Water‐soluble chromophore containing copolymers for bottom antireflection coating applications in lithography

Regulatory concerns in the semiconductor industry from both VOC emissions and solvent handling have prompted the desire to introduce water‐based formulations in spin‐coating fabrication processes. As resolution demands for i‐line lithography are driven to finer feature size and architecture, the need for antireflection coatings as a means of eliminating feature distortions from back reflected light is increasing. Common image irregularities, such as reflective notching and standing wave effects, can be effectively eliminated through application of an antireflection coating of optimal thickness between the resist layer and substrate. This work describes the design and development of novel side‐chain methacrylate copolymers for use in water‐based antireflection coating formulations. A pendant chromophore is incorporated into the polymer structure to allow optimization of the critical coating optical properties, refractive index, and absorption coefficient. The polymer solubility parameter and crosslinking density can be tailored by incorporation of appropriate functionality to allow compatibility with the device fabrication process. Terpolymers were designed, which were water‐soluble, had a thermally activated crosslinking mechanism, and contained a keto‐ester azobenzene chromophore that was highly absorbing at i‐line wavelength. Optical properties of polymer films were collected by spectroscopic elipsometry and utilized in the design process to identify the optimum chromophore structure. Lithographic images, fabricated utilizing these coatings, were of excellent quality, allowing critical dimension resolutions of less than 0.3 µm. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1304–1316, 1999     

Water‐soluble polymer and photocatalysis for arsenic removal

In this study, the photocatalytic oxidation of hazardous arsenite (As(III)) to arsenate (As(V)) and the sequential removal of arsenate from aqueous solution by liquid‐phase polymer‐based retention (LPR) were investigated. The photocatalytic oxidation of arsenite was performed using TiO₂ (P25 Degussa, Germany) under UV‐A light. The optimal photocatalytic conditions to oxidize 10 mg L^?1 of arsenite solution were achieved using a 0.5 g L^?1 of catalyst at a pH value of 2. The As(III) oxidation reached 100% after 30 min of illumination with UV‐A light. A water‐soluble polymer containing quaternary ammonium groups, poly(3‐acrylamidopropyl)trimethylammonium chloride (P(ClAPTA)), was used as an extracting reagent in the LPR process. To obtain the optimized conditions, the removal experiments were performed at various polymer : As(V) molar ratios using 10 mg L^?1 of arsenate solutions. After the oxidation of As(III) to As(V), the removal of arsenate by P(ClAPTA) was obtained in a 99% yield using a 20 : 1 polymer : As(V) molar ratio at a pH value of 9. The results demonstrate that the combination of these methods is highly useful for potential applications related to the treatment of wastewater contaminated with As(III). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40871.     

Polymeric ionic liquid—assisted polymerization for soluble polyaniline nanofibers

To enhance the solubility of polyanilines(PANI),polymeric ionic liquid(PIL)was introduced into the polymerization synthesis of PANI with various proportions.The structure and properties of the modified PANIs were characterized by 1H NMR,Fourier transform infrared spectroscopy,thermogravimetric analysis,ultraviolet-visible spectrum,etc.It was found that the obtained PANIs doped with PILs were soluble in various organic solvents such as N,N-dimethyl formamide and acetonitrile.Compared with the pure PANI,the PANIs doped by PILs showed remarkable solubility and their chemical structure and conductivity kept integrated.     

Structure and ionic conductivity of a series of di‐o‐butyrylchitosan membranes

Di‐o‐butyrylchitosan was prepared by reacting chitosan with butyric acid anhydride in the presence of perchloric acid as a catalyst. ¹³C‐NMR and IR spectra of the modified chitosan suggested that both hydroxyl groups, at the C‐6 and C‐3 positions, in the chitosan molecules were substituted. The maximum degree of substitution was found to be less than 28%. The results of X‐ray diffractograms revealed that, in comparison with the unmodified chitosan membrane, the crystallinity of di‐o‐butyrylchitosan membranes was remarkably decreased. Meanwhile, it was also observed that the swelling indices of modified membranes were increased significantly in direct proportion to the degree of substitution. Thermogravimetric analysis indicated that the modified membranes exhibited a slightly increased thermal stability compared to the unmodified membrane. The ionic conductivity of di‐o‐butyrylchitosan membranes after hydration was investigated using impedance spectroscopy. Compared to the unmodified chitosan membrane, the hydrated di‐o‐butyrylchitosan membrane with a relatively high degree of the substitution showed an increased ionic conductivity of more than one order of magnitude. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2309–2323, 2004     

Imidazolium-substituted ionic (co)polythiophenes: Compositional influence on solution behavior and thermal properties

A series of ionic polythiophenes, in homopolymer and random copolymer configurations, is prepared via the Grignard metathesis (GRIM) polymerization protocol and subsequent substitution on the bromohexyl side chains with N-methylimidazole. The introduced structural variations – comonomer ratio, side chain composition, counter ions – allow tuning of the thermal properties and solution behavior of the resulting conjugated polymers. As expected, the solubility depends majorly on the number of ionic groups and the counter ions. The most peculiar behavior is observed for the P3HT-P3(MIM)HT-Br 50/50 random copolymer, which shows organization of the polymer chains in solution and thin film dependent on the preparation conditions. Dynamic light scattering studies confirm that the ordered solid-state structure is somewhat maintained when the copolymer is dissolved in a bad solvent mixture. The ionic (co)polythiophenes are generally more resistant to thermal degradation than their precursors. The precursor polymers all show a clear semi-crystalline behavior, with a decrease in crystallinity upon decreasing the number of regular 3-hexylthiophene units. On the other hand, the studied ionic (co)polythiophenes are fully amorphous. Changes in the counter ions have dramatic effects on the thermal properties. Bromine counter ions render the polymers strongly hygroscopic. The novel materials are of particular appeal in the field of organic photovoltaics, in which the imidazolium-substituted (co)polythiophenes can be beneficially applied as constituents of either active layers or electron transport layers. Their processability from green solvents is also of major importance for the field.     

Water‐soluble photopolymers for rapid prototyping of cellular materials

Commercial light‐sensitive resins for Rapid Prototyping of cellular materials are often unsuitable for different molding techniques because removal of the mold uses thermal decomposition at temperatures of up to 600°C. In this study, a resin formulation based on water‐soluble polymers was developed and evaluated regarding its usability as sacrificial mold material. The base monomer dimethylacrylamide gave fast curing and excellent polymer solubility. Methacrylic acid was found to be a useful comonomer to improve mechanical strength and feature resolution. The latter criterion was also improved by adding poly(vinyl pyrrolidone) as filler and by using a hydrolytically cleavable crosslinking agent such as methacrylic acid anhydride. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2286–2298, 2005     

Water‐soluble and polymerizable thioxanthone photoinitiator containing imidazole

A novel free radical photoinitiator, 3‐allyl‐1‐[2‐hydroxy‐3‐(thioxanthen‐9‐one‐2‐yl)oxypropyl]imidazolium chloride ([AIPTX]Cl), is synthesized by the addition reaction of 2‐(2,3‐epoxy)propoxylthioxanthone (ETX) with a heterocyclic compound imidazole firstly, and the achieved intermediate 1‐[2‐hydroxy‐3‐(thioxanthen‐9‐one‐2‐yl)oxypropyl]imidazole (IPTX) is then reacted with allyl chloride. IPTX is chosen to evaluate the photoefficiency of [AIPTX]Cl. FTIR and ¹H‐NMR confirm the structures of [AIPTX]Cl and IPTX. UV‐Vis spectra of the two photoinitiators are similar and both exhibit the maximal absorption about 400 nm. Fluorescence spectra show [AIPTX]Cl/IMZ has slightly higher fluorescence intensity than IPTX system. Photopolymerization studies indicate that [AIPTX]Cl/IMZ is more efficient for the polymerization of water‐soluble monomer than IPTX. Moreover, due to its advantages of water solubility and polymerizability, [AIPTX]Cl is an environmental‐friendly photoinitiator and has potential for application in UV‐curing systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40659.     

Water‐soluble,antiyellowing polymeric fluorescence brighteners

In this study, a type of polymeric fluorescence brightener (PFB) with a triazine–stilbene structure was synthesized through a three‐step condensation reaction, and the performance of this PFB on antiyellowing was also investigated by the whiteness of paper coated with the as‐prepared PFB. Fourier transform infrared spectra revealed that the chlorine atom (·Cl) was substituted by a poly(vinyl alcohol) (PVA) group ([CH₂CHOH]_n). According to the UV aging experiment, the PFB not only enhanced the whiteness of the paper but also improved the anti‐UV aging properties [compared to those of VBL 4′‐double‐(6‐diethanolamine‐4‐sulfanilic acid‐1,3,5‐triazine‐2‐amino)‐stilbene‐2,2′‐disulfonic acid sodium, a type of commonly used fluorescent whitening agent as a light stabilizer and fluorescent brightening agent]. Moreover, the results of UV–visible spectra indicated that the substitution of PVA suppressed the isomerization of trans conformers to cis conformers under UV light irradiation; this was attributed to the big space steric hindrance of PVA in the as‐prepared samples being restricted the isomerization reaction. Meanwhile, the solubility of the as‐prepared sample was also improved because more hydroxyl groups were introduced into the PFB with the substitution of PVA. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45536.     

Water‐soluble urethane acrylate ionomers: Effect of molecular structure on ultraviolet coating properties

Water‐soluble urethane acrylate ionomers containing dimethylolpropionic acid (DMPA) were synthesized, changing the molecular components, and their ultraviolet (UV) coating properties were studied. It was found that the UV coating properties of the urethane acrylate ionomer films were very dependent on the molecular weight of the soft segment, the type of the diisocyanate, and the amount of neutralization. In general observations, the cured films displayed much improved mechanical properties, compared with conventional urethane acrylate film not containing ionic groups. The main reason for the improved film properties seemed to be attributed to the presence of ionic groups in the network. In dynamic mechanical analysis, two distinct glass transition temperatures, corresponding to the ionic hard domains and soft domains, were detected at high content of ionic groups. This suggested that the urethane acrylate network be composed of two phases. Consequently, the ionic hard domains formed by the phase separation from crosslinked network could act as a reinforcing filler, which possibly explains the improved film properties of the urethane acrylate ionomer films. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1853–1860, 2000     

Synthesis of a water‐soluble fullerene derivative nanoball and its biological activity

A novel fullerene–acrylamide copolymer was synthesized via radical polymerization. It is soluble in polar solvents such as water and dimethyl sulfoxide. The product was characterized by FTIR, UV–vis, and GPC. TEM analysis showed that the average particle diameter was about 46 nm. The in vitro antitumor activity of the fullerene–acrylamide derivatives was tested, and the results showed that the novel fullerene–acrylamide derivatives exhibited better antitumor activity in vitro against bone tumor cells. The cytotoxicity against the tumor cell mechanism of the fullerene copolymer nanoball was studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Water‐soluble macromolecular co‐assemblies of star‐shaped polyelectrolytes

This mini‐review reports on complex macromolecular architectures (interpolyelectrolyte complexes) based on star‐shaped polyelectrolytes. These complexes can be prepared in aqueous media via electrostatically driven co‐assembly of star‐shaped polyions (a) with oppositely charged linear homopolyelectrolytes or (b) with oppositely charged double hydrophilic (ionic/non‐ionic) diblock copolymers. In case (a), the complexes can be water‐soluble if the charge of the star‐shaped macromolecule is only partially compensated by a linear polyion. In case (b), the complexes retain their solubility in aqueous media even under a full charge compensation of the polymeric components. In both cases, the complex macromolecular architectures based on star‐shaped polyelectrolytes are characterized by a distinct compartmentalized structure of a micellar (‘core–corona’) type with an insoluble core, which is assembled from coupled monomer units of the oppositely charged polymeric components, and a hydrophilic, either ionic or non‐ionic, corona. Copyright © 2012 Society of Chemical Industry     

Water‐based non‐ionic polymeric surfactants as oil spill dispersants

In this paper, polyisobutylene succinic anhydride adduct (PIB‐SA) was modified by esterification with polyethylene glycol (PEG 600, 1000 and 2000) to obtain mono‐ and diterminal polyoxyalkynated PIB‐SA. The monoterminal products were reacted with pentamethylene‐hexamine (PMHA). The structures were confirmed by FT–IR and ¹H NMR analysis. The surface properties, interfacial tension and the effectiveness in oil dispersion of the synthesized polymeric surfactants are reported. The maximum efficiency of oil spill dispersants was reached when the surfactant molecule had two moities (polyoxyalkylene and polyamine units). © 1999 Society of Chemical Industry     

Water‐soluble allyl and diallyl camphor sulfonamides‐based polyacrylamide copolymers for enhanced oil recovery

The monomers N‐allyl camphor sulfonamide (CSAP) and N,N‐diallyl camphor sulfonamide (CSDAP) were copolymerized with acrylamide (AM), acrylic acid (AA) for EOR, respectively. The effect of the synthesis conditions on apparent viscosity was investigated, and the copolymers were characterized by Fourier transform infrared spectroscopy (FTIR), ¹H nuclear magnetic resonance (¹H NMR), environmental scanning electron microscope (ESEM), and thermogravimetric analysis (TGA). Increasing mass ratio of diallyl CSDAP could lead to the water‐insoluble of copolymer, and competition of free radicals could make polymerization of AM/AA/CSDAP more difficult than AM/AA/CSAP. The thickening function and temperature resistance of two copolymers were remarkably improved in comparison with similar molecular weight partially hydrolyzed polyacrylamide (HPAM). In addition, the pronounced temperature resistance of the copolymers has been also demonstrated by temperature resistance test. It has also found that copolymers AM/AA/CSAP and AM/AA/CSDAP brine solutions could obtain significant enhanced oil recovery at 70°C suggesting their potential being applied in chemical enhanced oil recovery. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41238.     

Lidocaine‐ibuprofen ionic liquid for dermal anesthesia

Local anesthesia in the skin occurs approximately 1 h after application of a commercial topical formulation of lidocaine and prilocaine prepared as a eutectic mixture. A number of lidocaine salts was screened and lidocaine‐ibuprofen was found to form a room‐temperature ionic liquid. When applied to the skin of rats, local anesthesia of skin was achieved within 10–20 min in the rats’ paws and tails with no apparent adverse effects to the skin as determined by histological analysis. We believe that the lidocaine‐ibuprofen ionic liquid increased lidocaine absorption into the skin due to the high lidocaine concentration in the ionic liquid and due to possible interactions between the ionic liquid and the skin to increase skin permeability. These findings suggest that lidocaine‐ibuprofen ionic liquid may provide a more rapid method of drug delivery to the skin for local anesthesia. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2732–2738, 2015     

Imidazolium ionic liquid incorporation on sulfonated poly(styrene‐isobutylene‐styrene) proton exchange membranes

Ionic liquids (ILs) with different anions and cations were incorporated in sulfonated poly(styrene‐isobutylene‐styrene) (SIBS) to modify its chemical, morphological, and transport properties for direct methanol fuel cell (DMFC) applications. Different loadings of IL and different solvents were studied to have a better understanding of the incorporation process and the ability of the solvent to affect the interaction of the IL with the sulfonated polymer. Morphological characterization with SAXS and AFM suggested changes caused by the incorporation of the IL and by the solvent used. FT‐IR spectra showed small variations in energy related to interactions of the IL with the sulfonic groups which caused thermogravimetric stabilization of the ionic domains. Other results suggest that water has a very significant effect on the morphology, interaction with the IL, and transport properties of the membranes. Optimal concentration of IL (～10 mol %) provides enough water to produce efficient proton conductivity (0.15 S/cm) and minimal methanol permeability (0.8 × 10^?6 cm²/s). © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44900.     

Water‐soluble dual responsive polythiophene‐g‐poly(methoxyethoxy ethyl methacrylate)‐co‐poly(N,N‐diethylamino ethyl methacrylate) for different applications

Polythiophene (PT) based dual responsive water‐soluble graft copolymer (PT‐g‐[poly(methoxyethoxy ethyl methacrylate)‐co‐poly(N,N‐diethylamino ethyl methacrylate)]) (PT‐g‐P(MeO₂MA‐co‐DEAEMA)) (PTDE) has been synthesized by random copolymerization of methoxyethoxy ethyl methacrylate (MeO₂MA) and N,N‐diethylamino ethyl methacrylate (DEAEMA) at 30 °C on the 2,5‐poly(3‐[1‐ethyl‐2‐(2‐ bromoisobutyrate)] thiophene) (PTI) macroinitiator using the Cu based atom transfer radical polymerization technique. The PTDE graft copolymer was characterized by gel permeation chromatography and ¹H NMR techniques and it exhibits thermo‐reversible solubility in water showing a lower critical solution temperature of ca 42 °C in neutral aqueous solution. The PTDE graft copolymer contains a fluorescent PT backbone, and interestingly the system exhibits doubling of fluorescence intensity with rising temperature over the temperature range 41–45 °C at pH 7. The PTDE system therefore acts following the principle of the polymeric AND logic gate and it is also found to be effective in sensing of nitroaromatics, particularly picric acid. The influence of chain hydrophobicity on the logic operation and on the sensing of nitroaromatics is discussed. © 2014 Society of Chemical Industry