Initiation reactions, chain polymerization

Some of these reactions are listed in Table 2.9, but they are not as clear as they are described in the table because catalysts that can also initiate a chain polymerization (tertiary amines, triphenylphosphine, imidazoles, chromates, etc see Sec 2.3.4) are practically always used. 

Once a radical enters a reaction locus, it is presumed to initiate a chain polymerization reaction which then continues at a constant rate until the activity of the radical is lost. The processes whereby the activity of the propagating radicals is lost from the reaction loci can be classified into two broad types ... 

Molecules that produce radicals upon excitation are capable of initiating radical chain-polymerization reactions of... 

The transition states for the steps of propagation are formed repeatedly in liquid medium systems, containing monomer, initiator, the formed polymer, and frequently a solvent. There are many different types of initiating reactions. These polymerization, however, never terminate by combination or by disproportionation as they do in free-radical chain-growth polymerizations. Instead, terminations of chain growths are results of unimolecular reactions, or transfers to other molecules, like monomers or solvents, or impurities, like moisture. They can also result from quenching by deliberate additions of reactive terminating species. 

The initialization process starts with the initiator decomposition into free radicals, which reacting with monomer molecules initiate the chain polymerization reaction ... 

Redox reactions of heavy metal ions with peroxides and hydroperoxides in which free radicals are generated are widely used for the initiation of chain polymerization and oxidation reactions. The H2O2 + Fe system known as Fenton s reagent has long ago been used for the hydroxylation and oxidative dimerization of organic compounds. These reactions occur during the catalytic decomposition of peroxides and in complicated processes of catalytic oxidation. 

Photolysis of aromatic ketones, such as benzophenone, in the presence of hydrogen donors, such as alcohols, amines, or thiols, leads to the formation of a radical stemming from the carbonyl compound (ketyl-type radical in the case of benzophenone) and another radical derived from the hydrogen donor [see reaction (14)]. Provided vinyl monomer is present, the latter may initiate a chain polymerization. The radicals stemming from the carbonyl compound are usually not reactive toward vinyl monomers due to bulkiness and/or the delocalization of the unpaired electron. 

Several studies have demonstrated the successful incoriDoration of [60]fullerene into polymeric stmctures by following two general concepts (i) in-chain addition, so called pearl necklace type polymers or (ii) on-chain addition pendant polymers. Pendant copolymers emerge predominantly from the controlled mono- and multiple functionalization of the fullerene core with different amine-, azide-, ethylene propylene terjDolymer, polystyrene, poly(oxyethylene) and poly(oxypropylene) precursors [63,64,65,66,62 and 66]. On the other hand, (-CggPd-) polymers of the pearl necklace type were fonned via the periodic linkage of [60]fullerene and Pd monomer units after their initial reaction with thep-xy y ene diradical [69,70 and 71]. 

In ionic polymerizations termination by combination does not occur, since all of the polymer ions have the same charge. In addition, there are solvents such as dioxane and tetrahydrofuran in which chain transfer reactions are unimportant for anionic polymers. Therefore it is possible for these reactions to continue without transfer or termination until all monomer has reacted. Evidence for this comes from the fact that the polymerization can be reactivated if a second batch of monomer is added after the initial reaction has gone to completion. In this case the molecular weight of the polymer increases, since no new growth centers are initiated. Because of this absence of termination, such polymers are called living polymers. 

The degree of polymerization is controlled by the rate of addition of the initiator. Reaction in the presence of an initiator proceeds in two steps. First, the rate-determining decomposition of initiator to free radicals. Secondly, the addition of a monomer unit to form a chain radical, the propagation step (Fig. 2) (9). Such regeneration of the radical is characteristic of chain reactions. Some of the mote common initiators and their half-life values are Hsted in Table 3 (10). 

Polymerization of raw feedstock. Aliphatic hydrocarbon resins. Raw feedstock contains straight-chain and cyclic molecules and mono- and diolefins. The most common initiator in the polymerization reaction is AICI3/HCI in xylene. The resinification consists of a two-stage polymerization in a reactor at 45°C and high pressure (10 MPa) for several hours. The resulting solution is treated with water and passed to distillation to obtain the aliphatic hydrocarbon resins. Several aliphatic hydrocarbon resins with different softening points can be adjusted. 

The function of emulsifier in the emulsion polymerization process may be summarized as follows [45] (1) the insolubilized part of the monomer is dispersed and stabilized within the water phase in the form of fine droplets, (2) a part of monomer is taken into the micel structure by solubilization, (3) the forming latex particles are protected from the coagulation by the adsorption of monomer onto the surface of the particles, (4) the emulsifier makes it easier the solubilize the oligomeric chains within the micelles, (5) the emulsifier catalyzes the initiation reaction, and (6) it may act as a transfer agent or retarder leading to chemical binding of emulsifier molecules to the polymer. 

In earlier investigations chain ends were suggested to be important initiation sites for dehydrochlorination. Provided there are no transfer reactions during polymerization, at least half the polymer chain ends will carry initiator fragments. In practice, transfer reactions swamp the normal termination processes and <30% of the chain ends carry initiator residues [59]. 

The trapped radicals, most of which are presumably polymeric species, have been used to initiate graft copolymerization [127,128]. For this purpose, the irradiated polymer is brought into contact with a monomer that can diffuse into the polymer and thus reach the trapped radical sites. This reaction is assumed to lead almost exclusively to graft copolymer and to very little homopolymer since it can be conducted at low temperature, thus minimizing thermal initiation and chain transfer processes. Moreover, low-molecular weight radicals, which would initiate homopolymerization, are not expected to remain trapped at ordinary temperatures. Accordingly, irradiation at low temperatures increases the grafting yield [129]. 

The thermal (or photochemical) decomposition of the azo group gives rise to a radically initiated polymerization. The reactive site F, the transformation site, however, can, depending on its chemical nature, initiate a condensation or addition type reaction. It can also start radical or ionic polymerizations. F may also terminate a polymerization or even enable the azo initiator to act as a monomer in chain polymerizations. 

With respect to the initiation of cationic chain polymerizations, the reaction of chlorine-terminated azo compounds with various silver salts has been thoroughly studied. ACPC, a compound often used in condensation type reactions discussed previously, was reacted with Ag X , X, being BF4 [10,61] or SbFa [11,62]. This reaction resulted in two oxocarbenium cations, being very suitable initiating sites for cationic polymerization. Thus, poly(tetrahydrofuran) with Mn between 3 x 10 and 4 x lO containing exactly one central azo group per molecule was synthesized [62a]. Furthermore, N-... 

In this section, the reactions undergone by radicals generated in the initiation or chain transfer processes are detailed. Emphasis is placed on the specificity of radical-monomer reactions and other processes likely to take place in polymerization media under typical polymerization conditions. The various factors important in determining the rate and selectivity of radicals in addition and... 

When a polymer is prepared by radical polymerization, the initiator derived chain-end functionality will depend on the relative significance and specificity of the various chain end forming reactions. Tlius, for the formation of telechelic polymers ... 

Chains with uttdesired functionality from termination by combination or disproportionation cannot be totally avoided. Tn attempts to prepare a monofunctional polymer, any termination by combination will give rise to a difunctional impurity. Similarly, when a difunctional polymer is required, termination by disproportionation will yield a monofunctional impurity. The amount of termination by radical-radical reactions can be minimized by using the lowest practical rate of initiation (and of polymerization). Computer modeling has been used as a means of predicting the sources of chain ends during polymerization and examining their dependence on reaction conditions (Section 7.5.612 0 J The main limitations on accuracy are the precision of rate constants which characterize the polymerization. 

Reaction conditions should usually be chosen such that the fraction of initiator-derived chains (should be greater than or equal to the number of chains formed by radical-radical termination) is negligible. The expressions for number average degree of polymerization and molecular weight (eqs. 13 and 14) then simplify to eqs. 15 and 16 ... 

The low yields of vinyl polymers (Ganushchak et al., 1972) are probably due to the arylethane radical 10.17 reacting more rapidly with CuCl2 than with the vinyl monomer. The formation of 10.17 is also the initiation of the polymerization chain reaction. 

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