ROMP based photoinitiator‐coinitiator systems with improved migration stability

Nowadays, migration stability is one of the key features for photoinitiators used in radiation curable formulations, especially when the material is in contact with food or the human body. Herein, the synthesis and characterization of statistical copolymers with covalently bound eosin and/or ethyl dimethylamino benzoate units by ring opening metathesis polymerization is presented. The prepared compounds were tested as macroinitiators for the photopolymerization of acrylates aiming at an initiator/coinitiator system which combines good polymerization activity with improved migration stability. An acrylate modified eosin derivative which is incorporated into the polymer network during the photopolymerization reaction and, therefore, less likely to leak from the polymer compound was used as reference. Photoinitiating activities of low and high molecular weight initiators and coinitiators were investigated by photo‐DSC. Moreover, leakage studies and viability tests with osteoblast‐like cells were performed to proof the suitability of this concept. The use of polymeric eosin in combination with a low molecular weight coinitiator was found to be a good compromise when aiming at a photoinitiating system with sound performance and improved migration stability. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3648–3661, 2008     

Controlled radical polymerization of 2‐hydroxyethyl methacrylate initiated by photofunctional 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid

We demonstrated that density functional theory calculations provide a reliable and quantitative prediction of the trends in C? S bond dissociation energies using several model compounds as photoinitiator. On the basis of this information, we designed a possible photofunctional initiator for the polymerization of hydrophilic vinyl monomers. Photopolymerization of 2‐hydroxyethyl methacrylate (HEMA) hydrophilic monomer was carried out in ethanol initiated by 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid (DTCA) under UV irradiation. We performed the first‐order time‐conversion plots in this polymerization system, and the straight line in the semilogarithmic coordinates indicated first order in monomer. The molecular weight of the poly(2‐hydroxyethyl methacrylate) (PHEMA) increased with increasing conversion. The molecular weight distribution (M_w/M_n) of the PHEMA was about 1.5. Methyl methacrylate (MMA) could also be polymerized in a living fashion with such a PHEMA precursor as a macroinitiator because PHEMA exhibited a dithiocarbamate (DC) group at its terminal end. This system could be applied to the architecture of amphiphilic block copolymers. It was concluded that these polymerization systems proceeded with controlled radical mechanism. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 76–82, 2004     

PHOTOPOLYMERIZATION OF PROPARGYL ACETATE WITH MICHLER’S KETONE AS PHOTOINITIATOR

Photopolymerization of propargyl acetate (PAT) with Michler's ketone (MK) asphotoinitiator in benzene has been investigated for the first time. Some features of the PATphotopolymerization with MK as photoinitiator is described.     

Kinetic study of light-induced polymerization by real-time UV and IR spectroscopy

Real time ultraviolet (RTUV) spectroscopy was used to study the photolysis kinetics of a radical-type morpholino initiator, during the polymerization of a multiacrylate monomer exposed to UV radiation in bulk, in solution, in a polyurethane-acrylate resin, and in a poly(methyl methacrylate) matrix. The photolysis rate constant k was determined from the exponential loss profile recorded; it was found to vary between 0.1 and 3s^?1, depending on the light intensity and on the monomer concentration. The quenching of the photoinitiator excited states by the acrylate monomer was shown to be an important deactivation pathway which substantially reduces the rate of initiation. The observed influence of the film thickness and photoinitiator concentration on the k value were accounted for by the internal filter effect. Conversion versus time curves were recorded by real time infrared (RTIR) spectroscopy for the various systems examined, thus allowing a direct comparison of both the actual polymerization rate and the residual unsaturation content of the cured polymer. Various factors were shown to be responsible for the early stop of the polymerization, such as depletion of the photoinitiator, O₂ inhibition, or vitrification of the polymer. The photoinitiated cationic ring-opening polymerization of a cycloaliphatic diepoxy monomer was also studied in real time by RTUV and RTIR spectroscopy. Despite a very fast photolysis of the triarylsulphonium initiator, the polymerization of the epoxy monomer developed less rapidly than for the acrylic monomer, with shorter kinetic chain lengths. A linear relationship was found to exist between the decay rate constant and the light intensity, for both the radical and the cationic photoinitiators, as expected for a direct photolysis process.     

Fluorescent Brighteners as Visible LED‐Light Sensitive Photoinitiators for Free Radical Photopolymerizations

The photochemical and electrochemical investigations of commercially available, safe, and cheap fluorescent brighteners, namely, triazinylstilbene (commercial name: fluorescent brightener 28) and 2,5‐bis(5‐tert‐butyl‐benzoxazol‐2‐yl)thiophene, as well as their original use as photoinitiators of polymerization upon light emitting diode (LED) irradiation are reported. Remarkably, their excellent near‐UV–visible absorption properties combined with outstanding fluorescent properties allow them to act as high‐performance photoinitiators when used in combination with diaryliodonium salt. These two‐component photoinitiating systems can be employed for free radical polymerizations of acrylate. In addition, this brightener‐initiated photopolymerization is able to overcome oxygen inhibition even upon irradiation with low LED light intensity. The underlying photochemical mechanisms are investigated by electron‐spin resonance‐spin trapping, fluorescence, cyclic voltammetry, and steady‐state photolysis techniques.

     

N‐alkoxy pyridinium ion terminated polystyrenes: A facile route to photoinduced block copolymerization

Photoactive N‐alkoxy 4‐phenyl pyridinium and N‐alkoxy isoquinolinium ion terminated polystyrenes with hexafluoroantimonate counter anion were prepared and characterized. For this purpose, mono‐ and dibrominated polystyrenes were prepared by atom transfer radical polymerization (ATRP). The reaction of these polymers with silver hexafluoroantimonate in the presence of 4‐phenylpyridine N‐oxide and isoquinoline N‐oxide in dichloromethane produced desired polymeric salts with the corresponding functionalities. Irradiation of these photoactive polystyrenes produced alkoxy radicals at chain ends capable of initiating free radical polymerization of methyl methacrylate (MMA). This way, depending on the number of functionality, AB or ABA type block copolymers were formed which were characterized with the aid of gel permeation chromatography and ¹H NMR spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 423–428, 2007.     

Amine-linked thioxanthones as water-compatible photoinitiators

Six amine-linked thioxanthones, i.e., 2-(2-hydroxy-3-[bis(2-hydroxyethyl)amino]propoxy)thioxanthone (HAPTX) and its 4-methyl, 1,3-dimethyl, 1,4-dimethyl, 3,4-dimethyl, and 1,3,4-trimethyl substituted derivatives, were synthesized as water-compatible photoinitiators and identified with FTIR, MS, NMR, and elementary analysis. The absorption and fluorescence properties were studied. Their photoinitiating polymerization efficiencies were tested with a recording dilatometer utilizing acrylamide as monomer in aqueous solution. The results show that the six amine-linked thioxanthones can independently initiate acrylamide polymerization efficiently without additional external amines as co-initiators. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2563–2570, 1998     

Photopolymerization of styrene,p-chlorostyrene,methyl methacrylate,and butyl methacrylate with polymethylphenylsilane as photoinitiator

The rates of photochemical polymerization of styrene (St), p-chlorostyrene (Cl-St), methyl methacrylate (MMA), and butyl methacrylate (BMA) with polymethylphenylsilane (PMPS) as an initiator were measured. Polymethylphenylsilane is photodegrated to form silyl radicals that may initiate polymerization of vinyl monomers. Rate constants k_p and k_t have been determined for these systems. A good correlation (log P = α + βμ) of the resonance stabilization (P) of the chain radicals and the dipole moment (μ) of the monomers is observed for these polymerization systems. This equation may be used to estimate the resonance stabilization (P) of a monomer and the polymerization rate constant (k_p). © 1996 John Wiley & Sons, Inc.     

Synthesis and study of a novel hybrid UV photoinitiator: p-benzoyldiphenyliodonium hexafluorophosphate (PhCOPhI+PhPF)

A novel hybrid photoinitiator, p-benzoyldiphenyliodonium hexafluorophosphate (PhCOPhI⁺PhPF⁻₆), was synthesized, characterized, and studied. It absorbs UV light not only below 300 nm, but above 300 nm as well. When exposed to UV light, it undergoes an asymmetrical photocleavage to produce cation-radicals and radicals which could induce cationic and radical polymerizations respectively. Compared with the simple iodonium salt PhI⁺PhPF⁻₆, and bimolecular sensitization system PhCOPh/PhI⁺PhPF⁻₆, the covalently bonded photosensitization system PhCOPhI⁺PhPF⁻₆ is much more efficient as a photoinitiator. Oxygen has a small negative effect on the cationic polymerization photoinitiated by PhCOPhI⁺PhPF⁻₆, while isopropanol has a small positive influence only in argon atmosphere. © 1996 John Wiley & Sons, Inc.     

新型水性硫杂蒽酮类光引发剂的合成与性质

合成了１２ 种新的水性硫杂蒽酮类光引发剂,并经红外光谱、质谱、核磁共振以及元素分析等手段确证了化合物的结构,测定了其最大紫外吸收波长,计算了摩尔消光系数和荧光量子效率,并对化合物结构及其光化学性能之间的关系作了初步的探索．