TiCl₄/MgCl₂/SiO₂ has been investigated in the range of temperatures between 40 and 90°C and in the range of ethylene pressures between 4 and 12.4 kg/cm². The role of MgCl₂ was discussed from the dependence of the Mg/Ti ratio on the catalytic activity. The polymerzation rate was first order with respect to the monomer concentration and the dependence of the polymerization rate on the concentration of Al(C₂H₅)₃ could be described by the Langmuir–Hinshelwood mechanism. The dependence of initial rate and the time to reach the maximum polymerization rate on the concentration of Al(C₂H₅)₃ was also discussed. Polymerization rates as a function of the polymerization temperature showed a maximum and the activation energy was 11.8 kcal/mol between 50 and 80°C. The polymerization rate decreased with the increase of hydrogen partial pressure. The active site concentration (C^*) was 1.9 × 10^?2 mol/mol Ti by the inhibition method with carbon monoxide.     

Effects of Ti oxidation state on ethylene, 1-hexene comonomer polymerization by MgCl<Subscript>2</Subscript>-supported Ziegler–Natta catalysts

In this study, the influences of the Ti oxidation state on the catalytic properties of MgCl₂-supported Ziegler–Natta catalysts in ethylene homo- and co-polymerization with 1-hexene were investigated. Three catalysts having different Ti oxidation states were synthesized by milling TiCl₄, TiCl₃, or TiCl₂ together with MgCl₂. With these catalysts having different Ti oxidation states, the polymerization conditions such as the Al concentration, temperature, and 1-hexene concentration were varied to figure out their catalytic abilities in ethylene homo- and co-polymerization. The Ti oxidation state affected the catalyst activity largely, having unique dependences on the polymerization conditions. A higher oxidation state led to a higher activity, slightly larger comonomer incorporation, and lower molecular weight as well as its narrower distribution. However, rough characteristics of copolymers were similar among the different Ti oxidation states.     

Comonomer enhancement effect of 1-hexene in ethylene copolymerization catalyzed over MgCl2/THF/TiCl4 catalysts

Homo- and copolymerization of ethylene were performed by using a catalyst system composed of TiCl₄/THF/MgCl₂ complex activated with AlEt₃ at 70°C and 3 atm. To investigate the effect of the compositional difference of the catalyst on the rates of homo- and copolymerization and on the reactivity in ethylene–hexene copolymerization, a series of six catalysts with different compositions (Mg/Ti = 0.4–16.5) were prepared by coprecipitation. The catalytic activity in ethylene polymerization increased sharply with the Mg/Ti ratio from 21 (Mg/Ti = 0.4) to 1477 kg PE/g-Ti h (Mg/Ti = 16.5). The activity in copolymerization with 1-hexene also increased with Mg/Ti ratio. The values of r₁ were 120, regardless of Mg/Ti ratios within the experimental error range. Enhancement of the polymerization rate by the addition of 1-hexene in the reaction medium was observed only for the catalysts of low Mg/Ti ratio. This unusual effect of 1-hexene on the polymerization rate was explained by chemical and physical processes that occurred during polymerization. © 1993 John Wiley & Sons, Inc.     

(nBuCp)2ZrCl2‐catalyzed ethylene‐4M1P copolymerization: Copolymer backbone structure,melt behavior,and crystallization

The judicious design of methylaluminoxane (MAO) anions expands the scope for developing industrial metallocene catalysts. Therefore, the effects of MAO anion design on the backbone structure, melt behavior, and crystallization of ethylene?4‐methyl‐1‐pentene (E?4M1P) copolymer were investigated. Ethylene was homopolymerized, as well as copolymerized with 4M1P, using (1) MAO anion A (unsupported [MAOCl₂]^?) premixed with dehydroxylated silica, (ⁿBuCp)₂ZrCl₂, and Me₂SiCl₂; and (2) MAO anion B (Si?O?Me₂Si?[MAOCl₂]^?) supported with (ⁿBuCp)₂ZrCl₂ on Me₂SiCl₂‐functionalized silica. Unsupported Me₂SiCl₂, opposite to the supported analogue, acted as a co‐chain transfer agent with 4M1P. The modeling of polyethylene melting and crystallization kinetics, including critical crystallite stability, produced insightful results. This study especially illustrates how branched polyethylene can be prepared from ethylene alone using particularly one metallocene‐MAO ion pair, and how a compound, that functionalizes silica as well as terminates the chain, can synthesize ethylene?α‐olefin copolymers with novel structures. Hence, it unfolds prospective future research niches in polyethyne systhesis. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1688–1706, 2016     

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     

Ethylene polymerization with heterogeneous Ziegler-Natta catalysts

Summary TiCl₄/SiO₂, Ti(OC₄H₉)₄/SiO₂, MgCl₂/TiCl₄/SiO₂ and MgCl₂/Ti(OC₄H₉)₄/SiO₂ catalysts were prepared by treating silica gel with TiCl₄, Ti(OC₄H₉)₄, MgCl₂/TiCl₄ or MgCl₂/Ti(OC₄H₉)₄ in tetrahydrofuran (THF) solution. Ethylene polymerization was performed with these catalysts activated by common alkylaluminum compounds. The influence of magnesium dichloride on catalyst performance was investigated. MgCl₂ has enhanced the catalyst activity for both titanium compounds. In addition, all catalyst systems were only active when they were washed with AlCl(C₂H₅)₂ (DEAC).     

Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

Palladium‐Catalyzed Efficient and One‐Pot Synthesis of Diarylacetylenes from the Reaction of Aryl Chlorides with 2‐Methyl‐3‐butyn‐2‐ol

An efficient and practical synthetic method has been developed for the preparation of symmetrical diarylacetylenes from the direct reaction of aryl chlorides with 2‐methyl‐3‐butyn‐2‐ol catalyzed by palladium(II) chloride‐bis(tricyclohexylphosphine) [PdCl₂(PCy₃)₂] under mild reaction conditions. Unsymmetrical diarylated acetylenes could be also obtained by using two different aryl chlorides simultaneously. The catalytic procedure includes a novel one‐pot palladium‐catalyzed, double Sonogashira coupling of inactivated aryl chlorides without use of copper(I) as co‐catalyst.     

Kinetics of ethylene polymerization at high temperature with Ziegler–Natta catalysts

A kinetic technique is developed for the study of ethylene polymerization reaction at high temperature with Ziegler–Natta catalysts. The technique is based on the calculation of polymerization rate parameters from the data on ethylene consumption vs. time. It takes into account increase of reaction temperature at the beginning of the reaction. Kinetic data in coordinates “polymerization rate–time” are presented for several pseudohomogeneous catalysts (TiCl₄? AlEt₂Cl, Ti(OiC₃H₇)₄? AlEt₂Cl), heterogeneous catalysts (δ-TiCl₃? AlEt₃, δ-TiCl₃? AlEt₂Cl, TiCl₄/MgCl₂? AlEt₃, TiCl₄/MgCl₂? AlEt₂Cl) and solubilized catalysts (δ-TiCl₃? poly-1-hexene? AlEt₂Cl) at 180°C and reaction pressure 14.6 atm for first 10 min of the reaction. These data are useful for the selection of Ziegler–Natta catalysts for testing in ethylene polymerization reaction in continuous high pressure reactors at short residence times.     

Novel binary chlorides containing TiCl3 as components of coordination catalysts for ethylene polymerization. II. Behavior of the resulting catalyst systems

Binary chlorides described in part I yielded very active catalyst systems for HDPE synthesis when they were associated with (i-C₄H₉)₃Al. Very high initial polymerization rates were observed for systems bases on MnCl₂·TiCl₃, MnCl₂·2TiCl₃, or FeCl₂·2TiCl₃ (III), but high yields, i.e., above 30 kg polymer/g Ti, could be reached only using moderate pressure of ethylene. Hydrogen consumption during ethylene polymerization was observed in the case of catalysts based on AlCl₃·3TiCl₃, CrCl₃·3TiCl₃, and other binary chlorides containing elements of the VIII group. Relevant amounts of ethane were found in the case of systems III, V, and VIII. All the mixed chlorides studied were able to reduce cyclohexene in the presence of H₂ and (i-C₄H₉)₃Al, even though with different kinetic courses. Compounds II, III, V, and VIII and (MgCl₂)_1.5·TiCl₃ and AlCl₃·3TiCl₃ were very active. The results have been explained on the basis of solubilization processes involving the heterogeneous catalysts which actually were experimentally verified during cyclohexene reduction. Analogous processes may occur also during HDPE synthesis.     

Ethylene-propylene copolymers by a supported Ziegler-Natta catalyst based on TiCl4/MgCl2

Ethylene-propylene copolymers have been prepared by using Ziegler-Natta catalysts based on TiCl₄, MgCl₂, PCl₃ and (n-Bu)₃PO₄. The catalysts TiCl₄/MgCl₂/PCl₃ and TiCl₄/MgCl₂/(n-Bu)₃PO₄ were prepared by reacting TiCl₄ with pretreated MgCl₂. The support was prepared by ball milling of MgCl₂ with varied amounts of PCl₃ or (n-Bu)₃PO₄. The addition of PCl₃ has remarkably increased the MgCl₂ surface area in comparison with (n-Bu)₃PO₄. The effects of PCl₃ and (n-Bu)₃PO₄ on ethylene homopolymerization, ethylene-propylene copolymerization and on copolymer properties were evaluated. The catalyst system containing PCl₃ permitted to synthesize propylene-ethylene copolymers with up to 75% (w/w) of propylene and provided control of copolymer crystallinity. The reduction of the copolymer molecular weight distribution suggested that PCl₃ acted as an internal donor, poisoning some active catalytic sites. Received: 2 April 1997/Revised: 6 June 1997/Accepted: 18 June 1997     

The influence of aluminum alkyls on the polymerization of ethylene with SiO2/MgCl2-supported TiCl4 catalysts

The influence of different aluminum alkyls (diethylaluminum chloride, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and isoprenylaluminum) on the ethylene polymerization activity of a laboratory prepared high-activity SiO₂/MgCl₂-supported TiCl₄ catalyst has been investigated. A slurry reactor (decane diluent) was used for measuring rates of polymerization. The average molar mass, the breadth of the molar mass distribution, the polymerization activity, and the shapes of the activity-time profiles, were strongly dependent on the nature of the aluminum alkyl. For several of the cocatalysts used, the catalytic activity approached a constant value after a certain amount of time under reaction conditions. In this constant activity region, a first-order dependence of the polymerization rate on the monomer concentration was found for all of the systems examined. However, the activation energy of the polymerization reaction was found to depend strongly on the type of cocatalyst which was used.     

Highly trans‐1,4‐specific polymerization of 1,3‐butadiene catalyzed by [2,6‐bis{(4S)‐ (−)‐isopropyl‐2‐oxazolin‐2‐yl}pyridine] chromium complex activated with modified methylaluminoxane

Chromium complexes with N,N,N‐tridentate ligands, LCrCl₃ (L = 2,6‐bis{(4S)‐(?)‐isopropyl‐2‐oxazolin‐2‐yl}pyridine ( 1 ), 2,2′:6′,2″‐terpyridine ( 2 ), and 4,4′,4″‐tri‐tert‐butyl‐2,2′:6′,2″‐terpyridine ( 3 )), were prepared. The structures of 1 and 2 were determined by X‐ray crystallography. Upon activation with modified methylaluminoxane (MMAO), 1 catalyzed the polymerization of 1,3‐butadiene, while 2 and 3 was inactive. The obtained poly(1,3‐butadiene) obtained with 1 ‐MMAO was found to have completely trans‐1,4 structure. The 1 ‐MMAO system also showed catalytic activity for the polymerization of isoprene to give polyisoprene with trans‐1,4 (68%) and cis‐1,4 (32%) structure. Copyright © 2011 Society of Chemical Industry