doi:10.1007/s10118-021-2539-6

Citation: Zhou, P.; Dai, X. G.; Kong, J.; Ling, J. Synthesis of well-defined poly(tetrahydrofuran)- b -poly( α -amino acid)s via cationic ring-opening polymerization (ROP) of tetrahydrofuran and nucleophilic ROP of N -thiocarboxyanhydrides. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-021-2539-6 doi: 10.1007/s10118-021-2539-6 shu

Synthesis of Well-defined Poly(tetrahydrofuran)-b-Poly(α-amino acid)s via Cationic Ring-opening Polymerization (ROP) of Tetrahydrofuran and Nucleophilic ROP of N-thiocarboxyanhydrides

Peng Zhou ^a ,
Xuan-Geng Dai ^a ,
Jie Kong ^b,, ,
Jun Ling ^a,,

a.
Ministry of Education Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
b.
Shaanxi Key Laboratory of Macromolecular Science and Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an 710072, China

Corresponding author: Jie Kong, E-mail: kongjie@nwpu.edu.cn
Jun Ling, E-mail: lingjun@zju.edu.cn
Received Date: 2020-11-02
Available Online: 2021-01-05

Figures(4) / Tables(2)

The synthesis of block copolymers of poly(tetrahydrofuran)-b-poly(α-amino acid) (PTHF-b-PAA) is challenging since it is difficult to combine the two blocks produced via different/conflicting ring-opening polymerization (ROP) mechanisms. In this contribution, the cationic ROP of THF is catalyzed by rare-earth triflate [RE(OTf)₃] and terminated by 2-(t-butyloxycarbonyl-amino) ethanol (BAE). After the deprotection of t-butyloxycarbonyl (Boc) group, the chain end of PTHF is quantitatively changed to amino group which thereafter initiates the nucleophilic ROP of α-amino acid N-thiocarboxyanhydrides (NTAs). Both polymerizations are well controlled, generating PTHF and PAA segments with designable molecular weights (MWs). PTHF-b-polylysine (PTHF-b-PLys) and PTHF-b-polysarcosine (PTHF-b-PSar) are obtained with MWs between 8.6 and 28.7 kg/mol. The above amphiphilic diblock copolymers form micelles in water. PTHF₄₀-b-PSar₃₂ acts as a surfactant to stabilize oil-in-water emulsions. Both segments of PTHF-b-PAA are biocompatible and promising in the biomedical application.
- Poly(tetrahydrofuran),
- Poly(α-amino acid),
- End group transformation,
- Quantitation,
- Copolymer
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