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TRIBHUVAN UNIVERSITY
INSTITUTE OF ENGINEERING
PULCHOWK CAMPUS
Pulchowk, Lalitpur

A JOURNAL ON INORGANIC POLYMERS

Date: 2078/4/16

Submitted By Submitted To
Name: Prajit Bhattarai Department Of Applied science
Group: Civil (e/f) And Chemical Engineering
Roll No:077BCE102 (Ram Kumar Sharma)
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TABLE OF CONTENTS
Topic Page No:-
1. Introduction to polymers and its classification 3
2. Types of inorganic polymer 4
3. Preparation of inorganic polymer 4
4. Poly phosphazenes 4
4.1) Polydimethoxy and poly diethoxy phosphazine 5
4.2) phosphonitrile chloride 5
5. Sulphur based inorganic polymers 6
5.1) . Linear chain polymer 6
5.1(a) polymeric Sulphur 6
5.1( b)Polymeric Sulphur nitride 6
5.2) Network polymers/chalcogenide glass/ chalconide glass 6
6. Silicones or silicone polymer 7
6.1) Liquid Silicones 9
6.2)Silicone greases 9
6.3)Silicone rubbers 10
6.4)Silicone resins(solid) 10
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INORGANIC POLYMERS

INTRODUCTION:-
Those substances which have large number of atoms of same type are known as
polymers. They are made up of combination of simple molecules known as monomers.
Monomers are simple molecules which repeatedly combine under suitable conditions to form
polymers. When two molecules combine with each other then thus formed molecule is known as
dimer and if three molecules combine with each other then thus formed unit is known as trimer.
Thus a polymer with two monomer unit is known as dimer and 3 monomer unit is known
as trimer.
M+M  M-M(dimer)
M+M +M  M-M-M(trimer)
M+M+M+………+M  nM(Polymer)

n-monomer units

The types of polymers on the basis of mode of formation are :-

1) Natural Polymers
2) Synthetic Polymers
3) Homo polymer and copolymer
1.Natural polymers :-
The polymers which are obtained from nature is known as natural polymers. They are
generally carbon containing organic polymers. For example, starch, cellulose etc.
2. Synthetic polymers :-
The polymers which are synthesized artificially in laboratory is known as synthetic
polymers. For example Bakealite, Teflon, PVC etc.
3.Homopolymer or Copolymer
A polymer made up of single monomer unit is known as Homo polymer. For example
polyethene. Polymer made up of multiple monomer unit is known as copolymer. For example
terylene.
There are two types of polymer
1) Organic polymer
2) Inorganic polymer
NOTE:-All macromolecule are not polymers but all polymers are macromolecule .
1.Organic Polymer
Those polymers which contain carbon in their backbone is known as organic polymers.
For example PVC, Cellulose etc. Organic polymers are ‘macromolecule’ built by the liking
together of large no. of small molecules called monomers.[2]
2.Inorganic polymer
Inorganic polymers are those polymers which do not contain carbon atoms in their backbone.
An inorganic polymer is a polymer with a skeletal structure that does not include carbon atoms in
the backbone[1].Inorganic polymers have wide and extensive use in today’s world. Inorganic
polymers are macromolecule formed
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Inorganic polymer

Polyphosphazines Sulphur based Polymers Silicones

1) Polydimethoxy and poly 1)Linear chain

diethoxy phosphazine a) polymeric Sulphur 1) Liquid Silicones
2) phosphonitrile chloride b)Polymeric Sulphur 2) Silicone greases
nitride 3) Silicone rubbers
2)Chalcogenide glass or 4) Silicone resins(so lid )
Network Polymer

Preparation and uses of inorganic polymer

Polyphosphazines
Polyphosphazines are inorganic polymers . they contain phosphorus atoms as central atom of
unit particles.[2] Polyphosphazines (PPHOs) are high molecular weight polymers with an
inorganic backbone of alternating phosphorus and nitrogen atoms with two side groups on each
phosphorus atom. Polymers with a wide range of properties can be synthesized from
this polymer backbone by incorporating different side groups, by varying the side group in
single-substituent PPHOs, and/or by using two or more co-substituents. Individual PPHOs may
be hydrophobic, amphiphilic, or hydrophilic; water-stable or water-erodible; crystalline or
amorphous; bioinert or bioactive. The hydrophobicity of the PPHO is increased by adding
hydrophobic side groups, such as aromatic groups, to the backbone.

RR
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Fig 1.1: Polyphosphazenes

[2]
Preparation :-
Polyphosphonitrile Chloride:-
They are prepared by heating cyclic tetramer in vaccum in about 2500 C.

Cl

nPCL5 +NH4 Cl C2 H2 Cl2H P=N-Cl +(PCl2 N)3 + (PCl2 N)3 + (PCl2 N)4
-(4n-1)HCL
Cl n

Cl

n (PCl2 N)4 H P=N-Cl +P4 +2N2 + 3Cl2

vaccum/2500c
Cl 4n-4
Chain polymer
The chain polymer has limited solubility n inorganic solvents and it also forms cross linked to
some extent

Polydimethoxy and poly diethoxy phosphazenes

They are prepared by reacting of phosphonitrile chloride with sodium methoxide (CH3 ONa)
respectively.

Cl OCH3

P=N- CH3 ONa P=N

Cl n OCH3 n
Polyphosphonitrile chloride Polydimethoxy phosphazenes

Cl OC 2 H5

P=N- C2 H5 ONa P=N

Cl n OC 2 H5 n
Polyphosphonitrile chloride Polydiethoxy phosphazenes

Uses:-[2]
i. They are used for making transparent and film foaming thermopolymers.
ii. They have much lower electrical conductivity so used as insulators
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SULPHUR BASED INORGANIC POLYMERS

Sulphur based polymers are classified as following:
a. Linear chain polymer
b. Network polymers/chalcogenide glass/ chalconide glass
a)Linear chain Polymer
i. Polymeric Sulphur (PS):
It is prepared by heating rhombic sulphur at 165 o C to 168 o C following by quenching the molten
mass on ice bath. The reaction mixture is washed with carbon disulphide (CS2) to remove excess
of S 8 (not with Water)[3]

S S
S S

ii.Polymeric Sulphur nitride

It is nearly plannar chain of S-N bonds of approximately identical length of nearly 16mm .
[3]
Polythiazyl also known as polymeric sulfur nitride (SN)n is an electrically conductive gold
coloured polymer with metallic luster.
S 16mm N S
120 0
N S S

Polythiazyl is synthesized by the polymerization of the disulfur dinitride (S 2 N 2 ; a dimer), which

is synthesized from the cyclic alternating tetrasulfur tetranitr ide (S 4 N 4 ; a tetramer) in the
presence of hot silver wool as catalyst.
8Ag+S 4 N 4 4Ag2 S + 2N 2
S 4 N 4(Vap) Ag2 S 2S 2 N 2
n(S 2 N 2 ) 00C (SN)2n
[2]
NOTE:- Its electrical conductivity at room temperature is about 1200 to 3700 siemen lowering
the temperature to 4.2k it becomes superconductor . This polymer is first non metallic super
conductor.
b) Network polymers/chalcogenide glass/ chalconide glass
[1]
Chalcogenide glass (pronounced hard ch as in chemistry) is a glass containing one or
more chalcogens (sulfur, selenium and tellurium, but excluding oxygen). Such glasses
are covalently bonded materials and may be classified as covalent network solids.
The chalcogenide glasses form a family of amorphous cross linked polymers formed by
compounds of chalcogens (ore forming: sulphur, selenium and tellurium) with one or more of
polyvalent elements such as arsenic, antimony, bismuth, indium, germanium, phosphors, tin and
thallium. The best known chalcogenide glass is (As2 S 3 )n.
Chalcogenide glasses are prepared by melt-quinching or passing the chalcogen compounds
vapour over the polyvalent elements like arsenic, antimony, indium, germanium, phosphorus, tin
and thallium.
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Fig 2.2:- A CD-RW (CD). Amorphous

Fig 2.1:- Chalconide glass(As2 S 3 )
chalcogenide materials form the basis of re-
writable CD and DVD solid-state memory
technology.[1]

Uses:-
i) Memory device for computers
ii) Electroluminescent displays
iii) High energy particle detector multipliers
iv) Ultra sonic delay lines
SILICONES OR SILICONE POLYMER
Silicon polymer contains silicon-oxygen alternate structure chain which hasnorganic
radicals as so a side chain attached to the silicon atoms. The common structure of silicon is as
follows.
R R R

R Si O Si O Si R

R R R
Where R=alkyl or phenyl radical

Preparation
The prepared by action of silicon with alkyl halide or silicon halide with Grignard
reagent.
CH3 Cl+Si CH3 SiCl3 ; (CH3 )2 SiCl2
SiCl4 +7CH3 MgCl (CH3 )3 SiCl;(CH3 )4 SiCl2 + 7MgCl2
The reacting products are formed are found in separate layer in the same reacting pot which is
separated by which is separated by fractional distillation and give organo silicon chlorides, which
are then polymerized by carefully controlled hydrolysis.

Molecular formula Name Type of functional group

CH3 SiCl3 Monomethyl silicon Monofunctional
trichloride
(CH3 )2 SiCl2 Dimethyl silicon dichloride Bifunctional
(CH3 )3 SiCl Trimethyl silicon chloride Trifunctional
(CH3 )4 Si Tetramethyl silicon Tetrafunctional
Table 3.1
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NOTE:- Tetramethyl silicon doesnot form any polymer or does not polymerise due to lack of
functional group

Linear silicones are prepared by the hydrolysis of bifunctional dimethyldichlorosilane

(CH3 )2 SiCl2 as following:

Monomethyl Silicon Trichloride

It is a ‘trifunctional’ unit particle and it gives cross linking to the final polymer. Its
proportion used in polymerization determines the amount of cross linking that can be obtained.

Fig:- synthesis of Monomethyl Silicon Trichloride

Dimethyl Silicon dichloride

It is a bifunctional unit particle after npolymerization. It gives klinear chain polymer or dimethyl
silicon polymer or silicon rubber.

CH3 CH3 CH3 CH3

Cl Si Cl + H2 O Cl Si Cl + HCl Si O Si O

CH3 n CH3 n CH3 n CH3

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Trimethyl Silicon chloride

It is a ‘monofunctional’ and it is also known as chain stopper unit particles. This is therefore used
in proportions to limit the chain length.
CH3 CH3 CH3 CH3

CH3 Si Cl + H2 O CH3 Si Cl + HCl CH3 Si O Si CH3

CH3 CH3 CH3 CH3

Different types of silicon polymer and their uses

Liquid silicons or silicon oils:-
A silicone oil is any liquid polymerized siloxane with organic side chains. The most important
member is polydimethylsiloxane. These polymers are of commercial interest because of their
relatively high thermal stability and their lubricating properties.[4]

Fig 3.1:- Structure of liquid silicone rubber[5] Fig 3.2:- Silicone oil
USES:-
a) Silicone oils have been used as a vitreous fluid substitute to treat difficult cases of retinal
detachment, such as those complicated with proliferative vitreoretinopathy, large retinal
tears, and penetrating ocular trauma.(Medical use)[5]
b) Additionally, silicone oil is used in general medicine and surgery. Because of silicone
oil's water repellent and lubricating properties, it is considered an appropriate material to
maintain surgical instruments. They are also used in digital rectal examinations (DRE).[5]
c) Silicone oil has been commonly used as the fluid in the automobile cooling fan
clutch assemblies, and is still being used in the newer electronic fan clutches.[7]

Silicon greases
Silicone grease, sometimes called dielectric grease, is a waterproof grease made by
combining a silicone oil with a thickener. Most commonly, the silicone oil
is polydimethylsiloxane (PDMS) and the thickener is amorphous fumed silica. Using this
formulation, silicone grease is a translucent white viscous paste, with exact properties dependent
on the type and proportion of the components. More specialized silicone greases are made from
fluorinated silicones or, for low-temperature applications, PDMS containing
some phenyl substituents in place of methyl groups. Other thickeners may be used,
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including stearates and powdered polytetrafluorethylene (PTFE).[8]

USES
They are particularly used in form of lubricants in situation where very high and very low
temperatures are encountered.
Solid silicon resins
Silicone resins are a type of silicone material which is formed by branched, cage-
like oligosiloxanes with the general formula of Rn SiXmOy , where R is a non reactive substituent,
usually Methyl (Me) or Phenyl (Ph), and X is a functional group Hydrogen (H), Hydroxyl
group (OH), Chlorine (Cl) or Alkoxy group (OR). These groups are further condensed in many
applications, to give highly crosslinked, insoluble polysiloxane networks

Fig 3.3 :- Structure of silicone resin

USES:-
They are used for making high temperature insulating foams for making high voltage insulators.

Silicone Rubbers():
Silicone rubber is an elastomer (rubber-like material) composed of silicone—itself
a polymer—containing silicon together with carbon, hydrogen, and oxygen. Silicone rubbers are
widely used in industry, and there are multiple formulations. Silicone rubbers are often one- or
two-part polymers, and may contain fillers to improve properties or reduce cost. Silicone rubber
is generally non-reactive, stable, and resistant to extreme environments and temperatures from
−55 to 300 °C (−70 to 570 °F) while still maintaining its useful properties. Due to these
properties and its ease of manufacturing and shaping, silicone rubber can be found in a wide
variety of products, including voltage line insulators; automotive applications; cooking, baking,
and food storage products; apparel such as undergarments, sportswear, and footwear; electronics;
medical devices and implants; and in home repair and hardware, in products such as silicone
sealants.[9]
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Fig 3.4:- structure of silicone rubbers[9]

Properties of Silicones
i. Depending on the proportion of various alkyl silicon halides used during the
preparation, silicones may be liquid, viscous liquids, semi-solid (grease), rubber and
solids.
ii. Because of the oxygen-silicon bonds (bond dissociation energy = 502kJmol-1 ), they
exhibit outstanding stability at high temperature.
iii. Because of the presence of alkyl groups surrounding the silico n atoms makes the
molecule hydrophobic and gives water repelling tendency of silicones.
iv. Their physical properties are less affected by the change of temperatures.
v. They are non-toxic.[3]

Uses:-
i. Straight chain polymers up to 500 units are silicones fluids. They are used as water
repellent for treating buildings, glassware and fabrics. They are also included in car
and shoe polish. Silicones fluids are non toxic and have low surface tension;
therefore, addition of a few parts per million of it greatly reduces foaming in sewage
disposal, textile dyeing, beer making and frothing of cooking oil in making potato
crisps and chips. Silicone oils are used as dielectric insulating material in high voltage
transformers. They are also used in hydraulics fluids.
iii. Silicone greases are made by mixing silicones oil with lithium stearate soaps and are
used as lubricants where high and low temperatures are encountered .
iv. Silicones rubbers are obtained by mixing long chain silicones with filler like silicon
dioxide in the presence of curing agent like peroxide. Rubber has 6000 to 600000 Si
units. Silicon rubber is useful because they retain their elasticity from -90 0 C to 250 0 C,
which is much wider range as compared to natural rubber. They are used in making
tyres of aircraft and racing cars, as sealing material in search lights and aircraft
engines, in making lubricants, paints and protective coatings. For making boots for
the use at very low temperature (Neil Armstrong used silicones rubber boots while
walking on the moon).
v. Silicones resins are highly cross-linked silicones. They are used in making high
voltage insulator, making printed circuit boards and to encapsulate integrated circuits
chips and resistors. They are also used as non-stick coatings for pans, moulds for
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making car tyres etc [3]

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REFERENCES:-

[2]
Sharma and panthi;A text book of engineering chemistry: first edition(2011),Atharai
Publication(Pvt.)Ltd.
[1]
Phosphazene - Wikipedia
[3]
Polymer-Notes-2017.pdf (kec.edu.np)
[5]
https://www.researchgate.net/figure/S tructure-of-Liquid-Silicone-Rubber_fig6_285619483
[7]
Doremus, R. H. (2002). "Viscosity of silica". J. Appl. Phys. 92 (12): 7619–7629
[8]
Thorsten Bartels et al. "Lubricants and Lubrication" in Ullmann's Encyclopedia of Industrial
Chemistry, 2005, Weinheim.
[9]
https://en.wikipedia.org/wiki/Silicone_rubber
[10]
c5ra06433c-s2_hi-res.gif (1536×1118) (rsc.org)
[4]
Silicone oil - Wikipedia