Molecular weight effect on the photoinduced birefringence and surface relief gratings formation of a methacrylate azopolymer

Samples of a methacrylic side-chain azopolymer were synthesized by a radical copolymerization of methyl-methacrylate with the methacrylic derivative of the commercial dye Disperse Red-13 (DR13). Copolymers with different molecular weight were obtained by varying the reaction time and the concentration of initiator. Samples with molecular weight averages (M_w) from 3 to 8 × 10⁴ g/mol and 1.4-1.7 polydispersity were obtained. The glass transition temperature of the samples increased linearly from the lower to the highest molecular weight. Optical quality cast films were prepared for all samples and photoinduced birefringence was successfully carried out in all samples as well as surface relief gratings could be inscribed in the cast films.     

BIOLOGICALLY DERIVED PHOTOACTIVE MACROMOLECULAR AZODYES

Azophenols with various substituents at the para position of the phenyl ring were enzymatically polymerized in the presence of H₂O₂. Structural characterization of the synthesized polymers by FTIR, FT-Raman, and NMR (¹H and ¹³C) spectroscopy confirms our previous observation that this enzymatically catalyzed coupling reaction occurs primarily at the ortho positions, with some substitution at the meta position of the phenol ring. The strong constraint and poor packing of the azobenzene chromophores in the polymer leads to a significant blue shift of the π-π^* transition absorption and slow photoisomerization and thermal relaxation in comparison to the monomers. Surface relief gratings (SRG) with large surface modulation have been fabricated on these enzymatically synthesized polymer films.

     

偶氮苯高分子的光致可逆固液转变

偶氮苯化合物是一种极具吸引力以及较为常用的光响应材料,本文主要介绍偶氮苯的光响应性质以及一些偶氮苯高分子的合成方法,解析光化学反应导致偶氮苯高分子固液转变的机理,并介绍其在粘结性材料、光致动器、光致热导开关器件及非热纳米压印中的应用。     

Hyperbranched Azopolymer with Quadruple Responsibility

Simply constructing multiple responsive polymers with obvious shape and dimension variations on their assemblies upon different stimuli is still rarely reported. In this study, we report a hyperbranched polymer named HPAzoBAHB-star-PEG9 with quadruple-response to light,temperature, pH and oxidation stimuli. The polymer contains azobenzene chromophore, sulfide, amide and amine groups in its hydrophobic hyperbranched core, and the core is capped with hydrophilic polyethylene glycol(PEG9) arms. HPAzoBAHB-star-PEG9 could assemble into unusual leaf-like lamellar micelles at 25 °C under the guidance of orderly arranged H-aggregate of azobenzene moieties. These leaf-like lamellar micelles can transform into vesicles upon UV irradiation and lower temperature, or convert to smaller spherical micelles in acidic or oxidative environments, respectively, with the destroy of ordered azobenzene arrangements. This quadruple-responsive hyperbranched polymer is suitable to construct multiple stimuli-responsive micro/nanostructures, or accurate delivery and release following subtle stimuli sequences.     

Synthesis and characterization of a dye-functionalized polythiophene with different chromic properties

As a preliminary study aiming to possible applications, a polythiophene derivative with an azobenzene moiety (polyazothiophene) was synthesized and characterized by FTIR, ¹H NMR, DSC and HPSEC. Some aspects on the thermo- and solvatochromic properties of polyazothiophene, such as the influence of different solvents and solution concentration on the thermochromic effect, and the use of a large polarity range of solvents as well as an acid media in the solvatochromic effect were explored. Reversible thermochromic properties of dimethylformamide and toluene solutions were analyzed in the temperature range of 10-70 °C showing a blue-shift spectrum variation with temperature increase. Solvatochromic properties were observed for pure solvents and THF/hexane mixtures. Another chromic effect was achieved upon the addition of a protonic acid to the azothiophene polymer solution as result of the side- and main-chain protonation.     

Birefringent azopolymer long period fiber gratings induced by 532 nm polarized laser

Based on the photoinduced birefringence in azo materials, the model of the birefringent long period fiber gratings (BLPFGs) has been proposed and the transmission of such birefringent fiber gratings was further simulated by the coupled mode theory. In order to obtain the optimum condition for making birefringent azopolymer optical fiber (APOF) gratings the photoinduced birefringence of azo dye and methyl methacrylate (MMA) copolymers was systematically studied. After photosensitivity study of azo samples, using Teflon technique, azo dye containing single mode polymer optical fiber (POF) was fabricated. Finally, BLPFGs can be fabricated in azopolymer fiber using polarized 532 nm laser. A 120 μm LPFG with a 50% duty cycle has been successfully written within the core of the fiber with 532 nm laser by an amplitude mask method. Under polarized microphotography, the grating was observed when the optical axis was set at 45° with the direction of the first polarizing lens of the polarization microscope.     

Methacrylic azopolymers for holographic storage: A comparison among different polymer types

The photoinduced anisotropy and volume holographic storage in a series of polymers with different architectures and azo contents of 7% and 20% in weight have been investigated. Measurements of the birefringence (Δn) induced with linearly polarised 488 nm light show that for polymers with an azo content of 20%, the highest and more stable Δn values are achieved in copolymers with a di-block architecture. The Δn induced in polymers with 7 wt% azo content is not stable. Volume holographic polarisation gratings have been stored in the polymers. Only in the case of the di-block copolymer with an azo content of 20% in weight, the stored gratings are stable. A diffraction efficiency higher than 90% and an angular selectivity of 4° have been achieved in gratings with a period of 2 μm. It can be concluded that the di-block copolymer with 20 wt% azo content is the most suitable, among the studied copolymers, as volume holographic storage material.     

The photochemical behavior of polyhydroxy styrene with azofragments containing free methacrylic double bounds

Polymer material which combines advantages of photoaligning azo-compounds with thermal stability of the induced anisotropy provided by free methacryloyl groups was synthesised. FTIR spectroscopy was employed for clarification its photochemical behavior. Two Fries rearrangements in arylester groups and photoinitiated cross-linking in methacryloyl functional groups were established after the action of UV-irradiation.