By J. M. G. Cowie (auth.), J. M. G. Cowie (eds.)

Examination of the early literature attests to the truth that the research of copolymerization was once initiated whilst polymer technology was once in its infancy. It has persisted to develop to a subject matter of significant significance and has been a resource of curiosity to either educational and industrialist alike. The huge spectrum of constructions and houses on hand within the statistical copolymer has made this a fruitful box of exploration, yet one specific and extra constrained shape which has held its personal fascination for plenty of is the proscribing case of the strictly alternating copolymer. this is often shaped, within the perfect state of affairs, while monomers in a response blend upload consecutively to create a polymer chain with a standard {ABABAB} constitution, without reference to the monomer feed ratio. while this occurs the ensuing copolymer will consistently have a similar composition, a function which are valuable but additionally a bit of restrictive, because the skill to change the houses is then constrained. inside of a sequence entitled Speciality Polymers it sort of feels acceptable then to house this topic, quite as no past test has been made to attract jointly a few of the features of alternating copolymerization into one quantity. It additionally turns out well timed to provide a extra unified photograph of the topic in an effort to additionally illustrate the growth made.

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24) where (25) and (26) If X = [M 2]/[M 1], the molar feed ratio of the monomers, R; is the rate of initiation, and K is the equilibrium constant for the CTC, then application of steady-state conditions leads to (27) with (28) and (29) 40 J. M. G. Cowie so that (30) A plot of Rp/[M] against [M] will then give A(X) and F(X) = K(k 1c/k 12 + k 2 cX/k21 ), for a given value of X. Substitution of these values into equations (28) and (29) will yield the rates of the reactions for free monomers and the CTC, respectively.

Figure It. Variation of the ratio of overall initial copolymerization rate RP to N-vinyl carbazole concentration [M 1], with [M 1], for the N-vinyl carbazole-diethyl fumarate system. 000. (From Ref. ,a:: 0 0 cY> 0 N merization in benzene and butanone were calculated and the differences can be seen in Figure 14. In benzene the participation of the CTC is very much higher than the free monomer, whereas in butanone the reverse is true although the concentration now plays a significant role and the free monomer becomes less dominant with increasing concentration.

G. Cowie so that (30) A plot of Rp/[M] against [M] will then give A(X) and F(X) = K(k 1c/k 12 + k 2 cX/k21 ), for a given value of X. Substitution of these values into equations (28) and (29) will yield the rates of the reactions for free monomers and the CTC, respectively. Furthermore, by plotting F(X) against X an estimate of K(k 1c/ k 12 ) and K(k 2 c/ k 21 ) can be obtained. Finally, by looking at the variation of A(X) with X, the termination process can be examined, and by defining G(X) = [___£_] A(X) 2 (31) then (32) will provide an estimate of the ratios of the various rate constants from a graph of G(X) against X.

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