Anchoring sulfonic acid on silica surface through Si C bond for immobilization of catalyst for polyketone synthesis

Eo, Seong Chan; Lee, Seul; Park, Geun Ho; Jeon, Jong Yeob; Lee, Hyun Ju

doi:10.1016/j.cattod.2015.08.060

Cited by 12 publications

(10 citation statements)

References 39 publications

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“…Homogeneous single-site catalysts, such as metallocene and half-metallocene, and post-metallocene catalysts are actively used in the production of polyethylene (PE) and polypropylene (PP), although most PE and PP is still produced by suing heterogeneous Ziegler-Natta catalysts [1,2]. While homogeneous catalysts can be directly used in a solution process where polymers (e.g., polyolefin elastomer (POE) with high α-olefin content) are formed by dissolution in solvent, they should be immobilized on an inorganic support, e.g., silica, in order to be applied in a slurry-process or a gas-phase process, where the morphology of the generated polymer particles is of importance for stable operation [3][4][5][6][7][8][9][10][11]. 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.…”

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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“…Considering the production costs and properties of polymers affected by reactor fouling, it is essential to resolve this issue. Although mechanical microemulsion methods and the addition of heterogeneous materials have been reported to resolve the fouling issue of polyketones, − to the best of our knowledge, there are no reports on the formation of antifouling polyketones without the use of exogenous heterogeneous seeds or microemulsion methods.…”

Section: Introductionmentioning

confidence: 99%

Self-Organized Nanosalts of Pd(II)-Ammonium-Tethered Carboxylic Acid for the Synthesis of Antifouling Polyketones

Lim

Noh

Cheong

et al. 2017

ACS Sustainable Chem. Eng.

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Pd(II) nanosalts formed from [LnPd(OAc)2] (Ln = 1,3-bis(di-o-methoxyphenylphosphino)propane) and ammonium tethered carboxylic acids in MeOH were utilized for the synthesis of antifouling polyketones from CO and olefin; this is the first instance of the synthesis of antifouling polyketones in the absence of additional heterogeneous seeds. The polymerization of CO and olefin achieved with the in situ-generated Pd(II) nanosalts was studied, and the nanosalts were analyzed by dynamic light scattering (DLS) experiments.

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“…Thus, antifouling technologies are critical for the commercialization of polyketones . As an antifouling method, seed materials have been added to the reaction media. , However, further exploration is required to reduce the amount of seed materials. Considering the catalyst activation of (P–P)Pd(OAc) 2 by sulfonic acids, we expect that solid materials having sulfonic acids can be used as seed materials in polyketone synthesis.…”

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Hollow and Microporous Organic Polymers Bearing Sulfonic Acids: Antifouling Seed Materials for Polyketone Synthesis

et al. 2016

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The reactor fouling is a notorious obstacle in managing continuous synthetic processes of polyketones. The fouling raises synthetic costs and reduces the bulk density of polymers. Thus, efficient seed materials are required for antifouling performance. Hollow microporous organic polymers (HMOPs) were prepared using ZIF-8 nanoparticles as templating materials. Sulfonic groups were incorporated into HMOP via a post synthetic approach. The resultant HMOP−SO 3 H (20−90 μg/mL in methanol) showed successful catalyst activation and antifouling performance in polyketone synthesis.

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Anchoring sulfonic acid on silica surface through Si C bond for immobilization of catalyst for polyketone synthesis

Cited by 12 publications

References 39 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

Self-Organized Nanosalts of Pd(II)-Ammonium-Tethered Carboxylic Acid for the Synthesis of Antifouling Polyketones

Hollow and Microporous Organic Polymers Bearing Sulfonic Acids: Antifouling Seed Materials for Polyketone Synthesis

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