Amidine-Mediated Zwitterionic Polymerization of Lactide

被引：128

作者：

Brown, Hayley A. ^{[1
]}

De Crisci, Antonio G. ^{[1
]}

Hedrick, James L. ^{[2
]}

Waymouth, Robert M. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

[2] IBM Corp, Almaden Res Ctr, San Jose, CA 95120 USA

来源：

ACS MACRO LETTERS | 2012年 / 1卷 / 09期

基金：

美国国家科学基金会;

关键词：

RING-OPENING POLYMERIZATION; MECHANISM; POLYMERS; DBU; GUANIDINE; BEHAVIOR;

D O I：

10.1021/mz300276u

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The ring-opening polymerization (ROP) of lactide with DBU (1,8-diazabicyclo[5.4.0) undec-7-ene) is described. Room temperature polymerization using the neutral amine catalyst DBU in the absence of any other initiator produces polymers with narrow polydispersities and shows a linear relationship between molecular weight and conversion. The resulting polymers were characterized and determined to be cyclic. DFT calculations support a mechanistic hypothesis Involving a zwitterionic acyl amidinium intermediate.

引用

收藏

页码：1113 / 1115

页数：3

相关论文

共 33 条

[1] Nucleophilicities and carbon basicities of DBU and DBN [J].

Baidya, M. ;

Mayr, Herbert .

CHEMICAL COMMUNICATIONS, 2008, (15) :1792-1794

[2] DABCO and DMAP - Why are they different in organocatalysis? [J].

Baidya, Mahiuddin ;

Kobayashi, Shinjiro ;

Brotzel, Frank ;

Schmidhammer, Uli ;

Riedle, Eberhard ;

Mayr, Herbert .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (32) :6176-6179

[3] Monomer versus alcohol activation in the 4-dimethylaminopyridine-catalyzed ring-opening polymerization of lactide and lactic O-carboxylic anhydride [J].

Bonduelle, Colin ;

Martin-Vaca, Blanca ;

Cossio, Fernando P. ;

Bourissou, Didier .

CHEMISTRY-A EUROPEAN JOURNAL, 2008, 14 (17) :5304-5312

[4] DBU-Promoted Nucleophilic Activation of Carbonic Acid Diesters [J].

Carafa, Marianna ;

Mesto, Ernesto ;

Quaranta, Eugenio .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2011, 2011 (13) :2458-2465

[5] Quantum Mechanical Investigations of Organocatalysis: Mechanisms, Reactivities, and Selectivities [J].

Cheong, Paul Ha-Yeon ;

Legault, Claude Y. ;

Um, Joann M. ;

Celebi-Oelcuem, Nihan ;

Houk, K. N. .

CHEMICAL REVIEWS, 2011, 111 (08) :5042-5137

[6] The reaction mechanism for the organocatalytic ring-opening polymerization of L-lactide using a guanidine-based catalyst: Hydrogen-bonded or covalently bound? [J].

Chuma, Anthony ;

Horn, Hans W. ;

Swope, William C. ;

Pratt, Russell C. ;

Zhang, Lei ;

Lohmeijer, Bas G. G. ;

Wade, Charles G. ;

Waymouth, Robert M. ;

Hedrick, James L. ;

Rice, Julia E. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (21) :6749-6754

[7] Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model [J].

Cossi, M ;

Rega, N ;

Scalmani, G ;

Barone, V .

JOURNAL OF COMPUTATIONAL CHEMISTRY, 2003, 24 (06) :669-681

[8] Zwitterionic polymerization of lactide to cyclic poly(lactide) by using N-heterocyclic carbene organocatalysts [J].

Culkin, Darcy A. ;

Jeong, Wonhee ;

Csihony, Szilard ;

Gomez, Enrique D. ;

Balsara, Nitash R. ;

Hedrick, James L. ;

Waymouth, Robert M. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (15) :2627-2630

[9] Increasing the Reactivity of Nitrogen Catalysts [J].

De Rycke, Nicolas ;

Couty, Francois ;

David, Olivier R. P. .

CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (46) :12852-12871

[10]

Frisch M. J., 2016, Gaussian 03 Revision B.03

← 1 2 3 4 →