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In this article, new compounds based on the carbazole scaffold (DMs = DM1 and DM2, constituted by a carbazole unit connected on positions 3 and 6 to a two 4,4′‐dimethoxydiphenylamine groups and differing by the substituent present on the nitrogen heteroatom of the carbazole core) were synthesized and proposed as high‐performance visible light photoinitiators/photosensitizers for both the free‐radical polymerization of methacrylates and the cationic polymerization of epoxides upon visible light exposure using LED@405 nm. Remarkably, DM2 leads to higher final conversions than DM1. In order to study the photophysical and photochemical properties of the carbazole derivatives, different parameters were taken into account such as the light absorption, the steady‐state photolysis, and the fluorescence spectroscopy. Using different techniques such as fluorescence quenching, redox behavior, and cyclic voltammetry, we are able to discuss the photosensitization/photoinitiation reactions providing a full coherent picture of the involved chemical mechanisms. The photosensitization of the carbazole derivatives occurred predominantly via singlet excited states at the rate of the diffusion limit. Upon exposure to laser diode at 405 nm, DMs show high performance in initiating systems for 3D resins. Remarkably, DM2 can also be used in photocomposite synthesis using light‐emitting diode conveyor. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2081–2092 [ABSTRACT FROM AUTHOR]

The UV‐induced and catalyst‐free photoiniferter surface grafting using xanthate RAFT agents is studied. First, a novel silane containing a xanthate RAFT agent moiety is synthesized and successfully grafted onto a silicon wafer as confirmed by secondary ion mass spectrometry (SIMS). Next, using only methyl acrylate, solvent and UV light (365 nm) polymer brushes are grafted rapidly from the surface with film thicknesses up to 25 nm reached within half an hour. The obtained polymer films are thoroughly analyzed by X‐ray photoelectron spectroscopy (XPS), ToF‐SIMS, and AFM. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2002–2007 [ABSTRACT FROM AUTHOR]

Highly porous polymers produced by polymerization of the continuous phase of a high internal phase emulsion have been developed as scaffolds for 3D culture of human pluripotent stem cells. These emulsion‐templated polymerized high internal phase emulsion (polyHIPE) materials have an interconnected network of pores that provide support for the cells, while also allowing both cell ingress and nutrient diffusion. Thiol‐acrylate polyHIPE materials were prepared by photopolymerization, which, due to a competing acrylate homopolymerization process, leads to a material with residual surface thiols. These thiols were then used as a handle to allow postpolymerization functionalization with both maleimide and a maleimide‐derivatized cyclo‐RGDfK peptide, via Michael addition under benign conditions. Functionalization was evaluated using an Ellman's colorimetric assay, to monitor the residual thiol concentration, and X‐ray photoelectron spectroscopy. Maleimide was used as a model molecule to optimize conditions prior to peptide‐functionalization. The use of triethylamine as a catalyst and a mixed ethanol‐aqueous solvent system led to optimized reaction between surface‐bound thiols and maleimide. Peptide‐functionalized materials showed improved attachment and infiltration of human pluripotent stem cells over 7 days, demonstrating their promise as a scaffold for 3D stem cell culture and expansion. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1974–1981 [ABSTRACT FROM AUTHOR]

Chitosan is a bioactive macromolecule with a wide variety of applications due to its excellent biological properties such as biodegradability, biocompatibility, and antibacterial activity, and so forth. This highlight focuses on the preparation of photoactive chitosans, the formation of photocrosslinkable chitosan hydrogels, and the related photopolymerization mechanisms. Moreover, the great potential applications of photocrosslinkable chitosan hydrogels for human tissues are also discussed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1862–1871 [ABSTRACT FROM AUTHOR]

Poly(vinyl alcohol) (PVA) hydrogels with high water content, good load‐bearing property, low frictional behavior as well as excellent biocompatibility have been considered as promising cartilage replacement materials. However, the lack of sufficient mechanical properties and cell adhesion are two critical barriers for their application as cartilage substitutes. To address these problems, herein, methacrylated PVA with low degree of substitution of methacryloyl group has been synthesized first. Then, methacrylated PVA‐glycidyl methacrylate/hydroxyapatite (PVA‐GMA/Hap) nanocomposite hydrogels have been developed by the photopolymerization approach subsequently. Markedly, both pure PVA‐GMA hydrogel and PVA‐GMA/Hap nanocomposite hydrogels exhibit excellent performance in compressive tests, and they are undamaged during compressive stress–strain tests. Moreover, compared to pure PVA‐GMA hydrogels, 8.5‐fold, 7.4‐fold, and 14.2‐fold increase in fracture stress, Young's modulus and toughness, respectively, can be obtained for PVA‐GMA/Hap nanocomposite hydrogels with 10 wt % Hap nanoparticles. These enhancements can be ascribed to the intrinsic property of PVA‐GMA and strong hydrogen bonding interactions between PVA‐GMA chain and Hap nanoparticles. More interestingly, significant improvement in the cell adhesion can also be successfully achieved by incorporation of Hap nanoparticles. These biocompatible nanocomposite hydrogels have great potential to be used as cartilage substitutes. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1882–1889 [ABSTRACT FROM AUTHOR]

Iodonium sulfonates are proposed here as a new class of high‐performance coinitiators for camphorquinone (CQ)‐based systems for the polymerization of methacrylates under blue light irradiation. When combined with CQ, the new proposed coinitiators present excellent polymerization performances and are excellent candidates for the replacement of tertiary aromatic amines subjected to toxicological concerns in the well‐established CQ/amine photoinitiating system (PIS). Remarkably, good bleaching properties are obtained after polymerization. The use of the new PIS for dental adhesives is also investigated. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1664–1669 [ABSTRACT FROM AUTHOR]

New polyoxometalate (POM)/polymer hybrid composites were prepared by photopolymerization under mild conditions for suitable photocatalytic processes. Polyoxometalates were incorporated in special photosensitive resins, which were photopolymerized under visible light to obtain new materials with photocatalytic activity for dye removal. The synthesized composites were characterized by real‐time FT‐IR, and the photocatalytic ability was investigated on Eosin‐Y removal using photolysis under near UV irradiation. Interestingly, the polyoxometalates keep their photocatalytic properties, while incorporated into the polymeric matrix since very high conversion rates of Eosin‐Y were achieved. Indeed, degradation efficiencies of about 98% and 93% were registered when using H3PMo12O40/polymer and 94% for SiMo12O40(IPh2)4/polymer composites, respectively. These first results reported in this article show that the new synthesized POM/polymer composites could be considered as promising materials for green and more suitable organic dye removal from aqueous solutions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1538–1549 [ABSTRACT FROM AUTHOR]

The effect of a two‐step free‐radical photopolymerization of an acrylate resin on the polymer properties in the presence of glass fibers is studied. It is found that a first irradiation leading to a partial conversion is effective for the fabrication of a preimpregnated glass‐fiber composite, which can be further processed and fully polymerized through a second irradiation. DMA analysis evidences the formation of a first relatively soft polymer embedding unreacted double bonds during the preirradiation. Further process allows the completion of the photopolymerization together with a reinforcement of the polymer network. This obviously affects the final mechanical properties of the photocomposite. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1440–1447 [ABSTRACT FROM AUTHOR]

Various PS‐based graft copolymers including polystyrene‐graft‐poly(methyl methacrylate) and poly(styrene‐graft‐poly(ethylene glycol) methacrylate) are prepared via subsequent visible light radical photopolymerization and iniferter processes. Thus, poly(styrene‐co‐4‐chloromethylstyrene) P(S‐co‐VBC) is synthesized by light induced free‐radical polymerization. Then, chloride moieties are substituted with triphenylmethyl (trityl) groups to give trityl‐substituted PS (PS‐trityl) under visible light irradiation using dimanganese decacarbonyl (Mn2(CO)10) photochemistry. Side chains are then grafted from PS‐trityl backbone via iniferter process to give desired graft copolymers in a controlled manner. The precursor intermediates and the final graft copolymers are analyzed by 1H NMR, FT‐IR, and GPC measurements. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1344–1348 [ABSTRACT FROM AUTHOR]

Highlights from the article: A visible light-induced metal-free atom transfer radical polymerization strategy for the efficient synthesis of polyacrylonitrile (PAN) with predictable molecular weights and low dispersities has been developed. While no absorbance of the phenothiazines at visible region can be observed, high energy ultraviolet (UV) light is necessary in this process, leaving a space for improvement of using the abundant and "green" visible light to achieve the controlled polymerization of AN. (a) Plot of monomer conversion versus time demonstrating the dependency of light on the polymerization: light on (blue regions) and light off (white regions). The results of polymerization kinetics, light on/off switching experiments and chain extension polymerizations together proved the living nature of the visible light catalytic system.

Free‐radical photopolymerization is scarcely used for the manufacturing of fiber‐reinforced polymers. The main issue relies on the penetration depth of light which affects the conversion degree when photopolymerizing thick samples. Consequently, this could lead to inhomogeneous polymer properties. The ability of acylphosphine oxides to photobleach under near UV irradiation makes them of great interest for the curing of thick samples. Therefore, the influence of (2,4,6‐trimethylbenzoyl) phosphine oxide on the curing of composites under LED is investigated. Although that a frontal photopolymerization process can be evidenced, it was found that full photobleaching is hardly obtained at high concentration of photoinitiator. Six layers laminates made of unidirectional fiber glass and unsaturated polyester resin were prepared. The existence of an optimal range of concentration for which the conversion of the resin is the most homogeneous throughout its thickness was pointed out, a fact that is confirmed by dynamic mechanical analysis. Interestingly, this effect is reflected in the shrinkage of the resin as shown by direct measurements or deflection experiments. Mechanical analysis was undertaken whose results correlate well with the aforementioned study, demonstrating the occurrence of a balance between the concentration of photoinitiator and the mechanical properties of the samples. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 898–906 The effect of the penetration depth of light during the frontal free‐radical photopolymerization of LED‐cured fiber‐reinforced polymers is studied. The photobleaching of the photoinitator is shown to be incomplete, leading to inhomogeneities in properties. An optimal range of photoinitiator concentration is pointed out which allows the formation of high performance composites. [ABSTRACT FROM AUTHOR]

Perfluoropolyalkylethers derived from hexafluoropropylene oxide were functionalized with maleimide groups. Irradiated by UV‐light, the new maleimide macromonomers demonstrated very fast polymerization kinetics with a curing time as fast as 8 s. The effect on photopolymerization of different features such as the molecular weight of the fluorinated chain and the chain length of the hydrogenated spacer were studied, as well as the influence of the type of photoinitiator and the presence of air. Thermal and surface properties of the UV‐cured polymers were examined and were typical to fluoropolymers in view of water–oil repellent coatings. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 699–707 The polymerization under UV‐light of maleimide perfluoropolyalkylethers (PFPAEs) is very fast. The example shown in the figure demonstrates a curing time of 8 seconds. After UV‐curing, the maleimide PFPAEs reveal excellent thermal stability. Moreover, hydrophobicity and oleophobicity are exhibited with contact angle values up to 124° with water and up to 82° with hexadecane. [ABSTRACT FROM AUTHOR]

Two series of photoreactive discotic liquid crystals consisting of a triphenylene core and six cinnamate units with one (TPC1n) or two (TPC2n) n‐alkoxy groups (CnH2n+1O; n = 10–14), respectively, as peripheral groups are synthesized. Both of them are polymerized into fibers up to 2 mm long by UV irradiation in liquid paraffin in the columnar LC temperature ranges. The fiber structures seem to be preconstructed in liquid paraffin. In addition, TPC2n are shown to form microporous films up to 15 μm in diameter by simply casting the solutions of some solvents followed by drying for several minutes in air at room temperature. Photoirradiation of the films in the LC temperature range converts them to polymeric ones while preserving the microporous and hexagonally ordered structure. From comparison with TPC1n and the hydrogenated derivative of TPC212, the porous film‐forming property is suggested to result from the combination of the double bond of the cinnamoyl group and the two long alkoxy chains on the phenyl ring. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 605–612 Triphenylene‐derived liquid crystals (TPC1n and TPC2n [n = 12–14]) are shown to self‐assemble to fibers in liquid paraffin at the columnar liquid crystalline temperature range and also to form microporous films for TPC2n by casting its solutions at room temperature. They can be crosslinked to polymers, preserving their morphology, fibers, and films, by the [2 + 2] photocyclization of cinnamate units in the periphery by UV irradiation in the columnar liquid crystalline states. [ABSTRACT FROM AUTHOR]

A signature of photo‐mediated controlled polymerizations is the ability to modulate the rate of polymerization by turning the light source 'on' and 'off.' However, in many reported systems, growth can be reproducibly observed during dark periods. In this study, emerging photo‐mediated controlled radical polymerizations are evaluated with in situ1H NMR monitoring to assess their behavior in the dark. Interestingly, it is observed that Cu‐mediated systems undergo long‐lived, linear growth during dark periods in organic media. [ABSTRACT FROM AUTHOR]

Providing access to the benefits of additive manufacturing technologies in tissue engineering, vinyl esters recently came into view as appropriate replacements for (meth)acrylates as precursors for photopolymers. Their low cytotoxicity and good biocompatibility as well as favorable degradation behavior are their main assets. Suffering from rather poor mechanical properties, particularly in terms of toughness, several improvements have been made over the last years. Especially, thiol–ene chemistry has been investigated to overcome those shortcomings. In this study, we focused on additional means to further improve the toughness of an already established biocompatible vinyl ester‐thiol formulation, eligible for digital light processing‐based stereolithography. All molecules were based on poly(ε‐caprolactone) as building block and the formulations were tested regarding their reactivity and the resulting mechanical properties. They all performed well as toughness enhancer, ultimately doubling the impact resistance of the reference system. © 2018 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 110–119 Novel toughness modifiers for photopolymerizable vinyl ester formulations based on poly(ε‐caprolactone) were synthesized. The pursued strategy is based on the concept of high‐molecular‐weight modifiers, which is further developed beyond simple blending by the introduction of copolymerizable end groups (enes and thiols). Finally, rigid cyclic structures and hydrogen bridging urethane moieties are introduced, providing additional design concepts to improve network toughness. [ABSTRACT FROM AUTHOR]

The first monomers containing both phosphonate and bisphosphonate (M1) or phosphonic and bisphosphonic acid (M2) functionalities are synthesized, aiming to improve binding abilities of self‐etching adhesive systems and composites: An amine having both phosphonate and bisphosphonate functionalities is prepared via Michael addition reaction between diethyl (6‐aminohexyl)phosphonate and tetraethyl vinylidene bisphosphonate, its reaction with 2‐isocyanatoethyl methacrylate gives M1 which is converted to M2 by selective dealkylation of the phosphonate/bisphosphonate ester groups. Their copolymerization with commercial dental monomers (bisphenol A glycidyl methacrylate, triethylene glycol dimethacrylate, and 2‐hydroxyethyl methacrylate) investigated by photo‐differential scanning calorimetry shows adequate photopolymerization rate and conversion. X‐ray diffraction, Fourier transform infrared, and X‐ray photoelectron spectroscopy analyses of M2‐treated hydroxyapatite particles show formation of stable M2‐calcium salts. These monomers are assessed to be not toxic according to MTT standards by in vitro cytotoxicity studies with NIH 3T3, U2OS, and Saos‐2 cells. All these properties make these monomers potential candidates as biocompatible components for dental adhesives and composites. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2739–2751 To improve efficiencies of dental materials, novel monomers containing both phosphonate and bisphosphonate/phosphonic and bisphosphonic acid are synthesized. Interaction of monomers with hydroxyapatite (mineral structure of teeth) is analyzed; their copolymerization rate and yield with the dental monomers are evaluated by using photo‐differential scanning calorimetry. [ABSTRACT FROM AUTHOR]

The use of ionic liquids (ILs) as media in radical polymerizations has demonstrated the ability of these unique solvents to improve both reaction kinetics and polymer product properties. However, the bulk of these studies have examined the polymerization behavior of common organic monomers (e.g., methyl methacrylate, styrene) dissolved in conventional ILs. There is increasing interest in polymerized ILs (poly(ILs)), which are ionomers produced from the direct polymerization of styrene‐, vinyl‐, and acrylate‐functionalized ILs. Here, the photopolymerization kinetics of IL monomers are investigated for systems in which styrene or vinyl functionalities are pendant from the imidazolium cation. Styrene‐functionalized IL monomers typically polymerized rapidly (full conversion ≤1 min) in both neat compositions or when diluted with a nonpolymerizable IL, [C2mim][Tf2N]. However, monomer conversion in vinyl‐functionalized IL monomers is much more dependent on the nature of the nonpolymerizable group. ATR‐FTIR analysis and molecular simulations of these monomers and monomer mixtures identified the presence of multiple intermolecular interactions (e.g., π–π stacking, IL aggregation) that contribute to the polymerization behaviors of these systems. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2364–2375 Styrene‐based ionic liquid (IL) monomers photopolymerize much more rapidly and completely than vinyl‐based IL monomers and conventional organic monomers. However, styrene‐based IL monomers are also subject to autopolymerization, which although problematic for storage does reveal that the resultant bulk poly(IL) materials have interesting shape‐memory and self‐healing properties. The photopolymerization efficiency of vinyl‐based IL monomers can be improved by increasing the size/length of the non‐polymerizable group to promote aggregation. [ABSTRACT FROM AUTHOR]

This work demonstrates the UV nanoimprinting lithography (UV‐NIL) of high refractive index and highly transparent polythioethers based on thiol‐ene click chemistry. Herein, 9,9‐bis(3‐mercaptopropylphenylether)fluorene (BMPF) is designed as a new thiol monomer with a high refractive index, high transparency, and good processability for UV‐NIL. Colorless polythioethers are synthesized from BMPF and ene monomers under mild thiol‐ene click reaction conditions. Excellent transmittance (96%) of 400 nm light is observed in all the polymer films and high refractive index values of 1.5972–1.6382 are attained. UV‐NIL using thiol‐ene photopolymerization affords polymer nanoimprinting patterns with various features on the order of 100–500 nm without any fractures. To the best of our knowledge, this is the first report on UV‐NIL of high refractive index and highly transparent polymers. Through proper monomer and polymer design, novel polythioethers with suitable glass transition temperature (Tg) values are developed with high refractive index, high transparency, and good UV‐NIL processability. Furthermore, UV‐NIL based on thiol‐ene click chemistry is accomplished at the nanoscale. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2175–2182 High refractive index and high transparent polythioethers with good UV nanoimprinting lithography (UV‐NIL) processability were developed by proper monomer and polymer design. These polymer nanoimprinting patterns with various features on the order of 100–500 nm were successfully fabricated without any fractures. [ABSTRACT FROM AUTHOR]

ABSTRACT: Thioxanthone–anthracene‐9‐carboxylic acid (TX‐ANCA) namely 14‐oxo‐14H‐naphthol [2,3‐b]thioxanten‐12‐carboxylic acid, is synthesized and characterized as part of our continuing interest for syntheses of polyaromatic initiators. Photoinitiator, TX‐ANCA have good absorption properties in the UV and visible region of the electromagnetic spectrum (ɛ370: 9080 M−1cm−1, ɛ430: 6151 M−1 cm−1). The fluorescence quantum yield is calculated as 0.1 which is slightly higher than of the parent thioxanthone compound (φf: 0.07). The phosphorescence lifetime is found to be 39 ms. The possible initiating mechanism of TX‐ANCA is based on photoexcitation of TX‐ANCA and quenching of triplet excited states of TX‐ANCA by molecular oxygen generates singlet oxygen. Singlet oxygen reacts with the anthracene moiety of TX‐ANCA possibly forms an endoperoxide. The endoperoxides undergoes photochemical or thermal decomposition to form radicals which are able to initiate free radical polymerization. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1878–1883 [ABSTRACT FROM AUTHOR]

ABSTRACT: The chain‐end structure of the photopolymerized acrylate using benzophenone as an initiator was investigated as well as polymerization behavior. Dodecyl acrylate was used as a monomer in this study. Gelation occurred during ultraviolet (UV) irradiation, whereas a cross‐linker was not employed. Conversion‐time profile below gel point gave a linear first‐order plot suggesting that the steady‐state was held throughout polymerization. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectra of the resultant polymer indicated that most polymers had an acryloyl group at one of the chain‐ends, while some polymers had an acryloyl group at each chain‐end. The cross‐linking reaction leading to gelation would have been caused by the subsequent copolymerization of the residual monomer with the latter polymer having two acryloyl groups. Dissolved oxygen in the monomer solution influenced the polymer structure giving hydroxyl group at chain‐end. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1545–1553 [ABSTRACT FROM AUTHOR]

ABSTRACT: Due to the longevity of the cationic active centers, cationic ring‐opening photopolymerization can continue after illumination ceases. In addition, substantial reactivity enhancement for epoxides is realized through copolymerization with oxetanes. Here, the separate reactions of epoxide and oxetane moieties were resolved during illumination and subsequent dark cure via real‐time Raman spectroscopy. Using oxetane additives, reactivity and conversion of 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (EEC) were improved during illumination and subsequent dark cure through modulation of the initial formulation viscosity and selection of the oxetane secondary functional groups. The largest enhancement in reactivity occurred with secondary groups comprising either aliphatic chains with their flexibility or hydroxyls with their chain‐transfer capacity. In contrast, oxetanes containing UV‐absorbing phenyl rings reduced the initiation efficiency, and difunctional oxetanes suppressed overall conversion through additional crosslinking. Although bulk conversion was directly related to initial formulation viscosity, the impact of the oxetane secondary functional groups was greater. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1436–1445 [ABSTRACT FROM AUTHOR]

ABSTRACT: Photopolymerization of thick pigmented systems still remains challenging due to the light screening effect of the pigments. Here, we present a facile method based on upconversion nanoparticles (UCNPs)‐assisted photochemistry to achieve efficient photopolymerization and improved curing depth of pigmented systems. Under a 980‐nm laser irradiation, UCNPs are able to convert NIR light into UV and visible light to activate photoinitiators for the initiation of polymerization. Influencing factors on photopolymerization were systematically investigated. With optimal parameters, 25.5 mm of photopolymerization depth combined with 70% of maximal double bond conversion was obtained. The peak temperature of 120.4 °C during UCNPs‐assisted photopolymerization is comparable with or lower than that of some reported frontal photopolymerization applied to prepare functional composite polymeric materials. Both indentation hardness and reduced modulus of the photocured materials using UCNPs as internal lamps were higher than those of the reference cured under traditional blue LED light. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 994–1002 [ABSTRACT FROM AUTHOR]

ABSTRACT: The ever increasing applications of photopolymers from historical thin (<50 µm) coatings to very deep samples (>1 cm) require the development of robust 4D monitoring strategies able to assess photopolymerization efficiencies (first dimension) as a function of time (second dimension) and position (third and fourth dimensions). Therefore, here, we demonstrated that thermal imaging is a valuable photopolymerization monitoring device showing: (a) very high response times (<1 s); (b) high repeatability of the measurement; (c) strong adaptability of the setup to various conditions (e.g., onto irregular surfaces or inside a real time Fourier transformed infrared spectrometer (RT‐FTIR)); (d) extremely deep photopolymerization follow‐ups (and subsequent rationalization) with good resolution in time and in space (real‐time thermal imaging microscopy experiments); (e) adaptability to applied materials. This monitoring strategy was found particularly robust when taking into account all the heat generating phenomena (i.e., direct heating from the lamp vs. temperature raised due to monomer conversion). As a result, we propose thermal imaging as the next reference monitoring system for the new ranges of thick and/or filled samples (e.g., 3D objects, composites) and/or applied photopolymerizations (e.g., 3D printing) more and more present in the literature. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 889–899 [ABSTRACT FROM AUTHOR]

ABSTRACT: Polymeric capsules with an aqueous core have great potential for a wide range of applications, for example food/biomedical applications. However, synthesis of such capsules often involves the use of toxic organic solvents. Herein, an organic solvent‐free approach is developed for the synthesis of polymeric microcapsules with an aqueous core. The method is based on RAFT polymerization of divinyl monomer around the periphery of inverse emulsion water droplets acting as templates, with an amphiphilic macroRAFT species fulfilling the dual roles of RAFT agent and colloidal stabilizer. Vegetable oils, which are non‐toxic and renewable, are used as the continuous phase of these inverse emulsions, which are prepared using membrane emulsification to control the emulsion droplet size and size distribution. Relatively monodisperse emulsions with tunable droplet size in the range of approximately 10–30 µm are prepared, followed by the RAFT polymerization step to generate polymeric microcapsules having similar size as the initial droplets. This approach will be beneficial for various applications where toxic solvents need be minimized or removed completely to avoid adverse effects. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 831–839 [ABSTRACT FROM AUTHOR]

ABSTRACT The benzaldehyde derivatives, such as 2,4-dimethoxy benzaldehyde (PC1) and p-anisaldehyde (PC2), were successfully used as photoredox catalysts (PCs) in combination with typical RAFT agent 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid (CTP) for the controlled photoinduced electron transfer RAFT polymerization (PET-RAFT) of methyl methacrylate (MMA) and benzyl methacrylate (BnMA) at room temperature. The kinetics of the polymerizations showed first order with respect to monomer conversions. Besides, the average number molecular weights ( Mn) of the produced polymers increased linearly with the monomer conversions and kept relatively narrow polydispersity (PDI = Mw /Mn). For example, the Mn of PMMA increased from about 3400 to 17,300 g mol−1 with the increasing in monomer conversion from 11% to 85%, and the PDI maintained around 1.36. The living features of polymerizations with the PC1 and PC2 as catalysts have also been further supported by chain extension and synthesis of PMMA- b-PBnMA diblock copolymer. As a result, the simplicity and efficiency of benzaldehyde derivatives catalyzed PET-RAFT polymerization have been demonstrated under mild conditions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 229-236 [ABSTRACT FROM AUTHOR]

ABSTRACT Cationic, amphiphilic microgels of differing compositions based on hydrophilic, pH, and thermoresponsive 2-(dimethylamino)ethyl methacrylate (DMAEMA) and hydrophobic, nonionic n-butyl acrylate (BuA) are synthesized using a lab-on-a-chip device. Hydrophobic oil-in-water (o/w) droplets are generated via a microfluidic platform, with the dispersed (droplet) phase containing the DMAEMA and BuA, alongside the hydrophobic cross-linker, ethylene glycol dimethacrylate, and a free radical initiator in an organic solvent. Finally, the hydrophobic droplets are photopolymerized via a UV light source as they traverse the microfluidic channel to produce the cationic amphiphilic microgels. This platform enables the rapid, automated, and in situ production of amphiphilic microgels, which do not match the core-shell structure of conventionally prepared microgels but are instead based on random amphiphilic copolymers of DMAEMA and BuA between the hydrophobic cross-links. The microgels are characterized in terms of their swelling and encapsulation abilities, which are found to be influenced by both the pH response and the hydrophobic content of the microgels. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 59-66 [ABSTRACT FROM AUTHOR]

ABSTRACT Novel thioxanthone (TX) derivatives are used as versatile photoinitiators upon visible light-emitting diode (LED; e.g., 405, 425, and 450 nm) exposure. The mechanisms for the photochemical generation of reactive species (i.e., cations and free radicals) produced from photoinitiating systems based on the photoinitiator and an iodonium salt, tris(trimethylsilyl)silane, or an amine, were studied by UV-vis spectroscopy, fluorescence, cyclic voltammetry, steady-state photolysis, and electron spin resonance spin-trapping techniques. The reactive species are particularly efficient for cationic, free radical, hybrid, and thiol-ene photopolymerizations upon LED exposure. The optimized photoinitiating systems exhibit higher efficiency than those of reference systems (i.e., isopropyl TX-based photoinitiating systems), especially in the visible range. According to their beneficial features, these photoinitiating systems have considerable potential in photocuring applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 4037-4045 [ABSTRACT FROM AUTHOR]

ABSTRACT Two one-component, double-chromophoric thioxanthone photoinitiators, namely TX-EDA and TX-DETA were synthesized by the reaction of thioxanthone aldehyde (TX-A) with ethylenediamine (EDA) and diethylenetriamine (DETA), respectively via a facile Schiff base reaction. Both photoinitiators were characterized by spectral analysis and photobleaching studies. DFT calculations are employed to reveal the contribution of the different orbitals to the excitation of the initiators. The double-chromophoric nature of the initiators gives rise to an increased absorption in the near UV region when compared with the pristine TX-A. Photoinitiated polymerization of various vinyl monomers with TX-EDA and TX-DETA has been investigated in the presence and absence of a co-initiator and compared for formulations consisting of precursor TX-A. In addition, real-time FTIR spectroscopic studies were performed in methyl methacrylate polymerization with both initiators. The higher efficiency observed with TX-DETA may be attributed to the additional hydrogen donating sites adjacent to nitrogen atoms. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3475-3482 [ABSTRACT FROM AUTHOR]

ABSTRACT Incorporation of bisphosphonate/bisphosphonic acid groups in dental monomer structures should increase interaction of these monomers with dental tissue as these groups have strong affinity for hydroxyapatite. Therefore, new urea dimethacrylates functionalized with bisphosphonate (1a, 1b) and bisphosphonic acid (2a, 2b) groups are synthesized and evaluated for dental applications. Monomers 1a and 1b are synthesized from 2-isocyanatoethyl methacrylate (IEM) and two bisphosphonated amines (BPA1 and BPA2), prepared as reported elsewhere. Selective dealkylation of the bisphosphonate ester groups of 1a and 1b using trimethylsilyl bromide (TMSBr) gives monomers (2a and 2b) with bisphosphonic acid functionality. X-ray diffractometer (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses of monomer-treated HAP particles show that 2a induces formation of stable monomer-calcium salts, similar to 10-methacryloyloxydecyl dihydrogen phosphate (MDP), with higher chemical interaction than 2b. The photopolymerization studies indicate good copolymerizability with commercial dental monomers. In vitro studies on NIH 3T3 mouse embryonic fibroblast cells have clearly shown that the tested monomers (1b and 2b) are not toxic according to the MTT standards. All these properties make these monomers suitable as biocompatible cross-linkers/adhesives for dental applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3195-3204 [ABSTRACT FROM AUTHOR]

ABSTRACT The nature of intramolecular charge transfer (CT) of N, N-diaryl dihydrophenazine photocatalysts (PCs) in different solvents is explored in context of their performance in organocatalyzed atom transfer radical polymerization (O-ATRP). PCs having a computationally predicted lowest energy excited state exhibiting CT character can operate a highly controlled O-ATRP in a wide range of solvent polarities, from non-polar hexanes to highly polar N, N-dimethylacetamide. For PCs having a computationally predicted lowest energy excited state not possessing CT character, their ability to operate a controlled O-ATRP is decreased. This study confirms the importance of CT character in the excited state for N, N-diaryl dihydrophenazine PCs, and a deeper understanding of the activity of CT PCs has enabled the synthesis of polymers of low dispersity (<1.10) in a controlled fashion. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3017-3027 [ABSTRACT FROM AUTHOR]

ABSTRACT A few N-alkoxypyridinium salts are developed as photoinitiators for efficient polymerization reactions. They are characterized by absorption properties below 300 nm, and generate alkoxy radicals on UV-Vis light exposure. The squarylium dye was used as a blue-light photosensitizer. Polymerization results are correlated with the photochemistry of N-alkoxypyridinium salts. The quenching of the excited singlet state of squarylium dye by pyridinium salt and the formation of the semioxidized species of squaraine suggests an electron transfer from an excited dye to a coinitiator, and that the resulting oxygen-centered radical initiates the polymerization process. The chemical mechanism was investigated by steady state photolysis and nanosecond laser flash photolysis experiments. Photoinitiating activity of new photoinitiators for initiation of polymerization of trimethylolpropane triacrylate in the UV-blue light region was compared with photoinitiating ability of selected commercially available initiators. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2840-2850 [ABSTRACT FROM AUTHOR]

ABSTRACT An inorganic-organic hybrid material, poly(dimethylsilylene ethynylenephenyleneethynylene) (PMSEPE), was synthesized in a mild condition and its microfiber was successfully produced by melt electrospinning. The electrospinning parameters, which affected the morphology and diameter of fibers, were well investigated. To maintain the fiber structure at thermal cured temperature (above melting point), the PMSEPE fibers were enhanced via thiol-yne photo polymerization. Followed by the thermal curing reaction, the heat-resistance and mechanical properties of fibers were enhanced. The mechanism of two-step curing was explored and confirmed by means of Fourier transform infrared, differential scanning calorimetry, and X-ray photoelectron spectroscopy (XPS). Thermaogravimetric analysis and scanning electron microscopy results show that after carbonization at 800 °C, the two-step cured fibers had only a small weight loss (20%) and the fibers can still maintain the original morphology. Moreover, the two-step cured fiber exhibited a high tensile strength (55.4 MPa) and a small elongation at break (0.02%). All the results indicate that the fibers could be applied as fiber-reinforced materials. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2815-2823 [ABSTRACT FROM AUTHOR]

ABSTRACT Engineering of molecular stacking arrangement via environmental stimuli is of particular interest in stimuli-responsive self-assembling architectures. A novel dual photo-functionalized diacetylene (( Z)-CNBE-DA) molecule was synthesized, in which photo-responsive cyanostilbene moieties exhibited interesting Z-E isomerization upon UV light irradiation and could be utilized to modulate mesomorphism, molecular stacking arrangement and resulting polymerization behavior. Rod-like ( Z)-CNBE-DA could self-assemble into well-defined lamellar structures and the helical polydiacetylene (PDA) chains could be formed upon irradiation with circularly polarized ultraviolet light (CPUL). However, the bent-shaped ( E)-CNBE-DA molecules only self-assembled into irregular loose packing, inhibiting the formation of ordered helical PDA chains upon CPUL irradiation. In this work, we established the links between chemical structures, molecular packing engineering and photophysical properties, which would be of great fundamental value for the rational design of smart soft materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2458-2466 [ABSTRACT FROM AUTHOR]

ABSTRACT A radical initiation ability of new initiating systems in photopolymerization of 2-ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate has been investigated and presented. The evaluation of alkyltriphenyl- and tetraalkylborates, iodonium salts, N-alkoxypyridinium salts, maleimides, phthalimides, 1,3,5-triazine derivatives and others as a free radical source in combination with suitable photosensitizer for radical polymerization of triacrylate is described. It is assumed that the photochemical decomposition of a coinitiator molecule results in formation of free radicals, which further initiate polymerization. The order of activity of free radical sources on kinetic of photopolymerization was also presented. Different initiator activity can be explained by the difference in the decomposition rate constant and the reactivity of radicals formed toward the double bond of monomer. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1575-1589 [ABSTRACT FROM AUTHOR]

ABSTRACT Linear poly(hydroxyethyl methacrylate-co-methyl methacrylate) P(HEMA-co-MMA) and poly(dimehylaminoethyl methacrylate-co-methyl methacrylate) P(DMAEMA-co-MMA) and their corresponding hyperbranched copolymers were synthesized by conventional photoinitiated free radical polymerization and self-condensing vinyl polymerization (SCVP) using Type I and Type II photoinitiators, respectively. Then, the polymers were processed by electrospraying in N, N-dimethylformamide. The surface of the resulting electrospray coatings was examined by SEM, XPS, and WCA then compared with those prepared by drop casting. Regardless of the structural nature of the polymers, electrospraying allows the preparation of rough surface that shows more hydrophobic behavior. Electrospray coatings with linear and hyperbranched copolymers exhibited WCA as ∼150° and ∼130°, respectively, indicating that branching reduces the WCA. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1338-1344 [ABSTRACT FROM AUTHOR]

In this article, novel azahelicenes (AZs) were synthesized and proposed as high performance visible light photoinitiators for both the free radical polymerization of acrylates and the cationic polymerization (CP) of epoxides upon visible light exposure using Light Emitting Diodes (LEDs) @405, @455, and @470 nm. Excellent polymerization initiating abilities are found and high final conversions were obtained. Remarkably, an exceptional long lifetime photoluminescence property of the polymer films was observed when synthesized in presence of AZs. A full picture of the involved chemical mechanisms is given. AZs being high performance photoinitiators, their use in new cationic LED 3D printing resins will be also presented, that is, the cationic process upon LED projector @405 nm can be useful to reduce the shrinkage usually observed for radical polymerization. LED projector printing is very interesting compared to laser writing as this technology projects the profile of an entire layer of a 3D object at one time. [ABSTRACT FROM AUTHOR]

ABSTRACT A new di- tert-butyl acrylate (diTBA) monomer for controlled radical polymerization is reported. This monomer complements the classical use of tert-butyl acrylate (TBA) for synthesis of poly(acrylic acid) by increasing the density of carboxylic acids per repeat unit, while also increasing the flexibility of the carboxylic acid side-chains. The monomer is well behaved under Cu(II)-mediated photoinduced controlled radical polymerization and delivers polymers with excellent chain-end fidelity at high monomer conversions. Importantly, this new diTBA monomer readily copolymerizes with TBA to further the potential for applications in areas such as dispersing agents and adsorbents. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 801-807 [ABSTRACT FROM AUTHOR]

ABSTRACT In this article, the ability of two-component photoinitiator systems for efficient polymerization of 2-ethyl-2-(hydroxymethyl)−1,3-propanediol triacrylate was presented. The photophysics and photochemistry of squaraine dyes in the presence of an electron donor as well as an electron acceptor was investigated, and it was found that the photosensitizer in an excited state might act as an electron acceptor or an electron donor. The excited states of squaraines may be quenched by tetramethylammonium n-butyltriphenylborate ( B2), diphenyliodonium chloride ( I1), and N-methoxy-4-phenylpyridinium tetrafluoroborate ( NO). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 471-484 [ABSTRACT FROM AUTHOR]

ABSTRACT Photopolymerization is extensively used in today's industrial field due to its advantages of rapid reaction, environmental friendly, energy saving and economical. Benzophenone is a most common photoinitiator (PI) using in photopolymerization because of its superior ability to initiate acrylate monomers. However, the intrinsic nature of initiator molecules is that they migrate out of polymer network, which limits its application, especially in the domain of food packaging materials. A polymerizable PI 4-methylbenzophenone acrylate (MBPAc) was synthesized by a facile procedure and characterized by 1H NMR, 13C NMR, and MS analyses. A systematic study of the photopolymerization kinetics of MBPAc was explored by the Real-Time Fourier Transform Infrared Spectrometer. The results show that the final conversion and photopolymerization rate of acrylate monomers are closely related to the factors of their chemical structure, viscosity, functionality and light intensity, which means MBPAc is an efficient PI. Ultraviolet-visible Spectrophotometer and vitro cytotoxicity measurement results indicate that the noncytotoxic MBPAc shows significantly lower migration than its analogue. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 313-320 [ABSTRACT FROM AUTHOR]

ABSTRACT This report introduces a novel UV-curing technology based on thiol-thiol coupling for polydisulfide network formation. Beginning with a model tris(3-mercaptopropionate) trithiol monomer and xanthone propionic acid-protected guanidine as photobase generator, a comprehensive characterization based on spectroscopic techniques supports the reaction of thiols into disulfides without side reactions. The best experimental conditions are described as regards to film thickness, irradiance, emission wavelength, and atmosphere composition. The results shed light on a step-growth photopolymerization mechanism involving two steps: first, the formation of thiyl radicals by thiolate air oxidation or/and thiol photolysis, and second, their recombination into disulfide. By varying thiol functionality and structure, oligomer chain length and monomer/oligomer ratio, the network architecture can be finely tuned. The molecular mobility of the polydisulfide network is crucial to high thiol conversion rates and yields as revealed by 1H T2 NMR relaxation measurements. Ultimately, spatial control enables the formation of a photopatterned poly(disulfide) film, used as next-generation high refractive index photoresist. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 117-128. [ABSTRACT FROM AUTHOR]

ABSTRACT Cationic photopolymerization has become increasingly important in thin-film applications for advantages including no oxygen inhibition and rapid polymerization rates. Photocurable cationic thin film properties are often modulated by incorporation of oligomeric and prepolymer materials, but little work has directly examined the effect of prepolymer structure and reactive group placement on the thermomechanical properties of the final material. To explore the role of molecular architecture, epoxy functionalized butyl acrylate gradient copolymers were synthesized with reactive groups in end segments or randomly distributed along the prepolymer chain. Polymerized end functionalized formulations exhibit moduli almost double that of random functionalized oligomer formulations. In addition, inclusion of end functionalized prepolymers decreases creep of resulting thin films by a factor of 10. Furthermore, decreasing the concentration of the cross-linking diluent in end functionalized prepolymer systems results in amorphous networks with significantly lower mechanical strength. Increasing reactive groups at the ends of prepolymers produces stronger materials without affecting tensile elongation at break. These properties indicate that the structured oligomers facilitate the formation of continuous hard domains with high cross-link density with inclusions of soft, flexible domains of low cross-link density. This study demonstrates that the prepolymer architecture governs network formation and ultimate properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 144-154 [ABSTRACT FROM AUTHOR]

ABSTRACT The surface chemistry of aryl diazonium salts has progressed at a remarkable pace in the last two decades, and opened many avenues in materials science. These compounds are excellent coupling agents for polymers to surfaces via several surface-confined polymerization methods. For the first time, we demonstrate that diazonium salts are efficient for surface initiating radical photopolymerization in the visible light of methyl methacrylate (MMA) and 2-hydroxyethyl methacrylate (HEMA) taken as model monomers. To do so, 4-(dimethylamino)benzenediazonium salt was electroreduced on gold plates or flexible ITO sheets to provide 4-(dimethylamino)phenyl (DMA) hydrogen donor layers; while excited state camphorquinone acted as the free hydrogen abstractor. In the same way, we co-polymerized HEMA and MMA with ethylene glycol dimethacrylate in order to obtain crosslinked polymer grafts. We demonstrate by XPS that gold was efficiently screened by the polymer layers and that the wettability of the surfaces accounts for the hydrophilic or hydrophobic characters of the tethered polymers. Homo- and crosslinked PMMA grafts were found to resist removal by the paint stripper methyl ethyl ketone. The grafted DMA/camphorquinone system operating in the visible light holds great promises in terms of adhesion of in situ designed continuous or patterned polymer coatings on various substrates. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3506-3515 [ABSTRACT FROM AUTHOR]

ABSTRACT A photoinitiating system composed of a sensitizer (isopropylthioxanthone, ITX) and a photobase generator (triazabicyclodecene tetraphenylborate TBD.HBPh4) was successfully applied to the photopolymerization of a thiol-isocyanate-epoxy mixture. The final polymer network was considered in term of the compositional ratio between the thiol-isocyanate and thiol-epoxy coupling reactions. In parallel with structural investigation by spectroscopic technics, the relationships between the compositional ratio and kinetics of photopolymerization, thermomechanical properties and hardness were investigated. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3119-3126 [ABSTRACT FROM AUTHOR]

ABSTRACT An efficient strategy for comprehensive utilization of the conjugated sulfonium salt photoacid generator (PAG), namely, 3-{4-[4-(4- N, N′-diphenylamino)-styryl]phenyl}phenyl dimethyl sulfonium hexafluoroantimonate, was developed through photoinitiated cationic photopolymerization (CP) of epoxides and vinyl ether upon exposure to near-UV and visible light-emitting diodes (LEDs; e.g., 365, 385, 405, and 425 nm). Photochemical mechanisms were investigated by UV-vis spectra, molecular orbital calculations, fluorescence, cyclic voltammetry, and electron spin resonance spin-trapping analyses. Compared with commercial PAGs, the prepared conjugated sulfonium salt generated H+, which can be used as photoinitiator. Moreover, the fluorescent byproducts from photodecomposition can be used as photosensitizer of commercial iodonium salt in the photoinitiating systems of CP. These novel D-π-A type sulfonium-based photoinitiating systems are efficient (epoxide conversion = 85-90% and vinyl conversion >90%; LEDs upon exposure to 365-425 nm) even in low-concentration initiators (1%, w/w) and low curing light intensities (10-40 mW cm−2). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2722-2730 [ABSTRACT FROM AUTHOR]

ABSTRACT We described the design and synthesis of a modified poly(aryl ether ketone) bearing phenolphthalein and allyl groups (P-PAEK) via nucleophilic polycondensation. A new kind of composite separator, crosslinked P-PAEK/polyvinylidene fluoride (c-P-PAEK/PVDF) membrane was successfully prepared using phase separation, phase inversion method, and UV crosslinking technique. As a separator of lithium-ion battery, c-P-PAEK/PVDF membrane demonstrates high porosity and uniform distribution of pores with interconnected pathways. Low thermal shrinkage, distinct shut-down effect, high liquid electrolyte uptake capacity, and exciting liquid electrolyte wettability of the prepared c-P-PAEK/PVDF membrane have been revealed through comprehensive study. Moreover, the c-P-PAEK/PVDF membrane was applied to assemble a conventional Li/LiFePO4 coin cell, which exhibited hopeful cell performance. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2714-2721 [ABSTRACT FROM AUTHOR]

ABSTRACT A novel strategy for the synthesis and characterization of branched polymer brushes by sequential light-mediated controlled radical polymerizations is described. Initially, linear brushes are prepared by surface-initiated copolymerization of methyl methacrylate and 2-hydroxyethyl methacrylate (HEMA). In a subsequent step, the HEMA side chains are functionalized with initiating groups for secondary graft polymerization, leading to hierarchical, branched architectures. The increased steric bulk due to the polymer side chains results in a dramatic increase in film thickness when compared to the starting linear brushes. This strategy also allows chemical gradient and complex three-dimensional structures to be obtained by employing grayscale photomasks in combination with controlled radical polymerization. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2276-2284 [ABSTRACT FROM AUTHOR]

ABSTRACT Two D-π-A-type 2,2,2-trifluoroacetophenone derivatives, namely, 4′-(4-( N, N-diphenyl)amino-phenyl)-phenyl-2,2,2-trifluoroacetophenone (PI-Ben) and 4′-(4-(7-( N, N-diphenylamino)-9,9-dimethyl- 9H-fluoren-2-yl)-phenyl-2,2,2-trifluoroacetophenone (PI-Flu), are developed as high-performance photoinitiators combined with an amine or an iodonium salt for both the free-radical polymerization of acrylates and the cationic polymerization of epoxides and vinyl ether upon exposure to near-UV and visible light-emitting diodes (LEDs; e.g., 365, 385, 405, and 450 nm). The photochemical mechanisms are investigated by UV-Vis spectra, molecular-orbital calculations, fluorescence, cyclic voltammetry, photolysis, and electron-spin-resonance spin-trapping techniques. Compared with 2,2,2-trifluoroacetophenone, both photoinitiators exhibit larger redshift of the absorption spectra and higher molar-extinction coefficients. PI-Ben and PI-Flu themselves can produce free radicals to initiate the polymerization of acrylate without any added hydrogen donor. These novel D-π-A type trifluoroacetophenone-based photoinitiating systems exhibit good efficiencies (acrylate conversion = 48%-66%; epoxide conversion = 85%-95%; LEDs at 365-450 nm exposure) even in low-concentration initiators (0.5%, w/w) and very low curing light intensities (1-2 mW cm−2). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1945-1954 [ABSTRACT FROM AUTHOR]

ABSTRACT Novel modifications of the synthetic polymer poly(vinyl alcohol) (PVA) were developed for application in the field of biomedical engineering. PVA was modified with allyl succinic anhydride, norbornene anhydride as well as with γ-thiobutyrolactone to produce macromers with reactive ene and thiol groups, respectively. Cytotoxicity studies have shown that the material exhibits almost no cell-toxicity, when used in concentrations of 1 and 0.1 wt % for 24 h. The obtained macromers were photocrosslinked via thiol-ene chemistry. Storage stability of the macromer mixtures with different concentrations of pyrogallol as stabilizer were investigated. Photorheometry was employed to optimize mixtures concerning reactivity based on their thiol-to-ene ratio, photoinitiator concentration, and macromer content. The crosslinked hydrogels were studied concerning their swellability. To form hydrogels with cellular structure two-photon-polymerization (2PP) was employed. Processing windows for 2PP of selected mixtures were determined. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2060-2070 [ABSTRACT FROM AUTHOR]

ABSTRACT Photocurable vinyl esters have recently been introduced as suitable alternatives to (meth)acrylates in biomedical applications. While (meth)acrylates exhibit good mechanical properties, their cytotoxicity and degradation products principally disqualify them from medical use. Vinyl esters exhibit much lower cytotoxicity and give biocompatible degradation products, but their disadvantage are relatively low mechanical properties, particularly brittleness. This study focuses on the identification of suitable functional groups that are capable of introducing enhanced impact strength into the vinyl ester network, for example, cyclic structures or urethane groups. A new pathway for the synthesis of vinyl esters carrying these groups was established and resulting monomers were tested regarding their photoreactivity and cytotoxicity. Mechanical properties and degradation behavior of the new materials were investigated as well. In addition, the thiol-ene reaction was utilized to enhance photoreactivity and tune hydrolytical degradation. The new vinyl esters exhibit excellent biocompatibility and good photoreactivity that can be significantly enhanced with thiols on to the level of highly photoreactive acrylates. Ultimately, the impact strength was improved by a factor of more than ten compared to commercial vinyl esters. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1987-1997 [ABSTRACT FROM AUTHOR]

ABSTRACT Here, we provide a detailed report on a new type of structured media for improving photopolymerizations: coordinated ionic liquids (ILs). Coordinated ILs are readily formed from the bistriflimide ([Tf2N]−) anion and coordination complexes composed of Li+ cations with polar organic monomers without an additional cosolvent. Photopolymerization kinetics and monomer conversion were monitored in real time using attenuated total reflectance Fourier transform infrared spectroscopy and the material properties of the products were examined using gel permeation chromatography and differential scanning calorimetry. Generally, coordinated IL monomers displayed improved reaction kinetics at both high and low salt concentrations as well as distinct product properties. The noncovalent (and reversible) interactions between monomer and salt in coordinated ILs hold promise as an efficient and versatile form of structured media for photopolymerizations. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2004-2014 [ABSTRACT FROM AUTHOR]