Refractive index monomers

Title High Refractive Index Monomers, Compositions, and Uses Thereof... 

Research Focus Synthesis of high refractive index monomers of mono- and dimethacry-lates containing thiophene and disulfide for crosslinking with 2-hydroxy-ethyl methacrylate. 

TABLE 1. Physical Properties of Selected High Refractive Index Monomers "... 

Medina et al. (2) prepared a high refractive index monomer component, (I), for use in optical lenses by the photoinduced [2 + 2] dimerization of dimethyl-maleiimide, (I), as illustrated in Eq. (1). 

The low refractive index monomer, diethylene glycol bis allyl carbonate, was prepared by Khandel et al. (4) and used in plastic ophthalmic lenses. 

Such a selfoc is obtained in an analogous device, in which the pipe and the tumbler possess an elliptical cross-section (Figure 44). Pipe (1) with elliptical cross-section is filled by the monomer I with high refractive index, and the space between pipe (1) and tumbler (2) is filled by the monomer II with low refractive index. Monomers I and II are of the same density. 

Polymer Monomer CAS Registry r Density, Refractive index. 

Numerous methods for the deterrnination of monomer purity, including procedures for the deterrnination of saponification equivalent and bromine number, specific gravity, refractive index, and color, are available from manufacturers (68—70). Concentrations of minor components are deterrnined by iodimetry or colorimetry for HQ or MEHQ, by the Kad-Eisher method for water, and by turbidity measurements for trace amounts of polymer. 

Monomer Molecular weight Boiling point, °C Melting point, °C Refractive index, Density, g/cm ... 

Monomers such as methyl methacrylate [80-62-6] are often used in combination with styrene to modify refractive index and improve uv resistance. Vinyltoluene [25013-15-4] and diaHyl phthalate [131-17-9] are employed as monomers in selective mol ding compositions for thermal improvements. 

Light-focusing plastic rods and other optical devices with graduated refractive indexes may use DADC and other monomers (29). Preparation and properties of plastic lenses from CR-39 are reviewed in reference 30. 

Purified monomer is usually inhibited before shipment by such materials as copper resinate, diphenylamine or hydroquinone, which are generally removed before polymerisation. The monomer is a sweet-smelling liquid partially miscible with water and with the following properties boiling point at 760mmHg, 72.5°C specific gravity at 20°C, 0.934 refractive index 1.395 vapour... 

A more difficult criterion to meet with flow markers is that the polymer samples not contain interferents that coelute with or very near the flow marker and either affect its retention time or the ability of the analyst to reproducibly identify the retention time of the peak. Water is a ubiquitous problem in nonaqueous GPC and, when using a refractive index detector, it can cause a variable magnitude, negative area peak that may coelute with certain choices of totally permeated flow markers. This variable area negative peak may alter the apparent position of the flow marker when the flow rate has actually been invariant, thereby causing the user to falsely adjust data to compensate for the flow error. Similar problems can occur with the elution of positive peaks that are not exactly identical in elution to the totally permeated flow marker. Species that often contribute to these problems are residual monomer, reactants, surfactants, by-products, or buffers from the synthesis of the polymer. 

The refractive index detector, in general, is a choice of last resort and is used for those applications where, for one reason or another, all other detectors are inappropriate or impractical. However, the detector has one particular area of application for which it is unique and that is in the separation and analysis of polymers. In general, for those polymers that contain more than six monomer units, the refractive index is directly proportional to the concentration of the polymer and is practically independent of the molecular weight. Thus, a quantitative analysis of a polymer mixture can be obtained by the simple normalization of the peak areas in the chromatogram, there being no need for the use of individual response factors. Some typical specifications for the refractive index detector are as follows ... 

The normalization method is the easiest and most straightforward to use but, unfortunately, it is also the least likely to be appropriate for most LC analyses. To be applicable, the detector must have the same response to all the components of the sample. An exceptional example, where the normalization procedure is frequently used, is in the analysis of polymers by exclusion chromatography using the refractive index detector. The refractive index of a specific polymer is a constant for all polymers of that type having more than 6 monomer units. Under these conditions normalization is the obvious quantitative method to use. 

Published refractive index data for the mobile phase, polystyrene, polyacrylonitrile, and the two monomers were used to calculate refractive index detector calibrations for the two homopolymers. The published data were used to determine relationship between refractive index increments of monomer and corresponding homopolymer. Chromatographic refractometer calibrations for the two homopelymers were then calculated from experimentally measured calibration data for the two monomers. 

The next step in this study is to test this control algorithm on the actual laboratory reactor. The major difficulty is the direct measurement of the state variables in the reactor (T, M, I, W). Proposed strategy is to measure total mols of polymer (T) with visible light absorption and monomer concentration (M) with IR absorption. Initiator concentration (I) can be monitored by titrating the n-butyl lithium with water and detecting the resultant butane gas in a thermal conductivity cell. Finally W can be obtained by refractive index measurements in conjuction with the other three measurements. Preliminary experiments indicate that this strategy will result in fast and accurate measurements of the state vector x. 

The cmc is a key property, because it is related to the free energy difference between monomer and micelles. The onset of micellization is detected by marked changes in such properties as surface tension, refractive index and... 

Fig. 56. Dependence of specific refractive index increment on conversion of monomers to polymer for a styrene/acrylonitrile/methyl methacrylate terpolymer in methyl ethyl ketone at 20 °C and 436 nm. (a) - partial azeotrope, (b) terpolymer with composition distribution163 ...

It is appropriate at this point to briefly discuss the experimental procedures used to determine polymerization rates for both step and radical chain polymerizations. Rp can be experimentally followed by measuring the change in any property that differs for the monomer(s) and polymer, for example, solubility, density, refractive index, and spectral absorption [Collins et al., 1973 Giz et al., 2001 McCaffery, 1970 Stickler, 1987 Yamazoe et al., 2001]. Some techniques are equally useful for step and chain polymerizations, while others are more appropriate for only one or the other. Techniques useful for radical chain polymerizations are generally applicable to ionic chain polymerizations. The utility of any particular technique also depends on its precision and accuracy at low, medium, and high percentages of conversion. Some of the techniques have the inherent advantage of not needing to stop the polymerization to determine the percent conversion, that is, conversion can be followed versus time on the same reaction sample. 

The DnPont photopolymeric system consists of polymeric binder resins, e.g. PVA, PMMA, cellnlose acetates and styrene-acrylates, reactive acrylic monomers, e.g. aryloxy or alkoxy acrylates, a dye sensitiser and a radical or charge transfer photoinitiator, e.g. DEAW and HABI respectively (see Chapter 4, section 4.5.2), and plasticisers. The process for producing the refractive index structures is as follows ... 

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