Synthesis and photopolymerization of 2‐(acryloyloxy)ethyl piperidine‐1‐carboxylate and 2‐(acryloyloxy)ethyl morpholone‐4‐carboxylate

Two low‐viscosity monomers, 2‐(acryloyloxy)ethyl piperidine‐1‐carboxylate (AEPC II) and 2‐(acryloyloxy)ethyl morpholone‐4‐carboxylate (AEMC), were synthesized with a non‐isocyanate route. The photopolymerization kinetics was monitored by real‐time infrared spectroscopy with a horizontal sample holder. The results indicated that AEPC II and AEMC had high ultraviolet curing rates and final double‐bond conversions, which could reach 90 and 95%, respectively. The glass‐transition temperatures of AEPC II/urethane acrylate resin (1/4 w/w), AEMC/urethane acrylate resin (1/4 w/w), and isobornyl acrylate/urethane acrylate resin (1/4 w/w) mixtures were 37.5, 45.6, and 57°C, respectively. The crosslink density of the AEMC/urethane acrylate resin (1/4 w/w) mixture was lower than that of the isobornyl acrylate/urethane acrylate resin (1/4 w/w) mixture. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Viscosity effects in the photopolymerization of two‐monomer systems

Photopolymerization kinetics and viscosity behavior of five different two‐monomer systems forming hydrogen bonds and composed of mixtures of a high viscosity monomer (HVM) and a low viscosity monomer (LVM) at various molar ratios were investigated at six polymerization temperatures. The monomers used were mono‐ or dimethacrylates. Detailed viscosity measurements of the monomer mixtures showed significant negative deviations from the theoretical values (characterized by excess logarithm viscosities) indicating that interactions between the molecules of the same type (in individual monomers) are stronger than those between two molecules of different types (HVM and LVM). The photopolymerization kinetics were analyzed from the point of view of the appearance, viscosity and temperature behavior of the most reactive composition (MRC), the one showing the highest value of the maximum polymerization rate within a range of the HVM: LVM ratios. It was found that MRC appearance is determined mainly by the initial viscosity of the two‐monomer system, whereas the functionality of the monomers (and network formation) is much less important (MRC is observed even in linear systems). The initial viscosity of all the monomer mixtures showing MRC lay in the range of 0.06–2 Pa s, which is narrow compared to the range of viscosities of the monomers (approximately 10^?3–10³ Pa s). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Impressive Rate Raise of the Hydrosilation Reaction Through UV‐Activation: Energy and Time Saving

Silicone materials are widely used in many fields such as electrical or food industries and their consumption is constantly growing. They are generally cured by vulcanization reaction for long time at high temperatures which requires high energy consumption. The possibility to achieve the polymerization of silicone rubbers by UV‐activation promotes the reduction of both time and temperature leading to an impressive energy saving. Indeed, this process is more than 30 times faster than the thermal one. Moreover, the properties of the two resulting materials are comparable, indicating that the low time of UV‐activated hydrosilation reaction is suitable for the formation of crosslinked silicone polymers.

     

Fourier transform infrared and wide‐angle X‐ray diffraction studies of the thermal cyclization reactions of high‐molar‐mass poly(acrylonitrile‐co‐itaconic acid)

The stabilization reactions of a high‐molar‐mass poly(acrylonitrile‐co‐itaconic acid) precursor in air at 200, 220, and 240°C were studied with Fourier transform infrared. Principally, the cyclization of nitrile groups leading to the ladder structures of tetrahydropyridine occurred. Evidence for oxidative reactions causing the conversion of the C? C structure to C?C and generating groups such as ? OH and C?O was also obtained. As the temperature of stabilization was increased, the rate of the reaction increased without causing great changes in the Fourier transform infrared spectral patterns. The maximum nitrile conversion achievable was limited by the temperature of stabilization. Although the reaction stagnated at 40 and 80% at 200 and 220°C, it was practically complete in about an hour at 240°C. Higher temperatures also favored the formation of extended conjugated structures. Wide‐angle X‐ray diffraction studies of the polymer stabilized at 300 and 400°C in argon confirmed that the aromatization index value and the crystallinity of the polymer increased proportionally to the temperature of pyrolysis. An analysis of the wide‐angle X‐ray diffraction pattern and the elemental composition of the stabilized polymer implied the formation of the tetrahydropyridine structure at 400°C. The higher pyrolysis temperature favored the formation of the lattice constituted by this group. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3055–3062, 2006     

Differential scanning photocalorimetry studies of 1,6‐hexanedioldiacrylate photopolymerization initiated by some organic azides

New types of radical photoinitiators, based on azido and diazido structures, were compared to the reactivity of pure xanthone by using a photocalorimetry technique. Our results show that these photoinitiators are good candidates for radical polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1096–1101, 2003     

Preparation and characterization of ultraviolet‐curable nanocomposite coatings initiated by benzophenone/n‐methyl diethanolamine

A series of ultraviolet‐curable nanocomposite coatings were prepared with condensed nanosilica particles and with benzophenone/n‐methyl diethanolamine as the initiator. The nanosilica that incorporated into the nanocomposites did not aggregate even when the nanosilica concentration was as high as 22.5%. Adding nanosilica increased the curing speed, thermal stability, and ultraviolet shielding properties of the nanocomposites without reducing the transparency of the ultraviolet‐curing coatings. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 912–918, 2005     

Synthesis and characterization of glutaraldehyde‐crosslinked calcium alginate for fluoride removal from aqueous solutions

A novel biosorbent was developed by the crosslinking of an anionic biopolymer, calcium alginate, with glutaraldehyde. The glutaraldehyde‐crosslinked calcium alginate (GCA) was characterized by Fourier transform infrared spectroscopy and porosity and surface area analysis. The batch equilibrium and column flow adsorption characteristics of fluoride onto the biosorbent were studied. The effects of the pH, agitation time, concentration of adsorbate, and amount of adsorbent on the extent of adsorption were investigated. The experimental data were fitted to the Langmuir and Freundlich adsorption isotherms. The data were analyzed on the basis of the Lagergren pseudo‐first‐order, pseudo‐second‐order, and Weber–Morris intraparticle diffusion models. The maximum monolayer adsorption capacity of the GCA sorbent as obtained from the Langmuir adsorption isotherm was found to be 73.5 mg/g for fluoride. The χ² and sum of squares of the error analysis were used to correlate the equilibrium isotherm models and kinetics. In addition, breakthrough curves were obtained from column flow experiments. The experimental results demonstrate that the GCA beads could be used for the defluoridation of drinking water through adsorption. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New aspects of viscosity effects on the photopolymerization kinetics of the 2,2‐bis[4‐(2‐hydroxymethacryloxypropoxy)phenyl]propane/triethylene glycol dimethacrylate monomer system

The photopolymerization kinetics and viscosity behavior of 11 2,2‐bis[4‐(2‐hydroxymethacryloxypropoxy)phenyl]propane/triethylene glycol dimethacrylate mixtures were investigated. The viscosity was studied at six temperatures (20–70°C), and the activation energies for the viscosity were determined. The excess logarithm viscosities were calculated and found to be negative over the whole composition and temperature ranges; they were fitted to the Redlish–Kister polynomial equation. The kinetic analysis of the photopolymerization was carried out at three polymerization temperatures (20, 40, and 60°C). The results proved the existence of the most reactive composition (reaching the highest value of the maximum polymerization rate), but the ratio of the monomers in this composition, close to equimolar, showed a tendency to change with the polymerization temperature. The viscosities of the most reactive compositions lay in the range of about 0.1–1.2 Pa s, which was narrow in comparison with the range of viscosities of all the compositions used in the kinetic studies (from 3 × 10^?3 to 1.5 × 10³ Pa s). The activation energies for the polymerization rates were calculated and correlated with the viscosity changes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Novel N‐ethyl‐2‐styrylquinolinium iodides as sensitizers in the photoinitiated free‐radical polymerization of trimethylolopropane triacrylate. II

Results of kinetic studies of two‐component photoinitiator systems used in the visible‐light photoinduced polymerization of 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol triacrylate are presented. Nine different styrylquinolinum dyes coupled with n‐butyltriphenylborate as a coinitiator have been used as photoinitiating systems. Reactive radicals that initiate the polymerization are formed by the well‐known mechanism of photoinduced electron transfer between dye cations acting as electron acceptors and borate anions acting as electron donors. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of oxygen on the crosslinking and mechanical properties of a thermoset formed by free‐radical photocuring

In this article, we report on the formation of optically transparent photopolymer films from hexanediol diacrylate (HDDA) by inkjet printing, where droplets of monomer approximately 5 μm in diameter were deposited onto a surface. The films were cured by irradiation with a UV‐light‐emitting‐diode light source. It was found that the inkjet‐printed HDDA films picked up a considerable amount of absorbed O₂ during printing. Exposure to increasing amounts of O₂ during photocuring severely restricted both the degree of conversion and the UV dose required for gelation in proportion to the O₂ concentration. Viscoelastic property data indicated that exposure to reduced oxygen concentrations during thermal postcuring (dark reaction) resulted in linear trends of increasing modulus above the glass‐transition temperature (T_g) and increasing T_g itself. Thus, the final crosslink density was greater in fully cured samples that were exposed to atmospheres with increasing inert gas concentrations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Asymmetric cyanine dyes as fluorescence probes and visible‐light photoinitiators of free‐radical polymerization processes

This article introduces asymmetric cyanine dyes employed as visible‐light photoinitiators of vinyl monomer polymerization and as fluorescence probes monitoring the progress of polymerization. A degree of polymer cure from the measurement of the changes in the probe emission intensity and position shifts during the thermally initiated polymerization of monoacrylate was obtained. A distinct increase in the intensity of the probe fluorescence was observed during polymerization when the degree of monomer conversion was gradually increasing. This effect was accompanied by a blue‐shift of the probe emission maxima. The second part of this work is focused on the possibility of an application of the tested dyes, in combination with borate anions, as photoinitiating systems. The kinetics of polymerization of trimethylolpropane triacrylate, with cyanine borates as photoinitiators, was studied by a microcalorimetric method. Asymmetric cyanine borates were found to be effective photoinitiators, and both the initiator and coinitiator concentration as well as the light intensity strongly affected the progress of photopolymerization, leading, for example, to an increase in the polymerization rate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 207–217, 2006     

Photocure properties of high‐heat‐resistant photoreactive polymers with cinnamate groups

New high‐heat‐resistant photoreactive polymers with cinnamate groups were synthesized by the reaction of cinnamic acid (CA) and epoxy resins. Their photocure properties were investigated with Fourier transform infrared spectroscopy, UV–visible spectroscopy, and thermogravimetric analysis (TGA). Their photocure reaction rates and the extent of reaction conversion increased with the intensity of UV irradiation. To investigate their photocure reaction kinetics, their reaction conversion rates were plotted against reaction conversion so that their photocure reactions could be analyzed in terms of an nth‐order kinetics reaction equation. The YX4000H–CA photoreactive polymer with a biphenyl moiety, which was expected to have strong molecular interactions, showed a lower reaction conversion rate and reaction constant, and the highest reaction conversion rate and reaction constant was observed in XP2030–CA with an optimum cure reaction space and a reduction of molecular interactions compared with the other photoreactive polymers. Thermal stability was studied by observation of the changes in the transmittance of the photocured polymer films upon heating and by measurement of the weight loss with temperature with TGA. These photoreactive polymers showed good thermal properties, with almost no transmittance change in the visible range even after they were heated at 250°C for 1 h, and they exhibited little weight loss up to about 250°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crosslinking of low‐density polyethylene by diisocyanates for superior barrier properties

The chemical modification of low‐density polyethylene (LDPE) resins with hexamethylene diisocyanate and toluene diisocyanate was achieved. The reaction of LDPE with diisocyanate was monitored by Fourier transform infrared spectroscopy, wherein the appearance of new peaks at 3326, 1620, and 1572 cm^?1 corresponding to ? N? H stretching, ? (C?O)? NH₂ stretching, and ? N? H bending in an amide moiety, respectively, was observed. Modified films of excellent clarity and uniform thickness were obtained by the solution casting of crosslinked polyethylene. The oxygen transmission rate (OTR), water vapor transmission rate (WVTR), grease resistance, and thermal properties of the modified films were studied. The results clearly indicate that the OTR was improved by 35% and that grease resistance was improved by 90–125% in the crosslinked LDPE films with little change in their strengths. The heat seal characteristics, however, showed that relatively higher temperatures were needed to achieve efficient sealing in these films. Differential scanning calorimetry showed a decrease in the melting temperature from 104°C for LDPE to 101°C for both of the crosslinked LDPE films. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1193–1199, 2005     

Properties of 2,2‐Bis[p‐(2′‐hydroxy‐3′‐methacryloxy propoxy)phenyl]propane/Isobornyl (Meth)acrylate copolymers

Isobornyl acrylate (IBOA) and isobornyl methacrylate (IBOMA) were used to replace triethylene glycol dimethacrylate (TEGDMA) as reactive diluents in dental restorative materials. Photopolymerization behaviors of mixtures of IBO(M)A and 2,2‐bis[p‐(2′‐hydroxy‐3′‐methacryloxy propoxy)phenyl]propane (Bis‐GMA) were investigated by Fourier transform infrared spectroscopy. The degree of conversion, volume shrinkage, contact angle, water sorption, water solubility, flexural strength, and modulus values of the Bis‐GMA/IBO(M)A formulations were measured and compared with those of a Bis‐GMA/TEGDMA formulation. The results illustrate that the degree of conversion, volume shrinkage, contact angle, water sorption, flexural strength, and modulus values of the Bis‐GMA/IBO(M)A systems were all lower than those of the Bis‐GMA/TEGDMA system; the water solubility values of the Bis‐GMA/IBO(M)A systems were higher than that of the Bis‐GMA/TEGDMA system. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Diffraction Gratings in Hybrid Sol‐Gel Films: On the Understanding of the Relief Generation Process

Hybrid organic‐inorganic materials based on the sol‐gel synthesis of an organically modified silicon alkoxide have demonstrated their great potential for optical applications. They offer a high versatility in terms of chemical, physical properties and macroscopic shape molding of the final component. Recently, a photolithographic process allowed the generation of relief optical elements without requiring a wet treatment to reveal the latent image. It enabled a low cost, simple and quick method for the fabrication of integrated optical components. The aim of the present paper is to give new insights into the mechanisms of surface self‐corrugation leading to gratings generation in hybrid sol‐gel films. A study of the relief formation was led by giving particular attention to the kinetic aspects of the polymerization of the organic component. The control of the C?C double bonds conversion of methacrylate functionalized alkoxides in case of photopolymerization is therefore an essential issue to tailor material properties. The study also focuses on the influence of physico‐chemical parameters that govern the relief generation and underlines the particular role of temperature. Kinetics of surface corrugation point out the importance of strain relaxation, mass‐transfer by flowing and organic network formation during the photolithographic process. Some illustrations of the generated diffraction gratings are given.

Interferogram of the diffraction grating obtained after 120 s exposure through a chromium mask.     

Study of cationic ring‐opening photopolymerizations using optical pyrometry

Studies of the photoinitiated cationic ring‐opening polymerizations of epoxide and oxetane monomers were conducted using optical pyrometry. Using this technique, the temperature of these photopolymerizations was monitored as a function of time. The effects of photoinitiator type and monomer structure on the rates of photopolymerization were investigated. Optical pyrometry was also used to investigate the acceleration of the photopolymerizations of various epoxide and oxetane monomers. Certain mixtures of monomers displayed synergistic effects that markedly increased their overall rates of polymerizations. In all cases in which acceleration of polymerization rate was noted, it could be attributed to an increase in the speed of ring opening of the initially formed protonated cyclic ether. The effects of relative humidity on the rate of cationic ring‐opening photopolymerizations of cyclic ether monomers were also investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3303–3319, 2004     

Ultraviolet photopolymerization induced by a triazine derivative

2‐(3,4‐Methdioxyphenyl)‐4,6‐bis(trichloromethyl)‐ 1,3,5‐triazine (MBTTR) was used as a photoinitiator for the polymerization of acrylate monomer. Ultraviolet–visible absorption spectroscopy was used to investigate the photochemical behavior during the photophysical process. The photopolymerization kinetics were monitored by real‐time Fourier transform infrared spectroscopy. The polymerization rates of the acrylates were significantly higher than those of the methacrylates. When MBTTR induced the polymerization of trimethylolpropane triacrylate, there was an optimum polymerization rate and the final conversion was obtained at 0.1 wt % MBTTR. MBTTR was an inefficient photoinitiator for ethyl vinyl. The final conversions of tripropylene glycol diacrylate induced by MBTTR and triazine/1,3‐benzodioxole were similar. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Photoinitiating free‐radical polymerization electron‐transfer pairs applying amino acids and sulfur‐containing amino acids as electron donors

A series of free‐radical polymerization initiation systems, based on xanthene dyes as the absorbing chromophores [Rose bengal derivative, 3‐(3‐methylbutoxy)‐5,7‐diiodo‐6‐fluorone and 3‐acetoxy‐2,4,5,7‐tetraiodo‐6‐fluorone] and sulfur‐containing amino acids as the electron donors, were investigated. The photoredox pair xanthene dye/sulfur‐containing amino acid was effectively used for photoinitiation of free‐radical polymerization of the mixture composed of poly(ethylene glycol)diacrylate–1% NH₄OH (3 : 1). The highest initiating efficiencies were observed for the system composed of methionine derivatives as the electron donor. The mechanism of photoinduced electron transfer between sulfur‐containing amino acids and triplet state of xanthene dye was investigated using laser‐flash and steady‐state photolysis techniques. Based on photochemistry of xanthene dyes, photochemistry of sulfur‐containing amino acids, and obtained results, the mechanism describing the major processes occurring during the photoinitiated polymerization by a photoinduced intermolecular electron‐transfer process was postulated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 358–365, 2005     

Applicability of hemicyanine phenyltrialkylborate salts as free‐radical photoinitiators in the visible‐light polymerization of acrylate

The photoinitiation ability of photoredox pairs composed of a hemicyanine dye cation and different borate anions for the radical polymerization of 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol triacrylate was investigated. In such a system, the excited dye chromophore is reduced by different tetraorganylborate anions. Upon irradiation at 488 nm, reductive carbon–boron bond cleavage occurs, producing reactive radicals, which start the chain reaction. The efficiency of bond‐breaking processes was found to be dependent on the nature of both the acceptors and the donors. The experimental results show that the photoinitiating ability of the tested photoredox pairs were controlled by both the driving force of the electron‐transfer process between the electron donor and the electron acceptor and the reactivity of the free radical that resulted from the secondary reactions occurring after the photoinduced electron‐transfer process. Using the nanosecond flash photolysis method, we studied the spectral and kinetic characteristics of the triplet state of cyanine dye and determined the rate constants of the triplet quenching by phenyltrialkylborate salts. The results obtained show that the tetramethylammonium phenyl‐tri‐n‐butylborate (TB7) has a faster electron‐transfer rate than the tetramethylammonium n‐butyltriphenylborate (TB2) salt, which bore only one butyl group attached to the boron. The relative initiator efficiency of the triphenylbutylborate salts, as compared to the corresponding phenyltrialkylborate salts with a common chromophore, was determined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Solid‐state polymerization of poly(ethylene 2,6‐naphthalate)

The solid‐state polymerization (SSP) of poly (ethylene 2,6‐naphthalate) (PEN) was studied and compared with that of poly(ethylene terephthalate) (PET). The SSP of PEN, like that of PET, could be satisfactorily described with a modified second‐order kinetic model, which was based on the assumptions that part of the end groups were inactive during SSP and that the overall SSP followed second‐order kinetics with respect to the active end‐group concentration. The proposed rate equation fit the data of the SSP of PEN quite well under various conditions. PEN prepolymers in pellet and cube forms with intrinsic viscosities (IVs) ranging from 0.375 to 0.515 dL/g, various particle sizes, and various carboxyl concentrations were solid‐state polymerized at temperatures ranging from 240 to 260°C to study the effects of various factors. The SSP data obtained in this study could be readily applied to the design of commercial PEN SSP processes. Because PEN and PET share the same SSP mechanism, in general, the SSP behaviors of PEN are similar to those of PET. Thus, the SSP rate of PEN increased with increasing temperature, increasing prepolymer IV, and decreasing prepolymer particle size. However, because of the much higher barrier properties of PEN, the prepolymer particle size and carboxyl concentration had much greater effects on the SSP of PEN than on the SSP of PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1075–1084, 2007