Effects of small molecular weight silicon‐containing acrylate on kinetics,morphologies, and properties of free‐radical/cationic hybrid UV‐cured coatings

A series of UV‐curable, silicon‐containing mixtures were prepared by adding different micro amounts of small molecular weight silicon‐containing acrylate KH570 to an interpenetrating polymer network system composed of cycloaliphatic polyurethane acrylate, trimethylolpropane triacrylate, cycloaliphatic epoxy resin, free‐radical photoinitiator Irgacure 754 and cationic photoinitiator Irgacure 250 with a weight ratio of 15 : 15 : 65 : 1 : 4. Hybrid coatings with different addition amounts of KH570 (0.2, 0.6, 1.0 wt %) were cured from the mixtures by UV‐initiated free‐radical/cationic dual curing technique. Final reactant conversions and photopolymerization rates of the hybrid UV‐cured coatings were improved with the increase of KH570 content, as evaluated by conversion profiles. The morphologies and microstructures were characterized by scanning electron micro‐scopic, atomic force micrographic, and fourier transform infrared spectrophotometer measurements. Thermal, mechanical, and surface properties of the hybrid UV‐cured coatings were investigated. The increase in KH570 content caused a decrease in mechanical properties besides the breaking elongation. Thermo‐gravimetric analysis revealed that the incorporation of silicon into cross‐linked network structure resulted in high thermal stability. The surface properties of hybrid UV‐cured coatings, such as hardness, contact angle, flexibility, and glossiness were also examined. It is found that transparent hybrid coating with the addition of 1.0 wt % KH570 exhibited a relatively higher contact angle as a direct result of a relatively higher hydrophobic surface. These researches showed that micro amounts of small molecular weight silicon‐containing acrylate could greatly influence the morphologies of liquid nitrogen quenching cross sections and properties of hybrid UV‐cured coatings and could be used to modify UV‐cured coatings for some superior properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40655.     

Preparation and characterization of UV‐cured hybrid coatings by triethoxysilane‐modified dimethacrylate based on bisphenol‐s epoxy

Novel hybrid oligomers based on a UV‐curable bisphenol‐S epoxy dimethacrylate (DBSMA) were synthetized. DBSMA was modified with various amount of (3‐isocyanatopropyl)triethoxysilane coupling agent. The modification degree of the hybrid oligomer was varied from 0 to70 wt %. The photopolymerization kinetics was monitored by a real‐time infrared spectroscopy. The conversion and rate of hybrid coatings increased with the increase in modification degree. UV‐curable, hard, and transparent organic–inorganic hybrid coatings were prepared. They were performed by the analyses of various properties such as surface and mechanical properties. Results from the mechanical measurements showed that the properties of hybrid coatings improved with the increase in modification degree. The thermal behavior of coatings was also investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of multifunctional thiol‐ and acrylate‐terminated polyurethane: A comparative study on their properties in UV curable coatings

The multifunctional thiol‐ and acrylate‐terminated polyurethane (PU) has been successfully prepared for using as the main resin in the UV curable coatings. The structure and molecule weight of prepared PUs were analyzed by fourier transformed infrared spectroscopy (FTIR) and gel permeation chromatography, respectively. The results showed that the different terminal multifunctional groups have been grafted onto the PU and their difference in molecule weight was significant. Used as the main resin in coatings, the curing kinetic and percentage conversion of the different UV curing coatings system were investigated by real‐time FTIR method, and the effects of terminal functional groups and photoinitiator on the final conversion percentage and conversion rate were also compared. It is observed that the thiol‐terminated PU had higher conversion speed and final conversion percentage due to the remarkable effect of mercapto groups on reducing oxygen inhibition during UV curing process. The shrinkage, viscosity, and adhesion of UV curable coatings with thiol‐ and acrylate‐terminated PUs were also investigated and compared, and the results indicated that the former exhibited lower shrinkage and higher adhesion performances than the latter, along with the lower viscosity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40740.     

Epoxy acrylate UV/PU dual‐cured wood coatings

For improving the finishing performances of complicated three‐dimensional coated wood products (e.g., furniture) with some shadow zones in the absence of ultraviolet (UV) light, resulting in incomplete curing of UV coatings, the aim of this study was to investigate the characteristics and effects of curing process on the properties of epoxy acrylate UV/PU dual‐cured resin for wood coatings when compared with traditional UV and polyurethane (PU) coatings. The epoxy acrylate oligomer was synthesized for providing a double bond of acryloyl group and a secondary hydroxyl group. The UV/PU dual‐cured coating was formulated with epoxy acrylate resin/tripropylene glycol diacrylate (TPGDA) monomer by the weight ratio of 80/20, 3% dosage of benzil dimethyl ketal as a photoinitiator, and the NCO/OH mole ratio of 1.0. The aromatic polymeric diphenylmethane diisocyanate was used as a hardener. The films of the dual‐cured coating, obtained from UV‐cured or room temperature‐cured process, showed an excellent tensile strength, elongation at break, impact resistance, and lightfastness when compared with traditional UV and PU coatings; especially, the adhesion of UV/PU dual‐cured coating by UV‐cured process was better than that of traditional UV coating. It can therefore be concluded that the epoxy acrylate oligomer‐based dual‐cured coating could readily be used for complicated wood products finishing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Development of Hybrid Polymeric Materials Based on Thiol‐Ene/Cationic Formulations

Novel materials were prepared from dual photo and thermal polymerization of hybrid thiol‐ene/cationic systems. In the first stage, the thiol‐ene system proceeded to high conversions, while the cationic photopolymerization was inhibited. The formation of sulfides during this stage was the main factor for the inhibition of the cationic photopolymerization of the epoxy monomers. Once those sulfides were formed, they reacted with the oxonium‐terminated growing polyether chains to form trialkylsulfonium salts. These salts promoted the thermal polymerization of the epoxy monomers in the second stage. The viscoelastic properties of the resulting polymers were measured by DMA.

     

UV curable soybean‐oil hybrid systems based on thiol‐acrylate and thiol‐ene‐acrylate chemistry

In this study, epoxidized soybean oil was modified to prepare acrylated epoxidized soybean oil (AESO) and vinyl/acrylate ended soybean oil (VASO), which were blended with mercaptopropyl polyhedral oligomericsilsequioxane (POSS‐SH) to prepare UV curable thiol‐acrylate and thiol‐ene‐acrylate hybrid coatings. Photopolymerization processes of the coatings were measured and the results showed that addition of POSS‐SH obviously increased the conversion of double bond. The physical and mechanical properties of all cured samples were investigated, which indicated that the pencil hardness, tensile strength, and fracture toughness were significantly improved by POSS‐SH. Moreover, with increasing POSS‐SH content, the water contact angles of cured samples were increased, and the water resistance was greatly improved. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42095.     

Synthesis and properties of ultraviolet‐curable resins via a thio–ene (thiol and allyl) addition reaction

Benzophenone diallyl ester (I) and benzophenone tetraallyl ester (II) based on 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) with allyl alcohol (AAL) were synthesized. Glycidyl methacrylate (GMA) was added to I and formed diallyl diglycidyl methacrylate (III). These BTDA‐based allyl‐containing compounds (II and III) reacted with 1,4‐butanedithiol and 4,4′‐thiol‐bisbenzene‐thiol to produce ultraviolet (UV)‐curable resins via a thio–ene addition reaction. The ester (III) was cured easily when exposed to UV or sunlight radiation without any photoinitiator and only required a lower thermal curing temperature. The diallyl ester (I) and tetraallyl ester (II) required the addition of benzophenone to increase the photosensitivity, which reduced the exposition time. These resins used AAL as a monomer to successfully reduce the oxygen effect of the photocuring. The resin BTDA–2Allyl–2GMA had a glass‐transition temperature of 166°C and a hardness of 6H. The resultant UV‐curable coatings had excellent hardness, chemical resistance, adhesion, and tensile properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1878–1885, 2002     

Fluorinated epoxides as surface modifying agents of UV‐curable systems

Two commercially available epoxy‐fluorinated monomers, 3‐(perfluorooctyl)‐1,2‐propenoxide and 3‐(1H, 1H, 9H‐hexadecafluorononyloxyl)‐1,2 propenoxide, were used as modifying additives for UV curable systems. These two fluorinated monomers were mixed, in small amounts (less than 1% w/w) with a hydrogenated epoxy monomer 1,4‐cyclohexanedimethanol‐diglycidyl ether. The mixtures were coated on glass substrate and UV‐cured, giving rise to transparent films. Notwithstanding their very low concentrations, the fluorinated monomers caused a change in the surface properties of the films, without changing their curing conditions and their bulk properties. The air side of the coatings became highly hydrophobic, while the substrate side was unmodified. As shown by XPS measurements, the fluorinated monomers were able to concentrate selectively on the air side of the films, forming a fluorinated layer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1524–1529, 2003     

UV‐curable,oxetane‐toughened epoxy‐siloxane coatings for marine fouling‐release coating applications

BACKGROUND: UV‐curable coatings are promising candidates for environmentally friendly marine fouling‐release coatings. Cationic UV‐curable epoxy‐siloxane release coatings show good release performance but suffer from poor coating mechanical properties. A difunctional oxetane monomer, DOX, was co‐photopolymerized with an epoxy‐siloxane oligomer at loading levels from 10 to 40 wt% to obtain toughened fouling‐release coatings. RESULTS: The DOX‐toughened coatings showed enhanced cationic photopolymerization activity, solvent resistance and modulus. DOX‐toughened coatings (10 and 20 wt%) exhibited higher impact resistance. The DOX‐toughened coatings showed no leachate toxicity and the coatings were hydrophobic and non‐toxic to biofilm growth when analyzed with marine bacteria and algae. In general, 10 and 20 wt% DOX‐toughened coatings exhibited better marine bacteria and algae fouling‐release performance among the DOX‐toughened coatings. Pseudo‐barnacle shear release stress for the DOX‐toughened coatings increased with increasing DOX content. Live barnacle reattachment assay showed that 10 and 20 wt% DOX‐toughened coatings had comparable barnacle removal stress to commercial silicone reference coatings. CONCLUSIONS: DOX‐toughened (10 and 20 wt%) UV‐curable epoxy‐siloxane coatings exhibited enhanced mechanical properties and better overall marine fouling‐release performance among the toughened UV‐curable release coatings studied. Copyright © 2008 Society of Chemical Industry     

Surface modification of nanosilica with 3-mercaptopropyl trimethoxysilane and investigation of its effect on the properties of UV curable coatings

This paper describes surface modification of commercial nanosilica with 3-mercaptopropyl trimethoxysilane (MPTMS) and its effect on the properties of UV curable coatings. The mercapto groups were grafted onto nanosilica surface by a condensation of the surface Si–OH with the hydrolysized Si–OH of MPTMS. Fourier transform infrared spectroscopy, thermal gravimetric analysis, and particle size distribution were employed to characterize nanosilica and modified nanosilica. It was demonstrated that the mercapto groups were successfully grafted onto the nanosilica surface with the grafting ratio of 16.8% and the mercapto groups content of 0.9 mmol/g. The dispersion and self-aggregation of nanosilica in UV curable coatings were improved significantly. The photopolymerization kinetics of UV curable coatings, containing various amounts of nanosilica and modified nanosilica, were evaluated by the photo differential scanning calorimetry technique. This indicated that nanosilica both before and after modification decreased UV curing speed and ultimate percentage conversion; however, in comparison with the coatings containing unmodified nanosilica, the coatings containing modified nanosilica exhibited higher curing speeds and conversion ratios. It can be ascribed that the mercapto groups on the nanosilica surface reduced oxygen inhibition during the UV curing process via the thiol–ene click reaction. The mechanical properties of UV curable coatings were also compared.     

Stabilized dispersions of titania nanoparticles via a sol–gel process and applications in UV‐curable hybrid systems

Organic–inorganic hybrid UV‐curable coatings were synthesized through blending UV‐curable components and stabilized titania sol prepared via a sol–gel process of tetrabutyl titanate (TBT) with three different stabilizers, acetylacetone (Acac), isopropyl tri(dioctyl)pyrophosphato titanate coupling agent (TTPO) and a polymerizable organic phosphoric acid (MAP). The size and the dispersion of titania particle in the UV‐cured organic matrix were dominated by the properties of these stabilizers. A cured hybrid film with titania particle size around 20 nm was obtained when TTPO was utilized as protection agent for the sol. It is interesting that the hardness and flexibility of the photocured hybrid films were improved simultaneously, in contrast to results with neat organic UV‐curable formulations. Copyright © 2006 Society of Chemical Industry     

A novel UV‐curable epoxy acrylate resin containing arylene ether sulfone linkages: Preparation,characterization, and properties

UV‐curing processes are used in industrial applications because of their advantages such as high‐speed applications and solvent‐free formulations at ambient temperature. UV‐curable epoxy acrylate resins containing arylene ether sulfone linkages (EAAES) were synthesized through the condensation of bis(4‐chlorophenyl)sulphone and bisphenol‐A, followed by end‐caping of epichlorohydrin and subsequently acrylic acid. UV‐cured coatings were formulated with epoxy acrylates, reactive diluents such as pentaerythritol tri‐acrylate and pentaerythritol dia‐crylate and photoinitiator. Fourier transfer infrared, ¹H NMR, and thermal gravimetrical analysis were employed to investigate the structures and thermal properties of the EAs films. The introduction of EAAES into epoxy acrylate substantially improves its thermal properties and thermo‐oxidative stability at high temperatures. In addition, the acrylate containing arylene ether sulfone linkages can also improve pencil hardness and chemical and solvent resistance of the epoxy acrylate. The obtained UV‐curable epoxy acrylate containing arylene ether sulfone linkages is promising as oligomer for UV‐curable coatings, inks, and adhesives in some high‐tech regions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41067.     

A new fluidized bed coating process via photo‐initiated cationic polymerization

An ultraviolet (UV) photo‐polymerization particle coating process was developed by coupling the photo‐initiated cationic polymerization with the fluidized bed coating techniques. Unlike the conventional air‐suspension coating in the fluidized bed, the new process employs a UV curable composition instead of a solvent/water‐borne system as a coating material, which has a rapid curing rate and virtually no inhibition to oxygen and moisture. A modified fluidized bed coater equipped with a quartz window allows UV light to penetrate and to initiate the curing of photo‐sensitive polymerizable chemicals coated on the particles. A UV‐curable liquid composed of cycloaliphatic epoxide, oxetane, and triarylsulfonium cationic photo‐initiator was specifically formulated for the fluidized bed particle coating process. A systematic experimental approach including photo‐Differential Scanning Calorimetry, Fourier Transform Infrared Spectroscopy, and tackiness measurements has been developed to characterize the curing mechanism of the cationic UV curable formulations and to optimize the chemical compositions. The effects of the UV curable chemicals, viscosity of coating liquid, and the fluidization operating conditions on the physical properties of coated particles have been thoroughly investigated. Under optimized conditions, this novel process is very efficient as follows: particles can be coated very rapidly with ultra‐thin films of the cured chemicals, with little, if any, formation of particulate agglomeration. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Synthesis and study of new radial organic/inorganic hybrid epoxides

A new approach to the synthesis of reactive organic/inorganic hybrid molecules was developed. Alternating hydrocarbon and siloxane segments were introduced into the arms of radial oligomers using hydrosilation chemistry. Cycloaliphatic and glycidyl epoxy‐terminal systems with bisphenol A‐based aromatic hydrocarbon cores and siloxane units derived from 1,1,3,3‐tetramethyldisiloxane were synthesized and fully characterized (molecules 7 and 6 , respectively). The cationic UV and thermal curing behavior of these two new radial hybrid epoxies was investigated using photo‐ and thermal‐ differential scanning calorimetry. Hybrid cycloaliphatic epoxy 7 exhibited good UV curing kinetics and photopolymerized to high conversion. The glycidyl analog 6 exhibited poor UV curing kinetics, but was readily cured using 2‐ethyl‐4‐methylimidazole as a nucleophilic curing agent. Both hybrid epoxysiloxanes exhibited extensive thermal cationic cure. The physical properties of cured films of the two new radial epoxysiloxanes were studied and compared with various commercially available hydrocarbon and siloxane benchmark materials. The cured systems exhibited lower moisture uptake and better thermal stability than most hydrocarbon epoxies examined. Several visually compatible blends of the new hybrid molecules with common hydrocarbon resins were identified, and in general organic compatibility was found to be intermediate among selected siloxane‐containing benchmarks. Molecules 6 and 7 represent progress towards the goal of synthesizing highly functional organic/inorganic hybrid molecules which combine the best attributes of both hydrocarbon epoxides and siloxane materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and evaluation of epoxy methacrylate UV‐curable coatings containing phthalazinone

Epoxy methacrylate resin (EMA) UV‐curable coatings exhibit high reactivity, low viscosity and excellent chemical resistance in environmentally friendly coatings. A novel EMA containing phthalazinone moieties for high temperature resistant UV‐curable coatings was synthesized. The formulations were cured with hexanediol diacrylate (HDDA) and trimethylol propane triacrylate (TMPTA) as reactive diluents promoted by a photoinitiator, and then interpenetrating polymer networks were generated. The mechanical, chemical and thermal properties of the clear coatings were characterized using Chinese National Standard methods (GB). EMA was used with UV radiation curing in combination with 6.7 wt% of HDDA and 13.4 wt% of TMPTA, and the properties of the cured films were as follows: pencil hardness of 5 H, 30% NaOH resistance for 30 days, 15% HCl resistance for 10 days, 3% NaCl resistance for 30 days and 5% weight loss temperature of 300.5 °C. EMA UV‐curable coatings containing phthalazinone exhibit excellent chemical and thermal stability, and could be potential candidates for UV‐curable zero volatile organic compound coatings applied in the fields of salt spray corrosion, strong radiation and high‐temperature resistance. Copyright © 2009 Society of Chemical Industry     

UV‐curable coatings with nano‐TiO2

Nano‐TiO₂ particles were first milled into butyl acetate or trimethylolpropane triacrylate (TMPTA) to obtain TSB and TST slurries, then embedded into epoxy acrylate to obtain UV‐curable coating. The influence of nano‐TiO₂ particles on the photopolymerization kinetics, tack free time, thermal and optical properties of UV‐curable coatings was investigated. It was found that TST‐based coating had a decreasing but TSB‐based coating had an increasing UV cured rate in comparison with the pristine epoxy acrylate. Nevertheless, the TST‐based coating occupied shorter tack free time, good thermal property and UV absorbance than their corresponding TSB‐based coating. POLYM. ENG. SCI. 46:1402–1410, 2006. © 2006 Society of Plastics Engineers.     

Allyl ether‐modified unsaturated polyesters for UV/air dual‐curable coatings. I: Synthesis and characterization of the oligomers and their cured films

Allyl ether (AE)‐modified unsaturated polyester oligomers were synthesized from polyethylene glycol (PEG), maleic anhydride (MAH), and trimethylolpropane mono allyl ether (TMPAE), and characterized by Fourier transform infrared (FTIR) spectra. The UV/air dual‐curable coatings were prepared from the oligomers using vinyl ether (VE) as a reactive diluent. FTIR spectra showed that C?C bonds in the coating composition had polymerized partially after cured by UV or air. The investigation of rheological behavior of the dual curable composition suggested that all the systems belonged to pseudoplastic fluid, and the increasing allyloxy content in oligomer resulted in a higher viscosity. Differential scanning calorimetry (DSC) analysis showed that the increasing TMPAE‐PEG molar ratio resulted in lower T_g, and all samples had the same glass transition temperature irrespective of the type of curing. The results of TGA for cured films indicated that UV‐cured film had better thermal stability than the air‐cured one. The air‐cured film showed superior pencil hardness, impact strength, and flexibility to the UV‐cured counterpart. However, the air‐cured film had poor adhesion and electric resistance properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2765–2770, 2004     

Synthesis of cationic UV‐curable methacrylate copolymers and properties of the cured films of their composites with alicyclic epoxy resin

Cationic UV‐curable methacrylate copolymers consisting of glycidyl methacrylate, iso‐butyl methacrylate, and 2,2,3,4,4,4‐hexafluorobutyl methacrylate were synthesized, and their structures were characterized by FTIR, ¹H NMR, and ¹³C NMR. A series of UV‐cured composite films based on the synthesized copolymers and an alicyclic epoxy resin, 3,4‐epoxycyclohexylmethyl‐3,4‐epoxycyclohexanecarboxylate (CE) were obtained through photopolymerization. Their surface contact angle, chemical ability, gloss, light transmittance, thermal behavior, micromorphology, and shrinkage were investigated. Results indicated that these cured resins showed excellent gloss and visible light transmittance; after the combination of the copolymers and CE, and in the presence of fluorine in the curing systems they exhibited relatively fine water resistance, chemical, and thermal stability. It was observed that these copolymers could decrease the degree of the volume shrinkage to CE. The UV‐curable materials may have promising applications in optical fiber coatings, flip chip and Organic Light‐Emitting Diode (OLED) packing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Photopolymerization and thermal behavior of phosphate diacrylate and triacrylate used as reactive‐type flame‐retardant monomers in ultraviolet‐curable resins

Tri(acryloyloxyethyl)phosphate (TAEP) and di(acryloyloxyethyl)ethyl phosphate (DAEEP) were used as reactive‐type flame‐retardant monomers along with commercial epoxy acrylate and polyurethane acrylate oligomers in ultraviolet (UV)‐curable resins. The concentrations of the monomers were varied from 17 to 50 wt %. The addition of the monomers greatly reduced the viscosity of the oligomers and increased the photopolymerization rates of the resins. The flame retardancy and thermal degradation behavior of the UV‐cured films were investigated with the limiting oxygen index (LOI) and thermogravimetric analysis. The results showed that the thermal stability at high temperatures greater than 400°C and the LOI values of the UV‐cured resins, especially those containing epoxy acrylate, were largely improved by the addition of the monomers. The dynamic mechanical thermal properties of the UV‐cured films were also measured. The results showed that the crosslink density increased along with the concentrations of the monomers. However, the glass‐transition temperature decreased with an increasing concentration of DAEEP because of the reduction in the rigidity of the cured films, whereas the glass‐transition temperature increased with the concentration of TAEP because of the higher crosslink density of the cured films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 185–194, 2005     

Photo‐curing behaviors of bio‐based isosorbide dimethacrylate by irradiation of light‐emitting diodes and the physical properties of its photo‐cured materials

Bio‐based isosorbide (1,4:3,6‐dianhydroglucitol), which was obtained from biomass‐derived carbohydrates, has recently attracted much attention as an alternative to bisphenol A (BPA) because of its rigidity and transparency. BPA is still widely used for a variety of chemical applications even though it is known to be an endocrine‐disrupting chemical. BPA is a key precursor to most photo‐curable materials ranging from encapsulants of electronic devices to dental sealants. In this study, photo‐curable isosorbide dimethacrylate (ISDM) was synthesized from bio‐based isosorbide as a substitute for BPA, and the photo‐curing behaviors of ISDM by irradiation with light‐emitting diode (LED) light were investigated. The photo‐curing conversion and rates of ISDM formation were determined based on the change in the peak corresponding to the double bond within the methacrylate groups using attenuated total reflectance Fourier transform infrared (ATR–FTIR) spectroscopy. The effects of initiators and the wavelength of LED light on the photo‐curing conversion and rates of ISDM formation were examined, and a comparative study was carried out with 2,2‐bis[4(2‐hydroxy‐3‐methacryloyloxy‐propyloxy)phenylpropane] (Bis‐GMA), which is a photo‐curing material bearing a BPA moiety. In addition, the mechanical properties, such as surface hardness, adhesion strength, and transparency, after photo‐curing of ISDM were evaluated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42726.