Polymethacrylates with anthryl and carbazolyl groups prepared by atom transfer radical polymerization

Abstract

Monomers containing chromophore groups, that is, 9-anthrylmethyl methacrylate (AMA) and 2-(9-carbazolyl)ethyl methacrylate (CMA), were copolymerized with methyl methacrylate (MMA) using atom transfer radical polymerization (ATRP) conditions, resulting in two series of (co)polymers with various amounts of included chromophore units, namely P(MMA-co-AMA) (3-30 mol%) and PAMA and P(MMA-co-CMA) (3-20 mol%). The relative reactivity ratios of both comonomer pairs were determined using the Fineman-Ross method (r MMA ¼1.19, r AMA ¼0.48 and r MMA ¼1.10, r CMA ¼0.77). Glass transition temperatures (T g s) of the polymers increased with the content of chromophore groups. A comparison of luminescence demonstrated more intense light emission by polymethacrylates with carbazolyl groups than by copolymers with anthryl groups. The wavelength of emitted light also differed in the range of blue-violet and blue-green fluorescence for carbazolyl and anthryl copolymers, respectively. Polymer Journal (2011) 43, 448-454; doi:10.1038/pj.2011.10; published online 2 March 2011Keywords: anthracene; ATRP; carbazole; luminescence; polymethacrylates INTRODUCTION Luminescent polymers that have the ability to emit light in response to a stimulus are known as smart polymers. These polymers can be used for fabricating light-emitting diodes, electrophotographic and photorefractive materials, as well as photoluminescent and electroluminescent devices. 1 A proper design of the molecular structure of polymers with luminescence is required to tune the emission color in various regions of the visible spectrum. The parameters responsible for this effect are related to the types of chromophore groups, and their content and density of incorporation in the polymer chain. Particularly, carbazole-and anthracene-based polymers, belonging to a large family of luminescent macromolecules, have found increasing interest because of their numerous industrial applications, such as coatings, inks, adhesives and photolithography, as well as their use in the construction of electrical switching devices. 2 Previously, copolymers containing carbazolyl groups were synthesized using various polymerization methods, such as the cationic photopolymerization of epoxy, 3 oxetane 4 and vinyl ether monomers (2-(9-carbazolyl)ethyl vinyl ether); 5-7 anionic polymerization of oxiranes ([(9-carbazolyl)methyl] or [(9-carbazolyl)ethoxymethyl]oxirane) 8 or methacrylates (2-(N-carbazolyl)ethyl methacrylate) 9 and free radical polymerization (FRP) of vinyl monomers (N-vinylcarbazole), 10,11 including (meth)acrylates. 12,13 The other luminescent copolymers with anthryl substituents were prepared by conventional FRP.

Synthesis of polymer–clay nanocomposites of some vinyl monomers by surface-initiated atom transfer radical polymerization

“…The separated bound polymers of the prepared nanocomposites were characterized by 1 [42][43][44] With respect to the MMA polymer (CDCl 3 , 25°C, TMS), the chemical shifts (δ) of CH 3 , CH 3 CBr, CH 2 , CH, COOCH 3 CBr, and COOCH 3 appeared at 0.8-1.5, 1.8, 1.8-2, 2-2.2, 3.9, and 3.5 ppm. In case of the St polymer (CDCl 3 , 25°C, TMS), the chemical shifts (δ) of CH 3 CH, CH 2 , CHCH 3 , CHph, COOCH 3 , BrCHph, and ph were 0.8, 1.3-1.8, 1.9, 2, 3.4, 3.5, and 6.5-7.2 ppm.…”

Novel Complex Polymers with Carbazole Functionality by Controlled Radical Polymerization

“…RAFT polymerization of these monomers using cumyl dithiobenzoate as a suitable CTA and AIBN as an initiator afforded well-defined polymethacrylates having hole-and electron-transporting groups. Monomers containing a chromophore group, that is, 9-anthrylmethyl methacrylate and CzEMA, were copolymerized with methyl methacrylate using ATRP, resulting in two series of copolymers with various amounts of included chromophore units [98]. Luminescence comparison demonstrated more intense light emission by polymethacrylates with carbazolyl groups than by copolymers with anthryl groups.…”

Vesicular and micellar self‐assembly of stimuli‐responsive poly(N‐isopropyl acrylamide‐b‐9‐anthracene methyl methacrylate) amphiphilic diblock copolymers

“…Along with this, anthracene's functionality is of great interest when it is used as a substrate material for crosslinking in reversible network polymeric materials because of its thermally reversible Diels–Alder [4 + 2] cycloadditions and reversible photodimerization, depending on the irradiated λ . Poly(anthracene methyl methacrylate) is a polycyclic hydrocarbon; because of its properties and interactions with other polymers and drug materials, various research teams have synthesized its polymers with conventional and controlled or living radical polymerization techniques and studied their properties for photoluminescent films, photoresists, and chemiluminescent fluorophores …”

“…Along with this, anthracene's functionality is of great interest when it is used as a substrate material for crosslinking in reversible network polymeric materials because of its thermally reversible Diels-Alder [4 1 2] cycloadditions and reversible photodimerization, depending on the irradiated k. 50 Poly(anthracene methyl methacrylate) is a polycyclic hydrocarbon; because of its properties and interactions with other polymers and drug materials, various research teams have synthesized its polymers with conventional and controlled or living radical polymerization techniques and studied their properties for photoluminescent films, photoresists, and chemiluminescent fluorophores. 51,52 To date, a limited number of reports have been published on well-defined (co)polymer synthesis based on 9-anthracene methyl methacrylate (AnMMA) and their photoresponsiveness. [51][52][53][54] To the best of our knowledge, no report has been published on the synthesis of poly(N-isopropyl acrylamide-b-9-anthracene methyl methacrylate) [poly(NIPAAm-b-AnMMA)] SRABCs with various hydrophobic poly(9-anthracene methyl methacrylate) [poly(AnMMA)] block lengths through RAFT polymerization with poly(NIPAAm) as a macro-RAFT agent and their self-assembly in solution.…”

“…51,52 To date, a limited number of reports have been published on well-defined (co)polymer synthesis based on 9-anthracene methyl methacrylate (AnMMA) and their photoresponsiveness. [51][52][53][54] To the best of our knowledge, no report has been published on the synthesis of poly(N-isopropyl acrylamide-b-9-anthracene methyl methacrylate) [poly(NIPAAm-b-AnMMA)] SRABCs with various hydrophobic poly(9-anthracene methyl methacrylate) [poly(AnMMA)] block lengths through RAFT polymerization with poly(NIPAAm) as a macro-RAFT agent and their self-assembly in solution. In this article, we report the successful synthesis of poly(NIPAAm-b-AnMMA) SRABCs with various hydrophobic poly(AnMMA) block lengths through RAFT polymerization with poly(NIPAAm) as a macro-RAFT agent.…”