Ethylene polymerization over (nBuCp)2ZrCl2/MAO catalytic system supported on aluminosilicate SBA‐15 mesostructured materials

Heterogeneous metallocene catalysts were prepared by incipient wetness impregnation of AlSBA‐15 (Si/Al = 4.8, 15, 30, 60, and ∞) mesostructured materials with (nBuCp)₂ZrCl₂/MAO. For comparative purposes commercial silica and silica–alumina (Si/Al = 4.8) supports were also impregnated with the MAO/metallocene catalytic system. A combination of X‐ray powder diffraction, nitrogen adsorption–desorption isotherms at 77 K, transmission electron microscopy, ICP‐atomic emission spectroscopy, and UV–vis spectroscopic data, were used to characterize the supports and the heterogeneous catalysts. Ethylene polymerizations were carried out in a schlenk tube at 70 °C and 1.2 bar of ethylene pressure. The polyethylene obtained was characterized by GPC, DSC, and SEM. Catalysts prepared with mesostructured SBA‐15 supports exhibited better catalytic performance than those supported on amorphous silica and silica–alumina. In general, higher ethylene polymerization activity was achieved if (nBuCp)₂ ZrCl₂/MAO catalytic system was heterogenized using supports with lower pore size in the range of the mesopores and lower Si/Al ratio. All catalysts produced high‐density polyethylene, with high crystallinity values and fibrous morphology when SBA‐15 mesostructured materials were used as supports. POLYM. ENG SCI., 2008. © 2008 Society of Plastics Engineers     

Organic Nanoparticles with Polypropyleneoxide Chains as Support for Metallocene Catalysts: Ethylene Homopolymerization and Ethylene/α-olefin Copolymerization

Summary Novel organic nanoparticles functionalized with nucleophilic polypropyleneoxide (PPO) chains on their surfaces for supporting metallocene catalysts in heterogeneous olefin polymerization are presented. The nanoparticles (60–100 nm) were obtained by miniemulsion polymerization of styrene, divinylbenzene and PPO functionalized styrene. It is demonstrated that Me₂Si(2MeBenzlnd)₂ZrCl₂/MAO supported on these nanoparticles is suitable for the homopolymerization of ethylene, resulting in excellent product morphologies and high activities. lt is shown that by varying the MAO/Zr ratios and Zr concentrations the activities and productivities of the catalysts as well as the qualities of the polyethylene products can be tuned. These new supported catalysts are also suitable for the copolymerization of ethylene with several comonomers (1-hexene, 1-octene, 1-decene or norbornene). As the obtained product properties like crystallinity, melting temperature or bulk density match the results of silica supported systems, these organic nanoparticles can be considered as alternative carriers in comparison to the established inorganic ones.     

Concentration effects of methylalumoxane,zirconocene dichloride and trimethylaluminum in ethylene polymerization

A quantitative study was carried out on the homogeneous zirconocene dichloride/methylalumoxane/trimethylaluminum (Cp₂ZrCl₂/MAO/TMA) catalyst system in ethylene polymerization. The effects of variation of the Al_MAO/Zr ratio, absolute Zr concentration, and addition of TMA on ethylene polymerization activity and polymer properties were investigated. The polymerization profiles for small Al_MAO/Zr ratios and the changes with the Zr concentration are explained with a complexation equilibrium for the active homogeneous complex and with the change to a heterogeneous catalyst upon polymer precipitation. Good polymer productivities can be achieved at Al_MAO/Zr < 1000 when working at Zr concentrations between 10^?4 and 10^?5 mol/l with addition of TMA (Al_MAO/Al_TMA≈ 1.4).     

Propylene polymerization using combined syndio‐ and isospecific metallocene catalysts supported on silica/MAO

Syndiotactic and isotactic polypropylene were produced using the metallocene compounds Ph₂C(Flu)(Cp)ZrCl₂ and SiMe₂(2‐Me,4‐Ph‐Ind)₂ZrCl₂ in homogeneous system and supported on silica/MAO. These catalysts were evaluated either isolated or as a binary system. In the latter case, the iso‐ and syndiospecific metallocene complexes were immobilized together during the preparation of the supported catalyst. In a further experimental set, the syndio‐ and isospecific isolated heterogeneous catalysts were mixed at the moment of propylene polymerization. The polypropylenes obtained were evaluated using differential scanning calorimetry. The catalytic activities were also investigated. At all the studied polymerization temperatures, the results showed that the binary catalyst produced polypropylenes with lower melting temperatures in comparison with those obtained when the mixture of isolated supported syndio‐ and isospecific catalysts was employed. Moreover, the activation energies for the polymerization of all catalysts systems were calculated, resulting in a lower value for the binary system when compared to that employing the catalyst mixture and to both the isolated supported metallocene catalysts. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 628–637, 2006     

Supported zirconocene catalyst for preventing reactor fouling in ethylene polymerization

The commercial interest of metallocene complexes for olefin polymerization has led to additional efforts to prepare suitable metallocene complexes efficiently and economically. Ethylene polymerization was carried out with a series of heterogeneous catalysts which were prepared in various Zr/silica ratios by immobilization of Ind₂ZrCl₂ preactivated with methylaluminoxane (MAO) on silica. This method to form the catalyst system resulted in a polymerization catalyst with reduced fouling tendencies and improved reactor operability. Polymerization of ethylene was conducted in Buchi reactors in a slurry phase under mild pressure. Some of the physical properties of the obtained polymers were also determined. Copyright © 2005 Society of Chemical Industry     

Supported hybrid catalysts based on zirconocene and tris(pyrazolyl)borate titanium derivatives

A series of hybrid supported catalysts were prepared by combining (iBuCp)₂ZrCl₂ and {Tp^Ms*}TiCl₃ complex (Tp^Ms* = HB(3‐mesityl‐pyrazolyl)₂(5‐mesityl‐pyrazolyl)^?) sequentially grafted onto MAO (methylaluminoxane)‐modified silica according to a Plackett Burmann 2³ design. Supported catalysts were prepared taking into account the immobilization order, silica pretreatment temperature, and grafting temperature. Grafted metal content was comparatively determined by Rutherford backscattering spectrometry (RBS), X‐ray photoelectronic spectroscopy (XPS), and inductively coupled plasma–optical emission spectroscopy (ICP–OES). The resulting catalysts were evaluated in terms of catalyst activity and polymer properties. According to RBS measurements, grafted metal content remained comprised between 0.1 and 0.5 wt % Zr/SiO₂ and 0.1 and 0.3 wt % Ti/SiO₂ depending on the immobilization order and on silica pretreatment temperature. All the systems were shown to be active in ethylene polymerization having external MAO as cocatalyst. Catalyst activity seemed to be governed by the zirconocene species, influenced slightly by Ti ones. Resulting polymers were characterized by DSC and GPC. The polyethylenes mostly presented higher molecular weight than those produced by homogeneous catalysts or by zirconocene grafted on bare or on MAO‐modified silica. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Polymerization of ethylene: Some aspects of metallocene catalyst stabilization under homogeneous and heterogeneous reaction conditions

The development of metallocene‐based catalysts is an important advance on the study of polyolefinic materials. However, due to the rather different conditions that are established in actual applications, only around 3% of these polymers are obtained from metallocene technology. In view of this, novel strategies must be developed to produce metallocene‐based catalysts that are more thermally stable, which is a fundamental requirement to establish metallocene technologies. Homogeneous and heterogeneous polymerizations of ethylene were compared, using the Ph₂C(Cp)(Flu)ZrCl₂/MAO system. Homogeneous polymerizations were more active than the corresponding supported reactions. At low ethylene pressure, the addition of 1‐hexene increases the activity under homogeneous conditions. Nevertheless, this is not observed on the respective supported systems. At higher pressure conditions, all polymerizations attained higher yields. However, when the reaction temperature increases the activity significantly decreases under homogeneous conditions. Furthermore, when the polymerization was performed under heterogeneous conditions the deactivation was lower. The homogeneous and supported catalytic systems show different characteristics and, in all attempted reactions, immobilization of the molecular catalyst reduces the activity. However, the deactivation ratio was lower when the polymerization was performed under heterogeneous conditions. This means that immobilization of Ph₂C(Cp)(Flu)ZrCl₂ on silica can improve the thermal stability of the catalytic species. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymerization of allylbenzene with metallocene catalysts

Summary Homopolymerization of allylbenzene was carried out with various metallocene/methylaluminoxane (MAO) catalysts. Different polymerization behavior was observed depending upon the catalysts empolyed. rac-Et(Ind)₂ZrCl₂ and rac-Me₂Si(Ind)₂ZrCl₂ gave semicrystalline polyallylbenzenes while i-Pr(CpFlu)ZrCl₂ and CpTiCl₃ did not give any polymeric product. The Cp₂ZrCl₂ gave amorphous polyallylbenzene with low molecular weight. The effect of temperature on the polymerization was investigated with a constant Al/Zr ratio. The temperature showing maximum catalyst activity is higher for the ansa metallocene catalysts than Cp₂ZrCl₂ catalyst. The IR and NMR spectra indicated that the polyallylbenzene consisted of allylbenzene repeating unit and no isomerization occurred. Received: 7 December 1998/Revised version: 29 January 1999/Accepted: 9 February 1999     

Development of novel chromium oxide/metallocene hybrid catalysts for bimodal polyethylene

The investigation of a multicomponent catalyst in polyolefin field came up as an alternative for synthesizing bimodal polymers in only one step process under constant reaction conditions.In the present work, new bifunctional catalysts were prepared by combining chromium and metallocene species on the same solid and tested in ethylene polymerization in order to evaluate the possibility of producing bimodal polyethylene. The catalytic system methylaluminoxane (MAO)/(nBuCp)₂ZrCl₂ was immobilized on activated chromium catalysts supported onto several inorganic carriers (silica, silica-alumina, aluminophosphate and mesostructured SBA-15-type materials). The reaction results showed a clear influence of the physicochemical properties of the support on the relative contribution of metallocene and chromium centers as well as on polymers molecular weight distribution. A bimodal polyethylene was obtained by supporting the MAO/metallocene system on a mesostructured chromium catalyst prepared by direct synthesis.     

Effects of aluminum alkyls on ethylene/1‐hexene polymerization with supported metallocene/MAO catalysts in the gas phase

The effects of aluminum alkyls on the gas‐phase ethylene homopolymerization and ethylene/1‐hexene copolymerization over polymer‐supported metallocene/methylaluminoxane [(n‐BuCp)₂ZrCl₂/MAO] catalysts were investigated. Results with triisobutyl aluminum (TIBA), triethyl aluminum (TEA), and tri‐n‐octyl aluminum (TNOA) showed that both the type and the amount of aluminum alkyl influenced the polymerization activity profiles and to a lesser extent the polymer molar masses. The response to aluminum alkyls depended on the morphology and the Al : Zr ratio of the catalyst. Addition of TIBA and TEA to supported catalysts with Al : Zr >200 reduced the initial activity but at times resulted in higher average activities due to broadening of the kinetic profiles, i.e., alkyls can be used to control the shape of the activity profiles. A catalyst with Al : Zr = 110 exhibited relatively low activity when the amount of TIBA added was <0.4 mmol, but the activity increased fivefold by increasing the TIBA amount to 0.6 mmol. The effectiveness of the aluminum alkyls in inhibiting the initial polymerization activity is in the following order: TEA > TIBA >> TNOA. A 2‐L semibatch reactor, typically run at 80°C and 1.4 MPa ethylene pressure for 1 to 5 h was used for the gas‐phase polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3549–3560, 2004     

The effect of aluminum alkyls and BHT‐H on reaction kinetics of silica supported metallocenes and polymer properties in slurry phase ethylene polymerization

In slurry and gas phase catalytic ethylene polymerization processes, aluminum alkyl (AlR₃) compounds are usually present inside the reactor and their role either as co‐catalyst or scavenger is of considerable importance. Silica supported metallocene/methyl aluminoxane (MAO) catalysts show specific interactions with AlR₃ compounds. Therefore, this study shows an attempt to analyze and compare the effect of concentration as well as type of commonly used AlR₃ on slurry phase ethylene homopolymerization kinetics of silica supported (n‐BuCp)₂ZrCl₂/MAO catalyst. The obtained results indicate that the lower the concentration of smaller AlR₃ compounds, the higher the instantaneous catalytic activity. Concerning the polymer particle size distributions, a rise in fines generation has been observed with increasing AlR₃ content inside the reactor. Finally, it has been shown that the addition of 2,6‐di‐tert‐butyl‐4‐methylphenol (a substituted phenol) into the reactor containing AlR₃ reduces the influence of AlR₃ compounds on the reaction kinetics of silica supported metallocene/MAO catalysts. Polyethylene properties remain similar in all the studied scenarios. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45670.     

(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     

Silica‐supported (nBuCp)2ZrCl2: effect of catalyst active center distribution on ethylene–1‐hexene copolymerization

Metallocenes are a modern innovation in polyolefin catalysis research. Therefore, two supported metallocene catalysts—silica/MAO/(ⁿBuCp)₂ZrCl₂ (Catalyst 1) and silica/ⁿBuSnCl₃/MAO/(ⁿBuCp)₂ZrCl₂ (Catalyst 2), where MAO is methylaluminoxane—were synthesized, and subsequently used to prepare, without separate feeding of MAO, ethylene–1‐hexene Copolymer 1 and Copolymer 2, respectively. Fouling‐free copolymerization, catalyst kinetic stability and production of free‐flowing polymer particles (replicating the catalyst particle size distribution) confirmed the occurrence of heterogeneous catalysis. The catalyst active center distribution was modeled by deconvoluting the measured molecular weight distribution and copolymer composition distribution. Five different active center types were predicted for each catalyst, which was corroborated by successive self‐nucleation and annealing experiments, as well as by an extended X‐ray absorption fine structure spectroscopy report published in the literature. Hence, metallocenes impregnated particularly on an MAO‐pretreated support may be rightly envisioned to comprise an ensemble of isolated single sites that have varying coordination environments. This study shows how the active center distribution and the design of supported MAO anions affect copolymerization activity, polymerization mechanism and the resulting polymer microstructures. Catalyst 2 showed less copolymerization activity than Catalyst 1. Strong chain transfer and positive co‐monomer effect—both by 1‐hexene—were common. Each copolymer demonstrated vinyl, vinylidene and trans‐vinylene end groups, and compositional heterogeneity. All these findings were explained, as appropriate, considering the modeled active center distribution, MAO cage structure repeat units, proposed catalyst surface chemistry, segregation effects and the literature that concerns and supports this study. While doing so, new insights were obtained. Additionally, future research, along the direction of the present work, is recommended. © 2013 Society of Chemical Industry     

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     

Influence of supported vanadium catalyst on ethylene polymerization reactions

BACKGROUND: In the research area of homogeneous Ziegler–Natta olefin polymerization, classic vanadium catalyst systems have shown a number of favourable performances. These catalysts are useful for (i) the preparation of high molecular weight polymers with narrow molecular weight distributions, (ii) the preparation of ethylene/R‐olefin copolymers with high R‐olefin incorporation and (iii) the preparation of syndiotactic polypropylenes. In view of the above merits of vanadium‐based catalysts for polymerization reactions, the development of well‐defined single‐site vanadium catalysts for polymerization reactions is presently an extremely important industrial goal. The main aim of this work was the synthesis and characterization of a heterogeneous low‐coordinate non‐metallocene (phenyl)imido vanadium catalyst, V(NAr)Cl₃, and its utility for ethylene polymerization. RESULTS: Imido vanadium complex V(NAr)Cl₃ was synthesized and immobilized onto a series of inorganic supports: SiO₂, methylaluminoxane (MAO)‐modified SiO₂ (4.5 and 23 wt% Al/SiO₂), SiO₂? Al₂O₃, MgCl₂, MCM‐41 and MgO. Metal contents on the supported catalysts determined by X‐ray fluorescence spectroscopy remained between 0.050 and 0.100 mmol V g^?1 support. Thermal stability of the catalysts was determined by differential scanning calorimetry (DSC). Characterization of polyethylene was done by gel permeation chromatography and DSC. All catalyst systems were found to be active in ethylene polymerization in the presence of MAO or triisobutylaluminium/MAO mixture (Al/V = 1000). Catalyst activity was found to depend on the support nature, being between 7.5 and 80.0 kg PE (mol V)^?1 h^?1. Finally, all catalyst systems were found to be reusable for up to three cycles. CONCLUSION: Best results were observed in the case of silica as support. Acid or basic supports afforded less active systems. In situ immobilization led to higher catalyst activity. The resulting polyethylenes in all experiments had ultrahigh molecular weight. Finally, this work explains the synthesis and characterization of reusable supported novel vanadium catalysts, which are useful in the synthesis of very high molecular weight ethylene polymers. Copyright © 2007 Society of Chemical Industry     

Supported SiO2‐nBuSnCl3/MAO/(nBuCp)2ZrCl2 catalyzing MAO cocatalyst‐free ethylene polymerization: Study of hydrogen responsiveness

A supported metallocene catalyst was synthesized by sequentially loading methylaluminoxane (MAO) (30 wt % in toluene) and (ⁿBuCp)₂ZrCl₂ on partially dehydroxylated silica ES 70 modified by ⁿBuSnCl₃. Its shock load hydrogen responsiveness was evaluated by polymerizing ethylene for 1 h at 8.5 bar (g) and 75°C without separately feeding the MAO cocatalyst. The shock load hydrogen feeding increased the ethylene consumption (at a fairly constant rate), catalyst productivity, as well as the resin bulk density and average particle size at ΔP (of hydrogen) ≥～3.0 psi. The bulk density increased from 0.25 to 0.31 g/cm³. This shows a procedure for overcoming the inherent drop in catalyst productivity caused by heterogenization of metallocenes (that is a method for catalyst activation) and improving the resulting resin bulk density. The volume‐weighted mean particle diameter of the resulting polyethylenes was found to be 5.80–11.12‐fold that of the catalyst corresponding to ΔP = 0.00–7.11 psi, respectively. The resulting kinetic profiles showed to be fairly stable. However, M_w and polydispersity index were not affected. The particle size distribution, average particle size, and the scanning electron microscope photographs of the resulting resin particles confirmed the occurrence of the replication phenomenon. On the basis of the above findings, the mechanism of ethylene polymerization under the present experimental conditions has been revisited. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

The influence of the preparing conditions of SiO2 supported Cp2ZrCl2 catalyst on ethylene polymerization

In this work, ethylene was polymerized by using Cp₂ZrCl₂ supported on silica pretreated with methylaluminoxane (MAO) as the catalyst system. The influence of the conditions for the preparation of the heterogeneous catalyst, such as temperature, washing method of the catalytic solid, MAO and metallocene concentration in the support treatment, time of MAO, and metallocene immobilization on the support, type of alkylaluminum used in the support pretreatment, and calcination temperature of the support were investigated. Aluminum and zirconium content fixed on the silica surface were determined by inductively coupled plasma emission spectroscopy. Polymer characteristics were determined by gel permeation chromatography and differential scanning calorimetry. According to the results, the activity of some supported catalysts were far higher than with the homogeneous system. Moreover, polyethylene with very high molecular weights were also obtained and with molecular weight distribution larger than those produced with the homogeneous precursor. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2054–2061, 2002     

Effect of swelling response of the support particles on ethylene polymerization

Macroporous and modified macroporous poly(styrene-co-methyl methacrylate-co-divinylbenzene) particles (m-PS and mm-PS) supported Cp₂ZrCl₂ were prepared and applied to ethylene polymerization using methylaluminoxane (MAO) as cocatalyst. The influences of the swelling response of the support particles on the catalyst loading capabilities of the supports as well as on the activities of the supported catalysts were studied. It was shown that the Zr loadings of the supports and the activities of the supported catalysts increased with the swelling extent of the support particles. The m-PS or mm-PS supported catalysts exhibited very high activities when the support particles were well swollen, whereas those catalysts devoid of swelling treatment gave much lower activities. Investigation on the distribution of the supports in the polyethylene by TEM indicated that the swelling of the support particles allowed the fragmentation of the catalyst particles. In contrast, the fragmentation of the support particles with poor swelling was hindered during ethylene polymerization.     

Polymerization of ethylene by supported zirconium alkoxide complex

Dichlorobis(3‐hydroxy‐2‐methyl‐4‐pyrone)Zr(IV) was grafted onto different inorganic supports, namely SiO₂, MAO‐modified SiO₂, MCM‐41, Al₂O₃, and MgO. The resulting supported catalysts were shown to be active in ethylene polymerization using methylaluminoxane (MAO) as the catalyst. Catalysts were characterized by Rutherford Backscattering Spectrometry (RBS) and nitrogen adsorption method. The highest catalyst activities were observed for the zirconium complex supported on MCM‐41. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010