Two-dimensional double metal cyanide complexes: highly active catalysts for the homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide

Robertson, Nicholas J.; Qin, Zengquan; Dallinger, Gregory C.; Lobkovsky, Emil; Lee, Stephen; Coates, Geoffrey W.

doi:10.1039/b607963f

Cited by 106 publications

(75 citation statements)

References 42 publications

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“…There was also obvious absorption peak at 3,480 cm −1 in a, which was ascribed to stretching vibration of hydroxyl end groups. [42], the signals at 5.0 ppm and 4.0-4.3 ppm were assigned to CH and CH 2 groups in carbonate segments in polymer chain, respectively, while the signals at 3.2-3.8 ppm were assigned to both CH and CH 2 groups in ether segments. Therefore, the existence of carbonate and ether linkages in oligo-diol chain was further confirmed.…”

Section: Resultsmentioning

confidence: 96%

“…The excess ZnCl 2 and the complexing agents are indispensable for high activity, since the crystallinity of DMC is reduced [38]. The formed DMC catalyst is highly active for ring opening homopolymerization of epoxides and copolymerization of epoxides with CO 2 or cyclic anhydrides [29][30][31][39][40][41] 4 ] (M0Ni, Pd, Pt) with two-dimensional structure for compolymerization of CO 2 /PO with a rapid initial reaction, and there was no cyclic propylene carbonate produced [42]. Unfortunately, the DMC catalyst is heterogeneous, the catalytic mechanism is still not clear, although Darensbourg prepared a series of homogeneous DMC catalyst for cyclohexene oxide/CO 2 copolymerization [43,44].…”

Section: Resultsmentioning

confidence: 99%

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Selective synthesis of oligo(carbonate-ether) diols from copolymerization of CO2 and propylene oxide under zinc-cobalt double metal cyanide complex

et al. 2012

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Colorless oligo(carbonate-ether) diols were selectively synthesized in high efficiency from copolymerization of CO 2 and propylene oxide (PO) using Zn 3 [Co(CN) 6 ] 2 -based double metal cyanide complex (DMC) as catalyst and different molecular weight polypropylene glycols (PPGs) as chain transfer agent. The catalytic activity was related to carbonate unit content and molecular weight of target oligo(carbonate-ether) diols, for oligo(carbonate-ether) diol with number average molecular weight of 6.4 kg/mol and carbonate unit content of 34.3 %, it reached 10.0 kg oligomer/g DMC catalyst during 10 h of copolymerization. Generally, the number average molecular weight of the oligo(carbonateether) diol was tunable between 1.8 kg/mol and 6.4 kg/mol, and the molecular weight distribution was controllable between 1.14 and 1.83. Moreover, the carbonate unit content in the oligo-diols can be adjusted between 15.3 % and 62.5 %, lower temperature and higher CO 2 pressure were favorable for higher carbonate content. Better selectivity of oligo(carbonateether)diol over propylene carbonate(PC) was realized, where the weight ratio of PC (W PC ) was controlled less than 8.0 wt%. We also found that the alkali metal ion residue may play an important role in PC formation, in some cases this effect may be more significant than backbiting process, removing the residual alkali metal ion should be meaningful in the future to further reduce the PC formation.

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Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 99%

Selective synthesis of oligo(carbonate-ether) diols from copolymerization of CO2 and propylene oxide under zinc-cobalt double metal cyanide complex

et al. 2012

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“…The main drawbacks of these homogeneous catalysts are their lower activities (TONs <20 g of polymer/g of Zn). Coates and co-workers developed two-dimensional Co[Ni(CN) 4 ] catalysts which showed good productivity for PO copolymerisation (TON,~1,860 g PO/g Co, at 130 C and 54.4 atm CO 2 ), albeit with rather lower CO 2 incorporation [20]. There are very few reports concerning the possible mechanisms for the heterogeneous catalysts [26,30].…”

Section: Early Discoveries and Heterogeneous Systemsmentioning

confidence: 99%

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Romain

Thevenon

Saini

et al. 2015

Topics in Organometallic Chemistry

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This review describes selected metal catalysts for the copolymerisation of epoxides and carbon dioxide to produce polycarbonates. It highlights kinetic and mechanistic studies which have implicated di-or (multi-) metallic pathways for this catalysis and the subsequent development of highly active and selective di-/(multi-) nuclear catalysts. The emphasis is on homogeneous di-/bimetallic catalysts.

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“…In some cases, Salen-Co(III) complexes may produce perfectly alternating CO 2 /PO copolymer not containing any ether linkage [14][15][16][17], ether linkage exists under high conversion rate or in case when higher molecular weight PPC is required. Heterogeneous zinc glutarate catalysts also produce PPC containing a certain amount of ether linkages (1-5 mol%) [9], while double metal cyanide catalysts give copolymers containing substantial amount of ether linkages during CO 2 /propylene oxide copolymerizations [18,19].…”

Section: Introductionmentioning

confidence: 99%

Ether linkage in poly(1,2-propylene carbonate), a key structure factor to tune its performances

et al. 2012

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As an alternating copolymer of CO 2 and propylene oxide, poly(1,2-propylene carbonate) (PPC) should be composed of fully carbonate structure, whereas it generally contains certain ether linkage due to the existence of competitive formation of ether linkage by consecutive epoxide enchainment. Though the ether linkage was not always the dominant structure in PPC, a new understanding was provided in that the ether linkage was crucial structure factor on the PPC performances, especially for oxygen barrier property, transparency, thermal and mechanical properties. The gas barrier properties and transparency of PPC film became worse with increasing ether linkages, the oxygen, nitrogen and carbon dioxide permeability of PPC with ether linkage of 0.6 % were 14 cm 3 /m 2 /24 h/0.1 MPa, 11 cm 3 /m 2 /24 h/ 0.1 MPa and 220 cm 3 /m 2 /24 h/0.1 MPa, respectively, while for PPC with ether linkage of 54.1 %, they became 116 cm 3 / m 2 /24 h/0.1 MPa, 108 cm 3 /m 2 /24 h/0.1 MPa and 599 cm 3 / m 2 /24 h/0.1 MPa, respectively. When the ether linkage in PPC increased from 0.6 % to 54.1 %, the thermal decomposition temperature at 5 wt% loss(T d-5% ) increased from 218.6°C to 241.0°C, while the glass-transition temperature (T g ) decreased from 45.2°C to 11.1°C, meanwhile, the room temperature tensile strength decreased from 55.4 MPa to 2.3 MPa, and the elongation at break increased from 8.5 % to 1558.2 %.

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Two-dimensional double metal cyanide complexes: highly active catalysts for the homopolymerization of propylene oxide and copolymerization of propylene oxide and carbon dioxide

Cited by 106 publications

References 42 publications

Selective synthesis of oligo(carbonate-ether) diols from copolymerization of CO2 and propylene oxide under zinc-cobalt double metal cyanide complex

Selective synthesis of oligo(carbonate-ether) diols from copolymerization of CO2 and propylene oxide under zinc-cobalt double metal cyanide complex

Dinuclear Metal Complex-Mediated Formation of CO2-Based Polycarbonates

Ether linkage in poly(1,2-propylene carbonate), a key structure factor to tune its performances

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