Supercritical carbon dioxide as solvent for the copolymerization of carbon dioxide and propylene oxide using a heterogeneous zinc carboxylate catalyst

Darensbourg, Donald J.; Stafford, Nicole White; Katsurao, Takumi

doi:10.1016/1381-1169(95)00142-5

Cited by 105 publications

(50 citation statements)

References 13 publications

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“…39 However, PPC was obtained in a relatively low yield of Յ11.64 g polymer per gram of catalyst and cyclic propylene carbonate, as a byproduct, was additionally synthesized in a yield of Յ14% of the total reaction products. This result suggests that the supercritical CO 2 fluid is not a good solvent for its copolymerization with PO.…”

Section: Copolymerization With Po In Excess: Po As Solventmentioning

confidence: 99%

“…12 g per gram of catalyst. 39 Here, we report a highly efficient synthetic process of polycarbonate from CO 2 with PO using zinc glutarate as a catalyst, which can produce poly(propylene oxide) in a much higher yield than 34 g per gram of catalyst. In this new copolymerization process, PO is used as a comonomer as well as a reaction medium, so that no organic solvent is involved in the copolymerization, consequently producing no organic solvent waste.…”

Section: Introductionmentioning

confidence: 98%

See 1 more Smart Citation

A new copolymerization process leading to poly(propylene carbonate) with a highly enhanced yield from carbon dioxide and propylene oxide

Ree

Bae

Jung

et al. 1999

J. Polym. Sci. A Polym. Chem.

196

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Section: Copolymerization With Po In Excess: Po As Solventmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

A new copolymerization process leading to poly(propylene carbonate) with a highly enhanced yield from carbon dioxide and propylene oxide

Ree

Bae

Jung

et al. 1999

J. Polym. Sci. A Polym. Chem.

196

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“…Recently, we have reported a highly efficient copolymerization process of CO 2 and PO using zinc glutarate as a catalyst, which can produce poly(propylene carbonate) in a highly enhanced yield never achieved before. 20 In general, for the alternating copolymerization catalyzed by organozinc systems, the mechanism has been proposed to be of a coordinated anionic nature, with propagation occurring by monomer insertion between the growing polymer chain end and a catalyst fragment. 21,22 In addition to the organozinc catalyzed copolymerizations, the discovery of immortal polymerization with using aluminum complexes has expanded the utility of CO 2 as a comonomer in the production of polycarbonates.…”

Section: Introductionmentioning

confidence: 99%

Copolymerization of carbon dioxide and propylene oxide using an aluminum porphyrin system and its components

Jung

Ree

Chang

1999

J. Polym. Sci. A Polym. Chem.

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The catalytic activities of tetraphenylporphinatoaluminum chloride (TPPAlCl) and its propylene oxide adduct (TPPAl(PO)2Cl) were investigated in detail together with a quarternary salt Et4NBr for the copolymerization of carbon dioxide and propylene oxide. In addition, for the components and starting raw materials of the catalyst systems, catalytic activities were examined for the copolymerization. The TPPAlCl catalyst delivered oligomers containing ether linkages to a large extent, regardless of its PO adduction. And cyclic propylene carbonate, as byproduct, was formed in a very small portion. Using the TPPAlCl coupled with Et4NBr as a catalyst system, the formation of ether linkages was reduced significantly in the copolymerization; however, the obtained oligomer still contained ether linkages of 25.0 mol % in the backbone. On the other hand, the formation of cyclic carbonate was increased to 22.4 mol % relative to the oligomer product. The results indicate that the salt, which was coupled with the TPPAlCl catalyst, plays a key role in reducing the formation of ether linkage in the oligomer and, however, in enhancing the formation of cyclic carbonate. Similar results were obtained for the copolymerization catalyzed by the TPPAl(PO)2Cl/Et4NBr system. That is, the formation of ether linkages was not restricted further by the PO adduction of the TPPAlCl component in the catalyst system. Only oligomers with a relatively high molecular weight were produced. This indicates that the PO adduction of the TPPAlCl component contributes highly to the initiation and propagation step in the oligomerization, consequently leading to a relatively high molecular weight oligomer. In contrast, the Et4NBr, as well as the Et2AlCl, produced only cyclic carbonate in a very low yield. Furthermore, tetraphenylporphine exhibited no catalytic activity, regardless of using together with Et4NBr. On the other hand, the Et2AlCl coupled with Et4NBr provided a low molecular weight oligomer having ether linkages of 92.3 mol % in addition to the cyclic carbonate. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3329–3336, 1999

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“…Darensbourg et al reported that by varying the carbon dioxide pressure from 52 to 82 atm at 60°C without cosolvent, the copolymerization of carbon dioxide and propylene oxide produced the alternating copolymer (9.6 -24 g of polymer/g of Zn) with a carbonate linkage of 95% or higher (M w ϭ 65,000 -153,000). 68 However, when the reaction was carried out at lower carbon dioxide pressures such as 20 -34 atm, the ether linkage in the copolymer was increased. When the polymerization temperature was raised up to 85°C, the polymer yield increased, but the molecular weight of the copolymer was lowered.…”

Section: Recent Topics Utilization Of Supercritical Fluid Carbon Dioxidementioning

confidence: 99%

Copolymerization of carbon dioxide and epoxide

Sugimoto

Inoue

2004

J. Polym. Sci. A Polym. Chem.

364

142

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An erratum has been published for this article in J Polym Sci Part A: Polym Chem (2005) 43(4) 916.The alternating copolymerization of carbon dioxide and epoxide to produce polycarbonate has attracted the attention of many chemists because it is one of the most promising methodologies for the utilization of carbon dioxide as a safe, clean, and abundant raw material in synthetic chemistry. Recent development of catalysts for alternating copolymerization is based on the rational design of metal complexes, particularly complexes of transition metals with well‐defined structures. In this article, the history and recent successful examples of the alternating copolymerization of carbon dioxide and epoxide are described. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5561–5573, 2004

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Supercritical carbon dioxide as solvent for the copolymerization of carbon dioxide and propylene oxide using a heterogeneous zinc carboxylate catalyst

Cited by 105 publications

References 13 publications

A new copolymerization process leading to poly(propylene carbonate) with a highly enhanced yield from carbon dioxide and propylene oxide

A new copolymerization process leading to poly(propylene carbonate) with a highly enhanced yield from carbon dioxide and propylene oxide

Copolymerization of carbon dioxide and propylene oxide using an aluminum porphyrin system and its components

Copolymerization of carbon dioxide and epoxide

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