Solvent reactivation

Bond strength can vary from a temporary bond (non-curing compound) to a substrate tearing bond (using phenolic-modified curing products). Solvent-borne CR adhesives can be formulated to have very short open times for fast production operations or to retain contact bond characteristics for up to 24 h. Heat and solvent reactivation can be used to re-impart tack to dried surfaces. 

Another method for studying solvent effects is the extrathermodynamic approach that we described in Chapter 7 for the study of structure-reactivity relationships. For example, we might seek a correlation between og(,kA/l ) for a reaction A carried out in a series of solvents and log(/ R/A R) for a reference or model reaction carried out in the same series of solvents. A linear plot of og(k/iJk ) against log(/ R/ linear free energy relationship (LFER). Such plots have in fact been made. As with structure-reactivity relationships, these solvent-reactivity relationships can be useful to us, but they have limitations. 

Based on alkylaluminum families, initiator reactivity is found to decrease as EtAlQ2 > Et2 A1X > Me3Al and for Et2AlX systems as, Et2 All > Et2 AlBr > Et2AlCl. Based on initiator efficiencies at —60 °C, an overall initiator/coinitiator/ solvent reactivity sequence has been developed. 

Non-Aqueous Colloidal Metal Solutions. It has been difficult to prepare colloidal gold in non-aqueous media due to limitations in preparative methods (low salt solubilities, solvent reactivity, etc.), and the fact that the low dielectric constant of organic solvents has hindered stabilization of the particles. In aqueous solution the gold particles are stabilized by adsorption of innocent ions, such as chloride, and thus stabilized toward flocculation by the formation of a charged double layer, which is dependent on a solvent of high dielectric constant. Thus, it seemed that such electronic stabilization would be poor in organic media. 

The second series of data on protic solvent effects in bromination that are related to transition states comprises the m-values of solvent-reactivity correlations. First, it is important to underline that 7-parameters, the solvent ionizing powers, established from solvolytic displacements, work fairly well in this electrophilic addition. This is expected since bromination, like SN1 reactions, leads to a cation-anion pair by heterolytic dissociation of the bromine-olefin CTC, a process similar to the ionization of halogenated or ether derivatives (Scheme 14). 

If the formation of bromination intermediates is reversible, the experimental rate constants obtained by following bromine uptake are not those of the first ionization steps. It is therefore important to know whether return, shown to occur in halogenated media, can also occur in protic media, in which most of the kinetic data have been measured and structure- or solvent-reactivity relationships established. 

The Ni(II) complexes 6 and 7 have been found by Stiles [60] to be soluble catalysts for reductive dehalogenation when combined with NaBH4 or hydrazine at 25-45 °C in protic solvents. Reactivity toward the reducing system increased with the halogen content of the substrate. Aryl bromides were converted much faster than chlorides, polychlorobenzenes, however, reacted readily with stepwise loss of chlorine. 

Scheme 4.14 Solvent reactivity effects in one-pot oligosaccharide synthesis.

A number of reactions between metals (or metals and semi-metals) may be carried out by dissolving the elements in a suitable solvent , technically also termed a flux . The solvent may also act as a reactant and be involved in the formation of the compound (reactive solvent, reactive flux). Several fluxes, ranging from simple metallic elements up to complex substances have been used. 

Chemical manufacturers Strong acids and bases Spent solvents Reactive materials... 

The mechanism and thermodynamics of transesterification of acetate-ester enolates in the gas phase have been investigated. The catalytic effect of alkali-metal t-butoxide clusters on the rate of ester interchange for several pairs of esters has been determined in non-polar and weakly polar solvents. Reactivities increase in the order (Li+ < Na+ < K+ < Rb+ < Cs+) with the fastest rates reaching lO catalytic... 

Carbon dioxide removal by reactive absorption in amine solutions is also applied on the commercial scale, for instance, in the treatment of flue gas (see later in this chapter). Another possible application field of the technique is gas desulfurization, in which H2S is removed and converted to sulfur by means of reactive absorption. Aqueous solutions of ferric chelates (160-162) as well as tetramethylene sulfone, pyridine, quinoline, and polyglycol ether solutions of S02 (163,164) have been proposed as solvents. Reactive absorption can also be used for NOx reduction and removal from flue or exhaust gases (165,166). The separation of light olefins and paraffins by means of a reversible chemical com-plexation of olefins with Ag(I) or Cu(I) compounds in aqueous and nonaqueous solutions is another very interesting example of reactive absorption, one that could possibly replace the conventional cryogenic distillation technology (167). 

USEPA (1974) Proceedings of the Solvent Reactivity Conference. U.S. Environmental Protection Agency, EPA-650/3-74/040. Research Triangle Park, North Carolina. 

Typically, reactions are carried out open to air, at room temperature (rt), using a mixture of tBuOH/water (9 1) or MeCN/water (9 1) as solvent and sodium or potassium hydroxide as base. The presence of water suppresses undesired side reactions (e.g., Cannizzaro reaction, Williamson alkylation, solvent reactivity) [37]. Benzyl bromides are most commonly reported as the halide component. 

Reactions are known to be highly dependent on solvents and the nature of solvent-reactive intermediate interactions solvents can affect the reaction coordinate, the activation energy, and the overall reaction thermodynamics. Clusters, especially ionic clusters, show this behavior as well. The systems we have studied are a-substituted toluenes phenol is known to transfer a proton upon Si <- S0 excitation, but what happens for excited states of a-substituted benyzl alcohols (C6H5CH2OH) The results, which are presented in detail by Li and Bernstein (Bernstein 1992 Li and Bernstein 1992a,b) are unique and quite informative. They are different than those discussed by Jouvet and Solgadi in chapter 4 of this volume. 

If the depolymerization reaction proceeds by the mechanism of equations (1), (2) and (3) it should be possible to predict a solvent reactivity sequence. The relative reactivity is thus expected to be 3,5-xylenol > naphthol "v phenol > xylene > toluene > naphthalene > aniline-v benzaldehyde. This order, as measured by the indices for reaction used here, is not followed. 

Sc(OTf)3-catalyzed aldol reactions of silyl enol ethers with aldehydes have recently been successfully performed in micellar systems [60]. Although the reaction proceeded sluggishly in water (without organic solvents), reactivity was remarkably enhanced by the presence of a small amount of a surfactant. In these systems, versatile carbon-carbon bond-forming reactions proceeded smoothly in water without the use of organic solvents. 

Lahmann, M, Oscarson, S, One-pot oligosaccharide synthesis exploiting solvent reactivity effects, Org. Lett., 2, 3881-3882, 2000. 

Metal electrodes of this kind require that neither the metal nor the metal cation reacts chemically with the solvent reactive metals may, however, be used as their amalgams. 

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