SILICONES

R.DEIVENDRAN
III
B.SC,CHEMISTRY
ST. JOHN’S COLLEGE.
 SILICONES
 Silicones are organo-silicone polymers.

 Thesilicon atom can hold three hydroxyl group but

carbon atom can hold one hydroxyl group.

 Thisproperty of silicone make organosilicon

polymers possible.
 Properties of Silicon
 fourth group in the periodic table.

 Valancy is four, similar to carbon

 Polymer of silicon produced through condensation.

 The si-si bond is unstable in cause of large

molecules.

 Silicone forms polymer mainly through si-o-si bond.

 HISTORY OF SILICONS
English chemist Frederic Stanley kipping “FATHER OF SILICONE CHEMISTRY”

 with the help of Grignard reaction produced

 large number of silicone polymers

 General Electric company– 1940’s

commercialized silicone polymers

 E.G.Rochow (1909-2002) -
an American inorganic chemist
Worked on organosilicones
Structures of silicones
 PREPATION
1. When methyl chloride is heated with si in the
presence of “Cu” catalyst at high temperature a
mixture of alkyl chlorosianes are obtained
2. Hydrolysis of alkyl chloro silane forms alkyl
silandiols or silanols.
3. Polymerization of silanols give silicone polymers.
Hydrolysis of alkyl trichloro silane give alkyl trihydroxy
silanols which on condensation give a very cross linked
polymers.
 PROPERTIES
 Bond energy - 502kJ/mole.
The silicon oxygen bond (si-o) is highly stable.

 Highly strong

 Inert

 Non-stick

 Resistant to heat

 Water repellents
 TYPES OF SILICONES

 Silicones fluids or oils

 Silicone resins

 Silicone rubber

 Silicone greases.
 Silicones fluids or oils
 low molar mass straight chain polymer

 obtained by the hydrolysis and poly-condensation of

chlorotrimethylsilane, ethyl chlorosilane, containing monoand
bifunctional group.

 The commonly called silicone oil means the

polydimethylsiloxane(PDMS)
 Properties
 Density - 0.963 g/mL at 25°C

 Boiling point -140°C/0.002 mmHg(lit.).

 low vapor pressure, i.e., 5 mm Hg at 20°C.

 tasteless and clear

 water repellent, this oil also has a low surface tension.

 non-toxic

 anti-foaming properties and is widely used in the food service

industry.
 uses
 lubricant in woodworking construction Medical instruments
 ointments and skin creams
 hydraulic oil in aircraft
 heating baths in laboratories
 fermenting process in breweries
SILICONE RUBBER OR
ELASTOMERS
COMPOUNDING

CROSSLINKING
 COMPOUNDING
 Itconsist of milling (mixing under pressure) of
poly siloxane gum, a filler and cross linking agent
together with certain additives to obtain desired
physical properties.
 CROSS LINKING
Connect the polymer molecule to one another. So it
is become an elastomer.
 Preparation
Most of the silicon rubbers are synthesized from the
dimethyldichlorosilane.
• It involves 2 important steps:
1. Hydrolysis
2. Condensation

Hydrolysis
Polydimethylsiloxanes obtained by the hydrolysis of
dimethyldichlorosilane gives disilanol “Me2Si(OH)2”
which readily condenses, with HCl (acting as a catalyst)
to give a mixture of linear [3] or cyclic [4] oligomers.

These oligomers are water-washed, neutralized and

dried.
 polycondensation
 The linear [3] and cyclic [4] oligomers are
polymerized to give macromolecules of sufficient
length.

 Poly siloxane gum required for making linear

polymer of high molar mass . Since the tensil
strength of elastomer increases with increase in
the size of the gum polymer.
 Filers are added to reinforce the poly silioxane
gum which in itself is soft and weak.silca used as
filler
 Cross linking
 Silicon rubbers are saturated , they can be only vulcanized by
peroxide cross linking agent such as dibenzoyl peroxide .

 In this the efficiency of peroxide cross linking can be increased by

incorporating small amount of co-monomer containing vinyl group
into the polymer.
 The vulcanising temperature range between 120 and 130 degree
celcius.
 When the cross-linking agent is benzoyl peroxide,
 Cross linking or vulcanisation can be affected even at room
temperature.
Properties
 fineelectrical properties
 good chemical stability
 flame retardancy
 excellent resistance to heat and cold.
 high elasticity and compressibility
 tensile strength, tear strength, are far superior to
conventional rubbers.
 exceptional weather resistance
 metal detectable.
 glows in the dark
 Uses
 High-temperature-vulcanizing
silicone rubbers are used in the
automotive industry, in the
electrical transmission and
distribution sector, electrical
applications

 food and personal hygiene,

 machinery and plant construction
and in the construction industry

 electronics and optoelectronics,

 household appliances, machinery
 industrial plant engineering,
 medical applications and
photovoltaics.
These silicone elastomer particles are used in skin creams.
Their small and perfectly spherical shape combined with a
rubbery texture improves the feel of the cream as it is
applied to the skin.
 SILICONE RESINS
Silicone resins contain ring structure.
They have much higher cross linking density
than is found in silicone elastomers.
It is prepared from alkyl chlorosilane are
hydrolysed
90% of silanol group (SI-OH)condense to
form siloxane linkage.
10% remove difficult because mollecular
collision.
 Properties
 Heat resistance
Able to withstand temperatures up to 250°C.

 Weatherability
Good resistance to UV rays.

 Hardness
They form hard films due to their three-dimensional network structure.

 Water repellency
They form films with excellent water repellency (especially those that contain
methyl groups).

 Dielectric properties
They show excellent dielectric properties across a wide range of temperatures.
 Uses
 hydrophobic agents
for building protection
 used as an insulating
varnish
 Silicone Resin Mold
 non-stick coating pan
SILICONE GREASES
 Siliconegreases are made by
adding carbon black , or finely
dispersed silicon di oxide to
silicone oil.

slicone greases do not freeze at

low temperature as --40 and do not
melt at 200 degree celcus, hence
used as lubricants in aeroplanes.
 Miscellaneous USES
 Silicone rubber :
 Electrical insulators.
 water repellents
 flexibility

 It is used in space suits.