Addition of Catalysts

The polymerization of monomers to form hydrocarbon resins is typically carried out by either the direct addition of catalyst to a hydrocarbon fraction or by the addition of feed to a solvent—catalyst slurry or solution. Most commercial manufacturers use a continuous polymerization process as opposed to a batch process. Reactor temperatures are typically in the range of 0—120°C. 

The unblocking temperature usually refers to the temperature at which the blocked urethane system must be heated for 30 min in order to achieve cure. The reaction can be accelerated by curing at higher temperatures and/or by the addition of catalyst, as shown in Fig. 6 [62]. Common urethane catalysts like dibutyltin dilaurate are known to decrease the unblocking temperature. 

Two-component systems consist of (1) polyol or polyamine, and (2) isocyanate. The hardening starts with the mixing of the two components. Due to the low viscosities of the two components, they can be used without addition of solvents. The mass ratio between the two components determines the properties of the bond line. Linear polyols and a lower surplus of isocyanates give flexible bond lines, whereas branched polyols and higher amounts of isocyanates lead to hard and brittle bond lines. The pot life of the two-component systems is determined by the reactivity of the two components, the temperature and the addition of catalysts. The pot life can vary between 0.5 and 24 h. The cure at room temperature is completed within 3 to 20 h. 

Probably the most useful data obtained kinetically are the rate constants themselves. They are important since they can tell us the effect on the rate of a reaction of changes in the structure of the reactants (see Chapter 9), the solvent, the ionic strength, the addition of catalysts, and so on. 

This dimerization is so rapid that ketene does not form P-lactones with aldehydes or ketones, except at low temperatures. Other ketenes dimerize more slowly. In these cases the major dimerization product is not the P-lactone, but a cyclobutanedione (see 15-61). However, the proportion of ketene that dimerizes to p-lactone can be increased by the addition of catalysts such as triethylamine or triethyl phosphite. Ketene acetals R2C=C(OR )2 add to aldehydes and ketones in the presence of ZnCl2 to give the corresponding oxetanes. ... 

In the work now reported coal fractions derived from a solubilised coal were reacted individually with Tetralin, without any additions of catalyst or gaseous hydrogen, and the reaction products studied to determine the effect that chemical type had on the reaction. The untreated whole coal was also reacted to test whether phenol, present in the coal fractions as a result of the fractionation procedure, was having any significant effect on the reaction with the fractions. 

Dining chlorination of hydrocarbons with Lewis acid catalysis, the catalyst must be premixed with the hydrocarbon before admission of chlorine. Addition of catalyst to the chlorine-hydrocarbon mixture is very hazardous, causing instantaneous release of large volumes of hydrogen chloride. 

Conditions employing elevated temperatures with less catalyst, a milder catalyst or without addition of catalyst, can supplant those utilizing aggressive reagents at lower temperatures. A recent example concerns a catalytic, thermal etherification that can be performed near neutrality and that produces minimal waste [41]. This represents a cleaner alternative to the traditional Williamson synthesis, in which the ether is... 

The curing reaction can be carried out thermally or with the addition of a catalyst. The thermal cure is strongly influenced by impurities associated with the synthesis. The greater the degree of monomer purity, the more slowly the thermal cure proceeds. If the monomer is sufficiently purified, the cure rate can be predictably controlled by the addition of catalysts. As with the aromatic cyanate esters, the fluoromethylene cyanate esters can be cured by the addition of active hydrogen compounds and transition metal complexes. Addition of 1.5 wt% of the fluorinated diol precursor serves as a suitable catalyst.9 The acetylacetonate transition metal salts, which work well for the aromatic cyanate esters,1 are also good catalysts. 

In the 1970s more-active zeolite catalysts were developed so that the cracking reaction could be conducted in the transport riser. Recently, heavier crude feedstocks have resulted in higher coke production in the cracker. The extra coke causes higher temperatures in the regenerator than are desired. This has resulted in the addition of catalyst cooling to the regeneration step, as shown in Fig. 17-25. 

These observations showed that the reaction can be simplified by preformation of the indanone enolate in toluene/50% NaOH and subsequent addition of catalyst and CH3CI (Figure 12). This eliminates the "induction period and most importantly the high sensitivity of rate and ee to the catalyst/indanone ratio. Detailed kinetic measurements on this preformed enolate methylation in toluene/50% NaOH determined that the reaction is 0.55 order in catalyst. This is consistent with our finding that the catalyst goes into solution as a dimer which must dissociate prior to com-plexation with the indanone anion. If the rate has a first order dependence on the monomer, the amount of monomer is very small, and the equilibration between dimer and monomer is fast, then the order in catalyst is expected to be 0.5. The 0.5 order in catalyst is not due to the preformation of solid sodium indanone enolate but is a peculiarity of this type of chiral catalyst. Vlhen Aliquat 336 is used as catalyst in this identical system the order in catalyst is 1. Finally, in the absence of a phase transfer catalyst less than 2% methylation was observed in 95 hours. 

The alternative regiochemical disposition of the diazo and tether of indole 260 failed to deliver any product upon addition of catalyst. Friedrichsen and co-workers (136) also applied this method to amine substituted tethers to generate polyaza-cyclic compounds (Scheme 4.70). The presence of the amino substituted furan subsequent to diazo-decomposition made it possible to cleave the ether bridge through the facility of the amino group formed to produce adduct 263. 

The rate of the second reaction is quite low as long as there is enough free sulfonyl chloride to react with additional amounts of aluminum chloride. Once this is no longer true, further additions of catalyst enormously increase the reaction rate (27). The recently discovered swamping catalyst effect in the halogenation of aromatic donor species (35) probably exhibits analogous kinetic behavior. The basic rate expression found by Olivier consisted of only one term for reaction when a relatively small amount of aluminum chloride was present ... 

The heat flux feedback from the gas phase to the burning surface is also determined by the chemical reaction rate in the gas phase. The reaction rate in the gas phase is altered by the addition of catalysts. The catalysts act either on the decomposition reaction of the condensed phase or on the reaction in the gas phase of the gaseous decomposition products. There are two types of catalysts positive catalysts that increase the burning rate and negative catalysts that decrease the burning rate. 

AP is a major ingredient of composite propellants and it amounts to -70-72%. Therefore, the mechanism of increase in the burn rate of composite propellants due to the addition of catalysts or BRMs largely depends on the decomposition of AP. This has been postulated by Rastogi and his team in their publication [265] and it is briefly as follows. 

In practice the epoxide-amine cure is often accelerated by the addition of catalysts such as boron trifluoride complexes, and the boron trifluoride-ethylamine adduct (BFE) is widely used for this purpose. In addition to catalysing the epoxide-amine reactions, BFE can initiate homopolymerisation of epoxide. The accelerating effect of BFE is illustrated by DSC scans for the TGDDM/DDS/BFE system in Figure 12. The multiple-peaked exotherm associated with the BFE-catalysed TGDDM/DDS cure indicates that the kinetics of this system are more complex than those for the cure with amine alone. For this system the overall heat of reaction was found to decrease with increasing BFE concentration 89). For DDS alone Q0 was about 110 kJ per mole epoxide while the value for BFE alone was 75 kJ/mole, and the DDS/BFE values were between these limits. It appears that the proportion of epoxide homo-polymerisation relative to amine or hydroxyl addition increases with increasing BFE concentration. 

The amine (5.0 mmol) and glyoxylic add monohydrate (5.5 mmol) were dissolved in a mixture of MeOH (10 mL) and H20 (5 mL). The pH of the soln was adjusted to 6 by the addition of 2 M NaOH. After the addition of catalyst [10% Pd/C (0.1 g) with 50% H20] the mixture was stirred in an autoclave with 50 bar H2 pressure at rt overnight. The catalyst was removed by filtration over silica gel and the filtrate was taken to dryness and dried in vacuo. To remove inorganic impurities, the solid residue was extracted with dry MeOH. The product can be used without further purification. 

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