Rationalizing the regioselectivity of cationic ring-opening polymerization of benzoxazines

被引:13
|
作者
Ozaltin, Tugba Furuncuoglu [1 ]
Catak, Saron [1 ]
Kiskan, Baris [2 ]
Yagci, Yusuf [2 ]
Aviyente, Viktorya [1 ]
机构
[1] Bogazici Univ, Dept Chem, TR-34342 Istanbul, Turkey
[2] Istanbul Tech Univ, Dept Chem, TR-34469 Istanbul, Turkey
关键词
PI-STACKING INTERACTIONS; PHENOLIC RESINS; NONCOVALENT INTERACTIONS; DENSITY FUNCTIONALS; BENZENE DIMER; CROSS-LINKING; 1,3-BENZOXAZINE; POLYMERS; POLYBENZOXAZINES; CONFIGURATIONS;
D O I
10.1016/j.eurpolymj.2018.05.024
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
Polybenzoxazines have gained increasing interest both in industry and academia for the last few decades due to their unique structural features. The ring-opening polymerization mechanism of 1,3-benzoxazine monomers and the regioselectivity during polymerization, still need further clarification. In this study, ring-opening polymerization mechanisms of two methyl substituted benzoxazine derivatives 3,6-dimethyl-3,4-dihydro-2H-benzo [e] [1,3] oxazine (pC-m) and 3,5,6,7-tetramethy1-3,4-dihydro-2Hbenzo[e][1,3] oxazine (345TMP-m) are investigated by quantum mechanical tools using density functional theory (DFT). Calculations have shown that in the presence of a nucleophile, pC-m can yield the phenolic polymer upon rearrangement of its intermediate phenoxy product. However, the polymerization of 345TMP-m results in a mixture of phenoxy and phenolic type polymers. The extra methyl groups on 345TMP-m have a dual role in preventing the pi stacking interactions observed in pC-m, and in decreasing the barrier yielding phenolic polymers by electron donation.
引用
收藏
页码:61 / 67
页数:7
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