Initiation of polymerization reactions

The addition of slaked lime and the initiation of polymerization reactions with 11.Og and feme 01 stannous salts are techniques employed to lemove aminophenols from wastewaters... 

Various types of radiation such as ultraviolet (UV) radiation, and electron beams can be used for initiation of polymerization reactions. Curing of polymer matrices by UV irradiation can be applied to a variety of processes in the production of composite components, as long... 

Many terpenes bear reactive groups such as hydroxyl and carboxyl, which can be used for covalent attachment of terpene entities to end-functionalized polymers (Sect. 3.1) or initiation of polymerization reactions (Sect. 3.2). Sometimes, chemical modification needs to be done to turn OH or COOH into other functional groups for these two purposes. The combined properties of the biological and synthetic components have made terpene-polymer conjugates, with one or two terpene moieties at chain end(s) or in the center, very attractive materials. Nevertheless, only a few terpenes have been used for this purpose, mostly cholesterol and bUe acids. 

Polymerization reactions. There are two broad types of polymerization reactions, those which involve a termination step and those which do not. An example that involves a termination step is free-radical polymerization of an alkene molecule. The polymerization requires a free radical from an initiator compound such as a peroxide. The initiator breaks down to form a free radical (e.g., CH3 or OH), which attaches to a molecule of alkene and in so doing generates another free radical. Consider the polymerization of vinyl chloride from a free-radical initiator R. An initiation step first occurs ... 

All of the reactions listed in Table 6.1 produce free radicals, so we are presented with a number of alternatives for initiating a polymerization reaction. Our next concern is in the fate of these radicals or, stated in terms of our interest in polymers, the efficiency with which these radicals initiate polymerization. Since these free radicals are relatively reactive species, there are a variety of... 

Bulk and solution polymerizations are more or less self-explanatory, since they operate under the conditions we have assumed throughout most of this chapter. A bulk polymerization may be conducted with as few as two components monomer and initiator. Production polymerization reactions are carried out to high conversions which produces several consequences we have mentioned previously ... 

Among other possible reactions, these free radicals can initiate ordinary free-radical polymerization. The Ziegler-Natta systems are thus seen to encompass several mechanisms for the initiation of polymerization. Neither ionic nor free-radical mechanisms account for stereoregularity, however, so we must look further for the mechanism whereby the Ziegler-Natta systems produce this interesting effect. 

Miscellaneous Reactions. Epoxy compounds yield chlorosubstituted carbonates (45). The reaction of chloroformates with hydrogen peroxide or metal peroxides results in the formation of peroxydicarbonates that are used as free-radical initiators of polymerization of vinyl chloride, ethylene, and other unsaturated monomers (46,47). 

I Initiation The polymerization reaction is initiated when a few radicals are generated on heating a small amount of benzoyl peroxide catalyst to break the weak 0-0 bond. A benzoyloxy radical then adds to the C=C bond of ethylene to generate a carbon radical. One electron from the C=C bond pairs up with the odd electron on the benzoyloxy radical to form a C-O bond, and the other election remains on carbon. 

Largely for these reasons, radicals are most often characterized indirectly by examining the products of their reaction. Many of the methods used to study radical reactions have been applied to study initiation of polymerization. Some of these techniques are detailed in Section 3.5. 

Only a few diacvl peroxides see widespread use as initiators of polymerization. The reactions of the diaroyl peroxides (36, R=aryl) will be discussed in terms of the chemistry of BPO (Scheme 3.25). The rate of p-scission of thermally generated benzoyloxy radicals is slow relative to cage escape, consequently, both benzoyloxy and phenyl radicals are important as initiating species. In solution, the only significant cage process is reformation of BPO (ca 4% at 80 °C in isooctane) II"l only minute amounts of phenyl benzoate or biphenyl are formed within the cage. Therefore, in the presence of a reactive substrate (e.g. monomer), tire production of radicals can be almost quantitative (see 3.3.2.1.3). 

The initiation of polymerization of styrene and isoprene in benzene by t-butyl lithium reveals some complexities129) (e.g. zero order kinetics in monomer) not observed in the reaction proceeding in cyclohexane. Further studies of that system are needed. 

The use of metal-complex initiating systems proved to be especially promising in carrying out the reactions with acrylic monomers which can be easily polymerized, when the common initiators of radical reactions are excepted. The use of Fe(CO)s -I- DMFA system allows us to perform homolytical addition of bromoform to acrylic monomers selectively at C-Br bond with no essential polymerization (ref. 10). 

An amide-type corrosion inhibitor is prepared as follows Methylmethacrylate is converted with tallow triamine or tallow tetramine at 80° to 90° C into the corresponding amides. After completion, the temperature is raised to initiate the polymerization reaction [1350]. The polymerization reaction is performed at temperatures up to 200° C. The polymer controls the corrosion of metal surfaces in contact with a corrosive hydrocarbon-containing medium. 

Because the polymerization with the thermal iniferters previously described was performed at a high temperature, some side reactions might be unavoidable, e.g., ordinary bimolecular termination between polymer radicals, disproportionation between a polymer radical and a small radical leading to deactivation of the iniferter site, initiation by the radical generated from the iniferter sites, rearrangements of the structure of the iniferter sites, and spontaneous initiation of polymerization. 

Capable of polymerization, decomposition or rearrangement. Initiation of the reaction can be spontaneous, by energy input such as thermal or mechanical energy, or by catalytic action increasing the reaction rate. 

The presence of lignin, resins or other extractives in the fibers may interfere with the initiation or polymerization reactions, e.g. by termination or chain transfer of free radical reactions from phenolic groups. In some cases, lignin has no adverse effect and may even be grafted . 

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