Citation: Yun-fei Wang, Hua Wei. Synthesis and Properties of Cyclic Thermo-responsive Double Hydrophilic Block Copolymers[J]. Acta Polymerica Sinica, ;2019, 50(3): 291-299. doi: 10.11777/j.issn1000-3304.2019.18219 shu

Synthesis and Properties of Cyclic Thermo-responsive Double Hydrophilic Block Copolymers

Yun-fei Wang ,
Hua Wei ^,

State Key Laboratory of Applied Organic Chemistry, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000

Corresponding author: Hua Wei, weih@lzu.edu.cn
Received Date: 15 October 2018
Revised Date: 29 October 2018
Available Online: 16 November 2018

Cyclic topology exerts significant effects on the properties and potential applications of polymers; however, the precisely controlled systhesis of cyclic diblock copolymers remains challenging. In this study, we reported a novel and versatile synthetic strategy toward cyclic diblock copolymers by using the linear polymer precursors generated from reversible addition-fragmentation transfer (RAFT) polymerization. Key innovation of the technique proposed lies in the facile and complete conversion of terminal RAFT groups on linear polymers into clickable alkyne groups via a one-pot aminolysis/Michael addition reaction, which laid a foundation for subsequent intrachain Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAc) on the linear α-alkyne-ω-azide preursors. Full decoration of the RAFT termini was confirmed by Ellman study. Specifically, a cyclic double hydrophilic block copolymer (DHBC), poly(N-isopropylacrylamide)-b-poly(oligo(ethylene glycol) monomethyl ether methacrylate) (c-(PNIPAAm-b-POEGMA)), with thermo-responsiveness was synthesized following this approach successfully as confirmed by ¹H-NMR, ¹³C-NMR, FTIR, and SEC-MALLS analyses. Thermo-induced phase transitions and self-assembly behaviors of the resulting cyclic DHBCs were then investigated by the combined analytical techniques of UV-Vis spectroscopy, dynamic light scattering (DLS), and transmission electron microscopy (TEM), and further compared with those of the linear analogues. Intriguingly, the cyclic thermo-sensitive DHBCs exhibited a lower critical solution temparature (LCST, 41.5 °C) significantly higher than the linear counterparts (39 °C), for POEGMA moiety with two block juntions in the cyclic copolymers could raise the LCST of PNIPAAm segment. More importantly, the spherical micelles self-assembled from cyclic DHBCs above LCST were smaller in size and narrower in size distribution compared with the ones derived from linear analogues, which resulted most likely from a more restricted cyclic topology. This study therefore developed an efficient alternative synthetic method for cyclic diblock copolymers and meanwhile provided new insights into the structure-property relationships of cyclic DHBCs.
- Cyclic polymer,
- Thermo-sensitivity,
- Double hydrophilic block copolymer,
- Lower critical solution temperature
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沈阳化工大学材料科学与工程学院沈阳 110142

Synthesis and Properties of Cyclic Thermo-responsive Double Hydrophilic Block Copolymers

南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com