Photoinitiators with functional groups. VII. Covalently bonded camphorquinone—amines

Camphorquinone (CQ), a widely used photoinitiator (PI) in dental applications, was covalently bonded to aromatic amines to enhance the rate of electron and proton transfer effect due to the close vicinity of the diketone and the amine group. 10‐bromocamphorquinone and 10‐bromomethylcamphorquinone were selected as suitable precursors for esterification with the carboxyl group containing aromatic amines based on 4‐dimethylaminobenzoic acid. Properties of the new photoinitiating systems were investigated by UV spectroscopy and differential scanning photocalorimetry in lauryl acrylate. Compared to physical mixtures, in all cases similar or even better performance was obtained. Surprisingly, 10‐acetyl derivatives 7 – 9 and 18 especially, were found to be highly reactive. Compared to CQ/ethyl 4‐dimethylaminobenzoate, the rate of photopolymerization was increased by a factor of up to 2. Intramolecular reaction was confirmed by photo‐differential scanning calorimetry experiments with varying PI concentrations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4948–4963, 2004     

Use of α‐diketones as visible photoinitiators for the photocrosslinking of waterborne latex paints

The efficiency of several α‐diketones as visible light photoinitiators for the crosslinking of waterborne latex dispersions in the presence of acrylic monomers was evaluated. Among the eight α‐diketones studied, camphorquinone allows the fastest curing speed, and the curing of the acrylic waterborne coating is not affected by the presence of oxygen. The properties of the sunlight‐cured volatile organic compound (VOC)‐free pigmented paints prepared from the waterborne latex are as good or better than the equivalent conventional paint containing VOCs. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3171–3181, 2002     

樟脑醌合成的研究进展

樟脑醌是由樟脑衍生的重要精细化工产品，它在国际市场上的价格是樟脑的数十倍甚至上百倍。我国主要将樟脑作为初级产品出口，在樟脑的高值化衍生物的开发方面还较薄弱。本文详述了近四十年来，国际上对樟脑醌的合成及应用的研究进展。     

Regioselective Short Synthesis of Epiisoborneol Neopentyl Ether as Chiral Auxiliary: An Absolute Configuration Reset

The regio-selective four step synthesis of (1S,2R,3S,4R)-4,7,7-trimethyl-3-(neopentyloxy)bicyclo[2.2.1]heptan-2-ol, as recognized efficient chiral auxiliary, is presented. The strategy based on opening of the key acetal 15 (=(2S,3aR,4S,7R,7aS)-2-tert-butyl-4,8,8-trimethylhexahydro-2H-4,7-methano-1,3-benzodioxole) thus circumvents the poor reactivity of the neopentyl electrophile under alkylation conditions. Following the same strategy, but using the unreported acetal 22 (=(2R,3aS,4S,7R,7aR)-2-tert-butyl-4,8,8-trimethylhexahydro-2H-4,7-methano-1,3-benzodioxole), the corresponding unreported bis-endo alcohol 23 (=(1R,2R,3S,4S)-3-(2,2-dimethylpropoxy)-4,7,7-trimethylbicyclo[2.2.1]heptan-2-ol) could be isolated only in poor yield. An alternative regioselective synthesis, including an ultimate endo-reduction remains to be found. Several erroneous chiroptical properties from the literature are corrected.     

Polymerization kinetics of phosphonic acids and esters using an iodonium initiator

Phosphonic acids are known to be useful monomers in dental restorative materials because of their good potential to provide enhanced adhesion to hydroxyapatite and their high hydrolytic stability. In this study, the photopolymerization of phosphonic acid‐based monomer via the camphorquinone (CQ)/ethyl‐4‐(dimethylaminobenzoate) (EDAB) photoredox system is compared with a ternary system composed of iodonium hexafluorophosphate and CQ/EDAB. Photocalorimetry shows that the ternary system does not provide a significant acceleration of the polymerization with either acrylamide or methacrylate phosphonic acids. The complexation of the iodonium by the phosphonic moiety of the acidic monomers leads to a lowered iodonium reactivity and reduced polarizability of the medium and as a consequence limits the rate enhancement effect normally observed by phosphonic acids on the polymerization rate. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5046–5055     

Physical aging and dye diffusion in polysulfone below the glass transition temperature

The effect of physical aging on the tracer diffusion coefficient D of camphorquinone in polysulfone is investigated. It is shown that if the sample is sufficiently annealed and physical aging is nearly complete, the temperature dependence of D will reflect the primary α-relaxation process of the host polymer. In the temperature range between T_g (=185°C) and 165°C, D is found to be a function of time, and the time dependence of D is given by D = At^?μ, with μ approximately equal to unity. © 1994 John Wiley & Sons, Inc.     

Diazonium salts for surface‐confined visible light radical photopolymerization

The surface chemistry of aryl diazonium salts has progressed at a remarkable pace in the last two decades, and opened many avenues in materials science. These compounds are excellent coupling agents for polymers to surfaces via several surface‐confined polymerization methods. For the first time, we demonstrate that diazonium salts are efficient for surface initiating radical photopolymerization in the visible light of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA) taken as model monomers. To do so, 4‐(dimethylamino)benzenediazonium salt was electroreduced on gold plates or flexible ITO sheets to provide 4‐(dimethylamino)phenyl (DMA) hydrogen donor layers; while excited state camphorquinone acted as the free hydrogen abstractor. In the same way, we co‐polymerized HEMA and MMA with ethylene glycol dimethacrylate in order to obtain crosslinked polymer grafts. We demonstrate by XPS that gold was efficiently screened by the polymer layers and that the wettability of the surfaces accounts for the hydrophilic or hydrophobic characters of the tethered polymers. Homo‐ and crosslinked PMMA grafts were found to resist removal by the paint stripper methyl ethyl ketone. The grafted DMA/camphorquinone system operating in the visible light holds great promises in terms of adhesion of in situ designed continuous or patterned polymer coatings on various substrates. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3506–3515     

Visible and long‐wavelength photoinitiated cationic polymerization

A new system for efficiently carrying out cationic photopolymerizations with visible and long‐wavelength UV light is described. This system is based on the principle that certain onium salt cationic photoinitiators can be reduced by free radicals produced by the hydrogen abstraction reactions of photoexcited ketones. Thus, when camphorquinone, benzil, 2‐isopropylthioxanthone, and 2‐ethylanthraquinone are irradiated in the presence of a monomer that can serve as a hydrogen donor, the resulting monomer‐bound radical rapidly reduces a diaryliodonium salt or a dialkylphenacylsulfonium salt, and the resulting monomer‐centered cations initiate the polymerizations of epoxides, vinyl ethers, and heterocyclic compounds. Onium salts with high reduction potentials, such as triarylsulfonium salts, do not undergo sensitization by this new system. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 343–356, 2001     

Thioxanthonation of fluorenone: Visible photoinitiator for radical polymerization

Thioxanthonation of fluorenone resulted in a new visible light initiator namely, indeno [1,2‐b]thioxanthene‐7,13‐dione (TX–FN). The detailed photophysical properties of the singlet and the triplet excited states of TX–FN are reported using steady‐state absorption, fluorescence, and phosphorescence, as well as laser flash photolysis techniques. Photoinitiated polymerization of MMA with TX–FN and CQ has been investigated in the presence and absence of a co‐initiator (MDEA). Additionally, Photo‐DSC studies were performed both in mono‐ and multiacrylate systems with TX–FN and parent compounds TX and FN. The obtained results were compared for formulations consisting of CQ. At low initiator concentrations, the conversions were lower than those obtained with TX–FN. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1012–1019     

Preparation and characterization of a water soluble methylated β‐cyclodextrin/camphorquinone complex

A water soluble methylated β‐cyclodextrin/camphorquinone (MCD/CQ) complex, based on methylated β‐cyclodextrin (MCD) and camphorquinone (CQ), was prepared and its structure was characterized by FTIR, ¹H‐NMR, and UV–vis spectra. The photopolymerization kinetics of MCD/CQ in the water soluble monomer system was studied by Real‐time Infrared spectroscopy (RT‐IR). Compared to the photopolymerization carried out under nearly identical conditions but without MCD, the polymerization rate and final conversion initiated by a CQ‐triethanolamine photoinitiator system were slightly lower. The effects of different MCD/CQ concentration, triethanolamine concentration, and light intensity were also studied. Copyright © 2009 John Wiley & Sons, Ltd.