SILICONES
[Link]
III
[Link],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
[Link] (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 [Link] 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.
