Final Double Bond Conversion Research Articles

A dual-functional α-diketone-based disulfide monomer for visible LED photopolymerization: Mitigating volumetric shrinkage and triggering polymerization

A α-diketone-based disulfide monomer (OHS), which serves the function of both volumetric shrinkage decreases and photopolymerization initiation under the irradiation of 405 light-emitting diode (LED) was designed and synthesized. The photochemical and photoinitiating performances were study by ultraviolet–visible spectrophotometer, electron spin resonance spin trapping (ESR-ST) experiments and real-time infrared spectrometer (FTIR). Despite OHS exhibits weak absorption at approximately 405 nm, OHS can effectively produce aromatic sulfur radicals to induce photopolymerization of itself and the bisphenol A glycerolate dimethacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) photopolymerizable system under 405 nm LED exposure. With increasing OHS addition, the final double bond conversion and maximum polymerization rate of the Bis-GMA/TEGDMA system improved, reaching up to 86.0% and 2.33% s-1, respectively. Importantly, OHS significantly reduces the volumetric shrinkage ratio of the Bis-GMA/TEGDMA photopolymerizable system, with the volumetric shrinkage ratio (5.01%) of the system containing 5% OHS declining by almost 50% compared to that (8.51%) of the control system without OHS. This reduction is attributed to reversible characteristic of the disulphide bonds and intermolecular hydrogen bondings. Furthermore, OHS has little influence on the gelation ratio, thermostability, and frictional resistance of the cured film.

Photopolymerization initiated by p-diethylene glycol monomethyl ether cinnamyl formamide-based disulfide under 455 nm LED with minimized volume shrinkage

This study introduces a novel p-diethylene glycol monomethyl ether cinnamyl formamide-based disulfide monomer, N,N′-(disulfanediylbis(2,1-phenylene)) bis(4-(4-(2-(2-methoxyethoxy)ethoxy) phenyl)-2-oxobut-3-enamide) (Mp-BSCF), designed to reduce the volume shrinkage of photosensitive resins and initiate monomer polymerization under 455 nm LED light irradiation. The photochemical properties and photoinitiation efficiency of Mp-BSCF are systematically investigated using UV–vis absorption spectroscopy, electron paramagnetic resonance (EPR) and real-time infrared spectroscopy. Although its weak absorption around 455 nm, Mp-BSCF can generate arylthiyl radicals under 455 nm LED irradiation, and then effectively initiate the polymerization of triethylene glycol dimethacrylate (TEGDMA)/A glycerolate dimethacrylate (Bis-GMA) system. Increasing Mp-BSCF addition enhances the final double bond conversion and maximum polymerization rate of the TEGDMA/Bis-GMA system, reaching up to 82.0 % and 2.02 % s−1, respectively. Notably, Mp-BSCF significantly reduces the volume shrinkage of the photopolymerization system, with the addition of 10 % Mp-BSCF resulting in a 50 % reduction compared to the control system. This reduction is attributed to the dynamic reversible nature of the SS bond “breaking-recovery” and the intermolecular hydrogen bond interaction. Additionally, Mp-BSCF improves the thermal stability, friction resistance, and hardness of the TEGDMA/Bis-GMA photopolymerization system.

Preparation and Mechanical Properties of UV-Curable Epoxy Acrylate/Modified Aramid Nanofiber Nanocomposite Films.

In order to enhance the mechanical properties of UV-curable epoxy acrylate (EA)-based coatings, 3-(trimethoxysilyl)propyl methacrylate modified aramid nanofibers (T-ANFs) were synthesized and used as nanofillers to prepare EA/T-ANF nanocomposite films. The morphology of T-ANFs was characterized by transmission electron microscopy. The chemical structure of T-ANFs was analyzed via infrared spectroscopy, confirming successful grafting of methyl methacryloyloxy groups onto the surface of aramid nanofibers (ANFs). Real-time infrared spectroscopy was employed to investigate the influence of ANFs and T-ANFs on the photopolymerization kinetics of the EA film. The results revealed that the addition of ANFs and T-ANFs led to a decrease in the photopolymerization rate during the initial stage but had little impact on the final double bond conversion, with all samples exhibiting a conversion rate of over 83%. The incorporation of ANFs improved the tensile strength of the films while significantly reducing their Young's modulus. In contrast, the addition of T-ANFs led to a substantial increase in both tensile stress and Young's modulus of the films. For instance, the tensile strength and Young's modulus of the 0.1 wt% of T-ANF film increased by 52.7% and 41.6%, respectively, compared to the pure EA film. To further study the dispersion morphology and reinforcement mechanism, the cross-sectional morphology of the films was characterized by scanning electron microscopy.

Preparation and property study of photocurable polysiloxane polyacrylate materials containing S—S bonds

In this article, three polymerizable polysiloxane monomers with different chain lengths (MA-Sin, n = 3,6,9) have been synthesized, and then MA-Sin was mixed with disulfide monomer (SA) and different acrylate monomers in certain proportion to obtain a series of photopolymerizable systems. The effects of the contents of SA and MA-Sin, and the chain length of MA-Sin on the photopolymerization kinetics, volume shrinkage, water contact angle, thermal resistance, glass transition temperature (T g), tensile properties and degradability of the photocured films were explored in detail. The results show that the content and the chain length of MA-Sin have no significant effect on the final double bond conversion, which reaches about 94%. With the increase of SA content, the volume shrinkage of the photocured film descends and eventually drops to 3.23%. The addition of MA-Sin contributes to improve thermal stability and hydrophobicity. With the lengthening of the chain length of MA-Sin, the water contact angle, tensile strength, elongation at break and thermal resistance of the photocured film were enhanced, whereas T g is decreased. More importantly, the SA endows the photocured films with good degradability.

Synthesis and Property of an Organosilicon Polyurethane Acrylate Prepolymer Containing Disulfide Bonds for Photopolymerization

AbstractPhotocurable organosilicon polyurethane acrylate materials combine the merits of both polyurethane and organosilicon and have become the most widely used class of photocurable resins due to the advantages of easy preparation and performance tunability, but they suffer from serious volume shrinkage and difficult degradation. In this article, an organosilicon polyurethane acrylate prepolymer (SSiPUA) containing disulfide bonds is designed and synthesized. The prepolymer exhibits good ability to photopolymerize and reduce the volume shrinkage. The final double bond conversion (DBC) of the system with SSiPUA reaches 92%, and the volume shrinkage is decreased to 4.9% that is much less than that (13.9%) without SSiPUA. Besides, with the increase of SSiPUA content within a certain range, the hydrophobicity, heat resistance, the tensile strength, and the elongation at break of the photocured films gradually increase. The water contact angle, initial decomposition temperature, the tensile strength, and the elongation at break reach up to 93°, 282 °C, 1.8 MPa, and 576.2%, respectively. However, the glass transition temperature is reduced with the increase of SSiPUA content owing to the excellent flexibility of polysiloxane chain segments. More significantly, the SSiPUA containing disulfide bonds endows the photocured film with good degradation properties.

Influence of the Addition of Sialon and Aluminum Nitride Fillers on the Photocuring Process of Polymer Coatings

This article presents the results of a study on polymer coatings containing poly ethoxylated bisphenol A diacrylate (Bis-AEA10) with aluminum silicon nitride oxide (Sialon) and aluminum nitride (AlN). The polymer coatings were obtained by the photopolymerization technique. Investigations were carried out to determine the effect of the AlN and Sialon content on the UV-curing kinetics, as well as on the mechanical (hardness), thermal (Tg, thermal stability), physicochemical (water contact angle), and structural properties of the polymer coatings. Polymerization rates were characterized as functions of double-bond conversion using the photo-Differential Scanning Calorymetry technique (photo-DSC). The results obtained showed that a small addition of sialon filler (3–5 wt.%) to Bis-AEA10 increases the photopolymerization rate of the varnish, while the addition of more Sialon decreases the rate of photopolymerization. However, for the systems containing AlN filler, the maximum polymerization rate was observed for samples containing 10 wt.% filler. In the case of a varnish composition containing AlN, the maximum polymerization rate is characterized by the system containing 10 wt.% of AlN. This shows that the AlN filler has a good influence on the polymerization process. In either case, the final double bond conversion was high (80%–95%). Mechanical tests have shown that introducing the filler into the polymer matrix increases its hardness. The content of Sialon and AlN in the coatings causes an increase (up to 4–5 wt.%) and a decrease (>4–5 wt.%) in the glass transition temperature. The effect of the addition of fillers on the physicochemical properties of the coating surface has also been investigated and characterized by the water contact angle method. The addition of 20 wt.% Sialon and AlN increased the contact angle of the samples by approximately 40% and 31%, respectively, resulting in coatings with hydrophobic surface properties.

A Martini 3 coarse-grain model for the simulation of the photopolymerizable organic phase in dental composites.

Light-hardening dental composites can be used in a large number of applications in restorative dentistry. They are based on photopolymerizable resins, which are highly relevant also in other industries like 3D printing. Much effort is therefore being put into developing and optimizing photopolymers. Currently used photopolymers still have limitations regarding mechanical properties, shrinkage and leaching of uncured monomers. These issues are strongly linked to the network structure of the polymer and are usually addressed using trial and error methods. Therefore, it is of interest to have a model for the network structure of such materials and to have a tool to facilitate scientific progress and the development of high-performance photopolymers. This work presents a coarse grain model of Bis-GMA/TEGDMA formulations and their corresponding networks, following the Martini 3 guidelines and using a simulated polymerization algorithm. The model proved to reproduce the densities and volumetric shrinkage values found in the literature well. Furthermore, it was possible to estimate the final double bond conversion of the polymer material. Martini's building block-like design makes it easy to extend the model to other monomers in the future.

Synthesis of allyl sulfones bearing urethane groups as efficient addition-fragmentation chain transfer agents for the development of low-shrinkage composites

Polymerization shrinkage represents one of the major drawbacks of dental composites. The incorporation of chain transfer agents into dental formulations is an efficient technology that enables a strong reduction of the shrinkage stress. In this contribution, the synthesis of four new addition-fragmentation chain transfer (AFCT) agents bearing urethane groups is described. These compounds were easily synthesized in three steps. Real-time (RT)-NIR photorheology measurements were performed to evaluate rheological behavior (i.e. time of gelation) and chemical conversion (i.e. double bond conversion at the gel point, final double bond conversion) of dimethacrylate resins containing the synthesized transfer agents. Composites based on these AFCT agents provide good mechanical properties as well as low shrinkage force. The presence of the urethane group results in a significant improvement of the mechanical properties. The addition of urethane AFCT agents to dental composites is an efficient technology that enables the formulation of low shrinkage materials having high flexural strength and modulus.

Preparation and properties of UV-curable diamine-based polyurethane acrylate hard coatings

Three polyurethane acrylate (PUA) branched compounds with different diamines (Norbornane dimethylamine, piperazine and ethylenediamine) were synthesized under the facile reaction condition. Coatings based on synthesized branched compounds were prepared under UV-irradiation, and used as hard coatings to protect the plastic surface. The structures of PUA branched compounds were characterised by proton nuclear magnetic resonance and gel permeation chromatography. The effect of rigid diamines on the properties of coatings was investigated regarding to the curing behaviour, dynamic mechanical property, mechanical property and coating surface property. The results indicate that the final double bond conversion is associated with the rigidity of the diamines and the viscosity of the prepared coating solution. The rigid diamine endows the coating with high Tg value, and leads to phase separation that creates rough coating surface. The tensile test shows that the coating with highest crosslinking and moderately rigid diamine possesses excellent mechanical property with 20.7 MPa in tensile strength and 6.8% in elongation at break. The pencil hardness of the prepared PUA-PZ coating can reach to 5H that is higher than the commercially available resin PUA-6, and this coating also shows good adhesion and flexibility, which has potential to be applied as protective coating to protect PC surface well. Moreover, all coatings exhibit good thermal properties.

Castor oil-based waterborne hyperbranched polyurethane acrylate emulsion for UV-curable coatings with excellent chemical resistance and high hardness

Synthesis, characterization, and coating performance of castor oil (CO)-based waterborne hyperbranched polyurethane acrylate (WHPUA) emulsions are highlighted in this work. Herein, a second-generation CO-based hyperbranched polyester (C20) was synthesized by introducing the renewable CO as a B3 core and dimethylolpropionic acid as an AB2 monomer via a pseudo-one-pot condensation procedure. Three types of CO-based WHPUA emulsions were prepared through the addition of the hyperbranched C20 with maleic anhydride (MA) and the isocyanate-bearing semiadduct (IPDI-HEA) at different MA/IPDI-IH molar ratios without the addition of any emulsifiers. The prepared emulsions were further formulated into UV-curable coating formulations and exposed to a medium-pressure mercury lamp. Consequently, the obtained UV-cured coatings exhibited outstanding adhesion performance, excellent transparency, and an acceptable degree of final double bond conversion. Owing to a relatively low concentration of hydrophilic units and a large number of acrylate functionalities in the waterborne oligomer, the obtained films were endowed with high crosslinking density and low hydrophilic nature, thus producing enhanced tensile strength, pencil hardness, water resistance, and chemical resistance. Due to their combination of renewable materials, a waterborne system and a UV-curing technique, these CO-based WHPUA emulsions offer promising opportunities to be used as environmentally friendly coatings.

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.

Synthesis and polymerization of vinylcyclopropanes bearing urethane groups for the development of low-shrinkage composites

Polymerization shrinkage of methacrylate-based dental composites remains a major concern in restorative dentistry. Cyclic monomers, such as 1,1-disubstituted 2-vinylcyclopropanes, might represent an interesting alternative to dimethacrylates in order to reduce shrinkage. In this contribution, the synthesis of seven crosslinking vinylcyclopropanes bearing urethane groups is described. These monomers were synthesized by esterification of 1-ethoxycarbonyl-2-vinylcyclopropane-1-carboxylic acid with either ethylene glycol or diethylene glycol, followed by a reaction with selected diisocyanates. In order to evaluate the reactivity of the synthesized vinylcyclopropanes, their photopolymerization behavior was investigated by photo-differential scanning calorimetry. Real-time (RT)-NIR-photorheology measurements were performed to evaluate rheological behavior (i.e. time of gelation, polymerization induced shrinkage force) and chemical conversion (i.e. double bond conversion at the gel point, final double bond conversion) of the vinylcyclopropanes in situ. Composites based on these monomers show good to excellent mechanical properties and exhibit low shrinkage. The presence of urethane groups provides a significant improvement of the mechanical properties. The replacement of methacrylates by urethane vinylcyclopropanes appears to be a promising approach to develop low-shrinkage dental composites without sacrificing the mechanical properties.

Effect of scattering nanoparticles on the curing behavior and conversion gradient of UV-curable turbid systems: two-flux Kubelka-Munk approach

Abstract UV-curable systems based on polyethylene glycol diacrylate (PEG-DA) containing various amounts of scattering silicon nitride nanoparticles were studied by real-time Fourier transform infrared (RT FTIR) and real-time UV–visible (RT UV–visible) spectroscopies. Increasing the percentage of nanoparticles into the UV-curable systems caused the photopolymerization rate and final double-bond conversion to increase. Principal component analysis (PCA) was applied to transmission spectra of samples with various amounts of nanoparticles. Results showed a significant correlation between the two most important principal components and the absorption and scattering phenomena. Absorption and scattering coefficients were evaluated from the reconstructed data using a two-flux Kubelka-Munk theory and radiative flux behavior was calculated. Conversion gradients inside a thick layer were simulated using the radiative flux and curing kinetics experimental values. Finally, the effect of scattering particles on the curing depth was studied.

Hyperbranched poly(ether amine) (hPEA) as novel backbone for amphiphilic one-component type-II polymeric photoinitiators

To make photoinitiators (PI) to be polymeric and water-soluble is an effective approach to develop the high efficient photoinitiator systems with low-migration, low-toxic and environment-friend. We developed a series of novel amphiphilic hyperbranched polymeric photoinitiators (hPEA-TXs, and hPEA-BPs) by introducing thioxanthone (TX) or benzophenone (BP) moieties into the periphery of the hyperbranched poly(ether amine) (hPEA) comprised of the hydrophilic poly(ethylene oxide) (PEO) short chain and coinitiator amine moieties in the backbone. Compared with their water-soluble low-molecular weight analogues, the resulting hyperbranched polymeric photoinitiators hPEA101-TX, hPEA211-TX, hPEA101-BP and hPEA211-BP could be dissolved very well not only in many organic systems including acrylate monomers, but also in water with high solubility of 10wt%. The photopolymerization kinetics of water-soluble monomer acrylamide (AM) and three hydrophobic multifunctional acrylate monomers initiated by these hyperbranched photoinitiators were investigated in detail by photo-differential scanning calorimetric (photo-DSC). Both hPEA-TXs and hPEA-BPs can initiate photopolymerization of AM as efficiently as their low-molecular weight analogues MGA-TX and MGA-BP, respectively. The final double bond conversion (DBC) of oil-soluble monomer hexanediol diacrylate (HDDA) photoinitiated by these hyperbranched photoinitiators can reach as high as 99%. Especially for photopolymerization of multifunctional monomers initiated by these hyperbranched polymeric photoinitiators, the final DBC of trimethylolpropane triacrylate (TMPTA) and pentaerythritol tetraacrylate (PETTA) can reach 80% and 60%, respectively, which is much higher than that of low-molecular weight photoinitiators.

Evaluation of Difunctional Vinylcyclopropanes as Reactive Diluents for the Development of Low‐Shrinkage Composites

Polymerization shrinkage of dental composites remains a major concern. Free‐radically polymerizable cyclic monomers can be a conceivable alternative to methacrylates for the development of low‐shrinkage composites. In this study, the one‐step synthesis of the novel low viscosity difunctional vinylcyclopropanes 1–4 is described. Photopolymerization kinetics of these monomers are investigated by photo‐differential scanning calorimeter, using bis(4‐methoxybenzoyl)diethylgermane as photoinitiator. Real‐time near‐infrared photorheology measurements are performed to evaluate rheological behavior (i.e., time of gelation, polymerization‐induced shrinkage force) and chemical conversion (i.e., double bond conversion at the gel point, final double bond conversion) of the vinylcyclopropanes in situ. The potential of these monomers as reactive diluents in dental restorative materials is evaluated. Composites based on vinycyclopropanes 1–4 show good mechanical properties and exhibit significantly lower volumetric shrinkage and shrinkage stress than corresponding dimethacrylate‐based materials. The results indicate that such monomers are promising candidates for the replacement of commonly used low viscosity dimethacrylates such as triethylene glycol dimethacrylate in dental composites. image

Application of an Addition-Fragmentation-Chain Transfer Monomer in Di(meth)acrylate Network Formation to Reduce Polymerization Shrinkage Stress.

A new addition-fragmentation chain transfer (AFT) capable moiety was incorporated into a dimethacrylate monomer that participated readily in network formation by copolymerizing with multifunctional methacrylates or acrylates. The process of AFT occurred simultaneously with photopolymerization of the AFT monomer (AFM) and other (meth)acrylate monomers leading to polymer stress relaxation via network reconfiguration. At low loading levels of the AFM, a significant reduction in shrinkage stress, especially for acrylate monomers, was observed with nominal effects on conversion. At higher loading levels of the AFM, the photopolymerization reaction kinetics and final double bond conversion were significantly lowered along with a delay in the gel-point conversion. Electron paramagnetic resonance studies during polymerization revealed the presence of a distinct radical species that was present in proportional quantities to the AFM content in the system. The lifetime and the character of the persistent radicals were altered due to the presence of the distinctive radical, in turn affecting the polymerization kinetics. With polymerization conducted at higher irradiance, the differential conversion between the control resin and samples with moderate AFM content was minimal, especially for the methacrylate-based formulations.

Photoinitiability of a water-borne polysiloxane-modified benzophenone macromolecular photoinitiator

This paper reported a water-borne polysiloxane-modified benzophenone macromolecular photoinitiator (WPSHBP), whose characteristics of the photopolymerization, the migration of photolysis fragments, the volatility, and reduction of oxygen inhibition were discussed in detail. WPSHBP has a maximum absorption peak at 286 nm, and the molar extinction coefficient (ε286 nm) is 23200 M−1 cm−1. The photopolymerization rate and final double bond conversion of the system initiated by WPSHBP were enhanced with the increasing contents of triethanolamine (TEOA) and WPSHBP and irradiation intensity. WPSHBP exhibits a low migration of photolysis fragments and volatility compared with small-molecular photoinitiator benzophenone (BP). The cured films initiated by WPSHBP have good mechanical properties and thermostability compared with that by 2-hydroxy-4’-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959). More importantly, the water-borne polysiloxane-modified photoinitiator can mitigate the oxygen inhibition in radical photopolymerization due to its enrichment on the surface of the photopolymerization system.

Synthesis of UV-curable polycarbonate diols (PCDL)-based polyurethane acrylate for negative photoresist

Two kinds of UV-curable polyurethane acrylates (PCDL-H-PUA and PCDL-P-PUA) were synthesized starting with polycarbonate diols (PCDL), isophorone diisocyanate and dimethylolpropionic acid and terminated with hydroxyethyl methacrylate or pentaerythritol triacrylate to impart mono-methacrylate or tri-acrylate end-group functionality, respectively. The structures and properties of the products were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, gel permeation chromatography and thermogravimetric analysis. The average molecular weights were between 7500 and 9300 g/mol, and the thermal properties of the products were excellent. The influence of the functionality of the end-capping functional group on the UV-curing behavior was investigated using real-time spectroscopy. Results showed that curing rate and conversion of PCDL-P-PUA were higher than those of PCDL-H-PUA, and the final double bond conversion of the polymers reached 95 %. PCDL-H-PUA and PCDL-P-PUA were applied to negative photoresists as the main film resin. The resolution of the optimal photoresist reached 40 µm.

Synthesis and characterization of photosensitive-fluorosilicone–urethane acrylate prepolymers

Two kinds of novel photosensitive-fluorosilicone–urethane acrylate prepolymers (Si-F15-IPDI-HEA/Si-F6-IPDI-HEA) were synthesized and characterized. Si-F15-IPDI-HEA and Si-F6-IPDI-HEA were able to form homogeneous mixtures with a number of acrylate monomers. Formulations with these prepolymers with common acrylic monomers exhibited high-polymerization rates and final double-bond conversion over 90% after irradiation for 60 s. It was found the final conversion decreased with the increase of the functionality of the monomer. The influence of the monomer and prepolymers on the properties of the UV-cured films was systematically studied. Thermostability property along with mechanical performance was improved with the increase of the functionality of monomers and prepolymers. A decrease of water absorption was also observed through water contact angle measurements. The UV-cured films of Si-F15-IPDI-HEA and Si-F6-IPDI-HEA possessed an excellent adhesion on the PU and PVC leather, providing a potential application in leather industry as a finishing and coating agent.

Imidazole-based ionic liquids for free radical photopolymerization

Ionic liquid (IL) monomers are receiving increased attention due to their versatile range of application, especially in the electrochemical and electromechanical fields. Within this study, imidazole-based ILs containing a polymerizable methacrylate (MA) group were synthesized to examine their influence on the viscosity and reactivity of typical (meth)acrylates. The IL-MAs were prepared from 1-butylimidazole and bromo methacrylates with different spacer lengths (C2–C6). The best results with respect to physicochemical properties and double bond conversions could be obtained for ILs with C3 and C6 spacers. Bulk polymerizations exhibited unusually high reactivity and double-bond conversion compared with typical mono-methacrylates. Addition of 10 wt% IL-MA to reactive diluents like hexane-1,6-diol diacrylate caused only minor reduction in reaction rate but increased final double bond conversion compared with the pure diacrylate.