Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copolymerization of Ethylene and Vinyl Fluoride by Self-Assembled Multinuclear Palladium Catalysts.

ABSTRACT: The self-assembled multinuclear PdII complexes {(Li-OPOOMe2)PdMe(4-5-nonyl-pyridine)}4Li2Cl2 (C, Li-OPOOMe2 = PPh(2-SO3Li-4,5-(OMe)2-Ph)(2-SO3--4,5-(OMe)2-Me-Ph)), {(Zn-OP-P-SO)PdMe(L)}4 (D, L = pyridine or 4-tBu-pyridine, [OP-P-SO]3- = P(4-tBu-Ph)(2-PO32--5-Me-Ph)(2-SO3--5-Me-Ph)), and {(Zn-OP-P-SO)PdMe(pyridine)}3 (E) copolymerize ethylene and vinyl fluoride (VF) to linear copolymers. VF is incorporated at levels of 0.1-2.5 mol% primarily as in-chain -CH2CHFCH2- units. The molecular weight distributions of the copolymers produced by D and E are generally narrower than for catalyst C, which suggests that the Zn-phosphonate cores of D and E are more stable than the Li-sulfonate-chloride core of C under copolymerization conditions. The ethylene/VF copolymerization activities of C-E are over 100 times lower and the copolymer molecular weights (MWs) are reduced compared to the results for ethylene homopolymerization by these catalysts.

SUBMITTER: Liu Q

PROVIDER: S-EPMC7407146 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Copolymerization of Ethylene and Vinyl Fluoride by Self-Assembled Multinuclear Palladium Catalysts.

Liu Qian Q Jordan Richard F RF

Polymers 20200719 7

The self-assembled multinuclear PdII complexes {(Li-OPOOMe2)PdMe(4-5-nonyl-pyridine)}4Li2Cl2 (C, Li-OPOOMe2 = PPh(2-SO3Li-4,5-(OMe)2-Ph)(2-SO3--4,5-(OMe)2-Me-Ph)), {(Zn-OP-P-SO)PdMe(L)}4 (D, L = pyridine or 4-tBu-pyridine, [OP-P-SO]3- = P(4-tBu-Ph)(2-PO32--5-Me-Ph)(2-SO3-</su ...[more]

PMID: 32707738

Similar Datasets

Direct copolymerization of ethylene with protic comonomers enabled by multinuclear Ni catalysts.

Project description:Ethylene/polar monomer coordination copolymerization offers an attractive way of making functionalized polyolefins. However, ethylene copolymerization with industrially relevant short chain length alkenoic acid remain a big challenge. Here we report the efficient direct copolymerization of ethylene with vinyl acetic acid by tetranuclear nickel complexes. The protic monomer can be extended to acrylic acid, allylacetic acid, ω-alkenoic acid, allyl alcohol, and homoallyl alcohol. Based on X-ray analysis of precatalysts, control experiments, solvent-assisted electrospray ionization-mass spectrometry detection of key catalytic intermediates, and density functional theory studies, we propose a possible mechanistic scenario that involves a distinctive vinyl acetic acid enchainment enabled by Ni···Ni synergistic effects. Inspired by the mechanistic insights, binuclear nickel catalysts are designed and proved much more efficient for the copolymerization of ethylene with vinyl acetic acid or acrylic acid, achieving the highest turnover frequencies so far for both ethylene and polar monomers simultaneously.

| S-EPMC8560877 | biostudies-literature

Mechanistic Studies for Palladium Catalyzed Copolymerization of Ethylene with Vinyl Ethers.

Project description:The mechanism of ethylene with vinyl ether (VE, CH2=CHOEt) copolymerization catalyzed by phosphine-sulfonate palladium complex (A) was investigated by density functional theory (DFT) calculation. On achieving an agreement between theory and experiment, it is found that the favorable 1,2-selective insertion of VE into the complex A originates from stronger hydrogen interaction between the oxygen atom of VE and the ancillary ligand of catalyst A. Additionally, VE insertion is easier into the ethylene pre-inserted intermediate than that into the catalyst to form the resultant copolymers with the major units of OEt in chain and minor units of OEt at the chain end. The effect of β-OEt and β-H elimination was explored to elucidate chain termination and the molecular weight of copolymers. Furthermore, a family of cationic catalysts has been demonstrated to copolymerize ethylene with VE along with our modified cationic complex B with higher incorporation of VE and reactivity in comparison with complex A, which was modelled computationally by increasing the strong interactions between the catalyst and monomer moiety. Other than VE, the activity of cationic complex B for copolymerization of vinyl chloride and methacrylate is also computed successfully.

| S-EPMC7603233 | biostudies-literature

Palladium-catalyzed allylic etherification of phenols with vinyl ethylene carbonate

Project description:The palladium-catalyzed decarboxylative reactions of phenols and vinyl ethylene carbonate to produce allylic aryl ethers under mild conditions have been established. Adopting an inexpensive PdCl2(dppf) catalyst promotes the efficient conversion of phenols to the corresponding allylic aryl ethers via the formation of a new C-O bond in good isolated yields with complete regioselectivities, acceptable functional group tolerance and operational simplicity. The robust procedure could be completed smoothly by conducting a scaled-up reaction with comparable efficiency to afford the target product.

| S-EPMC9354801 | biostudies-literature

Palladium-scavenging self-assembled hybrid hydrogels - reusable highly-active green catalysts for Suzuki-Miyaura cross-coupling reactions.

Project description:A hybrid hydrogel based on 1,3:2,4-dibenzylidene sorbitol (DBS) modified with acyl hydrazides combined with agarose was used for in situ reduction and binding of palladium from aqueous mixtures without the need for an external reducing agent. Palladium uptake was monitored and the formation of Pd nanoparticles (PdNPs) trapped within the gel and located close to the nanofibres was confirmed. This gel effectively scavenges palladium from solution to concentrations < 0.04 ppm - well below the recommended limits for pharmaceutical products. The resulting hybrid hydrogel with embedded PdNPs was used as a catalyst for Suzuki-Miyaura cross-coupling reactions. The gel network stabilises PdNPs, preventing aggregation/leaching and giving excellent catalytic lifetimes. The gel acts as a simple reaction dosing form, being simply added to reactions performed in green solvents in air. Once reactions are complete, the gel can be simply removed, recycled and reused (>10 times). Reactions were purified by simple washing protocols, and leaching of Pd from the gels is limited (<1 ppm). The gels were also used in flow-through mode, giving efficient, rapid reactions, with easy work-up. These catalytic gels combine advantages of homogeneous and heterogeneous catalysts - they are solvent compatible with the reaction taking place in a solution-like environment, while the solid-like gel network enables catalyst recycling. In summary, these hydrogels scavenge 'waste' palladium and convert it into gel 'wealth' capable of efficient, environmentally-friendly Suzuki-Miyaura catalysis.

| S-EPMC6301269 | biostudies-literature

Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst.

Project description:Density functional theory has been used to elucidate the mechanism of Pd copolymerization of cyclopropenone with ethylene. The results reveal that introducing ethylene and cyclopropenone to Pd catalyst is thermodynamically feasible and generates the α,β-unsaturated ketone unit (UnitA). Cis-mode insertion and Path A1a are the most favorable reaction routes for ethylene and cyclopropenone, respectively. Moreover, cyclopropenone decomposition can generate CO in situ without a catalyst or with a Pd catalyst. The Pd-catalyzed decomposition of cyclopropenone exhibits a lower reaction barrier (22.7 kcal/mol) than its direct decomposition. Our study demonstrates that incorporating CO into the Pd catalyst can generate the isolated ketone unit (UnitB). CO is formed first; thereafter, UnitB is generated. Therefore, the total energy barrier of UnitB generation, accounting for the CO barrier, is 22.7 kcal/mol, which is slightly lower than that of UnitA generation (24.0 kcal/mol). Additionally, the possibility of copolymerizing ethylene, cyclopropenone, and allyl acetate (AAc) has been investigated. The free energy and global reactivity index analyses indicate that the cyclopropenone introduction reaction is more favorable than the AAc insertion, which is consistent with the experimental results. Investigating the copolymerization mechanism will help to develop of a functionalization strategy for polyethylene polymers.

| S-EPMC9739415 | biostudies-literature

Supramolecular enzyme-mimicking catalysts self-assembled from peptides.

Project description:Natural enzymes catalyze biochemical transformations in superior catalytic efficiency and remarkable substrate specificity. The excellent catalytic repertoire of enzymes is attributed to the sophisticated chemical structures of their active sites, as a result of billions-of-years natural evolution. However, large-scale practical applications of natural enzymes are restricted due to their poor stability, difficulty in modification, and high costs of production. One viable solution is to fabricate supramolecular catalysts with enzyme-mimetic active sites. In this review, we introduce the principles and strategies of designing peptide-based artificial enzymes which display catalytic activities similar to those of natural enzymes, such as aldolases, laccases, peroxidases, and hydrolases (mainly the esterases and phosphatases). We also discuss some multifunctional enzyme-mimicking systems which are capable of catalyzing orthogonal or cascade reactions. We highlight the relationship between structures of enzyme-like active sites and the catalytic properties, as well as the significance of these studies from an evolutionary point of view.

| S-EPMC9830222 | biostudies-literature

Effect of Borate Cocatalysts toward Activity and Comonomer Incorporation in Ethylene Copolymerization by Half-Titanocene Catalysts in Methylcyclohexane

Project description:Ethylene copolymerizations with 2-methyl-1-pentene, 1-dodecene

| S-EPMC9955119 | biostudies-literature

Use of Vanadium Complexes Bearing Naphthalene-Bridged Nitrogen-Sulfonate Ligands as Catalysts for Copolymerization of Ethylene and Propylene.

Project description:Vanadium complexes bearing naphthalene-bridged nitrogen-sulfonate ligand ([ê²(N,O)-8-(PhN)-1-naphthalenesulfonato]VOCl (1a) and [ê²(N,O)-8-(PhN)-1-naphthalenesulfonato]VCl₂ (1b)) were synthesized. Activated by ethylaluminium sesquichloride (EASC) and in the presence of ethyl trichloroacetate (ETCA) as reactivator, complexes 1a and 1b showed activities of up to 39.1 kg polymer (mol V)-1 h-1, affording the copolymers with high molecular weights (Mw up to 28 × 10⁴) and narrow molecular weight distributions (Mw/Mn ~ 3.0) as well as high propylene incorporation of up to 49.4%. Compared to the traditional VOCl₃ system, these complexes exhibited higher propylene incorporation ability and higher catalytic activities especially at high polymerization temperatures of 50 °C and above. Determined by DSC and 13C NMR, the copolymers obtained with 1a and 1b had more random structures than that with the VOCl₃ system.

| S-EPMC6418982 | biostudies-literature

Titanium complex with an [OSSO]-type bis(phenolate) ligand for ethylene copolymerization with vinyl polar monomer based on group protection.

Project description:The [OSSO]-type bis(phenolate) titanium complex 1 activated by methylaluminoxane (MAO) was tested as a homogeneous catalyst for ethylene coordination copolymerization with protected vinyl polar monomer of p-tert-butyl-dimethylsilyloxystyrene (p-TBDMSOS). The results showed that the active species were almost not poisonous to the catalyst by the protected vinyl polar monomer. Moreover, the composition and sequence length as well as sequence distribution in the copolymers were investigated by theoretical calculation and 13C nuclear magnetic resonance (13C NMR) characterization. Especially, the incorporation ratio of p-TBDMSOS into the polyethylene chain could be controlled by changing p-TBDMSOS concentration in the feed. Interestingly, an approximate alternating copolymer of poly(E-alt-(p-TBDMSOS)) could be formed when the p-TBDMSOS feed concentration increased to 1.0 mol L-1. Subsequently, the poly(ethylene-co-(p-hydroxystyrene)) (poly(E-co-(p-HOS))) could be prepared by a facile deprotection in terms of desilylation of tert-butyldimethylsilyl ether. The hydrophilicity of poly(E-co-(p-HOS)) films were investigated by water contact angle measurements.

| S-EPMC9070498 | biostudies-literature

New Titanium(IV)-Alkoxide Complexes Bearing Bidentate OO Ligand with the Camphyl Linker as Catalysts for High-Temperature Ethylene Polymerization and Ethylene/1-Octene Copolymerization.

Project description:In order to increase the thermal stability of olefin polymerization precatalysts, new titanium(IV) complexes with diolate ligands differing in the degree of steric hindrances were synthesized from readily available precursor (±)camphor. The structures of the complexes 1-2 were established by X-ray diffraction. Complexes 1-4 in the presence of an activator {EtnAlCl3-n + Bu2Mg} catalyzed the synthesis of UHMWPE with an Mv up to 10 million and a productivity of up to 3300 kg/molTi·atm·h. The obtained polymers are obviously characterized by a low density of macromolecular entanglement, which makes it possible to use the solid-phase method for their processing. The mechanical characteristics of the oriented UHMWPE films had a breaking strength up to 2.7 GPa and an elastic modulus of up to 151 GPa. The precatalysts 1-4 were also active in ethylene/1-octene copolymerization. The comonomer content was in the range of 1.4-4.6 mol%. The use of a rigid linker and an increase in the steric load of the diolate complexes ensured the thermal stability of the catalytic system in the range of 50-70 °C.

| S-EPMC9658800 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data