Study of macrophotoinitiator containing in-chain thioxanthone and coinitiator amines

Three kinds of macrophotoinitiator, PTXB, PTXE and PTXP, were synthesized by step-polymerization of thioxanthone and different amino monomers. The UV-vis spectra of PTXP, PTXE and PTXB are similar with slightly-shifted maximum absorption, and the fluorescence emission varies. The photopolymerization of three monomers with different functionality, methyl methacrylate (MMA), poly(propylene glycol) diacrylate (PPGDA) and trimethylolpropane triacrylate (TMPTA), initiated by these three types of macrophotoinitiators was studied through dilatometer and photo-DSC. The results show different photoinitiators behaviors towards monomers efficiently: PTXP is the most efficient for MMA, PTXE is the most efficient for PPGDA and PTXB is the most efficient for TMPTA. The efficiency of the photopolymerization is mainly effected by structure of amine in macrophotoinitiator.     

Photopolymerization behavior and phase separation effects in novel polymer dispersed liquid crystal mixture based on urethane trimethacrylate monomer

Polymer dispersed liquid crystals (PDLCs) are often formed by polymer induced phase separation, based on photopolymerization of multifunctional acrylate monomers. The emerged morphology is controlled by the interplay between polymerization rate and phase separation dynamics, which depends on different parameters such as monomer structure and functionality. In this work, a new PDLC formulation containing urethane trimethacrylate (UTMA) monomer is introduced, which has different molecular weight evolution, polymer gel point, and polymerization kinetics in comparison with some common ester acrylate (such as TMPTA and DPHPA) based PDLC compositions. UTMA is synthesized and characterized by Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopic techniques. Simultaneous examination of polymer evolution and LC phase separation by real‐time infrared spectroscopy shows that the UTMA based PDLC, which contains trifunctional urethane acrylate monomer, has greater amount of bond conversion, polymerization rate, and liquid crystal (LC) phase separation in comparison with TMPTA based PDLC. In spite of the acrylate monomers, which show gel point conversions as low as 1.83–5.72%, UTMA reaches to its maximum rate at 19.5% conversion, which causes higher phase separation and therefore greater LC domain size. The experimental results are explained more precisely by means of SEM and optical microscopy analyses. The results are confirmed by electro‐optics measurements. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Interpenetrating polymer networks. I. Photopolymerization of multiacrylate systems

The light-induced polymerization of a triacrylate monomer (TMPTA) has been carried out in a polymer matrix to generate a semi-interpenetrating polymer network (IPN). The reaction kinetics was followed by IR spectroscopy for the various polymer binders studied: poly(vinyl chloride) (PVC), poly(methyl methacrylate), polystyrene, and crosslinked polyurethane. Under intense illumination, crosslinking occurred extensively within a fraction of a second, with formation of a hard and highly resistant polymer material. These semi-IPNs were found to be essentially insoluble in the organic solvents, thus indicating that the acrylate network is grafted onto the polymer matrix, probably because of an efficient chain transfer process. The monomer and photoinitiator concentration, as well as the light intensity were shown to have a great influence on both the rate of polymerization and the final degree of conversion. By using an acylphosphine oxide photoinitiator, PVC–;TMPTA blends have been cured within a few minutes in an accelerated QUV-A weatherometer, which emits low-intensity UV radiation similar to sunlight. © 1994 John Wiley & Sons, Inc.     

Benzophenone-di-1,3-dioxane as a novel initiator for free radical photopolymerization

Benzophenone-di-1,3-dioxane (BP-DDO), a novel photoinitiator for free radical polymerization, was synthesized and characterized. The photopolymerization kinetics of BP-DDO was studied by real-time infrared spectroscopy (FT-IR). When this photointiator was used to efficiently initiate polymerization of acrylates and methacrylates, there was an optimum cure rate with the increase in BP-DDO concentration. Both the polymerization rate and final conversion increased with the increase in light intensity. The kinetics study of photopolymerization of TMPTA showed that BP-DDO was a more effective photoinitiator than benzophenone and benzophenone/ethyl-4-dimethylaminobenzoate (EDAB).     

Behavior of quaternary ammonium salt photobase generators on initiating free radical photo‐polymerization

Series of quaternary ammonium tetraphenyl borates salt photobase generators (PBGs) were synthesized using p‐methoxyphenacylmethylene and 2‐naphthoymethylene as chromophores, and triethylene diamine, pyridine or 3‐methyl pyridine as tertiary amine. The kinetics for polymerization of trimethylolpropane triacrylate (TMPTA) monomer using PBGs as free radical photo‐initiator was monitored by differential photo‐calorimeter (DPC). It was found that all the quaternary ammonium tetraphenyl borate salt photobase generators synthesized could initiate free radical polymerization of the acrylate monomer TMPTA by exposure to UV irradiation, but the activity was relatively low. Addition of a small amount of polar solvent to the system could largely increase the polymerization rate and final conversion. Photo‐polymerization was also improved by increasing light intensity or raising reaction temperature. PBGs with p‐methoxyphenacylmethylene as chromophore had higher absorbance at around 280 nm and showed higher activity in initiating photo‐polymerization than those with N‐(2‐naphthoylmethyl) as chromophore. Copyright © 2006 Society of Chemical Industry     

ESR and kinetic study of a novel polymerizable photoinitiator comprising the structure of N‐phenylmaleimide and benzophenone for photopolymerization

A novel polymerizable photoinitiator, 4‐[(4‐maleimido)phenoxy]benzophenone (MPBP) comprising the structure of N‐phenylmaleimide and benzophenone was used for the photopolymerization with N,N‐dimethylaminoethyl methacrylate (DMAEMA) as coinitiator. The ESR spectrum of this photoredox system was studied and compared with BP/DMAEMA; the results showed the same signals of them and verified that N‐phenylmaleimide does not generate radicals. The kinetics for photopolymerization of methyl methacrylate (MMA) using such system was studied by dilatometer. It was found that the polymerization rate was proportional to the 0.3172th power of the MPBP concentration, the 0.7669th power and the 0.1765th power of MMA concentration and DMAEMA concentration respectively; the overall apparent activation energy obtained was 31.88 kJ/mol. The polymerization kinetics of 1,6‐hexanediol diacrylate (HDDA) initiated by such system was studied by photo‐DSC. It showed that the increase in the MPBP concentration, light intensity, and temperature leads to increased polymerization rate and final conversion. The apparent activation energy was 11.25 kJ/mol. This polymerizable photoredox system was significantly favorable for reducing the migration of active species but owning high efficiency. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2347–2354, 2006     

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     

Photopolymerization kinetics of cycloaliphatic epoxide–acrylate hybrid monomer

An epoxide–acrylate hybrid monomer was synthesized by the controlled reaction of a cycloaliphatic epoxide and acrylic acid. The photopolymerization kinetics was investigated using a real‐time infrared spectroscopy technique. The influences of photoinitiator concentration, free radical initiator and polymerization atmosphere on the polymerization were studied. The hybrid monomer showed unique photopolymerization kinetics in the photopolymerization process and the final conversions of epoxy groups and acrylate double bonds were improved synchronously. Dynamic mechanical analysis results demonstrated that the hybrid monomer cured film formed a more uniform polymer network than the blend of epoxy acrylate and epoxide. Copyright © 2007 Society of Chemical Industry     

邻羟基环己基丙烯酸酯光聚合动力学研究

采用实时红外光谱技术(RTIR)研究了邻羟基环己基丙烯酸酯(HCA)光聚合反应动力学,探讨了光照强度、光引发剂种类和浓度对其光聚合动力学的影响,并与脂肪族羟基丙烯酸酯单体丙烯酸羟乙酯(HEA)进行了对比。结果表明,最终双键转化率和相对反应速率随光强增大而增加;光引发剂浓度对最终双键转化率和反应速率的影响随引发剂不同呈现不同规律;与HEA相比,HCA具有更高的反应活性,但最终双键转化率较低。     

Investigation of cure advancement in dual-cure polyurethane-acrylate coatings over metal substrates

In the present study, a polyurethane acrylate (PUA) system cured via a thermal–UV (dual-cure process) was developed. The system selected for this work was a two-pack polyurethane acrylate with polyester polyol as the main component and urethane monoacrylate (UMA) as hardener. The polyester polyol was synthesized in a way to provide a final film coating containing both a suitable flexibility and high surface hardness. The thermal and photochemical curing behavior of the resin was studied via the chemorheology technique and the real-time FTIR. The Boltzmann sigmoidal model was implemented and well-fitted to the data obtained from the chemorheology measurements. The comparison between two reactive diluents, butanediol diacrylate (BDDA) and trimethylolpropane triacrylate (TMPTA) showed that BDDA reacts faster than TMPTA in the thermal curing condition. Nevertheless, the network buildup is stronger when TMPTA is used. The photopolymerization is also faster for the case of TMPTA. However, its final double bond conversion is restricted to a lower amount due to steric hindrance and higher viscosity of the system.     

The effect of interpenetrating polymer network formation on polymerization kinetics in an epoxy‐acrylate system

The kinetics of thermally initiated cationic epoxy polymerization and free radical acrylate photopolymerization were studied using photo-differential scanning calorimetry. The reactions of the neat monomers and diluted monomers as well as interpenetrating polymer networks (IPNs) were studied as a function of dilution by the other monomer and temperature. The reaction sequence was also varied to study its effect on the kinetics of formation of the simultaneous IPN's. Both reactions quickly become diffusion controlled. The effects of increasing temperature and dilution on the acrylate polymerization rate profiles are similar, leading to reduced polymerization rate and longer polymerization times. The dilution effect on the epoxy polymerization is similar to that of the acrylate. However, unlike the acrylate reaction the epoxy polymerization rate increases strongly with temperature. The preexistence of one polymer has a significant effect on the polymerization of the second monomer. This effect is larger for the acrylate than for the epoxy polymerization. New kinetic models are needed to capture these complex behaviors.     

Rapid solid‐state photopolymerization of octadecyl acrylate: low shrinkage and insensitivity to oxygen

Mobility restrictions in solid‐state photopolymerization give extremely poor polymerization kinetics, but octadecyl acrylate can be rapidly photopolymerized in the solid state. The XRD, real‐time Fourier transform IR and DSC analyses prove that the hexagonal packing of monomer molecules is favorable for UV‐initiated solid‐state polymerization, and crystalline long alkyl chains of monomers were preserved as the crystalline long alkyl side‐chains of polymers. More importantly, octadecyl acrylate provides a chance to investigate the shrinkage and oxygen inhibition of UV‐induced solid‐state polymerization. This novel radical‐mediated solid‐state photopolymerization is insensitive to oxygen and lowers the volume shrinkage (1.48%). © 2013 Society of Chemical Industry     

Synthesis,spectral characterization,and thermochemical studies of poly(phenyl methacrylate peroxide)

Light‐induced crosslinking polymerization of both bis‐methacrylates and bis‐epoxides yields highly transparent glassy products, suitable for optical applications. Rheological changes of vitrifying liquids during photopolymerization strongly influence the shape accuracy of the final product. Comparison of a free‐radical‐initiated methacrylate polymerization and a cationically initiated ring‐opening polymerization of an epoxide showed that different reaction mechanisms led to very different chemorheological responses and, hence, to pronounced differences in the shape accuracy of the products obtained with either of these materials. An ethoxylated bisphenol‐A dimethacrylate (HEBDM) gels below 1–2% conversion and vitrifies at 15%. At higher conversion, large stresses develop through polymerization shrinkage. Relaxation occurs upon release of a product from its mold, leading to large shape deviations. Ring‐opening polymerization of the diglycidyl ether of bisphenol‐A (DGEBA) has an intrinsically lower polymerization shrinkage. Moreover, gelation of DGEBA polymer networks occurs at 25–30% conversion, leading to much lower stresses since most of the volume change occurs in the liquid state in which replenishment of a monomer can still occur. Upon release from a mold, there is hardly any driving force for relaxation, so a much better copy of the mold is obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2364–2376, 2003     

Polymeric Michler's ketone photoinitiator containing coinitiator amine

Novel polymeric photoinitiator based on Michler's ketone (MK) (PMKPR) was synthesized by introducing coinitiator amine and MK into the same polymeric chain as well as the low‐molecular weight model compounds. UV–vis spectra show that PMKPR has the characteristic UV–vis absorption of MK. The photobleaching behavior of PMKPR and the model compounds were studied, indicating that the photobleaching rate of PMKPR is much faster than that of model compounds. Two types of monomer with different functionality, 2,2‐bis[4‐(acryloxypolyethoxy)phenyl] propane (A‐BPE‐10) and trimethylopropane triacrylate (TMPTA), were chosen to be initiated by these photoinitiators. The result indicates that PMKPR is an efficient photoinitiator for polymerization of A‐BPE‐10 and TMPTA. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

UV‐curable coatings with nano‐TiO2

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

Structure–property relationship and influences of phenolic compounds on the mechanical and thermomechanical properties of UV‐cured acrylic resin networks

Trimethylolpropane triacrylate (TMPTA) resin was cured under UV radiation, with 2,2‐dimethoxy‐2‐phenylacetophenon (DMPA) and a mixture of benzophenone and methyl‐diethanolamine (BP/MDEA) as initiators and three phenolic compounds as inhibitors, respectively. For each formulation, the curing enthalpy was measured by photocalorimetry and the modulus of elasticity (MOE) of cured resin films by thermomechanical analysis. The DMPA resulted in networks with higher rigidity that was slightly reduced by the addition of a phenolic compound; while the networks were more flexible and the effects in reducing the MOE by the phenols were much more pronounced when the BP/MDEA was used as an initiator. For the three phenolic compounds, their importance in reducing the MOE can be ranked in the order of eugenol > dimethoxyphenol > phenol. Three equations are proposed to model the structure–property relationship of TMPTA networks. These models suggest that 1) the MOE increases with the crosslinking density, which is proportional to the conversion degree to a power of about 1/3, indicating that cyclization becomes progressively more important as the photopolymerization advances; 2) the decrease of the MOE with temperature is mainly due to relaxation of pending chains and chain segments, and the activation energy needed to overcome such an energy barrier is greater for a less crosslinked network than for a more crosslinked one; and 3) the overall contribution of the crosslinking and the interactions between pending chains (secondary forces) can be expressed by a simple equation in which the network rigidity (MOE) is a function of the degree of conversion, the activation energy and the temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3499–3507, 2004     

Photoinitiating behavior of bifunctional photoinitiator containing α‐hydroxyalkylphenone group on free‐radical polymerization

Photoinitiating behaviors of bis[4‐(2‐hydroxy‐isopropionyl)]ether photoinitiator on free‐radical polymerization have been investigated. The kinetics of photopolymerization initiated by the photoinitiator was studied by means of differential photocalorimetry. The bifunctional photoinitiator showed comparative performance with those commercial photoinitiators with monofunctional chromophoric group. The effect of UV intensity on the polymerization rate was investigated, and the value of exponential factor was found to be 0.5 at the beginning of polymerization, suggesting that the photopolymerization initiated by bis[4‐(2‐hydroxy‐isopropionyl)]ether followed biradical termination mechanism. Photosensitizer triethylamine improves the initiating efficiency while oxygen is shown to restrict polymerization in this system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5297–5302, 2006     

On the inhibiting effect of phenolic compounds in the photopolymerization of acrylates under high‐intensity and polychromatic UV/visible lights

The photopolymerization of wood coatings under UV and visible light in industrial type conditions has been investigated. The inhibiting effect of the phenolic compounds found in wood extractives, especially quercetin, on the final properties of the coating (hardness, gel content) as well as the polymerization kinetics (rates, final conversion) has been discussed. Model clear‐coating formulations — based on an acrylate oligomer, a reactive diluent and a bis‐acylphosphine oxide as photo‐initiator — have been used. This article focuses on the influence of the nature of the acrylate oligomer (polyester, epoxy, polyurethane), the type of phenolic derivative (POHs) and the irradiation conditions (UV conveyor, Xe lamp). It appears that lead to through the strong inner‐filter effect in the presence of quercetin is responsible for the loss of all the observed properties. In order to mimic what happens at the wood–coating interface, the role of the diffusion of the phenolic derivatives have been also investigated and discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3285–3298, 2007     

Synthetic clay nanocomposite‐based coatings prepared by UV‐cure photopolymerization

The effect of synthetic clay on the photopolymerization kinetics and coating properties of methyl α‐hydroxymethylacrylate (MHMA) systems in the presence of novel hydroxylated dimethacrylate crosslinkers is reported. In the presence of clay earlier onset of autoacceleration was observed, high rates of polymerization were achieved, and high final overall conversions were reached. Higher rates and increase in conversions were also observed as the clay content increased in the medium. To increase compatibility between clay and polymer matrix the use of Jeffamines as polymer/clay compatibilizers, based on ion–dipole interactions between ethylene oxide units and clay ions, was also investigated. Nanocomposite‐based films by photopolymerization of the mixtures coated on glass microscope slides were prepared and evaluated using X‐ray and TEM. The absence of Bragg diffraction peaks in all nanocomposite films indicated loss of organization of the clay layers and formation of well‐dispersed, exfoliated systems was confirmed by TEM. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1252–1263, 2004     

Polymeric Michler's ketone photoinitiators: The effect of chain flexibility

Through introducing Michler's ketone (MK) moiety and diglycidyl ether monomers of different molecular chain into the same polymeric chain, polymeric photoinitiators of different chain flexibility, PMKPR, PMKPG and PMKPP were synthesized. These polymeric photoinitiators possess the similar characteristic UV–vis absorption of parent MK, and their photobleaching behavior is similar. The T_g of PMKPR, PMKPG and PMKPP is 58.1 °C, −24.9 °C and −12.5 °C, respectively. Three types of monomer with different functionality, phenoxy ethyleneglycol acrylate (AMP-10G), 2,2-bis[4-(acryloxypolyethoxy) phenyl]propane (A-BPE-10) and trimethylopropane triacrylate (TMPTA), were chosen to be initiated by these photoinitiators. The result indicates the chain structure of photoinitiators has significant influence on the polymerization of monomers. PMKPG is the most efficient polymeric photoinitiator for initiating the polymerization of AMP-10G and A-BPE-10, while PMKPP is the most efficient for TMPTA.