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Simultaneously with propagation by Eqs. 7-52 and 7-53, there is propagation by selfreaction of XXVII. XXVII is an AB type of monomer, and step polymerization occurs by reaction between amine and lactam end groups. Actually, the lactam end groups are protonated prior to reaction. The reaction is generally the same as Eq. 7-52 nucleophilic attack of amine on protonated lactam. Although this reaction is only a minor contribution to the overall conversion of lactam to polymer, it determines the nal degree of polymerization. There are also exchange reactions that involve intermolecular nucleophilic attack of amine on amide linkages within a polymer chain. Intramolecular versions of the various reactions result in cyclic oligomer formation. Overall, one generally observes the molecular weight distribution (MWD) of the polymer (excluding cyclic oligomer and monomer) to be close to the Flory most probable distribution. For cationic polymerization with an acid whose anion Z is nucleophilic, initiation involves the sequence described by Eq. 7-51 plus the formation of XXIX. XXIX propagates by a sequence similar to that described by Eqs. 7-52 and 7-53 except that a growing polymer chain possesses a Z end group instead of a lactam end group. CO



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7-54

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Various side reactions greatly limit the conversions and polymer molecular weights that can be achieved in cationic polymerization of lactams. The highest molecular weights obtained in these polymerizations are 10,000 20,000. The most signi cant side reaction is amidine (XXXI) formation [Bertalan et al., 1984]. Propagation of the polymer chain

7-55

[ ood1J !V(1J)1 2

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and amidine formation proceed through the common intermediate XXX formed by attachment of an amine group to the protonated carbonyl of any amide group (that in lactam monomer or the lactam end group in polymer or the amide groups in the repeat units of the polymer). Propagation involves cleavage of the C a bond (overall result is substitution N at carbonyl), while amidine formation involves loss of water from XXX (overall result is addition to carbonyl followed by dehydration). Amidine formation decreases the concentration of amine groups in the reaction system, and this leads to a slower rate of reaction. The water released during amidine formation can initiate polymerization (Sec. 7-3b), but at a slower rate. Furthermore, amidine groups react rapidly with acidic initiators to give relatively unreactive salts, and this limits the rate and degree of polymerization. Cationic polymerization is the only route to the polymerization of N-alkylated lactams. Both the hydrolytic and anionic routes require that a lactam have a hydrogen on the nitrogen. However, there are no commercial applications for N-alkylated polyamides, probably because their lack of hydrogen bonding results in lower melting points than for polyamides without an N-alkyl group.

t dt ,

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Hydrolytic polymerization of E-caprolactam to form nylon 6 (Sec. 2-8f) is carried out commercially in both batch and continuous processes by heating the monomer in the presence of 5 10% water to temperatures of 250 270 C for periods of 12 h to more than 24 h [Anton and Baird, 2002; Zimmerman, 1988]. Several equilibria are involved in the polymerization [Bertalan et al., 1984; Sekiguchi, 1984]. These are hydrolysis of the lactam to E-aminocaproic acid (Eq. 7-56), step polymerization of the amino acid with itself (Eq. 7-57), and initiation of ring-opening polymerization of lactam by the amino acid. The amino acid is

e i (t'-t) Tl f3(t')

7-56 7-57

~ !V(wo)1 2

the equivalent of XXIX in Eq. 7-54 (Z OH). The COOH group of the amino acid protonates the lactam to form XXVI followed by nucleophilic attack of amine on the protonated lactam. The propagation process follows in the same manner with nucleophilic attack of XXXII on protonated lactam to form XXXIII [R CH2 5 ]. Species XXXIII subsequently

ei(t'-t) Tl f3(t').

(n + 1)

Now do these integrals and derive (7.105). 2. As Wo : ~, the integral over 1J can be extended to contour integration and show that

7-58

ei(t'-t) Tl f3(t')

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