Polymers degradation formation

Well before the advent of modern analytical instruments, it was demonstrated by chemical techniques that shear-induced polymer degradation occurred by homoly-tic bond scission. The presence of free radicals was detected photometrically after chemical reaction with a strong UV-absorbing radical scavenger like DPPH, or by analysis of the stable products formed from subsequent reactions of the generated radicals. The apparition of time-resolved ESR spectroscopy in the 1950s permitted identification of the structure of the macroradicals and elucidation of the kinetics and mechanisms of its formation and decay [15]. 

In 1929 Carothers proposed a generally useful differentiation between two broad classes of polymers condensation polymers in which the molecular formula of the structural unit (or units) lacks certain atoms present in the monomer from which it is formed, or to which it may be degraded by chemical means, and addition polymers, in which the molecular formula of the structural unit (or units) is identical with that of the monomer from which the polymer is derived. Condensation polymers may be formed from monomers bearing two or more reactive groups of such a character that they may condense intermolecu-larly with the elimination of a by-product, often water. The polyamides and polyesters referred to above afford prime examples of condensation polymers. The formation of a polyester from a suitable hydroxy acid takes place as follows ... 

As mentioned in the introduction, there are conflicting views as to the contributions made to polymer degradation by various initiating species. Among these species, in addition to ketones, hydroperoxides are some of the more important chromophores. As it is known, the photolysis of hydroperoxides yields alkoxy and hydroxy radicals. In polymers, in the presence of oxygen, these radicals lead to the secondary formation of peroxy radicals. The latter in turn are converted by hydrogen abstraction into new hydroperoxides (Scheme I) ... 

One of the more important protective mechanisms is probably the ability of these substances to interact not only with various oxygen-centered radicals but also with hydroperoxides. This ability is supplemented by the formation of associates between the amine light stabilizer and species responsible for polymer degradation. 

On the basis of the results obtained from additional experiments with other metals it was concluded that in the presence of active metal such as Sb° or Bi° or Zn° direct attack on the DBDPO would readily occur. However, all attempts to directly measure the extent of Sb° formation from Sb203 during polymer degradation were unsuccessful. 

This reaction is very exothermic (A// —180 to —200kJ mol-1) and, therefore, seems to be very probable from the thermochemical point of estimation. The pre-exponential factor is expected to be low due to the concentration of the energy on three bonds at the moment of TS formation (see Chapter 3). To demonstrate that this reaction is responsible for the oxidative destruction of polymers, PP and PE were oxidized in chlorobenzene with an initiator and analyzed for the rates of oxidation, destruction (viscosimetrically), and double bond formation (by the reaction with ozone) [131]. It was found that (i) polymer degradation and formation of double bonds occur concurrently with oxidation (ii) the rates of all three processes are proportional to v 1/2, (iii) independent of p02, and (iv) vs = vdbf in PE and vs = 1.6vdbf in PP (vdbf is the rate of double bond formation). Thus, the rates of destruction and formation of double bonds, as well as the kinetic parameters of these reactions, are close, which corroborates with the proposed mechanism of polymer destruction. Therefore, the rate of peroxyl macromolecules degradation obeys the kinetic equation ... 

At elevated temperatures, the oxidation of PE occurs as a quasistationary process with the kinetic equilibrium between the formation and decay of hydroperoxyl groups (see Chapter 4). The ratio of the two discussed reactions of polymer degradation is ... 

Peroxide cure systems, in rubber compounding, 22 793-794 Peroxide decomposers, 3 111-114 Peroxide decomposition, 24 279-280 Peroxide formation, by VDC, 25 694. See also Hydrogen peroxide Peroxide initiators, 23 379-380 worldwide producers of, 24 303 Peroxide-ketazine process, 23 582-583 flow sheet for, 23 582 versus Raschig process, 23 583 Peroxide linkages, in VDC polymer degradation, 25 713... 

Esterification is the first step in PET synthesis but also occurs during melt-phase polycondensation, SSP, and extrusion processes due to the significant formation of carboxyl end groups by polymer degradation. As an equilibrium reaction, esterification is always accompanied by the reverse reaction being hydrolysis. In industrial esterification reactors, esterification and transesterification proceed simultaneously, and thus a complex reaction scheme with parallel and serial equilibrium reactions has to be considered. In addition, the esterification process involves three phases, i.e. solid TPA, a homogeneous liquid phase and the gas phase. The respective phase equilibria will be discussed below in Section 3.1. 

Crosslinking is distinguished by the occurrence of gelation at some point in the polymerization. At this point, termed the gel point, one first observes the visible formation of a gel or insoluble polymer fraction. (The gel point is alternately taken as the point at which the system loses fluidity as measured by the failure of an air bubble to rise in it.) The gel is insoluble in all solvents at elevated temperatures under conditions where polymer degradation does not occur. The gel corresponds to the formation of an infinite network in which polymer molecules have been crosslinked to each other to form a macroscopic molecules. The gel is, in... 

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