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Special Purpose Synthetic Rubbers

Properties or combination of properties which make them


suitable for a particular application e.g.
Oil resistance
Chemical resistance
Extreme temperature resistance
Important special purpose rubbers are
Nitrile rubber
Chloroprene rubber
Chlorosulphonated polyetylne rubbers
Slicone rubbers
Polysulphide rubbers
Flurocarbon rubbers
Polyurethane rubbers

Nitrile rubber is a synthetic rubber copolymer of


acrylonitrile (ACN) and butadiene. Some trade names are:
Nipol, Krynac and Europrene.
Acrylonitrile butadiene rubber (NBR) is a family of
unsaturated copolymers of 2-propenenitrile and various
butadiene monomers (1,2- butadiene and 1,3-butadiene).
Although its physical and chemical properties vary
depending on the polymers composition of acrylonitrile
(the more acrylonitrile within the polymer, the higher the
resistance to oils but the lower the flexibility of the
material), this form of synthetic rubber is generally resistant
to oil, fuel, and other chemicals. Contd

Its resilience makes NBR the perfect material for disposable lab,
cleaning, and examination gloves. In the automotive industry, it
is used to make fuel and oil handling hoses, seals and grommets.
NBRs ability to withstand a range of temperatures from -40C
to +120C makes it an ideal material for extreme automotive
applications. Acrylonitrile butadiene is also used to create
moulded goods, footwear, adhesives, sealants, sponge, and floor
mats. Compared to natural rubber, nitrile rubber is more
resistant to oils and acids, but has inferior strength and
flexibility. Nitrile rubber is generally resistant to aliphatic
hydrocarbons. However (like natural rubber), it can be attacked
by ozone, aromatic hydrocarbons, ketones, esters and
aldehydes.

Production Process
In the production of hot NBR, emulsifier (soap), 2propenenitrile (acrylonitrile), various butadiene
monomers (including 1,3-butadiene, 1,2-butadiene),
radical generating activators, and a catalyst are added to
polymerization vessels. Within the vessel, water serves
as the reaction medium. The tanks are heated to 30C40C to facilitate the polymerization reaction and to
promote branch formation in the polymer. Because
several monomers capable of propagation the reaction
are involved in the production of nitrile rubber, the
composition of each polymer can vary (depending on
the concentrations of each monomer added to the
polymerization tank and the conditions within the tank).
Contd

One repeating unit found throughout the entire


polymer may not exist. For this reason, there is also
no IUPAC name for the general polymer. The
reaction for one possible portion of the polymer is
shown below:
1,3-butadiene + 1,3 butadiene + 2-propenenitrile +
1,3-butadiene + 1,2-butadiene => acrylonitrile
butadiene rubber
Monomers are usually permitted to react for 5 to 12
hours. Polymerization is allowed to proceed to
~70% conversion before a shortstop agent (such
as dimethyldithioarbamate and diethyl
hydroxylamine) is added to react with the remaining
free radicals.
Contd.

Environmental Concerns
Acrylonitrile is considered an environmentally hazardous
substance that cannot be freely ejected into the
environment (it must be disposed through a rotary kiln,
fluidized bed, liquid injection incineration, or
underground injection). Because the compound is quite
volatile and readily soluble in water, its release to the
environment from waste sites is a concern. 1,3
butadiene is very reactive in the presence of hydroxyl
radicals, and therefore possess high ozone creation
potential. As mentioned previously, however, unreacted
monomer recovery is nearly 100% in the process outlined
above. Since unused monomers can easily be recycled, its
disposal is not an unbearable concern. Thus, despite more
stringent disposal restrictions, acrylonitrile butadiene
rubber is produced throughout North America.

Once the resultant latex has shortstopped, the unreacted


monomers are removed through a steam in a slurry
stripper. Recovery of unreacted monomers is close to
100%. After monomer recovery, latex is sent through a
series of filters to remove unwanted solids and then sent to
the blending tanks where it is stabilized with an
antioxidant. The yielded polymer latex is coagulated using
calcium chloride, aluminum sulfate, and other coagulating
agents in an aluminum tank. The coagulated substance is
then washed and dried into crumb rubber.
The process for the production of cold NBR is very similar
to that of hot NBR. Polymerization tanks are heated to
5C- 15C instead of 30C to 40C. Under lower
temperature conditions, less branching will form on
polymers (the amount of branching distinguished cold
NBR from hot NBR).

Better known as Nitriles, reinforced NBR rubbers have


good oil and gasoline resistance, tensile strength,
elongation properties, heat resistance and low
compression set. Special compounding is required for
good weatherability.
Typical application for these medium priced rubbers are
seals, O-rings, gaskets, diaphragms, pipe gaskets, tank
linings, boots and bellows. A carboxylated version of
high-acrylonitrile butadiene copolymer (XNBR) is
available for application requiring the ultimate in wear
resistance. In the reinforced state, this medium-priced
rubber also offers high tensile strength and elongation,
as well as, high load bearing capability. These properties
are obtained without any sacrifice in the other
properties of conventional, high-acrylonitrile
copolymers.

Nitrile Rubber
By the emulsion polymerisation of butadiene and acrylonitrile.

CH2=CHCH=CH2

CH2=CH

CN

CH2=CHCH=CH2

CH2=CH
CN

Nitrile rubber

Rubber Production

Dry rubber
Polymerisation
Coagulation
Washing
Drying

Latex
Polymerisation
Stabilization
Concentration

Nitrile Rubber Production

Hot polymerization
( 25- 50 oC )
High gel content
Tough
Difficult to process

Cold polymerization
( 5 oC )
Linear
No gel
Easy Processability

Polymerization
Butadiene

67

Acrylonitrile

33

Water

200

Emulsifier

3.5

Modifier

0.5

Electrolytes

0.3

Activator

0.05

Short stop

0.1

Stabilizer

1.25

Controlling factors
Monomer ratio
Temperature
Polymerisation nature
Amount of modifiers and emulsifiers

Producer

Trade Name

M/s. Synthetics & Chemicals

Chemaprene

Bayer, Germany

Perbunan

Polymer Corporation, France

Polysar

Aku-Goodrich, Netherlands

Hycar

Japan Synthetic Rubber Co.Ltd,


Japan

JSR

Fire-stone tyre &Rubber Co

Butaprene

Nitrile Rubber is available in several grades depending


on the acrylonitrile content

As the acrylonitrile content increases


Oil resistance improves
Fuel resistance increases
Tensile strength increases
Hardness increases
Abrasion resistance improves
Gas permeability increases
Heat resistance increases
Low temperature resistance decreases
Resilience decreases
Plasticizer compatibility decreases

Nitrile Rubber
Slab
Sheet
Crumb
Powder
Liquid

Widely used forms


Adhesives
Blends eg. NBR/PVC

Properties
Low tensile strength
Better heat resistance
Poor ozone resistance

Oil resistance
Tendency to retain the physical properties while in
contact with oils and fuels

Oil resistance depends on


Proportion of acrylonitrile
Chemical nature of fuel or chemical
Degree of crosslinking
Polymerization temperature
Homogeneity of the polymer
Lower the aniline point higher will be swell

Compounding of NBR
Preliminary breakdown of NBR is most important compared to NR
Less plastic than NR and will develop more heat.
Breakdown on a cold tight mill for 5-10 min is ideal

Activation
ZnO 5 parts is used for activation

Sulphur
Solubility of sulphur is less
1-2 parts of sulphur is sufficient

Fillers
Semi reinforcing carbon black is generally used
Phenolic resins and PVC are also used
(better ozone resistance, good weathering, better gloss,
high abrasion and oil resistance, bright colour)

Plasticizers
To improve the mixing and processing properties
To reduce the hardness
Ester and phenolic plasticizers are used
Aromatic oil can also be used

Accelerators
TMTM, MBTS and MBT are generally used
1.5 MBTS is sufficient
Peroxides can also be used for curing

Antioxidants and stabilisers


1-3 phr antioxidant/antiozonants is to be added
Blending with PVC also impart good ozone resistance

Lubricants
1 part of stearic acid is added for activation and processing

Applications
High acrylonitrile grade is for resistance to aromatic oils, fuels
and solvents eg. Oil well parts, fuel cell liners
Medium grades are used with oil of lower aromatic content
Low acrylonitrile is used where low temperature flexibility is required

Chloroprene Rubber
CH2= CCl CH = CH2

CH2- CCl =CH- CH2 n

Properties

Medium oil resistance


Metal oxides are used for vulcanisation
Good ozone/weather resistance
Good flame resistance

Producer

Trade name

Du pont

Neoprene

Bayer

Bayprene

Distugil

Butachlor

Rubber Production

General purpose

Sulphur
modified
(C- type)

Special purpose
(AC & CG

Rapid cure
High resilience
Good tear resistance

Mercaptan
modified
(W-type)

Adhesives
Paints

Excellent storage
Stability
Crystalization
resistant

Compounding
5 phr Zno + 4 phr MgO is the vulcanising agent
Ethylene thiourea (NA 22) also used
For W-type sulphur/accelerator is essential
Type GN

100

Type W

100

PBN

MgO

ZnO

NA 22

0.5

Antioxidant
Diaryl P-phenylene diamine is used as the antiozonant

Fillers
All types of fillers are suitable
Plasticisers are essential
Petroleum oil as softeners

Applications
Wire and cable industry
Hoses and beltings
Automobile parts

Chlorosulphonated Polyethylene
Made by substituting chlorine and sulphonyl chloride groups
into polyethylene
This modification changes the stiff plastic into a flexible rubbery
polymer and the sulphonyl chloride groups provide reactive centres
for cross linking
5 grades of hypalon are available. Their chlorine content varies
Fron 29-43% and sulphur content from 1-1.4%.

Properties
Outstanding ozone resistance
Light stability
Heat resistance
Weather resistance
Oil resistance
Abrasion resistance
Excellent storage stability

Compounding
Sulphonyl chloride + Traces of water + pentaerythritol+ divalent
metallic oxide
Accelerator+alky chloride+metalic oxide

Compounding
Hypalon

100

100

100

Litharge

25

20

MBTS

0.5

0.5

Tetrone A

2.0

0.75

2.0

Magnesia

10

Pentaerythritol

Recommended use

General
purpose

Heat
resistant

Non-black

Applications
Many domestic and industrial articles
Automobile industry
Conveyor belting
Coated fabrics
Wires and cable sheathing
Industrial roll covering
Discharge hoses

Polysulphide rubbers
Reaction of a dithalide and sodium or calcium polysulfides
Properties
The properties of polysulphide rubbers depend upon the
structure of polysulphide rubbers.
The vulcanizing agents are ZnO, Calcium peroxide and
lead peroxide

Applications
Printer rolls
Seals
Gaskets
Adhesives

Silicone Rubbers
The polymer backbone is formed by an alternating row of silicon
and oxygen atoms

Applications
High temperature applications
Cables, wires and general electrical goods
Illumination
In medicine

Fluoro Carbon Rubbers


Amines and MgO, PbO or ZnO are used as crosslinking agents

Applications
Seals
In aerospace
Chemical industry

Urethane Elastomers
Made from low molecular weight polyester or polyether

Applications
Solid tyres
Seals and boots
Calendered sheeting
General engineering mechanical goods