Atom Transfer Radical Polymerization and Third‐Order Nonlinear Optical Properties of New Azobenzene‐Containing Side‐Chain Polymers

Abstract

The atom transfer radical polymerization (ATRP) technique has been successfully applied to synthesize a series of nonlinear optically (NLO) active homopolymers, 4‐(4‐nitrophenyl‐diazenyl) phenyl acrylate (P‐NPAPA) and 4‐(4‐methoxyphenyl‐diazenyl) phenyl acrylate (P‐MPAPA), containing azobenzene groups on the side chain. The third‐order NLO properties of the polymer films were measured by the degenerated four‐wave mixing (DFWM) technique. A dependence of the χ(3) values and response times of polymers on their number‐average molecular weight and the electronic effect of the substituent (nitro‐ or methoxy‐) on the azobenzene group have been evidenced. The increasing χ(3) value of the polymer films at the magnitude of about 10−10 was displayed with increasing molecular weight and the presence of the push‐pull electronic system contributes much in enhancing the third‐order NLO susceptibility of polymers.

New Photoresponsive Poly(meth)acrylates Bearing Azobenzene Moieties Obtained via ATRP Polymerization Exhibiting Liquid-Crystalline Behavior

“…This indicates that the polymerization of AzoMA using CuBr/PMDTA as a catalytic system performed at 95 °C in dioxane was well controlled, and the termination processes were significantly limited. In addition, compared with the results reported by Lu and coworkers [ 15 ] for a similar system, under our conditions, a substantially shorter time of polymerization was necessary to achieve high conversion. This indicates that the monomers designed by us were more reactive than those prepared by Lu and coworkers [ 15 ].…”

“…Lu and coworkers reported the successful polymerization of several (meth)acrylates containing AZ groups via the ATRP technique. Namely, they used 4-(4-nitrophenyldiazenyl)phenyl acrylate (P-NPAPA) and 4-(4-methoxyphenyldiazenyl)phenyl acrylate (P-MPAPA) in the synthesis of homopolymers using N , N , N ′, N ″, N ″-pentamethyldiethylenetriamine (PMDETA)/CuBr as a catalytic system and ethyl 2-bromoisobutyrate (EBriB) as an initiator in dry cyclohexanone [ 15 ]. The azobenzene moiety in the monomers was substituted by methoxyl or nitro moiety in para position and directly connected with the carboxyl group of polymer backbone (without any linker) or separated from the polymer backbone by an alkoxyl group built of two or six carbon atoms.…”

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

“…In our lab, one of our researches has focused on the design and synthesis of various end-functional or side-chain functional polymers with optical properties such as fluorescence and nonlinear optics via ATRP [29][30][31][32] . Recently, we prepared a di-block copolymer, poly(4-(benzoxazole-2-yl)phenyl) methymethacrlate-bpoly(4-(2-(9-anthryl))-vinyl-styrene) (PMABE-b-PAVS) containing both benzoxazole and anthrancene groups through ATRP.…”

New side-chain azo-polymers for optical applications: synthesis and characterization

“…Various types of monomers are carefully designed to overcome these disadvantages, but the most succeeding are proven to be methacrylate/ acrylate-based monomers bearing an azobenzene group [26,27]. Hence, a variety of azobenzenecontaining macromolecular architectures are obtained through conventional or controlled radical (co)polymerization reactions of such azo-monomers.…”