Synthesis of AB‐type block copolymers containing benzoxazole and anthracene groups by ATRP and fluorescent property

Abstract

Two functional monomers, methacrylic acid 4‐(2‐benzoxazol)‐benzyl ester (MABE) containing the benzoxazole group and 4‐(2‐(9‐anthryl))‐vinyl‐styrene (AVS) containing the anthracene group were synthesized by rational design. The MABE was polymerized via atom transfer radical polymerization (ATRP) using ethyl 2‐bromoisobutyrate (EBIB) as initiator in CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) catalyst system; block copolymers poly(MABE‐b‐AVS) was obtained, which was conducted by using poly(MABE) as macro‐initiator, AVS as the second monomer, and CuBr/PMDETA as catalyst. The constitute of two monomers in block copolymers poly(MABE‐b‐AVS) by ATRP could be adjusted, that is the constitute of the benzoxazole group and the anthracene group could be controlled in AB‐type block copolymers. Moreover, the fluorescent properties of homopolymers poly(MABE) and block copolymers poly(MABE‐b‐AVS) were discussed herein. With the excitation at λex = 330 nm, the fluorescent emission spectrum of poly(MABE) solution showed emission at 375 nm corresponding to the benzoxazole‐based part; with the same excitation, the fluorescent emission spectrum of poly(MABE‐b‐AVS) solution showed a broad peek at 330–600 nm when the monomer AVS to the total monomers mole ratio was 0.31, and the fluorescent emission spectrum of poly(MABE‐b‐AVS) in film state only showed one peak at 525 nm corresponding to the anthracene‐based unit that indicated a complete energy transfer from the benzoxazole group to the anthracene group. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3894–3901, 2007

Well‐defined diblock copolymers possessing fluorescent and metal chelating functionalities as novel macromolecular sensors for amines and metal ions

“…Instead, most reports refer to the noncontrollable conventional free radical polymerization of anthracene‐containing monomers 17, 18. An established controlled radical polymerization process namely atom transfer radical polymerization, although successfully used in the preparation of well‐defined polymers based on anthracene,22, 23 fails in preparing well‐defined polymers based on 2‐(acetoacetoxy)ethyl methacrylate (AEMA), the second monomer used in this study 24…”

Synthesis and optical properties of poly[(4-(benzoxazole-2-yl)phenyl)methyl methacrylate] with 1,8-naphthalimide end group

“…The introduction of other optical moieties to these polymers may show some interesting emission tuning, as reported in our previous work [15] . Meanwhile, 1,8-naphthalimide moieties were widely used as emission color-tuning moieties in many systems because of their good fluorescent properties [16][17][18] .…”

“…4-Hydroxybenzaldehyde (99%), butan-1-amine (99%), 2-Bromo-2-methylpropanoyl bromide (99%) and other reagents were received from Sinopharm Chemical Reagent Co. Ltd, China. 4-Hydrazino-N-butyl-1,8-naphthalimide was prepared according to the literature procedure [33] , (4-(benzoxazole-2-yl)phenyl) methyl-methacrylate (MABE, Scheme 1) was prepared in our laboratory [15] . Scheme 2 Synthetic scheme of NAPH-PMABE.…”

“…The copolymer shows a composite fluorescent spectrum comprising an ultraviolet component originating from benzoxzole-based part and a green component originating from anthrancene-based part in DMF solution. However, only green emission is exhibited in film solid state due to complete energy transfer from the benzoxazole to the anthracene moieties [15] . Herein, as an extension of that work, we combined benzoxazole and 1,8-naphthalimide moieties together in order to get better emission color tuning of benzoxazole-based polymers in both solution and solid state.…”

“…Herein, as an extension of that work, we combined benzoxazole and 1,8-naphthalimide moieties together in order to get better emission color tuning of benzoxazole-based polymers in both solution and solid state. Firstly, we synthesized a novel compound, 6-(4-formylphenoxy)-hexyl-2-bromo-2-methyl-propanoate (CHOBr), and used it as an initiator for the ATRP of MABE [15] …”