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A pH- and temperature-sensitive macrocyclic graft copolymer composed of PEO ring and multi-poly(2-(dimethylamino) ethyl methacrylate) lateral chains

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  • Special Topic Advances in Principles of Polymerization
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Abstract

A novel method for the synthesis of macrocyclic graft copolymers was developed through combination of anionic ring-opening polymerization (AROP) and atom transfer radical polymerization (ATRP). A linear α,ω-dihydroxyl poly(ethylene oxide) with pendant acetal protected hydroxyl groups (l-poly(EO-co-EEGE)) was prepared first by the anionic copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE). Then l-poly(EO-co-EEGE) was cyclized. The crude cyclized product containing the linear byproduct was hydrolyzed and purified by being treated with α-CD. The pure cyclic copolymer [c-poly(EO-co-Gly)] was esterified by reaction with 2-bromoisobutyryl bromide, and then used as ATRP macroinitiators to initiate polymerization of 2-(dimethylamino) ethyl methacrylate (DMAEMA), and a series of pH- and temperature-sensitive macrocyclic graft copolymers composed of a hydrophilic PEO as the ring and PDMAEMA as side chains (c-PEO-g-PDMAEMA) were obtained. The behavior of pH- and temperature-sensitive macrocyclic copolymers was studied in aqueous solution by fluorescence and dynamic light scattering (DLS). The critical micellization pH values of macrocyclic graft copolymers and their corresponding linear graft copolymers (l-PEO-g-PDMAEMA) were measured. Under the same conditions, the cyclic graft copolymer with the shorter side chains gave the higher critical micellization pH value. The c-PEO-g-PDMAEMA showed the lower critical micellization pH value than the corresponding l-PEO-g-PDMAEMA. The average hydrodynamic diameters (D h) of the micelles were measured by DLS with the variation of the aqueous solution pH value and temperature.

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Authors and Affiliations

  1. Key Laboratory of Molecular Engineering of Polymers, Ministry of Education; Department of Macromolecular Science, Fudan University, Shanghai, 200433, China

    XinChang Pang, RongKuan Jing, MuGang Pan & JunLian Huang

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  1. XinChang Pang
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  2. RongKuan Jing
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  3. MuGang Pan
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  4. JunLian Huang
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Correspondence to JunLian Huang.

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Pang, X., Jing, R., Pan, M. et al. A pH- and temperature-sensitive macrocyclic graft copolymer composed of PEO ring and multi-poly(2-(dimethylamino) ethyl methacrylate) lateral chains. Sci. China Chem. 53, 1653–1662 (2010). https://doi.org/10.1007/s11426-010-3181-2

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