Effect of Zn/Co initial preparation ratio in the activity of double metal cyanide catalysts for propylene oxide and CO2 copolymerization

Dios, María Pinilla-de; Andrés-Iglesias, Cristina; Fernández, Antonio Maestro; Salmi, Tapio; Galdámez, J. Román; García-Serna, Juan

doi:10.1016/j.eurpolymj.2017.01.028

Cited by 16 publications

(6 citation statements)

References 29 publications

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“…The ratio of Zn and Co was unaffected by the procedure. The isostructural modification of the catalyst is giving the unusual opportunity to assess the importance of the zinc bonded anions, which may be used to tune the action of DMC complexes in propoxylation or other catalytic processes [109,111]. Semi-batch copolymerization experiments mediated by DMC-NO 3 were performed at 100 • C to find that the CO 2 incorporation is much higher than found for the parent catalyst (Tables 2 and 10 .…”

Section: Co 2 /Po Copolymerization With Ion-exchanged Dmc Surfacesmentioning

confidence: 99%

DMC-Mediated Copolymerization of CO2 and PO—Mechanistic Aspects Derived from Feed and Polymer Composition

Stahl

Luinstra

2020

Catalysts

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The influence of composition of liquid phase on composition of poly(propylene ether carbonates) in the copolymerization of CO2 with propylene oxide (PO), mediated by a zinc chloride cobalt double metal cyanide, was monitored by FT-IR/CO2 uptake/size exclusion chromatography in batch and semi-batch mode. The ratio of mol fractions of carbonate to ether linkages F (~0.15) was found virtually independent on the feed between 60 and 120 °C. The presence of CO2 lowers the catalytic activity but yields more narrowly distributed poly(propylene ether carbonates). Hints on diffusion and chemistry-related restrictions were found underlying, broadening the distribution. The incorporation of CO2 seems to proceed in a metal-based insertion chain process, ether linkages are generated stepwise after external nucleophilic attack. The presence of amines resulted in lower activities and no change in F. An exchange of chloride for nitrate in the catalyst led to a higher F of max. 0.45. The observations are interpreted in a mechanistic scheme, comprising surface-base-assisted nucleophilic attack of external weak nucleophiles and of mobile surface-bound carboxylato entities on activated PO in competition to protonation of surface-bound alkoxide intermediates by poly(propylene ether carbonate) glycols or by surface-bound protons. Basic entities on the catalyst may promote CO2 incorporation.

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Section: Co 2 /Po Copolymerization With Ion-exchanged Dmc Surfacesmentioning

confidence: 99%

DMC-Mediated Copolymerization of CO2 and PO—Mechanistic Aspects Derived from Feed and Polymer Composition

Stahl

Luinstra

2020

Catalysts

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“…S1-S3). 2,5,17,[22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] In addition, the content and type of complexing agents and residual salts from the synthesis (KCl) may have an impact on the overall activity. 29,[37][38][39][40][41][42] Efforts for optimizing a catalyst are directed towards increasing the accessibility of active sites by radiation treatment, by trying to control the morphology e.g.…”

Section: Introductionmentioning

confidence: 99%

Analysis of propoxylation with zinc–cobalt double metal cyanide catalysts with different active surfaces and particle sizes

Stahl,

Luinstra

2024

React. Chem. Eng.

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“…However, there are few reports on heterogeneous catalytic systems for ROCOP of epoxides and cyclic anhydrides. Among them, most of the active heterogeneous catalysts are double mental cyanide (DMC) [30][31][32][33] and zinc glutarate (ZnGA), [34][35][36][37] but the low active limits their industrial application prospects.…”

Section: Introductionmentioning

confidence: 99%

Alternating ring‐opening copolymerization of cyclic anhydrides and epoxides by zeolitic imidazolate framework‐67: A promising approach

Xiao,

Hu,

et al. 2024

Applied Organom Chemis

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The ring opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is one of the most important ways to synthesize polyesters both in industrial and academic fields. Herein, the zeolitic imidazolate framework‐67 (ZIF‐67) was used as a heterogeneous catalyst for the ROCOP of epoxides and cyclic anhydrides without co‐catalyst and initiator. Notably, the obtained polyesters with alternate structures were proved by the 1H NMR spectrum and FTIR spectrum, which indicate the ROCOP is alternatively copolymerized. Kinetic study of the ROCOP of cyclohexene oxide (CHO) and phthalic anhydride (PA) shows that the polymerization reaction is first‐order kinetics. The apparent activation energy (Ea) of the ROCOP of CHO and PA catalyzed by ZIF‐67 was found to be about 104.4 KJ/mol. A possible mechanism of ROCOP of CHO and PA is that the metal Co coordinates with the oxygen atom on the monomer to weaken the C‐O bond thereby opening the ring structure and initiating the copolymerization reaction. In this study, a new system for the copolymerization of epoxide and anhydride catalyzed by heterogeneous catalysts was discovered, which has important guiding significance.

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Effect of Zn/Co initial preparation ratio in the activity of double metal cyanide catalysts for propylene oxide and CO2 copolymerization

Cited by 16 publications

References 29 publications

DMC-Mediated Copolymerization of CO2 and PO—Mechanistic Aspects Derived from Feed and Polymer Composition

DMC-Mediated Copolymerization of CO2 and PO—Mechanistic Aspects Derived from Feed and Polymer Composition

Analysis of propoxylation with zinc–cobalt double metal cyanide catalysts with different active surfaces and particle sizes

Alternating ring‐opening copolymerization of cyclic anhydrides and epoxides by zeolitic imidazolate framework‐67: A promising approach

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