Silicones

Silicones
• These are organo- silicon polymers.
• These contain repeating siloxane –[Si – O – Si] – unit.
• The Si – O – Si linkage is very strong & makes the
silicones thermally stable and chemically resistant.
• The hydrophobic organo side chains or groups, R linked
to Si make these silicones water repellant.

• R groups can be methyl, ethyl, alkoxy, phenyl, vinyl, etc.

 Preparation of silicones

• Preparation of silicones involves TWO steps.

• 1. Preparation of intermediate organo halo

silanes
( or organo silicon halides); R2SiX2 , RSiX3.

• 2. Hydrolysis of halosilanes to silanols and then

condensation.
 Preparation of silicones

• Preparation of intermediate organohalosilanes:

• a. Reacting alkyl halide and Si catalysed by Cu at

300oC in the presence of HCl acid.

CH3Cl + Si + 2HCl CH3 Si Cl3 + H2 .

• b. Using Grignard reagent and SiCl4 or lower organo-

silicon halides.

CH3 Mg Cl + SiCl4 CH3SiCl3 + MgCl2 .

• CH3 Mg Cl + CH3SiCl3 (CH3)2SiCl2 + MgCl2 .

 Preparation of silicones

• c. Reacting metal alkyls with SiCl4 or RSiCl3.

SiCl4 + RNa RSiCl3 + NaCl.

RSiCl3 + RLi R2SiCl2 + LiCl.

 Preparation of silicones

• Hydrolysis and condensation of intermediates:

•
• Hydrolysis of organohalosilanes silanols which
condense to form silicones.
• Hydrolysis: R2SiCl2 + H2O R2Si(OH)2 + 2HCl

• R2Si(OH)2 forms the linear silicone polymers.

• Condensation:
 Preparation of silicones
• RSiCl3 upon hydrolysis and condensation give cross-
linked silicone polymers.
 Silicone fluids, gums & resins
• Silicone fluids, gums & resins are prepared from
cyclopolysiloxanes by a method known as equilibration.

• Silicone fluids:
• These are low mol.wt. straight chain polymers.

• These are prepared by hydrolysis of dichlorosilanes.

• Also prepared by equilibration of cyclopolysiloxanes
with a disiloxane as shown :
• Polysiloxane gums:
• These are straight chain high mol.wt. polymers.
• These are prepared by equilibration of cyclic siloxanes
in the absence of monofunctional groups.
• The resulting straight polymers are end-blocked by the
catalyst such as KOH.
 Silicone rubbers
• Silicone rubbers or elastomers are obtained from
silicone gums by compounding and cross linking
processes.
• Compounding:
• The polysiloxane gum is milled or mixed under high
pressure with a filler, cross linking agent and some
additrives to get desired properties.
• Example: Benzene-soluble polysiloxane gum (100 parts)
+ 25- 50 parts SiO2 filler, 6 parts benzoyl peroxide as
vulcanizing agent and suitable amounts of additives.

• Cross linking (vulcanization):

• This step involves cross-linking & curing processes.
• For producing silicone rubbers, linear polysilicone gums
with high mol.wt. are used.
• Cross-linking can be effected at room temp. using
catalysts like Pb compds or organotin.
• Silicone rubbers have good elastomeric property, high
thermal stability, resistance to oxidative degradation,
chemical stability and water repelling power.
• Silicon resins:
• These contain ring structures.
• Have high degree of cross-linking. The properties
depend upon the ratio of alkyl group R to Si.
•
• Preparation: Involves
• Hydrolysis of a mixture of chlorosilanes such as
CH3SiCl3, (CH3)2SiCl2 C6H5SiCl3, (C6H5)2SiCl2,
C6H5(CH3)SiCl2, etc.

• Nearly 90% of the silanol, Si- OH groups formed

condense to form siloxane linkages.
• Then the product is extracted into an organic solvent,
washed to remove Cl- ions to prevent reversibility of the
hydrolytic reaction.
• The viscosity of the finished resin depends upon the
residual silanol groups left uncondensed in the product.
• These groups undergo condensation when the resin is
applied.
• The substituents on Si alter the properties. CH3 - groups
give flexibility; C2H5-, C3H7-, etc make the resin softer,
increase solubility in organic solvent, & increase water-
repllence.
 Properties of silicone polymers

• Physical properties & uses of silicones(organopolysiloxanes)

are determined by the kind and number of organic groups
present on the silicon atoms. Also on the manner in which the
siloxane units are linked together.

• Thus, CH3 groups on Si promote fluidity, low viscosity, low

m.pt., and high liquid compressibility.

• But the Ph groups on Si induce the contrasting properties.

• The number of organic groups determine the functionality of

individual siloxane building units & control linearity or
complexity of silicones.
 Properties of silicone polymers
• Silicones are thermally stable and chemically inert due to the
strong Si – O bond.

• Strong bases and acids cause de-polymerization.

• Water repellant due to the presence of hydrophobic organic

side chains (groups, R)

• Have high electrical insulating property,

• Non- sticky and antifoaming.

• Depending upon the degree of polymerization and cross-

linking, silicones are obtained as fluids, rubbers and resins.
 Applications:

• 1. Silicone fluids have good insulating properties and

thermal stability; used in transformers, vacuum
pumps, high temp. oil baths,

• 2. Silicone greases have wide service temp. from -100oC

to 450oC; useful for high speed & high temperature
applications.

• 3. Silicone gums are used as lubricants, antifoams,

textile finishing.
 Applications:
• 4. Silicone rubbers are very useful due to their high
flexibility, thermal and chemical inertness, non-
wet ability, low temperature performance.
• 5. They have biocompatibility & useful in artificial veins.

• 6. Silicone resins are characterized by good thermal

stability, weather resistance, chemical inertness, water
repellency and electrical insulator property. They find
applications for laminating, coating, surface
water-proofing, moulding, coating cooking pans etc.