Using polysilanes

Photopolymerization using polysilanes can also be carried out to yield block copolymers containing runs of silicon atoms, for instance polysilane-methyl methacrylate. The resulting copolymer can then be used as a macro-photoinitiator for further free-radical polymerizations.144145... 

Titanates have been instrumental in the bonding of fluorinated resins to packaging films, poly(hydantoin)—polyester to polyester wire enamel, polysulfide sealant to polyurethane (a phosphated titanate is recommended), polyethylene to cellophane using a titanated polyethylenimine, and silicone mbber sealant to metal or plastic support using polysilane (Si—H) plus polysiloxane (Si—OR) and titanate as the adhesive ingredients (450—454). Polyester film coated first with a titanium alkoxide, then with a poly(vinyl alcohol)—polyethylenimine blend, becomes impermeable to gases (455). 

Ueno, M., Suzuki, T Naito, T., Oyamada, H., and Kobayashi, S. (2008) Development of microdiarmel reactors using polysilane-supported palladium catalytic systems in capillaries. Chem. Commun., 1647-1649. 

Ring-Opening Polymerization. As with most other inorganic polymers, ring-opening polymerization of cyclotetrasilanes has been used to make polysilanes (109,110). This method, however, has so far only been used for polymethylphenylsilane (eq. 12). Molecular weights (up to 100,000) are higher than from transition-metal catalyzed polymerization of primary silanes. 

Polymerization ofiVIasked Disilenes. A novel approach, namely, the anionic polymerization of masked disilenes, has been used to synthesize a number of poly(dialkylsilanes) as well as the first dialkylamino substituted polysilanes (eq. 13) (111,112). The route is capable of providing monodisperse polymers with relatively high molecular weight M = lO" — 10 ), and holds promise of being a good method for the synthesis of alternating and block copolymers. 

The polysdanes are normally electrical insulators, but on doping with AsF or SbF they exhibit electrical conductivity up to the levels of good semiconductors (qv) (98,124). Conductivities up to 0.5 (H-cm) have been measured. However, the doped polymers are sensitive to air and moisture thereby making them unattractive for practical use. In addition to semiconducting behavior, polysilanes exhibit photoconductivity and appear suitable for electrophotography (qv) (125—127). Polysdanes have also been found to exhibit nonlinear optical properties (94,128). 

Investigations of silicon-metal systems are of fundamental interest, since stable coordination compounds with low valent silicon are still rare [64], and furthermore, silicon transition-metal complexes have a high potential for technical applications. For instance, coordination compounds of Ti, Zr, and Hf are effective catalysts for the polymerization of silanes to oligomeric chain-silanes. The mechanism of this polymerization reaction has not yet been fully elucidated, but silylene complexes as intermediates have been the subject of discussion. Polysilanes find wide use in important applications, e.g., as preceramics [65-67] or as photoresists [68-83],... 

Recently, the compounds CpCp Hf(Cl)Si(SiMe3)3 and CpCp Zr(Cl)Si(SiMe3)3 have been used as homogenous catalysts for the formation of polysilanes. 

The history and development of polysilane chemistry is described. The polysilanes (polysilylenes) are linear polymers based on chains of silicon atoms, which show unique properties resulting from easy delocalization of sigma electrons in the silicon-silicon bonds. Polysilanes may be useful as precursors to silicon carbide ceramics, as photoresists in microelectronics, as photoinitiators for radical reactions, and as photoconductors. 

Proton, 13C and 29Si NMR spectra for polysilanes have been recorded.(32) The proton NMR provide little structural information, but integration of areas under the proton resonances is quite useful for determining the composition of copolymers. 

Possible ways in which polysilanes may be useful include, 1. As precursors to silicon carbide ceramics 2. As photoinitiators in radical reactions 3. As photoconductive materials, and 4. As photoresists in microelectronics. The last of these uses will be treated in the chapter by Miller,(31) and so will not be covered here. 

Soluble polysilane polymers can also be used as precursors to silicon carbide. The first such application, using (PhMeSi)n-(Me2Si)m copolymers ("Polysilastyrene"), was to strengthen silicon nitride ceramics. The Si3N4 ceramic body was soaked in polysilane and refired, leading to the formation of silicon carbide whiskers in the pore spaces and a consequent increase in strength. (U)... 

As these experiments indicate, polysilanes can in some cases be converted to silicon carbide directly, without the necessity for formation of polycarbosilane, fractionation, or oxidation. For example, polysilastyrene copolymers can be formed into films or fibers and then crosslinked by irradiation with UV light. The crosslinked polysilane forms silicon carbide when heated to 1100°C in vacuum. (1U This method can be used in a "printing" mode, if a film of polysilane is cast onto a ceramic or metal substrate, then... 

Polysilanes as Photoinitiators. Since polysilanes photolyze to give silyl radicals,(21) as explained in the section on photochemistry above, they can be used as photoinitiators for radical processes such as polymerization.38 As can be seen from the information in Table II, this process is a fairly general one a variety of... 

Although polysilanes have been used mostly as photoinitiators for polymerization, they may also find application as initiators for other radical reactions. Experiments to test this possibility are now being carried out. 

Thin films of this polymer generate third harmonic radiation upon irradiation at 1064 nm, believed to be due to a three-photon resonance. Thus polysilane polymers may eventually find use in laser technology. 

Table I. Some Representative Polysilanes Produced in Toluene Using Sodium in a Direct Addition Mode...

Contrast enhancement lithography is a clever procedure which uses a bleachable contrast enhancing layer to restore the distorted aerial image of the mask which has been blurred by diffraction effects into a sharp image at the underlying photoresist surface. The process is too complicated to explain in detail here and the interested reader is referred to the cited literature (60,61). Suffice it to say that the large extinction coefficients of most polysilane derivatives coupled with their ready bleachability make them ideally suited for such purposes and we have demonstrated this application at 313 nm (16,18). 

A rapidly increasing number of publications on polysilanes documents current interest in these polymers (JJ. Polysilanes are potentially applicable in microlithography as high resolution UV-resists (2J, imageable etch barriers ), or contrast enhancement layers (4). They have been successfully used as precursors to Si-C fibers (5J and ceramic reinforcing agents ((L). Polysilanes have also initiated polymerization of vinyl monomers (J ). Doping of polysilanes have increased their conductivity to the level of semiconductors (8). Very recently polysilanes were used as photoconductors (9) and non-linear optical materials (10b... 

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