Free solvent

In addition to demonstrating the excellent reaction control obtained through the use of continuous flow reactors, these examples also illustrate the ability to reduce reaction 

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An alternative hexafluorobenzene process features exchange fluorination (KF) of hexachlorobenzene in the presence of polar solvents (226,249) or under solvent-free conditions (450—540°C, autoclave) (250). Intermediates such as chloropentafluorobenzene can be further fluorinated to hexafluorobenzene (42—51% yield) by cesium fluoride in sulfolane (226,249). 

Triduoropyriaiidiae can be prepared ia 85% yield from 2,4,6-trichloropyrioiidiae [3764-01-0] and potassium fluoride ia sulfolane or solvent-free conditions (458,459). Derivatives such as l,l,l-trichloro-3-[5-(2,4,6-trifluoropyrimidyl)]-3,4-epoxybutane [121058-68-2] have been prepared as potential herbicides (460). 

Condensation ofDianhydrides with Diamines. The preparation of polyetherknides by the reaction of a diamine with a dianhydride has advantages over nitro-displacement polymerization sodium nitrite is not a by-product and thus does not have to be removed from the polymer, and a dipolar aprotic solvent is not required, which makes solvent-free melt polymerization a possibiUty. Aromatic dianhydride monomers (8) can be prepared from A/-substituted rutrophthalimides by a three-step sequence that utilizes the nitro-displacement reaction in the first step, followed by hydrolysis and then ring closure. For the 4-nitro compounds, the procedure is as follows. 

Higher alkoxides, such as tetra(2-ethylhexyl) titanate, TYZOR TOT [1070-10-6], can be prepared by alcohol interchange (transestenfication) in a solvent, such as benzene or cyclohexane, to form a volatile a2eotrope with the displaced alcohol, or by a solvent-free process involving vacuum removal of the more volatile displaced alcohol. The affinity of an alcohol for titanium decreases in the order primary > secondary > tertiary, and... 

The solvent-free mono- -butyl, monoisopropyl bis-acetylacetone titanate, TYZOR AA95 [9728-09-9] is a Hquid at room temperature. By carefully controlling the mixture of alcohols used as solvent, a product, TYZOR GBA can be obtained, which is cold-storage-stable even in the presence of nucleating agents (96). 

Drawing pseudo-binaryjy—x phase diagrams for the mixture to be separated is the easiest way to identify the distillate product component. A pseudo-binary phase diagram is one in which the VLE data for the azeotropic constituents (components 1 and 2) are plotted on a solvent-free basis. When no solvent is present, the pseudo-binaryjy—x diagram is the tme binaryjy—x diagram (Eig. 8a). At the azeotrope, where the VLE curve crosses the 45° line,... 

Fig. 8. Pseudo-binary (solvent-free)jy-x phase diagrams for determining which component is to be the distillate where (—) is the 45° line, (a) No solvent (b) and (c) sufficient solvent to eliminate the pseudo-a2eotiope where the distillate is component 1 and component 2, respectively (51) and (d) experimental VLE data for cyclohexane—ben2ene where A, B, C, and D represent 0, 30, 50, and 90 mol % aniline, respectively (52).

Several patents describe solvent-free bulk-phase halogenation (67—69). Dry soHd butyl mbber is fed into a specially designed extmder reactor and contacted with chlorine or bromine vapor. The by-product HCl or HBr ate vented directly without a separate neutralization step. Halogenated butyl mbbers produced are essentially comparable in composition and properties to commercial products made by the solution process. 

Owing to relatively low viscosity, these resins offer advantages for 100% soHds (solvent-free) systems. Higher filler levels are possible because of the low viscosity. Faster bubble release is also achieved. Higher epoxy content and functionaHty of bisphenol F epoxy resins can provide improved chemical resistance compared to conventional epoxies. 

Comparisons of the properties of solvent-free Hquid coatings based on unmodified bisphenol A epoxies cured with varying amine hardeners are shown in Table 6. Examples include diethylenetriamine [111-40-0] H2NC2H4NHC2H4NH2 (7), triethylenetetramine [112-24-3] ... 

High Solids Costings. High soHds coatings resemble the technology of solvent-free coatings but the compositions contain ca 70% by volume of soHd resin and are modified by reactive diluents, low viscosity multifunctional resins, or backbone stmctures other than the bisphenol A moiety. 

A solvent free, fast and environmentally friendly near infrared-based methodology was developed for the determination and quality control of 11 pesticides in commercially available formulations. This methodology was based on the direct measurement of the diffuse reflectance spectra of solid samples inside glass vials and a multivariate calibration model to determine the active principle concentration in agrochemicals. The proposed PLS model was made using 11 known commercial and 22 doped samples (11 under and 11 over dosed) for calibration and 22 different formulations as the validation set. For Buprofezin, Chlorsulfuron, Cyromazine, Daminozide, Diuron and Iprodione determination, the information in the spectral range between 1618 and 2630 nm of the reflectance spectra was employed. On the other hand, for Bensulfuron, Fenoxycarb, Metalaxyl, Procymidone and Tricyclazole determination, the first order derivative spectra in the range between 1618 and 2630 nm was used. In both cases, a linear remove correction was applied. Mean accuracy errors between 0.5 and 3.1% were obtained for the validation set. 

Mancozeb is a dithiocarbamate pesticide with a very low solubility in organic and inorganic solvent. In this work we have developed a solvent free, accurate and fast photoacoustic FTIR-based methodology for Mancozeb determination in commercial fungicides. The proposed procedure was based on the direct measurement of the solid samples in the middle infrared region using a photoacoustic detector. A multivariate calibration approach based on the use of partial least squares (PLS) was employed to determine the pesticide content in commercially available formulations. 

T Ichiye. Solvent free energy curves for electron transfer A non-lmear solvent response model. J Chem Phys 104 7561-7571, 1996. 

Films may be made by casting (I) and heating to produce the polyimide (II). Tough thin film may be obtained by heating for 1-2 hours at 150°C but thicker products tend to become brittle. A substantial improvement can be obtained in some cases if a further baking of solvent-free polymer is carried out at 300°C for a few minutes. 

Addition cure silicones can be delivered from solvent, waterborne emulsions, or 100% solids systems. The solvent free versions employ base polymers of intermediate molecular weight to achieve processable viscosity. These base polymers can have reactive moieties in terminal and/or pendant positions. These lower molecular weight, more functional systems result in a tighter crosslink network which feels rubbery to the hand. Low amounts of high molecular weight additives are included in some formulations to provide a more slippery feel [51,52]. 

Figure 43. Equilibrium curve on solvent free basis.

It may even be possible to eliminate solids handling by processing in a solution. However, this may require an assessment of the hazards of a toxic or flammable solvent in a process compared to the hazards of the solvent-free process. 

Treatment of the solvent-free chromatogram with iodine vapor or by dipping in or spraying with iodine solution (0.5 — 1%) is a rapid and economical universal method of detecting lipophilic substances. Molecular iodine is enriched in the chromatogram zones and colors them brown. 

In practice a few iodine crystals are usually placed on the bottom of a dry, closed trough chamber. After the chamber has become saturated with violet iodine vapor the solvent-free plates are placed in the chamber for 30 s to a few minutes. The iodine vapor condenses on the TLC layers and is enriched in the chromatogram zones. Iodine vapor is a universal detector, there are examples of its application for all types of substances, e.g. amino acids, indoles, alkaloids, steroids, psychoactive substances, lipids (a tabular compilation would be too voluminous to include in this section). 

It is becoming ever more usual to dip the solvent-free chromatograms into a... 

Ascending, one-dimensional development in a twin-trough chamber with chamber saturation with the layer being preconditioned in the solvent-free half of the trough for 15 min after application of the sample. 

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