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Various methods are employed for the experimental evaluation of the initiator ef ciency. (These methods are generally also applicable to determining f for photopolymerization). One method involves the determination and comparison of both the initiator decomposition and the production of polymer molecules. The initiator decomposition is best determined during an actual polymerization. Independent measurement of initiator decomposition in the absence of monomer can give erroneous results. The rates of decomposition of initiator can be quite different for pure initiator as compared to initiator in the presence of monomer, since f varies with monomer concentration. Also in some cases monomer is involved in the initiation step [e.g., molecule-induced homolysis (Eq. 3-35), certain redox initiations described in Sec. 3-4b-1]. AIBN decomposition can be followed relatively easily by following the evolution of nitrogen. Measurement of the polymer number-average molecular weight allows a determination of f by comparison of the number of radicals produced with the number of polymer molecules obtained. This method requires a knowledge of whether termination occurs by coupling or disproportionation, since the former results in two initiator fragments per polymer molecule and the latter in only one. The occurrence of induced decomposition must be taken into account in calculating the number of radicals produced. Induced decomposition is negligible for azonitriles but occurs to an appreciable extent with many peroxides. The second method is a variation of the rst in which the number of initiator fragments in the polymer is determined by direct analysis of the polymer end groups. The analysis is relatively dif cult to perform accurately because of the low concentration of the end groups. For a 50,000-molecular-weight polymer, the end groups constitute only $0.1% of the total



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(at + a) (b} + bj )

independent of whether the other functional groups in the monomer have reacted. Neither of these assumptions is valid for 2,4-tolylene diisocyanate (IV)

(:c Xj ).

which is one of diisocyanate monomers used in the synthesis of polyurethanes [Caraculacu and Coseri, 2001]. Urethane formation can be depicted as occurring by the sequence

(7.82)

2-36





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where B: is a base catalyst (e.g., a tertiary amine). The reaction involves a rate-determining nucleophilic attack by the alcohol on the electrophilic carbon-nitrogen linkage of the isocyanate. This is substantiated by the observation that the reactivity of the isocyanate group increases with the electron-pulling ability of the substituent attached to it [Kaplan, 1961]. In 2,4-tolylene diisocyanate several factors cause the reactivities of the two functional groups to differ. These can be discussed by considering the data in Table 2-3 on the reactivities of various isocyanate groups compared to that in phenyl isocyanate toward reaction with

'E <Pkjbj,

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TABLE 2-3 Reactivity of Isocyanate Group with n-C4H9OHa Rate Constantsb k2 k1 =k2 k1 0.406 0.210 0.0655 4.34 3.15 0.884 1.98 0.517 0.343 0.143 0.166 8.39 9.18 6.18 11.9

(7.83)

Isocyanate Reactant Monoisocyanate Phenyl isocyanate p-Tolyl isocyanate o-Tolyl isocyanate Diisocyanates m-Phenylene diisocyanate p-Phenylene diisocyanate 2,6-Tolylene diisocyanate 2,4-Tolylene diisocyanate

k+ 1 andk < N, (7.85)

n-butanol at 397 C in toluene solution with triethylamine as the catalyst [Brock, 1959, 1961] It is clear that a methyl substituent deactivates the isocyanate group by decreasing its electronegativity; the effect is greater when the substituent is at the nearby ortho position For the diisocyanates in Table 2-3 k1 is the rate constant for the more reactive isocyanate group, while k2 is the rate constant for the reaction of the less reactive isocyanate group after the more reactive one has been converted to a urethane group One isocyanate group activates the other by electron withdrawal, as shown by the increased reactivity in the diisocyanates relative to the monoisocyanates However, once the rst isocyanate group has reacted the reactivity of the second group decreases, since the urethane group is a much weaker electron-pulling substituent than the isocyanate group.

+ 1 and k =I N,

For 2,4-tolylene diisocyanate analysis of the experimental data at low conversion shows the para isocyanate group at be 27 times as reactive as the ortho groups However, the effective difference in reactivity of the two functional groups is much greater k1 =k2 11:9 , since the reactivity of the ortho group drops an additional factor of approximately 4 after reaction of the para isocyanate group The reactivity differences of the two functional groups in 2,4-tolylene diisocyanate result from its unsymmetric and aromatic structure The environments (steric and electrostatic) of the two isocyanate groups are different to begin with, and the effect of reaction of one group is ef ciently transmitted through the conjugated p-electron system of the aromatic ring.

(7.86) (7.87)

These differences disappear for a reactant such as 1,4-cyclohexylene diisocyanate, which is symmetric to begin with and possesses no aromatic system to transmit the effect of the reacted isocyanate group to the unreacted group The change in reactivity of one functional group upon reaction of the other has been noted in several systems as a diference in the reactivity of monomer compared to the other-sized species, although all other species from dimer on up had the same reactivity [Hodkin, 1976; Yu et al, 1986] This behavior usually occurs with monomers having two functional groups in close proximity and where polymerization involves a signi cant change in the electrondonating or electron-withdrawing ability of the functional group Thus the reactivity of the hydroxyl group in ethylene glycol (V) toward esteri cation is considerably higher than the hydroxyl of a half-esteri ed glycol (VI) [Yamanis and Adelman, 1976] The nucleophilicity.

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