Homopolymerization of 5-alkyl-2-norbornenes and their copolymerization with norbornene over novel Pd(acac)2/PPh3/BF3OEt2 catalyst system

Myagmarsuren, G.; Lee, Ki-Soo; Jeong, O-Yong; Ihm, Son‐Ki

doi:10.1016/j.polymer.2005.02.112

Cited by 41 publications

(24 citation statements)

References 28 publications

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“…Aluminum alkyl-free cationic Pd-catalyzed systems with O^O-chelating ligands (O^O ¼ b-diketonates or carboxylates) have shown promising results for oligomerization of ethylene, 28 selective dimerization of styrene, [29][30][31][32][33] and polymerization of norbornene and its derivates. [34][35][36] However, these Pd-catalyzed systems needed an additional Lewis acid such as BF 3 $OEt 2 , In(OTf) 3 or Cu(OTf) 2 to generate active catalytic species.…”

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confidence: 99%

[Pd(acac)(MeCN)₂]BF₄: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

et al. 2015

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confidence: 99%

[Pd(acac)(MeCN)₂]BF₄: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

et al. 2015

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“…Both norbornene derivatives exhibited high polymerization reactivities, and the corresponding polymers were obtained in good yields with high molecular weights (Table ). The syntheses of various addition homo‐ and copolymers from 5‐alkyl‐2‐norbornenes have been described in the literature; however, to the best of our knowledge, addition poly(5‐ n ‐octyl‐2‐norbornene) is a new polymer. The structure of the polymers was confirmed with the help of NMR‐ and IR‐spectroscopy (Figures S1 and S2, Supporting Information).…”

Section: Methodsmentioning

confidence: 69%

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Wozniak

Bermesheva

Borisov

et al. 2019

Macromol. Rapid Commun.

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ated petroleum gases. The realization of this process allows avoiding problems with the condensation of hydrocarbons (i.e., to reduce the dew point) and pre-detonating coking in compressor engines. [4,5] The separated C 2+ fraction will be a valuable feed for further chemical processing, or it can be used as a fuel. For a successful solution of the abovementioned task, membranes that show solubilitycontrolled permeation (i.e., which are characterized by higher permeability of heavier components of a mixture) seem to be the most attractive. For a long time, it was believed that the solubility-controlled permeation is a feature of rubbery polymers. In particular, it took place for the most permeable rubber-polydimethylsiloxane, while for convenient glassy polymers the permeability of hydrocarbons usually reduces with the size of penetrants mole cules. [5,6] At the same time, the use of glassy polymers in this process could extend frames and conditions of its application owing to high glass transition temperatures, good mechanical properties, and the promising combination of membrane characteristics of glassy polymers (glassy polymers dominate the polymers near or on the upper bound in contrast to rubbery polymers [7] ). The discovery of glassy poly(trimethylsilylpropyne) (PTMSP) and other highly permeable polyacetylenes in the last decades of the twentieth century quite unexpectedly revealed that glassy polymers indeed could possess the solubility controlled gas permeation of hydrocarbons. [8,9] Later it was shown that some other glassy polymers with large free volume polymers of intrinsic microporosity (PIM's) [10,11] and addition polynorbornenes bearing Me 3 Si-side groups [12,13] ) also exhibited the solubility controlled permeation. The main reasons for this phenomenon were the nanoporous nature of these glassy polymers and the presence of large free volume. Unfortunately, the abovementioned nanoporous polymers have not found a practical application for separation of hydrocarbons mainly due to the significant aging over time. These materials, as well as polysiloxanes, are extremely permeable membranes, so higher permeable polymers are not apparently required. Therefore, the process of hydrocarbon separation would be improved if the separation selectivity and polymers stability could be enhanced. To overcome these problems, low free volume glassy polynorbornenes [14][15][16][17] and polyacetylenes [18][19][20] have been successfully developed. The solubility-controlled permeation of hydrocarbons in these polymers Addition Poly(alkylnorbornenes) Nanoporous glassy polymers are perspective materials for the fabrication of gas separation membranes, especially for the application of gaseous hydrocarbon separation. However, the drawback of such materials is the pronounced physical aging resulting in the dramatic drop of gas transport properties due to relaxation of high-free-volume fraction in time. Herein, a novel and readily available group of such glassy polymers is reported based on 5-alkylnorbornenes. These polym...

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“…Beginning with the BF 3 adduct, the first step of the catalytic reaction involves the transformation of κ 2 ‐O,O‐acetylacetonate to a π‐complex with a γ‐bonded acetylacetonate ligand. [ 39,86–88 ] In the next step, insertion of the coordinated NB into the Pd–C bond occurs (Figure 7). The reaction of 1b – 7b with BF 3 ·OEt 2 in the presence of hex‐1‐ene as a model substrate was monitored by FTIR (see Figures S84–S91, SI).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

Suslov

Abramov

Babenko

et al. 2021

Applied Organom Chemis

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The Pd (II) complexes trans-[PdCl 2 (μ-L)] 2 and [Pd(acac)(L)][BF 4 ] (L = RS (CH 2 ) 2 O(CH 2 ) 2 SR, R = Me, Et, n Pr, i Pr, n Bu, i Bu, n-hexyl, benzyl) were obtained through the reaction of Pd(cod)Cl 2 or [Pd(acac)(MeCN) 2 ][BF 4 ] with one equivalent of oxadithioether (L). The structural features of these complexes were analyzed by nuclear magnetic resonance (NMR) and Fouriertransform infrared spectroscopy (FTIR), as well as electrospray ionisation mass spectrometry and density functional theory calculations. The complexes diμ-(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S,S 0 )-bis[trans-dichloropalladium (II)] and (acetylacetonate-κ 2 O,O 0 )(2,10-dimethyl-6-oxa-3,9-dithiaundecane-κ 2 S, S 0 )palladium (II) tetrafluoroborate were characterized by X-ray diffractometry. The X-ray structures of each complex indicate an axial M-O interaction formed by the endodentate conformation of the oxadithioether ligand. Palladium (II) dichloride complexes with oxadithioethers were demonstrated to have a 16-membered dinuclear structure with a trans-configured S 2 PdCl 2 fragment. In the case of cationic palladium acetylacetonate complexes, only mononuclear complexes with a cis configuration of the oxadithioether fragment were observed. Variable temperature 1 H and 13 C NMR studies of the complexes demonstrate dynamic bonding of the oxadithioether ligands consistent with the presence of diastereoisomers that differ in the orientation of the S-R groups along with both endodentate and exodentate bonding modes in solution. FTIR studies of the complexes indicate the presence of isomers in the solid state. The palladium catalyst precursors trans-[PdCl 2 (μ-L)] 2 and [Pd (acac)(L)][BF 4 ] were found to be active in the addition polymerization of norbornene. In the presence of cocatalysts, such as diisobutylaluminum chloride and boron trifluoride etherate, Pd (II) complexes exhibited activities in the range of 10 5 to 10 7 g of polymer (mol of Pd) À1 h À1 . The catalyst systems

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Homopolymerization of 5-alkyl-2-norbornenes and their copolymerization with norbornene over novel Pd(acac)2/PPh3/BF3OEt2 catalyst system

Cited by 41 publications

References 28 publications

[Pd(acac)(MeCN)₂]BF₄: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

[Pd(acac)(MeCN)₂]BF₄: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

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Homopolymerization of 5-alkyl-2-norbornenes and their copolymerization with norbornene over novel Pd(acac)2/PPh3/BF3OEt2 catalyst system

Cited by 41 publications

References 28 publications

[Pd(acac)(MeCN)2]BF4: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

[Pd(acac)(MeCN)2]BF4: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

Addition Polyalkylnorbornenes: A Promising New Class of Si‐Free Membrane Materials for Hydrocarbons Separation

Synthesis of mononuclear and dinuclear palladium (II) complexes containing oxadithioether ligands and their catalytic activities in norbornene polymerization

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Product

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[Pd(acac)(MeCN)₂]BF₄: air-tolerant, activator-free catalyst for alkene dimerization and polymerization

[Pd(acac)(MeCN)₂]BF₄: air-tolerant, activator-free catalyst for alkene dimerization and polymerization