In Lord We Trust

ISLAMIC AZAD UNIVERSITY - KARAJ BRANCH

FACULTY OF GRADUATE STUDIES
DEPARTMENT OF CHEMISTRY

Introduction to

INORGANIC POLYMERS
:By
Mohammad Barkhi

What is a Polymer ?
A polymer is a substance composed of
molecules with large molecular mass
composed of repeating structural units, or
monomers, connected by covalent chemical
bonds. The term is derived from the Greek
words: polys meaning many, and meros
meaning parts.

What is an inorganic polymer ?

Inorganic by its name implies nonorganic or
nonhydrocarbon. The most obvious definition
for an inorganic polymer is a polymer that has
inorganic repeating units in the backbone.
A giant molecule linked by covalent bonds
but with an absence or near-absence of
hydrocarbon units in the main molecular
backbone.
A polymer that don't have any carbon atoms
in the backbone chain.

Why inorganic polymers ?

The main reasons for scientist to be
interested in inorganic-base macromolecules
are connected with their unique property
profiles that make them different from their
totally organic counterparts.
The number and variety of elements found in
these polymers.
The relative high abundance of inorganic
elements in the earth's crust.

 Stronger bond formation, which are more resistant

to cleavage reactions (Si-O 110, P-N 140, and C-C 85
kcal/mol).
Different valancies for attachment of side groups.
Stability at high temperature.
Tailoring new and interesting structures with many
variations, which seem endless.
And finally, regarding the fact that most of the
organic polymers are made of oil, according to the
decrease of oil storages, the existence of them will
one day restricted.

Classification schemes
Inorganic polymers represent a rapidly growing
field of chemical research and already have many
applications and any classification is necessarily
somewhat arbitrary.
N. H. Ray, in his book on inorganic polymers(1978),
uses connectivity as a method of classifying
inorganic polymers.
The other classifying will be introduced
in the following:
- wholly inorganic polymers
- inorganic-organic polymers
- organometallic polymers
- hybrid organic-inorganic polymers

Classification by
connectivities
Ray defines connectivity as the number of atoms
attached to a defined atom that are a part of the
polymer chain or matrix. This polymer connectivity
can range from 1 for a side group atom or functional
group to at least 8 or 10 in some metal-coordination
and metal-cyclopentadienyl polymers, respectively.

Connectivities of 1
Anchored metal-containing polymers used for
catalysis can have connectivity values as low as 1
with respect to the polymer chain.

Schematic of anchored metal-containing polymer with a connectivity of 1, where M

might be palladium or platinum with three other ligands. For catalytic activity, at
least one of the three must be easily removed by a substrate.

Connectivities of 2

c
: Examples of inorganic polymeric species with connectivity of 2
poly-)sulfur nitride(; )b( linear polyphosphate; )c( poly)dichlorophosphazene(( a)

Connectivities of 3

,Examples of connectivity of 3: )a( boric acid, )b( arsenic)III( sulfide

Mixed Connectivities of 2 and 3

Example of polymeric inorganic species with mixed connectivities of 2 and3:

an ultraphosphoric acid

Connectivities of 4

Examples of polymeric inorganic species with mixed connectivities of 4:)a(

silica with silicon atoms of connectivities of 4 and )b( boron phosphate with
both phosphorus and boron atoms with connectivities of 4.

Connectivities of 6

Mixed Connectivities of 4 and 6

.An orthophosphate of mixed connectivites of 4 and 6

Connectivities of 8

.A Schiff-base polymer of zirconium with a connectivity of 8

wholly inorganic polymers

Inorganic polymers in this class constitute the major
components of soil, mountains and sand, and they are
also employed as abrasives and cutting materials
(diamond, silicon carbide (carborundum)), fibres (fibrous
glass, asbestos, boron fibres), coatings, flame
retardants, building and construction materials (window
glass, stone, Portland cement, brick and tiles), and
lubricants and catalysts (zinc oxide, nickel oxide, carbon
black, silica gel, aluminium silicate, and clays).

Structure of a typical silicon dioxide intensive glass

Inorganic-organic Polymers
inorganic polymers containing organic portions
attached to inorganic elements in their backbone. The
area of inorganic-organic polymers is very extensive.
Some examples of this class are: Polysilanes,
Polysiloxanes, Polyphosphazenes.

Organometallic Polymers
Organometallic polymers are made of over 40
elements including main group of metals )Si or Ge(,
transition metals or rare earth elements in addition to the
10 elements )C, H, N, O, B, P, halides( which is found in
organic polymers )Figure 10(.The variations of
organometallic polymers seem endless. Organometallic
polymers are new materials which combine the low
density and structural variations and functional group
varieties of organic materials with electrical conductivity
and the high temperature stability features of inorganic
compounds.

Different structures found in organometallic polymers

Hybrid organic-inorganic polymers

Hybrid organic-inorganic networks, prepared via sol-gel
process, are multi-functional materials offering a wide
range of interesting properties. Since there are countless
different combinations of the organic and inorganic
moieties, a large number of applications are possible by
incorporation of inorganic building blocks such as silica
networks, porous materials and metals.

-Conjugated polymers prepared via organometallic

condensation reactions

INORGANIC
POLYMERS
SYNTHESIS

 Several methods proposed for inorganic polymers

synthesis. We focus our discussion on some of them.

A classification of polymerization reactions

 Polyphosphazenes are inorganic polymers with a

phosphazene repeating unit and general structure )-RR'P=N-(. They
are
generally
prepared
from
the
intermediate
poly)dichlorophosphazene( and either amines or sodium salts of
alcohols. Poly)dichlorophosphazene( is prepared from the ring
opening polymerization of hexachlorocyclotriphosphazene.

 In 1949, Burkhard was invented a polysilane called

polydimethylsilane that it wasn't much good for anything. It formed crystals
that were so strong that nothing could dissolve them. In the seventies,
some scientists got the notion to make small rings of silicon atoms. But
unwittingly did something similar to what Burkhard had done. They
reacted sodium metal with dichlorodimethyl silane, but they also added
some dichloromethylphenylsilane to the brew. But they didn't get the rings
they wanted. they got a copolymer that was soluble and can be processed
and played with and studied.

 The major route to produce polysiloxane is Rochow process in

which ground silicon is reacted with chloromethane using a catalyst,
such as copper. These compounds react with water forming
dihydroxysilanes that in turn will be condensed, splitting out water,
eventually forming polysiloxanes.

A dual thermal ring-opening polymerization reaction between a

silyl-bridged ferrocene and a cyclic silane.

.The cationic initiated polymerization of divinylferrocene

The synthesis and electropolymerization of copper)II( and nickel)II(

3,4-bis)salicylaldimino(thiophene Schiff-base chelates

The photo activated platinum-catalyzed hydrosilylation polymerization of

vinyldimethylsilane

The synthesis of lanthanide polyelectrolytes with

Condensation Through Bridging Ligand Coordination.
)bis)tetradentate( Schiff-base bridging ligand(.

General synthesis pathway for hard type triazene polyurethanes were

obtained by a polyaddition performed in dry DMF

APPLICATIONS
OF
INORGANIC POLYMERS

 Amorphous silicon dioxide-intensive materials

include a wide variety of glasses such as fibreglass,
window glasses, Vycor glasses, borosilicate glass, which
can be shaped by drawing, pressing, casting, and
blowing. Colourless optical glasses, luminescence and
laser glasses are produced by using rare earth elements
as components of these special glasses. A scintillating
glass with fluorescence properties uses PbO-Bi2O3
heavy-metal oxides based materials. A new superionic
glasses )solid electrolyte( based on silver iodide with
organic monomer ions is reported, which exhibits high
ionic conductivity comparable to that of oxides based
superionic glasses, but 10 to 10000 times larger than of
typical Li+ polymer electrolytes.

 Poly (sulphur nitride) is the first reportednonmetallic covalent polymer, with electronic conductivity
properties comparable to that of metal, and is the first
example of a polymeric superconductor.
It is used as conductive material in the manufacturing
of a plasma display panel and in electrically
conductive plastic light sources such as batterypowered flash lights and lanterns. Battery housing or
head assemblies for light sources are formed from
electrically conductive polymers such as poly)sulphur
nitride(.

 Polysilanes are useful as precursors to silicon

carbide ceramics as photoresists, in microelectronics
as photoinitiators for radical reactions and as
photoconductors.

silicon carbide ceramics

 Siloxane polymers have numerous medical applications

such as: prostheses, artificial organs, facial reconstruction and
tubing and catheters take advantage of the inertness, stability, and
pliability of these polymers; artificial skin, contact lenses, and drug
delivery systems utilize their high permeability as well. A wide
range of medical-purpose items were manufactured using of
unsaturated siloxane rubbers with silicon hydrides of various
structures. These materials are biologically-compatible with a high
complex of medicals.

)a(Siloxane artificial pacemakers and )b( polysiloxane rubber beingb

used to make vinyl sheet with detailed surface.

 Polyphosphazenes or phosphonitrilic polymers are the most

interesting and commercially promising inorganic Polymers.
Applications based on structure-property correlations in technology or
medicine are as follows:
- Advanced elastomers, design for a rechargeable lithium battery based
on the conductivity of lithium triflate in solid poly[bis)methoxyethoxyethoxy( phosphazene.
- The extreme hydrophobicity of the surface minimizes the foreign body
interactions that normally occur when non-living materials are implanted
in contact with living systems, including blood.
- Solid polymer electrolytes have been extensively
investigated for their potential applications in highenergy
density batteries.

 Polymeric copper phthalocyanine containing

peripheral carboxyl groups is converted into polyimides
through polycondensation with aromatic diamine to
obtain a processable material for potential application in
the fabrication of electronic devices.

EPILOGUE
Numerous uses for inorganic polymers have been developed. For
many of these uses, the inorganic polymers have advantages over
their organic counterparts, but often relatively high cost has
precluded the use of the inorganic polymers, except where the cost
differential is less than the advantage perceived for the polymer. As
simpler synthetic methods and larger scale use occur, the differential
will diminish and more uses will flourish. For some uses where no
organic counterpart is satisfactory, the inorganic polymers have
been accepted.
Inorganic polymers will undoubtedly be featured in future high-tech
nanoscale materials, where cost may be less of a factor.
Thus the ultimate fate of inorganic polymers rests on future
practitioners in the field and the uses for which the polymers are
found to be superior over their organic counterparts. If recent
developments are a guide to the future, the future for inorganic
polymers is very bright indeed.

:Acknowledgement
Dr. Mohammad. R. Melardi; Dep. Of Chem. Karaj I.A.U.
Dr. Fariba Shokrolahi; Iranian Polymer & Petrochemical
Institute.

:Refrences
INORGANIC AND ORGANOMETALLIC POLYMERS; RONALD D.
ARCHER; A John Wiley & Sons, Inc., Publication
Inorganic and Organometallic Polymers: A Review; Azam
.Rahimi; Iranian Polymer Journal 13 )2(, 2004, 149-164
Bianconi et al; Macromolecules,1989, 22, 1697; 1989 American
Chemical Society.
E.C. Buruiana et al. / Journal of Photochemistry and Photobiology
A: Chemistry 171 )2005( 261267

Special thanks for your attention