Photopolymerization of methyl methacrylate using morpholine–bromine charge transfer complex as the photoinitiator
TL;DR: In this paper, the authors studied the photopolymerization of methyl methacrylate (MMA) using near UV/visible light at 40°C and employing the morpholine (MOR) −bromine (Br 2 ) charge transfer (CT) complex as the photoinitiator.
About: This article is published in European Polymer Journal.The article was published on 1998-05-01. It has received 12 citations till now. The article focuses on the topics: Bulk polymerization & Photopolymer.
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TL;DR: In this article, charge transfer complexes (CTC) between N-aromatic amines (donors) and iodonium salts (acceptors) are used as photoinitiating systems (PIS) for the polymerization of clear methacrylate formulations under a 405 nm LED irradiation.
Abstract: Charge transfer complexes (CTC) between N-aromatic amines (donors) and iodonium salts (acceptors) are used here as photoinitiating systems (PIS) for the polymerization of clear methacrylate formulations under a 405 nm LED irradiation. Outstandingly, a complete spatial and temporal resolution is kept for 50 μm resolved 3D printed photopolymers at 405 nm (50 μm being the size of the printing laser used here). Photocuring of a high thickness (31 cm) is also possible. The photopolymerization propagation is rationalized and interpreted from both experimental (using thermal imaging experiments) and predicted data. An experimental/molecular modeling study also attempts to rationalize the CTC structure/reactivity/efficiency relationships. These systems are commercially available, stable, and metal-free and have a low toxicity.
81 citations
TL;DR: In this paper, an update on charge transfer complexes (CTCs) as photoinitiating systems for photopolymerization applications is provided with examples of CTC-specific structure/reactivity/efficiency relationships.
61 citations
TL;DR: In this article, a novel strategy for the preparation of extremely thick composites by photochemical and/or thermal free radical polymerization (FRP) under low-energy consumption visible light emitted diodes (LEDs) is described.
Abstract: A novel strategy for the preparation of extremely thick composites by photochemical and/or thermal free radical polymerization (FRP) and/or cationic polymerization (CP) under low-energy consumption visible light emitted diodes (LEDs) is described. The approach is based on the use of charge transfer complexes (CTCs) formed between N-aromatic amines (donors) and iodonium salts (Iod, acceptors). Remarkably, it is demonstrated for the first time that these CTCs can be used as thermal initiators for free radical polymerization (FRP) initiation with performances comparable to dibenzoyl peroxide-based systems. The decomposition temperature of these CTC thermal initiators can be modulated through the selection of the amine, providing much safer conditions for synthesis, storage, and handling than that of the classical thermal initiators. A good stability in resin is also noted.
41 citations
TL;DR: In this article, the first polymeric charge transfer complexes (CTCs) based on iodinated polystyrene/amine interactions were used for photo-initiating in 3D polymer networks.
Abstract: In recent works, charge transfer complexes (CTCs) have proved to be useful photoinitiating agents to trigger free radical polymerization. However, because of their low molecular weights, migration issues remain very important. In line with pressing migration concerns around photoinitiating systems (e.g., in 3D polymer networks), we report here the use of the first polymeric CTC based on iodinated polystyrene/amine interactions. This study shows the formation of the CTC between the polystyrene derivative (electron acceptor EA) and a tertiary alkylamine (electron donor ED); the ability of this EA/ED couple in a CTC to act as a photoinitiator for the polymerization of multifunctional acrylates upon LED@405 nm irradiation is investigated. Examples of applications to 3D-resolved laser write of thick controlled samples (1 mm) are provided.
22 citations
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TL;DR: In this paper, the properties of dilute solutions of conventional polymethyl methacrylate designed to characterize the chain length and its distribution, the intramolecular chain interactions and the thermodynamic interactions with solvent and their effects on the chain dimensions, and to establish the accuracy and reproducibility of such data.
155 citations
TL;DR: In this paper, the authors derived an equation which allows determination of the classical efficiency of initiation as a function of [I]/[M]2 and also allowed a correction of Rp in handling the above equation by taking into account the small amount of monomer consumed in initiation.
89 citations
TL;DR: In this paper, low concentrations of bromine (0.008-0.06M) were used to initiate photopolymerization of MMA in bulk and in diluted (near bulk) systems, the diluents or solvents used being benzene, toluene, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, methylene chloride, and methanol.
Abstract: Low concentrations of bromine (0.008–0.06M) were used to initiate photopolymerization of MMA in bulk and in diluted (near bulk) systems, the diluents or solvents used being benzene, toluene, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, methylene chloride, and methanol. Polymerization in bulk follows usual free-radical kinetics. Inert solvents (benzene, toluene) as well as the other solvents used enhance the rate of polymerization MMA even when used in the range of catalytic concentrations (0.04–0.4M). An initiation mechanism involving solvent molecules appears to be predominant in diluted systems.
31 citations
15 citations