Polysulphide Rubber

Polysulfide rubber was discovered in 1926 by

an American chemist, Joseph Cecil Patrick
In commerce, the term "polysulfide" usually
refers to a class of polymers with alternating
chains of several sulfur atoms and
hydrocarbons. The general formula for the
repeat unit is –[(CH2)m–Sx]n– , where x indicates
the number of sulfur atoms (or rank), and n
indicates the number of repeating units,
Polysulfide rubbers were among the first commercial synthetic
rubbers produced. Two chemists, Joseph C. Patrick and Nathan
Mnookin, were trying to invent an inexpensive antifreeze in
1926.
In an experiment involving ethylene dichloride and sodium
polysulfide, they created a gum whose outstanding characteristic
was a terrible odor. Trying to dispose of it, the substance clogged
a sink in the laboratory, and none of the solvents used to remove
it were successful. The chemists realized that the resistance of the
material to any kind of solvent was a useful property.
They had invented synthetic rubber, which they christened
"Thiokol," from the Greek words for sulfur (theion) and glue
(kolla). The Thiokol Chemical Corporation was subsequently
founded on December 5, 1929.
Polysulfide polymers can be synthesized by condensation
polymerization reactions between organic dihalides and
alkal metal salts of polysulfide anions:
n Na2S5 + n ClCH2CH2Cl → [CH2CH2S5]n + 2nNaCl

Dihalides used in this condensation polymerization are

dichloroalkanes (such as 1,2-dichloroethane, bis-(2-
chloroethyl)formal (ClCH2CH2OCH2OCH2CH2Cl), and 1,3-
dichloropropane.
In some cases, polysulfide polymers can be formed by ring-
opening polymerization reactions. The polymers are called
thiokols.
Polysulfide rubbers are special-purpose polymers characterized by
High Resistance to Swelling in Solvents, Fuels, and Oils;
Resistance to Sunlight;
Resistance Moisture
Resistance Gas Impermeability;
Stability During Storage.

These properties result from the high sulfur content and the absence of
unsaturated bonds in the macromolecules.
density, 1.27–1.60 g/cm3;
glass transition point, –23° to – 57°C.
Zinc oxide, p-quinone dioxime, are used to vulcanize polysulfide rubbers.
Vulcanized polysulfide rubbers are inferior in mechanical properties to those
made from other synthetic rubbers—for example, their tensile strength is 6–
10 meganewton per sq m, or 60–100 kilograms-force per sq cm; relative
elongation, 200–400 percent.
Aplications
Polysulfide rubbers are used in rubberizing fuel storage tanks and
in the manufacture of oil- and gasoline-resistant tubing and of
gastight diaphragms for gas meters. Sealing compounds are
prepared from liquid Thiokols. Polysulfide polymers are
insoluble in water, oils, and many other organic solvents.
Because of their solvent resistance, these materials find use as
sealants to fill the joints in pavement, automotive window glass,
and aircraft structures.
 Silicone Elastomers

Nomenclature
Silane SiH4, corresponding to methane CH4.
Its Methyl Derivative will be
(CH3)2SiH2 dimethylsilane
CH3 Si*C13 trichloromethyl silane
(C6H5 )3 Si.C2H5 ethyltriphenylsilane
• Compounds having the formula
SiH3*(OSiH2)n0*SiH3 are referred to as
disiloxane, trisiloxane etc., according to
the number of silicon atoms.
 PREPARATION OF
INTERMEDIATES
• The polyorganosiloxanes are generally
prepared by reacting chlorosilanes with
water to give hydroxyl compounds
which then condense to give the
polymer structure, e.g.
 GENERAL METHODS OF PREPARATION
AND PROPERTIES OF
SILICONES
• Reaction of chlorotrimethylsilane with
water will produce a monohydroxy
compound which condense
spontaneously to form
hexamethyldisiloxane.
• Hydrolysis of dimethyldichlorsilane will
yield a linear polymer.

Hydrolysis of trichloromethylsilane yields a

network structure.
• A shorthand nomenclature is frequently
used in silicone
• For characterising branched and network
structures R/Si ratio is used.
 Process
Q rubbers are made commercially by the either the multistep
hydrolysis of dimethyldichlorosilane or by the ring opening
polymerisation of the cyclic oligomer
octamethylcyclosiloxane. In the hydrolysis procedure the
chlorine atoms are hydrolysed and replaced with a oxygen
atoms bonding a pair of silicon atoms.
Water is frequently replaced with methanol which leads to the
formation of methyl chloride rather than the more corrosive
hydrochloric acid.
In the ring opening polymerisation strong acid or base
catalysts are used to produce high molecular weight Q. The
ring opening polymerisation process can be conducted in an
aqueous emulsion procedure using dodecylbenzenesulphonic
acid as the catalyst.
 Structure
Most Q polymers have the repeat unit empirical formula of
((CH3)2SiO) and are referred to as polydimethylsiloxanes.
The elastomer consists of alternating silicon and oxygen atoms
with two methyl groups on each silicon. A significant departure
from most other elastomers is the absence of carbon in the
backbone.

Three reaction types are predominantly employed for the

formation of vulcanised Q:
 peroxide-induced free-radical vulcanisation,
 hydrosilylation addition cure,
 condensation cure.

Silicones have also been cross-linked using radiation to

produce free radicals or to induce photoinitiated reactions.
Condensation cure (Tin Catalyzed)
Condensation cure two-component silicone rubbers are excellent for most general mold making and
prototype applications. The rubbers are not sensitive to inhibition, meaning they will cure at room
temperature over virtually any surface. They're easy to mix and de-air, and they cure with only a slight
degree of shrinkage. The speed at which the rubber hardens can be accelerated with special activators.
Finished silicone molds are excellent for casting polyester, epoxy, polyurethane, gypsum and candle wax.

Addition cure (Platinum Catalyzed)

Addition cure two-component silicone rubbers offer superior heat resistance and cure with virtually no shrinkage.
Although the rubbers can be inhibited by tin, sulphur or amines, they can be cured in total confinement, and the cure rate
can be dramatically accelerated with heat. Finished P silicone molds are ideal for casting epoxies, low melting-point
metals.
MQ: silicone rubber with methyl substituent.
PMQ: silicone rubber with methyl and phenyl substituents.
VMQ: silicone rubber with methyl and vinyl substituents

In particular, phenyl vinyl methyl silicone (PVMQ) has the lowest glass transition
temperature (-120°C) of all elastomers, but its gas permeability is very high.
The typical silicones such as vinyl methyl siloxane, (VMQ) and PVMQ, are two
of the most permeable elastomers
Properties
Q does not crystallise even under strain and has very poor
physical properties.
Unfilled silicone rubber has only a 0.345 MPa tensile strength.
Q vulcanisates are reinforced with <25% finely divided fumed
silica. This reinforcing filler increases tensile strength, tear
strength, and abrasion resistance.
The Si-O-Si bonds in Q have a much lower energy of activation
for rotation than C-C bond or C-O bond. This makes Q
elastomers flexible and rubbery even at very low temperatures
and this elastomeric property is less affected by temperature
changes. This feature combined with the refractory
characteristics of Q makes these elastomers useful over a wide
temperature range.
Applications
Q elastomers are used for
electrical insulation,
medical devices,
seals,
elastic textile coatings
foams.
High permeability of silicone can be applied in
membranes for blood oxygenation, gas separation,
drug delivery.