Propagator Retarded

Chemical Interaction. Halogens and some phosphoms flame retardants act by chemical interaction. The flame retardant dissociates into radical species that compete with chain propagating and branching steps in the combustion process. 

Coating Theory. This theory includes fire retardants which form an impervious skin on the fiber surface. This coating may be formed during normal chemical finishing, or subsequently when the fire retardant and substrate are heated. It excludes the air necessary for flame propagation and traps any tarry volatiles produced during pyrolysis of the substrate. Examples of this type of agent include the easily fusible salts such as carbonates or borates. 

Thus the thiol 0 2 25511 is capable of terminating a growiug chain and also initiating a new chain. If the initiation-rate constant, k is not much slower than the propagation-rate constant, the net result is the growth of a new chain without any effect on the overall polymerization rate (retardation). That represents a tme chain transfer, ie, no effect on the rate but a substantial decrease iu molecular weight (12). 

The UL flammability ratings describe the relative ease of ignition and combustibiUty of plastics. Tests include the measurement of flame propagation, time to self-extinguish, melt and drip with and without flame, and oxygen indexes. Some engineering plastics, eg, polyetherimides, are, as ranked by this test, inherently nonflammable. Others can be made nonflammable by compounding with flame retardants (ERs) such as bromine... 

Records show that more fatalities occur through victims being suffocated by smoke or poisoned by toxic gases emitted during a fire than by being burnt to death. This is particularly worrying when it is realised that many additives incorporated into a polymer to retard its flammability are often found to increase the amount of smoke emitted as the rate of flame propagation decreases. Most... 

In addition, other additives may exist which react with R and RO2, introducing new propagation reactions which lead to a slower chain reaction. Such materials would be referred to as oxidation retarders. 

Some inorganic fillers are used as flame retardants in rubber base formulations. Flame retardants act in two ways (1) limiting or reducing access of oxygen to the combustion zone (2) reacting with free radicals (especially HO ), thus acting as terminator for combustion-propagation reaction. The additives most widely used as flame retardants for polymers are antimony oxides and alumina trihydrate. 

Chain transfer, the reaction of a propagating radical with a non-radical substrate to produce a dead polymer chain and a new radical capable of initiating a new polymer chain, is dealt with in Chapter 6. There are also situations intermediate between chain transfer and inhibition where the radical produced is less reactive than the propagating radical but still capable of reinitiating polymerization. In this case, polymerization is slowed and the process is termed retardation or degradative chain transfer. The process is mentioned in Section 5.3 and, when relevant, in Chapter 6. 

Tire elTecl observed is dependent on the reactivity of the monomer and other agents present in the polymerization medium towards hydropeioxy radicals 29. If addition of 29 to monomer is slow, in relation to normal propagation, then retardation or inhibition will be observed. It should also be noted that, polymeric peroxides, one of the products of reaction with oxygen are potentially sources of additional radicals. These may complicate polymerization and can impair the properties of the final polymer (Section 8.2). 

In fiber-reinforced composites the deformation of the matrix is then used to transfer stresses by means of shear tractions at the fiber-matrix interface, to the embedded high-strength fibers. On the other hand, fibers retard the propagation of cracks and thus produce a material of high strength. 

This reaction reduces the concentration of the free polystyryl anions, the only species capable of propagating the reaction in this system. The association constant of the above reaction deduced from the kinetics of retardation 78) agrees well with that reported previously 79) based on the results of conductance studies. 

As the polymerization reaction proceeds, scosity of the system increases, retarding the translational and/ or segmental diffusion of propagating polymer radicals. Bimolecular termination reactions subsequently become diffusion controlled. A reduction in termination results in an increase in free radical population, thus providing more sites for monomer incorporation. The gel effect is assumed not to affect the propagation rate constant since a macroradical can continue to react with the smaller, more mobile monomer molecule. Thus, an increase in the overall rate of polymerization and average degree of polymerization results. 

In astronomy, we are interested in the optical effects of the turbulence. A wave with complex amplitude U(x) = exp[ irefractive index, resulting in a random phase structure by the time it reaches the telescope pupil. If the turbulence is weak enough, the effect of the aberrations can be approximated by summing their phase along a path (the weak phase screen approximation), then the covariance of the complex amplitude at the telescope can be shown to be... 

Polymerization is inhibited or retarded by the presence of certain substances, e.g., p-benzoquinone, 4-t-butylcatechol, 1,3,5-trinitrobenzene, and oxygen. These substances react with radicals to yield species which are no longer capable of chain propagation. The deliberate addition of such substances is useful for stabilizing monomers during transportation and storage. 

The most studied catalyst family of this type are lithium alkyls. With relatively non-bulky substituents, for example nBuLi, the polymerization of MMA is complicated by side reactions.4 0 These may be suppressed if bulkier initiators such as 1,1-diphenylhexyllithium are used,431 especially at low temperature (typically —78 °C), allowing the synthesis of block copolymers.432,433 The addition of bulky lithium alkoxides to alkyllithium initiators also retards the rate of intramolecular cyclization, thus allowing the polymerization temperature to be raised.427 LiCl has been used to similar effect, allowing monodisperse PMMA (Mw/Mn = 1.2) to be prepared at —20 °C.434 Sterically hindered lithium aluminum alkyls have been used at ambient (or higher) temperature to polymerize MMA in a controlled way.435 This process has been termed screened anionic polymerization since the bulky alkyl substituents screen the propagating terminus from side reactions. 

The relative rates of polymerization of a series of substituted e-caprolactones initiated by (246) demonstrate that methyl groups, particularly adjacent to the acyl oxygen, retard polymerization.757 In addition, the rate of polymerization of the parent unsubstituted CL at 25 °C was found to be 4 x 102 times greater than L-LA at 70 °C. The slower propagation of LA is usually attributed to coordination of the nearest inserted carbonyl of the polymer chain to the A1 center, leading to formation of a stable 5-membered chelate, which hinders monomer uptake.758... 

Char formation and reduced monomer production are observed for all of these additives upon reaction with PMMA. Char formation increases as a function of temperature, for the hydrido cobalt compound, there is 5% char at 262°, 8.5% at 322°, 15% at 338°, and 19% at 375°C the cobalt(lll) cyanide produces 3% char at 338° and 11% at 375°C the cobalt(ll) cyanide yields 11% char at 375°C. At the highest temperature, 375°C, the amount of monomer formation is 22% for K3Co(CN)5, 11% for K3Co(CN)6, and 10% for HCo[P(OPh)3]4. Ideally one would hope to observe no monomer formation and complete char production. Such is not the case here, these materials probably have no utility as flame retardant additives for PMMA since monomer formation, even at a reduced level, will still permit a propagation of the burning process. While somewhat positive results for these three additives do not prove the validity of the hypothesis, we take this to be a starting point in our search for suitable additives, further work is underway to refine the hypothesis and to identify other potential hydrogenation catalysts and other additives that may prove useful as flame retardants for PMMA... 

The function of halogen-containing compounds as flame retardants has been explained by the radical trap theory. Liberated halogen acid (HX) competes in the above reactions for those radical species that are critical for flame propagation. 

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