INORGANIC CHEMISTRY- III BSCCH-301

UNIT-8 SILICONES AND PHOSPHAZENES

CONTENTS:
8.1 Objectives
8.2 Introduction
8.3 Classification of polymers
8.3.1 Classification of inorganic polymers
8.3.1 General properties of inorganic polymers
8.4 Phosphene phospho nitrilic halide
8.4.1 Phospho nitrilic chloride or phosphazenes
8.4.2 Nomenclature
8.4.3 Method of formation
8.4.4 Properties of the phosphor nitilic chloride
8.4.5 Structure of cyclic tri phospho nitrilic chloride
8.5 Silicones
8.5.1 Types of the silicon polymer on the industrial bases
8.5.2 Preparation of silicones
8.5.3 Properties and uses of silicones
8.6 Summary
8.7 Terminal questions
8.7.1 Short answer questions
8.7.2 Objective type questions
8.8 Answers

8.1. OBJECTIVES

The aims and objectives of this unit are to learn and discuss the structural features of different
types of inorganic polymers.

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8.2. INTRODUCTION

All the covalent macromolecules, which do not have carbon in their compounds, are
considered to be inorganic polymers. Covalently-bonded crystals (like oxides and halides),
condensed phosphate etc., are the examples of inorganic polymers. These polymers possess
distinctive physicchemical characteristics and unique physical, mechanical and electrical
properties. These polymers are of extensive utility in everyday life, particularly in the area of
engineering and technology.
The main point of similarity between inorganic and organic polymers is, that both can be
prepared by the addition and condensation methods. The former method is used when polymers
of higher molecular weight and greater mechanical strength are needed. Silicones and
phosphazenes are examples of inorganic polymers. Inorganic elements can have different
valences than carbon and therefore, different numbers of side groups may be attached to a
skeletal atom. This will affect the flexibility of polymers, their ability to react with chemical
reagents and interactions with other polymers. Among inorganic polymers, silicones and
phosphazenes are two important classes of polymers with high commercial potential.
All the macromolecules which are formed by the combination of a large number of the
small units are known as polymer and the process of their formation is called as polymerisation
process.

nM M
n

Where n= Degree of polymerisation

(M) n = Polymer
M = Monomer

8.3 CLASSIFICATION OF POLYMERS

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Depending on the catinating nature of elements, polymers can be divided into two
different types which are given below:

(a) Organic polymer: All the macro molecules which are formed by the catenation of the
carbon atom are known as organic polymers.
Example:
n CH2=CH2 CH2 - CH2
n

Organic polymers are further divided into types, which can be given as:-
i. Synthetic polymer.
ii. Natural polymer.

(b) Inorganic polymers: All the macromolecules which are formed by the catenation of elements
other then carbon are known as inorganic polymer.

Example:

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R R

Si O Si O
1.

n R
R
Silicon polymer

X
2.
P N

n
X
Phosphorzener

O
3.
P O

n
OR
Polyphosphate

SN
n
4.
Poly sulphur nitride

8.3.1 Classification of inorganic polymers

There are different ways of classifying inorganic polymers.

Classification I: Depending on whether the polymer contains the atoms of only one element or
of different elements in its back bone, the polymers are classified into the following two groups.
1. Homo-atomic polymers: These polymers contain the atoms of only one element in their back
bones. Silicon, phosphorus, sulphur, germanium and tin form homo-atomic inorganic
polymers. For example, sulphur has a tendency to form chain or rings in its elemental form
(S8) and in several compounds, like persulphides (H-S-S-H, H-S-S-S-H, H-S-S-S-S-H etc.),
polythionic acids etc.

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2. Hetero-atomic polymers: These contain the atoms of different elements in their backbones.
Classification II: Inorganic polymers can also be classified in another way, which is based on
the type of reaction by which the polymes are formed. On this basis, inorganic polymers may be
of the following ways:

1. Condensation polymers: Condensation polymers are those, which are formed by

condensation process. In this process, two or more simple molecules of the same substance
polymerize together and form the condensation polymer. One or more H2O, NH3, H2, HCl etc.
molecules are also eliminated.
Examples

(a) Cross-linked silicone is obtained by the polymerisation of many RSi(OH)3 units.

(b) When PCl5 is partially hydrolysed by water, dichloro phosphoric acid, PO(OH)Cl2 is
obtained. When PO(OH)Cl2 is heated, many molecules of this substance get polymerized and
give rise to the formation of a condensation polymer. In this process HCl is eliminated.

2. Addition polymers: These polymers are obtained, when many simple molecules (monomers)
combine together.

Examples:
(a) Many molecules of sulphur trioxide may be polymerized by the addition of a small
amount of water. This gives addition polymer.
(b) When SO2 reacts with propylene, CH3-CH=CH2 in presence of benzoyl peroxide, an
addition polymer is obtained.

3. Coordination polymers: These are formed by the addition of saturated molecules to each
other or by combining a ligand with a metal atom. These polymers contain chelated metal
atoms or ions.

Classification-III: According to this classification, the inorganic polymers can be classified into
the following categories:

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i. Polymes containing two bridgint bonds per units, e.g, homo-atomic sulphur, selenium
and teturium polymers.
ii. The alternating silicone-oxygen polymers. Examples are silicones and related
compounds.
iii. The alternating phosphorus-nitrgoen polymers. Examples are phosphonitrilic halides,
(NPX2)N.
iv. The alternating phosphorus-oxygen polymers. Examples are metaphosphates,
polyphosphates and cross-linked phosphates.

Classification-IV: The classification is based on the element which forms inorganic polymers.
Thus we have:

i. Polymers containing boron. Examples are: (a) Borazine, (BH)3 (NH)3 or B3N3H6. (b)
Substituted borzines like (i) B-trimethyl borzine, [B(CH3)3 (NH)3] (ii) Borozine (BH)3O3
(iii) N-timethyl borzine, [B(CH3)3(NH)3] (c) Boron nitride (BN)n.
ii. Polymers containing phosphours. Examples are: (a) Metaphosphates, (b) Polyphosphates,
(c) Cros-linked phosphates, (d) Phosphonitricli halides, [PNX2]n
iii. Polymers containg phosphorus. Examples are: (a) Metaphosphates, (b) Polyphosphates,
(c) Cross linked phosphates, (d) Phosphonitrilic hladies, [PNX2]n.
iv. Polymeic compounds of sulphur. Examples are nitrides of sulphur, thiazyl halides and
imides of sulphur.
v.
8.3.2 General properties of inorganic polymers

Some properties of inorganic polymers are given below:

(1) With a few exceptions, inorganic polymers do not burn. They soften or melt at high
temperatures.
(2) Most of the inorganic polymers are built up of highly polar substances. Most of these
polymers, however, react with the solvents. There are thus only a few inorganic polymers
which actually dissolve in solvents properly.

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(3) Inorganic polymers having cross-linked structures with a high density of covalent bonds are
generally stiffer and harder than the organic polymers.
(4) The chain segments between cross links in polymers having cross-linked structures are
usually short. Consequently, these structures are not flexible enough to permit interaction of
solvent molecules.
(5) Inorganic polymers are generally much less ductile than the organic polymers. Thus, while
organic polymers such as polyethylene can extend by about 20 percent or more before
breaking, inorganic polymers break even when stretched by about 10 percent.
(6) Inorganic polymers, in general, are stronger, harder and more brittle than the organic
polymers.
(7) Inorganic polymers can usually be obtained in pure crystalline as well as in pure amorphous
forms. Organic polymers, on the other hand, have partial crystalline and partial amorphous
structure.

8.4 PHOSPHO NITRILIC HALIDE

Those macro molecules which are having the general formula PNX2 are
n

called as phosphor nitrite halides where X = F, Cl, Br and n = 3 to 7

(1) Cyclic trimer

X X
P
N
N
X
X
P
P
X
X N

(2) Cyclic tetramer

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X X

X P N P X

N N

X P N P X

X X

(3) Linear polymer

X X X

P N P N P N

X X X

8.4.1 Phospho nitrilic chloride or phosphazenes

Phosphazenes were initially termed as phosphonitrilic polymers. Later on, the new term
was used to represent phosphorus, nitrogen (azo) and P = N double bonds (ene) which are always
present in these polymers. They are thus ‘unsaturated PN compounds’ containing phosphorus,
mostly in +V state. As is usual with polymers, they may have cyclic or chain structure. The
nitrogen in groups is in 2-coordination and phosphorus in 4-coordination. They contain the group
which is isoelectronic with the groups of silicones. Their polymers differ in substitution on
phosphorus and on the nature of those substitutents besides the way and the extent, to which
polymerization have taken place. They are usually classified on the basis of number of
phosphazene units that are incorporated in the structure:
All the compounds which having the general formula (-PNCl2-)n are known as phosphor
nitrialic chloride or those compound which having the (-PNCl2-)n repeating unit are known as a
phosphonitrilec chloride or phosphazene. In the phosphor nitrilic chloride n= 3 to7.
Phosphonitrilic chloride can exist in the three different forms which are given below:

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1. Cyclic trimer

Cl Cl
P
N
N
Cl
Cl
P
P
Cl N Cl

2. Cyclic tetramer

Cl Cl

Cl P N P Cl

N N

Cl P N P Cl

Cl Cl

3. Linear polymer

Cl Cl Cl

P N P N P N

Cl Cl Cl

8.4.2 Nomenclature

Phosphor nitrilic chlorides are nomenclatured according to the number of repeating

unites.
(PNCl2)3: Triphospho nitrilic chloride.

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(PNCl2)4: Tetra phospho nitrilic chloride.

(PNCl2)5: Penta phospho nitrilic chloride.
(PNCl2)6: Hexo phospho nitrilic chloride.
(PNCl2)7: Hipta phospho nitrilic chloride.

8.4.3 Method of formation

Some of the methods by which phosphornitrilic chloride can be obtained are given below

1. By the reaction of PCl5 with ammonia: Phosphorus penta chloride (PCl5 )when react with
ammonia gives corresponding phospho nitrilic chloride.

nPCl5 + nNH3 (PNCl2)n + 3 nHCl

Where n = 3 to 7

Example:
3PCl5 + 3NH3 (PNCl2)3 + 9HCl

4PCl5 + 4NH3 (PNCl2)4 + 12HCl

5PCl5 + 5NH3 (PNCl2)5 + 15HCl

2. By the reaction of PCl5 with NH4Cl: Phosphorus pentachloride (PCl5) when react with
ammonium chloride gives corresponding phospho nitrilic chloride.
nPCl5 + n NH4Cl (PNCl2)n + 4 nHCl

Where n = 3 to 7

3PCl5 + 3NH4Cl (PNCl2)3 + 9 HCl

4PCl5 + 4NH4Cl (PNCl2)4 + 16HCl

5PCl5 + 5NH4Cl (PNCl2)5 + 20HCl

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8.4.4 Properties of the phosphor nitilic chloride

A. Physical properties

(1) (NPCl2)3 have melting point 114ºC and boiling 256ºC at 1 atm. pressure. It is readily
soluble in ether, benzene and carbon tetrachloride.
(2) (NPCl2)4 have melting point 123ºC and boiling point 328.5ºC. It has lower solubility in
ether, benzene and carbon tetrachloride than (NPCl2).

B. Chemical properties

(1) Effect of heat: When the cyclic trimeric phosphor nitrilic chloride are heated than they
are converted into their corresponding liner trimer and tetramer respectively, but the liner
phosphor nitrilic choride are not effected on heating.

Cl Cl
P
Cl Cl Cl Cl
N N
∆
Cl Cl P N P N P N P N
P P
N Cl Cl Cl Cl
Cl Cl
Cyclic trimer Linear trimer

(2) Hydrolysis: When the cyclic trimeric or tetrameric phosphonitric chlorides undergo
hydrolysis than there can occur the formation of their hexa-hydroxy and octa-hydroxy
derivative which can further undergo telomerisation.

O OH
Cl Cl OH OH
P P P
N N N N NH NH
6H2O Tautomerization
Cl Cl OH OH OH OH
P P -6HCl P P P P
Cl N Cl N O NH
OH OH O
Cyclic trimer

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Cl Cl OH OH OH OH

Cl P N P Cl OH P N P OH O P NH P O

N N 8H2O N N Tautomerization NH NH
-8HCl
Cl P N P Cl OH P N P OH OH P NH P O
Cl Cl OH OH O OH
Cyclic tetramer

While, when the liner phosphor nitrilic chlorides react with the H2O than there occur the
formation of cross link polymer through the oxygen bridge.

Cl Cl Cl Cl
Cl Cl Cl Cl
P N P N P N P N
P N P N P N P N
Cl Cl Cl Cl
Cl Cl Cl
H
O -2HCl
O
H
Cl Cl Cl Cl
Cl Cl Cl
P N P N P N P N
P N P N P N P N
Cl Cl Cl Cl
Cl Cl Cl Cl
Linear trimer Cross link polymer

3. Reaction with the NH3: When the cyclic trimeric or tetrameric phosphonitrilic chloride
reacts with the NH3 than there occur the formation of hexa- amino derivative and octa-amino
derivative respectively, which can further eliminate the NH3 to form the imino derivative.

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NH
Cl Cl NH2 NH2
P P P
N N N N N N
6NH3 -3NH3
Cl Cl NH2 NH2
P P -6HCl P P NH P P NH
Cl N Cl NH2 N NH2 N

Cyclic trimer Phosphan

While when the liner phosphor nitrilic chloride reacts with the NH3 then there occurs the
formation of cross liked polymer with the -NH-bridge.
Cl Cl Cl Cl
Cl Cl
P N P N P N P N P N P N
Cl Cl Cl Cl Cl
H
-2 HCl
NH NH

H
Cl Cl Cl Cl Cl
P N P N P N P N P N P N
Cl Cl Cl Cl Cl Cl

4. Nucleophylic substitution reaction: When the phospho nitrilic chlorides react with the
nucleophilic reagents than there can occur the various nucleophilic substitution reaction,
some of them can be given as:

-6LiCl
(PNCl2)3 + 6 CH3- Li+ [PN(CH3)2]3
-6LiCl
(PNCl2)3 + 6 L+ F- (PNF2)3
-6NaCl
(PNCl2)3 + 6Na+ NH2- [(PN (NH2))2]3

8.4.5 Structure of cyclic tri phospho nitrilic chloride

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From X-ray diffraction method it was observed that each P atom and N atom in the cyclic
tri phosphor nitrilic chloride having sp3 and sp2 hybridization receptively, according the
Molecular orbital picture for this molecule can be represented as:

Cl

P dπ P π bond

Cl Cl
N
P N
N N Cl

Cl
Cl P Cl
Cl
P P
P
N Cl
Cl

Cl N Cl

Due to the presence of an electron pair at one of the sp2 hybrid orbital of each N atom, the
cyclic tri phosphornitrilic chloride exhibit basic character. According to the above stricture cyclic
tri-phosphonitrilic chloride should exhibit two types of the P-N bond length but experimentally it
was observed that all the P-N bond length in the cyclic tri phosphor nitrilic chloride bring
identical and intermediate to P=N and P-N, this indicate that this molecule will exist in the two
different resonating structure as like to C6H6 and its actual structure will be somewhere
intermediate to these two resonating structures known as resonance hybrid structure.

Cl Cl Cl Cl
Cl Cl
P P
P
N N N
N N
N
Cl Cl
Cl Cl P
Cl P
Cl P P P
P
N Cl N Cl
N Cl Cl Cl
Cl
Resonance Hybrid
Resonating Structure

8.5 SILICON POLYMER

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These compounds are polymeric organosilicone derivatives containing Si-O-Si linkages. These
are also called polysiloxanes. We can represent them by the general formula (R2SiO)n. These
may be linear, cyclic or cross linked polymers and have very high thermal stability and are
therefore, also called high temperature polymers. Because of the high thermal stability of Si-O-Si
chains, chemists have prepared a large variety of silicone polymers, which are very useful in
high temperature processes. Therefore, these find uses in high temperature applications such as
heat transfer agents and high performance elastomers. Such qualities are not expected of organic
polymers, which cannot withstand high temperatures.

Types of silicone polymers

1. Linear silicon polymer

R R R R
Si O Si O Si O Si O

R R R R

2. Cyclic silicon polymer

a. Cyclic trimer silicon polymer

R
R
Si

O O
R
R Si
Si R
R O

b. Cyclic tetra meric silicon polymer

R R

R Si O Si R

O O

R Si O Si R

R R

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c. Cross linked silicon polymer

R R R R
Si O Si O Si O Si O

R R

O O

R R
Si O Si O Si O Si O

R R R R

8.5.1 Types of the silicon polymer on the industrial bases

On the basis of industrial use silicon polymer can be divided into four different types,
which are given below:-

(i) High thermal silicon polymer: When hydrolysis of an organo silicon halde is carried out in
presence of the halides or alkoxides of Al, or Ti, two-dimensional linear or cyclic silicone
polymer is obtained. In this polymer, some Si-atoms are replaced by Al or Ti atoms. High
thermal silicones have exceptionally high thermal stability and remain unchanged, even in
contact with a white-hot electrically-heated wire. The presence of Al and Ti atoms in the
structure of the polymer increase the thermal stability.

CH3 OR CH3 OR CH3

OH Si OH + OR Al OR + OH Si OH + OR Al OR + OH Si OH
- nH2O
CH3 CH3 CH3 - ROH

CH3 OR CH3 OR CH3

OH Si O Al O Si O Al O Si OH
CH3 CH3 CH3

Linear polymer

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R R
R R
R Si O Si R
Si
O O O O
R
OR Al Si
R OR Al O Si R
O R
Cyclic trimer Cyclic tetramer

Uses: Due to the high thermal resistive this type of the silicon polymer can be use in the
formation of extern cover of the elective wires.

(ii) Silicon fluid/oil: When the alkyl di-hydroxyl saline undergoes condensation with the tri
alkyl monohydroxy silane, than there occur the formation short chain silicone polymer
known as silicon fluid or oil.

R R R R R R

R Si OH + OH Si OH + OH Si R - 2H O R Si O Si O Si R
2
R R R R R R
Silicon fluid/oil

Uses: Due to water repellent tendency of silicon fluid, it can be used as a water repentant
material in the bather industry or paper industry.

(iii) Silicon rubber: These are long china polymers, with some cross-linking between the
chains. They are made by the hydrolysis of (CH3)2 Si-O-Si(CH3)3 may be added to the reaction
mixture to control the chain length of the polymer. Silicone rubbers consist of cros-linked type
silicones with SiO2 or ZnO as filler and vulcanizer, such as benzoyl peroxide. Silicone rubbers
are especially valuable, since they retain their elasticity over a range of temperatures and are
resistant to oils.
Silicone rubbers, which can withstand temperature upto 400ºC for 200 hours and upto
540ºC for 90 hours, have also been prepared. Their resistance to 400ºC for 200 hours and upto
5400ºC for 90 hours have also been prepared. Their resistance to heat is much higher than that of

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many organic rubbers. It is due to their property to withstand high temperatures, that they are
used in sealing joints and steams of jet aircraft and insulating electrical parts like transistors,
which cannot be heated.
CH3 CH3 CH3

Si O Si O Si O
CH3 CH3 CH3
hv CH3 CH2 CH3
2 Si O Si O Si
O O
CH3 CH3 CH3 Ph C O O C Ph
CH3 CH2 CH3

Si O Si O Si O
CH3 CH3 CH3
Uses: Silicon rubber can be used in the formation of the parts of air craft.

(iv) Silicon resin: Silicone resin is obtained by blending silicone with organic resin, such as
acrylic ester. If the hydrolysis of (CH3)2SiCl2 is carried out in presence of (CH3) SiCl3 and then
polymerisation is allowed, a rigid silicone is obtained. This silicone is called silicone resin.
These are of many types, like coating resins, laminating resins, release resins, water-repellent
resins, mokding resins and electrical resins. These are stable to heat, water-repellent and have
good electrical conductivetiy, chemical inertness and weather resistance. To develop best
properties in them, baking or heat treatment in given to them. These can withstand temperature
as high as 250ºC and coating made up treatment is given to them. These can withstand
temperature as high as 250ºC and coating made up of silicone resin plus organic resins and Al
can withstand temperature upto 500ºC.
Silicone rubber retains its shape and elasticity permantely, even after vulcanisation and has,
therefore been used in a number of ways. High molecular weight silicones, containing long chain
or ring structure, are generally waxy or rubber-like solids.

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R R R R

OH Si OH + OH Si OH + OH Si OH + OH Si OH

R OH R OH

R OH R OH
+ + +
OH Si OH OH Si OH OH Si OH OH Si OH

R R R R

- nH2O
R R R R

Si O Si O Si O Si O

R
O R
R O
R

Si O Si O Si O Si O

R R R R
Silicon resin

8.5.2 Preparation of silicones

Silicones are prepared from pure silicon which has been obtained by the reduction of
silicon dioxide (silica) in the form of sand with carbon at high temperatures.

The production of silicones from silicon takes place in three stages:

a) Synthesis of chlorosilanes
b) Hydrolysis of chlorosilanes
c) Condensation polymerization

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a. Synthesis of chlorosilanes: Silicon is first converted into chlorosilanes, e.g. RSiCl3, R2SiCl2
and R3SiCl, where R is an organic group. When chloromethane is passed through heated silicon
at about 550 K under slight pressure and in the presence of a copper catalyst (often copper itself
but other copper-containing materials can be used, for example, brass or copper (II) chloride), a
volatile mixture of chlorosilanes distils over.
Si(s) + 2CH3Cl(g) (CH3)2SiCl2(g)

The mixture of liquids contains these three compounds:

b. Hydrolysis of chlorosilanes: A dichlorosilane is hydrolyzed to a molecule with two hydroxyl

groups:

R R
Cl Si Cl + 2H2O OH Si OH + 2HCl
R R
The product is a disilanol. The suffix -ol in a silanol is to show that the molecule contains
at least one hydroxyl group attached to a silicon atom and the simplest example is
dimethyldisilanol:

CH3

OH Si OH

CH3
Diethyldisilanol

The hydroxyl groups of silanols react spontaneously to form a siloxane:

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CH3 CH3

n OH Si OH OH Si H + (n-1)H2O

CH3 CH3 n

If R is a methyl group, the polymer is a poly(dimethylsiloxane).

Cyclic polymers, for example {(CH3)2SiO}4, are also produced and than separated out.

c. Condensation polymerization: The oligomers condense rapidly in the presence of an acid

catalyst to form long chain polymers:

CH3 CH3 CH3

OH Si H + OH Si H OH Si H + H2O

CH3 n CH3 n CH3 m+ n

Silicon fluid

The value of (m+n) is usually between 2000 and 4000.

8.5.3 Properties and uses of silicones

Physical properties: The following physical properties are common to all type of silicones:

(i) They have high thermal stability in the absence of air and withstand temperature upto 250-
3000C.

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(ii) They remain unaffected by most of the chemical reagents, such as weak acids, alkalies and
salt solutions. Thus, silicones are chemically inert.
(iii)Many of low molecular weight silicones dissolve in solvents like C6H6, ether and CCl4.
(iv) They do not become too viscous on cooling and are, therefore used for low-temperature,
lubrication.
(v) They are water repellent, i.e, they are not wetted by water and are, therefore used in
making waterproof cloth and paper by exposing cloth or paper to the silicone vapours.
(vi) All silicones have good insulating properties and can withstand high temperature without
charring. It is due to these properties that silicones are used as insulating materials for
electricotors and other electric appliances.
(vii) They are non-toxic.
(viii) Properties and uses of high-thermal silicones, silicones resins, silicones oils, silicone
rubbers and silicone greases have been give on the subsequent pages.
Uses:
a. Silicones have been used for making water-proof papers, wools, textiles, wood etc., after
coating these articles with silicones.
b. The viscosities of silicones do not change with changes in temperature; therefore, these are
used as all weather lubricants.
c. As antifoaming agent in industrial processes.
d. As a mould releasing agent in rubber industry and foundry. It avoids the sticking of the
castings to the mould.
e. For making body implants in cosmetic surgery due to its inert nature.
f. Silicones are now incorporated in paints for resisting dampness and for water proofing.
g. Due to their water repellent nature and high dielectric constant, silicones are used in
electrical condensers.

8.6 SUMMARY

Silicones and phosphazenes are examples of inorganic polymers. Inorganic elements can
have different valences than carbon and therefore, different numbers of side groups may be
attached to a skeletal atom. This will affect the flexibility of polymers, their ability to react with
chemical reagents and interactions with other polymers. Silicones are polymeric organo silicone

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derivative containing Si-O-Si linkages. These contain alternate silicon and oxygen atoms in
which the silicone atoms are joined to organic groups. These are also called Polysiloxanes.
These have the general formula (R2SiO)n.
The silicones polymers are highly stable towards heat. They exhibit thermal stability up
to 200 to 300°C and have low glass transition temperature.
The silicon fluids are usually linear polysiloxanes of 50 to 200 units having low
molecular weight. They make up about 60% the silicones used. If they are prepared by the
hydrolysis of a mixture of (CH3)2SiCl2 and (CH3)3SiCl, then the chain lengths may vary
considerably. Silicon oils/fluids are used as water repellents for treating building and fabrics.
Silicone resins are solvent solutions of branched chain siloxanes containing residual
hydroxyl groups. Silicone resins are made by dissolving a mixture of phenyl substituted
trichlorosilane, PhSiCl3 and dichlorosilane n toluene and hydrolysis with water.

8.7 TERMINAL QUESTIONS

8.7.1 Short answer questions

1. What is meant by glass transition temperature?

2. Draw the general repeating unit in silicones.
3. What is the structure of cyclic (NPF2)3?
4. Which groups of elements in the periodic table have been explored for the formation of
inorganic polymers?
5. Draw the general repeating unit in phosphazenes.
6. Draw resonance hybrid structures of cyclic (NPCl2)3.
7. Give one important use of silicone rubbers.
8. Give one important use of silicone oils.
9. What is meant by ring opening polymerisations?
10. Give the IUPAC names of Cl2siH2HSi(OH)3 and H3Si-O-SiH3

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11. General questions.How is cyclic (NPCl3)2 prepared? Give an account of it nucleophilic

substitution reactions.
12. Name four main structural units of silicones and designate them.
13. Why do polyphosphazene chains prefer cis-trans conformations to a trans-trans
conformation? Give thre important uses of polyphosphazenes.
14. Give equations to indicate the following reactions:
15. Draw polymeric backbones of silicones and phosphazenes.
16. Draw resonance hybrids of (HPCl2)3.
17. Explain important consequences of cross-linking in macromolecules.
18. Draw polymeric backbone of silicones.
19. What are silicones? How are cross linked silicones prepared?
20. Give islands model of bonding in cyclic (NPCl2)3.
21. Give a brief account of inorganic polymers with special reference to polyphosphazenes.
22. Silicones and phosphazenes are isoelectronic. What are its consequences?
23. Name three major classes of silicones elastomers.
24. What are silicones? Discus their polymerisation.
25. Draw polymeric backbones of silicones and phosphazenes.
26. Why does the π-system in cyclic (NPCl2)3 differ from p-system in C6H6?
27. What are silicones oils, silicones rubbers and silicones resins?
28. What is IUPAC name of [-Si (CH3)2O-]?
29. What are silicones? How will you prepare them?
30. What are phosphazenes? How will you prepare them? Discuss the structure of (PNCl2).
31. Write a short note on Silicones?
32. Discuss general properties of inorganic polymers.
33. What are different types of Silicones?
34. What are inorganic polymers? Classify them?
35. Discuss the preparation, properties and important reactions of phosphonitrilic halide.

8.7.2 Objective type questions

1. Hydrolysis of borazine gives:

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(a) B2O3 (b) B (OH)3

(b) B2H6 (d) H3N- BH3
2. Which of the following bonds is present in silicones?
(a) Si-Si-Si-Si (b) Si-C-Si-O-Si
(b) Si-C-Si-C-Si (d) –Si-O-Si-O-Si-

3. Hydrolysis of trialkyl chloro sialne gives:

(a) R3 Si-O-SiR3 dimer
(b) Cyclic (ring) silicone
(c) Cross-linked silicone
(d) None of these.

4. The strength and inetness of silicones are related to:

(a) Stability of silica-like skeleton of -Si-O-Si-O-Si-
(b) Very high bond energy of Si-O bond
(c) High strength of Si-C bond
(d) All of the above.

5. Hydrolysis of dialkyl dichloro silane gives:

(a) Linear silicone
(b) SiO2
(c) Cross-linked silicone
(d) None of these

6. The number of P-O-P bonds in cyclic metaphoshoric acid is:

(a) Zero (b) 2
(c) 3 (d) 4

7. Which of the following is a cyclic oxo acid?

(a) H5P3O10 (b) H6P4O13
(c) H5P5O15 (d) H7P5O16

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8. Sodium hexametaphosphate is used:

(a) As fertilizser
(b) For softening water
(c) In fruit ripening
(d) None of the above.
9. Which of the following is obtained when P4O10 is is heated with Na2O at 1000ºC.
(a) Sodium tripolyphoshate (Na5P3O10)
(b) Sodium tripolyphosphate hexahydrate (NaH2PO4)
(c) Sodium dihydrogen phosphate (NaH2PO4)
(d) Sodium hydrogen phosphate (Na2HPO4)
10. Sodium hexametaphosphate is known as:
(a Calgo (b) Permutit
(c) Nataliet (d) Nitrolim
11. Using Chlorobenzene (C6H5Cl) as solvent, the reagents needed for the synthesis fo
borazine are:
(a) NH4Cl, BCl3
(b) NH4Cl, BCl3, NaBH4
(c) NH4Cl, NaBH4
(d) NH3, BCl3

8.8 ANSWERS

1.(b) 2.(d) 3.(a) 4.(d) 5.(a) 6.(c) 7.(c) 8.(b) 9.(a) 10.(a) 11.(b)

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