Polysilanes and Related Polymers

In polysilane polymers, the polymer backbone is made up entirely of

silicon atoms. Therefore these materials differ from other important
inorganic polymers, the siloxanes and phosphazenes, in which the
polymer chain is heteroatomic. Structurally, they are more closely
related to homoatomic organic polymers such as the polyolefins.
However,because the units in the main chain are all silicon atoms, the
polysilanes exhibit quite unusual properties. The cumulated silicon-
silicon bonds in the polymer chain allow extensive electron
delocalization to take place, and this delocalization of the sigma
electrons in the Si-Si bonds gives the polysilanes unique optical and
electronic properties. Many of the potential technical uses, as well as
the remarkable properties, of polysilanes result from this unusual
mobility of the sigma electrons.
Linear polysilane polymers, properly called poly(silylene)s, can be obtained as
homopolymers or copolymers. Continuation of the polysilane chain consumes two
of the four valences of each silicon atom; the other two are taken up by pendent
groups, which may be the same (5.1) or different (5.2). Copolymers (5.3), which
contain two or more kinds of silicon atoms, can be made up from units like those in
5.1 or 5.2. A typical example is the copolymer of Me2Si and PhMeSi units,
poly(dimethylsilylene-co-phenylmethylsilylene) (5.4), which bears the popular
name “polysilastyrene.” The pendent groups are typically organic units and can
include alkyl, aryl, substituted aryl, hydrogen, Me3Si, ferrocenyl, and so on. An
unlimited number of different polymers are possible, and several hundred
compositions have been described in the literature.
 Synthesis
Condensation of Dichlorosilanes with Alkali Metals
Polysilanes are usually made by dehalogenation of diorganodichlorosilanes with
sodium metal in an inert diluent, following essentially the original method of
Burkhard. Single dichlorosilanes yield homopolymers, while mixtures of
dichlorosilanes lead to copolymers (equations (5), (6)). For many polysilanes,
good results are obtained using finely divided sodium, above its melting point, 98
°C.12 The sodium may be added as a preformed dispersion, or dispersed by
vigorous stirring in the diluent. Toluene is convenient as a diluent because its
boiling point of 111 °C allows the reaction to be carried out at reflux
temperature. An efficient condenser is required because the heat of reaction is
substantial. Other solvents such as alkanes (decane) or ethers (diglyme) may be
used, either alone or mixed with toluene or xylene. Often the chlorosilane(s) are
added slowly to the stirred sodium and diluent, but the reaction can also be
carried by “inverse addition” in which preformed sodium dispersion is added to a
stirred solution of the chlorosilane(s).
 Synthesis of Polysilanes by Wurtz-type Coupling Reactions
In spite of its many drawbacks, the alkali metal-assisted Wurtz-type coupling reaction
remains by far the most widely used procedure for the preparation of polysilanes This
is mainly because of its general applicability to alkyl/ aryldichlorosilanes. The
reaction involved can be represented as follows.

Usually a dispersion of finely divided sodium metal is required for the reaction. This
can be achieved by melting sodium metal in high-boiling solvents such as toluene,
xylene and decane under reflux conditions and by the use of efficient stirring. The
diorganodichlorosilane is added to the sodium dispersion at this stage. This reaction
is highly exothermic and needs to be performed carefully. The entire reaction mixture
is heated further (typically for 2-4 h), cooled and worked-up. One of the common
ways of work-up involves addition of methanol or z'-propanol to the reaction mixture
to destroy the excess of sodium metal. This is followed by precipitation of the
polymer by the addition of an excess of methanol or j-propanol. A large number of
polysilanes such as [R2Si]n and [RR'Si]n have been prepared by adopting this
general procedure. Representative examples of some of the polysilanes prepared by
the Wurtz-type of coupling reaction are shown in Figs. 7.9 and 7.10.
Even polymers
containing
trifluoromethyl
substituents such as
[(CF3CH2CH2)2(Me)
Si]n [28] or those that
contain pyrrolyl
substituents
[Ph(C4H4N)Si]n,
[Me(C4H4N)Si]n and
[«Bu(C4H4N)Si]n
have been prepare
 Polymerization by Anionic Initiators
Cyclosilanes can be used as monomers in a ROP to afford linear chains. Although, as
mentioned earlier the three-membered cyclic compound [(2,6-Et2C6H3)2Si]3 affords a stable
disilene upon photolysis, other strained rings that contain less sterically encumbered
substituents have been used for polysilane synthesis. However, it was observed that the
strained four-membered ring octaphenyltetrasilane [Ph2Si]4 cannot be polymerized to the
linear polymer. Attempts to polymerize this compound leads to a ring expansion and the
formation of the five-membered ring [Ph2Si]5. This led to a modification of the four
membered ring [Ph2Si]4 in the following manner. The reaction of octaphenyltetrasilane with
CF3SO3H leads to partial dearylation. This important reaction in organosilicon chemistry can
be controlled stoichiometrically to effect the replacement of four nongeminal phenyl
substituents from the starting cyclic ring [Ph2Si]4 and to afford the functional and reactive
silyl triflate [Ph(OSO2CF3)Si]4. Further reaction of this compound with
methylmagnesiumbromide leads to l,2,3,4-tetramethyl-l,2,3,4- Tetra phenyl cyclo tetra silane
[PhMeSi]4 which was shown to exist as four stereoisomers. Fractional crystallization of this
compound allowed the isolation of the all-trans derivative which has been used for further ring
opening polymerization
Polysilanes Obtained by Catalytic Dehydrogenation
 Summary of the Synthetic Procedures for Polysilanes
1. Polysilanes can be prepared by (a) a Wurtz-coupling process involving a
diorganodichlorosilane and an alkali metal (b) the use of anionic initiators and the
use of strained cyclosilanes or masked disilenes (c) catalytic dehydrogenation of
primary silanes, RSiH3 and (d) miscellaneous methods including electrochemical
reduction methods, condensation methods involving, for example, reactions
between a monomer containing two reactive Si-Cl end groups and another that has
silyllithium end groups.
2. The Wurtz-coupling is the most widely used synthetic method inspite of its
obvious limitations such as harsh reaction conditions, intolerance to many reactive
functional groups on the silicon monomers and so on. This process leads to
polymers that usually have a bimodal distribution of molecular weights. The yields
of polysilanes are low to moderate. Many poly(alky/arylsilane)s have been prepared
by the use of this method. Many modifications of the Wurtz-coupling reaction have
been tried including use of alternative reducing agents such as CgK. However, there
is still no general procedure that allows a high yield synthesis of polysilanes that
have monomodal, high molecular weights.
3. Strained cyclosilanes can be utilized as monomers in a ringopening
polymerization. These reactions are catalyzed by anionic initiators and can be carried
out by employing milder reaction conditions than the Wurtz-coupling reaction.
However, this process is not general and construction of appropriate strained
cyclosilane monomers is a prerequisite. Similarly, masked disilenes can
be polymerized by anionic initiators. Several interesting polymers have been
prepared by this method including stereoregular polymers. Design of the masked
disilenes has to be carefully carried out and should avoid the use of sterically
hindered groups.
4. Catalytic dehydrogenation is quite effective with monomers such as RSiH3
(particularly when R = an aryl group). Various types of catalysts can be employed to
effect the deydrogenation. Most wellused catalysts are metallocene catalysts
containing Group 4 metals such as titanium, zirconium or hafnium. Although high
molecular weights are not achieved in this process, the polysilanes obtained have
reactive Si-H functional groups that can be elaborated further.
 Modification of Polysilanes
Polysilanes can be elaborated, after their synthesis, by appropriate chemical
methods . Representative methods of such possibilities are discussed in this
section.Polysilanes containing Si-H groups can be reacted further, in a variety of
ways. Waymouth and coworkers have shown that free-radical-assisted addition of
C=C or C=O bonds can be effected.

Free-radical-assisted hydrosilylation can

be carried out on poly(phenylsilane),
H(PhHSi)nH. Various types of reactive
substrates such as 1-hexene,
cyclohexanone etc., have been utilized
and about 70-90% of substitution was
observed without much chain
degradation.
Similarly, the conversion of the Si-H unit in poly(phenylsilane) into the more reactive
Si-Cl and Si-Br functional group can be easily effected by the reaction with carbon
tetrachloride and carbon tetrabromide, respectively. The chlorination or
bromination does not affect the Si-Ph substituent but only involves the Si-H bonds.
In these reactions about 80% of the Si-H bonds can be converted into the
corresponding Si-X bonds. These halogenated polysilanes are reactive polymers that
can react with other types of nucleophiles such as alcohols to afford polysilanes
containing alkoxy groups.
 Physical Properties of Polysilanes
1. Most polysilanes are soluble polymers and dissolve in common organic solvents.
The solubility decreases with increasing crystal- Unity of the polymer. The classic
example of this feature is Burkhard's polymer [Me2Si]n. Other examples include
[Et2Si]n, [Ph2Si]n etc.,. However, disrupting the crystallinity by means of
copolymerization such as that found in [(Me2Si)n(PhMeSi)m] or in homopolymers
that contain longer alkyl chains makes the polymers soluble.
2. Polysilanes have unique electronic properties and this results from the electron
delocalization in the o-bonded chain. Although the Si-Si bond energy is
comparable to that of C-C bond energy, silicon has a lower ionization potential and
a greater electron affinity. The combination of these factors leads to electron
delocalization in the a-bonded chain of polysilanes. Thus, polysilanes can be
compared with organic polymers that have conjugated skeleton such as
polyacetylene. The important difference is that in the latter the conjugation occurs
as a result of delocalized JIelectrons. Because of the a-delocalization of the
electrons, polysilanes show strong absorption in the region between 300-400 nm.
Further, since the c-a* transitions are allowed, the extinction coefficients of the
optical absorption spectra are very high.
3. Polysilanes are radiation-sensitive polymers and degrade upon exposure to UV
light. This process is accentuated in solution.
4. The glass-transition temperatures of polysilanes range from very low values of-75
°C to high values up to +120 °C. Thus, polymers such as [(Me)(«-Hex)Si]n has the
lowest Tg of about -75 °C. As the hexyl group is replaced by shorter chain alkyl
substituents as in [(Me)(CH2CH2CH3)Si]n (-28 °C) the Tg increases. Interestingly,
the related polymer [(Me)(CH2CH2CF3)Si]n (-3 °C) has a higher Tg. In general,
polysilanes that contain long alkyl chains as substituents are elastomeric.
Crystallinity is introduced when the alkyl groups are smaller or when substituents
such as phenyl groups are present on the silicon. Polysilanes are thermally quite
stable. Most polymers are stable up to 200-300 °C without decomposition. It has
been already mentioned that poly(dimethylsilane) undergoes a rearrangement
without decomposition at 450 °C to afford the polycarbosilane [(H)(Me)SiCH2]n
which is converted to the ceramic silicon carbide only above 1000 °C.
5. Many polysilanes possess helical main-chain structures although the details of
these helical structures vary from case to case .
 Applications of Polysilanes
Polysilanes have many applications . These are based on the ability of some
members of their family to serve as precursors to silicon carbide. Other applications
of polysilanes stem from their interesting electronic and photophysical properties.
Apart from Yajima's procedure of utilizing [Me2Si]n as a precursor for silicon
carbide, many other polysilanes have also been found to be good precursors for
high-temperature processing into silicon carbide. These include the copolymer
[(Me2Si)x(PhMeSi)y]. The latter is photo-crosslinked and the fibers of the
crosslinked polymer upon heating at 1100 °C in argon atmosphere to afford SiC . A
high-molecular-weight poly(methylsilane) of composition
[(CH3SiH)x(CH3Si)y(CH3SiH2)z] was prepared by the sonochemical / Wurtz-
coupling condensation of CH3SiHCl2. This polymer upon pyrolysis in argon
affords silicon carbide. Silicon carbide in the form of fibers, films as well as solid
monoliths could be obtained by this method.
Other applications of polysilanes include their utility as photoinitiators for vinyl
polymerization. This application is based on the phenomenon of generating silyl
radicals upon photolysis. Although polysilanes are not efficient photoinitiators they
have unique properties such as being not susceptible to oxygen. Many organic
monomers such as acrylates, and styrene have been polymerized by this method.
Polysilanes have been examined as materials for photoresist applications involving
microlithography which has applications in microchip fabrication. This application
is based on the sensitivity of polysilanes towards Si-Si bond scission upon
photolysis.
Polysilanes are now being looked at from the point of view of electroluminescent
materials as these polymers have high-energy HOMO's. Because of this it is easy to
oxidize polysilanes. Consequently, polysilanes have been predominantly shown to be
hole transport materials. These features have enabled these materials to be considered
as possible electroluminescent materials particularly for emission in the near
ultraviolet (NUV) or ultraviolet (UV). These types of light sources are difficult to
obtain from conventional organic polymers such as poly(phenylenevinylene) which
have been vigorously examined as light emitting materials. A functional
electroluminescent device would consist of a thin film of polysilane sandwiched
between a hole and an electron injecting electrode. Electroluminescence is exhibited
by the recombination of holes and electrons which are injected by electrodes.
Typically the electrodes that are used are indium-tin oxide (ITO) for hole injection and
metals such as Ca, Al, or alloys of magnesium and silver for electron injection.
Polymers such as [PhMeSi]n have been found to show electroluminescence which can
be tuned over the range of colors from blue to red by the use of dye materials.
However, the electroluminescence of [PhMeSi]n is exhibited only at low temperatures
and is seen from 230-110 K. In contrast, the diaryl polymer [(«-C4H9-/?-C6H4)2Si]n
shows electroluminescence peaking at 407 nm at room temperature. The successful
implementation of these materials in EL devices would have to overcome the
weakness of the polysilane backbone under UV light irradiation. Polysilanes are also
attracting attention in application as photoreceptors in copiers and printers because of
their high carrier mobility.