Synthesis, Structure and 1,3-Butadiene Polymerization Behavior of Vanadium(III) Phosphine Complexes

Leone, Giuseppe; Zanchin, Giorgia; Pierro, Ivana; Sommazzi, Anna; Forni, Alessandra; Ricci, Giovanni

doi:10.3390/catal7120369

Cited by 10 publications

(9 citation statements)

References 39 publications

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“…The stereospecificity strongly depends reciprocal orientation of coordinated monomers and the allyic terminal, differing from non‐metallocene catalyst for propene polymerization 21,22 . The formation of exo – exo configuration is believed to the originals for alternation in 1,2 insertion as ascertained by Ricci et al 29,35,43 and Ashitaka et al 46,47 …”

Section: Resultsmentioning

confidence: 96%

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Synthesis and properties of syndiotactic 1,2‐polybutadiene catalyzed by iron catalyst with phosphate as additive

et al. 2020

J of Applied Polymer Sci

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1,2 Syndiotactic polymerization of butadiene is accessible by iron catalysts prepared from commercially available iron sources, trialkylaluminum with additional phosphate as additive. The catalyst formation is quite robust in terms of handling and stability under polymerization conditions. Activity equal to 115 kg (polymer)/mol(Fe)Áh is achieved at 10,000 equiv. of monomer relative to the catalyst loading in 2 h at 50 C. The resultant polymer possesses 1,2 incorporation up to 80.2-93.1% with syndiotactic configuration (rrrr) of 40.2-85.2%. Crystallinity of polymers can be also tuned over a wide range degree from weak (2.1%) to high crystallinity (68.2%) by varying catalyst component feeding, enabling potential application as both rubber and resin. The higher activity of iron catalyst is preferred at hydrocarbon solvent n-hexane, n-heptane or toluene, higher temperature as well as trialkylalumium, such as tri-iso-butylaluminum, tri-ethylaluminum, and tri-methylaluminum as cocatalyst. Significant stereospecificity stability to variation for monomer concentration, type of alkylaluminum and temperature is also found. The high activity and 1,2-stereoselectivity featured with these thermal robust iron catalysts sheds light on the significance of additive on regulating stereo-polymerization promoted by conventional Ziegler-Natta catalysts. These features collectively could offer advantages for application in industry production of 1,2-syndiotactic polybutadiene.

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Section: Resultsmentioning

confidence: 96%

“…The optimal additive feeding is around 2–3 equiv. to iron (Run 8 and 1 vs. Run 5, 7, and 9, Table 1), allowing us to figure out the profile of active center is ligated with one or two additives in addition to a butadiene and an allylic chain end 43 . The excess additive dose per iron compound is probably due to its consumption by TIBA.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and properties of syndiotactic 1,2‐polybutadiene catalyzed by iron catalyst with phosphate as additive

et al. 2020

J of Applied Polymer Sci

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“…However, no marked differences were noted regarding the selectivity of the polymerization. This is the first example of the use of VCl 3 (bisphosphine) complexes for butadiene polymerization [17].…”

Section: The Present Issuementioning

confidence: 89%

Catalysts for the Controlled Polymerization of Conjugated Dienes

Visseaux

2018

Catalysts

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“…A deuterated solvent for NMR measurements (C 2 D 2 Cl 4 ) (Aldrich, >99.5% atom D) was used as received. All the vanadium phosphine complexes were synthesized according to that already reported in the literature [47].…”

Section: Methodsmentioning

confidence: 99%

Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes

et al. 2019

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Herein, we report the homo- and co-polymerization of ethylene (E) with norbornene (NB) catalyzed by vanadium(III) phosphine complexes of the type VCl3(PMenPh3-n)2 [n = 2 (1a), 1 (1b)] and VCl3(PR3)2 [R = phenyl (Ph, 1c), cyclohexyl (Cy, 1d), tert-butyl (tBu, 1e)]. In the presence of Et2AlCl and Cl3CCOOEt (ETA), 1a–1e exhibit good activities for the polymerization of ethylene, affording linear, semicrystalline PEs with a melting temperature of approximately 130 °C. Mainly alternating copolymers with high comonomer incorporation were obtained in the E/NB copolymerization. A relationship was found between the electronic and steric properties of the phosphine ligands and the catalytic performance. Overall, the presence of electron-withdrawing ligand substituents increases the productivity, complexes with aryl phosphine (weaker σ–donor character) exhibiting a higher (co)polymerization initiation rate than those with alkyl phosphines (stronger σ–donor character). Steric effects also seem to play a key role since 1d and 1e, having large size phosphines (PCy3 θ = 170° and PtBu3 θ = 182°, respectively) are more active than 1a (PMe2Ph θ = 122°). In this case, the larger size of PtBu3 and PCy3 likely compensates for their higher donor strength compared to PMe2Ph.

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Synthesis, Structure and 1,3-Butadiene Polymerization Behavior of Vanadium(III) Phosphine Complexes

Cited by 10 publications

References 39 publications

Synthesis and properties of syndiotactic 1,2‐polybutadiene catalyzed by iron catalyst with phosphate as additive

Synthesis and properties of syndiotactic 1,2‐polybutadiene catalyzed by iron catalyst with phosphate as additive

Catalysts for the Controlled Polymerization of Conjugated Dienes

Homo- and Copolymerization of Ethylene with Norbornene Catalyzed by Vanadium(III) Phosphine Complexes

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