Improvement of catalytic activity of aluminum complexes for the ring-opening polymerization of ε-caprolactone: aluminum thioamidate and thioureidate systems

被引:2
|
作者
Ganta, Prasanna Kumar [1 ]
Teja, Mallemadugula Ravi [1 ]
Chang, Chun-Juei [1 ,2 ]
Sambandam, Anandan [3 ]
Kamaraj, Rajiv [1 ]
Chu, Yu-Ting [1 ,4 ]
Ding, Shangwu [1 ,4 ]
Chen, Hsing-Yin [1 ]
Chen, Hsuan-Ying [1 ,4 ,5 ,6 ]
机构
[1] Kaohsiung Med Univ, Drug Dev & Value Creat Res Ctr, Dept Med & Appl Chem, Kaohsiung 80708, Taiwan
[2] Natl Sun Yat Sen Univ, Dept Int PhD Program Sci, Kaohsiung 80424, Taiwan
[3] Natl Inst Technol, Dept Chem, Nanomat & Solar Energy Convers Lab, Tiruchirappalli 620015, India
[4] Natl Sun Yat Sen Univ, Dept Chem, Kaohsiung 80424, Taiwan
[5] Kaohsiung Med Univ Hosp, Dept Med Res, Kaohsiung 80708, Taiwan
[6] Natl Pingtung Univ Sci & Technol, Pingtung 91201, Taiwan
关键词
HIGHLY EFFICIENT; METAL-COMPLEXES; CYCLIC ESTERS; RAC-LACTIDE; LIGANDS; BEARING; PCL; ROP; POLYMERS; BASE;
D O I
10.1039/d3dt03198e
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
In this study, a series of Al complexes bearing amidates, thioamidates, ureidates, and thioureidates were synthesized and their catalytic activity for epsilon-caprolactone (CL) polymerization was evaluated. SPr-Al exhibited a higher catalytic activity than OPr-Al (3.2 times as high for CL polymerization; [CL] : [SPr-Al] : [BnOH] = 100 : 0.5 : 2; [SPr-Al] = 10 mM, conv. = 93% after 14 min at 25 degrees C), and USCl-Al exhibited a higher catalytic activity than UCl-Al (4.6 times as high for CL polymerization; [CL] : [USCl-Al] : [BnOH] = 100 : 0.5 : 2; [USCl-Al] = 10 mM, conv. = 90% after 15 min at 25 degrees C). Regardless of whether aluminum amidates or ureidates were present, thioligands improved the polymerization rate of aluminum catalysts. Density functional theory calculations revealed that the eight-membered ring [SPr-AlOMe2]2 decomposed into the four-membered ring SPr-AlOMe2. However, [OPr-AlOMe2]2 did not decompose because of its strong bridging Al-O bond. The overall activation energy required for CL polymerization was lower when using [SPr-AlOMe2]2 (18.1 kcal mol-1) as a catalyst than when using [OPr-AlOMe2]2 (23.9 kcal mol-1). This is because the TS2a transition state of SPr-AlOMe2 had a more open coordination geometry with a small N-Al-S angle (72.91 degrees) than did TS3c of [OPr-AlOMe2]2, the crowded highest-energy transition state of [OPr-AlOMe2]2 with a larger N-Al-O angle (99.63 degrees). S-Al system exhibited a higher level of catalytic activity (1.8-5.5 times) than did the O-Al system. Furthermore, the US-Al system exhibited a higher level of catalytic activity (1.7 - 4.6 times) than did the U-Al system.
引用
收藏
页码:17132 / 17147
页数:17
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