Mechanical properties study of photocured paperboard surface treated with aliphatic epoxy diacrylate

In order to improve the quality of paperboard (a well‐known packing material) surface by photocuring method, different formulations were developed with aliphatic epoxy diacrylate (EA‐1020) oligomer along with reactive monomers of various functionalities. The reactive monomers are tripropylene glycol diacrylate (TPGDA), a difunctional monomer, and trimethylol propane triacrylate (TMPTA), a trifunctional monomer. 2‐Benzyl‐2‐dimethylamino‐1(4morpholinophenyl) butanone‐1 (Irgacure 369), a photoinitiator (2%), was incorporated into the formulations to initiate photocuring reaction. The formulated solutions were coated on clean glass plate and irradiated under UV radiation of different intensities. Different physical properties like pendulum hardness and gel content of the cured films were studied. The formulation containing TMPTA showed better properties. After characterization of the films, these formulations were applied on paperboard surfaces and cured under the same UV radiation. Various physicomechanical properties such as pendulum hardness, tensile properties, surface gloss, adhesion, abrasion, and water uptake were studied. The best performance was obtained at 12 passes of radiation with 18% TMPTA‐containing formulation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1774–1780, 2003     

Superhydrophobic films of UV‐curable fluorinated epoxy acrylate resins

Photopolymerization processes are often used in industrial applications because of their solvent‐free formulations and various advantages over conventional thermal processes. Fluorinated monomers and oligomers yield coatings of great interest because of the peculiar characteristics of fluorine atoms: these coatings show hydrophobicity, chemical stability, weathering resistance, etc. Novel UV‐curable fluorinated epoxy acrylate oligomers were synthesized from 1H,1H‐perfluorohexan‐1‐ol, 1,6‐hexamethylene diisocyanate (HDI) and epoxy acrylate (EA). The HDI plays the role of a spacer group in the side chain between the EA backbone chain and the fluorinated segment. This new spacer containing a urethane moiety with long alkyl groups can exhibit a self‐organization effect through the formation of strong hydrogen bonding. This resulted in a stiffening of the whole HDI urethane–perfluoalkyl chain to form nanostructure surface segregation. The designed fluorinated EA with fluoroalkyl (C₅F₁₁) units in the side chain exhibited a contact angle of about 151°, which is in the superhydrophobic range. Copyright © 2010 Society of Chemical Industry     

High‐contrast,high‐sensitivity aqueous base‐developable polynorbornene dielectric

The impact of multifunctional epoxy‐based additives on the crosslinking, photolithographic properties, and adhesion properties of a tetramethyl ammonium hydroxide developable, polynorbornene (PNB)‐based dielectric was investigated. Three different multifunctional epoxy additives were investigated: di‐functional, tri‐functional, and tetra‐functional epoxy compounds. The tetra‐functional epoxy crosslinker enhanced the UV absorbing properties of the polymer at 365 nm wavelength. It was found that the epoxy photo‐catalyst could be efficiently activated without a photosensitizer when the tetra‐functional epoxy was used. The polymer mixture with additional (3 wt %) tetra‐functional epoxy crosslinker and without a UV sensitizer showed improved sensitivity by a factor of 4.7 as compared to a polymer mixture containing the same number of equivalents of non‐UV sensitive epoxy with a UV sensitizer. The contrast improved from 7.4 for the polymer mixture with non‐UV absorbing epoxy and a UV sensitizer to 33.4 for the new formulation with 3 wt % tetra‐functional epoxy and no UV sensitizer. The addition of the tetra‐functional epoxy crosslinker also improved the polymer‐to‐substrate adhesion, which permitted longer development times, and allowed the fabrication of high‐aspect‐ratio structures. Hollow‐core pillars were fabricated in 96‐µm thick polymer films with a depth‐to‐width aspect‐ratio of 14 : 1. The degree of crosslinking in the cured films was studied by nanoindentation and swelling measurements. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Cationic UV‐curing of epoxidized cardanol derivatives

This paper demonstrates the high reactivity and potentiality of bio‐renewably obtained cardanol‐based epoxy monomers as well as the possibility of tuning the final thermomechanical properties by changing either the epoxy content or the chemical structure of the starting photocurable resin. The reactivity of the cardanol monomers towards the cationic UV‐curing process was investigated by Fourier transform IR analysis and it was shown that a high epoxy group conversion was achieved. Furthermore, the thermomechanical properties were investigated on crosslinked films by means of DSC and dynamic thermomechanical analysis. © 2020 Society of Chemical Industry     

A novel mono‐methacryloyloxy terminated fluorinated macromonomer used for the modification of UV curable acrylic copolymers

A novel macromonomer containing fluorinated units (PHFBMA‐GMA) was synthesized through a two‐step procedure: firstly, hexafluoro‐butyl methacrylate (HFBMA) was polymerized in the presence of functional chain transfer agent 3‐mercaptopropionic acid (MPA) and then the carboxyl acid group terminated polymer was end‐capped with glycidyl methacrylate (GMA). Chemical structures of PHFBMA‐GMA were characterized by gel permeation chromatography, fourier transform infrared spectroscopy (FTIR), and ¹H nuclear magnetic resonance (NMR). Subsequently, PHFBMA‐GMA was employed as reactive surface additives added into UV‐cured polyacrylate to modify UV‐curable coatings. It is convenient to control the tail length of the fluorinated segments in this study by adjusting the ratio of initiator and chain transfer agent. The influence of both the concentration and the molecular weight of PHFBMA‐GMA on the surface properties of UV‐cured films was investigated. With increasing both the concentration and the molecular weight of PHFBMA‐GMA, the surface energy of the UV‐cured films decreased. X‐ray photoelectron spectroscopy was employed to characterize and quantify the surface composition and the results confirm the enrichment of fluorinate atoms on the surface. Moreover, the physical properties of UV‐cured films, such as gel content, water absorption, pencil hardness, adhesion, chemical resistance, mechanical properties, optical transmittance, and thermal properties, were also investigated in detail. The novel macromonomer was economical but effective to modify the properties of the UV‐curable coatings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43116.     

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.     

Design of New Camelina Oil‐Based Hydrophilic Monomers for Novel Polymeric Materials

Triglyceride‐based monomers represent a competitive alternative to petrochemical resources in the macromolecular compounds area. In the current study, several types of hydrophilic camelina oil (CO)‐based monomers were synthesized using tunable experimental protocols that involve three different steps: first—conversion of the double bonds into epoxy rings, second—partial opening of the epoxy rings and methacrylic groups grafting and last—opening of the unreacted epoxy rings and hydrophilic units attaching. 1H‐NMR, 13C‐NMR and FTIR spectroscopy demonstrate the success of the CO functionalization with polymerizable and hydrophilic moieties—polyethylene glycol units—with different molecular weights, exhibiting self‐emulsifiable properties. Several bulk and emulsion polymerization tests were performed for the synthesized monomers and their ability to build polymer networks using different photo‐chemical procedures (using visible and UV radiations respectively) was demonstrated, without additional surfactants. FTIR spectroscopy indicates the polymerization success by the disappearance of the specific bands assigned to the double bonds from methacrylic groups and thermogravimetric analysis demonstrates that the emulsion polymerization leads to materials with an improved thermostability.     

Gradient and weather resistant hybrid super‐hydrophobic coating based on fluorinated epoxy resin

A weather resistant super‐hydrophobic coating that can offer good substrate adhesion and yet to be easily processed at large scale can be of practical use in emerging fields of self‐cleaning and anti‐icing paint, combing all these properties together remains challenging task. Here we describe a composite coating composed of a fluorinated epoxy resin emulsion with embedded in situ surface‐modified dual‐scale nano‐silica, which displayed durable super‐hydrophobicity and excellent adhesive strength. The as‐prepared coating possesses water contact angle of 158.6 ± 1°, sliding angle around 3.8 ± 0.2° which remain stable even under acidic/alkaline, heat/cool, and accelerated aging treatment. The results demonstrate that surface roughness had a micron‐ and nanometer scale distribution with increased particle loading beyond 40 wt %. Through quantitative comparison of surface Attenuated Total Reflection (ATR) with bulk FT‐IR transmission spectra, a gradient coating with surface enrichment of hydrophobic groups was determined. The air‐side fluorinated polysiloxane‐rich layer endows coating with weather‐resistance and ultra‐hydrophobicity while bottom epoxy resin layer enhances substrate adhesion. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40955.     

Photopolymerizable hyperbranched (meth)acrylated poly(amine ester)

A hyperbranched (meth)acrylated poly(amine ester) (HPAE‐2‐A) was synthesized by the modification of the hydroxyl end groups of the second generation of a hyperbranched poly(amine ester) with acryloyl chloride and methacrylic anhydride. The photopolymerization kinetics were investigated with photo‐differential scanning calorimetry and Fourier transform infrared. The properties of HPAE‐2‐A, including the dynamic viscosity, pendulum hardness, and shrinkage, were also studied in comparison with those of a hyperbranched methacrylated poly(amine ester) (HPAE‐2‐MA) prepared in the laboratory and traditional epoxy acrylate and epoxy methacrylate. HPAE‐2‐A polymerized rapidly under UV irradiation in the presence of a photoinitiator and had a higher final conversion of double bonds. The thermomechanical properties of UV‐cured HPAE‐2‐MA films were compared with those of EB‐cured films measured with a dynamic mechanical thermal analyzer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 168–173, 2003     

Effect of chemical structure and shear force on the morphology and properties of jet printed black micropatterns using imide epoxy binders

Epoxy and epoxy acrylates with phthalimide groups on the main chain or pendent side chain were synthesized and used as binders for solvent‐free UV‐curable inks. Effects of chemical structures on the solubilities of binders in monomers, together with the influences of shear force and ink compositions on the morphology and nanoindentation properties of the microstripes were studied. PIK1 inks containing BAPSBD epoxy with phthalimide groups on the main chain showed shear‐thinning behaviors and pigment aggregation problems. Variations of the shear stress at different positions of the dispenser led to PIK1 microstripes with rough central regions and smoother edges. AMPDP acrylate with pendent phthalimide side chain afforded not only good solubility in monomers but also good thermal and mechanical properties after curing. Stripes prepared by the PIK2 ink containing AMPDP exhibited straight edge and smooth surface. Considering the solubility and compatibility in inks, together with properties of cured stripe, binders with pendent phthalimide groups are better candidate as UV‐curable ink compositions than those with main chain phthalimide groups. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Plasticization effects of dihydroxyl soybean oil improve flexibilities of epoxy‐based films for coating applications

Novel bio‐based coating materials were developed through cationic ring‐opening photopolymerization of dihydroxyl soybean oil (DSO) with commercial epoxy monomers [i.e., epoxidized soybean oil (ESO) and 3,4‐epoxycyclohexylmethyl‐3,4‐epoxycyclohexanecarboxylate (ECHM). The ether cross‐linking and post‐polymerization of the polymeric network were observed using Fourier transform infrared spectroscopy. Thermal properties of the bio‐based coating materials and their copolymerization behaviors were examined using differential scanning calorimetry and a thermogravimetric analyzer. Cross‐link density and molecular weight between cross‐link were obtained from dynamic mechanical analysis. ECHM/DSO (1 : 1.43 weight ratio) films showed the highest elongation at break (49.2%) with a tensile strength of 13.7 MPa. After 2 months of storage, the elongation at break and tensile strength of films were 32% and 15.1 MPa, respectively. ESO/DSO films (w/w ratios of 1 : 0.1, 1 : 0.15, and 1 : 0.2) exhibited stable flexibility of 11–13% of elongation at break without significant reductions in tensile strength (2.5–4.4 MPa) during a 2‐month shelf life. Optical transparencies of the films were comparable to commercial glass and polymers, and water uptake properties (0.72% and 2.83%) were significantly low. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41773.     

有机氟改性环氧丙烯酸阴极电泳涂料的研究

选择合适的丙烯酸类单体、有机氟单体与环氧树脂接枝共聚合成了用于阴极电泳涂料的阳离子型含氟环氧丙烯酸树脂.探讨了氟单体的用量、接枝反应温度、胺化温度、胺化时间等对树脂反应的影响,并对所得阴极电泳涂料的性能进行了测试.结果表明:在合适的电泳工艺参数下,所得漆膜与不含氟的环氧丙烯酸漆膜相比,其耐盐水性、耐老化性、冲击强度都有所提高.     

Interfacial micromechanics and effect of moisture on fluorinated epoxy carbon fiber composites

Carbon fiber composites have witnessed an increased application in aerospace and other civil structures due to their excellent structural properties such as specific strength and stiffness. However, unlike other structural materials, carbon fiber composites have not been as widely studied. Hence, their increased application is also accompanied with a serious concern about their long‐term durability. Many of these applications are exposed to multiple environments such as moisture, temperature, and UV radiation. Composites based on conventional epoxies readily absorb moisture. However, recently synthesized fluorinated epoxies show reduced moisture absorption and hence potentially better long‐term durability. The aim of this project is to study the effect of moisture absorption on fluorinated‐epoxy‐based carbon fiber composites and their comparison with conventional epoxy carbon fiber‐based composites. Microbond tests are performed on fluorinated and nonfluorinated epoxy‐based single fiber samples before and after boiling water degradation. It is found that fluorinated epoxy‐based single fiber coupons showed relatively reduced degradation of interface when compared with the nonfluorinated epoxy single fiber coupons. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Thermomechanical and barrier properties of UV‐cured epoxy/O‐montmorillonite nanocomposites

Mixtures of an epoxy resin and organophilic montmorillonites were subjected to ultraviolet (UV)‐induced photopolymerization. Two types of commercially available nanoclays, namely Cloisite 30B and Cloisite Na⁺, were modified through interaction with organic compatibilizers (dodecylsuccinic anhydride, octadecylamine, octadecyl alcohol, and octadecanoic acid). The modified nanoclays, dispersed in the liquid epoxy resin at 5 wt%, were photopolymerized to get nanocomposite films. The kinetics of the photopolymerization was evaluated by means of real‐time Fourier transform infrared spectroscopy. The modified nanoclays and their nanocomposites were characterized through X‐ray diffractometry; transmission electron microscopy showed the presence of intercalated and partially exfoliated morphologies in the nanocomposites. Thermogravimetric and dynamic‐mechanical analyses showed an increase of the thermal properties and an increase of the glass transition temperatures of the nanocomposites compared with that of the neat UV‐cured resin. Finally, the oxygen barrier properties of nanocomposite films, coated on a polyethyleneterephtalate substrate, were evaluated; the decrease of permeability was correlated with the degree of exfoliation of the nanocomposites. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Synthesis and application properties of fluorinated aromatic copolymers

Aromatic monomers with different fluorine concentrations and structural distribution patterns were synthesized. A series of copolymers based on methyl methacrylate, acrylate, and perfluorooctylalkyl acrylate were prepared by emulsion polymerization and were subsequently used as functional coatings to prepare water‐ and oil‐repellent cotton fabrics. The composition and structure of the outmost layer of the treated cotton surface were analyzed. A strong surface segregation of fluorinated segments was found for the treated samples, as shown by X‐ray photoelectron spectroscopy analysis. The basis for an in‐depth appreciation of the relationship between the molecular structure of the monomers and the properties of corresponding copolymer‐treated materials was provided (especially with regarding to their hydrophobic and oleophobic properties). The wetting characteristics of the fluorinated copolymers were found to be dependent on the density (number of side chains per constitutional repeat unit) and regularity of the fluorinated side chains. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4410–4418, 2013     

UV curing of epoxy functional hybrid silicones

Several epoxy difunctional hybrid alkylene‐silicone telomers with different silicone characters and organic spacers (linkers) were prepared via the platinum‐catalyzed polyhydrosilylation of α,ω‐dihydrosiloxanes and α,ω‐dienes. Thereafter, the resulting Si? H‐terminated prepolymers were terminally functionalized with 4‐vinyl‐1,2‐epoxycyclohexane or allyl glycidyl ether. In the presence of a lipophilic cationic photoinitiator, the terminally epoxy‐functionalized hybrid alkylene–silicone telomers were photopolymerized to give crosslinked, soft, elastomeric, and transparent films. The progress of the photoinitiated cationic ring‐opening epoxide polymerizations was monitored using optical pyrometry. Potential applications for these novel photocurable epoxy‐functional telomers are as modifiers for UV curable coatings, printing inks, adhesives, and release coatings. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and properties of novel fluorinated poly(arylene ether)s

Dibromomethylene‐containing monomer with a tetrafluorobenzene central unit was synthesized using 2,3,5,6‐tetrafluoro‐1,4‐bis(4‐methylphenoxy)benzene as a starting material. This approach enabled preparation of several fluorinated poly(arylene ether)s containing isomeric fragments, with or without allyl or acetyl side groups, which were prepared by interaction of the synthesized tetrafluorobenzene‐based monomer with various types of hydroxyl‐substituted diphenyl ethers. The structure of the synthesized compounds was determined using Fourier transform infrared, ¹H NMR and ¹⁹ F NMR spectroscopy techniques. Most of the resulting polyethers were soluble in chlorinated, ether‐type or polar amide solvents. The molecular weight, mechanical and thermal properties of the synthesized fluorinated poly(arylene ether)s were studied depending on the inherent isomery of macromolecular chains and the nature of functional groups. Some ways of functionalization of the prepared fluorinated polyethers with epoxy and triethoxysilyl groups were proposed. © 2015 Society of Chemical Industry     

Investigation of fluorinated polyacrylate latex with core–shell structure

Fluorinated polyacrylate latices with core–shell structure were prepared by semi‐continuous emulsion polymerization, using a mixed emulsifier system composed of a reactive emulsifier and a small amount of anionic emulsifier. The conversion and chemical components of the final latices were studied by gravimetric methods and Fourier‐transform infrared (FTIR) spectrometry, respectively. The structure of the latex particles was determined by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and particle size analysis. The latex films exhibited a low surface energy and high water‐contact angles. The surface analysis from X‐ray photoelectron spectroscopy (XPS) revealed that the fluorinated components preferentially self‐organized at the film–air interface. From XPS depth profiling of the film, it was found that a gradient concentration of fluorine existed in the structure of the latex film from the film–air interface to the film–glass interface. Compared with the core–shell structure with a fluorinated core, the core–shell structure with a fluorinated shell was more effective for modifying the properties of the latex films. Copyright © 2005 Society of Chemical Industry     

Acrylic polyester resins containing perfluoropolyethers structures: Synthesis,characterization, and photopolymerization

Poly(ε‐caprolactone‐b‐perfluoropolyether‐b‐εcaprolactone) (PCL–PFPE–PCL) block copolymers having different PCL block lengths and end‐capped with methacrylate groups were prepared and characterized. Spectroscopic analyses confirmed the expected molecular structure of the products. After UV curing, the films revealed the presence of two amorphous phases, corresponding to fluorinated and hydrogenated moieties, respectively. The material containing long PCL blocks showed also a crystalline phase. Surface properties of the UV‐cured films were evaluated: The surfaces have a very high hydrophobic character in spite of the presence of many polar OH groups present in the polymeric network and a high hysteresis in wetting. An enrichment of fluorine at the air‐side surface was shown by contact‐angle measurements, except when long PCL sequences are present. The θ_adv angles decreased by increasing the content of PCL, that is, by decreasing the content of fluorine. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 651–659, 2000