Porous organic polymer/MMT hybrid supports for efficient metallocene catalysts

Wang, Xiong; Kang, Wenqian; Li, Guangquan; Zhang, Pingsheng; Jia, Hui‐Qing; Gao, Dujuan

doi:10.1007/s10853-021-06518-5

Cited by 7 publications

(4 citation statements)

References 41 publications

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“…When a homogeneous catalyst is injected, as dissolved, into a slurry-or gas-phase reactor, the shape and size of the generated polymer particles are irregularly uncontrolled, making stable operation impossible (termed 'fouling') as well as causing low productivity due to low bulk density. Because a large portion of PE and PP is produced by the slurry and gas-phase processes, high-performance supported catalysts are essential in the industrial sector [12][13][14][15][16][17][18][19][20][21][22][23][24][25][26].…”

Section: Introductionmentioning

confidence: 99%

Syntheses of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for Preparing High-Performance Supported Catalyst

et al. 2022

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We synthesized a series of Me2Si-bridged ansa-zirconocene complexes coordinated by thiophene-fused cyclopentadienyl and fluorenyl ligands (Me2Si(2-R1-3-R2-4,5-Me2C7S)(2,7-R32C13H6))ZrMe2 (R1 = Me or H, R2 = H or Me, R3 = H, tBu, or Cl) for the subsequent preparation of supported catalysts. We determined that the fluorenyl ligand adopts an η3-binding mode in 9 (R1 = Me, R2 = H, R3 = H) by X-ray crystallography. Further, we synthesized a derivative 15 by substituting the fluorenyl ligand in 9 with a 2-methyl-4-(4-tert-butylphenyl)indenyl ligand, derivatives 20 and 23 by substituting the Me2Si bridge in 12 (R1 = Me, R2 = H, R3 = tBu) and 15 with a tBuO(CH2)6(Me)Si bridge, and the dinuclear congener 26 by connecting two complexes with a –(Me)Si(CH2)6Si(Me)– spacer. The silica-supported catalysts prepared using 12, 20, and 26 demonstrated up to two times higher productivity in ethylene/1-hexene copolymerization than that prepared with conventional (THI)ZrCl2 (21–26 vs. 12 kg-PE/g-(supported catalyst)), producing polymers with comparable molecular weight (Mw, 330–370 vs. 300 kDa), at a higher 1-hexene content (1.3 vs. 1.0 mol%) but a lower bulk density of polymer particles (0.35 vs. 0.42 g/mL).

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Section: Introductionmentioning

confidence: 99%

Syntheses of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for Preparing High-Performance Supported Catalyst

et al. 2022

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“…Polymer porous materials have become the focus of research in recent years because of their adjustable porosity, high specific surface area, adjustable mechanical strength, and so forth, and have been widely used in many fields such as adsorption, separation, 1–3 catalytic carriers, 4 energy storage, 5 and tissue engineering 6 . They were prepared by various methods, including direct synthesis, 7 block copolymer self‐assembly, 8 and emulsion template method 9 …”

Section: Introductionmentioning

confidence: 99%

κ‐Carrageenan/poly(sodium styrenesulfonate‐co‐acrylic acid) macroporous anionic monoliths: Dye adsorption and oil–water separation properties

Jia,

Cao,

et al. 2024

Polymers for Advanced Techs

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Abstractκ‐Carrageenan (κC) is a widely used food hydrogel, but its use as an environmental adsorption separation material still needs to be further developed. Herein, a novel macroporous anionic monolith was synthesized by the oil‐in‐water high internal phase emulsion template method. The monolith was obtained by the continuous phase polymerization of sodium styrenesulfonate (NaSS) and acrylic acid (AA), in which κC was introduced to form a semi‐interpenetrating network structure to improve its overall performance. The results showed that the mechanical strength of the monolith increased with κC content. Because of the use of two strong hydrophilic monomers, NaSS and AA, the porous monolith proved to be superoleophobic underwater. In addition, the porous materials had a strong cationic dye adsorption capacity (2455 mg/g for malachite green, 1180 mg/g for methylene blue) and a fast removal rate, good reusability, and oil–water separation. This work highlights their potential application value in the purification of complex water environments.

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“…However, the inorganic support components would eventually incorporate extra impurities and surface acidic groups in the final product, which might limit its applications in high value-added fields, such as the electronics and medical industries. As a potential clean and green alternative composed mainly of C, H and O atoms, etc., porous organic polymers (POPs) have received extensive attention in heterogeneous catalysis, including olefin polymerization, owing to their high surface area and controllable pore structure, flexible synthesis strategy and functionality [ 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. Moreover, the less hydrophilic surface of POPs allows them to endure higher impurity contents of moisture and oxygen in the polymerization medium, need no fastidious pre-treatment, and provides a polymerization medium more close to homogeneous catalysis [ 31 , 32 ].…”

Section: Introductionmentioning

confidence: 99%

Porous Organic Polymers-Supported Zeigler-Natta Catalysts for Preparing Highly Isotactic Polypropylene with Broad Molecular Weight Distribution

Wang

Xue-mei

et al. 2023

Polymers

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Porous organic polymers (POPs) have attracted much attention in numerous areas, including catalysis, adsorption and separation. Herein, POP supported Ziegler–Natta catalysts were designed for preparation of isotactic polypropylene (iPP). The POPs-based Ziegler–Natta catalysts exhibited the characteristic of broad molecular weight distribution (MWD > 11) with or without adding an extra internal electron donor. The added internal electron donor 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate (ID-2) used in cat-2 showed good propylene polymerization activity of 15.3 × 106 g·PP/mol·Ti·h, high stereoregularity with 98.2% of isotacticity index and broad molecular weight distribution (MWD) of 12.3. Compared to the MgCl2-supported Ziegler–Natta catalysts (cat-4) with the same ID-2, cat-2 showed higher chain stereoregularity for propylene polymerization. As seen in the TREF results, the elution peak of PP-2 (124.0 °C, 91.7%) is 1.5 °C higher than the isotactic fraction from PP-4 (122.5 °C, 87.2%), and even 1.2 °C higher than PP-5 prepared from ID-3 with the characteristics of high stereoregularity. Moreover, the pentad methyl sequence mmmm of PP-2 (93.0%) from cat-2 is 0.5% higher than that of PP-4 from cat-4. XPS analysis revealed that the minute difference in binding energy of Ti, Mg, C and O atoms exist between the inorganic MgCl2 and the organic polymer based Z–N catalysts. The plausible interaction mechanism of active sites of Mg and Ti with the functional groups in the POP support and the added ID was proposed, which could be explained by their high stereoregularity and the broad molecular weight distribution of the POP-based Z–N catalysts.

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Porous organic polymer/MMT hybrid supports for efficient metallocene catalysts

Cited by 7 publications

References 41 publications

Syntheses of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for Preparing High-Performance Supported Catalyst

Syntheses of Silylene-Bridged Thiophene-Fused Cyclopentadienyl ansa-Metallocene Complexes for Preparing High-Performance Supported Catalyst

κ‐Carrageenan/poly(sodium styrenesulfonate‐co‐acrylic acid) macroporous anionic monoliths: Dye adsorption and oil–water separation properties

Porous Organic Polymers-Supported Zeigler-Natta Catalysts for Preparing Highly Isotactic Polypropylene with Broad Molecular Weight Distribution

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