Ethylene–hexene copolymerization by heterogeneous and homogeneous Ziegler–Natta catalysts and the “comonomer” effect

Homopolymerization of ethylene and 1-hexene and their copolymerizations were compared to investigate the influence of α-olefin on the enhancement of ethylene polymerization rate (R_p), which is often referred to as the “comonomer” effect. With the two homogeneous Ziegler–Natta catalysts, Et[Ind]₂ZrCl₂/MAO and (π-C₅H₅)₂ZrCl₂/MAO (MAO = methylaluminoxane), hexene causes reduction of R_p—in other words a negative “comonomer” effect. In the case of the high activity MgCl₂ supported TiCl₃ catalysts there is a slight positive “comonomer” effect; the R_p increases by 25 to 70% with the addition of 15 mol % of hexene. The “comonomer” effects in there catalyst systems are much smaller than that observed for the classical TiCl₃ catalyst. © 1993 John Wiley & Sons, Inc.     

Evaluation of the Initial Stages of Gas‐Phase Ethylene Polymerizations with a SiO2‐Supported Ziegler–Natta Catalyst

The very early stages of gas‐phase ethylene polymerization on an SiO₂‐supported Ziegler–Natta catalyst were studied with the help of a short‐stop reactor. The short‐stop‐reactor‐based technique was useful in studying nascent polymerization, providing insights at very short, controlled times into important phenomena regarding catalyst fragmentation and the activation and deactivation of catalyst sites that take place during the very early stages of the reaction. Experimental results indicate that the growth of the polymer chains occurs at unsteady conditions during the initial stages of the polymerization. Hydrogen has a strong influence on the initial kinetics, leading to a significant decrease of polymerization activity. Polymer crystallinity increases with the reaction time, probably due to the formation of long chains with a high degree of crystallinity.

     

Preparation of Polyethylene/Graphene Nanocomposites with Octadecylamine‐Modified Graphene Oxide‐MgCl‐Supported Ziegler–Natta Catalyst

In this work, an octadecylamine‐modified graphene oxide (ODA‐GO)‐MgCl‐supported Ziegler–Natta catalyst was synthesized by reacting ODA‐GO with a Grignard reagent, followed by anchoring TiCl₄ to the structure. The effect of the ODA‐GO on the catalyst morphology and ethylene polymerization behavior was examined. The resultant polyethylene (PE)/ODA‐GO nanocomposites directly mirrored the catalyst morphology by forming a layered morphology, and the ODA‐GO fillers were well dispersed in the PE matrix and showed strong interfacial adhesion with it. The resultant PE/ODA‐GO nanocomposites exhibited better thermal stability and mechanical properties than neat PE, even with a small amount of ODA‐GO added. Thus, this work provides a facile approach to the production of high‐performance PE. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 855–860     

Ethylene polymerization reactions with Ziegler–Natta catalysts. III. Chain-end structures and polymerization mechanism

Ethylene polymerization reactions with many Ziegler–Natta catalysts exhibit a number of features that differentiate them from polymerization reactions of α olefins: (1) a relatively low ethylene reactivity, (2) markedly higher polymerization rates in the presence of α olefins, (3) a high reaction order with respect to ethylene concentration, and (4) a strong reversible rate depression in the presence of hydrogen. A detailed kinetic analysis of ethylene polymerization reactions¹ provided the basis for a new kinetic scheme that postulates the equilibrium formation of Ti C₂H₅ species with the H atom in the methyl group β-agostically coordinated to the Ti atom in an active center. This mechanism predicts several new features of ethylene polymerization reactions, one being that chain initiation via insertion of any α-olefin molecule into the Ti H bond should proceed with an increased probability compared to that via ethylene insertion into the same bond. As a result, a significant fraction of ethylene/α-olefin copolymer chains should contain α-olefin units as the starting units. This article provides experimental data supporting this prediction on the basis of both a detailed structural analysis of co-oligomers formed in ethylene/1-pentene and ethylene/4-methyl-1-pentene copolymerization reactions and a spectroscopic analysis of chain ends in the copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4281–4294, 1999     

Peculiarities of Ethylene Polymerization Reactions with Heterogeneous Ziegler–Natta Catalysts: Kinetic Analysis

The previously developed kinetic scheme for olefin polymerization reactions with heterogeneous Ziegler–Natta catalysts states that the catalysts have several types of active centers which have different activities, different stabilities, produce different types of polymer materials, and respond differently to reaction conditions. In the case of ethylene polymerization reactions, each type of center exhibits an unusual chemical feature: a growing polymer chain containing one ethylene unit, Ti—C₂H₅, is unusually stable and can decompose with the formation of the Ti—H bond. This paper examines quantitative kinetic ramifications of this chemical mechanism. Modeling of the complex kinetics scheme described in the Scheme demonstrates that it correctly and quantitatively predicts three most significant peculiarities of ethylene polymerization reactions, the high reaction order with respect to the ethylene concentration, reversible poisoning with hydrogen, and activation in the presence of α‐olefins.     

Preparation of polyethylene/lignin nanocomposites from hollow spherical lignin‐supported vanadium‐based Ziegler–Natta catalyst

In the present article, a novel hollow spherical lignin‐supported vanadium‐based Ziegler–Natta catalyst was synthesized. The active centers of the obtained catalyst well dispersed in the lignin through the SEM‐EDX analysis. The resultant catalyst was investigated in ethylene polymerization and found to exhibit remarkable catalytic activity upon activation with ethylaluminium sesquichloride cocatalyst and ethyl trichloroacetate activator. During the polymerization, the lignin was gradually exfoliated by the polymerization force arising from the propagation of ethylene chain. The resultant PE/lignin nanocomposites preformed higher thermal stability compared to virgin PE. Copyright © 2016 John Wiley & Sons, Ltd.     

Multi‐center nature of heterogeneous Ziegler–Natta catalysts: TREF confirmation

A new approach to detailed Tref analysis of ethylene/α‐olefin copolymers prepared with multi‐center polymerization catalysts is developed. It is based on resolution of complex Tref curves into elemental components described with the Lorentz distribution function. This approach was applied to the study of a series of ethylene/1‐butene copolymers prepared with a supported Ti‐based catalyst. The analysis showed that the copolymers, which, on average, contain from 6.5 to 3.5 mol % of 1‐butene, consist of seven discrete components with different compositions, ranging from a completely amorphous material with a 1‐butene content of > 15–20 mol %, to two highly crystalline components with 1‐butene contents < 1 mol %. A comparison of these Tref results with the data on the molecular weight distribution of the copolymers (based on resolution of their GPC curves) shows that Tref and GPC data provide complimentary information on the properties of active centers in the catalysts in terms of the molecular weights of the material they produce and their ability to copolymerize α‐olefins with ethylene. Tref analysis of copolymers produced at different reaction times showed that the active centers responsible for the formation of various Tref components differ in the rates of their formation and in stability. The centers that produce copolymer molecules with a high 1‐butene content are formed rapidly but decay rapidly as well whereas the centers producing copolymer molecules with a low 1‐butene content are formed more slowly but are more stable. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4351–4362, 2005     

Influence of Copolymerization on Fragmentation Behavior Using Ziegler‐Natta Catalysts

Summary: A morphological investigation was carried out on different Ziegler‐Natta catalysts during the early stages of propylene homo‐ and propylene‐ethylene copolymerization. For similar polymerization conditions, but dependent on the nature of the catalysts, fragmentation occurs layer‐by‐layer or instantaneously into a large amount of small pieces. However, the incorporation of comonomer ethylene slows down the fragmentation progress. This is believed to be the result of the higher mobility of the just formed propylene‐ethylene copolymer molecules at the active sites.

SEM images of the cross‐sectional morphology of polymer particles from catalyst‐I.     

Melting behavior of polyethylene/α‐olefin copolymers: Narrow composition distribution copolymers and fractions from Ziegler–Natta and single‐site catalyst products

The melting temperature and heat of fusion were measured for an extensive series of compositionally uniform copolymers of ethylene with butene‐1, hexene‐1, and octene‐1. Fractions and whole polymers that exhibited minimal interchain compositional heterogeneity were from commercial copolymers made with either Ziegler–Natta (ZN) or single‐site metallocene catalysts. The present results do not support recent claims that ZN and corresponding metallocene catalyst copolymers melt at significantly different temperatures, nor the implication that comonomer incorporation is “blocky” in ZN copolymers. In five of the six comonomer/catalyst systems the dependencies of the melting temperature on comonomer type and amount were scarcely distinguishable. This common behavior is the same as that for a model random copolymer, so we conclude that most ethylene/α‐olefin copolymers have random distributions of ethylene sequences. The exception in the present study is a metallocene ethylene/butene‐1 copolymer that melts at lower temperatures and apparently has perceptibly alternating sequence distributions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3416–3427, 2004     

Analysis of Ethylene/1‐Olefin Copolymers Made with Ziegler–Natta Catalysts by Deconvolution of Molecular Weight and Average Short Chain Branching Distributions

In this article a systematic method is proposed to deconvolute the time‐dependent molecular weight distributions (MWD) and average comonomer fraction profiles of ethylene/1‐olefin copolymers made with heterogeneous Ziegler–Natta catalysts. These distributions with a high‐temperature gel permeation chromatography equipped with an infrared detector at four different polymerization times have been measured and used this information to infer how the fractions of polymer made on each site type varied with polymerization time. The model estimates here the minimum number of active site types needed to describe these copolymers, the MWD of polymer populations made on each site type, and their average comonomer fractions. This method is useful to quantify the microstructure of olefin copolymers made with multiple site type catalysts using the least number of adjustable parameters.

     

Monomer-isomerization polymerization. XXXVIII. Monomer-isomerization copolymerizations of styrene and 2-Butene with Ziegler–Natta catalyst

Monomer-isomerization copolymerizations of styrene (St) and cis-2-butene (c2B) with TiCl₃-(C₂H₅)₃Al catalyst were studied. St and c2B were found to undergo a new type of monomer-isomerization copolymerization, i.e., only isomerization of 2B to 1-butene ( 1B ) took place to give a copolymer consisting of St and 1B units. The apparent copolymerization parameters were determined to be r_st = 16.0 and r_c2b = 0.003. The parameters were changed by the addition of NiCl₂ (r_St = 8.4, r_c2b = 0.05). The copolymers containing the major amount of St units were produced easily through monomer-isomerization copolymerization of St and 2B. © 1995 John Wiley & Sons, Inc.     

Estimation of Apparent Kinetic Constants of Individual Site Types for the Polymerization of Ethylene and α‐olefins with Ziegler–Natta Catalysts

This article proposes a method to quantify the polymerization kinetics of ethylene and α‐olefins with commercial TiCl₄/MgCl₂ Ziegler–Natta catalysts. The method determines the leading apparent polymerization kinetic constants for each active site in a Ziegler–Natta catalyst by simultaneously fitting the instantaneous polymerization rate, cumulative polymer yield, and polymer molecular weight distribution measured at different times during a series of semi‐batch polymerization experiments. This approach quantifies the behavior of olefin polymerization with multisite catalysts using the least number of adjustable parameters needed to consistently model polymerization kinetics and polymer microstructural data.

     

AlR2Cl/MgR2 combinations as universal cocatalysts for Ziegler–Natta,metallocene, and post‐metallocene catalysts

Combinations of dialkylaluminum chlorides and dialkylmagnesium compounds, when used at molar [AlR₂Cl]:[MgR₂] ratios ≥ 2, act as universal cocatalysts for all three presently known types of alkene polymerization catalysts—Ziegler–Natta, metallocene, and post‐metallocene. When these cocatalysts are used with supported Ti‐based Ziegler–Natta catalysts, they produce catalyst systems which are 1.5–2 times more active than the systems utilizing AlR₃ compounds as cocatalysts. Combinations of AlR₂Cl/MgR₂ cocatalysts and various metallocene complexes produce single‐center catalyst systems similar to those formed in the presence of MAO. The same cocatalysts activate numerous post‐metallocene Ti complexes containing bidentate ligands of a different nature and produce multicenter systems of very high activity. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3271–3285, 2009     

Preparation of linear α‐olefins to high‐molecular weight polyethylenes using cationic α‐diimine nickel(II) complexes containing chloro‐substituted ligands

A series of α‐diimine nickel(II) complexes containing chloro‐substituted ligands, [(Ar)N?C(C₁₀H₆)C?N(Ar)]NiBr₂ ( 4a , Ar = 2,3‐C₆H₃Cl₂; 4b , Ar = 2,4‐C₆H₃Cl₂; 4c , Ar = 2,5‐C₆H₃Cl₂; 4d , Ar = 2,6‐C₆H₃Cl₂; 4e , Ar = 2,4,6‐C₆H₂Cl₃) and [(Ar)N?C(C₁₀H₆)C?N(Ar)]₂NiBr₂ ( 5a , Ar = 2,3‐C₆H₃Cl₂; 5b , Ar = 2,4‐C₆H₃Cl₂; 5c , Ar = 2,5‐C₆H₃Cl₂), have been synthesized and investigated as precatalysts for ethylene polymerization. In the presence of modified methylaluminoxane (MMAO) as a cocatalyst, these complexes are highly effective catalysts for the oligomerization or polymerization of ethylene under mild conditions. The catalyst activity and the properties of the products were strongly affected by the aryl‐substituents of the ligands used. Depending on the catalyst structure, it is possible to obtain the products ranging from linear α‐olefins to high‐molecular weight polyethylenes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1964–1974, 2006     

Synthesis of polypropylene-co-p-methylstyrene copolymers by metallocene and Ziegler–Natta catalysts

This paper discusses the copolymerization reaction of propylene and p-methylstyrene (p-MS) via four of the best-known isospecific catalysts, including two homogeneous metallocene catalysts, namely, {SiMe₂[2-Me-4-Ph(Ind)]₂}ZrCl₂ and Et(Ind)₂ZrCl₂, and two heterogeneous Ziegler–Natta catalysts, namely, MgCl₂/TiCl₄/electron donor (ED)/AlEt₃ and TiCl₃. AA/Et₂AlCl. By comparing the experimental results, metallocene catalysts show no advantage over Ziegler–Natta catalysts. The combination of steric jamming during the consective insertion of 2,1-inserted p-MS and 1,2-inserted propylene (k₂₁ reaction) and the lack of p-MS homopolymerization (k₂₂ reaction) in the metallocene coordination mechanism drastically reduces catalyst activity and polymer molecular weight. On the other hand, the Ziegler–Natta heterogeneous catalyst proceeding with 1,2-specific insertion manner for both monomers shows no retardation because of the p-MS comonomer. Specifically, the supported MgCl₂/TiCl₄/ED/AlEt₃ catalyst, which contains an internal ED, produces copolymers with high molecular weight, high melting point, and no p-MS homopolymer. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2795–2802, 1999     

Polymer-supported Ziegler–Natta catalysts. II. Ethylene homo- and copolymerization with TiCl4/MgR2/poly(ethylene-co-acrylic acid) catalyst

A novel polymer-supported titanium-based catalyst shows high activity and nondecaying kinetic profiles for ethylene polymerization. The presence of 1-hexene comonomer drastically increases the catalyst activity, exhibiting a similarity to the MgCl₂-supported catalysts. However, the nondecaying kinetic profiles of copolymerization distinguish this catalyst from the latter. Infrared analysis indicates that the transition metals were immobilized on the polymer support via functional groups. The effects of polymerization conditions on catalyst activity have been assessed. Characterization of the resulting polymer product by means of ¹³C-NMR, DSC, and SEM demonstrates a branch-free structure with high melting point, high crystallinity, and high molecular weight for the ethylene homopolymer. The reactivity ratios of ethylene-1-hexene copolymerization are evaluated from ¹³C-NMR analysis data. © 1994 John Wiley & Sons, Inc.     

Active center determinations on MgCl2‐supported fourth‐ and fifth‐generation Ziegler–Natta catalysts for propylene polymerization

Active center determinations on different Ziegler–Natta polypropylene catalysts, comprising MgCl₂, TiCl₄, and either a diether or a phthalate ester as internal donor, have been carried out by quenching propylene polymerization with tritiated ethanol, followed by radiochemical analysis of the resulting polymers. The purpose of this study was to determine the factors contributing to the high activities of the catalyst system MgCl₂/TiCl₄/diether—AlEt₃. Active center contents (C*) in the range 2–8% (of total Ti present) were measured and a strong correlation between catalyst activity and active center content was found, indicating that the high activity of the diether‐containing catalysts is due to an increased proportion of active centers rather than to a difference in propagation rate coefficients. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1635–1647, 2006