Effect of the zeolite support on the polymerization of propylene with immobilized ansa-zirconocene catalysts

Meshkova, I. N.; Кудинова, О. И.; Kovaleva, N. Yu.; Гринев, В. Г.; Ladygina, T. A.; Киселева, Елена; Новокшонова, Л. А.

doi:10.1134/s1560090409090127

Cited by 10 publications

(4 citation statements)

References 12 publications

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“…A great deal of researches focusing on inorganic supports such as silica gel, magnesium dichloride, molecular sieves, aluminium oxide, zeolite and clays have been reported [3][4][5][6][7] for olefin polymerization. The inorganic MgCl 2 and SiO 2 have been successfully applied in the conventional Ziegler-Natta or metallocene catalysts.…”

Section: Introductionmentioning

confidence: 99%

Immobilized Polyolefin Catalysts: Organic Versus Inorganic Supports

Wang¹

2023

ACSR

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The polyolefins are the most widely used synthetic resin and greatly influence nearly every walks of life. About 70% polyolefin production is made from the immobilized polyolefin catalysts in gas-phase, slurry or bulk process equipment. Although the inorganic supports have been successfully industrialized, some inconvenient drawbacks calls for a new type of support to solve those problems. Porous organic polymers (POPs) have proved to be an excellent choice and have been considered as a versatile platform for the deployment of catalysts. The flexible design and synthesis approach provides POPs with high surface area and bulk density, excellent flowability, and various functionalities for desired catalysts performance. The POPs-based polyolefin catalysts obtained high polymerization activity and tailored molecule structure including molecular weight, molecular weight distribution, chemical composition distribution, stereoregularity, etc. due to the nature of the organic support.

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Section: Introductionmentioning

confidence: 99%

Immobilized Polyolefin Catalysts: Organic Versus Inorganic Supports

Wang¹

2023

ACSR

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“…Heterogeneous catalysis is required in the gas-phase or the slurry process for industrial applications to avoid reactor fouling and to control the polymer morphology or the forming granule reactor by immobilization of the homogeneous catalytic sites into a carrier [ 16 , 17 , 18 , 19 , 20 ]. Inorganic supports, such as silica gel, magnesium chloride, aluminum oxide, zeolite, molecular sieves, etc., have been reported as metallocene catalysts carriers in numerous literatures.…”

Section: Introductionmentioning

confidence: 99%

Highly Flowable Nano TiO2/Porous Organic Polymer (POP) Supports for Efficient Metallocene Catalysts

et al. 2020

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Porous organic polymers (POPs) have proven to be an efficient support in the olefin polymerization catalyst field. In this paper, nano TiO2 beads were used to modulate the pore structure, bulk density, and surface morphology and flowability of the prepared POPs. With the incorporation of the hydrophilic nano TiO2 beads, the prepared TiO2/POP supports obtained reasonable specific surface area (100–300 m2/g) and higher bulk density (0.26–0.35 g/mL) and flowability than the pure POP supports. The results show that bulk density of the prepared TiO2/POP particles increased when adding an increased amount of TiO2, and when 37.5% TiO2 (weight percent to the total comonomers divinylbenzene (DVB) and 2-hydroxyethyl methacrylate (HEMA)) and 3:1 DVB/HEMA (molar ratio) were added, highly flowable TiO2/POP composites (POP-6 and POP-7) were obtained. With the modulation of the nano TiO2 template during the support synthesis, the prepared POP-7 particles successfully achieved a normal distribution with a narrow particle size distribution (PSD) of 0.717 and average particle size of 24.1 m, a specific surface area (SSA) of 279 m2/g, and relatively high bulk density of 0.30 g/mL. Furthermore, all the prepared TiO2/POP supports obtained higher ethylene polymerization activity than silica gel-supported commercial metallocene catalyst. The immobilized (n-BuCp)2ZrCl2/MAO@POP-7 catalyst exhibited the highest ethylene polymerization activity of 4794 kg PE/mol Zr.bar.h and productivity of 389 g PE/g cat, more than twice that of the commercial counterpart. Even higher catalyst productivity (3197 g PE/g cat) and bulk density of the produced PE (0.36 g/mL) could be obtained in higher ethylene partial pressure at 80 ∘C for 2 h, and the prepared TiO2/POP catalyst shows no obvious Zr+ active sites decay during the ethylene polymerization.

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“…In order to fulfill important requirements such as the control of product morphology, prevention of reactor fouling, and control of the catalyst cost for slurry or gas-phase process [4,5], immobilization of the metallocenes on suitable supports is necessary. Numerous studies on inorganic supports (MgCl 2 , MgF 2 , Al 2 O 3 , molecular sieves, zeolite, and clays) and immobilization procedures have been investigated [6][7][8][9][10][11][12][13][14]. However, these supports suffer from several drawbacks, including the need for complex chemical treatments to get rid of acidic groups on their surfaces and to obtain appropriate particle morphology, and the presence of residual inorganic fragments within the produced polyolefins that may affect their mechanical and optical properties [15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Porous Organic Polymers-Supported Metallocene Catalysts for Ethylene/1-Hexene Copolymerization

et al. 2018

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Porous organic polymers (POPs) have received much attention in adsorption, separation, and catalysis. In this paper, porous organic polymers with different pore structure were used as metallocene catalyst supports, and ethylene/1-hexene copolymerizations were conducted using the POPs-supported metallocene catalyst. The pore structure of the prepared POPs and the supported metallocene catalyst were characterized by nitrogen sorption porosimetry and non-local density functional theory simulation, and the molecular chain structure of the produced ethylene/1-hexene copolymers were investigated through gel permeation chromatography (GPC), IR analysis, differential scanning calorimetry (DSC), and temperature rising elution fractionation (TREF). The results show that the loading amount of active sites varied with different pore structures of the POP supports, and the active species scattered in different pore sizes had a moderate impact on the molecular chain growth and the molecular weight distribution. The IR, DSC, and TREF analysis revealedthat different branching degree, double bond content, and chemical composition distributions were detected from the molecular chain structure of the ethylene/α-olefin copolymers from different POPs and silica-supported metallocene catalysts, despite their similar IR, DSC, and TREF curves due to the same active species. Scanning electron microscopy (SEM) showed that porous ethylene/α-olefin copolymers with varied surface morphology were obtained from the POPs-supported metallocene catalysts with different pore structure.

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Effect of the zeolite support on the polymerization of propylene with immobilized ansa-zirconocene catalysts

Cited by 10 publications

References 12 publications

Immobilized Polyolefin Catalysts: Organic Versus Inorganic Supports

Immobilized Polyolefin Catalysts: Organic Versus Inorganic Supports

Highly Flowable Nano TiO2/Porous Organic Polymer (POP) Supports for Efficient Metallocene Catalysts

Porous Organic Polymers-Supported Metallocene Catalysts for Ethylene/1-Hexene Copolymerization

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