Application of electrochemically generated molybdenum-based catalyst system to the ring-opening metathesis polymerization of norbornene and a comparison with the tungsten analogue

Dereli, Okan; Aydoğdu, Cemil; Düz, Bülent; İmamoǧlu, Yavuz

doi:10.1002/aoc.907

Cited by 6 publications

(5 citation statements)

References 43 publications

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“…Before quenching, each polymerization was usually monitored for 99+% conversion via 1 H NMR. The olefinic proton peaks were used to determine the cis : trans ratio via peaks at ∼5.3 and ∼5.5 ppm, respectively, as reported by others. − Although in some cases these peaks were unresolved, in others they could be individually integrated and indicated a predominance of trans double bonds, on average 74 ± 6% for polymer series 2 ; this is similar to other reports for polynorbornenes made with Grubbs 1 catalyst …”

Section: Results and Discussionsupporting

confidence: 85%

“…The number-average molecular weights for the polymers were calculated from the 1 H NMR spectra as outlined above and, although generally higher than targeted, were close to the theoretical values. 1 H NMR spectra, via the olefinic signals at 5.45 and 5.26 ppm − in a ratio of 3:1, indicated that polymers 5 all had 75% cis linkages.…”

Section: Results and Discussionmentioning

confidence: 97%

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Studies of Ion Conductance in Polymers Derived from Norbornene Imidazolium Salts Containing Ethyleneoxy Moieties

Price¹,

Choi

Schoonover³

et al. 2019

Macromolecules

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“Two-armed” imidazolium polymers 2a–2f, most of which contain oxyethylene moieties as linkers and ethyleneoxy terminal units, were prepared via ROMP. These polymers were thermally stable, with 5% weight losses occurring at 350 ± 5 °C under nitrogen. Their glass transitions were −22 to −51 °C, mostly ∼3 °C higher than those of the respective monomers. The conductivities of the polymers were 4–30-fold lower than those of the respective monomers. The maximum room temperature (RT) conductivity, σ25 = 2.27 × 10–5 S/cm, was observed with the polymer 2f with a tetra(oxyethylene) linker (X = 4) and a terminal di(ethyleneoxy) unit (Y = 2). Reduction of the double bonds in polymers 2 resulted in only small changes in T g of the resultant 3 but 2.4-fold loss in RT conductivities. Four “one-armed” norbornene imidazolium TFSI monomers via ROMP produced polymers 5, whose T gs were generally low (−50 to −65 °C) and very close to those of the monomers. Although the RT conductivities were reduced by about an order of magnitude from the monomers, the polymers with tetra(oxyethylene) linkers (X = 4) and di- and triethyleneoxy terminal units (Y = 2 or 3) (5c and 5d) had σ25 ∼ 3 × 10–5 S/cm, similar to the best two-armed polymer. Two ABA triblock copolymers 8 were successfully synthesized from norbornene-N-phenylimide and two-armed monomers with different terminal ethyleneoxy units (1d and 1e); these polymers demonstrated single direction actuation, but their performance was mediocre because of phase mixing that prevented the formation of the required bicontinuous phase morphology.

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Section: Results and Discussionsupporting

confidence: 85%

Section: Results and Discussionmentioning

confidence: 97%

Studies of Ion Conductance in Polymers Derived from Norbornene Imidazolium Salts Containing Ethyleneoxy Moieties

Price¹,

Choi

Schoonover³

et al. 2019

Macromolecules

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“…[3] Several recent studies describe the use of WCl 6 -ē-Al-CH 2 Cl 2 and the MoCl 5 -ē-Al-CH 2 Cl 2 catalyst systems to effect ring-opening metathesis polymerization of norbornene. [17,18] The electrochemical W-based catalyst produces mainly cispolynorbornene (ca. 60%) whereas Mo-based catalyst produces mainly trans-polynorbornene (ca.…”

Section: Introductionmentioning

confidence: 99%

“…60%). [18] In light of our recent carbon arc work that was applied successfully in olefin metathesis reactions, [14] we describe the application of the MoCl 5 -C and WCl 6 -C systems to the ROMP of norbornene.…”

Section: Introductionmentioning

confidence: 99%

Application of carbon arc‐generated Mo‐ and W‐based catalyst systems to the ROMP of norbornene

Düz

Elbistan

Ece

et al. 2009

Applied Organom Chemis

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This study focuses on the application of the carbon arc-generated molybdenum-and tungsten-based catalyst systems, MoCl 5 -C and WCl 6 -C, to effect ring-opening metathesis polymerization (ROMP) of bicyclo[2.2.1]hept-2-ene (norbornene). The results are compared with those previously obtained by the electrochemically generated MoCl 5 -ē-Al-CH 2 Cl 2 and WCl 6 -ē-Al-CH 2 Cl 2 systems. The polymer products are characterized using 1 H and 13 C NMR, gel permeation chromatography, differential scanning calorimetry and thermo gravimetric analysis. According to NMR spectra analyses, the molybdenum-based catalyst system produced polynorbornene with ca 48% cis structure whereas tungsten system produced ca 56% cis structure polynorbornene and in both cases the polynorbornene had a blocky distribution.

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“…21,22 We previously reported many scientific studies on the application of WCl 6 -e À -Al-CH 2 Cl 2 catalyst system to olefin metathesis reactions [23][24][25][26][27][28][29] but only one study on MoCl 5 -e À -Al-CH 2 Cl 2 catalyst system to ROMP of norbornene. 30 In this paper we described the synthesis of ROMP of COT with the electrochemically generated W and Mo-based catalyst. The major advantages of these catalyst systems (WCl 6 -e À -Al-CH 2 Cl 2 and MoCl 5 -e À -Al-CH 2 Cl 2 ) electrochemically generated are easily preparation and higher selectivity.…”

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confidence: 99%

Electro-Induced Early Transition Metal Metathesis Catalyst Systems for the Production of Polyacetylene

Karabulut

2009

Polym. J.

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The use of electro-induced Mo and W-based catalysts has been investigated in the ring opening metathesis polymerization (ROMP) of 1,3,5,7-cyclooctatetraene (COT). The soluble and conjugated polyacetylene (PA) was obtained under ambient temperature and pressure without employing any secondary reagent (comonomer, chain transfer agent) or substituted monomer (R-COT). NMR analysis results show that the electrochemical Mo-based system leads to a completely (100%) trans product, however, mainly (80%) trans polymer was obtained with W-based analogue for PA.KEY WORDS: Ring Opening Metathesis Polymerization (ROMP) / 1,3,5,7-Cyclooctatetraene (COT) / Polyacetylene (PA) / Transition Metal Catalyst / Electrochemistry / Conjugated polymers, the simplest being polyacetylene, are of current interest because the substantial electronic delocalization along their backbones gives rise to interesting optical and nonlinear optical properties and allows them to become good electrical conductors. These properties might lead to a variety of applications including optical signal processing and information storage, lightweight substitutes for metals in batteries and materials for solar energy conversion.

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Application of electrochemically generated molybdenum-based catalyst system to the ring-opening metathesis polymerization of norbornene and a comparison with the tungsten analogue

Cited by 6 publications

References 43 publications

Studies of Ion Conductance in Polymers Derived from Norbornene Imidazolium Salts Containing Ethyleneoxy Moieties

Studies of Ion Conductance in Polymers Derived from Norbornene Imidazolium Salts Containing Ethyleneoxy Moieties

Application of carbon arc‐generated Mo‐ and W‐based catalyst systems to the ROMP of norbornene

Electro-Induced Early Transition Metal Metathesis Catalyst Systems for the Production of Polyacetylene

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