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There is usually little or no difference in reactivity between free ions and ion pairs, similar to the situation in the polymerization of carbon carbon double bond monomers [Penczek, 2000]. Covalent species are present in many systems as detected by NMR and other methods, but whether they are reactive or dormant is not always clear. When propagation by covalent species occurs, it is not covalent-to-covalent propagation in which monomer is inserted into a covalent bond to produce a new covalent propagating species containing an additional monomer unit [Penczek et al., 1995]. Covalent propagation is a two-step process. Monomer adds to the covalent species to form an ionic species (Eq. 7-22a), which collapses to (is in



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equilibrium with) the covalent species (Eq. 7-22b). Covalent propagation has been con rmed in the polymerization of THF by tri ic esters. Whereas methyl tri ate is covalent, a mixture

(7.127)





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of oxonium ion and macroester is obtained when methyl tri ate is mixed with THF. Covalent propagation is slower than ionic propagation, typically by a factor of 102 103 or more. The covalent species predominate over ionic species in most systems. In the THF/methyl tri ate system, covalent species account for about 95% of species in CCl4 solution. Ionic species predominate, about 95%, in the very polar solvent CH3NO2, but this solvent is not one that would generally be employed in industrial applications. When covalent species are the major species present, they act effectively as dormant species because of their lower reactivity compared to ionic species. This slows down propagation and allows suf cient time for initiation to be complete. The result is living polymerization by reversible deactivation of ionic propagating species, similar to the situation in living radical and ionic polymer izations of C C monomers.

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as it is trivially satisfied by definition with B(v) given by (7.124). So (7.124), (7.125), and (7.126) are enough to define B(v) uniquely except for a global phase factor. We must now determine a( v) and {3( v, 1]) and show that the diagonalization is consistent. From (7.124) and (7.125), we obtain the following system of coupled equations (Problem 7.4):

7-2b-2

va(v) v{3(V,1])

A variety of initiator systems, of the types used in the cationic polymerization of alkenes (Sec. 5-2a); can be used to generate the tertiary oxonium ion propagating species [Dreyfuss and Dreyfuss, 1969, 1976; Inoue and Aida, 1984; Penczek and Kubisa, 1989a,b]. Strong protonic acids such as tri uoroacetic, uorosulfonic, and tri uoromethanesulfonic (tri ic) acids initiate polymerization via the initial formation of a secondary oxonium ion

+ d1] V(1]){3(v, 1]), = 1]{3(v, 1]) + V(1])a(v).

7-23

woa(v)

When you move the mouse pointer to the bottom left corner, faint slide show control buttons appear.

7-24

(7.128) (7.129)

This type of initiation is limited by the nucleophilicity of the anion A derived from the acid. For acids other than the very strong acids such as uorosulfonic and tri ic acids, the anion is suf ciently nucleophilic to compete with monomer for either the proton or secondary and tertiary oxonium ions. Only very-low-molecular-weight products are possible. The presence of water can also directly disrupt the polymerization since its nucleophilicity allows it to compete with monomer for the oxonium ions.

IOPor a general demonstration that the formal expression derived by Huttner and Barnett is indeed the same dielectric permittivity that appears in the classical theory, see [167].

Lewis acids such as BF3 and SbCl5, almost always in conjuction with water or some other protogen, initiate polymerization of cyclic ethers. The initiator and coinitiator form an initiator coinitiator complex [e.g., BF3 H2O, H (SbCl6) ], which acts as a proton donor (Sec. 5-2a-2). Cationic photopolymerizations are achieved when similar proton donors are formed by the photolysis of diaryliodonium and triarylsulfonium salts (Sec. 5-2a-4). The use of a cationogen such as an alkyl or acyl halide with a Lewis acid generates carbocations and acylium ions, either in situ or as isolable salts, which can initiate polymerization, for example

3CCl + AgSbF6 O 3CCl + SbCl5 AgCl + 3C +(SbF6) O C+(SbCl6)

+ z(v)8(v -

7-26 7-25

ry).

The initiation with some carbocations, especially trityl, does not involve direct addition to monomer. The carbocation abstracts a hydride ion from the a-carbon of monomer and the newly formed carbocation initiates polymerization [Afsar-Taromi et al., 1978; Kuntz, 1967]. This hydride ion abstraction is so facile with 1,3-dioxolane that it is used to preform stable 1,3-dioxolan-2-ylium salts (XII) that can be used subsequently as initiators [Jedlinski et al., 1985].

(7.130)

7-27

z(v)

Click anywhere in the slide to advance to the next slide or click the Next button ( ).

Since the tertiary oxonium ion is the propagating species, preformed oxonium ions such as triethyloxonium tetra uoroborate can be used for initiation (Eq. 7-28) [Meerwein et al., 1960]:

thus,

7-28

-V-a(v);

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