Random scission, thermal degradation

The monomeric 3deld from thermally degraded PE is very low, less than one percent. The mechanism is a random scission type giving many volatile degradation products with a very complex pattern. This... 

Unlike the polyalkyl acrylates, which are thermally degraded by random chain scission, polyalkyl methacrylates unzip when heated, and excellent yields of the monomers are produced when the polymers of the lower homologues are heated. When higher homologues are heated, there is also some thermal degradation of the alkyl substituents. 

It was found that the scission of terminal double bounds contributes to the thermal degradation much more than random scission (48). Thus, hydrogenation results in a markedly decrease of the kinetics of degradation. 

PEG can be severely degraded in air. Its melting point and heat of fusion are reduced by as much as 13 °C and 32 kJ kg"1, respectively [81]. The thermal degradation of PEG in air follows a random chain scission oxidation mechanism, and could be suppressed by addition of an antioxidant, 2, 2,-methylene-bis (4-methyl-6-tert-butylphenol) (MBMTBP), due to the reaction of MBMTBP with ROO radicals formed in the propagation step [79]. Low-molecular-weight esters including formic esters are produced as the main products of the thermal degradation of PEG (Scheme 3.17) [80]. 

For both polyethylene and its many copolymeric variants and polypropylene, the main thermal degradative routes follow initial random chain scission. These reactions are only slightly affected by the differences in the physical structure such as crystallinity, but are influenced by the presence of impurities. However, it is largely true that while these may influence the proces-sibility and long-term stability of respective polyolefins, they may have little or no effect on the flammability. 

Although population balance methods are relatively undeveloped for interesting polymers, the author believes they have great potential. Each of the four distinct thermal degradation mechanisms mentioned earlier will be analyzed in detail and examples involving specific polymers will be discussed wherever possible. Furthermore, some relevant combinations of mechanisms (such as combined random scission and end-chain scission) will also be discussed. 

It has already been noted above that the thermal degradation of PS is thought to involve a mixture or end-chain and random scission mechanisms. Guaita et al. have investigated this case using a mixture of experimental and Monte Carlo methods32 and we now consider the corresponding PBM. 

A better model of thermal degradation by depropagation may be obtained if we distinguish between polymer molecules and radical fragments in the population. Here, we consider radical species being formed from an initial random scission reaction. Once formed, the radical species then undergo... 

Inaba, A. and Kashiwagi, T. A calculation of thermal degradation initiated by random scission. I. Steady state radical concentration. Macromolecules 1986 19 2412. 

In cases where no additional oxygen is present, polystyrene can undergo nearly pure thermal degradation. The two prevalent mechanisms are sequential elimination of monomer units, which is called unzipping or depolymerization. In this case, styrene monomer is formed. Random chain scission can also occur. It is sometimes combined with unzipping at the reactive broken chain ends. At temperatures approaching 300 °C, up to 40 % of a polystyrene molecule can be converted to styrene monomer. 

A new macroscopic degradation mechanism of polymers studied by Murata et al. [6] was suggested with two distinct mechanism in the thermal degradation of PE, PP and PS. One is a random scission of polymer links that causes a decomposition of macromolecnles into the intermediate reactants in liquid phase, and the other is a chain-end scission that caused a conversion of the intermediate reactants into volatile prodncts at the gas-liqnid interface. There are parallel reactions via two mechanisms. The random scission of polymer links causes a reduction in molecular weight of macromolecules and an increase of the number of oligomer molecules. The chain-end scission causes a dissipation of oligomer molecules and a generation of volatile products. 

While condensation polymers such as PET and polyamides can be broken down into their monomer nnits by thermal depolymerization processes, vinyl (addition) polymers snch as polyethylene and polypropylene are very difficnlt to decompose to monomers. This is becanse of random scission of the carbon-carbon bonds of the polymer chains during thermal degradation, which prodnces a broad prodnct range. 

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