Alternating copolymerization of carbon dioxide and epoxide catalyzed by the aluminum porphyrin-quaternary organic salt or -triphenylphosphine system. Synthesis of polycarbonate with well-controlled molecular weight

Aida, T.; Ishikawa, Masahide; Inoue, Shohei

doi:10.1021/ma00155a002

Cited by 225 publications

(127 citation statements)

References 4 publications

Supporting

Mentioning

121

Contrasting

Unclassified

Order By: Relevance

“…40 The copolymerization of carbon dioxide and cyclohexene oxide at room temperature under 50 atm of carbon dioxide pressure by the aluminum porphyrin (10a)-ethyltriphenylphosphonium bromide system produced a polycarbonate with the perfect alternating structure (M n ϭ 6800). The copolymerization produced an alternating copolymer with a very narrow molecular weight distribution (M w /M n ϭ 1.06).…”

Section: Copolymerization By Aluminum Porphyrinsmentioning

confidence: 99%

Copolymerization of carbon dioxide and epoxide

Sugimoto

Inoue

2004

J. Polym. Sci. A Polym. Chem.

Self Cite

364

142

View full text Add to dashboard Cite

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

show abstract

Section: Copolymerization By Aluminum Porphyrinsmentioning

confidence: 99%

Copolymerization of carbon dioxide and epoxide

Sugimoto

Inoue

2004

J. Polym. Sci. A Polym. Chem.

Self Cite

364

142

View full text Add to dashboard Cite

show abstract

“…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. [23][24][25][26] For example, aluminum porphyrin complexes have found to form alternating copolymer of CO 2 and cyclic ether. In particular, (5,10,15,20-tetraphenylporphinato)aluminum chloride (TPPAlCl) complexed with an appropriate quaternary salt such as ethyltriphenylphosphonium bromide (EtPh 3 PBr) and tetraethylammonium bromide (Et 4 NBr) was reported to be an effective catalyst for the alternating copolymerization of CO 2 with cyclic ethers (ethylene oxide, propylene oxide and cyclohexene oxide).…”

Section: Introductionmentioning

confidence: 99%

“…24 -26 The mechanism of this copolymerization was proposed to be an activation of the anion of the quarternary salt as the nucleophile by the metalloprophyrin. 25 A more detailed mechanism has been recently proposed to involve a nucleophilic attack of the axial ligand at the six-coordinate aluminum species onto the epoxide coordinated at cationic aluminum species. 25 That is, an important feature of the polymerization with metalloporphyrin catalysts is its living character.…”

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.

View full text Add to dashboard Cite

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

show abstract

“…The immobilized ILs could be reused up to four consecutive runs without considerable loss of activity and f(CO 2 ). Several research groups reported that various ILs could be effective cocatalysts in the copolymerization of CO 2 and epoxides with metal salen or metal porphyrin complexes [126][127][128][129][130]. In some cases, it was shown that the activities of theses metal complexes were drastically enhanced by the co-presence of IL, although they had no or a very low activity for the coplymerization in the absence of IL.…”

Section: Polycarbonate Synthesis In/by Ilmentioning

confidence: 99%

“…In some cases, it was shown that the activities of theses metal complexes were drastically enhanced by the co-presence of IL, although they had no or a very low activity for the coplymerization in the absence of IL. Inoue and co-workers reported the successful alternating copolymerization of CO 2 with EO, PO, or CHO (cyclohexene oxide) by the use of Al porphyrin complexes in combination with quaternary phosphonium or ammonium salts [126]. The copolymerization of CO 2 and PO or CHO was conducted at room temperature and 5 MPa CO 2 , producing polycarbonates with the perfect alternating structure (f(CO 2 ) = 100%) and a very narrow molecular weight distribution (Mw/Mn < 1.1).…”

Section: Polycarbonate Synthesis In/by Ilmentioning

confidence: 99%