Primary mean chain length

Assuming that Ti(IV) is distributed statistically in all tetrahedral positions, it can be easily seen that even for crystallite sizes of 0,2 m the great majority of T1(IV) is located inside the pore structure. Assuming that every Ti(IV) is a catalytic centre with equal activity, diffusion limitations for molecules of different sizes should be observed. This is in fact the case. It has been shown [27] that the rate of oxidation of primary alcohols decreases regularly as the chain length increases, while for iso-butyl alcohol a sudden drop in the rate is observed. Also the reactivity order of olefins on TS-1 is different from the order observed with homogeneous electrophilic catalysts, while as already indicated very bulky molecules are unreactive when TS-1 is used as the catalyst. All these facts can only be interpreted as due to diffusion limitations of the larger molecules, which means that the catalytic sites are located inside the pore structure of the solid. 

Fig. 6. A primary means of regulating polyethylene chain length is through control of reactor temperature. Increasing the temperature enhances termination, probably by destabilizing the Cr-chain bond, resulting in shorter chains.

In the above scheme M stands for the monomer concentration, I is the concentration of the initiator, and [R ] and [P ] mean the concentration of primary and polymer radicals, respectively S stands for the chain transferring agent, Ri denotes the decomposition rate of the initiator, and Rp the rate of polymerization. The rate constant for initiator decomposition is kd, for initiation is ki, for propagation Ap, and for termination is hr. The above is based on an assumption that kp and ki are independent of the sizes of the radicals. This is supported by experimental evidence, which shows that radical reactivity is not affected by the size, when the chain length exceeds dimer or trimer dimensions. ... 

The inhibition method has found wide usage as a means for determining the rate at which chain radicals are introduced into the system either by an initiator or by illumination. It is, however, open to criticism on the ground that some of the inhibitor may be consumed by primary radicals and, hence, that actual chain radicals will not be differentiated from primary radicals some of which would not initiate chains in the absence of the inhibitor. This possibility is rendered unlikely by the very low concentration of inhibitor (10 to 10 molar). The concentration of monomer is at least 10 times that of the inhibitor, yet the reaction rate constant for addition of the primary radical to monomer may be less than that for combination with inhibitor by only a factor of 10 to 10 Hence most of the primary radicals may be expected to react with monomer even in the presence of inhibitor, the action of the latter being confined principally to the termination of chain radicals of very short length. ... 

---