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Original Articles

Preparation and Characterization of Linear and Miktoarm Star Side-Chain Liquid Crystalline block Copolymers with p-Methoxyazobenzene Moieties via a Combination of ATRP and ROP

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Pages 876-885 | Received 01 Mar 2009, Accepted 01 Mar 2009, Published online: 03 Aug 2009
 

Abstract

One linear and two miktoarm star side-chain liquid crystalline (LC) block copolymers with p-methoxyazobenzene moieties were prepared by a combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) techniques. First, ROPs of ε -caprolactone (ε -CL) were carried out catalyzed by Sn(Oct)2 using three multifunctional initiators, hydroxyethyl 2-bromoisobutyrate (AB type), 3-hydroxy-2-(hydroxymethyl)-2-methylpropyl 2-bromo-2-methylpropanoate (A2B type) and 2,2-bis(hydroxymethyl)propane-1,3-diyl bis(2-bromo-2-methylpropanoate) (A2B2 type), at 110°C in toluene, respectively. Second, the previously obtained poly(ε -caprolactone)s (PCLs) with bromines functionalities were used as the macroinitiators to conduct ATRP of 6-(4-methoxy-4-oxy-azobenzene) hexyl methacrylate (MMAZO) with CuBr/PMDETA as the catalyst systems at 85°C in anisole to prepare the linear and miktoarm side-chain LC block copolymers (PCL-b-PMMAZO, (PCL)2-(PMMAZO) and (PCL)2-(PMMAZO)2). The produced polymers were well-controlled with the controlled molecular weights and the relatively narrow molecular weight distributions (M w/M n ≤ 1.35). The structures of the obtained polymers were all characterized by NMR, FT-IR and GPC analysis. Furthermore, the LC properties of the linear and miktoarm star block copolymers were also investigated by differential scanning calorimetry (DSC) and thermal polarized optical microscopy (POM).

Acknowledgments

The financial support of this work by the National Nature Science Foundation of China (No.20874069 and 50803044), the Science and Technology Development Planning of Jiangsu Province (No. BK2007702 and BK2007048), the Nature Science Key Basic Research of Jiangsu Province for Higher Education (No. 05KJA15008), Qing Lan Project, Program of Innovative Research Team and the Pre-research Project of Soochow University are gratefully acknowledged.

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