Ring-opening Polymerization of 2-Oxabicyclo[2.2.2]octan-3-one and the Influence of Stereochemistry on the Thermal Properties of the Polyesters

被引：0
作者：
Tong Zhou
Yu-Ting Guo
Fu-Sheng Du
Zi-Chen Li
机构：
[1] Peking University,Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polym. Chem. & Physics of Ministry of Education, Department of Polymer Science & Engineering, College of Chemistry and Molecular Engineering, Center for Soft Ma
来源：
Chinese Journal of Polymer Science | 2022年 / 40卷
关键词：
2-Oxabicyclo[2.2.2]octan-3-one; Ring-opening polymerization; Stereochemistry; Polyester; Thermal properties;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Polyesters with cyclic structures in the main chain typically possess superior mechanical and thermal properties together with chemical recyclability. Ring-opening polymerization (ROP) of bridged or fused bicyclic lactones is a simple, and in most cases controlled method to synthesize polyesters with alicyclic moieties in the polymer backbone. The stereochemistry of the alicyclic structures has a great effect on the polymer properties, which can be regulated by varying the polymerization conditions. Here, we report a systematic investigation on the ROP of 2-oxabicyclo[2.2.2]octan-3-one ([2.2.2]VL) under different conditions. When initiated by n-butyl lithium (n-BuLi) or catalyzed by trifluoromethanesulfonic acid (TfOH) in the presence of benzyl alcohol, P[2.2.2]VLs containing all cis-1,4 disubstituted cyclohexane ring were obtained. However, P[2.2.2]VLs initiated by sodium methoxide (MeONa) or catalyzed by organic superbase contained both cis and trans isomeric structural units. The cis to trans transformation mechanism under these conditions was manifested, and the effect of stereochemical variations on the properties of P[2.2.2]VL was revealed. The stereoregular P[2.2.2]VLs, both cis and trans, exhibited higher crystallinity and melting temperatures (Tm) than those of the stereoirregular isomers. Finally, the degradation of P[2.2.2]VL with acid at high temperature could recover 3-cyclohexenecarboxylic acid.
引用
收藏
页码：1173 / 1182
页数：9
相关论文
共 230 条
[1]  
Dechy-Cabaret O(2004)Controlled ring-opening polymerization of lactide and glycolide Chem. Rev. 104 6147-6176
[2]  
Martin-Vaca B(2008)Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization Adv. Drug Deliv. Rev. 60 1056-1076
[3]  
Bourissou D(2012)Biodegradable synthetic polymers: preparation, functionalization and biomedical application Prog. Polym. Sci. 37 237-280
[4]  
Jerome C(2010)Stereocontrolled ring-opening polymerisation of lactide Chem. Soc. Rev. 39 486-494
[5]  
Lecomte P(2018)Functional biodegradable polymers Chem. Soc. Rev. 47 7739-7782
[6]  
Tian H(2010) ring-opening polymerization of monomers without protective groups Chem. Soc. Rev. 39 165-173
[7]  
Tang Z(2007)Stereocontrolled ring-opening polymerization of cyclic esters: synthesis of new polyester microstructures Chem. Rev. 107 5813-5840
[8]  
Zhuang X(2010)Organocatalytic ring-opening polymerization Macromolecules 43 2093-2107
[9]  
Chen X(2012)Organocatalysis: opportunities and challenges for polymer synthesis ACS Macro Lett. 1 1409-1412
[10]  
Jing X(2018)Organic catalysis for ring-opening polymerization Chem. Rev. 118 839-885
12345678910