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TABLE 3-2 Half-Lives of Initiators a;b Half-Life at 70 C 85 C 100 C 130 C 175 C 50 C 74 h 158 h 4.8 h 7.3 h 8.1 h 1.4 h 1.1 h 88 h 7.2 min 20 min 13 h 218 h 338 h 18 min 1.7 h 6.4 h 4.81 h

Initiator Azobisisobutyronitrile Benzoyl peroxide Acetyl peroxide t-Butyl peracetate Cumyl peroxide t-Butyl peroxide t-Butyl hydroperoxide

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Data from Brandrup and Immergut [1989], Brandrup et al. [1999], and Huyser [1970]. Half-life (t1=2 ) values are for benzene or toluene solutions of the initiators.

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t1=2 0:693 kd 3-29

Select the cell, range or data that you want to format. Click the Home tab on the Ribbon. Click the Number Format Click a number format. Excel applies the number format to the data.

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by setting I I 0 =2. Table 3-2 lists the initiator half-lives for several common initiators at various temperatures. 3-4a-2 Kinetics of Initiation and Polymerization

(3.164)

The rate of producing primary radicals by thermal homolysis of an initiator Rd (Eqs. 3-13 and 3-26) is given by





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This is not equivalent to the description in terms of;f; because now a photon of negative helicity has positive energy. This and the analogy with the case of the electron, which can take all the available values of its helicity, show that there must be two positiveenergy (negative-energy) photon states for each given momentum: one with positive helicity, the other with negative helicity. To accommodate this, we define the photon wavefunction to be the six-component column matrix (just as Bialynicki-Birula does in [53-55])

Rd 2fkd I 3-30

1/;= [

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where [I] is the concentration of the initiator and f is the initiator ef ciency. The initiator ef ciency is de ned as the fraction of the radicals produced in the homolysis reaction that initiate polymer chains. The value of f is usually less than unity due to wastage reactions. The factor of 2 in Eq. 3-30 follows the convention previously discussed for Eq. 3-23. The initiation reaction in polymerization is composed of two steps (Eqs. 3-13 and 3-14) as discussed previously. In most polymerizations, the second step (the addition of the primary radical to monomer) is much faster than the rst step. The homolysis of the initiator is the rate-determining step in the initiation sequence, and the rate of initiation is then given by

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Ri 2fkd I 3-31

Xanthates have also been used as RAFT agents. RAFT polymerization has been observed for methacrylate monomers using double bond end-capped methacrylate oligomers [Gridnev and Ittel, 2001]. RAFT is actually a specialized form of degenerative transfer (DT). In DT using alkyl iodides as the transfer agent, there is a direct transfer of iodide between dormant polymer chains and propagating radicals instead of the addition fragmentation sequence [Goto et al., 1998]. The method works primarily with styrene, but narrow molecular weight distributions are not achieved with other monomers. The chain transfer constants for alkyl iodides are not suf ciently high, which results in slow consumption of the DT agent, broad PDI, and much normal termination. The presence of 1,1-diphenylethene (DPE) in the polymerization of a monomer results in a living polymerization [Raether et al., 2002; Wieland et al., 2002]. DPE adds reversibly to a propagating chain to form a dormant stable radical with no (or very low) reactivity to add monomer. This sets up an equilibrium between propagating chains (active species) and dormant DPE-terminal radicals. Other systems include organotellurium and boroxyl-based initiators [Chung et al., 1996; Yamago et al., 2002).

(3.165)

Organometallic compounds containing polymerizable carbon carbon double bonds have been synthesized and their polymerization studied [Archer, 2001; Pittman et al., 1987]. Among the organometallic monomers studied are vinylferrrocene and trialkyltin methacrylate. Much of the interest in these polymerizations has been to obtain polymers with

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3 1 4

improved thermal stability or electrical (semi)conductivity, but these objectives have not been realized. Trialkyltin methacrylate polymers have been studied for formulating antifouling marine paints to prevent growth of barnacles and fungi on shore installations and ship bottoms [Yaeger and Castelli, 1978]. 3-16b Functional Polymers

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A functional polymer is a polymer that contains a functional group, such as a carboxyl or hydroxyl group. Functional polymers are of interest because the functional group has a desired property or can be used to attach some moiety with the desired property [Patil et al., 1998]. For example, a medication such as chloroamphenicol, a broad-spectrum antibiotic,

(3.166)

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