We report a one-pot synthesis of ABC triblock copolymers of poly(ethylene glycol)− (PEG−) polystyrene− (PS−) poly(methyl methacrylate) (PMMA), and poly(ε-caprolactone)− (PCL−) PS−PMMA by combining in situ click [3 + 2] and Diels−Alder [4 + 2] reactions. For this purpose, furan-protected maleimide end-functionalized PMMA, PS with α-anthracene and ω-azide end-functionality, and PEG or PCL with an alkyne end-functional group were reacted in N,N-dimehtylformamide (DMF) for 36 h at 120 °C in order to give the corresponding triblock copolymers. All polymeric precursors with narrow molecular weight distribution and well-defined chain-end functionalities were achieved from living polymerization methods, except PEG. The obtained polymers were characterized by 1H NMR (250 MHz), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) measurements.

An ABC‐type miktoarm star polymer was prepared with a core‐out method via a combination of ring‐opening polymerization (ROP), stable free‐radical polymerization (SFRP), and atom transfer radical polymerization (ATRP). First, ROP of ϵ‐caprolactone was carried out with a miktofunctional initiator, 2‐(2‐bromo‐2‐methyl‐propionyloxymethyl)‐3‐hydroxy‐2‐methyl‐propionic acid 2‐phenyl‐2‐(2,2,6,6‐tetramethyl‐piperidin‐1‐yl oxy)‐ethyl ester, at 110 °C. Second, previously obtained poly(ϵ‐caprolactone) (PCL) was used as a macroinitiator for SFRP of styrene at 125 °C. As a third step, this PCL–polystyrene (PSt) precursor with a bromine functionality in the core was used as a macroinitiator for ATRP of tert‐butyl acrylate in the presence of Cu(I)Br and pentamethyldiethylenetriamine at 100 °C. This produced an ABC‐type miktoarm star polymer [PCL–PSt–poly(tert‐butyl acrylate)] with a controlled molecular weight and a moderate polydispersity (weight‐average molecular weight/number‐average molecular weight < 1.37). The obtained polymers were characterized with gel permeation chromatography and 1H NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4228–4236, 2004

Heteroarm H‐shaped terpolymers, (polystyrene)(poly(methyl methacrylate))‐ poly(tert‐butyl acrylate)‐(polystyrene)(poly(methyl methacrylate)), (PS)(PMMA)‐PtBA‐(PMMA)(PS), and, (PS)(PMMA)‐poly(ethylene glycol)(PEG)‐(PMMA)(PS), through click reaction strategy between PS‐PMMA copolymer (as side chains) with an alkyne functional group at the junction point and diazide end‐functionalized PtBA or PEG (as a main chain). PS‐PMMA with alkyne functional group was prepared by sequential living radical polymerizations such as the nitroxide mediated (NMP) and the metal mediated‐living radical polymerization (ATRP) routes. The obtained H‐shaped polymers were characterized by using 1H‐NMR, GPC, DSC, and AFM measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1055–1065, 2007

A novel miktofunctional initiator (1), 2‐hydroxyethyl 3‐[(2‐bromopropanoyl)oxy]‐2‐{[(2‐bromopropanoyl)oxy]methyl}‐2‐methyl‐propanoate, possessing one initiating site for ring‐opening polymerization (ROP) and two initiating sites for atom transfer radical polymerization (ATRP), was synthesized in a three‐step reaction sequence. This initiator was first used in the ROP of ϵ‐caprolactone, and this led to a corresponding polymer with secondary bromide end groups. The obtained poly(ϵ‐caprolactone) (PCL) was then used as a macroinitiator for the ATRP of tert‐butyl acrylate or methyl methacrylate, and this resulted in AB2‐type PCL–[poly(tert‐butyl acrylate)]2 or PCL–[poly(methyl methacrylate)]2 miktoarm star polymers with controlled molecular weights and low polydispersities (weight‐average molecular weight/number‐average molecular weight < 1.23) via the ROP–ATRP sequence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2313–2320, 2004

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