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Once we solve (2.63) and find G(tlt'), the solution (t) of (2.56) for an arbitrary driving force F( t) can be obtained by doing the integral

larger than monomer (i.e., for dimer and larger) [Goel et al., 1977; Gupta et al., 1979a,b]. The following terms are de ned:



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You can view your table data using two different view modes: Datasheet view and Design view. In Datasheet view, the table appears as a grid of intersecting columns and rows where you can enter data. In Design view, you can view the skeletal structure of your fields and their properties and modify the design of the table. For example, you can add fields by typing new field names in the Field Name column. You can also change the field names or change the type of data that is allowed within a field, such as text or number data.

(t) =

u km kp 2-55 2-56





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where km is the rate constant for A and B groups that are part of monomer molecules and kp is the corresponding rate constant for A and B groups that are part of all species larger than monomer Figure 2-6 shows the results plotted as the polymer degree of polymerization versus t for various values of u The mathematical solution of this case shows that the initial limiting slope (at t ! 0) is u=2 while the nal limiting slope (at large values of t) is 1 independent 2 of the value of u Most of these features are evident in Fig 2-6 Dimer is produced more rapidly when monomer is more reactive than the larger-sized species (that is, the larger the value of u) There is a subsequent slower rate of increase in X n with the limiting slope of 1 being reached more rapidly for larger u values.

dt' G(tlt')F(t')

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The initial rate of increase of X n is slower 2 for u < 1 (monomer less reactive than larger sized species), and it takes longer to reach the limiting slope of 1 More signi cantly, it takes much longer reaction times to reach a parti2 cular degree of polymerization when u < 1 This is a kinetic characteristic of consecutive (series) reaction systems the overall rate of production of the nal product (high polymer) is faster when the initial reaction (reaction of monomer) is faster and the later reaction (reaction of dimer and larger sized species) is slow than vice versa The trends described in this section would also apply (qualitatively at least) for the case where k is a continuously varying function of molecular size If k increases with molecular size, the situation is qualitatively analogous to the above system for u < 1.

(2.64)

The situation is analogous to u > 1 when k decreases with molecular size..

I =

2-3 ACCESSIBILITY OF FUNCTIONAL GROUPS In order for a polymerization to yield high polymers the polymer must not precipitate from the reaction mixture before the desired molecular weight is reached. Premature precipitation effectively removes the growing polymer molecules from the reaction; further growth is prevented because the polymer s functional end groups are no longer accessible to each other. The effect can be seen in Table 2-4 for the polymerization of bis(4-isocyanatophenyl)methane with ethylene glycol [Lyman, 1960]:

dt' c5(t - t')F(t')

7-96

(2.65)

Propagation follows in a similar manner (Eq. 7-97), and the overall result is the insertion of the halves of the double bond of monomer into the metal carbene bond. Evidence for

Note: An even quicker way to switch from Datasheet view to Design view is to click the top half of the View button.

= F(t).

7-97

Let us use a Fourier transform to solve (2.63):

cleavage of the double bond instead of an adjacent single bond comes from analysis of the ozonolysis products from a copolymer of cyclooctene and 1-14C-cyclopentene. The metal carbene propagating centers can be terminated by conversion to double bonds by a Wittig-type reaction with an aldehyde. The nal polymer has terminal double bonds at both chain ends as well as a double bond in the repeat unit. Aside from cyclohexene, which yields only very-low-MW oligomers, a wide range of cycloalkene and bicycloalkenes have been polymerized to high-MW products. There are

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