Lecture - VI

Inorganic Polymers
• Inorganic Polymers
• Types of Inorganic Polymers

Date : 2079- 10- 04

• Silicones (Polysiloxanes)
• Preparation of Silicones
• Characteristics of Silicones
• Applications of Silicones
• Polyphosphazines
• Preparation of Polyphosphazines
• Applications of Polyphsphazines
• Sulphur based polymers
• Polymeric Sulphur +Polymeric Sulphur
nitride+ Chalcogenide glasses 1
 Inorganic Polymers
The polymers in which backbone chain contains other atoms like Si,S,P,N
etc. than carbon atoms are called inorganic polymers. The atoms are joined
by covalent bonds.
The atoms present in backbone chain- marked with Red .

P N O Si O

Inorganic polymers offer some properties not found in organic materials

including low temperature flexibility, electrical conductivity, and non-
flammability.
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 Organic Polymers

Catalyst.
High temp.
High press.

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Organic Polymers

Backbone chain- Only C-atoms

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 Characteristics of Inorganic Polymers
• Inorganic polymers are generally harder, stronger
and more brittle than organic polymers.
• Inorganic polymers do not burn except the
polymers containing sulphur.They melt at high
temperature.
• They are much less ductile than organic polymers.
• So they cannot be extended much as organic by
about 12 % while organic polymers such as
polyethylene can be stretched by about 25 %
before breaking.
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 Characteristics of Inorganic Polymers…
• Inorganic polymers can be obtained in pure
crystalline as well as amorphous forms while
organic polymers are partially crystalline and
amorphous forms.
• Because of having cross–linked structures they
have higher density of covalent bonds and are
generally stiffer than organic polymers.
• Most of inorganic polymers being highly polar
substances dissolve in polar solvents.

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 Types of Inorganic Polymers…
Inorganic polymers are of many types, among
them following types are of important inorganic
polymers.
• Silicone based polymers that include Silicones
(Polysiloxanes)
• Phosphorous based polymers that include
Polyphosphazines
• Sulphur based polymers that include polymeric
sulphur nitride, polymeric sulphur, chalcogenide
glasses etc.
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 Silicones (Polysiloxanes)

Silicones are polymeric organosilicon

compounds containing Si−O−Si
linkages and Si − C bonds. They are
generally very stable, because of the
presence of strong silicon-oxygen and
silicon-carbon bonds. A general
formula for silicones is (R2SiO)x,
where R can be any one of a variety of
organic groups.

Silicones may be linear, cyclic, or

cross-linked polymers.
Silicones
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 Silicones (Polysiloxanes)….
They are called inorganic polymers Organic
because of following reasons. groups
• High percentage of ionic bond
character of silicon-oxygen
bond.
• Presence of other atoms than
carbon atoms in backbone chain.

Similarly they resemble organic

polymers because of following
reason. Organic
• Organic groups are attached to groups
silicon atoms.
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 Preparation of Silicones
The preparation involves following steps.
Preparation of chlorosilanes (alkyl or aryl substituted
silicon chloride)

The mixture formed can be separated by fractional

distillation since the components of the mixture have
different boiling points.
Chlorosilanes can also be prepared by heating
chloroalkane or chlorobenzene with silicone in the
presence of Copper as a catalyst at 300 oC
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 Preparation of Silicones…

R = Methyl & R= phenyl in 1st and 2nd reactions

Hydrolysis of Chlorosilanes (alkyl or aryl substituted
silicon chloride)
The hydrolysis should be carried out in inert condition by using N2
carefully since different reactive and inflammable intermediates are
also formed.

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 Preparation of Silicones…
Condensation polymerization of Silicols or Silanols.
Types of Silicones formed by condensation polymerization
of Silicols are dependent upon the nature of R and the way
in which hydroxyl derivative undergo polymerization.
Polymerization of R3Si (OH) forms dimer

R R R R

Polymerization
R Si O- H + HO Si R R Si O Si R
- H2O

R R R R

Where, R may be alkyl or aryl group (Dimer) hexa alkyl or aryl disiloxane

After the formation of dimer, the polymerization

does not occur due to the absence of hydroxyl groups.
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 Preparation of Silicones…
Polymerization of R2Si(OH)2 forms long chain linear
polymer.

Further polymerization occurs due to the presence of hydroxyl

group at each end of the chain to form straight long chain polymer
as shown below.
R R R R

O Si O Si O Si O Si O

R R R R

Long straight chain polymer

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 Preparation of Silicones…
The polymerization of R2Si (OH)2 also forms cyclic polymers with
rings containing three, four five or six Si-atoms.

CH3 O CH3
Si Si
CH3 CH3
O O

Si
CH3 CH3

Tricyclodimethyl siloxane Tetracyclodimethyl siloxane

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 Preparation of Silicones…
Polymerization of RSi (OH)3
Polymerization of RSi (OH)3 forms a complex cross-linked silicones.
R R R R

Polymerization
HO Si O- H + HO Si OH HO Si O Si OH
- H2O

OH OH OH OH

Further polymerization continues due to the presence of hydroxyl

group at each end of the chain to form a complex cross linked
polymer as shown below.
Continuation
R R R
of the chain R

HO Si O Si OH O Si O Si O

O O O O

HO Si O Si OH … OH Si O Si O
O
R R ContinuationR R

of the chain 15
 Characteristics of Silicones
The physical properties of silicones depend upon the kind and number of
organic groups attached to the silicon backbone whereas the chemical
properties are controlled by Si-O-Si bonds.
Silicones can be obtained in the form of oils, viscous-liquid, resins or
rubber like solids. Organic
parts
• Water repellant: In silicones the atoms of silicone
are surrounded by organic parts. The content of
the organic groups make silicones highly water
Organic
repellant. This property is increased by aromatic parts
parts. n
• Resistance to oxidation: Silicones are resistance to oxidation due to the
organic parts. Aromatic parts enhances the property i.e. the stability
towards oxygen increases by the presence of aromatic parts.
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 Characteristics of Silicones…
• Toxicity: Silicones are nontoxic.
• Thermal stability: They are stable towards heat
due to stable silica like arrangement of Si – O–
Si and high bond energy of Si – O bond.
Silica like arrangement
• Resistance to Chemicals: Most of mild acids and alkalis do not react with
with silicones. However other chemicals react with silicones due to polar
nature of Si – O bond and ability of silicone to expand its valency due to
presence of vacant orbitals.
• They do not melt at high temperature and do not freeze at low temp
• Silicon oils are highly stable non-volatile even on heating.
• The boiling point and viscosity of silicones are highly affected by
chain length.
• Since they can withstand high temperature without charring, they
are used for making insulating materials for electric motor and other
electric appliances.
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 Applications of Silicones…
• Silicones oils are used for high temperature oil bath, vacuum pumps
etc. because they are very stable and non- volatile even on heating.
• They are used as low temperature lubricants since they do not
become viscous on cooling.
• They are also used to make Vaseline like grease, which are used as
lubricants in aero plane since they do not freeze at – 40 o C and do
not melt at 200 o C.
• Silicones resins being highly water repellent are used for making
water proof clothes and papers.
• Silicones fluids are mixed with paints, enamels to resist to the
effect of high temperature, sunlight, chemical and damp.
• They are used for making nonstick pans since they are thermally stable.
• Silicones rubbers are used in transplant surgery for making
artificial heart valves , artificial breasts etc.
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Phosphorous based polymers: Polyphosphazines
Nitrogen and phosphorus have little tendency to undergo
catenation but much more less than carbon atoms. However
nitrogen and phosphorus undergo catenation resulting in
the formation of polymeric compounds known as
Polyphosphazines. The general formula of the polymer is
represented by
Where, R may be variable
R
R = - Cl in Polyphosphonitrilic chlorides
P N R = - OCH3 in Polydimethoxy phosphazines
R = - OC2H5 in Polydiethoxy phosphazines
R n
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Preparation of Polyphosphonitrilic chlorides
By the reaction between phosphorus pentachloride and
ammonium chloride in presence of C6H5Cl or by heating PCl5 with
NH4Cl at 120-150 °C.
N

C6H5Cl Cl + (PCl2N)3 + (PCl2N)4

n PCl5 + n NH4Cl H P N
- 4n HCl

N n
cyclic trimer cyclic
a linear polymer tetramer

The trimeric or tetrameric compounds are easily

separated by distillation method.
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 Cl Cl
P
N N
Cl
Cl
P P
Cl Cl
N
Trimer Tetramer
Properties of Polyphosphonitrilic chlorides
• They have high elastic properties and can be extended many
times reversibly so called inorganic rubbers.
• When stored in the absence of moisture they do not lose
elastic properties but becomes brittle if stored in moisture
because of reaction with moisture.
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 Properties of Polyphosphonitrilic chlorides…
• Freshly prepared polymers are soluble in chloroform. They are not
soluble in petroleum and ether. The solution on standing slowly
changes to gel and cross linked.
Applications of Polyphosphonitrilic chlorides
• They are used as high stretched rubbers.
• As a catalyst for polymerization of Polysiloxanes from Silanol.
Polydimethoxy phosphazines and Polydiethoxy phosphazines

Preparation
Polydimethoxyphosphazines and Polydiethoxyphosphazines are
prepared by treating Polyphosphonitrilic chloride with sodium
methoxide (CH3ONa) and sodium ethoxide (C2H5ONa) respectively
as follows .
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Polydimethoxy phosphazines and Polydiethoxy phosphazines…
OCH3 Cl OC2H5

CH3ONa C2H5ONa
P N P N P N

OCH3 n Cl n OC2H5 n
Polydimethoxyphosphazines Polydiethoxyphosphazines
Polyphosphonitrilic chloride

Properties
• They are transparent, colorless and film thermoplastics.
• On heating above 100 °C they slowly changes to cyclic polymers.
Applications
• They are applied as metal coatings and insulations for wire.
• Form flexible plastics which have been used for fuel hoses
(flexible tube for flowing fuel).
• They are used in the manufacture of gaskets.
• Some polymers being water repellant they are used to water proof t
• thermoplastics.
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 Sulfur based polymers
Because of ability to form catenation but much less than that of
carbon sulphur can form open or cyclic sulphur based polymer (Sn).
Types of Sulphur based polymers
• Linear chain polymers (Polymeric sulphur & polymeric sulphur nitride
• Network polymers (Chalcogenide glasses)

Polymeric sulphur(PS)
Ordinary variety of Sulphur
Preparation
It is prepared by melting the rhombic sulphur at 165- 168 °C. The
molten sulphur is poured into ice water, the polymer formed is called
polymeric sulphur. On heating the rhombic structure of sulphur (S8)
opens up to form free radicals which combine with other S8 to form
long chains.
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 Polymeric Sulphur (PS)…

free radicals

The product thus formed is purified by washing with carbon

disulphide (CS2) to remove traces of S8. The removal of S8 is
necessary because the transition from polymeric sulphur to
rhombic sulphur is accelerated by the presence of S8.The removal
of S8 by washing the sulphur with carbon disulphide slows down
the transition.
Below the boiling point of sulphur i.e. 114°C the polymeric
sulphur is unstable and changes back to rhombic sulphur S8.
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 Uses of Polymeric sulphur
• Used in flame proofing fabric.
• As plasticizers.
• As a catalyst in the manufacture of silicones
Polymeric sulphur nitride (SN) n
Polymeric sulphur nitride consists of nearly planar chains with
S N bonds of approximately bond length (1.16 Å). The bond
angle is 120 o.

Plasticizer -a substance (typically a solvent) added to a synthetic resin to produce

or promote plasticity and flexibility and to reduce brittleness.

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