Homopolymerization and copolymerization of cyclohexene oxide with carbon dioxide using zinc and aluminum catalysts

被引:67
作者
Sârbu, T [1 ]
Beekman, EJ [1 ]
机构
[1] Univ Pittsburgh, Dept Chem Engn, Pittsburgh, PA 15261 USA
关键词
D O I
10.1021/ma990463t
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Homopolymerization of cyclohexene oxide and copolymerization of cyclohexene oxide and carbon dioxide using zinc and aluminum catalysts having the same type of substitution were studied. The aluminum derivatives are more active, in both homopolymerization and copolymerization of cyclohexene oxide and carbon dioxide. From Al-27 NMR spectra it was observed that aluminum catalysts consist of both penta- and hexacoordinated species but after reaction with monomer predominantly become pentacoordinated. During initiation the equilibrium between five and six hypercoordinated species is shifted toward lower coordination. The nature of the catalysts and their symmetry influence the yield in the copolymerization of CHO and CO2 and the amount of carbon dioxide inserted. The yield obtained with aluminum derivatives luring the copolymerization of CHO and CO2 ranged between 41.2 and 93.6% (149.85-340.4 g of polymer/g of metal).
引用
收藏
页码:6904 / 6912
页数:9
相关论文
共 42 条
[1]   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 [J].
AIDA, T ;
ISHIKAWA, M ;
INOUE, S .
MACROMOLECULES, 1986, 19 (01) :8-13
[2]   SYNTHESIS OF POLYETHER POLYCARBONATE BLOCK CO-POLYMER FROM CARBON-DIOXIDE AND EPOXIDE USING A METALLOPORPHYRIN CATALYST SYSTEM [J].
AIDA, T ;
INOUE, S .
MACROMOLECULES, 1982, 15 (02) :682-684
[3]   POLYMERIZATION OF ALICYCLIC EPOXIDES WITH ALUMINUM ALKYL CATALYSTS [J].
BACSKAI, R .
JOURNAL OF POLYMER SCIENCE PART A-GENERAL PAPERS, 1963, 1 (09) :2777-&
[4]   Catalytic reactions involving C1 feedstocks:: New high-activity Zn(II)-based catalysts for the alternating copolymerization of carbon dioxide and epoxides [J].
Cheng, M ;
Lobkovsky, EB ;
Coates, GW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (42) :11018-11019
[5]   Catalytic activity of a series of Zn(II) phenoxides for the copolymerization of epoxides and carbon dioxide [J].
Darensbourg, DJ ;
Holtcamp, MW ;
Struck, GE ;
Zimmer, MS ;
Niezgoda, SA ;
Rainey, P ;
Robertson, JB ;
Draper, JD ;
Reibenspies, JH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (01) :107-116
[6]   CATALYTIC ACTIVITY OF ZINC(II) PHENOXIDES WHICH POSSESS READILY ACCESSIBLE COORDINATION SITES - COPOLYMERIZATION AND TERPOLYMERIZATION OF EPOXIDES AND CARBON-DIOXIDE [J].
DARENSBOURG, DJ ;
HOLTCAMP, MW .
MACROMOLECULES, 1995, 28 (22) :7577-7579
[7]   SUPERCRITICAL CARBON-DIOXIDE AS SOLVENT FOR THE COPOLYMERIZATION OF CARBON-DIOXIDE AND PROPYLENE-OXIDE USING A HETEROGENEOUS ZINC CARBOXYLATE CATALYST [J].
DARENSBOURG, DJ ;
STAFFORD, NW ;
KATSURAO, T .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1995, 104 (01) :L1-L4
[8]   Catalysts for the reactions of epoxides and carbon dioxide [J].
Darensbourg, DJ ;
Holtcamp, MW .
COORDINATION CHEMISTRY REVIEWS, 1996, 153 :155-174
[9]  
DARENSBOURG DJ, 1996, POLYM MAT SCI ENG, V74, P431
[10]   POLYMERIZATION OF EPOXIDES CATALYZED BY THE TITANIUM TETRAISOPROPOXIDE PHENOL SYSTEM AND ITS MECHANISM [J].
FUKUCHI, Y ;
TAKAHASHI, T ;
NOGUCHI, H ;
SABURI, M ;
UCHIDA, Y .
JOURNAL OF POLYMER SCIENCE PART C-POLYMER LETTERS, 1988, 26 (09) :401-403