Bulk reactions

Shafer N E, Orr-Ewing A J, Simpson W R, Xu H and Zare R N 1993 State-to-state differential cross sections from photoinitiated bulk reactions Chem. Phys. Lett. 212 155-162... 

Acid chlorides are generally more reactive than the parent acids, so polyester formation via reaction 5 in Table 5.3 can be carried out in solution and at lower temperatures, in contrast with the bulk reactions of the melt as described above. Again, the by-product molecules must be eliminated either by distillation or precipitation. The method of interfacial condensation, described in the next section, can be applied to this type of reaction. 

The first pubHshed information on the halogenation of butyl mbber was provided by B. F. Goodrich Co. (2). Brominating agents such as /V-bromosuccinimide were used the bromination occurred ia a bulk reaction. This technology was commercialized ia 1954, but withdrawn ia 1969 (3). Exxon Chemical researchers pursued the chlorination of butyl mbber ia hexane solution usiag elemental chlorine, and a continuous process was commercialized ia 1961 (4). Currentiy, both chlorination and bromination are carried out ia continuous-solution processes. 

Bead Polymerization Bulk reaction proceeds in independent droplets of 10 to 1,000 [Lm diameter suspended in water or other medium and insulated from each other by some colloid. A typical suspending agent is polyvinyl alcohol dissolved in water. The polymerization can be done to high conversion. Temperature control is easy because of the moderating thermal effect of the water and its low viscosity. The suspensions sometimes are unstable and agitation may be critical. Only batch reaciors appear to be in industrial use polyvinyl acetate in methanol, copolymers of acrylates and methacrylates, polyacrylonitrile in aqueous ZnCh solution, and others. Bead polymerization of styrene takes 8 to 12 h. 

It may also be possible to crosslink the acrylic PSA with the help of multifunctional acrylates or methacrylates [87], These monomers can simply be copolymerized with the balance of the other monomers to form a covalently crosslinked network in one step. Since the resulting polymer is no longer soluble, this typ)e of crosslinking is typically limited to bulk reactions carried out as an adhesive coating directly on the article or in emulsion polymerizations where the crosslinked particles can be dried to a PSA film. 

Generally, and in analogy with bulk reactions, this expression is formally written as... 

Tang and Yao s works have been used as a reference by many authors who found orders of 2.5 or 2 for the whole reaction. This was the case for Vancso-Smercsanyi9-12, Matsuzaki268 and Kirivahk269 who studied bulk reactions of diols with diadds. 

Since the interposition of a barrier layer diminishes the effective contact between reactants, the nucleation step in solid + solid reactions is Usually completed very rapidly at temperatures conveniently used in studies of the bulk reaction and, accordingly, the rate processes are often deceleratory throughout. In addition to the progressive diminution in rate... 

High-temperature bulk reactions, 63 High-temperature condensation, in cresolic medium, 302... 

Thermal properties of several chlorinated phenols and derivatives were studied by differential thermal analysis and mass spectrometry and in bulk reactions. Conditions which might facilitate the formation of stable dioxins were emphasized. No two chlorinated phenols behaved alike. For a given compound the decomposition temperature and rate as well as the product distribution varied considerably with reaction conditions. The phenols themselves seem to pyro-lyze under equilibrium conditions slowly above 250°C. For their alkali salts the onset of decomposition is sharp and around 350°C. The reaction itself is exothermic. Preliminary results indicate that heavy ions such as cupric ion may decrease the decomposition temperature. 

Characterization is an important field in catalysis. Spectroscopy, microscopy, diffraction and methods based on adsorption and desorption or bulk reactions (reduction, oxidation) all offer tools to investigate the nature of an active catalyst. With such knowledge we hope to understand catalysts better, so that we can improve them or even design new catalysts. 

However, it is known that, even when using construction materials only (no fimc-tional polymer resin or catalyst), bulk reactions can change to surface reactions with the surface acting as a real reactant . Here, the functional groups of the surface act as reactants. Such findings have only recently been identified (see Section 1.6.10). 

From all that we know, reactions in micro reactors still have to be considered as bulk reactions, i.e. they follow all the whole known rules which we know for conventional synthesis. In particular, we expect the same reaction mechanisms to occur. However, there may be exceptions to this rule. 

Another exception to the known mechanisms of conventional chemistry may arise when dominance of surface reactions is achieved in micro reactors. This holds for all catalytic reactions on solid contacts. Beyond that, it was shown that some formerly homogeneous bulk reactions may become heterogeneous when carried out in a micro reactor owing to the very large surface-to-volume ratio [155,171,172],... 

The key to obtaining pore size information from the NMR response is to have the response dominated by the surface relaxation rate [19-26]. Two steps are involved in surface relaxation. The first is the relaxation of the spin while in the proximity of the pore wall and the other is the diffusional exchange of molecules between the pore wall and the interior of the pore. These two processes are in series and when the latter dominates, the kinetics of the relaxation process is analogous to that of a stirred-tank reactor with first-order surface and bulk reactions. This condition is called the fast-diffusion limit [19] and the kinetics of relaxation are described by Eq. (3.6.3) ... 

A new method has been proposed for obtaining organotin acrylates and methacrylates by a bulk reaction of the corresponding acids in stoichiometric quantities with trialkyl(triaryl)tin hydroxides and hexaalkyldistannoxanes in the presence of... 

Poly(boronic carbamatejs were prepared by alkoxyboration polymerization of diisocyanates with mesityldimethoxyborane (scheme 33).59 The polymers obtained have boronic carbamate functions in their repeating units and can be expected to be novel reactive polymers. First, alkoxyboration polymerization between mesityldimethoxyborane and 1,6-hexamethylene diisocyanate was examined, and the optimized reaction conditions were bulk reactions at 140°C. Both aliphatic and aromatic diisocyanates gave the corresponding polymers. When aromatic diisocyanates were employed, the... 

The paper first considers the factors affecting intramolecular reaction, the importance of intramolecular reaction in non-linear random polymerisations, and the effects of intramolecular reaction on the gel point. The correlation of gel points through approximate theories of gelation is discussed, and reference is made to the determination of effective functionalities from gel-point data. Results are then presented showing that a close correlation exists between the amount of pre-gel intramolecular reaction that has occurred and the shear modulus of the network formed at complete reaction. Similarly, the Tg of a network is shown to be related to amount of pre-gel intramolecular reaction. In addition, materials formed from bulk reaction systems are compared to illustrate the inherent influences of molar masses, functionalities and chain structures of reactants on network properties. Finally, the non-Gaussian behaviour of networks in compression is discussed. 

Gel Point and Properties of Networks from Bulk Reaction Systems The results in Figure 9 show clearly that the modulus of (dry) networks formed at complete reaction depend strongly on the amount of pre-gel intramolecular reaction that has occurred. 

The moduli and Tg s of the networks formed from the bulk reactions of the five systems of Figure 9 are shown in Table IV(29). The first five columns define the systems, the next two give the experimental values of G(at 298K) and Tg, and the last three give the values of pr,c, Mc, and G/G°. The last quantity is the reduction in rubbery shear modulus on the basis of that expected for the perfect network(G°). G/G° is in fact equal to M /Mc. 

In general, the factor by which G is reduced depends on Me, f, chain stiffness, and the initial concentrations of reactive groups obtainable in bulk, in a manner which still needs to be resolved in detail. However, for bulk reaction mixtures, the moduli of networks with relatively flexible chain structures can be reduced by a factor of five below those expected for network formation in the absence of pre-gel intramolecular reaction. 

The factors which influence pre-gel intramolecular reaction in random polymerisations are shown to influence strongly the moduli of the networks formed at complete reaction. For the polyurethane and polyester networks studied, the moduli are always lower than those expected for no pre-gel intramolecular reaction, indicating the importance of such reaction in determining the number of elastically ineffective loops in the networks. In the limit of the ideal gel point, perfect networks are predicted to be formed. Perfect networks are not realised with bulk reaction systems. At a given extent of pre-gel intramolecular... 

Decomposition of H2S over MoS2 [92]. The rate enhancement, quantitatively unspecified, was attributed to the creation of hot spots with temperatures 100-200 K above that of the bulk. Reaction conditions a flow fixed-bed single-mode reactor. 

Scheme 20. Bulk Reaction between Electrolyte Components at Elevated Temperatures...

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