Computational Studies on Mechanisms for the Organocatalytic Depolymerization of Poly(ethylene) Terephthalate

被引：0

作者：

Jones, Gavin O. ^{[1
]}

Horn, Hans W. ^{[1
]}

Wei, Didi S. ^{[1
,2
]}

Fukushima, Kazuki ^{[4
]}

Lecuyer, Julien M. ^{[1
,3
]}

Coady, Daniel J. ^{[1
]}

Hedrick, James L. ^{[1
]}

Rice, Julia E. ^{[1
]}

机构：

[1] IBM Almaden Res Ctr, 650 Harry Rd, San Jose, CA 95120 USA

[2] Univ Denver, Dept Phys & Astron, Denver, CO 80208 USA

[3] San Jose State Univ, Chem & Mat Engn Dept, San Jose, CA 95192 USA

[4] Yamagata Univ, Dept Biochem Engn, Yonezawa, Yamagata, Japan

来源：

NANOTECHNOLOGY 2012, VOL 3: BIO SENSORS, INSTRUMENTS, MEDICAL, ENVIRONMENT AND ENERGY | 2012年

关键词：

Depolymerization; organocatalysis; TBD; poly(ethylene) terephthalate; density functional theory; RING-OPENING POLYMERIZATION; CYCLIC ESTERS; ENERGIES; DENSITY; GUANIDINE; CARBONATE; ALCOHOLS; MODEL;

D O I：

暂无

中图分类号：

TE [石油、天然气工业]; TK [能源与动力工程];

学科分类号：

0807 ; 0820 ;

摘要：

We describe computational investigations on mechanisms for the organocatalyzed trans-esterification and amidation of poly(ethylene)terephthalate (PET). These processes were modeled by the reactions of methylbenzoate (MB) with ethylene glycol (EG), ethylenediamine (EDA) and ethanolamine (EA) organocatalyzed by 1,5,7-triazabicyclododecene (TBD). Mechanistic pathways for reactions in which TBD acts as the lone catalyst have been compared with mechanisms in which an additional molecule of the amine or alcohol acts as a cocatalyst. Calculations suggest that the combination of an organocatalyst with a molecule of an alcohol or amine cocatalyst is typically more activating than a lone catalyst. Our results demonstrate that alcohols are more activated than amines during nucleophilic attack. However, while transesterification may be faster than amidation, this process may be reversible, in contrast with amidation which leads to stable products.

引用

页码：736 / 739

页数：4

共 23 条

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