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     

Novel N‐ethyl‐2‐styrylquinolinum iodides as sensitizers in photoinitiated free radical polymerization of trimethylolopropane triacrylate (TMPTA), part 3

Three‐component systems, which contain a light‐absorbing species (dye), an electron donor (n‐butyltriphenylborate salt), and a third component (N‐alkoxypyridinum salt or 1,3,5‐triazine derivative), have emerged as efficient, visible‐light sensitive photoinitiators of free radical polymerization. It was found that three‐component systems are more efficient than their two‐component counterparts. Kinetic studies based on microcalorimetry revealed a significant increase in polymerization rate with increasing concentration of N‐alkoxypyridinum salt. Such results were not obtained for photoinitiating systems possessing 1,3,5‐triazine derivative as a second coinitiator. Based on the experimental results we concluded that the primary photochemical reaction involves electron transfer from the borate anion to the excited dye followed by the reaction of resulting dye‐based radical with second coinitiator that regenerates the original dye and simultaneously produces the alkoxy radical or triazynyl radical which could start the polymerization chain reaction. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Kinetic study of the aqueous free‐radical polymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid via an online proton nuclear magnetic resonance technique

The free‐radical polymerization of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) in aqueous media and in the presence of potassium persulfate (KPS) as a thermal initiator was studied. The ¹H‐NMR method was applied to record the reaction data in online gain. The effects of the monomer and initiator concentrations and also the reaction temperature were studied. The order of reaction with respect to the monomer was much greater than unity (1.94). None of the three theories describing an order of reaction higher than unity could predict the AMPS polymerization mechanism in this study. So, a new mechanism is presented. It is suggested that initiation took place through the formation of a complex between the initiator and monomer, and termination occurred not only by a bimolecular reaction but also by a monomolecular reaction. The order with respect to KPS was 0.49; this was consistent with classical kinetic theory. The determined activation energy at the overall rate of reaction was 92.7 kJ mol^?1 K^?1. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

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     

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     

Kinetic study of the free‐radical polymerization of vinyl acetate in the presence of deuterated chloroform by 1H‐NMR spectroscopy

The free‐radical polymerization of vinyl acetate was performed in the presence of deuterated chloroform (CDCl₃) as a chain‐transfer agent (telogen) and 2,2′‐azobisisobutyronitrile as an initiator. The effects of the initiator and solvent concentrations (or equivalent monomer concentration) and the reaction temperature on the reaction kinetics were studied by real‐time ¹H‐NMR spectroscopy. Data obtained from analysis of the ¹H‐NMR spectra were used to calculate some kinetic parameters, such as the initiator decomposition rate constant (k_d), k_p(f/k_t)^1/2 ratio (where k_p is the average rate constant for propagation, f is the initiator efficiency, and k_t is the average rate constant for termination), and transfer constant to CDCl₃ (C). The results show that k_d and k_p(f/k_t)^1/2 changed significantly with the solvent concentration and reaction temperature, whereas they remained almost constant with the initiator concentration. C changed only with the reaction temperature. Attempts were made to explain the dependence of k_p(f/k_t)^1/2 on the solvent concentration. We concluded from the solvent‐independent C values that the solvent did not have any significant effect on the k_p values. As a result, changes in the k_p(f/k_t)^1/2 values with solvent concentration were attributed to the solvent effect on the f and/or k_t values. Individual values of f and k_t were estimated, and we observed that both the f and k_t values were dependent on the solvent (or equivalent monomer) concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

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     

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     

Pseudo‐first‐order kinetic studies of the sorption of acid dyes onto chitosan

The adsorption of five acid dyes onto chitosan, derived through the deacetylation of crab‐shell chitin, from aqueous solutions was studied. The equilibrium isotherms were measured and analyzed with the Langmuir, Freundlich, and Redlich–Peterson equations; the results correlated well with the Langmuir equation. Kinetic studies were also performed in an agitated batch adsorber to study the effect of the initial dye concentration and the mass of chitosan. The kinetics were analyzed with the pseudo‐first‐order rate equation, and the rate constants were determined. The first‐order kinetic model correlated the experimental concentration and time data at short times and even up to 60% of the total adsorption period in a number of systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1633–1645, 2004     

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     

Methylmethacrylate polymerization photoinitiated by 1‐(bromoacetyl)pyrene

The photopolymerization of methylmethacrylate induced by pyrene, 1‐acetylpyrene (AP), and 1‐(bromoacetyl)pyrene (BP) has been investigated. Under all conditions employed, pyrene was completely ineffective. Introduction of a carbonyl and a bromo group in pyrene enhanced the polymerization efficiencies. Efficiency of AP as photoinitiator was very low; however, BP was proved to be a good photoinitiator. The polymerization with BP follows first‐order kinetics with respect to monomer conversion, with a shorter induction period as compared with that of AP. The value of the initiator exponent (0.5) and the linear dependence of reciprocal average degree of polymerization on the square root of the initiator concentration suggest radical polymerization with bimolecular termination. IR and NMR spectra showed the atactic nature of polymethylmethacrylate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 920–926, 2006     

Photo‐Induced atom transfer radical polymerization with nanosized α‐Fe2O3 as photoinitiator

Photo‐induced atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was achieved in poly(ethylene glycol)‐400 with nanosized α‐Fe₂O₃ as photoinitiator. Well‐defined poly(methyl methacrylate) (PMMA) was synthesized in conjunction with ethyl 2‐bromoisobutyrate (EBiB) as ATRP initiator and FeCl₃·6H₂O/Triphenylphosphine (PPh₃) as complex catalyst. The photo‐induced polymerization of MMA proceeded in a controlled/living fashion. The polymerization followed first‐order kinetics. The obtained PMMA had moderately controlled number‐average molecular weights in accordance with the theoretical number‐average molecular weights, as well as narrow molecular weight distributions (M_w/M_n). In addition, the polymerization could be well controlled by periodic light‐on–off processes. The resulting PMMA was characterized by ¹H nuclear magnetic resonance and gel permeation chromatography. The brominated PMMA was used further as macroinitiator in the chain‐extension with MMA to verify the living nature of photo‐induced ATRP of MMA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42389.     

Kinetic study of radical polymerization. III. Solution polymerization of acrylamide by 1H‐NMR

Solution and radical polymerization of acrylamide in the presence of potassium persulfate in D₂O was investigated up to high conversion by high‐field ¹H‐NMR spectroscopy. The kinetics of reaction was studied according to the data obtained from the corresponding spectra at various times during the polymerization reaction progress. Processing of the data led us to derive the rate equation of this polymerization reaction and determine the reaction order of each component in the rate equation. The order, with respect to initiator, was consistent with the classical kinetic rate equation (0.45), whereas the order with respect to monomer was greater than unity (1.49). The effect of temperature on the polymerization rate was also investigated and the activation energy of 48.4 kJ mol^?1 was obtained over the temperature range of 60–75°C. Also some mechanistic studies were discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2007–2013, 2004     

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     

Copolymerization of styrene with N‐phenyl maleimide in the presence of montmorillonite

The copolymerization of styrene with N‐phenyl maleimide in the presence of organomodified montmorillonite or Na⁺ montmorillonite was investigated. The conversion of the monomer was determined dilatometrically or gravimetrically. The copolymerization rate was accelerated and the polymerization activation energy in bulk and solution copolymerization decreased in the presence of montmorillonite. The tendency of alter‐copolymerization was enhanced for bulk and solution polymerization, but not affected for emulsion polymerization, by the addition of organomodified montmorillonite or Na⁺ montmorillonite. X‐ray diffraction studies showed that the methods of emulsion and bulk intercalative polymerization were more appropriate techniques for preparing nanocomposites with good dispersibility of clay. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1932–1937, 2005