期刊
POLYMER CHEMISTRY
卷 12, 期 27, 页码 3917-3924出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d1py00639h
关键词
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资金
- National Natural Science Foundation of China (NSFC) [51803045, 21971052, 22071041, 51673057]
- Fundamental Research Funds for the Central Universities [JZ2021HGTB0084, PA2020GDSK0069, PA2020GDSK0070]
- Thousand Young Talents Program of China
Starlike hybrid helical PPIs with well-defined structures were designed and prepared using POSS as the core; chiral and amphiphilic hybrids were obtained by modifying the monomers and conducting polymerization with POSS-Pd(ii) as the initiator, exhibiting thermoresponsive behaviors and excellent enantioselective crystallization abilities.
Polyhedral oligomeric silsesquioxane (POSS) based starlike hybrid helical poly(phenyl isocyanide)s (PPIs) with well-defined structures were designed and prepared in this contribution. The POSS modified with Pd(ii) complexes (POSS-Pd(ii)) was firstly obtained. Then well-defined starlike hybrid helical PPIs with POSS cores were synthesized through the polymerization of phenyl isocyanide monomers using POSS-Pd(ii) as the initiator. The polymerization proceeded in a living and controlled manner. Meanwhile, polymerization of chiral phenyl isocyanides with decyl chain modified pendant l- or d-alanine afforded optically active hybrid starlike helical PPIs with preferred handedness. What's more, amphiphilic starlike hybrid helical PPI block copolymers showing thermoresponses were easily obtained, and their self-assembly and thermo-responsive behaviours were studied. In addition, cross-linked hybrid helical PPIs were obtained via the transesterification reaction between pentafluorophenyl ester and cystamine. Benefitting from the essential chirality of the handed helical PPIs, the cross-linked hybrid PPIs showed excellent ability in the enantioselective crystallization of racemic compounds. The enantiomeric excess (ee) of the induced crystal of threonine could be up to 95%.
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