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of cyclotriphosphazenes without any halogens (e.g., hexamethylcyclotriphosphazene or hexamethylaminocyclotriphosphazene) to polymerize is ascribed to the absence of an easily ionizable bond to phosphorus. However, polymerization is possible for partially substituted chlorocyclotriphosphazenes, although the reaction is less ef cient than that for the fully halogenated monomer. Many mechanistic features of (NPCl2 3 polymerization are unclear. Termination may involve reaction of propagating centers with PCl5 (which is used in monomer preparation and may be present as a trace impurity) or other Lewis acid (including water) present as a catalyst. The branching and crosslinking that can occur during polymerization are increased by the presence of water concentrations above $0.1%, although the water also acts as a retarder. Below the 0.1% level water accelerates the polymerization rate. This is reminiscent of the effect of water in many cationic polymerizations of alkenes (Sec. 5-2a-2). Alkyl and aryl derivatives of poly(dichlorophosphazene) are not ef ciently synthesized by nucleophilic reaction of LXXXIV with metal alkyls or aryls. The halogen substitution reaction occurs but is accompanied by polymer chain cleavage. Use of poly(di uorophosphazene) or introduction of aryl and alkyl groups at the monomer stage offer some improvement, but neither method is fully satisfactory. The best route to alkyl and aryl derivatives is polymerization of N-(trimethylsilyl)-P,P-dialkyl-P-halophosphoranimines at moderate temperatures (25 60 C) in the presence of a Lewis acid [Allcock et al., 1996, 2000, 2001a,b; Neilson and Wisian-Neilson, 1988]. The reaction proceeds as a cationic chain polymerization:

NSi(CH3)3

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Bounds on the values of the constants kl and can be readily determined by considering the modulus of the expression in (8.4): exp(w7z)

The phosphoranimine route also allows an alternate route to poly(dichlorophosphazene) by using N-(trimethylsilyl)-P,P,P-trichlorophosphoranimine as the monomer. The phosphoranimine route not only ef ciently produces alkyl and aryl poly(phosphazene)s but also offers

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Perhaps the biggest vulnerability is that enterprises are unable to efficiently patch laptops when they are mobile That is exactly the problem that caused Sharelle s machine to become infected If her machine had contained all the necessary patches, then it wouldn t have been susceptible to Lane s exploit This is a huge concept to understand The enterprises that I speak with on a daily basis very often have a solution in place to patch their desktop computer systems They utilize SMS, Radia, Altiris or similar technologies These solutions may not do a bad job ensuring that their desktops have patches, but they are notorious for doing a bad job ensuring that mobile devices receive their patches Think about how Sharelle would operate She would bounce from office to office doing her job, never staying in one spot for very long.

other potential bene ts compared to the ROP route from hexachlorocyclotriphosphazene [Allcock et al., 2001a,b]. The ROP route produces high-molecular-weight polymers (up to 105 106 ), but the molecular weights are not easily controlled and the molecular weight distributions are broad (usually bimodal). The phosphoranimine reaction has some characteristics of a living polymerization. Polymers with narrower MWD with molecular weights as high as 105 have been obtained. The polymerizations of other cyclic phosphazenes have also been studied, including carbophosphazene, thiophosphazene, and thionylphosphazene [De Jaeger and Gleria, 1998; McWilliams et al., 2000]

The silicon-bridged [1]ferrocenophane LXXXV undergoes polymerization at 120 150 C to yield polymers of number-average molecular weights up to 105 with PDI $1.5 2.5

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l{exp(-w7s/2)

[Manners, 2002]. Anionic polymerization proceeds under milder conditions (25 C) with good MW control (PDI <1.2) [Kulbaba and Manners, 2001; Ni et al., 1996]. A variety of other metallocenophanes have also been studied, including ferrocenophanes with GeR2 , S, CH2 CH2 , and CH2 S bridges and the chromium and ruthenium analogs.

Anionic polymerization of cyclic phosphates (LXXXVI) and phosphonates (LXXXVII) yields high-MW polymers,

As a result, she was never around when the patches were being pushed This is one of the major ironies of technology and mobility The machines that are already the most protected, the stationary desktops on the LAN, are the ones that are able to receive the patches The mobile devices that are the most susceptible to exploitation don t have a good way of receiving the patches on a regular basis This type of problem reminds me of what happened during the 2005 holiday season As with Christmastime most years, people were working from home more than at any other time of the year In addition, they were using their work computers for personal use more than ever They were buying things online, surfing the Internet, playing games online, and so forth Then a bunch of Internet Explorer vulnerabilities became exposed.

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+ exp(w7x/2))21

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