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A substituent that increases monomer reactivity does so because it stabilizes and decreases the reactivity of the corresponding radical A consideration of Table 6-4 shows that the effect of a substituent on radical reactivity is considerably larger than its effect on monomer reactivity Thus vinyl acetate radical is about 100 1000 times more reactive than styrene radical toward a given monomer, while styrene monomer is only 50 100 times more reactive than vinyl acetate monomer toward a given radical A comparison of the self-propagation rate constants (kp ) for vinyl acetate and styrene shows that these two effects very nearly compensate each other The kp for vinyl acetate is only 16 times that of styrene (Table 3-11) The interaction of radical reactivity and monomer reactivity in determining the rate of a radical monomer reaction can be more clearly seen by the use of the reaction coordinate diagram in Fig 6-11.



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p(t+c5t) =

Figure 6-11 shows the potential-energy changes accompanying the radical monomer reaction as a function of the separation between the atoms forming the new bond These energy changes are shown for the four possible reactions between resonance-stabilized and nonstabilized monomers and radicals.

d 2aP(a) le-ttot/2a) (ae- ttOt/2 1

radicals. Polymerization to high-molecular-weight polymer is observed but the conversions are low (<15%). The polymerization is self-limiting because of the high viscosity produced even at low conversion. High viscosity hinders cavitation and radical production [Price et al., 1992]. 3-4g 3-4g-1 Initiator Ef ciency De nition of f

(6.64)





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When a material balance is performed on the amount of initiator that is decomposed during a polymerization and compared with that which initiates polymerization, it is apparent that the initiator is inef ciently used. There is wastage of initiator due to two reactions. One is the induced decomposition of initiator by the attack of propagating radicals on the initiator, for example

Let us calculate la exp( -I\: c5t/2)) (a exp( -I\: c5t/2) I:

3-65

- 'ila}(alatac5t + I\:lal2la} (alc5t + 0 (c5t 2)

This reaction is termed chain transfer to initiator and is considered further in Sec. 3-6b. The induced decomposition of initiator does not change the radical concentration during the polymerization, since the newly formed radical (fCOO ) will initiate a new polymer chain. However, the reaction does result in a wastage of initiator. A molecule of initiator is decomposed without an increase in the number of propagating radicals or the amount of monomer being converted to polymer. The second wastage reaction is that involving the side reaction(s) of the radicals formed in the primary step of initiator decomposition. Some of the radicals formed in the primary decomposition step, for example, in the reaction

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la}(al- {ata, la)(al} at + I\:ala)(ala t c5t + 0 (c5t2) . (6.66)

3-66

If you create a presentation that you particularly like you can turn that presentation into a template file that you can reuse. Click the File tab and then click Save As. In the Save As dialog box, click the Save as type and choose PowerPoint Template.Type a name for the template in the File name field and click Save. PowerPoint saves the presentation as a template.

p(t + c5t)

undergo reactions to form neutral molecules instead of initiating polymerization. It is this wastage reaction that is referred to when discussing the initiator ef ciency f. The initiator ef ciency f is de ned as the fraction of radicals formed in the primary step of initiator decomposition, which are successful in initiating polymerization. The initiator ef ciency is considered exclusive of any initiator wastage by induced decomposition. The reader is cautioned, however, that reported literature values of f do not always make this distinction. Very frequently, the calculations of f neglect and do not correct for the occurrence of induced decomposition. Such f values may be considered as the effective or practical initiator ef ciency in that they give the net or overall initiation ef ciency of the initial catalyst concentration. The preferred method of quantitatively handling induced decomposition of initiator, however, is that which is discussed in Sec. 3-6b-3. 3-4g-2 Mechanism of f < 1: Cage Effect

The values of f for most initiators lie in the range 0.3 0.8. To understand why the initiator ef ciency will be less than unity, consider the following reactions that occur in

p(t) -

polymerizations initiated by benzoyl peroxide:

0 (c5t2) ,

COO OOC [2 COO ] [2 COO ] + M [2 COO ] COO COO 2 + M + COO + M + M COO 2 COO COOM CO2 [2 COO ] [ COO + CO2] CO2 + COOM

(6.67)

3-67 3-68 3-69 3-70 3-71 3-72 3-73 3-74 3-75

where the braces stand for the anticommutator. The master equation is given by (411]

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