Photopolymerization thin films

This effect is particularly important for photopolymerized thin films. In an open air environment, oxygen continually diffuses into the film from the air-film interface ... 

The objective of the present work was to determine the influence of the light intensity on the polymerization kinetics and on the temperature profile of acrylate and vinyl ether monomers exposed to UV radiation as thin films, as well as the effect of the sample initial temperature on the polymerization rate and final degree of cure. For this purpose, a new method has been developed, based on real-time infrared (RTIR) spectroscopy 14, which permits to monitor in-situ the temperature of thin films undergoing high-speed photopolymerization, without introducing any additive in the UV-curable formulation 15. This technique proved particularly well suited to addressing the issue of thermal runaway which was recently considered to occur in laser-induced polymerization of divinyl ethers 13>16. 

In this contribution we present results obtained with tetra-ethyleneglycol diacrylate (TEGDA). This compound was chosen since its polymer shows an easily discernible maximum in the mechanical losses as represented by tan 5 or loss modulus E" versus temperature when it is prepared as a thin film on a metallic substrate. When photopolymerized at room temperature it forms a densely crosslinked, glassy polymer, just as required in several applications. Isothermal vitrification implies that the ultimate conversion of the reactive double bonds is restricted by the diffusion-limited character of the polymerization in the final stage of the reaction. Therefore, the ultimate conversion depends strongly on the temperature of the reaction and so does the glass transition. 

In both of these cases, the ligand (sialic acid) for the analyte of interest (influenza vims) was covalently linked to the PDA backbone generated upon photopolymerization. Functional sensors based on ligands that are noncovalently incorporated into liposomes have also been reported (Charych et al. 1996 Pan and Charych 1997). Mixed liposomes as well as mixed thin films on glass containing a combination of the ganglioside GMl and diacetylene lipids detect the presence of cholera toxin, a protein that binds to GMl. 

Photopolymerization in thin films was carried out at 514 nm, the rate of heat evolution being measured by thin-foil photocalorimetry. The monomer formulation consisted of 85% TMPTA and 15% HDDA, giving a concen-... 

Because the cast films are relatively thin, the optical density of the light absorbing species can he low and can vary with time of exposure. Additionally, the depth penetration of the absorbed light can be inhomogeneous in some systems. However, thin films can be mounted directly in UV/visible or infrared spectrometers, and so the course of the photopolymerization (and the rate) can be monitored directly in some systems. The most common observation made is the disappearance of monomer (e.g., loss of double bond absorption in the IR) as a function of irradiation time. It must be emphasized that in most thin film compositions important industrially, the monomers used are multifunctional. The polymer which results is then highly cross-linked and simple kinetic arguments are usually not valid. 

Polymeric fullerene materials can be obtained by many methods, for example by irradiation with electrons or ions, treatment in a plasma generator, doping with alkali metals [9,28,46], direct chemical synthesis [47], or mechanical milling [29]. Because of the small penetration depth of light fullerenes can only be photopolymerized as thin films, but bulk photopolymer can be obtained by polymerization in solution [48,49]. Diffraction studies show that photopolymers usually have a disordered fee structure. Although some ordered films have been... 

Differential calorimetry has been applied to the study of rapid photopolymerizations. This new technique holds great promise for basic and applied research on photopolymerization and other photochemical reactions. The method requires only a few milligrams of sample, can be used on network-forming systems, and can approximate actual conditions of thin film and coating technologies. 

Polymerization of mesogenic monomers is very effective for obtaining more stable ordered thin films. Triphenylene monomer containing acrylate moiety 18 was photopolymerized by UV light irradiation (Fig. 17). UV light was shone onto the mixture of the triphenylene derivative and a photoinitiator under inert atmosphere. Carrier transport characteristics of the ob-... 

For application to thin film transistors (TFTs), which can operate electronic papers, high carrier mobility exceeding 0.01 cm2 V-1 s-1 is necessary. For this purpose, nematic semiconductors with low molecular order, resulting in relatively low carrier mobility, are not suitable. For application of thin films of semiconductors to TFTs, stabilization of the highly ordered smectic phases, which exhibit high carrier mobility, by photopolymerization may be desirable. Kreouzis et al. studied the carrier transport properties of photopolymer-izable phenylnaphthalene, diphenylbithiophene, and quaterthiophene derivatives having an oxetane moiety or l,4-pentadien-3-yloxy in their alkyl side chain (Fig. 21) [107,108],... 

Thin films of poly-l,2-azepines formed by the photopolymerization of phenyl azides exhibit electric conductivities of up to 0.01 S cm upon oxidative doping with iodine or arsenic pen-tafluoride <88JA7209>. 

Keller and coworkers synthesized monodomain nematic side-on elastomers containing azobenzenes (Components 18a,b) by photopolymerization with a near-infrared photoinitiator (Li et al., 2003). The photopolymerization was performed with aligned nematic azobenzene monomers in conventional LC cells. Thin films of these LCEs showed fast (less than 1 min) photochemical contraction of up to 18% upon irradiation with UV light and a slow thermal back-reaction in the dark (Fig. 3.22). 

Thus, research on ways to refine the use of polymer stationary phases within the pGC channel design also continues. Examples include using UV photopolymerization of gas-phase monomers for thin-film depositimi [8] and plasma polymerization [9]. 

The photoinitiated polymerizations were followed by real-time infrared spectroscopy on thin films, radiation. The rates of polymerization were reported by them to increase with the light intensity according to a nearly square root law, up to an upper limit. The upper limit or the saturation effect was attributed by them to a fast consumption of flie photoinitiator under intense illumination. A strong correlation was found to exist between flie rate at which the temperature increases and fire rate of polymerization. The temperature shows the same light intensity dependence as the reaction rate, and levels off to a maximum value under intense illumination. Photopolymerization experiments carried out at a constant temperature of 25"C show that thermal runaway is not responsible for the increase of the polymerization rate observed at the beginning oftheUV exposure. 

Thermal or photo-polymerization of multi-functional low molar mass monomer results in a high, densely crosslinked network. Liquid crystallinity of monomers or precursors can be frozen in after in situ polymerization. Interestingly, some monomers are not liquid crystalline themselves however, as the curing reaction proceeds, a nematic phase is developed and finally remained. Photopolymerization is divorced from the thermal properties of the material, while thermal polymerization is limited by the finite temperature range over which the liquid crystal phase can exist. But photopolymerization can be only suitable for thin film sample due to the limitation of the penetrating ability of the light used. 

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