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Keywords = TPO-L photoinitiator

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10 pages, 2327 KB  
Article
Cure Efficiency and Biocompatibility of an Iron-Based Coordination Complex as a Photoinitiator for Dental 3D-Printed Resins
by Sharanya Singh, Mateus Garcia Rocha, Mario Alexandre Coelho Sinhoreti, Alexandre Carneiro Silvino and Dayane Oliveira
J. Compos. Sci. 2025, 9(1), 26; https://doi.org/10.3390/jcs9010026 - 8 Jan 2025
Viewed by 1694
Abstract
Objective: The aim of this study was to evaluate the cure efficiency and biocompatibility of a novel iron-based coordination complex used as a photoinitiator in comparison to conventional ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate (TPO-L) and camphorquinone (CQ) as photoinitiators in dental 3D-printed resins. Materials and [...] Read more.
Objective: The aim of this study was to evaluate the cure efficiency and biocompatibility of a novel iron-based coordination complex used as a photoinitiator in comparison to conventional ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate (TPO-L) and camphorquinone (CQ) as photoinitiators in dental 3D-printed resins. Materials and Methods: Experimental dental resin formulations were prepared by blending 1:1 ratio of Bis-GMA and TEGDMA, to which 0.2 wt% of either the iron-based coordination complex or CQ were added, along with 0.2 wt% EDAB and 0.4 wt% IOD, and the TPO-L. The degree of conversion (DC) was measured using Fourier transform infrared spectroscopy (FTIR). Biocompatibility was assessed by evaluating the viability of L929 fibroblast-like cells using the MTT assay 24 h post-exposure. Statistical analyses included a two-way ANOVA followed by Tukey’s test for post hoc comparisons, with significance at p < 0.05. Results: The degree of conversion for the iron-based coordination complex (84.54% ± 1.69%) was significantly higher than that for the TPO-L (78.77% ± 1.25%) and CQ-based resins (73.21% ± 0.47%) (p < 0.001). The iron-based coordination complex and TPO-L resins exhibited significantly higher conversion than CQ-based resins (p < 0.001). Regarding biocompatibility, the cell viability test revealed that the iron-based coordination complex demonstrated the highest cell viability at 86.5% ± 10.24%, followed by TPO-L with 80.03% ± 11.07%. CQ showed the lowest cell viability of 51.29% ± 8.44% (p < 0.05). Tukey’s test confirmed significant differences between CQ and other photointiators (p < 0.05), while no significant difference was found between TPO-L and the iron-based coordination complex. Conclusions: This study introduces a novel iron-based coordination complex photoinitiator that demonstrates enhanced cure efficiency and comparable biocompatibility to TPO-L, while significantly reducing the cytotoxicity associated with CQ. Its longer absorption wavelength supports deeper layer curing, making it a promising alternative for dental 3D printing, particularly in bioactive scaffold applications requiring minimized cytotoxicity. Full article
(This article belongs to the Section Biocomposites)
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11 pages, 868 KB  
Article
Residual TPO Content of Photopolymerized Additively Manufactured Dental Occlusal Splint Materials
by Philipp Messer-Hannemann, Max Wienhold, Hoda Esbak, Alexander Brunner, Andreas Schönebaum, Falk Schwendicke and Susanne Effenberger
Biomedicines 2025, 13(1), 44; https://doi.org/10.3390/biomedicines13010044 - 27 Dec 2024
Cited by 4 | Viewed by 4118
Abstract
Background/Objectives: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO) is widely used in the dental industry as a photoinitiator for resin-based materials, while its use may be further limited given its toxicological risks. The aim of this study was, therefore, to analyze the residual TPO [...] Read more.
Background/Objectives: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO) is widely used in the dental industry as a photoinitiator for resin-based materials, while its use may be further limited given its toxicological risks. The aim of this study was, therefore, to analyze the residual TPO content of 3D-printed resin-based dental splint materials. Methods: Six resin-based splint materials were analyzed: LuxaPrint Ortho Plus (DMG), FREEPRINT splint 2.0 (Detax), optiprint splint (Dentona), KeySplint Soft (KeyPrint), FREEPRINT ortho (Detax), V-Print splint comfort (Voco). Grid-shaped specimens were fabricated using the recommended workflow of each manufacturer (n = 18). TPO extraction was conducted using a maximum of eight extraction cycles of 72 h at a temperature of 37 °C until no more TPO eluates were detected by high-performance liquid chromatography (HPLC). The margin of safety (MoS) was calculated as the ratio between the Derived No-Effect Level (DNEL) and the estimated exposure based on the amount of TPO extracted. Results: The total amount of extracted TPO was the lowest for LuxaPrint Ortho Plus (Mean ± SD; 44.0 ± 17.1 ng/mL), followed by optiprint splint (80.6 ± 21.1 ng/mL), FREEPRINT splint 2.0 (127.4 ± 25.3 ng/mL), FREEPRINT ortho (2813.2 ± 348.0 ng/mL), V-Print splint comfort (33,424.6 ± 8357.9 ng/mL) and KeySplint Soft (42,083.5 ± 3175.2 ng/mL). For all tested materials, the calculated MoS was above the critical value of 1, demonstrating toxicological safety in the cured, clinically relevant state. Conclusions: Large differences in the residual TPO content were observed between the materials. Although the TPO content in the uncured state may exceed toxicological safety limits, appropriate curing of the investigated materials resulted in a significant reduction in TPO elution and, thus, in products with a very low toxicological risk for the patient. Full article
(This article belongs to the Special Issue Feature Reviews in Biomaterials for Oral Diseases)
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12 pages, 3057 KB  
Article
Effects of Photoinitiators on Curing Performance of Wood Wax Oil Coating on Wood
by Dan Zhang and Kuiyan Song
Coatings 2024, 14(1), 2; https://doi.org/10.3390/coatings14010002 - 19 Dec 2023
Cited by 6 | Viewed by 3093
Abstract
With the increasing shortage of petroleum resources and the growing seriousness of environmental pollution, the exploitation and application of bio-based coatings derived from renewable resources have become increasingly important for the woodworking industry. Wood wax oil (WWO) is a new type of bio-based [...] Read more.
With the increasing shortage of petroleum resources and the growing seriousness of environmental pollution, the exploitation and application of bio-based coatings derived from renewable resources have become increasingly important for the woodworking industry. Wood wax oil (WWO) is a new type of bio-based natural coating material that offers an eco-friendly solution for wood protection. This paper focused on the utilization of tung oil and beeswax as the primary raw materials for the preparation of wood wax oil. The WWO was based on the oxidation polymerization of tung oil, which served as the foundation for the preparation process. The effects of the photoinitiator TPO-L on the curing performance of the WWO were investigated, and the curing mechanism of the WWO system induced by photoinitiators was analyzed and characterized by infrared spectroscopy. Through ultraviolet irradiation experiments and coating quality tests, the effects of incremental photoinitiators on the properties of the surface drying time, gloss, color, hydrophobicity, and solution resistance of the treated ash wood were studied. The results indicated that the addition of photoinitiators was beneficial for the rapid polymerization of wood wax oil. A UV light intensity of 30 w was found to be sufficient to initiate the curing process. Specifically, when using TPO-L as the initiator at a concentration of 3 wt%, the surface could be surface-dried within 10 min under UV exposure. Under these curing conditions, wood wax oil coatings based on tung oil with comprehensive curing properties can be obtained. Additionally, adding 6% beeswax to the tung oil can effectively enhance the hydrophobicity of pure tung-oil-based wood protective coatings. Full article
(This article belongs to the Special Issue Recent Advances in Wood Coatings)
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16 pages, 4552 KB  
Article
Radiation Curing of Phosphorus Telomer-Based Coatings Using UV LEDs or Medium-Pressure Mercury Lamp
by Agata Kraśkiewicz and Agnieszka Kowalczyk
Materials 2023, 16(23), 7493; https://doi.org/10.3390/ma16237493 - 4 Dec 2023
Cited by 3 | Viewed by 2586
Abstract
In the presented study, UV LEDs (365 nm) or a medium-pressure mercury lamp (UV-ABC) were verified as UV radiation sources initiating the photocrosslinking process of varnishes based on novel photopolymerizable phosphorus (meth)acrylate oligomers. Coating formulations were composed of (meth)acrylic/styrene telomers with terminal P-atoms [...] Read more.
In the presented study, UV LEDs (365 nm) or a medium-pressure mercury lamp (UV-ABC) were verified as UV radiation sources initiating the photocrosslinking process of varnishes based on novel photopolymerizable phosphorus (meth)acrylate oligomers. Coating formulations were composed of (meth)acrylic/styrene telomers with terminal P-atoms (prepared via a UV phototelomerization process) and different photoinitiators (HAPs, APOs, or APO blends). The kinetics of the UV crosslinking process of the coating formulations depending on UV irradiation and the UV range was investigated by the photo-DSC method. Moreover, the hardness of the varnishes and the conversion of double bonds using the FTIR method were tested. The photopolymerization rate and the photoinitiation index, depending on the type of photoinitiator, were as follows: APOs < APO blends < HAPs. However, the highest coating hardness results were obtained using the least reactive photoinitiator from the APO group, i.e., Omnirad TPOL, or a mixture of three different types of acylphosphine (Omnirad BL 750). The greater effectiveness of the above-mentioned APOs over HAP was also demonstrated when using a UV LED lamp at 365 nm with a low UV dose and UV irradiance, thanks to the presence of phosphoric acid diester in the coating composition, acting as both a telogen and an antioxidant. Full article
(This article belongs to the Topic Advances in Functional Thin Films)
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13 pages, 1149 KB  
Article
Can TPO as Photoinitiator Replace “Golden Mean” Camphorquinone and Tertiary Amines in Dental Composites? Testing Experimental Composites Containing Different Concentration of Diphenyl(2,4,6-trimethylbenzoyl)phosphine Oxide
by Andrea Kowalska, Jerzy Sokołowski, Małgorzata Iwona Szynkowska-Jóźwik, Tomasz Gozdek, Karolina Kopacz and Kinga Bociong
Int. J. Mol. Sci. 2022, 23(19), 11594; https://doi.org/10.3390/ijms231911594 - 30 Sep 2022
Cited by 12 | Viewed by 6894
Abstract
The aim of this research was to compare the biomechanical properties of experimental composites containing a classic photoinitiating system (camphorquinone and 2-(dimethylami-no)ethyl methacrylate) or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as a photoinitiator. The produced light-cured composites consisted of an organic matrix-Bis-GMA (60 wt.%), TEGDMA (40 [...] Read more.
The aim of this research was to compare the biomechanical properties of experimental composites containing a classic photoinitiating system (camphorquinone and 2-(dimethylami-no)ethyl methacrylate) or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) as a photoinitiator. The produced light-cured composites consisted of an organic matrix-Bis-GMA (60 wt.%), TEGDMA (40 wt.%) and silanized silica filler (45 wt.%). Composites contained 0.27; 0.5; 0.75 or 1 wt.% TPO. Vickers hardness, microhardness (in the nanoindentation test), diametral tensile strength, resistance to three-point bending and the CIE L* a* b* colorimetric analysis was performed with each composite produced. The highest average Vickers hardness values were obtained for the composite containing 1 wt.% TPO (43.18 ± 1.7HV). The diametral tensile strength remains on regardless of the type and amount of photoinitiator statistically the same level, except for the composite containing 0.5 wt.% TPO for which DTS = 22.70 ± 4.7 MPa and is the lowest recorded value. The highest average diametral tensile strength was obtained for the composite containing 0.75 wt.% TPO (29.73 ± 4.8 MPa). The highest modulus of elasticity characterized the composite containing 0.75 wt.% TPO (5383.33 ± 1067.1 MPa). Composite containing 0.75 wt.% TPO has optimal results in terms of Vickers hardness, diametral tensile strength, flexural strength and modulus of elasticity. Moreover, these results are better than the parameters characterizing the composite containing the CQ/DMAEMA system. In terms of an aesthetic composite containing 0.75 wt.%. TPO is less yellow in color than the composite containing CQ/DMAEMA. This conclusion was objectively confirmed by test CIE L* a* b*. Full article
(This article belongs to the Section Materials Science)
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16 pages, 2066 KB  
Article
Cytotoxicity, Colour Stability and Dimensional Accuracy of 3D Printing Resin with Three Different Photoinitiators
by Gi-Tae Kim, Hye-Bin Go, Jae-Hun Yu, Song-Yi Yang, Kwang-Mahn Kim, Sung-Hwan Choi and Jae-Sung Kwon
Polymers 2022, 14(5), 979; https://doi.org/10.3390/polym14050979 - 28 Feb 2022
Cited by 70 | Viewed by 9595
Abstract
Biocompatibility is important for the 3D printing of resins used in medical devices and can be affected by photoinitiators, one of the key additives used in the 3D printing process. The choice of ingredients must be considered, as the toxicity varies depending on [...] Read more.
Biocompatibility is important for the 3D printing of resins used in medical devices and can be affected by photoinitiators, one of the key additives used in the 3D printing process. The choice of ingredients must be considered, as the toxicity varies depending on the photoinitiator, and unreacted photoinitiator may leach out of the polymerized resin. In this study, the use of ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate (TPO-L) as a photoinitiator for the 3D printing of resin was considered for application in medical device production, where the cytotoxicity, colour stability, dimensional accuracy, degree of conversion, and mechanical/physical properties were evaluated. Along with TPO-L, two conventional photoinitiators, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BAPO) and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (TPO), were considered. A total of 0.1 mol% of each photoinitiator was mixed with the resin matrix to prepare a resin mixture for 3D printing. The specimens were printed using a direct light processing (DLP) type 3D printer. The 3D-printed specimens were postprocessed and evaluated for cytotoxicity, colour stability, dimensional accuracy, degree of conversion, and mechanical properties in accordance with international standards and the methods described in previous studies. The TPO-L photoinitiator showed excellent biocompatibility and colour stability and possessed with an acceptable dimensional accuracy for use in the 3D printing of resins. Therefore, the TPO-L photoinitiator can be sufficiently used as a photoinitiator for dental 3D-printed resin. Full article
(This article belongs to the Special Issue Polymeric Biomaterials and Drug Delivery Systems)
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12 pages, 4427 KB  
Article
Ultra-High Through-Cure of (Meth)Acrylate Copolymers via Photofrontal Polymerization
by Catharina Ebner, Julia Mitterer, Paul Eigruber, Sebastian Stieger, Gisbert Riess and Wolfgang Kern
Polymers 2020, 12(6), 1291; https://doi.org/10.3390/polym12061291 - 4 Jun 2020
Cited by 24 | Viewed by 5263
Abstract
Photopolymerization offers substantial advantages in terms of time, temperature, energy consumption, and spatial control of the initiation. The application however is strongly limited due to the constrained penetration of light into thick films. Strategies to overcome the problem of limited curing depth, as [...] Read more.
Photopolymerization offers substantial advantages in terms of time, temperature, energy consumption, and spatial control of the initiation. The application however is strongly limited due to the constrained penetration of light into thick films. Strategies to overcome the problem of limited curing depth, as well as to improve the curing of shadow areas, involve dual curing, frontal polymerization, and upconversion of particles. Whereas excellent results have been accomplished applying photofrontal polymerization on a theoretical level, few studies report on practical applications achieving high curing depth within short time. This study aims to investigate the potential of photofrontal polymerization, performed only with photoinitiator and light, for the fast and easy production of several-centimeter-thick (meth)acrylic layers. Monomer/ initiator systems were evaluated with respect to their optical density as well as photobleaching behavior. Moreover, depth-dependent polymerization was studied in specimens of varying monomer ratio and photoinitiator concentration. When an ideal photoinitiator concentration was selected, curing up to 52 mm in depth was accomplished within minutes. Full article
(This article belongs to the Special Issue Photopolymers)
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9 pages, 1787 KB  
Article
New Phosphine Oxides as High Performance Near- UV Type I Photoinitiators of Radical Polymerization
by Céline Dietlin, Thanh Tam Trinh, Stéphane Schweizer, Bernadette Graff, Fabrice Morlet-Savary, Pierre-Antoine Noirot and Jacques Lalevée
Molecules 2020, 25(7), 1671; https://doi.org/10.3390/molecules25071671 - 4 Apr 2020
Cited by 80 | Viewed by 8110
Abstract
Carbazole structures are of high interest in photopolymerization due to their enhanced light absorption properties in the near-UV or even visible ranges. Therefore, type I photoinitiators combining the carbazole chromophore to the well-established phosphine-oxides were proposed and studied in this article. The aim [...] Read more.
Carbazole structures are of high interest in photopolymerization due to their enhanced light absorption properties in the near-UV or even visible ranges. Therefore, type I photoinitiators combining the carbazole chromophore to the well-established phosphine-oxides were proposed and studied in this article. The aim of this article was to propose type I photoinitiators that can be more reactive than benchmark phosphine oxides, which are among the more reactive type I photoinitiators for a UV or near-UV light emitting diodes (LED) irradiation. Two molecules were synthesized and their UV-visible light absorption properties as well as the quantum yields of photolysis and photopolymerization performances were measured. Remarkably, the associated absorption was enhanced in the 350–410 nm range compared to benchmark phosphine oxides, and one compound was found to be more reactive in photopolymerization than the commercial photoinitiator TPO-L for an irradiation at 395 nm. Full article
(This article belongs to the Special Issue Photosensitizer: Design, Characteriazation and Application)
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11 pages, 3703 KB  
Article
Visible Light Photoinitiator for 3D-Printing of Tough Methacrylate Resins
by Bernhard Steyrer, Philipp Neubauer, Robert Liska and Jürgen Stampfl
Materials 2017, 10(12), 1445; https://doi.org/10.3390/ma10121445 - 19 Dec 2017
Cited by 127 | Viewed by 15798
Abstract
Lithography-based additive manufacturing was introduced in the 1980s, and is still the method of choice for printing accurate plastic parts with high surface quality. Recent progress in this field has made tough photopolymer resins and cheap LED light engines available. This study presents [...] Read more.
Lithography-based additive manufacturing was introduced in the 1980s, and is still the method of choice for printing accurate plastic parts with high surface quality. Recent progress in this field has made tough photopolymer resins and cheap LED light engines available. This study presents the influence of photoinitiator selection and post-processing on the thermomechanical properties of various tough photopolymers. The influence of three photoinitiators (Ivocerin, BAPO, and TPO-L) on the double-bond conversion and mechanical properties was investigated by mid infrared spectroscopy, dynamic mechanical analysis and tensile tests. It was found that 1.18 wt % TPO-L would provide the best overall results in terms of double-bond conversion and mechanical properties. A correlation between double-bond conversion, yield strength, and glass transition temperature was found. Elongation at break remained high after post-curing at about 80–100%, and was not influenced by higher photoinitiator concentration. Finally, functional parts with 41 MPa tensile strength, 82% elongation at break, and 112 °C glass transition temperature were printed on a 405 nm DLP (digital light processing) printer. Full article
(This article belongs to the Special Issue NextGen Materials for 3D Printing)
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