Chain scissioning molecular weight distribution

Because of the absence of chain limiter, the catalyst itself may initially act as the chain limiter (Fig. 8.22). The catalyst reacts with the olefinic regions of the polymer backbone and causes chain scission to occur, forming two new chains. The reactive carbene which is produced then moves from chain to chain, forming two new chains with each scission until the most probable molecular weight distribution is reached (Mw/Mn = 2), producing linear chains end capped with [Ru] catalyst residues. 

Although polymers in-service are required to be resistant toward hydrolysis and solar degradation, for polymer deformulation purposes hydrolysis is an asset. Highly crystalline materials such as compounded polyamides are difficult to extract. For such materials hydrolysis or other forms of chemolysis render additives accessible for analysis. Polymers, which may profitably be depolymerised into their monomers by hydrolysis include PET, PBT, PC, PU, PES, POM, PA and others. Hydrolysis occurs when moisture causes chain scissions to occur within the molecule. In polyesters, chain scissions take place at the ester linkages (R-CO-O-R ), which causes a reduction in molecular weight as well as in mechanical properties. Polyesters show their susceptibility to hydrolysis with dramatic shifts in molecular weight distribution. Apart from access to the additives fraction, hydrolysis also facilitates molecular characterisation of the polymer. In this context, it is noticed that condensation polymers (polyesters, -amides, -ethers, -carbonates, -urethanes) have also been studied much... 

The resolution capability of a resist is directly related to resist contrast (7) which, for a negative resist, is related to the rate of crosslinked network formation at a constant input dose. It is somewhat more complicated for a positive resist being related to the rate of chain scission and the rate of change of solubility with molecular weight with the latter being markedly solvent dependent. Contrast, like sensitivity, is governed by the type of chemical reactions that occur in the polymeric resist and is affected by molecular parameters such as molecular weight distribution and chemical composition. 

Sol-Gel Measurements. The relative rates of crosslinking and scission may be estimated from soluble-fraction measurements. For an initial random molecular weight distribution and random chain scission, extrapolating a curve of S + S vs. 1/D, where S = sol fraction and D —... 

In ideal random crosslinking polymerization or crosslinking of existing chains, the reactivity of a group is not influenced by the state of other groups all free functionalities, whether attached or unattached to the tree, are assumed to be of the same reactivity. For example, the molecular weight distribution in a branched polymer does not depend on the ratio of rate constants for formation and scission of bonds, but only on the extent of reaction. Combinatorial statistics can be applied in this case, but use of the p.g.f. simplifies the mathematics considerably. 

Molecular Weight Distribution. A given polymer sample is composed of many polymer chains, which in most cases are not of the same length. This variability can be a result of the synthesis process or of possible random scission and cross-linking that can occur upon processing. For economic reasons, it is not possible to separate the various polymer chains by length prior to use so it is important to characterize this distribution in order to describe the polymer and understand its performance. As with any distribution, no single number is a totally satisfactory descriptor. 

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