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Many monomers appear to undergo a spontaneous polymerization when heated in the apparent absence of catalysts. On careful investigation few of these involve the thermal production of radicals from the monomer. In most cases the observed polymerizations are initiated by the thermal homolysis of impurities (including peroxides or hydroperoxides formed due to O2 ) present in the monomer. Most monomers, when exhaustively puri ed (and in exhaustively puri ed reaction vessels), do not undergo a purely thermal, self-initiated polymerization in the dark. Only styrene has been unequivocally shown to undergo self-initiated polymerization. Methyl methacrylate was also considered to undergo self-initiated polymerization, but more recent work indicates that most, but not all, of the previously reported selfinitiated polymerization was caused by adventitious peroxides that were dif cult to exclude by the usual puri cation techniques [Lehrle and Shortland, 1988]. Other monomers that may be susceptible to self-initiated polymerization are substituted styrenes, acenaphthylene, 2vinylthiophene, and 2-vinylfuran as well as certain pairs of monomers [Brand et al., 1980; Hall, 1983; Lingnau et al., 1980; Sato et al., 1977]. The rate of self-initiated polymerization is much slower than the corresponding polymerization initiated by thermal homolysis of an initiator such as AIBN, but far from negligible; for example, the self-initiated polymerization rate for neat styrene at 60 C is 1:98 10 6 mol L 1 s 1 [Graham et al., 1979]. The initiation mechanism for styrene has been established [Graham et al., 1979; Kaufman, 1979; Kothe and Fischer, 2001; Mayo, 1968; Olaj et al., 1976, 1977a,b]. It involves the formation of a Diels Alder dimer (XII) of styrene followed by transfer of a hydrogen atom from the dimer to a styrene molecule (Eq. 3-63). Whether formation of the



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where we have inserted a complete set of unperturbed atomic eigenstates between Pa, and Pa, ' The angular frequencies Wab == Wa - Wb correspond to the atomic transitions from la} to Ib).

(3-63a)

(3-63b)

3Equation (6.25) only involves the unperturbed momentum, p .. , because the perturbation does not affect momentum. The perturbation only affects functions of the canonically conjugate variable r such as the Coulomb potential.

124 132 11 Creating a Presentation 12 Populating Presentation Slides 13 Assembling and Presenting a Slide Show





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Diels Alder dimer or its reaction with styrene is the rate-determining step in initiation is not completely established. The dependence of Rp on [M] is closer to third-order than secondorder, indicating that Eq. 3-63b is the slow step. The Diels Alder dimer has not been isolated, but ultraviolet spectroscopy of the reaction system is entirely compatible with its presence. There are indications that the photopolymerization of neat styrene proceeds by a similar mechanism. The initiation mechanism for methyl methacrylate appears to involve the initial formation of a biradical by reaction of two monomer molecules followed by hydrogen transfer from

W~b (a IPa, (t) I b)

3-64

(a ifa, (t)I b),

some species in the reaction system to convert the biradical to a monoradical (Eq. 3-64) [Lingnau and Meyerhoff, 1984a,b]. Spontaneous polymerization is also observed in certain pairs of monomers such as styrene-acrylonitrile and maleimide vinyl ether [Decker, 2000; Liu et al., 1995]. These are monomer pairs in which one double bond is electron-rich and the other is electron-poor (Sec. 6-3b-3).

(6.30)

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3-4f Other Methods of Initiation Electrolysis of monomer solutions has been studied as a means of initiating polymerization [Olaj, 1987; Otero and Mugarz, 1987] Aqueous and various organic solvents (eg, DMF, methylene chloride, methanol) have been employed in the presence of various inorganic compounds The latter are used either to conduct current or participate in the initiation process Depending on the components present, radicals and/or ions are formed when current is passed through the reaction system, and these initiate polymerization Such polymerizations are referred to as electroinitiated or electrolytic polymerizations An interesting example is the electrolysis of an acetonitrile solution of acrylamide containing tetrabutylammonium perchlorate [Samal and Nayak, 1988] Radical polymerization occurs at the anode initiated by ClO4 formed by oxidation of ClO Anionic polymerization occurs at the cathode initiated 4 by direct transfer of electrons to the monomer (Sec 5-3a-2).

(~Hatom) =-~~{

Plasma polymerization occurs when a gaseous monomer is placed in an electric discharge at low pressures under conditions where a plasma is created [Boenig, 1988; Yasuda, 1986] A plasma consists of ionized gaseous molecules In some cases, the system is heated and/or placed in a radiofrequency eld to assist in creating the plasma A variety of organic molecules including alkenes, alkynes, and alkanes undergo polymerization to high-molecularweight products under these conditions The propagation mechanisms appear to involve both ionic and radical species Plasma polymerization offers a potentially unique method of forming thin polymer lms for uses such as thin- lm capacitors, antire ection coatings, and various types of thin membranes Sonication, the application of high-intensity ultrasound at frequencies beyond the range of human hearing (16 kHz), of a monomer results in radical polymerization Initiation results from the effects of cavitation the formation and collapse of cavities in the liquid.

L(alfa(t)lb}.(blfa(t)la}

The collapse (implosion) of the cavities generates very high local temperatures and pressures This results in the formation of excited states that leads to bond breakage and the formation of.

(a Ira(t) I b} . (b Ira(t)1 a)}.

f1 0

PowerPoint is a presentation program you can use to convey all kinds of messages to an audience. You can use PowerPoint to create slide shows to present ideas to clients, explain a concept or procedure to employees or teach a class. In this part, you learn how to create slide shows; add text, tables, charts, video clips and pictures to your slide show; and package your show on a CD-ROM or output it as a movie file. You also learn how to add special effects, including animations, sound effects, and transitions to make your slide show lively and engaging.

6-33

(6.31)

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