Inorganic polymers

Classification by chemical structure

In section 2.1 we defined inorganic polymers as polymer having other atoms than
C, O and N in their main chain .we shall hold this definition here, even though such
a tracing of the terms inorganic and organic may apper strange in some case.
In organic polymers can be devided into three basic types :
a) homoatomic polymers with one kind of atom in the main chain like :
polymeric sulphur
b) heteroatomic polymers with more than one type of atom in the main chains;
mostly two types of atom alternate along the main chain like
polysioxanes
polysulphuricnitride
c) hybrid heteroatomic polymers where in inorganic atoms alternate with typical
organic unit as in
poly(phenylane sulphide)
poysiloxanes have very flexible chains, polysulphurnitride is electrically conducting
and poly(phenylene sulphide) is an engineering plastic.
It should be noticed that we consider materials only as inorganic homo or
heteroatomic polymers if the bonds between the main chain atoms are
predominantly covalent, so that metals and salts are excluded. Inorganic polymers
often show improvedproperties like better heat and chemical stability or interesting
electronic properties. Some can be processed like normal organic polymers and
yield ceramic fibres and coatings pyrolysis (preceramic polymers ).
The tendency to from homoatomic chains (catenation) is very strong for carbon, but
it exists also for silicon and germanium, and especially for sulphur, selenium and
tellurium, wich demonstrate as elements a rubbery state above the floor
temperature where long linier homoatomic chains are formed (as discussed for
sulphur in section 3.4). other atoms show only small or no tendency to catenation
and can from long polymer chain only via alternation with other atoms. Therefore
heteroatomic polymers predominate in inorganic polymer science.
Depending on the valency of the atoms the main chais can carry a number of
substituents. These substituents may be inorganic or organic by nature. This is
illustrated by a few important polymers :
a) poly(phosphanzene chloride; an elastomeric material sensitive to hydrolysis
from the former polymer by reaction with NaOR; for R=CH 2CF3 and

CH2CF2CF2CF3 solvent- and water-resistant rubbers for low temperatures

are obtained.

b) Poly(diphenyl siloxane), by far the largest silicone product with better

thermal stability than dimethyl derivative
c) Polysilanes with interasting opto-electronic and conducting properties
by delocalization of -orbitals in the homoatomic main chain;the
homopolymer with R=CH3 is insoluble and unmeltable, but copolymers
with different Rs are soluble and processable
Polymer chain containing OH-groups will be formed as intermediates during
dehydration of metal hydroxide precipitates :

The actual composition of these metal hydroxides is difficult to verify

because the precipitates form strongly swollen gels in water. Also
poly(phosphoric acid),formed by dehydration of H3PO4, and potassium
polyphosphate posses such typical inorganic chains :

Even better known examples from this category are the silicates. Starting
from Si(OH)4 the successive condensation of OH-groups yield water and a
series of silicates with different structures and properties (the poly anions are
shown by leaving out protons and metal cations and 4Si-O bonds are
directed toward the vertices of a tetrahedron)
Separate monomeric SiO4-4 units in ionic lattices of heavy minerals

A linier chain with overall composition SiO2-3, present in fibrous silicates and
also in silicic acid

A double chain or ladder polymer with overall composition Si4O6-11 present in

fibrous silicates like asbestos

A two-dimensional network with overall composition Si2O2-5 present in

platelets of talc

A three-dimensional network with overall composition SiO2 as in silica or

quartz

9.2 some important inorganic polymerization reactions

Inorganic polymers can also be, or thought to be, formed by condensation,
addition or ring opening polymerization. Some examples can serve to
illustrate this.
9.2.1 condensation polymerization
a)
CH3
n CI

Si

+H2O
CI

n HO

Si

it is also possible to prepare first a cyclic tetramer (-SiMe2-O-)4from SiMe2CI2

and to polymerize this by a ring opening mechanisn (see below). The
poly(dimethyl siloxane) is well-known as silicone oil and can afterwards be
crosslinked to obtain silicone rubber.
This can be achieved by the splitting of H atoms from CH3 groups with
peroxide radicals yielding CH2CH2- crosslinks between two Si atoms in
different chains. Of course, direct network formation takes place when small
amounts of trifunctional MeSiCI3 or tetrafunctional SiCI4 are added to the
monomer MeSiCI2. On the other hand, addition of monofunctional Me3SiCI
would yield shorter linier chains and serve to adjust the desired values of P n
b) n CICH2CH2CI+nNa2Sx

[ CH2CH2Sx ]

+2n NaCI

the polisulphide fomed separates from the aqueos reaction medium as a

latex, and produces oil-resistant Thiokol rubber after crosslinking. This is a
typical hybrid heteroatomic polymer with alternatingethylene and
polysulphide units in the main chain
c)a similar, but not aqueos , polycondensation is

n CI
NaCI

CI + n Na2

S ]

+ 2n

this poly(phenylene sulphide) (PPS) is fame-resistant and has a high

crystalline melting point above 500 K
d)a commercial plastic with good thermal stability, flame-resistant and
insulating properties is polysulphone obtained by polycondensation of the
sodium salt of bisphenol-A with 4,4-dichlorophenyl sulphone :

9.2.2 addition polymerization

a) another polysulphone, viz. poly(propylene sulphone), is prepared by
alternating radical addition polymerization of propene and SO2 :
n CH
generally, such hybrid polymers show better solubility, fusibility and
processability compared to their fully inorganic counterparts.
b) polysilanes can be prepared by an anionic polymerization :
n R2SiCI2
it comprises a surface reaction on sodium metal, forming ion pairs which can
give chain extension :

however, since each propagation step requires the the formation of a new
ion pair (on the monomer of chain end) it is not really a chain reaction.
9.2.3 ring opening polymerization
a) we have seen from the above that poly(dimethyl siloxane) can also be
produced from the cyclic tetramer, octamethyl cyclotetrasiloxane, e.g.
trough ring opening by a base :

this rection probably involves initiation by formation of a linier tertramer with

one active Me2SiO- and group, which attacks and opens the next cyclic

tetramer etc. the ring opening polymerization can also be initiated by a

strong acid like CF3COOH.
b) similarly,the rubbery poly(dichloro phosphazene) [-PCI2=N-]n.discussed in
section 9.1, can be produced by ring opening polymerization of the cyclic
trimer. This polymerization is initiated by cyclic phosphazenium cations
formed by dissocation of (NPCI2)3 at high temperature :
CI2

The more stable phosphazanes with suitable organic substituents can be

obtained by starting from the substituted cyclic trimers.
c)finally, a well-known example of spontaneous ring opening polymerization
is that of elementary sulphur, a cyclic octamer, above the floor temperature
of 160oC :
n

in this reaction the S8-ring is opened first,yielding a diradical (or possibly

some ionic species) which then attacks and opes the next ring, et cetera . it
is a real chain reaction because the new radical end groups are reactive
again. As required by thermodynamics, the long chain of sulphur revert to
smaller cyclic structures below the floor temperature (sec section 3.4)