Photopolymerization of acrylates without photoinitiators with short‐wavelength UV radiation: A study with real‐time fourier transform infrared spectroscopy

This article reports on the UV photopolymerization of acrylates without photoinitiators. Initiation of the reaction was achieved by direct excitation of the acrylates during irradiation with short‐wavelength UV light by use of the 222‐nm emission of a KrCl^* excimer lamp. The reactivity of various acrylates was studied by real‐time Fourier transform infrared–attenuated total reflection spectroscopy. The rate and the extent of the reaction within the layer were strongly dependent on the depth of penetration of UV light, which was determined by the molar extinction coefficient of the acrylate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 894–901, 2004     

FTIR Microscopy for Kinetic Measurements in High‐Throughput Photopolymerization: Experimental Design and Application

Libraries with varying composition and exposure time were developed to enable high‐throughput analysis of conversion using FTIR spectroscopy. This technique was demonstrated by measuring viscosity and backbone chain structure effects using four monomers: DPGDA, TEGDA, bisphenol‐A‐glycidyl diacrylate and ethoxylated bisphenol‐A diacrylate. DPGDA has equivalent viscosity and double bond concentration with a shorter backbone chain length as compared to TEGDA. The ultimate conversion of TEGDA copolymerizations as compared to equivalent DPGDA copolymerizations is lowered from 15 to 5% due to differences in crosslink space chemistry and glass transition temperatures of the copolymer formulation.

     

Factors affecting the sensitivity to acid inhibition in novel acrylates characterized by secondary functionalities

Here we demonstrate that acrylates exhibit significant rate reductions in the presence of small concentrations of protic acids (0.1–0.5 wt %) compared with the bulk monomer concentration. Dramatically different sensitivities to acid inhibition, differing by up to 2 orders of magnitude, are exhibited for various acrylates. This study examines the various factors that cause enhanced sensitivity toward acid inhibition in novel acrylates characterized by carbamate and cyclic carbonate secondary functionalities. Acid inhibition studies conducted in the presence of a highly polar solvent, such as propylene carbonate, have been performed to determine the impact of overall medium polarity and the extent of acid dissociation on the sensitivity to acid inhibition. The studies depict only a twofold increase in the parameters associated with acid inhibition, upon the addition of 70 wt % propylene carbonate, in comparison with an increase of 2 orders of magnitude for the novel acrylates. These studies indicate that the susceptibility to acid inhibition is primarily determined by the stability of the hypothesized radical–acid complex as well as its propensity to terminate with other species in the system and not by the extent of acid dissociation in the system. Furthermore, it is implied that the stability of the radical–acid complex and its propensity to terminate with other species in the system are dominated by intramolecular interactions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1287–1295, 2007     

New aliphatic poly(ester‐carbonates) based on 5‐methyl‐5‐allyloxycarbonyl‐1,3‐dioxan‐2‐one

The synthesis, characterization, and ring‐opening polymerization of a new cyclic carbonate monomer containing an allyl ester moiety, 5‐methyl‐5‐allyloxycarbonyl‐1,3‐dioxan‐2‐one (MAC), was performed for the first time. MAC was synthesized in five steps in good yield beginning from the starting material, 2,2‐bis(hydroxymethyl)propionic acid. Subsequent polymerization and copolymerizations of the new cyclic carbonate with rac‐lactide (rac‐LA) and ?‐caprolactone (CL) were attempted. Rac‐LA copolymerized well with MAC, but CL copolymerizations produced insoluble products. Oligomeric macroinitiators of MAC and rac‐LA were synthesized from stannous ethoxide, and both macroinitiators were used for the controlled ring‐opening polymerization of rac‐LA. The polymerization kinetics were examined by monitoring the disappearance of the characteristic C? O ring stretch of the monomer at 1240 cm^?1 with real‐time in situ Fourier transform infrared spectroscopy. Postpolymerization oxidation reactions were conducted to epoxidize the unsaturated bonds of the MAC‐functionalized polymers. Epoxide‐containing polymers may allow further organic transformations with various nucleophiles, such as amines, alcohols, and carboxylic acids. NMR was used for microstructure identification of the polymers, and size exclusion chromatography and differential scanning calorimetry were used to characterize the new functionalized poly(ester‐carbonates). © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1978–1991, 2003     

Analysis of association constant for ground‐state dye‐electron acceptor complex of photoinitiator systems and the association constant effect on the kinetics of visible‐light‐induced polymerizations

We investigated the formation of ground‐state donor/acceptor complexes between xanthene dyes [rose bengal (RB) and fluorescein (FL)] and a diphenyliodonium (DPI) salt, which is dissolved in 2‐hydroxyethyl methacrylate (HEMA) monomer. To characterize the association constant of the complex, we have suggested a new analysis model based upon the Benesi–Hildebrand model. Because the assumption of the original Benesi–Hildebrand model is that the absorption bands are only due to the presence of the complex and that the absorption by the free component is negligible, the model cannot be applied to our systems, which is a dye‐based initiator system. For each dye, the molar absorptivity of the ground‐state complex was evaluated as a function of wavelength, and this analysis confirmed the validity of the modified Benesi–Hildebrand model. In addition, we observed that the RB/DPI photoinitiator system failed to produce a perceptible polymerization rate but the FL/DPI photoinitiator system provided high rates of polymerization. On the basis of the association constant for these complexes, we concluded that the observed kinetic differences arise from the different association constant values of the ground‐state dye‐acceptor complex, resulting in back‐electron transfer reaction. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1429–1439, 2009     

Influence of the alkene structure on the mechanism and kinetics of thiol–alkene photopolymerizations with real‐time infrared spectroscopy

The effect of the chemical structure on the reactivity of alkenes used in thiol–ene photopolymerizations has been investigated with real‐time infrared spectroscopy. Model studies of thiol–ene photoreactions with various monofunctional hydrocarbon alkenes and the monofunctional thiol ethyl‐3‐mercaptopropionate have been performed to identify and understand structure–reactivity relationships. The results demonstrate that terminal enes react very rapidly with thiol, achieve complete conversion, and are independent of the aliphatic hydrocarbon substituent length. Disubstitution on a single carbon of a terminal ene significantly reduces the reactivity, whereas substitution on the carbon α to the terminal ene has a minimal influence on the reactivity. Internal trans enes display reduced reactivity and a lower overall conversion and deviate from the standard thiol–ene reaction mechanism because of steric strain induced by 1,3‐interactions. The reactivity and conversion of internal trans enes decrease as the substituents on the ene become larger, reaching a minimum when the substituent size is greater than or equal to that of propyl groups. Internal cis enes react rapidly with thiol; however, they undergo a fast isomerization–elimination reaction sequence generating the trans ene, which proceeds to react at a reduced rate with thiol. The reactivity of cyclic enes is dictated by ring strain, stereoelectronic effects, and hydrogen abstractability. The reactivity trends in the model studies have been used to explain the photopolymerization mechanism and kinetics of a series of multifunctional thiol–ene systems. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6283–6298, 2004     

Thiol‐ene photopolymerization of polymer‐derived ceramic precursors

The liquid, ceramic precursor monomer VL20 was copolymerized with a thiol monomer in a traditional radical thiol‐ene photopolymerization. Polymerization occurred via addition of the thiol functional group to the vinyl silazane functional group in a 1:1 ratio consistent with a step‐growth polymerization. Gelation occurred at a high conversion of functional groups (70%) consistent with an average molecular weight and functionality of 560 and 1.7, respectively, for VL20 monomers. Initiatorless photopolymerization of the thiol‐VL20 system also occurred upon irradiation at either 365 or 254 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1752–1757, 2004     

Influence of the secondary functionality on the radical‐vinyl chemistry of highly reactive monoacrylates

The impact of secondary functionalities on the radical‐vinyl chemistry of monoacrylates characterized by secondary functionalities that dramatically enhance their polymerization rate was elucidated utilizing experimental and computational techniques. Firstly, bulk interactions affecting the acrylate reactivity towards photopolymerization were removed by polymerizing at 5 wt % monomer in 1,4‐dioxane. Following deconvolution of bulk interactions impacting reactivity towards photopolymerization, a linear correlation between average polymerization rates and Michael addition reaction rate constants was observed on a logarithmic scale. This result indicates that the presence of the secondary functionality intramolecularly alters the monomer chemistry in a manner which impacts both of these distinct reaction types in a similar manner. These monomers exhibited reduced activation energies in both Michael addition and photopolymerization reactions as compared to hexyl acrylate. Reduction up to 20 ± 8 kJ mole^?1was observed for Michael addition reactions and 12 ± 1 kJ mole^?1 for photopolymerization reactions, thereby explaining the higher reactivity of the acrylates characterized by the secondary functionalities. Cyclic voltammetry experiments conducted to investigate the nature of the acrylic double bonds indicated that the rapidly polymerizing acrylates are more readily reduced as compared to traditional acrylates. Further, a distinct monotonic correlation of the irreversible cathodic peak potentials of the (meth)acrylates to photopolymerization and Michael addition reactivity was observed. The computationally estimated acrylic LUMO energies characterized by the secondary functionalities (?2.3 eV to ?2.7 eV) were also found to be lower relative to hexyl acrylate (?2.2 eV). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4859–4870, 2009     

Real‐time Fourier transform infrared study of the free‐radical ultraviolet‐induced polymerization of a hybrid sol–gel. II. The effect of physicochemical parameters on the photopolymerization kinetics

Free‐radical photocurable hybrid sol–gel materials have gained special interest during the last decades. Compared to thermally processed materials, they present the advantages of fast curing, low energy consumption, and spatiotemporal control of the reaction. Although comprehension of the photochemical step is fundamental, little is known about the characteristic of photochemistry in this kind of material. Real‐time Fourier transform infrared spectroscopy was used to study the photopolymerization of a hybrid sol–gel upon ultraviolet irradiation. Various photoinitiator systems were tested for their efficiency in inducing the polymerization of pendant polymerizable moieties anchored on a partially condensed silicate network. The presence of O₂ and the nature of the polymerizable function were shown to be crucial factors in the photoinduced process. The effects of the photoinitiator concentration and light intensity were also studied. These results were explained in terms of classical kinetic models developed for all‐organic photopolymers to point out the distinctive aspects related to the use of photoinitiated polymerization in hybrid sol–gel materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 831–840, 2003     

Dark‐cure studies of cationic photopolymerizations of epoxides: Characterization of the active center lifetime and kinetic rate constants

We have characterized the effective rate constants for termination/trapping (k_t/t) and propagation (k_p) for solvent‐free cationic photopolymerizations of phenyl glycidyl ether for conversions up to 50%. We have performed dark‐cure experiments in which active centers are produced photochemically for a specified period of time until the initiating light is shuttered off, and then the polymerization rate is monitored in the dark. This method is especially well suited for characterizing cationic polymerizations because of the long active center lifetimes. Our analysis provides profiles of the instantaneous kinetic rate constants as functions of conversion (or time). For photopolymerizations of phenyl glycidyl ether initiated with iodonium photoinitiators, k_t/t and k_p remain essentially invariant for conversions up to 50%. For the photoinitiator (tolycumyl) iodonium tetrakis (pentafluorophenyl) borate (IPB), the values of k_t/t at 50 and 60 °C are 0.027 and 0.033 min^?1, respectively. The corresponding values of k_t/t for diaryliodonium hexafluoroantimonate (IHA) are 0.041 and 0.068 min^?1. The values of k_p at 50 °C for IPB and IHA are 0.6 and 0.4 L mol^?1 s^?1, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2064–2072, 2003     

Continuous Distribution Kinetics for Photopolymerization of Alkyl Methacrylates

The photopolymerization of methyl, ethyl, butyl, and hexyl methacrylates in solution was studied. The effect of initial initiator and monomer concentrations on the time evolution of polymer concentration, , and PDI was examined. The reversible chain addition and β‐scission, and primary radical termination steps were included in the mechanism along with the classical steps. The rate equations were derived using continuous distribution kinetics and solved numerically to fit the experimental data. The regressed rate coefficients compared well with the literature data. The model predicted the instantaneous increase in and PDI to steady state values. The rate coefficients exhibited a linear increase with the size of alkyl chain of the alkyl methacrylates.

     

Reaction kinetics and microgel particle size characterization of ultraviolet‐curing unsaturated polyester acrylates

The free‐radical reaction kinetics and microgel formation of UV‐curing unsaturated polyester acrylates were studied in terms of the effects of internal maleic and terminal acrylate unsaturations. A triacrylate‐functional monomer, trimethylolpropane triacrylate, was used as the reactive diluent. A time‐resolved Fourier transform infrared technique was used to evaluate the consumption of double bonds and showed that internal (maleic) double bonds were involved in microgel formation at a rate similar to that of the more reactive terminal (acrylic) double bonds. Dynamic light scattering was used to measure the microgel particle size. The introduction of internal unsaturations caused smaller microgels, whereas terminal acrylate unsaturations resulted in larger particle sizes. These results were attributed to the higher tendency of the internal maleic double bonds toward intramolecular cyclization reactions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6544–6557, 2006     

Termination in Dilute‐Solution Free‐Radical Polymerization: A Composite Model

Literature data are summarized for the chain‐length‐dependence of the termination rate coefficient in dilute solution free‐radical polymerizations. In essence such experiments have yielded two parameter values: the rate coefficient for termination between monomeric free radicals, kequation/tex2gif-stack-1.gif, and a power‐law exponent e quantifying how k_t values decrease with increasing chain length. All indications are that the value e ≈ 0.16 in good solvent is accurate, however the values of kequation/tex2gif-stack-2.gif which have been deduced are considerably lower than well‐established values for small molecule radicals. This seeming impasse is resolved by putting forward a ‘composite’ model of termination: it is proposed that the value e ≈ 0.16 holds only for long chains, with e being higher for small chains – the value 0.5 is used in this paper, although it is not held to dogmatically. It is then investigated whether this model is consistent with experimental data. This is a non‐trivial task, because although the experiments themselves and the ways in which they are analyzed are elegant and not too complicated, the underlying theory is sophisticated, as is outlined. Simulations of steady‐state polymerization experiments are first of all carried out, and it is shown that the composite model of termination both recovers the e values which have been found and beautifully explains why these experiments considerably underestimate the true value of kequation/tex2gif-stack-3.gif. Simulations of pulsed‐laser polymerizations find the same, although not quite so strikingly. It is therefore concluded that our new termination model, which retains the virtue of simplicity and in which all parameter values are physically reasonable, is consistent with experimental data. Taking a wider view, it seems likely that the situation of the exponent e varying with chain length will not just be the case in dilute solution, but will be the norm for all conditions, which would give our model and our work a general relevance.

Normalized chain length distributions from PLP simulations.     

Thiol‐isocyanate‐acrylate ternary networks by selective thiol‐click chemistry

Thiol‐isocyanate‐acrylate ternary networks were formed by the combination of thiol‐isocyanate coupling, thiol‐acrylate Michael addition, and acrylate homopolymerization. This hybrid polymerization reaction sequence was preferentially controlled by using phosphine catalyst systems in combination with photolysis. The reaction kinetics of the phosphine/acrylate thiol‐isocyanate coupling reactions were systematically investigated by evaluating model, small molecule reactions. The thiol‐isocyanate reaction was completed within 1 min while the thiol‐acrylate Michael addition reaction required ～10 min. Both thiol‐isocyanate coupling and thiol‐acrylate Michael addition reactions involving two‐step anionic processes were found to be both quantitative and efficient. However, the thiol‐isocyanate coupling reaction was much more rapid than the thiol‐acrylate Michael addition, promoting initial selectivity of the thiol‐isocyanate reaction in a medium containing thiol, isocyanate, and acrylate functional groups. Films were prepared from thiol‐isocyanate‐acrylate ternary mixtures using 2‐acryloyloxyethylisocyanate and di‐, tri‐, and tetra‐functional thiols. The sequential thiol‐isocyanate, thiol‐acrylate, and acrylate homopolymerization reactions were monitored by infrared spectroscopy during film formation, whereas thermal and mechanical properties of the films were evaluated as a function of the chemical composition following polymerization. The results indicate that the network structures and material properties are tunable over a wide range of properties (T_g ～ 14–100 °C, FWHM ～ 8–46 °C), while maintaining nearly quantitative reactions, simply by controlling the component compositions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3255–3264, 2010     

Synthesis and photopolymerization kinetics of benzophenone piperazine one‐component initiator

A one‐component type II photoinitiator (PDBP), based on 4‐hydroxybenzophenone (HBP), acryloyl chloride, and piperazine, was synthesized and its structure was confirmed by ¹H‐NMR. The photopolymerization kinetics of the photoinitiator was studied by real‐time Infrared spectroscopy (FT‐IR). It indicated that PDBP was a more effective photoinitiator than that of BP/triethylamine (TEA). The rate of polymerization, final conversion increased and the induction period shortened with increase in PDBP concentration, light intensity, and amine concentration. The kinetics of photopolymerization for TPGDA incorporating PDBP in the presence of different tertiary amines as the initiating system indicated that the PDBP/TEA combination exhibited the highest polymerization rates among the PDBP/amine combinations. Copyright © 2007 John Wiley & Sons, Ltd.     

Real‐time monitoring of the ring‐opening polymerization of rac‐lactide with in situ attenuated total reflectance/Fourier transform infrared spectroscopy with conduit and diamond‐composite sensor technology

Polymerization rates were proportional to initial Sn(Oct)₂ concentration at low [Sn(Oct)₂]₀/[PrOH]₀ values, but began to level off at higher values. When [Sn(Oct)₂]₀/[PrOH]₀ was significantly greater than unity, the opposite behavior occurred. Tin(II) alkoxide concentration became limited by the initial PrOH concentration and independent of initial Sn(Oct)₂ concentration. Addition of 2‐ethylhexanoic acid caused polymerization rate retardation, without affecting molecular weight. A control polymerization was conducted in the absence of PrOH. The molecular weight of the resulting polymer was consistent with the measured water content (3.7 wt % by Karl Fisher titration) of the as‐received Sn(Oct)₂. The polymerization rate in the absence of PrOH was slow, and this suggested that water is less efficient than an alcohol in creating polymerization‐active stannyl ether bonds. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6238–6247, 2004     

Photopolymerization kinetics of tributylmethylammonium‐based (meth)acrylate ionic liquids and the effect of water

Polymerizable ionic liquids were synthesized from the neutralization reaction between tributylmethylammonium hydroxide and methacrylic or acrylic acid, and their photopolymerization kinetics have been determined. The acrylate monomer polymerization rate exhibited a profound dependence on the water content as follows: the monomer viscosity was a strong function of the water content, increasing substantially as the water content increased from less than 5 to 30%. For the tributylmethylammonium acrylate with less than 5% water, the viscosity was 2000 times greater than that of butyl acrylate. The high viscosity is proposed to reduce both the propagation and termination steps. Both monomers exhibited an increase in rate with temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3766–3773, 2008     

Photopolymerization of ternary thiol–ene/acrylate systems: Film and network properties

Photocurable, ternary‐component mixtures of a 1:1 molar multifunctional thiol–ene (trithiol and triallyl ether) blend and a 16‐functional acrylate based monomer have been photopolymerized, and the final film properties of the ternary crosslinked networks have been measured. The photopolymerization kinetics, morphology, and mechanical and physical properties of the films have been investigated with real‐time infrared, atomic force microscopy, and dynamic mechanical analysis. The photopolymerization process is a combination of acrylate homopolymerization and copolymerizations of thiol with allyl ether and acrylate functionalities. The tan δ peaks of the photopolymerized ternary systems are relatively narrow and tunable over a large temperature range. The morphology is characterized by a distinct phase‐separated nanostructure. The photocured thiol–ene/acrylate ternary systems can be made to exhibit good mechanical properties with enhanced energy absorption at room temperature by the appropriate selection of each component concentration. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 822–829, 2007.     

“Kick‐Starting” oxetane photopolymerizations

In the presence of small amounts of 2,2‐dialkyl‐, 2,2,3‐trialkyl‐, or 2,2,3,3‐tetraalkyl substituted epoxides such as isobutylene oxide, 1,2‐limonene oxide, and 2,2,3,3,‐tetramethyl oxirane, the photoinitiated cationic ring‐opening polymerizations of 3,3‐disubstituted oxetanes are dramatically accelerated. The acceleration affect was attributed to an increase in the rate of the initiation step of these latter monomers. Both mono‐ and disubstituted oxetane monomers are similarly accelerated by the above‐mentioned epoxides to give crosslinked network polymers. The potential for the use of such “kick‐started” systems in applications such as coatings, adhesives, printing inks, dental composites and in three‐dimensional imaging is discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2934–2946     

Real‐Time IR Study of Ultra‐Thin Film Photopolymerization of Liquid Porphyrin Monomer

By using an advanced polarization modulation infrared reflection adsorption spectroscopy (PM‐IRRAS) device it is possible to study the photopolymerization of an ultrathin layer of a porphyrin monomer in real time. The method can be compared with the indirect UV/Vis method previously introduced by our group. With PM‐IRRAS it is possible to analyze polymerization kinetics of photopolymerization at various temperatures to determine the activation energy of the reaction.