Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points†

doi:10.7503/cjcu20150570

Abstract

Abstract:

Synthesis of diblock copolymers containing disulfides at the junction points was reported. Rever-sible addition-fragmentation chain transfer(RAFT) polymerization of styrene was employed to prepare polystyrene marco RAFT agent(PS-RAFT). The terminal RAFT agents of PS were reduced to sulfhydryl groups(PS-SH) in the presence of primary amine, and the atom transfer radical polymerization(ATRP) macroinitiator(PS-S-S-ATRP) was prepared by an exchange reaction between PS-SH and an ATRP initiator containing disulfide bonds. PS-S-S-ATRP was used to initiate the polymerization of 2-hydroxyethyl methacrylate(HEMA) and PS-S-S-PHEMA diblock copolymers with disulfides at the junction points were obtained. The structures and molecular weights of the diblock copolymers were characterized by proton nuclear magnetic resonance(¹H NMR) and gel permeation chromatography(GPC). Kinetics study of ATRP of HEMA shows the characteristic of living polymerization. In methanol, the diblock copolymer self-assembles into polymeric micelle with PS cores and PHEMA coronae. Transmission electron microscopy and dynamic light scattering were used to study the morphology changes of the micelles after cleavage of the disulfide bonds. The result shows a new methd to prepare block copolymers with disulfide bonds at the junction points. The self-assenbly strecture of the copolymers will have a wide application in drug release and biological imaging techniques.

Key words: Disulfide bond, Diblock copolymer, Self-assembly, Reversible addition-fragmentation chain transfer polymerization, Atom transfer radical polymerization

CLC Number:

O633.3

TrendMD:

ZHANG Lixin, WANG Jintao, YANG Yongfang, ZHAO Hanying. Novel Method of Preparation of Diblock Copolymers with Disulfide Bonds at Junction Points^†[J]. Chem. J. Chinese Universities, 2016, 37(1): 161.

Figures/Tables 9

Scheme 1 Schematic illustration for the preparation of PS-S-S-PHEMA

Fig.1 1H NMR spectra of PS-RAFT(a), PS-SH(b) and PS-S-S-Br(c)

Fig.2 UV-Vis Spectra of PS-SH(a), PySSPy(b) and mixture of PS-SH and Py-SS-Py(c)

Fig.3 1H NMR spectra of PS-S-S-PHEMA

Fig.4 GPC curves of PS-RAFT(a), PS-S-S-Br(b), PS-S-S-PHEMA(c) and block copo-lymer after DTT treatment(d)^Mobile phase is DMF.

Fig.5 GPC curves of PS-S-S-PHEMA at different polymerization time(A) and dependence of Mn and PDI on polymerization time(B)

Fig.6 DLS curves of PS-S-S-PHEMA micelles in methanol(a), PS-S-S-PHZMA micelles treated with DTT for 6 h(b) and 24 h(c)

Fig.7 TEM image of PS-S-S-PHEMA micelle in methanol^Inset: tyndall effect of PS-S-S-PHEM micelle in methanol.

Fig.8 TEM image of PS-S-S-PHEMA micelle in methanol after DTT treatment^Inset: photograph of precipitation of PS-S-S-PHEMA.

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