Enhanced dissolution of copolymers bearing photobase- or photoacid-generating groups in polar solvents by photochemical formation of ionic pairs

Solubility changes in the irradiation of copolymers bearing photoacid- or photobase-generating groups and low molecular weight photobase generators (PBGs) or photoacid generators (PAGs) were investigated. Copolymers bearing acyloxyimino (AOI) groups were used as those generating pendant amino groups photochemically. Copolymers bearing o-nitrobenzyloxycarbonyl and imino sulfonate groups were used as those generating carboxy and sulfo groups, respectively. The solubility of copolymers bearing AOI groups into polar solvents was enhanced by added PAGs such as β-keto sulfones or imino sulfonates after irradiation. A similar enhancement was observed in copolymers bearing o-nitrobenzyloxycarbonyl groups in the presence of PBGs such as oxime esters or o-nitrobenzyl carbamates. These results showed that the formation of acid–base pairs on irradiation was effective for dissolution into polar solvents. Copolymers bearing imino sulfonate groups showed a high solubility, and no such enhancement was observed by PBG. Films of copolymers bearing β-keto sulfone groups became insoluble because of crosslinking. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1708–1715, 2001     

Synthesis of new reactive dyes containing commercial UV-absorbers with enhanced simultaneous dyeing and anti-UV properties for cotton fabric

Two new reactive anti-UV dyes were synthesized based on two commercial UV-absorbers, ethyl 4-aminobenzoate for dye 1 and 4-aminobenzophenone for dye 2, which were incorporated in a structure modified from commercial reactive dye CI Reactive Red 198 (dye 3). Optimum exhaustion and total fixation values were achieved at 80 ​g/l sodium sulphate for dye 1 and 60 ​g/l sodium sulphate for dye 2, 20 ​g/l sodium carbonate at 70 ​°C for dye 1 and 80 ​°C for dye 2 and 60 ​min fixation time for both dyes. The two new reactive dyes exhibited higher dyeing properties and UPF values than the commercial reactive dye over all the dye concentrations studied. The new reactive dye 1 achieved the highest exhaustion, total fixation and UPF values. The fastness properties obtained for all the dyeings ranges from good to excellent.     

Crosslinking of oligomers bearing carbamoyloxyimino groups with their photochemical and thermal reactions

Carbamoyloxyimino (COI) groups are precursors of photochemically base‐generating groups as well as those of thermally isocyanate‐generating groups. In this study, photochemical and thermal reactions of COI groups in oligomers were investigated by spectral analyses and solubility changes. Oligomers bearing three types of COI groups were prepared. COI groups in all oligomer films were photolyzed on irradiation with 254 nm of light and were deblocked to form isocyanato groups on heating. From the IR spectral analyses, the formation of urea linkage was confirmed by the decrease in isocyanato groups and peak generation because of urea groups on postexposure bake (PEB) treatment. For all oligomer films, PEB was effective for the enhancement of insolubilization of the films in tetrahydrofuran. Heating followed by irradiation was also effective for the insolubilization. These results indicated that photochemical and thermal treatments of COI groups afforded highly sensitive crosslinking systems because of photochemically generated basic groups and thermally generated isocyanato groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2612–2620, 2004     

An anionic In(III)-based metal-organic framework with Lewis basic sites for the selective adsorption and separation of organic cationic dyes

An In(Ⅲ)-based metal-organic framework (BUT-29) can selectively absorb cationic dyes in DMF even in the presence of other organic dyes, and has the higher adsorption capacity.     

Synthesis of poly (acrylamide-co-aconitic acid) adsorbents by gamma-irradiation,characterization, adsorption studies and application for cationic dyes removal

In this study, acrylamide (AAm)/aconitic acid (ACA) copolymers were prepared with two different mol% of aconitic acid 4%, 17% and were irradiated with gamma irradiation at different irradiation doses (4 - 25kGy). The percent yield was assigned by gravimetrical method. The effect of irradiation dose, pH and involved amounts of monomers (AAm/ACA) in hydrogels on swelling properties were investigated. The conversion of monomers to hydrogels was 100% at 25kGy. Poly(acrylamide-co-aconitic acid) P(AAm/ACA) hydrogels have been used for the adsorption of some aqueous solutions of dyes such as Methylene Blue (MB) and Safranine-O (S). The hydrogels were swollen in distilled water at pH 3, 5, 7, 8 and in aqueous solutions of dyes. The initial swelling rates of hydrogels are increased by increasing of pH. The effects of concentration of the aqueous solutions of dye and hydrogel composition on the adsorption were investigated. The adsorption is increased and changed depending on the structure of dye and composition of hydrogel.     

Photochemical modification of polymer surface by the pendant photobase generator containing oxime‐urethane groups and its application to an image‐recording material

Copolymers containing oxime‐urethane groups were prepared by the copolymerization of methyl methacrylate and benzophenoneoximinocarbonylaminoethyl methacrylate (BCM), and their photochemical properties were examined from the UV and IR absorption spectral changes. The decomposed fraction of oxime‐urethane groups in the copolymer increased with irradiation time, but it decreased with the content of BCM units in the copolymer. Changes of the surface properties of the copolymer film on irradiation were studied by measurements of the contact angle and dyeing with an acid dye. The surface of the copolymer film changed to become more hydrophilic upon irradiation with 254 nm of UV light. After the irradiated copolymer films were treated with HCl or methanol, changes of the contact angle of water on irradiation were compared. The copolymer film was dyed by acid dyes after treatment of the irradiated film with HCl. The degree of dyeing increased with irradiation time and BCM units in the copolymer, but it was unaffected by the film thickness. Various colors were developed on the irradiated area depending on the acid dye as the developer. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1200–1207, 2002     

Synthesis and characterization of D‐(−)‐Salicine‐based star copolymers containing pendant carboxyl groups with fluorophore dyes

Salicin was modified to monoacetals and diacetals with bromoester groups (f_Br = 4 and 6) initiating atom transfer radical polymerization (ATRP). These glucoinitiators were used to synthesize 4‐ and 6‐arm star copolymers of tert‐butyl methacrylate (tBMA) and methyl methacrylate (MMA) with different arm polymerization degree (DP_arm = 13 ? 79), and composition (25–75 mol % of tBMA). The transformation of hydrophobic stars into amphiphilics by acidolysis of tert‐butyl groups resulted in copolymers with various contents of hydrophilic fraction based on methacrylic acid (MAA) units (13–75 mol %), which were labeled with fluorescein amine (FA) for the future studies of targeted internalization. The UV spectroscopy and fluorescence measurements of the prepared copolymers confirmed the incorporation of fluorophore moieties (1–14 FA labeled units as max. 5% of total MAA units). The solution properties of star polyacids observed by DLS in a function of a pH show a specific behavior related to the interchain/intrachain interactions yielding particles with diameter sizes in the range from 3 to 15 nm, which can be significantly increased to 180–270 nm by addition of NaCl. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2399–2411     

Supramolecular assembly of H‐bonded side‐chain polymers containing conjugated pyridyl H‐acceptor pendants and various low‐band‐gap H‐donor dyes bearing cyanoacrylic acid groups for organic solar cell applications

Novel supramolecular side‐chain polymers were constructed by complexation of proton acceptor (H‐acceptor) polymers, i.e., side‐chain conjugated polymers P1–P2 containing pyridyl pendants, with low‐band‐gap proton donor (H‐donor) dyes S1–S4 (bearing terminal cyanoacrylic acids) in a proper molar ratio. Besides unique mesomorphic properties confirmed by DSC and XRD results, the H‐bonds of supramolecular side‐chain structures formed by pyridyl H‐acceptors and cyanoacrylic acid H‐donors were also confirmed by FTIR measurements. H‐donor dyes S1–S4 in solid films exhibited broad absorption peaks located in the range of 471–490 nm with optical band‐gaps of 1.99–2.14 eV. Furthermore, H‐bonded polymer complexes P1/S1–P1/S4 and P2/S1–P2/S4 exhibited broad absorption peaks in the range of 440–462 nm with optical band‐gaps of 2.11–2.25 eV. Under 100 mW/cm² of AM 1.5 white‐light illumination, the bulk heterojunction polymer solar cell (PSC) devices containing an active layer of H‐bonded polymer complexes P1/S1–P1/S4 and P2/S1–P2/S4 (as electron donors) mixed with [6,6]‐phenyl C₆₁ butyric acid methyl ester (i.e., PCBM, as an electron acceptor) in the weight ratio of 1:1 were investigated. The PSC device containing H‐bonded polymer complex P1/S3 mixed with PCBM (1:1 w/w) gave the best preliminary result with an overall power conversion efficiency (PCE) of 0.50%, a short‐circuit current of 3.17 mA/cm², an open‐circuit voltage of 0.47 V, and a fill factor of 34%. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5998–6013, 2009     

Synthesis and characterization of fluorine‐containing polyacrylate latex with core–shell structure by UV‐initiated seeded emulsion polymerization

A core–shell fluorine‐containing polyacrylate emulsion was successfully prepared by UV‐initiated seeded emulsion polymerization in two stages in the presence of two photoinitiators. The water‐soluble photoinitiator for the core polymerization and the oil‐soluble photoinitiator was used for the shell polymerization. Both of the two stage polymerizations could be completed within 15 min and displayed a conversion above 94%. The emulsion and the films were characterized by Fourier transformed infrared spectrometry, transmission electron microscopy, dynamic light scattering, X‐ray photoelectron spectroscopy (XPS), contact angle (CA), and thermogravimetry analysis, respectively. The analysis results indicated that the fluorine‐containing latex particles had very small particle size (40 nm) with a core–shell structure and a narrow particle size distribution. XPS analysis revealed that a gradient concentration of fluorine excited in fluorine‐containing emulsion film from the film–air interface to the film–glass interface. In addition, the film formed from the fluorine‐containing emulsion exhibited not only higher thermal stability but also better hydrophobicity than that of the fluorine‐free emulsion. Copyright © 2010 John Wiley & Sons, Ltd.